65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
55
Palaeoenvironmental variation of a sub-mountainous Holocene peat
in North Spain based on biomarkers and FTIR proxies
M. Arboleya, J. Pellegrini, J. Urbanczyk, V. López-Dias, C.G. Blanco, A.G. Borrego
Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain; [email protected]
The interest of peatlands as palaeoenvironmental records has increased in the recent years
because they may represent a continuous record of vegetation growth with a limited number
of species, peat profiles are in-land records close to populated areas and especially those fed
only by rainfall (ombrotrophic peats), are not affected by external supplies (Barber et al.,
2003). The North of Spain contains a number of peat bogs at littoral, submountainous and
mountainous locations, in which increasing height also correspond to increasing distance to
the coastline. Those at moderate height are known as cántabro-atlantic mires and
characterized by the association Erico mackaianae-Sphagnetum papillosi (Fernandez Prieto et
al., 1987). The Peat bog considered in this study is La Molina (UTM 29 T 716294 4806806,
height 648 m above sea level=m.a.s.l), whose profile reached a depth of 295 cm. The profile
consisted of ten top centimeters of living vegetation followed by brown-reddish bryophytic
peat from 10-230 cm, turning darker in the deepest 40 cm. This part of the profile has a
mineral matter content below 10%. The mineral matter content increases fast from 10 to 90 %
in the following 40 cm interval and it is higher than 90% from the cm 270 downwards
exhibiting an intermediate grey colour. The sample at 279 cm depth of the profile has yield an
AMS 14
C date of 9384 ± 45 cal. yr BP (Arboleya, 2011).
The biomarkers study by Gas Chromatography/Mass Spectrometry of the
dichloromethane/methanol peat extracts has allowed the establishment of humid/dry periods
on the assumption that herbs and heather dominate in dry periods with higher concentration of
n-C29 and n-C27 and Sphagnum dominate in humid periods with higher concentration of n-C23
and n-C25 (Bass et al., 2000; Bingham et al., 2010). High values of n-C23/n-C29, associated to
humid periods, have been recorded in two episodes in La Molina profile corresponding to
4200-4350 and 4500-5100 cal yr BP. These episodes have been also registered in other peats
of the region at slightly different ages (López-Dias et al., 2013). The combustion profiles of
the Sphagnum-rich intervals indicate a dominance of the first combustion peak in the profiles
(Borrego et al., 2011). This has been also observed during the humid episodes in La Molina
profile.
The Fourier Transformed Infrared (FTIR) spectra of peat provide an additional tool to find
out about organic matter input considering that different peat-forming plants slightly differ in
the relative intensity of their FTIR bands (Urbanczyk et al., 2012). The FTIR spectra exhibit
bands at 2920 and 2850 cm-1
corresponding to stretching of antisymmetric and asymmetric
CH2 groups in fats, wax and lipids; 1700 cm-1
band of carbonyl and carboxyl groups in
carboxylic acids, aromatic esters and free acids; 1600 cm-1
band of aromatic C=C stretching;
1265 cm-1
band of C–O stretching of phenolic groups and arylmethylethers; 1080-1030 cm-1
band of O–H deformation in polysaccharides (Fig. 1). The spectra of peat-forming plants
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
56
typically show bands at 1080-1030
cm-1
assigned to cellulose, and both
Ericaceae and Poaceae show two
distinct bands in the region 1700-
1600 cm-1
(Urbanczyk et al., 2012).
Typical spectra of peat from dry
periods, as derived from biomarker
analysis, show better resolved 1700
cm-1
band compared with peat from
humid periods, which could be
attributed to a higher proportion of
woody material in the former.
Acknowledgement: Financial support from
MICINN (CGL2009-13990-C02-01/02) is
gratefully acknowledged. J. Urbanczyk
thanks MEC for a FPU fellowship.
References
Arboleya M., 2011 - Biomarcadores moleculares como indicadores paleoclimáticos en turberas asturianas de
ambiente submontano. MSc Thesis. University of Oviedo, Spain: 1-30.
Bass M., Pancost R., van Geel B., Sinninghe-Damsté J. 2000 - A comparative study of lipids in Sphagnum
species. Org. Geochem. 31: 535–541.
Barber K.E., Chambers F.M., Maddy D. 2003 - Holocene palaeoclimates from peat stratigraphy: macrofossil
proxy climate records from three oceanic raised bogs in England and Ireland. Quaternary Science Reviews
22: 521–539.
Bingham E.M., McClymont E.L., Väliranta M., Mauquoy D., Roberts Z., Chambers F.M., Pancost R.D.,
Evershed R.P. 2010 - Conservative composition of n-alkane biomarkers in Sphagnum species: Implications
for palaeoclimate reconstruction in ombrotrophic peat bogs. Org Geochem. 41: 214-220.
Borrego A.G., López-Dias V., Arboleya M., Urbanczyk J., de Luca V., Blanco C.G. 2011 - Variation of organic
matter input in peat as seen by combustion profiles. 63th ICCP Meeting, 10-16 September Porto, Portugal.
Fernández Prieto J.A., Fernández Ordóñez M.C., Collado Prieto M.A. 1987 - Datos sobre la vegetación de las
“turberas de esfagnos” galaico-asturianas y orocantábricas. Lazaroa7: 443-47.
Lopez-Dias, V., Urbanczyk J., Blanco, C.G., Borrego, A.G. 2013 - Biomarkers as palaeoclimate proxies in
peatlands from coastal high plains in Asturias, N Spain. Int J. Coal Geol.
dx.doi.org/10.1016/j.coal.2013.04.006.
Urbanczyk J., López Dias V., Borrego A.G. 2012 - Infrared Spectra: an additional tool to study organic matter
input in peat bogs. 64th
ICCP Meeting, 15-24 September, Beijing, China.
Fig. 1. FTIR spectra of representative samples of humid
and dry periods in La Molina. =stretching, =bending.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
57
Differentiation of Ni, Co, Cr, Cu, Zn and Pb content in coal seams
from the Orzesze beds SW-part of Upper Silesia Coal Basin – Poland
B. Białecka1, J. Całusz-Moszko
1, Z. Adamczyk
2, J. Komorek
2, M. Lewandowska
2
1Central Mining Institute, Plac Gwarków 140-166 Katowice, Poland
2Silesian University of Technology, Faculty Of Mining And Geology, Institute of Applied Geology Akademicka 2,
44-100 Gliwice, Poland
The subject of the study were channel coal samples taken from the Orzesze beds of the coal
seams 360/1, 361, 362/1 from the southwest part of Upper Silesia Coal Basin (“Pniówek” coal
mine). The values of mean average reflectance of vitrinite was measured according to PN-
ISO 7404-5:2002 and maceral composition was analysed according to PN-ISO 7404-3:2001.
All measurement were carried out under reflected light (=546 nm) in immersion oil
(no=1.5176 at 23oC ) using an Axioscope Zeiss microscope. The coal samples were averaged,
then grinded to the grain below 0.2 mm. The high-temperature ashes (HTA) were prepared in
an electric furnace at 815oC. For all samples ash content (A
d) according to the PN-80/G-
04512, was determined. Inductively coupled plasma Fussion-ICP and ICP/MS analysis for Si,
Ti, Al, Fe, Mg, Ca, Na and K oxides and elements Ni, Co, Cr, Cu, Zn and Pb were performed
for a characterization of the bulk chemical composition of HTA. Chemical analysis were
performed with use Perkin Elmer SCIEX ELAN 6000 ICP/MS in the Activation Laboratories
Ltd. in Canada.
The total chemical composition of
coals and their ashes is important but
insufficient characteristic for a
reliable explanation of coal
properties. Most important are the
modes of element occurrence namely
whether a particular element is
present in minerals and other phases,
their origin and amount in coal, as
well as their behavior during
coalification process. The noted
characteristics may be a guide for
prediction of some properties,
benefits and behavior of coals and
their products during coal use
(Vassiliev 1998).
It was found that examined coal
samples represent high grade (Ad<10%), medium- rank metabituminous coal – B (ECE
Geneva 1994) with high vitrinite content (>60%). The normalized chemical composition of
HTA samples and an ash classification system based on the quantities of main five oxides
Fig. 1 Chemical classification system for the main
composition of HTA Samples [wt.%]
(Vassilev, 1998)
M9
M1
M3
M14
M7
M8
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
SiO2 + Al2O3
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
CaO + MgO
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Fe2O3
M9
M1
M3
M14
M7
M8
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
58
(Vassiliev 1998) show that the specimens belong to, ferrisialic and ferricalsialic HTA types
(Fig. 1.). Maximum concentration Cr, Co, Ni, Cu and Zn was found in the HTA sample from
362/1 seam (sample 6). Minimum concentration of examined elements was found in HTA
from stratigraphically younger seams 360 and 361. The research showed differences in
contents of analyzed elements within a single seam (Fig 2.)
Adjusted to organic matter content of examined elements has value from the range
determined for most coals (Taylor 1998). Coal clark (Ketris and Yudovich 2009) for Cr, Co
and Cu has lager value than observed in analyzed samples. Coal clark Ni has lower value than
in coal samples (Fig 3).
References
Ketris M.P., Yodovich Ya.E. 2009 - Estimation of Clarkes for Carbonaceous biolithes: world averages for trace
element contents in black shales and coals. International Journal of Coal Geology, 78: 135-148.
Taylor G.H., Teichmüller M., Davis A., Diessel C.K.F., Littke R., Robert T. 1998 - Organic Petrology. Gebr.
Borntraeger, Berlin-Stuttgart.
Vassilev S.V., Vassileva C. G. 1998 - Comparative chemical and mineral characterization of some Bulgarian
coals. Fuel Processing Technology, 55: 55-69.
Wang X. 2009 - Geochemistry of Late Triassic coals in the Changhe Mine, Sichuan Basin, southwestern China:
Evidence for authigenic lanthanide enrichment. International Journal of Coal Geology, 80: 167-174.
Cr Co Ni Cu Zn Pb0
200
400
600
800
1000
1200
1800
2000
Conte
nt
[ppm
]
- 360/1 seam, sample M9- 361 seam, sample M1- 361 seam, sample M3- 361 seam, sample M14- 362/1 seam, sample M7- 362/1 seam, sample M8
Fig. 2. Content of Cr, Co, Ni, Cu, Zn and Pb
in HTA samples
Cr Co Ni Cu Zn Pb0
20
40
60
80280
300
Conte
nt
[ppm
]
- content of trace element in coals (G.H.Taylor et.al. 1998) with coal clark (X. Wang 2009)
- range of element content in examined coals
Fig. 3. Content of Cr, Co, Ni, Cu, Zn and Pb
in coal samples against a background of content of
trace element in coals (G.H. Taylor et.al., 1998) with
coal clark (Wang, 2009; Ketris and Yodovich, 2009)
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
59
The possibility of underground gasification of lignite from Polish deposits
B. Bielowicz, K. Matl
AGH University of Science and Technology, Mickiewicza 30, 30-059 Kraków, Poland;
+48 12 617 23 75; [email protected]
Polish economic reserves of lignite occur in the Miocene formations in numerous deposits
within the Polish-German Lowland. Aforementioned reserves can be used for heating
purposes, mainly in power plants, for chemical processing, in order to obtain gaseous and
liquid products in chemical plants, and for underground gasification processes.
The annual production of lignite in Polish open cast mines amounts to 65.0 million tons per
year, while it is primarily used by power plants. However, chemical processing of lignite is
not yet developed. It is planned to develop pilot plants for underground lignite gasification in
the near future.
Currently studied conditions of this process are resulting from the geology of Neogene and
Paleogene coal formations, coal quality, chemical and technological parameters of coal and
from the limitations related to environmental protection and land development.
Lignite from the Polish deposits coal has the characteristics of low rank coal (mean Rr 0.2
- 0.35), an average carbon content at around 62 - 65% C, high moisture content (> 50%) and
net calorific value (NCV ) 6 - 20 MJ/kg (mean 8.0 MJ / kg). Petrographic composition of
lignite (> 80% humic components) makes it a preferred material for chemical processing.
Geological parameters, deposit parameters, chemical and technological properties of coal
are all very important for the proper course of the underground gasification process (Table 1).
The process of underground lignite gasification will face significant technological barriers
associated with high humidity of coal and water accumulation.
Even though a large number of reserves meet the aforementioned criteria, only a small part
is planned to be subjected to underground gasification process.
Work performed under task of research No. 3 funded under the Agreement NCBiR No.
SP/E/3/7708/10".
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
60
Table 1 Criteria for lignite deposits for underground gasification processes.
No. Criterion Range of variability
1 Type of coal and physicochemical
parameters:
calorific value
volatile matter
ash content
natural moisture
sulfur content
Minimum amount not specified (from 6.5 MJ/kg)
below 50%
below 20% optionally 25%
below 55%
below 4.0%
2 Deposit thickness:
minimal
maximum
2 m up to 4 m (optimal)
dependent on hydraulic insulation, overall conservation and the conservation
of the boreholes (controlling overburden collapse)
3 Depth:
minimal
over 150 m* - below erosion washouts and glacitectonic channels. In case of
the deposits not associated with glacial activity, the depth may be lower
4 Deposit type:
single-seam deposit
multi-seam deposit,
preferred
possible when using advanced technology (e.g. using backfill), the distance
between. seams >20m
5 Overburden ratio: > 12 (10) roof of the deposit at a depth of up to 350 m**
6 Inclination angle of the deposit horizontal or slightly inclined
7 Thermal insulation of the
surrounding rocks
Roof rocks are clays and silts of very low permeability (k ≤ 9 10-8m/s) with a
thickness of≥10-20m; 2,8 of deposit thickness **
8 The hydrogeological conditions:
position in relation to aquifer
volume of water flow to the
seam
below the usable aquifers and outside the Major Groundwater Reservoirs, the
minimum distance is 40m.
Below 2 m3 / Mg of lignite without additional draining
9 Tectonics No cracks and faults, no significant tectonic disturbances within the mining
fields
10 The porosity of the surrounding
rocks
Roof rocks and the floor rocks should have lower gas permeability than
lignite seam, while the thickness of poorly permeable rocks surrounding the
seam should be 1-2 meters or 2-4 meters for 2 meters and 3-10 meters of
seam thickness, respectively **
11 The amount of reserves Reserves required for pilot plant are around 75 - 450 thousand. Mg, while
commercial project will need a minimum of 3,5 Mt**
12 Filtration properties of the rock The ratio of porosity of lignite seam to that of surrounding rocks should not
be less than mD 18:20**
Depending on location
13 The area of required for
underground lignite gasification
plant
minimal area for the pilot plant is 50 - 100 ha (0.5 - 1 km 2
), while for the
commercial installation it is over 100 hectares **
Safety conditions minimum distance from: residential areas (1-3km), rivers and lakes (1-3km),
protected areas (5km), currently exploited mines / mining areas (5km),
abandoned mines / workings (3km), transmission lines and railways (1-3km)
**
* in specific cases - including no glacial activity - conditions may be less restrictive
** criteria according to Cupprum
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
61
Oligocene bituminous marls of Eastern Carpathians –
geochemical appraisal using Rock-Eval and vitrinite reflectance data
M.D. Ghiran1, S. Gheorghe
1, I. Maris
2
1 OMV Petrom S.A., E&P Development Business Unit – ICPT Campina, 29 Culturii Bulevard;
[email protected]; [email protected] 2 OMV Petrom S.A., E&P, Easter Carpathians Department, 22 Coralilor St., Bucharest;
The study area is located on the Teleajen Valley (Romania), in the Southern-East side of
Eastern Carpathian Belt, in the Tarcau Nappe. The outcrop is represented by Oligocene
marine sedimentary deposits. Based on geological setting, this structure is a part of the over
thrust system, which evolution started in the Middle Cretaceous – Pleistocene. The
sedimentary formations from this area are part of a single sedimentary cycle of the Cretaceous
– Miocene. The characteristic lithofacies are siliciclastic and sometimes mixed siliciclastic –
carbonated. The most important petroleum system is being found in the Oligocene level, and
contains source rocks, reservoir rocks and protector rocks.
The outcrop researched is located on the right side of the Teleajen River, next to the
Valenii de Munte City. The formation is approximately 120 m long and 20 m high. The
sedimentary succession from the outcrop is built up on the vertical. The profile to be
researched is part of an synclinal overthrust. The facies is represented by intercalation of
quartzose sandstone and bituminous marls. The bituminous marls look like a tabular body
with sedimentary structure - parallel laminated. The colour of the bituminous marls is dark –
brown, bright, due to the presence of high quantity of organic material. There is also present
strong smell of hydrocarbon. On the strata face pyrite can be seen. Eight outcrop samples
were collected from the Teleajen Valley and these rock samples were crushed and grinded
before analysis. The samples were then pyrolized using Rock-Eval 6 in order to determinate
the following parameters: S1 (free hydrocarbon), S2 (oil potential), S3 (CO2 organic source),
Tmax (maximum temperature), TOC% (Total Organic Carbon), HI (Hydrogen Index) and OI
(Oxygen Index). These parameters indicate the maturation conditions of the source rocks and
detect the petroleum potential of sediments. Interpretation of these results leads to
determination of kerogen type, maturity level, generated hydrocarbons and generation
potential. All the samples with higher TOC content were selected for vitrinite reflectance
measurements. The samples for vitrinite reflectance were cut perpendicularly to the bedding
plane, mounted in epoxy resin and polished. Using a J& MMSP 200 software the results were
plotted as histograms and interpreted based on different maceral population occurrence
modes.
The samples have not reached maturity since Tmax individual values are less than 435°C
but it must be considered that they were collected from outcrops which are subjected to
surface environmental conditions and due to this fact the maturity level resulted cannot be
interpreted as accurate. The pseudo-Van Krevelen diagram indicates that organic matter
belongs to kerogen type II and III.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
62
Source potential is interpreted according to TOC% values which range between 2.33% and
12.87% and S2 with very good values (32.42%, 39.96%, 42.57% and 71.01%), indicating
that the samples have very good to excellent source rock generation potential.
a b c
d e f
Fig. 1. Photomicrographs of different types of macerals, reflected light, oil immersion, 50X;
a, b, d, f: vitrinite; c, e: inertinite.
The samples collected from Oligocene sedimentary formation located in the Teleajen
Valley, indicate a very good to excellent source rocks formation for generating oil and gas,
and kerogen types II and III.
Acknowledgments: The authors sincerely thank Prof. Dr. Cornelia Panaitescu and Dr. Georgeta Predeanu from
the University Politehnica Bucharest for their assistance and kind support when learning coal petrology.
References
Peters K.E., Cassa M.R. 1994 - The Petroleum System – From Source to Trap. Chapter 5: Applied Source Rock
Geochemistry: 93-120.
Panaitescu C. 1991 - Coal Petrography, Cokes and Carbon Products. Ed. Enciclopedica: 1-323.
Panaitescu C., Predeanu G. 1999 - Atlas Carbopetrografic. Ed. Academiei Romane, (Romanian-English version):
1-264.
Peters K.E. 1986 - Guidelines for Evaluating Petroleum Source Rock Using Programmed Pyrolysis: 318-329.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
63
Petrographic characteristics of the solid bitumen present in the samples
from Cabaços Formation (Lusitanian basin, Portugal)
P.A. Gonçalves1, F.S. da Silva
2, J.G. Mendonça Filho
2, D. Flores
1,3
1Centro de Geologia da Universidade do Porto, Rua Campo Alegre, 687, 4169-007 Porto, Portugal;
[email protected] 2 Laboratório de Palinofácies & Fácies Orgânica (LAFO), Departamento de Geologia, Instituto de Geociências,
Universidade Federal do rio de Janeiro, Av. Athos da Silveira, 274, prédio do CCMN, sala J1020, Campus
Ilha do Fundão, Cidade Universitária, CEP 21.949-900 Rio de Janeiro, RJ, Brasil 3 Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências, Universidade
do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
Solid bitumens (“migrabitumen”) are secondary organic matter products that filling voids and
fractures in rocks (Jacobs, 1989) and can occur in carbonate and siliciclastic rocks. In the
Lusitanian basin (Portugal), several formations, from the Early Jurassic until the Cretaceous,
revealed the presence of solid bitumen. The study of the Freixial-1 and Benfeito-1 wells
(Arruda sub-basin, Lusitanian basin) revealed large amounts of solid bitumen in the Cabaços
Formation, the lowermost formation of the Upper Jurassic. This formation comprises
limestones and anhydrite-limestone sequence. To study the petrographic characteristics of
solid bitumen present in these samples, microscopy techniques (reflected and transmitted
white light, incident blue light and SEM) were used.
Solid bitumen occurs in all the samples of the Cabaços Formation but it increased in the
anhydrite rich samples in which, when observed in transmitted white light, the solid bitumen
represent over 50% of the organic matter fraction.
In transmitted white light the solid bitumen had amorphous aspect with dark color (Figure
1A) and no fluorescence under incident blue light. SEM observations confirm the amorphous
aspect (Figure 1B). In both methods of observation is possible to notice the cratered aspect of
the solid bitumen resulting from the dissolution of carbonate minerals by the HCl treatment.
In whole rock samples and under reflected white light, these solid bitumens had a grey
color, brittle aspect and appear filling the inter-mineral spaces (Figure 1C). The solid bitumen
shape varies according to the pores shape where it occurs. The bitumen reflectance ranges
from 1.5 to 1.8%Ro. According to the classification proposed by Jacob (1989), and based only
in the %Ro values, the solid bitumen identified in these samples are classified as epi-
impsonites.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
64
Fig. 1. Photomicrographs illustrating solid bitumen in Cabaços Formation (Upper Jurassic sediments from the
Lusitanian basin). a) transmitted white light; b) SEM; c) reflected white light.
Geochemical studies will be carried out to provide a better understanding of these solid
bitumens.
Acknowledgments: The first author is grateful to Fundação para a Ciência e Tecnologia (FCT) for the financial
support (scholarship SFRH/BD/60875/2009). This work was sponsored by the Scientific and Technical
Cooperation Agreement FCT (Portugal)/CAPES (Brazil) project titled “Caracterização das variações
organofaciológicas e identificação dos horizontes potencialmente geradores de petróleo no Jurássico da Bacia
Lusitânica”; and partially funded by FEDER funds through the Operational Program Competitiveness Factors -
COMPETE and by national funds through FCT - Fundação para a Ciência e Tecnologia, under the project PEst-
OE/CTE/UI0039/2011.
