Ranking and evaluating light to heavy rare earth deposits worldwide
exploration considerations to economic assessment
Mushghi
Khudag
-
Mongolia
David Lentz amp Anthony N Mariano
Major Considerations
Assuming a favourable political climate and good logistics conditions determining the viability of deposits that can compete in the world market are as followshellip
1) Mineralogy and favourable lanthanide distribution
2) Grade and tonnage
3) Amenability to mining and mineral processing at low costs and successful chemical cracking of the individual lanthanides for their isolation
4) Acceptable low values of accompanying deleterious impurities
5) Minimum impact on the environment
Any lower production costs can significantly reduce the grade requirements
USGS facts
USGS facts
USGS facts
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Major Considerations
Assuming a favourable political climate and good logistics conditions determining the viability of deposits that can compete in the world market are as followshellip
1) Mineralogy and favourable lanthanide distribution
2) Grade and tonnage
3) Amenability to mining and mineral processing at low costs and successful chemical cracking of the individual lanthanides for their isolation
4) Acceptable low values of accompanying deleterious impurities
5) Minimum impact on the environment
Any lower production costs can significantly reduce the grade requirements
USGS facts
USGS facts
USGS facts
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
USGS facts
USGS facts
USGS facts
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
USGS facts
USGS facts
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
USGS facts
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
106 107 108 109 1010
Tonnes
of Ores
Gra
de (w
t)
01
10
10
100
Richardson amp Birkett
1996
GSCCarbonatites
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Tonnes
of ore Richardson amp Birkett
1996
GSCPeralkalic
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Richardson amp Birkett
1996
GSCPeralkalic
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Tonnes
of ore Richardson amp Birkett
1996
GSC
Peralkalic
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Kvanefjeld REE-U deposit Ilimaussaq Complex
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
bull
This new resource statement estimates the inventory of contained metal within
a 457 Mt
ore body to be 491 Mt
of Total Rare Earth Oxide (TREO) 099 Mt and Zinc 012 Mt of Uranium Oxide (283 Mlbs) and 309 Mt of NaF
bull Indicated amp Inferred 457 Mt0028 U3O8 107 TREO 022 Zn at a015 U3O8 cut off
Kvanefjeld REE-U deposit Ilimaussaq Complex
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Kvanefjeld REE-U deposit
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Model for Peralkalic Magma Systems
BrecciasBrecciasBrecciasdiatremesdiatremesdiatremes
Contact pegmatiteContact pegmatiteapliteaplite
EndograniticEndograniticpegmatitepegmatite
Late Late apliteaplite--pegmatitepegmatitedike(sdike(s))
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
APLITERiebeckiteK-feldsparZircon(Baddellyite)Nb-Fe oxideAeschyniteFergusoniteEuxeniteREE carbonate
WelsfordWelsford Dyke swarmsDyke swarms
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Welsford
model
Marsh (1995)
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Major Rare Earth Sources
Mineral
Composition
Occurrence
Bastnaumlsite
(Ce) (REE) CO3
F
Carbonatites
Monazite (Ce) (REE) PO4
Beach Sands Hydrothermal
Xenotime
(Y) (YREE) PO4
Beach Sands Hydrothermal
Loparite
(Ce) (REENaCa) (Ti NbTa)O3
Alkaline igneous massif
South China Clays (Ion-adsorbed REE+Y in Clays)
Uraninite
(REE and Y mdash
Released as dissolved elements
in rafinates
from uraninite)
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Monazite pseudomorph
after apatite Monazite pseudomorph
after Rhabdophane
Florencite
pseudomorph
after pyrochlore Churchite
YPO4
middot2H2
O
Supergene Minerals ndash
MT Weld Australia
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Apatite
with Substitutional
REE
Oka Quebec
Carbonatite
Nolanrsquos Bore Australia
Carbonatite
Mushgai
Khudag Mongolia
Carbonatite
Phalaborwa South Africa
Carbonatite
Kola Peninsula
Carbonatite
and Alkaline Massifs
Hoidas
Lake Saskatchewan
Hydrothermal in Granites
Mineville New York
Tailings from Magnetite Mining
Mineville may be the only Y and HREE dominant source currently known
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
HD -
176 mm HD -
44 mm
XPL MicrographsBastnaumlsite
in Carbonatite
Mountain Pass CA
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
BSE Image AncyliteHD ndash
07 mm
PPL Micrograph Ancylite
Ancylite
(Ce)
SrREE(CO3
)2
(OH)H2
O
LREE -
dominant ndash
50 wt REO
An exploration target in the
Bear Lodge Carbonatite
Complex of northeastern Wyoming
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Red Wine Complex Labrador Dora Bay Alaska
Eudialyte
Na15
Ca6
(Fe2+Mn2+)3
Zr3
(SiNb)(Si25
O73
)(OOHH2
O)3
(CLOH)2
Eudialyite
may also contain Y and HREE
in amounts exceeding 4 wt The
mineral is easily dissolved in weak acids
but colloidal silica currently presents a
problem in the isolation of Y REE and Zr
oxides
Kipawa Quebec
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Massive Britholite
