International Journal of Coal Geology 225 (2020) 103501

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International Journal of Coal Geology

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Study of a Silurian sequence of Dornes region (Central Iberian Zone, T

Portugal): The contribution of organic petrology and palynofacies
⁎
Paula Alexandra Gonçalvesa, , Sérgio Pinheirob, João Graciano Mendonça Filhoc,
Joalice Oliveira Mendonçac, Deolinda Floresa
a
Instituto de Ciências da Terra - Pólo da Faculdade de Ciências da Universidade do Porto and Departamento de Geociências, Ambiente e Ordenamento do Território,
Faculdade de Ciências, Universidade do Porto, Rua Campo Alegre 687, 4169-007 Porto, Portugal
b
Faculdade de Ciências e Tecnologia da Universidade de Coimbra, Rua Sílvio Lima, Universidade de Coimbra - Pólo II, 3030-790 Coimbra, Portugal
c
Laboratório de Palinofácies & Fácies Orgânica (LAFO), Departamento de Geologia, Instituto de Geociências, Universidade Federal do Rio de Janeiro, Av. Athos da
Silveira, 274, prédio do CCMN, sala J1020, Campus Ilha do Fundão, Cidade Universitária, CEP 21.949-900 Rio de Janeiro, RJ, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: A Wenlock (Silurian) sedimentary continuous sequence was sampled in the Dornes region (Central Iberian Zone,
Foz da Sertã Formation Portugal) to characterize the organic matter type using different microscopic analyses (organic petrology and
Graptolite palynofacies). Total organic carbon (TOC) was also determined. Samples are part of Foz da Sertã Formation and
Solid bitumen correspond to mudstone, punctually with sandstone, rich in organic matter (mean TOC value of 5.1%).
Graptolite reflectance
Whole rock samples showed a dominance of non-granular graptolites (lath- and blocky-shape) and solid
Solid bitumen reflectance
bitumen. Lath-shape graptolites display the characteristic segmented structure. In the blocky-shape graptolites,
the fusellar layers of the graptolite wall are well marked and are an important distinctive feature. Foz da Sertã
graptolites are optically anisotropic as well as the solid bitumen. Non-granular graptolite's maximum reflectance
varies from 1.43 to 3.94% and solid bitumen maximum reflectance oscillates between 1.09 and 2.22%. Vitrinite
reflectance equivalent was calculated using Bertrand and Malo's equation (values between 1.97 and 3.72%)
denoting a post-mature stage for the organic matter. No relation was established with confidence between
graptolite maximum reflectance and solid bitumen maximum reflectance.
The palynofacies study confirmed not only the presence of graptolite and solid bitumen but also amorphous
material derived from graptolite. Under transmitted white light, graptolite features were not noticed. To improve
the palynofacies characterization, reflected white light was used on slides, thus exposing distinctive graptolite
features. The different lights and preparation types used allowed a better characterization of the organic matter
present in Foz da Sertã Formation samples, mainly the graptolites. The use of reflected white light, in the
palynofacies study, proved to be extremely important in the description of the graptolite features.

1. Introduction
Graptolites (from Greek, grapto + lithos: writing on rock) occur as
fragments showing complex skeletal morphology or as elongated par-
ticles called tubaria (Maletz et al., 2017; previously called rhabdo-
some). Fossil graptolites correspond to marine colonial animals that
emerged in the Cambrian and persisted until the Carboniferous. Grap-
tolite fossils are common, especially in shales, having a worldwide
distribution, being important tools in biostratigraphy as well as in or-
ganic petrology studies (Goodarzi, 1984; Maletz, 2017a).
In Portugal, shales are common in the Silurian of the Central Iberian
Zone (CIZ) and contain abundant graptolite faunas (Piçarra, 2003). The
CIZ (Fig. 1A) is located in the central part of the Iberian Massif, between
the Asturian-Leonese zone (North) and the Ossa-Morena zone (South)
(Vilas and de San José, 1990). The CIZ integrates the internal orogenic
domain of the Iberian Variscan belt, which is dominated by granitoid
rocks that intruded a succession composed of metasedimentary and
metavolcanic sequences with ages between the Neoproterozoic and the
Carboniferous (Mateus and Noronha, 2010, and references therein).
The Lower Paleozoic record, in the Dornes area (Fig. 1), consists of a
sequence of alternating beds of resistant quartzite and quartz-sand-
stones and less resistant argillaceous formations (Cooper, 1980). The
most complete Silurian sequence in Portugal occurs this area (Piçarra,
2003), and is divided into four formations from the Llandovery to the
Pridoli, namely, Vale da Ursa, Foz da Sertã, Vale Serrão, and Mendeira
formations (from the bottom to the top; Gutierrez-Marco et al., 1990;