References
Jacob H. 1989 - Classification, structure, genesis and practical importance of natural solid oil bitumen
(“migrabitumen”). International Journal of Coal Geology 11: 65–79.
b c a Solid Bitumen
20µm 20µm 100µm
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
65
Changes in optical properties of liptinite macerals from early mature to
post mature stage in Posidonia Shale (Lower Toarcian, NW Germany)
O.O. Gorbanenko1,2
, B. Ligouis1
1Eberhard Karls University Tübingen, Institute for Archaeological Sciences, Work Group of Geoarchaeology,
Laboratory for Organic Petrology, Rümelinstr. 23, 72070 Tübingen, Germany; +49-(0)7071-29-74688,
+49-(0)7071-29-74087; [email protected], [email protected] 2Eberhard Karls University Tübingen, Department of Geosciences, Work Group of Biogeology, Sigwartstr. 10,
72076 Tübingen, Germany
Detailed organo-petrological analysis was carried out on core samples from two wells, which are
located in North-Western Germany. The distance between wells is about 60 km. Organic matter in
one well is early mature, whereas that in the other is post mature. A total of 72 samples of
Posidonia Shale (Lower Toarcian) were analyzed to investigate the optical properties of three
macerals of the liptinite group: telalginite, bituminite and sporinite.
Results of organo-petrological analyses demonstrate that telalginite (Tasmanales alginite)
in early mature oil shales was observed as a disk-shape body with length ranging between 60
and 120 μm. In reflected white light telalginite appears brown to dark brown, whereas in
fluorescence mode it shows yellow color of high intensity. In contrast, in post mature oil
shales, relics of former telalginite occurs in three forms. One consists of a chain of calcareous
crystals or of a completely recrystallized calcareous mass. Both are associated with
homogeneous and heterogeneous reflecting solid bitumen. Second form is composed
completely of epigenetic pyrite. The third form is rare and consists of “telalginite” completely
replaced by reflecting homogeneous bitumen (impsonite; Jacob, 1983, 1989). All forms of
telalginite relics in post mature oil shales show no fluorescence and are non-fluorescing. In
addition, the shape and size of the algae are preserved.
In oil shales of early mature stage, bituminite I (Teichmüller, 1977) is characterized by a
very low reflectance and a brownish fluorescence color. It often includes yellow fluorescent
liptodetrinite. Bituminite I has indinstinct lense shape with length reaching up to 60 μm. On
the contrary, in post mature oil shales on the basis of morphology, it appears as light-grey
lenses, consists of massive micrinite and shows no fluorescence.
Bituminite II (Teichmüller, 1977), in early mature oil shales, occurs as thick elongated
homogeneous lenses associated with carbonate crystals and with yellow-brownish
fluorescence often with greenish fluorescent oil expulsions. In post mature oil shales,
“bituminite II” consists of a network of micrinite and has no fluorescence.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
66
Sporinite is very rare in the investigated oil shales. It has very low reflectance and orange-
brown fluorescence of moderate intensity. In post mature oil shales, sporinite is filled with
pyrite crystals which emphasize the sporinite form, is characterized by reddish-orange internal
reflections, and is either non-fluorescent or shows weak fluorescence of mineral origin.
Australian petrologists Cook (1986) and Hutton (1987) has developed the most widely
accepted nomenclature of liptinite macerals in oil shales. Particularly, they proposed the terms
telalginite (Botryococcus, Tasmanites, Leiosphaeridia) and lamalginite (lamellar alginite).
However, their work was focused on the alginite in early mature and mature oil shales.
Teichmüller and Ottenjann in 1977 defined bituminite I, bituminite II and bituminite III in
early mature and mature Toarcian oil shales. They study the modifications in optical
properties of bituminite in several oil shales of increasing maturity, and used the term “meta-
bituminite” to classify the organic substances generated from bituminite (Teichmüller, 1974).
This study demonstrates that the existing terms (micrinite, micritic residues, solid bitumen,
overmature exsudatinite…, Taylor et al, 1998) are not completely suitable to describe the
various organic substances form especially from the telalginite, bituminite and sporinite in the
post mature oil shales.
Acknowledgements: This work was financed by Shell International Exploration and Production B.V.,
Netherlands, which is gratefully acknowledged. We would also like to thank ExxonMobil Production
Deutschland GmbH and Shell Erdgas Beteiligungsgesellschaft mbH for the permission to share the data.
References
Cook A.C., Hutton A.C., Sherwood N.R. 1986 - Classification of oil shales. Bull. Cent. Rech. Explor.- Prod.
Elf.-Aquitaine, 5, 2: 353-382.
Hutton A.C. 1987 - Petrographic classification of oil shales. Int. J. Coal Geol., 8: 203-231.
Jacob H. 1983 - Neuere Untersuchungen zur Genesis natürlicher, fester Erdölbitumina. Geol. Jahrb., D59: 3-61.
Jacob H. 1989 - Classification, structure, genesis and practical importance of natural solid bitumen
(“migrabitumen”). Int. J. Coal Geol., 11, 1: 65-79.
Taylor G.H., Teichmüller M., Davis A., Diessel C.F.K., Littke R., Robert P. 1998 - Organic petrology. Gehrüder
Borntraeger, Berlin, Stuttgart: 1-704.
Teichmüller M. 1974 - Entstehung und Veränderung bituminöser Substanzen in Kohlen in Beziehung zur
Entstehung und Umwandlungdes Erdöls. Fortschr. Geol. Rheinl. u. Westf., 24: 65-112.
Teichmüller M., Ottenjann K. 1977 - Liptinite und lipoid Stoffe in einem Erdölmuttergestein. Erdöl und Kohle,
30, 9: 387-398.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
67
Variation of coke optical texture with the addition of artificially prepared
inertinite size fractions
A. Guerrero, M.A. Diez, A.G. Borrego
Instituto Nacional del Carbón (INCAR-CSIC); C/ Francisco Pintado Fe 26, 33011 Oviedo, Spain
The inertinite in coal, and its behavior during the coking process, is a key factor in the
mechanical strength and reactivity of the resultant cokes (Mackowsky 1976). It is generally
considered that the small inertinite particles (<50 m) may be well-integrated in the coke
matrix, having a beneficial effect in the mechanical strength, whereas the large particles
represent surfaces of discontinuity (Brown et al. 1964). This work address the effect of
“inertinite” addition in the optical properties of a good coking coal, having well-controlled
both the particle size and the amount.
For this propose a relatively low fluidity coal (LFC) with Gieseler maximum of 373 ddpm,
1.24% vitrinite reflectance and vitrinite/inertinite content of 77/23 has been selected. The coal
has been blended with charcoal (CH) attempting to represent artificially-prepared inertinite
under controlled conditions. Three fractions have been prepared from the charcoal (Fig.1):
<20m (CH20); 20-80 m (CH80) and 80-212 m (CH212) and have been added to coal in
amounts of 5 and 15 wt%.
Fig.1. SEM images from: a) CH20, b) CH80 c) CH212.
The LFC-CH blends have been carbonized at 500ºC (residue from Gieseler fluidity tests)
and 1000ºC to obtain both semicoke and coke samples. For each sample an optical texture
analysis has been performed recording around 500 counts.
Most inertinite in the coal had low relief, except fusinite and some inertodetrinite. This
give rise to smooth contact edges between the coke matrix and the inertinite in the coke. The
added charcoal particles maintain cell-wall structure, resembling fusinite, but lack any
evidence of deformation/compaction. They typically exhibited high polishing relief and this
feature has been distinguished in the classification scheme, together with their size (Table 1).
The inertinite particles still retain their optical features in the semicoke and therefore they
are more easily distinguished from the charcoal particles than in the coke. In the semicoke the
inertodetrinite can be distinguished from CH20, whereas in the coke most inertodetrinite have
a) b) c)
100μm 200μm 20μm
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
68
adquired high relief, being virtually indistinguishable from the charcoal. The LFC coke matrix
is mainly formed by domain texture and most of the inertinite have smooth edges. The
addition of charcoal to the coal generally causes a size decrease of the optical texture in the
matrix of both coke and semicoke. A 5% of charcoal addition causes significant decrease in
the size of the optical texture. This decrease is more pronounced adding a higher amount of
charcoal. This effect is more pronounced in the case of the finest charcoal. This can be
explained by both a physical and a chemical effect. On the one hand, close association of
coal-charcoal in the fine sizes impedes the growth of large anisotropic domains. On the other
hand, the small particles provide higher surface area for reaction favoring the nucleation of
larger amount of anisotropic structures.
Table 1. Optical texture (vol %) analyses of cokes and semicokes.
Values in bold refer to the percentage in the sample and the others to the percentage in their respective class.
OG LFC-CH212
15%
LFC -
CH212
5%
LFC -
CH80
15%
LFC -
CH80
5%
LFC -
CH20
15%
LFC -
CH20
5%
SE
MIC
OK
E (
50
0 º
C)
MATRIX 71.6 59.4 71.1 57.0 66.2 54.1 65.2
Isotropic 1.7 3.7 1.9 10.3 5.1 16.7 2.1
Mosaic 3.1 17.5 1.9 42.0 20.2 51.5 16.6
Domain 93.1 74.1 95.3 46.6 74.0 27.7 75.8
Fibers 2.0 4.7 0.9 1.1 0.6 4.2 5.5
INERT INCLUSIONS 26.8 39.4 28.0 41.3 31.6 44.5 32.2
Smooth Edges Inertinite 71.0 40.6 57.6 24.7 36.7 33.2 45.3
Inertodetrinite 18.3 11.2 9.6 8.4 15.2 7.8 13.7
Sharp E. .I. 212-80 µm 6.1 35.5 20.8 7.9 10.8 1.8 5.0
Sharp E. I. 80-20 µm 2.3 7.6 6.4 46.3 25.9 6.0 3.7
Sharp.E. I. <20 µm 2.3 1.5 3.2 10.5 10.8 51.2 31.1
Div. Isotropic Inclusions 0.0 3.6 2.4 2.1 0.6 0.0 1.2
MINERAL MATER 1.6 1.2 0.9 1.7 2.2 1.4 2.6
CO
KE
(100
0 º
C)
MATRIX 70.2 57.2 67.1 62.2 68.2 50.2 63.6
Isotropic 6.4 8.4 6.2 1.9 5.3 23.9 4.4
Mosaic 15.6 39.2 33.5 21.2 26.7 57.0 38.7
Domain 67.6 50.3 56.2 69.1 65.1 17.9 52.8
Fibers 10.4 2.1 4.0 7.7 2.9 1.2 4.1
INERT INCLUSIONS 29.0 41.6 31.0 37.0 31.0 49.0 35.2
Smooth E. Inertinite 65.7 6.7 26.8 24.3 18.7 5.7 18.8
Sharp E. .I. 212-80 µm 13.3 37.5 44.3 8.1 20.0 12.7 22.2
Sharp E. I. 80-20 µm 2.1 33.2 9.4 45.4 30.3 4.9 9.1
Sharp.E. I. <20 µm 14.0 14.9 12.8 20.0 30.3 73.1 50.0
Div. Isotropic Inclusions 4.9 7.7 6.7 2.2 0.6 3.7 0.0
MINERAL MATER 0.8 1.2 1.9 0.8 0.8 0.8 1.2
Acknowledgement: The research leading to these results has received funding from the Research Programme of
the Research Fund for Coal and Steel (Grant Agreement number RFC-PR- 09024). The financial support of
MICINN through a bilateral Spain-Brazil project PIB2010BZ-00418 and PCTI through COF11-39 is also
gratefully acknowledged.
References
Mackowsky,, M-Th. 1976 - Prediction methods in coal and coke microscopy. J. Microscopy 109: 119-137.
Brown H.R., Taylor G.H., Cook A.C., 1964 - Prediction of coke strength from the rank and petrographic
composition of Australian coals. Fuel 43: 43–54.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
69
Migration ability of the trace elements from the overburnt mining waste
material depending on the pH of the aqueous environment
B. Hanak, J. Nowak, M. Kokowska-Pawłowska, K. Nowińska Silesian University of Technology
Mining waste materials are the largest group of post-industrial wastes in Poland. From the
petrographic point of view, the mining wastes are mainly sedimentary clastic rocks
(mudstones, sandstones and claystones), which contain a variable amount of organic matter
(carbon). Most of mining wastes produced is currently developed, but in XIX and XX century
this wastes were mainly deposited on the dumping grounds.
Oxidation of organic matter (coal) and ferrous sulfides contained in wastes leads to their
self-heating and consequently to initiating of endogenous fires. During the fires a temperature
on dumping ground increases to hundreds and even up to more than thousand degrees Celsius.
High temperature interaction caused changes of the mineralogical and petrographic
properties of the wastes.
On the basis of the studies conducted on mining wastes dumping ground on the GZW area,
three zones of varying degrees of thermal alteration of wastes were separated. There are:
- Thermally untransformed zone (the wastes with petrographic characteristic
and mineralogical composition close to original, high concentration of organic matter)
- Moderately thermally transformed zone (in the wastes metakaolin is presented, lack
or low concentration of organic matter),
- Intensively thermally transformed zone (in the wastes glaze is presented).
Formations from intensive thermally altered zone, except glaze, are characterized by the
presence of high-temperature minerals, such as cordierite, mullite, sillimanite, magnetite and
other spinels, pyroxene. Pores in different sizes often occur in this formations.
Wastes, depending on presence in one of this zones, exhibit variable properties, which
determine their practical application. One of the most important information, which decide
about the direction of wastes utilization, is determination of their harmful effects on
environment, by the release of trace elements in water presence. It was found that the highest
release of elements take places in the case of waste from intensive thermally altered zone.
Five samples of intensive thermally altered mining wastes of diverse glaze participation
were subjected to leaching tests. Leaching were conducted in water of 5; 6; 7,5 and 8 pH.
Mixture of HCl and H2SO4 1:1 was used for acid reaction, NaOH for alkaline reaction. The
samples were shaken during 24 hours. Concentrations of As, Ba, Cr, Cu, Ni, V were analyzed
in eluates using ICP-AES spectrometer type JY 2000. Concentrations of aforementioned
elements were also analyzed in solutions of dissolved wastes samples.
The highest concentration in wastes of analyzed metals showed barium, whose content in
samples ranged from 313 to 390 ppm (average 357). Average concentration of
vanadium was 78 ppm (min. 30, max. 120 ppm). Relatively high concentration showed also
copper (average 42 ppm, range 30 – 51 ppm) and nickel (average 30 ppm, range 8 – 91 ppm).
Significantly lower concentration of arsenic was found, which averaged 6 ppm (min, 4 max.
9). The lowest concentration showed chromium (1-4 ppm).
On the basis of the studies, high mobility of chromium was found (in spite of the low Cr
concentration); in extreme cases even above 5% chromium contained in the sample have been
leached to solution during 24 hours. This element stronger was eluted in acid environment
(pH 5 or 6) than neutral and alkaline environments.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
70
Arsenic was the another element, which easy eluted to solution. During 24 hours of
leaching time, even up to 2,3% of As contained in wastes have been leached to solution.
Clearly marked decline in the ability of arsenic elution with increasing pH.
Although the concentration of barium in analyzed samples was the highest, this
element showed limited ability to leach. During leaching maximally about 0,5% barium
contained in waste eluted to solution. This element concentration clearly decreased with the
increase of pH.
Nickel and vanadium showed much lower capacity to leach. In the cases of nickel only
tenths of percent of this element have been leached to solution, and vanadium only
hundredths of percent. For both of these elements decrease of their concentrations in eluates
with the increase of pH was observed.
The studies showed that least mobile element was copper. In the eluates there was no or
trace concentrations of Cu.
Individual samples also showed differentiation capacity of the elements leaching depend
on glaze content in sample. Unfortunately, dependence between the glaze content and
leaching capacity elements was not confirmed. Probably this capacity depends not only on
glaze content, but also on quantity and type of high-temperature minerals. This problem
requires further, more detailed mineralogical studies.
Studies have been financed in the framework BK-290/RG7/2012.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
71
Petrographic and geochemical investigation of coal slurries
and its products as the results of the combustion process
I. Jelonek, Z. Mirkowski
University of Silesia, Faculty of Earth Sciences, 41-200 Sosnowiec, Będzińska 60, Poland;
+48 32 3689498; [email protected]
Coal slurries are a very fine-grained by-products of coal enrichment, which was stored in the
recent past as a waste product in ground ponds. Currently, with the introduction of fluid
boilers into the Polish energy sector, coal slurries are becoming a sought-after fuel. Coal
slurries are a lower quality fuel characterised by a high ash (24-35 %) and moisture (31-38 %)
content, and therefore a low lower heating value (8-11 MJ/kg). Its weak and variable quality
parameters mean that coal slurries are not used in power plants as an independent fuel, but as
an additive to pure coal in quantities from 17 to 40 %.
The maceral content of samples of coal slurries, taken from a single manufacturer but
different times of the year, was tested. One characteristic feature is the high proportion of
macerals from the inertinite group (from 51.7% to 57.6%), with a simultaneous decrease in
the content of macerals from the liptinite group (from 3.0% to 5.5%). There is also a clear
dominance of detrital macerals (up to 71 %), of which the most numerous group is
inertodetrinite (up to 47 %). In the sample of enriched coal from the same producer tested for
comparison, the detrital maceral content reached 20 %.
An analysis was conducted of the forms of unburnt organic materials in samples of ash
obtained from burning a mixture of coal and the coal slurries described above. The results
obtained with regard to mineral content (around 80 %) and carbon content (around 0.6 %)
indicate that even the addition of a significant amount of coal slurries to fuel does not cause it
to burn any less efficiently. Detritus clearly dominates among the unburnt organic material,
alongside smaller amounts of solid forms, networks and cenospheres. In the sample of ash
from coal with added slurries, detritus appears in much smaller quantities alongside every
possible form of unburnt organic material.
Tests of coal slurries samples using a scanning microscope show a similar set of minerals
as in coal samples. There is a clear dominance of iron silicates and sulphates, with a smaller
amount of silty minerals and mica. Analogous tests on ash samples show a dominance of silty
minerals and iron oxides. The varied constitution of volatile and bottom ashes is evident. The
bottom ashes contain larger accumulations of sulphates, silicates and clay silicate enamel. The
mineral phases indicated are confirmed by X-ray analysis which demonstrates a large
proportion of quartz, anhydrite, haematite, illite and feldspar.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
72
The relationship between methane contents and variability of coal rank
within the Upper Silesian Coal Basin, Poland
S. Kędzior University of Silesia, Faculty of Earth Sciences; +48 32 36 89 329; [email protected]
The process of coalification results in changes in coal inner structure concerning both
chemical composition and physical properties of coal substance. One of the most important
stages in development of bituminous coal is so called “second coalification jump”
corresponding to medium volatile coals (e.g. Teichmüller 1989), which is distinguished by
decay of aliphatic bonds and expand of aromatic hydrocarbons in vitrinite macerals with
increasing arrangement of them. A distinctive feature of this stage is significant decrease of
volatile matter from 33% to 20% (Kruszewska, Dybova-Jachowicz 1997). Decreasing of
volatiles is accompanied by release of methane, carbon dioxide and water (e.g. Kopp et al.
2000; Moore 2012).
The Upper Silesian Coal Basin (USCB) is characterized by diversity of coalbed methane
occurrence. The outhern, western and central parts of the basin are methane rich while the east
and north parts are poorer in methane. In general, the upper parts of the rock mass in the basin
have a lower methane content, next it increases up with depth and achieves the highest values
within the interval of ca 800-1500 m under the surface of area, whereas deeper it decreases.
The purpose of this study is a comparison between methane spatial distribution (methane
content in coal) and variations of coal rank, represented by vitrinite reflectance (Ro), volatiles
content (Vdaf
) and H/C atomic ratio. The data of methane contents and the parameters given
above, obtained from 21 bore-holes drilled in order to explore the coal deposits within the
USCB Main Syncline, are now archived in Polish Geological Institute.
The comparison results of methane contents and selected parameters of coalification show
that the highest values of methane content (>10 m3/t coal daf) correspond to 35-22% volatiles
range, and to 0.84-1.26 % vitrinite reflectance respectively. The value of 0.70 H/C atomic
ratio matches the highest value of methane content equal 9,1 m3/t coal daf.
The highest values of methane content are more or less in accordance with coalification
parameters corresponding to the second coalification jump (Vdaf
– 29%, Ro – 1.3%), i.e.
cooking coals. Within this stage coal loses about 10% of volatiles, what involves the
producing of significant amount of thermogenic gases (including methane).
In the USCB the configuration of the top of high methane zone (4.5 m3/t coal daf) is quite
similar to the lay of the cooking coals top (Kwarciński, Hadro 2008). That is why increasing
methane contents in the southern and western parts of the basin can be explained by the
increasing percentage of cooking coals towards these directions. The values of volatiles,
vitrinite reflectance and H/C atomic ratio corresponding to the highest methane content (>10
m3/t coal daf) in relation to cooking coals occurrence is shown in Table 1.
Presented data reveal that coalification stage related to the second coalification jump plays
a part in the process of methane generation. Similar results were obtained in Czech part of the
USCB (Hemza et al. 2009). However, quite weak correlation between present methane
content and individual parameters of coal rank (correlation coefficient about 0.3) results in
subsequent processes including gas migration and accumulation caused by such geological
conditions like lithology, tectonics, maceral composition of coal, hydrodynamics etc. (eg
Kędzior 2009; Moore 2012).
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
73
Table 1. The intervals of volatiles (V
daf) and vitrinite reflectance (Ro) correspond to the highest values of
methane content (>10 m3/t coal daf) in relation to presence of cooking coals
Areas
Without cooking coal With cooking coal below
top surface of the
Carboniferous strata
With cooking coal
reaching the top surface
of Carboniferous strata
Vdaf
[%] - 35-23 28-23
Ro [%] - 0.82-1.25 1.05-1.25
“-“ no value of methane content > 10 m3/t coal daf
References
Hemza P., Sivek M., Jirásek P. 2009 - Factors influencing the methane content of coal beds of the Czech part of
the Upper Silesian Coal Basin, Czech Republic. International Journal of Coal Geology, 79: 29 – 39.
