Journal of South American Earth Sciences 110 (2021) 103362

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Journal of South American Earth Sciences

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Geochemical study on fossil vertebrates from some specific Permian and

Triassic beds of the Paraná Basin (Brazil): A preliminary approach
Leonardo Corecco a, *, Vitor P. Pereira b, Marina B. Soares c, Cesar L. Schultz a, d
a
Programa de Pós-graduação de Geociências, Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Brazil
b
Departamento de Mineralogia e Petrologia (DEMIP), Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Brazil
c
Departamento de Geologia e Paleontologia, Museu Nacional, Universidade Federal do Rio de Janeiro, Brazil
d
Departamento de Paleontologia e Estratigrafia, Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Brazil

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

Keywords: Access to the geochemical conditions of paleoenvironments is made through the analysis of the chemical
Bioapatite composition of the hydroxyapatite of fossil bones. This is because the bones were able to incorporate chemical
Fossildiagenesis elements from adjacent fluids into their pores and channels during the fossildiagenesis process, and as a result,
Gondwana
have their original apatite substituted. The main goal of the present study was to seek geochemical signatures in
Paraná Basin
Permian
bones and related sedimentary rocks from three well-known fossiliferous units of the Paraná Basin in southern
Triassic Brazil: Irati Formation, Cisuralian (three bones/rocks sampled); Rio do Rasto Formation, Guadalupian (three
bones/rocks sampled) and Santa Maria Supersequence, Late Ladinian–Early Norian (nine bones/rocks sampled).
Fossils and rocks were analyzed by ICP-MS. Although the Permian fossil and rock samples (from Irati + Rio do
Rasto Formations) have variations among them, some geochemical parameters are common (high
Be–Co–Cu–Zn–Y–W–Pb contents). This composition differentiates them from the Triassic fossils and rocks (from
Santa Maria Supersequence - high contents of V–As–Ba). The P content (essential in apatite) was used to
determine the degree of preservation of the studied material. The better-preserved Permian specimen has a mean
= 434.19 ratio (P content of fossil bones/P content of rock) and the lowest ratio = 1.87. Within the Triassic
specimens, the better preserved has ratio = 205.64 and lowest = 2.24. In Permian specimens, Y shares similar
ionic radio with Ca. For Triassic specimens, Y replaces Ca and As either replaces P or is associated with minerals
in bone cavities. So, Y and As substitute Ca in the analyzed material. Therefore, the Permian samples are better
preserved than the Triassic ones based on their P contents; Y and As can be used as indicators to differentiate
Permian fossils (high Y values) from Triassic ones (high As values). These geochemical signatures can help in
forensic cases, such as robbery or illegal transport of fossils.

1. Introduction
The intracratonic Paraná Basin (PB) is composed of an 8000 m thick
volcano-sedimentary package without depositional continuity (Milani,
1997). Polycyclic events resulted from successive sedimentation epi­
sodes related to tectonic events in the SW portion of the Gondwana
(Milani, 1997; Milani and Ramos, 1998; Zerfass et al., 2003, 2004).
Complexity led to many different proposals for PB subdivision (e.g.,
Milani, 1997; Milani and Ramos, 1998; Zerfass et al., 2003; Milani,
2007). In this study, we follow the Milani and Ramos (1998) and Milani
(2007) propositions in the stratigraphic context.
The sedimentary rocks of the PB contain significant amounts of
microfossils (Calça and Fairchild, 2012; Grahn et al., 2013), plant
fragments and tree trunks (Guerra-Sommer and Klepzig, 2000; Holz
et al., 2010) and invertebrates such as trilobites, gastropods, bivalves
and echinoderms (Marchioro et al., 1998; Simões et al., 2009; Chahud
and Fairchild, 2020). However, their most remarkable fossil content are
vertebrates such as fishes (Richter and Langer, 1998; Chahud et al.,
2010), temnospondyl amphibians (Dias and Schultz, 2003; Strapasson
et al., 2015; Dias et al., 2020), rhynchosaurs, dicynodonts, cynodonts
and some of the oldest dinosaurs (e.g., Staurikosaurus pricei; Colbert,
1970; Kellner and Campos, 1999; Oliveira et al., 2010; Melo et al., 2015;
Lacerda et al., 2016; Schultz et al., 2016; Schultz et al., 2020).
Vertebrate fossil samples from different PB Permian and Triassic

* Corresponding author. Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves, 9500, Porto Alegre, RS, CEP: 91.501-970,
Brazil.
E-mail address: leocorecco@gmail.com (L. Corecco).

https://doi.org/10.1016/j.jsames.2021.103362
Received 5 March 2021; Received in revised form 26 April 2021; Accepted 26 April 2021
Available online 1 May 2021
0895-9811/© 2021 Elsevier Ltd. All rights reserved.
L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

strata display variations in color and texture. These variations reflect
different fossilization processes mediated by specific preservation en­
vironments (Fig. 1). Previous studies (e.g., Holz and Schultz, 1998;
Reichel et al., 2005; Bertoni-Machado and Holz, 2006; Azevedo et al.,
2018; Xavier et al., 2018) performed petrographic and X-ray diffrac­
tometry analysis in fossil samples from Permian and Triassic strati­
graphic units in the basin. These analyses determined the mineralogical
composition associated with those fossils and determined how the
composition interfered with fossilization quality. A study applying
chemical data (ICP-MS) is required to elucidate those processes.
For the geochemical analyses, vertebrate fossils and host sedimen­
tary rocks were selected from three stratigraphic units. The samples used
in this study are from the Irati (Cisuralian) and Rio do Rasto (Guada­
lupian) formations and from the Santa Maria Supersequence (Late
Ladinian–Early Norian). Outcrops are located in the countryside of the
Rio Grande do Sul state and in northern Paraná state (Fig. 2).
The main objective of the study is the differentiation of the
geochemical conditions of fossilization and characterization of related
environments.
2. Study site
The depositional environment of the Irati Formation varied from
shallow marine to sub-aerial expositions and inner evaporitic ramps,
and to stratified external ramps and deoxidized to anoxic waters
(Araújo, 2001; Goldberg and Humayun, 2016). Santos et al. (2006)
dated the Irati Formation by SHRIMP based on U–Pb isotopic contents of
zircons that were present in volcanic ashes intercalated with shale suc­
cessions, obtaining a 278.4 ± 2.2 Ma age. Based on stratigraphic studies,
this formation was subdivided into Taquaral (lower) and Assistência
(upper) members (Barbosa and Almeida, 1949; Schneider et al., 1974;
Xavier et al., 2018). The Taquaral Member is composed of medium to
dark gray siltstone and claystones whereas the Assistência Member is a
thick carbonatic succession (Araújo, 2001; Goldberg and Humayun,
2016; Xavier et al., 2018). The fossiliferous assembly of Irati Formation
has palynomorphs and plants (Mussa, 1978; Souza and Marques-Toigo,
2003; Adami-Rodrigues et al., 2004; Holz et al., 2010), Pygocephalo­
morpha crustaceans (Matos et al., 2013; Xavier et al., 2018), vertebrates,
such as paleonisciformes fishes (Chahud et al., 2010; Xavier et al.,
2018), and mesosaurid reptiles (Oelofsen and Araújo, 1983; Soares,
2003).
The depositional context of Rio do Rasto Formation varied from
shallow lacustrine with fluvial incursions and influence of storm waves
to deposits influenced by fluvial, lacustrine, deltaic and wind environ­
ments (Rohn, 1994; Holz et al., 2010). This stratigraphic unit was dated
by Francischini et al. (2018) by SHRIMP based on U–Pb isotopic con­
tents of zircons. Results display a 270.61 + 1.76/-3.27 Ma age (Gua­
dalupian). This formation was subdivided into two members; Serrinha
(lower) and Morro Pelado (upper) (Schneider et al., 1974; Ng et al.,
2019). The Serrinha Member has finely granulated sandstone facies,
with swaley/hummocky crossed stratification, intercalated with het­
erolytic and laminated gray claystones. The Morro Pelado Member is
composed of finely granulated, tabulate, lenticular or laminated sand­
stone, as well as by red claystones (Rohn, 1994; Holz et al., 2010;
Francischini et al., 2018). This formation records a huge vertebrate fossil
diversity that contains temnospondyl amphibians (Barberena and Dias,
1998; Dias and Barberena, 2001; Strapasson et al., 2015; Dias et al.,
2020), the pareiasaur Provelosaurus americanus (Araújo, 1985), carni­
vore and herbivore dinocephalians (Langer et al., 2000; Cisneros et al.,
2012; Boos et al., 2015), Hybodontiformes sharks (Pauliv et al., 2017),
actinopterygian fishes (Richter and Langer, 1998; Malabarba et al.,
2003) and ichnofossils of vertebrates (Silva et al., 2012; Francischini