⁎
Corresponding author.
E-mail address: paula.goncalves@fc.up.pt (P.A. Gonçalves).

https://doi.org/10.1016/j.coal.2020.103501
Received 4 November 2019; Received in revised form 27 April 2020; Accepted 4 May 2020
Available online 06 May 2020
0166-5162/ © 2020 Elsevier B.V. All rights reserved.
P.A. Gonçalves, et al. International Journal of Coal Geology 225 (2020) 103501

Fig. 1. A - Location of the Central Iberian Zone in the regional context of the Iberian Peninsula; B -Simplified geology of the studied area and approximate location of
Foz da Sertã (FS) outcrop (adapted from the Geological Map of Portugal, scale 1:500000).

Oliveira et al., 1992). The Foz da Sertã Formation, the target of this organic petrology techniques to identify/characterize the dispersed
study, ranges from the topmost Llandovery to the Wenlock (or Lu- organic matter or its thermal evolution. Therefore, organic petrology
dlow?) and is composed by mudstones and siltstones, interbedded with and palynofacies methodologies will be used for the first time in
fine-grained sandstones (mainly restricted to the middle part) (Cooper, southern of the CIZ, applied to Foz da Sertã Formation (Dornes area) to
1980; Young, 1988). This formation has 100 to 200 m thick and yields study its organic content and its thermal maturation. Thus, the main
an abundant graptolite fauna with scarce orthoceratids, bivalves, and goals are as follows: i) characterize the organic matter present in Dornes
brachiopods (Piçarra, 2003). The graptolites assemblage documented samples; ii) present the distinctive graptolites features under trans-
for the Foz da Sertã Formation indicates ages between the Llandovery mitted and reflected white lights; iii) investigate the applicability of
and Wenlock, in which the Aeronian Demirastrites triangulatus Biozone, reflected white light in palynofacies studies; and iv) assess the thermal
Telychian Spirograptus turriculatus Biozone, Sheinwoodian Monograptus maturity of the studied sequence.
belophorus Biozone, and Homerian Gothograptus nassa Biozone are re-
cognized (Oliveira et al., 1992; Piçarra, 2003, 2007; Young, 1988).
2. Graptolites: A review
Organic petrology is a useful tool to characterize OM and allowed a
better understanding of the optical properties of graptolites (e.g.,
Graptolites were colonial marine living beings common in the Early
Goodarzi, 1984, 1985; Goodarzi and Norford, 1987). Furthermore, the
Paleozoic that, according to Zalasiewicz and Maletz (2017), are biolo-
determination of graptolite reflectance is of particular importance for
gical enigmas. Their phylogenetic relationships were for a long time
the evaluation of the thermal maturity of source rocks due to the ab-
unknown and were interpreted by Linnæus, in the 18th century, as
sence of vitrinite, as land plants do not exist in pre-Devonian succes-
inorganic marks on the rocks (Maletz, 2017b). Since Linnæus, several
sions. Graptolite studies can provide information on: 1) thermal ma-
authors (see Maletz, 2017b, and references therein) attempted to es-
turity and burial history (e.g., Bertrand, 1990; Bertrand and Héroux,
tablish the biological affinities of graptolites classifying them as ce-
1987; Buchardt and Lewan, 1990; Bustin et al., 1989; Cole, 1994;
phalopods, bryozoans or hydroids. Nowadays, graptolites are included
Goodarzi, 1984; Goodarzi and Norford, 1985, 1989; Landis and
in the Class Graptolithina, Phylum Hemichordate (Benton and Harper,
Castaño, 1995; Link et al., 1990; Obermajer et al., 1996; Petersen et al.,
2009; Maletz, 2017b), being the pterobranch Rhabdopleura the only
2013; Rantitsch, 1995; Riediger, 1993; Schoenherr et al., 2007;
representative of this Class today (Maletz, 2014). The graptolite colony
Xianming et al., 2000); 2) source rocks (e.g., Goodarzi et al., 1985;
originated from an initial specimen, the sicular zooid, being all zooids
Varol et al., 2006); and 3) correlations between the reflectance of or-
offspring of the colony (Crowther and Rickards, 1977; Mitchell et al.,
ganic particles, such as vitrinite, zooclast and solid bitumen (e.g.,
2013).
Bertrand, 1990; Bustin et al., 1989; Cole, 1994; Petersen et al., 2013;
The graptolite morphology has been described since the 1970s by
Rantitsch, 1995). Organic petrology techniques have not been widely
organic petrographers, mainly in reflected white light (e.g. Bertrand
used to study the organic matter of the CIZ. To the north of the CIZ,
and Héroux, 1987; Bustin et al., 1989; Goodarzi, 1984, 1985; Goodarzi
research was carried out applying these techniques to the study of coals
and Norford, 1985, 1987; Goodarzi et al., 1992; Kurylowicz et al., 1976;
and dispersed organic matter (Carboniferous and Permian ages), in the
Ma et al., 2016; Morga and Pawlyta, 2018; Riediger et al., 1989),
Buçaco Basin (Flores et al., 2010) and the Douro Coalfield Basin (e.g.
transmitted white light (Cole, 1994), and more recently by SEM (e.g.
Lemos de Sousa, 1983; Lemos de Sousa and Wagner, 1983; Marques
Luo et al., 2016; Ma et al., 2016; Maletz et al., 2016; Mierzejewski and
et al., 2009) to evaluate their thermal maturity. In the southern CIZ,
Kulicki, 2001). Morphologically, the tubarium comprises several tub-
which includes the Dornes area, there is no published data, using
ular structures called thecae, occupied by the zooids, which terminated

