International Journal of Coal Geology 111 (2013) 2336

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International Journal of Coal Geology

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Permian carbonaceous rocks from the Bonito Coaleld, Santa Catarina, Brazil:
Organic facies approaches
J.G. Mendona Filho a,, M.G. Sommer b, M.C. Klepzig b, J.O. Mendona a, T.F. Silva a, M.L. Kern a,
T.R. Menezes c, A. Jasper d, M.C. Silva a, L.G.C. Santos a
a
Palynofacies and Organic Facies Laboratory (LAFO)/DEGL/IGEO/CCMN/UFRJ, Av. Athos da Silveira, 274 - Prdio do CCMN, Sala JI-020, Cidade Universitria, CEP 21.941-916,
Rio de Janeiro, RJ, Brazil
b
Geoscience Institute, UFRGS, Porto Alegre, RS, Brazil
c
Petrobras R and D Center, Rio de Janeiro, RJ, Brazil
d
Centro Universitrio UNIVATES, Lajeado, RS, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Permian sedimentary rocks of the Rio Bonito Formation, Paran Basin, in the Santa Catarina state, Brazil, con-
Received 15 February 2012 tain three important coal seams, in a descending order: Barro Branco, Bonito Superior and Pre-Bonito Supe-
Received in revised form 9 July 2012 rior. Artinskian carbonaceous shale samples corresponding to the so called Bonito coal were sampled at the
Accepted 23 July 2012
mine face of the coal bed of the Bonito I underground mine. These samples were analyzed in order to discuss
Available online 29 July 2012
their petrographical, geochemical, palynological, and paleobotanical characteristics. Palynological analyses
Keywords:
demonstrated abundant and well-preserved palynomorphs showing a dominance of bisaccate pollen grains
Carbonaceous shale related to gymnospermic plants. Wood fragments preserved as coalied compression show the presence of
Palynofacies lycophyta. Palynofacies on samples demonstrated good results for the recognition of preserved organic mat-
Palynology ter and changes in paleoenvironmental conditions along the sedimentary sequence. Palynofacies and palyno-
Charcoal logical analyses indicate changes in paleoecological conditions that have favored the development of
Biomarkers different plant communities during the depositional time span from a forested gymnosperm at the base to
a lycophyte, arborescent plant dominated scenario at the top suggesting a shift to coastal environment. The
microscopic maceral-group analyses reveal a predominance of liptinite and vitrinite over inertinite, while
among microlithotypes, carbargilite is abundant. The joint occurrence of inertinite as a maceral in the carbo-
naceous rock and charcoal in associated shales suggests that the mire and near surroundings were regularly
subject to wildres. Mean random vitrinite reectance (Rr) varies from 0.88 to 1.04%. The liptinite spectral
uorescence parameters obtained for samples show the max values varying from 610 to 650 indicating
equivalent vitrinite reectance (Rreq) values from 0.83 to 1.10%. These results show that the equivalent
vitrinite reectance (Rreq) correlates well with the measured vitrinite reectance (Rr). The Bonito Coal is
a high-volatile bituminous coal according to the ISO, 11760: 2005 standard. Total organic carbon varies
from 2.4 to 44.0 wt.% and sulfur is present in moderate to high contents. GC-MS analyses evidenced a pre-
dominance of even saturated hydrocarbons and the presence of -hopanes and -steranes.
2012 Elsevier B.V. All rights reserved.

1. Introduction claystones), siltstones, sandstones, marlstones, and carbonates. Al-

According to Taylor et al. (1998), carbonaceous shale is a transition
from humic coals into coaly shale. It can be black, dull, hard, and com-
pact, although a ne stratication is frequently recognizable. Most
sediments and sedimentary rocks contain organic matter in minor
quantities, from less than 1 to more than 10%. Sedimentary rocks,
which can be rich in organic matter, comprise shales (mudstones,
Corresponding author at: Laboratrio de Palinofcies and Fcies Orgnica (LAFO)/
DEGL/IGEO/CCMN/UFRJ, Av. Athos da Silveira, 274 - Prdio do CCMN, Sala JI-020,
Cidade Universitria, CEP 21.941-916, Rio de Janeiro, RJ, Brazil. Tel.: +55 21 2598
3094; fax: +55 21 25989465.
E-mail address: graciano@geologia.ufrj.br (J.G. Mendona Filho).
though the rocks may contain large amounts of organic matter,
which may act as the principal source of oil and gas, there is no com-
monly used logical classication yet, which includes the organic mat-
ter content. However, some informal names such as oil shale, black
shales, or carbonaceous shale are widely used, although many of
these rocks are not shales in the strict sense.
For this paper, carbonaceous shales (mudstones, limestones, silt-
stones and coaly shales, so called Bonito coal, Table 1) from the Bonito
coal bed were sampled at the mine face of the coal bed of the Bonito I
underground mine (Rio Bonito Formation, Paran Basin, in the Santa
Catarina state, Brazil). These samples were analyzed in order to discuss
their petrographical, geochemical, palynological, and paleobotanical
characteristics.

