Marine and Petroleum Geology 126 (2021) 104917

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Marine and Petroleum Geology

journal homepage: www.elsevier.com/locate/marpetgeo

Changes in depositional paleoenvironment of black shales in the Permian

Irati Formation (Paraná Basin, Brazil): Geochemical evidence and
aromatic biomarkers
Caroline Adolphsson do Nascimento a, Eliane Soares de Souza a, *, Laercio Lopes Martins a,
Hélio Jorge Portugal Severiano Ribeiro a, Victor Hugo Santos a, René Rodrigues b
a
Laboratory of Petroleum Engineering and Exploration (LENEP), North Fluminense State University (UENF). Rodovia Amaral Peixoto, Km 163, Avenida Brennand,
Imboassica. Macaé, Rio de Janeiro, 27925-535, Brazil
b
Department of Stratigraphy and Paleontology, Faculty of Geology, Rio de Janeiro State University (UERJ). Rua São Francisco Xavier 524, Maracanã, Rio de Janeiro,
Rio de Janeiro, 20550-013, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Physicochemical changes that occurred during deposition of Irati black shales were investigated via outcrop
Irati Formation samples collected in the northeastern and central-eastern Paraná Basin. Various traditional geochemical in­
Source rock dicators were used, in addition to newly detected biomarkers: C32 lanostane, simonellite, sempervirane, and
Lanostane
C32–C35 benzohopanes. Bulk geochemistry parameters, mineralogy, and conventional saturated biomarkers, such
Multivariate statistical analysis
Simonellite
as tetracyclic polyprenoids (TPPs), reflect restricted and hypersaline marine deposition with freshwater input
Sempervirane and increased terrigenous contribution toward the top of the studied outcrops. This led to stratification of the
Benzohopanes water column, establishing euxinic conditions in the photic zone and reducing conditions at the bottom of the
Aryl isoprenoids water column, which enhanced preservation of organic matter. Principal component and hierarchical cluster
analyses were performed to group the samples according to their similar geochemical characteristics: prevailing
marine environment (basal outcrop samples) and higher freshwater inflow with greater terrigenous contribution
(top outcrop samples). These geochemical observations were corroborated by aromatic biomarkers such as tri­
aromatic steroids, trimethylnaphthalenes, simonellite, and sempervirane. The aryl isoprenoid ratio (AIR) in­
dicates persistence of photic zone euxinia (PZE) during Irati black shale deposition. The presence of C32 lanostane
and C32–C35 benzohopanes is directly related to the hypersaline depositional environment of the analyzed
samples. Finally, the C32-33/C32-35 benzohopane ratio is proposed as a thermal maturity proxy because variations
in the ratio can be linked to the presence of a diabase sill and temperature catalyst minerals near one of the
outcrops.

1. Introduction
The intracratonic Paraná Basin is situated in the central-eastern
portion of South America, and its evolutionary history consists of cy­
cles of accelerated subsidence induced by orogenic events (Zalán et al.,
1990). As a consequence of these cycles, marine incursions into the
paleocontinent allowed deposition of organic-rich sediments in an
anoxic epicontinental sea, such as the black shales of the Irati Formation
(Araújo et al., 2001; Milani et al., 2007).
The Irati Formation exemplifies some of the most favorable
geochemical conditions for excellent potential source rock in the world,
with type I/II organic matter content reaching over 20 wt% (Mello et al.,
1993; Reis et al., 2018). Although these black shales have been the
subject of several studies, there is still disagreement regarding the
physicochemical conditions of the paleoenvironment during their
deposition. While many works have proposed a normal to hypersaline
marine environment based on faciological analyses, fossil content, and
organic and inorganic geochemistry parameters (Rodrigues and Quad­
ros, 1976; Cerqueira and Santos Neto, 1986; Hachiro, 1997), others have
suggested deposition of the Irati Formation in fresh or brackish waters
based on the almost complete absence of marine diagnostic elements in
the palynology, geochemical parameters, and stable isotope data

* Corresponding author.
E-mail address: eliane@lenep.uenf.br (E.S. Souza).