2
P.A. Gonçalves, et al.
in a thecal aperture. The various thecae that comprise the colony are
connected through internal openings. Growth lines are observed on the
thecal walls. Although uncertainties regarding the graptolite walls
composition, it is currently accepted to be constituted by an organic
substance, a collagen-like protein (e.g., Gupta et al., 2006; Towe and
Urbanek, 1972; Zalasiewicz and Maletz, 2017). Two different building
materials can be distinguished in the graptolite wall, the fuselli and the
cortex. The fuselli is the main material of the graptolite walls and
segregated mainly as full rings or half-rings to constitute the graptolite
tubes. The cortex corresponds to a secondary material spread on the
fusellar surface to stabilize and support the colony (Maletz et al., 2017).
When observed in reflected white light, graptolites can exhibit two
different types of texture, non-granular or granular. Goodarzi (1984)
stated that the non-granular surface is brittle, hard, presenting high
reflectance, strong anisotropy, and stronger bireflectance. On the other
hand, granular graptolite texture shows a fine granular to reticular
appearance and are also anisotropic. These surface textures seem to be
associated with the different parts of the tubarium, being the non-
granular linked with the external wall with fusellar layers of the
graptolite and the granular to the common canal (Goodarzi, 1984;
Goodarzi et al., 1992). Non-granular graptolite is usually found in
shales, while granular graptolite is more common in carbonates
(Goodarzi and Norford, 1985, 1987). According to the same authors, in
the same sample, graptolites show higher anisotropy values than other
organic particles, such as bitumen or chitinozoans.
3. Samples and experimental methods
3.1. Samples
A total of ten samples, of Silurian age, were collected from Foz da
Sertã (FS) Formation (Dornes, CIZ, Portugal; Fig. 1). The sampled site is
located approximately 4 km from the place where the Foz da Sertã
Formation type section was defined by Cooper (1980). The outcrop
sampled is located nearby Dornes village (Central Portugal) in the N238
road, near the Vale da Ursa Bridge. It corresponds to a continuous
section with approximately 100 m and comprises mudstones, some-
times interbedded with sandstones (Fig. 2).
3.2. Basic geochemical analysis
A LECO® analyzer SC-144DR (oxygen atmosphere at a temperature
of 1350 °C) was used to quantify TOC content. The carbonated fraction
of the sediment introduced into the analyzer was previously removed
with HCl. The insoluble residue (sample fraction that has not been
eliminated by the acid treatment) was also determined. These analyses
were performed in the Palynofacies and Organic Facies Laboratory
(LAFO) at the Federal University of Rio de Janeiro (Brazil).
3.3. Petrographic analyses
Standard procedures (ASTM D2797-11a, 2011) were followed to
prepare whole rock polished blocks as well as concentrated kerogen
blocks. Microscopic observations were made under reflected white
(RWL) and incident blue lights. Graptolite and solid bitumen re-
flectance were measured following the ASTM D7708-14 (2014) stan-
dard and Hackley et al. (2015), on a Leica DM4000 microscope using a
50× oil immersion objective. The microscope was calibrated with YAG
and strontian‑titanium standards (0.905 and 5.38%Rr, respectively).
The number of reflectance measurements on each sample depended on
the availability of organic particles in each sample. The vitrinite re-
flectance equivalent (%VReq) was calculated through the formulas
proposed by Bertrand and Malo (2012) for graptolites (%
VReq = 0.9376 x %Rgrap + 0.0278) and by Jacob (1989) for solid bi-
tumen (%VReq = 0.618 x %RSB + 0.40).
Palynofacies procedures (non-oxidative isolation of the organic
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International Journal of Coal Geology 225 (2020) 103501
matter) were followed in the preparation of the kerogen slides
(Mendonça Filho et al., 2011; Tyson, 1995). The palynofacies classifi-
cation proposed by Mendonça Filho and Gonçalves (2017), Mendonça
Filho et al. (2014) and Tyson (1995) were used. Observations were
conducted on a Zeiss microscope under transmitted (TWL) and reflected
white lights and blue incident light.
4. Results and discussion
4.1. Geochemical data
TOC values (Table 1) are usually higher than 2 wt%, with a mean
value of 5.09 wt%, indicating a very good to excellent organic content
(Peters and Cassa, 1994), except for two samples (FS5 and FS6) which
contain TOC values less than 1%. The insoluble residue (IR) values are
always high (mean value 96%) confirming the pelitic character of the