0166-5162/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.coal.2012.07.008
24 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336

Table 1 Geological studies on the Sakmarian coalelds in the southern-

Samples from Bonito coal seam.
most Paran Basin (Fig. 1) have been developed more intensively in
Samples Lithology Thickness (m) the last decades with different approaches, including stratigraphy
XII Carbonaceous shale Bonito coal 0.16
XI siltstone 0.17 (Holz, 1998; Holz et al., 2002), palynology (Cazzulo-Klepzig et al.,
X Carbonaceous shale Bonito coal 0.15 2005, 2007; Marques-Toigo and Corra da Silva, 1984), palynofacies
(Cazzulo-Klepzig et al., 2009), paleobotany (Guerra-Sommer et al.,
IX Siltstone 0.55
1991), organic petrography and geochemistry (Alves and Ade, 1996;
Kalkreuth et al., 2006; Silva and Kalkreuth, 2005; Silva et al., 2008),
VIII
Bonito coal and isotopic dating (Guerra-Sommer et al., 2008a,b), in order to char-
seam VII Carbonaceous shale Bonito coal 1.05
acterize the biological and geological conditions, which prevailed
3.40 during the peat accumulation and also to obtain geochronological
VI data for the coal-bearing interval.
V Limestone 0.14 The integrated geological and biological results lead to the conclu-
sion that tectonic and environmental conditions, as well as the peat
IV
forming plant communities were important factors that inuenced
Carbonaceous shale Bonito coal 0.85
III the formation and characterization of coal deposits.
While the available geological literature on the coals of the south-
II Mudstone 0.10
ern Paran Basin is very extensive, it has been concentrated mainly on
I Carbonaceous shale Bonito coal 0.23
the coalelds of Rio Grande do Sul state. In contrast, few geological
studies can be found for nearby South of Santa Catarina state coaleld.
The most important Lower Permian coal deposits in Brazil occur in The most important geological study for the South Catarinense Coal-
the southern portion of Brazil, with major coal development in the eld was produced by Bortoluzzi et al. (1978), focusing on different
States of Rio Grande do Sul and Santa Catarina. coal seams and including sedimentology, stratigraphy, organic pe-
Proven reserves are in the order of 32 10 9 tons, of which 89.2% trography, paleobotany and palynological data. Since then, different
are located in Rio Grande do Sul, 10.4% in Santa Catarina and the studies have been done on the Barro Branco coal seam, which has ex-
remainder 0.4% in the Paran and So Paulo states. tensively been exploited in the last decades.

Fig. 1. Map and stratigraphic framework of the Paran Basin (Santos et al., 2006).
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336 25

Taking into account the need to assess the carbonaceous rocks
known as Bonito Coal seam, aiming to subsidize a proper technical
utilization; an extensive research project was proposed by an inter-
institutional network (REDECARVAO), with nancial support from
the National Council for Scientic and Technological Development
(CNPq). Palynofacies and organic matter determination are among
the goals of the project for their importance as tools for a more accu-
rate interpretation of the ancient peat-forming plant-community and
paleoenvironmental conditions of coal formation.
The main focus of the present study is to characterize the
organic matter of the carbonaceous shales (mudstones, limestones,
siltstones and coaly shales or so-called Bonito coal seam) exploited
in the Bonito I mine located in Santa Catarina Coaleld, including
palynofacies, palynology, charcoal characterization, organic geochem-
istry, organic petrography and biomarker analyses giving support to
technological approaches.
2. Geological setting
The Paran Basin is a vast sedimentary basin situated in central-
eastern South America, including parts of Brazil, Argentina, Paraguay
and Uruguay, with an area of about 1,500,000 km 2 (Fig. 1). In its cen-
tral portion, this basin holds a stratigraphic record of over 7500 meter
thickness. Eight Brazilian states are partially included in the area of the
basin. Six second order allostratigraphic units, each of them compris-
ing a geological record of some tens of million years, dene the strat-
igraphic framework of the Paran Basin. The overall record spans from
450 to 65 Ma, but much of the time is taken up by the hiatus that split
apart the various supersequences (Milani et al., 2007). The Rio Iva
(OrdovicianSilurian), Paran (Devonian), and Gondwana I (Upper
Carboniferous-Lower Triassic) sequences document major Paleozoic
transgressiveregressive cycles, whereas the Gondwana II, Gondwana
III and Bauru sequences comprise Mesozoic continental sedimentary
successions and associated igneous rocks.
The coal-bearing strata of the lithostratigraphic unit called Rio
Bonito Formation (Schneider et al., 1974) were included by Milani
et al. (2007) in the Gondwana I supersequence (Fig. 1). The most im-
portant coal deposits in Brazil occur in the southern portion of the
Paran Basin, with major coal development in the States of Rio Grande
do Sul and Santa Catarina (Fig. 2).
The parautochthonous accumulation of peat-forming organic
matter, typical of Brazilian coalelds, was rst inferred by Corra da
Silva (1991). A similar origin was proposed by Glasspool (2003) for
peat deposition in the Permian Gondwana of South Africa (Witbank
Basin). Sedimentological, petrographic and stratigraphic work in-
ferred that important coal deposits in southern Parana Basin occur
adjacent to paralic, i.e., estuarine, deltaic, backshore, foreshore and
shoreface siliciclastic deposits, and that peat was deposited in coastal
swamp and back-barrier environments (Alves and Ade, 1996; Holz
et al., 2002). Deposition occurred within the cool temperate climatic
belt (Scotese, 2000) at an approximate paleolatitude of 50.
The Sul Catarinense Coaleld is located in the southeastern por-
tion of the state in a polygon of approximately 1200 km 2 that includes
24 municipalities with a total population of 659,000 (SIESESC, 2008).
The basin comprises portions of the Tubaro, Ararangu, Urussanga
and Mampituba River Basins with a length of 95 km and an average
width of 20 km, within an area delimited by coordinates 2811 to
2930 (southern latitude) and 4910 to 4937 (western longitude).
Using lithostratigraphic criteria, Schneider et al. (1974), ratied by
Bortoluzzi et al. (1978), subdivided the Rio Bonito Formation in Santa
Catarina in into three major packages with a hierarchy of members
labeled from the base to top: Triunfo (coastal and uvial sandstones),
Paraguau (marine mudstones and ne-grained sandstones) and
Siderpolis (coastal and uvial sandstones). The coal seams were

