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Appendices – Table of contents
I
Appendices – Table of contents Appendix 1 - Stratigraphy of the Late Cretaceous deposits: previous work ........................................... 1
1.1 The Piñón Formation..................................................................................................................... 1 1.2 The Las Orquídeas unit ................................................................................................................. 3 1.3 The Calentura Formation............................................................................................................... 4 1.4 The Cayo Formation...................................................................................................................... 6 1.6 The Guayaquil Formation ........................................................................................................... 13
Appendix 2 - Field and sample locations .............................................................................................. 19
Appendix 3 - Methodology for mineralogical characterization .............................................................19
3.1 Sample preparation for X-ray diffraction .....................................................................................19
3.2 Methodology for cation exchange capacity measurements of zeolitic rocks ...............................20
3.3 Staining of feldspars & zeolites....................................................................................................23
3.4 Digestion of silicate rock samples: LiBO2 fusion in graphite crucible for AAS and ICP-MS
analysis ...............................................................................................................................................25
Appendix 4 - Mineralogical characterization of the Late Cretaceous Deposits .................................... 27
4.1 Structures used in the Rietveld refinement.................................................................................. 27
4.2 XRD quantifications.................................................................................................................... 33
4.2.1 Río Guaraguao section (samples are ordered from the base to the top of the section)
.....................................................................................................................................33
4.2.2 Guayaquil (samples are ordered from the base to the top of the section) ...............41
4.2.3 Río Derecha - Río Zamoreño................................................................................46
4.2.4 Manabí área .........................................................................................................47 4.3 EPMA.......................................................................................................................................... 49
4.3.1 HEU-type zeolites ................................................................................................49
4.3.2 Mordenite ............................................................................................................55
4.3.3 Laumontite...........................................................................................................56
4.3.4 Chlorite-Smectite .................................................................................................57
4.3.5 Celadonite............................................................................................................60 4.4 SEM-EDX ................................................................................................................................... 61
4.4.1 Heu-type zeolites .................................................................................................61
4.4.2 Mordenite ............................................................................................................62
4.4.3 Analcime..............................................................................................................63
4.4.4 Chlorite/smectite ..................................................................................................64
4.4.5 Plagioclase ...........................................................................................................65
4.4.6 Pyroxene ..............................................................................................................69 4.5 ICP-OES...................................................................................................................................... 70
Appendix 5 - Terrain observations and petrogrophical analyses of the volcanic components, structures
and textures of the samples of the Río Guaraguao section.................................................................... 73
5.1 The Piñón and Calentura Formations .......................................................................................... 73
5.1.1 The Piñón Formation............................................................................................73
5.1.2 The Calentura Formation......................................................................................73 5.2 The lower unit of the Cayo Formation (Río Guaraguao unit) ..................................................... 74
5.2.1 Coarse breccia at the base of the Cayo Formation.................................................74
5.2.2 The basal part of the lower unit ............................................................................76
5.2.3 The middle part of the lower unit .........................................................................76
5.2.4 The upper part of lower unit .................................................................................80
Appendices – Table of contents
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5.3 The upper unit of the Cayo Formation ........................................................................................ 81
5.3.1 The base of the upper unit of the Cayo Formation ................................................81
5.3.2 The lower part of the upper unit of the Cayo Formation .......................................82
5.3.3 The middle part of the upper unit of the Cayo Formation......................................83
5.3.4 The upper part of the upper unit of the Cayo Formation .......................................85
Appendix 9 - Petrographical analyses of the alteration of the samples of the Río Guaraguao section . 89
9.1 Alteration in the Piñón Formation............................................................................................... 89
9.2 Alteration in the Calentura Formation......................................................................................... 89
9.3 Alteration in the lower unit of the Cayo Formation .................................................................... 89
9.3.1 Coarse breccia at the base of the Cayo Formation.................................................89
9.3.2 Lower part of the lower unit .................................................................................89
9.3.3 Middle part of the lower unit ................................................................................90
9.3.4 Upper part of the lower unit .................................................................................97 9.4 Alteration in the upper unit of the Cayo Formation .................................................................. 100
9.4.1 The lower part of the upper unit .........................................................................100
9.4.2 The middle part of the upper unit .......................................................................102
9.4.3 The upper part of the upper unit .........................................................................103
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
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1.1 The Piñón Formation
Early investigations
The formation was first recognized by Wolf
(1892 – in Goossens and Rose, 1973), who
named the rocks: “Grunstein formation”. The name Piñón was first introduced by Tschopp
(1948 – in Goossens and Roose, 1973), who
named the formation after its type locality in
the Río Piñón, 20 km southwest of Portoviejo
in the Manabí area. Sauer (1965 – in Goossens
and Rose, 1973) defines the Piñón Formation
as a series of basaltic lavas, diabases,
pyroclastic rocks, gabbros and diorites
Bucaram (1966) describes the Piñón Formation
in the region of Guayaquil, where it consists of
diabase flows which become amygdaloidal
higher in the section. A few thin tuff and tuffaceous sandstone beds are found
interbedded with amygdalar diabase. The
upper part of the formation is essentially a light
green, finely crystalline basic igneous
porphyry with interbedded tuffaceous shale
and gray to cream and reddish-coloured,
tuffaceous and siliceous siltstone. It is locally
intruded by granodiorites. Bucaram (1966)
attributes a Jurassic to Cretaceous age to the
Piñón Formation, but has no fossil or
radiometric data to prove this.
The basic igneous complex
Goossens and Rose (1973) present the results
of an aeromagnetic and radioactive survey of
1964–1965 performed by the UNDP. The
author’s state that the Piñón Formation
corresponds to a complex of so many different
lithologies and ages that the whole mafic-rock
sequence in the Ecuadorian coastal plain can
best be classified as a basic igneous complex
(Goossens, 1970 – in Goossens and Rose,
1973). Included in the basic igneous complex
are the rocks with the same lithologies
cropping out along the western slopes of the
Western Cordillera, called Formación
Diabásica–Porfirítica by Sauer (1965 – in
Goossens and Rose, 1973) and ultramafic
rocks in Colombia. The rocks are submarine
effusions overlying (or intruded by) coarse
grained rocks (gabbro-harzburgite) and
intruded by diorite-tonalite bodies representing
the products of differentiation of the same
basaltic magma (Goossens, 1968 – in
Goossens and Rose, 1973).
The basic igneous complex was divided in two
members by Goossens and Rose (1973): The
lower member, equivalent to the Piñón sensu
stricto formation, was explained as a principal
phase of magmatism represented by fine
grained, hypabyssal, and coarse grained
ultramafic to intermediate rocks, which were
emplaced some time after the Middle Jurassic and before the end of the Cretaceous. This
magmatic phase includes harzburgite bodies,
diabase, gabbro and basalt. The upper member
is composed of effusive phases of younger
tholeiites erupted along east-trending fractures
and occurred during the Late Cretaceous until
the early Eocene.
Because of the tholeiitic character of the rocks,
Goossens et al. (1977) state that the basic
igneous complex was either formed at an
oceanic ridge, or in an immature island arc.
The suite is clearly bimodal (high Ca basalt
and low Ca basaltic andesite) and formation of
the basaltic andesites by fractional
crystallization of the basalts can be ruled out.
Geochemical data seem in general to support
an ocean floor tholeiite interpretation for the
rocks, but the higher concentration of K2O and
Sr and the relative prominence of andesites are
features of the chemistry that are not consistent
with this conclusion. The authors suggest that
there is perhaps no sharp distinction between
ocean floor tholeiites and these tholeiites
developed in “youthful” island arcs. No
APPENDIX 1 - STRATIGRAPHY OF THE LATE
CRETACEOUS DEPOSITS: PREVIOUS WORK
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
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distinction has been made between the lower
and upper member in the geochemical
analyses.
On the 1:100 000 geological maps of the Costa
published in 1974 and 1975 the name basic
igneous complex was used for the Piñón
Formation and all other effusive volcanic rocks
regardless of their age, which lead to a lot of
misinterpretations. In most later publications,
no distinction is made between the Piñón sensu
stricto formation and later effusive volcanic
rocks (e.g., Wallrabe-Adams, 1990;
Marksteiner and Aleman, 1990).
Piñón Formation sensu stricto
Feininger and Bristow (1980) proposed to use
the name Piñón for the pre–Cayo volcanic
rocks of the coastal region only. According to
them, a continuous series of the Piñón
Formation occurs in the Cordillera Chongón–
Colonche, while a discontinuous series can be
found near the Coast of Portoviejo, between
Portoviejo and Esmeraldas, and southeast of
Esmeraldas. Small exposures of the formation
on the Santa Elena Peninsula are described as olistoliths. Next to basalt and diabase, they
also include basaltic agglomerate and tuff, and
sparse and thin layers of argillite and wacke in
the Piñón Formation (Carnfield, 1966 in
Feiniger and Bristow, 1980).
Feininger (1986) defines the Piñón terrane as
an area of 62000 km2 between the Romeral
fault and the Pacific coast extending
northwards into Colombia for an unknown
distance. All basement of the Piñón terrane is
formed by the Piñón Formation. The most
remarkable feature of the Piñón terrane is its
huge positive simple Bouguer gravity anomaly
where the Piñón Formation crops out or where
it is covered only thinly by younger rocks.
Anomalies in the town of Daule, 45 km
northwest of Guayaquil, reach +179 mGal (1
mGal = 10 µm s-1
) and are the largest on-land
positive anomalies recognized in the western
hemisphere, at the time when the article was
written. Anomalies over a surrounding area of
6000 km2 exceed +100 mGal. Such large
positive anomalies demonstrate the oceanic
nature of the Piñón Formation and confirm that
it is not underlain by continental crust.
Santos and Alvarado (1989) state that the
Piñón Formation (sensu stricto) only occurs in
the Cordillera Chongón–Colonche. The
majority of the rocks occurring in the Manabí
and Borbón basins belong to a later volcanism
named Volcanismo tardío de Cayo by the
authors.
Lebrat et al. (1987) refer to cumulate gabbros
associated with the Piñón dolerites in a hill
three kilometres northeast of Cerro de
Masvale, near Guayaquil. North of Guayaquil,
isolated outcrops of peridotites, among them
the Pascuales harzburgite, occur. Pillow lavas
range from aphyric to porphyritic, containing
phenocrysts of plagioclase, clinopyroxene and
Fe-Ti oxides. Massive fine grained dolerites
contain the same mineral phases but display
intersertal or ophitic texture. Pervasive
hydrothermal alteration and mineralization
(Fe-Cu sulphides) are common in both basalts
and dolerites, and low-grade metamorphism of
zeolite, pumpellyite-prehnite, and in some case
greenschist facies have been reported (Lebrat
et al., 1985).
The age of the Piñón Formation Mamberti et al. (2003) and Kerr et al. (2003)
state that the Piñón Formation in the Guayaquil
area is older than 90 Ma or even older than 95
Ma because it is overlain by arc-derived
sediments of Turonian and Cenomanian age.
However, later dating (see Calentura
Formation) shows that these sediments are of
Middle Coniacian age (Ordóñez, 2003, 2005;
Ordóñez et al., 2006; Mendoza and Velasco,
2003).
Van Melle et al. (2008) investigate cherts
between pillows in the upper part of the Río
Guaraguao section. They yield the planktonic
foraminifera Hedbergella holmdelensis
(Coniacian–Maastrichtian), and the
radiolarians Cryptamphorella sp.,
Orbiculiforma sp., Praeconocaryomma sp.,
Spongosicus sp., Theocampe tina and
Theocampe ascalia, associated with
palynomorphs (Cicatricosisporites sp.,
Psilatricolporites sp.). The association of
Hedbergella holmdelensis, Theocampe ascalia
and Theocampe tina suggests an age comprised
within the Coniacian – Middle Campanian
interval. This means that the Piñón Formation
has to be of Early to Middle Coniacian age, as
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
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the Calentura Formation is of Middle
Coniacian age (Ordóñez 2003, 2005; Ordóñez
et al., 2006; Mendoza and Velasco, 2003).
Early radiometric dating was performed in the
Manabí area where it is not possible to know if
the measured rocks are from the Piñón
Formation or from more recent volcanics.
Snelling (1970 – in Goossens and Roose,
1973) obtains dates of the basic igneous
complex of 72, 85 and 104 Ma by K/Ar dating.
Kennerly (1980) dates the Piñón Formation as
113±10 Ma and, 107±15 Ma in the Manta
region.
Luzieux et al. (2006) analysed a gabbro located
near the town of Nobol (UTM coordinates:
610094; 9787726, WGS84). They obtained a
plateau hornblende 40
Ar/39
Ar age of 88.8 ± 1.6
Ma from a gabbro. The chondrite-normalized
plot of the rare earth elements shows a flat
pattern, which is comparable to previously
published data of the Piñón Formation and
confirms the stratigraphic attribution of the
investigated sample to the Piñón Formation.
Origin of the Piñón Formation
The Piñón Formation was interpreted as a
remnant of oceanic basement or as primitive
oceanic island arc tholeiites. The interpretation
as an oceanic arc is mainly because a lot of
samples were measured in the Manabí area,
and these samples probably belong to younger
formations and not to the Piñón Formation.
Reynaud et al. (1999) interpret the Piñón
Formation as the remnants of an oceanic
plateau, similar as did other authors in
Colombia (e.g., Kerr et al., 1997). Kerr et al.
(2003) confirm that the Piñón Formation is
part of an oceanic plateau and state that it is
geochemically very similar to the Pallatanga
unit in the western Cordillera. This is
confirmed by Vallejo et al. (2006) who obtains
similar radiometric ages for the Pallatanga unit
as Luzieux (2006) does for the Piñón unit.
The geochemical and age similarities of the
Piñón unit with other units in the Cordillera
Occidental of Ecuador, in Colombia and in the
Caribbean, suggest that all these fragments are
derived from the same oceanic plateau
(Reynaud et al., 1999, Mamberti et al., 2003;
Kerr et al., 2002, 2003; Luzieux et al., 2006;
Luzieux, 2007; Vallejo et al., 2006).
Luzieux (2007) performs paleomagnetic
measurements on sample of the oceanic
plateau basement in the Piñón block. From this
study it can be concluded that the oceanic
plateau was formed around equatorial latitudes,
making it possible that the Galápagos hotspot,
which lays at equatorial latitudes, formed the
oceanic plateau.
1.2 The Las Orquídeas unit
“The arco Cayo”
The Las Orquídeas unit was previously named
as “arco Cayo” by Benítez (1995). It occurs
between Guayaquil (Pascuales) and the Río
Bachillero in the Cordillera Chongón–
Colonche. It occurs on top of the Piñón
Formation and consists of basaltic andesitic
porphyritic pillow lavas, columns, lava flows and volcanic breccia. They are altered to
smectite, chlorite, calcite and locally epidote
and pumpellyite, which are interpreted as
marine alteration during its deposition by
Benítez (1995).
The name “Las Orquídeas” was introduced by
Reynaud et al. (1999) as: “Las Orquídeas
member of the Piñón Formation” but, has lead
to a lot of confusion ever since. Reynaud et al.
(1999) use the name for “a thin layer of
pillowed phyric basalts” overlying the Piñón
Formation in the neighbourhood of Las
Orquídeas in Guayaquil and in the Cordillera
Chongón–Colonche. Luzieux et al (2006) also
include mafic intrusions in the Guayaquil
region and name the unit: “Las Orquídeas
Formation”. Luzieux (2007) states that the
Cayo Formation should strictly refer to
sedimentary rocks and hence the volcanic
rocks located proximal to Guayaquil are
assigned to the Las Orquídeas formation.
Luzieux (2007) also places the stratigraphic
position of the Las Orquídeas unit in doubt,
because the contact with overlying formations
is not exposed in outcrop. Reynaud et al.
(1999) argue that in the type locality, which no
longer exists, pillow basalts of the Las
Orquídeas formation are conformably overlain
by the Calentura Formation. However, a
previous study by Benítez (1995) states that no
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
4
pillows were present at the type locality.
Consequently, the samples referred to by
Reynaud et al. (1999) may have been collected
from an intrusive body, and unfortunately the
issue will never be resolved due to the
destruction of the outcrop (Luzieux, 2007).
Benítez (1995) investigates the geochemistry
of the rocks of the arco Cayo and, interprets
them as tholeiitic orogenic basalts. Reynaud et
al. (1999) investigate the geochemistry of two
samples of the Las Orquídeas member. One
has calc-alkaline affinities, while the other is
arc-tholeiitic. The rocks are LREE–enriched
and their N–MORB normalized diagrams are
very similar to those of orogenic suites. They
have a negative Nb–Ta anomaly, similar to
arc-related rocks. They have very low levels of
Y and HREE, suggesting the presence of
residual garnet in the mantle source.
Volcanic breccias covering the Piñón
Formation
Several authors demonstrate the presence of
volcanic breccia covering the Piñón Formation.
Wolff (1874 – in Labrousse, 1989) and Bristow (1977 – in Labrousse, 1989) include
these rocks in the Piñón Formation, but
Labrousse (1986) includes them in the
Calentura Formation. According to Labrousse
(1986), these breccias occur localized along
the Cerro Germania north of Guayaquil which
has the morphology of a caldera. At the base, a
mélange occurs of tholeiitic basalt blocks,
andesite or diorite bodies which are later
intrusions, pyroclastic flow deposits, welded
tuffs, coarse well cemented tuffs, blocks with
coarse ferruginous nodules (1–2 cm)
containing quartz. The contact of this part of
the Calentura Formation with the “real
Calentura Formation” is made up of a unit of
Piñón rocks rich in barite and authigenic
quartz.
Santos and Alvarado (1989) demonstrate the
presence of volcanic breccias composed of
basaltic or basaltic andesitic clasts on top of
the Piñón Formation in the Estero Arenoso,
near Guayaquil. Similar breccias are described
in the Río Guaraguao, overlying the Piñón
Formation (Vilema, 2004a, 2008). Van Melle
et al. (2008) define the name: “Las Orquídeas
member of the Calentura Formation”, for the
andesitic volcanic breccia overlying the Piñón
Formation along the Cordillera Chongón–
Colonche. Vilema (2004a, 2008) and Van
Melle et al. (2008) observe these volcanic
breccias both below and above the typical fine
grained beds of the Calentura Formation. The
relation of these breccias with the Las
Orquídeas unit of Reynaud or the Las
Orquídeas formation of Luzieux (2007) is
unclear.
Van Melle et al. (2008) investigate the
geochemistry of the breccia of: “Las Orquídeas
unit of the Calentura Formation” in the Río
Guaraguao. At the base of the formation, the
lavas have moderate Mg content (3.83–5.6
wt%), the rare elements diagram normalized to
chondrites exhibits a flat pattern, but multi-
elementary diagrams, normalized to primitive
mantle, exhibit negative anomalies for Nb and
Ta for all rocks, evidencing a magmatic arc.
Higher in the sequence, the lavas have lower
Mg content (1.3–1.9 wt%) are moderately
alkaline (5.18–7.26 wt% [Na2O + K2O]) and,
have high Si contents (> 60% wt%), displaying
features of andesites to dacites. The REE plot
normalized to chondrites exhibit light REE
enrichments and a flat pattern for heavy REE. Van Melle et al. (2008) interpret the Las
Orquídeas member as tholeiitic arc lavas,
which evolve to calc-alkaline series through
time. Another possibility is that they are
formed by partial melting of deeper parts of the
underlying oceanic plateau, as proposed by
Haase et al. (2005) for arc-lavas associated
with mid-oceanic ridges.
Allibon et al. (2008) investigates the same
rocks in the Guaraguao and Derecha rivers.
They contribute the high Mg content (6–11.5
wt%), the LREE enrichment and the high
percentage of clinopyroxene to a high
percentage of partial melting at the magmatic
source. The origin of the LREE enrichment can
be due to subduction of pelagic sediments.
They suggest an anomalous thermal regime
responsible for the high partial melting of the
plateau, which was relatively young when
subduction started (a few Ma).
1.3 The Calentura Formation
History
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
5
Thalmann (1946) defines the Calentura
member as the basal part of the Cayo
Formation. He defines the type locality as an
old quarry at Calentura, on the east side of the
Guayas River near Guayaquil. At this location
thin bedded dark-grey and black calcareous
shales and limestones occur. According to
Bristow (1976), the lithology at the type
locality consists of argillites, calcareous
argillites and sandstones which are highly
silicified and dark grey and red in colour. The
outcrop presents an old island now surrounded
by alluvium which extends for a minimum of
six kilometres in all directions. The nearest
outcrops are all of the Cayo Formation, with
the nearest outcrop of the Piñón Formation
nine kilometres to the northwest. Therefore the
designation of the Calentura outcrop as the
base of the Cayo Formation is in doubt
(Bristow, 1976).
A second outcrop of the Calentura member
described by Thalmann (1946) occurs in the
Río Paco (Pascuales area), where it overlies
Pre–Upper Cretaceous pyroclastics and
igneous intrusives. At this location, hard black
shales are found. Bristow (1976) confirms that this outcrop belongs to the basal Calentura
member of the Cayo Formation. It lies at, or
close to the base of the Cayo Formation.
Bristow further describes the presence of
breccias and tuffaceous sandstones in the Río
Paco which do not warrant the separation of
the Calentura unit as a member from the rest of
the Cayo Formation. Therefore he proposes
that the name Calentura should not further be
used.
Alvarado and Santos (1983), describe a section
of the Calentura member in the Estero Villegas
(alternatively named Estero La Mina). They
propose to keep the name Calentura as a
member of the Cayo Formation, because the
Calentura Formation can be followed as a
stratigraphical marker throughout the
Cordillera Chongón–Colonche and because it
has an age deferring from the overlying Cayo
sensu stricto member. They also note the high
amount of organic material in the fine grained
beds of the unit. Benítez (1988), investigates
the same section, but demonstrates that this
170 m thick section does not belong to the
Calentura member, but to the Cayo sensu
stricto formation, because the real contact
between the Cayo and Calentura Formation is
three kilometres more to the northeast, in La
Mina.
Santos and Alvarado (1989) mention that large
variations in thickness exist between different
sections through the Calentura unit. In the Río
Bachillero the thickness is strongly reduced
while in other areas (Estero Villegas–Paco) the
thickness is 150 metres. Benítez (1988) states
that the Calentura member does not occur in
the Río Bachillero.
Labrousse (1986) describes the Calentura
Formation at the Cerro Germania in
Guayaquil, where it covers the coarse breccia
mentioned above. He interprets the Calentura
member as distal pelagic limestones and a
proximal flysh which is commonly slumped.
Slumps indicate a paleo surface dipping to the
south.
Benítez (1990) describes the Calentura
member in the area north of Guayaquil. At this
location it has a thickness of 450 metres and it
consists of fine decimetric tobaceous turbidites
with fish remains, silicified tobaceous
claystones and micritic limestones. Coarse grained rocks like metrical white tobaceous
sandstones and conglomerates are interpreted
as turbiditic. He also observes decimetric dikes
of porphyritic rocks passing through the beds.
Because of its distinctive lithology, widespread
distribution and mappeability, Marksteiner and
Aleman (1990) suggest raising the Calentura
member to the rank of formation. They also
propose the name Chongón group, which
includes the Calentura, Cayo and Guayaquil
Formations. They still maintain the original
type locality of Thalmann (1946) for the
Calentura Formation. They state that the base
of the Calentura Formation unconformably
overlies the Piñón Formation in the Río Paco,
and that the top of the Calentura Formation is
transitional to the Cayo Formation.
Age
In the Río Paco, Thalmann (1946) found the
Cenomanian–Turonian index species
Globotruncana renzi, together with
Globigerina cretacea D’Orbigny, Guembezlina
cf. striata (Ehrenberg), G. cf. paucustriata
Albritton, G. cf. globulosa (Reuss)
Globorotalia sp., flabellammina sp., Nodosaria
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
6
sp., Bolivina sp. and Rheophax sp. and at least
two species of well preserved Inoceramus.
Thalmann (1946) therefore concluded that the
Calentura member must not be older than
Cenomanian and not younger than Turonian.
At the type location in Guayaquil Marks (1956
– in Alvarado and Santos, 1983) dated the
Calentura member as Upper Turonian based on
the Inoceramus species Inoceramus plicatus
d’orbigny, Inoceramus roemeri Karsten and
Inoceramus striatoconcentricus Gümbel.
Bristow (1976) does not agree with the age
proposed by Thalmann (1946). Most of the
determinations are tentative. Globotruncana
Renzi, which Thalmann (1946) regarded as a
Cenomanian–Turonian index marker, is now
known in the upper part of the Napo Formation
(Coniacian–Santonian) in the Ecuadorian
Oriente, associated with Globotruncana
globulosa. Guembezlina cf. striata is known in
the middle Napo Formation (Turonian). The
age has to be at least Coniacian. The same age
was proposed in the léxico estratigráfico of
Bristow and Hofstetter (1977).
Gamber et al. (1990 – in Marksteiner and Aleman, 1990) described the microfossil
assemblage at the Cerro Jordan in Guayaquil.
They report nanofossils Lithatrinus floralis,
Eiffelithus eximius, Marthasterites furcatus of
Coniacian age and Corollithion achysolum and
Lithastrinus planus of Turonian age, but the
Turonian nano fossils are probably reworked.
Ordóñez et al. (2006) described the fossil
assemblage of the Calentura Formation in the
Cordillera Chongón–Colonche in the Estero
Las Minas, Río Paco, Estero Limón, Estero
Guaraguau, Estero La Naranja, Estero La
Derecha, Estero Zamoreño, Río del Diablo,
Estero de Caña and the Río Grande. The
microfossil content is composed of sporadic
foraminifera, radiolaria and calcareous
nanofossils and some molluscs of the
Inoceramus species. The presence of
Archaeoglobigerina cretacea (Coniacian –
Lower Maastrichtian), Pseudotextularia nuttalli
(Coniacian–Maastrichtian), Hedbergella
holmdelensis (Coniacian – Lower
Maastrichtian), Whiteinella baltica (Upper
Cenomaniano – Lower Santonian), Whiteinella
archaeocretacea (Turonian – Coniacian),
Heterohelix moremani (Upper Albian – Lower
Santoniano), Whiteinella paradubia (Middle
Cenomanian – Upper Coniacian) and
Dicarinella imbricata (Upper Turonian –
Middle Coniacian), make it possible to infer a
Lower Coniacian to Middle Coniacian age for
the Calentura Formation.
Paleoenvironment
Ordóñez et al. (2006) report a marine reducing
environment because of the presence of early
formed pyrite (100–200 metres). In the more
calcareous part of the Calentura Formation,
more benthonic foraminifera occur represented
by Dentalina sp., Lenticulina sp., Bolivina sp.
y Cibicides sp. and the planktonic foraminifera
Heterohelix, Hedbergella, Whiteinella,
Dicarinella y Rotalipora. Because of the high
amount of heterohelícidos and hedbergélidos, a
continental platform environment is proposed
(100–200 metres). The rocks were deposited in
a quiet, warm and poorly oxygenated
environment, where a high amount organic
material was reduced by bacteria.
1.4 The Cayo Formation
Pioneering work
The first report of the Cayo Formation is found
in Olsson (1942 – in Thalmann, 1946). The
classical orthography used at that time was
Callo; but, the name Cayo, initially used only
locally, was used later on topographical maps,
and was also adapted for the 1:100 000
geological maps. The Cayo Formation was part
of the Kreideformation of Wolf (1874 – in
Bristow and Hofstetter, 1977) or the
Formación cretácica del Litoral (Wolf, 1892 –
in Bristow and Hofstetter, 1977). Wolf
recognized limestones, silicic limestone,
silicified beds, quartzite, yellow sandstone,
green sandstone and claystones in the
formation.
The type locality was defined by Olsson (1942
– in Thalmann, 1946) at the shoreline
southwest of the village of Callo (at present
times named Puerto Cayo). From its type
locality the Cayo Formation can be followed through the Cordillera Chongón–Colonche
towards the southeast in Guayaquil. North of
Puerto Cayo there are isolated outcrops of the
Cayo Formation between Jipijapa and Cerro de
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
7
Hojas west of Portoviejo. Thalmann (1946),
geologist of the International Ecuadorian
Petroleum Cooperation (I.E.P.C.), made an
important contribution to the stratigraphy of
the Cayo Formation. The following is cited
from his work:
The geologists of the International Ecuadorian
Petroleum Company have made a two-fold
subdivision of the Upper Cretaceous beds in
western Ecuador, that is, the coastal region
west of the Andean ranges. The lower part,
Callo Formation, is a series of compact well
bedded dark green to greenish gray tuffs
weathering pale green to ash gray, grits, and
sandstones made up of fine breccias of
volcanic material. The sediments are hard and
erosion resisting, and reach a thickness
between 10,000 and 11,000 feet. The type
locality is situated along the southern shore of
the Callo Bay, Manabí province. Excellent
exposures can be studied in the Sierras de
Chongón and Colonche, which stretch in the
form of a boomerang-shaped arch, 8
kilometres broad, from Guayaquil as far as the
sea coast north of Salango
According to Thalmann (1946) the Cayo
Formation is only 500 feet thick in the Manabí
area.
Early stratigraphical work
Sutton (1959), geologist of the I.E.P.C.,
studied the Cayo Formation in the Río
Bachillero. He was the first author to make an
entire cross-section through the formation. The
contact with the Piñón Formation was not
observed. He encounters agglomerates and
lapilli tuffs at the bottom of the Cayo
Formation, near the contact of the Piñón
Formation and states that this is an evidence
for continued volcanic activity after the
deposition of the Piñón Formation. The contact
with the overlying Guayaquil Formation is
gradational. The depositional environment of
the basal part was either terrestrial or
subaqueous since there is little rounding of the
ejecta. The later sedimentation was subaqueous
and shows an increasing amount of rounding
and a decrease in the size of the transported
material. The bedding is fairly even and little
cross-bedding is observed. He describes the
Cayo Formation as follows:
The Callo formation is a monotonous
succession of thin to massive beds of
sandstone, claystones, conglomerates, cherts,
tuffs and agglomerates. The sandstones and
conglomerates range from boulders (3 feet)
down to silt size particles. The composition of
the conglomerates which occur in the bottom
third of the section are 90 % igneous material
with the other 10 % made up of claystones,
sandstones and some cherts. The sandstones
are olive drab to brown in colour and contain
small igneous rock fragments as well as other
igneous minerals. Quartz is the most abundant
with lesser amounts of calcite, pyroxene,
plagioclase, hornblende, magnetite and some
garnets. The thickness of the beds ranges from
50 feet near the bottom of the section to only a
few inches near the top. The claystones are
very hard and well bedded and break with
conchoidal fractures while some exhibit
fissility and can be called shales. The colour of
these beds ranges from a very light cream to
olive-drab. The average thickness is two feet
and near the top they contain microfauna. The
cherts are grey to black, even to warbly
bedded, and from a few inches to two feet in
thickness. The cherts of the Callo formation differ very little from the overlying series of the
Guayaquil cherts. The tuffs are hard, silicified,
and green to bluish-gray near the bottom of the
series while at the top they are soft, white and
calcareous. The thicknesses range from 20 feet
to stringers and inch thick which separate
chert beds. The agglomerates are restricted to
the lower portion of the series and reach
approximate thickness of 400 feet. They are
characterized by a greenish colour and contain
up to cobble-size of basalt and other related
rock fragments and crystals. The matrix is
crystalline to vitric tuff.
The thickness obtained by Sutton in the Río
Bachillero was 8000 feet.
Bucaram (1966) gives a similar description of
the Cayo Formation. He distinguishes between
volcanic agglomerates at the lower part of the
formation and conglomerates in the upper part.
Agglomerates can locally attain thicknesses of
about 125 metres and are usually green to
greenish-gray and black, and composed of
small cobble-size basalt and related igneous
rock fragments and, crystals with some
associated angular lapilli ejecta.
Conglomerates in the upper part of the
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
8
formation are composed of up to 90 % basalt
clasts. Large boulders up to 120 centimetres in
diameter to fine grained sandstones occur.
Goossens and Rose (1973) state that the Cayo
Formation is composed of shales, siliceous
tuffs with a large amount of glauconite
(Denayer, 1968, written communication in
Goossens and Rose), chert, sandstone, and
mafic pyroclastic rocks.
In the article “The age of the Cayo Formation”,
Bristow (1976) describes the formation as
3000 metres of argillites, tuffaceous
sandstones, tuffaceous conglomerates,
greywackes, agglomerates and volcanic
breccias. The volcanic material is dominant in
the lower part of the sequence and there is
often a basal breccias at the junction with the
Piñón Formation which everywhere underlies
it. The argillites are the dominant lithology of
the succession and are often silicified. At the
top there is a gradual passage into the silicified
and chertified sediments of the overlying
Guayaquil Formation.
Feininger and Bristow (1980) demonstrate the presence of volcanic breccia of intermediate to
basic composition at the base of the Cayo
Formation. The entire lower part is dominated
by green tuffaceous sandstone and wacke.
Higher in the section, the Cayo Formation is
less volcanic, and argillite and chert are the
prevalent rock types at the top of the
formation. They state that the source of the
Cayo Formation is the Macuchi arc in the
Western Andean Cordillera. Feininger (1986)
described the Cayo Formation volcaniclastic
and sedimentary apron deposited on the sea
floor behind the Macuchi arc.
Alvarado and Santos (1983) described a
complete section of the Cayo Formation in the
Estero el Arenoso. They propose to abandon
the type locality of the Cayo Formation in
Puerto Cayo and to define a new type locality
at the Estero el Arenoso. The thickness of the
Cayo Formation is 2400 metres.
The first 70 metres of the formation consist of
porphyritic volcanic rocks, stratified, green in
colour, alternating with greenish grey calcite
rich claystones and limestones. From 70 to 450
metres the section consists mainly of hard dark
grey grauwackes, with fine intercalations of
greenish gray clay stone. From 450 to 530
metres greenish grey claystones occur, and
from 530 to 800 metres, the section is not
exposed. From 800 to 1000 metres,
grauwackes occur with thin intercalations of
clay stone, sometimes rich in calcite. From
1000 to 1180 metres grey hard silicified
claystones occur, intercalated with two levels
of grauwackes of 30 metres thick. Between
1180 and 1245 metres a conglomerate occurs
with volcanic fragments up to five centimetres
and a sandy matrix. From 1245 to 1410 metres
grauwackes occur. From 1410 to 1570 metres
claystones with thin intercalations of
grauwacke occur. From 1570 to 1930 metres
grauwackes and conglomerates alternate with
thin beds of silicified claystones. From 1930 to
2170 metres green silicified lutites occur and at
2170 metres lenticular nodules of dark-
coloured chert occur till 2400 metres. At this
point the top of the formation is in discordant
contact with the San Eduardo Formation. They
consider the inferior part as the Calentura
member, the middle part as the Cayo sensu
stricto member and the upper silicified part as
the Guayaquil member.
Santos (1983) described the Calentura
Formation as calcareous sedimentation, and the
Cayo Formation as detritic sedimentation.
During the deposition of the Cayo Formation,
“invasions” of volcanic lavas occurred, but
only in the Manabí area.
Benítez (1983) describes the Cayo Formation
as erosion of a continental volcanic arc. He
performs a petrographical study.
“Conglomerates” are lapilli tuffs, deposited in
a marine environment. He encounters samples
with 100 % volcanic fragments among which
are vitric lavas, compact or vesicular, of
basaltic or andesitic composition. The fine
material of the same rocks is hyaloclastic.
Sandstones are tuffs or tuffaceous sandstones,
deposited in turbiditic currents and show
typical Bouma sequences. Clay stones are
composed of vitric material, solidified before
the ultimate deposition and mixed with marine
sediments and microfauna. Benítez (1983)
described the cyclical deposition of the Cayo
Formation. He interprets the cycles as periods
of submarine volcanic eruptions or marine
deposits of eruptions of volcanic arcs. He also
observes a double size grading of the beds,
which requires a deep marine deposition.
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
9
Lapilli are deposited quickly, sand sized tuffs
fall more slowly and are transported by
turbidity currents, fine ash is sedimented
slowly, pumice floats and is dispersed by
currents.
Lebrat et al. (1987) described the Cayo
Formation as turbiditic series comprising thick
debris flows including blocks, cobbles, and
pebbles of volcanic rocks ranging from
andesite to rhyolitic welded tuffs. According to
them the volcaniclastic layers overlying ocean
floor (Piñón Formation) where issued from the
Macuchi island arc. They define the San
Lorenzo Formation in the Manabí area
consisting of a limited amount of island arc
tholeiites erupted on top of the Piñón oceanic
floor and isolated from the Macuchi arc.
Benítez (1988) investigated the Cayo
Formation in the Río Bachillero. The thickness
is 1900 metres. The Calentura member is not
present in the section. Benítez (1988)
attributed a turbiditic origin of the deposits and
recognized similar sequences as described later
in Guayaquil (Benítez, 1990). The Cayo
Formation is interpreted as prograding lobes of a marine fan. The basal part of the section is
230 metres thick and contains the thickest
sequences of the section (decametric). The
middle part is 950 metres thick and consists of
prograding sequences with a general decrease
in thickness towards the top of this part of the
section. The upper part is 160 metres thick and
contains a “slump” facies. This corresponds to
the internal part of the fan (upper fan). The
entire formation is volcanoclastic, but in the
upper 160 metres an increase in organic
material is observed, and algal fragments are
found. Benítez (1988) reports a main
paleocurrent of N260 towards the west in the
Río Bachillero. The depositional depth is
between 500–1000 m (external platform to
upper bathyal). Compared to the Guayaquil
region, the Cayo Formation is more sediment-
rich in the Río Bachillero (Benítez et al., 1996)
According to Labrousse (1986), in Guayaquil
the Cayo Formation consists at the base of
thinly bedded chocolate-coloured claystones,
alternating with 0.5–5 metre thick greenish
sandstones. The first debris flows consist of
andesitic blocks only. The Cayo Formation is
composed of four superimposed “terms”. The
basal term is a thick “debris flow” with angular
“cinerites” green or white of tuffs, green
claystones and brown sandstones. The second
term is a greenish grain flow separated from
the lower unit by an erosive surface. The third
term consists of green “cinerites” and white
tuffs. He interprets the third term as
pyroclastics reworked by sub-marine currents.
The forth term are abyssal claystones.
Labrousse (1986) interprets the Cayo
Formation as a submarine fan, situated on the
paleotallud of a volcanic arc, the Macuchi arc.
Redefinition of the type locality in
Guayaquil
Benítez (1990) suggests moving the type
locality of the Calentura, Cayo and Guayaquil
Formations to the region of Guayaquil,
because in this area, the three formations are
very well exposed. Benítez (1990) described
four types of sequences in the Cayo Formation
in the Guayaquil area:
Type 1: Decametric sequences (Ta, b) with
grain size classification conglomerates or
breccia at the base, grading into sandstones or
siltstones at the top of a sequence. The base of a sequence is generally planar, but can be
erosive too, indicating deposition in channels.
He named those sequences megaturbidites.
Type 2: Metric sequences consist of sandstone
at the base, siltstone at the top. They can be
massive at the base and laminated at the top
(terms a and b of Bouma). The base is
generally flat.
Type 3: Decimetric sequences contain micro-
stratification and convolute bedding. These
structures are not very common, decimetric
sequences consist mainly of Ta,b or maximum
Tab,c.
Type 4: Fine grained sequences. Silicic or
calcareous lutites with a microfauna of
foraminifera and radiolaria. They can be
tobaceous. They are interpreted as fine
turbidites.
He divides the Cayo (sensu stricto) Formation
in the region of Guayaquil into four members,
depending on the amount of fine grained rocks.
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
10
Unit C4 is 770 metre thick and consists mainly
of coarse “megaturbidites” of the following
lithologies:
- metric to decametric breccias formed
by spilitic andesitic rock fragments,
- turbiditic metric to decametric
sandstones,
- tobaceous claystones intercalated in
lower amounts,
- spilitic choritized sandy tuffs
composed of crystal clasts and glass,
- igneous dikes, metric to decimetric.
He correlated this unit with a 220 metre thick
unit of decametric megaturbidites in the Río
Bachillero. He states that the weathering of
pyroxenes shows that the rocks have a
subaereal origin.
Unit C3 is 580 metre thick and consists
predominantly of fine grained rocks, with
intercalations of metric sandstones. The base
of this unit (at the American college) consists
of 20 metres of pelites, which were dated as
Coniacian with the planktonic foraminifera
Globotruncana cf. renzi (Ordóñez). This level
can be laterally followed to Peñon del Río, the original type locality of the Calentura
Formation as defined by Thallman (1946), who
attributed a Middle Turonian to Coniacian age
with Marginotruncana cf. Renzi. However, the
assemblage should be reinterpreted as
Coniacian with Globotruncana cf. renzi
(Ordóñez). Inoceramus fragments dated as
Turonian by Marks (1956 – in Benítez, 1995)
are probably also of younger age. As this part
overlies the C4 unit, and as the underlying
Calentura Formation is of Coniacian age,
Benítez (1995) stated that the basal part of the
Cayo Formation is also of Coniacian age.
Unit C2 is 630 metre thick and consists of
decametric mega turbidites of 10–20 metre
thick. They are composed of micro breccias at
the base with a greenish colour, very hard in
fresh state, and yellowish brown when altered.
They are intercalated with decimetre thick
silicic tobaceous claystones and metric
lithofeldspatic sandstones. The green colour is
caused by chloritization. Benítez (1996) is the
first author to describe this unit
microscopically. The grauwackes are
lithofeldspatic with a smectitic or vitric matrix.
The volcanic fragments are andesitic basalts,
vesicular to fluidal dacites, dacitic perlites,
vesicular lavas with pumpellyite, and
fragments of molluscs.
Unit C1 is 280 metre thick and consists of
decimetre thick fine grained beds. The beds are
composed of tobaceous claystones and fine
decimetric turbidites. They are intercalated
with decimetric to metric sandstones and mega
turbidites. Even near the contact with the
Guayaquil Formation, mega turbidites occur.