https://doi.org/10.1016/j.marpetgeo.2021.104917
Received 22 May 2020; Received in revised form 5 January 2021; Accepted 7 January 2021
Available online 16 January 2021
0264-8172/© 2021 Elsevier Ltd. All rights reserved.
C.A. Nascimento et al.
(Mendes et al., 1966; Amaral, 1971; Petri and Coimbra, 1982; Correa da
Silva and Cornford, 1985; Faure and Cole, 1999).
According to Araújo et al. (2001), oscillations of the paleoenvir­
onmental redox potential, the organic primary productivity rate, and
relative sea-level led to compositional heterogeneities, which are re­
flected in different organic facies in this unit. Geochemical indicators
based on organic carbon content, stable carbon isotope ratios, Rock-Eval
pyrolysis, and saturated biomarker results have been used to interpret
these depositional conditions (e.g., Reis et al., 2018; Nascimento et al.,
2018; Martins et al., 2020a). More recently, Goldberg and Humayun
(2016) used redox-sensitive elements to infer the degree of oxygenation
of the water column during deposition of the Irati black shales.
In addition to saturated biomarkers used in conventional geochem­
ical analyses, aromatic biomarkers, although little used in Irati Forma­
tion studies, can play an important role in the interpretation of organic
Fig. 1. Paraná Basin location, with outcrop area and thickness of the supersequence Gondwana I and outcrops of Irati black shales [Amaral Machado (1) and São
Mateus do Sul quarries (2)] used in this research (Modified from Milani, 2004).
2
Marine and Petroleum Geology 126 (2021) 104917
matter source input, degree of maturity, and paleoredox conditions.
Aromatic compounds first detected in the Irati Formation show that
freshwater inflows into the Irati Sea promoted algal blooms, water col­
umn stratification, and photic zone euxinia (Martins et al., 2020b), and
carried terrigenous organic matter into the Irati Sea (Martins et al.,
2020c).
The aim of this research was to interpret the physicochemical con­
ditions during deposition of the Irati black shales with outcrop samples
from two different and distant sites at the northeastern border and the
central east of the Paraná Basin, in addition to samples from the Serra
Alta Formation. A variety of geochemical indicators, including some
newly detected biomarkers, were used to retrace the depositional con­
ditions that led to organic facies with some of the highest observed
organic carbon contents in the world.
C.A. Nascimento et al.
2. Geological settings
The intracratonic Paraná Basin is located in the central-eastern
portion of the South American continent and covers approximately 1.5
million square kilometers in Brazil, Paraguay, Argentina, and Uruguay
(Fig. 1). Paleozoic, Mesozoic, and Cenozoic sedimentary rocks in the
basin are associated with Cretaceous volcanic rocks (Zalán et al., 1990;
Milani et al., 2007).
Milani et al. (2007) recognized six supersequences in the stratig­
raphy of the Paraná Basin. These are defined as distinct rock layers
delimited by regional unconformities, which represent long periods of
erosion and non-deposition during the geological history of this basin.
The supersequences are characterized by (i) Paleozoic
transgressive-regressive sea-level cycles, represented by the super­
sequences Rio Ivaí (Ordovician to Silurian), Paraná (Devonian), and
Gondwana I (Carboniferous to Lower-Triassic), and (ii) cycles of conti­
nental systems deposition associated with strong magmatism, repre­
sented by the supersequences Gondwana II (Middle to Upper-Triassic),
Gondwana III (Upper-Jurassic to Lower-Cretaceous), and Bauru
(Upper-Cretaceous) (Fig. 2).
According to Milani et al. (2007), the supersequence Gondwana I, at
approximately 2300 m thick, includes a complete
transgressive-regressive cycle that was the result of the invasion and
subsequent withdrawal of the Panthalassa Ocean over the Gondwana
continent. The cycle started with periglacial deposits from the Itararé
Group, passed through the coastal and platformal deposits from the
Guatá Group and the base of the Passa Dois Group, and finally reached
continental conditions with deposition of lacustrine, fluvial, and eolian
sediments on the top of the Passa Dois Group.
The Permian (Artinskian-Kungurian) Irati Formation (Santos et al.,
2006; Rocha-Campos et al., 2011) is subdivided into Taquaral and
Assistência Members (Barbosa and Gomes, 1958). The Taquaral Member
(at the base) is characterized by a normal salinity marine environment
with a restricted connection to the ocean, whereas the Assistência
Member (at the top) has carbonates interbedded with bituminous shales,
which are related to southwest-inclined ramps, connected to the Pan­
thalassa only in the southernmost region of the paleocontinent (Santos
Neto and Cerqueira, 1993; Araújo et al., 2001; Rodrigues et al., 2010).
Reis et al. (2018) divided these sediments into chemostratigraphic units
based on their total organic carbon (TOC) and insoluble residue values
as well as their saturated biomarker contents. According to this study,
the bituminous shales in the Irati Formation are located in units E and H,
which represent a transgressive systems tract in two fourth-order
sequences.
The Irati Formation outcrop extends approximately 1700 km and its
Fig. 2. Simplified stratigraphic chart of the Paraná Basin with emphasis on supersequence Gondwana I, showing the Taquaral and Assistência Members from the Irati
Formation (modified from Milani et al., 2007) and its chemostratigraphic units based on Reis et al. (2018).
3
Marine and Petroleum Geology 126 (2021) 104917
average thickness is 40 m, reaching 70 m in the basin depocenter
(Mendes et al., 1966; Corrêa and Pereira, 2005). The end of deposition of
these bituminous shales is marked by non-bituminous gray laminated
shales of the Serra Alta Formation (Gama Jr., 1979). The base of this
formation was deposited in a highstand systems tract marked by a
pronounced decrease in TOC and sulfur (S) values (Araújo et al., 2001).
The Irati black shales are the source rock of the atypical petroleum
system Irati-Rio Bonito/Pirambóia(!) (Zalán et al., 1990; Milani and
Zalán, 1999). These black shales are generally immature because they
were not sufficiently buried to enter the oil window (Zalán et al., 1990;
Milani and Zalán, 1999; Milani et al., 2007). However, it has been
suggested that Cretaceous igneous intrusions of the Serra Geral Forma­
tion provided the necessary temperature for oil generation in some lo­
cations of the Paraná Basin (Cerqueira and Santos Neto, 1986; Araújo
et al., 2000; Corrêa and Pereira, 2005; Thomaz Filho et al., 2008; Santos
et al., 2009).
3. Materials and methods
3.1. Samples
A total of 20 samples from the Irati Formation were collected from
outcrops in two cities in the Paraná Basin (Fig. 1) - seven from a quarry
in the Amaral Machado Mining Company area near Saltinho City (1,
Fig. 1; São Paulo State), and the other 13 from two outcrops 700 m from
each other representing two organic-rich layers, the Lower and the
Upper Shale (designated SM Lower and SM Upper outcrops), at the
Petrobras Shale Industrialization Unit (SIX) quarry in the São Mateus do
Sul City (2, Fig. 1; Paraná State). Additionally, four samples were
collected in the outcrop of Amaral Machado (AMa) above the horizon of
black shales in order to understand the conditions at the end of Irati
Formation deposition. These samples represent dark gray shales that are
interpreted here as belonging to the Serra Alta Formation. Table S1
(Supplementary Material) displays the code for samples and heights in
relation to the base of the outcrops. Although the lower and upper shales
were collected from two outcrops in the São Mateus do Sul (SM) SIX
quarry, these horizons stratigraphically overlap and are separated by a
5-m carbonate layer (Alferes et al., 2011), while all samples from AMa
were interbedded with thin carbonate layers in outcrop.
3.2. TOC and Rock-Eval pyrolysis
The TOC and sulfur content were determined using 1 g of pulverized
rock samples (<80 mesh) in a LECO 628CN instrument, and the results
are expressed as a mass percentage relative to the total mass of the
C.A. Nascimento et al.
analyzed sample. Prior to these analyses, the samples were treated with
4 M HCl to remove the carbonates. Rock-Eval pyrolysis was performed
using the Rock-Eval 6 instrument (Vinci Technologies), at programed
temperatures between 300 and 650 ◦ C, where the S1, S2, S3, and TMAX
values were determined. It was also possible to calculate the hydrogen
index (HI) and the oxygen index (OI) using the TOC, S2, and S3 values.
3.3. Extraction and separation
Organic extracts were obtained from 90 to 150 g of each sample
using a Soxhlet system for 48 h with dichloromethane as the solvent
(300 mL). The organic extract was separated into three fractions by
liquid chromatography using silica gel in a glass column 10 mm in
diameter and 25 cm in length. For this fractionation, 40 mg of each
sample was separated into fractions of saturated hydrocarbons, aromatic
hydrocarbons, and polar (NSO) compounds using the mobile phases
hexane (30 mL), hexane:dichloromethane 8:2 v/v (30 mL), and
dichloromethane:methanol 9:1 v/v (30 mL), respectively, as previously
described by Nascimento et al. (2018). Serra Alta shales were pretreated
with colloidal copper to remove crystals of sulfur (Blumer, 1957)
precipitated after extraction with dichloromethane.
3.4. X-ray diffraction
X-ray diffraction analyses were performed using 5 g of whole rock
powder (<270 mesh) through a D2 Phaser diffractometer (Bruker AXS)