Kędzior S. 2009 - Accumulation of coal-bed methane in the south-west part of the Upper Silesian Coal Basin
(southern Poland). International Journal of Coal Geology, 80: 20 – 34.
Kopp O.C., Bennett III M.E., Clark C.E. 2000 - Volatiles lost during coalification. International Journal of Coal
Geology, 44, 69 – 84.
Kruszewska K., Dybova-Jachowicz S. 1997 - The outline of coal petrology. Wyd. Uniw. Śląskiego, Katowice
[in Polish].
Kwarciński J., Hadro J. 2008 - Coalbed methane in the Upper Silesian Coal Basin. Przegląd Geologiczny, 56:
485 – 490 [in Polish with English abstract].
Moore T. A. 2012 - Coalbed Methane: A review. International Journal of Coal Geology, 101: 36-81.
Teichmüller M., 1989 - The genesis of coal from the viewpoint of coal petrology. International Journal of Coal
Geology, 12: 1 – 87.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
74
Relationship between the content of trace elements in coal lithotypes
and their ashes (405 coal seam, USCB)
M. Kokowska-Pawłowska
Institute of Applied Geology, Faculty of Mining and Geology, Silesian University of Technology, Akademicka 2,
44-100 Gliwice, Poland
Variable concentrations of trace elements in coal seams depend mainly on their genesis and
differentiated geochemical affinity with the organic and mineral matters of coal (Winnicki
1973; Widawska-Kuśmierska 1981; Różkowska, Ptak 1995; Lewińska-Preis et al., 2001;
Hanak, Kokowska-Pawłowska, 2006).It has been found that a variable level of mineralization
and composition of mineral matter in coal influences the differentiation of trace elements
contents in the lithotypes. Most frequently, the highest concentrations of trace elements have
been observed in dull coal, a lower one in semi-vitrous and vitrous coals (Hanak, Kokowska-
Pawłowska, 2007).
Because of differentiated character of mineralization in individual lithotypes, a decision
has been taken to investigate dependence between variability of trace elements concentrations
in lithotypes and in the ashes on the basis of coal samples from the 405 coal seam (Załęże
beds). 61 piece-form samples of petrographic types of coal from 6 profiles from 405 coal
seam have been investigated. Geochemical measurements of samples representing
distinguished lithotypes have been conducted by the Geoanaliza company with use of
Instrumental Neutron Activation Analysis (INAA). In lithotypes and ashes the following trace
elements concentrations have been measured: Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn, Mn, Be, Li, V,
As, and Ga.
To demonstrate a relationship between contents of elements in the lithotypes with organic
or mineral matter in coal, enrichment coefficient (W) values have been calculated for the
ashes of lithotypes as a ratio of an element contents in the ash to its contents in the lithotype.
The assumption was that coefficient W values increase with increasing contents of an element
related to the organic matter of coal.
In samples of lithotypes from 405 coal seam and their ashes, analyzed trace elements
exhibited variable concentration in a differentiated range.
Within all distinguished lithotypes the highest contents was shown by elements Ba and
Mn. The other evaluated elements could be categorized due to average contents in the
lithotypes in following order: Zn<Pb<V<Cu<Ni<Cr<Ga<Co<Be<Li<As<Cd. The similar
trend of elements contents has been observed also by the ashes from the lithotypes.
Variability of the enrichment coefficient values is also quite evident. The highest values of
these coefficients (from 5 to 7) were shown by Cr, Be, Cd, and Cu. The other elements exhibit
lower values (from about 2 to about 3) and the lowest values of the enrichment coefficient
most frequently were observed in case of Co, Li, and Mn.
On the basis of calculated enrichment coefficient values in the ashes it has been found out
that such elements as Ba, Mn, Li, As, Co, Ga, Ni, Pb, and Zn demonstrated high affinity to the
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
75
mineral substance (low enrichment coefficient in the ash). Their maximal concentrations
decreased for the strongly mineralised lithotypes – dull coal or semi-vitrous coal.
However, a small number of elements as Cr, Be, Cd, and Cu demonstrated high affinity to
organic matter of coal (high enrichment coefficient in the ash) and a trend to maximal
concentration in vitrous lithotype.
References
Hanak B., Kokowska -Pawłowska M. 2006 - Variability of the trace element contents in the coal lithotypes and
their ashes presented on the background of the 630 coal seam (U.S.C.B.). Gospodarka Surowcami
Mineralnymi, 22, 3, Kraków: 68-77.
Hanak B., Kokowska-Pawłowska M. 2007 - The influence of the mineral substance on the content of the
selected trace elements of the lithotypes from the coal seam 308 (Ziemowit Coal Mine). Kwartalnik, seria
Górnictwo i Geologia, 3, 2, Gliwice: 31-41.
Lewińska-Preis L., Biedroń J., Fabiańska M. 2001- Geochemical assessment of the trace elements concentrations
distribution in fractions of coal after bio-desulfurization process. Zeszyty Naukowe Politechniki Śląskiej.
Seria: Górnictwo, 249.
Różkowska A., Ptak B.1995 - Minor and trace elements in the Upper Silesian coal. Przegląd Geologiczny, 43, 6:
478-481.
Widawska – Kuśmierska J. 1981 - The occurrence of trace elements in Polish coal. Przegląd Górniczy, 7-8:
455-459.
Winnicki J. 1973 - Presence and the way of occurrence of the rare elements in the national coals. Scientific
Papers of the Institute of Inorganic Chemistry and Metallurgy of Rare Elements. Conferences no. 8: 3-71.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
76
Changes of the vitrinite and liptinite structures during heating
under inert conditions according to the results of Micro-FTIR spectroscopy
J. Komorek
Silesian University of Technology, Faculty of Mining and Geology, Institute of Applied Geology, Akademicka 2,
44-100 Gliwice, Poland; [email protected]
The examination was performed on vitrinite and liptinite concentrates. They were prepared
from three channel steam coal samples from Upper Silesian Coal Basin. The samples were
collected from the coal seam 405. The concentrates were obtained by gravity separation in the
mixture of toluene and tetrachloroethylene. About 500mg of each concentrate was heated in a
Carbolite pipe oven at temperatures 400, 500, 600, 800, 1000 and 1200oC for 1h in an argon
atmosphere. The concentrates were inserted in the oven at room temperature. The rate of
temperature increase was 60oC/min.
Micro-FTIR analysis was performed on individual raw and carbonized vitrinite and
liptinite (sporinite) grains. Micro-FTIR measurements were performed in reflectance mode
with use of Bio-Rad FTS-6000 spectrometer equipped in the Bio-Rad UMA-500 microscope.
Spectra were obtained within range 4500-700cm-1
, with resolution 4cm-1
. Interferograms were
collected by cumulating of 512 scans. The spectra were converted using a Fourier and Kramer
Kronig transformation.
To analyze the micro - FTIR spectra it was necessary to take into account absorption bands
present in the the following ranges:
- 3030-2800 cm-1
– band associated with the stretching of aliphatic groups
(CH2+CH3),
- 1650-1500 cm-1
– band associated with the aromatic rings C=C stretching,
- 900-750 cm-1
– band associated with the aromatic groups CHar out of plane
deformations.
Changes in the vitrinite and sporinite structure after heating were described by the
following ratios of spectral bands integrations areas:
i . These ratios were used to
demonstrate relative content of aliphatic and aromatic components.
Changes of the condensation structure aromatic rings were described by the ratio
(Guo & Bustin, 1998).
It was found that raw vitrinite is characterized by higher relative content of aromatic than
aliphatic components. Whereas the structure of raw sporinite is characterized by higher
content of aliphatic than aromatic bonds. The results show that when the temperature rises the
relative content of aromatic hydrogen functional group CHar and condensation of the structure
of carbonized vitrinite and liptinite increase.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
77
The significant negative correlation between I3 and I2 ratios calculated for all examined raw
and heated vitrinites was observed. With increase of the aromatic hydrogen group CHar
content aromatic ring C=C stretching decreases. This phenomenon has been observed by
Amijaya et.al. (2006) and Vassallo et.al.(1991). The decrease of absorbance in the 1600 cm-1
band is probably a consequence of the loss of phenolic OH bond than/or the change of
aromatic ring content.
Studies have shown that in the structure of carbonized liptinite, with the increase of CHar
aromatic hydrogen group relative content, aliphatic components (CH2+CH3) relative content
decrease. It can be concluded that the increase in aromaticity of carbonized liptinite with the
rises of temperature causes the loss of aliphatic components.
It was found that although apparent differences in the structure of vitrinite and liptinite
before heating was observed, the final products of thermal treatment of analyzed samples
(concentrates after heating at 1000 and 1200°C) are characterized by similar participation of
particular functional groups (CH2+CH3), C=C, CHar. Likewise, the degree of condensation of
aromatic rings expressed by a ratio I4, for the products carbonization vitrinite and liptinite
after heating of samples at 1200oC present similar values, take into account the standard
deviation.
References
Amijaya H., Littke R. 2006 - Properties of thermally metamorphosed coal from Tajung Enim area South Sumatr
Basin, Indonesja with special reference to the coalificaton path of macerals. Int. Journal of Coal Geology, 66:
271-295.
Guo Y., Bustin R.M. 1998 - FTIR spectroscopy and reflectance of modern charcoals and fungal decayed woods:
implication for studies of inertinite coals. Int. Journal of Coal Geology, 37: 29-53.
Vassallo A. M., Liu Y. L., Pang L. S. K., Wilson M 1991 - A infrared spectroscopy of coal macerals
concentrates at elevated temperatures. Fuel, 70: 635-639.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
78
Application of confocal laser-scanning microscopy (CLSM) to qualitative
and quantitative examination of bituminite in Jurassic oil shales
J. Kus, Ch. Ostertag-Henning Federal Institute of Geosciences and Natural Resources, Stilleweg 2, D-30655 Hannover; 0049 (0) 511
6432629; [email protected]
Oil shales represent conventional and unconventional source rocks and are expected to
become far more relevant resources in the global and national economies, especially in the
Austral-Asian region as strong demand from the emerging economies of China and India
impacts on the upwards trend of the “Brent” crude oil and the OPEC basket price, (BGR
2012).
Within the currently undertaken study by the Federal Institute for Geosciences and Natural
Resources on the Gas and Oil Potential from Shales (NIKO), assessment of untapped
potential in unconventional oil shale resources of Germany is conducted (BGR 2011). The
multidisciplinary survey explores also novel techniques in characterisation of intra- and
intergranular pore space in siliciclastic and carbonate sedimentary source rocks as well as
cementation processes and adsorption characteristics.
The aim of this study is the in-depth investigation of bituminite enclosed in organic-rich,
marine, Mesozoic oil shales with the aid of the CLSM method. The studied samples
correspond to immature and mature source rocks of Posidonia Shale (Lower Jurassic,
Toarcian, Lower Saxony, Germany), Kimmeridge Clay (Upper Jurassic, Kimmeridge, Dorset,
UK) and black shales of the Agua de Madeiros Formation (Lower Jurassic, Sinemurian,
Lisbon District, Portugal).
The current study examines appearance, ultrastructure and spectral fluorescence of
autofluorescent bituminite present in the investigated oil shale samples. The qualitative
CLSM analysis reveals distinct appearance of bituminite at micron scale as observed in
polished particulate pellets. The overall appearance of detected bituminite excited at various
visible laser wavelengths varies markedly displaying the highest contrast at excitation laser
lines of 496 and 633 nm. The most dominant appearance of bituminite exhibits streaks
(“Schlieren”), stringers and lenses and that are tightly packed among the surrounding
inorganic mineral grains. As opposed to its amorphous appearance observed under
conventional incident light microscopes, bituminite can exhibit well defined and differentiated
margins under CLSM. At the ultrastructural level, bituminite stringers or lenses are generally
composed of fine lensoidal to laminae-like constituents of various sizes and fluorescence
spectras being embedded in a fluorescent organic matrix. This network-like character of
bituminite ultrastructure resembles to a certain degree larger bundles of ultralaminae detected
in TEM studies by Largeau et al. (1989). The quantitative CLSM analysis involved
application of spectral fluorescence laser scanning microscopy method enabling
measurements of fluorescence intensity and fluorescence intensity alteration at various laser
wavelengths and time.
The in depth qualitative characterisation of the in general second most abundant maceral
type in oil shales with aid of CLSM method complements multidisciplinary approach of
ultrastructural analysis of mineral and kerogen framework as well as pore systems. Further, it
can support detection of micropores as intraparticle organic porosity in autofluorescent
bituminite.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
79
References
BGR 2012 - DERA Rohstoffinformationen 15 (2012). Energy Study. Reserves, Resources and Availability of
Energy Resources 2012.
http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/DERA_Rohstoffinformationen/rohstoffinformat
ionen-15e.pdf?__blob=publicationFile&v=3
BGR 2011 - Aktuelle Projekte der Bundesanstalt für Geowissenschaften und Rohstoffe 2012-2016.
http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/Resource/resource-2012-
2016.pdf?__blob=publicationFile&v=4
Largeau C., Derenne S., Casadevall E., Berkaloff C., Corolleur M., Lugardon B., Raynaud J.F., Connan J. 1989 -
Occurrence and origin of ‘ultralaminar’ structures in ‘amorphous’ kerogens of various source rocks and oil
shales. Organic Geochemistry, 16: 889–895.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
80
Highly metamorphosed organic matter – origin and some properties
B. Kwiecińska1, S. Pusz
2
1AGH-Technical University, Al. Mickiewicza 30, PL-30059 Krakow, Poland, [email protected]
2Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Skłodowskiej 34,
41-819 Zabrze, Poland
The group of highly metamorphosed organic matter comprises: graphites, semi-graphites,
anthracites, natural cokes and chars, pyrocarbons and shungites. Investigations made with
OM, SEM and TEM revealed transitional forms: anthracite, meta-anthracite semi-graphite
and graphite (A-MA-SG-G) according to intensification of metamorphism. The stage A has
the greatest interlayer spacing (d002 > 3.40 Ǻ), the lowest degree of graphitization (u < 0.3)
and the smallest crystallite size (Lc and La < 50 Ǻ).
The most metamorphosed form of organic matter is graphite that can have biogenic or
inorganic origin. Biogenic graphite is formed through transformation of carbonaceous
sediments that are usually rich in organic remnants. Inorganic way of formation of graphite is
more difficult to prove, thus several hypotheses concerning the mechanism of deposition of
graphite from gaseous emanations exist. Pure graphite is composed solely of carbon atoms
bonded in a honeycomb network within each graphene sheet. The model of graphitic structure
assumes the existence of the basal hexagonal crystalline lattice of the A9 type.
Graphite shows an amazing versatility to form a wide variety of unusual morphologies,
textures and structures from the macroscopic to the nanoscale. In nature one can find e.g.
tabular hexagonal flakes, plates, irregular impregnations, barrel-shaped crystals, fibrous
crystals, rosette structure or spherical aggregates, ranging from sub-micrometers to 2 cm
across. The variety of morphologies and microstructures results from distortions of the
graphene sheets during growth and by the incorporation of dislocations, disclinations, twin
planes, pentagonal and heptagonal rings.
Specific structure of graphite causes its peculiar properties. Graphite is opaque to the light
- reflectance measurements made on natural cleavage surfaces reveal the value Rmax 17.5%. It
is a good conductor of heat and electricity, resistant to chemicals, with ability to absorb fast-
moving neutrons. Hence, natural graphite is used in variety of application, e.g. as lubricants,
insulation, fillers, refractories, electrodes, moderators in nuclear reactors and others.
Anthracites, from one side, are the final stage of metamorphism of bituminous coals and
from the other side the precursor of the series A-MA-SG-G. They contain more than 91% by
weight of element C and their basic structure consists of stacks of parallel graphene layers,
with the size of about several nanometers. Spatial organization of graphene stacks in
anthracites depends on the degree of their metamorphism and transform gradually from
poorly ordered turbostratic structure up to better-ordered graphite-like structure. In sufficient
thermal-pressure conditions certain anthracites pass to semi-graphite or graphite. Some others
not, dependently on the character of initial organic materials and metamorphic process.
Together with structural alteration of anthracites, the changes in their physical and
chemical properties are observed.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
81
Shungite represents strongly metamorphosed, highly condensed carbonaceous matter
occurring in Precambrian sediments in Karelia, Russia. Shungite-bearing rocks have been
classified on their carbon content that can change from above 90 to 10 wt. %. In a further
classification, shungite is subdivided into bright, semi-bright, semi-dull and dull on the basis
of their luster. There are a lot of hypothesis of shungite origin, from being a noncrystalline
carbon form, through some type of bituminous coal, kerogen, bitumen or carbonized
hydrocarbon. Shungites are characterized by curved carbon layers similar to that in natural or
synthetic cokes, organized in turbostratic structure. In individual cases one can see the
relationships between morphology, structure and physical properties of shungites. According
to the Franklin classification, shungites seem to be non-graphitizable variety of carbon. In
shungites, there were found carbon forms very similar to fullerenes.
Because of their specific properties shungites are widely applied as water purifier, paint
pigment, fillers, insulating material and many others.
The term natural coke has been used to describe coal thermally affected by an igneous
intrusive body. The kind of coal alteration depends on the temperature of the intrusion, the
duration of magmatic heating and the distance from direct contact with the igneous rock.
Natural coke is usually dull, compact and hard. It has vacuoles (pores) which are empty or
filled with mineral matter. Close to intrusions there were found small amounts of
carbonaceous materials deposited from a gas phase – natural pyrocarbon.
Natural chars are organic particles with pyrolysis chars morphology occurring in coal
seams and carbonaceous mudstones independently on geological age of the deposits. The rank
of the deposits ranges from lignite to medium volatile bituminous coals. They are formed in
relatively low temperatures while fire on coals or peats.
Natural carbon materials are very important from practical point of view because they are
used as precursors or substitutes of energy- and time-consuming man-made carbon materials.
Natural cokes and chars occurring in nature in rather small amounts are indicators of
paleoenvironments.
References
Jaszczak J.A., Robinson G.W., Dimovski S., Gogotsi Y. 2003 - Naturally occurring graphite cones. Carbon, 41:
2085-92.
Kwiecinska B.K., Murchison D.G., Scott E. 1977 - Optical properties of graphite. Journ.Microscopy, 109.
Kwiecińska B.K., Petersen H.I. 2004 - Graphite, semi-graphite, natural cokes, and natural chars classification –
ICCP system. Int. J. Coal Geol., 57: 99-116.
Duber S., Pusz S., Kwiecińska B.K., Rouzaud J.N. 2000 – On the optically biaxial character and heterogeneity of
anthracites. Int J. Coal Geol., 44: 227-250.
Kwiecińska B.K., Pusz S., Krzesińska M., Pilawa B. 2007 - Physical properties of shungite. IJCG, 77: 455-461.
Melezhik V.A., Fallick A.E., Fillipov M.M., Larsen O. 1999 – Karelian shungite – an indication of 2.0-Ga-old
metamorphosed oil-shale and generation of petroleum: geology, lithology and geochemistry. Earth-Science
Reviews, 47: 1-40.
Kovalevski V.V., Buseck P.R., Cowley J.M. 2001 - Comparison of carbon in shungite rocks to other natural
carbons: An X-ray and TEM study. Carbon, 39: 243-256.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
82
Changes in concentrations of selected heavy metals and trace elements
in microbial desulphurization of bituminous coals
(the Lublin Coal Basin, Poland)
L. Lewińska-Preis1, M.J. Fabiańska
1, R. Galimska-Stypa
2, A. Kita
3
1Faculty of Earth Sciences, University of Silesia, 41-200 Sosnowiec, 60 Będzińska Street, Poland
2University of Silesia,
2) Faculty of Biology and Environmental Protection, 4 Jagiellońska Street,
42-700 Katowice, Poland 3 Faculty of Mathematics, Physics and Chemistry, University of Silesia, 40-006 Katowice, 9 Szkolna Street,
Poland
The improvement of environmental and economic coal combustion efficiency is related to a
number of factors from improving the quality of coal, combustion technologies, controlling
devices to emission reducing. So called Clean Coal Technologies (CCT) are defined as
processes and technologies that reduce the negative impact of burning coal in three stages:
pre-combustion, the combustion and post-combustion (Lorenz 2005). One of these methods
improving the quality of the coal (i.e. removing harmful components emitted to the
atmosphere) before its combustion is a method of microbial desulfurization of coal. This
method relies primarily on the removal of pyritic sulfur from coal by oxidation of sulfides to
sulfates, with the participation of microorganisms. Bioleaching process efficiency is very
high. The reduction of pyritic sulfur by leaching with bacteria of the genus Thiobacillus
ferrooxidans and Thiobacillus thiooxidans, can reach up to 97% (Acharya et al. 2001). An
additional effect of this process is the reduction of heavy metals and trace elements
concentrations (Bos et al. 1992; Naganoka et al. 1999; Lewińska-Preis et al. 2008). Trace
elements and metals released by coal combustion are a potential source of pollution. These
elements are mainly concentrated in fly ash. For coals of the Upper Silesian Coal Basin the
estimated emissions of trace elements in fly ash are 32.6-121.5 Mg/y for Cr, 46.5-1287.7
Mg/y for Zn, 3.6 Mg/y for Cd, 17.5-68.7 Mg/y for Co, 38.9-185.1 Mg/y for Cu, 1.6-6.4 Mg/y
for Mo, 19.9-79.4 Mg/y for Pb, and 72.3-237.1 Mg/y for V (Staisz et al. 2000). The use of
biodesulphurized coal can significantly decrease these elements emissions to the atmosphere.
In the projects bituminous coals from the Lublin Coal Basin (LCB) were studied, which
were subjected to microbiological leaching. The process was carried out using a suspension
bioreactor. The ratio of powdered coal to the number of bacteria was 1:2. The suspension was
prepared from the strains of bacteria Thiobacillus ferrooxidans, and Thiobacillus thiooxidans
HR27 KH45 (1:1), a density of 108 cells in 1 cm
3. Samples were introduced into the
Silverman and Waksman modified medium containing the suspension of bacteria in a ratio of
1: 1. The samples of raw (not desulphurized) coal and desulphuriozed coals were combusted
at 525oC. In coal ash, the selected elements (Be, Cd, Co, Cr, Cu, Mo, Pb, V, and Zn) were
investigated by Inductively Coupled Plasma - Atomic Emmision Spectrometry (ICP) whereas
C and S contents were found using the Eltra CS 530 analyser.
