UNIVERSIDADE FEDERAL DO CEARÁ

INSTITUTO DE CIÊNCIAS DO MAR - LABOMAR

PROGRAMA DE PÓS- GRADUAÇÃO EM CIÊNCIAS MARINHAS
TROPICAIS

QUIMIOESTRATIGRAFIA DA BACIA SEDIMENTAR DO ARARIPE

(CRETÁCEO INFERIOR), NORDESTE DO BRASIL

IGOR HAMID RIBEIRO AZEVEDO

FORTALEZA- CE,
2024
 IGOR HAMID RIBEIRO AZEVEDO

QUIMIOESTRATIGRAFIA DA BACIA SEDIMENTAR DO ARARIPE

(CRETÁCEO INFERIOR), NORDESTE DO BRASIL

Tese apresentada ao Programa de Pós-

graduação em Ciências Marinhas
Tropicais do Instituto de Ciências do
Mar da Universidade Federal do Ceará
como requisito para obtenção do título
de Doutor em Ciências Marinhas
Tropicais.

Orientador: Prof. Dr. Luiz Drude de

Lacerda

Co-orientador: Prof. Dr. Antônio

Álamo Feitosa Saraiva

FORTALEZA-CE,
2024
À toda minha família e amigos
 AGRADECIMENTOS

Primeiramente, gostaria de agradecer ao meu Orientador, Professor Dr. Luiz

Drude de Lacerda, por todo apoio, suporte, orientação, paciência e grande conhecimento
transmitido durante o desenvolvimento deste projeto. A finalização desta tese tem grande
contribuição do senhor, pois a sua curiosidade e o seu apreço em aprender e ensinar é um
espelho para os futuros pesquisadores deste país.
À Professora Dra. Rozane Valente Marins o meu muito obrigado pelo apoio,
confiança e paciência para o desenvolvimento desse trabalho. Agradeço muito por suas
indagações que me auxiliaram na produção desta Tese.
Gostaria de agradecer ao meu Co- Orientador, Professor Dr. Álamo Saraiva, e a
toda equipe do Laboratório de Paleontologia (LPU) da URCA, pelo grande conhecimento
compartilhado, pela lógica e atividades de campo. O meu muito obrigado ao Professor
Álamo pela disponibilidade, mesmo à distância, em auxiliar no desenvolvimento desta
pesquisa. A sua paixão pelo Cariri e pelo conhecimento são de grande inspiração.
Agradeço também ao Dr. Lucas Antonietto e Dr. Borja Holgado pela parceria para o
desenvolvimento desta pesquisa. Agradeço ao Museu de Paleontologia Plácido Cidade
Nuvens por auxiliar no desenvolvimento desta pesquisa.
Agradeço também ao professor Dr. Alcides Sial e aos técnicos do Laboratório de
Isótopos Estáveis (NEG- LABISE) pela parceria e contribuição para o desenvolvimento
do projeto.
Meu muito obrigado aos professores Dra. Taissa Rodrigues, Dr. Tristan
Rousseau e Dr. Renan Bantim por aceitarem participar da defesa da tese e colaborar
para a melhoria do trabalho.
O meu muito obrigado aos professores Dra. Samara Eschrique, Dr. Edvar
Aguiar e Dr. Franscisco Dias (UFMA) pelo conhecimento transmitido por vocês
durante a minha formação acadêmica. Aos professores Dra. Ana Paul Benigno (IFCE)
e Dr. Tristan Rousseau (UFC) pelas contribuições na qualificação deste trabalho e pelas
sugestões na elaboração da Tese.
Agradeço a toda equipe do Laboratório de Biogeoquímica Costeira (LBC) da
Universidade Federal do Ceará (UFC): Andréa Consolação, Andréia Campos
“Tubarão”, Cesar Barrios, Isabelle Caracas, Leticia Paulino, Liana Raquel, Marcus
Vinicius, Maria Andreia, Mariana Silvestre, Mariany Cavalcante, Moises Bezerra,
Thays Santos, Wesleandro Vasconcelos, Victor Lacerda e Victoria Emily pela ajuda
nas análises e pelos momentos de descontração tão necessários.
Aos docentes do Programa de Pós- Graduação em Ciências Marinhas
Tropicais (PPGCMT) pela oportunidade no desenvolvimento desse projeto; e aos
funcionários do LABOMAR pela atenção e presteza diária.
Aos meus pais (Stélio e Socorro), irmã (Susane) e sobrinha (Alice) que sempre
acreditaram na minha capacidade. O apoio dos meus pais foi extremamente importante
para a realização deste trabalho, auxiliando nas viagens de campo. À família Azevedo:
primos (Abdul, Enéias, Guy, Hugo, Filipe e Cauê) e tios/ tias (Ana, Ana Lúcia, Paulo,
Conceição, Eurinice, Guy Júnior, Karine e Verlene) que sempre me ajudaram nos
encontros de família. À família Ribeiro, em especial, minha segunda mãe (Júlia Ribeiro),
meus primos (Eduardo Chaves, Maiara Chaves, Priscila Chaves, Júnior “Neném”,
Carol Portela e Felipe Toledo) e “aos pequenos” (Arthur, Malu, Maju, Manu e Laís),
que apesar da distância sempre me incentivaram e ajudaram nos momentos de
dificuldade.
O meu muito obrigado à Lourena Abreu Magalhães por me acompanhar nessa
jornada, por todo o apoio, companheirismo, paciência, incentivo e pelos momentos felizes
proporcionados ao longo dos anos.
Aos meus grandes amigos do Estudo Bíblico/ UFMA (Clarisse Figueiredo,
Daniel Dionísio, Eduardo Kayk, Fernanda Filgueira, Jamerson Aguiar, Laiane
Lima, Lucas Silva, Matheus Maia, Renan Mescouto, Rubens Marques e Samara
Saraiva), que me auxiliaram e me aguentam desde a graduação. Aos meus amigos
grandes amigos Hugo Pereira, Jefferson Horley, Mariana Correa, Thamires Torres e
Vinícius Henrique.
Gostaria de agradecer à FUNCAP e ao INCT-TMCOcean pelo apoio financeiro
para concluir o doutorado. O presente trabalho foi realizado com o apoio da Coordenação
de Aperfeiçoamento de Pessoal de Nível Superior- Brasil (CAPES)- Código de
Financiamento 001, através da bolsa de doutorado.
Por fim, gostaria de agradecer a Deus por todas as pessoas que foram colocadas
em minha vida, que contribuíram de alguma forma para o meu crescimento pessoal e
profissional.
 IGOR HAMID RIBEIRO AZEVEDO

QUIMIOESTRATIGRAFIA DA BACIA SEDIMENTAR DO ARARIPE

(CRETÁCEO INFERIOR), NORDESTE DO BRASIL

Tese apresentada ao Programa de Pós-

graduação em Ciências Marinhas
Tropicais do Instituto de Ciências do
Mar da Universidade Federal do Ceará
como requisito para obtenção do título
de Doutor em Ciências Marinhas
Tropicais.

BANCA EXAMINADORA

_____________________________________________
Prof. Dr. Luiz Drude de Lacerda (Orientador)
Universidade Federal do Ceará (UFC)

_____________________________________________
Prof. Dr. Antônio Álamo Feitosa Saraiva (Co-orientador)
Universidade Regional do Cariri (URCA)

______________________________________________
Prof. Dr. Tristan Charles Clitandre Rousseau
Universidade Federal do Ceará (UFC)

_____________________________________________
Profa. Dra. Taissa Rodrigues Marques da Silva
Universidade Federal do Espírito Santo (UFES)

_____________________________________________
Prof. Dr. Renan Alfredo Machado Bantim
Universidade Regional do Cariri (URCA)
 RESUMO

A Quimioestratigrafia é uma ferramenta essencial para compreender as características

deposicionais e os processos responsáveis pelas mudanças paleoclimáticas da Terra.
Através do uso dos metais-traço e isótopos estáveis pode-se entender os processos
geológicos ao longo da evolução do planeta e sua interferência na evolução da vida. Os
eventos de vulcanismo são responsáveis pela injeção de CO2 na atmosfera causando
grandes crises biológicas e oscilações paleoclimáticas globais e regionais. Deste modo,
esta tese buscou compreender o comportamento dos indicadores geoquímicos durante as
perturbações paleoambientais que ocorreram no Cretáceo Inferior (Aptiano-Albiano) na
Bacia do Araripe (Ceará, Nordeste, Brasil). A bacia do Araripe é caracterizada por
apresentar um rico acervo fossilífero (Konservat -Lagerstätte), em que, os processos que
foram responsáveis pela preservação dos fósseis estão vinculados com as mudanças
paleoambientais. Para avaliar as variações paleoambientais, determinou-se os indicadores
geoquímicos do vulcanismo (Hg/COT, Hg/Al e Hg/Fe), paleosalinidade (Sr/Ba), as
condições de oxirredução (V/Cr, V/V+Ni e V/Ni), oscilações isotópicas (δ13CVPDB e
δ18OVPDB), anomalias de paleoprodutividade (CuFE, ZnFE, NiFE e BaFE) e paleoredox (VFE,
FeFE, CrFE, MnFE e PbFE). Os eventos de vulcanismo foram responsáveis pelas mudanças
da paleoprodutividade e condições paleoredox durante a deposição das formações
Barbalha, Crato e Romualdo podendo estar associados aos vulcanismos dos platôs
Ontong Java (OJP, 124 – 120 Ma) e Rajmahal-Kerguelen Sul (SKP, 119 – 110 Ma). Neste
caso, o aumento do CO2 atmosférico gerado pelo vulcanismo pode ter gerado o
desenvolvimento da produtividade e da anoxia nos ecossistemas aquáticos. Além disso,
os processos globais resultaram em mudanças locais na Bacia do Araripe, podendo estes
eventos estarem vinculados com os eventos cíclicos de mortalidade em massa registrados.

Palavras- chave: Quimioestratigrafia. Metais-traço. Fator de Enriquecimento. Condições

paleoredox. Paleoprodutividade. Vulcanismo. Isótopos Estáveis.
 ABSTRACT

Chemostratigraphy is an essential tool for the understanding of the depositional

characteristics and the processes that are responsible for the paleoclimatic changes on
Earth. Trace metal and stable isotopes are used to understand geologic processes during
planetary evolution and how they interacted with life. Therefore, the aim of this work was
to understand the behavior of geochemical indicators during the paleoenvironmental
perturbations that occurred during the Lower Cretaceous (Aptian-Albian) in the Araripe
Basin (Ceará, Northeast, Brazil). The Araripe Basin is characterized by a rich fossil
assemblage (Konservat -Laggerstätte), in which the processes responsible for fossil
preservation are linked to paleoenvironmental changes. To evaluate the
paleoenvironmental variations, geochemical indicators of volcanism (Hg/TOC, Hg/Al,
and Hg/Fe), paleosalinity (Sr/Ba), redox conditions (V/Cr, V/V+Ni and V /Ni), isotopic
oscillations (δ13CVPDB and δ18OVPDB), paleoproductivity (CuEF, ZnEF, NiEF, and BaEF), and
paleoredox anomalies (VEF, FeEF, CrEF, MnEF, and PbEF) were determined. Volcanic
events were responsible for changes in paleoproductivity and paleoredox conditions
during deposition of the Barbalha, Crato, and Romualdo formations and could be
associated with the volcanism of the Ontong Java (OJP) and Rajmahal-Kerguelen South
(SKP) plateaus. Increased anomalies in proxies of paleoproductivity, and paleoredox
conditions were observed during volcanism events. In this case, the development of
productivity and anoxia in aquatic ecosystems may have been triggered by the increase
in atmospheric CO2 caused by volcanism. Furthermore, the cyclic mass mortality events
recorded may be related to global processes that caused local changes in the Araripe
Basin.

Keywords: Chemostratigraphy. Trace Metals. Enrichment Factor. Paleoredox conditions.

Paleoproductivity. Volcanism. Stable isotopes.
 LISTA DE FIGURAS

Figura 1. Localização e distribuição das litofácies da Bacia do Araripe ....................... 19