(Ce) Oka Quebec
Britholite
(Ce) Concentrate from Skarn
Kipawa Quebec
Britholite
ndash
(REEYCa)5
(SiO4
PO4
)3
(OHF)
This mineral has the potential for occurring in ore quantities in skarn
associated with syenite
gneiss in Kipawa Quebec
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Allanite
(Ce) (CeCaY)2
(AlFe2+Fe3+)3
(SiO4
)3
(OH)
Allanite
is found in abundant quantities in many different geologic environments and in almost all cases is LREE dominant Low quantities of sumREE+Y relative to bastnaumlsite and its refractory nature diminish its value as an economic source for REE and Y
Allanite
ndash
Hydrothermal Mountain Pass CA Allanite
ndash
Pegmatite Timmins Ontario
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Eudialyte
and Mosandrite
in Peralkaline
Syenite
Kipawa Quebec
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Britholite-Rich Skarn
All brown prisms are britholite
(Horizontal Distance ndash 46 mm)
Britholite
Concentrate
(mm scale)
Britholite
ndash
(CeYCa)5 (SiO4PO4 )3 (OHF)
Kipawa Quebec
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Cathodoluminescence
Macrograph of Iimoriite
in Syenite
ndash
Bokan
Mountain
Mottled light blue and tan clusters -
Iimoriite
Red groundmass ndash
Feldspar
(Horizontal distance of rock slab ndash 46 mm)
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Iimoriite
(Y)
Y2 (SiO4 )(CO3 )
Yttrofluorite
(CaY)F2
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Iimoriite
Concentrate ndash
Bokan
MT (1 mm scale)
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Wicheeda
Lake Heavy Mineral Composite mdash
(from samples 828951 52 53)
These grains range in size between 02 and 05 mm The left micrograph consists of major monazite and parisite
and minor grains of pyrite Dolomite is also attached to some of these grains The right micrograph shows selective reflection of the green part of the visible spectrum under unfiltered shortwave UV examination This test is diagnostic for the identification of LREE minerals
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
As a final statement it should be emphasizedhellip
1) Carbonatites containing as much as 5 wt LREE must compete with Bayan Obo Maoniuping and Mountain Pass which have much higher grade and have established physical and chemical processing plants
2) Deposits that are mineralized with allanite and LREE-enriched apatite can not compete economically with carbonatites or peralkalic systems that have the high REE mineralogy
3) Naturally higher radioactivity in all REE systems makes them easier to find with airborne and ground gamma-ray spectrometry
4) Uraniferous systems commonly have anomalous LREE amp HREE which has been recovered in some deposits ie rafinates from uranium mining
5) Although ion-adsorbed REE in clays from South China provide the bulk of HREE to the market place in other countries high costs for labor and necessary supplies power costs and environmental restrictions may render similar deposits uneconomical
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Rare Earth Elements
bull
Name something of a misnomerndash
Rarest REEs
are over 200 times more
abundant then gold
bull
Variation in distribution for two reasons ndash
Compatibility with common rock forming materials
ndash
CosmicCrustal abundances
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Crustal Abundances of Elements
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Occurrencebull
REEs
occur mostly as
substitutional
impurities in many rock forming minerals
bull
Only a few the REE minerals have sufficient quantities to be considered important sources
bull
Defined as minerals having at least one site that is filled by REEs
andor Yttrium more often then any other elementMonazite
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Rare Earth Minerals
bull
Form by primary crystalization
from magma or by hydrothermal reactions
bull
Found hosted in carbonate rocks in pegmatites
and as accessory minerals in
igneous rocks
bull
Stable REE minerals and can be concentrated in weathering zones
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
REE Mineralsbull
The most important REE minerals is bastnaumlsite
REE(CO3)F
bull
Other notable sources are ndash
Monazite REE(PO4) ndash
Xenotime
YPO4
bull
All may contain radioactive species such as thorium
and uraniumndash
are avoided as source materials
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Bastnesitebull
Bastnasite
[(REE)(CO3)F] is the worldrsquos most important source of rare earth elements
bull
Containing 60 to 70 rare earth oxides (REOs)
bull
REE site is most commonly filled by LREEs
and Y
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Other REE mineralsbull
Monazite [(LREEYTh)PO4] ndash
Contains about 50ndash78 rare earth oxides
ndash
Forms in heavy mineral sands placer deposits associated with beach environments
bull
Xenotime
[(YPO4)] ndash
Contains 54ndash65 rare earth oxides
ndash
Yttrium Erbium and Cerium most common ndash
Found in heavy mineral sands can also be a component in pegmatite and igneous rocks
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Electron Configuration
bull
The similarities in chemical and physical properties arise due to the grouprsquos common electron configuration