Fig. 2. Location of study area and stratigraphic position of the coal-bearing Rio Bonito Formation in Paran Basin. The South Santa Catarina Coaleld is located in the southeastern
portion of the state in a polygon of approximately 1200 km2 that includes 24 municipalities with a total population of 659,000 (SIESESC, 2008). The greater Paran basin is com-
prised of portions of the Tubaro, Ararangu, Urussanga and Mampituba River Basins with a length of 95 km and an average width of 20 km, within an area delimited by coordi-
nates 2811 to 2930 (southern latitude) and 4910 to 4937 (western longitude).
26 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336
designated by Bortoluzzi et al. (1978), from the top to the base,
as: Barro Branco, Irapu, A, B, Ponte Alta, Bonito and the minor
coal layers Pre-Bonito C and D. The top Barro Branco coal seam,
which occurs throughout the basin, was included in the Sideropolis
member. The coal has been extensively mined, whereas Irapua and
Ponte Alta, Bonito (included in Triunfo Member) as well the minor
Pre-Bonito seams appear to be irregularly distributed in the basin.
They have been exploited either in open casts or sub-surface mines.
In terms of sequence stratigraphy, but also taking into account pa-
leontological and former lithostratigraphic criteria, Holz et al. (2010)
concluded that the Rio Bonito succession in Parana Basin included
two third order sequences. The Sideropolis Member (as dened by
Schneider et al., 1974) and almost all its coal seams in Santa Catarina
and Paran States are linked to the LPTS-4, of Artinskian age. In the
State of Rio Grande do Sul, the Rio Bonito Formation is not formally
subdivided into different lithostratigraphic members, and the coal
seams were deposited at the Sakmarian Stage.
The Bonito I mine, which is the object of the present analyses, is
located near the municipality of Lauro Mller. It exploits the
so-called Bonito coal seam, which is approximately 3.4 m thick in
this area (Fig. 2, Table 1). Nevertheless, only the basal 2.0 m has
been exploited in the underground mine. Together with the upper
Barro Branco coal seam, the Bonito has been considered the most
important coal reserve in the Santa Catarina state, occurring continu-
ously almost throughout the South Catarinense Coaleld, whereas
Irapua and Ponte Alta, as well as the minor Pre Bonito seams are irreg-
ularly distributed in the basin.
3. Material and methods
The studied interval is about 3.4 m thick. A total of 12 samples
(among them: mudstones, limestones, siltstones and coaly shales, so
called Bonito coal) from the Bonito coal bed were collected from
Bonito I mine in the State of Santa Catarina (Fig. 2, Table 1), and ana-
lyzed. This has involved microscopic kerogen counts of 300 to 500
particles per sample in both transmitted white light and incident uo-
rescence mode using blue/ultraviolet excitation. Additional studies
included palynomorph and maceral identication, supported by
sulfur, biomarker and 12 TOC analyses.
3.1. Sample preparation
3.1.1. Palynology
Palynological analyses were done on twelve samples, collected
along the Bonito coal seam in the Bonito I underground mine, but
only four were selected for the study, on account of their better pres-
ervation and/or signicance for the paleoecological interpretation.
Two samples correspond to the basal level (Samples I and III), one to
the intermediary level (Sample VII) and the last one to the top (Sam-
ple XII) of the coal seam (Fig. 2, Table 1). Samples were processed in
Schulze's Solution (65% nitric acid; HNO3), saturated with potassium
chlorate (KClO3) and neutralized in potassium hydroxide (KOH), en-
abling the rapid maceration of the palynomorphs. A total of 200
miospores were counted from each sample to determine the relative
proportions of miospore taxa, following the method of percentage fre-
quency cited by Jekhowsky (1963). Assignments of dispersed spores
and pollen grains to their respective parent plant groups were based
on the compilations of Gould and Delevoryas (1977), Balme (1995)
and Quadros et al. (1995).
3.1.2. Palynofacies
Palynofacies analyses were developed on twelve (12) samples
from the Bonito coal seam in the Bonito I underground mine (Fig. 2,
Table 1). The material preparation for the palynofacies analysis was
made using the standard non-oxidative palynological procedures
described by Tyson (1995) and Mendona Filho et al. (2011a, 2012).
For the purpose of studying kerogen concentrations, the samples
were ground to approximately 2-mm size. Samples were treated suc-
cessively to remove carbonates (HCl 37% for 18 h), silicates (HF 40%
for 24 h), and neoformed uorides (HCl 37% for 3 h). Between steps,
samples were washed with distilled water until washing water was
neutral. After this procedure, ZnCl2 (density = 1.9 to 2 g/cm3) was
added, stirred, and then centrifuged in order to separate suldes. The
oated material was also washed and HCl (10%) drops+ distilled
water were added to eliminate the heavy liquid. The isolated kerogen
was sieved at 20 m diameter. After this procedure, strew slides were
made with the organic residue.
The palynofacies analyses involved the quantitative (counting
from 300 to 500 particles) and qualitative (organic particle compo-
nent identication) examinations of the kerogen component groups
and subgroups. These were achieved by means of microscopy tech-
niques under transmitted white light and blue/ultraviolet incident
light (uorescence). The count followed the organic matter groups
and subgroups classication proposed by Tyson (1995), Menezes
et al. (2008), and Mendona Filho et al. (2010, 2011b,c, 2012). Fol-
lowing the organic particulate component count, absolute values
were recalculated for percentages and normalized to 100% and binary
diagrams were produced to have a better visualization of the results.
A Zeiss microscope (AXIOSKOP 2 PLUS model with 10 oculars and
20 objective) was used to count the particles in each sample.
The Kerogen classication used in this study was modied and
extended from Tyson (1995) and Mendona Filho et al. (2010).
The kerogen assemblage is arranged in three main groups of mor-
phological constituents: Phytoclast, a continental fraction derived
from macrophyte tissue ora (Mendona Filho et al., 2011c, 2012;
Tyson, 1995), Amorphous Organic Matter (AOM), bacterial derived
organic matter (2011c, 2012, Mendona Filho et al., 2010; Tyson,
1995) and Palynomorph, a continental fraction including pollen
grains, spores, freshwater algae and marine components, and zoo-
morphs (Mendona Filho et al., 2011c, 2012; Tyson, 1995).
3.1.3. Organic petrographic analysis
Preparation of 12 samples for petrographic analysis involved sam-
ple drying, followed by reduction in grain size (jaw breaker, sieving),
and reduction to sub-samples (rife sampler) for chemical and petro-
graphic analyses according to ASTM D2797/D2797M-11a (2011).
The petrographic composition of the coal samples was determined
by maceral analysis (ISO 7404-3, 2009) using the maceral classica-
tion as established by ICCP (1998, 2001). The rank of the coal seams
was established by random vitrinite reectance measurement follow-
ing standard procedures (ISO 7404-5, 2009 and Bustin et al., 1989).
Petrographic analyses included the identication of lithotype proles
that provided the coal intervals for the maceral analyses according to
ICCP (1998, 2001).
3.1.4. Vitrinite reectance (Rr%)
3.1.4.1. Whole-rock preparation procedure. The samples were ground
to approximately 2 mm size and embedded in resin. A single block
was prepared for each sample.
3.1.4.2. Plug of kerogen concentrate preparation procedure. The samples
were ground to approximately 2 mm top size. HCl (37%) was added to
the sample and left for 18 h. After this procedure the sample was
washed with distilled water until the washing water was neutral. In
the next step HF (40%) was added to the sample and left for 24 h,
followed by a neutral wash and addition of 37% for 3 h to remove
uorides and a nal neutral wash. Samples were washed with water
again until neutralization. After this procedure, they were oated
using ZnCl2 ( = 1.9 to 2 g/cm3) and centrifuged to separate suldes.
The washing procedures were repeated adding some HCl (10%)
drops + distilled water to eliminate the heavy liquid. The isolated
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336 27