Fig. 1. Stratigraphic column section of Paraná Basin with some examples of the different modes of fossil preservation with their variations in color and texture. a)
Axial skeleton of Mesosaurus tenuidens (UFRGS-PV-0209-P), in dorsal view; b) Skull of Provelosaurus americanus (UFRGS-PV-0231-P), in dorsal view; c) Skull of
Dinodontosaurus sp. in left lateral view; d) Skull and mandible of Prestosuchus chiniquensis (UFRGS-PV-156-T) in left lateral view; e) Skull of Massetognathus ochagaviae
(UFRGS-PV-0712-T), in ventral view; f) Partial skull of Santacruzodon hopsoni (MCN-PV 2768), in palatal view; g) Skull of Teyumbaita sulcognathus (UFRGS-PV-0232-
T) in ventral view; h) Skull and mandible of Gnathovorax cabreirai (CAPPA/UFSM 0009) in right lateral view; i) Skull and mandible of Exaeretodon riograndensis
(CAPPA/UFSM 0033) in left lateral view; j) Skull and jaw of Riograndia guaibensis (UFRGS-PV-596-T) in right lateral view; k) Skull of Clevosaurus brasiliensis (UFRGS-
PV-748-T) in dorsal view. The lithostratigraphy was adapted from Horn et al. (2014) and the fossils’ pictures came from De Queiroz et al. (2020) and Schultz
et al. (2020).

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L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

Fig. 2. a) Geographical map of the Paraná Basin within South American context, highlighting the geological sequences where the studied samples were collected.
Irati Formation (1 – Aceguá; 2 – São Gabriel); Rio do Rasto Formation (1 – Bagé; 6 – Ortigueira and São Jerônimo da Serra); Santa Maria Supersequence (3 – Santana
da Boa Vista; 4 – Agudo and Dona Francisca; 5 – Candelária, Santa Cruz do Sul and Venâncio Aires/Mariante); Outcrops localization, respectively in Rio Grande do
Sul (b) and Paraná (c) states.

et al., 2018). Also presents are spores and pollen grains (Neregato et al.,
2008), ichnofossils of invertebrates (Dentzien-Dias et al., 2012; Azevedo
et al., 2018) and root marks (Azevedo et al., 2018).
The studied Triassic fossils are from three third-order sequences of
SMS (Pinheiros-Chiniquá, Santa Cruz and Candelária - sensu Horn et al.,
2014). The SMS is interpreted as fluvial deposition, with high sinuosity.
The upper portions display rhythmites (sandstones and claystone)
intercalated with fine sandstone lenses with crossed stratification and
climbing cross-lamination, characterizing a lacustrine-deltaic environ­
ment (Zerfass et al., 2003). Some of these strata were dated by zircon
U–Pb (CA-ID-TIMS) by Langer et al. (2018). Ages are between 233.23 ±
0.73 for the Santa Maria Formation, base of the Candelária Sequence
and 225.42 ± 0.37 Ma for the Caturrita Formation, top of the Candelária
Sequence. The Santa Cruz Sequence also has a recent U–Pb determina­
tion of 236.1 Ma age (Philipp et al., 2018). These results confirm the
Middle-Late Triassic age, as previously pointed out in relative dating.
The SMS is recognized worldwide by its vertebrate fossil content that
includes Synapsida – dicynodonts and cynodonts and Diapsida – rhyn­
chosaurs, “rauisuchians” and other archosaurs, also including some of
the oldest dinosaurs (Schultz et al., 2020). Fossilized logs, leaf impres­
sions and conchostracans were also found in these strata (Guerra-Som­
mer and Klepzig, 2000; Da-Rosa, 2008; Barboni and Dutra, 2015). The
remarkable vertebrate content of the SMS, characterizing different
faunas succeeding in time, allowed the construction of a biostratigraphic

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L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

framework (Barberena, 1977; Schultz et al., 2000). Four assemblage
zones (AZs) are recognized from the base the top: Dinodontosaurus AZ in
the Pinheiros-Chiniquá Sequence (Ladinian), SantacruzodonAZ in the
Santa Cruz Sequence (early Carnian), Hyperodapedon AZ (Carnian) and
Riograndia AZ (early Norian), respectively, at the base and top of the
Candelária Sequence.
3. Materials and methods
For the present study fifteen samples of fossil bones and host sedi­
mentary rocks were selected. These analyzed samples are in the
collection of the Paleovertebrate Section of the Geosciences Institute of
Universidade Federal do Rio Grande do Sul (UFRGS-PV-T and UFRGS-
PV-P), Museu Municipal Aristides Carlos Rodrigues collection
(MMACR-PV-T), from Candelária, Rio Grande do Sul state and Paleon­
tology laboratory of the Universidade Federal do Paraná (UFPR-PV).
Additional information about fossils and their provenance are in Table 1.
The studied samples were analyzed by inductively coupled plasma -
mass spectrometry (ICP-MS) at Acme Analytical Labs Ltd., located in
Vancouver, Canada.
For interpretations of the depositional environments where the fos­
silizations processes took place, the chemical elements contents of the
sedimentary rocks adjacent to fossils were compared with the mean
values of sedimentary rocks on the Earth’s crust determined by Yar­
oshevsky (2006). This comparison was made to verify the relative
mobility of the elements in the different studied depositional environ­
ments. The normalization between the elements contained in the bones
to the respective host rocks indicated the elements most important in the
fossilization process. The sedimentary rocks analyzed by Loring (1990)
and Sakan et al. (2015) were also considered. These authors applied
normalization processes to evaluate the variability of trace metals in
silicate sediments from Canada and the contamination by heavy metals
in river sediments from Siberia. These chemical variations also allowed
characterizing these environments and differentiating the fossils that
came from those distinct localities.
4. Results
The mean values of element contents of sedimentary rocks and fossil
bones are presented in Table 2.
Considering the significant variation in chemical composition among
the studied samples, no generalizations were made regarding the
Permian and Triassic samples. Variation is due to different sediments
sources, topography and distinct weathering ranges. Low number of
samples also inhibited generalizations. Comparison of rock composi­
tions with NASC - The North American Shale Composite (Gromet et al.,
1984) and PAAS - Post-Archean Australian Average Shale (Nagarajan
et al., 2007) was not attempted. Those international patterns are from
distinct lithologies, collected from different portions of the Earth’s crust,
and from different geochronological provinces when compared to the
rocks of this study. We made a comparison between the analyses of this
study and those from Goldberg and Humayun (2016) and De Queiroz
et al. (2020), who studied the composition of rocks from the Irati For­
mation and its correlate in Uruguay, the Mangrullo Formation. We also
compared our results with Pierini et al. (2002), who investigated the
composition of rocks from the Santa Maria Supersequence, and Horn
et al. (2013) from the carbonatic sequences of the same supersequence
(Table 3). Quantitative geochemical study has not been made of the
sedimentary rocks and vertebrate fossils of the Rio do Rasto Formation.
The comparisons leads to distinction of the sedimentary rocks in this
study from those in the literature based on contents of P, Ca, V, Sr, Y, Zr
and Ba (Permian) and P, Ca, V, Sr, Y and Ba (Triassic). Due to the het­
erogeneous results, each locality is evaluated separately.
Despite heterogeneity, the P contents in the studied rock samples
(Permian and Triassic) are significantly higher than the consulted
literature. This arises from the possible presence of microfragments of
bones in the analyzed rocks, or from P incorporation in clays or
adsorption to other minerals. This aspect requires additional studies.
Variable Ca concentrations were also observed among different sedi­
mentary units, interpreted as larger of smaller amounts of calcite con­
cretions. The Triassic pelitic rocks have many centimetric limestone
concretions, as observed by Horn et al. (2013). Bones of this period that
were fossilized in pelites or siltstones have significant calcite in their
pores and other internal structures (Holz and Schultz, 1998). This sec­
ondary calcite was formed by dissolution of minerals from sedimentary
rocks (including calcite) with subsequent precipitation inside the bones
(Holz and Simões, 2002).
Results show high contents of V (96 ppm in Triassic and 311 ppm in
Permian), Y (164 ppm in Triassic and 1370 ppm in Permian) and Ba
(1045 ppm in Triassic and 16465 ppm in Permian) in comparison to