bull
REEs
have same outer electronic configuration (+3) they differ in their number of 4f electrons
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Electron Configuartion
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
REE Behaviorbull
Because of their shared behaviour REEs
tend to be
present in nature as a group All REEs
commonly substitute for one another in minerals
bull
Yet the REEs
are capable of showing great variation in their distributions
bull
Comes about due to ndash
Differences in ionic radius ndash
Crystal structure (Coordination Number)ndash
Basicity
of the mineral ndash
The elementrsquos solubility and ability to migrate in the environment ndash
Content of REEs
in source fluids
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Ionic Radiusbull
The ionic radius of the REEs
is inversely related to atomic number
bull
The heavy rare earths are smaller ndash
more similar to Mn2+ (ionic radius 008 nanometers)
bull
LREEs
are largerndash
more comparable in size to Ca2+ (ionic radius 01 nanometer)
bull
Charge balance achieved through some sites being left vacant or
by coupled substitution with lower charged mineral (Na+)
In nanometers
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Coordination Number
bull
Coordination number the number of atoms touching a particular atom in a crystal lattice
bull
Coordination number for this structure is 8
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Coordination Numberbull
The heavy and light REEs
differ in the coordination
numbers (CN) with oxygenndash
HREEs
have CN between six to nine ndash
LREEs
have higher CNs
bull
Minerals with high CNs
associated with REE site
will favor LREEsndash
Bastnasite
CN = 11 ndash
Monazite CN = 9
bull
Those with low CNs
will preferentially select HREEs ndash
Xenotime
has a value of 8
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Other Factorsbull
Minerals basicityndash
Alkalic
rocks host minerals with elevated LREE content ndash
Rocks with lower basicity
have lower amounts of LREEs
relative to their HREE content
bull
Solubilityndash
LREEs
are more soluble in water then the HREEsndash
Important characteristic for hydrothermally derived minerals
bull
MagmaHydrothermal fluid compositionndash
Minerals will take what they can get
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
REEs
and Economicsbull
The REEs
and Yttrium have a very broad range of applications mostly in high technology fields
bull
84 of Y acquired by the United States used in light and cathode ray tube phosphors The remainder was used in ceramics (7) electronics (7) and metallurgy (2)
bull
REEs
used primarily for automotive (25) petroleum (22) and metallurgic (20)
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
HREEs
and Magnetism
bull
HREEs
exhibit complex magnetic behaviour on account of electron structurendash
They share the same outer shell electron configuration (valence = +3)
ndash
Differ in number of 4f electrons
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Applications in Magnetismbull
Terbium and
Dysprosium
bull
Components of Terfenol-D
alloy
with the formula Tb(03) Dy(07) Fe(19)
bull
Has the higher magnetostriction
then any other alloyndash
expands and contracts in magnetic field
bull
Developed by American Navy for sonar
systems ndash
Now has applications in magnetomechanical
sensors and other electronic devices
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Applications in Magnetism
bull
Holmium
bull
Possesses the highest magnetic moment (106microB) of any of the naturally-occurring
elements
bull
Creates the strongest artificially generated magnetic fieldsndash
In research where strong magnetic fields are needed
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
HREEs
and Nuclear Technology
bull
Dysprosium Homium Erbium
bull
High neutron
absorption cross-section ndash
Measure of probability of neutron capture
bull
Used in neutron-absorbing control rods in nuclear reactors
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
HREEs
and Nuclear Technology
bull
Lutetiumbull
Radioactive isotope used in radiometric dating
bull
Thulium bull
Stable thulium used as a radiation
source
in portable X-ray
devices
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Mountain Passbull
Bastnasite
is the major REE mineral bull
High grade accessory mineral of igneous or hydrothermal originsbull
31 million tons of 886 by weight of rare earth oxides (REO) bull
Mining stopped in 1994 ndash
Thorium content of waste rock ndash
Availability of inexpensive REEs
from China
San Bernardino County
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Bayan
Obobull
The worldrsquos primary source for both yttrium and the rare earth elements
bull
37 million tons of ore bull
Main REE source there is Bastnasite
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
World Production
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Explorationbull
84 of REE imports to US are from China
bull
Increasing demand for high tech applications spurred increase in exploration in 2007
bull
Economic assessments of known deposits such as Canadian Thor Lake and Hoidas
Lake as well as in
Malawi Africa