samples. Higher values of IR (98%) correspond to samples with low
TOC and TS contents.
4.2. Organic matter assemblage
A uniform organic matter assemblage was identified in Foz da Sertã
Formation with a predominance of well-preserved graptolites remains
(Figs. 3–7), solid bitumen and amorphous particles (Fig. 8). Rare “vi-
trinite-like” particles (in RWL) were observed and, although they do not
exhibit a particular feature, are probably graptolite fragments since
they present similar reflectance values. This type of assemblage is
comparable to other Paleozoic sediments such as in the Czech Republic
(Suchý et al., 2002).
The fractures in the walls of graptolites (Fig. 3) are related to tec-
tonic deformation, resulting in parallel faulting and intense chevron
folding that occurs in the CIZ associated with Variscan orogeny
(Cooper, 1980).
4.2.1. Graptolites
Graptolites are rare at the bottom of the sequence, increasing in size
and quantity to the FS4 sample, and dramatically decreasing in samples
FS5 and FS6. To the top, graptolites are usually in small amounts and
occasionally fragmented, sometimes not presenting distinctive features.
Graptolites exhibit a grey to white color under RWL, and fluorescence is
absent. Whole rock block observations allowed the recognition of non-
granular and granular graptolites with the predominance of non-gran-
ular. Non-granular fragments are common in shales (Goodarzi and
Norford, 1985) and, although their affinity with the granular fragments
is not well known, they are likely different parts of the graptolite wall
(Goodarzi et al., 1992).
The two shapes of graptolites (blocky- and lath-shape fragments)
proposed by Riediger et al. (1989) were also recognized in Foz da Sertã
samples (Figs. 4, 5). Goodarzi et al. (1992) and Link et al. (1990) stated
that these shapes can represent different parts or tissues of the tu-
barium. Lath-shape non-granular graptolites are more abundant,
mainly in the upper part of the studied sequence, and were easily dis-
tinguished due to their uniquely segmented structure (Fig. 4) as de-
scribed by Goodarzi (1984) and Goodarzi et al. (1992), and the occa-
sional remains of thecae.
Some fragments exhibit the common canal (filled by sediment), si-
milar to those observed by Goodarzi (1984), Link et al. (1990) and
Suchý et al. (2002), and the respective external walls.
Blocky-shape non-granular graptolite is mainly angular, with dif-
ferent sizes, and in most of the particles is possible to observe the fu-
sellar layers of the wall (Fig. 5). Some blocky-shape graptolites exhibit
small pores on the surface (Fig. 5a).
As can be seen in Fig. 6, the graptolite fragments (both lath- and
blocky-shape) are anisotropic. In the studied sequence, the anisotropy
increases with increasing in the graptolite reflectance. According to
Goodarzi and Norford (1985), graptolites developed anisotropy at a
P.A. Gonçalves, et al.
Fig. 2. Simplified stratigraphic log of Foz da Sertã Formation in Dornes region and sampling distribution.
maximum reflectance value lower than vitrinite. The same authors re-
ported that this alteration was due to changes in the molecular structure
of the organic particles.
Kerogen slides observation (in TWL) showed a dominance of par-
ticles with a dark brown to black color, and no fluorescence under in-
cident blue light. These particles showed different shapes, from equant,
lath to sharp and appear flattened without specific features on the
surface (Fig. 7a, c, e). Optically, they are very similar to phytoclast
(particles derived from higher plants) however, this type of organic
matter had not yet existed in Wenlock (Silurian). Given the age of the
samples and the features observed in the WR blocks, the particles were
classified as zooclasts, namely fragments of graptolites. To recognize
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International Journal of Coal Geology 225 (2020) 103501
the graptolite features, kerogen slides were also observed under re-
flected white light using an oil immersion objective. In RWL, graptolite
had a grey color, and smooth to a rough surface (Fig. 7b, d, f). They are,
sometimes, well preserved, having a tubular shape (Fig. 7) where it was
possible to observe some apertures on the graptolite wall and wrinkled
lines around it.
Although in this work there are no doubts regarding the identifi-
cation of graptolites, in samples younger than Upper Silurian (until
Carboniferous), in which graptolite fragments and phytoclast particles
can coexist, the use of RWL in studies of palynofacies will differentiate
these two types of organic particles.
P.A. Gonçalves, et al. International Journal of Coal Geology 225 (2020) 103501