The concentrations of the selected elements in raw coals and their ashes are at the level of
the average concentration of these elements in coals and ash coals in the world. In the
biodesulphurization ash content and the concentration of Be, Cd, Co, Cr, Cu, Mo, Pb, V, Zn
were reduced. The highest degree of reduction is shown by Co (90%), Mo (85%), and Be
(84%) and the lowest Cr (36%) and V (46%). For Cd concentration reduction degree is 74%,
for Cu - 67%, for Zn - 66% Pb - 60%, and for total ash content - 16%.
As a result of microbial desulfurization of LCB bituminous coals there were also changes
in the occurrence variability of elements and the degree of their affinity for organic matter and
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
83
mineral matter of coal. In general, the elements variability of after the biodesulphurization
decreases; only Zn and Cd show an increase of over 100%. Changes in the elements affinity
to organic and mineral matter of desulphurized coals indicate that these elements are leached
mainly from coal inorganic substances, and only to a lesser extent from organic matter.
Coals with high ash contents have the highest degree of reduction in the concentrations of
elements, apart from Zn, Cd and Be. For Zn and Cd the highest concentration decrease was
observed for low-ash coals (ash content less than 10%). For Be concentrations decrease was
the same in low-and high ash coals (> 20%).
References
Acharya C., Kar R.N., Sukla L.B. 2001 - Bacterial removal of sulphur from three different coals. Fuel, 80: 2207-
2216.
Bos P., Boogerd F., Kunen J.G. 1992 - Microbiol desulfurization of coal. In: Environmetal Microbiolagy, Ed: R.
Mitchell, Wiley-Lisse, Jnc., New York: 375 – 403.
Lewińska-Preis L., Fabiańska M.J., Parzentny H., Kita A. 2008 - Geochemical characteristics of the
macromolecular part of crude and biodesulphurised flame coal density fractions. Chemie der Erde, 68:
279-293.
Lorenz U., 2005 - Skutki spalania węgla kamiennego dla środowiska przyrodniczego i możliwości ich
ograniczania. Materiały Szkoły Eksploatacji Podziemnej. Sympozja i Konferencje, 64, Wyd. Instytut
GSMiE PAN, Kraków: 97-112.
Nagaoka T., Ohmura N., Saiki H. 1999 - A Novel Mineral Flotation Process Using Thiobacillus ferrrooxidans.
Applied and Environmental Microbiology, 65: 3588-3593.
Staisz J., Pasoń-Konieczyńska A., Konieczyński J. 2000 - Wstępna ocena emisji pierwiastków śladowych
w wyniku spalania węgla kamiennego. Archiwum Ochrony Środowiska, 26, 1: 7-20.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
84
Organic petrology of two condensed Middle Holocene peat deposits
in N Spain in relation to their origin
V. López-Dias, J. Urbanczyk, C.G. Blanco, A.G. Borrego
Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain; [email protected]
Peatlands have been successfully used to study the evolution of climate during the Holocene
(Barber et al. 2003). Peatlands formation require a positive balance of organic matter
accumulation and are particularly abundant in cold to temperate humid regions in which the
rate of organic matter destruction is relatively low or in tropical regions where the rate of
organic matter accumulation is particularly high. The north of Spain is the southernmost limit
for ombrothrophic blanket bogs in the Atlantic region and provides the opportunity to study
their palaeoenvironmental evolution in an area in contact with the more arid Mediterranean
region. A number of peats have been developed in the plane reliefs of Asturias ranging in age
from around 10000 cal. yr BP to present day. They are either raised bogs or blanket bogs and
show growth rates ranging from 0.7 and 0.05 mm/yr (López-Días et al. 2013a).
This study focuses on the Buelna and La Borbolla peat profiles, both exhibiting a very low
growth rate (0.05-0.07 mm/yr) and having profiles whose record extends from around 9000 to
2500 cal. yr BP. La Borbolla bog (UTM 30 T 365813 4804949) has an extension of 6 ha, is
situated 227 m above sea level (masl) and the profile reaches a depth of 56 cm, consisting of
around 8 cm of living vegetation dominated by Sphagnum, followed by a 20 cm interval of
bryophytic reddish peat with abundant roots and by 14 cm of darker and clayish peat, which
becomes lighter towards the end. The Buelna bog (UTM 30T 369898 4805333) has a surface
of around 9 ha and is located at a height of 133 masl. The sampled core reaches a depth of 87
cm, The first 15 cm consisting of unconsolidated living vegetation with many roots, followed
by 9 cm of more bryophytic peat with common roots. The next 36 cm consist of compact dark
reddish peat. This interval is followed by 8 cm of dark clayish material and the last 20 cm are
a light grey siltstone with low organic content. The two profiles differ in the type of organic
matter which is more bryophytic in La Borbolla and more herbaceous in Buelna (López-Dias
et al., 2013b).
Alternating humid/dry periods have been established in the two profiles based on lipid
concentrations. The main humid intervals detected are dated as 5000-7500 cal. yr BP in
Buelna and as 6000-3500 cal. yr BP and 2500 cal. yr BP in La Borbolla and correlate with the
humid periods detected in other peat locations in the region (López-Dias et al., 2013a). The
study of linear lipids indicates that the Sphagnum-rich intervals are more sensitive than
herbaceous peat to humid/dry variations. The transition Middle-to-Late Holocene is
characterized by humid conditions in the region which favoured the Sphagnum growth in the
peats.
The petrographic analyses were used to determine the degree of humification in the peat
profiles through the measurement of huminite reflectance and the degree of preservation of
the different components. Both telohuminite, detrohuminite and corpohuminite components
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
85
were identified in the profiles in addition to their translucent ungelified precursors. The
reflectance of huminite was very low (0.25-0.12%) and without significant differences
between telohuminite and detrohuminite. Corpo-huminite reflectances were systematically
higher. The reflectances tended to be higher towards the top, where humification processes
could have been intensified as consequence of the stopping of peat growth. The level of tissue
preservation was observed to be lower in La Borbolla, in which extensive tissue destruction
resulted in comminute organic debris. This was accompanied in this profile by abundant
inertodetrinite, particularly concentrated at around 5000 cal. yr BP, a period character-rized
by a marked change from higher-plants derived n-alkane to Sphagnum-derived n-alkane
(López-Dias et al., 2013b). The Buelna profile, with a more herbaceous vegetation, and higher
mineral matter content throughout the profile, shows a higher level of tissue preservation
(dominance of telohuminite) and lower inertinite content.
Acknowledgement: Financial support from MICINN (CGL2009-13990-C02-01/02) is gratefully acknowledged.
J. Urbanczyk thanks MEC for a FPU fellowship.
REFERENCES
Barber K.E., Chambers F.M., Maddy D. 2003 - Holocene palaeoclimates from peat stratigraphy: macrofossil
proxy climate records from three oceanic raised bogs in England and Ireland. Quaternary Science Reviews
22: 521–539.
Lopez-Dias V., Urbanczyk J., Blanco C.G., Borrego A.G. 2013a - Biomarkers as palaeoclimate proxies in
peatlands from coastal high plains in Asturias, N Spain. Int J. Coal Geol.
dx.doi.org/10.1016/j.coal.2013.04.006.
Lopez-Dias V., Urbanczyk J., Blanco C.G., Borrego A.G. 2013b - Palaeohydrological evolution of the Middle-
to-Late Holocene transition in North Spain as recorded by biomarkers in peat bogs. Palaeogeography
Palaeoclimatology Palaeoecology (submitted).
Fig.1. Images showing inertinite-rich levels in La Borbolla at ~5000 cal. yr BP.
Arrows mark inertinite, Ul=Ulminite. Incident white light
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
86
Transmittance Color Index of Amorphous Organic Matter (TCIAOM)
as thermal maturity parameter: a new approach
J.G. Mendonça Filho1, J.O. Mendonça
1, T.R. Menezes
2, F.S. Silva
1
1Palynofacies & Organic Facies Laboratory (LAFO), Federal University of Rio de Janeiro (UFRJ), Brazil;,
[email protected] 2Research and Development Center, PETROBRAS, Brazil
The Transmittance Color Index (TCI) of Amorphous Organic Matter (AOM) was proposed firstly
by Van Gijzel (1989) as a new thermal maturity indicator for hydrocarbon source rocks, due to the
need for an improvement to assess the thermal history in petroleum basins and the lack of
accuracy in the current techniques for determining thermal maturity on severe limitations, i.e. lack
of vitrinite particles or sporomorphs, presence of supressed vitrinite in Type I/II kerogen, etc.
TCI eliminates most limitations of these techniques and it is measured on amorphous material,
the most abundant type of organic matter in hydrocarbon source rocks of all geologic ages and for
instance where vitrinite is scarce. According to Van Gijzel et al. (1992), TCI is measured by
quantitative microscope spectrophotometry (the quantitative measurement of the reflection or
transmission properties of a material as a function of wavelength), making it easy to develop
standards among different laboratories.
Based on Robison et al. (2000), the range of TCI values covers all zones of petroleum
generation and preservation. However, it can be more useful in those situations where the rocks
have not yet reached the semi-anthracite coalification stage (about 2.0% vitrinite reflectance). TCI
can provide an accurate basis for maturation interpretations equivalent in quality to those obtained
from vitrinite reflectance, zooclast reflectance (graptolites, chitinozoans), Spore Color Index
(SCI), Thermal Alteration Index (TAI) or Conodont Color Index (CAI). In addition, TCI
correlates with conventional organic petrologic maturity parameters such as TAI/SCI and vitrinite
reflectance. Thus, TCI is a quantitative method to determine the thermal stress and it can be used
as an indicator of thermal maturity in sapropelic organic facies, where other elements such as
vitrinites and sporomorphs are scarce or even absent.
According to Suárez-Ruiz et al. (2012), this method is applied to oil-prone amorphous kerogen
in transmitted light. The assignment of particular TCI values is based on the increasing curvature
of spectra with increasing maturity. TCI curves shift from a peak wavelength at around 580 nm
for samples of immature, amorphous kerogen (mean random vitrinite reflectance equivalent of
about 0.20%) to about 660 nm for samples containing very dark brown to some black particulate
material (mean random vitrinite reflectance equivalent of about 2.15%).
This work is part of the activities of a research project financially supported by PETROBRAS-
Brazil´s Research and Development Center and, for this new approach, more than 150 samples
from different ages (Carboniferous, Permian, Jurassic, Cretaceous, Oligocene and Eocene) with
vitrinite reflectance measured were tested for use in the development of the Linear Equation in
two variables for correlation between TCI and Equivalent Vitrinite Reflectance (Req), i.e. these
samples were used to build the Straight-Line Equation ("slope-intercept" form), represented by y
= m.x+b, where m and b assign constants (parameters). In this particular equation, the constant m
determines the slope or gradient of that line, and the constant term b determines the point at which
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
87
the line crosses the y-axis, also known as the y-intercept. Thus, the equation for correlation can be
written as %Req = slope x TCIAOM - (Y intercept).
Out of the total samples, only 80, appointed the following equation: %Req = 0.0217 x TCIAOM –
11.327 (against that obtained by Robson et al., 2000; %Req = 0.0253 x TCI – 14.35), where the
linear correlation coefficient obtained, r, which measures the strength and direction of a linear
relationship between two variables) was 0.978. This was obtained by comprising both vitrinite
measurable particles and AOM, covering different values of thermal maturity. The value of r is
such that -1 < r < +1. The + and – signs are used for positive linear correlations and negative
linear correlations, respectively. For our equation the value of r = 0.978 indicates a strong positive
linear correlation between x and y variables such that as values for TCIAOM increase, as well
as Req. Now, the coefficient of determination, r2, which is useful because gives the proportion
of the variance (fluctuation) of one variable that is predictable from another, is 0.959. It is a
measure that allows us to determine how certain one can be in making predictions from a certain
model/graph. The coefficient of determination (r2) is the ratio of the explained variation to the
total variation. The coefficient of determination is such that 0 < r2 < 1, and denotes the strength of
the linear association between x and y. The coefficient of determination represents the percent of
the data that is the closest to the line of best fit. In this case, if r = 0.978, then r2 = 0.959, which
means that approximately 96% of the total variation in Req can be explained by the linear
relationship between Req and TCIAOM (as described by the regression equation). The other 4% of
the total variation in Req remains unknown.
TCI values are obtained by the analysis of white light originating from a 100-W 6-V tungsten
lamp attached to a microscope (Axioskop 2 plus Zeiss) and photometric (J&M – MSP 200 –
TidasDAQ). Measurements for 30 to 40 particles are sufficient to produce good data and TCIAOM
measurements were made on AOM in those samples in which vitrinite reflectance measurements
were reliable. Based on the Linear Equation, values obtained for TCIAOM between 532 and 544
can be correlated to Req varying between 0.16 and 0.45% Req, TCIAOM from 550 to 576 can be
correlated to 0.7-1.1 %Req and TCIAOM values from 583 to 593 correlates 1.4-1.6%Req.
Acknowledgments: The authors are grateful to PETROBRAS-Brazil for the financial support through the
project entitled “Faciologia Orgânica, Maturação Térmica e Modelagem Geológico-Geoquímica de Seqüências
Sedimentares Paleozóicas, Mesozóicas e Cenozóicas".
References
Robison C.R., Van Gizel P., Darnell L.M. 2000 - The Transmittance Color Index of amorphous organic matter:
a thermal maturity indicator for petroleum source rocks. International Journal of Coal Geology, 43: 83-103.
Súarez-Ruiz I., Flores D., Mendonça Filho J.G., Hackley P.C. 2012 - Review and update of the applications of
organic petrology: Part 1, Geological Applications. International Journal of Coal Geology 99: 54-112.
Van Gijzel P. 1989 - Transmittance Color Index _TCI. of amorphous organic matter: new thermal maturity
indicator for hydrocarbon source rocks-correlation with mean vitrinite reflectance and thermal alteration
index _TAI. AAPG Bull. 73: 1177.
Van Gijzel P., Robison C.R., Smith M.A., Bissada K.K., Lerche I., Liu J.-C. 1992 - Thermal history modeling of
the Georges Bank, U.S.A.: thermal inversion of transmittance color index _TCI. Vitrinita reflectance _VR.
data. Appl. Geochem. 7: 135–143.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
88
Offshore from the Lusitanian Basin, Portugal:
new insights into depositional settings and hydrocarbon source potential
based on palynofacies and organic geochemistry
T.R. Menezes1, J.G. Mendonça Filho
2, D. Flores
3, L.A.F. Trindade
4
1Research and Development Center, PETROBRAS,[email protected]
2Palynofacies & Organic Facies Laboratory, Federal University of Rio de Janeiro (UFRJ), Brazil
3Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências, Universidade
do Porto, Portugal 4PESA, Petrobras Argentina
This study provides an organic facies characterization using palynofacies and organic
geochemical parameters of the Mesozoic sedimentary sections offshore part of the Lusitanian
Basin (Portugal) in order to obtain new insights into depositional paleoenvironments and
hydrocarbon source potential. The studied samples were collected from two exploratory wells
(MO-1 and 14A-1) at shallow water depth. This basin is one of a family of Atlantic margin
rift-basins and it is located along the western Iberian margin which has formed as a response
to Mesozoic extension and subsequent opening of the North Atlantic Ocean, covering some
20.000 km2 in the west-central part of the Portuguese mainland and the adjacent continental
shelf (e.g. Wilson et al., 1989, Rasmussen et al., 2008). The geological database was based on
Well Geological Report from company completion logs available on request at GPEP
(Gabinete para a Pesquisa e Exploração de Petróleo).The discussion below will focus on the
characterization of sedimentary organic matter based on Total Organic Carbon (TOC%),
Rock-Eval Pyrolysis, kerogen assemblages characterized by palynofacies analyses, thermal
maturity (Vitrinite Reflectance –%Ro, Spore Coloration Index – SCI) and biomarker
parameters. The studied samples in both sections shown TOC values less than 1.00wt % and
insoluble residue values (IR) indicated mainly carbonate/marls deposits. Indeed, the bulk
TOC values reflected strong dilution effects ordinarily in carbonate facies. In general, the
main palynofacies assemblage has a predominance of macrophytes tissues remains
(Phytoclast Group). The differences detected in microscopic examination along the two
analyzed sedimentary sections point out variations in depositional settings: The palynofacies
from the Dagorda Formation (Upper Triassic-Lower Jurassic deposits) consists predominantly
of coarse to medium sized woody organic matter (non-opaque non-biostructured phytoclats)
and has a high relative abundance of tetrads of Classopollis and Amorphours Organic Matter
(AOM) with inclusions of palynomorphs debris. Marine palynomorphs are rare (acritarchs,
foraminiferal test linings and dynocist). Under reflected white light a significant proportion of
inertinite maceral was identified. The kerogen assemblage suggests a depositional set
associated with an aridity trend and nearest to the source area from the studied intervals. By
contrast, some samples from the MO-1 well are represented by carbonaceous marls, presented
TOC values from 6.4 to 30 wt%, which could be related to a more humid episode. The
Sinemurian age (Coimbra Formation) is characterized by a major percentage of AOM and a
predominance of biostructured phytoclasts. It was observed a decrease of relative abundance
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
89
of terrestrial palynomorphs. The palynofacies signature indicates moderately deeper water
than that of the Dagorda Formation. In the Brenha Formation, from Lower Jurassic-Middle
Jurassic, the MO-1 well kerogen assemblage has shown a balanced content of orange
fluorescing AOM and phytoclasts. It was identified the presence of continental palynomorphs
(e.g. Botryococcus, spores from Zygnemataceae Family, Azolla sp.) and rare marine
palynomorphs. Moreover, the palynofacies from 14A-1 is overwhelmingly dominated by
biostructured phytoclast. Thus, the organic facies of this unit suggested a variation in the
hydrodynamic regime between two depositional settings. The Oxfordian section was
described in the 14A-1 well. In this interval, the palynofacies reveals, from the base to the top,
the increase of poorly preserved sporomorphs and a high relative abundance of dynocists due
to probably a fluvial-deltaic progradation. The Kimmeridgian and Upper Cretaceous
sediments were found only in the MO-1 well, where sedimentation is more influenced by
terrigeneous contribution and reflected a poorly preserved organic matter with very low TOC
values and IR > 70, indicating a siliciclastic sedimentation and high energy environment in
oxic conditions. Concerning biomarkers characterization, though based on a restricted number
of samples, the study showed a good correlation with palynofacies data. The main biomarkers
parameters e.g., Hopane/Sterane ratio < 0.5, C21Tricyclic/C23Tricyclic and
C26Tricyclic/C25Tricyclic ratios< 1, TPP/TPP+DIA < 0.4, low occurrence of methylsteranes,
C29 sterane > C27 and C28, C24 Tetracyclic Terpane/C26 Tricyclic Terpane ratio > 0.5, C35
homohopane/C34 homohopane ratio varies from 0.52 to 1.09, pointing to a carbonate marine
deposition with strong contribution of continental organic matter. The source rock potential
represented by S2 peak from pyrolysis are very poor (< 5 mg HC/g rock) and Hydrogen Index
(HI) are typical from type III-IV kerogen. In contrast, the carbonaceous marls from the MO-1
well presenting a S2 values reaching up 40 mg HC/g rock showed an excellent potential for
hydrocarbon generation. Now, the correlation of optical thermal maturity parameters (%Ro
and SCI) to 20S/(20S+20R) sterane, C29βββ/(αα+ββ) steranes, and Ts/Ts+Tm ratios indicated
that the studied sedimentary sections are in the oil window.
Acknowledgments: This work has been sponsored by the Scientific and Technical Cooperation Agreement
CAPES (Brazil)/FCT (Portugal), through the project entitled “Caracterização das variações organofaciológicas e
identificação dos horizontes potencialmente geradores de petróleo no Jurássico da Bacia Lusitânica”.
References
GPEP (Gabinete para a Pesquisa e Exploração de Petróleo) 1986 - Petroleum potential of Portugal: 1-62.
Rasmussen E.S., Lomholt S., Andersen C., Vejbæk O.L. 1998 - Aspects of the structural evolution of the
Lusitanian Basin in Portugal and the shelf and slope area offshore Portugal. Tectonophysics, 300: 199 – 225.
Wilson R.C.L., Hiscott R.N., Willis M.G., Gradstein F.M. 1989 - The LusitanianBasin of west-Central Portugal:
Mesozoic and Tertiary tectonic, stratigraphic and subsidence history. AAPG Bulletin 46: 341–362.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
90
Preliminary organic geochemical study of lignites
from Smederevsko Pomoravlje field, Kostolac Basin, Serbia
D. Mitrović1, N. Đoković
1, K. Stojanović
2, S.K. Das
3, A. Ekblad
4, A. Mikusinska
4,
D. Životić5
1University of Belgrade, Innovation Center of the Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade,
Serbia 2University of Belgrade, Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia;
[email protected] 3Presidency University, Department of Geology, College Street 86/1, 700073 Kolkata, India
4School of Science & Technology, Örebro University, S-701 82 Örebro, Sweden
5University of Belgrade, Faculty of Mining and Geology, Djušina 7, 11000 Belgrade, Serbia;
The Kostolac Coal Basin, covering an area of 145 km2, is located about 90 km east of
Belgrade. The coal basin is divided into Drmno, Ćirikovac and Smederevsko Podunavlje
fields situated in eastern, central and western part of the basin, respectively. Drmno and
Ćirikovac fields were exploited, while Smederevsko Podunavlje field is still under
preliminary exploration.
Lignite samples of Pontian age (Upper Miocene) from 27.40 to 85.20 m depth in two
boreholes (A1J-369 and A2I-414) at Smederevsko Pomoravlje field were investigated.
Organic geochemical (organic carbon content, ash yield, moisture, sulfur and nitrogen
contents, extract yield and content of hydrocarbons) and bulk stable carbon and nitrogen
isotopes (δ13
C and δ15
N, respectively) in the samples were analyzed. Objectives of the study
were to understand depositional conditions of the peat in the study area, and compare the
results with similar studies in other coal basins in Serbia and worldwide. Moreover, based on
bulk and specific organic geochemical data, the possibility of exploitation of lignite from
Smederevsko Pomoravlje field in future was considered.