Table 1
Information about the sampling used for the geochemical analyses by ICP-MS. Adapted from Corecco et al. (2020).
SAMPLE T.I. BONE UNIT AZ AGE SED. LOCALITY CATALOG NO

O1A, S1A Rauisuchia Prestosuchus Rib Pinheiros-Chiniquá Dinodontosaurus Late Ladinian Clayey siltite; Pelite Dona Francisca, RS UFRGS-PV-0629-T
O1B, S1B Dicynodontia Vertebra Mariante, RS UFRGS-PV-0300-T
Dinodontosaurus
O2A, S2A Cynodontia Lower jaw Santa Cruz Santacruzodon Early Carnian Clayey siltite; Pelite Santa Cruz do Sul, RS UFRGS-PV-1165-T
Menadon
O2B, S2B Cynodontia Undetermined Skull Venâncio Aires, RS UFRGS-PV-0457-T
O3A, S3A Cynodontia Lower jaw Candelária (base) Hyperodapedon Late Carnian Clayey siltite; Pelite Agudo, RS UFRGS-PV-1226-T
Exaeretodon
O3B, S3B Rhynchosauria Hyperodapedon Rib Vale do Sol, RS UFRGS-PV-1206-T
O3C, S3C Rhynchosauria Hyperodapedon Skull Santana da Boa Vista, RS UFRGS-PV-1248-T
O4A, S4A Dicynodontia Rib Candelária (top) Riograndia Early Norian Clayey siltite; Pelite Candelária, RS UFRGS-PV-0540-T
Jachaleria
O4B, S4B Archosauria Undetermined Limb bones Candelária, RS MMACR-PV-012-T
O5A, S5A Mesosauridae Rib Irati n.a. Cisuralian Marl São Gabriel, RS UFRGS-PV-0272-P
O5B, S5B Mesosauridae Vertebra Aceguá, RS UFRGS-PV-0607-P
O5C, S5C Mesosauridae Rib São Gabriel, RS UFRGS-PV-0597-P
O6A, S6A Temnospondyli Undetermined Skull fragments Rio do Rasto n.a. Guadalupian Clayey siltite; Pelite São Jerônimo da Serra, PR UFPR-0150-PV
O6B, S6B Temnospondyli Australerpeton Limb bones Ortigueira, PR UFRGS-PV-0320-P
O7A, S7A Pareiasauria Limb bones Bagé, RS UFRGS-PV-0231-P
Provelosaurus

T.I. = Taxonomic identification; SED. = Sedimentary rocks; AZ = Assemblage Zone; n.a. = not applicable; RS = Rio Grande do Sul state. Triassic samples – O1A, S1A to
O4B, S4B; Permian samples – O5A, S5A to O7A, S7A.

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L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

Table 2
– Average contents of the analyzed elements present in sedimentary rocks and their respective fossil bones from Permian (6 samples) and Triassic (9 samples).
Sedimentary rocks average Fossil bones average

Elements (Wt%) Triassic samples Permian samples Triassic samples Permian samples

Average (SD) Average (SD) Average (SD) Average (SD)

F 0.13 (σ = 0.23) 0.17 (σ = 0.20) 0.76 (σ = 0.35) 0.93 (σ = 0.18)

Na 0.89 (σ = 0.43) 0.65 (σ = 0.76) 0.34 (σ = 0.25) 0.52 (σ = 0.17)
Mg 0.72 (σ = 0.24) 2.55 (σ = 3.72) 0.18 (σ = 0.06) 0.21 (σ = 0.14)
Al 7.40 (σ = 2.72) 5.33 (σ = 2.91) 0.78 (σ = 0.37) 3.02 (σ = 4.36)
Si 26.62 (σ = 9.75) 18.75 (σ = 6.70) 2.44 (σ = 1.07) 3.89 (σ = 2.75)
P 0.55 (σ = 1.29) 1.2 (σ = 2.59) 7.13 (σ = 4.41) 9.54 (σ = 2.24)
K 1.71 (σ = 0.68) 1.38 (σ = 1.18) 0.13 (σ = 0.07) 0.34 (σ = 0.35)
Ca 7.65 (σ = 11.40) 11.93 (σ = 6.14) 33.02 (σ = 4.44) 24.73 (σ = 11.13)
Ti 0.36 (σ = 0.14) 0.19 (σ = 0.10) 0.04 (σ = 0.02) 0.07 (σ = 0.07)
Cr 0.003 (σ = 0.001) 0.0025 (σ = 0.002) 0.004 (σ = 0.004) 0.003 (σ = 0.002)
Mn 0.1 (σ = 0.12) 0.26 (σ = 0.22) 0.78 (σ = 0.86) 7.64 (σ = 9.46)
Fe 1.76 (σ = 0.73) 3.52 (σ = 4.02) 0.28 (σ = 0.13) 0.85 (σ = 0.54)

Elements (ppm) Triassic samples Permian samples Triassic samples Permian samples

Average (SD) Average (SD) Average (SD) Average (SD)

Be 4.33 (σ = 1.32) 5.00 (σ = 5.59) 4.33 (σ = 3.43) 23 (σ = 28.64)