kerogen was sieved (20 m) and the fraction + 20 m was embedded

in resin (SERIFIX-STRUERS).

3.1.4.3. Sample polishing. The particulate blocks had their surfaces

ground down using progressively ner grades of wet silicon carbide
papers; the grinds used were 800, 1200 and 4000 grit wet silicon
carbide paper. A single set of samples was sent to each laboratory.
The analyses were performed by a Carl Zeiss Axioskop 2Plus
microscope equipped with a spectrophotometer JandM (MP 200).
An YttriumAluminumGarnet reectance standard of %Rr = 0.893
was used to calibrate the microscope, while the measurements were
performed using the immersion oil Imersol 518F. The analyses were
performed at 200 magnication at room temperature of 23 C.

3.1.5. Spore Coloration Index (SCI)

Fig. 3. Ternary diagram showing the constitution of the kerogen assemblage from
Bonito coal seam samples. Note that the Bonito coal seam is essentially formed from
phytoclasts and palynomorphs association showing a high degree of preservation of
the Permian vegetation near the Artinskian/Kungurian uvio-deltaic system of the
Rio Bonito Formation.
Based on Tyson (1995).
The SCI used in this work was developed by Barnard et al. (1981),
and has a scale of 1 to 10 with intervals of 0.5. The color of the spores
in this method increases with the increase of depth and temperature.
The analyses were performed on samples using transmitted white
light at 200 magnication by comparing the pollen grains and
spore colors of the kerogen strew slides with the standard scale.
3.1.6. Spectral uorescence analysis
Spectral uorescence analysis is based on the measure of the spec-
tral intensity between 400 and 700 nm (Ottenjann, 1975; Ottenjann
et al., 1974, 1981, 1982). Spectral uorescence measurements were
taken with a Zeiss Axioskop 2-plus microscope, with 50 magnication
in immersion oil (e = 1.518 to 23 C), and (Zeiss) ultraviolet G 365, FT