Table 1
Total Organic Carbon and reflectance values Foz da Sertã (Dornes) samples.
Sample TOC Lath-shape Graptolite Blocky-shape Graptolite Lath + blocky-shape Graptolite VReq-grap Solid Bitumen VReq-bit
Code
Rmax Stdev Rr Stdev Rmax Stdev Rr Stdev Rmax Stdev Rr Stdev % Rmax Stdev (n) Rr Stdev %
(%) (n) (%) (n) (%) (n) (%) (n) (%) (n) (%) (n) (%) (%) (n)

FS1⁎ 9.14 1.98 0.35 1.72 0.34 1.35 0.01 1.22 0.02 1.92 0.38 1.67 0.36 2.02 0.21 1.61 0.32
(30) (30) (3) (3) (33) (33) (4) (4)
FS2 9.19 3.04 0.31 2.61 0.32 3.12 0.30 2.72 0.27 3.08 0.31 2.67 0.30 2.91
(22) (22) (22) (22) (44) (44)
⁎
FS3 2.69 1.70 0.27 1.41 0.23 1.55 0.24 1.30 0.20 1.64 0.27 1.37 0.22 1.15 0.15 1.08 0.13
(77) (77) (47) (47) (124) (124) (15) (15)
FS4 8.97 3.87 0.43 2.93 0.34 3.94 0.37 3.13 0.32 3.94 0.40 3.06 0.33 3.72 2.22 0.31 2.10 0.30 1.77
(18) (18) (43) (43) (61) (61) (6) (6)
FS5 0.81 2.53 - 2.08 - 2.47 0.52 2.12 0.37 2.47 0.50 2.12 0.36 2.34 1.43 0.21 1.33 0.22 1.28
(1) (1) (22) (22) (23) (23) (6) (6)
FS6⁎ 0.85 1.80 0.19 1.65 0.23 1.76 0.26 1.61 0.24 1.77 0.24 1.63 0.23
(13) (13) (24) (24) (37) (37)
FS7 2.82 2.05 0.17 1.96 0.17 2.13 0.16 2.06 0.17 2.07 0.17 1.98 0.17 1.97 1.92 0.17 1.83 0.14 1.59
(29) (29) (9) (9) (38) (38) (8) (8)
FS8⁎ 7.95 1.83 0.26 1.56 0.18 1.77 0.18 1.61 0.20 1.81 0.24 1.57 0.18 1.54 0.26 1.44 0.20
(23) (23) (9) (9) (32) (32) (5) (5)
FS9 3.72 2.21 0.25 2.06 0.21 2.20 0.29 2.02 0.26 2.21 0.27 2.04 0.23 2.10 1.50 0.32 1.45 0.32 1.33
(36) (36) (33) (33) (69) (69) (3) (3)
⁎
FS10 4.73 1.46 0.17 1.23 0.22 1.42 0.16 1.16 0.19 1.44 0.17 1.20 0.21 1.09 - 0.85 -
(28) (28) (26) (26) (54) (54) (1) (1)