Organic carbon content, ash yield, moisture, sulfur and nitrogen contents, extract yield and
content of hydrocarbons in lignites of Smederevsko Pomoravlje field fall within the range of
corresponding parameters for lignites from other deposits in Serbia (Stojanović, Životić,
2013). High yield of soluble organic matter (bitumen), represented by asphaltenes and polar,
NSO compounds, is attributed to high proportion of biogenic and diagenetic compounds.
16(H)-Phyllocladane and pimarane are dominant in saturated hydrocarbon fractions. A high
amount of 16α(H)-phyllocladane and pimarane, as well as presence of ferruginol, totarane and
hibaene indicate conifers (Taxodiaceae, Podocarpaceae, Cupressaceae, Phyllocladaceae and
Pinaceae) as primary constituent of the peat forming plants. Presence of diterpenoids as the
main constituents of both saturated and aromatic fractions supports our finding. Aromatic
diterpenoids consist predominantly of aromatized abietane derivatives. Long-chain
homologues (C27-C31, maximum at n-C29) n-alkanes with marked odd over even
predominance indicate significant contribution of epicuticular waxes to the organic matter
(OM) pool. Pristane to phytane, Pr/Ph ratio (0.72−1.65) most likely indicates changing redox
(Eh) setting from anoxic to slightly oxic conditions during peat deposition.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
91
Samples contain very low amount of non-hopanoid triterpenoids and des-A-ring degraded
triterpenoids. Hopanoid patterns are characterized by occurrence of C2717(21)-hop-ene,
17α,21β(H)- and 17β,21β(H)- hopanes from C27 to C32 (C28 was absent). Steroid biomarkers
consist of C27-C29 Δ2-, Δ
4- and Δ
5-sterenes with sharp domination of C29 homologues.
Bulk δ13
C values vary from −26.66 to −25.25‰. Average carbon isotopic composition of
all samples (δ13
C=−26.01‰) falls within the range of δ13
C values reported for the upper
Oligocene Trbovlje coal seam in Slovenia (Bechtel et al., 2004), early Miocene Oberdorf
lignite in Austria (Bechtel et al., 2002) and Oligocene-Miocene lignites from New Zealand
(Vu et al., 2009). The δ13
C isotope values of Smederevsko Pomoravlje lignites do not vary
much with age and borehole location, and lie within the range of typical terrestrial OM in
Cenozoic sediments (Hoefs, 1997). δ15
N values range from 2.81 to 5.54 ‰. A lack of
systematic trend in δ13
C and δ15
N values with depth suggests that climate and/or
environmental conditions did not vary drastically during the deposition of peat although the
variations in δ13
C and δ15
N may reflect seasonal changes in climate condition (cycling change
of humid/dryer and warmer/cooler conditions; Ivanov et al., 2011). Pronounced seasonal
changes in local climate can affect ground water table resulting in changes in the Eh
conditions and microbial activity during peatification. Positive correlation between δ13
C and
δ15
N and Pr/Ph ratio, and negative correlation between δ13
C and δ15
N and C30ββ/(αβ+ββ)
hopane ratio support our assumption. Nonetheless, significant positive correlation between
C/N and δ13
C, and abundance of hopanes in the lignite extracts indicate influence of microbial
degradation on the stable isotope records.
Bulk organic geochemical data and distribution of biomarkers in lignite extracts from
Smederevsko Pomoravlje field are very similar to those, observed in other Pontian lignite
fields in Serbia (e.g. Drmno field, Kostolac Basin and A field, Kovin deposit; Stojanović,
Životić, 2013) indicating a similar genesis and geological evolution. Obtained results could
imply that lignite from Smederevsko Pomoravlje field can also be used in the large scale,
particularly for electricity generation in thermal power plants.
References
Bechtel A., Sachsenhofer R.F., Gratzer R., Lücke A., Püttmann W. 2002 - Parameters determining the carbon isotopic
composition of coal and fossil wood in the Early Miocene Oberdorf lignite seam (Styrian Basin, Austria). Org.
Geochem., 33: 1001–1024.
Bechtel A., Markic M., Sachsenhofer R.F., Jelen B., Gratzer R., Lücke A., Püttmann W. 2004 - Paleoenvironment of the
upper Oligocene Trbovlje coal seam (Slovenia). Int. J. Coal Geol., 57: 23– 48.
Hoefs J., 1997 - Stable Isotope Geochemistry. Springer-Verlag, Berlin: 1-201.
Ivanov D., Utescher T., Mosbrugger V., Djordjević-Milutinović D., Molchanoff S. 2011 - Miocene vegetation and climate
dynamics in Eastern and Central Paratethys (Southeastern Europe). Palaeogeogr. Palaeoclimatol. Palaeoecol., 304: 262–275.
Stojanović, K., Životić, D., 2013. Comparative study of Serbian Miocene coals – insights from biomarker composition. Int. J.
Coal Geol.107, 3–23.
Vu T.T.A., Zink K.-G., Mangelsdorf K., Sykes R., Wilkes H., Horsfield B. 2009 - Changes in bulk properties and molecular
compositions within New Zealand Coal Band solvent extracts from early diagenetic to catagenetic maturity levels. Org.
Geochem., 40: 963–977.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
92
Raman microspectroscopy of funginite from the Upper Silesian Coal Basin
(Poland) - preliminary results
R. Morga
Silesian University of Technology, Gliwice, Poland; [email protected]
Introduction
Funginite is a relatively rare but also weakly recognized coal maceral from the inertinite
group. The purpose of this study was to obtain, for the first time worldwide, structural
characteristics of funginite with the use of the micro-Raman spectroscopy.
Method
Examination was performed on inertinite concentrates (I content: 80 – 84%) prepared from
four samples of the coking coal from the Upper Silesian Coal Basin of Poland. Selected
properties of the parent coals are summarized in Table 1. Micro-Raman measurements were
carried out with the use of a Renishaw inVia spectrometer (excitation line λ0=514 nm) on
6-10 funginite grains in each mount. Spectral range was 1000-1800cm-1
, and resolution 2cm-1
.
During each measurement four acquisitions of 10s were co-added. Measurement area was
2x2μm. The spectra were deconvoluted with the use of GRAMS 32 software, following the
Sadezky's et al. (2005) method. Four Lorentzian (G, D1, D2 and D4 band) and one Gaussian
(D3 band) lines were used. Goodness of fit was checked by χ2 test. Based on that, position of
the Raman bands and their width (FWHM) were found. Following spectral parameters were
determined: AG/AALL, AD1/AALL, AD2/AALL, AD3/AALL and AD4/AALL (all calculated as the area
ratios) as well as ID1/IG and ID2/IG (both calculated as the band height ratios). The results were
compared with those, obtained during previous examination of semifusinite and fusinite
(Morga, 2011). For this purpose, the t-Student test was performed, preceded by the Shapiro-
Wilk normality test and the Fisher-Snedecor test to assess the equality of variance.
Table 1. Selected properties of the parent coals used in the study
Sample
Seam
Age
Rr
%
sr
%
Vdaf
%
RI
Vitrinite
%
Liptinite
%
Inertinite
%
MM
%
1 358/1 Westphalian A 0,92 0.05 33.81 71 73 6 19 2
2 703 Namurian A 0,94 0.06 33.70 75 70 8 20 2
3 358/1 Westphalian A 0,97 0.05 30.83 80 65 9 24 2
4 403/1 Westphalian A 1,11 0.06 26.25 64 66 3 29 2
Results
The D2 band position in the Raman spectra of funginite is situated between 1612cm-1
and
1613cm-1
. The G band falls between 1587cm-1
and 1591cm-1
. The other bands occur within
the following spectral ranges: D3 – 1441-1489cm-1
, D1 – 1343-1348cm-1
and D4 – 1238-
1254cm-1
. The G band FWHM varies between 55cm-1
and 61cm-1
and that of the D1 band
between 119cm-1
and 147cm-1
. The other bandwiths are presented in Table 2. The AD2/AALL
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
93
ratio ranges from 0.12 to 0.15. The values of the other structural ratios are: AG/AALL – 0.15-
0.18, AD3/AALL – 0.13-0.17, AD1/AALL – 0.29-0.44, AD4/AALL – 0.13-0.22, ID1/IG – 0.83-1.18
and ID2/IG – 0.97-1.34 (Table 3).
When samples 1 and 3 are considered, results obtained for funginite do not vary
significantly from those recorded for fusinite (Morga, 2011). In the case of sample 2 there are
only minor differences in the spectral parameters between these two macerals, but much more
important betwee funginite and semifusinite (Morga, 2011). Spectral parameters of funginite
obtained from sample 4 show very close similarity to those of semifusinite.
Conclusion
Funginite microstructure may have many common features with that of fusinite or
semifusinite. Broader demonstration of these similarities requires further investigation.
Table 2. Position and the FWHM of the Raman bands for funginite
Sample
D2 band
position
[cm-1
]
D2 band
FWHM
[cm-1
]
G
band
position
[cm-1
]
G
band
FWHM
[cm-1
]
D3 band
position
[cm-1
]
D3 band
FWHM
[cm-1
]
D1 band
position
[cm-1
]
D1 band
FWHM
[cm-1
]
D4 band
position
[cm-1
]
D4 band
FWHM
[cm-1
]
1 1613.3 40.0 1590.5 59.2 1485.2 184.6 1343.7 132.4 1238.0 181.1
1.04 5.07 2.78 3.96 34.76 18.68 1.99 13.38 9.90 16.08
2 1611.7 41.6 1587.3 61.4 1489.2 180.6 1343.3 147.3 1237.7 177.3
0.97 3.76 2.39 3.07 23.22 19.41 2.26 15.16 9.25 12.51
3 1611.6 40 1588.9 55.2 1472.1 187.4 1345.0 125.6 1248.6 171.7
0.65 1.44 1.28 1.11 21.04 17.50 2.60 12.04 5.00 13.44
4 1612.0 42.0 1588.4 58.3 1440.8 188.5 1347.5 119.1 1253.6 179.4
0.48 3.69 1.88 3.02 9.45 15.66 1.78 9.31 3.37 7.91
Table 3. Values of the Raman spectral ratios for funginite
Sample AD2/AALL AG/AALL AD3/AALL AD1/AALL AD4/AALL ID1/IG ID2/IG
1 0.12 0.18 0.16 0.39 0.16 1.07 0.97
0.02 0.02 0.06 0.15 0.07 0.28 0.16
2 0.12 0.18 0.13 0.44 0.13 1.12 1.00
0.02 0.02 0.03 0.12 0.06 0.32 0.12
3 0.15 0.15 0.14 0.39 0.17 1.18 1.34
0.01 0.01 0.03 0.09 0.05 0.25 0.16
4 0.14 0.18 0.17 0.29 0.22 0.83 1.12
0.01 0.01 0.03 0.04 0.04 0.11 0.09
References
Morga R. 2011 - Reactivity of semifusinite and fusinite in the view of micro-Raman spectroscopy examination.
Int. Journal of Coal Geol., 88: 194-203.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
94
Influence of temperature on mineral composition changes of coal mine
waste; an example of waste dump sites in Upper Silesia Coal Basin (Poland)
J. Nowak
Silesian University of Technology; [email protected]
Extraction of hard coal is being inseparably bound with generation of large amounts of mineral
waste. These are mainly waste rock mined out directly during driving development headings,
preparation workings and coal faces or being removed from the output during its processing.
Coal mine waste in the Upper Silesia Coal Basin (USCB) area consists mainly of claystones,
mudstones, and sandstones. In these rocks there is also different, frequently high, amount of
organic matter – coal. In the mineral composition of these waste quartz and clayey minerals
dominate, mainly kaolinite, illite and other. Among the carbonates most frequently siderite occurs,
but also calcite and dolomite are present. Among the other minerals pyrite, feldspars, and
muscovite should be mentioned.
Due to the influence of hypergenic factors, especially precipitation waters and atmospheric
oxygen, weathering processes take place. At this stage, in the waste dumps grain-size
decomposition is dominating and the mineral composition undergoes only small transformations.
The most vulnerable for weathering processes are sulphides, which undergo transformation into
sulphates, gypsum, jarosite, and others. Also organic matter undergoes weathering. Oxidation of
coal and pyrite being contained in the coal mine waste is an exothermal reaction. As a result of
this process, self-heating of the waste takes place. In advantageous conditions, the temperature is
able to exceed temperature of ignition of the waste, which equals of about 250-350oC, what in a
consequence leads to generation of endogenic fires at the coal waste dumps. Combustion of coal
contained in the waste generates large amounts of heat, what contributes further increase of
temperature in the dump, even over one thousand degree Celsius.
The first mineral metamorphoses, which occur as the result of organic matter combustion are
decomposition of carbonates and dehydroxylation of clayey minerals.
Siderite, commonly present in the rocks accompanying coal seams, decays into FeO and CO2.
The process begins in the temperature of 380oC and ends in about 550oC. Simultaneously occurs
oxidation of FeO into Fe2O3. As a result of FeO oxidation, hematite, maghemite, or their mixture
may be created.
Hematite may be also a product of thermal transformations of pyrite. If pyrite is located in a
fire zone, then in the range of temperatures from 400 to 650oC, its decomposition into iron and
sulphur occurs. Sulphur oxidases into SO2, while iron into Fe2O3.
Presence of hematite and maghemitetaints overburnt coal mine waste are reflected by its
colours from pale pink, through orange, up to cherry red.
Kaolinite, the most frequent clayey mineral present in coal mine waste, in the result of high
temperature undergoes a range of transitions. The first of these reactions, which occurs in
temperature of round 800oC relates to its dehydroxylation. Amorphic metakaolinite is being
created as its result.
Quartz, which belongs to the main mineral components of coal mine waste, exhibits high
tolerance to high temperatures. Changes that take place in this mineral are of polymorphic
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
95
transitions character. Their effect is the volume change of quartz grains, which may lead to
generation of tensions and fractures.
When the temperature of the dump does not reach one thousand degree Celsius, coal mine
waste does keep its original structure and texture, which it possessed at the moment of its
dumping on the site. Only the colour and mineral composition undergoes changes. Properties of
the overburnt coal mine wastes make them similar to the clinker.
Further increase of temperature leads to another transitions of mineral composition of the
waste. In temperature of about 980oC metakaolinite melts into spinel Si-Al and mullite. Around
1100oC sillimanite phase appears, from which, in case of increasing of temperature by next
100oC, another generation of mullite occurs. The last exogenous reaction, which occurs in
temperature of about 1250 – 1350oC is being interpreted by researchers as crystallization of
cristobalite.
When the temperature increased to more than 1050oC destruction of internal structure of illite
takes place and its melting. Melting of illite, feldspars, muscovite, and other minerals followed by
fast cooling of the alloy, leads to creation of glass. From the alloy minerals from the spinel group
may crystalize: magnetite, hercynite, magnesioferrite and also from the pyroxene group:
clinoferrosilite, hedenbergite, and other. Favourable for the creation of spinels and pyroxenes in
coal mine waste are the reduction conditions resulted from the presence of fire gases, which are
reach in CH4, H2, and CO2. High temperature and reduction conditions lead to generation of small
aggregations of metallic iron.
Coal mine waste, which underwent described above transformations, lost their original
structures and textures. Most frequently they resemble metallurgical slags, sometimes they are
also being referred as paralava.
On the basis of the colour, structural properties, and especially mineral composition, three
zones of different thermal transformation levels may be distinguishedon a coal mine waste dumps,
namely:
Thermally untransformed zone (characterised by grey-black colour and preservation of the
original mineral composition and structures of the waste),
Moderately thermally transformed zone (characterised by orange-brick red colour, burnout of
coal, presence of metakaolinite and hematite/ maghemite),
Intensively thermally transformed zone (characterised by disappearance of original textures
of rocks, presence of glass, and high temperature minerals).
Precipitation waters, which infiltrate the coal mine waste dumps, are warmed up by the rocks
heated due to fires and create pseudo-hydrothermal conditions in the dump. These waters are able
to leach substances from the waste and transport them into the body of a dump. When the
conditions change, minerals may precipitate from these solutions, especially carbonates and
sulphates. In thermally transformed coal mine waste, between other, calcite, aragonite,
hydromagnesite, gypsum, and anhydrite have been identified.
On the coal mine waste dumps, nearly active fire areas, minerals generated by the
resublimation of fire gases may to be found also. Between them, native sulphur and sal ammoniac
have been identified.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
96
Rare Earth Elements (REE) in the overburnt mining waste material
J. Nowak
Silesian University of Technology; [email protected]
Rare Earth Elements (REE) represent nowadays an important raw material being used in
many areas of life related to modern technologies. Although they are rather widely spread in
the Earth’s crust, due to their dispersion, it is highly difficult to extract them. All over the
world there are sparsely occurred natural beds of concentration being high enough to make
their mining justified. Increasing demand for REE together with their reduced supply from
China – the main producer of REE, results in the necessity of searching for new sources of
REE as well as tracking of their concentration changes in various processes both natural and
technological.
The paper presents variability of selected REE contents in coal mining waste thermally
transformed in the results of endogenous fires, which occur in the waste dump sites. The
research has been granted by the Ministry of Science and Higher Education of Poland within
the research project N 525 035 32/3750.
For the investigation 33 mining waste samples have been collected from the dump site No.
IV of the Nowy Wirek coal mine. The site contains rocks coexisting with coal seams of the
Ruda and Saddle beds of the Upper Silesia Coal Basin; mainly there were claystones, but also
mudstones and sandstones. The waste on the dump underwent self-heating resulted in
endogenous fires. Influence of high temperature led to transformation of the wastes, changing
their mineral composition and petrographic properties. Samples have been taken from the
zones of different thermal transformation level: macroscopically thermally untransformed
zone (unburnt), moderately thermally transformed zone (overburnt), and intensively thermally
transformed zone (sintered).
Contents of selected REE have been determined with use of the Instrumental Neutron
Activation Analysis (INAA). Due to limitations of this method following elements have been
measured: scandium (Sc), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm),
europium (Eu), terbium (Tb), ytterbium (Yb), and lutetium (Lu). Presence of yttrium (Y) has
been determined with use of the Fusion-Inductively-Coupled Plasms method (FUS-ICP).
With the use of the latter method main chemical components have been also assessed: SiO2,
Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, TiO2, P2O5, and the loss of ignition (LOI).
In the Table 1 arithmetic means of contents of each REE and their standard deviations have
been presented. Additionally, waste from the moderately thermally transformed zone has been
divided accordingly to their petrographic character, showing average values for sandstones,
mudstones, and claystones.
Average REE contents in the investigated waste (Table 1) amount: cerium Ce (58 –
70 ppm), lanthanum La (30 – 40 ppm), yttrium Y (35 – 56 ppm), neodymium Nd (24 – 33
ppm), and scandium Sc (13 – 17 ppm). In case of samarium Sm it was 5 ppm, ytterbium Yb
round 3 ppm, and amounts of terbium Tb and lutetium Lu did not exceed 1 ppm. REE
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
97
concentrations exhibited high differentiation indicated by high standard deviations. This is
reasoned by high heterogeneity of the waste, which originated from different seams, mining
levels, mine parts, as well as different mining and processing procedures.
The sum of contents of investigated REE in the thermally untransformed waste (193 ppm)
is slightly higher than in average REE sum in the moderately thermally transformed waste
(181 ppm). Burning of organic matter together with dehydroxylation of clay minerals and
thermal decomposition of minerals (i.e. from carbonates group) implicate loss of mass of the
waste, what is supposed to influence relative increase of concentration of the components.
Such a relation takes place in the case of the main chemical components – decreasing LOI
contents is accompanying by a significant increase of the contents of other components.
However, such relation does not occur in case of REE. Lower REE contents in the moderately
thermally transformed waste, could indicate smaller sorption properties of clayey minerals,
resulted from high temperature influence, what implicates the increased mobility of REE, and
partial removal of the REE out of the dump site area could happened. Within the thermally
untransformed waste all investigated REE, except yttrium (Y), exhibited highly positive
correlation with Al2O3, K2O, and TiO2, while in the thermally transformed waste this
correlation was significantly weaker or even vanished. This observation confirms the
connection between REE (except Y) with clayey minerals.
Tab. 1 Contents of investigated REE in the waste of various thermal transformation level
Ele
men
t
Waste from the
thermally
untransformed
zone
(9 samples)
Waste from the
moderately
thermally
transformed
zone
(17 samples)
Sandstones from
the moderately
thermally
transformed zone
(7 samples)
Mudstones from
the moderately
thermally
transformed zone
(5 samples)
Claystones from
the moderately
thermally
transformed zone
(5 samples)
Waste from the
intensively
thermally
transformed zone
(7 samples)
Mean
[ppm]
Std.
dev.
Mean
[ppm]
Std.
dev.
Mean
[ppm]
Std.
dev.
Mean
[ppm]
Std.
dev.
Mean
[ppm]
Std.
dev.
Mean
[ppm]
Std.
dev.