Figura 2. Carta estratigráfica da Bacia do Araripe ....................................................... 20
Figura 3. Esquema ilustrativo do ciclo do mercúrio (Hg), destacando o seu papel como
indicador geoquímico de atividade vulcânica. ............................................................... 23
Figura 4. Classificação redox utilizando a razão entre metais proposta por Jones e
Manning (1994). ............................................................................................................. 26
Figura 5. Comportamento dos indicadores geoquímicos das condições paleoredox no
ambiente aquático. ........................................................................................................ 265
Figura 6. Comportamento dos indicadores geoquímicos da paleoprodutividade no
ecossistemas aquáticos. ................................................................................................ 308
Figura 7. Comportamento isotópico do δ13Ccarbonato de acordo com os períodos de
variações magmáticas. .................................................................................................... 33
Figure 8. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the
location of the Araripe Basin- BSA (yellow circle) and the volcanisms of Ontong Java-
OJP (red star) and Southern Kerguelen Plateau- SKP (white star). B) Map of the location
of the sampling points in the Araripe Basin. .................................................................. 41
Figure 9. Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of
the sampled sections, lithofacies, and height based on Benigno et al. (2021), Coimbra et
al. (2002) e Fara et al. (2005). B) Aptian and early Albian depositional sequence of the
studied interval, according to Fauth et al. (2023); Guzmán et al. (2023); Ogg et al. (2016);
Varejão et al. (2021a, b). DS- Depositional system. ....................................................... 47
Figure 10. Chemostratigraphy of the Barbalha Formation. A) Hg/TOC (Volcanism); B)
Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni,
G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M)
CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity). ....... 51
Figure 11. Chemostratigraphy of the Crato Formation. A) Hg/TOC (Volcanism); B)
Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni,
G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M)
CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity). ....... 53
Figure 12. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B)
Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni,
G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M)
CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13CVPDB. ................................................ 55
Figure 13. Location map of the Araripe basin (ASB). A) Distribution area and location of
lithofacies in the ASB (Modified from Assine, 2007 and Warren et al., 2017). B) Location of the
ASB at 120 Ma (Modified from Scotese, Wright, 2018). S- Stage; T– Tectonostratigraphic; Sand-
Sandstone, Silt- Siltstone, Sha- Shale, Gyps- Gypsum.......................................................... 71
Figure 14. Profile of the controlled excavation of the Crato Formation at the Antonio
Finelon mine (modified from Storari et al., 2021). The samples come from the C6 layer
of the Crato Formation, identifying 10 mortalities events (Dastilbe sp and Hexagenitidae)
in the Crato paleolake. .................................................................................................... 72
Figure 15. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies (Al and
Fe); volcanism proxies (Hg/Al and Hg/Fe ratios) and Hg concentration (ng g-1). B)
Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation in the depth of the lake
system (Fe/Mn) and δ18OVPDB. ....................................................................................... 78
Figure 16. Enrichment factor of paleoredox proxies (PbEF, MnEF and FeEF), and
paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13CVPDB) in the Crato paleolake.
A) Enrichment factor using Aluminum (Al) as a normalizer; B) Enrichment factor using
Iron (Fe) as a normalizer. ................................................................................................ 79
Figure 17. Principal component analysis with enrichment factor of trace metals (Ba, Cu,
Zn, Pb, Fe, Mn, and Ni), volcanism (Hg/Al and Hg/Fe), paleodetritic (Al and Fe), lake
lavel (Fe/Mn), paleoclimate conditions (Sr/Cu), paleosalinity (Sr/Ba) and the correlations
with mortality events. A) Enrichment factor using Aluminum as a normalizer; B)
Enrichment factor using Iron as a normalizer. ................................................................ 80
Figure 18. Scheme demonstrating the paleoenvironmental variations (wet-dry) of the
Konservat -Laggerstätten of the Crato paleolake. A) Arid paleoclimatic conditions and
mortality of Ephemeroptera; B) Humid paleoclimatic conditions and mortality of Dastilbe
sp..................................................................................................................................... 92
Figure 19. Map of the Araripe Basin, northeastern Brazil, highlighting the geographic
distribution of the Santana Group (including the Romualdo Formation)....................... 98
Figure 20. Average results of (Hg)sample in fossil taxa of the Romualdo Formation
analyzed in the present work ........................................................................................ 101
Figure 21. A summary of the Romualdo Formation trophic web based on litarature and
present Hgsample results, including the following groups or taxa 1) Phytoplankton; 2)
Zooplankton; 3) Santanichthys diasii; 4) Rhacolepis buccalis; 5) Tharrhias araripis; 6)
Vinctifer comptoni; 7) Neoproscinetes penalvai; 8) Batoidea indet.; 9) Benthic
invertebrates; 10) Cladocyclus gardneri; 11) Calamopleurus cylindricus; 12)
Ornithocheiriformes; 13) Thalassodrominae; 14) Other terrestrial Tetrapoda ............. 104
 SUMÁRIO
1. INTRODUÇÃO ..................................................................................................... 15
2. BACIA DO ARARIPE .......................................................................................... 20
2.1 Contexto Histórico .............................................................................................. 20
2.2 Contexto Geológico ............................................................................................. 21
3. INDICADORES GEOQUÍMICOS PALEOAMBIENTAISErro! Indicador não
definido.
3.1 Indicador de vulcanismo (Hg)............................................................................ 23
3.2 Indicadores das condições Paleoredox .............................................................. 25
3.3 Paleoprodutividade ............................................................................................. 29
3.4 Isótopo de Carbono (δ13CVPDB) .......................................................................... 32
3.5 Isótopo de oxigênio (δ18OVPDB) ........................................................................... 33
HIPÓTESE .................................................................................................................... 35
4. OBJETIVOS .......................................................................................................... 35
4.1 Objetivos Específicos .......................................................................................... 35
CAPÍTULO 1 ................................................................................................................ 37
5.1 Introduction ......................................................................................................... 40
5.2 Stratigraphic Settings ......................................................................................... 41
5.2.1 Barbalha Formation..................................................................................... 43
5.2.2 Crato Formation ........................................................................................... 44
5.2.3 Romualdo Formation ................................................................................... 45
5.3 Materials and methods ....................................................................................... 46
5.3.1 Total Organic Carbon (TOC) ...................................................................... 48
5.3.2 Stable isotopes (C and O)............................................................................. 48
5.3.3 Metals concentrations .................................................................................. 48
5.3.4 Mercury ......................................................................................................... 49
5.3.5 Enrichment factor ........................................................................................ 49
5.3.6 Statistics......................................................................................................... 50
5.4 Results .................................................................................................................. 51
5.4.1 Barbalha Formation..................................................................................... 51
5.4.2 Crato Formation ........................................................................................... 54
5.4.3 Romualdo Formation ................................................................................... 56
5.5 Discussion ............................................................................................................ 58
5.5.1 Paleosalinity .................................................................................................. 58
5.5.2 Paleoredox conditions .................................................................................. 60
 5.5.3 Volcanism and palaenvironmental changes ............................................... 62
5.7 Conclusion ........................................................................................................... 67
CAPÍTULO 2 ................................................................................................................ 69
6.1 Introduction ............................................................................................................ 71
6.2 Material and methods ............................................................................................ 73
6.2.1 Material studied............................................................................................ 73
6.2.2 Metals analysis .............................................................................................. 75
6.2.3 Mercury analysis .......................................................................................... 75
6.2.4 Stable isotopes (δ13CVPDB and δ18OVPDB) ..................................................... 75
6.2.5 Enrichment Factor (EF) .............................................................................. 76
6.2.6 Statistics methodology ................................................................................. 77
6.3 Results .................................................................................................................. 78
6.3.1 Characterization of the Crato paleolake .................................................... 78
6.3.2 Volcanism, paleoproductivity and paleoredox conditions in the Crato
paleolake................................................................................................................. 78
6.4 Discussion ............................................................................................................ 83
6.4.1 Characterization of the Crato paleolake .................................................... 83
6.4.2 Paleoproductivity ......................................................................................... 87
6.4.3 Paleoredox conditions of the Crato paleolake ........................................... 88
6.4.4 Volcanism ...................................................................................................... 88
6.4.5 Mortality events and paleoenvironmental changes ................................... 91
6.4.6 Exceptional fossil preservation in the Crato paleolake............................. 95
6.5 Conclusion ........................................................................................................... 96
CAPÍTULO 3 ................................................................................................................ 97
7.1 Introduction ......................................................................................................... 99
7.2 Methodology ...................................................................................................... 100
7.3 Trophic relations between fish species ............................................................ 102
7.4 The role of pterosaurs as mesopredators and opportunists .......................... 104
7.5 An integrative analysis of the Romualdo vertebrate assemblage ................. 104
8. Considerações finais ............................................................................................... 107
REFERÊNCIAS ......................................................................................................... 109
Material Suplementar- CAPÍTULO 1 ...................................................................... 136
Material Suplementar- CAPÍTULO 2 ...................................................................... 142
Material Suplementar- CAPÍTULO 3 ...................................................................... 148
1. INTRODUÇÃO
O planeta Terra passou por cinco grandes extinções em massa (Big five) ao longo
de sua história geológica: final do Ordoviciano (~ 444 Ma), quando cerca de 85% das
espécies presentes na época foram extintas; no Devoniano Superior (~ 372 Ma, 75% das
espécies extintas); no final do Permiano (~ 252 Ma, 95% das espécies extintas); no final
do Triássico (~ 201 Ma, 80% das espécies extintas) e no final do Cretáceo (~ 66 Ma, 75%
das espécies extintas, incluindo os dinossauros não-avianos) (Racki, 2021; Raup, 1986;
Raup, Sepkoski, 1982). Esses acontecimentos servem como base para compreender os
processos envolvidos durante as transições geológicas. Para isso, destacamos a
importância de informações essenciais para elucidar os fenômenos responsáveis pelos
eventos de extinção e os processos que os desencadearam, como através da
Quimioestratigrafia. A Quimioestratigrafia tem demonstrado ser uma ferramenta
essencial para caracterizar as condições deposicionais nas extinções do Ordoviciano (Lu
et al., 2021), Devoniano (Kuwahara et al., 2022; Lu et al., 2021), Permiano (Shen et al.,
2019; Sial et al., 2021), Triássico (Sun et al., 2015; Thibodeau et al., 2016) e Cretáceo
(Abu-Ali, El-Kammar, Kuss, 2020; Alvarez et al., 1980; Benigno, Sial, Lacerda, 2018;
Font et al., 2016; Sial et al., 2013).
Através da aplicação da Quimioestratigrafia observou-se anomalias de Irídio (Ir),
um elemento químico de origem sideral, associadas à extinção do Cretáceo-Paleógeno
com o impacto de um bólido e como principal causa da extinção dos dinossauros não
avianos (Alvarez et al., 1980). Através da aplicação da quimioestratigrafia também foi
possível observar anomalias do Hg, um indicador geoquímico do vulcanismo,
simultâneas às extinções nas Cretáceo-Paleógeno, Permiano-Triássico, Triássico-
Jurássico, Devoniano e Ordoviciano, podendo os eventos magmáticos terem
desencadeado mudanças climáticas através da emissão de CO2 e outros gases (e.g. SO2,
HCl, HF e CH4) (e.g. Font, Bond, 2021; Racki, 2021; Sial et al., 2013, 2016, 2021). Neste
contexto, vários indicadores geoquímicos como os metais-traço têm demonstrado ser
excelentes na identificação das variações da paleoprodutividade (Tribovillard et al., 2006,
1994), paleosalinidade (Wei, Algeo, 2020), estado paleoredox (Algeo, Li, 2020; Algeo,
Liu, 2020; Lewan, Maynard, 1982) e vulcanismo (Sanei, Grasby, Beauchamp, 2012; Sial
et al., 2010) durante os eventos mais extremos e de maiores crises biológicas da história
da Terra.
Vários proxies geoquímicos têm sido usados para a reconstrução paleoambiental,
possibilitando entender a origem de vários elementos químicos e, portanto, seus processos

15
de transporte e deposição. Aportes detríticos para bacias sedimentares são bem
identificados através da variação da concentração e distribuição de elementos geogênicos
como: Titânio (Ti), Silício (Si), Alumínio (Al) e Potássio (K) (Calvert, Pedersen, 1993;
Soua et al., 2011; Touati, Haji, 2019; Tribovillard et al., 1994). As condições paleoredox
no momento da deposição dos sedimentos é geralmente caracterizada pelo uso de
oligoelementos sensíveis ao estado redox, como: Ferro (Fe), Cádmio (Cd), Cromo (Cr),
Manganês (Mn), Molibdênio (Mo), Chumbo (Pb), Vanádio (V) e Arsênio (As) (Algeo e
Li, 2020). Enquanto para avaliar a magnitude da paleoprodutividade, geralmente são
usados metais-traço e suas razões de concentração, particularmente o Cobre (Cu), Zinco
(Zn), Níquel (Ni) e Bário (Ba) (Tribovillard et al., 2006). Além disso, macronutrientes
como o carbono e o fósforo também podem ser utilizados para determinar as condições
de produtividade (e.g. Steiner et al., 2017; Touati, Haji, 2019; Tribovillard et al., 2006).
Mais recentemente, o mercúrio (Hg), em conjunto com o carbono orgânico total (COT),
o Alumínio e o Ferro, tem sido utilizado para indicar contribuições vulcânicas em bacia
sedimentares marinhas e continentais (e.g. Benigno et al., 2018, 2021; Font et al., 2016;
Galloway et al., 2023; Grasby et al., 2019; Sial et al., 2016, 2013).
A Bacia do Araripe é reconhecida internacionalmente pelo seu rico acervo
fossilífero e excelente qualidade da preservação dos fósseis, sendo classificada como
Konservat- Lagerstätte (Assine, 2007). Esta bacia sedimentar estende-se por 9.000 km² e
abrange três estados do Nordeste brasileiro (Ceará, Pernambuco e Piauí) (Figura 1). É
considerada o registro sedimentar mais completo do Cretáceo Inferior das bacias
sedimentares do interior do Nordeste do Brasil (Assine, 1992, 2007; Neumann, 1999;
Valença, Neumann, Mabesoone, 2003). A sua complexidade está relacionada com o
registro dos processos de abertura e desenvolvimento do oceano Atlântico, apresentando
informações do processo de abertura do oceano Atlântico- períodos Pré-Rifte, Rifte, Pós-
Rifte I e Pós-Rifte II (Assine, 2007; Fambrini et al., 2020).
A aplicação da quimioestratigrafia na Bacia do Araripe ainda é pouco explorada em
comparação aos estudos fossilíferos, estratigráficos e sedimentológicos. Entre os estudos
quimioestratigráficos utilizando metais-traço destacam-se: Benigno et al. (2021), Bom et
al. (2021), Lúcio et al. (2022) e Salgado-Campos et al. (2021). Benigno et al. (2021)
identificaram eventos de vulcanismo no processo deposicional do Grupo Santana e
possíveis interferências paleoambientais locais. Bom et al. (2021), Lúcio et al. (2022) e
Salgado-Campos et al. (2021) identificaram mudanças da paleosalinidade,
paleoprodutividade e paleoredox nas Formações Romualdo, Ipubi e Crato,

16
respectivamente. Os estudos que visam a caracterização isotópica (δ13C, δ18O e δ34S)
restringem- se a Castro et al. (2017), Pontes et al. (2021), Varejão et al. (2021a, 2021b).
Castro et al. (2017) e Varejão et al. (2021a, 2021b) destacaram oscilações na
paleoprodutividade e paleotemperatura, enquanto Pontes et al. (2021) identificaram
condições extremamente redutoras influenciados pela sulfato-redução bacteriana.
Considerando as variações paleoambientais e os períodos caracterizados nos estudos
citados esses trabalhos estão focados principalmente no intervalo Aptiano-Albiano (~
121,4 a 113 Ma) do Cretáceo Inferior.
Em relação aos eventos globais que ocorreram durante o Aptiano, e que podem ter
influenciado as alterações paleoambientais já observadas na Bacia do Araripe, destacam-
se os Eventos Anóxicos Oceânicos (OAE) 1a e 1b, vinculados à ativação de Grandes
Províncias Ígneas (LIP’s) do Ontong Java e do Platô Kerguelen Sul (e.g. Coffin et al.,
2006; Erba et al., 2015; Keller, 2008; Walker-Trivett et al., 2024). Esses eventos citados,
no contexto global, foram responsáveis pelo soterramento de grande quantidade do COT,
anomalias na razão Hg/COT (vulcanismo) e enriquecimento por metais-traço. O
vulcanismo foi responsável pela emissão de grande quantidade de CO2 para atmosfera,
gerando perturbações no ciclo do carbono global (Bodin et al., 2023; Grasby et al., 2019).
Vale destacar que Benigno et al. (2021) encontraram anomalias de Hg no intervalo
Aptiano-Albiano na Bacia do Araripe e as associaram ao vulcanismo do Platô Kerguelen
Sul.
Dentro desse contexto, o presente estudo visa caracterizar a quimioestratigrafia da
Bacia do Araripe através da utilização de indicadores metálicos, com o intuito de
determinar: os aportes paleodetríticos (Al), paleoprodutividade (δ13CVPDB, COT, Cu, Ni,
Ba e Zn), condições de paleoredox (Cr, Fe, Pb, V, Mn, V/Cr, V/Ni e V/V+Ni), vulcanismo
(anomalias de Hg- Hg/TOC, Hg/Al e Hg/Fe), paleoclima (δ18OVPDB e Sr/Cu) e suas
relações com as mudanças paleoclimáticas e biológicas registradas na Bacia do Araripe
durante o Cretáceo Inferior.
O presente estudo é apresentado em 3 capítulos principais, a saber:

• CAPÍTULO 1: Caracterizar a geoquímica paleoambiental da transição

Aptiano-Albiano na Bacia do Araripe. Apresenta-se uma avaliação das condições
deposicionais do Grupo Santana (formações Barbalha, Crato e Romualdo), sendo possível
estabelecer uma correlação com os Eventos Anóxicos Oceânicos (OAE 1a e 1b).

17
 • CAPÍTULO 2: Avaliar as correlações bioestratigráficas entre os eventos de
mortalidade registrados no Konservat-Lagerstätte do paleolago Crato e a
quimioestratigrafia no Cretáceo Inferior (Formação Crato) da Bacia do Araripe. Neste
caso o manuscrito irá demonstrar os fatores responsáveis pelos eventos cíclicos de
mortalidade registrados na Formação Crato.
• CAPÍTULO 3: Estudo com o objetivo de identificar o desenvolvimento da
cadeia paleotrófica no Konservat -Lagerstätte da Formação Romualdo através das
variações das concentrações do mercúrio (Hg). Observou-se o desenvolvimento da
paleoictiofauna e o comportamento de outros organismos (pterossauros) na Formação
Romualdo.

18
Figura 1. Localização e distribuição das litofácies da Bacia do Araripe.

Figura 2. Localização e distribuição das litofácies da Bacia Sedimentar do Araripe. Fonte: Assine (2007).

Figura 3. Localização e distribuição das litofácies da Bacia Sedimentar do Araripe.

Figura 4. Localização e distribuição das litofácies da Bacia Sedimentar do Araripe. Fonte: Assine (2007).

Fonte: Assine (2007).