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Environmental Considerations
bull
REE soil and food contaminationbull
Acid Mine Drainage and groundwater systems
bull
Radioactive elements
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
REE Fertilizerbull
In China REE enriched fertilizer has been used in crop fields since 1990
bull
At the turn of the century 50 to 100 million tons of REEs were being applied to an area of about 4 million hectares
every year
bull
Research and agricultural practice that provides evidence that REEs
will improve crop quality an yield
bull
The ramifications environmental and human exposure to REEs
are not well understood
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Investigation by T Liang et albull
Revealed that the average concentration of total REEs
in Chinese soil is
1768 mgkg ranging between 850 to 5227 mgkg
bull
In wheat grains the REE distribution as similar to that of the soil with a content about 3 or 4 orders of magnitude
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Implicationsbull
Human health effects not completely understood
bull
REE soil content shown to be detrimental to some plant speciesndash
100 of ryegrass specimens involved in the study that were reared with REE fertilizer showed poor development relative to the control group that was reared without elevated exposures to REEs
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Acid Mine Drainage (AMD)bull
Rain waters contacts waste rock facilitating acid forming reactions
bull
Increases the capacity of the water to leach potentially harmful elements from waste piles
bull
Process mobilizes established ecotoxins
(lead and mercury) as well as elements whose effects are less understood namely the rare earth elements
bull
Historically dismissed as minor environmental risk
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Radioactive Elements
bull
REEs
associated with uranium and thorium
bull
Bastnesite 32 thorium
bull
Monazite sands 6 to 12 thorium oxide
bull
Ores containing radioactive elements are avoided as sources of REEs
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Radioactive Hazardsbull
Mountain Pass
bull
Accidentsndash
In 1977 major pipeline break spilled over 2 million gallons of radioactive water
bull
Health Effectsndash
inflammatory bowel disease ndash
Prolonged seizures ndash
Cysts ndash
Cancers
bull
Waste Disposal ndash
Yucca Mountain
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Summarybull
REE concentrations in the crust are rare
bull
Several geochemical factors influencing distribution including ionic radius and coordination number
bull
Main REE minerals are bastnasite monazite and xenotime
bull
Most important deposits are found at Bayan
Obo China and Mountain Pass USA
bull
Important electronic and nuclear applications
bull
Environmental concerns associated with REE production and use are exposure to the environment and people liberation and water
system contamination though acid mine drainage association with
radioactive elements
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
bull
Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
bull
G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
bull
B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
webmineralcomdataMonazite-(Ce)shtmlbull
wwwnaturecomnaturejournalv446n7136absnature05668htmlbull
wwwstevegbcomimagesscienceorbital_fillingpngbull
wwwchemicalelementscomelementseuhtmlbull
boomeriaorgchemlecturestextass2table10-9jpgbull
lostcontentquakecomfiles200802holmiumpngbull
chinageocitylocatorcomcitiesChinaQinghaibull
geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
Referencesbull
E Orvini M Speziali A Salvini C Herborg ldquoRare earth elements determination in environmental matrices by INAArdquo Microchemical Journal 67 2000 97-104
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Tao Liang et al ldquoEnvironmental biogeochemical behaviors of rare earth elements in soi-plant systemsrdquo Environmental Geochemistry and health 27 2005 301-311
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G Protano and F Riccobono ldquoHigh contents of rare earth elements (REEs) in stream wates of a CU-Pb-Zn mining areardquo Environmental Pollution 117 2002 499-514
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B Lipin ldquoGeochemistry and mineralogy of rare earth elementsrdquo Mineralogical Association of America 1989bull
The Government of South Australia wwwpirsagovaubull
The US geological Survey Mineralsusgsgovbull
wwwelementsdatabasecombull
wwwastrolsaumichedu~cowleyintro2htmlbull
wwwjohnbetts-finemineralscomjhbnycgifs40129htmbull
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geowebrudruzal-Bayan-Obohtmbull
enwikipediaorgwikiSan_Bernardino_County_Californiabull
wwwworldcountriesinfoMapsRegionEurope-450-Italyjpgbull
enwikipediaorgwikiMonazitebull
webmineralcomdataBastnasite-(La)shtmlbull
wwwgbrworgindexphpoption=com_contentampview=categoryamplayout=blogampid=58ampItemid=73bull
httpwwwavalonventurescombull
wwwnewsweekcomid43884bull
httpaccipiterhawk-conservancyorgMeadowMuses200608shtmlbull
httpwwwcsescitechacukabout_usFrontiers2007Hughes20-20Lanthanide20contraction20- 20CSE20Frontiers202007pdf
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