To describe the vertical variation through the
Cayo Formation, Benítez (1990) differentiates
between two types of sequences: A–sequences
present a decrease in thickness and grain size.
They are mainly channels and are deposited
proximal to the source area. They occur mainly
in the C2 to C5 members of the Cayo
Formation. E–sequences: are coarsening
upwards and increase in thickness. They
characterize deposits of a more distal fan.
Benítez (1990) sees an increase in A: E ratio
towards the top of the Cayo Formation, which
he interprets as more proximal facies towards
the top of the formation. He interprets the
Cayo Formation to be deposited in the middle
part of a submarine fan.
Marksteiner and Aleman (1990) describe
thinning and fining cycles in the Cayo
Formation in the Guayaquil region with
scoured bases interpreted as submarine
channels. Marksteiner and Aleman note that
some shales may represent ash-fall tuffs and
other tuffaceous sediments with abundant
silica cement are derived from devitrification
of volcanic glass. Sandstones are cemented
with zeolites, chlorite and calcite.
Agglomerates are common with hyaloclastic
breccias present in the lower part of the
section. Basaltic and basaltic andesitic lavas
occur but are sometimes difficult to distinguish
from sills. Some of the volcanoclastic
sandstones and conglomerates as well as the
lava flows show indications of greenschist
metamorphism. The composition of the
sandstones (tuffs) varies from volcanic lithic
rich to feldspar rich. Some of them contain
abundant pumiceous fragments (vitric rich).
The volcanic fragments vary from vitric to
lathwork and the plagioclase varies from
intermediate to high anorthite contents and can
be zoned.
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
11
Gamber et al. (1990) interpret the formation to
be deposited subaqueously by sediment gravity
processes similar to those described elsewhere.
The sediments were derived from the erosion
or contemporaneous volcanic activity of an
immature arc building subaerially or
subaqueously. Deposition took place from
turbidity currents and debris flows in the deep
marine to slope environment. Several thinning
and fining upward cycles and erosional
scouring suggest the existence of deeply
incised channels, and the documentation of
discrete thickening and coarsening cycles
could be indicative of a middle fan
environment. However, this facies might
represent a response to volcanic activity and
rate of sediment input rather than depositional
processes.
Wallrabe-Adams (1990) states that the contact
between the Piñón and Cayo Formation is
mostly unconformable. Most of the Cayo
Formation consists of a variety of
volcaniclastic rocks (breccias, conglomerates,
fine grained tuffs) with rare sedimentary
intercalations. Subordinate effusive volcanic
rocks are restricted to the lower part, consisting of submarine lavas (partly pillowed) and sub-
volcanics. In contrast to the Piñón Formation,
vesicular textures are common, possibly
indicating emplacement at a lesser water depth.
Near Puerto Cayo the formation is dominated
by volcanoclastic rocks with some intercalated
lavas and sedimentary rocks. Near Guayaquil
the abundance of sediments increases upward
within the volcaniclastic sequences. The
uppermost unit in Guayaquil, the Guayaquil
unit consists of cherts. Most of the volcanic
rocks of the Cayo Formation are layers of
massive lavas of a few metres thick, but some
pillow lavas are present. In addition, sub-
volcanic rocks occur as large volcanic stocks
or discordant dykes. Pillow lavas are filled
with a mixture of celadonite (and/or saponite),
calcite and quartz. Massive lavas and pillow
lavas are porphyritic with only rare fluidal
textures. Sub-volcanic rocks are medium or
seldom coarse grained and holocrystalline. The
main constituents are plagioclase (andesine–
labradorite), augite and some hypersthene. No
amphibole or olivine is present. Wallrabe-
Adams only refers to the Guayaquil Formation
as sedimentary. Wallrabe-Adams (1990)
interprets the Cayo Formation as
volcaniclastic-epiclastic beds, partly build up
from the erosion of the Macuchi island arc.
Jaillard et al. (1995) interpret the Cayo
Formation as a 2000 metre thick succession of
fining-upwards, coarse grained volcaniclastic
sandstones and conglomerates, including a
spectrum from high- to low-density turbidites
with shaly intercalations. The Coarse grained
sedimentation contrast markedly with the
underlying fine grained deposits and indicate
that an important geodynamic change occurred
by Late Coniacian – Early Santonian time.
Reynaud et al. (1999) describe the Cayo
Formation as 2000 metres of turbiditic shales,
greywackes and conglomerates.
Luzieux et al. (2006) defined the Cayo
Formation as a 2000–3000 metre thick series
of debris flows and turbidites, which display a
general upwards thinning trend. Coarse debris
flows at the base of the formation may be
synchronous with volcanic activity, but there is
no clear evidence for arc activity until the end
of the Cayo Formation. Part of the sequence
could be derived from the erosion of a non-
active arc.
Luzieux (2007) described the Cayo Formation,
as typically repeated thinning and fining
upward sequences of light olive green-
coloured, volcano-derived debris flows and
silicified turbidites. The coarse, less silicified
basal beds, with bed thicknesses of
approximately one to five metres, often show
concentric, onion-type weathering structures.
Most of these beds show a bimodal grain-size
distribution, although upward grading (T) and
laminar bedding (Tb) can sometimes be
observed at the top of the beds. The upper part
of the sequence is characterized by silicified,
decimetre to centimetre scale thick turbidites,
which regularly show T to T, Bouma–
sequences, although T structures can be
occasionally observed. The wavy aspect
sometimes observed between beds is due to
“boudinaging” caused by the irregular
diagenetic compaction of the siliceous
sediments.
Luzieux (2007) estimated the maximal
thickness of the Cayo Formation at Guayaquil
to be approximately 2400m. The formation
thickness decreases gradually towards the
northwest, and the formation disappears in the
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
12
area of Portoviejo–Manta. The Cayo
Formation is generally more silicified in the
Piñón Block than elsewhere and contains only
a few pumice clasts, which are commonly
observed in more northern exposures. The with
the Calentura Formation contact cannot be
observed, but similar regional dips observed in
both formations indicate either a conformable
to para-conformable nature. The lower part of
the series is mainly composed of angular to
sub-angular volcanic clasts, embedded into a
matrix of smaller volcanic fragments of ortho-
and clinopyroxene, hornblende, plagioclase,
oxides and volcanic glass.
Luziex (2007) stated that the Cayo Formation
becomes finer grained towards its upper part,
which is accompanied by a gradual increase in
the fraction of bioclasts, which become
dominant at the top of the formation. Sponge
spicules and radiolarian skeletons are mainly
responsible for siliceous cementation in the
upper part of the Cayo Formation. Both
benthonic and planktonic foraminifera are also
present. The planktonic foraminifera have
abnormally thin tests, which are often broken
and squeezed due to sediment compaction. The abundance of millimetre to centimetre wide
burrow structures towards the top of the
formation is indicative of significant
bioturbation activity. The overall fining
upward trend observed in grain-size and
bedding thickness probably reflects the
progressive erosion of the volcanic arc source
area. However, deepening of the basin due to
general subsidence (associated with
submergence of the sourcing arc), may also
have contributed to the fining upward trend.
The smaller, second–order fining upward
cycles are interpreted to be the result of lateral
migration of mid- and lower fan depocenters in
a deep-sea environment.
Age
The age of the Cayo Formation determined by
Thalmann (1946) in the Guayaquil region is
Upper Cretaceous, as confirmed by other
authors in other regions (Sutton, 1959;
Bucaram, 1966; Feininger, 1986) and more
specifically Senonian (Turonian–
Maastrichtian), as is confirmed by Bristow
(1976). A further specification could not be
made, because of the lack of good
foraminiferal assemblages. According to
Marksteiner and Aleman (1990) the Cayo
Formation might be of Late Turonian to Early
Maastrichtian age. Gamber et al. (1990)
identified the presence of dinocysts of Late
Santonian to Maastrichtian age in the Cayo
Formation, although these beds could belong
to the upper Calentura Formation.
In more recent biostratigraphical work, the age
is refined. Ordóñez et al (2006) described the
microfossil assemblage of the Cayo Formation
in the Cordillera Chongón–Colonche. The
microfauna is composed of foraminifera,
calcareous nanofossils, dinoflagellata,
radiolaria and palinomorphs. A Middle
Campanian age was determined, with
radiolaria as guiding fossils Pseudoaulophacus
lenticulatus (Middle Campanian), Vitorfus
morini (Campanian) and Amphipyndax tylotus
(Middle Campanian – Maastrichtian). Gomez
and Minchala (2003) dated the Middle Cayo
Formation (right above the Lower Cayo
Formation) in the Río Derecha as Middle
Campanian. Luzieux et al. (2006) dated the
middle and the upper part of the formation at
two locations. The following associations were
observed:. 1.- Radotruncana subspinosa, Rugotruncana subcircumnodifer,
Globotruncana aegyptiaca, Globotruncana
linneiana (M. Caron); and. 2.- Abathomphalus
intermedius, Globotruncanita stuarti,
Radotruncana subspinosa, Globotruncana
linneiana, Globotruncanita species (Caron – in
Luzieux et al., 2006). These associations
correlate with the Middle–Late Campanian.
Paleoenvironment
As indicated above, various authors interpret
the deposits of the Cayo Formation as formed
on the talud of an active or inactive volcanic
arc. Although previous authors suggested that
the source of the Cayo Formation was the
Maccuchi Formation, which crops out in the
western Cordillera, it is now known that the
Maccuchi arc is of much younger Paleocene to
Eocene age (Vallejo et al., 2006). Ordóñez et
al. (2006) interpred the paleoenvironment
bathyal, based on assemblages of benthic
foraminifera, radiolaria and dinoflagellata.
Jaya et al. (2006) interpreted the rocks of the
Cayo Formation as back-arc deposits because
of the caesium anomalies they encounter in the
rocks. Luzieux (2007) states that the source
area must have been in the east, but as
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
13
sediment deposition can occur both parallel as
orthogonal to the arc axis, it is difficult to
know if it was deposited in the arc area or in a
back-arc environment. From the study of
heavy mineral assemblages Luzieux (2007)
states that all Cretaceous formations are devoid
of continent derived heavy minerals indicating
that the Cayo Formation was deposited in a
intra oceanic volcanic arc. Van Melle et al.
(2008) attributed the deposits of the Cayo
Formation as formed from the erosion
associated to the growth of a nearby arc and
interpret the Cayo Formation as a back-arc
deposit.
1.6 The Guayaquil Formation
Thalmann (1946) distinguished the Cayo
Formation from the overlying Guayaquil
Formation and correlated the Guayaquil and
Santa Elena Formation, which occurs towards
the south in the Santa Elena Peninsula. The
type locality is defined by Thalmann (1946)
and Sheppard (1946) in the old neighbourhood of Ferroviaires a San Pedro in Guayaquil, but
the old type section is removed by
urbanization.
The contact with the overlying part, the
Guayaquil formation (Guayaquil chert series),
is gradational, as shown where the coarse
clastic and tuffaceous sediments of the Callo
formation pass upwards into cherts with tuffs.
The Guayaquil formation is composed
essentially of silicified tuffs with thin-bedded
buff to black cherts and thin partings of hard
dark grey tuffaceous shales, reaching about
1500 feet in thickness in the Sierras of
Chongón and Colonche, and, under the name
of “Santa Elena cherts” in the Santa Elena
Peninsula, attaining a thickness of 2000 feet.
The type locality of the Guayaquil formation is
opposite the bridge over the Estero Salado at
the western exit of the town of Guayaquil.
…
It is found in the Sierra de Chongón and
Colonche from Guayaquil as far west as the
headwaters of the Río de la Pampa (about 80
kilometres west of Guayaquil). The highly
fractured, hard and brittle, buff, light gray and
white siliceous tuffs with veins or stringers of
chalcedony and black or gray “augen”–
growth chert, known as the “Santa Elena
cherts” in the Santa Elena Peninsula-, are an
age-equivalent of the Guayaquil formation.
Locally they include thin sandstone beds made
up of volcanic material and greenish or dark
greyish shales. The maximum thickness is 2000
feet.
…
In western Ecuador, Manabí province, the
Guayaquil formation reaches a thickness of
4500 feet and is composed mainly of thin chert
beds with seams of tuffaceous shales,
siliciceous ash, and tuffs. Good outcrops can
be observed in the Río Mariano, in the Río Viti
and along the borders f the Jama–Cuaque
Mountains.
Thalmann (1946) attributed the paucity of
microfossils largely to the great volcanic
activity which prevailed during the end of the
upper Cretaceous time in western Ecuador.
The high degree of silicification of the water
laid tuffs (percolation of siliceous solutions)
was undoubtly a greatly destructive ecologic
factor in the biofacies of the sediments.
Nevertheless Thalmann (1946) believed that a
Maastrichtian age can be attributed to the
Formation.
Bristow (1976) stated that since much of the
silicification is secondary (Sinclair and Berkey,
1924 – in Bristow, 1976), it is presumed that
the level of silicification is not always the same
and it is thought that the Cayo-Guayaquil
contact is not everywhere of the same age.
This is supported by the fauna. For this reason
Bristow proposes to relegate the Guayaquil
Formation to member status at the top of the
Cayo Formation. In the léxico estrátigrafico of
Bristow and Hofstetter (1977), the Guayaquil
Formation is considered as the upper member
of the Cayo Formation.
Sigal (1969 – in Bristow, 1976) recorded a
Maastrichtian fauna in the Soledad–Buena
vista area at 20 kilometre SSE of Puerto Cayo.
The lithology of silicified argillites pertains to
the Guayaquil member and Sigal has suggested
that the planktonic foraminifera (small
globigerinas seen in thin section) may be as
young as Danian.
Marksteiner and Aleman (1990) demonstrated
the important volcanic contribution to the
rocks of the Guayaquil Formation. Benítez
Appendix 1 – Stratigraphy of the Late Cretaceous deposits: previous work
14
(1988) proposed to raise the Guayaquil
member to formation.
Benítez (1990) proposed a new type section of
the Guayaquil Formation along the Via
Perimetral in Guayaquil. Benítez distinguished
two members:
- Lower member: alternation of black
pelites of centimetre to decimetre
thickness which are silicified to
nodules of silex, and subordinary
brown, tuff-like siltstones. The
thickness is 85 metres in Bellavista.
The benthic foraminifera Bolivinoides
draco draco indicate a Late
Maastrichtian age (M. Ordóñez in
Benítez, 1990). The Cretaceous–
Tertiary boundary occurs 35 metres
from the top of the lower member.
- Upper member: occurs in the
Hormigonera quarry in Guayaquil. At
the base it is composed of tuffs with
calcite cement in centimetre to metre
beds. Higher in the section, pelites
occur. The member is 240 metres thick.
The depositional setting is interpreted as
bathyal (200–2000 metres) by Unocal (1987–
in Benítez, 1995).
Luzieux (2007) finds rounded zircons in the
Guayaquil Formation which indicate a
continental attribution, meaning that the Piñón
block was approaching, or was already
accreted to the South American margin.
Appendix 1 – Stratigraphy of the Late Cretaceous deposits – previous work
15
References
Only the references which were not given in
the List of References of the main text, are
given here.
Allibon, J., Monjoie, P., Lapierre, H., Jaillard,
E., Bussy, F., Bosch, D., Senebier, F., 2008.
The contribution of the young Cretaceous
Caribbean Oceanic Plateau to the genesis of
Late Cretaceous arc magmatism in the
Cordillera Occidental of Ecuador. Journal of
South American Earth Sciences, 26: 355-368.
Alvarado G., Santos M., 1983. El Miembro
Calentura y la Formción Cayo. Tercer Congreso
de Geología Minas y Petróleo. 13 p.
Bristow, C., 1976. The age of the Cayo
Formation, Ecuador. Newsletters on
Stratigraphy, 4: 169-173.
Bristow, C., Hoffstetter, R., 1977. Lexique
stratigraphique International. Volumen V.
Amerique Latine (Sous La Direccion de R
Hoffstetter.). Facicule 5 a 2. Ecuador.
Deuxième Edition par C.R. Bristow et R
Hoffstetter avec la collaboration de T.
Feininger et M.T. Hall.
Bucaram, R., 1966. Reporte Geológico de la
Costa Ecuatoriana. Ministerio de Industrias y
Comercio, Asesoria Tecnica de Petroleos,
Quito, Ecuador. 13p.
Feininger, T., 1986. Allochthonous terranes in
the Andes of Ecuador and northwestern Peru.
Canadian Journal of Earth Sciences, 24: 266-
278.
Feininger, T., 1986. Allochthonous terranes in the Andes of Ecuador and northwestern Peru. Canadian Journal of Earth Science, 24, 266-278.
Gamber, J.H., Barker, G.W., Stein, J.A., Carney, J.L., Geen, A.F., Krebs, A.F., Salomon, R.A., White, R.J., 1990. Biostratigraphic report on Coastal Ecuador. Unpublished report of Amoco, Guayaquil, Ecuador. 65 p.
Goossens, P.J., Rose, W.I., 1973. Chemical
composition and age determination of tholeiitic rocks in the basic Cretaceous Complex,
Ecuador. Geological Society of America
Bulletin, 84: 1043–1052.
Goossens, P.J., Rose, W.I., Flores, D., 1977.
Geochemistry of tholeiites of the Basic
Igneous Complex of Northwestern South
America. Geological Society of America
Bulletin, 88: 1711–1720.
Haase, K.M., Stroncik, N.A., Hékinian, R. &
Stoffers, P. 2005. Nb-depleted andesites from
the Pacific-Antarctic Rise as analogs for early
continental crust. Geology, 33, 921-924.
Santos, M. N., Alvarado, G.S., 1989. Informe
geológico. Bordes de la subcuenca Manabí.
Unpublished report of CEPE, Ecuador. 44p.
Sutton, E.H., 1959. Geology of the Colonche
hills, Julio Moreno and Los Pocas area,
progresso basin, guayas province – Ecuador.
Unpublished report of California Ecuador
Petroleum Company. Guayaquil, Ecuador. 71
p.
Lebrat, M., Mégard, F., Juteau, T., Calle, J.,
1985. Pre-orogenic volcanic assemblages and structure in the Western Cordillera of Ecuador
between 1°40’S and 2°20’S. Geologische
Rundschau, 74 (2): 343-350.
Appendix 2 – Field and sample locations
17
This appendix is included at the end of this pdf
All GPS coordinates are in the coordinate Prov. S. Am. 1956. All data fall in the UPM zone 17s.
APPENDIX 2 – FIELD AND SAMPLE LOCATIONS
Appendix 3 – Methodology for mineralogical characterization
19
3.1 Sample preparation for X-ray
diffraction
Micronizing of the sample
- Take representative amounts of sample (50-
100 g). Crush the sample by hand in a
porcelain mortar. Use shock impact for
grinding, avoid shearing. Pass the entire
sample through a 500 µm sieve.
- Pre-hydrate the sample in an equilibration
chamber of 52% relative humidity for at least
16 hours to achieve complete hydration of all
zeolites, to minimize weighing errors. This
equilibration chamber can be easily
constructed with a standard laboratory glass
dessicator and an oversaturated
Mg(NO3)2.6H2O solution.
- Weigh 2.7 grams of sample; add 0.3 g (10%)
of ZnO internal standard. Note down the exact
weights.
- Micronize the samples in a McCrone
Micronizing mill using 5 ml of methanol as
grinding agent and a grinding time of 7.5
minutes.
- After micronizing, recuperate the sample in
porcelain cups. Cover the cups with plastic foil, because recovery of powder from the
porcelain is difficult. Wash with methanol to
recuperate as much as possible of the sample.
- Dry for one-two days under a fume hood
(methanol is toxic). Do not use any extra
heating to speed up drying (oven).
Preparation for X-ray diffraction
- Dried samples are gently disaggregated in an
agate mortar and passed through a 250µm
sieve, to ensure good mixing of sample and
ZnO standard.
- To ensure that samples are ground up to < 10
µm, the size required for X-ray quantification,
the grain size is checked by (wet) laser
diffraction analysis.
- +/- 0.5 g of sample is needed for the X-ray
analysis. Side-loading with frosted glass is
recommended to fill sample holders, to prevent
preferential orientation of fibrous zeolites and
clay minerals. Sample holders are gently
tapped while filling, to ensure good packing of
the grains. Alternatively, back loading is used.
- Samples (in sample holders) are pre-hydrated
at 52% relative humidity for at least 16 hours
to prevent peak-shifts caused by dehydration.
If swelling occurred (surface is not flat
anymore), sample holders are refilled.
X-ray measurement
The following parameters were used for X-ray
measurement:
Philips PW1830 diffractometer with
Bragg/Brentano θ – 2 θ setup, CuK radiation,
45kV and 30 mA, graphite monochromator,
receiving slit width: 1 mm; divergence slit
width: 1 mm. Antiscatter slit width: 0.1 mm,
stepscan or continuous scan.
- Scan range: 3-70° 2θ.
- Stepsize: 0.02° 2θ.
- Time/step: at least 2 seconds, longer than 5
seconds is not recommended, because of
possible dehydration of the zeolites during the
measurement.
APPENDIX 3 – METHODOLOGY FOR
MINERALOGICAL CHARACTERIZATION
Appendix 3 – Methodology for mineralogical characterization
20
3.2 Methodology for cation
exchange capacity measurements
of zeolitic rocks
Method
Method of Vassilieva & Machiels modified
from Kitsopoulos (1999).
Principle
The AMAS method involves the saturation of
the zeolite with ammonium (NH4+) ions that
replace exchangeable cations. The number of
NH4+ ions retained by the zeolite, is a measure
of the CEC. There are four steps: 1) NH4OAc
saturation and cations exchange; 2)
measurements of cations in solution by AAS;
3) release of NH4 and generation of NH4
solution; 4) measurements of NH4+ in solution
by Nessler.
Standard Reference Material
Th 002 CEC Ca Mg K Na
meq/1
00g
d.w.
160 40 10 82 28
Reagents
1. Ammonium acetate NH4Ac, 2M. Dissolve
154 g of C2H7NO2, p.a. in 1000ml DW
2. Sodium Chloride 10% acidified with HCl to
0.005M. Dissolve 100g of NaCl, p.a. in
some DW, add 0.5ml HCl conc. and make
up to 1000 ml with DW.
3. Ca, Mg, K, Na Standard stock solutions
1000 ppm for AAS.
4. NH4 Standard stock solution 1000 ppm:
Dissolve exactly 1.4878 oven dried (105°C)
NH4Cl p.a. in some DW. Make up to 500
ml.
5. NH4 Standard solution 10 ppm: Prepare
fresh! Take 1ml of NH4 1000ppm and make
up to 100ml with DW. 6. Nessler reagents: Dissolve 2.5g Potassium
Iodide (KI p.a.) in 10 ml DW. Place on the
magnetic stirrer. Add saturated solution of
HgCl2 (dissolve about 3.7 g HgCl2 p.a. in
50ml DW under strong stirring, let it stay
overnight, decant the clear solution) until
the precipitation occurs. Add 25ml of 30%
NaOH solution (30 g NaOH p.a. in 100ml).
Make up to 200 ml with DW and mix
thoroughly. The solution has to be filtered
with 0.45µm Milli-pore filters before use.
HgCl2 (mercury(II)chloride): R28: Very toxic
if if swallowed, R34: Causes burns; R50/53:
Very toxic to aquatic organisms, may cause
long-term adverse effects in the aquatic
environment; 48/24/25: Toxic: danger of
serious damage to health by prolonged
exposure in contact with skin and if swallowed;
S45: In case of accident or if you feel unwell,
seekmedical advice immediately (show the
label where possible); S60 : This material
and/or its container must be disposed of as
hazardous waste; S61: Avoid release to the
environment. Refer to special
instructions/safety data sheets. S36/37/39:
Wear suitable protective clothing gloves, and
eye/face protection; S(01/02): (Keep locked up
and out of reach of children); Hazard symbol
T+ : Very toxic
7. K, Na-tartrate 20%. Dissolve 20g of K, Na-
tartrate p.a. in 100 ml DW.
Apparatus
1. Analytical balance
2. Centrifuge tubes, Nalgene, 80ml
3. Horizontal shaker
4. Funnels
5. Volumetric flasks: 1 L, 500 ml, 200ml, 100
ml, 25 ml
6. ICP tubes 15ml 7. Automatic pipettes: 1-5 ml, 200-1000 µl,
10, 15, 20ml volumetric pipettes
8. Cuvettes for spectrophotometer
9. Spectrophotometer
1. Sample preparation
1. Samples are ground by hand in a mortar
and passed through a 125 µm sieve.
2. Place sample in centrifuge tube, add
deionised water and centrifuge 10
Appendix 3 – Methodology for mineralogical characterization
21
minutes at 4000 rpm and decanted to
remove soluble salts.
3. This procedure is repeated twice
4. Samples are dried < 40°.
5. Samples are prehydrated prior to
weighing for at least 16h in a desiccator
with a saturated solution of
MgNO3.6H2O.
2. NH4+ -saturation and HN4
+ -cations
exchange
1. Weigh 0,50g of sample in a clean centrifuge
tube. Include one reference sample and one
blank (it will serve as a matrix for standards
and as a blank for colorimetric
determination of NH4+, so you MUST
handle the blank the same way you do your
samples). Take 2 replicates for each sample!
It is important because the procedure is
quite long and complicated, the chance of
mistake is sufficient.
2. Add 20 ml of NH4OAc 2M.
3. Mount the tubes on the horizontal shaker
and let it shake for 24 hours
4. Centrifuge 10 minutes at 4000 rpm
5. Decant the supernatant carefully in 100ml
flask.
6. Repeat the procedure (extraction with 20ml
NH4OAc) twice with the shaking time 5
days (day 5 and day 10). Collect the
supernatant in 100ml flask (one for each
sample). 7. “Wash” the residue 2 times with 10 ml
NH4OAc and collect clear supernatant in the
100ml flask. Make up to 100ml. Close,
shake to mix.
This solution (A) is to be measured by AAS for
Ca, Mg, K, Na (exchangeable cations).
3. Release of saturating NH4+
1. “Wash” the residue at least 3 times with
50ml of DW. Do not loose any residue
while poring away the rinse water.
2. Add 20ml NaCl solution, shake thoroughly
by hand, centrifuge 10 minutes at 4000 10
minutes and collect the clear supernatant in
200ml flask.
3. Repeat the procedure at least 6 times. Make
up to 200ml with DW. Close the flask,
shake to mix. Take about 15ml of the
solution and filter it with 0.45µm filter in
15ml ICP tube.
This solution (B) is to be measured for NH4+
by VIS-spectrophotometry after Nessler’s
reaction
.
4. NH4+ measurements
Note: Switch ON the spectrophotometer and
adapt the wavelength at 400nm at least 2 hour
before the measurements.
1. Take 25ml flasks. Add some (±10ml) DW
in each flask.
2. Add 500µl of the blank (NaCl solution) in
each flask for the standards and 500µl of
the NH4+ released solution (B) for each
sample.
3. Add HN4+ 10 ppm in volumes according to
the table below.
4. Add 1ml of K,Na-tartrate.
5. Add 1ml of Nessler’s reagents
6. Make up to 25 ml with DW. Close and mix
thoroughly.
The concentration of the standards are shown
in the table:
blank st1 St2 st3 st4
Ml stock 10
ppm 0 0.5 1 1.5 2
Concentrati
on, ppm 0 0.2 0.4 0.6 0.8
st5 st6 st7 st8 st9 st10
2.5 3.0 3.5 4.0 4.5 5.0
1.0 1.2 1.4 1.6 1.8 2.0
7. Let react for 10 minutes.
8. Measure the absorbance at 400nm. Zero is
blank-to-blank.
Calculate the results using linear regression in
Excel.
Disposal of chemical waste
As HgCl2 is very toxic, all solutions containing
this product should be disposed off via
chemical waste containers category 5.
Appendix 3 – Methodology for mineralogical characterization
22
References:
[1] Pabalan, R.T., Bertetti, F.P., “Cation-
Exchange Properties of Natural Zeolites,”
In: Bish, D.L., Ming, D.W., Editors,
Natural Zeolites: Occurence, Properties,
Applications, Mineralogical Society of
America, Washington D.C., 2003, pp. 453-
517.
[2] Kitsopoulos, P.K., “Cation-exchange
capacity (CEC) of zeolitic volcaniclastic
materials: applicability of the ammonium
acetate saturation (AMAS) method,” Clays
and Clay Minerals 47, Vol. 6, 1999, pp.
688-696.
[3] Leonard, R.H., 1961. Quantitative Range of
Nessler’s Reaction with ammonia. Clinical
chemistry 9 (4): 417-421.
Appendix 3 – Methodology for mineralogical characterization
23
3.3 Staining of feldspars & zeolites
Method
Modified from
http://www.scn.org/~bh162/staining_feldspars.
CHEMICALS
Hydrofluoric Acid = concentrated (52 percent),
which is how it comes from the bottle.
Sodium Cobaltinitrite = saturated solution; 1g
in 4 ml H2O (D253)
Barium Chloride = saturated solution; start
with 5 grams in 25 ml of distilled, deionized
water; add more Barium Chloride and stir until
some will not dissolve. Allow some of the
undissolved residue to remain in the bottom of
the jar, but do not stir or shake immediately
before using. (D42)
Amaranth = saturated solution; use about 1
grams of the purple-red amaranth powder in 10
ml of distilled, deionized water. (D9)
Potassium chloride => saturated solution
THIN SECTION STAINING PROCEDURE (standard)
Caution: Use the required chemicals in a fume
hood and do not get any on your skin.
For sedimentary petrology, half-stained
sections are desirables; therefore you must
mask the half of the section that is to be left
unstained. Wrap one-inch wide masking tape
gently around one end of the slide, overlapping
the loose ends on the back. Seal tightly the
edge of the tape crossing the center of the slide
but do not push hard on the rest of the tape or
you may have trouble removing the tape later.
If the thin section may be greasy (from
fingerprints and such), wipe it gently with
acetone or denatured alcohol, being careful not
to touch the tape.
Etch the face of the thin section with
concentrated hydrofluoric acid for 1 to 3
seconds. Use extreme caution in handling HF:
wear a rubber apron, goggles, and rubber
gloves (test your gloves in water to be sure
they have no leaks). Do the etching in a fume
hood that is turned on. You will need a plastic
eyedropper, a shallow plastic dish, and a
plastic beaker full of water. Do not put HF in a
glass container: the acid dissolves glass. Hold
the thin section, rock side up, over the shallow
dish. Take a dropper full of HF and, beginning
in the center of the thin section and moving
towards the sides, cover the unmasked half of
the sample with acid, letting excess acid run
off into the dish. Put the dropper down in a
safe spot and then dip the thin section several
times in the beaker of water to rinse it. Move to
the sink, and rinse off any remaining acid with
running water. Gently blow the thin section
dry.
Immerse the unmasked end of the thin section
in a saturated solution of sodium cobalinitrite
for 15 seconds. Rinse off the excess
cobaltinitrite in tap water and dry gently but
thoroughly with compressed air (you may also
warm the section in a warm oven to dry it
completely).
Immerse the unmasked end of the section in a
saturated solution of barium chloride for 15
seconds. Dip in water to rinse off excess
solution, and blow dry.
Hold the unmasked end of the section in a saturated solution of amaranth for 5 seconds.
Dip twice in standing water to rinse off some
of the excess amaranth (do not overrinse or the
red dye will be removed from the plagioclase)
and blow dry.
Gently remove masking tape, taking care not to
peel the rock off the slide.
Results: K-feldspar and K-zeolites will be
stained yellow, plagioclase and Ca-zeolites
will be stained purple. Na-zeolites and albites
are not stained. A small amount of Ca in Na-
zeolites or albite will give it a light pink
colour. The intensity of the colour can be
related to the Ca-content
Appendix 3 – Methodology for mineralogical characterization
24
THIN SECTION STAINING
PROCEDURE (staining albite and Na-zeolites)
Method
Modified from Bailey and Stevens (1960)
Procedure
Etch the sample with HF (see standard
procedure)
Immerse the unmasked end of the section in a
saturated solution of potassium chloride for 15
seconds. Dip in water to rinse off excess solution, and blow dry.
Immerse the unmasked end of the thin section
in a saturated solution of sodium cobalinitrite
for 15 seconds. Rinse off the excess
cobaltinitrite in tap water and dry gently but
thoroughly with compressed air (you may also
warm the section in a warm oven to dry it
completely).
Results: K will replace Na in zeolites and in
etched albite. The K will react with sodium
cobalinitrite and stain the zeolites and albite
yellow.
Reference: Bailey, E.H., Stevens, R.E., 1960. Selective
staining of K-feldspar and plagioclase on rock
slabs and thin sections. The American
Mineralogist, 45, 1020-1025.
Appendix 3 – Methodology for mineralogical characterization
25
3.4 Digestion of silicate rock
samples: LiBO2 fusion in graphite
crucible for AAS and ICP-MS
analysis
Method
Method of Vassilieva (modified from: Solution
technique for analysis of silicates. N.H.
Suhr&C.O. Ingamells. Anal.Chemistry Vol.,
38 N° 6. May 1966 (p. 730-734)
Principle
Fusion with LiBO2 followed by rapid
dissolution in 0.42M nitric acid brings all
constituents in solution.
Standard Reference Material
Ask lab responsible for suitable standard and
include it in the batch.
Reagents
1. Lithium metaborate, LiBO2, 100% non
fused, CAS 13453-69-5. (Flux Nr 100A.
from Spectroflux)
2. Nitric acid (HNO3), 0.42M. Dilute 30 ml
of concentrated nitric acid to 1 L with
distilled water. 3. Cesium chloride Lanthanum chloride
AAS buffer solution (10% La, 1% Cs)
4. For dilutions: Nitric acid (HNO3),
0.42M. Dilute 30 ml of concentrated
nitric acid to 1 L with distilled water (for
ICP-MS use Milli-Q).
Apparatus
1. 5ml tubes
2. Graphite crucible (Carbon of America
002380-000, Crucible YU40)
3. Analytical balance
4. Muffle furnace
5. Magnetic stirrer
6. 100 ml polypropylene beaker
7. 50 ml PP bottles of ICP tubes
Procedure
1. Put ON muffle furnace 2 hours before
you start.
2. Weigh 100.0 mg of the sample in a
5ml tube. Include at least one blank
and 4 reference samples in each batch.
3. Add 500 mg LiBO2 to the sample.
Close the tube and shake it to mix.
4. Transfer the mixture in a graphite
crucible.
5. Place the graphite crucible in the
muffle furnace and heat at 1000°C for
10 minutes.
6. Place a polypropylene beaker with 50
ml HNO3 0.42M in a magnetic stirrer
and let it stir.
7. Take out the graphite crucible and
swirl the content gently (to ensure melt
is homogeneous and that complete
solution is achieved) and quickly pour
out in the beaker with HNO3.
8. Stir the mixture until everything is
dissolved and replace the solution in a
50 ml plastic bottle.
9. This solution should be measured with
AAS or ICP-OES (1/10!!!) after
dilution.
10. For AAS: Take 20ml of the solution
and add 1 ml of Cs-La AAS buffer
solution.
Note: Always use thermo gloves and a pincer
while handling hot graphite crucibles. Be
careful and stay calm!
In the case of using only ICP-OES or ICP-
MS do not add Cs-La solution!
Appendix 4 – mineralogical characterization of the Late Cretaceous deposits
27
4.1 Structures used in the Rietveld refinement.
Table 1 Structures used in the Rietveld refinement.
Possible ranges of cell parameters for zeolites are from Passaglia and Sheppard (2001). The column
reference refers to the references below.
APPENDIX 4 – MINERALOGICAL
CHARACTERIZATION OF THE LATE CRETACEOUS
DEPOSITS
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
28
Name a (Ǻ) b (Ǻ) c (Ǻ) α (°) β (°) γ (°) reference space group chemistry
adularia 8.55-8.729 12.8-13.058 7.118-
7.262 115.48-117 8 C 1 2/m 1
K4Al4Si12O32
albite (An0) 8.12-8.15 12.7-12.81 7.13-7.20 94-95 116.4-117 87.0-
88.2 4 C-1
NaAlSi3O8
analcime 13.66-
13.73 9 I a -3 d
Na(AlSi2O6)(H2O)
andesine (An52) 8.16-8.19 12.85-12.88 7.07-7.12 93.4-
93.7 116.0-116.4
89.5-
90.0 16 C -1
Na0.622Ca0.368Al1.29Si2.71O8
apophyllite 8,979 15,83 28 P 4/m n c KCa4(Si8O20)(OH)(H2O)8
augite 9.597-
9.791 8.762-8.940
5.217-
5.323 106-107.6 22 C 1 2/c 1
(Mg0.72Fe0.25Al0.02Ti0.01)
(Ca0.78Na0.02Mg0.03Fe0.16Mn0.01)
(Si1.95Al0.05O6)
barrerite 13.59-
13.64 18.18-18.20
17.79-
17.84 29 A m m a
Na9.9K3.46Ca3.52 Al15.9Si56.1O144(H2O)44.68
bytownite (An
85) 8.17-8.195 12.86-12.91
14.17-
14.22
93.1-
93.6 115.5-116.3
90.2-
91.4 7 P -1
Ca0.85 Na0.14 Al1.94 Si2.06 O8
calcite 4.95-5.0 16.9-17.1 33 R -3 c R Ca(CO3)
celadonite 5,23 9,05 10,15 100,58 34 C 1 2/m 1 KFe1.5Mg0.5Si4O10(OH)2
chabazite 13.69-
13.86
14.18-
15.42 23 R -3 m R
(Ca0.85K0.66)Mg0.66(Al3.31Si8.69O24)(H2O)13.22
chlorite 5.25-5.5 9.15-9.45 14.1-14.6 95.0-97.0 19 C 1 2 1 Mg2.5Fe1.65Al1.5Si2.2Al1.8O10(OH)8
cristobalilte 27 P 41 21 2 SiO2
diopside 9.653-
9.849 8.842-9.020
5.255-
5.308 105-107 15 C 1 2/c 1
(Ca0.96Na0.04)(Mg0.86Al0.07Fe0.06)(Si1.89Al0.11O6)
dolomite 4.8-4.88 15.90-
16.42 26 f c b a
CaMg(CO3)2
epistilbite 9.08-9.10 17.74-17.80 10.20-
10.24
124.55-
124.68 2 C 1 2 1
Na0.95Ca2.85(Al6Si18O48)(H2O)14
erionite 13.19-
13.34
15.04-
15.22 12 P 63/m m c
K2Ca2.44Mg0.52(Al7.908Si28.092O72)(H2O)21.6
goethite 466,894 1.016.243 306,247 13 P b n m FeO(OH)
Appendix 4 – mineralogical characterization of the Late Cretaceous deposits
29
Name a (Ǻ) b (Ǻ) c (Ǻ) α (°) β (°) γ (°) reference space group chemistry
hematite 5.01-5.07 13.7-13.83 3 R -3 c H Fe2O3
hornblende 9.73-9.94 17.9-18.2 5.25-5.37 104 17 C 1 2/m 1 (K.3 Na.6) (Ca1.7 Mg0.3) (Mg3 Fe Fe0.5 Al0.3Ti0.2)
Al1.6 Si6.4 O22.5(OH)1.5
Heu-type 17.62-
17.74 17.81-18.05 7.39-7.53
116.13-
116.90 5 C 1 2/m 1 (Na1.32 K1.28 Ca1.72 Mg0.52)(Al6.77 Si29.23
O72).26.84(H2O)
labradorite
(An65) 8.17-8.182
12.86-
12.883 7.08-7.12
93.3-
93.7 115.9-116.3
90.2-
90.9 20 P 1 1 21/a
Ca7.902 Na1.73 (Al5.5 Si0.5 O18)
laumontite 14.69-
14.89 13.05-13.17 7.53-7.61 110-113 30 C 1 2/m 1
Ca4(Al8Si16O48) (H2O)ue
magnetite 83,958 104.5-106 32 F d -3 m Z Fe3O4
mordenite 18.05-
18.25 20.35-20.53 7.49-7.55 18 C m c 21
K2.99Ca1.85Na1.06Al7.89Si40.15O96.28H2O
oligoclase
(An16) 8.15-8.165 12.81-12.84 7.13-7.16
93.8-
94.3 116.3-117
88.0-
89.0 25 C-1
(Na0.84Ca0.16) Al1.16Si2.84O8
pumpeleyite 8,83 5,9 19,17 97,12 11 A 1 2/m 1 Ca8Mg1.4 Fe.6 Al10 Si12O44 (OH)10(H2O)2
pyrite 54,179 6 P a -3 FeS2
quartz 4.9-4.935 5.38-5.45 21 P 32 2 1 SiO2
stellerite 13.57-
13.63 18.16-18.27
17.82-
17.87 24 F m m m
Ca4(Al8.32Si27.68)O72 (H2O)35.36
stilbite 18.18-
18.33 18.18-18.33
17.71-
17.84 90.20-91.15 10 C 1 2/m 1
Na1.76 Ca4.00 (Al10.29Si25.71O72)(H2O)29.4
thomsonite 13.00-
13.18 13.04-13.16
13.09-
13.24 1 P n c n
Na1.08 Ca1.84 Sr.08 (Al5 Si5 O20) (H2O)6
tridymite 4.95-5.00 8.62-8.65 8.31-8.35 93-95 14 C 1 c 1 SiO2
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
30
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Kristallchemie, 135: 240-252.
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(11) Galli, E.;Alberti, A., 1969. On the crystal structure of pumpellyite. acta Crystallographica B, 25:
2276-2281.
(12) Gualtieri, A., Artioli, G., Passaglia, E., Bigi, S., Viani, A., Hanson, J.C., 1998. Crystal structure -
crystal chemistry relationships in the zeolites eríonite and offretite. The American Mineralogist, 83:
590-606.
(13) Hazemann, J.L., Berar, J.F., Manceau, A., 1991. Rietveld studies of the aluminium-iron
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(14) Graetsch, H.A., 2003. Rietveld refinement of incommensurate low tridymite. acta
Crystallographica C, 218: 531-535.