19
2. BACIA DO ARARIPE
2.1 Contexto Histórico
Os primeiros registros de descrição dos fósseis na Bacia do Araripe são de 1800,
quando foram enviados relatórios do pesquisador português João da Silva Feijó ao
governador da Capitania do Ceará sobre a ocorrência de peixes e anfíbios com tecidos
moles (Silva, 2007). Posteriormente, expedições alemãs ocorreram entre 1817 – 1823,
chefiadas por von Spix e von Martius na província do Siará, atual Estado do Ceará
(Maisey, 1991). No século XIX, as primeiras descrições fossilíferas foram de peixes,
principalmente, nas concreções calcárias da Formação Romualdo. No século XX grandes
expedições da Inspetoria Federal de Obras contra as Secas, atual Departamento Nacional
de Obras contra as Secas (DNOCS), desenvolveram estudos focados em fósseis de peixes
(Bantim, Lima, Saraiva, 2021). Apenas em meados dos anos 60, foram realizados os
primeiros estudos voltados a outros grupos fósseis na Formação Romualdo, como: o
primeiro crocodiliano, moluscos e equinóides-registro da influência marinha nesta
formação (Braun, 1966; Price, 1959). Além disso, o trabalho inicial de Beurlen (1962)
estabeleceu os primeiros critérios estratigráfico da Bacia do Araripe, definindo as
Formações Cariri, Missão Velha, Santana e Exu.
Nas décadas de 70 e 80, a expansão dos estudos gravimétricos (Rand, Manso,
1984), do mapeamento geológico de Ghignone (1986) e o início da exploração do calcário
laminado da Formação Crato auxiliaram no desenvolvimento e conhecimento sobre a
estratigrafia e a biodiversidade na Bacia do Araripe, como: copépodes (Cressey,
Patterson, 1973), ostracodes (Bate, 1972), pólens (Lima, 1978), tartarugas (Price, 1973),
pterossauros (Price, 1971) e vários grupos de insetos, como: os Blattodea (Pinto, Purper,
1986) e Lepidoptera (Martins-Neto, 2006). Para a Formação Romualdo, observou-se a
presença de tubarões (Brito, Ferreira, 1989), tecido moles de peixes bem preservados
(Martill, 1988), crocodilos (Kellner, 1987), pterossauros (Kellner, 1996; Kellner, Almeida
Campos, 1988, 1994; Pêgas, Costa, Kellner, 2021) e dinossauros (Kellner, 1996; Sayão
et al., 2020). Devido ao grande acervo fossilífero da Bacia do Araripe, em 1985 foi criado
por Plácido Cidade Nuvens o Museu de Fósseis de Santana do Cariri, com o objetivo de
proteger os exemplares fósseis encontrados na Bacia do Araripe (Bantim, Lima, Saraiva,
2021; Bétard et al., 2018).
No final do século XX e início do século XXI as descobertas fossilíferas e estudos
estratigráficos (Assine, 1992, 2007; Ponte, Ponte-Filho, 1996) estabeleceram as

20
sequências deposicionais na Bacia do Araripe associando-as com o processo de abertura
do oceano Atlântico. Além disso, a descrição fossilífera dos calcários laminados da
Formação Crato e dos folhelhos betuminosos da Formação Romualdo auxiliaram na
classificação destas formações como Konservat-Lagerstätte, devido ao excelente estado
de preservação do conteúdo fossilífero e grande quantidade de fósseis (Maisey, 1991;
Martill, 1988). Como resultado de impedir o tráfico de fósseis e devido à alta qualidade
de preservação dos fósseis, a parceria entre a Universidade Regional do Cariri (URCA) e
o Governo do Estado do Ceará solicitou em 2005 a candidatura do Geopark Araripe para
ingressar na Rede Global de Geoparques. No ano de 2006 a UNESCO (Nações Unidas
para a Educação, a Ciência e a Cultura) reconheceu o Geopark Araripe incluso na Rede
Global de Geoparks (Global Geoparks Network), tornando-se o primeiro geoparque da
América Latina e Caribe (Bantim, Lima, Saraiva, 2021; Bétard et al., 2018; Mochiutti et
al., 2012).

2.2 Contexto Geológico

A Bacia do Araripe, com área de 9.000 km² abrange os Estados do Ceará, Piauí e
Pernambuco (Nordeste do Brasil) (Assine, 1992, 2007). A Bacia do Araripe desenvolveu-
se através da reativação das falhas do embasamento cristalino Pré-Cambriano da Zona
Transversal da Província Borborema, formada durante a Orogênese Brasiliana-Pan-
Africana. Além disso, encontra-se delimitada pelas Zonas de cisalhamento
Neoproterozóicas de Pernambuco e Patos (Assine, 2007; Brito Neves; Santos; Van
Schmus, 2000; Neves et al., 1995). A origem e a evolução da Bacia do Araripe decorrem
do processo de ruptura do supercontinente Gondwana e abertura do oceano Atlântico,
sendo este evento o responsável pelo desenvolvimento das bacias marginais brasileiras e
africanas (Alkmim, 2015; Godot Souza et al., 2022).
A Bacia do Araripe apresenta a maior complexidade entre todas as bacias
sedimentares do interior do Nordeste brasileiro, pois ocorrem 5 sequências deposicionais,
além de apresentar duas feições geomorfológicas: a Chapada do Araripe e o Vale do Cariri
(Assine, 2007; Peulvast e Bétard, 2015). A Chapada do Araripe apresenta orientação
Leste-Oeste e abrange as sequências deposicionais Cretáceas dos eventos Pós-Rifte I e II
(Aptiano-Cenomaniano) do processo de abertura do Oceano Atlântico (Figura 2). O Vale
do Cariri contém os registros dos períodos mais antigos da Bacia do Araripe, englobando
as sequências Paleozoicas, Pré-Rifte e Rifte do evento de ruptura do Gondwana (Fambrini
et al., 2020).

21
 Como relatado anteriormente, a Bacia do Araripe apresenta sequência cinco
sequências tecno-sedimentares (Assine, 2007; Fambrini et al., 2019):
• Sequência Sinéclise: Arenitos médios a grossos fluviais da Formação Cariri, com
idade neordoviciana a eossiluriana;
• Sequência Pré-Rifte: Apresentam idade Jurássica e são compostos por pelitos
vermelhos alternados com arenitos calcíferos da Formação Brejo Santo
(Neojurássico) e pelos arenitos da parte basal da Fm. Missão Velha;
• Sequência Rifte: Neste estágio a idade é Cretácea Inferior, representado inicialmente
pelos arenitos da parte superior da Fm. Missão Velha e pelos pelitos da Formação
Abaiara;
• Sequência Pós-Rifte: Possui dois estágios, o estágio Pós-Rifte I, com idade Aptiana-
Albiana é representado pelo Grupo Santana (Formações Barbalha, Crato, Ipubi e
Romualdo); enquanto o estágio Pós-Rifte II, com idade Albiana-Cenomaniano,
apresentam ambiente deposicional aluvial das Formações Araripina e Exu.
Figura 2. Carta estratigráfica da Bacia do Araripe.

Figura 5. Esquema ilustrativo do ciclo do mercúrio (Hg), destacando o seu papel como
indicador geoquímico de atividade vulcânica.Figura 2. Carta estratigráfica da Bacia do Araripe.

Fonte: Fambrini et al., (2020)

22
3. INDICADORES GEOQUÍMICOS PALEOAMBIENTAIS
3.1 Indicador de vulcanismo (Hg)
As atividades vulcânicas têm papel importante na emissão do mercúrio (Hg),
sendo a principal forma de entrada natural desse elemento para a atmosfera (Pyle e
Mather, 2003). O Hg é emitido para a atmosfera na forma de vapor (Hg0), com grande
distribuição global atingindo a estratosfera e com tempo de residência de 1 a 3 anos
(Benigno, Sial, Lacerda, 2018). Na atmosfera, o mercúrio pode sofrer oxidação e formar
o Hg2+, forma iônica mais reativa e solúvel em água. Levando em conta essa
característica, o Hg pode ser incorporado no ciclo hidrológico e sofrer deposição através
da precipitação (Figura 3). Após a deposição, este elemento pode ser adsorvido aos
minerais presentes no solo e na água, e fazer parte do ciclo das rochas, sendo um excelente
indicador de atividades vulcânicas tanto no presente quanto em situações pretéritas (e.g.
Benigno et al., 2018; Grasby et al., 2019; Sial et al., 2016).
Figura 6. Esquema ilustrativo do ciclo do mercúrio (Hg), destacando o seu papel como indicador
geoquímico de atividade vulcânica.

Figura 7. Classificação redox utilizando a razão entre metais proposta por Jones e Manning
(1994).Figura 8. Esquema ilustrativo do ciclo do mercúrio (Hg), destacando o seu papel como
indicador geoquímico de atividade vulcânica.

Fonte: Adaptado de Percival et al., (2015).

23
 No ambiente terrestre, o mercúrio pode sofrer a influência de diversos processos
bióticos e abióticos, podendo complexar com o COT, Al e em sulfetos (H2S) (Ericksen et
al., 2003). No caso da relação Hg com o COT e o sulfetos, há a formação dos complexos
orgânicos estáveis e precipitados em sulfetos-Hg (Gamboa Ruiz, Tomiyasu, 2015; Pyle,
Mather, 2003). A utilização do COT destaca-se devido a sua grande capacidade de formar
complexos orgânicos, sequestrando o Hg ao longo do tempo geológico (Grasby et al.,
2019; Sial et al., 2010). Estudos anteriores encontraram uma correlação estratigráfica
entre as anomalias da razão Hg/COT com os eventos extinção em massa, indicando a
interferência da ativação de Grandes Províncias Ígneas (LIP’s) nas mudanças climáticas,
resultando na deterioração das condições da vida nos ecossistemas aquáticos e terrestres
(Grasby et al., 2019). Entretanto, é possível utilizar correlações geoquímicas entre
Hg/paleodetríticas (Al, Fe, Zr, Ti e filossilicatos), indicando a interferência dos processos
detríticos no soterramento do Hg (Font et al., 2016; Sabatino et al., 2018; Sanei, Grasby,
Beauchamp, 2012; Sial et al., 2013)
Anomalias do Hg foram encontradas na transição Cretáceo-Paleógeno
(vulcanismo do Deccan) (Font et al., 2016; Sial et al., 2013, 2016, 2018) , Triássico-
Jurássico (Província Magmática do Atlântico Central - CAMP) (Thibodeau et al., 2016),
Permiano-Triássico (Siberian Trap) (Sanei, Grasby, Beauchamp, 2012; Sial et al., 2021),
Devoniano (Viluy Trap) (Lu et al., 2021) e Ordoviciano-siluriano (Lu et al., 2021). Além
disso, perturbações de menor impacto também estão associadas com ativação das grandes
LIP’s, denominadas de Eventos de Anoxia Oceânica (OAE’s). Ao longo do tempo
geológico, foram identificadas as seguintes anomalias na razão Hg/COT associadas a
eventos de OAE: OAE Toarciano (~ 183 Ma) (Gambacorta et al., 2023; Liu et al., 2020),
OAE 1a (~ 120 Ma) (Erba et al., 2015; Fan, et al., 2021; Núñez-Useche et al., 2020),
OAE 1b (~ 113 Ma) (Galloway et al., 2023; Sabatino et al., 2015, 2018) e OAE 1d (~ 103
Ma) (Rodríguez-Cuicas, Montero-Serrano, Garbán, 2019).
As ativações das LIP’s foram responsáveis pelo enriquecimento dos oceanos por
metais-traço, aumento da produtividade, anoxia oceânica, mudanças da comunidade
planctônica, crises dos organismos calcificadores, mudanças climáticas e pequenas
extinções (e.g. Bodin et al., 2023; Bond, Grasby, 2017; Davies et al., 2020; Davis, 2023;
Keller, 2008). De acordo com Robock, (2000), a ativação das LIP’s ocasiona aumento no
teor de dióxido de carbono (CO2) na atmosfera, podendo causar acidificação dos oceanos;
maior incidência de chuva ácida; danos à camada de ozônio (O3) atmosférico; aumento
da radiação UV-B; aumento na concentração de metais tóxicos; resfriamento da

24
superfície; aquecimento da estratosfera; aumento da poeira atmosférica, causando
bloqueio da luz solar e diminuição da temperatura.

3.2 Indicadores das condições Paleoredox

Os metais-traço são sensíveis às mudanças do estado redox, sendo removidos do
ambiente aquoso e transferidos para o sedimento quando submetidos a alterações do
potencial redox do meio. Esta transferência pode ocorrer por adsorção com os oxi-
hidróxidos (Fe, Al e Mn), soterramento com a matéria orgânica (formação de compostos
organometálicos), e co-precipitação com minerais (Tribovillard et al., 2006). As
condições deposicionais são influenciadas diretamente pela disponibilidade de oxigênio
e enxofre no ambiente, o que pode gerar o aumento ou a diminuição das concentrações
desses elementos no sedimento (Algeo, Li, 2020; Tribovillard et al., 2006). Estudos
anteriores demonstraram a eficácia na aplicação de V, Cr, Fe, Mn, Ni e Pb para identificar
as alterações do estado paleoredox em diversos períodos, ambientes deposicionais e
distintas estratigrafias: Criogeniano, Cambriano (evento SPICE) (Mackey, Stewart,
2019), Edicarano-Cambriano (Guo et al., 2007), Devoniano (Kuwahara et al., 2022),
Aptiano-Albiano (Hamid et al., 2024; Sabatino et al., 2015; Saucedo-Samaniego et al.,
2021), Cenomaniano-Turoniano (Bentum et al., 2009) e grandes eventos de extinção em
massa (Permiano-Triássico e Cretáceo-Paleógeno) (Abu-Ali; El-Kammar; Kuss, 2020;
Benigno; Sial; Lacerda, 2018; Sial et al., 2018, 2021).
Além disso, com o intuito de determinar a característica geral dos ambientes
deposicionais, nós seguimos a classificação proposta por Jones, Manning (1994) e Tyson,
Pearson (1991) (Figura 4). Nesta condição o ambiente é categorizado de acordo com a
concentração de oxigênio e a presença dos sulfetos oriundos da sulfato-redução
bacteriana no ambiente deposicional. Neste contexto, os ambientes são classificados em
óxico (> 2mL O2L-1), dióxico (2 a 0 mL O2L-1), subóxico (0 mL O2L-1, Fe2+> 0, H2S= 0)
e anóxico-euxínico (0 mL O2L-1, Fe2+= 0, H2S > 0) (Algeo, Li, 2020; Algeo, Maynard,
2004; Tribovillard et al., 2006).
Jones e Manning (1994) classificaram as condições paleoambientais (óxido,
dióxico e anóxico) através das razões: V/Cr (Vanádio/Cromo) e V/V+Ni
(Vanádio/Vanádio + Níquel). Galarraga et al., (2008) utilizaram a razão bimetal V/Ni
também para classificar as condições óxicas deposicionais. A razão V/Cr < 2,0 indica que
o ambiente é óxico; condições dióxicas ocorrem entre 2,0 – 4,25; e subóxicas a anóxicas
quando a razão V/Cr > 4,25. Para a razão V/Ni, os valores entre 1,9 - 3 indicam ambiente

25
 subóxico, enquanto valores de V/Ni > 3,0 são típicos de ambiente anóxicos. Utilizando-
se a razão V/V+Ni, os valores > 0,84 indicam condições euxínicas, entre 0,54 – 0,83
ambiente anóxico, enquanto valores entre 0,46 a 0,54 dióxico (Galarraga et al., 2008;
Jones, Manning, 1994; Rivera et al., 2018).

Figura 9. Classificação redox utilizando a razão entre metais proposta por Jones e Manning (1994).

Figura 10. Classificação redox utilizando a razão entre metais proposta por Jones e Manning, (1994).

Figura 11. Classificação redox utilizando a razão entre metais proposta por Jones e Manning (1994).

Figura 12. Classificação redox utilizando a razão entre metais proposta por Jones e Manning, (1994).

Fonte: Adaptado de Jones; Manning (1994) e Algeo; Liu (2020).

Para determinar as alterações relevantes das mudanças paleoredox pode ser

utilizado o fator de enriquecimento (EF) dos metais: PbEF, VEF, CrEF, MnEF e Fe EF
.A
aplicação desses metais leva em consideração o seu comportamento em ambiente redutor
e ambiente óxico (Algeo, Liu, 2020; Algeo, Maynard, 2004). Em ambientes óxicos a
tendência dos metais-traço é adsorver aos oxi-hidróxidos de Al, Fe e Mn, além de co-
precipitar com a matéria orgânica formando complexos orgânicos. Para ambiente
anóxicos e submetidos à sulfato- redução bacteriana, os metais-traço adsorvem com o
sulfeto de hidrogênio (H2S) e são transferidos para o compartimento sedimentar. A figura
5 demonstra o comportamento dos metais-traço indicadores de paleoredox no ambiente
aquático.

26
Figura 5. Comportamento geoquímico dos indicadores geoquímicos das condições paleoredox no ambiente
aquático.

Figura 6. Comportamento dos indicadores geoquímicos da paleoprodutividade no ecossistema

aquático.Figura 5. Comportamento geoquímico dos indicadores geoquímicos das condições paleoredox no
ambiente aquático.

Fonte: Autor.