TOC: Total Organic Carbon (wt%); Rmax: maximum reflectance; Stdev: standard derivation; n: number of particles measured; Rr: Random reflectance; VReq-grap:
vitrinite reflectance equivalent calculated from graptolite maximum reflectance (using Bertrand and Malo's equation); VReq_bit: vitrinite reflectance equivalent
calculated from bitumen maximum reflectance (using Jacob's equation).
⁎
Samples with slight signs of weathering.

4.2.2. Other organic particles

The whole rock analysis revealed the presence of solid bitumen in
the majority of the samples (see Table 1). Two groups of solid bitumen
were identified based on optical characteristics. One has a grey color,
easy polishing, smooth surface, mosaic structure (Fig. 8a, c–d), and is
optically anisotropic, named solid bitumen A; and the other (solid bi-
tumen B) has a brittle aspect, very small with an irregular surface
(Fig. 8b). Due to its size and surface, it was not possible to determine
whether solid bitumen B is anisotropic. They appear filling the inter-
mineral spaces and dispersed in the mineral matrix. Compared to
graptolite, solid bitumen presents lower anisotropy. This trend was also
described by Goodarzi et al. (1985) and Goodarzi and Norford (1987) in
samples from Canada. Solid bitumen was also identified in the kerogen
slides, presenting a brown to black color (in TWL), without fluorescence
(under incident blue light), and smooth surface, occasionally with
cracks (Fig. 9e–h).
Amorphous particles (Fig. 9a–d) cannot be distinguished in the
whole rock blocks yet their presence was confirmed in kerogen con-
centrated blocks. These particles were identified in all the samples
observed under TWL, decreasing from the bottom up to the FS9 sample
and increasing in the FS10 sample. They have a brown to dark brown
color (in TWL) and do not exhibit fluorescence color (under incident
blue light). Amorphous particles are mostly homogeneous with an un-
structured aspect, and often have pyrite inclusions and remains of
graptolites. This material shows different amorphization stages and can
result from microbial rework of graptolite, that according to Hoffknecht
(1991) usually occurred after the death of the animal or very early after
burial. In some particles is still possible to observe graptolite remains
partially amorphized (Fig. 9d), and in other cases, although graptolite is
completely amorphized, the amorphous material keeps the original
shape (mainly in sample FS1; Fig. 9a, b).
In some samples, solid bitumen and amorphous particles present
similar features under transmitted white light (Fig. 9c, g). To distin-
guish these two types of organic particles, kerogen slides were observed
Fig. 3. A well-preserved graptolite fragment (sample FS4) under RWL.
under RWL, with solid bitumen having a flatter surface with a concrete
aspect than amorphous particles (Fig. 9).

5
P.A. Gonçalves, et al. International Journal of Coal Geology 225 (2020) 103501

Fig. 4. Photomicrographs of Foz da Sertã lath-shape graptolites under RWL (whole rock).