(15) Herd, C.D.K., Peterson, R.C., Rossman, G.R., 2000. Violet-colored diopside from Southern
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(16) Horst, W., Tagai, T., Korekawa, M., Jagodzinski, H., 1981. Modulated structure of a plagioclase
An52: Theory and structure determination. Zeitschrift fuer Kristallographie, 157: 233-250.
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(17) Kawahara, A., Ohno, M., Takano, Y., 1972. Structural Study of the Amphibole in Volcanic Tuff.
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zeolite mordenite: A single-crystal X-ray study. The American Mineralogist, 89: 421-431.
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stellerite, Ca (Al8 Si28) O72 . 28 (H2 O). Crystal Research and Technology, 21(8): 1029-1034.
(25) Phillips, M.W.,Colville, A.A.,Ribbe, P.H., 1971. The crystal structures of two oligoclases: A
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(26) Pilati, T., Demartin, F., Gramaccioli, C.M., 1998. Lattice-dynamical estimation of atomic
displacement parameters in carbonates: Calcite and aragonite Ca C O3, dolomite Ca Mg (C O3)2, and
magnesite Mg C O3. acta Crystallographica B, 54: 515-523.
(27) Pluth, J.J., Smith, J.V., Faber, J., 1985. Crystal structure of low cristobalite at 10, 293, and 473 K:
Variation of framework geometry with temperature. Journal of Applied Physics, 57: 1045-1049
(28) Rouse, R.C., Peacor, D.R., Dunn, P.J., 1978. Hydroxyapophyllite, a new mineral and a
redefinition of the apophyllite group. II. crystal structure. The American Mineralogist, 63: 196-202.
(29) Sacerdoti, M., Sani, A., Vezzalini, G., 1999. Structural refinement of two barrerites from Alaska.
Microporous and Mesoporous Materials, 30: 103-109.
(30) Stahl, K., Artioli, G., Hanson, J.C., 1996. The dehydration process in the zeolite laumontite: a
real-time synchrotron X-ray powder diffraction study. Physics and Chemistry of Minerals (Germany),
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(31) Steinfink, H., 1958. The Crystal Structure of Chlorite. I. A Monoclinic Polymorph. acta
Crystallographica, 11: 191-195.
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titanomagnetites (Fe3-x Tix O4). The American Mineralogist, 69: 754-770.
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Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
32
(34) Zhukhlistov, A.P., Zvyagin, B.B., Lazarenko, E.K., Pavlishin, V.I., 1977. Refinement of the
crystal structure of ferrous seladonite. Kristallografiya, 22: 498-504.
33
4.2 XRD quantifications
4.2.1 Río Guaraguao section (samples are ordered from the base to the top of the section)
Sample name qua cal lau alb oli and lab pla adu aug mag pum pre Hor NQ chl remarks
04LM095Q 6 17 19 36 27 1 30 x
09LM072Q 6 0 0 5 23 0 16 38 0 28 2 0 0 0 21 x Opal-CT
09LM071Q 14 0 37 37 0 0 0 0 0 3 0 0 0 0 9
09LM076K X
09LM078Q 21 8 31 22 0 0 0 0 0 4 1 4 0 0 9
09LM079Q 75 0 0 1 4 0 0 4 3 0 0 0 0 0 17
09LM081Q 23 2 4 3 31 0 0 31 3 7 1 0 0 0 25
09LM082K X ?
09LM083Q 21 0 0 2 10 4 25 39 2 8 0 0 0 0 28
06LM001Q 96 5 0 0 0 0 0 0 0 0 0 0 0 0 0
06LM011Q 50 46 0 0 0 0 0 0 0 0 0 0 0 0 4
06LM012Q 38 4 0 0 16 0 0 16 0 3 1 0 0 0 44
06LM013Q 10 0 34 0 26 0 0 26 0 3 1 0 0 0 27
06Lm014Q 57 9 0 0 17 0 0 17 0 0 0 0 0 0 17
06Lm015Q 51 39 0 0 0 0 0 2 0 0 0 0 0 0 8
06LM005Q 77 0 0 13 0 0 0 0 0 1 0 0 0 0 9 x
06LM006Q 14 12 57 5 0 0 0 0 0 2 0 0 0 0 10
06LM007Q 15 11 59 5 0 0 0 0 0 2 0 0 0 0 8 x
06LM009Q 2 2 53 0 0 0 0 0 0 8 0 0 0 0 35
06LM008Q 66 16 3 0 0 0 0 2 0 2 0 0 0 0 11 x
06LM003Q 37 0 4 36 0 0 0 0 0 7 1 4 10 0 0
06LM004Q 28 0 7 31 0 0 0 0 0 8 1 7 0 0 18 x epistilbite?
06Lm016Q 37 0 8 0 41 0 0 41 0 4 1 0 0 0 10 clast
09LM085Q 18 0 20 0 29 0 0 29 0 9 2 4 0 0 20
06LM096Q 1 0 0 36 0 0 0 0 0 3 0 58 0 0 2 clast
06Lm097Q 36 0 3 0 0 46 0 46 0 6 0 0 0 0 9
06LM098G 49 0 7 4 20 0 0 20 0 2 0 0 0 0 17
06LM098R 62 0 0 0 0 0 0 9 0 2 0 0 0 0 27
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
34
Sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
06LM099Q 61 1 0 2 0 0 0 0 0 5 0 0 0 5 0 2 0 0 0 0 28
06LM100Q 32 0 0 2 0 0 0 0 0 21 0 0 0 21 0 3 0 0 0 0 42 missing?
06LM101Q 14 0 7 59 0 0 0 0 0 0 0 0 0 3 0 2 0 0 0 0 15
09LM086Q 21 0 0 0 21 0 0 0 5 19 0 0 0 19 0 15 0 6 0 0 12 missing?
06LM102Q 34 0 0 0 35 0 0 0 26 0 0 0 0 0 0 0 0 0 0 0 1 hor: 2%
09LM088Q 29 0 0 0 51 0 0 0 17 0 0 0 0 0 0 4 0 0 0 0 0
09LM089Q 27 0 46 0 0 0 0 0 6 5 0 0 0 5 4 3 0 0 0 0 10
06LM103Q 50 0 6 3 0 0 0 0 0 0 0 0 0 4 0 2 0 0 0 0 34
09LM001Q 36 0 0 0 29 0 0 0 30 0 0 0 0 0 0 0 2 0 0 0 3
09LM002Q 32 1 0 0 0 0 0 0 21 0 0 0 0 0 0 0 0 0 0 0 46
09LM003Q 31 0 29 3 0 13 10 0 11 0 0 0 0 0 0 0 0 0 0 0 3 x
09LM004Q X x x x
09LM005Q 35 0 0 0 39 3 0 0 16 0 0 0 0 0 0 0 1 0 0 0 7
09LM006K 35 0 0 0 5 0 0 0 21 0 0 0 0 0 0 0 0 0 0 0 39
09LM007K 35 0 0 0 21 0 0 0 21 0 0 0 0 0 0 0 0 0 0 0 23
09LM008Q 33 0 0 0 24 0 0 0 32 0 0 0 0 0 0 0 1 0 0 0 9
09LM009Q 33 0 0 0 20 0 0 0 37 0 0 0 0 0 0 0 0 0 0 0 10
09LM010Q 21 0 0 0 38 0 0 0 21 0 0 0 0 0 0 5 0 0 0 0 16 ?
09LM011Q 17 1 0 0 11 0 0 0 36 0 0 0 0 0 0 11 0 0 0 0 23 ? x
06LM104Q 25 0 0 0 12 0 0 0 53 0 0 0 0 0 0 0 0 0 0 0 10
06LM105Q 46 6 0 0 0 0 0 0 0 17 0 8 0 25 0 2 1 0 0 0 35 14 clast
06LM106-2 12 0 20 3 2 4 0 0 0 17 0 13 0 30 0 9 0 0 0 0 28 8 x
09LM012Q 50 0 0 0 29 0 0 0 8 0 0 0 0 0 0 0 0 0 0 0 12
09LM013Q 25 0 4 40 0 0 0 0 6 0 0 0 0 10 2 3 1 0 0 0 10 ?
09LM014Q 21 0 0 38 0 0 0 0 2 5 6 9 0 20 2 2 0 0 0 0 15 ?
09LM015Q 24 1 30 0 0 8 7 0 0 15 0 0 0 15 0 3 0 0 0 0 12 x
09LM016Q 19 0 10 34 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 33 x x
09LM017Q 47 0 0 0 28 0 0 0 11 0 0 0 0 0 0 0 0 0 0 0 15
09LM018Q 29 9 0 0 36 3 0 0 11 0 0 0 0 0 0 2 1 0 0 0 9 x x
35
Sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
09LM019Q 31 7 21 15 0 0 0 0 4 0 0 3 0 3 0 3 0 0 0 0 16 x x
09LM020Q 31 4 0 0 35 0 0 0 8 0 0 0 0 0 0 2 1 0 0 0 19 ?
09LM021Q 25 0 1 21 0 0 0 0 2 0 0 22 0 22 0 4 0 0 0 0 26 x
09LM022Q 69 0 0 0 5 8 0 0 0 16 0 0 0 16 0 1 0 0 0 0 0 ste?
09LM023Q 25 0 7 21 0 0 0 0 4 0 0 19 0 19 0 5 0 0 0 0 20 x x
09LM024Q 26 0 13 0 9 0 0 0 3 18 8 0 0 26 2 8 0 0 0 0 13 x
09LM025Q 24 0 4 31 0 0 0 0 4 0 0 15 0 15 0 4 0 0 0 0 19 x
09LM026Q 28 0 7 40 0 0 0 0 0 3 0 9 0 12 0 2 0 0 0 0 11 x
09LM027Q 15 0 0 0 37 0 0 0 27 0 0 0 0 0 0 7 0 0 0 0 13 x
09LM028Q 23 0 8 13 5 0 0 0 3 8 0 0 13 20 0 6 2 0 0 0 19 x
06LM108Q 23 0 12 26 0 0 0 0 0 0 0 29 0 29 0 10 0 0 0 0 1 x x
09LM029Q 29 0 0 0 37 0 0 0 20 0 0 0 0 0 0 0 2 0 0 0 11 ? x
09LM030Q 24 0 3 39 0 0 0 0 0 10 0 0 0 10 0 0 0 0 0 0 24 x x
09LM031Q 44 32 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 21
06LM109Q 27 3 0 0 43 0 0 0 18 0 0 0 0 0 0 3 0 0 0 0 5 x
06LM110Q 33 0 0 0 47 0 0 0 18 0 0 0 0 0 0 0 0 0 0 0 2 x
09LM032Q 17 0 0 0 49 0 0 0 21 0 0 0 0 0 0 0 1 0 0 0 12 ? x
09LM033Q 24 0 0 0 31 0 0 0 29 0 0 0 0 0 0 0 2 0 0 0 14 ? x
06Lm112Q 8 0 5 0 0 0 0 0 0 0 16 0 0 16 0 11 0 0 0 0 59
06LM113Q 15 0 0 0 16 11 0 0 26 0 0 0 0 0 0 7 1 0 0 0 23 x
06LM114Q 12 0 34 0 0 0 0 0 7 16 0 0 0 16 0 8 0 0 0 0 24 x
09LM035Q 16 0 0 0 28 0 0 0 23 0 0 0 0 0 0 6 1 0 0 0 25 x
09LM036Q 14 0 32 3 4 0 0 0 0 16 0 0 0 16 0 8 1 0 0 0 23 x x
06LM115Q 19 0 17 20 0 0 0 0 0 13 0 6 0 19 0 7 0 0 0 0 18 x x
09LM038Q 19 0 14 28 0 0 0 0 0 8 0 4 0 12 0 6 0 0 0 0 20 ? x
06LM116Q 21 0 5 40 0 0 0 0 0 11 0 4 0 15 0 3 0 0 0 0 17 x x
09LM039Q 22 0 32 0 0 10 8 0 0 13 0 0 0 13 0 3 0 0 0 0 12 x
09LM040Q 41 20 5 7 0 0 0 0 0 11 0 0 0 11 0 0 0 0 0 0 16 x
09LM041Q 39 8 28 7 0 0 0 0 0 3 0 0 0 3 0 0 0 0 0 0 16 x
09LM042Q 15 0 18 21 0 0 0 0 2 6 0 9 0 15 0 4 1 0 0 0 24 x
06LM118b 23 19 31 5 0 0 0 0 0 3 0 3 0 6 0 2 0 0 0 0 17 3
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
36
sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
06Lm118t 4 0 30 4 0 0 0 0 0 12 0 15 0 27 0 8 0 0 0 0 32 6 x
06LM119Q 12 0 37 15 0 0 0 0 0 0 0 0 0 9 0 3 0 0 0 0 31 5 x
09LM043Q 27 0 23 26 0 0 0 0 0 12 0 0 0 12 0 0 0 0 0 0 12 x
06LM120Q 27 8 14 0 0 0 0 0 0 21 0 0 0 21 0 6 0 0 0 0 25 x
06LM121Q 4 0 47 0 0 0 0 0 0 0 0 0 0 13 0 7 0 0 0 0 28 x x
06LM122Q 16 0 44 11 0 0 0 0 0 0 0 0 0 10 0 5 0 0 0 0 14 x
06LM178Q 6 0 53 0 0 0 0 0 0 10 0 0 0 10 0 8 0 0 0 0 23
06LM179Q 44 0 14 20 0 0 0 0 0 0 0 0 0 7 0 0 0 0 0 0 15
06LM123Q 37 0 29 16 0 0 0 0 0 2 0 0 0 2 0 3 0 0 0 0 13
06LM176Q 3 1 59 0 0 0 0 0 0 16 0 0 0 16 0 8 0 0 0 0 14 x
06LM177Ge 51 0 0 0 8 0 0 0 24 0 0 0 0 0 0 0 1 0 0 0 17 missing?
06LM177Gr 58 0 0 0 16 0 0 0 20 0 0 0 0 0 0 0 1 0 0 0 5 missing?
06LM124Q 24 0 7 0 19 0 0 0 13 23 0 0 0 23 0 3 1 0 0 0 11
06LM073Q 37 0 6 43 0 0 0 0 0 0 0 0 0 8 0 0 0 0 0 0 6
06LM074Q 2 0 55 3 0 0 0 0 0 0 0 11 0 11 0 6 0 0 0 0 23 ? Sti?
06LM075Q 50 2 18 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 21 ? Sti?
06LM077Q 20 0 12 47 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 17 5
06Lm078Q 40 0 5 46 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8
06LM079Q 8 1 9 0 0 0 0 8 0 20 0 0 0 20 0 10 0 0 0 0 44 ?
06Lm080Q 26 3 13 0 0 0 0 5 0 9 4 0 0 13 0 0 0 0 0 0 12 apo:
28%
06LM081Q 29 0 0 58 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 16 3
06Lm082Q 36 4 0 0 0 55 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5
06LM085Q 9 0 44 0 0 7 0 0 0 24 0 8 0 32 0 4 0 0 0 0 5 x x
06Lm086Q 12 0 15 36 0 0 0 0 0 0 0 0 0 9 0 3 0 0 0 0 25 x
06LM087Q 32 13 0 0 42 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 8
06LM088Q 36 18 26 4 0 7 0 0 0 0 0 0 0 7 0 0 0 0 0 0 2
09LM051K 37 20 14 13 0 0 0 0 2 0 0 1 0 1 0 1 1 0 0 0 11
09LM052Q 8 4 12 16 0 0 0 0 2 9 0 21 11 40 0 5 0 0 0 0 13 ?
09LM053Q 11 2 19 21 0 0 0 0 2 7 0 7 8 22 0 4 1 0 0 0 19 x x
09LM054Q 16 0 12 29 0 0 0 0 4 0 0 6 9 16 0 4 0 0 0 0 19 x x
09LM055Q 11 1 13 20 0 0 0 0 2 5 0 15 5 25 0 6 0 0 0 0 20 x
37
sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
09LM056Q 16 7 13 44 0 0 0 0 2 0 0 0 3 3 0 3 0 0 0 0 12 x
09LM057Q 11 5 12 30 0 0 0 0 0 6 0 13 0 19 0 5 0 0 0 0 17
09LM058C 19 15 8 39 0 0 0 0 0 2 0 2 0 5 0 1 0 0 0 0 12 ?
09LM058F 40 12 13 12 0 0 0 0 0 3 0 2 0 6 0 2 1 0 0 0 16
09LM059K 31 7 20 9 0 0 0 0 0 0 0 5 0 5 0 2 1 0 0 0 27
09LM060Q 9 2 14 20 0 0 0 0 4 0 0 24 0 24 0 5 1 0 0 0 20 x
06LM089Q 17 0 16 28 0 3 0 0 0 0 0 0 0 19 0 0 0 0 0 0 17 x x
09LM061Q 16 0 8 27 0 0 0 0 0 10 0 20 0 29 0 4 0 0 0 0 16 ? ?
09LM062Q 13 0 9 21 0 0 0 0 0 9 0 13 15 38 0 5 0 0 0 0 14
09LM063Q 5 0 12 49 0 0 0 0 0 2 0 4 0 5 0 3 0 0 0 0 26
09LM069Q 41 0 2 42 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 15
06Lm090Q 13 0 10 58 0 0 0 0 0 0 0 4 0 4 0 0 0 0 0 0 15 ?
06LM091Q 33 0 3 51 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 12
09LM066Q 20 0 7 52 0 0 0 0 0 1 0 0 2 3 0 2 0 0 0 0 15
06LM093Q 37 1 11 37 0 0 0 0 0 0 0 0 0 5 0 1 0 0 0 0 6
06LM125Q 37 28 8 5 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 20
06LM126Q 24 0 12 49 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 15
06LM127F 32 2 44 0 0 0 0 0 0 0 0 0 0 3 0 3 0 0 0 0 16
06LM127G 19 7 14 25 0 0 0 0 0 0 0 0 0 14 0 3 0 0 0 0 18
06LM128Q 14 9 18 4 0 0 0 0 0 0 0 0 0 20 0 5 1 0 0 0 29 x
06LM129Q 9 4 13 0 11 0 0 0 12 19 0 0 0 19 3 6 1 0 0 0 20 x x
06LM131Q 7 2 13 0 0 0 0 0 0 31 0 0 0 31 0 9 2 0 0 0 36 x
06LM132Q 10 4 25 14 0 0 0 0 0 0 0 0 0 20 0 6 2 0 0 0 19 x
06LM133Q 8 0 37 17 0 0 0 0 0 0 0 0 0 4 0 4 0 0 0 0 30
06LM135Q 35 10 19 0 0 0 0 0 5 10 0 0 0 10 0 2 0 0 0 0 19
06LM136Q 1 7 38 4 1 0 0 0 0 0 0 0 0 37 0 8 0 0 0 0 3
06Lm138Q 27 18 18 2 0 0 0 0 0 0 0 0 0 12 0 4 0 0 0 0 19
06LM138B 25 17 14 3 0 0 0 0 0 0 0 0 0 12 0 4 0 0 0 0 25
06LM145Q 2 0 22 0 0 0 0 0 0 18 0 19 0 37 0 9 2 0 0 0 28 x
06Lm146Q 12 3 11 2 6 0 0 0 0 39 0 0 0 39 11 7 2 0 0 0 8 x
06LM148Q 3 0 44 3 0 0 0 0 0 12 0 15 0 27 0 8 1 0 0 0 14 x
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
38
sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
06LM149Q 14 2 0 0 21 0 0 0 12 21 0 0 0 21 0 12 0 0 0 0 19 x
06LM150Q 4 1 37 3 2 0 0 0 4 10 0 18 0 28 0 9 1 0 0 0 9 x
06LM151Q 1 0 23 0 0 0 0 0 0 0 0 0 0 24 0 8 1 0 0 0 43
06LM153Q 4 4 0 0 23 0 0 0 0 0 0 0 0 36 0 7 0 0 0 0 27 pum?
06LM154Q 1 0 24 1 8 0 0 0 0 30 0 0 0 30 0 12 1 0 0 0 22 x
06LM155Q 5 4 32 0 0 0 0 0 0 0 0 0 0 29 0 11 1 0 0 0 19
06LM157Q 0 0 36 2 0 0 0 0 0 35 0 0 0 35 0 16 1 0 0 0 9
06LM158Q 4 0 45 2 0 0 0 0 0 27 0 0 0 27 0 9 1 0 0 0 13 x
06LM159Q 10 2 33 3 0 0 0 0 0 31 0 0 0 31 0 9 0 0 0 0 12
06LM160Q 24 5 54 2 0 0 0 0 0 0 0 0 0 12 0 0 3 0 0 0 7 ?
06LM161Q 17 6 64 0 0 0 0 0 0 0 0 0 0 5 0 0 1 0 0 0 8
06LM162Q 3 1 25 0 0 0 0 10 0 22 0 0 0 22 0 14 0 0 0 0 25 x
06LM163Q 8 11 47 0 0 0 0 0 0 11 0 0 0 11 0 3 0 0 0 0 20
06LM164Q 11 0 40 0 0 0 0 0 0 17 0 0 0 17 0 0 0 0 0 0 31
06LM165Q 4 0 40 2 0 0 0 0 0 31 0 0 0 31 0 8 0 0 0 0 15
06LM166Q 0 2 4 0 0 0 0 28 0 0 0 0 0 5 0 22 1 0 0 0 38
06LM167Q 0 3 34 0 0 0 0 0 0 17 0 0 0 17 0 13 0 0 0 0 33 x
06LM168Q 0 4 26 0 0 0 0 0 0 27 0 0 0 27 0 16 0 0 0 0 27
06LM168R 0 2 59 0 0 0 0 0 0 15 0 0 0 15 0 5 0 0 0 0 19
06LM169Q 6 0 67 0 0 0 0 0 0 7 0 0 0 7 0 3 0 0 0 0 15
06LM170Q 14 3 55 0 0 0 0 0 0 16 0 0 0 16 0 0 0 0 0 0 12
06LM171Q 0 3 34 0 5 0 0 1 0 0 0 0 0 22 0 14 0 0 0 0 20 x
06LM172Q 2 0 64 0 0 0 0 0 0 9 0 0 0 9 0 4 0 0 0 0 21
06LM175Q 48 0 36 0 0 0 0 0 0 8 0 0 0 8 0 2 0 0 0 0 6
06LM180T 0 5 25 0 0 0 0 0 0 17 0 18 0 35 0 14 0 0 0 0 21
06LM180T2 0 5 25 0 0 0 0 0 0 13 9 24 0 47 0 13 0 0 0 0 10
06LM181Q 30 6 33 0 0 0 0 0 0 15 0 0 0 15 0 3 0 0 0 0 14
06LM182Q 5 4 19 0 0 0 0 0 0 31 0 0 0 31 0 7 0 0 0 0 34
06LM184Q 44 0 30 0 0 0 0 0 0 4 0 0 0 4 0 0 0 0 0 0 22
06LM186Q 57 2 17 0 0 0 0 0 0 8 0 0 0 8 0 3 0 0 0 0 12
06LM187Q 6 2 11 0 0 0 0 0 0 11 17 13 0 40 4 11 0 0 0 0 30 5? x mor?
39
sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
06LM188Q 5 2 12 0 0 0 0 0 0 17 0 18 0 35 6 11 0 0 0 0 30 x
06LM190b 28 6 34 0 0 0 0 0 0 10 0 0 0 10 0 2 0 0 0 0 19
06LM192Q 41 0 16 0 0 0 0 0 0 9 4 17 0 30 0 0 0 0 0 0 14
06LM193bl 27 0 49 4 0 0 0 0 0 13 0 0 0 13 0 0 0 0 0 0 7
06LM193Br 6 4 48 2 0 0 0 0 0 17 0 4 0 21 0 6 0 0 0 0 14
06LM194Q 5 6 21 0 0 0 0 0 0 13 21 0 0 34 0 9 0 0 0 0 24 ?
06LM196Q 52 0 39 0 0 0 0 0 0 5 0 0 0 5 0 0 0 0 0 0 4
06LM198Q 1 6 24 0 0 0 0 12 0 0 0 0 0 1 0 10 0 0 0 0 46
06LM199Q 60 0 15 3 0 0 0 0 0 9 0 0 0 9 0 3 0 0 0 0 10
06LM201Q 3 0 27 2 0 0 0 0 0 18 0 16 0 34 6 10 1 0 0 0 15
06LM202Q 44 0 36 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 18
06LM072Q 10 4 25 0 0 0 0 0 0 0 22 0 0 22 0 6 1 0 0 0 32
06LM067Q 7 3 38 0 0 0 0 0 0 8 8 0 0 16 0 5 0 0 0 0 38 7 x
06LM068Q 13 2 26 0 0 0 0 0 0 0 0 0 0 28 2 5 0 0 0 1 24 4 x
06LM069Q 50 6 31 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 10
06LM066Q 44 6 30 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 17
06LM070Q 1 7 38 0 0 0 0 0 0 0 0 0 0 27 0 7 1 0 0 0 18
06LM071Q 2 14 28 0 0 0 0 0 0 4 0 0 0 4 0 0 0 0 0 0 53
06LM065Q 2 14 29 0 0 0 0 0 0 4 0 0 0 4 0 0 0 0 0 0 51
06LM063Q 29 0 46 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 21
06LM064Q 31 0 54 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 14
06LM061Q 9 2 42 0 0 0 0 0 0 12 0 0 0 12 0 6 1 0 0 0 29 x
06LM060Q 4 1 34 0 0 0 0 0 0 0 0 0 0 16 0 5 1 0 0 0 38
06LM058Q 43 0 31 0 0 0 0 0 0 10 0 0 0 10 2 2 0 0 0 1 11 6?
06LM057Q 4 0 50 0 0 0 0 0 0 0 0 0 0 18 0 7 1 0 0 0 27 6?
06LM054Q 2 0 48 0 0 0 0 0 0 0 0 0 0 14 0 4 1 0 0 0 31
06LM051Q 74 0 9 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 15
06LM047Q 46 21 16 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 13
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
40
sample name qua cal heu mor lau sti ste ana alb oli and lab byt pla adu aug mag pum cri try NQ cel chl remarks
06LM043Q 4 4 51 0 0 0 0 0 0 0 0 0 0 11 0 6 1 0 0 0 24
06LM040Q 62 0 29 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 5
06LM036Q 53 0 42 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 1
06LM035Q 10 0 38 4 0 0 0 0 0 0 0 0 0 20 6 4 1 0 3 0 16 6
06LM034Q 6 0 53 0 0 0 0 0 0 0 0 0 0 17 5 4 1 0 0 2 11
06LM033Q 67 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 21
06LM031Q 5 0 43 0 0 0 0 0 0 0 15 0 0 15 6 5 1 0 0 2 21
06LM026Q 65 0 15 0 0 0 0 0 0 0 0 0 0 2 0 2 0 0 1 0 15
06LM024Q 65 0 10 0 0 0 0 0 0 0 0 0 0 0 0 2 1 0 2 0 19
06LM022Q 18 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 43 25 14
06LM021Q 4 0 2 0 0 0 0 0 0 0 20 0 0 20 0 3 2 0 4 0 66
06LM020Q 24 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 37 23 17
06LM019Q 92 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8
06LM017W 96 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4
06LM017Z 100 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
NQ = not quantified
41
4.2.2 Guayaquil (samples are ordered from the base to the top of the section)
Sample name qua cal heu-
type mor lau ana alb oli and lab byt pla
K-
fsp aug chl mon cel mag act others NQ Remarks
06LM204 6 0 0 0 0 0 14 17 0 0 0 31 2 24 0 0 0 0 0 0 38
06LM205 28 0 0 0 0 0 14 31 0 0 0 45 0 0 0 0 0 0 11 0 27
06LM207 30 0 0 0 0 0 3 10 15 3 0 31 0 0 0 0 0 0 10 0 39
06LM263 47 0 0 0 0 0 41 0 0 0 0 41 0 0 0 0 0 0 0 0 11 ankerite?
06LM264 34 0 0 0 0 0 8 34 0 0 0 41 0 0 0 0 0 0 5 0 25
06LM265 48 0 0 0 0 0 40 11 0 0 0 51 1 0 0 0 0 0 0 0 0
06LM215 X 0 epidote
06LM217 33 0 0 0 0 0 15 29 0 0 0 44 3 0 0 0 0 0 0 0 20
06LM219 28 9 0 0 0 0 19 21 0 0 0 40 0 0 0 0 0 0 0 3 21 barite
06LM221 30 0 0 0 0 0 11 36 0 0 0 47 1 4 0 0 0 0 3 0 18 ankerite?
06LM222 29 0 0 0 0 0 6 16 0 0 0 21 0 0 0 0 0 0 9 0 49
06LM223 29 0 0 0 0 0 23 16 0 0 0 39 0 0 0 0 0 0 1 0 32
06LM224 26 0 0 0 0 0 12 8 0 0 0 20 0 0 0 0 0 0 22 0 54
06LM225 47 0 0 0 0 0 47 0 0 0 0 47 0 0 0 0 0 0 0 0 6
06LM226 62 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 7 31 goethite
06LM255 51 6 0 0 0 0 11 0 0 0 0 11 0 0 0 0 0 2 0 0 31
06LM256 62 2 0 0 0 0 22 0 0 0 0 22 0 0 0 0 0 0 0 0 14
06LM260 51 2 0 0 0 0 22 0 0 0 0 22 0 0 0 0 0 2 0 0 24
06LM261 41 11 0 0 0 0 8 0 0 0 0 8 0 0 0 0 0 0 0 0 40
06Lm282 33 60 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 7
04LM014Q 57 32 0 0 0 0 0 4 0 0 0 4 0 0 0 0 0 0 0 0 6
06LM242 15 8 0 0 0 0 6 15 0 0 0 21 0 6 0 0 0 0 0 0 50
06LM243 2 7 0 0 0 0 22 19 0 0 0 42 0 15 0 0 0 1 0 10 23 prenite
06LM229 23 5 0 0 0 0 23 13 0 0 0 35 0 0 0 0 0 0 0 0 37
06LM232 17 5 0 0 0 0 52 0 0 0 0 52 0 0 0 0 0 0 0 0 26
06LM233 21 5 0 0 0 0 15 28 0 0 0 43 0 0 0 0 0 0 0 0 30
06LM236GROEN 45 1 0 0 0 0 34 7 0 0 0 40 0 0 0 0 0 0 0 2 12 cristobalite
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
42
Sample name qua cal heu-
type Mor lau ana alb oli and lab byt pla
K-
fsp aug chl mon cel mag act others NQ Remarks
06LM237 24 6 0 0 0 0 15 22 0 0 0 37 0 0 0 0 0 0 0 0 33
06LM238 26 6 0 0 0 0 42 0 0 0 0 42 0 0 0 0 0 0 0 0 25
06LM241 14 45 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 40
06LM267 37 0 0 0 0 0 33 0 0 0 0 33 11 0 0 0 0 0 0 0 19
06LM268 30 0 0 0 0 0 5 23 0 0 0 28 11 2 0 0 0 1 0 0 28
04LM118Q 47 8 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 45
06LM276 24 5 0 0 0 0 19 13 0 0 0 33 5 4 0 0 0 0 0 0 30
06LM277 55 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 41
06LM279 30 0 0 0 17 0 35 0 0 0 0 35 0 0 0 0 0 1 0 0 17
06LM280 62 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 38
06LM281 88 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 12
06LM283 6 9 0 0 0 0 0 0 10 6 0 15 0 26 0 0 0 1 0 0 43
04LM084Q 50 13 0 0 0 0 18 16 0 0 0 34 3 0 0 0 0 0 0 0 1
04LM128Q 2 0 11 5 0 0 0 0 9 0 0 9 4 0 0 0 0 0 0 0 69
05RS051Q 77 0 0 0 0 0 0 4 0 0 0 4 13 0 0 0 0 0 0 4 2 Barite
05RS052Q 82 0 0 0 0 0 17 0 0 0 0 17 0 0 0 0 0 0 0 0 2
05RS053Q 25 0 0 0 0 0 56 0 0 0 0 56 0 0 0 0 0 0 0 0 19
05RS054Q 47 36 0 0 0 0 0 5 0 0 0 5 10 0 0 0 0 0 0 0 2
05RS055Q 38 0 0 0 0 0 50 0 0 0 0 50 0 0 0 0 0 0 0 0 12
05RS057Q 74 0 0 0 0 0 0 5 0 0 0 5 8 0 0 0 0 0 0 0 13
05RS058Q 84 1 0 0 0 0 0 13 0 0 0 13 0 0 0 0 0 0 0 0 3
05RS059Q 45 1 0 0 13 0 16 23 0 0 0 39 0 0 0 0 0 0 0 0 2
05RS062Q 65 21 0 0 2 0 10 0 0 0 0 10 4 0 0 0 0 0 0 0 3
43
Sample name qua cal heu-
type Mor lau ana alb oli and lab byt pla
K-
fsp aug chl mon cel mag act others NQ Remarks
04LM085Q 34 0 0 0 15 0 36 0 0 0 0 36 2 0 0 0 0 0 0 0 13
06LM304Q 31 12 0 0 0 0 6 21 0 0 0 28 22 0 0 0 0 0 0 0 8
06LM306Q 20 4 0 0 0 0 0 0 0 31 0 31 3 0 0 0 0 1 0 0 41
04LM086Q 20 0 0 0 0 0 5 34 0 0 0 39 0 0 0 0 0 0 0 0 42
04LM130Q 45 0 0 0 0 0 11 27 0 0 0 37 0 0 0 0 0 0 0 0 17
06LM286 26 1 0 0 0 0 8 25 0 0 0 33 16 2 0 0 0 1 0 0 21
06LM290 23 0 0 0 13 0 24 31 0 0 0 55 0 0 0 0 0 1 0 0 8
06LM291Q 29 0 0 0 19 0 40 0 0 0 0 40 0 3 0 0 0 1 0 0 8
06LM308Qb 18 0 0 6 0 0 0 8 0 37 0 45 0 15 0 0 0 1 0 0 16
06LM308Q 19 0 0 6 0 0 0 10 0 38 0 48 0 14 0 0 0 1 0 0 12
06LM310Q 6 0 0 11 0 0 0 14 7 0 0 21 3 12 0 0 0 0 0 9 39 epistilbite
06LM311Q 11 34 0 0 0 0 0 0 9 6 0 15 0 0 0 0 0 1 0 0 39
06LM292Q 4 11 7 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 78
06LM293Q 69 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 30 hematite
06LM295Q 7 2 0 0 0 0 0 0 0 10 0 10 0 3 0 0 53 0 0 0 78
06LM296Q 42 2 0 0 0 0 21 21 0 0 0 42 0 0 0 0 0 1 0 0 13
06LM297Q 20 0 0 0 0 0 13 25 0 0 0 38 0 0 0 0 0 1 0 0 42
06LM298Q 19 0 0 0 44 0 17 0 0 0 0 17 0 0 0 0 0 0 0 2 18 hematite
06LM299Q 42 0 0 27 0 0 0 0 7 0 0 7 0 0 0 0 0 1 0 0 24
06LM312Q 33 0 0 0 0 0 11 36 0 0 0 46 16 2 0 0 0 0 0 0 3 hematite?