A seguir, serão descritos os comportamentos dos metais-traço utilizados como

indicadores das condições paleoredox em ambientes aquáticos quando submetidos a
ambiente óxicos e anóxicos:
Vanádio (V): apresenta três espécies iônicas (penta-, tetra- e tri- valente), sendo
a sua espécie predominante modificada de acordo com o estado redox do ambiente
deposicional influenciado diretamente pelas perturbações climáticas do ambiente (Fan et
al, 2021; Wu et al., 2020). A forma pentavalente do V é comum em condições óxicas e
normalmente encontra-se adsorvido aos oxi-hidróxidos de Fe-Mn (Wu et al., 2019). Em
ambientes redutores, há a redução da forma oxidada para a forma V(IV), e co-
precipitação com minerais e, principalmente, com a matéria orgânica, conforme
observado durante o evento OAE 2- Cenomaniano-Turoniano (94 Ma) (Ostrander,
Owens, Nielsen, 2017). Ambientes extremamente redutores, onde há a presença de H2S
livre devido à sulfato-redução bacteriana, favorecem a redução para a forma trivalente
predominante nem condições anóxicas (Gustafsson, 2019; Lewanand, Maynard, 1982;
Tribovillard et al., 2006; Wu et al., 2020, 2019).
Cromo (Cr): O Cr (VI) é predominante em ambientes oxigenados (CrO42-),
enquanto sua forma reduzida, Cr (III), principal espécie encontrada no sedimento, é
predominante em ambientes subóxicos na forma de Cr(OH)3 (Calvert, Pedersen, 1993;

27
Nasemann et al., 2020). O processo de sedimentação do Cr inicia-se no processo de
adsorção às partículas de matéria orgânica, sendo depositados em condições com pouco
oxigênio disponível (Reinhard et al., 2014). A redução do cromo em ambientes óxicos
pode ser catalisada pela presença de agentes redutores, como: matéria orgânica, H2O2 e
Fe (II) (Saad et al., 2017). Além disso, há indícios da mediação microbiana na zona de
mínimo de oxigênio marinho (OMZ), favorecendo a predominância do Cr trivalente
(Huang et al., 2021). Estudos anteriores identificaram que há períodos da história da Terra
que a forma Cr (III) foi predominante, devido à desoxigenação marinha e expansão da
OMZ (Nana Yobo et al., 2022).
Chumbo (Pb): o Pb em condições óxicas encontra-se na forma de cátion livre
(Pb+), podendo ser adsorvido com o carbonato (PbCO3). Em condições anóxicas, a
tendência é haver precipitação com espécies de sulfeto (Algeo, Maynard, 2004; Morse,
Luther, 1999). A assimilação do Pb com os sulfetos ocorre também em condições
euxínicas (2 a 0 mL O2 L-1) demonstrando alta capacidade desse elemento em precipitar
quando submetido à redução do oxigênio (Gregory et al., 2015). O processo de deposição
do Pb em ambientes anóxicos está associado com a presença de piritas diagenéticas em
xisto preto e outras litofácies (Tribovillard et al., 2006). Os estudos de Algeo, Liu (2020)
e Milot et al. (2021) demonstraram o enriquecimento de Pb em rochas do Fanerozóico
durante grandes eventos de anoxia (Criogeniano- 613 Ma, Devoniano Superior- 395 Ma,
OAE Toarciano- 186 Ma, e nos eventos OAE 1a- 120 Ma, OAE 1b -114 Ma, OAE 2- 93
Ma), indicando a influência direta na formação dos minerais de sulfetos (pirita) no
processo deposicional do Pb devido à baixa concentração de oxigênio do ambiente.
Manganês (Mn): o Mn é encontrado na natureza nas formas Mn2+ e MnCl+, sendo
comum a forma Mn (II) em ambientes anóxicos. Nos ambientes sedimentares com altas
concentrações de oxigênio é comum suas formas insolúveis Mn (III) e Mn (IV) (Algeo,
Maynard, 2004; Tribovillard et al., 2006). As formas oxigenadas do Mn são responsáveis
pela transferência de metais-traço do compartimento aquoso para o sedimento através da
formação de oxihidróxidos (MnO2) (Gambacorta et al., 2023). Estudos anteriores
demonstraram que durante o Grande Evento de Oxidação (GOE, entre 2.501 e 2.220 Ga)
o Mn teve grande capacidade de precipitar de metais-traço (As, Cu, Zn, Pb, Co, Ni, Cr e
U), transferindo-os do ambiente aquático para o sedimento (Hashempour et al., 2023;
Konovalov et al., 2004). Na interface água-sedimento, em contato com o ambiente
redutor, pode ocorrer a dissolução do manganês para a forma Mn (II) (Robbins et al.,
2023). Neste caso, retorna para a coluna de água por difusão ascendente podendo

28
precipitar novamente através da adsorção com o carbonato de cálcio formando o mineral
rodocrosita (MnCO3) e/ou precipitar com a pirita (Santos et al., 2022).
Ferro (Fe): o ferro é encontrado na natureza em duas formas principais, nas quais
o seu comportamento está associado com as concentrações de oxigênio do ambiente. O
Fe (II) é comum em ambientes anóxicos, enquanto o Fe (III) está associado com os oxi-
hidróxido (Tribovillard et al., 2006). A forma oxi-hidróxido de Fe possui grande
capacidade de transporte e transferência de outros metais-traço para o compartimento
sedimentar (Ramírez-Pérez, Blas, 2017). Este elemento atua como limitante no
desenvolvimento da cadeia trófica dos ambientes aquáticos e forma complexos com a
matéria orgânica (Weber, Allard, Benedetti, 2006). Sob condições redutoras e ricas em
matéria orgânica, ocorre a formação de piritas (FeS2) mediada pela sulfato-redução
bacteriana. Quando há o aumento do oxigênio, o Fe (II) é liberado na interface-água
sedimento e retorna para sua fase Fe (III) (Chen et al., 2022; Tribovillard et al., 2006).
Como exemplo de mudanças do estado redox no passado geológico, pode-se destacar o
evento OAE-Toarciano, a ativação da LIP Karoo -Ferrar foi responsável panoxia oceânica
e formação de piritas framboidais, que também foi capaz de adsorver metais-traço e
transferir esses elementos para o compartimento sedimentar (Chen et al., 2023).

3.3 Paleoprodutividade
Para determinar a variação da paleoprodutividade em eventos de perturbações no
ciclo do carbono (OAE e extinções em massa), normalmente utilizam-se o carbono
orgânico total (COT) e os isótopos de carbono (δ13CCarbonato e δ13COrgânico). Estes eventos
normalmente são marcados pela deposição de folhelhos ricos em COT e/ou mudanças
isotópicas no comportamento do carbono (Davis, 2023; Grasby et al., 2019). Entretanto,
a adição de outros indicadores geoquímicos, como os metais-traço, auxilia a determinar
as mudanças da paleoprodutividade durante os eventos onde há a perturbações no ciclo
do carbono (Galloway et al., 2023; Sabatino et al., 2015). Neste contexto, o uso de metais-
traço essenciais e/ou que tem forte correlação com a matéria orgânica (Bário, Cobre,
Zinco e Níquel) têm demonstrado ser uma importante ferramenta para determinar
alterações na paleoprodutividade durante as mudanças climáticas globais (Lu et al.,
2021).
Para determinar as alterações da paleoprodutividade foi aplicado o Fator de
Enriquecimento (FE) para o CuEF, ZnEF, NiEF e BaEF. O uso desses elementos está
vinculado a suas capacidades de adsorção com o COT e por serem elementos essenciais

29
 no desenvolvimento da cadeia trófica, indicando oscilações e condições anômalas da
paleoprodutividade (Steiner et al., 2017; Tribovillard et al., 2006). A figura 6 demonstra
o comportamento dos metais-traço de paleoprodutividade no ambiente.

Figura 6. Comportamento dos indicadores geoquímicos da paleoprodutividade no ecossistema aquático.

Figura 13. Comportamento dos indicadores geoquímicos da paleoprodutividade no ecossistema aquático.

Figura 7. Comportamento isotópico do δ13Ccarbonato de acordo com os períodos de variações magmáticas.Figura

6. Comportamento dos indicadores geoquímicos da paleoprodutividade no ecossistema aquático.

Figura 14. Comportamento dos indicadores geoquímicos da paleoprodutividade no ecossistema aquático.

Fonte: Autor.

A seguir serão descritos o comportamento dos metais-traço utilizados como

indicadores geoquímicos da paleoprodutividade em ambientes aquáticos e os processos
deposicionais que influenciam em sua deposição:
Cobre (Cu): o cobre apresenta uma correlação positiva com a produção primária
funcionando como um micronutriente para o desenvolvimento da cadeia trófica (Pinedo-
González et al., 2015). Além disso, forma complexos organometálicos estáveis
acelerando o processo de deposição e enriquecimento do sedimento, sendo assim um
importante indicador geoquímico das variações dos fluxos deposicionais da matéria
orgânica. Esta aplicabilidade foi usada nos estudos de Sabatino et al. (2015) e Núñez-
Useche et al. (2020), durante os eventos de anoxia oceânica (OAE 1a e 1b), os autores
observaram que durante a ativação dos vulcanismos do Ontong Java e do Planalto
Kerguelen, respectivamente, foram registrados o aumento do Cu devido ao aumento da
paleoprodutividade. No sedimento, o Cu (II) é complexado com a matéria orgânica em
condições anóxicas, pode ser reduzido via sulfato-redução bacteriana, tendo como

30
resultado dessa mineralização o Cu(I). Posteriormente, pode precipitar na forma de
sulfeto de cobre (CuS) (Ai et al., 2023; Steiner et al., 2017).
Zinco (Zn): em condições óxicas o Zn encontra-se em sua forma solúvel (Zn2+ ou
ZnCl+), podendo complexar com a matéria orgânica e adsorver aos oxi-hidróxidos de Fe
e Mn (Tribovillard et al., 2006). O Zn em sua forma oxidada é um micronutriente
essencial e limitante para o desenvolvimento da produtividade primária nos ambientes
aquáticos (Gueguen, Rouxel, Fouquet, 2022). A correlação existente do Zn com o COT
ao longo do tempo geológico demonstra a importância do Zn na base da cadeia trófica e,
portanto, capaz de identificar períodos com maiores contribuições orgânicas (Benamara
et al., 2020). Além disso, quando submetidos a condições anóxicas (principalmente
quando influenciado pela sulfato-redução), esse elemento pode precipitar com os sulfetos
livres, adsorvendo às piritas framboidais, formando a esfarelita (Ai et al., 2023).
Níquel (Ni): é encontrado em duas formas principais nos ambientes óxicos (Ni+2
e NiCl+), sendo frequentemente encontrado na natureza complexado com carbonatos
(NiCO3) (Algeo, Liu, 2020; Algeo, Maynard, 2004; Calvert, Pedersen, 1993). Em altas
concentrações podem estar vinculados com condições deposicionais anóxicas, sendo
comum estar associado com os folhelhos ricos em matéria orgânica e em ambientes ricos
em sulfetos (Galarraga et al., 2008). O processo deposicional do Ni em condições
anóxicas ocorre com a sedimentação e complexação com a matéria orgânica, formando
compostos organometálicos (Rinklebe, Shaheen, 2017). Este processo foi demonstrado
por Sabatino et al. (2015) durante o OAE 1b, onde há o aumento da concentração do Ni
em conjunto com o soterramento do COT devido ao aumento da anoxia. Quando
submetido a ambiente onde ocorre sulfato redução bacteriana, o Ni liga-se aos sulfetos
formando sulfeto insolúvel (NiS) que pode ser adsorvido por solução sólida das piritas
autigênicas (Lewan, Maynard, 1982; Lúcio et al., 2022).
Bário (Ba): Nos ambientes aquáticos o Ba associa-se com os sulfatos formando a
barita (BaSO4), onde este mineral pode associar-se aos carbonatos, matéria orgânica e
sílica biogênica (Robin et al., 2003). Este elemento é adsorvido pelo sulfato (SO4) oriundo
da degradação da matéria orgânica, formando este mineral e precipitando no
compartimento sedimentar (House, Norris, 2020; Tribovillard et al., 2006). Neste caso,
os cristais de barita têm a capacidade de registrar as oscilações da paleoprodutividade
devido a correlação com a matéria orgânica (Liguori, Almeida, Rezende, 2016; Shen et
al., 2015).

31
3.4 Isótopo de Carbono (δ13CVPDB)
Os isótopos de carbono estão nos ambientes aquáticos em duas formas estáveis:
12 13
C (99% do carbono) e C (1% do carbono). As suas proporções variam na natureza
mediadas por processos químicos, físicos e biológicos variando as suas concentrações de
acordo com os eventos a que são submetidos no espaço e no tempo (Pessenda et al., 2005).
Para determinar os desvios das proporções entre 12C e 13C utiliza-se a notação δ13CVPDB
(Vienna Pee Dee Belemnite) (Hoefs, 2009). Na atmosfera, os valores do δ13CO2
atmosférico apresentam valores negativos (-6,6 ‰), sendo sua concentração alterada
quando por processos bioquímicos e físicos nos reservatórios marinhos e continentais
(Graven, Keeling, Rogelj, 2020).
No ambiente terrestre os isótopos de δ13CO2 são fracionados durante a fotossíntese
(~ 8‰). É importante destacar que dependendo do tipo de planta, C3 (árvores) e C4
(gramíneas), também há discriminação isotópica (Swart, 2015). No ambiente aquático, o
CO2 entra por difusão, carregando a assinatura isotópica do δ13CO2 atmosférico. Em
seguida, os processos físico-químicos (bomba de solubilidade) e biológicos (bomba
biológica) modificam a assinatura isotópica do δ13CCO2 atmosférico (Eide et al., 2017).
No caso da bomba de solubilidade, há a reação química do CO2 com a água formando o
Carbono Inorgânico Dissolvido (DIC), formando outros compostos: H2CO3, HCO-3 e
CO2-3 (Millero, 2007). No caso da bomba biológica, os processos que mediam a assinatura
isotópica do δ13C são a fotossíntese (~ -24 a -20‰) e a degradação bacteriana
(McCormack, Kwiecien, 2021). Quando o fitoplâncton incorpora o 12C, fração mais leve,
13
ocorre o enriquecimento do C nas águas superficiais. Neste caso, a matéria orgânica
particulada formada assimila a assinatura e registra as condições da paleoprodutividade
(Swart, 2015).
As oscilações do δ13CCarbonato são controladas pela variação do pH, pois controlam
a relação entre a precipitação ou dissolução dos minerais de aragonita e calcita nos
ecossistemas aquáticos (Weissert et al., 1998; Weissert, Erba, 2004). Dentro desse
contexto, incursões positivas do δ13CCarbonato são indícios de um período com maior
preservação e produção dos organismos calcificadores, enquanto incursões negativas do
δ13CCarbonato assinalam uma crise biológica dos calcificadores, diminuindo o
enriquecimento deste elemento e aumentando o soterramento do carbono orgânico (Eide
et al., 2017; O’Leary, 1981).

32
 Exemplo da oscilação do δ13CCarbonato pode ser destacado durante as transições
Cretáceo-Paleógeno (~ 66 Ma) e Permiano-Triássico (~ 251 Ma), foram constatadas
crises biológicas do plâncton marinho (Shen et al., 2019; Sial et al., 2013). As incursões
negativas do δ13CCarbonato e as anomalias de Hg demonstram que as ativações das grandes
LIP’s (Deccan e Siberian Trap) foram responsáveis por injetar grandes quantidades de
CO2 na atmosfera, tendo como resultado acidificação oceânica e crises biológicas,
principalmente sobre os organismos calcificadores (Figura 7) (Font et al., 2016; Sanei,
Grasby, Beauchamp, 2012; Sial et al., 2018, 2021). Nos eventos de extinções do PTE e
KPg as perturbações do plâncton marinho resultaram na supressão das plataformas
continentais carbonáticas e expansão das plataformas siliciclásticas (Beauchamp; Grasby,
2012; Grasby et al., 2015).

Figura 7. Comportamento isotópico do δ13CCarbonato de acordo com os períodos de variações magmáticas.

Figura 15. Comportamento isotópico do δ13Ccarbonato de acordo com os períodos de variações

magmáticas.