Sc 7.22 (σ = 2.77) 6.33 (σ = 3.27) 10.78 (σ = 8.93) 8.33 (σ = 3.93)
V 96.11 (σ = 154.81) 28.75 (σ = 21.16) 311.11 (σ = 276.96) 136.67 (σ = 147.15)
Co 7.27 (σ = 6.44) 13.77 (σ = 20.34) 23.47 (σ = 22.41) 50.55 (σ = 37.60)
Ni 4.89 (σ = 2.32) 8.75 (σ = 10.83) 1.89 (σ = 2.52) 7.07 (σ = 4.38)
Cu 4.33 (σ = 2.01) 10.43 (σ = 11.75) 5.1 (σ = 4.47) 48.38 (σ = 56.68)
Zn 14.78 (σ = 9.96) 30.67 (σ = 30.61) 25.33 (σ = 16.77) 40 (σ = 41.31)
Ga 12.86 (σ = 4.36) 9.12 (σ = 4.50) 3.38 (σ = 2.15) 13.65 (σ = 14.52)
As 12.54 (σ = 26.25) 16.43 (σ = 27.66) 255.24 (σ = 228.43) 69.9 (σ = 98.13)
Rb 92.11 (σ = 34.97) 60.63 (σ = 45.75) 7.32 (σ = 3.59) 13.13 (σ = 14.18)
Sr 510.98 (σ = 746.98) 480.98 (σ = 234.92) 2892.78 (σ = 2857.74) 6971.67 (σ = 12,163.04)
Y 164.24 (σ = 345.54) 149.98 (σ = 285.21) 1370.78 (σ = 996.90) 1906.53 (σ = 1514.90)
Zr 323.83 (σ = 132.14) 126.82 (σ = 68.25) 92.64 (σ = 74.20) 71.28 (σ = 48.16)
Nb 9.97 (σ = 3.91) 5.92 (σ = 2.97) 1.38 (σ = 0.61) 3.08 (σ = 2.62)
Sn 1.67 (σ = 0.71) 1.50 (σ = 0.55) 1.00 (σ = 0.00) 1.00 (σ = 0.00)
Ba 1045 (σ = 816.97) 437.67 (σ = 323.77) 16,465.56 (σ = 18,270.66) 15,213 (σ = 18,112.13)
W 1.40 (σ = 0.73) 0.87 (σ = 0.37) 5.26 (σ = 5.33) 15.82 (σ = 24.12)
Pb 24.20 (σ = 35.55) 11.22 (σ = 6.78) 115.03 (σ = 81.44) 1576.55 (σ = 3278.31)

*σ = standard deviation of the average content.

**In italic the standard deviation values bigger than 10.

those existing in consulted literature.
Although the chemical results from sedimentary rocks are hetero­
geneous, we compared the chemical composition of fossil bones with the
host rocks. The fossilization process was thus characterized, along with
the differences among the sedimentary environments of the studied
localities.
5. Fossilization
5.1. Permian samples
Bone composition was modified in previous processes, requiring
additional evaluation of element concentration. Volcanic activity (e.g.,
Choiyoi Group volcanism) can be influenced the Permian and Triassic
fossils, because Philipp et al. (2018) observed that some zircon crystals
of Permian and Triassic units of the Paraná Basin were derived from
Argentinean volcanoes. Fluid percolation through these stratigraphic
units was relevant. Nevertheless, the composition of the rocks that
contain the fossils was a main determinant of the modifications that
occurred in the fossils hosted in fossils. Such influences accentuated the
differences among the fossilization processes. The comparison between
elements in fossils and those in the host rocks shows that the Permian
fossils (based on the average chemical compositions) are relatively
enriched in Be, F, P, Ca, Mn, Sc, V, Co, Cu, Zn, As, Sr, Y, Ba, W and Pb.
High standard deviations place restraints on the interpretation. The
evaluation of a set of elements renders the geochemical characterization
of rocks from this period more reliable. Bones are composed dominantly
of hydroxyapatite (Toledo and Pereira, 2001; Straight et al., 2004;
Fricke et al., 2008), thus high Ca and P contents indicate a better pres­
ervation. Ca is easily leached in sedimentary environments (Harriss and
Adams, 1966; Zevenbergen and Comans, 1994), including as a carbon­
ates constituent (Reimann and Caritat, 1998). Based on these premises,
only P will be considered to evaluate the preservation degree of the
studied fossils. Thus, fossil bones that have high P content will be
considered better preserved. As observed by Reimann and Caritat
(1998), P has low mobility in any environment (e.g., oxidizing,
reducing, acid or basic).
The substitution of hydroxyl by F− , a common constituent in surface
waters, is widely described in secondary phosphate formations. Substi­
tution occurs due to the F− greater electronegativity (Toledo and Per­
eira, 2001). The substitution of the hydroxyl by F− increases bones
stability (abrasion resistance and chemical reactions) owing to higher
stability of fluorapatite compared to hydroxyapatite (Nasution and
Zawil, 2014).
P is here considered as an evaluating factor for the preservation
degree of the studied fossils. This selection is based on the high degree of
F− dissolution in water combined with high percolation rate in the
sediments and also the facility of F− complexation with other ions,
including the carbonate. Sedimentary rocks have significantly lower F
contents than fossils contained in them, thus becoming another factor to
be considered. There is no statistical correlation between F and P in the
analyzed rocks; however, the F content is near the limit of detection
(10,000 ppm) in several fossil samples, which indicates that the bones
stability increased in relation to the host rocks. The graphic in Fig. 3
illustrates the normalization between the elements present in the
Permian bones and those from the sedimentary rocks that contain them.

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L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

Table 3
– Comparison of the geochemical data from the studied sedimentary rocks and data available in the literature on Permian and Triassic sedimentary rocks of the Paraná
Basin. Adapted from Pierini et al. (2002), Horn et al. (2013), Goldberg and Humayun (2016), De Queiroz et al. (2020).
Sedimentary rocks average

Elements (Wt%) Triassic samples Permian samples

This work Pierini et al. (2002) Horn et al. (2013) This work Goldberg and Humayun (2016) De Queiroz et al. (2020)

F 0.13 – – 0.76 – –
Na 0.89 0.70 0.50 0.34 – –
Mg 0.72 1.16 0.41 0.18 1.03 –
Al 7.40 6.69 3.56 0.78 6.75 1.87
Si 26.62 28.96 16.42 2.44 – 8.50
P 0.55 0.02 0.01 7.13 – 2.85
K 1.71 2.43 0.76 0.13 – –
Ca 7.65 1.17 21.21 33.02 0.96 15.15
Ti 0.36 0.38 – 0.04 0.29 –
Cr 0.003 – – 0.004 – 0.005
Mn 0.1 0.05 0.28 0.78 0.04 –
Fe 1.76 2.77 0.76 0.28 4.67 8.92

Elements (ppm) Triassic samples Permian samples

This work Pierini et al. (2002) Horn et al. (2013) This work Goldberg and Humayun (2016) De Queiroz et al. (2020)

Be 4.33 – – 4.33 – –
Sc 7.22 – – 10.78 – –
V 96.11 69 – 311.11 110.33 –
Co 7.27 9.67 – 23.47 16.3 –
Ni 4.89 16.67 – 1.89 25.22 –
Cu 4.33 16.67 – 5.1 34.61 –
Zn 14.78 58 – 25.33 66.47 247.60
Ga 12.86 16 – 3.38 – –
As 12.54 – – 255.24 – –
Rb 92.11 116.33 – 7.32 – 101.20
Sr 510.98 119 – 2892.78 – 1903.20
Y 164.24 32 – 1370.78 – 731,20
Zr 323.83 396 – 92.64 – 8.00
Nb 9.97 – – 1.38 – 8.00
Sn 1.67 4.33 – 1.00 – –
Ba 1045 406.67 718 16,465.56 – 641.60
W 1.40 – – 5.26 – –
Pb 24.20 21 – 115.03 – 78.80

Fig. 3. Normalization between the elements content present in the Permian bones from the Paraná Basin and the host sedimentary rocks. a) Fluorine and major
elements; b) Trace elements. Log10* = Log10 (fossil bones average content/sedimentary rocks average content).