04LM131Q 21 2 0 0 5 0 56 0 0 0 0 56 3 0 0 0 0 2 0 0 12
04LM132Q 18 2 0 0 0 0 0 24 18 5 0 48 0 0 0 0 0 0 0 0 32
04LM087Q 9 2 0 0 0 0 0 0 22 0 0 22 0 0 0 0 0 2 0 0 65
04LM088Q 13 2 0 0 0 0 0 0 9 10 0 18 0 0 0 0 0 0 0 0 66
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
44
Sample name qua cal heu-
type mor lau ana alb oli and lab byt pla
K-
fsp aug chl mon cel mag act others NQ
06LM284 23 0 0 0 0 0 22 39 0 0 0 60 0 0 0 0 0 1 0 0 15
04LM015Q 22 0 9 58 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 11
06LM303Q 3 0 28 0 3 0 15 12 0 0 0 27 4 0 0 0 0 1 0 0 35
06LM313Q 41 0 22 0 0 0 0 11 0 0 0 11 1 0 0 0 0 1 0 0 24
06LM314Q 32 0 18 0 0 0 0 0 18 0 0 18 0 0 0 0 0 1 0 0 31
06LM315Q 4 0 50 0 0 0 0 4 0 0 0 4 0 4 0 0 0 1 0 0 37
04LM089Q 6 8 32 0 0 0 0 7 0 0 0 7 0 5 0 0 13 0 0 0 42
06LM317Q 45 20 0 0 15 0 9 0 0 0 0 9 0 0 0 0 0 0 0 0 11
04LM090Q 43 16 7 4 0 0 0 4 0 0 0 4 0 4 0 0 0 0 0 0 21
06LM321Q 23 2 47 0 0 0 0 10 0 0 0 10 0 4 0 0 0 0 0 0 14
06LM323Q 12 26 12 0 0 0 0 11 0 23 0 34 0 0 0 0 0 1 0 0 14
06LM324Q 34 30 3 0 0 0 0 5 0 0 0 5 0 0 0 0 0 0 0 0 28
06LM325Q 6 11 7 8 0 0 0 0 0 9 12 9 0 2 0 0 0 2 0 0 43
04LM116Q 39 0 9 0 0 0 0 0 10 0 0 10 0 0 0 0 0 1 0 0 41
06LM319Q 8 0 33 0 4 0 18 0 0 0 0 18 3 0 0 0 0 1 0 0 33
06LM285 31 0 0 0 19 0 12 26 0 0 0 38 0 0 0 0 0 1 0 0 10
04LM094Q 7 0 0 0 22 0 24 0 0 0 0 24 0 16 0 0 0 0 0 0 32
04LM149Q 20 19 13 0 0 0 0 22 0 0 0 22 0 4 0 0 0 0 0 0 21
04LM023Q 41 0 19 0 0 0 0 5 0 5 0 9 0 3 0 0 0 1 0 0 27
04LM142Q 5 0 0 0 0 0 0 0 0 13 0 13 0 9 0 0 0 2 0 0 72
04LM025Q 5 0 40 0 0 0 0 11 11 0 0 22 3 5 0 0 6 1 0 0 23
04LM143Q 5 0 27 0 0 0 0 16 0 14 0 29 6 5 0 0 7 2 0 0 24
04LM026Q 0 3 10 9 2 14 0 0 0 22 22 22 0 0 39 9 0 0 0 5 2
05RS001aQ 0 4 16 0 9 0 7 27 0 0 0 34 9 10 0 0 0 2 0 0 16
05RS003bQ 0 4 23 0 6 0 9 23 0 0 0 32 8 9 0 0 0 1 0 0 15
05RS004Q 3 4 0 0 21 0 10 27 0 0 0 37 8 9 0 0 0 2 0 0 17
05RS005Q 0 3 17 0 9 0 10 23 0 0 0 33 9 10 0 0 0 1 0 0 18
05RS006Q 0 4 23 0 7 0 13 18 0 0 0 31 8 10 0 0 0 1 0 0 17
05RSK008 1 5 31 0 4 0 7 23 0 0 0 30 4 10 0 0 0 1 0 0 15
45
Sample name qua cal heu-
type mor lau ana alb oli and lab byt pla
K-
fsp aug chl mon cel mag act others NQ
05RS009Q 7 3 27 0 0 0 0 17 19 0 0 36 5 8 0 0 0 2 0 0 12
05RS010aQ 6 0 66 0 0 0 0 0 0 6 0 6 0 5 0 0 0 0 0 0 18
05RS010bQ 11 3 39 4 0 0 0 4 0 12 0 16 0 6 0 0 0 0 0 0 21
05RS011q 17 2 51 7 0 0 0 4 0 0 0 4 0 0 0 0 0 0 0 0 19
05RS012q 14 3 16 0 0 0 0 13 0 22 0 34 7 6 0 0 0 1 0 0 19
05RS013Q 2 3 18 4 0 0 6 25 0 0 0 31 9 10 0 0 0 1 0 0 21
05RS014Q 3 3 37 0 0 0 0 14 14 0 0 28 5 7 0 0 0 1 0 0 16
05RS015q 5 2 33 0 0 0 0 8 13 12 0 33 5 6 0 0 0 1 0 0 14
05RS016Q 12 1 35 9 0 0 0 7 0 17 0 24 0 4 0 0 0 1 0 0 13
05RS017q 13 0 58 14 0 0 0 4 0 0 0 4 0 0 0 0 0 0 0 0 11
05RS018Q 16 3 31 0 0 0 0 0 0 23 0 23 0 5 0 0 0 1 0 0 21
05RS019Q 12 7 17 2 0 0 0 15 0 28 0 43 8 5 0 0 0 1 0 0 5
05RS020Q 8 7 24 4 0 0 0 11 15 7 0 33 5 5 0 0 0 1 0 0 11
05RS021Q 55 21 0 0 0 0 0 6 0 0 0 6 3 2 0 0 0 0 0 0 14
05RS022Q 44 4 23 0 0 0 0 4 0 0 0 4 3 0 0 0 0 0 0 0 22
05RS025Q 37 1 22 0 0 0 0 8 0 0 0 8 5 3 0 0 0 0 0 0 24
04LM080Q 41 0 24 0 0 0 0 9 0 0 0 9 6 0 0 0 0 0 0 0 20
04LM078Q 11 4 24 11 0 0 0 7 0 18 0 25 5 5 0 0 0 0 0 0 15
04LM064Q 0 0 0 0 6 24 0 23 0 0 0 23 0 13 0 0 0 0 0 0 35
04LM144Q 0 3 0 0 0 40 0 4 0 0 0 4 4 20 0 0 0 2 0 0 27
04LM068Q 9 0 36 0 0 0 0 26 0 0 0 26 0 5 0 0 0 0 0 0 24
04LM069Q 65 0 4 0 0 0 0 3 0 0 0 3 0 2 0 0 0 0 0 0 25
04LM070Q 50 0 19 0 0 0 0 9 0 0 0 9 0 0 0 0 0 0 0 0 23
04LM073Q 37 0 25 0 0 0 0 6 0 10 0 15 1 0 0 0 0 0 0 0 20
04LM074Q 11 3 24 0 0 0 0 0 0 21 0 21 2 5 0 0 0 0 0 0 34
04LM075Q 66 0 25 0 0 0 0 5 0 0 0 5 0 0 0 0 0 0 0 0 4
04LM041Q 5 0 20 0 0 0 0 6 9 0 0 15 3 6 0 0 15 1 0 0 49
04LM042Q 55 1 10 0 0 0 0 0 8 4 0 13 0 0 0 0 0 0 0 0 22
04LM091Q 49 13 0 0 0 0 0 0 16 0 0 16 0 0 0 0 0 1 0 0 21
04LM092Q 44 40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 16
04LM147Q 2 0 0 0 0 0 0 0 0 22 0 22 0 11 0 0 0 2 0 0 63
04LM148Q 21 0 9 0 0 0 0 0 20 17 0 36 4 0 0 0 0 2 0 0 28
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
46
4.2.3 Río Derecha - Río Zamoreño
Rio Derecha
sample name qua cal heu mor alb byt Pla Adu vel mag NQ
09LM090 26 0 12 34 3 2 7 0 0 1 14
09LM091 21 0 61 2 0 2 6 0 6 0 12
09LM092 13 2 5 29 0 4 17 0 0 1 31
09LM093 21 2 3 44 0 2 6 3 0 1 18
Rio Zamoreño
sample
name qua cal heu mor lau ana alb oli lab byt pla aug mag pum pre NQ
09LM104Q 9 0 46 0 0 0 11 0 0 0 0 4 0 0 0 30
09LM105Q 7 0 45 0 0 0 5 0 5 0 5 5 0 0 0 33
09LM106K x
09LM107Q 7 0 52 0 0 0 4 0 4 0 4 5 0 0 0 22
09LM108Q 11 0 27 21 0 0 2 0 3 0 3 3 0 0 0 32
09LM109 8 0 21 35 0 1 0 1 3 0 4 3 0 0 0
09LM110Q 38 0 5 28 0 2 0 0 2 0 2 2 0 0 0 23
09LM111K x x x x x
09LM113Q 13 0 11 37 0 0 2 0 2 3 6 3 0 0 0 28
09LM114Q 22 2 44 3 0 0 4 0 1 2 3 4 0 0 0 17
09LM115Q 32 7 11 2 2 6 5 0 24 0 24 4 0 0 0 7
09LM116K x x
09LM118Q 29 0 0 0 0 0 50 0 0 0 0 2 1 5 1 11
09LM119Q 16 1 0 0 0 0 59 0 0 0 0 3 2 4 0 15
47
4.2.4 Manabí área
Agua Blanca, Puerto Cayo, Puerto López and Río Mocora
Sample Names qua cal heu mor ana lau tho sti eri epi alb oli and lab byt pla k-
fsp aug ens mag cri try NQ
CZ35 12 4 6 0 0 0 0 0 0 0 0 0 0 9 0 9 0 0 0 0 24 16 22
EC06LM428
bis 2 1 16 0 1 0 0 0 24 0 0 0 5 10 0 14 0 6 0 1 0 0 21
EC06LM430 2 2 16 0 1 0 0 0 14 0 0 0 11 7 0 18 1 7 0 1 0 0 19
EC06LM430
bis 10 7 0 0 0 0 0 0 0 0 0 0 2 0 0 2 2 0 0 0 27 55 0
EC06LM431 1 4 36 0 0 0 0 0 0 0 3 0 12 0 0 12 4 8 0 1 0 0 18
EC06LM431bi 1 3 34 0 0 0 0 0 0 0 3 0 12 0 0 12 3 8 0 1 0 0 22
05RS137 1 0 10 0 3 0 0 0 0 0 0 1 7 23 2 33 14 7 0 0 0 0 0
05RS139 1 0 28 0 0 0 0 0 6 0 0 0 0 17 0 17 6 5 0 0 0 0 20
CZ33 3 2 37 0 0 0 0 0 0 0 0 7 0 0 0 7 0 0 0 0 0 0 43
EC06LM427 1 5 22 0 0 0 0 0 6 0 0 0 0 2 0 2 26 5 0 2 0 0 31
EC06LM428 1 12 78 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 7
EC06LM406 0 0 0 0 2 1 2 9 0 7 0 32 0 0 0 32 3 0 0 0 0 0 12
EC06LM407 3 8 49 0 0 0 0 0 0 0 2 0 8 0 0 8 1 4 0 1 0 0 15
EC06LM411 3 0 32 27 0 0 0 0 0 0 0 0 8 0 0 8 1 3 0 1 0 0 16
EC06LM421 3 0 47 0 0 0 0 0 0 0 0 0 17 0 0 17 0 3 0 1 0 0 13
EC06LM424 1 4 53 0 0 0 0 0 0 0 1 0 7 0 0 7 7 4 0 1 0 0 16
EC06LM425 2 1 45 0 0 0 0 0 0 0 2 2 13 12 2 29 6 4 3 0 0 0 0
Appendix 4 - Characterization of the Late Cretaceous deposits of Coastal Ecuador
48
Río Ayampe
Sample
names qua cal heu mor ana lau tho sti cha alb oli and lab byt pla
K-
fsp aug dio pum ens fer mag NQ
04LM049Q 1 0 7 0 12 0 13 0 0 0 0 0 17 0 17 2 33 0 0 0 0 1 0
04LM059 16 5 0 0 19 0 0 0 0 2 4 12 14 0 30 0 0 4 0 0 0 0 0
04LMXP2 1 1 84 0 0 0 0 0 0 0 0 4 5 0 9 0 0 0 0 0 0 0 0
04LMXP3 0 0 93 0 0 0 0 0 0 0 0 2 1 0 3 0 0 0 0 0 0 0 1
05RS065 0 0 0 0 7 0 0 0 15 3 0 0 0 18 18 3 37 0 0 0 0 0 0
05RS071 1 0 98 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
05RS091b 11 2 24 26 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 35
05RS101 4 0 51 29 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 13
05RS110 3 5 35 5 3 0 0 0 0 0 0 8 12 2 22 3 8 0 0 0 0 0 0
05RS114 9 7 27 31 0 0 0 0 0 0 0 0 14 0 14 2 0 0 0 0 0 0 0
06LM337 38 0 0 0 0 9 0 0 0 29 9 0 0 0 9 4 3 0 0 0 0 0 1
06LM341 26 0 0 2 0 14 0 0 0 11 25 0 0 0 25 4 4 0 0 0 0 0 0
06LM343 39 1 24 0 0 0 0 22 0 6 0 0 0 0 0 1 2 0 0 0 0 0 5
06LM345 11 0 18 9 0 0 0 2 0 0 6 6 17 0 29 3 7 0 0 0 0 1 0
06LM347 33 3 0 47 0 0 0 0 0 0 1 1 0 0 2 3 0 0 0 0 0 0 11
06LM350 41 2 0 0 0 0 0 0 0 33 0 0 0 0 0 8 2 0 0 0 0 0 13
06LM351 43 0 0 0 0 33 0 0 0 15 0 0 0 0 0 2 3 0 0 0 0 0 5
06LM378 3 3 22 0 0 0 0 0 0 2 1 2 22 2 27 7 9 0 0 0 0 1 0
06LM396 2 18 46 4 0 0 0 0 0 0 0 0 14 0 14 2 6 0 0 0 0 0 0
06LM397 8 5 27 46 0 0 0 0 0 0 0 0 2 0 2 2 1 0 0 0 0 0 8
EC06LM402 0 0 0 0 20 8 4 3 0 0 0 0 0 0 0 2 31 0 0 0 0 1 31
EC06LM404 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 27 2 5 3 0 63
49
4.3 EPMA
4.3.1 HEU-type zeolites
1.
Sample 06LM015
Num 6 7 1 2 3 4 5 6 7 8
Na2O 0.07 0.25 0.05 0.26 0.24 0.20 0.72 1.88 0.24 0.38
K2O 0.49 0.38 0.40 0.49 0.52 0.47 0.16 0.20 0.21 0.16
SiO2 59.79 59.43 59.29 59.21 59.56 58.52 64.75 66.07 66.99 65.68
Al2O3 16.02 16.28 15.84 16.13 15.78 16.22 13.10 13.42 12.44 12.61
FeO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.42 0.00 0.02 0.03 0.03 0.00 0.72 0.03 0.69 0.73
CaO 7.44 7.82 7.92 7.77 7.81 7.65 5.30 4.41 5.40 5.46
SrO 0.32 0.43 0.29 0.36 0.33 0.37 0.00 0.00 0.00 0.00
BaO 0.00 0.63 0.64 0.70 0.39 0.74 0.00 0.00 0.00 0.00
Na 0.06 0.22 0.04 0.24 0.22 0.18 0.63 1.62 0.21 0.33
K 0.29 0.22 0.24 0.29 0.30 0.28 0.09 0.11 0.12 0.09
Si 27.41 27.26 27.40 27.27 27.43 27.20 29.10 29.26 29.56 29.36
Al 8.65 8.80 8.63 8.75 8.56 8.89 6.94 7.01 6.47 6.64
Fe 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.28 0.00 0.02 0.02 0.02 0.00 0.48 0.02 0.45 0.49
Ca 3.65 3.84 3.92 3.83 3.86 3.81 2.55 2.09 2.56 2.61
Sr 0.09 0.12 0.08 0.09 0.09 0.10 0.00 0.00 0.00 0.00
Ba 0.00 0.11 0.11 0.13 0.07 0.13 0.00 0.00 0.00 0.00
E% 3.05 2.52 1.08 0.88 -0.27 3.91 2.26 17.79 2.02 0.33
Si/Al 3.17 3.10 3.18 3.11 3.20 3.06 4.19 4.18 4.57 4.42
R 0.76 0.76 0.76 0.76 0.76 0.75 0.81 0.81 0.82 0.82
M/M+D 0.08 0.10 0.06 0.11 0.11 0.10 0.19 0.45 0.10 0.12
Na/Na+K 0.18 0.50 0.15 0.45 0.42 0.40 0.87 0.94 0.64 0.79
50
2.
Sample 06LM027
Num 9 10 14 15 16 17 35 36 37 38
Na2O 0.25 0.12 0.20 0.20 0.40 0.20 0.24 0.60 0.29 0.30
K2O 0.15 0.15 0.19 0.20 0.18 0.18 0.37 0.44 0.52 0.38
SiO2 66.52 67.15 66.58 65.92 66.13 67.36 66.74 65.42 60.90 63.39
Al2O3 12.80 12.64 13.26 12.91 12.67 13.41 12.86 12.92 15.35 14.02
FeO 0.00 0.00 0.11 0.22 0.00 0.00 0.00 0.10 0.00 0.00
MnO 0.00 0.08 0.12 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.92 0.26 0.53 0.48 0.42 0.95 0.36 0.16 0.04 0.00
CaO 5.35 6.15 6.11 6.04 6.27 5.58 6.11 6.23 8.12 7.09
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.30 0.00 0.00 0.00 0.00
Na 0.21 0.10 0.17 0.17 0.34 0.17 0.21 0.52 0.25 0.26
K 0.08 0.08 0.11 0.11 0.10 0.10 0.21 0.25 0.30 0.22
Si 29.36 29.50 29.15 29.23 29.30 29.17 29.34 29.16 27.69 28.58
Al 6.66 6.55 6.84 6.75 6.62 6.85 6.66 6.79 8.22 7.45
Fe 0.00 0.00 0.04 0.08 0.00 0.00 0.00 0.04 0.00 0.00
Mn 0.00 0.03 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.61 0.17 0.34 0.31 0.27 0.61 0.24 0.11 0.03 0.00
Ca 2.53 2.89 2.87 2.87 2.97 2.59 2.88 2.97 3.96 3.42
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00
E% 1.32 3.88 2.85 2.57 -4.68 0.97 0.30 -1.57 -4.02 1.68
Si/Al 4.41 4.51 4.26 4.33 4.43 4.26 4.40 4.30 3.37 3.84
R 0.82 0.82 0.81 0.81 0.82 0.81 0.81 0.81 0.77 0.79
M/M+D 0.09 0.06 0.08 0.08 0.12 0.08 0.12 0.20 0.12 0.12
Na/Na+K 0.72 0.56 0.61 0.61 0.77 0.63 0.50 0.67 0.46 0.55
51
3.
Sample 06LM026
Num 39 41 42 57 58 59 60 61 62 63
Na2O 0.30 0.21 0.25 0.16 0.20 0.27 0.50 0.35 0.26 0.38
K2O 0.43 0.21 0.25 0.15 0.30 0.36 0.76 0.49 0.56 0.27
SiO2 61.24 66.14 65.97 68.16 67.95 67.54 59.47 60.40 60.68 67.27
Al2O3 15.21 12.73 12.67 12.00 12.29 12.14 16.40 15.29 15.21 11.99
FeO 0.00 0.00 0.13 0.23 0.23 0.49 0.00 0.00 0.10 0.00
MnO 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.00 0.00 0.38 0.86 1.15 1.15 0.00 0.00 0.00 0.38
CaO 8.02 6.72 6.12 5.31 5.21 4.82 8.12 8.14 8.11 5.88
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.34 0.16 0.21 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.36 0.00
Na 0.27 0.18 0.21 0.14 0.17 0.23 0.44 0.31 0.23 0.33
K 0.25 0.12 0.14 0.08 0.17 0.20 0.44 0.29 0.33 0.15
Si 27.80 29.34 29.33 29.75 29.56 29.60 27.14 27.65 27.67 29.69
Al 8.14 6.66 6.64 6.18 6.30 6.27 8.82 8.25 8.17 6.24
Fe 0.00 0.00 0.05 0.08 0.08 0.18 0.00 0.00 0.04 0.00
Mn 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.00 0.00 0.25 0.56 0.75 0.75 0.00 0.00 0.00 0.25
Ca 3.90 3.19 2.91 2.48 2.43 2.26 3.97 3.99 3.96 2.78
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.04 0.06 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.06 0.00
E% -2.21 -0.49 0.12 -0.81 -4.46 0.00 -1.98 -4.77 -5.83 -4.59
Si/Al 3.42 4.41 4.42 4.82 4.69 4.72 3.08 3.35 3.39 4.76
R 0.77 0.82 0.82 0.83 0.82 0.83 0.75 0.77 0.77 0.83
M/M+D 0.12 0.09 0.10 0.07 0.09 0.12 0.18 0.13 0.12 0.14
Na/Na+K 0.52 0.60 0.60 0.62 0.50 0.53 0.50 0.52 0.41 0.68
52
4.
Sample 06LM026
Num 64 65 66 67 69 70 71 72 73 74
Na2O 0.26 0.25 0.24 0.26 0.29 0.26 0.24 0.31 0.34 0.32
K2O 0.24 0.28 0.22 0.19 0.25 0.24 0.25 0.35 0.27 0.24
SiO2 61.73 64.07 67.99 68.92 65.01 65.68 64.76 66.65 64.83 64.50
Al2O3 14.65 12.73 13.29 12.94 12.68 12.97 12.67 12.85 12.85 12.89
FeO 0.00 0.00 0.00 0.13 0.00 0.00 0.00 0.00 0.10 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.03 0.35 1.06 0.53 0.00 0.06 0.04 0.00 0.00 0.00
CaO 7.91 6.12 5.55 5.87 6.57 6.55 6.64 6.69 6.74 6.81
SrO 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na 0.23 0.22 0.20 0.21 0.25 0.22 0.21 0.27 0.30 0.28
K 0.14 0.16 0.12 0.10 0.14 0.14 0.14 0.20 0.16 0.14
Si 28.07 29.17 29.25 29.49 29.27 29.23 29.24 29.31 29.14 29.11
Al 7.85 6.83 6.74 6.53 6.73 6.80 6.74 6.66 6.81 6.85
Fe 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0.04 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.02 0.24 0.68 0.34 0.00 0.04 0.03 0.00 0.00 0.00
Ca 3.85 2.99 2.56 2.69 3.17 3.12 3.21 3.15 3.24 3.29
Sr 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E% -3.73 0.02 -0.82 3.04 0.04 1.85 -1.22 -1.55 -1.45 -2.17
Si/Al 3.58 4.27 4.34 4.52 4.35 4.30 4.34 4.40 4.28 4.25
R 0.78 0.81 0.81 0.82 0.81 0.81 0.81 0.81 0.81 0.81
M/M+D 0.09 0.11 0.09 0.09 0.11 0.10 0.10 0.13 0.12 0.11
Na/Na+K 0.62 0.57 0.63 0.68 0.64 0.62 0.59 0.58 0.66 0.67
53
5.
Sample 06LM026
Num 75 90 91 92 93 94 95 117 118 120
Na2O 0.23 0.33 0.32 0.28 0.19 0.42 0.28 0.31 0.42 0.71
K2O 0.34 0.31 0.26 0.29 0.24 0.28 0.26 0.41 0.55 0.69
SiO2 61.40 60.81 64.10 64.72 65.60 65.08 66.34 60.19 60.13 59.44
Al2O3 14.61 14.86 12.60 12.67 12.79 12.47 12.23 14.90 15.55 16.40
FeO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CaO 7.83 8.15 6.75 6.83 6.63 6.61 6.54 7.93 8.07 8.20
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.16 0.26
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na 0.21 0.29 0.28 0.24 0.17 0.37 0.24 0.27 0.38 0.63
K 0.20 0.18 0.15 0.17 0.14 0.16 0.15 0.24 0.32 0.40
Si 28.08 27.86 29.18 29.20 29.29 29.31 29.53 27.81 27.53 27.10
Al 7.87 8.03 6.76 6.74 6.73 6.62 6.42 8.12 8.39 8.81
Fe 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ca 3.84 4.00 3.29 3.30 3.17 3.19 3.12 3.93 3.96 4.00
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.04 0.07
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E% -2.57 -5.20 -3.63 -3.88 1.28 -4.20 -3.08 -3.64 -3.56 -3.94
Si/Al 3.57 3.47 4.32 4.33 4.35 4.43 4.60 3.43 3.28 3.07
R 0.78 0.78 0.81 0.81 0.81 0.82 0.82 0.77 0.77 0.75
M/M+D 0.10 0.10 0.11 0.11 0.09 0.14 0.11 0.12 0.15 0.20
Na/Na+K 0.51 0.62 0.65 0.59 0.55 0.69 0.62 0.53 0.54 0.61
54
6.
Sample 06LM026
Num 121 122 123 124 125 126 127 128 129 130
Na2O 0.26 0.41 0.50 0.24 0.22 0.25 0.25 0.28 0.36 0.31
K2O 0.63 0.71 0.24 0.59 0.25 0.24 0.23 0.24 0.53 0.42
SiO2 58.83 59.42 63.48 59.55 66.30 66.36 65.50 66.89 60.55 61.68
Al2O3 15.90 16.33 13.76 15.71 12.86 13.29 13.81 12.56 15.34 15.29
FeO 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.00 0.00 0.03 0.03 0.16 0.69 0.04 0.03 0.00 0.00
CaO 8.15 8.15 7.52 8.47 6.63 6.12 7.21 6.78 8.17 8.25
SrO 0.22 0.33 0.00 0.21 0.00 0.00 0.00 0.00 0.16 0.00
BaO 0.32 0.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na 0.23 0.36 0.44 0.22 0.19 0.21 0.21 0.24 0.32 0.27
K 0.37 0.42 0.14 0.35 0.14 0.13 0.13 0.13 0.31 0.24
Si 27.25 27.14 28.56 27.36 29.27 29.08 28.83 29.42 27.64 27.79
Al 8.68 8.79 7.29 8.51 6.69 6.86 7.17 6.51 8.25 8.12
Fe 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.00 0.00 0.02 0.02 0.11 0.45 0.03 0.02 0.00 0.00
Ca 4.05 3.99 3.63 4.17 3.14 2.88 3.40 3.19 3.99 3.98
Sr 0.06 0.09 0.00 0.06 0.00 0.00 0.00 0.00 0.04 0.00
Ba 0.06 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
E% -2.84 -3.06 -7.33 -5.95 -1.82 -1.41 -0.42 -4.25 -5.19 -4.13
Si/Al 3.14 3.09 3.92 3.22 4.37 4.24 4.02 4.52 3.35 3.42
R 0.76 0.76 0.80 0.76 0.81 0.81 0.80 0.82 0.77 0.77
M/M+D 0.13 0.16 0.14 0.12 0.09 0.09 0.09 0.10 0.14 0.11
Na/Na+K 0.38 0.46 0.76 0.39 0.57 0.61 0.62 0.64 0.51 0.52
55
4.3.2 Mordenite
Sample 04LM026 04LM015
Num 104 105 106 107 1 2 3 4
Na2O 1.16 1.12 0.95 0.79 1.11 1.22 1.49 1.59
K2O 0.18 0.25 0.24 0.23 0.11 0.06 0.08 0.05
SiO2 60.72 57.54 63.60 68.47 68.42 68.41 67.62 68.03
Al2O3 11.12 10.83 11.45 11.74 12.77 12.52 12.99 12.58
FeO 0.22 0.16 0.24 0.25 0.00 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.19 0.19 0.05 0.06 0.00 0.00 0.00 0.00
CaO 3.55 3.46 3.84 3.61 3.96 3.92 4.10 4.01
TiO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
H2O 22.87 26.43 19.62 14.85 13.64 13.86 13.73 13.74
Na 1.48 1.50 1.15 0.90 1.25 1.38 1.69 1.80
K 0.15 0.22 0.19 0.17 0.08 0.05 0.06 0.04
Si 39.76 39.57 39.93 40.38 39.86 39.95 39.56 39.78
Al 8.58 8.78 8.48 8.16 8.77 8.62 8.96 8.67
Fe 0.12 0.09 0.13 0.12 0.00 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.19 0.19 0.05 0.05 0.00 0.00 0.00 0.00
Ca 2.49 2.55 2.58 2.28 2.47 2.45 2.57 2.51
Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Si/Al 4.63 4.51 4.71 4.95 4.55 4.64 4.42 4.59
R 0.82 0.82 0.82 0.83 0.82 0.82 0.82 0.82
E% 24.42 23.08 30.24 44.22 39.71 36.14 30.05 26.16
56
4.3.3 Laumontite
Sample 04LM094
Num 26 27 28 30 31 33
Na2O 0.19 0.14 0.14 0.24 0.00 0.00
K2O 0.53 0.40 0.37 0.41 0.06 0.06
SiO2 53.17 52.85 52.14 53.36 51.63 51.18
Al2O3 20.88 21.07 20.97 21.16 21.62 21.75
FeO 0.11 0.16 0.48 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.00 0.00
MgO 0.00 0.00 0.32 0.00 0.00 0.00
CaO 11.17 11.24 11.37 11.39 12.26 12.31
TiO2 0.00 0.00 0.24 0.00 0.00 0.00
SrO 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00
H2O 13.95 14.16 13.98 13.46 14.44 14.70
Na 0.12 0.08 0.08 0.14 0.00 0.00
K 0.21 0.16 0.14 0.16 0.02 0.02
Si 16.38 16.31 16.13 16.33 16.02 15.95
Al 7.58 7.67 7.65 7.63 7.91 7.99
Fe 0.03 0.04 0.13 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00 0.00
Mg 0.00 0.00 0.15 0.00 0.00 0.00
Ca 3.69 3.72 3.77 3.74 4.08 4.11
Ti 0.00 0.00 0.06 0.00 0.00 0.00
Sr 0.00 0.00 0.00 0.00 0.00 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00
Si/AL 2.16 2.13 2.11 2.14 2.03 2.00
R 0.68 0.68 0.68 0.68 0.67 0.67
E% -1.12 0.46 -3.60 -1.76 -3.31 -3.13
57
4.3.4 Chlorite-Smectite
1.
Sample 04LM094
Num 18 20 21 23 29
Na2O 0.00 0.05 0.07 0.11 0.04
K2O 0.30 0.45 0.05 0.07 0.30
SiO2 27.90 30.98 29.83 29.71 27.30
Al2O3 11.38 12.39 11.29 11.04 11.13
FeO 19.76 20.09 25.41 23.94 19.71
MnO 0.27 0.33 0.63 0.60 0.33
MgO 13.10 12.10 15.17 14.46 12.91
CaO 1.12 5.36 1.05 1.04 1.12
TiO2 0.10 0.64 0.06 0.00 0.07
SrO 0.00 0.00 0.00 0.00 0.00
BaO 0.23 0.00 0.00 0.00 0.00
H2O 25.84 17.62 16.45 19.05 27.09
Na 0.00 0.02 0.03 0.05 0.02
K 0.09 0.13 0.01 0.02 0.10
Si 6.87 6.91 6.67 6.80 6.84
Al 3.30 3.26 2.97 2.98 3.29
Fe 4.07 3.75 4.75 4.58 4.13
Mn 0.06 0.06 0.12 0.12 0.07
Mg 4.81 4.02 5.05 4.94 4.82
Ca 0.29 1.28 0.25 0.25 0.30
Ti 0.02 0.11 0.01 0.00 0.01
Sr 0.00 0.00 0.00 0.00 0.00
Ba 0.02 0.00 0.00 0.00 0.00
Tot K + Ca +
Na 0.39 1.43 0.30 0.32 0.41
Al Vi 1.13 1.09 1.33 1.20 1.16
Al Vi 2.17 2.17 1.64 1.78 2.13
Tot iv 8.00 8.00 8.00 8.00 8.00
Tot Vi 11.12 10.11 11.57 11.42 11.16
Fe/(Fe + Mg) 0.46 0.48 0.48 0.48 0.46
58
2.
Sample 04LM026
Num 76 77 78 79 80 81 82 84 85 86 87
Na2O 0.07 0.06 0.20 0.18 0.13 0.13 0.12 0.06 0.10 0.11 0.14
K2O 0.07 0.04 0.19 0.11 0.47 0.74 0.31 0.23 0.50 0.33 0.22
SiO2 29.90 28.17 33.23 30.19 29.36 31.28 28.95 27.44 29.20 27.86 29.03
Al2O3 12.40 11.88 11.79 12.40 11.15 11.15 11.27 10.82 11.04 10.33 11.14
FeO 28.72 27.40 25.75 28.01 21.63 22.12 21.49 20.42 20.91 18.95 21.33
MnO 1.39 1.29 0.89 1.33 0.67 0.56 0.53 0.55 0.62 0.51 0.57
MgO 13.26 12.42 13.07 12.83 11.67 11.67 11.77 11.12 11.13 11.36 11.78
CaO 0.80 0.60 1.69 0.91 1.53 1.81 1.62 1.38 2.77 1.42 1.40
TiO2 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.07 0.00 0.00
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.38
H2O 13.40 18.13 13.19 14.06 23.40 20.44 23.96 28.00 23.67 29.15 24.01
Na 0.03 0.03 0.08 0.08 0.06 0.06 0.05 0.03 0.05 0.05 0.07
K 0.02 0.01 0.05 0.03 0.14 0.22 0.09 0.07 0.15 0.11 0.07
Si 6.56 6.54 7.09 6.65 7.05 7.22 7.00 7.00 7.05 7.16 7.03
Al 3.21 3.25 2.97 3.22 3.16 3.03 3.21 3.25 3.14 3.13 3.18
Fe 5.27 5.32 4.60 5.16 4.35 4.27 4.34 4.35 4.22 4.07 4.32
Mn 0.26 0.25 0.16 0.25 0.14 0.11 0.11 0.12 0.13 0.11 0.12
Mg 4.34 4.30 4.16 4.21 4.18 4.02 4.24 4.23 4.01 4.35 4.26
Ca 0.19 0.15 0.39 0.21 0.39 0.45 0.42 0.38 0.72 0.39 0.36
Ti 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.00 0.00
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04
Tot
K+Ca+N
a
0.24 0.19 0.52 0.32 0.60 0.72 0.57 0.48 0.92 0.55 0.50
Al Vi 1.44 1.46 0.91 1.35 0.95 0.78 1.00 1.00 0.95 0.84 0.97
Al Vi 1.77 1.79 2.06 1.86 2.21 2.26 2.21 2.25 2.19 2.28 2.22
Tot iv 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Tot Vi 11.63 11.66 10.97 11.48 10.87 10.67 10.90 10.95 10.56 10.81 10.91
Fe /
(Fe+Mg) 0.55 0.55 0.52 0.55 0.51 0.52 0.51 0.51 0.51 0.48 0.50
59
3.
Sample 04LM026
Num 88 89 98 99 100 102 103 108 109 110 111
Na2O 0.07 0.17 0.15 0.11 0.16 0.07 0.10 0.10 0.14 0.09 0.08
K2O 0.05 0.16 0.44 0.27 0.46 0.60 0.40 0.36 0.38 0.24 0.29
SiO2 29.85 30.32 29.55 26.47 33.77 31.58 31.59 35.07 35.25 27.33 29.70
Al2O3 12.56 12.44 11.18 10.14 12.36 10.88 11.83 10.12 9.78 10.60 11.23
FeO 28.31 28.11 21.37 19.87 23.89 21.41 23.42 21.48 21.33 20.62 20.81
MnO 1.23 1.28 0.46 0.50 0.59 0.41 0.59 0.50 0.55 0.42 0.47
MgO 13.53 12.47 12.02 10.53 12.92 11.57 12.14 13.07 14.10 11.06 11.59
CaO 0.59 0.85 1.54 1.13 2.08 2.89 2.23 2.56 2.25 1.16 1.59
TiO2 0.00 0.00 0.00 0.00 0.00 0.00 0.07 0.00 0.00 0.00 0.08
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
H2O 13.81 14.19 23.29 30.97 13.77 20.59 17.62 16.73 16.23 28.48 24.15
Na 0.03 0.07 0.07 0.06 0.07 0.03 0.04 0.04 0.06 0.04 0.04
K 0.01 0.04 0.13 0.09 0.12 0.18 0.12 0.10 0.11 0.08 0.09
Si 6.55 6.68 7.07 7.05 7.17 7.28 7.07 7.61 7.60 7.02 7.15
Al 3.25 3.23 3.15 3.18 3.09 2.96 3.12 2.59 2.49 3.21 3.18
Fe 5.20 5.18 4.27 4.43 4.24 4.13 4.39 3.90 3.84 4.43 4.19
Mn 0.23 0.24 0.09 0.11 0.11 0.08 0.11 0.09 0.10 0.09 0.10
Mg 4.43 4.10 4.28 4.18 4.09 3.98 4.05 4.23 4.53 4.24 4.16
Ca 0.14 0.20 0.39 0.32 0.47 0.71 0.53 0.59 0.52 0.32 0.41
Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01
Sr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ba 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Tot K+Ca+Na 0.18 0.32 0.60 0.47 0.66 0.92 0.69 0.74 0.68 0.44 0.54
Al Vi 1.45 1.32 0.93 0.95 0.83 0.72 0.93 0.39 0.40 0.98 0.85
Al Vi 1.80 1.92 2.21 2.24 2.27 2.24 2.19 2.20 2.08 2.23 2.33
Tot iv 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Tot Vi 11.66 11.44 10.86 10.96 10.71 10.42 10.75 10.43 10.56 10.99 10.79
Fe/(Fe + Mg) 0.54 0.56 0.50 0.51 0.51 0.51 0.52 0.48 0.46 0.51 0.50
60
4.3.5 Celadonite
Sample 09LM094 04LM026
Num 19 24 25 44 45 46 53 54 55 56
Na2O 0.00 0.00 0.00 0.07 0.10 0.05 0.05 0.04 0.06 0.00
K2O 5.34 7.81 7.76 8.44 9.39 6.96 10.09 8.04 9.84 9.91
SiO2 39.36 45.11 45.09 45.82 49.35 42.59 53.06 51.71 52.71 52.74
Al2O3 9.72 8.42 8.86 5.93 6.39 7.37 4.36 5.07 4.18 4.24
FeO 14.69 13.74 13.59 14.23 14.28 15.10 18.36 14.42 19.10 19.00
MnO 0.15 0.15 0.16 0.13 0.00 0.23 0.18 0.00 0.00 0.17
MgO 7.48 5.15 5.09 4.92 4.70 6.20 4.36 3.95 4.39 4.44
CaO 0.60 0.35 0.35 0.19 0.18 0.50 0.44 0.36 0.35 0.35
TiO2 0.11 0.21 0.27 0.43 0.45 0.32 0.57 0.40 0.43 0.41
H2O 22.55 19.08 18.83 19.84 15.16 20.68 8.53 16.02 8.94 8.74
Na 0.00 0.00 0.00 0.01 0.02 0.01 0.01 0.01 0.01 0.00
K 0.61 0.84 0.83 0.93 0.97 0.78 0.99 0.83 0.97 0.97
Si 3.50 3.82 3.80 3.95 4.00 3.73 4.08 4.18 4.07 4.07
Al 1.02 0.84 0.88 0.60 0.61 0.76 0.39 0.48 0.38 0.39
Fe 1.09 0.97 0.96 1.03 0.97 1.11 1.18 0.97 1.23 1.23
Mn 0.01 0.01 0.01 0.01 0.00 0.02 0.01 0.00 0.00 0.01
Mg 0.99 0.65 0.64 0.63 0.57 0.81 0.50 0.48 0.51 0.51
Ca 0.06 0.03 0.03 0.02 0.02 0.05 0.04 0.03 0.03 0.03
Ti 0.01 0.01 0.02 0.03 0.03 0.02 0.03 0.02 0.02 0.02
61
4.4 SEM-EDX
4.4.1 Heu-type zeolites
Sample 06LM116 06LM079
circle circle 2 circle 3 Circle 5
NUM 1_4 1_1 1_2 2_3 2_4 1b
O 49.12 49.54 48.62 49.45 51.10
Na2O 9.92 1.75 1.25 1.46 1.56 2.41
MgO 0.12
Al2O3 16.67 19.08 17.44 17.99 17.33 17.40
SiO2 71.65 68.37 72.27 72.37 71.65 70.88
K2O 0.08 1.86 1.18 1.43 1.07
CaO 1.56 8.37 7.77 8.09 8.19 5.71
Fe2O3 0.97
wt% heu heu heu heu heu impure Heu?
Na 8.41 1.34 0.94 1.08 1.18 1.85
Mg 0.07
Al 7.63 8.88 7.97 8.14 7.95 8.13
Si 27.81 27.00 28.03 27.79 27.90 28.08
K 0.04 0.93 0.58 0.70 0.53
Ca 0.65 3.54 3.23 3.33 3.42 2.42
Fe 0.29
R 0.78 0.75 0.78 0.77 0.78 0.78
Si/Al 3.65 3.04 3.52 3.41 3.51 3.46
M/M+D 0.92 0.39 0.32 0.35 0.33 0.43
Na/Na+K 1.00 0.59 0.62 0.61 0.69 1.00
E% -22.90 -5.07 -0.11 -3.55 -6.92 25.61
62
4.4.2 Mordenite
Sample 06LM108
Circle circle6 Other
NUM 1_1 1_2 2_1 1_1 1_2
O 50.80 51.11 51.10
Na2O 4.80 4.29 4.99 4.09 3.82
MgO 0.08
Al2O3 15.04 14.30 14.96 16.04 16.29
SiO2 72.52 73.19 71.18 75.23 75.02
K2O 0.13 0.20
CaO 5.29 5.50 5.60 4.51 4.59
Na 4.91 4.39 5.17 4.56 4.26
Mg 0.06
Al 9.35 8.91 9.43 9.64 9.79
Si 38.26 38.67 38.04 38.37 38.27
K 0.08 0.13
Ca 2.99 3.11 3.20 2.46 2.51
Si/Al 4.09 4.34 4.04 3.98 3.91
R 0.80 0.81 0.80 0.80 0.80
M/M+D 0.62 0.59 0.62 0.65 0.63
E% -14.11 -16.11 -18.59 0.73 2.79
Sample 09LM028
Circle circle1 circle 2
NUM 1_1 1_2 1_3 3_1 3_2 5_3 5_4 6_1 7_2 3_3
Na2O 1.01 0.82 1.07 3.32 2.75 2.46 1.20 1.92 1.98 1.85
MgO 0.32 0.53 0.74 0.24 0.07 0.15 0.14 0.15 0.22
Al2O3 15.92 16.86 17.08 16.44 16.77 16.73 17.10 16.81 16.62 14.74
SiO2 77.03 75.73 74.97 75.30 75.76 76.25 76.99 76.68 76.81 79.32
K2O 0.85 0.87 1.06 0.66 0.56 0.63 0.71 0.41 0.51 0.71
CaO 4.88 5.19 5.08 3.75 3.79 3.87 3.85 4.03 3.92 3.15
Fe2O3 0.29 0.36
Na 1.12 0.91 1.19 3.70 3.05 2.72 1.32 2.12 2.19 0.18
Mg 0.24 0.40 0.56 0.18 0.05 0.11 0.11 0.11 0.01
Al 9.50 10.09 10.25 9.87 10.04 9.99 10.17 10.01 9.90 0.78
Si 39.01 38.45 38.18 38.37 38.48 38.64 38.83 38.75 38.83 3.57
K 0.55 0.56 0.69 0.43 0.36 0.41 0.46 0.26 0.33 0.04
Ca 2.65 2.82 2.77 2.05 2.06 2.10 2.08 2.18 2.12 0.15
Fe 0.11 0.14
Si/Al 4.11 3.81 3.72 3.89 3.83 3.87 3.82 3.87 3.92 4.57
R 0.80 0.79 0.79 0.80 0.79 0.79 0.79 0.79 0.80 0.82
M/M+D 0.37 0.31 0.36 0.65 0.62 0.59 0.45 0.51 0.53 0.57
E% 27.62 27.35 19.95 16.30 34.96 34.31 64.85 43.86 41.69 40.61
63
4.4.3 Analcime
Sample 06LM079
circle circle 5 circle 6 circle 9
NUM 1 1c 1_b1 1_b2 1_02
O 47.73 47.73 48.93 48.92 51.84
Na2O 11.67 11.11 11.20 10.88 10.99
Al2O3 21.73 21.35 22.69 21.94 21.03
SiO2 68.71 70.02 65.78 67.20 61.77
Tot 102.12 102.48 99.68 100.01 93.79
Na 11.61 10.96 11.42 11.02 11.94
Al 13.14 12.81 14.07 13.51 13.88
Si 35.25 35.65 34.60 35.11 34.60
R 0.73 0.74 0.71 0.72 0.71
Si/Al 2.68 2.78 2.46 2.60 2.49
E% 13.15 16.85 23.14 22.58 16.31
64
4.4.4 Chlorite/smectite
Sample 06LM079 06LM108 09LM028
Circle circle 3 circle 4 circle 6 circle 1 circle 1
NUM 2_01 2_02 2_05 1_01 1_04 5_03 3_8 1_4 4_6 7_7 7_10
Na2O 0.40 0.46 0.47 0.46 0.98 0.94 2.29 0.29 0.25 0.20
K2O 0.93 0.89 0.80 1.37 2.64 1.26 1.40 0.27 0.41
SiO2 48.11 47.69 50.25 48.20 44.09 43.79 45.88 48.62 44.52 48.21 51.92
Al2O3 11.94 12.24 12.45 10.88 15.47 15.23 17.85 19.08 18.69 14.72 21.99
FeO 23.59 24.56 25.04 25.41 23.17 21.06 18.55 15.17 17.79 15.78 7.23
MgO 9.52 8.61 9.19 9.75 10.73 10.12 12.34 14.22 18.17 1.91 2.39
CaO 4.31 4.95 4.53 4.77 1.61 1.83 1.82 1.22 0.83 18.85 15.87
H2O 1.20 0.60 -2.72 0.53 2.57 4.40 0.01 0.01 -0.01
Tot 98.80 99.40 102.72 99.47 97.43 95.60 99.99 100.00 100.00 99.99 100.01
Na 0.14 0.16 0.16 0.16 0.34 0.33 0.77 0.09 0.09 0.06
K 0.21 0.20 0.17 0.32 0.62 0.28 0.30 0.06 0.09
Si 8.59 8.52 8.63 8.60 7.99 8.08 7.92 8.14 7.56 8.48 8.56
Al 2.51 2.58 2.52 2.29 3.31 3.31 3.63 3.76 3.74 3.05 4.27
Fe 3.52 3.67 3.60 3.79 3.51 3.25 2.68 2.12 2.53 2.32 1.00
Mg 2.53 2.29 2.35 2.59 2.90 2.78 3.18 3.55 4.60 0.50 0.59
Ca 0.82 0.95 0.83 0.91 0.31 0.36 0.34 0.22 0.15 3.55 2.80
K+Ca+Na 1.17 1.31 1.17 1.07 0.97 1.32 1.38 0.61 0.15 3.70 2.95
AlVi -0.59 -0.52 -0.63 -0.60 0.01 -0.08 0.08 -0.14 0.44 -0.48 -0.56
AlVi 3.10 3.10 3.16 2.88 3.30 3.39 3.55 3.90 3.30 3.54 4.84
Tot iv 8 8 8 8 8 8 8 8 8 8 8
Tot Vi 9.16 9.06 9.11 9.27 9.71 9.42 9.41 9.57 10.42 6.36 6.42
z>y 0.74 0.74 0.74 0.75 0.79 0.77 0.78 0.77 0.84 0.59 0.59
z<y 0.90 0.91 0.89 0.91 0.87 0.88 0.86 0.83 0.86 1.24 1.02
Fe/Fe+mg 0.58 0.62 0.60 0.59 0.55 0.54 0.46 0.37 0.35 0.82 0.63
65
4.4.5 Plagioclase
1.