Figure 8. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the location of the
Araripe Basin- BSA (yellow circle) and the volcanisms of Ontong Java- OJP (red star) and Southern
Kerguelen Plateau- SKP (white star). B) Map of the location of the sampling points in the Araripe
Basin.Figura 7. Comportamento isotópico do δ13Ccarbonato de acordo com os períodos de variações
magmáticas.

Figura 16. Comportamento isotópico do δ13Ccarbonato de acordo com os períodos de variações

magmáticas.

Fonte: Autor.

3.5 Isótopo de oxigênio (δ18OVPDB)

Os isótopos de oxigênio (δ18O) são encontrados na natureza nas fases sólidas,
16
líquidas e gasosas. As três formas isotópicas principais existentes na natureza são O
(99,757%), 17O (0,038%) e 18O (0,205%) (Gradstein, Ogg et al., 2020). Por conta de sua
18 16
abundância isotópica, utiliza-se a razão O/ O para determinar as alterações

33
paleoclimáticas (Hoefs, 2009). O δ18OVPDB é utilizado para carbonatos de baixa
temperatura, enquanto o δ18OSMOW são usuais em outras matrizes (água, silicatos,
fosfatos, sulfatos e carbonatos de altas temperatura) (Gradstein, Ogg et al., 2020; Pearson,
2012). Durante a sua deposição, os registros do δ18O em carbonatos são influenciados
pela temperatura, fluido precipitante, mineralogia e pH da solução (Swart, 2015). Existem
duas escalas na determinação do isótopo de oxigênio: δ18OVPDB (Vienna Pee Dee
Belemnite) e δ18O SMOW (Standard Mean Ocean Water), sendo suas aplicabilidades
distintas.
Portanto, a aplicação do δ18OVPDB visa determinar períodos de glaciação e
interglaciais em escalas de tempo curta. O empobrecimento desse isótopo assinala
períodos interglaciais, enquanto o enriquecimento demonstra estágios glaciais
(Ruddiman, 2008). Também é possível determinar as oscilações da pluviosidade, onde os
valores negativos do δ18OVPDB assinalam períodos com maior evaporação, enquanto o
enriquecimento deste elemento assinala períodos com aumento da pluviosidade (Pearson,
2012). Além disso, o δ18OVPDB também é utilizado para determinar as variações da
paleotemperatura através das proporções existentes nos registros de 16O e 18O. No caso,
o enriquecimento do δ18OVPDB caracteriza um ambiente com diminuição da
paleotemperatura, enquanto períodos com empobrecimento do δ18OVPDB indica o
aumento (Gradstein, Ogg et al., 2020; Scotese et al., 2021).

34
HIPÓTESE
A Bacia do Araripe é caracterizada por apresentar grandes variações litológicas e
paleoambientais, rico acervo fossilífero e o registro de crises biológicas. O uso da
Quimioestratigrafia pode colaborar na compreensão das relações entre as mudanças
paleoambientais climáticas e as crises biológicas que ocorreram na Bacia do Araripe.
Dentro desse contexto, a ativação das Grandes Províncias Ígneas (LIP’s) do intervalo
Aptiano-Albiano foram responsáveis mudanças nos processos deposicionais, gerando o
aumento da produtividade, paleredox, paleosalinidade, oscilações paleoclimáticas
(períodos úmidos-secos) e eventos de mortalidade na Bacia do Araripe.

4. OBJETIVOS
O presente estudo tem o objetivo de caracterizar através da Quimioestratigrafia as
mudanças paleoambientais que ocorreram na Bacia do Araripe durante o Cretáceo
Inferior (Formações Barbalha, Crato e Romualdo). Além disso, correlacionar e identificar
prováveis interferência dos eventos vulcânicos que foram responsáveis por mudanças
paleoambientais na Bacia do Araripe e, consequentemente, associá-las com as crises
biológicas registradas no ambiente deposicional.

4.1 Objetivos Específicos

• Apresentar os processos paleoambientais que ocorreram na Bacia do Araripe no
Grupo Santana (formações Barbalha, Crato e Romualdo), identificando as alterações da
paleoprodutividade, paleoredox e paleoclima durante Cretáceo Inferior (Aptiano-
Albiano) na Bacia do Araripe;
• Correlacionar as anomalias de mercúrio (Hg) oriundas do vulcanismo e seus
impactos locais na Bacia do Araripe através das anomalias de metais-traços. A
interferência dos eventos de vulcanismo foi avaliada através das análises das razões
(Hg/COT, Hg/Al e Hg/Fe). Para identificar as anomalias dos metais-traço foi determinado
os fatores de enriquecimento da paleoprodutividade (CuEF, ZnEF, NiEF, BaEF) e do estado
paleoredox (PbEF, VEF, CrEF, MnEF, FeEF). Além disso, aplicou-se a razões elementares
dos metais-traço para determinar as oscilações paleoredox (V/Cr, V/Ni e V/V+Ni),
paleosalinidade (Sr/Ba), paleoclimatologia (Sr/Cu) e aportes detríticos (Al e Fe);
• Determinar as condições deposicionais através dos isótopos estáveis de carbono
(δ13CVPDB) e oxigênio (δ18OVPDB), sendo possível estabelecer as oscilações da
paleoprodutividade e o paleoclimáticas, respectivamente;

35
 • Determinar através dos métodos geoestatísticos e oscilações dos metais-traço os
mecanismos responsáveis pelas mudanças paleoambientais que resultaram nos eventos
de mortalidade registrados na Formação Crato;
• Identificar o desenvolvimento da cadeia trófica da paleoictiofauna e outros
organismos através das concentrações do Hg nos registros fossilíferos da Formação
Romualdo.

36
CAPÍTULO 1

Aptian-Albian Paleoenvironmental Geochemistry: Araripe

Basin, Northeastern Brazil
O primeiro manuscrito, em síntese, trata-se da caracterização geoquímica do intervalo
Aptiano e transição com o Albiano na Bacia do Araripe. O objetivo principal é
caracterizar as mudanças paleoambientais influenciadas pelos eventos de vulcanismo que
ocorreram no Cretáceo Inferior. Este trabalho possibilitou observar mudanças
paleoclimáticas influenciadas, provavelmente, pelo vulcanismo do Ontong Java (OJP) e
platô Kerguelen Sul (SKP). Ambos foram responsáveis pelos eventos de anoxia oceânica
1a e 1b (OAE) e podem ter desencadeados grandes modificações do estado paleoredox,
paleoprodutividade e paleoclimáticas na Bacia do Araripe. Autorias de Igor Hamid
Ribeiro Azevedo, Luiz Drude Lacerda, Antônio Álamo Feitosa Saraiva, Alcides Nóbrega
Sial, Ana Paula Aquino Benigno e José Edvar Aguiar, intitulado “Aptian-Albian
Paleoenvironmental Geochemistry: Araripe Basin, Northeastern Brazil”.

__________________________
1
Hamid, I. R. A.; Lacerda, L. D.; Saraiva, A. A. F.; Sial, A. N.; Benigno, A. P.; Aguiar, J. E. Aptian-
Albian paleoenvironmental geochemistry: Araripe Basin, Northeastern Brazil. Journal of South
American Earth Sciences. https://doi.org/10.1016/j.jsames.2024.104856.

37
Highlights

• Changes in paleoproductivity, paleoredox state, paleosalinity and

paleoclimate occurred in Aptian- Albian (Araripe Basin).
• Activation of LIPs and oceanic anoxia events (OAE).
• Stable isotopes (δ13C and δ18O) and trace metal enrichment were consistent
proxies of paleoenvironmental changes.

38
 Abstract

The geochemical record of the early Aptian and the transition to the Albian exposes the
presence of Hg/TOC anomalies, revealing the interference of LIPs in paleoenvironmental
changes in the Araripe basin. Redox-sensitive (VEF, FeEF, CrEF, MnEF, PbEF, V/Cr,
V/V+Ni and V/Ni) and paleoproductivity (CuEF, ZnEF, NiEF and BaEF) proxies in the
Santana Group (Barbalha, Crato and Romualdo formations) indicate conditions ranging
from oxic to anoxic, and increased paleoproductivity and of trace elements concentrations
during LIPs activation. Statistical analyses demonstrated that volcanism was associated
with oscillations in paleosalinity (Sr/Ba) and detrital supply (Al). LIPs activity was
responsible for the emission of CO2 into the atmosphere, generating paleoclimatic
changes in temperature (δ18O), a crisis in the productivity of calcifying organisms
(δ13Ccarbonate), and an increase in the load of organic matter (TOC). We suggest that trace
elements anomalies found in the early Aptian (Barbalha Formation) are associated with
Ontong Java Plateua (OJP), responsible for OAE 1a, while the volcanism’s proxies found
in the Romualdo Formation occurred due to the Kerguelen South Plateau (SKP)
volcanism, triggering the OAE 1b.

39
5.1 Introduction
The Aptian and the Aptian-Albian transition (121.4 to 113 Ma), Early Cretaceous,
are marked by great transformations on Earth, including sea-level rise, volcanism, global
warming, oceanic anoxia events (OAE) and marine and terrestrial biotic changes (Ogg et
al., 2016). Extreme events in the Aptian-Albian transition are associated with the
activation of Large Igneous Provinces (LIPs), generating an increase in atmospheric
carbon dioxide and other gases (HS, HCl, and HF), intensifying greenhouse effect
(Sabatino et al., 2018; Xu et al., 2022). The rapid injection of CO2 and methane into the
atmosphere is responsible for drastic changes in the hydrological cycle; global warming;
ocean acidification; acid rain; depletion of the ozone layer; trace metals and organic
matter enrichment of sediment; primary productivity and terrestrial and marine biological
global crises (Davis, 2023; Font, Bond, 2021; Grasby et al., 2019; Racki, 2021).
The application of geochemical proxies such as trace metals and isotopes of
δ13Ccarbonate and δ18O are essential tools for determining variations in seawater chemistry,
correlating global stratigraphic changes, and understanding impact of the LIPs on
sedimentary basins. (Madhavaraju et al., 2021; Saucedo-Samaniego et al., 2021;
Tribovillard et al., 2006). Mercury anomalies are associated with emissions from
volcanisms of LIPs during that period, the Ontong Java (OJP) and South Kerguelen
Plateau (SKP). These LIPs were also responsible for Ocean Anoxic Events (OAE)
(Charbonnier, Föllmi, 2017; Sabatino et al., 2018). OAEs promoted changes in the carbon
cycle, suggested by δ13Ccarbonate oscillations (reduction of planktonic calcification) and
increase in the organic carbon deposition (Tedeschi et al., 2020; Weissert, Erba, 2004).
OAEs also caused variations in paleotemperature (δ18O), increased chemical weathering
(Ti, Si, Al, and K) (Calvert, Pedersen, 1993; Touati, Haji, 2019), enrichment of
geochemical proxies of paleoproductivity (Cu, Zn, Ni, and Ba), and redox-sensitive trace
elements (Fe, Cd, Mn, Mo, Ni, V, and As) (Algeo, Li, 2020; Algeo, Liu, 2020;
Tribovillard et al., 2006).
The OJP volcanism occurred in the early Aptian (~120 Ma), with higher CO2
emissions indicating perturbations on the global climate and holding it directly
responsible for the OAE 1a (Mehay et al., 2009). It has been estimated that approximately
9,600 Gt of CO2 were emitted by OJP into the atmosphere, resulting in the high carbon
deposition, changes in δ13Ccarbonate, global changes in paleoproductivity and paleoredox
state (Adloff et al., 2020; Erba et al., 2015; Fan et al., 2021; Naafs et al., 2016; Weissert,

40
Erba, 2004). The SKP (~118 – 110 Ma) was responsible for the OAE 1b, which caused
enrichment of trace metals, increased TOC burial in sediments, biological crises of
calcifying marine organisms, and oceanic anoxia (Erba et al., 2015; Sabatino et al., 2015).
Most affected calcifying organisms in OAE 1b, were planktonic organisms with biogenic
silica, as suggested by the decrease of ornamented calcifying species and the
predominance of small-sized calcium carbonate species (Huber, Leckie, 2011; Leckie et
al., 2002; Petrizzo et al., 2012). The OAE 1b as a longer perturbation (~ 3,8 Ma) presented
four sub-events (Jacob, Kilian, Paquier, and Leenhardt) based on different disturbance
strength of the carbon cycle (Coccioni et al., 2014; Leckie et al., 2002; Sabatino et al.,
2015).
The Araripe Basin in Northeastern Brazil has been the subject of numerous
sedimentological, paleontological, and stratigraphic studies (Assine et al., 2014; Fara et
al., 2005; Martill, 1988; Rios-Netto et al., 2012; Silvestre et al., 2020; Valença et al.,
2003). However, geochemical investigations capable of revealing the paleoenvironmental
conditions of this basin are still scarce, although a general description Hg
chemostratigraphy and some other proxies can be found in Benigno et al. (2021). The
Early Aptian to Aptian-Albian transition (Early Cretaceous) in this basin witnessed a
global variation in the carbon cycle, causing several climate changes and biological crises.
Thus, this study focuses on geochemical proxies to interpret the paleoenvironmental
consequences of LIPs activation eventually registered in the Araripe Basin. The
application of geochemical multi-proxies (trace metals) helps interpreting the
environmental evolution of the events that occurred during the deposition of the Santana
Group (Barbalha, Crato, and Romualdo formations), making it possible to interpret and
reconstruct the paleo redox, paleoproductivity and paleodetrital changes in the Araripe
sedimentary basin.

5.2 Stratigraphic Settings

The Araripe Sedimentary Basin extends over 9,000 km² included in three states in
the Brazilian Northeast (Figure 8) (Ceará, Pernambuco and Piauí). It is considered the
most complete sedimentary record from the Cretaceous of the sedimentary basins in
Northeastern Brazil (Assine, 1992, 2007; Neumann, 1999; Valença et al., 2003). The
geological history of this intrachronic basin is associated with the break-up of Gondwana
and the opening of the South Atlantic, dating back to 150 Ma. The basin comprises four

41
technostratigraphic stages: syneclisis, pre-rift, rift, and post-rift (I and II) (Assine et al.,
2014; Fambrini et al., 2011; Martill et al., 2007; Paula Freitas, Borghi, 2011; Silvestre et
al., 2020). This study followed the dates proposed by Assine (2007), Fauth et al. (2023),
Guzmán et al. (2023), Melo et al. (2020), and Silvestre et al. (2020), who used
biostratigraphic and lithostratigraphic correlations. Therefore, it is restricted to the post-
rift I Aptian sequence (Figure 8), which includes a fluvio-lacustrine system, the Barbalha,
Crato and Ipubi formations and a heterogeneous system with marine incursions, the
Romualdo Formation (Assine, 2007; Melo et al., 2020; Silvestre et al., 2020).

42
Figure 8. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the location of the
Araripe Basin- BSA (yellow circle) and the volcanisms of Ontong Java- OJP (red star) and Southern
Kerguelen Plateau- SKP (white star). B) Map of the location of the sampling points in the Araripe Basin.

Figure 17. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the location of the
Araripe Basin- BSA (yellow circle) and the volcanisms of Ontong Java- OJP (red star) and Southern
Kerguelen Plateau- SKP (white star). B) Map of the location of the sampling points in the Araripe Basin.

Figure 9 Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of the sampled
sections, lithofacies, and height based on Benigno et al. (2021), Coimbra et al. (2002) and Fara et al.
(2005). B) Aptian and early Albian depositional sequence of the studied interval, according to Fauth et al.
(2023); Guzmán et al. (2023); Ogg et al. (2016); Varejão et al. (2021a, b). DS- Depositional system.Figure
8. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the location of the Araripe
Basin- BSA (yellow circle) and the volcanisms of Ontong Java- OJP (red star) and Southern Kerguelen
Plateau- SKP (white star). B) Map of the location of the sampling points in the Araripe Basin.

Figure 18. A) 120 Ma paleogeographic map (modified from Scotese, 2016) showing the location of the
Araripe Basin- BSA (yellow circle) and the volcanisms of Ontong Java- OJP (red star) and Southern
Kerguelen Plateau- SKP (white star). B) Map of the location of the sampling points in the Araripe Basin.