using CuKα radiation (30 kV/10 mA), with patterns of 0.02◦ 2θ and
collection time of 2 s per step, from 5 to 70◦ 2θ (Martins et al., 2020c).
After the acquisition of diffractograms, the qualitative analysis was
conducted using Diffrac.EVA 4.0 software, which enables identification
of crystalline substances by comparing the diffractogram with individ­
ual phase diffractometric patterns provided by the International Center
for Diffraction Data (ICDD). DIFFRACplus TOPAS version 4.2 (Bruker
AXS), which is based on the Rietveld process for phase refinement, was
used to obtain the results in quantitative terms.
3.5. Stable carbon isotope composition
The stable carbon isotope composition of 1 mg of the whole organic
extract was analyzed using a Thermo Finnigan Mass Spectrometer (Delta
V Advantage), and the δ13C (‰) was reported in relation to the inter­
national PDB (Peedee Formation Belemnitella americana, from Upper
Cretaceous, South Carolina, USA) standard. The gases used were helium
as the carrier, O2 for combustion, and CO2 as the standard. Isodat 2.5
software was used for data acquisition and treatment.
3.6. Gas chromatography with flame ionization detector
The whole organic extracts of the Irati black shales and Serra Alta
shales were analyzed by gas chromatography with flame ionization
detector to assess the n-alkanes and the isoprenoids pristane and
phytane. The analysis was performed using an Agilent 6890N gas
chromatograph, equipped with an HP-5 fused silica capillary column
(30 m × 0.32 mm x 0.25 μm). Helium was used as the carrier gas in
splitless mode at a constant flow of 2.2 mL min− 1. The oven temperature
program was initially held at 40 ◦ C for 1 min, then heated at 6 ◦ C min− 1
to 310 ◦ C, followed by an isothermal period of 16 min. The injector and
detector temperatures were 290 and 320 ◦ C, respectively.
3.7. Gas chromatography coupled to mass spectrometry
The saturated and aromatic fractions from the organic extracts of the
Irati black shales and Serra Alta shales were analyzed using an Agilent
7890A gas chromatograph equipped with an HP-5 MS column (30 m ×
0.25 mm x 0.25 μm film thickness) coupled to an Agilent 5975C-MSD
selective mass detector. Helium was used as the carrier gas at a
4
Marine and Petroleum Geology 126 (2021) 104917
constant flow of 1 mL min− 1. The mass spectrometer was operated on
full scan (50–550 Da) and selected ion monitoring (SIM) modes in
splitless mode. For the saturated fraction, the oven temperature program
was initially held at 60 ◦ C for 2 min, then heated at 22 ◦ C min− 1 to
200 ◦ C, held for 3 min, and heated again at 3 ◦ C min− 1 to 300 ◦ C, fol­
lowed by an isothermal period of 25 min (based on the procedure
described by Martins et al., 2017). β-carotane, regular hopanes and
gammacerane, steranes, and tetracyclic polyprenoid were examined
using m/z 125, 191, 217, and 259, respectively, in SIM mode. The initial
oven temperature for the aromatic fractions was 80 ◦ C. It was heated at
2 ◦ C min− 1 to 300 ◦ C, held for 20 min, then heated at 10 ◦ C min− 1 to
310 ◦ C, and held for 1 min (based on Nytoft et al., 2016). Aryl iso­
prenoids, trimethylnaphthalenes, cadalene, benzohopanes, retene, C18
1,1,7,8-tetramethyl-1,2,3,4- tetrahydrophenanthrene, triaromatic ste­
roids, and simonellite and sempervirane were examined using m/z 133,
170, 183, 191, 219, 223, 231 and 237, respectively, in SIM mode. The
injector and transfer line temperatures were 300 ◦ C for both methods.
The biomarker ratios were calculated based on peak areas from the
selected mass chromatograms.
3.8. Principal component and hierarchical cluster analyses
Multivariate statistical analysis of the geochemical data was per­
formed using R software (R Core Team, 2013) for data processing. Ten
geochemical parameters were used in the analyses, including TOC, S2,
carbon isotope ratio (δ13C), tetracyclic polyprenoid ratio (TPP/Dia27),
hopane/sterane (Hop/Ste), C29/C27 steranes (C29/C27 Ste), gammacer­
ane/C30 hopane (Gam/C30H), β-carotane/C30 hopane (βC/C30H), and
pyrite and sulfur percentages. Principal component analysis (PCA) was
performed from a 24 × 10 correlation matrix (24 samples x 10 param­
eters), where Eigenvalues and eigenvectors were extracted from the
original data to construct the new variables or principal components,
which are linear combinations of all the independent variables. For the
hierarchical cluster analysis (HCA), it was used the Ward.D grouping
method, and the Canberra metric distance.
4. Results and discussion
4.1. Conventional geochemical analyses
4.1.1. Bulk parameters
The studied Irati sample set consists of bituminous shales with high
TOC content (3.2–25.4 wt%), high values of S2 (13.7–135.8 mg HC/g
rock), and HI (366–716 mg HC/g TOC), pointing to excellent potential
for oil generation, although TMAX values below 430 ◦ C suggest thermally
immature organic matter (Fig. 3; Tissot and Welte, 1984; Espitalié et al.,
1986). These results can be related to the Reis et al. (2018) studies using
well samples, in which the two organic-rich layers from the Irati For­
mation were classified as units E, which corresponds to the SM Lower
outcrop in the current study, and H, which corresponds to the SM Upper
outcrop and the AMa Irati black shales. On the other hand, Serra Alta
shales AMa 25, 26, 28, and 29 at the top of the AMa outcrop contain very
low TOC (<0.5%), low values of S2 (<0.5 mg HC/g rock), and HI (<90
mg HC/g TOC; Fig. 3), relating to non-bituminous shales with low
oil-generating potential. TOC and Rock-Eval pyrolysis data are available
in Table 1. According to the modified Van Krevelen diagram (Espitalié
et al., 1986, Fig. 4), the Irati black shales contain type I and II organic
matter likely formed from a mixture of autochthonous organic matter
(phytoplankton, zooplankton, and bacteria), which may represent
lacustrine or marine facies (Tissot and Welte, 1984). In contrast, Serra
Alta shales from the top of the AMa outcrop contain type III organic
matter, probably formed from continental plants and detritus, typical of
highstand systems tract (Araújo, 2001).
4.1.2. Thermal maturity
In order to further evaluate the maturity of the samples on the
C.A. Nascimento et al.
Fig. 3. TOC and Rock-Eval pyrolysis data for the Irati black shales and Serra Alta shales.
molecular level, the parameters C29 20S/(20S + 20R), C29 ββ/(ββ + αα),
and C31 22S/(22R + 22S) were assessed based on the isomerization of
the C29 steranes and C31 homohopanes (Fig. 5; calculation procedures in
the Supplementary Material Table S2). Generally, the endpoint values
for these parameters range from 0.52 to 0.55, 0.67 to 0.71, and 0.57 to
0.62, respectively (Seifert and Moldowan, 1980, 1986). It was observed
that most of the samples were below these values except for samples
AMa 1 and 5, which were more thermally evolved than the others,
having values within or above the endpoint range for the C31 22S/(22R
+ 22S) ratio.
Although samples AMa 1 and 5 had the lowest TMAX values (404 and
405 ◦ C, respectively), Martins et al. (2020c) noted the presence of more
clay minerals, mainly montmorillonite (from the smectite group), in the
basal samples of the AMa outcrop (see also the x-ray diffractograms in
Fig. 6). Clay-rich rocks can influence pyrolysis experiments (Horsfield
et al., 1983; Yang and Horsfield, 2016) and according to Dembicki
(1992), montmorillonite can act as a catalyst, decreasing the tempera­
ture required for kerogen cracking in Rock-Eval pyrolysis, and conse­
quently the TMAX values. In addition, studies carried out by Seifert
(2013) in well FP-12 (Anhembi, SP) in the same region of the AMa
outcrop showed a 2.4 m diabase sill below the samples that would
5
Marine and Petroleum Geology 126 (2021) 104917
correspond to the AMa outcrop base. Therefore, the sum of the igneous
effect of the intrusive rock together with the presence of clay minerals is
the most plausible explanation for the greater thermal maturity
observed in these samples.
4.1.3. Depositional paleoenvironment
The depositional paleoenvironment and organic matter input for the
Irati black shales and Serra Alta shales were investigated using δ13C, key
saturated biomarker parameters including TPP/Dia27, Hop/Ste, C29/
C27 Ste, pristane/nC17 (Pr/nC17), phytane/nC18 (Ph/nC18), Gam/C30H,
βC/C30H, and by their mineralogical composition (Figs. 6 and 7;
Table 1). All of these parameters show a decreasing trend in marine
input with a concomitant increase in terrigenous input toward the top of
the outcrops, except for sample SM 3.7.
Analyses of δ13C values suggest an increase in terrigenous input to­
ward the top of the three outcrops since the values decrease from
approximately − 22 to − 28‰ at the AMa outcrop and − 22 to − 25‰ at
the SM outcrops and, according to Meyers (1994), δ13C values decrease
from marine algae (− 16 to − 23‰) to freshwater algae (− 26 to − 30‰;
Fig. 7). Araújo (2001) previously suggested that the most positive δ13C
values (− 22 to − 25‰) in the Irati black shales are associated with
 C.A. Nascimento et al.
Table 1
TOC, sulfur content (S), Rock-Eval, carbon isotope ratio (δ13C), and saturated biomarker data used for the interpretation of the Irati black shales and Serra Alta shales, including the geochemical parameters used in the PCA
and HCA analyses.
Samples TOCa Sa S1 (mg HC/ S2a (mg HC/ S3 (mg HC/ HI (mg HC/ OI (mg CO2/ TMAX PI (wt. δ13Ca Hop/ TPP/ C29/ Gam/ βCIa Pyritea Pr/ Ph/
(%) (%) g rock) g rock) g rock) g TOC) g TOC) (◦ C) ratio) (‰) Stea Dia27a C27 C30Ha (%) nC17 nC18
Stea