Because the better preserved fossil bone samples have the highest
contents of P compared with their host rocks, Fig. 3a displays the
following decreasing order of preservation: 5A, 6B, 7A, 5C, 6A and 5B.
The low and heterogeneous contents of Ca in these samples indicates
different leaching degrees and consequently of alteration.
F concentrations are higher than 10,000 ppm in many samples, and
were not to determine degree of preservation. The use of Mn to
discriminate the better preserved fossil samples was discarded, because
there is no correlation between Mn and P or Mn and F in these samples.
Besides that, the Mn does not replace Ca in the hydroxyapatite structure,
because the Mn is oxidized in sedimentary environments. Mn does not
occur in VII or IX coordination, and no Ca coordination is present in the
apatite structure. Mn occurs in +2 valency in waters rich in organic
matter and does not connect to OH− ions (Marshall, 1979). Thus, the Mn

6
L. Corecco et al.
is associated with weathering minerals, such as pyrolusite (MnO2) and
psilomelane ((BaH2O)2 Mn5O10) or even adsorbed to the bones. The
presence of holandite (BaMn8O16) as a secondary mineral of Ba and Mn
was registered in fossil bones from the Oligocene of the USA (Parker and
Toots, 1972). Therefore, the presence of psilomelane or holandite ex­
plains the high Ba contents in the studied rocks and bones, but this
interpretation requires additional works.
Among all the elements present in Fig. 3b, only Y has ionic radium
similar to Ca. Consequently, this substitution is quite common in apatite
varieties from different localities (Toledo and Pereira, 2001; http://
abulafia.mt.ic.ac.uk/shannon/). The fixation of Y in phosphates, in
replacement of Ca or in the absence of Ca is widely recognized in the
literature (e.g., Bastos Neto et al., 2012; Atencio et al., 2015).
Regarding the other trace elements presently evaluated, no pattern
was observed in their geochemical distribution; some samples are more
enriched than others. Based on the absence of pattern, these elements
were not used to characterize the Permian samples.
5.2. Triassic samples
The comparison between the chemical composition of the Triassic
fossils and their sedimentary rocks led to verification that these bones
are relatively enriched in F, P, Ca, Sc, V, Mn, Co, Cu, Zn, As, Sr, Y, Ba, W
and Pb. Similarly to the Permian bones, the standard deviation of ele­
ments from the Triassic fossils and sedimentary rocks are also high and,
because of that, these samples also need to be examined with parsimony.
The graphic in Fig. 4 illustrates the normalization between the ele­
ments present in the Triassic bones with the host sedimentary rocks.
The following decreased order of preservation was established for
these samples: 2B, 3A, 3B, 1A, 2A, 4B, 1B, 4A and 3C. This order follows
the principle that bones with high P contents compared to host sedi­
ments are better preserved. The remaining major elements do not
display correlation to P content; they reflect heterogeneity in the
fossilization process in the different sampled locations.
Regarding F, Permian rocks have the higher average levels (1,707
ppm) than the Triassic (1,311 ppm). In both periods their concentrations
increase significantly in bones (9,281 ppm in Permian and 7,549 ppm in
Triassic). Therefore, the enrichment factors are similar in both periods.
When the P and F concentrations are compared (excluding the samples
that reached the detection limit of 10,000 ppm), F contents increase
with P logarithmically and with correlation = +0.92. Despite that, and
owing to the lack of correlation between F content and degree of pres­
ervation in Permian samples this criterion will be applied to both
Permian and Triassic samples. In addition, rock samples S4A (Upper
Triassic) and S5B (Lower Permian) present anomalously high levels of P,
respectively 39,900 ppm and 64,790 ppm. This is due to the possible
Fig. 4. Normalization between the elements content present in the Triassic bones from the Paraná Basin and the host sedimentary rocks. a) Fluorine and major
elements; b) Trace elements. Log10* = Log10 (fossil bones average content/sedimentary rocks average content).
7
Journal of South American Earth Sciences 110 (2021) 103362
presence of microfragments of bones in the mineral grains or previously
exposed reasons. The Irati Formation (Passo do São Borja outcrop) has
around 85% of fossils assemblage composed by isolated bones with high
degree of fragmentation that resulted from successive storm events
(Soares, 2003).
As is high among the Triassic trace elements, and either replaces P or
is contained in bones cavities. However, concentration processes of As in
fossil bones are complex, because As is expected to replace IVP in the
tetrahedron structure. Despite that, the difference in ionic radii of these
elements in IV coordination is very high (http://abulafia.mt.ic.ac.uk/sh
annon/. Accessed in: 02/28/21). The high difference indicates that such
substitution occurs in very particular conditions. Therefore, the high
contents of As observed in the studied fossils (especially in those from
the Triassic) must be investigated further in future studies. In general,
high contents of Y and As are qualified indicators to differentiate the
Triassic fossil bones (high As and Y contents) from those from the
Permian (high Y contents, but with a greater enrichment factor in
relation to the host sedimentary rocks) in the studied stratigraphic units.
5.3. Comparison between Permian and Triassic samples fossilization
Comparing the chemical elements concentration of bones with those
of the host sedimentary rocks, we verify that the same elements
concentrate in Permian (from both units) and Triassic fossils in relation
to Yaroshevsky (2006) Earth’s crust composition. This leads to the
conclusion that the studied bones have characteristics that facilitated
the precipitation of some chemical elements in comparison to others that
remained in the host sedimentary rocks. Despite that, comparing spe­
cifically the Permian and Triassic data to each other, we observe that the
Permian samples have high contents of Be, F, P, Mn, Co, Cu, Zn, Sr, Y, W
and Pb and those from the Triassic have high contents of Ca, Sc, V, As
and Ba. Among these elements, some stand out for displaying significant
differences between these periods; these outstanding elements will be
commented next.
A comparison was made between the F, P, Ca and Mn contents in
sedimentary rocks and the hosted bones (based on Table 2). The Permian
bones are enriched in F, P and Mn and the Triassic ones in Ca. The
enrichment factor of these elements was calculated for each geological
period by subtracting the averaged content values of the elements pre­
sented in bones from host rocks. As an example, the mean F value in
Permian bones is 0.93 and in rocks 0.17, so the difference between them
(enrichment factor) is 0.76. Similar calculation indicates that the
Triassic samples have value = 0.63. The Permian bones have high
contents of F, not related to the concentration in the host sedimentary
rocks. Similar to the F contents, the relatively high contents of P and Mn
in the bones are not due to the contents in the host rocks. Therefore, the
L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