Sc 14.7 6.0 15.5 5.2 14.6 6.6 13.2 4.1 19.2 1.2 17.4 5.1
Y 35.0 6.4 36.2 9.8 36.3 9.2 38.0 15.4 34.2 3.3 55.6 11.4
La 35.8 13.1 32.9 9.3 30.4 10.2 32.3 12.2 36.8 3.1 40.1 7.1
Ce 70.1 25.7 61.5 17.3 57.7 18.6 61.4 24.1 66.8 6.6 67.7 14.0
Nd 27.3 11.0 25.6 6.6 23.7 7.8 26.0 8.1 28.0 1.9 32.9 6.6
Sm 5.0 2.0 4.6 1.3 4.2 1.4 4.8 1.6 4.8 0.5 5.8 1.0
Eu 1.3 0.5 1.1 0.3 1.1 0.3 1.1 0.3 1.2 0.2 1.3 0.3
Tb 0.3 0.5 0.6 0.3 0.6 0.4 0.6 0.3 0.7 0.1 0.6 0.5
Yb 3.2 0.9 2.8 0.7 2.6 0.6 2.9 1.1 3.0 0.2 3.7 0.6
Lu 0.4 0.1 0.4 0.1 0.4 0.1 0.4 0.2 0.5 0.0 0.5 0.1
∑* 193.0 181.2 171.6 180.7 195.2 254.4
*The sum relates to 10 investigated elements instead of all REE
In the waste from moderately thermally transformed zone, three main lithological types of
rocks may be distinguished: sandstones, mudstones, and claystones. All the types are
characterized by insignificant differentiation of the REE contents, although claystones exhibit
the highest one. This is probably related to the sorption properties of clay minerals.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
98
In the waste form the intensively thermally transformed zone, where high amount of glass
is present, largely higher amount of REE has bee noticed. Average sum of investigated range
of REE from this zone amounted 254 ppm. Increased contents of REE in the waste from the
intensively thermally transformed zone probably results from the loss of mass, which occurs
during the fires, with simultaneously occurring binding of REE in high temperature minerals
or the glass, what prevented their migration out of the dump site.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
99
Rare Earth Elements (REE) in the rocks accompanying selected coal seams
of the Mudstone and Sandstone Series of the Upper Silesian Coal Basin
J. Nowak, M. Kokowska-Pawłowska, B. Hanak
Silesian University of Technology
Rare Earth Elements (REE) form a group of 17 elements, to which belong lanthanides
together with scandium and yttrium – elements, which coexist in minerals with lanthanides
and possess similar chemical properties. These metals are not present on the Earth so rarely as
it suggested by their name, however they are strongly dispersed and they should occur at
significant concentration to make their mining production feasible. Due to their properties,
REE are of great importance by the use of advanced technologies, so they became considered
as strategic raw materials. Increased demand for REE together with reduced supply of them
from China – their major producer, result in prioritizing of the searching for new sources of
these raw materials.
In this paper results of investigation on the variability of REE contents in the rocks
accompanying selected coal seams from Zaleskie and Ruda beds of western part of Upper
Silesia Coal Basin (USCB) have been presented. 116 samples have been analysed from the
rocks coexisting with coal seams 405 and 408 collected from the USCB area.
Contents of selected REE have been assessed with a use of the Instrumental Neutron
Activation Analysis (INAA). In regard to the constraints of this method following elements
underwent evaluation: scandium (Sc), lanthanum (La), cerium (Ce), neodymium (Nd),
samarium (Sm), Europium (Eu), terbium (Tb), ytterbium (Yb), and lutetium (Lu). Contents of
yttrium (Y) was determined with a use of the Fusion-Inductively-Coupled Plasma (FUS-ICP)
method.
As it can be seen from the data listed in Table 1, the highest mean contents of the 10
considered REE has been observed by claystones (222 ppm). Slightly lower was the sum of
mean contents of analysed REE in sandy claystones (216 ppm), mudstoned (213 ppm) and
sideritic claystones (207 ppm). Probably it results from high amount of clayey minerals in
these rocks, which express high sorption properties. Significantly lower REE contents have
been observed by sandstones (183 ppm) and coal shales 9179 ppm). The lowest contents
have been noticed for clayey siderites, where mean sum of analysed REE amounted only
105 ppm.
Considering amounts of each particular element, the conclusion is that independently to the
petrographic character of a rock, the highest contents exhibited Ce, La, Y, Nd, and Sc.
Contents of the other REE are definitely smaller (by one or two orders of magnitude). Also,
high differentiation of REE contents have been observed between individual samples, what is
reflected by large values of standard deviations. This differentiation results probably from the
large area of research.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
100
Table 1. REE contents[ppm] in analysed samples of rocks coexisted with coal seams
Ele
men
t
Claystones
46 samples
Sandy
claystones
17 samples
Sideritic
claystones
12 samples
Coal shales
10 samples
Mudstones
14 samples
Sandstones
9 samples
Siderites
8 samples
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Mea
n v
alu
e
Std
. d
ev.
Sc 20.7 2.2 19.2 2.0 19.8 2.3 14.5 4.6 20.2 2.0 14.3 3.0 11.5 5.2
Y 28.9 6.5 28.7 3.7 28.5 5.1 22.2 10.6 30.9 4.8 32.1 7.4 19.0 11.3
La 47.5 7.1 45.4 4.1 42.7 4.5 36.4 9.0 46.5 3.6 39.9 11.6 19.8 11.6
Ce 82.4 14.4 80.1 8.6 77.6 14.4 68.3 19.0 77.2 6.3 68.6 20.0 36.6 19.2
Nd 30.8 9.3 31.6 6.8 27.5 8.6 27.6 10.3 27.4 5.8 18.7 14.7 12.0 9.8
Sm 5.9 1.5 5.9 1.4 5.4 1.4 5.1 2.2 5.4 1.1 5.0 1.6 2.9 2.0
Eu 1.6 0.4 1.6 0.3 1.7 0.4 1.6 0.7 1.6 0.2 1.2 0.6 0.9 0.5
Tb 0.3 0.4 0.3 0.5 0.3 0.5 0.4 0.6 0.4 0.5 0.1 0.3 0.2 0.4
Yb 3.0 0.6 3.0 0.5 3.0 0.7 2.4 1.1 2.9 0.6 2.7 0.7 1.8 1.1
Lu 0.5 0.1 0.5 0.0 0.5 0.1 0.4 0.2 0.5 0.0 0.4 0.1 0.3 0.1
Suma* 221.6
216.2
206.8
178.9
212.8
183.0
105.0
*listed sum covers only 10 investigated REE
As concluded, most of the analysed REE exhibit increased concentrations in roof strata in
relation to their presence in floors and interburden. Higher mean contents in claystones from
roof strata demonstrated La and Y, in sideritic claystones La, Nd, and Ce. Higher amounts of
Sc, Y, La, Nd and Ce have been noticed for clayey siderites from roof strata In mudstones
from roof strata Nd were dominating. In roof sandstones mean contents of Sc, Y and La were
the highest.
Increased concentration of such numerous elements in the roof strata suggests their
infiltration origin.
The research has been granted by the Polish Ministry of Science and Higher Education in the frame of the
research project No. N524 463236.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
101
Nano-compounds from Brazilian Coal Fires
M.L.S. Oliveira1, S.R. Taffarel
2, C.M.N.L. Cutruneo
2, L.F.O. Silva
1,2
1Institute of Environmental Research and Human Development – IPADH, Capivari de Baixo, Santa Catarina,
Brazil 2Laboratory of Environmental Researches and Nanotechnology Development, Centro Universitário La Salle.
Victor Barreto, 2288 Centro 92010-000 - Canoas, RS – Brasil
Burning coal-waste (spoil) heaps produce atmospheric pollution, environmental degradation,
and may seriously threaten the health and life of residents living nearby.
Coal fires can occur within in-situ coal deposits, active or abandoned coal mines, and in
waste piles produced from coal mining. Ignition sources may include forest fires, lightning
strikes, spontaneous combustion due to exothermic oxidation in the coal, and human activity.
Some coal fires are difficult to extinguish and individual fires can burn for decades or even
centuries. However, can be the consequence of spontaneous combustion; incidental natural
sparks (lightening strikes, forest fires); or malicious, negligent, or accidental human
intervention. A number of coal properties, often interrelated, affect the potential for
spontaneous combustion, including:
(1) Moisture content and volatile matter,
(2) Particle size and available surface area,
(3) Mineral matter type and pyrite content in particular,
(4) Coal rank,
(5) Petrographic composition (coal type).
This study describes nanominerals and associated trace elements in minerals nucleated in
conjunction with Brazilian coal fires. Petrological and geochemical analysis of the organic
and mineral matter from burning and unburnt zones in coal-waste piles have allowed
preliminary identification of the mineral and gas products that resulted from the combustion
process. The present work complements previous studies by identifying and providing
detailed characterization of carbon nanoparticles, agglomerates and mineral phases formed in
the burning waste piles. Any health and environmental consequences associated with these
particles would be expected to have a close relationship to their physical and chemical
characteristics, such as their size, morphology, composition, solubility, and oxidation state.
The study provides data not previously available from bulk characterization, and thus
contributes to assessing further the environmental and human health impacts of burning coal-
waste materials.
The principal components of the work are: (1) collecting samples from burning areas of
solid coal-waste piles (CWP) in Brazil; (2) investigating a potential method for estimating
emissions of nanominerals and ultrafine particles, based on direct measurements and
emphasizing the importance of electron microscope investigations; (3) identifying any
potentially toxic by-products from spontaneous combustion and the possible effects on human
health from nanominerals and ultrafine particles; (4) providing the scientific community with
initial order-of magnitude nanomineral emission estimates from Brazilian coal- fire zones.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
102
Many sulfate minerals (gypsum, mascagnite, letovicite, barite, jarosite, and iron sulfate);
elemental sulfur; and other S–Cl–N–H, Hg, As, Pb, and Se compounds are currently detected
in researched coal fires. The blocks assemblage of CWPM ranged in color from white
(kaolinite, gypsum, and barite) to yellow-brown and red (oxidation of high pyrite resulting
ultrafine cubic jarosite pseudomorph and nanohematite crystals) and a relatively low amount
of amorphous Si–Al–Fe–Ti–Zr nanospheres. Native sulfur in spontaneous CWPM
combustion occurs as bright yellow micro/nanocrystalline botryoidal crusts. In addition,
several members of the MgSO4∙nH2O series, epsomite, hexahydrite, and pickeringite, were
identified by XRD, Raman, HR-TEM, and FE-SEM. Dehydration of epsomite to hexahydrite
is strongly dependent on the relative humidity. In the present case, the relative abundance of
these two phases may be expected to be quite variable, depending on the ambient conditions
in the field or the analytical process.
The utilization of XRD, FE-SEM/EDS, and HR-TEM provided detailed identification and
characterization of nanoparticles, agglomerates, and mineral phases formed from burning
Brazilian coal-cleaning rejects, and permitted identification of the potential effects of such
particles on the environment and human health. Both cubic and dendritic crystal habits of
salammoniac were observed, along with sulfates (gypsum and jarosite), and Fe-minerals. The
cubic form of jarosite suggests that it is a pseudomorph after pyrite. Dehydration of jarosite
can lead to the formation of less hydrous Fe-sulfates and hematite. Hematite, with some Cr in
the mineral structure, was noted in association with jarosite. In addition, HR-TEM studies
revealed the presence of fullerene carbons and multi-walled carbon nanotubes that contain
some potentially hazardous elements with varying degrees of crystallinity. This suggests that
the particles experienced a variety of high-temperature thermal histories. Future work will
include studying the thermodynamics and by-products of combustion, estimating emissions
from fires associated with coals of different rank, and examining the potential environmental
and health impacts on residential communities near the fires. This information will be
beneficial in understanding the potential human health and environment impacts of coal fires,
the importance on national and global scales of nanoparticles and toxicants from coal fires,
and the understanding of environmental controls on coal fires and related emissions.
However, only scientific, technological, economic, and political collaboration will lead to
solutions associated with various coal-fire problems on a global scale.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
103
Coal-petrography and mineralogical studies
of the Çardak coal deposit (SW Turkey)
R.G. Oskay1, A.İ. Karayiğit
2, K. Christanis
1
1University of Patras, Department of Geology, Rio-Patras, Greece; [email protected]
2Hacettepe University, Department of Geological Engineering, Ankara, Turkey
Coal deposits formed under various conditions and in various geological times, are widely
spread over Turkey. The most significant deposits are of Tertiary, especially Neogene age.
During Pliocene times the palaeoenviromental conditions used to be favourable for peat-
formation in the territory, resulting in large reserves (7 Gt). This study aims to determine coal-
petrographical and mineralogical features of samples from the Çardak coal deposit in south-
western Turkey.
Huminite is the dominant maceral group (up to 92 vol.%, on mineral matter free; mmf)
basis consisting mostly of detrohuminite (up to 46 vol.%, mmf). Gelohuminite (up to 15
vol.%, mmf) is also common. The inertinite group, mainly inertodetrinite, appears in variable
amounts (up to 10 vol.%, mmf). Liptinite macerals are common and variable in quantity (up
to 14 vol.%). The mean random reflectance of huminite is about 0.28%. The identified
minerals in the lignite samples are quartz, pyrite, clay minerals (illite-smectite group),
feldspars, calcite, and aragonite. Most of the minerals determined applying X-ray
diffractometry, are also identified under the coal-petrography microscope, i.e. framboidal
(common type) and massive pyrite, clay minerals, quartz and carbonates.
Coal facies indices (moderate Gelification Index and Ground Water Index), as well as the
presence of framboidal pyrite, indicate wet, slightly anoxic conditions and relatively stable
water level during peat accumulation. Carbonate minerals (calcite and aragonite) and shell
fragments result in calcium-rich coal. Also the presence of mollusc shell fragments indicates
that the water level was above the peatland surface. Moderate detrohuminite content could be
related to reed-sedge vegetation, although moderate Tissue Preservation and Vegetation
Indices and high telohuminite content point to woody peat-forming vegetation. Therefore
mixed vegetation might have contributed to peat formation.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
104
Petrographic characteristics of Karapınar-Ayrancı Lignite
(Konya, Central Turkey)
R.G. Oskay1, M. Salman
2, K. Christanis
1, M. Taka
2, H. İnaner
3
1Department of Geology, University of Patras, Rio-Patras, Greece; [email protected]
2General Directorate of Mineral Research and Exploration (MTA), Ankara, Turkey
3Department of Geological Engineering, Dokuz Eylül University, İzmir, Turkey
As a result of collision between the Arabian and the Anatolian plates (Middle Miocene to
Quaternary) sedimentary basins were formed and volcanism was activated in Central
Anatolia. These sedimentary basins host coal-bearing sedimentary sequences with important
coal reserves. The Karapınar-Ayrancı deposit is the most significant one due to its big
reserves (1.8 Gt). The basement rock is a Jurassic-Cretaceous marine limestone. The basin
filling consists of Miocene lacustrine and Pliocene coal-bearing sediments that are overlain by
Upper Pliocene-Quaternary lacustrine and fluvial sediments and volcanic rocks. Coal-
petrology studies were carried out on 29 core samples from two boreholes drilled in the north-
eastern part of the deposit. Matrix and mineral-rich lithotypes are common, char-rich coal also
occurs. In the studied lignite samples huminite macerals (up to 98 vol.%, on mineral matter
free basis; mmf) dominate. Detrohuminite is the most common maceral sub-group (up to 82
vol.%, mmf); telohuminite sub-group varies from 5 to 38 vol.%, mmf). Inertinite, mainly
fusinite and inertodetrinite, shows a great variety (up to 21 vol.%, on mmf basis). Liptinite,
commonly liptodetrinite, occurs in lower concentrations than the other groups (up to 13
vol.%, mmf). Inorganic constituents, namely clay minerals, carbonates, as well as framboidal
or euhedral pyrites, are common (up to 29 vol.%). Even though the dominance of
detrohuminite can be related with reed-sedge vegetation, the variable telohuminite quantities,
as well as the moderate tissue preservation and vegetation indices might be related to changes
in vegetation (dominance of herbaceous plants to mixed herbaceous and woody vegetation)
during peat formation. Low to moderate ground water influence and gelification indices, as
well as alternation between matrix and mineral-rich lithotypes could be related to water level
fluctuation. The predominance of herbaceous vegetation, along with high water table, resulted
in the fragmentation of the plant material and the predominance of detrohuminite. On the
other hand, high intertinite contents might indicate low water levels and thus, slightly oxic
conditions during peat accumulation. Fusinite and semi-fusinite along with char-rich lithotype
point to wild fires on and/or around the palaeomire. Also the occurrence of syngenetic
(framboidal) pyrite is related to anoxic conditions. The Karapınar-Ayrancı lignite formed in a
reed-sedge mire with subordinate contribution of woody vegetation under slightly anoxic
limno-telmatic conditions.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
105
Mineral matter and trace elements in the Karapınar-Ayrancı lignite
(Konya, Central Turkey)
R.G. Oskay1, M. Salman
2, M. Taka
2, K. Christanis
1, H. Inaner
3
1Department of Geology, University of Patras, Rio-Patras, Greece; [email protected]
2General Directorate of Mineral Research and Exploration (MTA), Ankara, Turkey
3Department of Geological Engineering, Dokuz Eylül University, Turkey
The Karapınar-Ayrancı coal deposit (south-Central Turkey) hosts the second biggest lignite
deposit (1.8 Gt) of Turkey. As it is planned to be exploited for power generation,
understanding the mineralogical and elemental composition is important for technological and
environmental aspects. This paper presents preliminary results on mineralogical and
geochemical composition of the lignite samples and their ash residues from one borehole at
NE part of the deposit. The samples display high ash yield (average 37.30%; on dry basis),
high volatile matter content (average 74.00%; on daf basis), high total S (up to 11.68%, daf)
and H contents (up to 10.35%, daf). The identified minerals in the bulk lignite samples are
quartz, clay minerals (illite, kaolinite/chlorite and smectite), mica, halite, feldspar, calcite,
pyrite, bassanite/gypsum. Most of the minerals, i.e. framboidal (common type) and euhedral
pyrite, clay minerals, quartz and carbonates, are also identified under the microscope.
Minerals and other inorganic constituents in coal have different reaction pathways during
combustion, thus the identified minerals in ash residues at 750°C vary strongly.
Quartz/cristobalite, forsterite, feldspar, akermanite, gehlenite, illite/mica, haematite, Ca-
ferrites, lime, anhydrite, and rarely dolomite are identified in the ash. Factor analysis on
geochemical data shows that the elements have intermediate affinities; except of Ag, Al, Cu,
Li, V, and Ni. Also the HAPs such As, Be, Cr, Co, Pb, Mn, and Ni are determined in the
studied samples; however, their contents are below the world and Turkish feeding coal
average values. Beside, high total S content will cause environmental and technological
problems (e.g. acid drainage at a dumping site or boiler corrosion), although the presence of
calcite in lignite and anhydrite in ash indicate that sulphur contained is bound by carbonates
during combustion; hence wet scrubber could be effective as a desulphurization technique. On
the other hand, the presence of lime, haematite and Ca-ferrites in ash will cause slagging and
fouling problems in the boilers. Applying reasonable exploitation planning, appropriate
beneficiation techniques and choosing suitable boiler system, technological and
environmental impacts of lignite from Karapınar-Ayrancı deposit could be successfully faced.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
106
Monitoring progress of combustion under oxy-fuel atmosphere of coals
and charcoals of similar volatile matter content by microscopy techniques
J.G. Pohlmann1,2
, E. Osório1, A.C.F. Vilela
1, M.A. Diez
2, A.G. Borrego
2
1Iron and Steelmaking Laboratory (LASID), UFRGS, PO Box 15021, 91501-970, Porto Alegre, Brazil; ++ 55 51
3308 7074; [email protected] 2Instituto Nacional del Carbón (INCAR-CSIC). Francisco Pintado Fe, 26, 33011 Oviedo, Spain
Pulverized coal is widely used to be burned in boilers for power generation or as a source of
heat and reducing gases in the ironmaking process whereas charcoal is a promising fuel to
partially replace it because of its renewable origin and neutrality in CO2 emissions (Norgate
and Langberg 2009). Oxy-fuel combustion technology consists of burning the fuel in a N2-
free atmosphere, which is replaced by a CO2-rich gas facilitating the subsequent capture of
CO2. Both incorporation of biomass in the process and oxy-fuel combustion can be combined
for a greater abatement in industrial processes. Biomass is known to be more reactive than
coal under similar combustion conditions (Kastanaki and Vamvuka 1996) but its low density,
low calorific value and high hygroscopic character typically prevents a wider incorporation
into operating industrial processes. Densification of biomass reduces its volatile matter
content, increases its calorific value and facilitates the handling of the material by
approaching its characteristics to those of the fuel to be replaced (Arias et al. 2008). In this
context two fuels with similar volatile matter content (~23%), one being a medium volatile
bituminous coal (CRA) and the other one the fines generated during industrial charcoal
production from eucalyptus (CCF), have been selected for this study in order to follow the
transformation occurring during their combustion under oxy-fuel atmosphere with increasing
oxygen content.
The CRA coal has a vitrinite reflectance of 1.23% and an inertinite content of 47%, mostly
teloinertinite having an average reflectance of 1.88%. CCF has higher reflectance (Rr=2.27%)
and higher scatter in the readings than the coal (standard deviation of 1.3 vs. 0.4%), but
similar modal values around Rr=1.7%. Combustion of pulverized samples (36-80µm) at 2.5, 5
and 10% O2 in CO2 has been carried out in a Drop Tube Furnace (DTF) at 1300 ºC. Optical
microscopy analysis was performed on the samples as well as test of reactivity to CO2 in
thermobalance and specific surface area measurements by adsorption isotherms.
As expected, char conversions increased with oxygen content in the DTF and were
significantly higher for the charcoal than for the coal for similar oxygen concentrations.
Figure 1 shows the appearance of the chars obtained under different O2/CO2 conditions. Coal
chars yielded generally cenospheric particles with abundant secondary porosity within the
walls. Vitrinite transformed to form anisotropic domains in swollen particles whereas a
significant part of the inertinite remained unfused generating massive isotropic particles. The
high degree of association between the vitrinite and inertinite in the coal results in common
mixed particles containing material derived from both components. CCF chars consisted of
mostly isotropic particles, some of them with massive and compact appearance and some
formed by cell-walls with empty channels as also observed in fusinite. During the combustion
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
107
tests some of the massive particles developed devolatilization vacuoles. Higher conversions
lead to smaller particles in the coal chars and to the collapse of the most delicate particles with
cellular structure, being concentrated in the most combusted chars the massive and larger
particles. Combustion progressed in the coal chars through the boundaries of the anisotropic
domains whereas in the charcoal chars the surfaces of the particles were finely spotted.
Specific surface area of both fuels significantly increased in the reactor with CCF chars
reaching significantly higher surface areas of both mesopores (BET) and micropores (CO2-
DR) than the CRA chars. In both cases micropore surface areas were higher than those of
mesopores. Both mesopore and micropore specific surface areas firstly increased with
conversion and then decreased for the most burned chars in CCF chars, whereas a continuous
increase in mesopores and decrease in micropores is observed in the coal chars. The specific
surface areas control the reactivity to CO2 results, being the coal chars, with much anisotropic
material, less reactive than the isotropic CCF chars.