AMa 29 0.07 0.40 0.02 0.27 0.20 64 2.86 431 0.07 − 28.30 12.37 1.23 0.62 0.01 0.00 0.33 0.57 0.18
AMa 28 0.05 0.43 0.01 0.17 0.17 53 3.40 432 0.06 − 28.17 10.42 1.06 0.60 0.01 0.00 0.24 0.63 0.19
AMa 26 1.48 1.32 0.02 0.35 0.20 73 0.14 427 0.05 − 28.71 12.21 1.45 0.58 0.01 0.00 0.75 0.35 0.16
AMa 25 0.40 0.96 0.02 0.44 0.21 88 0.53 427 0.04 − 28.16 10.35 2.04 0.60 0.01 0.00 0.28 0.35 0.15
AMa 24 7.18 1.34 1.83 48.31 0.16 716 0.02 439 0.04 − 27.99 5.47 4.02 0.52 0.02 0.01 1.20 3.84 2.27
AMa 23 6.40 5.59 3.66 32.89 0.28 552 0.04 428 0.1 − 26.61 9.32 2.16 0.54 0.03 0.02 5.66 5.08 3.27
AMa 17 5.99 4.57 2.27 29.01 0.19 569 0.03 424 0.07 − 23.06 7.56 0.07 0.49 0.89 0.02 3.33 4.39 5.46
AMa 11 6.38 4.95 3.86 33.73 0.16 620 0.03 421 0.1 − 22.01 3.31 0.07 0.42 0.92 0.03 3.31 3.90 6.19
AMa 7 5.52 4.81 3.94 26.73 0.35 564 0.06 418 0.13 − 22.22 2.53 0.04 0.40 0.96 0.05 2.85 2.89 5.78
AMa 5 4.30 4.50 2.59 13.71 0.20 406 0.05 402 0.16 22.95 2.24 0.03 0.36 0.53 0.05 2.23 2.51 6.77
6