Fig. 5. Photomicrographs of Foz da Sertã blocky-shape graptolites under RWL (whole rock).

6
P.A. Gonçalves, et al. International Journal of Coal Geology 225 (2020) 103501

Fig. 6. Photomicrographs of the graptolite wall (under RWL), showed marked anisotropy (a and c rotated 90° to b and d, respectively).

4.3. Graptolite and solid bitumen reflectance reflectance (Rgrap) was measured to determine the organic maturity of
Foz da Sertã samples. Despite the presence of granular and non-gran-
Due to the lack of vitrinite in Dornes samples, the graptolite ular graptolites fragments, only the reflectance of non-granular

Fig. 7. Photomicrographs of graptolites taken under TWL (a, c, e) and RWL (b, d, f) (kerogen slide).

7
P.A. Gonçalves, et al.
Fig. 8. Photomicrographs of Foz da Sertã solid bitumen (white arrow) taken under RWL (whole rock).
graptolites was measured due to the limited amount available of
granular graptolites and its poor surface quality. Lath- and blocky-shape
graptolite reflectance was measured. Reflectance values are presented
in Table 1.
Lath-shape non-granular graptolites have a maximum reflectance in
a range of 1.45–3.86% and random reflectance values between 1.23
and 2.91%. Relatively to the blocky-shape non-granular graptolite, the
reflectance values varied between 1.35 and 3.97% and 1.16–3.15%
(maximum and random, respectively). Since graptolites exhibit a strong
anisotropy, maximum reflectance (%Rmax) is used to study the thermal
maturity of Foz da Sertã samples, as suggested by Goodarzi (1984).
There are slight differences between the maximum reflectance of lath-
and blocky-shape graptolite mainly at the bottom of the sequence
where reflectance values are higher. However, the correlation
(Fig. 10a) between lath-shape and blocky-shape non-granular grapto-
lites is robust, demonstrating a correlation coefficient of r2 = 0.95. This
indicates that these two shapes correspond to different parts of the same
specimen, as already mentioned by Goodarzi et al. (1992) and Link
et al. (1990), presenting similar thermal evolution. Since lath-shape and
blocky-shape fragments are different parts of the graptolite's reflectance
values were merged (Table 1). Maximum graptolite (lath + blocky)
reflectance values varied between 1.43 and 3.94%, while random re-
flectance oscillates from 1.20 to 3.08% (Table 1). Reflectance values
reveal a bimodal distribution, and this trend is probably associated with
the increase of the burial temperature that leads to an increase of the
bireflectance (Goodarzi and Norford, 1987) and/or with the weathering
effects.
The graptolite reflectance variation does not show a discernible
pattern (Table 1) along the sequence. Goodarzi et al. (1992 and refer-
ences therein) refereed that exist several factors that can modify the
graptolite reflectance, such as, temperature, the rock matrix, the sup-
pression of reflectance, the weathering, and thermal perturbations. In
the case of Foz da Sertã samples, it is possible to observe some slight
signs of weathering (oxidized pyrite and graptolite wall microfractures)
8
International Journal of Coal Geology 225 (2020) 103501
in the samples with lower reflectance values (both in graptolites and
solid bitumen). According to some authors (Bustin et al., 1983; Link
et al., 1990; Taylor et al., 1998), oxidized coals from outcrops show a
decrease in vitrinite reflectance values that can be related to the che-
mical alteration resulting in changes of their physical properties. Since
graptolites exhibit vitrinite-like behavior, the suppression of graptolite
reflectance can be related to this fact. Given this fact, only samples
without weathering evidence were used to determine the maturity of
the sequence. As referred above, the vitrinite reflectance equivalent was
calculated through the formula proposed by Bertrand and Malo (2012)
and show values that range from 1.97 to 3.71% (Table 1). These data
suggest that the organic matter of Foz da Sertã samples is post-mature
in terms of hydrocarbon generation. Despite the high TOC values still
present in some samples, they represent inert or “died” carbon, which
implies that no longer has the potential to produce hydrocarbons.
Maximum and random reflectance values measured on solid bi-
tumen A display a wide range of values, ranging from 1.09 to 2.22%
and 0.85 to 2.10%, respectively (see Table 1). Solid bitumen B re-
flectance was not measured due to its irregular surface and the very low
number of particles. In the samples, where graptolites and solid bi-
tumen coexist, graptolite reflectance values are always higher than
those of solid bitumen (Table 1). This trend has also been reported by
Goodarzi et al. (1985) and Riediger et al. (1989) for samples from
Canada. As can be seen in Fig. 10b, statistically, there is not a sig-
nificant correlation (r2 = 0.38) between the maximum graptolite re-
flectance (lath plus blocky) and maximum solid bitumen reflectance.
Just as graptolite reflectance values, solid bitumen reflectance va-
lues do not display a linear maturity trend with depth. As referred by
Gentzis and Goodarzi (1990), autochthonous solid bitumen reflectance
should increase with increasing depth, a behavior not observed in these
samples (Table 1). Plotting the equivalent vitrinite reflectance calcu-
lated from graptolite versus equivalent vitrinite reflectance calculated
from bitumen (Fig. 10c) of the samples without weathering evidence, it
is possible to verify that there is no statistical significance (r2 = 0.48).
P.A. Gonçalves, et al. International Journal of Coal Geology 225 (2020) 103501