Fig. 1. Optical microscopy images of chars under different O2/CO2 atmospheres.
Acknowledgement: This work has been financed through a bilateral Spain-Brazil project PIB2010BZ-
00418/CNPq 560839/2010-3 and the Brazilian Coal Net. The assistance of Dr. D. Álvarez from INCAR in the
preparation of the chars is gratefully acknowledged.
References
Norgate T. Langberg D. 2009 - Environmental and Economic Aspects of Charcoal Use in Steelmaking. ISIJ
International, 49, 4: 587-595.
Kastanaki E. Vamvuka D. 2006 - A comparative reactivity and kinetic study on the combustion of coal–biomass
char blends. Fuel, 85: 1186-1193.
Arias B., Pevida C., Fermoso J., Plaza M. G., Rubiera F., Pis J.J. 2008 - Influence of torrefaction on the
grindability and reactivity of woody biomass. Fuel Processing Technology, 89: 169-175.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
108
Microscopical characterization of carbon materials derived from coal and
petroleum and their interaction phenomena on making steel electrodes,
anodes and cathodes blocks
G. Predeanu1, C. Panaitescu
1, M. Balanescu
1, G. Bieg
2, A. Gómez Borrego
3, M.A. Diez
3,
B. Kwiecińska4, M. Marques
5, M. Mastalerz
6, M. Misz-Kennan
7, S. Pusz
8, I. Suárez Ruiz
3,
S. Rodriguez5, A.K. Singh
9, A. Varma
10, A. Zdravkov
11, D. Životić
12
1University Politehnica Bucharest, Bucharest, Romania
2Mikroskopische Untersuchungen, Haltern am See, Germany
3Instituto Nacional del Carbón (INCAR-CSIC) Oviedo, Spain
4AGH University of Science and Technology, Kraków, Poland
5Universidade do Porto, Porto, Portugal
6Indiana University, Indiana Geological Survey, Indiana, USA
7University of Silesia Sosnowiec, Poland
8Polish Academy of Sciences, Gliwice, Poland
9TATA Iron & Steel Comp. Ltd, Jamshedpur, India
10Indian School of Mines, Dhanbad, India
11University of Mining and Geology “St. Ivan Rilski”, Sofia, Bulgaria
12University of Belgrade, Belgrade, Serbia
Introduction
The Microscopy of Carbon Materials Working Group of Commission III of the International
Committee for Coal and Organic Petrology was established to investigate the efficiency of
microscopical methods to the study of carbon materials derived from coal and petroleum, with an
emphasis on quality control of raw materials either on different technological stages, in order to
evaluate the physical-chemical properties of the parent, intermediary, and final products.
The WG is focused to consolidating and completing the existent methods developed for carbon
materials structural and textural characterization: (i) Describe of the optical appearance of the
carbon textures and identify the morphological differences as: optical texture and shape, optical
type and size; (ii) Use the previouse exercises classification scheme to distinguish between
different classes considered both for the optical texture (isotropic/anisotropic), and shape, optical
type (punctiform, mosaic, fiber, ribbon, domain) and size; (iii) Evaluate the origin of optical
texture and the porosity development.
Experimental
A very simple classification scheme was used, in which the criteria to distinguish between
different classes considered both the optical texture, type and size, origin and the porosity
development. The results were evaluated on 4 levels: (i) optical texture (isotropic or anisotropic);
(ii) optical type and size (punctiform, mosaic, fiber, ribbon, domain); (iii) origin of the inclusions;
(iv) all levels together. The exercises consisted on 372 fields in black and white pictures. The
criteria proposed for the classifications of optical appearance of mesophase during thermal
evolution to semicoke and coke were according to the terminology belonging to the ASTM D
5061/1997, Microscopical determination of volume percent of textural components in
metallurgical coke.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
109
Results and discussions
The activities developed were focused to: (2009) Identify the petrographic textures representing
the structural organization of the organic matter corresponding to solid carbon precursors, as:
coal-tar pitch coke, petroleum coke, calcinated anthracite; (2010) Identify the mesophase
formation from the isotropic aromatic parent liquid to an anisotropic solid texture (nucleation,
coalescing, mesophase coalescing final stage) of coal-tar pitches: binder pitch (type A) and
impregnating pitch (type C) currently used as matrix precursors of many carbon materials;
describe the evolution of optical characteristics of pitches during heating up to 480, 500, 800 and
1000oC that influences their preparation within the production industrial steps; (2011) Identify of
the morphological differences occurred between the three different samples of steel electrodes
used: baked electrodes, re-baked electrodes and graphitized electrodes and the interaction
phenomena between calcinated petroleum coke and binders: binder pitch and impregnating pitch;
(2013) Identify of the morphological differences occurred in the anodes and cathodes blocks used
in aluminum industry which petrographic composition depends on the grain size distribution of
the blended solids (petroleum coke, anthracite and the quality of the binding material (pitch).
A B C D
Fig. 1. Photomicrographs of needle calcinated petroleum coke (A), mesophase formation in impregnation pitch
(B), anisotropic calcinated anthracite (C), graphitized petroleum coke (D) 500X, glycerin imm.
Fig.2. Average level of agreement of each analyst during participation in 2009-2011 ICCP CM WG
Conclusions
It has been realized in a good agreement between the 15 active participants who attended about all
the exercises.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
110
Characterization and petrographic composition of ash and slag from
the Turceni coal-fired power plant, South-West Romania
G. Predeanu1, C. Panaitescu
2, L.G. Popescu
1
1University “Constantin Brancusi” of Targu Jiu, 30 Calea Eroilor, Targu Jiu, Gorj County, Romania
[email protected]; [email protected] 2University “Politehnica” Bucharest, 1 Polizu St. Bucharest, Romania [email protected]
Introduction
A variety of combustion waste products are generated during burning lignite in power plants.
They exhibit complex composition depending mostly on coal type and technological
processes used. The aim of the present study is the chemical and petrographic characterization
of some lignite combustion residues, ash and slag sampled from the storage deposit of the
Ceplea Valley belonging to the Turceni power plant historical dump, covering an area of
approx. 50 ha, and in which the accumulated amount is of approx. 20 million tons.
The physical-chemical composition of ash and slag depends on physical-chemical
composition of parent coals and of a series of particular factors, as are the rank and
petrographic composition (Levandowski, Kalkreuth 2009; Moreno et al. 2005; Suárez-Ruiz et
al. 2008; Panaitescu et al. 2008). Knowledge of the properties of coal ashes is an important
parameter also due to the fact that ash and slag deposits may create environmental problems
through leaching of toxic substances, in decisions on their industrial use and in evaluation of
their environmental impacts.
Experimental
Laboratory measurements of X-ray fluorescence (XRF) have confirmed that, in terms of
chemical composition the ash from the Ceplea Valley deposit matches the oxidic class SiO2 -
Al2O3 - Fe2O3 - CaO, being from this point of view relatively similar to feldspathic calcareous
clays, partially calcined (weakly burned firebrick): 40-50% SiO2, 16-21% Al2O3, 8-9% Fe2O3,
9-14% CaO, 1.5-3% Na2O+K2O (Abagiu et al. 2013).
Results and discussions
Low rank of lignite is represented by the increased proportion of wood components, in
particular of those structured (textinite), and the presence of attrinite and densinite,
corpohuminite and gelinite components (Table 1). Behavior of organic and mineral matter
during combustion is shown in photomicrographs of Fig.1.
Table 1. Structural composition of lignite, % vol (Predenau et al. 2013)
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
111
Pet
rog
rap
hic
com
po
nen
t
Tex
tin
ite
(ro
un
d c
ells
)
Tex
tin
ite
(elo
ng
ated
cell
s)
To
tal
stru
ctu
red
wo
od
en m
ater
ial
Ulm
init
e
Org
anic
w
oo
den
mat
eria
l
Att
rin
ite
+ d
ensi
nit
e
Co
rpo
hu
min
ite
Gel
init
e
Lip
tin
ite
Iner
tin
ite
To
tal
org
anic
mat
ter
Cla
y m
iner
als
Fer
rou
s m
iner
als
To
tal
min
eral
mat
ter
To
tal
org
anic
+
min
eral
mat
ter
% 0.5 27.2 27.7 20.5 48.2 2.5 6.7 13.3 1.0 0.5 72.2 24.0 3.8 27.8 100.0
a b c d
Fig. 1. Photomicrographs of ash and slag, reflected light, glycerin immersion, 500X: a) inertinite tissue, b)
carbominerite and pirite, c) textinite and fungi, d) mineral oxides.
Conclusions
The paper presents the petrographic analyses carried out with the goal of identifying the
behavior of organic and mineral material of lignite of Oltenia basin during combustion.
The results of this study provide information which can be applied throughout power plant
operation and for environmental impact studies.
Acknowledgements. The present research has been carried out through the LIFE10 ENV/RO/729 Project.
References
Abagiu T., Volceanov E., Predeanu G., Zăman F., Popescu L. G., Slăvescu V. 2013 - Physical-chemical
characteristics of some industrial wastes arguments for their use in the field of building materials
manufacturing. 13th
Int. GeoConference SGEM 2013, Albena 17-23 June, in press.
Levandowski J., Kalkreuth W. 2009 - International Journal of Coal Geology, 77: 269-281.
Moreno N., Querol X., Andre J.M., Stanton K., Towler M., Nugteren H. et al. 2005 - Fuel, 84: 1351–1363.
Panaitescu C., Predeanu G., Miu M. 2008 - 60-th ICCP Meeting, 25th Meeting of TSOP, Oviedo, Spain.
Predeanu G., Abagiu T., A.,, Popescu L. G., Cruceru M. 2013 - Evaluation of structural changes that occur
during the combustion of coal of Oltenia basin at turceni power plant. 13th
Int. GeoConference SGEM 2013,
Albena 17-23 June, in press.
Suárez-Ruiz I., Valentim B., Bouzinos A., Flores D., Gómez Borrego A., Kalaitzidis S. Predeanu G. et al. 2008 -
The Society of Organic Petrology (TSOP) Newsletter, 25, 3: 10-13.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
112
Qualitative improvement of xylite by mechanical preparation
G. Predeanu1, O.V. Scorţariu
2, C. Panaitescu
3
1Metallurgical Research Institute, Mehadia St. 39, Sector 6, 060543 Bucharest, Romania
2Energy Complex Oltenia, Branch Mining Division Targu Jiu, T. Vladimirescu St. 1-15, 210143 Tîrgu Jiu,
Gorj County, Romania 3University Politehnica, Bucharest, Polizu St. 1, Sector 1, 011061, Bucharest, Romania
Introduction
This paper presents the results obtained at pilot level of preparation (by crushing and
volumetric classifying) of xylite, for obtaining structural unchanged varieties sizes suitable for
experiments to obtain charcoal and activated carbon (Predenau et al. 2005; Predenau,
Panaitescu 2007). The experiments were performed to improve the xylite quality recovered
from the Oltenia lignite basin, by mechanical preparation. The study analyzes the most
important parameters that involves the selective grinding of a representative amount of 15.7
tone xylite (moisture, mineral content, botanic origin), using an industrial equipment (a
hammer-crusher of 50 tone/h) and the yields and quality of the fractions obtained on passing
through 30, 20, and 10 mm sieves. The key objectives of this study are: (1) to establish yields
and quality of the fractions obtained by processing a representative amount of xylite (2) to
reveal the occurrence, selection methods and preliminary assessment of the xylite reserves
necessary for designing a capacity for commercial-scale processing installation. It was proved
that selective crushing and sieving is a very effective technique to obtain > 80% yields of
xylite fractions over 10 mm, used for charcoal and activated carbon making. Selected xylite
fractions were characterized by analytical methods, including optical microscopy.
Experimental
The study is based on about 35 tones of xylite hand picked from Lupoaia open pit mine (coal
seam VIII, Motru Coalfield) and transported by railway, to the raw material deposit. In order
to perform xylite mechanical processing by crushing and sizing, the sample was stored on a
concrete covered platform, to decrease the total moisture content from 45-50% (deposit total
moisture) up to 20-25%, with positive influence on the energy consumption during
pyrogenation stage. At the end of the storage period, the whole xylite amount was transferred
to the coal preparation unit, belonging to the Motru thermal power plant UAATA of 6 MW/h.
The preparation flowsheet included: the underground storage bunker (capacity of 5 tone);
scoope elevator; hammer-crusher of 50 tone/h capacity; conveyor belt no.1; intermediary
bunker; conveyor belt no.2; vibrating sieve (with a capacity of 5 to/h) with round meshes of
10, 20 and 30 mm. After the first passing through the crushing equipment, xylite was sorted to
grain sizes using 10, 20 and 30 mm sieves (phase I).
The unsieved fraction on the 30 mm sieve, having a coarse-robust, wooden or fibrous
aspect, was weighed and separately deposited for further crushing (phases II and III).
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
113
Results and discussion
The petrographic researches of the fractions obtained by crushing and screening demonstrated
a preferential repartition of the macerals by grain size categories depending of their natural
grindability is shown in Fig.1. The large scale experiments confirmed the previous results
concerning the quantitative structural aspects of the organic and mineral composition, as
follows: increasing of structured wooden material to the large grain sizes: 71.2% (+30 mm)
and 69.5% (20-30 mm); increasing of total wooden to the large fractions: 86.6% (+30 mm)
and 78.2% (20-30 mm); mineral mass is accumulated mostly in the fine fraction: 10.5% (10-
20 mm) as in coarse fraction 5.0% vol. (+30 mm) due to preferential distribution of clay
minerals in structurated material and high crushing capacity of carbagilite.
a b c
Fig. 1. Photomicrographs of some petrographic constituents in xylite fractions, reflected light, oil immersion,
250x: a) Cellulose impregnation (dark grey); b) Fissured gelinite with mono-, bi- and pluricellular funginite
(white); c) Textinite with pressed round cells and small mineral impregnation.
Conclusions
In the present investigation was demonstrated the positive effect of mechanical preparation of
xylite samples by crushing and sizing to be used for char and activated carbon making. The
results are extremly encouraging from the quality of size fractions obtained taking into
account the xylite amount that was processed, and the mechanical preparation performed on
an industrial flowsheet.
References
Predeanu G., Vacarciuc I., Scorţariu O., Hanu D. 2005 - LIFE 02 ENV /RO/46, Final report EnvACTCARB,
Special Issue, www.icem.ro/life1/SiteLife/index.html.
Predeanu G., Panaitescu C. 2007 - Petrographical evaluation of xylite activated carbon. Int. J. Coal Geol. 71:
542-553.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
114
Vitrinite Thermal Maturation Profiles and Comparative Study for Five
Yukon Petroleum Exploration Wells
J.C. Reyes, S. Saad, L.S. Lane
Geological Survey of Canada 3303 33rd
St. NW Calgary, Alberta, Canada, T2L 2A7; 1- 403 292-7120;
Eagle Plain Basin is one of eight prospective basins in the Yukon identified as having
significant oil and gas potential. To date, more than 34 wells have been drilled in the basin,
many of which show evidence of the presence of conventional oil and gas. An understanding
of these multifaceted petroleum systems is imperative for present and future development in
the area. In this study, quantitative vitrinite reflectance and qualitative analyses of dispersed
organic matter (DOM) from five petroleum exploration wells in Eagle Plain, north-Central
Yukon were summarized in order to determine thermal maturity profiles in Silurian to Upper
Cretaceous strata throughout the basin. These five wells are representative of eight wells that
are summarized in a soon-to-be released GSC Open File Report (Open File 7056). This study
integrates data from previous work by Link and Bustin (1989) as well as recent analyses from
the Geo-Mapping for Energy and Minerals (GEM) Yukon Basins Project, a four year project
aimed at upgrading geoscience knowledge of Yukon’s sedimentary basins.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
115
Evaluation of Cretaceous coals from western India
through petrographical and geochemical parameters
B.D. Singh1, S. Mahesh
1, S. Paul
2, A. Singh
1, S. Dutta
2
1Organic Petrology Group, Birbal Sahni Institute of Palaeobotany, 53 University Road, Lucknow-226 007;
[email protected] 2Department of Earth Sciences, Indian Institute of Technology Bombay, Powai, Mumbai-136 119
The Early Cretaceous coal deposit in the Thangad area of the Surendranagar district (Gujarat
State) is associated with the Than Formation of the Saurashtra Basin. The data generated on
organic composition (macerals), mineral matter contents, rank, total organic carbon (TOC),
biomarkers, etc. of the deposits of Thangad, through petrographic and geochemical studies,
are utilized to characterize these western Indian coals for their optimal utilization. The
quantitative estimation of macerals indicates that the coals are rich in vitrinite macerals (39-
57%) followed by inertinite (9-33%) and liptinite (2-16%) macerals. Among the vitrinite
group of macerals, telovitrinite (collotelinite + telinite) is dominant in these coals followed by
detrovitrinite (collodetrinite + vitrodetrinite). The liptinites are chiefly constituted by
liptodetrinite and bituminite. Semifusinite/ fusinite and inertodetrinite represent the inertinite
group. The coals have moderate to high contents (8-36%) of associated mineral matters
represented mainly by clastic minerals and pyrite (10-12%). The rank, determined through
vitrinite reflectance measurements (Rr mean values: 0.86-1.05%), indicates that the studied
coals are of high-volatile bituminous A stage.
The saturated hydrocarbon in the studied samples is characterized by C14 to C32 n-alkanes
with a unimodal distributional pattern. Isoprenoids pristane to phytane ratio varies from 1.1 to
2.8. The major diterpenoids in the samples are 19-norisopimarene, labdane,
sandaracopimarane and unknown C18 and C19 diterpenoids. Presence of these diterpanes
suggests the terrigenous land plants (as also indicated by Phytane/n-C18 vs Pristane/n-C17
plot), more precisely conifers were the contributor to the precursor organic matter. Absence of
extended tricyclic terpanes series and the association of C19 and C20 tricyclic terpanes with
conifer derived diterpenoids indicate that these compounds were derived from the higher
plants. Rock-Eval Tmax and vitrinite reflectance data indicate that the studied coals have fall in
the catagenetic zone of hydrocarbon generation. The TOC content (20-60%) and presence of
Type III/II kerogen suggest that the coal-bearing sequence has the potential to generate both
oil and gaseous hydrocarbons.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
116
Structure and reactivity of pyrolitic carbon
collected from the coke oven chamber
Ł. Smędowski
Institute for Chemical Processing of Coal, 1 Zamkowa St., 41-803 Zabrze; +48 32 271 0041-355;
Carbon deposits, called by cokemakers as ‘graphites’, form as a result of thermal cracking of
tars and gas hydrocarbons that are released during industrial coking of coal charge (Zymla
and Honnart 2007). There are a lot of papers where the mechanisms of deposits’ forming are
described (Mianowski et al. 2006; Zymla and Honnart 2007). In this work the knowledge
about carbon deposits that consist mainly of pyrolitic carbon was fill up with the results of
studies on their structure. The aim of this work is to characterize structure and reactivity of
pyrolitic carbon collected from the coke oven chamber.
Four samples of carbon deposits were collected from different parts of coke oven chamber,
e.g.: form the oven wall (dep. 1), from the oven door (dep.2), oven roof (dep.3), ascension
pipe (dep.4). This chamber works in ArcellorMittal Poland – division Zdzieszowice coking
plant. Samples were studied with use of: Raman spectroscopy (RS) and X-ray diffraction
(XRD). Basing on analysis of XRD and Raman spectra sets of structural parameters were
determined for each sample and the quantitative characterization of carbon deposits structural
ordering was done. Furthermore, it was found that structure of pyrolitic carbon depends on
thermal conditions that took place while carbon deposits were formed. Basic parameters of
the deposits studied are presented in Table 1. It can be seen that the moisture and ash contents
are similar for all samples studied while the volatiles and carbon contents change with the
temperature in chamber – the dep.1 sample that formed in the highest temperature the is most
devolatilized and mainly consist of carbon while the dep.4 sample (formed in the lowest
temperature) has quite high content of volatiles and low content of carbon.
Table 1. Basic characteristics of samples studied.
dep.1 dep.2 dep.3 dep.4
Moisture content, Ma, % 0.1 0.2 0.6 0.8
Ash content, Ad, % 1.5 3.3 2.4 4.5
Volatiles content, Vdaf
, % 0.23 0.28 1.42 8.15
Carbon content, Cdaf
, % 97.6 96.2 94.2 92.9
Values of the structural parameters of pyrolitic carbons are presented in Table 2. It can be
seen that the crystal stacking and interlayer spacing changes in similar order as the volatiles
and carbon contents and differs from 7,83 to 3,10 nm and from 0,345 to 0,352 nm
respectively. However, there is an deviation from this trend for both the Raman parameters.
The ID1/IG as well as AD3+D4/Aall reach the lowest values for the dep.3 sample, collected from
the oven roof. The ID1/IG parameter corresponds to the lateral size of the crystalites, La, while
AD3+D4/Aall corresponds to the amounts of amourphous and very poor ordered carbon in the
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
117
structure of the material (Ferrari and Robertson 2000). Both of these parameters correspond to
the reactivity of the structure with depends on the amounts of disordered carbon atoms as well
as on the accesibility to the carbon atoms that form aromatic layers of pyrolitic carbon. If the
lateral size of crystalizes is small and there is a lot of disordered material than reactivity of
such material is relatively high. The potentially higher reactivity of the dep.3 sample is an
important conclusion for cokemakers because the pyrolitic carbon is unwanted material in the
coke oven chamber, especially on its roof because the presence of ‘graphite’ in high amounts
can seriously disturb technological operations performed durng production of coke. The most
popular method of the deposits removal is their burning off. For that reason, conlusion
presented in this work seems to be interesting for the cokemakers, because it indicates that the
smaller amounts of oxygen can be used for the burning off the deposits on the roof than in the
case of the ovens wall and door.
Table 2. Values of structural parameters of samples studied.
dep.1 dep.2 dep.3 dep.4
Lc, nm 7.83 3.55 3.32 3.10
d002, nm 0.345 0.347 0.350 0.352
ID1/IG 2.25 2.18 1.62 1.93
AD3+D4/Aall 0.24 0.26 0.43 0.28
Notation: Lc – crystal stacking (XRD), d002 – interlayer spacing (XRD), ID1/IG – ratio of D1 and G bands
intensities (RS), AD3+D4/Aall – ratio of D3+D4 bands area to the sumaric area of all bands (Raman).