−
AMa 1 3.83 2.60 4.19 17.37 0.12 534 0.03 397 0.19 − 23.52 2.07 0.02 0.37 0.28 0.05 1.78 2.81 9.48
SM 3.7 23.17 3.43 7.53 102.60 1.08 443 0.05 422 0.07 − 25.43 1.26 0.13 0.42 0.49 0.02 4.57 8.03 13.96
SM 3.6 14.99 4.07 5.61 78.50 0.48 524 0.03 424 0.07 − 22.65 11.08 3.90 0.47 0.50 0.06 5.92 8.34 11.11
SM 3.5 15.37 3.79 6.34 109.49 0.40 712 0.03 423 0.05 − 22.94 9.64 4.64 0.48 0.59 0.08 4.78 8.52 12.00
SM 3.4 12.66 2.72 5.92 88.35 0.32 698 0.03 424 0.06 − 22.36 6.17 1.63 0.49 0.68 0.13 3.36 8.17 11.28
SM 3.3 7.23 3.48 3.45 45.39 0.28 628 0.04 424 0.07 − 23.10 5.04 1.84 0.49 0.88 0.13 4.44 8.16 11.71
SM 3.2 11.89 4.85 5.26 76.16 0.37 641 0.03 425 0.06 − 21.98 4.49 1.80 0.47 1.21 0.14 4.97 5.90 9.67
SM 3.1 9.50 4.91 3.74 59.47 0.37 626 0.04 422 0.06 − 22.10 2.76 1.50 0.46 1.36 0.13 6.33 3.80 7.22
SM 2.6 5.48 5.10 2.48 20.07 0.19 366 0.03 424 0.11 − 25.09 7.20 3.06 0.49 0.04 0.04 4.74 6.87 11.04
SM 2.5 25.38 4.49 9.01 135.80 0.61 535 0.02 428 0.06 − 24.17 4.63 1.08 0.49 0.27 0.01 5.41 3.96 7.14
SM 2.4 22.60 6.87 7.24 114.61 0.49 507 0.02 425 0.06 − 23.57 2.99 1.43 0.42 0.43 0.05 10.22 3.29 6.37
SM 2.3 11.67 8.89 4.67 65.11 0.26 558 0.02 424 0.07 − 22.84 2.21 1.25 0.42 0.80 0.09 6.55 4.29 8.51
SM 2.2 9.10 8.20 4.54 52.77 0.23 580 0.03 421 0.08 − 22.81 1.96 1.86 0.42 0.77 0.13 7.80 4.41 8.69
SM 2.1 6.27 5.33 3.71 33.80 0.21 539 0.03 420 0.1 − 23.39 1.46 1.32 0.41 0.99 0.17 7.08 5.46 9.48