5.2.1 Barbalha Formation

The Barbalha Formation, from the base of the Aptian, has a stratigraphic profile
marked by fluvial-lacustrine cycles (Figure 8B) (Assine, 2007; Coimbra et al., 2002;
Rios-Netto et al., 2012; Vallejo et al., 2023). The 60 meters-thick base of this formation,
is an intertwined fluvial environment with multi channels and characterized by upward
fining, composed of coarse to medium sandstones, conglomerate levels, cross-bedding,
and interspersed with red mudstones (Assine, 2007; Scherer et al., 2015; Silvestre et al.,

43
2020). Following the deposition of the basal part, depositional conditions changed, and
sedimentation was characterized by the predominance of mudstones, green shales, and
black pyrobitumen, rich in carbonate algae, ostracods and fish remains, known as the
Batateira beds (Figure 8B) (Assine, 2007, 1992; Fambrini et al., 2019). These suggest an
anoxic continental lacustrine system, rich in pyrite and a high load of organic matter
(>30% TOC) (Claes et al., 2021). However, biological multiproxies (especially
microfossils) have shown increased salinity in the Batateira beds, which may be
influenced by saline water intrusion associated with depositional characteristics of a
deltaic system (Varejão et al., 2021). Subsequently, fluvial conditions in the Barbalha
Formation return, presenting medium to fine sandstones with the presence of shales, being
typical of river systems anastomosed with extensive floodplains (Assine, 2007; Fambrini
et al., 2019; Silvestre et al., 2020).

5.2.2 Crato Formation

The Crato Formation of Aptian age is the second lacustrine phase of the post-rift
event of the opening of the Atlantic Ocean (Figure 8B) (Coimbra et al., 2002). It is 90
meters thick, and rich fossil content and displaying six carbonate layers (C1 to C6) formed
by calcitic limestones, a micritic matrix with micro to nanometric rhombohedral crystals
(Assine, 2007; Catto et al., 2016; Neumann, 1999). The origin of these limestones
associates with authigenic chemical precipitation and biologically induced precipitation
by calcifying organisms (Cabral et al., 2019; Catto et al., 2016; Heimhofer et al., 2010).
Due to its rich fossil content and excellent preservation, this formation is classified as
Konservat-Lagerstätte (CKL), presenting a rich diversity of fossils: vertebrates
(dinosaurs, pterosaurs, and fishes) and invertebrates (shrimp, insects, plants, and spiders).
As for environmental conditions, limestone laminations, the presence of halite and pyrite
crystals indicate a lacustrine environment (Crato paleolake), under saline to hypersaline
and anoxic conditions (Barling et al., 2015; Martill et al., 2005; Osés et al., 2016; Varejão
et al., 2019; Fambrini et al., 2020; Storari et al., 2021;). Overlying the CKL is the Caldas
bed, characterized by lithofacies alternating between silty and clayey sandstones, with the
fossiliferous presence of mollusks (bivalves and gastropods) and fragments of carbonized
plants (Varejão et al., 2021). The upper part of the Crato Formation suggests marine
incursions or restricted contact with the sea, as per its composition of sandstone, black to
green shales, and limestone (Salgado-Campos et al., 2021; Varejão et al., 2021).

44
5.2.3 Romualdo Formation
The Romualdo Formation, an Aptian-Albian 120 meters-thick layer, is also
recognized as Konservat-Lagersttätte for its rich fossil content and preservation of fossil
soft tissues (dinosaurs, pterosaurs, turtles, and fishes) (Figure 8B) (Duque, Barreto, 2018;
Fambrini et al., 2020; Oliveira, Kellner, 2007; Sayão et al., 2020). A palaeoichthyological
fauna typical of a marine environment (Fara et al., 2005) and the composition of
microfossils corroborates the characteristics of a marine depositional system (Custódio et
al., 2017; Melo et al., 2020).
The lithofacies of the Romualdo Formation exhibits large variability, being
composed of stratified conglomerates, fine to coarse sandstones, laminated limestones,
marls, dark gray and greenish shales, being rich in organic matter and calcareous levels
(Assine, 2007; Custódio et al., 2017; Fambrini et al. al., 2020). The variety of lithofacies
suggests large variation in sea- level, with the occurrence of shales common in marine
transgression events, and the predominance of sandstones in regression events (Assine et
al., 2014; Custódio et al., 2017). This condition was observed in other studies using
microfossils (foraminifera and ostracods), through the composition of organic matter and
geochemical studies, demonstrates periods of greater coastal influence and marine
transgression events (Araripe et al., 2019, 2021; Bom et al., 2021; Pontes et al., 2021;
Teixeira et al., 2018). The presence of Classopollis and Araucariacites pollens indicates
a strong influence of a marine regression event in a typical coastal system (Arai and
Assine, 2020). According to Araripe et al. (2021), the Center-South part of the Araripe
basin presented marine conditions, while in the Southwest of the basin, deposition
occurred under coastal conditions.
The Romualdo Formation is also marked by fish mortality events (Martill et al.,
2008), which may be associated with major paleoenvironmental changes. Effects of distal
volcanism were recorded in the Araripe basin in the Romualdo Formation and could
impact and alter paleoclimate processes and, consequently, leading to biological crises
(Benigno et al., 2021; Sabatino et al., 2018). The paleoenvironmental conditions in this
environment were of great stress to organisms, presenting dyoxic to anoxic conditions,
with little oxygen and great saline variability (Bom et al., 2021; Fürsich et al., 2019;
Pontes et al., 2021). These conditions directly interfered with the distribution of
microfossils along the stratigraphic column (Araripe et al., 2021).

45
5.3 Materials and methods
The present study analyzed 47 samples collected by the transversal excavation of
the outcrops, using only the non-weathered surfaces. Samples were collected from the
post-rift I period of the Santana Group (Barbalha, Crato, and Romualdo formations),
stranding from the base of the Aptian to the base of the Albian. Thirteen samples were
collected from the Barbalha Formation (Batateira beds), 21 from the Crato Formation,
and 13 from the Romualdo Formation. Samples collected in the Crato Formation have
varied layers, including the laminated limestones of the Konservat-Lagerstätten layer (14,
13, and 1E) and sandstones and shales of the Caldas bed (1B, 1C, and 1D). At the top of
the Crato Formation, there is an alternation between sandstones, shales, and limestones
(5 A – E, 10 A – E, and 12). In the case of the samples from the Romualdo Formation,
there is intercalation of sandstones, limestones, and black to green shales. The location of
the samples in the stratigraphic profile of the Santana Group is shown in Figure 9.
Samples were grounded, homogenized and dried (60°C for 12 hours), and preserved in
hermetically closed flasks until analysis. Previous results of Total Organic Carbon (TOC),
mercury (Hg), and isotopes (δ13Ccarbonate and δ18O) are available in Benigno et al., (2021).

46
Figure 9 Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of the sampled sections,
lithofacies, and height based on Benigno et al. (2021), Coimbra et al. (2002) and Fara et al. (2005). B) Aptian and
early Albian depositional sequence of the studied interval, according to Fauth et al. (2023); Guzmán et al. (2023);
Ogg et al. (2016); Varejão et al. (2021a, b). DS- Depositional system.

Figure 19. Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of the sampled sections,
lithofacies, and height based on Benigno et al. (2021), Coimbra et al. (2002) e Fara et al. (2005). B) Aptian and
early Albian depositional sequence of the studied interval, according to Fauth et al. (2023); Guzmán et al. (2023);
Ogg et al. (2016); Varejão et al. (2021a, b). DS- Depositional system.

Figure 10. Chemostratigraphy of the Barbalha Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital
supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF
(paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate
(Paleoproductivity).Figure 9 Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of the
sampled sections, lithofacies, and height based on Benigno et al. (2021), Coimbra et al. (2002) and Fara et al.
(2005). B) Aptian and early Albian depositional sequence of the studied interval, according to Fauth et al. (2023);
Guzmán et al. (2023); Ogg et al. (2016); Varejão et al. (2021a, b). DS- Depositional system.

Figure 20. Stratigraphic characterization of the Araripe Basin. A) Stratigraphic profile of the sampled sections,
lithofacies, and height based on Benigno et al. (2021), Coimbra et al. (2002) e Fara et al. (2005). B) Aptian and
early Albian depositional sequence of the studied interval, according to Fauth et al. (2023); Guzmán et al. (2023);
Ogg et al. (2016); Varejão et al. (2021a, b). DS- Depositional system.

47
5.3.1 Total Organic Carbon (TOC)
Total organic carbon (TOC) was quantified according to Yeomans, Bremner,
(1988) in 0.5 g subsamples, digested with 5 mL K2Cr2O7 0.167 M solution and 7.5 mL of
concentrated H2SO4 at 170º C for 30 min. After cooling in room temperature, 3 to 5 drops
of ferroin (1.485 g o-fenatrolin, plus 0.695 g Fe2SO4) were added to 80 mL of the extract
and followed by titration with (Fe(NH4)2(SO4)2) 0.2 M).

5.3.2 Stable isotopes (C and O)

Stable isotopes of Carbon (δ13C) and Oxygen (δ18O) were quantified in the CO2
extracted from samples by digestion with orthophosphoric acid at 25ºC, in a
Thermofinnigan Delta V Advantage mass spectrometer. Results are expressed in the δ
notation (‰) with accuracy above ± 0.1‰; Vienna Pee Dee Belemnite international
standards calibrated the isotopic data. Eventual C or O-signals showing post-depositional
change of their isotope values were identified by Mn/Sr ratio; values lower than 10
suggest near primary isotopic abundances (Kaufman, Knoll, 1995; Kaufman et al., 1993).
See Benigno et al., (2021) for details of procedures adopted to verify pos-depositional
changes of stable isotopes of Carbon (δ13CVPDB) and Oxygen (δ18OVPDB).

5.3.3 Metals concentrations

The concentrations of Al, Fe, Mn, Sr, Cu, Pb, Ni, V, Ba, Cr and Zn were quantified
using subsamples of approximately 0.5 g mixed in teflon tubes with 20 mL Aqua Regia
(50% v/v) and digested in a microwave (at 1,600 W and 175 ºC, for 20 min). Extracts
were taken in volumetric flasks to 25 mL with HNO3 0.2% v/v. All glassware were
previously washed with deionized water in a 10% v/v (10% v/v) solution bath for 24
hours and then in an HCl bath (Sigma-Aldrich) 10% v/v for 24 hours. The reliability of
the analytical results was monitored by means of the simultaneous analysis of certified
sediment standard (NIST 1646A) and duplicate analyses of all samples. Standard
recovery varied from 79% to 95%, whereas the detection limit of the procedure varied
from 0.01 µg g-1 to 0.03 µg g-1, depending on the metal. Quantification of the metals used
Flame Atomic Absorption Spectrometry - AAS (AA 6200, SHIMADZU), with calibration
curves of each metal constructed from MERCK standard solutions (1,000 µg g-1).

48
5.3.4 Mercury
Mercury (Hg) concentrations were quantified in duplicates after digestion of 0.5
g of the samples in 125 mL Erlenmeyer flasks, containing 20 mL of aqua regia (50% v/v),
in a water bath at a temperature between 70 and 80° C for two hours. Erlenmeyer flasks
were closed using thermokinetic reactors (cold fingers). The resulting extracts were
quantitatively transferred to volumetric flasks (50 mL) and calibrated with deionized
water (Aguiar et al., 2007). All glassware were previously washed with deionized water
in an Extran® solution bath (10% v/v) for 24 hours and then in an acid bath of HCl
(Sigma-Aldrich) 10% v/v also for 24 hours. Quantification used a Cold Vapor Generation
Atomic Absorption Spectrometry (CVAAS), in a NIC RA-3 (NIPPON®)
spectrophotometer. Analyses of reference material (NIST-1646A) were performed
simultaneously with the samples, and mean recovery was 78.4 ± 6.6%; the limit of
detection of the procedure was 0.02 ng g-1 and the limit of quantification was 0.06 ng g-
1
.

5.3.5 Enrichment factor

Aluminum (Al) was used to identify the contributions and paleodetrital processes,
as it is a constituent element of the siliciclastic group that is associated with silt and clay
particles and is part of the composition of the main detrital minerals (phyllosilicates,
quartz, plagioclase, and K-feldspar). In addition, Al presents high stability and low
mobility in the environment (Barbieri, 2016; Merli et al., 2020; Montero-Serrano et al.,
2015; Rodríguez-Cuicas et al., 2019; Montero-Serrano and Garbán, 2019).
Trace metals are especially enriched in shales and claystone compared to the upper
crust, thus to remove interference from proximal sediment sources and decrease the
potential dilution effects of biogenic components (carbonates, silica, and phosphorites),
the present study used Al as a normalizer to determine the sudden changes in
paleoproductivity (NiEF, CuEF, ZnEF e BaEF) and the paleoredox proxies (PbEF, VEF, MnEF,
CrEF, FeEF) (Sabatino et al., 2015; Soua et al., 2011; Touati, Haji, 2019; Tribovillard et
al., 2006). The EF allows a general assessment regarding the enrichment/impoverishment
of metals, evidencing relevant paleoenvironmental changes in the formations under study,
deeming its applicability in chemostatigraphy extremely important (Algeo, Liu, 2020).
The application of these metals considers their behavior in a reducing environment, to
which organic matter adsorbs and co-precipitates with sulfur when subjected to bacterial
sulfate reduction (Algeo, Liu, 2020; Algeo, Maynard, 2004; Herndon et al., 2018;
Tribovillard et al., 2006).

49
 The calculation of the enrichment factor (EF) consists of the ratio between the
concentration of the element in shales or claystone and the corresponding average
concentration of the element in the upper middle crust (Cao et al., 2012). The EF is
determined using the equation: EFElement= [(X/Al)Sample) /(X/Al)Average shale], where
(X/Al)(Sample) represents the concentrations of elements X and Al measured in the samples,
while (X/Al)(Average shale) corresponds to the concentrations of elements in the "average
shale" of the crust according to the values proposed by Turekian, Wedepohl (1961), and
Wedepohl (1995).

5.3.6 Statistics
The statistical analysis used the RStudio software (version 4.3.1 – © 2009 – 2023
RStudio, Inc.) after performing homogeneity and normality tests to the data which
suggested Spearman's correlation coefficient (p < 0.05, n= 47) (Correlation Index from -
1 to +1) (Miller, 2010) to be used.

50
5.4 Results
Variability of geochemical proxies of paleoproductivity, paleoredox, and
volcanism are shown in Figures 10, 11, and 12. There is a clear association between
Hg/TOC peaks (volcanism events) and trace metal enrichment in all studied Formations.
Volcanism may have been responsible for global paleoenvironmental changes with local
impacts in the Araripe Basin during the Aptian and Albian (Cretaceous). It is worth noting
that volcanism events during the Cretaceous marked main global climate changes, being
responsible for marine plankton shifts and oceanic anoxia events (OAE 1a and 1b) (Adloff
et al., 2020; Benigno et al., 2021; Erba et al., 2015; Li et al., 2023; Sabatino et al., 2015).
Proxies of other drivers of environmental changes in the Araripe Basin are presented
separately according to the specific Formation.