Sample 06LM079 06LM108
circle circle 1 circle 4 circle 9 circle 1 circle 2
NUM 1d 1_02 2_01 2_02 1_1 1_2 3_7 3_9 1_1 1_2 2_1
O 45.55 44.89 45.38 45.14 52.79 51.84
Na2O 9.99 10.27 10.86 5.70 8.12 10.99 10.01 10.81 4.10 4.11 3.65
Al2O3 22.92 21.33 21.62 27.66 20.85 21.03 17.14 19.46 32.33 32.03 32.58
SiO2 70.70 74.02 75.15 60.07 58.78 61.77 72.22 68.62 50.10 50.20 49.57
K2O 1.51 1.93 0.34 13.47 13.67
CaO 0.87 11.08 3.75 0.62 14.19
MgO 0.29 0.49
Tot 105.99 107.55 107.63 104.52 91.51 93.79 100.00 100.00 100.00 100.01 99.99
Na 0.80 0.81 0.85 0.47 0.76 0.99 0.94 1.02 0.42 0.42 0.36
Al 1.12 1.02 1.02 1.40 1.18 1.16 0.87 0.99 1.79 1.77 1.75
Si 2.92 3.01 3.02 2.58 2.83 2.88 3.10 2.97 2.35 2.36 2.25
K 0.08 0.10 0.02 0.81 0.82
Ca 0.04 0.51 0.19 0.03 0.69
Mg 0.02 0.03
R 0.72 0.75 0.75 0.65 0.71 0.71 0.78 0.75 0.57 0.57 0.56
Si/Al 2.62 2.94 2.95 1.84 2.39 2.49 3.58 2.99 1.31 1.33 1.29
Si+Al 4.04 4.03 4.04 3.98 4.01 4.04 3.97 3.96 4.14 4.13 4.00
Ca 0.04 0.00 0.00 0.52 0.20 0.00 0.00 0.03 0.00 0.00 0.66
Na 0.87 0.89 1.00 0.48 0.80 1.00 0.98 0.97 0.34 0.34 0.34
K 0.09 0.11 0.00 0.00 0.00 0.00 0.02 0.00 0.66 0.66 0.00
Type alb alb alb lab oli alb Alb alb san san lab
66
2.
Sample 06LM108
Circle circle 3 circle 6 circle 7
NUM 3_1_1 3_1_2 3_2_1 3_2_2 6_003_01 7_001_03 7_001_04 7_001_05
O 50.61 44.23 45.26 45.43
Na2O 3.43 2.77 3.43 3.96 3.26 4.92 10.93 10.20
Al2O3 32.34 33.07 19.44 20.93 20.07 30.61 20.86 19.22
SiO2 49.89 49.91 69.50 67.17 66.28 54.02 73.81 77.36
K2O 0.20 0.26 1.25 0.87
CaO 13.99 13.82 6.20 6.95 7.51 14.92 1.53 0.43
MgO 0.15 0.16 0.18 0.12 0.60
Tot 100.00 99.99 100.00 100.00 97.12 104.46 107.12 107.81
Na 0.34 0.27 0.32 0.38 0.28 0.42 0.86 0.79
Al 1.73 1.77 0.99 1.07 1.06 1.58 1.00 0.91
Si 2.27 2.26 3.01 2.92 2.96 2.36 3.00 3.10
K 0.01 0.02 0.07 0.05
Ca 0.68 0.67 0.29 0.32 0.36 0.70 0.07 0.02
Mg 0.01 0.01 0.01 0.01 0.00 0.04
R 0.57 0.56 0.75 0.73 0.74 0.60 0.75 0.77
Si/Al 1.31 1.28 3.03 2.72 2.80 1.50 3.00 3.42
Si+Al 4.00 4.03 4.00 4.00 4.01 3.94 4.00 4.00
Ca 0.66 0.70 0.42 0.43 0.56 0.63 0.07 0.02
Na 0.33 0.29 0.48 0.50 0.44 0.37 0.93 0.98
K 0.01 0.02 0.10 0.06 0.00 0.00 0.00 0.00
Type lab byt and and lab lab alb alb
67
3.
Sample 09LM028
circle circle 1 circle 2
NUM 4_1 4_2 4_5 5_1 5_2 5_5 2_4 2_5 2_6 4_2
Na2O 3.28 10.53 9.84 0.55 3.31 1.08 0.22 2.15 2.48 2.73
Al2O3 32.57 22.51 22.59 20.39 33.02 37.32 24.15 20.86 32.30 31.39
SiO2 52.42 64.62 64.83 71.02 52.20 52.87 53.11 69.82 52.79 54.10
K2O 0.16 0.09 0.69 1.56 0.22 7.95 0.21 1.13 1.26 1.80
CaO 10.97 2.02 2.05 6.25 11.15 0.47 19.66 5.71 10.95 9.92
MgO 0.13 0.24 0.24 0.11 0.31 2.65 0.34 0.22 0.06
Tot 99.53 100.01 100.00 100.01 100.01 100.00 100.00 100.01 100.00 100.00
Na 0.32 1.01 0.94 0.05 0.32 0.11 0.02 0.24 0.26 0.29
Al 1.72 1.16 1.16 1.03 1.74 1.97 1.34 1.25 1.85 1.80
Si 2.36 2.82 2.83 3.04 2.34 2.36 2.50 3.55 2.56 2.63
K 0.01 0.01 0.04 0.09 0.01 0.45 0.01 0.07 0.08 0.11
Ca 0.53 0.09 0.10 0.29 0.53 0.02 0.99 0.31 0.57 0.52
Mg 0.01 0.02 0.02 0.01 0.02 0.19 0.03 0.02
R 0.58 0.71 0.71 0.75 0.57 0.55 0.65 0.74 0.58 0.59
Si/Al 1.37 2.44 2.44 2.96 1.34 1.20 1.87 2.84 1.39 1.46
Si+Al 4.08 3.98 4.00 4.07 4.08 4.33 3.84 4.79 4.41 4.43
Ca 0.61 0.09 0.09 0.68 0.61 0.04 0.97 0.50 0.63 0.56
Na 0.37 0.91 0.87 0.12 0.37 0.18 0.02 0.38 0.29 0.32
K 0.01 0.00 0.04 0.20 0.01 0.78 0.01 0.12 0.09 0.12
Type lab alb alb ? lab san ano lab byt lab
68
4.
Sample 06LM116 06LM129
circle circle 1 circle 2 Circle 2 circle 4
NUM 1_1 1_2 2_1 2_2 2_3 2_4 1_01 1_02 1_01 1_02
O 46.58 41.89 46.65 46.47
Na2O 22.09 22.76 15.78 15.73 12.48 21.02 0.82 11.07 1.01 0.86
Al2O3 17.97 12.67 20.38 20.82 16.29 15.15 24.98 23.16 24.05 24.37
SiO2 59.10 62.05 63.47 62.91 69.25 62.35 62.32 80.50 62.87 63.39
K2O 0.29 0.50 0.16 0.21 0.51 0.27 1.34 2.36 2.71
CaO 0.49 2.02 0.06 0.23 1.33 1.21 12.44 11.92 11.33
MgO 0.05 0.15 0.10 0.15 0.76
Tot 99.99 100.00 100.00 100.00 100.01 100.00 102.66 114.73 102.22 102.67
Na 2.21 2.29 1.53 1.52 1.19 2.09 0.07 0.81 0.09 0.07
Al 0.97 0.69 1.06 1.09 0.84 0.81 1.27 1.03 1.24 1.25
Si 2.70 2.86 2.81 2.79 3.03 2.84 2.70 3.03 2.74 2.75
K 0.02 0.03 0.01 0.01 0.03 0.02 0.07 0.13 0.15
Ca 0.02 0.10 0.00 0.01 0.06 0.06 0.58 0.56 0.53
Mg 0.01 0.01 0.01 0.05
R 0.74 0.81 0.73 0.72 0.78 0.78 0.68 0.75 0.69 0.69
Si/Al 2.79 4.16 2.64 2.56 3.61 3.49 2.12 2.95 2.22 2.21
Si+Al 3.67 3.54 3.88 3.88 3.87 3.65 3.97 4.05 3.98 3.99
Ca 0.01 0.04 0.00 0.01 0.05 0.03 0.80 0.72 0.70
Na 0.98 0.95 0.99 0.99 0.93 0.97 0.10 0.17 0.20
K 0.01 0.01 0.01 0.01 0.02 0.01 0.10 1.00 0.11 0.10
Type alb alb alb alb alb alb Byt alb byt byt
69
4.4.6 Pyroxene
Sample 06LM079 06LM108
circle circle 9 circle 3 circle 4
NUM 2 1_02 1_03 1_01
O 42.04 40.37 39.22 40.40
Na2O 1.21 2.47 2.52 1.54
Al2O3 1.86 1.40 1.81 1.42
SiO2 52.70 53.44 55.79 55.73
K2O 0.00 0.34 0.00 0.00
CaO 18.21 22.00 21.52 22.21
Fe2O3 18.75 14.90 15.18 14.13
MgO 8.82 9.37 9.75 9.78
Total 101.53 103.90 106.58 104.80
Na 0.09 0.18 0.18 0.11
Al 0.08 0.06 0.08 0.06
Si 2.02 2.00 2.01 2.03
K 0.00 0.02 0.00 0.00
Ca 0.75 0.88 0.83 0.87
Fe 0.54 0.42 0.41 0.39
Mg 0.50 0.52 0.52 0.53
R 1.08 0.97 0.96 0.97
Si/Al 24.09 32.43 26.10 33.37
Ca 0.42 0.48 0.47 0.49
Mg 0.28 0.29 0.30 0.30
Fe 0.30 0.23 0.23 0.22
Type aug dio dio Dio
70
4.5 ICP-OES
Major and minor elements
wt% SiO2 Al2O3 Fe2O3 MgO CaO BaO SrO K2O Na2O MnO TiO2 P2O5 TOT TOFe0 H2O-
CO2
09LM060 57.24 15.30 6.79 2.04 5.72 0.20 0.07 1.20 2.44 0.08 0.43 0.13 91.69 91.01 8.99
09LM059 65.12 10.77 3.75 1.49 6.39 0.24 0.07 1.59 2.01 0.05 0.25 0.15 91.97 91.60 8.40
09LM058F 64.62 7.75 3.69 1.37 8.45 0.08 0.04 0.96 0.93 0.06 0.25 0.14 88.40 88.03 11.97
09LM058 58.15 9.40 2.53 0.66 11.11 0.09 0.02 0.37 1.88 0.07 0.30 0.09 84.71 84.46 15.54
09LM057 57.48 13.22 6.49 1.15 6.67 0.14 0.05 0.58 2.39 0.10 0.55 0.13 88.99 88.34 11.66
09LM056 62.74 10.96 2.52 0.80 7.46 0.10 0.05 1.21 1.85 0.06 0.27 0.10 88.18 87.93 12.07
09LM055 57.53 13.83 7.90 2.57 5.37 0.08 0.03 1.27 2.39 0.11 0.51 0.15 91.79 90.99 9.01
09LM054 62.66 13.23 5.53 1.88 4.36 0.11 0.06 1.55 2.21 0.12 0.37 0.12 92.24 91.69 8.31
09LM053 57.12 14.01 6.71 2.47 5.61 0.11 0.04 1.69 2.05 0.11 0.41 0.14 90.54 89.87 10.13
09LM052 54.87 16.47 6.20 1.65 7.88 0.10 0.04 0.71 2.97 0.11 0.37 0.15 91.54 90.92 9.08
09LM051 61.19 6.64 2.42 0.89 13.19 0.08 0.03 0.96 0.75 0.06 0.23 0.08 86.57 86.33 13.67
09LM042 66.20 14.55 7.86 2.47 4.69 0.11 0.03 1.45 2.24 0.13 0.55 0.14 100.48 99.69 0.31
09LM041 68.79 7.92 2.67 0.90 7.10 0.04 0.02 0.72 1.40 0.07 0.27 0.08 90.06 89.80 10.20
09LM040 69.10 8.55 3.80 1.41 14.24 0.10 0.04 1.42 1.41 0.12 0.25 0.10 100.59 100.21 0.00
09LM039 78.55 15.26 5.03 1.48 5.16 0.36 0.08 1.02 2.26 0.08 0.37 0.13 109.86 109.35 0.00
06LM116 65.65 11.87 4.90 1.41 3.54 0.04 0.01 0.52 2.92 0.11 0.37 0.31 91.72 91.23 8.77
09LM038 64.80 12.09 5.38 1.76 3.92 0.05 0.02 1.03 2.42 0.12 0.38 0.23 92.28 91.74 8.26
06LM115 62.67 12.39 6.71 2.36 3.72 0.03 0.02 1.05 2.53 0.14 0.41 0.13 92.21 91.54 8.46
09LM036 58.63 13.10 7.80 3.28 4.48 0.08 0.05 1.16 1.96 0.16 0.45 0.10 91.30 90.51 9.49
09LM035 65.12 16.21 10.73 3.97 6.44 0.01 0.00 0.52 3.31 0.17 0.64 0.12 107.31 106.23 0.00
06LM108 61.09 14.79 5.85 2.29 5.45 0.06 0.04 1.27 2.22 0.13 0.34 0.25 93.88 93.30 6.70
09LM028 62.81 14.47 5.69 2.11 6.67 0.06 0.04 1.21 2.20 0.10 0.32 1.62 97.60 97.03 2.97
09LM027 58.47 15.58 6.77 2.89 5.89 0.01 0.00 0.47 3.31 0.12 0.33 0.09 93.98 93.30 6.70
09LM026 70.78 11.90 1.78 0.60 3.56 0.09 0.05 1.07 2.14 0.04 0.22 0.07 92.32 92.14 7.86
09LM025 68.27 13.12 2.45 0.88 3.82 0.07 0.07 1.13 2.49 0.09 0.23 0.10 92.75 92.51 7.49
09LM024 65.77 12.94 6.02 1.37 3.41 0.19 0.07 1.38 3.22 0.11 0.40 0.13 95.05 94.45 5.55
71
Trace elements
ppm Cd Co Cr Cu La Ni Rb Sc V Y Zr
09LM060 b.d. b.d. 27.69 73.85 9.23 b.d. 30.58 13.85 55.39 23.08 36.93
09LM059 b.d. b.d. 73.40 0.00 39.15 9.79 109.14 9.79 58.72 29.36 371.91
09LM058F b.d. b.d. 14.44 86.65 115.54 b.d. 9.69 14.44 67.40 14.44 38.51
09LM058 b.d. b.d. 52.65 57.44 14.36 b.d. 1.29 23.93 234.54 14.36 28.72
09LM057 b.d. b.d. 19.20 48.00 4.80 4.80 29.50 14.40 57.60 14.40 38.40
09LM056 b.d. b.d. 29.80 79.45 9.93 b.d. 16.45 29.80 203.60 14.90 29.80
09LM055 b.d. b.d. 19.24 57.71 28.86 b.d. 13.12 19.24 110.62 19.24 33.67
09LM054 b.d. b.d. 24.76 79.22 14.85 b.d. 18.39 24.76 168.34 14.85 34.66
09LM053 b.d. b.d. 28.97 53.11 9.66 14.48 8.63 28.97 173.80 14.48 19.31
09LM052 b.d. b.d. 23.89 52.55 4.78 b.d. 23.48 9.56 23.89 14.33 47.78
09LM051 b.d. b.d. 14.72 44.17 9.82 b.d. 25.29 29.45 152.14 19.63 44.17
09LM042 b.d. b.d. 19.26 38.51 139.61 b.d. 16.52 14.44 38.51 19.26 43.33
09LM041 b.d. b.d. 71.73 0.00 38.26 b.d. 105.02 9.56 57.39 23.91 363.44
09LM040 b.d. b.d. 41.96 51.29 18.65 13.99 33.73 13.99 60.61 23.31 55.95
09LM039 b.d. b.d. 71.26 47.51 9.50 23.75 28.09 19.00 76.01 23.75 52.26
06LM116 b.d. b.d. 29.19 48.65 9.73 b.d. 15.45 24.33 180.01 14.60 34.06
09LM038 b.d. b.d. 14.60 48.65 9.73 b.d. 20.29 24.33 92.44 19.46 38.92
06LM115 b.d. b.d. 19.16 81.45 9.58 b.d. 24.23 14.37 86.24 14.37 38.33
09LM036 b.d. b.d. 24.66 49.32 4.93 b.d. 17.86 29.59 123.30 19.73 39.45
09LM035 b.d. b.d. 39.15 88.08 9.79 24.47 15.53 44.04 225.10 19.57 39.15
06LM108 b.d. b.d. 14.74 44.21 9.83 b.d. 10.49 29.48 117.90 19.65 34.39
09LM028 b.d. b.d. 14.96 29.91 4.99 b.d. 0.00 19.94 64.81 24.93 44.87
09LM027 b.d. b.d. 19.71 34.49 4.93 b.d. 9.72 29.56 133.03 14.78 29.56
09LM026 b.d. b.d. 23.08 32.31 0.00 9.23 24.07 13.85 32.31 18.46 73.85
09LM025 b.d. b.d. 19.29 33.76 4.82 b.d. 23.95 14.47 48.23 14.47 43.41
09LM024 b.d. b.d. 34.80 39.77 9.94 14.91 22.53 19.88 164.03 9.94 24.85
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
73
5.1 The Piñón and Calentura Formations
5.1.1 The Piñón Formation
The Piñón Formation crops out north of the
study area in the mountainous region named
“Cerro Azul” or blue hill, referring to the
greenish blue colour of massive basalts of the
Piñón Formation. Massive volcanic rocks can
be observed in fresh outcrops along the road
towards Isidro Ayora. Pillow lavas are
observed along the same road and in the quarry
near the village Las Mercedes. Pillow lavas are
brown in colour because of intensive
weathering to clay minerals.
The contact of the Piñón Formation with lapilli
tuffs can be observed in a road cut west of the
Guaraguao section (Sample 04LM095, figure
4.2). At this location the Piñón Formation
consists of dark green volcanics, is strongly
magnetic and intensely veined with quartz. A
conform contact with incompetent brown
lapilli tuffs is observed at this location. The
sample of the Piñón Formation is composed of
plagioclase laths, euhedral to anhedral Fe-Ti
oxides in a fine matrix of mosaic crystals. No
pyroxenes are observed, but these are probably
replaced by alteration minerals.
In the Río Guaraguao, typical green massive
basalts were observed at the top of the Piñón
Formation (Sample 09LM072). The Río
Guaraguao runs parallel to the contact of the
Piñón and Calentura Formation at this location.
The contact can not be seen in outcrop, but is
inferred from a change in soils and vegetation,
as pillow lavas of the Piñón Formation are
typically weathered to dark brown greywackes
and brown clayey soils. The sample of the
Piñón Formation is composed of large euhedral
plagioclase laths with carlsbad twins,
clinopyroxenes and Fe-Ti oxides.
5.1.2 The Calentura Formation
The major part of the Calentura Formation
consists of fine-grained (silt to sub-silt)
competent light grey to black beds of 10 to 30
centimetres in thickness (e.g. 06LM011).
Hundreds of these beds are exposed in a high
section at GPS 09–101. Weathering causes a
white porous outlook in outcrop. Some beds
are black in colour (Sample 06M001), because
of a high organic content. Most beds are very
competent because of high silicification. In
sample 04LM001, Inoceramus shells can be
found in life position. Some beds are
homogeneous, while others have a fine
undulose lamination (grey-brown-black).
Sample 06LM011 is composed of
homogeneous submicroscopic matrix.
Foraminifera occurs spread through the matrix.
Crystal clasts occur, but are rare. Sample
06LM012 is similar in composition, but
contains more clays.
Some thin (smaller than 20 cm) fine lapilli tuff
beds and clay beds (smaller than 20 cm) are
present near the top of the Calentura
Formation (Samples 06LM12–14). These beds
are incompetent, iron brown in colour, with
some large green irregular argillized glass
remains present. Other lapilli tuffs are
composed of black and white clasts in a white
matrix. Sample 06LM013 is composed of
feldspar crystal clasts, minor augite crystal
clasts and some volcanic particles. A large
amount of laminated particles, which are
completely replaced by a brown clay, occur.
These particles were possibly originally
pumice, which were strongly compacted
between the more competent crystal clasts. No
remaining vesicles can be observed.
APPENDIX 5 - TERRAIN OBSERVATIONS AND PETROGROPHICAL ANALYSES OF THE VOLCANIC COMPONENTS, STRUCTURES AND TEXTURES OF THE SAMPLES OF THE RÍO GUARAGUAO SECTION
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
74
Sample 06LM014 is composed of undulose
laminae rich in microorganisms, crystal clasts
(mainly rounded to angular plagioclase and
some quartz) and possibly some blocky glass
fragments. The different types of clasts occur
together, are moderately well sorted and some
laminae are concentrated in microorganisms or
crystal clasts.
Higher in the section, 20 to 30 centimetre thick
incompetent brown clayey layers alternate with
more competent beds (GPS 06–009). The
competent beds are dark grey to black in
colour and have a fine undulose lamination or
black nodules occur parallel to the lamination.
At this point, 200 meters of the section is
unexposed. It is suggested that this part mainly
consists of easily weathered layers, which alter
to brownish clays which can not be seen in
outcrop.
5.2 The lower unit of the Cayo Formation (Río Guaraguao unit)
5.2.1 Coarse breccia at the base of the
Cayo Formation
In the Río Guaraguao, the base of the
Calentura/Cayo Formation is faulted by NNE–
SSW oriented transform and/or thrust faults.
At the base intensely silicified light brown
cherts and fine breccias occur. Because the
river follows the contact, these rocks are
observed at different locations (Samples
09LM073–074, GPS09–85–86). At location
09LM077 black lavas are in conform contact
with brown cherts and breccias, composed
mainly of crystal clasts.
Apart from the cherts and fine-grained breccias
occurring at the contact with the Piñón
Formation, the basal part of the Cayo
Formation is composed of competent well
cemented coarse breccia sequences. No contact
with the first breccia sequence and underlying
strata could be observed in outcrop.
Northern unit of breccia
A first sequence was observed near the contact
with the Piñón Formation (Samples 09LM075–
076). It consists of large clasts of 10 to 50
centimetres in size with a greyish or green
colour, which appear porphyritic volcanics.
Similar, more angular finer grained clasts are
embedded in a greyish microcrystalline matrix,
which is similar in appearance as the rock
fragments. At several locations, greenish and
white microcrystalline alteration/vein zones
penetrate between clasts and alter the matrix
and finer grained clasts. Similar outcrops of
coarse breccia are observed higher in the
sequence, but because no continuous outcrop is
exposed, it can not be deduced if they belong
to the same sequence or to multiple sequences
(Samples 09LM070–71, GPS 09–88–94 and
GPS 97–100). When different outcrops are
compared, a grading of clasts is observed,
which it is an argument for the presence of
multiple sequences.
It could not be deduced if sequences are
coarsening or fining upwards. The matrix of
the breccia is observed in sample 09LM078.
The matrix contains lapilli clasts of different
types of porphyritic volcanics, and mainly
angular fractured plagioclase crystal clasts.
These are embedded in a fine-grained mosaic
of feldspar and quartz. No remains of pumice
are visible. Two meter large blocks of greenish
aphanitic volcanics of the Piñón Formation are
present in samples 09LM070–71.
At GPS 09–095–96, the upper part of a coarse
breccias sequence is in conform contact with a
unit of fine-grained siltstones. The unit is 5
meters thick, individual beds are 10 to 30
centimetres thick and have undulose bedding.
The outer part of the rocks is greyish-white
when weathered, which gives the appearance
of limestones to the rocks. On fresh cuts, the
rocks are light grey to black in colour, are
highly silicified and have a carbonate and
organic material content. Large nodules, up to
five centimetres in size, occur, contain iron
oxides, but were probably originally pyrite.
Black structures are interpreted as
bioturbations. It can not be observed in outcrop
which rocks are exposed above these
sequences and it is thus not known if coarse
breccia where deposited above this point.
A second contact of coarse breccias with fine-
grained sequences is observed at location GPS
09–100. At this location, the uppermost part of
a sequence of coarse breccia, at this location
fining upwards (GPS 09–97–100), is overlain
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
75
by an 80 centimetre thick layer of greyish-
green compacted lapilli tuffs (Sample
09LM081). These lapilli tuffs consist of
rounded clasts embedded in a fine matrix.
When weathered, the clasts give an undulose,
“mottled” appearance to the rocks. Because of
their characteristic appearance, this lithology
will further be called “grey mottled lapilli
tuffs”. At this location, the unit is intensely
veined. The sample is composed of different
types of porphyritic andesitic volcanic clasts
and crystal fragments of clinopyroxene,
plagioclase, Fe-Ti oxides and some
amphiboles. Some clasts are entirely replaced
by a brown clay mineral. They contain large
phenocrysts of plagioclase. These clasts are
strongly compacted and indented by the harder
volcanic clasts around and no vesicles are
visible. These clasts possibly represent
compacted pumice.
The grey mottled lapilli tuffs are covered by
two meters of claystones, which are composed
of alternating beds of 10 to 30 centimetres
thick clay-rich incompetent and hard silicified
rocks. The clayey rocks are greenish in colour
and contain nodules of pyrite, oxidized by
weathering. On top of this, a 40 centimetre
thick chert horizon occurs, which underlays a
thick sequence of lapilli tuffs. These lapilli
tuffs defer from the coarse breccia observed
below, because they are iron brown,
incompetent, have a smaller clast size (up to 5
cm) and show typical onion weathering
structures.
Southern unit of breccia
At GPS 006–004,005,010 a several meter thick
breccia occurs. It is similar in appearance as
the breccias observed in the northern unit
although clasts may be more rounded and in
some outcrops a larger amount of matrix is
present. A noted difference is the occurrence of
red rounded clasts and the absence of basalt
clasts. Both clasts and matrix are very
competent, light-grey to yellow-grey in colour
(Sample 06LM004), lighter than the matrix
and clasts range from centimetre to larger than
50 centimetres in size (06LM002) and contain
two grain-size populations (between 3 to 5 cm
and larger than 30 cm). Samples 06LM003 and
06LM004 consists for the major part of a fine
cryptocrystalline matrix. Euhedral pyroxene,
amphibole, plagioclase and Fe-Ti oxides
phenocrysts occur. Some phenocrysts are
completely altered. Because of the high degree
of alteration, it is difficult to see if these
samples were originally composed of multiple
clasts, which were cemented together or if the
sample is a volcanic rock with a
cryptocrystalline matrix and phenocrysts.
The red colour of some clasts of the coarse
breccia is noted also in the fine beds above the
breccia. Light purple to pink homogeneous
porous siltstones are observed. They are
interbedded with fine lapilli tuffs with white
clasts (feldspars?) in a white to purple matrix
(Samples 06LM05–010). These layers are
strongly faulted and tilted, and because no
contact with the breccias can be observed, it is
not sure that they stratigraphically overlay the
breccias. At location GPS 09–102, red beds are
interstratified with incompetent brownish
claystones and silicified beds of up to 30
centimetres thick. The claystones are iron
brown and very incompetent. The silicified
rocks are black and very competent. Beds have
an undulous lamination and contain dark grey
to black nodules parallel to lamination.
Above these fine beds a new coarse breccia
unit occurs, similar in appearance as the
breccia unit below. Next to grey porphyritic
volcanics, greenish and reddish clasts occur.
Microcrystalline quartz veins and amygdules
up to 15 centimetres in size occur in the
matrix. These breccia layer is overlain by a 4
meter thick layer of “grey mottled lapilli tuffs”,
similar in appearance as the ones observed in
GPS 09–100. This lithology is built up of
different grey, rounded and slightly flattened
clasts, which are cemented together into a
competent rock. These clasts have a
homogeneous size of two to five centimetres,
although it can change gradually through the
unit. The erosion of some of the matrix around
the clasts at the surface is responsible for the
ondulating “mottled” appearance of the rocks.
Sample 09LM085 is composed of rounded
andesitic volcanic fragments and plagioclase,
feldspar, Fe-Ti oxides and quartz crystal clasts.
Laminated, compacted and indented clay-rich
particles were probably strongly compacted
pumice. No remaining vesicles are visible.
Some larger accessory well rounded clasts
occur in the grey mottled lapilli tuffs, which
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
76
can be up to one meter large. Three different
types can be distinguished. A green competent
rock, resembling the parent lithology, grey-
yellowish clasts (probably the same material as
in the coarse breccias) and red homogeneous
fine-grained rocks (silt to sub-siltsize).
On top of this unit a 30 centimetre thick,
red/green chert unit occurs, similar in
appearance as the red clasts occurring in the
underlying lithologies (06LM098). Above this,
two coarse breccia units occur, with clasts up
to 40 centimetres in size. The sequence is
fining upwards and terminates in a black
laminated siltstone, which grades into a
greenish tuff. Above this point, no coarse
breccia are observed.
5.2.2 The basal part of the lower
unit
The depositional sequences above are typically
of metre thickness. They can have the same
appearance as the grey mottled lapilli tuffs
described in the beds below (e.g. 06LM102),
though the majority of the beds is less
competent and have a typical brownish onion
weathering surface. Clasts are of centimetre
size, fresh cuts are greenish in colour
(06LM100, 09LM086-087) and accessory red
rounded chert clasts, up to one metre in size,
are present. Sample 06LM102 is highly
altered, which makes it difficult to identify any
primary structures. It contains angular crystal
clasts (feldspar, quartz, augite, amphibole, Fe-
Ti oxides), other particles could be strongly
altered glass shards. Sample 09LM086 is
composed mainly of crystal clasts (plagioclase,
augite) and different types of volcanic
particles. Probably some glass shards and
pumice were present. The high concentration
of crystal clasts and volcanic fragments and the
rounding of the clasts shows that the rock
could be epiclastic.
Finer grained greenish lapilli tuff beds,
containing compacted pumice clasts, are
interbedded (06LM101). This sample is
composed mainly of tubular pumice, which is
moderately compacted. Next to pumice,
elongated shards, which results from the same
pumices are present. Crystals clasts are mainly
plagioclase. The sequences are alternated with
black or reddish to green fine-grained rocks.
The red beds are similar in appearance as the
red clasts occurring in the lapilli tuff
sequences.
Higher in the sequence the “mottled”
appearance of lapilli tuffs disappears. Lapilli
tuff sequences are densely compacted
(06LM102, 09LM88, 09LM001), fining
upwards and are generally not thicker than a
metre. They are reddish green to white in
colour. Sample 09LM088 is composed mainly
of tubular pumice, contains some andesitic
volcanic fragments and large quartz, alkali-
feldspar and plagioclase phenocrysts. Sample
09LM001 is highly altered, some ghost suggest
a possible original pumiceous composition.
Crystal clasts are alkali feldspars, plagioclase
and Fe-Ti oxides.
The lapilli tuff sequences are intercalated with
multiple 20-30 cm thick bluish green hard and
brown porous tuff layers (06LM10, 09LM89).
These tuff layer horizons can be correlated
over large distances and when several metres
thick, they are exploited for their zeolite
content. Several small quarries exits west of
the section along the Casas Viejas – Isidro
Ayura road (e.g. 04LM009) and north of
Guayaquil (04LM015).
Tuffs of the lower unit of the Cayo Formation
are typically intensely light green to beige or
have a flaser bedding structure of red and
green. Some tuffs are silicified, hard and
dense, while others are light weighted, have a
concoidal fracture and absorb water easily.
Another characteristic is their homogeneity,
they possess no internal lamination.
5.2.3 The middle part of the lower
unit
The middle part of the lower unit of the Cayo
Formation is dominated by metre to decametre
size sequences of coarse green lapilli tuffs. The
sequences typically have a flat base, can
coarsen upwards, are massive and compacted
at the base, are composed of spherical particles
of two to six centimetres in size in the middle
part and can be layered near the top. The top is
generally finer, denser, well cemented and less
porous than the base.
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
77
The particles occurring in the middle part of
the sequences, can be round in form or have a
triangular form with a convex lower surface
and a rounded upper surface, or alternatively
the lower surface is flat and the upper surface
convex. They are composed of several tubular
pumice clasts and sometimes volcanic rock
fragments, which are embedded in a matrix of
finer pumice or pumice shards. It is not clear if
these particles are clasts or if they were formed
by later fracturation or alteration.
Vilema (pers. com., 2006) introduced the term
“almeja”, the Spanish word used for shells, to
describe the structures of the clasts. When
weathered, almeja sequences are similar in
appearance as the grey mottled lapilli tuffs.
Therefore the informal terms “green mottled
lapilli tuffs” or “almejas sequences” will
further be used to describe the sequences and
the term “almejas” will be used to describe the
particles. These “almeja” sequences are very
characteristic for the lower unit of the Cayo
Formation, and can be found in the entire
region from Guayaquil through the Cordillera
Chongón-Colonche and parts of the Cordillera
Costera.
At this part of the section some sequences were
studied in detail to get a better understanding
of the origin of these deposits.
Section 1 of the lower unit of the Cayo
Formation
This section is 25 metres thick and contains the
lowermost “almeja” unit observed in the Río
Guaraguao section, although Vilema (2008)
observes almejas lower in the section.
A black competent siltstone (09LM002) and 20
centimetres of brown clays underlay three
metres of bluish green almejas (09LM003),
which are covered by a metre of five to ten
centimetre thick beds of tuffs. Veins cut trough
the basal part of the almejas and through the
underlying strata. The almejas are composed of
large particles of compacted tubular pumice
embedded in a matrix of smaller glass, crystal
and pumice clasts. Vesicles are bent off around
phenocrysts in the pumice. Glass shards are
angular, blocky to irregular and show no
vesicle wall remains. Crystal clasts are mainly
quartz and alkali feldspars.
Above this first almeja unit, hard and
competent metre thick lapilli tuffs with
compaction structures occur (09LM005). They
fill up deeply incised erosive gullies.
Sequences are clearly fining upwards and
grade into thin beds, which are deposited
parallel to the gully incisions. The rocks are
grey in outcrop, but bluish to white in fresh
cuts. The lapilli tuffs are similar in particle
composition as the almeja sequence below, but
pumice clasts are somewhat smaller. The
sample contains some volcanic fragments and
quite a lot of angular fractured quartz and
feldspar crystal clasts. The sequences are
covered by oxidized brown clays (0.5 m) and
by one and a half metres of 10 to 15 centimetre
thick green tuff beds (09LM006) and a second
similar thinner lapilli tuff sequence. White
veins are visible in and around the clay bed.
The tuff beds grade into light grey siltstones
(09LM007-008,06LM104) which underlay
three metre thick incompetent fine brown
lapilli tuffs (09LM009-011). The lapilli tuffs
are composed of pumice and different kinds of
volcanic clasts of three to four centimetres in
size and accessory large red and brown
rounded clasts (up to 0.5 m). The sequence is
coarsening upwards and becomes also more
competent upwards. Sample 09LM009 is
composed of volcanic clasts and pumice.
Pumice is somewhat different from the pumice
below, it has larger vesicles, with both tubular
and larger round vesicles with thicker walls
occurring. Other pumice has a lot of
plagioclase phenocrysts, or a microlitic matrix.
This material was possibly already crystallized
before eruption and is named “schlacke”.
Perlitic volcanic particles are also quite
common. Volcanic particles are microlitic or
contain spherulitic structures. Crystal clasts are
fractured alkali feldspar, augite, plagioclase
and quartz. Some splintery glass shards occur
in the matrix. Sample 09LM011 is similar to
sample 09LM009. It contains a high amount of
vesiculated perlites. Some volcanic particles
with a mosaic structure occur.
The next layer, has an irregular contact at the
base and is composed mainly of pumice,
contains no lithoclasts and is fining upwards.
Near the top, centimetre size holes occur which
have a long axis aligned along layering. This
sequence is topped by a second “almeja” unit
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
78
of several metres thick (06LM106). Red fine
(sub-silt size) clasts occur (06LM105). These
clasts are rounded and can be particularly large
(up to 1.5 metres) and are concentrated near
the base of the layer, where they are aligned
along the layering. The almejas are mainly
composed of tubular pumice, which was
compacted moderately. Flow deformation
around phenocrysts can be observed in the
tubular pumice. A second type of pumice has
larger round vesicles with thicker walls. Next
to pumice, the sample contains plagioclase,
quartz, augite and Fe-Ti oxide crystal clasts
and porphyritic or mosaic type volcanic
fragments. The rock is grain supported, but
large thick bubble wall shards with remains of
large round vesicles occur. The sequence is
fining upwards and the top consists of grey
hard dense tuffs with a mottled structure
(09LM012). This sample is mainly composed
of glass shards, derived from tubular pumice
and contains some angular quartz crystal
clasts. The reddish clasts occurring at the base
of the sequence, are composed of a mixture of
angular fractured crystal clasts, pelagic
microorganisms, limestone fragments and
irregularly shaped to angular glass, some
strongly compacted in situ (06LM105).
The contact with the next sequence was not
observed. A coarse almeja sequence occurs at
09LM013. The main component is tubular
pumice but some andesitic volcanic clasts
occur (mosaic and microlitic type). Pumice is
compacted between harder volcanic clasts,
resulting in a low intergranular porosity.
Quartz, augite, alkali feldspars and Fe-Ti
oxides are present as crystal clasts or as
phenocrysts in the pumice. The upper part of
the sequence is similar as the lower part, at the
top centimetre size round to oval holes occur
(09LM014).
The sequence is eroded at the top by a new
almeja sequence (09LM015). In this unit a
metre size hole was observed. This sequence is
composed mainly of large tubular pumice,
which is compacted around quartz and feldspar
phenocrysts and microlitic volcanic particles.
There is no evidence of a fine matrix. The unit
is fining upwards into a fine-grained hard and
dense green, well cemented rock (09LM016).
Tubular pumice in this part is similar as in the
lower part, but a second type of pumice with
large round to irregular vesicles occurs. A third
type of pumice, which contains flow structures
around phenocrysts, is strongly compacted.
Crystal clasts are fractured, zoned feldspar and
augite. No fine matrix is observed. The
uppermost part of the sequence is a very fine,
relatively hard tuff.
The next sequence is incompetent at the base
and is fining upwards into a brown hard
competent tuff (09LM017). The rock is a
mixture of tubular pumice, less vesiculated
pumice with thicker walls, glass shards and
crystal clasts. Because of the high-grade of
alteration it is difficult to recognize the original
structures. The overlying sequence is
extremely hard and is composed of similar
material as the previous sequence. It is also
highly altered (09LM018). It grades upwards
into grey hard tuffs which further grade into a
green tuff at the top of the sequence
(06LM019). The upper part is composed of
fine tubular glass shards and pumice shards,
which occur together with tubular pumice and
larger pumice clasts with larger round to
irregular vesicles and thicker walls. Plagioclase
and pyroxene occur mainly in strongly
compacted flow banded pumice.
On top of this, a new thick almeja sequence
occurs, which is incompetent at the base
(09LM020). The base is composed of mainly
thick wall to large round vesicle type pumice
and some, more tubular pumice. A large
amount of large quartz and alkali feldspar
crystal clasts occur, or are present as
phenocrysts in the pumice. The pumice is
strongly compacted around these crystal clasts.
In some parts of the rock, a fine matrix is
observed. Higher, the sequence is fine-grained,
greenish and cross-cut by a large amount of
white veins.
The next thick sequence has an upper layered
part, which is coarser than the lower massive
part. The upper part is composed mainly of
tubular pumice and contains a large amount of
quartz and feldspar phenocrysts (09LM021).
The sequence is covered by a light-brown fine
tuff, composed of blocky angular glass shards
(09LM022).
Above this, a new fining upwards almeja unit
occurs (09LM023). The base is composed of
large pumice with large round to irregular
vesicles, tubular pumice and volcanic particles
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
79
(microlitic or perlitized). Large quartz and
feldspar phenocrysts occur in the pumice and
vesicles are folded around them.
Section 2 of the lower unit of the Cayo
Formation
A first sequence is composed of tubular
pumice, minor pumice with larger round
vesicles and thicker walls, different types of
volcanic clasts (mosaic type, microlitic,
porphyritic) and a high amount of fractured
quartz, pyroxene, feldspars and Fe-Ti oxides
(09LM024). Higher in the sequence, the
amount of tubular pumice increases and
crystals are only present as large phenocrysts
in the pumice. Microlitic and perlitized
volcanic particles occur (09LM025). Sample
09LM026 at the top of the sequence, is
composed mainly of finer tubular pumice and
glass shards. Some pumice is highly
compacted.
The sequence is covered by a new coarse and
thick unit, which contains centimetre size holes
near the base (09LM027). The basal part is
composed mainly of compacted tubular
pumice. The sequence is fining upwards. At
this point it is not clear if a new sequence starts
or if this part is the upper part of the previous
sequence. Sample 09LM028 consists of large
clasts of tubular pumice and some large quartz,
feldspar, pyroxene and Fe-Ti oxides, which
occur as crystal clasts or in the pumice, and
some volcanic clasts occur. Near the top, the
sequence is composed of layered almejas.
Sample 06LM108 consists of tubular pumice
and pumice with round vesicles which is
embedded in a matrix of glass shards and
fractured quartz, plagioclase and pyroxene
phenocrysts. The upper part of the sequence is
composed of a hard tuff (09LM030), which is
topped by a grey limestone layer (09LM031).
Sample 09LM030 is a glass shard tuff, which
is composed of blocky shards and elongated
shards derived from tubular pumice.
The limestone layer of the previous sequence
is covered by fine-grained brownish to greyish
lapilli tuffs with a white matrix (Samples
06LM109-110, 09LM032). Large holes are
observed in this sequence (GPS 09-39). This
sequence is highly altered and it is therefore
difficult to recognize its original components.
Crystal clasts of quartz, feldspar and Fe-Ti
oxides are recognized. Some areas are replaced
by clays and could have been strongly
compacted pumice.
Section 3 of the Lower unit of the Cayo
Formation
Higher in the section, no continuous outcrops
are exposed and therefore it is not possible to
determine how many sequences occur or how
thick they are (GPS 09–39 to 09–50 and
samples 06LM112–114, 09LM033). Lapilli
tuffs are iron brown, dark grey to kaki green,
can be strongly weathered and are intercalated
with thin greenish red to brown tuff beds.
Some accessory red clasts up to 60 cm in size
occur. Sample 09LM033 contains a high
amount of different types of andesitic volcanic
clasts, pumice with large irregular vesicles,
some tubular pumice and feldspar crystals.