Fig. 9. Photomicrographs of Dornes organic matter (bitumen and amorphous particles) taken under TWL (a, c, e, g) and RWL (b, d, f, h) in kerogen slides.

These data demonstrate that solid bitumen suffered a different thermal
evolution from that of graptolite, indicating that this is an allochtho-
nous/migrated bitumen. Solid bitumen reflectance is usually used as a
maturity parameter in samples devoid of vitrinite, however, in Foz da
Sertã samples it cannot be used.
5. Conclusion
A combination of organic microscopy (reflected and transmitted
white lights) and basic organic geochemistry technique was used to
improve the knowledge of the organic matter of Foz da Sertã Formation

9
P.A. Gonçalves, et al.
Fig. 10. a - Plot between lath-shape and blocky shape non-granular graptolites reflectance; b - Plot between graptolites (lath + blocky) reflectance and solid bitumen
reflectance; c - Plot equivalent vitrinite reflectance calculated from graptolite maximum reflectance (VReq-grap) and equivalent vitrinite reflectance calculated from
bitumen maximum reflectance (VReq-bit).
(Dornes, Portugal), with emphasis on graptolites morphology. The fol-
lowing conclusions were drawn:
1) Dornes assemblage consists of excellent well-preserved graptolite
fragments, amorphous particles and solid bitumen;
2) regarding graptolites fragments, non-granular graptolites prevail
over granular and exhibit different shapes (lath and blocky). The
morphological features of graptolites, including the fusellar layers,
are very well visible in reflected white light;
3) the observation of kerogen slides, under transmitted white light,
showed that some organic particles have similar features, which
may lead to misunderstandings in the identification and conse-
quently in the interpretation of the data. Using reflected white light,
in this type of preparation, it turned out an important tool to dis-
tinguish the morphologic features of graptolites and to discern solid
bitumen and amorphous particles in the Foz da Sertã samples.
Therefore, in palynofacies studies, where phytoclast and graptolite
coexist (Upper Silurian to Carboniferous), it is important to use re-
flected white light to distinguish these two types of organic parti-
cles;
4) based on the graptolite reflectance, Foz da Sertã organic matter is in
a post-mature stage and has not potential to generate hydrocarbons.
There is no relationship between the graptolites and solid bitumen
reflectance. This fact indicates that this solid bitumen is allochtho-
nous, i.e., migrated bitumen.
10
International Journal of Coal Geology 225 (2020) 103501
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
Paula Alexandra Gonçalves is grateful to Fundação para a Ciência e
Tecnologia (FCT) for the financial support (SFRH/BPD/114696/2016).
This work was co-financed by the European Union through the
European Regional Development Fund, framed in COMPETE 2020
(Operational Programme for Competitiveness and Internationalization),
through the project ICT (UIDB/04683/2020) with reference POCI-01-
0145-FEDER-007690. The authors are grateful to three anonymous
reviewers for their insightful reviews.
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