Fig. 4. View of some of the abundant and well-preserved palynomorphs showing a dominance of bisaccate pollen grains related to gymnospermic plants. A) Alisporites splendens
(Leschik) Foster, 1979; B) Vesicaspora wilsonii (Schemel) Wilson and Venkatachala, 1963; C) Scheuringipollenites medius (Burjack) Dias-Fabrcio, 1981; D) Cannanoropollis diffusus
(Tiwari) Dias-Fabrcio, 1981; E) unidentied monosaccate pollen grain; F) Caheniasaccites ovatus (Bose and Kar) Archangelsky and Gamerro, 1979; G) Protohaploxypinus hartii
Foster, 1979; H) Fusacolpites fusus Bose and Kar, 1966; I) General view of the palynogical content in the intermediary coal level (dominance of bisaccate pollen grains).
28 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336

395 and LP 420 lters. The correction factor was obtained based on the
calibration of a lamp (Baranger et al., 1991).
3.2. Charcoal
Macroscopic fossil charcoal samples were extracted mechanically
from sediment samples with the aid of preparation needles and twee-
zers under a binocular microscope in the laboratory. Due to the very
fragile nature of all the specimens, they could not be cleaned with
water or acids to remove adhering mineral remains. The fragments
were mounted on standard stubs, and subsequently examined with
the aid of a JEOL JSM 6490 LV Scanning Electron Microscope (SEM)
at the Senckenberg Forschungsinstitut und Naturmuseum, Frankfurt
a. M., Germany.
3.3. Total organic carbon (TOC) and total sulfur (TS)
increasing polarity, such as n-hexane (6 ml), followed by 10 ml
of dichloromethane/hexane (8:2) and 10 ml dichloromethane/
methanol (1:1), respectively.
Saturated hydrocarbons were analyzed using an Agilent Technolo-
gies (Palo Alto, CA, USA) instrument comprising a 7890 model gas chro-
matograph equipped with a 7683 auto sampler and coupled to a triple
quadrupole 7000A mass spectrometer (GC/MSMS). The carrier gas
was He at 1.2 ml/min, in constant ow mode; a DB-5 column (5% phe-
nyl, 95% methylsiloxane, 30 m 0.25 mm ID, lm thickness 0.25 m)
was used. The injector temperature was 280 C. The GC oven tempera-
ture program was: 70 C (1 min) to 170 C at 20 C/min and to a 310 C
at 2 C/min. MS was operated by electron impact ionization mode at
70 eV; ionic temperature at 280 C; interface temperature at 300 C;
quadrupole temperature at 150 C. Samples were analyzed by selected
ion monitoring (SIM) using m/z 85 for alkanes, m/z 191 for terpanes
and m/z 217 and 218 for steranes.

Following acidication to remove carbonates, the TOC and S analy- 4. Results

ses were made for all samples with a LECO SC 144 device. The adopted
methods were ASTM D 4239 (2008) and NCEA-C-1282 (United States
Environmental Protection Agency-US EPA, 2002).
3.4. Biomarkers
The soluble organic matter was extracted from the samples (50 g
of 5 mm ground size) with dichloromethane in the Soxhlet appa-
ratus. The extracts were fractionated using open column liquid chro-
matography of activated silica gel. The saturate, aromatic and polar
fractions were collected by the successive elution of solvents with
4.1. Palynofacies
Palynofacies analyses performed on samples demonstrated good
results for the recognition of preserved organic matter and changes
in paleoenvironmental conditions along the sedimentary sequence.
The ternary diagram illustrated in Fig. 3 shows the constitution
of the kerogen assemblage in the Bonito coal seam samples. Please
note that the investigated carbonaceous interval of the Bonito coal
seam was formed from a phytoclast and palynomorph association
that shows a high degree of preservation of the Permian vegetation

Fig. 5. View of some of the abundant and well-preserved palynomorphs. A) Punctatisporites gretensis Hart, 1964; B) Calamospora sahariana Bharadwaj, 1957; C) and D) Lundbladispora
braziliensis (Pant and Srivastava) Marques-Toigo and Picarelli, 1984; E) Cycadopites glaber (Luber and Waltz) Hart, 1964; F) Lundbladispora sp; G) tetrad of Cyclogranisporites sp;
H) tetrad of Lundbladispora sp; I) Cyclogranisporites parvigranulosus (Leschik) Ybert, 1975.
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336 29

Fig. 6. A), B), and C) Adpressions of lycophyte stems, showing preserved leaf cushions (Brasilodendron sp.) and also charred surface from the roof in the underground mine
(ch. charcoal; st. stems).

close to the Artinskian/Kungurian uvio-deltaic system of the Rio
Bonito Formation.
4.2. Palynology
The palynological content of the basal coaly level of Samples I
and III is dominated by bisaccate pollen grains, which are common-
ly derived from gymnosperms. The most common forms identied
were Vesicaspora, Scheuringipollenites, Alisporites, Cannanoropollis
and Caheniasaccites, with botanical afnity with cordaitales or
glossopteridales (Gould and Delevoryas, 1977; Quadros et al., 1995).
These forms were recorded together with some striate pollen grains
such as Protohaploxypinus produced probably by coniferales, besides
scarce monocolpates, represented by forms of Cycadopites, with botan-
ical afnity with gymnosperms (Balme, 1995; Quadros et al., 1995).
The most signicant forms identied are shown in Figs. 4 and 5.
The palynological content of the intermediary level (Sample VII) is
partly coalied and difcult to identify due to the low stage of preser-
vation. It contains an abundance of bisacate pollen grains found
together with scarce pteridophytic spores.
A well preserved palynological assemblage (Sample XII) occurs at the
uppermost level. It is marked by the dominance of trilete spores from