5.4.1 Barbalha Formation

In the Batateira beds, Al ranged from 0.72% to 8.86% in superposed limestone
beds (Figure 9B). A probable paleodetrital source is indicated by a direct correlation
between Al and Fe (p < 0.05; n = 13, Spearman) (Fe r = 0.62), Ni (r = 0.76), Cr (r = 0.81)
and V (r = 0.79) (Figure 10 B), and a negative correlation between Al and Hg/TOC (r = -
0.58) and Sr/Ba (r = -0.74). The Sr/Ba ratio (a paleosalinity proxy) observed in the
Batateira beds varied from 0.03 to 1.37 (Figure 10 C), with the highest ratio found in
sample 17A (1.37) and the lowest in 21B (0.04), indicating paleosalinity ranging from
freshwater to marine. Metals concentrations ratios proxies of paleoredox conditions
(V/Cr, V/Ni, and V/V+Ni) indicate depositional conditions ranging from anoxic to
suboxic, 2.24 to 8.24, 0.67 to 0.84, and 2.05 to 5.09, respectively (Figures 10 D, E, and
F).
Spearman analysis (p < 0.05; n = 13) showed significant correlation between
paleoredox proxies and TOC (Pb = 0.65, V = 0.72, Fe = 0.54, and Mn = 0.62). Enrichment
factors for PbEF ranged from 0.3 to 60.0, for VEF from 0.4 to 5.5, for CrEF from 0.1 to 0.5,
for MnEF from 0.03 to 34.39 and for FeEF from 0.2 to 2.85 (Figure 10 G – K). Significant
Spearman's correlations of the paleoproductivity proxies with TOC (Zn = 0.65, Cu = 0.91,
Ni = 0.66, and Ba = 0.70). The Batateira beds showed CuEF ranging from 0.6 to 43.6, ZnEF
from 0.4 to 59.5, NiEF from 0.2 to 3.1, and BaEF from 0.04 to 1.2, whereas TOC ranged
from 0.3 to 3.2% (Figure 10 M - Q). Hg concentrations ranged from 2.7 to 43.6 ng g-1,
and the Hg/TOC ratio varied from 2.5 to 20.2 showing 4 sharp peaks (Figure 10A).
δ13Ccarb. and δ18O, were, unfortunately, only quantified in sample 17A, and showed values

51
of +0.72‰ and -8.65‰, respectively (Figures 10 L, and R). Sample 17A of the Batateira
beds recorded anomalies of all paleoproductivity (CuEF, ZnEF, NiEF, BaEF, and TOC), and
paleoredox (PbEF, VEF, CrEF, MnEF, and FeEF) proxies. This enrichment of trace metals
and a positive incursion of the Hg/TOC ratio suggest strong a paleoenvironmental
disturbance.

52
Figure 10. Chemostratigraphy of the Barbalha Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) Pb EF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 21. Chemostratigraphy of the Barbalha Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 11. Chemostratigraphy of the Crato Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).Figure 10. Chemostratigraphy
of the Barbalha Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H) MnEF, I) VEF, J) CrEF and K)
FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 22. Chemostratigraphy of the Barbalha Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) Pb EF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

53
5.4.2 Crato Formation
The Crato Formation presented Al values ranging from 0.02 to 8.25%, with lower
concentrations in the laminated limestone (point 13) and higher concentrations in the
black shale (point 5C) (Figure 10B). Significant positive Spearman correlations (p < 0.05;
n = 21) between Al (detrital supply) and Cr (r = 0.50), Ni (r = 0.90), V (r = 0.50), and
TOC (r = 0.47), suggest possible paleodetrital contributions of these elements to the
depositional environment. Furthermore, negative correlations were observed between Al
and Zn (r = -0.32), Mn (r = -0.59), Pb (r = -0.31), Sr/Ba (r = -0.59), and Hg/TOC (r = -
0.62). The Sr/Ba ratio in the Crato Formation ranged from 0.02 – 3.93 (Figure 10C), with
highest values found in samples 14, 13, 1E, 11B and 11C, suggesting a marine
environment (Sr/Ba > 0.5). Followed by intermediate values, suggesting brackish waters
(Sr > Ba between 0.2 to 0.5) in samples 10A, 10B, 10D, 5E, 5B, 5A, 11A, 11D and 11E.
Freshwaters depositional conditions (Sr/Ba> 0.2) were observed in samples 1D, 1C, 1B,
10C, 5D, 5C and 12. Paleoredox proxies suggest a predominantly reducing
paleoenvironment. Metals ratios (V/Cr, V/Ni, and V/V+Ni) varied from 2.0 to 10.9 (oxic
to suboxic), 0.58 to 0.91 (dyoxic to euxinic), and 1.4 to 10.1 (oxic to anoxic), respectively
(Figures 10D, E, and F).
Significant positive Spearman's correlation (p < 0.05; n = 21) in the Crato
Formation were observed between paleoredox proxies with Hg/TOC ratios (Pb = 0.66, V
= 0.43, Mn = 0.32, and Fe = 0.77). Enrichment factors for PbEF varied from 0.5 to 4.246;
for VEF from 0.5 to 229; for CrEF from 0.08 to 76; for MnEF from 0.3 to 1.99; and for FeEF
from 0.5 to 171 (Figure 10G – K). Paleoproductivity proxies varied from 0.7 to 901 for
CuEF, from 1.8 to 1.36 for ZnEF, from 0.5 to 63 for NiEF, 0.1 to 138 for BaEF, and from 0.1
to 1.84% for TOC (Figure 10M – Q). There were significant positive correlations between
Ni and Ba with TOC (r = 0.30 and r = 0.38, respectively). Hg concentrations varied from
1.2 to 44 ng g-1, and the Hg/TOC ratio showed 5 peaks with values ranging from 1.2 to
106 (Figure 10A). δ13Ccarbonate varied from -8.90‰ to +0.61‰ (Figure 10R), with
significant peaks in samples 13 (+0.61‰) and 10C (-0.22‰). δ18O values ranged between
-7.77‰ and -1.77‰ (Figure 10L), with sharp peaks observed in stations 10A (-1.17‰)
and 10D (-3.94‰).

54
Figure 11. Chemostratigraphy of the Crato Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 23. Chemostratigraphy of the Crato Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 12. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF,
H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate.Figure 11. Chemostratigraphy of the Crato
Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox);
L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

Figure 24. Chemostratigraphy of the Crato Formation. A) Hg/TOC (Volcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G) Pb EF, H)
MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate (Paleoproductivity).

55
5.4.3 Romualdo Formation
Aluminum concentrations (paleodetrital contributions) in the Romualdo
Formation varied from 1.02 to 6.72%, with higher values in sample 4.1.1 (black shale)
and lower in 23 (green shale) (Figure 12 B). Significant positive Spearman correlation (<
0.05, n = 13) was found between Al and Fe (r = 0.83), Zn (r = 0.84), Ni (r = 0.84), Cr (r
= 0.84), V (r = 0.68) and TOC (r = 0.46). Furthermore, significant negative correlations
were found between Al and the Sr/Ba ratio (r = -0.53). The Sr/Ba ratio varied from 0.05
– 0.76 (Figure 12 C), where the highest concentrations (marine environment) were at
points 3D, 3C, 15B, 15C, 4.1 and 23. Samples 3A, 15A, 15D, 4.2.1 and 4.1.1 showed
characteristics of brackish water, while samples 3E and 3B suggest a freshwater
environment. The paleoredox proxies in Romualdo Formation varied from: V/Cr:1.3 to
12.8 (oxic to anoxic), V/V+Ni: 0.53 to 0.93 and V/Ni 1.5 to 12.7 (anoxic- euxinic)
(Figures 12 D, E, and F).
Positive, significant (p < 0.05, n = 13) Spearman's correlation were observed
between TOC and the concentrations of V (r = 0.89), Cr (r = 0.55) and Fe (r = 0.54), while
Pb concentrations correlated only with the Hg/TOC ratio. Enrichment factors varied from
0.6 to 9.0 for PbEF, 0.4 to 4.7 for VEF, the 0.1 to 0.7 for CrEF, 0.3 to 31.4 for MnEF and 0.2
to 3.2 for FeEF (Figure 12 G – K). Paleoproductivity proxies, CuEF varied from 0.4 to 6.7,
ZnEF from 0.3 to 4.7, NiEF from 0.7 to 5.1, BaEF from 0.03 to 1.2 and TOC from 0.5 to
1.4% (Figure 12 M – Q). Significant positive correlations were found for TOC with Cu
(r = 0.70), Zn (r = 0.73), Ni (r = 0.57), and Ba (r = 0.72). Hg concentrations varied from
1.1 to 26.3 ng g-1, and the Hg/TOC ratio from 1.8 to 39.3, with peaks recorded in 3
samples (Figure 12 A). δ13Ccarbonate and δ18O varied from -11.5 to -1.61‰ (Figure 12 R)
and from -10.1 to -5.3‰ (Figure 12 L), respectively.

56
Figure 12. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G)
PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate.

(Paleoproductivity).

Figure 25. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G)
PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate.

(Paleoproductivity).

Figure 13. Figure 12. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F)
V/Ni, G) PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate.

(Paleoproductivity).

Figure 26. Chemostratigraphy of the Romualdo Formation. A) Hg/TOC (Vulcanism); B) Aluminum (Detrital supplay); C) Sr/Ba (Paleosalinity); D) V/Cr, E) V/V + Ni, F) V/Ni, G)
PbEF, H) MnEF, I) VEF, J) CrEF and K) FeEF (paleoredox); L) δ18O (Paleoclimate); M) CuEF, N) ZnEF, O) NiEF, P) BaEF, Q) TOC, R) δ13Ccarbonate.

(Paleoproductivity).

57
5.5 Discussion
5.5.1 Paleosalinity
To determine the paleosalinity of depositional environments, we used the
classification proposed by Wei, Algeo (2020), which divides the saline conditions of the
environment according to ranges of the Sr/Ba ratio: < 0.2, freshwater environment;
between 0.2 – 0.5, brackish water; and Sr/Ba ratios > 0.5, typical of marine environments.

5.5.1.1 Barbalha Formation

Previous studies characterize the Batateira beds as a freshwater, low-energy
lacustrine environment (Assine et al., 2014; Fambrini et al., 2020; Scherer et al., 2015).
However, the present study demonstrated saline characteristics ranging from freshwaters
to marine waters along lithofacies composed of black shales and limestones. The Sr/Ba
ratios of black shales suggest a typical freshwater to brackish environment (Sr/Ba < 0.2
and between 0.2- 0.5), whereas those of the limestones a marine deposition (Sr/Ba > 0.5),
indicating a marine environment in the Araripe Basin by the early Aptian. The
paleoenvironment of the Batateira beds has characteristics of a coastal transgressive
system (fluvial-deltaic) (Varejão et al., 2021) toward a marine environment (Fauth et al.,
2023). Marine transgressions in Batateira beds are supported by typical marine
microfossils (foraminifera, dinocysts, and calcareous nannofossils; Leupoldina cabri and
Subtilisphaera) (Fauth et al., 2023; Vallejo et al., 2023). The increase in salinity in
Batateira beds caused a local biological crisis, as evidenced by the observed local
mortality of non-marine adult ostracods, situated in the same layer as the foraminifera,
and marine calcareous nannofossils, indicating that the increase in salinity generated a
stressful environment for the development of ostracods (Fauth et al., 2023).
It is worth noting that the early Aptian is marked by marine transgression events
and increased salinity in continental environments, with these changes in paleosalinity
being associated with major global climate changes (Fan et al., 2021; Peropadre, Liesa e
Meléndez, 2013; Tedeschi et al., 2020). Global events associated with sea- level rise and
higher aridity events during the Ontong Java volcanism have been suggested to have
triggered changes in paleosalinity in different sedimentary basins (Sergipe-Alagoas,
Brazil; Hongmiaozi, China; Hailar, Mongolia; and Liaoning Province, China) (Min-Na et
al., 2013; Fan et al., 2021; Li et al., 2023; Tedeschi et al., 2020).

58
6.5.1.2 Crato Formation
The base of the Crato Formation is composed by a laminated siliciclastic-
limestone layer, internationally recognized as Konservat-Lagerstätte (CKL). These
carbonates are authigenic, originating from biochemical processes, with microbial mats
and cyanobacteria responsible for the precipitation of calcium carbonate (Catto et al.,
2016). Values of Sr/Ba ratio > 0.5 in this layer may be related to the high concentrations
of calcium carbonate and/or the hypersaline environmental conditions of the Crato
paleolake (Barling et al., 2015; Barling, Martill, Heads, 2020; Heimhofer et al., 2010). Sr
can replace Ca2+ in the mineral structure of the rock, including dolomite and calcite, which
can lead to increased concentrations of this element in limestone layers and strontianite
(SrCO3) precipitation resulting in high Sr concentrations in laminated limestones (Roden,
Leonardo, Ferris, 2002; Wei, Algeo, 2020). Another factor that might be related to the
high Sr/Ba ratios is the hypersalinity found in the Crato paleolake. Halite crystals were
found in the CKL, indicating dry periods, influenced by high evaporation and low rainfall
(Martill, Loveridge, Heimhofer, 2007; Storari et al., 2021). For example, the depositional
conditions and fossil content (fauna and flora) of the Crato paleolake were associated with
modern African hypersaline and alkaline lakes (Ribeiro et al., 2021). Similarly, for the
carbonate paleolake of the Serra do Tonã Formation (Tucano Basin, Northeast Brazil),
stratigraphically correlated with the CKL, indicating variation in lake level with rainwater
(Silveira et al., 2014).
The Caldas bed has Sr/Ba ratio values < 0.2, suggesting a freshwater environment,
in agreement with a reduction in paleosalinity as observed in the Caldas bed when
compared to the hypersalinity of the Crato paleolake (CKL level). This scenario
corroborates earlier studies (Silva et al., 2020; Vallejo et al., 2023; Varejão et al., 2021)
characterizing the Caldas bed as a closed freshwater lacustrine system with an abundance
of non-marine fossils and peaks of freshwater microphytoplankton.
The upper Crato Formation is a succession of layers classified as a heterolithic
succession of facies (Assine et al., 2014; Varejão et al., 2021). There, Sr/Ba ratios indicate
a transition from freshwater to marine paleoenvironments, suggesting an increase in
salinity (Sr/Ba between 0.25 to 0.68) towards the upper Crato Formation. Studies on
microfossils showing a reduction of terrigenous phytoclasts, growth of clustered marine
foraminifera, and Classopolis pollens, common in warm, and dry coastal systems, also
demonstrate a variation in the transition of the Ipubi and Crato formations, from a
predominantly freshwater paleoenvironment to a transgressive system influenced by

59
brackish waters (tidal-dominated bays and confined bays, coastal lakes, and sabkha)
(Goldberg et al., 2019; Guzmán et al., 2023; Vallejo et al., 2023; Varejão et al., 2021).

6.5.1.3 Romualdo Formation

Paleosalinity varied in the Romualdo Formation with periods of marine and
continental contributions. The observed Sr/Ba ratios < 0.2 and between 0.2 – 0.5 points
to an environment with great saline variations, with periods of highest continental fluvial
contributions, also with strong positive correlation between Al and TOC. Periods with
Sr/Ba > 0.5 indicate the lowest fluvial contributions and the dominance of a paleosalinity
typical of a marine environment. This agrees with the scenario proposed by Custódio et
al. (2017) and Melo et al. (2020), the Romualdo Formation is characterized by being a
transgressive-regressive system, with the presence of coastal alluvium, tidal-dominated
facies, and marine shales rich in fish and marine microfossils.
Previous geochemical studies have demonstrated a variation of paleosalinity in
the Romualdo Formation, ranging from an estuarine to a marine system (Bom et al., 2021;
Pontes et al., 2021). Saline oscillation in the Romualdo Formation has been associated
with the interference of OAE 1b in the regional hydrological cycle, with alternating
periods of greater freshwater contribution and greater marine influence (Bom et al.,
2023). Periods of greater continental contributions are demonstrated by the pollen
enrichment (Araucariacites and Classopolis) (Arai, Assine, 2020; Fürsich et al., 2019;
Teixeira et al., 2018), whereas influences from a marine environment are supported by
the occurrence of fossiliferous crustaceans, fish, mollusks, and microfossils (planktonic
foraminifera and ostracods (Arai, 2014; Fara et al., 2005; Guzmán et al., 2023; Martill et
al., 2008; Prado et al., 2019; 2018).

5.5.2 Paleoredox conditions

Trace metals are sensitive to redox state changes being removed from the aqueous
environment and transferred to the sediment when subjected to changing reducing
conditions. This transfer can occur by adsorption with oxyhydroxides (Fe, Al, and Mn),
burial with organic matter, generating organometallic compounds, and co-precipitation
with minerals (Tribovillard et al., 2006). Redox classification of environments followed
Algeo, Li (2020); Algeo, Liu (2020); Algeo, Maynard (2004) and Tribovillard et al.
(2006), being are classified as oxic (> 2mL O2L-1), dyoxic (2 a 0 mL O2L-1), suboxic (0
mL O2L-1, Fe2+> 0, H2S= 0), and anoxic-euxinic (0 mL O2L-1, Fe2+= 0, H2S > 0). The

60
paleoredox proxies V/Cr < 2.0 indicates an oxic environment; V/Cr between 2.0 - 4.25 a
dyoxic environment and V/Cr > 4.25 suggests suboxic to anoxic conditions (Jones,
Manning, 1994). For the V/Ni ratio, values between 1.9 - 3 indicate a suboxic
environment, while V/Ni values > 3.0 are typical of anoxic environments (Galarraga et
al., 2008). Using the V/V+Ni ratio, values > 0.84 indicate euxinic conditions; an anoxic
environment between 0.54 - 0.83; while values between 0.46 to 0.6 indicate dyoxic
conditions (Rivera et al., 2018).