Many components are difficult to identify
because of the high degree of alteration. Lapilli
tuffs contain generally mainly brownish to kaki
flattened pumice and different types of
volcanic clasts. The lapilli tuffs are well sorted,
and when no fine matrix is present a white
mineral fills pores between the clasts
(06LM113–114, 09LM35). Sample 06LM113
is composed of pumice clasts with large round
to irregular to stretched vesicles. It also
contains a lot of vesicular volcanic particles.
Other volcanic particles are porphyritic, with
an intergranular matrix or with feldspar laths
and contain pyroxene phenocrysts. Quartz
occurs as a phenocryst in some volcanic
particles. Other volcanic particles have a fine-
grained mosaic matrix. No fine matrix occurs
between the clasts. Samples 09LM035 and
06LM114 are similar in composition, but also
contain tubular pumice.
A gradual evolution towards a thick light
greenish almeja sequence can be observed
(GPS 09–049–051). This sequence has a
massive lower part (09LM036–038), which is
similar in clast composition as the lower
sequences, but contains a higher amount of
tubular pumice, which is moderately
compacted. Higher in the sequence (sample
09LM038, 06LM116) tubular pumice is the
most important component. Vesicles are larger
in size and are bended off around phenocrysts.
Compaction is larger higher in the sequence.
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
80
The sequence is fining upwards and layered in
the upper part (09LM039, 06LM116), although
it is possible that this layered part composes a
new sequence. Sample 09LM039 contains
more quartz, feldspar and augite phenocrysts
and is composed mainly of pumice with small
stretched thick wall pumice. Sample 06LM116
of the layered part, contains again pumice with
larger stretched vesicles. The sequence is
topped by a dark grey fine-grained siltstone
(09LM040). Because of the strong competence
of the almeja sequences, a second large
waterfall is present at this location.
This unit is covered by numerous metre thick
sequences of lapilli tuffs with compaction
structures which are interbedded with reddish
green fine-grained tuffs (09LM041–043).
Sample 09LM042 is a lapilli tuff similar in
composition as the previous sequence. Pumice
is typically tubular, but larger stretched
vesicles occur. Pumice is stretched around
quartz phenocrysts. In this sample a disk-type
foraminifera is observed.
5.2.4 The upper part of lower unit
Higher in the section, beds become more fine-
grained and are very hard and competent. At
this point, the Río Guaraguao bends off to the
northwest, and follows the strike of these
competent rocks for about a kilometre, where it
bends off again to the SW, perpendicular to the
strike. Sample 06LM118 is the contact of a
fine tuff with a lapilli tuff. The fine tuff is
composed mainly of blocky glass shards. It has
no internal lamination. The lapilli tuff is
composed mainly of pumice of tubular shape
or pumice with small stretched vesicles and
thick walls. Some porphyritic volcanic
particles with a black to dark grey
microcrystalline matrix occur. Sample
06LM123 is composed mainly of blocky to Y-
shaped glass shards. The sample is well sorted
but no internal lamination occurs.
A thick unit of brown incompetent lapilli tuffs
with onion weathering structures occurs. These
are intercalated by thin (<50 cm) brown to
yellow tuff layers (06LM176–179). Sample
06LM178 consists mainly of pumice with
small round vesicles and thick walls and a high
amount of plagioclase (polysynthetic twins),
augite and dark prorphyritic volcanic
fragments. Sample 06LM176 consists mainly
of strongly compacted tubular pumice and
contains some pyroxenes, plagioclase and dark
porphyritic volcanic fragments.
At GPS 06–124 a brown tuff is in contact with
a unit of dark brown lapilli tuffs (06LM124,
04LM008). These are covered by a green tuff
layer, a 50 centimetre thick black compacted
lapilli tuff sequence and again a greenish tuff
layer (06LM074–78). Sample 06LM074 is
composed almost entirely of tubular pumice
clasts. Some large phenocrysts of mainly
plagioclase and augite occur. Bubbles are
bended off around the phenocrysts. Rare dark
porphyritic volcanic fragments occur. The
greenish tuffs are light in weight,
homogeneous and have no internal lamination.
Only the upper 1.5 metres of the next sequence
were observed. A coarse-grained fining
upwards sequence of lapilli tuff with a purple
matrix colour occurs. Sample 06LM079 is
composed of large clasts of pumice, which can
be tubular, or pumice with large vesicles with
thick walls. Next to pumice, volcanic schlacke
with a matrix of fine feldspar laths and large
irregular to round vesicles and some dark
porphyritic volcanic fragments occur. Some
pumice is strongly compacted. Some accessory
red clasts which are up to 20 cm in size occur
in the lapilli tuffs. The lapilli tuffs are overlain
by green tuff layers, which are covered by
coarse-grained lapilli tuffs. This second lapilli
tuff sequence is topped by porous green tuffs
and light beige tuffs (06LM082), which are
intensely veined with calcite. Sample
06LM082 is pervasively altered and it is
difficult to identify its original components.
On top of this, a fining upwards intensely
veined sequence of beige-green banded
competent lapilli tuffs occurs (06LM085). The
sample is highly altered, but remaining tubular
pumice is visible. Quartz, amphibole and Fe-Ti
oxides occur as crystal clasts and in the
pumice. Sample 06LM087 is a beige,
competent, well cemented breccia consisting of
very angular fragments. Because of the high-
grade of alteration, it is difficult to see what the
original components were, but the presence of
microorganisms and the high amount of
calcite, suggest that the sample contains an
amount of sedimentary material. It is covered
by fine green compacted lapilli tuffs.
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
81
The next sequence consists of a green tuff with
flaser bedding, covered by 80 centimetres of
almejas, which are covered by thin sequences
of green tuffs and brown lapilli tuffs and a
metre thick fine lapilli tuff (09LM046–049).
The sequence is repeated above, possibly
because of a fault contact (GPS 09–69–071).
Section 4 of the lower unit of the Cayo
Formation
At this point a fault (inferred) changes the
strike of the layers. A tuff underlies a sequence
of compacted green lapilli tuffs (09LM051–
056). Sample 09LM052 at the base of the
sequence contains a high amount of
polysynthetic or zoned plagioclase crystal
clasts and minor pyroxene and Fe-Ti oxides.
Next to crystal clasts volcanic schlacke and
andesitic volcanic particles occur (mosaic,
microlitic). Both pumice with round vesicles
and thick walls and tubular pumice occur.
Tubular pumice is compacted between the
harder volcanic and crystal clasts. Sample
09LM053 is similar in composition, but
pumice is more abundant, is larger and has
larger vesicles. The vesicle type varies from
fine tubular to large stretched to smaller thick
wall vesicles and vesicles are bended around
phenocrysts. Sample 09LM054 is similar in
composition, but clasts are smaller in size.
Some larger pumice is strongly compacted.
Sample 09LM055 has somewhat smaller clasts
but contains some large pumice clasts. The
number of crystal clasts is higher than in the
previous sample, so possibly this could be the
base of a new sequence. Sample 09LM056 is
composed of smaller tubular pumice and fine
Y-shaped glass shards.
The sequence is covered with thin lapilli tuff
and tuff beds (09LM057–059). Sample
06LM088 contains microorganisms. Higher, a
second thinner compacted lapilli tuff sequence
occurs (09LM060–062). Sample 06LM090 is
composed mainly of compacted tubular
pumice, but contains also some large shards
which originate from pumice with very large
round vesicles. This sequence is covered by a
grey tuff, a fine lapilli tuff and a thick layer of
white tuffs (09LM063–066). These white tuffs
are composed of tubular pumice with very
small vesicles but contain also very large Y-
shaped glass shards which can not originate
from the same pumice (sample 09LM066).
These are covered by grey tuffs (09LM068–
069).
In the last few metres of the lower unit of the
Cayo Formation, large lithological variations
are present. The following lithologies are
observed near the top: brown tuffs, green
compacted lapilli tuffs, a fine strongly
compacted beige lapilli tuff, a beige tuff, a
dark grey tuff, a homogenous beige tuff, a
black heavy laminated tuff, a black competent
heavy tuff, a beige tuff heavily eroded by a
beige sandstone (06LM127). The top of the
lower Cayo Formation is placed at this point.
Above this point, no typical greenish or beige
homogenous lightweight tuffs, almeja
sequences or green lapilli tuffs rich in tubular
pumice occur. Sample 06LM129 is a mixture
of crystal clasts (plagioclase and augite),
tubular pumice, pumice with large round to
irregular vesicles and different types of
andesitic volcanic clasts (mosaic, microlitic).
This sample contains some limestone particles
and has a fine micritic matrix.
5.3 The upper unit of the Cayo
Formation
5.3.1 The base of the upper unit of
the Cayo Formation
The base of the upper unit of the Cayo
Formation is composed of numerous thin beds
of different lithological types (06LM128-144).
Characteristic is a several metre thick unit of
dark grey hard and dense fine-grained rocks.
When cut, the rocks are dark brown, blue,
green, grey to black in colour, of sub-silt to
sand grain size and several rocks are
characterized by an internal lamination. They
can contain erosional surfaces, with alternation
of silt and sand size layers, can be bioturbated
and contain soft sediment deformation
structures. These rocks are much heavier than
the tuffs of the upper part of the lower unit of
the Cayo Formation and can easily be
distinguished. The fine-grained rocks are
intercalated with thin beds of fine well-sorted
lapilli tuffs which have clasts of silt to pebble
size and larger accessory green clasts. They are
very heterogeneous in clast composition and
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
82
all are cemented by a white mineral. As the
fine-grained rocks, they can be laminated, can
have erosional surfaces and can be fluidized or
bioturbated.
These fine-grained lithologies contain crystal
fragments, blocky glass and pumice fragments,
and a high amount of foraminifera and
radiolaria. Interlayered lapilli tuffs contain
basaltic and orange reddish andesitic
fragments, blocky glass fragments and
different kinds of pumice (06LM136-145,146).
Sample 06LM135 is a laminated siltstone
composed of blocky glass fragments derived
from pumice with thick walls and round
vesicles, limestone fragments, a high amount
of pelagic microorganisms and rounded to
angular crystal fragments of quartz, feldspar,
augite and Fe-Ti oxides. Sample 06LM136 is a
fine lapilli tuff composed of irregular
compacted pumice, a high amount of angular
crystal clasts of plagioclase, K-feldspar, augite,
andesitic volcanic fragments, some reddish
vesicular volcanic fragments and limestone
fragments embedded in a fine ash matrix.
Sample 06LM138 is a laminated tuff
composed mainly of small blocky glass and
pumice clasts and some crystal clasts. Pumice
has small round vesicles and thick walls. Clasts
are quite angular and embedded in a
microcrystalline matrix. Some pelagic
microorganisms are present. The clasts are
quite well sorted.
5.3.2 The lower part of the upper
unit of the Cayo Formation
At this point, the river splits up and the eastern
branch is followed. Fourty meters are not
visible in outcrop. In this part of the section
lapilli tuff sequences are thicker and clast size
is larger compared to the underlying part. The
thick lapilli tuff sequences alternate with thin
beds of grey to black heavy tuffs (06LM145-
159). Lapilli tuffs are well sorted and fining
upwards and contain clasts of three to four
centimetres at the base of the sequences to a
few millimetres at the top. Accessory red fine-
grained clasts can be up to 20 centimetres in
size. The contact of the lower coarse part of a
sequence with the upper grey heavy tuff part is
sharp. Individual sequences can be up to 30
meters thick, though it could not be excluded if
these beds consist of one or multiple
depositional units. Some lapilli tuffs are well
cemented and hard, while others are strongly
weathered and iron-brown in colour. Individual
differently coloured clasts are easily visible
and are cemented together by a white cement.
In some samples this cement fills only part of
the pores resulting in a very bad cohesion of
the rocks.
These lapilli tuffs are predominantly composed
of non-vesiculated to vesiculated to compacted
pumice. Volcanic clasts can make up to 40%
of the rocks and are basaltic porphyritic to
reddish or grey andesitic with feldspar laths
and pyroxene. In some rare fine-grained layers
blocky glass shards occur.
Sample 06LM145 is a fine lapilli tuff
composed mainly of well sorted and rounded
effusive volcanic clasts and crystal clasts. The
clast types are: effusive dark porphyritic,
greyish microlitic and orange-brown volcanics,
all are rich in phenocrysts. Rounded crystal
clasts are mainly plagioclase and some K-
feldspar, amphibole and Fe-Ti oxides.
Schlacke with irregular vesicles occur. Pumice
is rare, different types occur: pumice with thick
walls, irregular vesicles, stretched vesicles,
tubular vesicles. Some microorganisms are
present. Sample 06LM146 is composed of
different types of well crystalline and well
rounded effusive rock fragments and schlacke
embedded in a fine matrix which contains
some blocky glass and pumice fragments, algal
and pelagic microorganisms. Sample
06LM148 is a tuff composed mainly of small
sized angular glass, pumice and feldspar
crystal clasts, some rounded dark porphyritic
volcanic fragments, tubular pumice and some
pumice with larger stretched vesicles,
containing augite phenocrysts and some
pelagic microorganisms. No internal
lamination is present. Sample 06LM149 is a
coarse lapilli tuff composed mainly of angular,
well crystalline andesitic effusive volcanic
fragments, schlacke, some reddish volcanic
fragments, some fragments containing
recrystallized spherulites and minor pumice.
Pumice has thick walls and large round
vesicles and can be compacted. No fine matrix
is present. Sample 06LM150 is a fine lapilli
tuff composed of volcanic clasts, pumice and
crystal clasts. Volcanic clasts are black to
orange brown porphyritic or microlitic. Pumice
is larger than other particles and has large
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
83
irregular to stretched vesicles and is compacted
between the harder clasts. Some smaller
pumice clasts with only 2 to 3 round vesicles
are present. Volcanic clasts are moderately
rounded, but pumice is not rounded. Crystal
clasts are large rounded plagioclase, pyroxene
and Fe-Ti oxides. Some foraminifera occur. No
fine matrix occurs. Sample 06LM153 is a
lapilli tuff composed mainly of rounded
porphyritic effusive clasts, others volcanic
clasts with interterstal texture, large pumice
clasts with round vesicles and thick walls
containing feldspar phenocrysts. No fine
matrix occurs. The sample contains a red
boulder which is composed mainly of blocky
glass shards and some pelagic microorganisms.
Sample 06LM154 is a coarse lapilli tuff
composed of different types of porphyritic to
well crystalline effusive volcanic clasts (some
reddish in colour), schlacke and large pumice
clasts with round to elongated or irregular
vesicles. No fine matrix is present. Sample
06LM155 is a coarse lapilli tuff composed of a
large variety of rounded volcanic clasts,
schlacke, pumice with large regular vesicles
and thick walls, pumice with small rounded
vesicles, pumice with thin walls, pumice with
irregular vesicles. This sample is uncompacted
and no fine matrix occurs.
The next part of the section is not well exposed
in outcrop, but the main lithologies observed
are thin layers of fine-grained lapilli tuffs and
tuffs. It differs from the underlying unit
because of the appearance of greenish
laminated tuffs (e.g. sample 06LM160). This
lithology is characteristic for the upper Cayo
Formation. The difference with the
homogeneous porous tuffs in the lower unit of
the Cayo Formation is that these tuffs are
laminated, heavier and less porous. Laminae
show centimetre to millimetre fining upwards
sequences of sand to clay size, are ondulating
and erosive and show fluidisation structures.
Sand- and silt size laminae are greenish to
bluish, while clay-rich laminae are brownish.
The following lithologies are observed: black
heavy siltstone (6m), intercalated with two thin
beds of beige lutites (30cm, 06LM160);
siltstones; fine lapilli tuffs (sand size); green
tuffs with fluidisation structures (06LM161);
fine lapilli tuffs (sand size); a coarser yellow
lapilli tuff (06LM162); a green tuff with
fluidisation; grey heavy siltstones; fine-grained
lapilli tuffs interstratified with dark brown
siltstones (or fine lapilli tuffs) (06LM163),
topped by a green tuff bed (06LM164); fine
homogeneous lapilli tuffs (sand size)
(06LM164). This part of the section consists
mainly of fine-grained lithologies composed
mainly of blocky glass shards (up to 100%)
and some vesiculated pumice, crystal clasts
and volcanic fragments. Coarser lithologies
consist mainly of pumice.
Sample 06LM158 is composed mainly of
blocky glass shards and angular crystal clasts
and some rare pelagic microorganisms. The
sample is laminated. Sample 06LM160 is a
laminated tuff composed mainly of fine glass
shards and some crystal fragments and mica
flakes. Algal fragments and pelagic
microorganisms occur. Erosive surfaces occur
between the laminae. Sample 06LM161 is a
fine laminated tuff composed entirely of
acicular glass shards. Sample 06LM162 is a
fine-grained lapilli tuff composed mainly of
pumice and some schlacke, dark porphyritic
and reddish effusive volcanic clasts,
plagioclase, Fe-Ti oxide and pyroxene crystal
clasts and some rare pelagic microorganisms.
The most common pumice clasts have round
vesicles and thick walls, others have more
irregular vesicles and some of the pumice is
compacted. Clasts are quite angular and quite
well sorted. Sample 06LM163 is a laminated,
well sorted tuff composed mainly of blocky
glass shards, some crystal clasts and pelagic
organisms. Sample 06LM165 is a laminated
and well sorted tuff composed of blocky glass
shards and angular crystal clasts of plagioclase,
minor pyroxene and Fe-Ti oxides and some
small black porphyritic clasts.
5.3.3 The middle part of the upper unit of the Cayo Formation
In the next part of the section, lapilli tuff
sequences are thicker, coarse-grained and most
lapilli tuffs are well cemented and competent.
In most rocks, different types of angular to
well-rounded clasts are present embedded in a
bluish green matrix. This type of lapilli tuff is
characteristic for the middle part of the upper
unit of the Cayo Formation. Next to the
greenish laminated tuffs with fluidisation
structures, a dark grey very fine-grained (clay
size) competent homogeneous tuff is present,
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
84
which is also characteristic for this part. At the
top of the middle part, a thick sequence of light
brown tuffs can be observed. 06LM166 is a
sample of a first coarse lapilli tuff sequence.
The sequence is fining upwards. The rocks are
grey in outcrop and kaki-green on fresh cuts.
Matrix and clasts have the same colour, except
for some red clasts (up to 3 cm large). The
second lapilli tuff sequence (06LM168) erodes
the fine lapilli tuffs of the upper part of the
previous sequence and has a light brown
matrix, and a large variety in clast types. The
top of these lapilli tuffs is in sharp contact with
a 2 meter thick laminated brown-green tuff
sequence.
Sample 06LM167 is a well sorted tuff
composed mainly of blocky glass shards,
pumice and black volcanic fragments. Pumice
contains small vesicles and has thick walls and
some tubular pumice occurs. Crystal clasts are
feldspar, augite and Fe-Ti oxides. Some
prismatic clasts composed of calcite are
probably of organic origin and pelagic
microorganisms occur. Sample 06LM168 is a
lapilli tuff composed of effusive volcanic clasts
and minor pumice clasts, some algal and
limestone fragments and feldspar crystal clasts
occurring in a fine matrix. Rock fragments are
dark porphyritic volcanics, schlacke and red
vesiculated volcanic fragments. Pumice has
round to elliptical vesicles, thick walls and is
small in size. Sample 06LM170 is a laminated,
well sorted tuff composed of blocky rounded
glass shards, some black effusive volcanic
fragments, Fe-Ti oxides which are
concentrated in bands and pelagic
microorganisms. Sample 06LM169 is a well
sorted and well laminated tuff composed
mainly of acicular to Y-shaped glass shards,
some angular feldspar and quartz crystal clasts
and pelagic microorganisms. Sample
06LM171 is a well sorted lapilli tuff composed
of effusive volcanic clasts and pumice in a
vitroclastic matrix. Volcanic clasts are
porphyritic or microlitic with larger
plagioclase phenocrysts and can be
vesiculated. All volcanic clasts are quite well
rounded. Pumice is tubular or has thick walls
and large vesicles and is irregular in shape.
Crystal clasts are pyroxene and amphibole.
Glass is irregular to blocky. Some limestone
fragments, algal fragments and pelagic
microorganisms occur.
Below the third lapilli tuff sequence, a thin
layer of green laminated tuffs occurs. This
sequence is also fining upwards. On top of this
sequence a series of thin beds occurs: a
laminated dark green-brown sandstone with
flattened green clasts (06LM172); a lapilli tuff
(4-5m); green tuffs; a brown green laminated
tuff (06LM174); a light green tuff; a fine grey
lapilli tuff (1m); a light green tuff; a fine grey
lapilli tuff; a brown tuff (2-3m); a fine grey
lapilli tuff (1m); a brown tuff (2m); a grey
lapilli tuff (1m); a white tuff (3m), green
laminated when cut; a fine grey lapilli tuff
(1,5m); a brown tuff (2m); a fine grey lapilli
tuff (2.5m); a brown tuff.
A fourth and a fifth competent lapilli tuff
sequence occur with clasts up to 5 cm large.
The matrix is light green to white
(macroscopic crystals) and different types of
clasts occur (06LM182-183). Between the two
sequences a porous green lightweight tuff
occurs. On top of the fifth sequence a very fine
homogeneous competent grey lutite is
deposited (06LM184), which evolves into a
grey laminated lutite. Sample 06LM182 is a
coarse lapilli tuff composed of andesitic well
crystalline volcanic particles, schlacke,
pumice, glass shards, crystal clasts, algal
fragments and pelagic microorganisms.
Pumice can be tubular or has thick walls and
round vesicles. Glass shards are irregularly
shaped, blocky or Y-shaped. Crystal clasts are
plagioclase, pyroxene and Fe-Ti oxides. No
fine matrix is present. Sample 06LM180 is a
lapilli tuff composed mainly of coarse volcanic
fragments and some pumice, and large
plagioclase and pyroxene crystal clasts.
Pumice has small round to large irregular
vesicles with thick walls. Volcanic fragments
are schlacke, red porphyritic effusive, black
vesiculated, or porphyritic with a fine
crystalline matrix. The clasts are embedded in
a fine matrix composed of large blocky shards
with large vesicle walls and smaller tubular or
acicular shards, algal fragments and pelagic
organisms. An erosive contact is seen with a
fine-grained bed composed of glass shards and
pelagic organisms embedded in a fine-grained
matrix.
The next thin lapilli tuff sequence is topped by
light brown tuffs (06LM187). A sixth coarse
competent lapilli tuff sequence with a green
matrix and different kinds of clasts occurs
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
85
(06LM188). The base is very erosive, clasts
are very coarse, and both angular and rounded
at the base (7-8 cm). Further from the base,
clasts are more homogeneous in type and size.
The sequence is fining upwards into a brown
homogenous lapilli tuff (06LM189). It is
deposited as wedge-shaped meter size banks.
The uppermost part of this sequence consists
of a thick layer of light brown fine
homogeneous tuffs (06LM190) that evolve
into laminated brown tuffs at the top
(06LM196). In the middle of this tuff layer a
thin fine-grained lapilli tuff layer is present
(06LM194). On top of these brown tuffs two
thin sequences of thin green lapilli tuffs and
thin green tuffs are present.
Fine lithologies are similar as in the lower part
and consist mainly of blocky to elongated glass
shards, aligned along the layering (06LM169-
171, 187,190,191,196). Crystal clasts and
pumice also occur. Sample 06LM190 contains
a large amount of pelagic organisms next to
glass shards. Coarse lithologies consist of
pumice (vesiculated to non-vesiculated, some
compacted) and basaltic (porphyritic,
interterstal) to andesitic (reddish) clasts, crystal
clast and in some cases (06LM180,188) blocky
glass shards.
Sample 06LM187 is a laminated, well sorted
tuff. It is composed of blocky glas shards,
contains quite much pelagic organisms and
some crystal clasts. Sample 06LM188 is a
coarse lapilli tuff composed of different types
of volcanic clasts. Most clasts are well
crystalline, with a microcrystalline matrix and
larger phenocrysts or schlacke. The clasts are
embedded in a fine matrix which contains
angular plagioclase and Fe-Ti oxide crystal
clasts, small pumice clasts of both tubular and
thick wall types, large blocky shards with
remaining bubble walls, finer grained Y-
shaped glass shards and fine blocky shards.
Algal fragments and pelagic microorganisms
are quite common.
Sample 06LM190 is a laminated, well sorted
tuff composed of acicular fine glass shards and
pelagic microorganisms (20%). Some small
volcanic rock fragments and crystal clasts
occur. The clasts are embedded in a fine
matrix. Sample 06LM191 is a laminated, well
sorted tuff composed of irregularly shaped
blocky to prismatic shards and some crystal
fragments embedded in a fine matrix. Sample
06LM194 is a fine lapilli tuff composed
mainly of pumice and minor angular
plagioclase, quartz, pyroxene and Fe-Ti oxide
crystal clasts. Rock fragments are less
common. Different types occur: black
porphyritic and interterstal effusive volcanic
clasts, some vesiculated and reddish volcanic
clasts, schlacke, grey microcrystalline andesitic
clasts. Organic fragments are quite abundant.
Tabular organic fragments and algal fragments
occur. The sample is well sorted and fragments
are moderately rounded. Sample 06LM196 is a
laminated, well sorted tuff composed mainly of
aligned acicular glass shard and Y-shaped
glass shards. Some blocky shards occur.
Sample 06LM198 is a lapilli tuff composed
mainly of effusive volcanic fragments. The
main type of clasts are schlacke, brownish in
colour, with irregular vesicles. Coarse-
crystalline volcanics are less common, some
interterstal volcanic fragments occur, and some
fragments with spherulitic texture and red
effusive fragments. Pumice is less common
(20%) and has large round to irregular vesicles.
Some algal and pelagic organisms occur, no
fine matrix is present.
5.3.4 The upper part of the upper unit of the Cayo Formation
The upper part of the Cayo Formation
demonstrates a clear cyclic pattern. It consists
of thin sequences of lapilli tuffs containing
brownish to greenish particles that are mostly
not well cemented. These lapilli tuffs are
frequently strongly weathered and have an iron
brown colour. All sequences are fining
upwards. The lapilli tuffs are in sharp contact
with brown to green laminated fluidized tuffs.
In most sequences the lapilli tuff part is thicker
than the tuff part, though the opposite is
possible.
29 lapilli tuff – tuff sequences were
distinguished in this part. Sequence 1 is a thin
sequence of 3 meters (lapilli tuff + tuff). The
lapilli tuff part consists mostly of light brown
particles, well compacted, without the green
cementation typical for the middle part of the
upper Cayo Formation. It is poorly sorted and
incompetent (06LM201). Most of the
sequences in this part are similar in
appearance, only the total thickness and the
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
86
thickness of the lapilli tuff and tuff part in each
sequence differs. The sequences that differ
somewhat from this general model are
described here: The lapilli tuff of sequence 4 is
very competent, greenish and with pervasive
alteration (06LM067). Below this lapilli tuff, a
very competent heavy black sandstone occurs
(06LM068). The base of sequence 16 consists
of green competent lapilli tuffs with green
flattened particles (06LM061).
Because of the presence of a thrust fault
between sequences six and seven, it is possible
that part of the Cayo Formation is missing
here. Light beige powder material is found in
this fault zone (06LM065).
Sample 06LM068 is a well-sorted fine lapilli
tuff, composed of porphyritic and vesicular
black clasts and irregular to blocky pumice
shards. Crystal clasts (10%) are plagioclase,
Fe-Ti oxides, pyroxene and quartz. Some
pelagic organisms and limestone fragments are
present. Sample 06LM067 is composed mainly
of pumice. It has irregular to round vesicles but
some is not vesiculated and some has
phenocrysts. Some pumice is compacted. Rock
fragments are smaller than the pumice
particles, are black to brown porphyritic or
schlacke. Some rare volcanic fragments with
mosaic texture occur. Crystal clasts are quite
common and are amphibole and pyroxene.
Some algal and pelagic organisms occur.
Sample 06LM070 is a lapilli tuff composed of
different types of volcanic clasts. Clast types
are: andesitic or with felsitic texture, others are
coarsely crystalline, some are reddish, others
black vesiculated or schlacke. Glass and
pumice are rare. No fine matrix is present.
Sample 06LM064 is a laminated vitroclastic
tuff composed of acicular fine glass shards.
Sample 06LM061 is a compacted lapilli tuff
composed mainly of pumice. Pumice has
irregular small to large vesicles and some
tubular pumice occurs. Some volcanic
fragments occur which are black to red
porphyritic. Some pyroxene crystal clasts,
pelagic organism and calcite prisms (algal?)
occur. Sample 06LM060 is composed of
irregular glassy particles, blocky angular
shards, pumice with thick walls or stretched to
irregular vesicles. Volcanic clasts are larger
than glassy particles, brown, black or grey with
interterstal or microcrystalline texture. Crystal
clasts are angular plagioclase and minor
pyroxene, Fe-Ti-oxides, augite and K-feldspar.
Some rare pelagic organisms occur.
Section 1 of the upper unit of the Cayo
Formation
In the uppermost part some sequences have
been sampled in detail (sequence 20: 06LM42-
59 and sequences 28-29: 06LM30-39).
Coarse rocks at the basal part consist
predominantly of pumice or of pumice and
coarse black to brown volcanic particles. In
sample 06LM061, the pumice is clearly
welded. In finer grained rocks the same
components occur associated with irregularly
shaped glass, crystal clasts, some algal
fragments and pelagic organisms.
Samples 06LM058,057,047,053,051,049,044
belong to the same sequence. Coarse lapilli
tuffs are composed mainly of vesiculated
pumice and some basaltic rocks fragments.
Finer tuffs are composed of glass shards. The
finest rocks consist of pelagic organisms
(radiolaria and foraminifera) embedded in a
fine-grained matrix. It is not clear if this matrix
was originally build up of glass or not, no
primary structures are preserved. The
uppermost lapilli tuff – tuff sequence of the
Cayo Formation, near the contact with the
Guayaquil Formation, consists of similar lapilli
tuffs, fine-grained glass-tuffs with blocky glass
shards interlayered with pelagic layers rich in
microorganisms (06LM032-035).
Sample 06LM058 is a fine-grained well sorted
laminated tuff composed of irregular glass
shards, plagioclase and Fe-Ti oxide crystal
clasts and some rare pelagic organisms.
Sample 06LM057 is a coarse lapilli tuff
composed mainly of pumice with large
irregular vesicles and thick walls rich in
phenocrysts. Rock fragments (30%) are black
porphyritic and vesiculated effusive clasts,
coarse crystalline volcanic rocks, orange red
volcanic rocks and brown schlacke. Crystal
clasts are amphibole and augite. All clasts are
angular. Sample 06LM054 is a massive well
sorted tuff composed of acicular glass shards.
Sample 06LM053 is a laminated tuff
composed of blocky glass shards, pumice
shards with round bubble walls and angular
shards. Some feldspar crystal clasts occur.
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
87
Sample 06LM051 is a very fine laminated
fallout with a fine matrix. Pelagic organisms
are common (20-30%). Sample 06LM049 is a
laminated tuff composed of Y-shaped to
blocky glass, angular glass shards, acicular
glass shards and pumice shards with round
vesicles and thick walls. Some rounded dark
brown glassy fragments occur. Quartz and
feldspar crystal clasts are rare and some pelagic
organisms occur.
Section 2 of the upper unit of the Cayo
Formation
Sample 06LM044 is a laminated siltstone with
a fine matrix and a high amount of pelagic
organisms. Sample 06LM043 is a lapilli tuff
composed mainly of pumice with perfectly
round to irregular vesicles and rare tubular
pumice. Volcanic fragments are dark
porphyritic effusive fragments, vesiculated
fragments, fragments with a microcrystalline
matrix and schlacke with large phenocrysts,
which are quite common. Some pyroxene and
Fe-Ti oxides crystal clasts occur. No fine
matrix is present. Sample 06LM036 is a
laminated tuff composed of blocky to acicular
glass shards and Y-shaped glass shards.
Crystal clasts are mica and some plagioclase.
Some rare pelagic microorganisms occur.
Sample 06LM035 is a lapilli tuff composed
mainly of pumice with irregular vesicles. Some
fine tubular pumice occurs. Schlacke are
common and contain phenocrysts. Black
porphyritic and vesiculated effusive volcanic
clasts and perlitic clasts occur. Others have
intergranular or microlitic texture. Crystal
clasts are K-feldspar, plagioclase, pyroxene,
quartz and amphibole and are all angular and
fractured. All components are angular and
badly sorted. Sample 06LM034 is a lapilli tuff
composed mainly of pumice which is
irregularly shaped, has small vesicles, and is
compacted along the layering. Some tubular
pumice and some schlacke occur. Dark
porphyritic volcanic clasts and volcanic clasts
with mosaic texture and perlites occur. Crystal
clasts are angular plagioclase, pyroxene and
Fe-Ti oxides. The sample does not contain
much fine components. Sample 06LM033 is
composed mainly of pelagic organisms in the
bottom part, while the upper part is composed
of blocky glass shards and the uppermost part
of shards with thick bubble walls and fine
acicular shards. Sample 06LM032 is composed
of blocky glass shards and Y-shaped glass
shards (less common) in the lower part, while
the upper part is composed of pelagic
microorganisms embedded in a fine matrix.
Sample 06LM031 is a lapilli tuff composed
mainly of pumice which is tubular or has large
round vesicles. Volcanic fragments are black
cryptocrystalline, microlitic, reddish or
schlacke. Some plagioclase and pyroxene
crystal clasts occur. Clasts are angular but
quite well sorted, and not much fine matrix is
present.
Appendix 5 – Terrain observations and petrographical analyses of the samples of the Río Guaraguao section
88
Appendix 9 – Petrographical analyses of the alteration of the samples of the Río Guaraguao section
89
9.1 Alteration in the Piñón
Formation
Only two samples were studied of the Piñón Formation (04LM095, 09LM072). One sample is effusive, the other subvolcanic. The samples are altered to fine-grained calcite which is spread in the groundmass of the rocks and to well crystalline coarse spherical relatively pure chlorite and greenish opal-CT occurring in amygdules. Feldspars are generally not, or only partially albitized. Alteration zones of opal and veins of quartz penetrate through permeable areas in the rocks. All opal-CT is recrystallised to quartz. No zeolites were found in the samples of the Piñón Formation.
9.2 Alteration in the Calentura
Formation
The fine-grained beds of the Calentura Formation have typically a high quartz (40-95%) and calcite contents (5-45%). Their matrix is fine-grained making it difficult to distinguish between different alteration minerals. Clay minerals are generally brownish and have high interference colours.
9.3 Alteration in the lower unit of
the Cayo Formation
9.3.1 Coarse breccia at the base of the Cayo Formation
Sample 09LM078 is pervasively altered, very few original structures can be recognized. The fine matrix contains calcite and a mosaic of quartz and albite. Laumontite occurs as larger crystals enclosing clasts and smaller crystals, among which are calcite and quartz. No fresh
feldspar crystal clasts occur, all are albitized or replaced by laumontite. Clay minerals occur and are brownish, coarse, spherical in form and have high interference colours. Iron oxides occur in cracks and at particle rims. Sample 06LM004 is altered to albite, quartz, laumontite and pumpellyite. Pumpellyite occurs as spherical yellow brown booklets in clasts and voids and in the matrix as microcrystalline aggregates intergrown in a mosaic of feldspars and quartz. Laumontite occurs in zones and is probably replacing clasts. Other clasts have a similar alteration type as the matrix. Sample 06LM003 is a large clast of the same breccia. It has a similar alteration as sample 06LM004 with mainly a fine-crystalline matrix of albite, quartz and minor pumpellyite, while clasts and crystal clasts (hornblende?) are replaced by laumontite and pumpellyite. Veins are composed of pumpellyite at their boundaries, while laumontite occurs more central.
‘Mottled’ lapilli tuffs
In sample 06LM085 similar observations can be made. Brown clays replace particles and occur in the matrix between clasts. An evolution can be seen from early formed red iron oxides to brownish, quite coarse clays to greenish clays. In some zones clays seem to be partially replaced by laumontite crystals enclosing albite, quartz, small iron oxide aggregates and anatase. Sample 06LM096 is a clast occurring in the grey mottled lapilli tuffs. It contains a high amount of yellow to light brown fine crystalline pumpellyite, which is intergrown with albite.
9.3.2 Lower part of the lower unit
Sample 06LM101 is a thin fine lapilli tuff occurring between two clayey beds and is composed mainly of pumice occurring in a fine
APPENDIX 9 - PETROGRAPHICAL ANALYSES OF THE ALTERATION OF THE SAMPLES OF THE RÍO GUARAGUAO SECTION
Appendix 9 – Petrographical analyses of the alteration of the samples of the Río Guaraguao section
90
altered glass matrix. Mordenite (60%) forms very fine radial aggregates in the matrix. Pumice is altered to iron brown smectite which rims vesicles while heu-type zeolites replace glass. Euhedral anatase crystals are quite common in this pumice. In other pumice, large heu-type zeolite crystals enclose large parts of the pumice. Glass shards contain no clay minerals, non vesiculated glass is mainly replaced by heu-type zeolites. Clays are relatively rare in the sample, they rim vesicles of some pumice, are the major component of some pumice clasts and occur as late phases in cracks. Feldspars contain round bubbles, which are filled with clays, mordenite replaces the rest of the crystal clasts. Calcite occurs as a late phase, forming large euhedral twinned crystals filling voids and also occurs dispersed through the matrix. Sample 09LM086 has a similar appearance as the mottled lapilli tuffs occurring below. Some zones of the sample contain more iron oxides, which rim particles and also contain completely argillitized particles which can have been pumice originally. Clays are brownish and have high interference colours. Other zones are lighter in colour, contain more laumontite, which occurs as larger crystals enclosing several smaller crystals of albite and quartz. Primary clays seem to be replaced by laumontite. Pumpellyite is quite common, but only occurs in a certain type of irregular particles, where it forms microcrystalline crystals or radiating bundles. Sample 06LM102 is a competent fine lapilli tuff. Because of the high degree of alteration, no primary structures can be recognized. The sample is build up of fine-grained randomly oriented interlocking laumontite, albite and quartz. Some larger particles, which were possibly pumice, are replaced by larger laumontite crystals. Clays form as late phases, are light to dark brown and seem to fill the remaining pore spaces. Sample 09LM088 is composed mainly of pumice. Fine-grained quartz preserves the pumice and vesicle outlines. Large albite and laumontite crystals, possessing undulous extinction, enclose these clasts. The distribution of albite and laumontite seems to be more or less random, as a pumice clast can be replaced at one side by laumontite and at
the other side by albite. All feldspar crystal clasts are albitized. Small clusters of anatase occur in the pumice. Clays seem to be rare to absent, some pumpellyite possibly occurs. Sample 09LM001 is pervasively altered, no primary structures are preserved, only feldspar crystal clasts can be recognized. These are albitized and are enclosed in large laumontite crystals. Sample 09LM089 is a typical fine-grained bluish green tuff occurring in the upper part of C1a. It is altered to heu-type zeolites and contains a high amount of quartz. Similar tuffs are exposed west of the section, where they are exploited. Sample 04LM009, obtained from a small zeolite quarry west of the section, is a glass shard tuff altered to quartz, mordenite and heu-type zeolites.