high P concentration (>25.26%) in Permian bones leads to the conclu­

sion that the values remained close to the natural values for bones,
which are around 29.20%–33.33% (Skinner, 2005); in consequence,
Permian bones are better preserved than the Triassic. Regarding Ca,
contents are higher in the Permian rocks than in the Triassic. Despite
this, the Ca contents are higher in the Triassic bones compared to host
rocks (high enrichment factor). Triassic bones have high quantities of
calcite in their pores, Haversian canals and adsorbed to the bones walls.
The calcite associated to hematite in Rio Grande do Sul Triassic bones
was described by Holz and Schultz (1998), Reichel et al. (2005) and
Horn et al. (2013). These authors found that these bones deformations
occurred by an expansion caused by carbonate growth in channels and
bone cavities. The searched literature lacks studies focusing on the
relevance of hematite in the Paraná Basin fossil bones preservation.
The bones samples 5A, 5B and 5C (Permian) were preserved in marls
(limestones with 35–60% of clay content), but have low Ca content.
Soares (2003) and Xavier et al. (2018) reported carbonatic matrices and
shale intercalations in some carbonatic outcrops (e.g., Passo do São
Borja) of Permian age; also from the same localities where some fossils
were collected and here described. The possibility of Ca being more
extensively leached during the Permian than during the Triassic is not
supported because Na had a reverse behavior in this period. So, Na was
leached along with Ca. The geochemical factor and the sedimentary
rocks characteristics (e.g., porosity and permeability) that were
responsible for such concentrations must be better investigated in future
studies.
Mn accumulated especially in bones that fossilized in Permian pelites Fig. 5. Main fossilization characteristics observed in the Permian (a) and
(samples 6A, 6B and 7A). Mn substitutes Ca in the apatite structure in Triassic fossil bones from the Paraná Basin.
the reduced state, where VIIMn2+ (0.9 Å ionic radii) can replace the VIICa
(1.06 Å ionic radii). According to Lynn and Bonati (1965), Mn tends to Formation are relatively enriched in Be, F, Na, Al, P, Ca, Zn, Sr, Y and Ba
be mobile in reducing conditions with high biological productivity and in relation to host rocks. Similar comparison was performed for bones
high sedimentation rates. These conditions limit the contact between from the Rio do Rasto Formation; they are relatively enriched in Be, F, P,
organic matter and oxygen that are responsible for oxidation and dete­ Ca, Sc, V, Mn, Co, Cu, Ga, As, Sr, Y, Ba, W and Pb. However, comparison
rioration (Wakeham and Canuel, 2006). Samples enriched in Mn came of the elements concentrated in bones shows that the fossils from the
from a more oxidized environment (Rio do Rasto Formation), and Mn Irati Formation are enriched in Be, F, Na, Al, P, Ca, Zn and Sr and those
did not replace the Ca and is not related to the characteristics of the fossil from the Rio do Rasto in Mg, Si, K, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Ga, As,
bones. Bones were fossilized along associated hematite that existed in Rb, Zr, Nb, Ba, W and Pb. Elements with similar contents in bones from
pores and cavities. both periods were not listed. Because standard deviation is high, caution
Therefore, the Permian bones stands out by the relatively high Be, must be taken in the evaluation. Thus geochemical characterization of
Co, Cu, Zn, Y, W and Pb contents. The Triassic bones, on the other hand, the samples is more reliable in set of elements rather than a single one.
stand out by the high contents of V, As and Ba. Some of these concen­ Presuming that the better preserved fossil bones have higher P
trations are due in both Permian and Triassic samples the high contents content than host sedimentary rocks, data in Fig. 4a display the
of the elements in the host sedimentary rocks, with exceptions. As an following decreasing order of preservation in the Irati Formation: 5A, 5C
example, the Cu contents in Triassic rocks are little modified in relation and 5B. For the Rio do Rasto Formation, the following decreasing order
to bones of this period. Permian samples are different, because these of preservation is established: 6B, 7A and 6A. Furthermore, comparing
values are higher in the fossil bones. Another example is Ga which de­ the average contents of P, the Irati Formation samples are better pre­
creases in the Triassic bones in relation to host sedimentary rocks. served (P = 12.98%), followed by SMS (P = 7.13%) and Rio do Rasto
However, Ga increases in the Permian bones in comparison to host Formation (P = 6.09%). This ordering must also be seen with caution
rocks. Therefore, the interpretation of the contents variation in trace due to the high standard deviation values for the SMS samples in relation
elements requires addtional in-depth geochemical studies, with more to the Permian formations.
samples evaluated per outcrop. Despite that, the results differentiate the
Permian bones from the Triassic in the studied locations. The main 6. Discussion
fossilization characteristics of the studied bones are given in the scheme
of Fig. 5. Geochemical influences promoted significant compositional differ­
ences in the studied fossils, including pH and Eh variations, chemical
5.4. Comparison between samples fossilization in each studied activity and elements complexation associated with degree of diagenesis
stratigraphic unit and to the taphonomic processes. The interpretations also corroborate
differences described in previous petrological studies in some of the
Following fossilization of Permian and Triassic bones, we place the sampled localities (Reichel et al., 2005; Horn, 2013; Azevedo et al.,
focus on each stratigraphic unit. Table 4 contains the average contents of 2018; Fanti and Soares, 2018; Xavier et al., 2018). Similar studies have
Irati and Rio do Rasto formations while Table 2 has the Santa Maria been conducted in many different parts of the world (e.g., USA, China
Supersequence. and Brazil) and with different taxonomic groups (Carpenter et al., 1988;
The comparison between the studied sedimentary rocks and the Koch et al., 1997; Kohn et al., 1999; Martin, 1999; Trueman and Tuross,
fossil bones allowed marked the differences in bones mineralization 2002; Paes Neto et al., 2016; Keenan and Engel, 2017; Callefo et al.,
processes in each unit and also separated Permian from Triassic samples. 2018; Bezerra et al., 2020; Corecco et al., 2020; De Queiroz et al., 2020;
The mean values of chemical analyses of Permian fossils from the Irati

8
L. Corecco et al. Journal of South American Earth Sciences 110 (2021) 103362

Table 4
– Average contents of the analyzed elements presented in sedimentary rocks and their respective fossil bones from the Irati and Rio do Rasto formations.
Elements (Wt%) Irati Fm. (marine) Rio do Rasto Fm. (continental)

Sedimentary rocks average Fossil bones average Sedimentary rocks average Fossil bones average

Average (SD) Average (SD) Average (SD) Average (SD)

F 0.26 (σ = 0.28) 1.0 (σ = 0.00)* 0.09 (σ = 0.04) 0.86 (σ = 0.25)

Na 0.23 (σ = 0.11) 0.57 (σ = 0.23) 1.07 (σ = 0.96) 0.47 (σ = 0.10)
Mg 3.68 (σ = 5.50) 0.11 (σ = 0.04) 1.41 (σ = 0.71) 0.32 (σ = 0.13)
Al 3.30 (σ = 2.91) 3.69 (σ = 6.67) 7.36 (σ = 0.54) 2.07 (σ = 0.57)
Si 13.04 (σ = 1.28) 2.03 (σ = 2.15) 24.46 (σ = 3.59) 5.74 (σ = 2.00)
P 2.38 (σ = 3.63) 12.98 (σ = 0.72) 0.10 (σ = 0.04) 6.09 (σ = 2.96)
K 0.46 (σ = 0.42) 0.07 (σ = 0.08) 2.31 (σ = 0.88) 0.59(σ = 0.31)
Ca 14.61 (σ = 7.64) 29.99 (σ = 11.77) 9.24 (σ = 3.80) 19.46 (σ = 9.39)
Ti 0.11 (σ = 0.09) 0.01 (σ = 0.009) 0.26 (σ = 0.04) 0.12 (σ = 0.05)
Cr 0.003 (σ = 0.002) 0.003 (σ = 0.003) 0.003 (σ = 0.001) 0.003 (σ = 0.002)
Mn 0.38 (σ = 0.26) 0.29(σ = 0.11) 0.14 (σ = 0.11) 14.99 (σ = 7.85)
Fe 5.35 (σ = 5.48) 1.53 (σ = 0.19) 1.70 (σ = 0.72) 1.16 (σ = 0.65)

Elements (ppm) Sedimentary rocks average Fossil bones average Sedimentary rocks average Fossil bones average

Average (SD) Average (SD) Average (SD) Average (SD)

Be 7.33 (σ = 7.77) 29.67 (σ = 43.62) 2.67 (σ = 1.15) 16.33 (σ = 3.79)