Marine and Petroleum Geology 126 (2021) 104917

a
Geochemical parameters used in the PCA and HCA analyses.
C.A. Nascimento et al.
Fig. 4. Modified Van Krevelen diagram showing the sample distribution rela­
tive to types I, II, and III organic matter pathways.
autochthonous amorphous organic matter deposited in a transgressive
systems tract, while the most negative values (≈− 27‰) are from
allochthonous terrigenous organic matter deposited in a highstand sys­
tems tract context.
The C30 tetracyclic polyprenoid 18α(H) 21R and 21S isomers (I, TPP;
see chemical structure in Appendix A) were detected in all Irati samples
(monitoring m/z 259; Fig. 8), and the increase in TPP/Dia27 (Fig. 7; see
calculation procedures in the Supplementary Material Table S2 ac­
cording to Silva et al., 2011) toward the top of the outcrops may reflect
an increase of non-marine organisms such as freshwater algae (Holba
et al., 2000, 2003; Araújo et al., 2018). The values of this ratio behave
Fig. 5. Thermal maturity plots of (a) C29 20S/(20S + 20R) vs. C29 ββ/(ββ + αα) and (b) C29 20S/(20S + 20R) vs. C31 22S/(22R + 22S), and a representative
distribution of biomarkers in the mass chromatograms (c) m/z 191 and (d) m/z 217 of the Irati and Serra Alta shales.
7
Marine and Petroleum Geology 126 (2021) 104917
like to those of δ13C (Figs. 7 and 9a; top outcrop samples AMa 23 and 24,
SM 2.6, 3.3 to 3.6 with higher TPP/Dia27 and δ13C values), corrobo­
rating freshwater influx into the depositional paleoenvironment, except
for sample SM 3.7, where the low TPP/Dia27 value could characterize a
new episode of a rise in sea level and loss of freshwater input. Following
this reasoning, TPP/Dia27 can be applied to retrace freshwater in­
cursions in a depositional paleoenvironment.
Along with δ13C and TPP/Dia27, the Hop/Ste values increase toward
the top of the outcrops (Fig. 7), corroborating the rising terrigenous
contribution to the organic matter in the Irati black shales, since low
Hop/Ste values are typical of marine organic matter with higher
planktonic contribution and/or benthic algae, while high Hop/Ste ratios
are more common in terrigenous organic matter (Moldowan et al.,
1985). Also, Reis et al. (2018) reported higher values of the Hop/Ste
ratio together with a higher proportion of pollen grains toward the top of
the organic-rich shale layers (units E and H), indicating the influence of
higher plants. Once again, sample SM 3.7 behaved differently from the
others, showing a low value of Hop/Ste, which points to its more marine
character.
The increase in the C29/C27 Ste ratio toward the top of the outcrops
(Fig. 7) also supports freshwater input into the Irati Sea with increasing
higher plant or green algae contribution. The origin of C29 steranes has
been attributed to land plants or green algae, the ancestors of land
plants, while plankton-derived organic matter is richer in C27 steranes,
having red algae as its source (Huang and Meinschein, 1979; Hoffmann
et al., 1984; Volkman et al., 1994; Schwark and Empt, 2006; Kodner
et al., 2008).
Accordingly, more marine contribution is proposed for the basal
outcrop samples, mainly samples AMa 1, 5, 7, 11, and 17 from the AMa
outcrop and sample SM 3.7 from the SM Upper outcrop, with lower
values of δ13C, TPP/Dia27, Hop/Ste, and C29/C27 Ste (Fig. 9). However,
when these data values for the analyzed samples were higher, greater
freshwater and terrigenous organic matter input into the paleoenvir­
onment was assumed (Fig. 9). The TPP/Dia27 ratio does not separate
Serra Alta samples from most of the SM outcrop samples. Several factors
may influence this response, such as the low organic content of the Serra
C.A. Nascimento et al. Marine and Petroleum Geology 126 (2021) 104917

Fig. 6. X-ray diffractograms of the Irati black shales, showing the mineralogical differences between Amaral Machado and São Mateus do Sul shales. Sme = Smectite;
Ilt = Illite; Ms = Muscovite; Gp = Gypsite; Qz = Quartz; Py = Pyrite.

Fig. 7. δ13C, TPP/Dia27, Hop/Ste, C29/C27 Ste (as indicative of organic matter input), Gam/C30H, βC/C30H, and percentages of S and pyrite (as indicative of
physicochemical conditions) showing the depositional paleoenvironment behavior of the Irati and Serra Alta shales.

Alta shales and low concentrations of biomarkers, or the possibility of
different types of organic matter, such as greater input of freshwater
algae and bacteria (Correa da Silva and Cornford, 1985) in SM shales
than Serra Alta shales, which contain abundant phytoclasts (Martins
et al., 2020a).
Organic matter input is linked to physicochemical conditions of the
depositional paleoenvironment, which can be illustrated by the Pr/nC17
vs. Ph/nC18 plot (Fig. 10; Peters et al., 1999; see representative gas
chromatograms from GC-FID in the Supplementary Material Fig. S1),
where samples from the top of the outcrops, especially AMa 23 and AMa
24, exhibit more oxidizing characteristics and mixed organic matter
input (types II/III), while the samples from the base of the outcrops are

8
C.A. Nascimento et al. Marine and Petroleum Geology 126 (2021) 104917

Fig. 8. Distribution of C27 diasteranes, TPP, and C32 lanostane in mass chromatograms m/z 259 for samples from Amaral Machado and São Mateus do Sul outcrops.

Fig. 9. Distributions of the samples with higher marine or terrigenous contributions based on the plots of (a) TPP/Dia27 vs. Hop/Ste, (b) TPP/Dia27 vs. δ13C, and (c)
TPP/Dia27 vs. C29/C27 Ste.

more reducing and have an algal marine input (type II). In this case, the freshwater. It is interesting to note that Serra Alta samples have Pr/nC17
increase in oxidation and terrigenous input toward the top of the and Ph/nC18 values < 1 (Table 1; Fig. S1 for representative sample AMa
outcrop samples is also presumably linked to the greater influx of 26), resulting in negative logarithmic values. This is due to the greater