9.3.3 Middle part of the lower unit
Section 1 of the lower unit
Sample 09LM002 is from a tuff underlying the first almeja sequence. The sample is altered to albite, quartz and brownish clay minerals. A brownish incompetent clay bed underlies the first almeja sequence. Sample 09LM003 was taken from the lowermost observed almeja layer in the Río Guaraguao section. Some zones of the sample are replaced by fine crystalline alteration minerals (< 10 µm) and are almost isotropic. In other zones, where alteration minerals are coarser (100 µm to 2 mm), remains of spherical mordenite aggregates can be observed, but these are replaced by heu-type zeolites. Stilbite crystals, ranging from small and anhedral to very large in size (100 µm – 2 mm) also replace mordenite aggregates (50 µm). Individual stilbite crystals can replace several mordenite aggregates. Small impurities, probably of quartz and Fe-oxides, occur mainly in the outer rims and around spherical mordenite aggregates and preserve the shape of mordenite aggregates in these stilbite and heu-type zeolite crystals. Although a high amount of replaced mordenite aggregates can be observed in the sample, only 3 % of remaining mordenite is detected by XRD. Clays are relatively rare in the sample
Appendix 9 – Petrographical analyses of the alteration of the samples of the Río Guaraguao section
91
and are greenish in colour. XRD confirms the presence of a 10 Å clay, probably celadonite. Bedding parallel stylolites are formed late and are penetrating through all mineral phases. Stellerite was identified in the XRD pattern, but not in thin section. Plagioclase crystal clasts are albitized, as is confirmed by XRD. The sample is cross-cut by veins of laumontite and stilbite (09LM004) and is overlain by thin tuff beds. Sample 09LM005, from a second coarse-grained sequence, consists of a fine matrix which is composed of a fine mosaic of interlocking feldspar and quartz. Pumice clasts are replaced by large laumontite (up to 2 mm) and in some cases albite crystals. In these crystals vesicle outlines are preserved by fine-crystalline quartz (< 5 µm) or fluid inclusions which rim these vesicles. Remains of spherical mordenite aggregates can also be recognized, but these aggregates are larger and more loosely packed compared to sample 09LM003. In other zones laumontite forms smaller “puzzle type” crystals (40-200 µm). A large amount of feldspar crystal clast occurs, all are albitized. Fire red anatase occurs in pumice clasts. Clays are dark brown to orange in colour and occur around crystals clasts but also at the contacts of different laumontite crystals or in cleavages of laumontite crystals. These clays are thus formed after laumontite crystallisation or are redistributed during recrystallisation of primary clays. Some greenish clay minerals are present. Stylolites penetrate through all alteration minerals, including laumontite. Possibly some pumpellyite occurs as a late phase, but because of the low amount present, this could not be confirmed by XRD. This rock unit is overlain by incompetent brownish clays. Sample 09LM009 is a pervasively altered lapilli tuff. Its matrix is very fine-grained and is composed mainly of quartz, which also replaces certain particles. Yellow to iron brown clays rim clasts, fill vesicles and also partially replace glass. Glass of pumice is replaced by large laumontite and albite crystals (up to 2 mm) which enclose several vesicles. In these pumice clasts, clays have higher interference colours. All plagioclase is very dirty and albitized. A great number of late fractures occur and penetrate all alteration minerals, primary clasts and crystal clasts. Iron
oxides and dark brown clays rim clasts and occur in fractures, which also penetrate laumontite crystals. Sample 09LM010, occurring higher in the same lapilli tuff bed, contains fine-grained zones (crystals < 5 µm), where albite and quartz are concentrated and coarser zones (laumontite to 1.5 mm), where laumontite is concentrated. Large laumontite crystals contain small euhedral albite crystals (10-100 µm). All feldspar crystal clasts and phenocrysts are albitized. Clays are common, are iron brown and coarse crystalline. The distribution of clays, quartz and fluid inclusions in laumontite remind of relatively large vesicles in pumice, but also to round mordenite aggregates, which are all replaced. Reddish iron oxides occur mainly along cracks which also penetrate laumontite crystals. Laumontite has undulous extinction. Sample 09LM011, occurring in the upper part of the same lapilli tuff bed, contains more clay minerals compared to sample 09LM010. Some clasts, which are highly crystalline, are not effected by alteration. Clays are yellow brown and can be very fine-grained or can form coarse bundles (up to 40 µm). Clays mainly fill vesicles but some particles are completely or for a major part replaced by clay minerals. Laumontite mainly replaces glass in pumice together with clay minerals and also occurs in voids between clasts. Dark brown iron oxides occur at particle rims, cracks and in porous zones, formed as a late phase. All plagioclase phenocrysts in pumice and crystal clasts are dirty and albitized. Clay minerals in pumice delineate forms which were probably round vesicles, while spherically aligned fluid inclusions possibly indicate replaced spherical mordenite aggregates. Albite occurs in albitized plagioclase crystal clasts or together with quartz in volcanic clasts. Sample 06LM104, which is underlying the next almeja sequence, was probably a crystal-glass tuff, but very little of its original structure has been preserved. The sample is composed of an interlocking pattern of albite, quartz and laumontite. Pumice clasts are mainly replaced by laumontite. Red iron oxides and reddish brown clay minerals occur, but are the last minerals being formed, filling remaining voids. Anatase is common. The sample has a
Appendix 9 – Petrographical analyses of the alteration of the samples of the Río Guaraguao section
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“mottled” appearance, because of the occurrence of zones where dark iron oxides are concentrated and zones where laumontite is concentrated. Sample 06LM106 is from a second almeja sequence. Clays, mostly dark brown but also greenish (celadonite and chlorite), are common in the sample and are relatively fine-grained. They rim clast, fill voids and vesicles and replace the major part of some particles. Mordenite is visible in voids between particles and replacing glass in pumice, but is replaced by heu-type zeolites and stilbite. Only 3% of remaining mordenite is detected by XRD. Heu-type zeolite and stilbite (up to 2 mm) crystals are particularly large in pumice with larger round vesicles, where they enclose several vesicles. Other pumice and the fine matrix of the sample seem to be replaced mainly by fine-crystalline quartz. Plagioclase phenocrysts are altered, but not albitized. Sample 06LM105 is a reddish clast occurring in sample 06LM105. Its matrix is composed of fine-grained quartz and red iron oxides. Some clast are completely altered to green clays (celadonite). The fine-grained sample 09LM012 contains a fine altered glassy matrix composed of iron brown clays, iron oxides and quartz. Laumontite occurs in zones, where it replaces glass shards. This zonal distribution gives a “mottled” appearance to the rocks. Iron oxides occur in cracks, more or less parallel to bedding. Sample 09LM013 of a next almeja sequence, contains a high amount of fine-grained spherical mordenite aggregates (5-20 µm), which can form larger aggregates (up to 80 µm) in vesicles, mainly occurring around phenocrysts in pumice. The alteration in the majority of the sample is fine-grained (< 10 µm). Clays are mostly green but iron brown well crystalline clays also occur. Green clays rim and fill vesicles, line particles and seem to be common in layer parallel dissolution zones, where they can be associated with iron oxides, for example on top or below crystal clasts. In these cases, they not necessarily form before zeolites. In some areas mordenite is replaced by heu-type zeolites and stilbite. Sample 09LM014 occurs higher in the same layer and has a similar alteration as the
underlying sample. Mordenite, occurring in voids, forms spherical aggregates, which can be large (up to 100 µm) in size and which are typically rimmed by impurities. Next to mordenite, quartz is the main alteration mineral. Most pumice is replaced by fine crystalline mordenite (10-50 µm) and quartz (< 10 µm). Compacted pumice is altered to brownish green clays, which are more common compared to sample 09LM013. Iron oxides occur along bedding parallel dissolution fronts. Sample 09LM015, from the base of the overlying bed, has a similar early mordenite formation, but all mordenite has been replaced by large stilbite and heu-type zeolite crystals (up to 2 mm). No remaining mordenite is detected by XRD. Spherical mordenite aggregate ghosts remain visible in these crystals (30-100 µm), and several aggregates can occur in one crystal. Stilbite is concentrated in pumice clasts, where it forms large interlocking and sometimes typically twinned crystals. Smaller euhedral crystals (50-200 µm) are enclosed in larger crystals, which enclose entire pumice clasts. Quartz crystallites preserve vesicle rims. In other zones a fine-crystalline mosaic of alteration minerals occurs. Both iron brown, bluish green (celadonite) and green clays occur, but are not very common. Some greenish clays (chlorite) occur along dissolution fronts aligned along layering. Sample 09LM016 occurs higher in the same bed. Dark brown to bluish green (celadonite) to green (chlorite) clay minerals rim and fill vesicles of pumice clasts. Quartz also rims vesicles and replaces glass. In some vesicles, it can be seen that greenish blue clays form first, rimming vesicles, that brownish clays form later and that greenish (chloritic) clays are the latest to form. Mordenite mainly fills vesicles in pumice and also replaces glass. Heu-type zeolites are formed after mordenite, and sometimes replace it. Some green clay minerals occur in pumice clasts, which are strongly compacted along layering. Some particles are mainly altered to heu-type zeolites, while others are mainly altered to mordenite. Heu-type zeolites seem to be associated with pumice with larger vesicles which contain mainly brownish clays. Pumice with finer, more tubular vesicles tends to
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contain more quartz and mordenite and less brownish clays. Sample 09LM017 from the upper part of the next layer contains zones of very fine-grained alteration, which are mainly composed of quartz. Round spherical forms in these zones remind of spherical mordenite aggregates of more or less 100 µm in size. Some of these spheres were definitely vesicles in pumice, but most are equally sized, perfectly round and too close together to be vesicles, and were thus probably mordenite aggregates. Other zones of the sample are replaced by large euhedral laumontite. Similar round shapes, formed by quartz and clay minerals, remind of pumice. Euhedral anatase is common. Clays are yellow brown and have relatively high interference colours. Dissolution occurs at rims of particles and iron oxides are concentrated along these rims. This dissolution is not only along layering, but also perpendicular to layering and penetrates laumontite crystals. All feldspars are albitized. Sample 09LM018 contains a matrix of microcrystalline laumontite, albite and quartz. Other zones contain larger (~ 200 µm) crystals and are composed of laumontite, stilbite and calcite, which typically have a puzzle shaped interlocking form. Quartz is always very fine crystalline (< 5 µm) and spread through the laumontite crystals. In some cases, shapes which remind of round vesicle outlines or spherical shapes of mordenite aggregates (~ 50 µm), can be recognized, because they are delineated by fine quartz crystals, filled with clay minerals, or because calcite and laumontite crystals are formed in these round shapes. In most cases, laumontite does not form large crystals enclosing several vesicles, as is seen in previous samples, but crystals which are more interlocking in form and which could be pseudomorphs after heu-type zeolites or stilbite. Clays are iron brown or green and well crystalline. Albite occurs as smaller euhedral crystals (10-50 µm) in laumontite and stilbite. Sample 09LM019, occurring higher in the same layer, is composed mainly of very fine-grained (< 10 µm) alteration minerals with low interference colours. From XRD it is derived that these minerals are mainly quartz, heu-type zeolites and mordenite. In some zones,
alteration minerals are coarser (20 – 50 µm, 100 µm for mordenite aggregates) and mainly brown but also greenish clays occur. Greenish clays also occur at dissolution fronts around phenocrysts. Iron oxides occur in stylolites parallel to bedding. Mordenite forms radiating bundles replacing glass and also fills vesicles in pumice. Calcite occurs in round forms, replacing mordenite (aggregates of ~ 50 - 100 µm) or is filling vesicles. It also seems to form pseudomorphs after heu-type zeolites. Euhedral pyrite forms in some clay-altered pumice, but is overgrown by Fe oxides. Sample 09LM020 from the layer above, contains a high amount of iron brown clays, which rim vesicles, fill vesicles but also replace glass in pumice. Some particles are replaced completely by clays. In some areas, even the entire matrix between crystal clasts is replaced by clay minerals. Clays can have high interference colours. Laumontite replaces glass or possibly clay minerals and form relatively large crystals (up to 400 µm), but smaller compared to the samples below. Its shape is similar to the shape of heu-type zeolites, possibly it replaces them. In other regions the shape of laumontite is more interlocking, which could be because of a replacement of earlier heu-type zeolites. Laumontites with spherical extinction could be replacing mordenite. Other zones of the sample 09LM020 are replaced by very fine-grained quartz. Pressure dissolution of pumice around large quartz crystal clasts concentrates brown clays. A high amount of plagioclase crystal clasts is present. All are dirty and completely altered. Quartz crystal clasts seem to be altered at their rims. Sample 09LM021 contains very fine-grained alteration minerals with low birefringence. According to XRD, these minerals are mainly mordenite, quartz and clay minerals. Greenish to brownish clays rim clasts and fill vesicles. They have relatively high interference colours. Bedding parallel stylolites occur. Sample 09LM022 contains a high amount of quartz. Laumontite occurs in veins and is concentrated in zones, where it replaces glass, giving a mottled appearance to the rocks. In other zones, reddish iron oxides are concentrated. Most alteration minerals are very fine-grained (< 10 µm), only laumontite
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crystals, enclosing hundreds of glass shards and thousands of fine quartz crystallites, can be very large (up to 2 mm). Sample 09LM023 contains iron brown clays which rim particles and fill vesicles in pumice. Some zones of the sample contain very fine-grained alteration minerals, mainly mordenite and quartz. In other zones, where pumice has larger vesicles, commonly near crystal clasts, larger spherical mordenite aggregates crystallise (up to 150 µm). In some voids radial bundles of coarse clays, with high interference colours crystallise (up to 150 µm). Calcite also fills large voids in these locations. Some clasts are replaced by mainly brownish clays and calcite, which can form large crystals (up to 1mm). Next to mordenite, another mineral (heu-type zeolites or albite?) crystallizes in spherical forms. Heu-type zeolites replace glass as euhedral intergrown crystals.
Section 2 of the lower unit
Sample 09LM024 contains a high amount of crystal clasts and crystalline particles which are only partially affected by alteration. Plagioclase is mainly affected by clay alteration and can be partially albitized. The high amount of quartz detected in the sample by XRD, is partially due to the large amount of quartz crystal clasts. Greenish to dark brown clays and Fe-oxides rim particles and occur in the matrix together with fine crystalline quartz. Crystal clasts and volcanic clasts seem to be fractured in situ. Mordenite forms relatively large (200 µm is common), not very dense aggregates in pumice but is completely replaced by heu-type zeolites, no remaining mordenite is found in XRD. Heu-type zeolites form interlocking anhedral to subhedral crystals. Some clays form along cleavage planes of heu-type zeolites. Laumontite occurs mainly in pumice, where it replaces glass as large crystals enclosing large parts of single pumice clasts. Heu-type zeolites and laumontite do not occur together, but in different clasts, although in some cases possible evidence of heu-type zeolite replacement by laumontite can be observed. In sample 09LM025, occurring higher in the same layer, quartz and greenish clays are the main alteration minerals. All alteration
minerals are very fine crystalline. Mordenite forms small radial aggregates. Some zones of the sample are completely replaced by mordenite, in other zones quartz is more concentrated. Mordenite spheres are very fine in tubular pumice and in fine-grained zones in the matrix (< 20 µm), but in larger vesicles they can form larger bundles (50-200 µm). Irregular cracks penetrate through the rock and are filled with iron oxides. Sample 09LM026, occurring higher in the same layer, has a similar alteration as 09LM025. Alteration minerals are typically very fine-grained (<20 to 30 µm), although in more porous zones they can be larger. Clays are mainly concentrated along bedding parallel stylolites which develop in tubular pumice oriented in this direction. Sample 09LM027 contains clays with relatively high interference colours, which rim particles, compose part of the matrix of the rocks, fill vesicles, replace glass in pumice and form along cracks. Remains of mordenite aggregates can be observed in pumice, but all mordenite has been replaced by laumontite, which forms large crystals (up to 1 mm) which enclose small euhedral albite crystals (50-100 µm). Laumontite also forms spherical aggregates and in some zones smaller (40-60 µm) crystals. Quartz occurs as very small crystallites. Plagioclase crystal are common in the sample and are all replaced by albite. Calcite grows in cracks, mainly in pyroxenes. Sample 09LM028 contains a high amount of brownish clay minerals, which are generally fine crystalline (< 5 µm). They mainly fill and rim vesicles in tubular pumice. More crystalline clays rim particles and cracks. Mordenite occurs in the fine matrix of the sample, replaces glass in tubular pumice and forms large spherical aggregates (~ 100 µm) near phenocrysts. Heu-type zeolites replace pumice clasts as euhedral crystals and are nicely visible in pumice with larger vesicles, where they crystallise after mordenite. Laumontite is concentrated in zones where it replace pumices as “puzzle formed” crystals with undulous extinction. Tiny crystals of mainly quartz and minor albite are included in the larger laumontite crystals (mainly puzzle shaped crystals occurring in aggregates up to 500 µm in size). The shape of some laumontite
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crystals reminds of round mordenite aggregates, which were probably replaced by laumontite. The Ca-rich centre of plagioclase is replaced by calcite while the more Na-rich rims are unaltered and no albitization of plagioclase crystal clasts occurs. Some large spherulites occur, but these are probably formed by high temperature devitrification. In sample 06LM108 greenish to brownish clays rim pumice and fill vesicles. Mordenite occurs as very fine to large spherical aggregates filling empty spaces and replacing tubular pumice. Heu-type zeolites replace glass. Alteration minerals are mostly fine crystalline (<10µm), except in some larger vesicles or in the vicinity of phenocrysts or crystal clasts. Plagioclase crystal clasts can be unaltered or can be partially altered to clays, but are not albitized. Sample 09LM029 probably originally contained a high amount fine-grained spherical mordenite aggregates (spheres of ~100µm), but all are replaced by large to moderate sized laumontite (100 µm to 1 mm) and albite or microcrystalline quartz and albite. Laumontite crystals can have a puzzle shape and/or undulous extinction, which could reflect recrystallisation from smaller mordenite aggregates and heu-type zeolite crystals (analogue sample 09LM028). Clays are brownish with relatively high interference colours. Clays mainly occur in strongly compacted pumice particles. Compaction and pressure dissolution occurred in the sample. Dissolution rims can be seen at edges of particles. The clays now present in the sample, could be recrystallised from primary clays, because they seem to be redistributed along dissolution/compaction fronts. In sample 09LM030 alteration minerals are very fine-grained. Clays and quartz rim glass shards and occur between shards as fine spherical aggregates, while mordenite nucleates from the shard rims inwards. Sample 06LM109 is pervasively altered, no primary structures remain. Laumontite is the main alteration mineral, forming very large crystals (1 mm or bigger) and enclosing small quartz crystallites (< 10 µm) and small euhedral albites (40-80 µm). Calcite forms large twinned crystals (0.5-2 mm), which
enclose smaller albite and quartz crystals. In other zones alteration minerals are smaller, a mosaic of quartz, feldspar and laumontite occurs. Anatase and reddish iron oxides form relatively large euhedral crystals and smaller anhedral crystals (80µm). Clays are rare, some brownish clays occur. Crystal clasts are strongly fractured in situ and plagioclase crystal clasts are albitized. Round edges of calcite crystals remind of mordenite aggregates. Sample 06LM110 is similar in appearance as sample 06LM109. Laumontite forms very large crystals (1 mm) which overgrow all clasts and other alteration minerals. In other zones crystals are finer grained and interlocking (puzzle of laumontite and quartz). Brown clays are formed in remaining voids and fractures and many are formed along laumontite cleavages. Calcite also forms in cracks. Some clasts are altered to greenish C/S clays, which crystallise in spherical aggregates with high interference colours. Plagioclase is albitized. Some spherulitic structures occur, but these were formed by high-T devitrification in pumice. Sample 09LM032 contains more clay minerals compared to the underlying samples. Clasts are rimmed by iron brown clays, some are entirely replaced by brown clays. In other areas, all clasts are replaced by laumontite and albite. All plagioclase is albitized. Small euhedral albites occur in larger albite and laumontite crystals. Some small quartz crystals are aligned along semi-rounded primary structures, which could have been vesicles or spherical mordenite aggregates (~200 µm). Late illitic clays form in cracks.
Section 3 of the lower unit
In sample 09LM033, a high amount of clays is present. Brown clays rim particles and vesicles and partially replace glass. Some particles are entirely replaced by brown clays, or by brown clays and quartz. Some particles contain vesicles filled with brown clays and are replaced by large albite or laumontite crystals (up to 500 µm). In other zones, more fine-grained albite and quartz occur (<10 µm). All plagioclase is albitized. Larger laumontite and albite enclose smaller euhedral albite crystals.
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Iron oxides occur in cracks and voids. Some round spheres (50-100 µm) delineated by fluid inclusions occurring in laumontite crystals, or shapes of laumontite crystal surfaces evidence a possible early mordenite crystallisation. Most volcanic clasts of sample 06LM113 are crystalline and not, or only partially altered. Clays mainly fill vesicles, but also replace some particles almost entirely. Greenish clays (chlorite) form after brownish clays. Most clays have high interference colours and can be coarse-grained (several µm). Some late clay minerals occur in cracks. Clays seem to differ in different particles and in the matrix of the rocks. Laumontite, albite and stilbite all replace glass in pumice. They form large crystals which enclose several vesicles (up to 500 µm). Stilbite crystals can be twinned. Some particles are partially replaced by laumontite and partially by stilbite. Both minerals also fill voids (crystals up to 1 mm) between clasts or this could be locations where they replace a fine interstitial matrix. In other locations, a fine matrix is observed, which is mainly altered to fine crystalline quartz and clay minerals. In laumontite, some spherical forms remain which could have been mordenite (100 µm). Calcite forms small irregular veins which crosscut laumontite. Sample 06LM114 contains relatively much clay minerals which mainly fill vesicles and also partially replace glass. Voids are filled with very large (up to 500 µm) spherical mordenite aggregates, but these aggregates are replaced by heu-type zeolites and quartz. As quartz replaces some of these spherical aggregates, some of them can have been opal-CT and not mordenite. Heu-type zeolite crystal aggregates can preserve the spherical shape of mordenite aggregates. In schlacke, which have a crystalline matrix, heu-type zeolites and spherical bundles of C/S fill vesicles (C/S crystal size up to 20 µm). In pumice, yellow Fe-clays rim and fill vesicles and heu-type zeolites replace glass. Other clasts and the matrix are mainly replaced by fine-grained quartz, heu-type zeolites and clay minerals. Anatase only occurs in certain particles, where it occurs in the outer rim, formed before zeolites. In sample 09LM035 iron brownish clays rim pumice and also fill vesicles. Fine-grained
laumontite, albite and quartz replace the glass in most clasts (~20 µm), while brown clays fill vesicles. In other regions, laumontite is coarser grained (up to 500 µm). All plagioclase occurring in clasts is albitized. Large laumontite also occurs between the clasts, but undulous extinction can possibly indicate that at least some of these crystals replace earlier formed alteration minerals. Iron oxides occur in cracks. Sample 09LM036 has a fine matrix, which was originally altered to mordenite and later recrystallised to heu-type zeolites. Compacted pumice is rimmed by iron brown to greenish clays and fine-grained silica and radial mordenite bundles replace glass (10-20 µm). Almost all mordenite is replaced by heu-type zeolites, but mordenite ghosts are present because small inclusions of clays, iron oxides and quartz remain around the former aggregates. A second type of pumice, with larger round vesicles, is rimmed and its vesicles are filled by brownish clays, while heu-type zeolites replace glass (50-100 µm). Other zones are replaced by fine-crystalline quartz and clay minerals. Some zones are recrystallised to stilbite. Feldspars are not albitized but are partially replaced by calcite, clay minerals and laumontite. A fracturation phase occurred through crystals and matrix. In sample 06LM115, alteration of tubular pumice is generally very fine-grained (10-20 µm). Alteration minerals are mordenite, quartz, heu-type zeolites and greenish clay minerals. Mordenite occurs in vesicles and fills interstitial voids with large spherical aggregates (100 µm). In some pumice particles, vesicles are rimmed by greenish clays and silica, while mordenite crystallises from the rims. Heu-type zeolites are formed after mordenite, partially replace it and crystallise central in vesicles. In the interstitial voids between particles, mordenite crystallises outwards from the particles and heu-type zeolites overgrow mordenite more central in the voids. In some pumice, heu-type zeolites crystallise directly on clays and no mordenite occurs. Calcite forms as a late phase in cracks. Iron oxides form where clasts are affected by dissolution and also fill late cracks. In sample 09LM038 most alteration minerals are fine-grained (<10 µm), with the major
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alteration minerals being quartz, mordenite and clay minerals. Around large phenocrysts in pumice, where vesicles are unstretched, larger alteration minerals can crystallise (up to 100µm). Quartz and albite possibly crystallise in some fine tubular pumice. Brown clays are concentrated in certain zones, where they replace the majority of the pumice. In sample 06LM116, alteration minerals are also fine-grained (< 30 µm). The main alteration minerals are quartz and spherical mordenite aggregates, which replaces glass and also fill voids and vesicles. Fine-grained green clays (chlorite) are concentrated in certain zones, fill larger unstretched vesicles and also occur in cracks. Part of the mordenite crystals are recrystallised to heu-type zeolites and heu-type zeolites also occur in pumice with larger unstretched vesicles. Sample 09LM039 contains larger alteration minerals (100-300 µm) compared to the underlaying samples. It contains dark brown clays which rim particle and vesicle outlines, but others seem to have also a more random distribution, possibly because of recrystallisation of primary clay minerals or other minerals which caused a redistribution of clay minerals. Mordenite replaces glass, but is replaced by heu-type zeolites and stilbite. Stilbite forms small twinned crystals which are enclosed in larger crystals. Fine quartz crystallites are spread through the sample (10 µm). In sample 09LM042, pumice is rimmed by quite common brownish to greenish clays, which also fill vesicles and replace some particles entirely. These particles seem to be stretched/compacted to such a high degree, that no remaining vesicles occur. Mordenite occurs as spherical aggregates in pumice with irregular vesicles and in voids between the particles. Quartz crystallises after mordenite in the centre of voids. In other regions alteration minerals are very fine crystalline. In other pumice particles, heu-type zeolites replace glass, while clay minerals fill vesicles and no mordenite is present. In other pumice heu-type zeolites and mordenite occur together, with heu-type zeolites forming after mordenite. Calcite occurs as large twinned crystals. Plagioclase can be albitized or partially altered to clay minerals. Late fractures cross-cut
spherical mordenite, heu-type zeolites and plagioclase. Mordenite seems to nucleate more from quartz, while heu-type zeolites nucleate mainly from brownish clay minerals.
9.3.4 Upper part of the lower unit
In the coarse part of sample 06LM118, greenish and brownish clays form a thin film around all particles and fill vesicles in pumice. Almost all zeolites have a spherical form and nucleate from the outer rim of glassy particles towards their centre. The shape of these aggregates is somewhat different from typical mordenite aggregates in the underlying samples, individual crystals are thicker. It is not always clear if these aggregates are composed of mordenite, heu-type zeolites, or mordenite replaced by heu-type zeolites. Only 5% of mordenite is found in XRD, so probably most of these aggregates are heu-type zeolites. Heu-type zeolites crystallise after mordenite, central in voids. Some plagioclase crystal clasts are relatively fresh, or are only partially altered, others are more altered, albitized, or partially replaced by zeolites, clay minerals and calcite. The fine-grained part contains fine alteration minerals and more quartz and calcite. In sample 06LM123, alteration minerals are very fine-grained and mainly quartz, heu-type zeolites and minor mordenite occur. Glass shards are completely replaced by zeolites, while quartz is concentrated in the matrix of the sample. Fine-grained red iron oxides occur spread through the rocks. Laumontite veins cross-cut the sample. Iron oxides are concentrated in zones. In sample 06LM178, yellow clays seem to replace the majority of the sample. Glass is replaced by zeolites with low interference colours. Plagioclase crystal clasts are very fresh in comparison to the underlying rocks of C1a and C1b, where plagioclase is very dusty and where it is partially replaced by clay minerals or albitized. Plagioclase crystal clasts can be heavily fractured, clay minerals occur in cracks. 50% of the sample is composed of heu-type zeolites, as detected by XRD, but all heu-type zeolites are very fine-crystalline and therefore difficult to observe under the
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microscope. The amount of quartz is also very low (6%). Sample 06LM176 is heavily compacted and fractured. Some zones are composed of very dark brown to orange brown to red and some green clay minerals. Clay minerals replace glass, some clasts are entirely altered to clay minerals. Reddish iron oxides occur in clay-rich zones and along cracks. Other zones are composed of fine-crystalline heu-type zeolites. Some zones are entirely replaced by heu-type zeolites and contain no clays. Heu-type zeolites crystallise from particle rims towards the centre of particles. This mode of crystallisation is different from the samples of C1b, where heu-type zeolites crystals are more randomly oriented. The quartz content of the sample is very low. Early mordenite crystallisation is possible, but mordenite is replaced, as it is not detected by XRD. Sample 06LM074 is composed mainly of dark brown clay minerals and heu-type zeolites. Clay minerals fill vesicles and partially replace glass in pumice. Possibly the more permeable zones (pumice with larger vesicles) are preferentially replaced by clay minerals, while the finer zones (smaller, more impermeable pumice clasts, fine matrix and glass), are replaced by heu-type zeolites. The quartz content is very low. Heu-type zeolites crystallise inwards from particle and vesicle rims. Heu-type zeolite can be euhedral, radial or anhedral, blocky, as is typical for all coarser and clay rich samples of this part (06LM118 and above). Plagioclase phenocrysts are relatively fresh. In sample 06LM079, dark iron brown clay minerals rim particles and fill vesicles. Some clay minerals occur in cracks. Some greenish coarser clay minerals (up to 60 µm) form central in vesicles. Glass in pumice is replaced by heu-type zeolites (50-100 µm), which are relatively coarse and more randomly oriented, not crystallising from particle rims or vesicle rims. Anhedral analcime (100-300 µm) fills vesicles in clasts, which are mainly altered to brownish clays, fills vesicles in schlacke or occurs central in voids, where it overgrows heu-type zeolites. Irregular fine calcite veins are common. In some of the heu-type zeolite crystals dusty spherical rims are observed, which can have been mordenite aggregates
which are now recrystallised. This can also explain the spherical shape in which heu-type zeolite crystals grow. Analcime also possibly replaces mordenite aggregates in some pumice. Sample 06LM080 is a red clast occurring in sample 06LM079. It is composed of spherically formed quartz, which contains calcite in its centre. It is not know how these structures were formed. The reddish colour is caused by iron oxides. Using X-ray diffraction, apophyllite was identified in the sample. Sample 06LM082 is composed completely of large euhedral twinned stilbite laths (1-1.5 mm), no original structures are preserved. Calcite and quartz are microcrystalline and are overgrown by the stilbite laths. Clay minerals are dark brown and irregularly spread over the sample. In sample 06LM085, most of the pumice is altered to puzzle shaped anhedral heu-type zeolites. Quartz and clay minerals form small crystallites. Round forms of some heu-type zeolite crystals remind of mordenite spheres. Stilbite forms blocky and twinned crystals and also replaces plagioclase. In other zones of the sample, green and brown clays replace pumice. These zones are heavily compacted and stylolitized. Feldspars are altered. Calcite forms large twinned crystals (200-500 µm), which are corroded at their edges. Sample 06LM087 is composed of fine laumontite, quartz and calcite, which form a fine interlocking irregular pattern. Especially calcite is very common in the sample. Cracks are easily identified in the sample, are full of iron oxides and calcite is concentrated in and around them. In some zones calcite forms larger twinned crystals. As is observed in other samples, sample 06LM086 contains certain zones which are altered to clay minerals and other zones which are altered to zeolites. Clay minerals are iron brown and green in colour, and the zones where they occur can be strongly compacted. Zeolitic zones generally contain very fine crystalline zeolites (< 10 µm). In some larger vesicles in pumice clasts or voids near crystal clasts or phenocrysts, zeolites can crystallise larger (50µm). In pumice, clays can replace the majority of the glass, can fill vesicles or can be rare to absent. Heu-type zeolites and/or
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mordenite replace glass, with heu-type zeolites crystallising after mordenite. Mordenite crystallises as spherical bundles nucleating from small quartz aggregates, which occur at the outer rims of particles.
Section 4 of the lower unit
Sample 09LM052 is altered to brownish clays, heu-type zeolites and mordenite. Clays are quite common, mostly dark brown, but can be greenish (celadonite). Greenish clay minerals occur centrally in pumice clasts and not at their rims and always crystallise before brown clay minerals. Brownish clay minerals rim particles, fill vesicles in pumice, replace glass of some particles and occur in voids and cracks. Both spherical mordenite aggregates and heu-type zeolites replace glass in pumice (30-100 µm). Mordenite forms before heu-type zeolites and nucleates on fine-crystalline quartz. All plagioclase crystal clasts ad phenocrysts are fresh. Calcite occurs in certain zones, its shape reminds of the shape of radial mordenite aggregates. The quartz content in the rocks is relatively low. In sample 09LM053, a more clear distinction can be made between zones of clay alteration and zones of zeolitic alteration. Clay minerals are iron brown to brownish green or green. Zones rich in clays generally contain pumice, which can be strongly compacted. Where strong compaction occurs, greenish (C/S or chloritic) clays occur. Zeolitic zones contain few clay minerals and are composed mainly of spherical mordenite aggregates (20-100 µm). A larger spread in the size of mordenite aggregates occurs compared to the previous sample and more fine-grained aggregates occur. Mordenite is also more common compared to the previous sample. In voids, an evolution can be seen from crystallisation of spherical mordenite aggregates to spherical heu-type zeolite aggregates with thicker crystals to more randomly oriented heu-type zeolites with larger crystals central in the voids. Clays have higher interference colours compared to the underlying sample and greenish (celadonite) clays are more common. When occurring, celadonite crystallises before iron brown clays, as it rims vesicles in pumice, and brownish clays occur more central in
vesicles. Plagioclase is moderately altered, the quartz content is relatively low. As the underlying sample, sample 09LM054 contains well defined zones with more clayey and more zeolitic alteration. Clay minerals are iron brown to greenish brown, with greenish clay minerals mainly concentrating in compacted pumice zones. Zeolitic alteration is similar as in the underlying sample, but quartz and mordenite are more common compared to heu-type zeolites. Mordenite typically nucleates on quartz, while heu-type zeolites nucleate more on brownish clays. In zones where both zeolites occur, which are mostly zones with a higher porosity, heu-type zeolites can nucleate on mordenite. Zones with low amounts of clay thus tend to contain less heu-type zeolites, unless heu-type zeolites crystallise on mordenite if any remaining space is left. Zones with more brownish clays, which are also porous (large vesicles), tend to contain more heu-type zeolites. Sample 09LM054 seems to be less porous than the underlying sample, it also contains less brownish clays. Zeolites in fine zones are typically 10µm, while in coarser zones 50-100 µm. In sample 09LM055 clast outlines are more easily distinguished compared to the underlying samples. (more volcanic fragments, probably separate pyroclastic flow deposit). Some clasts are more argillitized, while in others, clay minerals fill vesicles while zeolites replace glass. Clays are iron brown to brownish green to green in colour. Zeolitic alteration is very similar compared to the underlying samples. The size of zeolite crystals is 20-50 µm. In contradiction to the underlying samples, brownish clays are not common in sample 09LM056, while greenish clays (celadonite) are common. Zeolitic alteration is similar as in underlying sequences, with mordenite dominating. The sample is composed mainly of fine tubular pumice. The size of zeolite crystals is generally smaller than 10 µm. Sample 06LM090 is strongly compacted, with brownish clays and iron oxides formed mainly in compaction/dissolution fronts and in rare very fine vesicles. Mordenite greatly dominates over heu-type zeolites. The size of alteration minerals is smaller than 10 µm.
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In sample 09LM066, alteration minerals are all very fine-grained (< 10 µm). Clay minerals are not common and occur mainly along dissolution fronts and fill vesicles in some coarser pumice clasts. Most of the sample is altered to very fine-grained mordenite aggregates (<10µm).
9.4 Alteration in the upper unit of
the Cayo Formation
9.4.1 The lower part of the upper unit
The base of the upper unit
The fine-grained rocks at the base of the upper unit of the Cayo Formation have a high content in calcite, quartz and clay minerals. Heu-type zeolites only occur as glass replacement and filling voids in microorganisms, but are not present in the matrix of the rocks. Greenish clay minerals replace some glassy particles. A remarked difference with the lower unit of the Cayo Formation is the abrupt decrease in the mordenite content at the base of the upper unit. Mordenite only occurs in amounts lower than 5% in the basal part of the upper unit and is rare to absent higher in the section.
Lower part
Fine-grained tuffs occurring higher in C2a, are altered to brownish and greenish clay minerals and heu-type zeolites, have low quartz contents and can contain some mordenite fibres (06LM145, 148). The coarser lapilli tuffs in the lower part of C2a can be altered to heu-type zeolites, can have a mixed heu-type zeolite – laumontite alteration, or can have a laumontite alteration. All rocks have a very low quartz content, except the rocks containing laumontite, which have a low to moderate quartz content (<15%).
Lapilli tuffs with heulandite-type zeolite
alteration
Coarse to relatively fine-grained rocks with a heu-type zeolite alteration (samples 06LM150–151), contain a very low amount of quartz (<5%), a high amount of plagioclase (25–
30%), a moderate to high amount of clay minerals (10–45%) and a moderate amount of augite (8–10%). Feldspars are altered and can be albitized. Calcite and iron brown to greenish brown clays, with low interference colours, rim particles and pumice. Pumice is compacted and dissolved, greenish C/S clays with higher interference colours and relatively fine crystalline subhedral to anhedral heu-type zeolites replace glass in pumice and fill voids. Some mordenite needles can be observed. Brownish clays and calcite form as late phases in cracks.
Lapilli tuffs with co-occurrence of heulandite-type zeolite and laumontite
alteration
Sample 06LM129 occurs in the uppermost beds of the lower unit of the Cayo Formation, but has a similar alteration as the samples of this group and is therefore discussed here. The sample contains a fine matrix composed of fine crystalline alteration minerals, which are probably iron oxides, quartz, calcite and heu-type zeolites. Brownish clay minerals rim all particles, while greenish clay minerals only occur in clasts. Some particles are more argillitized than zeolitised. Some particles are entirely replaced by clay minerals, while calcite fills vesicles. Plagioclase is albitized or altered to laumontite, but not all plagioclase is altered. Heu-type zeolites and laumontite occur in different clasts. Celadonite occurs in some clasts. Using hot cathodoluminescence observations, the distribution of the alteration minerals can be observed more easily in the sample. Heu-type zeolites, which have a light bluish luminescence colour, replace glass shards in the matrix and replace glass in pumice clasts. The fine matrix is mainly replaced by quartz and clay minerals with kaki green to brown luminescence colours and these minerals also seem to replace and rim glass before heu-type zeolite crystallisation. Calcite, with orange luminescence colours, is present in the matrix, fills mainly voids, such as vesicles, but also replaces particles. Laumontite, with light green luminescence colours, replaces glass in particles, but occurs also in certain areas in the matrix. Authigenic albite, fluogreen in colour, forms fine-grained euhedral crystals.
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Sample 06LM146, probably of epiclastic origin, has a cryptocrystalline matrix, that is composed of clay minerals, quartz and calcite and that contains some glass fragments, which are replaced by heu-type zeolites. Calcite rims particles and is an important component of some particles (mainly schlacke) and is formed before clay minerals. Possibly some clay and calcite alteration occurred previous to the final deposition of the rocks. Early formed clay minerals are cryptocrystalline and precede the formation of large euhedral heu-type zeolites, which replace glass in pumice and fill empty spaces. The alteration is different in different particles. In some particles clays have higher interference colours, are coarser and laumontite and calcite occur as alteration minerals. Sample 06LM154 contains a high amount of brownish clay minerals which rim particles, rim and fill vesicles and replace pumice. No fine matrix is present, feldspar crystal clasts are albitized. Heu-type zeolite formation is preceded by the formation of spherical mordenite aggregates, but all mordenite is completely replaced by heu-type zeolites and laumontite. Some ghosts of mordenite aggregates can be observed in the large heu-type and laumontite crystals. Heu-type zeolites and laumontite replace glass in pumice and mainly laumontite and minor heu-type zeolites are common in large voids between the clasts, where they replace mordenite or an interstitial fine matrix. Schlacke and semi-crystalline effusive volcanic particles are mainly altered to clay minerals, while zeolites fill vesicles. Some pumice is somewhat compacted, primary clays are recrystallised to coarser clays with higher interference colours and anhedral and interlocking heu-type zeolites are replacing glass. In these particles it can also be observed that fine brownish clays are possibly recrystallised to coarser C/S clays with higher interference colours and that during this process the distribution of the clays was changed, while pumice compaction occurred. Heu-type zeolites form during this process. Other glassy particles are mainly altered to brownish clay minerals. In less compacted pumice, clays fill vesicles, while randomly oriented subhedral heu-type zeolites replace glass. Some late clays and calcite occur in cracks and are formed after heu-type zeolites.
Lapilli tuffs with laumontite alteration
In sample 06LM149, laumontite is the only zeolite mineral present. The sample contains a high amount of clay minerals, plagioclase (21%) and augite (12%). Primary clays are dark brown, fine-grained and with low interference colours. In many particles, such as schlacke, clay minerals are the main alteration minerals. Some pumice is compacted and primary clays are redistributed and recrystallised to coarser C/S clays with higher interference colours. In pumice clasts, clays rim and fill particles, while zeolites replace glass. Possibly early formed fine-grained zeolites are replaced by larger albite and laumontite crystals, although it is difficult to find proof for this. During the conversion of primary clays and zeolites, authigenic quartz (14% in the sample) was probably formed. Laumontite is found in all voids, is replacing pumice and is intergrown with calcite. Voids between particles can be very large and contained probably originally glassy particles, which were completely dissolved during alteration. Some remains of these particles can be observed by the shapes of clay aggregates occurring in the centre of these voids. In highly altered particles dusty shapes in laumontite crystals remind of clays which were rimming round vesicles but which were later dissolved or replaced by laumontite. Primary clays were dissolved to form C/S, which is intergrown with laumontite and calcite. In other particles, primary clays remain and the alteration did not proceed to the higher grade alteration. Anatase occurs as an alteration mineral in pumice. In sample 06LM153, a high amount of mordenite and possibly heu-type zeolite ghosts are present, but no remains of these minerals can be detected in the XRD pattern. Needle-like forms show the presence of early mordenite and some shapes (at a high magnification) remind of heu-type zeolites, but all these minerals are replaced. Laumontite is the main alteration mineral. It occurs as large euhedral crystals between particles, and as large crystals replacing pumice in which round vesicles ghost are formed by clay minerals, although these minerals can be replaced afterwards. Primary clays rim vesicles, are fine-grained and have low interference colours. These clays are the main alteration minerals in (semi-) crystalline clasts. Some clays are
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102
coarser and have higher interference colours. Some euhedral authigenic albite is intergrown with these clays. Calcite occurs intergrown with laumontite or as a late phase.
The upper part
Tuffs Higher in the section, coarse lithologies are rare in outcrop, but probably, because of their low competence, they were easily weathered and removed by erosion. The fine-grained rocks in this part of the section (06LM157-161) are altered to fine-grained brownish clays, can contain early formed calcite and fine-grained heu-type zeolites which nucleate on these clay minerals.
Lapilli tuffs The only coarse sample, 06LM155, contains a high amount of clay minerals, augite and plagioclase. The sample contains light orange to brown cryptocrystalline clay minerals, rimming effusive volcanic clasts and pumice clasts and filling vesicles in pumice. Alternatively, reddish brown iron oxides rim particles. In some pumice, a sharp contact exists with bluish green clays, probably celadonite, which occurs more central in vesicles or which replaces glass. All clays are fine-grained, cryptocrystalline and with low interference colours. Heu-type zeolites are generally euhedral and clearly nucleate on these clay minerals and can grow spherically from their nucleation point, making their form and distribution different compared to the underlaying coarse beds, where they tend to be more randomly oriented and subhedral to anhedral. Early formed zeolites are smaller in size, with their long axis oriented from their nucleation point, while later formed zeolites are more randomly oriented, nucleate from earlier formed zeolites and fill all the remaining pore space. Some spherical forms could be ghosts of mordenite which crystallised before heu-type zeolites.