Fig. 7. A) and C) stem casts of lycophyte (Brasilodendron sp.) identied in siliciclastic levels associated to coals. B adpression of lycophyte (Brasilodendron sp.) identied in the roof in
the underground the mine (Bonito coal mine).
30 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336

pteridophytic vegetation, such as Lundbladispora and Vallatisporites, Table 2

SEM images of the macroscopic fossil charcoal samples from siliciclastic levels to the
including also some tetrads of Cingulicavati spores. This evidence indi-
Bonito coal seam.
cates the dominance of arborescent and herbaceous lycophytes in the
Charcoal
peat-forming plant community. Inertinite
record (in
Locality Age record Charcoal type Description
clastic
In addition, several Laevigati spores with botanical afnity with (in coal)
levels)
licopsids were identied, such as (Punctatisporites) and sphenopsids Pycnoxylic secondary
(Calamospora). Wood. In radial view
tracheids are 21 33 m.
Their radial walls exhibit
biseriate, sub-opposite to
Santa alterne pits. Uniseriate
4.3. Paleobotany Catarina Bortoluzzi rays are present.
coal basin et al. Jasper et
Artinskian
(1978) al. (2011) Pycnoxylic secondary
(Bonito I
A formal description of megaoras associated specically with coal mine)
Wood. In radial view
tracheids are 11 42m.
the Bonito coal seam is still lacking despite the abundance of fossil Their radial walls exhibit
uniseriatepits. Spiral
plants described from the suprajacent Irapu coal seam (Bernardes thickenings in sub-
de Oliveira, 1977) in the Santa Catarina coal basin. Bernardes de horizontal disposition are
abundant.
Oliveira (1977) classied the megaora as a Pure Glossopteris
Flora showing extreme scarcity of lycophytes. A particular pattern
observed in the present study is the presence of dense associations 4.4. Macroscopic charcoal
of compressed casts of arborescent lycophyta, preserved in horizontal
disposition, without preferential orientation, at the roof of the mine SEM analyses in leaf cushions of compressed stems of arborescent
mentioned by Mendona Filho et al. (2010). Additionally, dense lycophytes, preserved in randomly oriented, horizontal position in the
thickets of compressed casts showing homogeneous morphological roof of the mine (Fig. 8A and B), revealed details of the surface show-
parameters (Brasilodendron sp.) can be recognized as dominant ing leaf cushions (Fig. 8C, D and E) and a surface covered with charred
plant fossils in different outcrops (probably overlying the Bonito material (Fig. 8F and G). Since only parenchyma was preserved, it was
coal layer) in the vicinity of Lauro Mller (Figs. 6 and 7). The wood not possible to identify distinctive features that would allow more de-
fragments preserved as coalied compression showing the presence tailed taxonomic identication.
of lycophytes and can be considered material that could have given Charred wood samples recovered from a silty layer at the base the
rise to vitrinite and inertinite macerals in coal and carbonaceous coaly bed (base from Sample I, Fig. 2, Table 1) display the presence of
shale samples from Bonito coal seam. secondary xylem showing homogenization of the cell walls. These

E
A B

F
C

D G

Fig. 8. A) lycophyte compressed stem at the roof of the coal seam; B) Bonito coal seam; C, D and E) details of the surface showing leaf cushions; F) charred surface; G) charred wood
with gymnospermic afnity (SEM image).
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336 31

features reveal true spiral thickenings associated with coniferous Table 3

abietinean bordered pits (Fig. 8G, Table 2). The presence of abrupt, Petrographic composition of the Bonito coal seam samples (macerals and mineral
matter).
non abraded edges was a common characteristic in almost all macro-
scopic fossil charcoal. Samples Vitrinite Liptinite Inertinite Mineral matter Total
(vol.%) (vol.%) (vol.%) (vol.%) (vol.%)

4.5. Organic petrography I 25 22 30 23 100

II 12 3 13 72 100
III 20 40 17 23 100
Petrographic analysis in carbonaceous samples shows that the
IV 25 30 22 23 100
samples are composed of a trimaceralic association with varying com- V 23 37 20 20 100
position (Fig. 9). Carbargilite is the more abundant microlithotype. VI 22 23 32 23 100
Petrographic composition of the Bonito coal seam samples VII 28 23 22 27 100
(macerals and mineral matter) is shown in Table 3. The samples are VIII 23 25 22 30 100
IX 12 15 20 53 100
vitrinite-rich, high-ash carbonaceous shale with moderate to high
X 20 25 30 25 100
sulfur content. Sporinite is the major liptinite group maceral, fusi- XI 70 0 2 28 100
nite and semifusinite contents are balanced and telovitrinite slightly XII 23 30 20 27 100

Fig. 9. Photomicrographs taken in oil immersion under reected white (14 and 78) and incident blue light (56) conditions showing the maceral composition of the Bonito coal
seam: 1) vitrinite (VT) with pyrite inclusions and inertodetrinite (ID); 2) funginite (FG), inertodetrinite (ID), liptodetrinite (LD), round body of corpogelinite (CG); 3) bands of
liptodetrinite (LD), sporinite (ES), vitrinite (VT), cutinite (CT) and inertodetrinite (ID) with small inclusions of the framboidal pyrite (PI); 4) bands of the liptodetrinite (LD), cutinite
(CT) intercalated with vitrinite (VT) bands and inertodetrinite (ID) with small pyrite inclusions; 5) cutinite (CT), sporinite (ES), and liptodetrinite (LD) involving mineral matter
(MM); 6) sporinite (ES), cutinite (CT) and mineral matter (MM); and 7) fusinite (FS) with mineral matter (MM); 8) fusinite and mineral matter (MM).
32 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336