9
C.A. Nascimento et al.
Fig. 10. Pr/nC17 vs. Ph/nC18 plot showing the classification of the Irati black
shales according to their oxicity and organic matter type.
n-alkanes abundance in these samples, compatible with the greater
contribution of terrigenous organic matter (Mello et al., 1988). In
addition, Martins et al. (2020b) showed that Pr/Ph ratios < 1 in the
basal samples of the AMa outcrop point to a reducing and hypersaline
environment.
Gam/C30H and βC/C30H responses (Jiang and Fowler, 1986; Mello
et al., 1988; ten Haven et al., 1988; Sinninghe et al., 1995), show the
same trends of variation of the previous parameters, generally
decreasing toward the top of the outcrops (Fig. 7). This suggests a
decrease in salinity and stratification of the water column as a result of
freshwater entering the black shale depositional environment. This
behavior is consistent with increased terrigenous input that probably
resulted from the increased inflow of freshwater toward the top of these
outcrops.
Stratification of the water column and high salinity at the bottom of
the Irati Sea is the probable cause of the reducing conditions verified in
the samples from the base of the outcrops through redox-sensitive pa­
rameters such as sulfur and pyrite percentages (Fig. 7; Lyons and Sev­
ermann, 2006; Goldberg and Humayun, 2016). The marked presence of
pyrite in the Irati black shales from the SM outcrops, particularly for the
SM Lower outcrop (4.7–10.2%), was previously demonstrated by Correa
da Silva and Cornford (1985), who related this to extreme reducing
conditions in an oxygen-deficient water column. At the top of the SM
Upper outcrop (SM 3.5, 3.6, and 3.7 samples; Fig. 7), however, although
salinity declined (see Gam/C30H and βC/C30H ratios), reducing condi­
tions remained strong, as shown by the high values of S (3.4–4%) and
pyrite (4.6–5.9%). This is consistent with the reducing conditions in the
Irati Sea due to water column stratification during deposition of the high
TOC Irati black shales (Martins et al., 2020b). On the other hand, Serra
Alta shales show very low percentages of S and pyrite and very low
Gam/C30H values (Fig. 7), suggesting the absence of salinity-related
density stratification during deposition (Tulipani et al., 2015). This
interpretation is consistent with higher abundance of C30 tetracyclic
polyprenoids (higher TPP/Dia27 ratio) and lower values of δ13C, sug­
gesting extensive freshwater incursion during deposition of these sam­
ples. Depositional dysoxic/oxic conditions during deposition of these
shale rocks also are consistent with very low TOC content (<0.5 wt%)
and low oil generation potential.
In addition to pyrite, other minerals can reflect specific character­
istics of the paleoenvironment during deposition of the Irati black shales
(Holanda et al., 2019). Chemical precipitation of the gypsite (Gp) occurs
in saline environments with little water circulation (Droste, 1961;
Warren, 1999), and its occurrence in the basal Irati black shales from the
AMa outcrop (Supplementary Material Table S3) and absence in the top
outcrop samples (AMa 23 and 24; Fig. 6) is consistent with the hyper­
saline environment. Quartz, on the other hand, shows higher percent­
ages in the SM outcrops, reflecting their more siliciclastic character in
10
Marine and Petroleum Geology 126 (2021) 104917
relation to the AMa outcrop. This behavior occurs because paleogeo­
graphically, SM was located in deeper portions of the Paraná Basin with
greater siliciclastic input while AMa was located in an arid and restricted
environment at the edge of the basin, forming part of an internal car­
bonate ramp (Faure and Cole, 1999; Araújo et al., 2001), which is why
the black shales in this outcrop are interbedded with carbonate layers.
Finally, C32 lanostane (II, Lan32; see chemical structure in Appendix
A and the mass spectrum in Appendix B) was detected for the first time
in the Irati black shales (monitoring m/z 259; Fig. 8). The relative
abundance of this compound does not vary as a function of TPP/Dia27,
with high values corresponding to non-marine organisms, although its
presence can be attributed to hypersaline conditions of the depositional
environment since its relative abundance decreases in samples with
higher freshwater input and decreased salinity (AMa 23 and SM 2.6;
Figs. 7 and 8). Chen et al. (1989) first identified the C30–C32 lanostanes
in Tertiary saline sediments in China. These compounds were also re­
ported in low-maturity crude oils (Peng et al., 1998), in fossilized
immature organic matter derived from hypersaline lakes (Parfenova,
2011), and in sulfur-rich crude oils (Lu et al., 2011). Although lanosterol
is the most likely precursor of lanostane (Birgel and Peckmann, 2008), a
direct correlation cannot be made between C32 lanostane and its bio­
logical precursor since lanosterol can be biosynthesized by plants, ani­
mals, fungi, dinoflagellates, sponges, and methanotrophic bacteria
(Peckmann et al., 2004; Lamb et al., 2007). Like in previous works,
lanostane in Irati black shales characterizes: (1) immature organic ex­
tracts since it was not detected in the more mature samples AMa 1 and 5;
(2) deposition under high salinity conditions since it has lower relative
abundances in the samples with higher freshwater input and was not
detected in Serra Alta shales; and (3) sulfur-rich environments.
4.1.4. Multivariate statistical analysis
Taking into account the conventional geochemical parameters used
to analyze the organic input, salinity, and physicochemical conditions at
the time of deposition of the Irati and Serra Alta shales, PCA was per­
formed to describe patterns in the multivariate data (Syms, 2008) by
graphically displaying groupings of samples with similar geochemical
characteristics. PCA was performed using a 24 × 10 correlation matrix
(used parameters marked in Table 1) in which principal components 1
and 2 (PC1 and PC2) explained 72.7% of the total variation of the data
and the components were split into four groups (Fig. 11), which repre­
sent: (1) Serra Alta shales (AMa 25, 26, 28, and 29) with lower TOC and
higher freshwater and terrigenous input; (2) Irati Formation base sam­
ples from the AMa outcrop (AMa 1, 5, 7, 11, and 17) with higher salinity
Fig. 11. Principal component analysis chart with principal components 1 and 2
grouping the samples into four groups based on geochemical characteristics.
C.A. Nascimento et al.
and stronger marine characteristics; (3) Irati Formation top samples
(AMa 23 and 24) plus sample SM 2.6, with lower salinity and higher
freshwater and terrigenous input; and (4) the other samples from SM
outcrops (SM 2.1 to 2.5 and 3.1 to 3.7), with the highest TOC values and
great freshwater input. The ellipses were traced using R software with a
95% confidence level. PC1 explained 53.6% of the data variation, being
influenced more heavily by the parameters δ13C, C29/C27 Ste, Pyrite and
S percentages, Hop/Ste, and Gam/C30H while PC2 explained 19.1% of
the data variation, being represented primarily by the TPP/Dia27, S2,
and TOC, which mainly separated the Irati Formation base samples
(AMa outcrop) from the Irati Formation top samples (AMa outcrop) plus
sample SM 2.6 (Supplementary Material Fig. S2).
In order to confirm the characterization of the samples in terms of
organic and freshwater input and better understand the changes in the
depositional paleoenvironment in each outcrop, an HCA was performed
using the Ward.D method and the Canberra metric distance (Fig. 11).
HCA provides a tree dendogram that classifies objects based on their
similarities (Johnson, 1967). As can also be observed in the PCA
two-dimensional plane chart (Figs. 11), Fig. 12 shows that the strong
marine characteristics observed in the Irati samples from the base of the
AMa outcrop (group G3, samples AMa 1, 5, 7, 11, and 17) change to
more terrigenous toward the top (group G2, samples AMa 23 and 24),
reaching dysoxic/oxic conditions and the low TOC Serra Alta shales
(group G1, samples AMa 25, 26, 28, and 29) due to episodes of fresh­
water inflow into the Irati Sea (Goldberg and Humayun, 2016; Martins
et al., 2020b). Irati black shales from the SM outcrops also have more
marine characteristics in the base of the outcrops (group G4; samples SM
2.1, 2.2, 2.3, 3.1, 3.2, 3.3, and 3.4), changing to a depositional setting
under more freshwater influence with greater terrigenous input in the
top of the outcrops (group G5; samples SM 2.4, 2.5, 2.6, 3.5, 3.6, and
3.7).
Inside the group G5, samples SM 2.4, 2.5, and 3.7 are in a subgroup,
which reflects their transitional characteristics. Accordingly, although
samples SM 3.3 and 3.4 are in the group G4 due to their likely affinity
with the other samples conforming to some variables such as δ13C and
βC/C30H, they show a transitional character, as they also have
geochemical affinities with samples from the G5 group, as can be seen by
the parameters TPP/Dia27 and Gam/C30H (Fig. 7).
4.2. Geochemical analyses for aromatic biomarkers
Although often used to assess thermal maturity of petroleum source
rocks, aromatic biomarkers have been little used to study the organic
matter source and physicochemical characteristics of the Irati Formation
(Afonso et al., 1994; Osorio et al., 2017; Martins et al., 2020a, 2020b,
2020c). In the present study, we detected key aromatic biomarkers and
used some diagnostic ratios to characterize the organic matter source of
Fig. 12. Hierarchical cluster analysis grouping samples in G1, G2, G3, G4, and G5, where groups G1, G2, and G5 present higher terrigenous contribution while
groups G3 and G4 have characteristics of higher marine contribution.
11
Marine and Petroleum Geology 126 (2021) 104917
the Irati black shales (chemical structure in Appendix A). These bio­
markers include triaromatic steroids (III, TAS), trimethylnaphthalenes
(IV, TMN), simonellite (V, Sim) and sempervirane (VI, Semp). More­
over, detection of a series of benzohopanes (VII, C32 to C35) and aryl
isoprenoids (VIII, AI) provides further evidence of the restricted and
hypersaline depositional paleoenvironment during the deposition of the
Irati black shales, in agreement with their higher amounts of sulfur,
pyrite, gammacerane, and the presence of the C32 lanostane. These ar­
omatic biomarkers were not detected (or detected in very low abun­
dance) in the low TOC Serra Alta shales, in accordance with their
deposition under oxic paleoenvironment conditions.
The triaromatic steroid (TAS) distribution (26S and R, 27S and R,
28S and R TAS; monitoring m/z 231, Fig. 13a) typically resembles the
regular sterane distribution associated with the organic matter input,
meaning that C26 TAS (26S and R TAS) can be related to marine envi­
ronments, while C28 TAS is associated with greater terrigenous contri­
bution (Mackenzie et al., 1982). This association can also be made by
compounds of the trimethylnaphthalene family (monitoring m/z 170,
Fig. 13b). Strachan et al. (1986) proposed the TDE-1 ratio (1,2,
5-TMN/1,2,4-TMN) for differentiating coal samples from marine,
lacustrine, and deltaic environments. According to their study, the
relative concentrations of 1,2,5-TMN were higher in oils derived from
Cretaceous or younger rocks dominated by large input from higher
plants. Grice et al. (2001), however, proposed cyanobacterial hopanoids
as a precursor for 1,2,5-TMN in Permian and Carboniferous torbanites
(boghead coal), which predate the evolution of angiosperms. The plot of
TDE-1 vs. C28/C26 TAS (Fig. 13c) shows higher values of C28/C26 TAS for
the samples with greater terrigenous contribution based on conventional