Sc 6.00 (σ = 5.00) 7.00 (σ = 4.36) 6.67 (σ = 1.15) 9.67 (σ = 3.79)
V 23.00 (σ = 16.70) 8.00 (σ = 0.00) 41.00 (σ = 24.43) 265.33 (σ = 66.83)
Co 22.03 (σ = 28.69) 23.47 (σ = 33.82) 5.50 (σ = 2.35) 77.63 (σ = 13.76)
Ni 10.63 (σ = 16.05) 3.50 (σ = 3.10) 6.87 (σ = 5.00) 10.63 (σ = 0.49)
Cu 13.67 (σ = 16.82) 10.67 (σ = 17.09) 7.20 (σ = 5.55) 86.10 (σ = 58.92)
Zn 31.33 (σ = 47.44) 53.67 (σ = 60.12) 30.00 (σ = 9.54) 26.33 (σ = 9.61)
Ga 5.77 (σ = 3.72) 1.40 (σ = 1.56) 12.47 (σ = 1.77) 25.90(σ = 8.61)
As 30.40 (σ = 36.39) 7.47 (σ = 6.59) 2.47 (σ = 1.95) 132.33 (σ = 111.07)
Rb 25.23 (σ = 25.89) 2.47 (σ = 2.93) 96.03 (σ = 28.33) 23.80 (σ = 12.35)
Sr 570.37 (σ = 276.50) 12,275.97 (σ = 16,885.70) 391.60 (σ = 193.78) 1667.37 (σ = 561.41)
Y 257.63 (σ = 410.37) 1371.33 (σ = 693.36) 42.33 (σ = 14.03) 2441.73 (σ = 2096.96)
Zr 77.80 (σ = 58.57) 30.13 (σ = 16.44) 175.63 (σ = 31.40) 112.43 (σ = 21.19)
Nb 3.97 (σ = 3.23) 0.77 (σ = 0.38) 7.87 (σ = 0.45) 5.40 (σ = 0.95)
Sn 1.00 (σ = 0.00) 1.00 (σ = 0.00) 2.00 (σ = 0.00) 1.00 (σ = 0.00)
Ba 307.33 (σ = 385.47) 1702.00 (σ = 1616.29) 568.00 (σ = 250.03) 28,724.00 (σ = 16,427.69)
W 0.80 (σ = 0.52) 0.67 (σ = 0.21) 0.93 (σ = 0.25) 30.97 (σ = 27.67)
Pb 9.33 (σ = 7.25) 6.10 (σ = 5.19) 13.10 (σ = 7.19) 3147.00 (σ = 4412.41)

σ = standard deviation of the average content. In italic the standard deviation values bigger than 10.
*value above the detection limit.

Wang et al., 2020). These studies involving geochemical content vari­
ations, mainly addressing REE (e.g., Nd and Sm), and isotopic (e.g., C
and O), differences in the diagenetic patterns (e.g., concretions forma­
tion and bones recrystallization). Studies also focused on taphonomic
topics (e.g., bones porosity and microbiological activity). Our results are
in agreement with Pfretzschner (2004): “The process of fossilization is
still in many respects poorly understood”. Besides that, our results are
significant about the fossilization conditions that acted on the studied
rocks. They also allowed to differentiate the studied bones from different
stratigraphic units and geological periods, comparable to some of the
mentioned studies (e.g., Carpenter et al., 1988; Corecco et al., 2020).
The studied Triassic sedimentary rocks have high contents of Al, Ti,
Nb and Zr (Table 2). These elements are used to determine the sediments
and sedimentary rocks maturity degree because they are immobile in
most geochemical conditions (Little and Lee, 2006). Thus, based on this
criterion, the Triassic sedimentary rocks went through more intense
weathering. This corroborates with what was presented by Algeo and
Twitchett (2010), where Triassic sections have higher weathering taxa
than Permian ones. However, analyzing the contents of these elements
in the fossil bones, we found that those from the Permian have high Al,
Ti and Nb concentrations, while the Triassic ones are enriched in Zr (see
Table 2). This observation confirms that these elements have different
geochemical behavior in the bones and in the host sedimentary rocks. As
most likely none of these elements can substitute the Ca or the P in the
hydroxyapatite structure, they must be associated with the minerals in
the bone cavities. Consequently, their concentrations do not indicate
bone preservation degree. Besides that, this is a good criterion for the
identification of the studied fossil origins and for distinguishing Triassic
from Permian rocks. But only the variations in concentration do not
allow the interpretation of the diagenetic differences in these environ­
ments. Possible Ca substitutions in apatite consist mainly of Sr, Ba and
REE, and P by As and V, as described by McConnell (1973). These dia­
dochic substitutions depends on the physicochemical conditions of the
crystallization environments, and on the ionic radii that varies according
to the Ca and P coordination numbers (http://abulafia.mt.ic.ac.uk/sh
annon/) in the hydroxyapatite structure.
The Ca contents of the studied sedimentary rocks and fossil bones are
not associated with variations in P contents. This was expected because
Ca is an easily leached and highly mobile element (Harriss and Adams,
1966; Zevenbergen and Comans, 1994). However, observing the varia­
tions in Na contents, we conclude that Ca was more extensively leached
in the Triassic.
The geochemical variation in the studied environments must have
provided the elements mobilization and deposition several times, both
in Permian and Triassic, changing the typical Ca/P (~2.15) ratio of
hydroxyapatite. Thus, due to its heterogeneous behavior, Ca contents
are not qualified indicators of preservation or fossilization processes.
The absence of igneous apatite in the sampled sedimentary rocks
allows us to conclude that the high P observed in these rocks is due to the
presence of bone microfragments and/or the formation of complexes
with P, which may be adsorbed on clays and other minerals. These
microfragments or phosphorous complexes can be generated by the
bones breaking during the diagenetic processes or even because of
chemical weathering. Besides that, according to Pfretzschner (2004), the