Fig. 10. Photomicrographs taken in oil immersion under reected white light (12) and incident blue light (36) conditions showing the maceral composition of the Bonito coal
seam: 1) bands of mineral matter (MM), inertodetrinite (ID), vitrinite (VT), liptinite (LP) 2) fusinite (FS) with pyrite inclusions, mineral matter (MM), inertodetrinite (ID)
3) lamalginite, which forms long anastomosing lamellae of pale orange uorescence, sporinite (ES), telalginite (TA Botryococcus genus), mineral matter (MM), and cutinite
(CT); 4) sporinite (ES) and spores inclusions in amorphous organic matter; 5) sporinite (ES) and fragments of megaspores (ES), mineral matter (MM), liptodetrinite (LD);
6) cutinite (CT), sporinite (ES) of pale orange uorescence, and mineral matter (MM).

predominates over collodetrinite. The major organic component in
the carbonaceous shale is lamalginite, which appears as long anasto-
mosing lamellae of pale orange uorescence. Sporinite and telalginite
(algae from Botryococcus genus) are also common. Vitrinite is not dif-
cult to nd and various populations coexist (Fig. 10).
The mean random reectance of the collotelinite particles (Rr)
varies from 0.88 to 1.04% (Fig. 11, Table 4). The liptinite spectral uo-
rescence parameters obtained for samples show the max values vary-
ing from 610 nm to 650 nm (Fig. 12, Table 4). These max values,
based on Mukhopadhyay (1994), indicate equivalent vitrinite reec-
tance (Rreq) values from 0.83 to 1.10%. The Spore Coloration Index
(SCI) ranges from 6.5 to 7.0 and from 7.5 to 8.0 (Table 4) corroborating
with vitrinite reectance data.
4.6. Geochemistry analysis
Total organic carbon varies from 2.4 to 44.0 wt.%, and sulfur is
present in moderate to high contents (Table 5). GCMS analyses
evidenced a predominance of odd even saturated hydrocarbons and
the presence of -hopanes and and steranes (Fig. 13).
Biomarker ratios, such the 20S/(20S + 20R) and /( + )
for C29 regular steranes, conrm the maturity of the organic matter
as determined by optical parameters (e.g. vitrinite reectance, uo-
rescence spectra and SCI).
5. Discussion
Among the maceral groups, microscopic analysis revealed a pre-
dominance of lipitinite and vitrinite over inertinite, while carbargilite
is the most abundant microlithotypes. The TOC content is bellow
50 wt.% and sulfur is present in moderate to high proportions.
Palynofacies analyses demonstrated good results for the recognition
of preserved organic matter, including changes in paleoenvironmental
conditions throughout the sedimentary succession.
The random vitrinite reectance (Rr) varies from 0.88 to 1.04%. The
liptinite spectral uorescence parameters obtained for samples show
the max values varying from 610 to 650 indicating equivalent vitri-
nite reectance (Rreq) values from 0.83 to 1.10%. These results conrm
that the equivalent vitrinite reectance (Rreq) for samples presents
an excellent correlation with the measured vitrinite reectance (Rr).
GCMS analyses evidenced a predominance of even saturated hydro-
carbons and the presence of -hopanes and -steranes. The
coaly samples t in the category of High-Volatile A Bituminous
Coal (ISO, 11760: 2005).

Fig. 11. Photomicrographs taken under reected white light showing vitrinite particles used to determine the rank of the Bonito coal samples (VT vitrinite; MM mineral matter).
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336 33

Table 4 Table 5
Vitrinite reectance (Rr%), SCI (spore coloration index) and uorescence spectra Geochemical data (TOC and TS) of the Bonito coal seam samples.
(max) data of the Bonito coal seam samples. Samples TOC TS (%) IR Thickness (m)
(wt%)
Samples Vitrinite reectance SCI max XII 41.50 1.00 92 0.16
XI 26.10 0.62 96 0.17
Whole rock Kerogen concentrate
X 29.80 5.70 96 0.15
N. Rr% SD V N. Rr% SD V
IX 20.70 9.20 96 0.55
I 50 0.96 0.096 0.0086 50 0.98 0.0543 0.0031 7.58.0 625
II 50 0.97 0.0508 0.0026 50 0.95 0.0871 0.0076 7.58.0 630
III 50 0.91 0.061 0.0037 50 0.91 0.0628 0.0039 6.57.0 VIII 37.70 9.90 95
IV 50 0.95 0.0324 0.0010 50 0.94 0.022 0.0050 7.58.0 625 Bonito coal
seam VII 40.80 0.60 98
V 30 1.04 0.1084 0.0117 50 0.97 0.0743 0.0055 7.58.0 650 1.05
3.40
VI 50 0.97 0.0671 0.0045 50 0.95 0.0475 0.0023 7.58.0
VII 50 0.88 0.068 0.0046 50 0.89 0.0393 0.0015 6.57.0 610 VI 44.00 1.55 97
VIII 50 0.92 0.0478 0.0023 50 0.92 0.0308 0.0009 6.57.0 610
V 2.40 3.45 45 0.14
IX 50 0.89 0.0998 0.0100 50 0.92 0.0311 0.0100 6.57.0 610
X 50 0.88 0.0258 0.0007 50 0.93 0.0382 0.0015 6.57.0 610 IV 24.60 15.50 96
XI 50 0.89 0.0068 0.0046 50 0.91 0.0651 0.0042 6.57.0 610 0.85
XII 50 0.97 0.1084 0.0550 50 0.98 0.034 0.0012 7.58.0 630 III 26.30 1.30 98
N. (number of measures); Rr% (random vitrinite reectance); SD (standard deviation); II 2.60 0.45 96 0.10
V (variance); SCI (spore coloration index); max (lambda maximum).
I 39.40 2.70 94 0.23