geochemical analyses (G2 and G5 samples, plus samples SM 3.3 and
3.4). However, samples from the AMa outcrop (G2 and G3) show higher
TDE-1 values than samples from SM outcrops (G4 and G5), which could
suggest that higher plants are not the only precursor of 1,2,5-TMN in
these samples, strengthening the cyanobacterial origin suggested by
Grice et al. (2001). The fact that black shales from the AMa outcrop are
interbedded with carbonates whose microbial mats formed by cyano­
bacteria (Warren et al., 2017) reinforces that suggestion.
In addition to trimethylnaphthalenes, simonellite and sempervirane
(V and VI, see the chemical structure in Appendix A and the mass
spectrum in Appendix B) were also detected in all Irati Formation
samples (monitoring m/z 237; Fig. 14a), as well as cadalenes, whose
increase toward the top of the outcrops points to greater terrigenous
contribution as already been suggested by Martins et al. (2020c).
Simonellite and sempervirane have higher relative abundances in sam­
ples with a greater terrigenous contribution (G2 and G5, plus samples
SM 3.3 and 3.4), as observed in the plot of the proposed ratio (Sim +
Semp)/C26 TAS vs. C28/C26 TAS (Fig. 14b), while the groups with more
marine characteristics (G3 and G4) have lower values for these ratios.
C.A. Nascimento et al.
Fig. 13. Distribution of the (a) triaromatic steroids in the mass chromatogram m/z 231 and the (b) trimethylnaphthalenes in m/z 170. (c) The plot of TDE-1 vs. C28/
C26 TAS shows higher values in each outcrop for the samples with greater terrigenous contribution interpreted based on conventional geochemical analyses (G2 and
G5 samples).
Fig. 14. (a) Mass chromatogram m/z 237 showing the relative abundance of
simonellite and sempervirane in samples from Amaral Machado e São Mateus
do Sul and (b) plot of (Sim + Semp)/C26 TAS vs. C28/C26 TAS showing an in­
crease of terrigenous contribution toward G2 and G5 samples.
These biomarkers may also suggest higher-plant input since they have
conifer resins as precursors (Simoneit and Didyk, 1986; Alexander et al.,
1988; Otto and Wilde, 2001; Cox et al., 2007). It was also observed that
the SM Upper samples (G5) have higher values for the (Sim + Semp)/C26
TAS ratio compared to the AMa top samples (G2). This behavior can be
associated with the paleogeography of the outcrops, since the region of
the SM outcrops had greater sea depths (restricted deep sea; Araújo
et al., 2001; Martins et al., 2020b) than the region of the AMa outcrop,
which was more restricted and arid (restricted shallow sea; Faure and
Cole, 1999; Araújo et al., 2001). For this reason, although the AMa re­
gion was shallower and proximal and had a contribution of plant debris
(phytoclasts), in SM there was greater humidity and better conditions
for the proliferation of higher plants, characterized primarily by co­
nifers, which were dominant in the Paraná Basin during the early
Permian (Ricardi-Branco et al., 2013).
A family of hopanoid-related monoaromatic biomarkers was also
detected (monitoring m/z 191; Fig. 15) for the first time, as far as we
know, in the organic extracts of the Irati Formation: the cyclized at C20
benzohopanes (VIII, C32–C35, see the chemical structure in Appendix A
12
Marine and Petroleum Geology 126 (2021) 104917
and the mass spectrum in Appendix B). These compounds are particu­
larly abundant in carbonate and evaporitic environments and it was
suggested that they form in the subsurface from bacteriohopanepolyol
precursors (Hussler et al., 1984; He and Lu, 1990; Oba et al., 2009). In
the present work, the presence of the benzohopane homologues is
consistent with the inferred hypersaline conditions in the stratified
waters of the depositional environment for the Irati black shales.
The distribution of benzohopanes varies among the samples, and this
variation may be related to different degrees of maturity (Nytoft et al.,
2016). In samples AMa 1 and 5, for example, the relative abundances of
C32 and C33 benzohopanes are notably lower than in other samples
(Fig. 15). Therefore, the C32-33/C32-35 benzohopane ratio is proposed
here as a maturation indicator since there is correlation between this
ratio and the maturity parameters C29 ββ/(ββ + αα), C29 20S/(20S +
20R), and C31 22S/(22S + 22R), where samples AMa 1, 5, and 7 are
more mature and have the lowest values for C32-33/C32-35 benzohopanes
(Fig. 16).
Finally, a series of aryl isoprenoids ranging from C14 to C29 was also
detected in all Irati black shales (monitoring m/z 133, Fig. 17a), with
different relative abundances among the samples. These compounds
appear to have the same origin as the green sulfur bacteria based on
their structure and isotopic composition (Summons and Powell, 1986;
Grice et al., 2005; Tulipani et al., 2015). Therefore, the identification of
aryl isoprenoids suggests that euxinia reached the photic zone during
deposition of the Irati black shales since these compounds are diagenetic
or catagenetic products of isorenieratene, a photosynthetic pigment in
green sulfur bacteria (Schaeffer et al., 1997; Clifford et al., 1998; Sousa
et al., 2013; Martins et al., 2020b). This interpretation is corroborated by
C18 1,1,7,8-tetramethyl-1,2,3,4-tetrahydrophenanthrene (THP), which
was noted for the first time in the Irati black shales by Martins et al.
(2020b) and was detected by monitoring m/z 223 for all analyzed Irati
black shales herein with great relative abundance (Supplementary Ma­
terial Fig. S3). Sinninghe Damsté et al. (1999) suggested that this com­
pound originates from tetrahymanol. The principal source of this lipid
appears to be bacterivorous ciliates, which occur at the interface be­
tween oxic and anoxic zones in stratified water columns (Sinninghe
et al., 1995). This is consistent with salinity-related density stratification
in the depositional setting of the Irati black shales.
To our knowledge, the aryl isoprenoids ratio (AIR), given by the ratio
of C13-17 to C18-22 AI, was applied to the Irati Formation samples for the
first time in the present work. AIR has values < 1 in all analyzed samples
C.A. Nascimento et al.
Fig. 15. Mass chromatogram m/z 191 showing the distribution of the C32–C35 benzohopanes in samples from the Amaral Machado e São Mateus do Sul outcrops.
(Fig. 17b), suggesting persistence of the anoxia/euxinia photic zone
(PZE; Schwark and Frimmel, 2004; Martinez et al., 2018), and is also
inversely proportional to the C28/C26 TAS ratio. It is interesting to note
that for samples that have a greater terrigenous contribution (G2 and G5
samples, plus samples SM 3.3 and 3.4) AIR decreases, meaning that PZE
persistence is increased, which is consistent with the freshwater inflow
and stratification of the water column.
5. Conclusions
Changes in paleoenvironmental depositional conditions for the Irati
black shales were interpreted based on a series of geochemical param­
eters, and the investigated samples were separated into groups by
principal component and hierarchical cluster analyses based on their
source-related geochemical characteristics. These interpretations sup­
port deposition in a restricted and hypersaline marine paleoenvironment
(G3 and G4 samples) with episodes of freshwater input. Freshwater
inflow led to stratification of the water column, generating a euxinic
photic zone and reducing bottom conditions that enhanced preservation
13
Marine and Petroleum Geology 126 (2021) 104917
of deposited organic matter. In addition, freshwater input brought
greater terrigenous organic matter (G2 and G5 samples) to this deposi­
tional paleoenvironment, culminating in the low TOC shales and more
oxidizing conditions interpreted for the Serra Alta Formation (G1
samples).
The assessed parameters are based on bulk geochemical data,
mineralogical composition, and mostly on saturated and aromatic bio­
markers. The TPP/Dia27 ratio was indicative of non-marine organic
input and freshwater incursion, in addition to the TDE-1 and C28/C26
TAS ratios. The detection of cadalene corroborates the input of higher
plants into the Irati Sea, in addition to simonellite and sempervirane,
which suggest greater contribution of conifer resins in the SM Upper
outcrop based on the proposed (Sim + Semp)/C26 TAS ratio, consistent
with its paleogeographic position, greater water depth, and humidity
compared to the AMa outcrop samples.
C32 lanostane and the C32-35 benzohopanes were detected for the first
time in organic extracts from the Irati Formation, and their presence
supports a hypersaline and sulfur-rich paleoenvironment. The presence
of tetrahydrophenanthrene (THP) and aryl isoprenoids ratio (AIR) also
C.A. Nascimento et al.
Fig. 16. Plot of (a) C32-33/C32-35 benzohopanes vs. C29 ββ/(ββ + αα), (b) C29
20S/(20S + 20R), and (c) C31 22S/(22S + 22R) showing samples AMa 1, 5, and
7 more thermally evolved than the other samples.
14
Marine and Petroleum Geology 126 (2021) 104917
Fig. 17. (a) Representative mass chromatograms m/z 133 showing the aryl
isoprenoid distribution in samples with marine (AMa 1) and terrigenous (SM
3.6) contributions and (b) plot of C28/C26 TAS vs. AIR showing G2 + G5
samples with greater terrigenous contribution, deposited under increased PZE
persistence.
supports persistence of photic zone euxinia (PZE) during deposition of
the Irati black shales. Additionally, the proposed C32-33/C32-35 benzo­
hopane ratio seems to be related to different thermal maturities
observed in the Amaral Machado outcrop, with higher values for sam­
ples from its base, which are more thermally evolved than the others due
to igneous intrusive rock and the presence of catalyst clay minerals.
CRediT author statement
Caroline Adolphsson do Nascimento: Formal analysis, Investiga­
tion, Writing - Original Draft, conducted the experimental work, which
was developed during her PhD; Eliane Soares de Souza: Conceptuali­
zation, Resources, Writing - Review & Editing, Supervision, Project
administration; Laercio Lopes Martins: Writing - Review & Editing,
Supervision; Hélio Jorge Portugal Severiano Ribeiro: Resources, Su­
pervision, Funding acquisition; Victor Hugo Santos: Investigation;
René Rodrigues: Investigation, Writing - Review & Editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors are grateful for support from the North Fluminense State
University – UENF (Macaé, Brazil), the Laboratory of Petroleum Studies
(LEPETRO) at the Bahia Federal University, and the Laboratory of
Chemostratigraphy and Organic Geochemistry at the Rio de Janeiro
State University (UERJ). LEPETRO provided TOC and Rock-Eval pyrol­
ysis analyses, and the Laboratory of Chemostratigraphy and Organic
Geochemistry at UERJ provided δ13C analysis. We also thank CAPES for
the doctoral scholarship of Caroline Adolphsson do Nascimento. Finally,
the authors thank BG E&P Brasil Ltd. for sponsorship that allowed the
field trip for sample collection through the “Commitment to Research
and Development Investments” with the ANP (National Agency of Pe­
troleum, Natural Gas and Biofuels). We also thank the Section Editor Hui
Tian, the reviewer Kenneth Peters, and an anonymous reviewer for the
relevant comments that improved the quality of this manuscript.
C.A. Nascimento et al. Marine and Petroleum Geology 126 (2021) 104917

Appendix A

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C.A. Nascimento et al. Marine and Petroleum Geology 126 (2021) 104917

Appendix B

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C.A. Nascimento et al. Marine and Petroleum Geology 126 (2021) 104917

Appendix C. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.marpetgeo.2021.104917.

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