9
L. Corecco et al.
redox conditions at the beginning of the diagenesis processes are already
controlled by the phosphate contents in the bones. Because of this
control, pH is buffered at high values. According to Pfretzschner (2004),
the formation of pH-dependent minerals, including secondary phos­
phates, occurs during late diagenesis.
According to Kohn et al. (1999), enrichment in Ba, Fe and Mn and
none in Al and Si indicates that oxyhydroxides contributed more
strongly to the observed fossil changes than clay minerals. Climatic
variations responsible for the calcite geochemical behavior are associ­
ated to hematite crystallization and to quartz precipitation into the
bones (Bao et al., 1998; Holz and Schultz, 1998). The presence of these
minerals into the pores and cavities, as well as the isolation from the
environment, helped in the studied sample preservation. As observed by
Holz and Schultz (1998) and Bertoni-Machado and Holz (2006), in some
cases the permineralization causes deformation in Rio Grande do Sul
Triassic specimens. According to Ely (2015), these processes depend on
many factors; following Skinner (2005) and Reis et al. (2017), bacteria
influence biomineralization processes (e.g., Fe). Zazzo et al. (2004) said
that bacteria also influence fossil bones formation and preservation or
the P fixation process. According to these authors, bacteria contribute to
inorganic O2 changes through fluids in porous environments (e.g.,
bones), and thus catalyzing reactions by these bacteria. This exchange of
the phosphate-bacteria-O2 process acceleration must indicate the dif­
ferences in the P fixation in the studied fossils. Possibly the highest P
contents are related to samples exposed to climatic condition for a long
time before the fossildiagenesis processes began.
The similar ionic radii of Ca and Y leads to easy access of Y to the
apatite structure. As a consequence, the positive correlation of Y to P
occurs in both Permian and Triassic samples where Y accumulated in the
fossils. In the studied samples, the absence of negative correlation be­
tween the Y and Ca is due to this heterogeneous behavior. This behavior
occurs because of carbonate accumulation in bones cavities concomitant
with its leaching from the hydroxyapatite structure. Y enrichment and
Ce depletion were used by Fleischer and Altschuler (1986) to identify
apatite of sedimentary origin. This is because Y has a heavy REE
behavior, and the mobility is different from the light REE, such as Ce
(Bau and Dulski, 1999). The studied rocks are enriched in Y, which is
also concentrated in the hosted bones, most probably replacing Ca in
apatite. However, the significant Y variations allow the use of this
element to distinguish the Permian fossils (high Y contents) from those
of the Triassic.
As, on the other hand, has low concentration in the Earth’s crust (1.8
ppm Clarke – Lide, 2004) and in sediments and rocks. Arsenium is a
commonly found non-metal from natural sources, commonly formed by
rocks weathering and enriched soils or even from anthropic sources,
such as mineral exploitation and processing (Ng et al., 2003; Gontijo and
Bittencourt, 2005). For the studied samples, anthropic factors do not
explain the high As values in both sedimentary rocks and fossil bones.
Therefore, the As geochemical behavior should be further investigated
with more samples and spot chemical analysis to determine associated
minerals and substitution for P in hydroxyapatite.
Among the analyzed elements Pb is highly enriched in the bones of
both periods, but especially in those from the Permian samples (1,576
ppm). 207Pb/206Pb dating of bones were performed in human bones
(Smith et al., 1996) and dinosaurs teeth (Sano et al., 2006). Thus, the
high Pb contents in both bones and sedimentary rocks under study make
it possible to obtain radiometric ages to verify possible diagenetic in­
fluences in the obtained ages. The allochthonous origin of the bones can
also be tested, because the bone ages may be older than the rocks in
which they reside.
The Irati (I) and Rio do Rasto (RR) formations have different ages and
different depositional contexts, but they belong to the same geological
period (Permian), which explains some of the similarities presented
here. According to the ages by Francischini et al. (2018) and Santos et al.
(2006), the deposition of these stratigraphic units was separated by six
to eight million years. We cogitate that the Irati and Rio do Rasto
10
Journal of South American Earth Sciences 110 (2021) 103362
formations share their sediment sources. This interpretation is based on
several evidences, including the small depositional age difference, the
source of part of the RR Formation was from the continent, and the
smaller temporal resolution of marine strata (not being closer than 1 or
2 Ma) related to slow clay deposition (Thiry, 2000). In addition, some
zircon crystals of Permian and Triassic units of the Paraná Basin are
related to volcanic events in Argentina (e.g., Choiyoi Group; Philipp
et al., 2018). In addition to different ages and sedimentary context, the
largest extinction in Earth’s history (End Permian Mass Extinction)
occurred between the Permian and Triassic units. Extinction devastated
almost 95% of all species on Earth (Benton and Twitchett, 2003; Chen
et al., 2020). According to Algeo and Twitchett (2010), a clay mineral
enrichment occurred at the beginning of the Triassic sections when
compared to the end Permian. They argued that the extinction happened
because of a seven-fold increase in the sediment input from the conti­
nents that was triggered by a series of events – high physical and
chemical weathering taxa, changes in precipitations pH, high tempera­
tures. Extinction was caused by the devastation of the ecosystem. Such
brutal environmental change affected fauna and flora and also the
chemistry of the sedimentary system, where fossils were eventually
preserved. Our study focused on the different compositions between the
studied Permian and Triassic units, although the differences need to be
better understood through additional studies.
The better-preserved fossil bone samples have high contents of P in
relation to the host sedimentary rocks, so the Irati Formation has the
better preserved bones among the studied stratigraphic units. This is in
agreement with Medeiros (2010) and Simões et al. (2010) that state that
marine environments tend to better preserve fossils. The carbonatic
shallow sea, restricted and anoxic Irati Formation context was highly
conducive to preservation of bones than the sandstone and clay facies of
the Rio do Rasto Formation or even from those pelites and sandstones
from the SMS. RR Formation had fluvial, deltaic and wind influences
arising from transgressive and regressive cycles, while the SMS had a
fluvial with high sinuosity environment. The observed P accumulation
in the Rio do Rasto Formation bones should be enhanced by the action of
bacteria, which is a common process in paludal environments (Ismail-­
Meyer and Rentzel, 2017).
7. Conclusions
The conclusions of this work are preliminary and must be seen with
parsimony due to the low number of analyzed samples and high stan­
dard deviations of the chemical analyses. Nevertheless, the compositions
of the studied sedimentary rocks and fossils allow us to verify the dif­
ferences in the mineralization processes of the bones in the different
units and separate the Permian samples (high Be, Co, Cu, Zn, Y, W and
Pb contents) from those from the Triassic (enriched in V, As and Ba). The
bones from the Irati Formation are relatively enriched in Be, F, Na, Al, P,
Ca, Zn and Sr, and those from the Rio do Rasto Formation in Mg, Si, K,
Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Ga, As, Rb, Zr, Nb, Ba, W and Pb.
Based on Al, Ti, Nb and Zr contents presented in the Triassic sedi­
mentary rocks, we conclude that weathering was more intense in those
rocks than in the Permian. Besides that, these geochemical behaviors in
bones are different from the host sedimentary rocks because the highest
Al, Ti and Nb concentrations were recorded in Permian bones and
highest Ca and Zr in those from the Triassic.
The significant Y variations differentiate the Permian fossils (high
contents) from those from the Triassic.
Among all analyzed elements, high contents of Pb occur in both
sedimentary rocks and fossil bones in both periods. The Permian bones
have the highest contents of Pb (1,576 ppm). Additional work on Pb/Pb
ratios is required to verify the ages and possible diagenetic influences in
the fossilization process, as well as possibly verify the fossils origins
(autochthonous or allochthonous).
In spite of differences in age and depositional context, the Irati and
Rio do Rasto formations still belong to the same geological period
L. Corecco et al.
(Permian), so they may share their sediment sources (probably related to
Choiyoi Group volcanism), which can explain some of the similarities
presented here. In addition to ages and depositional contexts, differ­
ences between Permian and Triassic units marked the biggest extinction
in Earth’s history. The extinction impacted the fauna and flora and also
the chemistry of the sedimentary system where fossils were preserved.
Examining the average contents of P, the Irati samples are better
preserved (P = 12.98%), followed by the SMS (P = 7.13%) and Rio do
Rasto Formation (P = 6.09%) samples. These results are coherent
because the Irati and Rio do Rasto formations were deposited, respec­
tively, in marine and paludal paleoenvironmental contexts that tend to
better preserve the bones. The SMS fossils, in turn, were exposed to more
oxidized conditions, which contributed to the heterogeneity in their P
contents.
In spite of similar geochemical behavior, the relative enrichment of
some elements in the fossil bones presents significant differences, which
are useful to identify the original formation of a particular specimen.
Thus, these geochemical patterns help in solution of forensic questions
such as robbery or illegal transport of fossils from these stratigraphic
units.
Future spot quantitative chemical analyses and distribution maps of
the elements in fossil bones cavities and in minerals can be compared to
the geochemical analyses of this work to verify which elements are
replacing Ca and P in hydroxyapatite. These results will further the
understanding of the fossilization environment and processes involved.
Author statement
L.C., V.P.P., and C.L.S. wrote the first draft of the manuscript. L.C.
prepared Figs. 1–5. L.C., C.L.S., and M.B.S. revised Irati and Rio do Rasto
Formations, and Santa Maria Supersequence geology and biostratig­
raphy. L.C. and V.P.P. revised the geochemical contexts. All the authors
revised and improved the final draft before submission.
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
This work is the end product of LC’s Master’s degree dissertation at
Programa de Pós-graduacão em Geociências, Instituto de Geociências,
Universidade Federal do Rio Grande do Sul, Brazil. This study was
financed, in part, by the Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior, Brazil (CAPES) — Finance Code 001, granting the
scholarship for this student. Support was also given by research project
No. 476868/2010–6 from Conselho Nacional de Desenvolvimento
Científico e Tecnológico, Brazil (CNPq), coordinated by MBS. MBS was
also supported by grants from CNPq (307938/2019–0) and Fundação de
Amparo à Pesquisa do Estado do Rio de Janeiro - FAPERJ (E-26/010;
002178/2019). CLS is supported by a grant from CNPq (process number
397711/2017–0). We thank Dr. Leo A. Hartmann for revising English,
which greatly increased the quality of the final text.
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