TOC (total organic carbon); TS (total sulphur); IR (insoluble residue).

Palynological analyses demonstrated abundant and well-preserved
palynomorphs showing a dominance of bisaccate pollen grains related
to gymnospermic plants. Wood fragments preserved as coalied com-
pression show the presence of lycophyta. Changes in the palynooral
composition were observed from the base to the top of the analyzed
prole. The basal palynological association, which is dominated by
palynomorphs with gymnosperm afnity, indicates a close relationship
with the ScheuringipollenitesCaheniasaccites association, according the
criteria of Marques-Toigo and Corra da Silva (1984). This peat plant-
community was interpreted by the authors to occupy moist soils just
outside the precursor mires. The abundance of poorly preserved,
coalied material in the intermediary level supports the inferences of
Kalkreuth et al. (2010) about the locally thermally altered conditions
by igneous intrusions (diabase).
The palynological association identied in the top level shows a
different composition in relation to those of the basal and intermedi-
ate levels, showing a clear dominance of pteridophytic spores. It could
be included in the PunctatisporitesLundbladisporaPortalites associa-
tion related by the authors to peat-forming vegetation developed at
the swamp margin.
The peat-forming environments that generated the palynological
association under review in this study can be compared with those
inferred by Cazzulo-Klepzig et al. (2005, 2007) for the most impor-
tant coal seams in the southernmost Paran basin.
Based on the evidence presented above, it can be inferred that paleo-
ecological conditions favorable to the development of the different plant
communities have changed along the depositional interval, from a gym-
nosperm to an arborescent lycophyte-dominated plant community.
Evidence from the absence of abraded edges in almost all macro-
scopic fossil charcoal indicates short transport and autochthonous/
hypoautochtonous origin for this material. Otherwise, the homogeni-
zation of the cell walls indicates a maximum temperature of charring
of between 340 and 600 C. These are also temperatures characteris-
tic of the burning region in actual smoldering peat ground res
(Jasper et al., 2011).
The abundance of macroscopic fossil charcoal in samples subjacent
and suprajacent to the Bonito coal Sample I is presently considered

Fig. 12. Diagram showing uorescence spectral curves of the liptinites from Bonito coal samples.
34 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336

Fig. 13. Gas chromatograms of n-alkanes, isoprenoids, terpanes, and steranes of Bonito coal extracts.

as a direct evidence of wildres (Scott, 2010). Besides, the presence of
inertinite along almost all the coaly prole leads of the hypothesis that
the occurrence of this maceral can be considered as direct evidence of
re during peat deposition, as accepted by Scott (2002, 2010).
The occurrence of abundant gymnosperm wood charcoal in
the base of the coaly bed (just underlying the basal gymnosperm-
dominant palynological association) and the dense association of
highly compressed lycophyte stems in the roof of the mine overlying
the spore-dominant (pteridophytic) association support the inferred
paleoecological change in the plant association detected by palyno-
logical analyses.
Taking into account the paleoecological interferences established
by Guerra-Sommer et al. (1991, 2008b) about the adaptation of the
arborescent lycophytes communities of the Brasilodendron type to
coastal environments in south Brazilian Gondwana, a shift to a more
coastal depositional environment can be hypothesized for the roof
shale in relation to the coaly material underlying shale level.
Recently, Kalkreuth et al. (2010) using sequence stratigraphy
method for analyzing the coal-bearing interval in the Santa Catarina
coal basin concluded that major peat accumulation occurred in
estuarine-barrier, shore face depositional environment. Based on
organic petrography and geochemical studies, the same authors
 J.G. Mendona Filho et al. / International Journal of Coal Geology 111 (2013) 2336
identied a highly variable maceral composition and a coal rank
ranging from HVB to LVB.
6. Conclusions
Changes in the palynooral composition indicate changes in paleo-
ecological condition that have favored the development of different
plant communities during the time span of deposition. Firstly, the
forested scenario would be dominated by plants with gymnosperm
afnities, and after it would change to a lycophyte, arborescent-like
plant domain. The presence of coalied palynological material in the
intermediate level of the studied sequence corroborates the interpre-
tation that locally the carbonaceous rocks were thermally altered by
igneous (diabase) intrusions.
According to petrographic and geochemical parameters, the coaly
samples t in the category of High-Volatile A Bituminous Coal. The
joint occurrence of charcoalinertinite in the Bonito prole suggests
that the system (mire and near surroundings) was regularly subject
to wildres.
Acknowledgments
The authors express gratitude to the nancial support of Conselho
Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq).
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