Acknowledgements: This study was financed under the Smart Coking Plant R&D Project (Innovative Economy
Programme (POIG), Contract no 01.01.02.-24-017/08).
References
Ferrari A.C., Robertson J. 2000 - Interpretation of Raman spectra of disordered and amorphous carbon, Physical
Review B - Condensed Matter and Materials Physics. 61: 14095-14107.
Mianowski A., Bigda R., Zymla V. 2006 - Study on kinetics of combustion of brick-shaped carbonaceous
materials. Journal of Thermal Analysis and Calorimetry 84: 563 – 574.
Zymla V., Honnart F. 2007 - Coke oven carbon deposits growth and their burning off, ISIJ international, 2007,
10: 1422 - 1431.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
118
Organic petrology and geochemistry of the Oligocene source rocks
in the Glina Depression (Croatia)
D. Španić, T. Troskot-Čorbić
INA-Industrija nafte d.d., E&P Research Laboratory Department, Zagreb, Croatia, [email protected]
The outcrop samples from four locations of the Oligocene source rocks from Glina
Depression in the Croatian part of Internal Dinarides were geochemically and petrologically
analyzed and typified. Glina Depression occupies the southwestern portion of the Pannonian
basin and is situated at its margin south from the petroleum productive Sava depression unit.
External or Karst Dinarides represent carbonate platform which exists from the Jurassic to
the Middle Eocene, while Internal Dinarides correspond to contemporaneous periplatform
carbonate flysch interlayered with distal pelagic sediments of the Tethys Sea. At the Eocene-
Oligocene boundary, plate tectonic activity caused destruction of the western part of the
Tethys Sea, which resulted in the appearance of the Mediterranean Basin in the south and the
intracontinental euxinic Paratethys Basin in the north.
Present-day Internal Dinarides corresponds to southern margin of the Paratethys. Glina
Depression was probably restricted lagoon with brackish influences and periodically suboxic
to anoxic bottom conditions.
Dark laminated carbonaceous shales have organic carbon in the range from 2.03 to 13.61
%. Rock Eval pyrolysis indicates kerogen type I-II with consequently good to excellent
potential for hydrocarbon generation (HI= 331-946 mg HC/g TOC; S2= 6.71-128.78 mg
HC/g rock). Pyrolytic maturity parameters show diagenetic stage in thermal evolution
(Tmax= 428-438°C, PI= 0.01-0.06).
Microscopic examinations and stable carbon isotope analyses on kerogen concentrates, as
well as gas chromatographic analyses of the alkane fraction of extractable organic matter
revealed two types of organic facies:
1. Strong yellow fluorescing bituminite (amorphous organic matter) without any traces of
structured macerals. Thermal alteration indices, estimated on isolated amorphous
organic matter, are 2- (0.35-0.45 VR). Stable carbon isotope analyses give values from -
28.61 to - 31.08 δ13CPDB. Gas chromatographic analyses show dominance of C18-C24
normal alkanes and Pr/Ph ratio <0.8, which is evidence for algal origin of organic
matter and anoxic environment of deposition.
2. Moderate yellow-orange to orange-brown fluorescing bituminite with traces of yellow
fluorescing alginite (Botryococcus), liptodetrinite and up to 20 % vitrinite (huminite).
Vitrinite reflectance values are from 0.33-0.49 % VR. This type of kerogen is richer in
heavy stable carbon isotope (-25.16 to -27.22 δ13CPDB) in comparison with former
type of organic facies. In the gas chromatograms dominate odd alkanes in the range
C25-C31 and Pr/Ph ratio is over 1, which means high terrestrial organic matter input
and suboxic to oxic environment of deposition.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
119
Study on morphology, structure and composition
of thermally altered coal and biomass
I. Sýkorová, M. Havelcová, Z. Weishauptová, H. Trejtnarová, J. Blažek
Institute of Rock Structure and Mechanics AS CR,v.v.i. V Holešovičkách 41, 182 09 Praha 8, Czech Republic;
+420 266009 280; [email protected]
Products of thermal degradation of fossil fuels and vegetation formed in nature and human
life embody very interesting carbonaceous materials. They can represent raw materials for
electricity production, preferably from renewable energy sources, for other industrial
purposes, e.g. steel and chemical industry, and for ecological applications, e.g. preparation of
sorbents for treatment of sewage, gasses. The relatively resistant carbonaceous residues
remaining after incomplete combustion of fossil fuels and vegetation can contribute
significantly to the carbon content in soil in recent, and in sediments in the past. On the other
hand the carbonaceous compounds and solid products can cause problems in the environment
and health.
The first part of the solution of the grant project (No. 13-18482S of the Czech Science
Foundation Research Grants) was focused on the study of changes in morphology, structure
and composition of thermally degraded coal and biomass due to two basic processes of
incomplete combustion in air and reduction atmosphere. The attention was paid to ecological
aspects expressed by “black carbon” (BC) and PAHs production.
Six original raw materials of various rank: bituminous coal (the Czech Part of the Upper
Silesian Basin), lignite (the Tertiary Sokolov Basin), peat from the Krásno peat bog in
western Bohemia, and biomass (oak and spruce wood and grain of the wheat) were subjected
to char production. Raw materials were heated to temperatures of 350, 450, 600, 800oC in a
muffle furnace in the air and nitrogen atmosphere. Produced chars as the raw materials were
divided into samples for petrographic, sorption and chemical analyses.
The results showed significant effects of increased temperature and atmosphere on mass
loss, reflectance values, petrological composition, porous characteristics, elemental and
hydrocarbon composition. Mass losses increased up to 66% during the exposure of coal
samples to temperatures of 25 – 600oC in the air atmosphere and up to 39% in the nitrogen
atmosphere. Maximal mass losses up to 89% were found in chars from peat and plant
materials at 350oC in the air and up to 72% in the nitrogen atmosphere. Random reflectance,
porous character of chars, and portion of fine fragments primarily of soot particles lower than
1µm produced from all raw materials increased rapidly in the air atmosphere but final
reflectance at 800 oC is lower (Rr = 3.9- 5.7%) than that of the chars from the nitrogen
atmosphere (Rr = 4.1 – 6.8%).
The changes in random reflectance observed with the increasing extent of thermal
alteration were consistent with decreasing- hydrogen content, increasing - carbon content and
volumes, and surface area of micropores. All studied raw materials have developed
microporous texture with volume of micropores from 0.0248 to 0.0406cm3/g, and surface area
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
120
of micropores between 63 and 113m2/g. The highest values of micropores volumes above
0.1300cm3/g and surface area of micropores above 400m
2/g were determined in chars
produced from plant materials. The parameter characteristic energy E plays a fundamental
role in the characterization of carbons. It rapidly increases in chars produced in air atmosphere
particularly in chars from lignite.
Random reflectance correlated well with H/C atomic ratios and BC values obtained by
chemo-thermal oxidation method. The highest BC values in raw materials were found in
lignite (0.32%wt BC) and in chars from bituminous coal (3.29% wt BC). The results show
that BC forms only small percentage of the total organic carbon in produced chars.
By the use of Py-GC/MS compounds were identified in the chars that were found also in
the raw materials and represent their remnants (phenol, benzofuran, indene, naphthalene and
their alkyl derivatives). However, there were also found compounds developed during
material alteration or rather originating from aromatic structures from which they were
released during Py-GC/MS. BC, formed by the incomplete combustion of fossil fuels,
biofuels, and biomass, is a broad range of combustion products, from slightly charred forms
of low condensation degree to the most condensed and graphitic forms of carbon. Formed at
lower temperatures, BC consists mainly of smaller clusters of condensed carbon, and the
identified compounds correspond to this imperfect structure (quinoline, biphenylene,
methylbiphenyles, dibenzofuran). The condensed aromatic network was formed at higher
temperature and the number and intensity of components in pyrograms decreased.
The composition of chars was dependent on the used conditions and indicated that
incomplete combustion leads to the formation of aromatic structures and regions.
Compounds typical for the BC presence were identified and there were no essential
differences in compound compositions between the two used environments.
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121
Organic facies of the Upper Jurassic sediments
in the Poštak Mountain, Croatia
T.Troskot-Čorbić1, D. Španić
1INA-Industrija nafte d.d., E&P Research Laboratory Department, Zagreb, Croatia;
Carbonate deposits of the Karst (External) Dinarides ranging from the Lower Jurassic to
Cretaceous were formed on the Adriatic Carbonate Platform (AdCP). The Late Jurassic
megafacies of “limestones with cherts” was deposited within tectonically formed
intraplatform troughs which had temporary or continuous connection to the open sea. During
recent investigations the most complete succession of Kimmeridgian deeper marine deposits
has been documented at the slopes of Poštak Mt. New informal stratigraphic unit Poštak is
proposed composed of three members: Rastičevo, Dimići and Lemeš.
The objective of this study is detailed organic geochemical characterization of the Dimići
member in Poštak Mt.
Standard organic geochemistry analyses were performed on more than 100 outcrops. An
integral interpretation of this data was made in the sense of comprehensive organic facies
study in order to define organic matter types, source rocks and their generative potential as
well as genetic correlations.
Based on the integration of analytical data organic facies AB/B (after Jones 1987) it is
recognized as follows: Organic facies AB/B is characterized with high organic matter content,
excellent hydrocarbon potential and high transformation ratio. Type II kerogen dominates in
the organic-rich laminated limestones. Occasionally, the type I kerogen is present as well.
Organic facies AB/B is of marine, algal-bacterial origin. According to microsolubility and
strong yellow to yellow-orange fluorescence effect, organic matter is a mixture of algal,
bacterially degraded kerogen and migrated bitumen. Bitumen reflectance is in the range from
0.15 to 0.30% Ro (asphaltite group). Organic facies AB/B is characterized with high organic
sulfur content (from 6 to 10%). Stable carbon isotope values are in range from 1 3
C -27.79
to -24.65‰ in kerogen and from -29.53 to -25.55‰ in bitumen. Correlation is mainly
positive. These values are frequent in the Jurassic rocks and they are generally attributed to
the specific algal and bacterial lipids, as well as to the developed water anoxia.
The Upper Jurassic fine-grained, laminated limestones have an excellent generation
potential and represent very good to excellent oil-prone source rocks.
Organic matter content is in range from 0.35 and 11.9%, in average 2.97% TOC).
Petroleum potential is from good to excellent (between 1.17 and 67.00 mg HC/g rock, in
average 18.25 mg HC/g rock). Amorphous organic matter gradually changes from lamalginite
to bituminite I and finally to organo-bituminous-mineral groundmass, i.e. to matrix
bituminite. Solid bitumen is incorporated in all structural types. Phytoplankton is represented
by prasinophycean phycomata and dinoflagellate cysts. Throughout the geological columns
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quantitative variations in cyanobacterial and liptinite/liptodetrinite content are
microscopically observed. Variations in C27 and C29 regular sterane were documented as well.
These dark organic-rich laminated limestones (mudstones) with cherts form the older part
of Lemeš trough deposits. Organic matter was deposited in deeper trough of the Adriatic
Carbonate Platform. Deposition occurred in the low energy environment within intraplatform
trough. Water stratification and bottom waters euxinia were occasionally disturbed by inflow
of the open sea water masses.
The laminated organic matter in a form of lamalginite was deposited in calm, stable
environment with developed water mass stratification, under oxygen–depleted conditions. In
relatively disturbed unstable conditions organic matter deposited as lamalginite became
decomposed and bacterially degraded which led to a gradual transition into bituminite I and
finally into organo-bituminous-mineral groundmass, matrix bituminite.
According to maturity parameters (Tmax, PI, TAI, fluorescence color, vitrinite reflectance,
bitumen reflectance, biomarker maturity parameters M/H, 22S/(22S+22R), Rc, Rm(MDR),
20S/(20S+20R), Ts/Tm), the organic facies AB/B generally reach onset of oil
generation.
High percentages of organic-bonded sulfur confirm that organic matter formation took
place in the marine, carbonate environment with contemporaneous sulfur incorporation into a
kerogen macromolecule structure. This kind of organic facies enabled hydrocarbon generation
at lower degree of thermal transformation. Consequently, the total bitumen yields are high.
The extractable fractions are dominated by resins and asphaltenes which reflect these specific
organic facies enriched in sulfur, but also some degradation effects due to the atmospheric
influence. Gas chromatograms of alkane fraction of bitumen show predominance of n-alkane
in lower molecular range, domination of phytane over pristane and n-alkane over iso-alkane,
respectively. These profiles are typical for bitumen of algal-bacterial origin and anoxic
(reducing) depositional environment and correspondent to the defined maturity level. Source
rock extracts and bitumens or bituminous coatings show high degree of similarity which
indicates short migration paths. Migrabitumen, which fill fissures, cavities and pores in the
rocks, is classified as the natural asphalt. That bitumen is product of early generation from
sulfur and organic rich kerogen. In the absence of the cap rocks, bitumen reached the surface,
and was degraded and transformed from primary viscous liquid into a solid bitumen.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
123
Spectral fluorescence variability of pollen and spores
from peat-forming plants
J. Urbanczyk1, M.A. Fernandez Casado
2, T.E. Díez
2, A.G. Borrego
1
1Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain;
[email protected] 2BOS Department. University of Oviedo. Catedrático Rodrigo Uría s/n, 33006 Oviedo, Spain
Fluorescence is the ability of the organic compounds to produce visible light when irradiated
with short wavelength light. The fluorescence properties of liptinite macerals are widely used
to assess the maturity of source rocks (Teichmüller and Wolff, 1977). They also have shown
to vary with the degree of alteration (Michelsen and Kohrasani, 1990). In extremely immature
sediments as is the case of peat, the fluorescence properties of the different components are
strongly influenced by their botanical characteristics such as species, taxon and state of
preservation of the material (van Gijzel, 1967) and has been applied to follow environmental
changes (Yeloff and Hunt, 2005). In this context this study aims to a characterization of
fluorescence spectra of pollen and spores of peat-forming plants in order to assess the intrinsic
variability within a single taxon. This is the first step of a wider study on the factors affecting
fluorescing properties in peat.
Pollen and spores of up to 26 different species of fresh peat-forming plants have been
spread over a glass as typically done for palynological preparations. An incident light optical
microscope with oil immersion objective has been used to collect the fluorescence spectra in
range of 420-750 nm using UV excitation. The spectra have been corrected for the optical
system using a quartz iodine lamp (Baranger et al., 1991). For each species at least 10 spectra
were collected on different grains to obtain average spectra to be compared.
Significant differences were found between the spectra of the various species with spectral
maxima ranging from 430 to 675 nm and intensity from around 20 to over 300 arbitrary units
(Fig.1). Obtained spectra could be assigned to either bluish wavelengths or to yellowish-
orange colors. The majority of species fell on the second color group: Serratula tinctoria
(Asteraceae family) with very strong intensity followed by Equisetum palustre
(Equisetaceae), Calluna vulgaris (Ericaceae) or Salix atrocinerea (Salicaceae). Lower
intensities in that colour group showed, among others: Tilia cordata (Malvaceae), Quercus
robur (Fagaceae) and Betula pubescens. Within species with intense bluish spectra we can
mention: Narcissus asturiensis (Amaryllidaceae), Ranunculus repens (Ranunculaceae) and
Molinia caerulea (Poaceae) whereas Sphagnum sp. (Sphagnaceae) and Corylus avellana
(Betulaceae) show spectra of
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124
medium to low intensities. The variability within each species has been assessed using the
standard deviation and the coefficient of variation. The standard deviations were generally
This effect can be minimized when the coefficients of variation are considered. They ranged
between 0.10 and 0.30 for most of the species and were higher in the extreme of the spectra.
Among the species with the lowest intrinsic variability Q. robur and Castanea sativa can be
mentioned, whereas the largest variability was observed for Polypodium vulgare and Erica
mackaiana. This study has shown moderate variability within a single species in a single
sample, but significant variability within different peat-forming species. Further studies are
under development to study the spectral variability of similar species in peat.
Acknowledgement: Financial support from MICINN (CGL2009-13990-C02-01/02) and a FPU fellowship from
MEC for J. Urbanczyk are gratefully acknowledged.
References
Baranger R., Martinez L., Pittion J., Pouleau J. 1991 - A new calibration procedure for fluorescence
measurements of sedimentary organic matter. Organic Geochemistry 17: 467-475.
Michelsen J.K., Khorasani G.K. 1990 - Monitoring chemical alterations of individual oil-prone macerals by
means of microscopical fluorescence spectrometry combined with multivariate data analysis. Organic
Geochemistry 15: 179-192.
Teichmuller M., Wolf M. 1977 - Application of fluorescence microscopy in coal petrology and oil exploration.
Journal of Microscopy 109: 49-73.
van Gijzel P. 1967 - Palynology and fluorescence microscopy. Review of Palaeobotany and Palynology 2:
49-79.
Yeloff D., Hunt C. 2005 - Fluorescence microscopy of pollen and spores: a tool for investigating environmental
change. Review of Palaeobotany and Palynology 133: 203-219.
Fig.1. Fluorescence spectra of pollen and spores of some peat-forming plants.
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
125
Organic petrology of the Aptian section in the downdip Mississippi Interior
Salt Basin, Mississippi, USA
B.J. Valentine, P.C. Hackley, A.M. Bove, C.B. Enomoto, C.D. Lohr, K.R. Scott
U.S. Geological Survey, MS 956 National Center, Reston VA 20192; [email protected] 703-648-6480
This basin analysis study investigates a thermal maturity anomaly within the downdip
Mississippi Interior Salt Basin (MISB) of southern Mississippi, USA, by examining the
organic petrology of Aptian shales (Pearsall-equivalent Rodessa and Pine Island Formations).
A stratigraphically equivalent section contains an unconventional shale gas play in the
Maverick Basin of south Texas with an estimated mean undiscovered gas resource of 8.8 TCF
(Hackley, 2012). The USGS reconnaissance conducted in 2011-2012 examined Aptian
thermal maturity across the onshore Gulf Coast Region and indicated the section was
approaching the wet gas/condensate window in the downdip MISB (Enomoto et al., 2012). A
more focused study in 2012-2013 used six core samples and forty-six high-graded cuttings
samples (depth range of 12,000-15,000 ft below surface) collected from 15 wells in the
downdip MISB for Rock-EvalTM
pyrolysis, LecoTM
TOC, and organic petrography analysis.
Geochemical screening analysis found that samples were organically lean with TOC values
between 0.01-1.21 wt.%, averaging 0.5 wt.% (n=51). S2 ranged 0.14-2.33 mg HC/g rock,
averaging 0.40, indicating little present-day hydrocarbon generative potential. More than 70%
of the S2 values were >0.2 mg HC/g rock; however, of 51 pyrolysis analyses, only 11 gave
reasonable Tmax values (~430-530°C, converting to ~0.6-2.2% Ro), possibly due to low TOC
content. Therefore, the pyrolysis approach to characterizing these high maturity-organic lean
rocks is discounted in favor of petrographic analysis (e.g., Peters, 1986).
Despite being organic-lean, all samples contained solid bitumen and inertinite with only
two samples containing fragments of vitrinite. Due to the overlap of maceral-type reflectance
ranges, macerals were identified during analysis as either secondary solid bitumen (Ro
generally <0.8 %; recently migrated and cracked oil?), primary solid bitumen (Ro generally
>0.8%; indigenous hydrocarbons matured in situ?), solid bitumen/inert (macerals could not be
identified with absolute certainty), vitrinite or inertinite.
Based on primary solid bitumen reflectance, Ro values increase regionally across the MISB
from the southeast to the northwest. Thermal maturity in the eastern half of the basin (Ro
range 1.0 to 1.25%) appears to be related to present-day burial depth, showing a gradual
increase with respect to depth. However, thermal maturity continues to increase even as the
Aptian section shallows structurally on the Adams County High towards the western margin
of the basin (Ro range 1.4 to >1.8%). Possible explanations for this thermal anomaly include
agents such as igneous activity or salt emplacement, differences in regional crustal heat flux,
or relatively greater uplift and erosion during the regional mid-Cretaceous sea level regression
and development of the mid-Cenomanian unconformity. Extensive igneous activity during the
Late Cretaceous is known to have regionally occurred in the Monroe Uplift and Jackson
Dome structures (Salvador, 1991); however, our samples are >50 km (35 mi) distant from
65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland
126
known igneous activity. Salt is ruled out because samples in the eastern portion of the basin
adjacent to salt structures did not display elevated thermal maturity. Limited evaluation of
present-day bottom-hole temperatures within the area showed no distinct trends, suggesting
past/present variations in regional heat flux do not influence thermal maturity. Therefore, we
propose that significant differential uplift and erosion at the western end of the MISB could be
responsible for the thermal maturity anomaly. The cause of the uplift and igneous activity in
the region is not well understood. A possible theory involves the reactivation of an ancient
plate boundary or graben due to rapid subsidence of the Gulf of Mexico basin (Salavador,
1991). Further sampling and analysis to examine if source rocks of Oxfordian and Late
Cretaceous age within the MISB exhibit a similar east-west thermal maturity trend as found in
the Aptian section will continue in 2013-2014.
References
Hackley P.C. 2012 - Geological and geochemical characterization of the Lower Cretaceous Pearsall Formation,
Maverick Basin, south Texas, USA: a potential shale gas resource? American Association of Petroleum
Geologists Bulletin, 96, 8: 1449-1482.
Enomoto C.B., Scott K.R., Valentine B.J., Hackley P.C., Dennen K.O., Lohr C. 2012 - Preliminary evaluation of
the shale gas prospectivity of the Lower Cretaceous Pearsall Formation in the onshore Gulf Coast region,
United States. Gulf Coast Association of Geological Societies Transactions, 62: 93-115.
Peters K.E. 1986 - Guidelines for evaluating petroleum source rock using programmed pyrolosis. The American
Association of Petroleum Geologists Bulletin, 70, 3: 318-329.
Salvador A. 1991 - Origin and development of the Gulf of Mexico Basin. in Salvador, A., ed., The Gulf of
Mexico Basin (The Geology of North America, Vol. J): Boulder, CO, Geologic Society America: 389-444.
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