9.4.2 The middle part of the upper unit
Lapilli tuffs
Samples 06LM162, 166, 168 and 171 are coarse-grained and have a high augite content. Sample 06LM162 is a relatively fine-grained lapilli tuff. Primary clays are iron brown, occur in the pore space and rim and replace pumice and fill vesicles in pumice. Fine crystalline calcite is also early formed. Blue green celadonite can be clearly distinguished from these brownish clays, but occurs only in certain particles. Anhedral heu-type zeolites nucleate on clay minerals and form spherical or axiolitic structures. Later formed zeolites are larger, more euhedral and nucleate on earlier formed zeolites. Analcime is formed after heu-type zeolites and overgrows them. It forms large anhedral crystals in the remaining voids and also replaces plagioclase. A part of the primary clays is recrystallised to C/S, is well crystalline and has higher interference colours. This recrystallisation occurred during or after zeolite formation, as these clays also fill the remaining pore spaces and they seem to be redistributed during zeolite growth. Sample 06LM166 contains no quartz, has a high clay mineral content, a high augite content (22 %) and has a similar type of alteration as the underlaying sample. It contains only 4 percent of heu-type zeolites, while the analcime percentage is 28%. Sample 06LM168 contains a low amount of fine-grained iron brown clay minerals which rim pumice and line vesicles. Heu-type zeolites are blocky, large, euhedral and replace glass. In schlacke they fill vesicles and in some pumice clasts they replace clay minerals in vesicles. Euhedral calcite is intergrown with zeolites. In some vesicles coarse-grained clays occur. Some celadonite occurs in pumice. Sample 06LM171 contains poorly crystalline schlacke and pumice similar in appearance as the schlacke. Clasts are rimmed by yellow brown clay minerals and calcite, vesicles in pumice are filled with similar clays, while clays in the clasts are more reddish in colour. Clays have relatively high interference colours. Glass is replaced by anhedral to subhedral blocky and interlocking heu-type zeolites and these also fill voids. Analcime occurs as a later phase overgrowing heu-type zeolites.
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Feldspars are replaced by heu-type zeolites, calcite or analcime.
Tuffs
The fine-grained rocks generally contain early formed fine-crystalline calcite spread through the matrix and fine-crystalline brownish clay minerals and they can contain celadonite which is mainly concentrated in certain glassy particles. Heu-type zeolites are fine-grained, anhedral to subhedral and nucleate from the clays rimming the glass (samples 06LM163-165, 167, 169, 170, 172). Most alteration minerals are fine-grained, which makes it difficult to distinguish them optically. Secondary calcite occurs in layer parallel veins. When pumice is present, clays can be coarser in size and they can have higher interference colours. These clays seam to have been recrystallised from primary clays and are redistributed during the compaction of the pumice and the growth of zeolites.
9.4.3 The upper part of the upper unit
From sample 06LM169 and higher in the cross-section, quartz is found as a crystal clast in the rocks and the augite content is lower compared to the underlaying part. Volcanic schlacke are more common in the lapilli tuffs, argillitization is common and pervasive and heu-type zeolites are typically euhedral and axiolitic.
Lapilli tuffs
In sample 06LM182, the alteration differs clearly in the different clasts and in the matrix. The matrix of the sample is composed of plagioclase, Fe-Ti oxide crystal clasts, glass shards and small pumice clasts. The glassy particles in the matrix are rimmed by brownish clays and replaced by heu-type zeolites. In other areas, no fine matrix is present or it is completely replaced by large euhedral heu-type zeolites, which are crystallised from the particle rims, but which do not seem to be preceded in growth by clay minerals. Some clasts posses no zeolitisation and glass is replaced by fine-grained brown clays. Other particles are completely replaced by large
euhedral heu-type zeolites. Pumice clasts are rimmed by brown clays, while celadonite and heu-type zeolites replace the centre of the clasts. Other particles contain a high amount of calcite next to heu-type zeolites. Some clay minerals have high interference colours and in the central part of vesicles very coarse radial clay aggregates can occur. The alteration of sample 06LM180 is similar to sample 06LM182. Brownish and greenish clays (celadonite) rim particles and zeolites nucleate on these clays. In zones where a fine matrix occurs, heu-type zeolites are fine-grained and blocky, while in other zones, where heu-type zeolites seem to fill empty voids, they are larger in size and euhedral. These zones are too large to be voids, probably they were composed of a fine glassy matrix which was completely dissolved and replaced by alteration minerals. Late calcite crystals can be large in size, euhedral and fill the interstitial voids after zeolite crystallisation. Other finer calcite could be formed earlier in the matrix. Sample 06LM188 displays a large argillitisation of clasts. Clays are brownish yellow in colour. A very fine glassy matrix was present, which has been replaced by greenish to brownish clays and fine calcite and later by heu-type zeolites. In other zones, where the matrix was probably completely dissolved, or where no matrix was present, zeolites are larger in size and euhedral and nucleate from clay minerals at particle rims.
Tuffs
The fine-grained rocks of this part were composed mainly of silicic glass, as can be seen in the low augite content and the presence of quartz crystal clasts. The amount of authigenic quartz increases in these rocks. Samples 06LM175, 181, 184, 186, 190-194, 196 have a quartz content of 30-60%. They are very fine-grained and were composed mainly of fine glass shards. They are altered to fine crystalline quartz, generally low amounts of brownish clay minerals and contain relatively high amounts of calcite and heu-type zeolites.
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The uppermost part of the Cayo
Formation
Lapilli tuffs In sample 06LM194, relatively fine pumice is replaced mainly by iron brown clays, which also rim particles. Heu-type zeolites occur as euhedral crystals in interstitial voids and as anhedral crystals in pumice and nucleate on clays. A high amount of schlacke clasts occurs, and these are mainly argillitized, while their zeolite content is low. Opal-CT probably nucleated before zeolites and mordenite possibly occurs. Sample 06LM198 is composed mainly of schlacke clasts, which are altered to orange brown to dark brown clays. Subhedral heu-type zeolites nucleate on these clays. Many particles contain mainly clays as alteration minerals. Analcime forms after heu-type zeolites, fills vesicles and replaces all plagioclase. Calcite forms as the last phase and occurs mainly in layer parallel cracks, which form around lithics and cross-cut zeolites. Samples 06LM201 and 06LM072 are similar as the underlying samples. They contain a high amount of augite crystal clasts and are highly argillitized. Sample 06LM067 is relatively fine and is altered to a light brown clay, which rims clasts and fills vesicles. Celadonite is common in this sample, occurring in pumice, where it fills vesicles and replaces glass. Some pumice particles are replaced by iron brown clays in one part, while celadonite replaces the other part. Heu-type zeolites form after clays and replace glass in pumice and occur in interstitial voids. They can be small and blocky to large and euhedral in form. Feldspars are all fresh. Calcite occurs as a late phase, mainly in layer parallel cracks. Probably some opal-CT was formed before heu-type zeolite formation. Sample 06LM070 was pervasively altered to iron brown clays, which are darker in colour in the clasts compared to the matrix. Clays in clasts are fine-grained and have low interference colours. Clays between the clasts are coarser and have higher interference colours. In some clasts, greenish clays, probably celadonite, occur. Heu-type zeolites
occur mainly between the particles, where they form large euhedral crystals which nucleate on particle rims. They also fill vesicles in crystalline volcanic particles. In other areas, heu-type zeolites are more blocky, more randomly oriented and they are not nucleating from particle rims only. It seems that they replace a fine matrix at these locations. After zeolite formation, euhedral calcite and coarse clays with high interference colours fill the remaining empty spaces. Quartz is absent (<1%). Sample 06LM071 contains much clays (50%), calcite (14%) and has a low amount of quartz (<2%). Sample 06LM061 contains brownish clays, rimming particles and vesicles, while greenish clays are limited to certain particles. Opal-CT clearly crystallised before heu-type zeolites, but is partly replaced by heu-type zeolites or quartz (10%). Heu-type zeolites are the main alteration minerals, replacing all glass in pumice and can be very small and anhedral to large and euhedral in form. Calcite occurs as a late phase in irregular veins.
Tuffs
The fine-grained tuffs 06LM199, 202, 63-64 have high quartz contents (30-60%). Sample 06LM068 is altered to brownish clays, greenish clays (celadonite) and heu-type zeolites. Opal-CT nucleates before zeolites. Calcite is formed before or during the formation of zeolites, as can be seen by heulandite veins cross-cutting calcite veins. It is not clear if celadonite nucleates before or after zeolite formation. Possibly some mordenite occurs. Sample 06LM060 is replaced by iron brown clays, calcite, heu-type zeolites and possibly analcime. Calcite occurs in cracks along layering.
Section 1 of the upper unit
Sample 06LM058 is a fine-grained tuff underlaying a coarse lapilli tuff sequence. The sample contains very fine-grained alteration minerals (<10 µm), mainly quartz (43%), minor irregularly shaped heu-type zeolites and some brownish clay minerals and opal–CT. Some angular glass shards are replaced by heu-type zeolites, but the majority of the more rounded clasts are altered to iron brown clays
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105
and quartz. Quartz occurs mainly between the particles, filling the interstitial pores.
Sample 06LM057 from the basal part of the coarse lapilli tuff sequence, is pervasively altered to mainly brownish clays and minor heu-type zeolites. Greenish celadonite fills vesicles and replaces glass. Brown clays replace the main part of the glass. Opal–CT nucleates on brownish clays, forming spherical pyramidal crystals. Heu-type zeolites nucleate on opal–CT crystals, brownish clays or celadonite. They seem to replace opal–CT partially, and they take over the spherical shape of their nuclei. Heu-type zeolites are generally euhedral and are especially large in voids between particles. Probably they grow in spaces where pumice is dissolved. The quartz content is very low in the sample. Some late cracks cross-cut all pyrogenetic and authigenic phases and are rimmed by Fe-oxides. Sample 06LM054 is a fine tuff occurring higher in the same sequence, composed mainly of glass shards. The alteration minerals and their relative amounts are similar as in the underlying sample, but they are much finer grained. Yellowish brown clay minerals fill vesicles and replace glass partially. Heu-type zeolites replace the remaining glass. The quartz content is very low. Sample 06LM053 is a fine lapilli tuff occurring higher in the sequence, composed of pumice clasts and some effusive volcanic clasts. It is well compacted. Alteration is similar as in the underlying samples, with clays filling vesicles and replacing glass partially. Heu-type zeolites fill the remaining glass. Sample 06LM051 is a very fine claystone formed by pelagic fall-out, containing a high amount of quartz (74%) and minor brownish clays. Zeolites are rare and occur in voids which are mainly formed by dissolved microorganisms. Sample 06LM049 is a fine tuff containing a high amount of argillitized particles. The sample is probably reworked, because of the high amount of rounded particles. These particles are entirely replaced by brownish clays. Pumice and glass particles are rimmed by yellow clays, which also fill vesicles, while heu-type zeolites replace glass. Sample 06LM047 contains a high amount of quartz and calcite (21%). Sample 06LM044 is a tuff composed of small clasts, which are mainly
replaced by quartz. Other particles are replaced by brownish clays. Sample 06LM043 from the base of an overlying lapilli tuff layer, contains a low amount of quartz. It has a similar alteration as sample 06LM057. Glass is mainly palagonitized, smectite is filling vesicles, opal–CT is formed before large euhedral heu-type zeolites which replace opal–CT and which are filling voids of dissolved glass. Celadonite crystallises before brownish clays, but greenish chloritic clays can occur central in vesicles and are formed after smectite.
Section 2 of the upper unit
Sample 06LM036 was taken from a tuff layer underlaying a coarse lapilli tuff sequence. It is composed mainly of glass shards. Because alteration minerals are very fine-grained, it is difficult to distinguish between them. Glass shards are replaced mainly by heu-type zeolites, while fine quartz occurs between them. Sample 06LM035, from the base of a lapilli tuff sequence, is altered to a high amount of iron brown clays and reddish iron oxides. Clays rim particles, fill vesicles and replace part of the glass or all the glass of pumice clasts. Mordenite and opal–CT crystallise before heu-type zeolites. Heu–type zeolites replacing pumice are highly irregular and interlocking and replace opal–CT and mordenite. Mordenite forms very thin and long crystals in very loose aggregates, very different from the aggregates occurring in the lower unit of the Cayo Formation. Some particles contain very few vesicles and are replaced entirely by heu-type zeolites, but probably at these locations heu-type zeolites replace mordenite and opal–CT. In voids and vesicles, heu-type zeolites are more euhedral. Some particles were probably dissolved completely, resulting in the formation of euhedral and large heu-type zeolites crystallising in these empty voids. The quartz content is low in the sample (10%). Sample 06LM034 occurs higher in the same lapilli tuff sequence. It is altered to brownish clays and irregularly shaped heu-type zeolites. In voids, heu-type zeolites are larger and more euhedral. Radial opal–CT crystallises before
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106
heu-type zeolites. No celadonite occurs, the quartz content is low (6%) and empty voids and cracks occur, which are not filled by late calcite as in the sequences occurring below. It is not always clear if zeolites fill vesicles or replace glass. Probably the glass was initially completely palagonitized, and heu-type zeolites fill the remaining voids. Samples 06LM032–033 are from a tuff bed occurring above the coarse lapilli tuff sequence. They are very fine-grained pelagic fallouts. Alteration is very fine-grained and composed of greenish to brownish clays, opal–CT and mainly quartz (68%). Sample 06LM031 is from a new coarse lapilli tuff sequence. It is altered to dark brown to yellow clays, which rim particles and fill vesicles and partly replace glass. Probably a high amount of mordenite formed in empty voids before heu-type zeolites, but all mordenite is replaced by heu-type zeolites. Heu-type zeolites preserve the radial shape of these mordenite aggregates. Some heu-type zeolite crystals are blocky, while others are more euhedral in shape. It is difficult to be sure if it was mordenite that is replaced by heu-type zeolites in these beds, because no remaining mordenite is detected by XRD, except for a low amount in sample 06LM035. Opal–CT seems to form smaller aggregates with thicker crystals, which have pyramidal terminations. Sample 06LM026 occurs in an overlying tuff layer and contains opal–CT and a high amount of quartz (65%). Higher in the section, the zeolite percentages drop drastically and opal-CT (nearly 80% in sample 06LM022) and quartz become the dominant alteration minerals (100% quartz in sample 06LM017). Sample 06LM024 is the uppermost sample containing heu-type zeolites of the Cayo Formation. The Guayaquil Formation has a similar mineralogy. The fine-grained beds are composed almost completely of quartz and minor opal-CT.
Rio Guaraguao
GPS point Sample Name X Y Height
06-001 593168 9768720 334
06-002 593951 9775242 130
06-003 06LM001 595877 9775746 65
06-004 06LM002 595877 9775746 65
06-004 06LM003 595148 9775894 75
06-005 06LM004 595214 9775846 67
06-006 06LM005 595446 9775490 65
06-006 06LM006 595446 9775490 65
06-006 06LM007 595446 9775490 65
06-006 06LM008 595446 9775490 65
06-006 06LM009 595446 9775490 65
06-006 06LM010 595446 9775490 65
06-007 06LM011 595639 9775618 62
06-008 06LM012 595661 9775652 68
06-008 06LM013: 595661 9775652 68
06-008 06LM014 595661 9775652 68
06-008 06LM015 595661 9775652 68
06-009 595808 9775606 55
06-010 06LM016 595678 9775322 72
06-011 595192 9775270 83
06-012 06LM017 595192 9775270 83
06-013 06LM018 595192 9775270 83
06-014 06LM019 595192 9775270 83
06-013 06LM020 593632 9768558 0
06-013 06LM021 593632 9768558 0
06-013 06LM022 593632 9768558 0
06-014 06LM023 593639 9768736 261
06-015 06LM024 593620 9768750 262
06-015 06LM025 593620 9768750 262
06-016 06LM026 593616 9768792 260
06-016 06LM027 593616 9768792 260
06-016 06LM028 593616 9768792 260
06-016 06LM029 593616 9768792 260
06-017 06LM30 593630 9768804 259
06-017 06LM031 593630 9768804 259
06-017 06LM032 593630 9768804 259
06-018 06LM033 593635 9768816 260
06-018 06LM034 593635 9768816 260
06-018 06LM035 593635 9768816 260
06-018 06LM036 593635 9768816 260
06-019 06LM064 593396 9769256 247
06-020 06LM040 593611 9768844 260
06-021 593614 9768856 0
06-022 593518 9768908 254
06-023 06LM041 593515 9768928 254
06-024 593507 9768940 254
06-025 593498 9768946 0
06-026 593481 9768990 243
06-027 593458 9769014 266
06-028 593447 9769032 257
06-029 593437 9769040 249
06-030 593413 9769068 245
06-031 593412 9769078 239
GPS point Sample Name X Y height
06-032 06LM060 593402 9769096 239
06-033 06LM061 593386 9769122 241
06-034 593371 9769142 249
06-035 593381 9769166 243
06-038 06LM042 593487 9768988 249
06-038 06LM043 593487 9768988 249
06-038 06LM044 593487 9768988 249
06-038 06LM045 593487 9768988 249
06-038 06LM046 593487 9768988 249
06-038 06LM047 593487 9768988 249
06-038 06LM048 593487 9768988 249
06-038 06LM049 593487 9768988 249
06-038 06LM050 593487 9768988 249
06-038 06LM051 593487 9768988 249
06-038 06LM052 593487 9768988 249
06-038 06LM053 593487 9768988 249
06-038 06LM054 593487 9768988 249
06-038 06LM055 593487 9768988 249
06-038 06LM056 593487 9768988 249
06-038 06LM057 593487 9768988 249
06-039 593470 9768996 249
06-040 593392 9769110 250
06-041 593378 9769124 250
06-042 06LM058 593377 9769184 247
06-042 06LM059 593377 9769184 247
06-043 593371 9769200 244
06-044 06LM062 593380 9769222 240
06-044 06LM063 593380 9769222 240
06-044 06LM064 593380 9769222 240
06-045 593340 9769286 233
06-046 593332 9769304 233
06-047 06LM065 593263 9769390 233
06-047 06LM070 593263 9769390 233
06-048 06LM071 593263 9769390 233
06-049 06LM066 593278 9769414 226
06-049 06LM067 593278 9769414 226
06-049 06LM068 593278 9769414 226
06-049 06LM069 593278 9769414 226
06-050 06LM072 593260 9769450 227
06-051 593235 9769472 224
06-052 593220 9769502 218
06-053 593211 9769538 222
06-054 06LM073 593235 9773908 111
06-055 06LM074 593214 9773918 115
06-055 06LM075 593214 9773918 115
06-055 06LM076 593214 9773918 115
06-055 06LM077 593214 9773918 115
06-056 06LM078 593170 9773940 115
06-057 06LM079 593054 9773834 114
06-057 06LM080 593054 9773834 114
06-058 593033 9773760 119
06-059 592998 9773660 112
06-060 06LM081 592986 9773630 120
06-060 06LM082 592986 9773630 120
06-060 06LM083 592986 9773630 120
GPS point Sample Name X Y height
06-061 06LM084 592986 9773630 120
06-061 06LM085 592986 9773630 120
06-062 06LM086 592973 9773588 127
06-063 06LM087 592976 9773572 126
06-064 06LM087bis 592995 9773488 125
06-065 06LM088 593058 9773388 131
06-066 593069 9773340 137
06-067 06LM089 593050 9773332 0
06-068 593032 9773326 126
06-069 06LM090 593003 9773336 126
06-069 06LM091 593003 9773336 126
06-070 06LM092 592972 9773342 128
06-071 06LM093 592887 9773342 129
06-071 06LM094 592887 9773342 129
06-075 595665 9775268 62
06-076 06LM095 595628 9775258 66
06-077 595600 9775260 71
06-078 06LM096 595502 9775294 65
06-078 06LM097 595502 9775294 65
06-078 06LM098 595502 9775294 65
06-079 595491 9775302 72
06-080 06LM098 595459 9775318 80
06-081 595396 9775410 74
06-082 595294 9775454 67
06-083 06LM099 595245 9775434 72
06-084 595236 9775406 72
06-085 06LM100 595212 9775394 70
06-085 06LM101 595212 9775394 70
06-086 06LM102 595173 9775240 65
06-087 595129 9775202 69
06-088 595081 9775142 72
06-090 06LM103 595035 9775012 69
06-092 594977 9774904 0
06-093 594972 9774802 56
06-094 06LM104 594975 9774776 54
06-095 06LM105 595024 9774654 78
06-095 06LM106 595024 9774654 78
06-096 595026 9774598 79
06-097 06LM107 594881 9774666 80
06-098 594815 9774680 76
06-099 594774 9774764 143
06-100 594661 9774670 134
06-101 594565 9774530 78
06-102 06LM108 594410 9774458 85
06-103 06LM109 594456 9774410 80
06-104 594515 9774370 81
06-105 06LM110 594552 9774356 91
06-106 06LM111 594577 9774282 101
06-107 594485 9774194 85
06-108 594450 9774240 108
06-109 06LM112 594360 9774240 91
06-110 06LM113 594305 9774162 93
06-111 06LM114 594213 9774130 82
06-112 594161 9774048 91
06-113 06LM115 594151 9773992 94
GPS point Sample Name X Y height
06-114 06LM116 594142 9773936 106
06-115 06LM118 594130 9773896 94
06-116 06LM117 594133 9773910 104
06-117 06LM119 594113 9773880 105
06-118 06LM120 594068 9773838 106
06-118 06LM121 594068 9773838 106
06-119 06LM122 594050 9773840 113
06-120 06LM123 594002 9773952 112
06-121 594022 9773996 117
06-122 593742 9774196 110
06-123 06LM178 593329 9774204 116
06-123 06LM179 593329 9774204 116
06-124 593279 9774136 120
06-125 06LM177 593281 9774040 118
06-126 06LM176 593322 9773990 118
06-127 06LM124 593293 9773896 120
06-128 06LM125 592805 9773334 128
06-128 06LM126 592805 9773334 128
06-128 06LM127 592805 9773334 128
06-128 06LM128 592805 9773334 128
06-129 06LM129 592786 9773316 132
06-129 06LM130 592786 9773316 132
06-129 06LM131 592786 9773316 132
06-129 06LM132 592786 9773316 132
06-129 06LM133 592786 9773316 132
06-129 06LM134 592786 9773316 132
06-129 06LM135 592786 9773316 132
06-130 06LM136 592739 9773318 126
06-130 06LM137 592739 9773318 126
06-131 06LM138 592715 9773274 129
06-131 06LM139 592715 9773274 129
06-133 06LM143 592603 9773366 127
06-133 06LM144 592603 9773366 127
06-134 06LM145 592461 9773240
06-134 06LM146 592461 9773240
06-134 06LM147 592461 9773240
06-135 06LM148 592454 9773228 133
06-136 06LM149 592286 9773214 135
06-137 592492 9773278 0
06-138 592750 9773006 131
06-139 592784 9772950 132
06-140 592785 9772892 132
06-141 592842 9772774 139
06-142 06LM150 592867 9772664 140
06-143 06LM151 592840 9772628 140
06-143 06LM152 592840 9772628 140
06-144 06LM153 592849 9772512 133
06-144 06LM154 592849 9772512 133
06-145 06LM155 592904 9772418 140
06-145 06LM156 592904 9772418 140
06-145 06LM157 592904 9772418 140
06-146 06LM158 592904 9772408 142
06-146 06LM159 592904 9772408 142
06-148 592915 9772372 142
06-149 592918 9772348 150
GPS point Sample Name X Y height
06-150 592885 9772322 146
06-151 06LM160 592751 9772344 147
06-152 592750 9772188 148
06-153 592719 9772116 157
06-154 592713 9772080 155
06-155 592777 9772014 156
06-156 592781 9771978 161
06-157 06LM161 592786 9771950 149
06-158 06LM162 592786 9771936 157
06-159 592780 9771906 155
06-160 06LM163 592683 9771702 157
06-161 592661 9771672 156
06-162 06LM164 592701 9771648 159
06-163 592916 9771654
06-164 06LM165 592943 9771608 166
06-165 592939 9771508 170
06-166 06LM166 592789 9771276 163
06-167 592712 9771252 168
06-168 592654 9771156 171
06-169 592661 9771082 169
06-170 06LM167 592652 9771044 172
06-171 06LM168 592634 9771012 175
06-172 592598 9770960 172
06-173 06LM169 592551 9770984 171
06-173 06LM170 592551 9770984 171
06-174 592532 9770800 177
06-175 592537 9770750 173
06-176 592577 9770674 170
06-177 06LM171 592597 9770574 179
06-177 06LM172 592597 9770574 179
06-177 06LM173 592597 9770574 179
06-178 06LM174 592566 9770568 190
06-179 592516 9770548 192
06-180 592453 9770550 188
06-181 592405 9770564 188
06-182 06LM175 592364 9770554 207
06-183 593214 9769550 230
06-184 592301 9770578 205
06-185 592288 9770584 205
06-186 06LM180 592268 9770472 174
06-186 06LM181 592268 9770472 174
06-186 06LM182 592268 9770472 174
06-187 06LM183 592325 9770418 190
06-188 06LM184 592567 9770342 188
06-188 06LM185 592567 9770342 188
06-188 06LM186 592567 9770342 188
06-189 592558 9770336 181
06-190 06LM187 592545 9770300 187
06-190 06LM188 592545 9770300 187
06-191 06LM189 592485 9770218 206
06-192 592530 9770182 200
06-193 592596 9770148 198
06-194 06LM190 592598 9770084 197
06-195 06LM191 592617 9769996 189
06-195 06LM192 592617 9769996 189
GPS point Sample Name X Y height
06-196 06LM193 592684 9769950 197
06-197 06LM194 592708 9769906 196
06-197 06LM195 592708 9769906 196
06-198 06LM196 592700 9769874 224
06-198 06LM197 592700 9769874 224
06-199 592755 9769786 213
06-200 592797 9769734 213
06-201 592814 9769726 209
06-202 592856 9769702 211
06-203 06LM198 592878 9769686 224
06-205 06LM199 592964 9769642 214
06-205 06LM200 592964 9769642 214
GPS point Sample Name X Y height
09-003 593300 9773804 148
09-004 589317 9794519 46
09-005 582726 9785605 72
09-006 595000 9774884 98
09-007 09LM001 594981 9774979 69
09-008 594979 9774801 58
09-009 09LM002 594980 9774830 70
09-009 09LM003 594980 9774830 70
09-009 09LM004 594980 9774830 70
09-010 09LM005 594972 9774822 71
09-010 09LM006 594972 9774822 71
09-011 09LM007 594981 9774814 97
09-012 09LM008 594979 9774782 78
09-012 09LM009 594979 9774782 78
09-012 09LM010 594979 9774782 78
09-012 09LM011 594979 9774782 78
09-013 594990 9774727 72
09-014 595022 9774667 84
09-015 09LM012 595038 9774650 87
09-016 09LM013 594977 9774615 97
09-017 09LM014 594939 9774634 92
09-017 09LM015 594939 9774634 92
09-018 09LM016 594891 9774672 101
09-019 09LM017 594856 9774682 81
09-020 09LM018 594846 9774682 74
09-021 09LM019 594836 9774680 69
09-022 594819 9774695 85
09-023 594807 9774719 98
09-024 09LM020 594689 9774703 149
09-025 09LM021 594657 9774670 132
09-026 09LM022 594650 9774661 106
09-027 09LM023 594643 9774651 103
09-028 594609 9774598 114
09-029 09LM024 594549 9774535 109
09-030 09LM025 594540 9774530 104
09-031 09LM026 594521 9774521 97
09-032 09LM027 594524 9774515 85
09-033 09LM028 594423 9774492 101
09-034 594413 9774474 88
09-035 09LM029 594422 9774450 89
09-036 09LM030 594398 9774451 98
09-037 09LM031 594409 9774447 100
GPS point Sample Name X Y height
09-038 594451 9774419 101
09-039 594476 9774393 112
09-040 09LM032 594564 9774289 107
09-041 594544 9774197 104
09-042 594501 9774190 103
09-043 09LM033 594441 9774232 102
09-044 594441 9774232 102
09-045 594402 9774253 86
09-046 594393 9774255 84
09-047 09LM034 594288 9774174 90
09-048 594243 9774143 91
09-049 594185 9774113 86
09-050 09LM035 594149 9774053 97
09-051 594166 9774017 97
09-052 09LM036 594153 9774015 97
09-053 09LM037 594151 9773992 103
09-054 09LM038 594139 9773970 104
09-055 09LM039 594138 9773936 104
09-056 09LM040 594140 9773931 100
09-057 09LM041 594142 9773919 94
09-057 09LM042 594142 9773919 94
09-058 594135 9773907 110
09-059 594127 9773893 113
09-060 09LM043 594054 9773835 115
09-061 594006 9773905 106
09-062 594007 9773932 117
09-063 592987 9773627 118
09-064 09LM044 592977 9773600 115
09-065 09LM045 592969 9773581 121
09-066 592976 9773538 119
09-067 09LM046 592967 9773542 118
09-067 09LM047 592967 9773542 118
09-067 09LM048 592967 9773542 118
09-067 09LM049 592967 9773542 118
09-068 09LM050 592968 9773526 124
09-069 592997 9773493 121
09-070 593013 9773456 123
09-071 09LM051 593071 9773374 127
09-071 09LM052 593071 9773374 127
09-071 09LM053 593071 9773374 127
09-072 593070 9773338 133
09-073 09LM054 593068 9773327 117
09-074 09LM055 593046 9773331 115
09-074 09LM056 593046 9773331 115
09-074 09LM057 593046 9773331 115
09-074 09LM058c 593046 9773331 115
09-074 09LM058f 593046 9773331 115
09-075 09LM059 593033 9773331 118
09-075 09LM060 593033 9773331 118
09-076 09LM061 593024 9773328 121
09-077 09LM062 593014 9773332 121
09-078 09LM063 593003 9773332 121
09-078 09LM064 593003 9773332 121
09-079 09LM065 592990 9773336 120
09-079 09LM066 592990 9773336 120
GPS point Sample Name X Y height
09-079 09LM067 592990 9773336 120
09-080 09LM068 592959 9773344 122
09-080 09LM069 592959 9773344 122
09-081 592931 9773345 124
09-082 09LM072 597401 9775988 87
09-083 09LM073 597318 9775916 79
09-083 09LM074 597318 9775916 79
09-084 09LM075 597273 9775903 95
09-084 09LM076 597273 9775903 95
09-085 09LM077 597221 9775954 66
09-085 597221 9775954 66
09-086 597109 9775969 86
09-087 09LM070 597052 9775914 78
09-087 09LM071 597052 9775914 78
09-088 596837 9776002 82
09-089 596760 9776004 70
09-090 596751 9776081 67
09-091 596584 9776094 81
09-092 596536 9776062 76
09-093 596497 9776077 72
09-094 09LM078 596447 9776047 61
09-095 09LM079 596373 9775918 74
09-095 09LM080 596373 9775918 74
09-096 596299 9775938 89
09-097 596281 9776008 75
09-098 596174 9776041 72
09-099 595971 9776057 67
09-100 09LM081 595892 9775961 65
09-100 09LM082 595892 9775961 65
09-100 09LM083 595892 9775961 65
09-101 595870 9775668 83
09-102 595627 9775263 72
09-103 595550 9775268 72
09-104 09LM084 595541 9775271 67
09-105 09LM085 595487 9775301 71
09-106 595467 9775306 65
09-107 595368 9775417 63
09-108 595260 9775431 66
09-109 09LM086 595225 9775327 72
09-110 09LM087 595169 9775249 62
09-111 09LM088 595049 9775064 75
09-111 09LM089coarse 595049 9775064 75
Guayaquil area
GPS point Sample Name X Y Height
06-223 06LM203 619348 9773486 14
06-224 06LM204 619951 9773874 118
06-225 06LM205 619997 9774002 120
06-226 06LM206 620073 9773870 113
06-226 06LM207 620073 9773870 113
06-227 06LM208 620081 9773856 105
06-227 06LM209 620081 9773856 105
06-228 06LM210 620310 9773618 59
06-228 06LM211 620310 9773618 59
06-229 06LM212 622032 9773802 20
06-231 06LM213 625372 9772654 21
06-231 06LM214 625372 9772654 21
06-231 06LM215 625372 9772654 21
06-231 06LM216 625372 9772654 21
06-233 626868 9776810 22
06-236 06LM217 627084 9776342 29
06-236 06LM218 627084 9776342 29
06-236 06LM219 627084 9776342 29
06-241 06LM220 621655 9771476 26
06-241 06LM221 621655 9771476 26
06-242 06LM222 620847 9770948 47
06-242 06LM223 620847 9770948 47
06-242 06LM224 620847 9770948 47
06-243 06LM225 620871 9770894 40
06-243 06LM226 620871 9770894 40
06-244 06LM227 619268 9770474 19
06-244 06LM228 619268 9770474 19
06-246 06LM229 620360 9768700 14
06-246 06LM230 620360 9768700 14
06-247 06LM231 620357 9768688 15
06-247 06LM232 620357 9768688 15
06-248 06LM233 620366 9768680 15
06-249 06LM234 620355 9768650 13
06-249 06LM235 620355 9768650 13
06-249 06LM236 620355 9768650 13
06-250 06LM237 620351 9768622 15
06-251 06LM238 620335 9768610 16
06-252 06LM239 620319 9768584 24
06-265 06LM243 619044 9770520 29
06-266 06LM242 619120 9770514 20
06-267 06LM241bis 619155 9770514 31
06-268 622770 9771422 16
06-269 06LM244 622864 9771136 17
06-269 06LM245 622864 9771136 17
06-270 06LM246 622837 9771190 11
06-271 06LM247 622821 9771236 17
06-272 06LM248 622805 9771298 12
06-272 06LM249 622805 9771298 12
06-273 622795 9771324 15
06-274 06LM250 622762 9771384 15
06-276 06LM251 622997 9770586 12
GPS point Sample Name X Y Hight
06-277 06LM252 622992 9770694 14
06-285 06LM253 621531 9770304 50
06-286 06LM254 621420 9770288 34
06-287 06LM255 621435 9770002 16
06-287 06LM256 621435 9770002 16
06-287 06LM257 621435 9770002 16
06-288 06LM258 621465 9770012 17
06-290 06LM259 621457 9769968 24
06-291 06LM260 621473 9769914 27
06-291 06LM261 621473 9769914 27
06-292 06LM262 621481 9770014 20
06-294 619974 9771868 23
06-296 06LM263 620070 9772240 17
06-297 06LM264 620093 9772126 18
06-298 06LM265 620200 9768700 17
06-298 06LM266 620200 9768700 17
06-300 06LM267 619874 9767614 24
06-300 06LM268 619874 9767614 24
06-300 06LM269 619874 9767614 24
06-300 06LM270 619874 9767614 24
06-303 06LM271 617007 9774144 46
06-304 06LM272 617255 9773884 25
06-305 06LM273 617316 9774382 39
06-305 06LM274 617316 9774382 39
06-305 06LM275 617316 9774382 39
06-306 06LM276 615109 9772376 52
06-310 614988 9770394 80
06-311 06LM277 614945 9770428 90
06-311 06LM278 614945 9770428 90
06-311 06LM279 614945 9770428 90
06-312 06LM280 614944 9770472 99
06-312 06LM281 614944 9770472 99
06-313 06LM282 614959 9770176 60
06-315 06LM283 614888 9769980 55
06-320 06LM284 614489 9766244 157
06-321 06LM285 614309 9766188 115
06-322 613859 9769116 81
06-323 613851 9769328 77
06-324 613815 9769124 76
06-325 613855 9769012 79
06-326 613702 9768878 76
06-327 613824 9769184 75
06-328 613879 9769034 75
06-329 613805 9760914 74
06-330 613675 9768804 73
06-331 613674 9768676 74
06-332 613674 9768590 66
06-334 613654 9768350 75
06-335 613668 9768212 74
06-336 613719 9768116 76
06-338 06LM288 613733 9768052 78
GPS point Sample Name X Y Hight
06-339 06LM286 613682 9768010 75
06-340 06LM287 613639 9767986 75
06-341 613568 9767956 76
06-343 06LM288bis 613519 9767948 81
06-344 06LM289 613499 9767940 79
06-345 06LM290 613460 9767926 72
06-345 06LM291 613460 9767926 72
06-346 06LM287bis 613533 9767966 70
06-350 613583 9767010 68
06-351 613598 9766988 70
06-352 613612 9766960 70
06-353 06LM292 613630 9766914 66
06-353 06LM293 613630 9766914 66
06-353 06LM294 613630 9766914 66
06-353 06LM295 613630 9766914 66
06-354 613670 9766836 64
06-355 06LM296 613682 9766810 65
06-356 613697 9766790 69
06-357 06LM297 613713 9766754 72
06-357 06LM298 613713 9766754 72
06-358 06LM299 613733 9766714 69
06-359 613749 9766684 75
06-360 06LM300 613755 976678 78
06-361 613773 976636 76
06-362 614224 9766104 65
06-365 614105 9770286 36
06-366 615205 9771650 78
06-369 06LM301 615081 9771480 75
06-370 614966 9771328 81
06-371 614961 9771018 82
06-372 615050 9770796 81
06-373 615015 9770558 79
06-374 06LM302 614886 9770454 80
06-375 614947 9770502 0
06-376 614604 9770394 78
06-378 06LM303 613399 9765504 48
06-379 613429 9765028 71
06-380 613282 9764716 71
06-381 612977 9764436 73
06-382 612740 9764334 78
06-383 612537 9764422 75
06-384 612209 9764402 73
06-385 612015 9764452 72
06-386 613489 9765342 73
06-387 613484 9765972 59
06-388 06LM304 616513 9768572 41
06-389 06LM305 616720 9768526 51
06-389 06LM306 616720 9768526 51
06-390 617232 9768398 46
06-391 617232 9768362 44
06-392 617223 9768326 45
GPS point Sample Name X Y Hight
06-393 617242 9768296 43
06-394 617242 9768222 41
06-395 06LM307 617248 9768184 44
06-396 617249 9768166 48
06-397 06LM308 617264 9766306 11
06-397 06LM309 617264 9766306 11
06-397 06LM310 617264 9766306 11
06-398 06LM311 617341 9766236 37
06-399 06LM312 617078 9765766 36
06-400 617201 9764694 45
06-401 06LM313 617217 9764660 45
06-401 06LM314 617217 9764660 45
06-401 06LM315 617217 9764660 45
06-402 06LM316 617222 9764630 50
06-403 06LM317 617236 9764604 46
06-404 06LM318 617241 9764580 48
06-406 617466 9763988 45
06-407 06LM319 617467 9763974 45
06-408 617470 9763962 45
06-409 06LM320 617476 9763952 49
06-410 617475 9763943 48
06-411 617478 9763926 50
06-412 617479 9763908 50
06-413 617276 9764572 45
06-414 06LM321 617286 9764546 49
06-415 617295 9764522 50
06-416 06LM322 617304 9764500 0
06-417 617304 9764500 0
06-418 06LM323 617304 9764500 0
06-418 06LM324 617304 9764500 0
06-419 06LM325 617304 9764500 0
06-420 617304 9764500 0
06-421 617332 9764408 49
06-422 617453 9763846 56
06-423 617452 9763824 54
06-424 617462 9763774 59
06-425 617466 9763760 58
06-426 617466 9763750 56
06-427 617463 9763754 55
06-428 617469 9763706 56
06-429 617482 9763606 0
06-430 06LM327 617301 9764507 53
Rio de la Derecha
GPS point Sample Name X Y Height
09-124 09LM090 578163 9781440 122
09-125 09LM091 578161 9781418 141
09-126 09LM092 578162 9781406 137
09-126 09LM093 578162 9781406 137
09-127 09LM094 578164 9781404 139
09-128 09LM095 578157 9781395 136
09-129 09LM096 578155 9781392 138
09-130 09LM097 578151 9781384 138
09-131 09LM098 578150 9781381 141
09-131 09LM099 578150 9781381 141
Rio Zamoreño
GPS point Sample Name X Y Height
140 09LM104 574413 9783733 70
140 09LM105 574413 9783733 70
142 09LM100 574495 9784020 69
151 09LM101 574399 9783892 176
151 09LM102 574399 9783892 176
151 09LM103 574399 9783892 176
152 09LM106 574397 9783693 194
153 09LM107 574394 9783683 195
154 09LM108 574377 9783661 200
155 09LM109 574378 9783652 189
156 09LM110 574374 9783651 199
156 09LM111 574374 9783651 199
157 09LM112 574361 9783648 203
159 09LM113 574349 9783631 225
160 09LM114 574317 9783623 212
161 09LM115 574300 9783615 202
162 09LM116 574295 9783616 201
166 09LM117 574219 9783502 187
167 09LM118 574256 9783363 201
168 09LM119 574271 9783316 192
Manabí area
GPS point Sample Name X Y Height
583 06LM428bis 533074 9831388 97 Agua Blanca
585 06LM430 534871 9832864 133 Agua Blanca
586 06LM430bis 536211 9833596 160 Agua Blanca
585 06LM431 534871 9832864 133 Agua Blanca
587 06LM431bis 535421 9833146 120 Agua Blanca
578 06LM427 521906 9828938 22 Puerto Lopez
578 06LM428 521906 9828938 22 Puerto Lopez
542 06LM406 527996 9824070 188 Rio Mocora
543 06LM407 527736 9824330 176 Rio Mocora
558 06LM411 531814 9822416 408 Rio Mocora
569 06LM421 530250 9822864 227 Rio Mocora
572 06LM424 529553 9823220 197 Rio Mocora
572 06LM425 529553 9823220 197 Rio Mocora
450 06LM337 550049 9816632 385 Rio Ayampe
454 06LM341 545456 9815410 277 Rio Ayampe
453 06LM343 545792 9815256 279 Rio Ayampe
461 06LM345 546471 9815330 261 Rio Ayampe
472 06LM347 547941 9815580 291 Rio Ayampe
477 06LM350 548151 9815906 309 Rio Ayampe
480 06LM351 549050 9816440 314 Rio Ayampe
504 06LM378 540789 9817082 171 Rio Ayampe
527 06LM396 527719 9815264 49 Rio Ayampe
527 06LM397 527719 9815264 49 Rio Ayampe
534 06LM402 525737 9814742 28 Rio Ayampe
536 06LM404 525429 9814938 35 Rio Ayampe