6.5.2.1 Barbalha Formation

The depositional conditions of the Batateira beds presented a depositional
environment ranging from suboxic to anoxic characterized by the presence of lithofacies
composed by black bituminous shales, mineralized pelagic limestone rich in sulfide,
pyrite-rich minerals, fragments of charred vegetation, and a high TOC (Assine, 2007;
Claes et al., 2021; Paula Freitas, Borghi, 2011; Silvestre, Fambrini, Costa, 2020). The
exclusive presence of Ammobaculites (benthic foraminifera) and agglutinated
foraminifera are indicative of a marine paleoenvironment with restricted circulation,
eutrophic and anoxic (Guzmán et al., 2023). Sulfur isotopic analysis (δ34S) in the
Batateira beds demonstrates negative values, typical of bacterial origin produced by
bacterial sulfate reduction under anaerobic conditions (Pontes et al., 2021). Under anoxic
conditions, bacteria promote sulfate reduction with H2S as a product, producing
sedimentary pyrite (Jørgensen, 1982; Liu et al., 2021).

6.5.2.2 Crato Formation

The CKL levels were deposited under dyoxic to anoxic conditions and were
characterized by siliciclastic-calcareous lithofacies. Excellent fossil preservation is
directly related to the reducing conditions of the Crato paleolake. The presence of
microbial mats, the absence of bioturbation, as well as the formation of microframboidal
pyrites in the fossils indicate a reducing environment, with low oxygenation, allowing the
preservation of the soft tissues of the fossils (Heimhofer et al., 2010; Osés et al., 2016).
The formation of pyrite is attributed to bacterial sulfate reduction, an event that occurs
with the degradation of organic matter under reducing conditions (Jørgensen, 1982).
The Caldas bed and the upper Crato Formation showed decreasing oxygenation,
resulting in predominantly reducing conditions from dyoxic to anoxic. The Caldas bed

61
and the upper Crato showed an increase in organic matter contents supporting a
paleoenvironment with low oxygen and preservation of organic matter. In addition, metals
ratios also characterize environmental conditions varying from oxic to anoxic (Salgado-
Campos et al., 2021; Tyson, 1995; Vallejo et al., 2023; Varejão et al., 2021).

6.5.2.3 Romualdo Formation

The metal ratios identified conditions that ranged from oxic to anoxic, indicating
that the environment of the Romualdo Formation presented oscillation in oxygen
concentrations and, consequently, extremely stressful conditions for organisms. It is
possible to observe that during periods of lower salinity and high detrital input, the
conditions range from oxic to dyoxic, while when there is an increase in salinity, anoxic
conditions predominate and the detrital supply input decreases. Bom et al. (2023, 2021)
suggested the Kilian event (OAE 1b) as responsible for the input of phosphorus allowing
for excellent fossil preservation in the Romualdo Formation, associating high sediment
deposition of continental detrital input and a eutrophic environment favoring anoxic
conditions.
The enrichment in sulfur isotopes (δ34S), the production of framboidal pyrite and
preservation of labile materials were observed, indicating a paleoredox dyoxic-anoxic
condition, with a strong influence of bacterial sulfate reduction (Custódio et al., 2017;
Fürsich et al., 2019; Heimhofer et al., 2008; Pontes et al., 2021; Varejão et al., 2019).
These depositional conditions played a role in the excellent preservation of the fossils
(three-dimensional fish, muscles, and blood vessels of pterosaurs). The 20 meters interval
composed of dark gray to black shales, with a high load of organic matter is an indication
of the strong reducing conditions that dominated the Romualdo Formation (Assine, 2007;
Custódio et al., 2017; Kellner, 1996).

5.5.3 Volcanism and palaenvironmental changes

Hg/TOC peaks indicate activation of LIPs, and the use of TOC as a normalizer is
due to its affinity for Hg, acting as the main mechanism capable of retaining Hg over the
geological time (Grasby et al., 2019). Volcanism is responsible for releasing Hg in its
elemental form (Hg0) to the stratosphere causing a global distribution. Gaseous elemental
Hg0 is oxidized in the atmosphere forming the reactive form Hg2+. Subsequently, the

62
reactive Hg2+ associates with the water present in the atmosphere, precipitating with
rainwater (Bond, Grasby, 2017; Font, Bond, 2021; Sial et al., 2016).
Considering the activation of LIPs during the Early Cretaceous, we highlight the
Paraná-Etendeka (~132 Ma), Ontong Java (~124 to 120 Ma), Southern Kerguelen Plateau
and Rajmahal (~119 to 110 Ma), Elan Bank (~110 Ma) and Central Kerguelen Plateau
(~105 Ma) volcanisms (Coffin et al., 2006; Erba et al., 2015; Keller, 2008; Li et al., 2023).
Among these LIPs, the OJP and the SKP stand out, as they were responsible for the
oceanic anoxia events OAE 1a and OAE 1b, respectively (Erba et al., 2015; Li et al.,
2023; Sabatino et al., 2018).

6.5.3.1 Barbalha Formation

Biostratigraphically the Batateira beds was associated with the global foraminifera
biozones Leupoldina cabri and Globigerinelloides algerianus, indicating an early Aptian
deposition (Fauth et al., 2023; Ogg et al., 2016; Weissert, Erba, 2004). The Batateira beds
showed four Hg/TOC peaks, indicating the activation of volcanism at the Early Aptian,
with sample 17A (limestone) standing out due to the simultaneous enrichment of all
proxies of paleoproductivity and paleoredox. Regarding the activation period of the LIPs
and their association with the Araripe sedimentary basin, we can suppose that the
principal mechanism responsible for the paleoenvironmental disturbances in the Batateira
beds was the Ontong Java Plateau. The activation age of Ontong Java ranges from 124
Ma to 120 Ma and this volcanism was responsible for the oceanic anoxia event (OAE 1a),
which had a large impact on marine plankton, responsible for the burial of a large TOC
load and enrichment of trace metals (Erba et al., 2015; Ogg, Ogg, Gradstein, 2016; Stein
et al., 2011; Weissert, Erba, 2004).
Disturbances events in the carbon cycle were related in the Araripe basin: one
associated with the Batateira beds; and the other with the Romualdo Formation
(Heimhofer, Hochuli, 2010). The activation of OJP is responsible for the TOC and metals
enrichment during early Aptian (Bottini, Mutterlose, 2012; Erba et al., 2015). The same
process was observed for the extinction events of the Ordovician-Silurian and Permian-
Triassic, in which the increase of the CO2 emission by volcanic activities was able to
modify the global carbon cycle (Lu et al., 2021; Sial et al., 2021; Tang et al., 2020).Thus,
we can infer that trace metal anomalies found in the Batateira beds were influenced by
the volcanic emissions of OJP, resulting in increased CO2 in the atmosphere, intensifying
the biological pump and the supply of nutrients to the aquatic environment. Consequently,

63
the increase in primary production generates a higher TOC and higher deposition of
paleoproductivity anomalies metals (CuEF, ZnEF, BaEF, NiEF, δ13Ccarb. and TOC) due to the
intensification of the degradation process of organic matter, which results in an anoxic
environment, as seen by the anomalies of the paleoredox proxies (PbEF, CrEF, FeEF, MnEF
e VEF) in the Araripe Basin.

6.5.3.2 Crato Formation

The Crato Formation is from late Aptian, corresponding to the Alagoas level
(Assine, 2007; Fambrini et al., 2020; Guzmán et al., 2023) and with the presence of the
foraminifera groups P. blakenonsensis, H. gorbachikae, and M. miniglobularis (Guzmán
et al., 2023) demonstrating the location between the foraminifera zones Hedbegella
infracretacea (~ 118 Ma) and P. rohri (~ 114 Ma) (Ogg et al., 2016). Considering the
volcanism events that occurred in this period, we highlight the activation of the Southern
Kerguelen plateau (~ 119 to 110 Ma) and of the Rajmahal (118 – 113 Ma) (Coffin et al.,
2002, 2006).
The CKL levels (Crato paleolake), presented the enrichment of paleoproductivity
and paleoredox proxies and changes in the δ13Ccarbonate and δ18O isotopes values. The
peaks found in CKL of Crato Formation showed enrichment of all paleoproductivity and
paleoredox proxies. This enrichment may be related to the anoxic condition characteristic
of this layer and/or to the high paleoproductivity. The high primary productivity and low
oxygen concentration at the bottom of the Crato paleolake generated excellent conditions
for the reduction of bacterial sulfate reduction, which is responsible for the formation of
hydrogen sulfide (H2S) (Osés et al., 2016). In an anoxic environment rich in sulfides, the
tendency is for trace metals to adsorb with sulfur and enrich the sediment (Tribovillard et
al., 2006). Galene and sphalerite minerals were recorded in the limestone layers of the
Crato Formation, confirming reducing conditions by bacterial sulfate-reduction (Martill,
Loveridge, Heimhofer, 2007; Osés et al., 2016).
The enrichment of trace metals in samples 1E, 11C, 10A, and 10D, together with
Hg/TOC peaks signals the action of volcanisms and their record in the Araripe Basin.
Spearman's correlation demonstrated the relationship between Hg/TOC (vulcanism) and
trace metals (Pb, V, Mn, Fe, Cu, and Zn), indicating the interference of volcanism in the
trace metals deposition, following increasing biological productivity, changes in redox
state, and paleoclimatic conditions.

64
 During volcanic degassing, trace metals are emitted into the atmosphere
(associated with dust, volcanic ash, and sulfides) (Mason et al., 2021), increasing
deposition, further favored by increased paleoproductivity and anoxic conditions (Fan et
al., 2021; Galloway et al., 2023). Furthermore, low correlation between Al with Pb, Mn,
Fe, Cu, and Zn indicates little contribution of detrital elements (Tribovillard et al., 2006).
Only Ni, V, and Cr concentrations were correlated with those of Al, demonstrating the
influence of external detrital input on the deposition of these metals.
δ18O and δ13Ccarbonate in samples 1E, 11C, 10A, and 10D mark sudden changes
when there are peaks of Hg/TOC, indicating the interference of volcanism in
paleotemperature and paleoproductivity in the Araripe basin. During the Aptian,
variations of δ18O and δ13Ccarb. were recorded, indicating oscillations in carbon cycle as
well as in paleotemperatures (Bottini, Erba, 2018; Li et al., 2014). Occurrence of
evaporites, the absence of coal seams, and the xerophytic vegetation resistant to drought
demonstrate that the depositional conditions of the Crato Formation are in the Tropical
Equatorial Hot belt (Chumakov et al., 1995; Ribeiro et al., 2021).
When there is an injection of CO2 originating from the terrestrial mantle, the
imbalance in the carbonate system occurs, directly influencing the mixture of calcifying
organisms (Bond, Grasby, 2017). In this context, δ13Ccarb. and δ18O oscillations in the
Crato Formation occurs because the disturbances in the carbon cycle, in which the CO2
(intensifying the greenhouse effect), sulfur dioxide and atmospheric dust (decreasing the
temperature) emitted by volcanism were able to generate changes in paleotemperature
and changes in paleoproductivity.

6.5.3.3 Romualdo Formation

The Romualdo Formation dates between the Aptian-Albian transition (~ 113.1
Ma), based on the presence of benthic foraminifera Paraticinella rohri (middle Aptian),
Microhedbergella miniglobularis (late Aptian - 113.1 Ma), and the nannofossil Hayesites
albiensis (early Albian) (Araripe et al., 2021, 2022; Assine, 2007; Assine et al., 2014;
Fambrini et al., 2020; Melo et al., 2020). Among the volcanism events that occurred
during the late Aptian and early Albian are the Southern Kerguelen and Raajmahal
plateaus (118 – 110 Ma) (Coffin et al., 2002; 2006). Sabatino et al. (2018, 2015) and
(Galloway et al., 2023) found Hg/TOC anomalies in the foraminifera zones P. rohri, M.
miniglobularis, and Hayesites albiensis and associated these anomalies to the event ocean
anoxia 1b (OAE 1b) resulting from the Southern Kerguelen (SKP) plateau volcanism,

65
which also caused the enrichment of trace metals, biological crises of calcifying marine
organisms, the burial of TOC, and oceanic anoxia (Erba et al., 2015; Sabatino et al.,
2015).
The Hg/TOC anomalies found in the present study in the Romualdo Formation, in
addition to the burial of TOC and trace metals enrichment, are indicative of changes in
paleoproductivity and paleoredox, which may be associated with to the OAE 1b event,
influenced by the SKP. This is consistent with a scenario of distal effects of the OAE 1b
in the Araripe basin, biostratigraphic correlations (Guzmán et al., 2023), and
accumulation of organic matter (Heimhofer et al., 2008). More recently, metal enrichment
and δ13Corganic isotopic signatures were also related to the activation of volcanism on the
SKP- Kilian subevent (Benigno et al., 2021; Bom et al., 2023).
Metals anomalies found of paleoproductivity (CuEF, ZnEF, BaEF, NiEF and TOC)
and paleoredox (PbEF, CrEF, MnEF, VEF and FeEF) proxies in the Romualdo Formation
were linked to the influence of SKP volcanism in the Araripe basin, as observed by the
Hg/TOC peaks in the same layers. Li et al. (2014) found increasing CO2 emissions during
the activation of the Southern Kerguelen plateau. The injection of CO2 and other gases
(HCl and SO4-) led to the development of the biological pump, resulting in greater
productivity, metals enrichment, ocean acidification, as well as increased weathering due
to the acidity of the atmosphere (Bodin et al., 2023; Coffin et al., 2006; Grasby et al.,
2019). Spearman correlation coefficients were significantly positive between TOC and
detrital supply (Al), paleoproductivity and paleoredox proxies. Whereas a negative
correlation was observed with paleosalinity. These suggest the impact of the SKP
volcanism in the paleoenvironmental depositions of the Araripe Basin. The increase in
atmospheric CO2 from SKP generates continuous consequences to the paleoenvironment,
such as: intensified continental input, more nutrients to the coastal environment, increased
primary production, the greater deposition of organic matter, and the immobilization of
metals in environment with low oxygenation, and these are reflected in the variability of
proxies observed in the Romualdo Formation.
The changes in δ13Ccarbonate marked variations in paleoproductivity, and depletion
of δ13Ccarb. occurs due to changes in the carbon cycle, directly impacting calcifying
organisms, while enrichment indicates a stable environment with the re-establishment of
those organisms (Weissert et al., 1998). δ13Ccarbonate showed impoverishment in the basal
samples of the Romualdo Formation, while towards the upper samples there is an
enrichment of δ13Ccarbonate. This behavior demonstrates that during Hg/TOC anomalies

66
there is a reduction in δ13Ccarb. and an increase in the TOC, while after volcanic anomalies
an increase in δ13Ccarb. is observed, indicating the recovery of calcifying organisms.
Heimhofer et al. (2008) identified that the organic matter in the Romualdo Formation
comes mainly from autochthonous material (primary production) and continental
contributions. During different OAE events, where there is a decrease in planktonic
calcifying organisms, there is growth of siliciclastic planktonic organisms and
cyanobacteria, and consequently, an increase in organic matter deposition (Coccioni et
al., 2014; Kuypers et al., 2004; Petrizzo et al., 2012).
The δ18O showed enrichment at the base of the Romualdo Formation, while
towards the upper part there is a decrease. The activation of LIPs was responsible for CO2
and SO2 emissions, impacting the hydrological cycle and global paleoclimatic conditions
(Bond, Grasby, 2017). Weissert, Erba (2004) observed paleotemperature variations during
OAE 1b associated with volcanism on the Kerguelen plateau. δ18O in the Romualdo
Formation demonstrated probable oscillation in the hydrological cycle, with hot humid
and hot dry cycles. Paleoclimatic changes were previously reported in this environment,
demonstrating that interference in the hydrological regime may had been influenced by
CO2 oscillations due to volcanism and, consequently, fluvial discharge (Araripe et al.,
2019; Bom et al., 2021, 2023; Teixeira et al., 2018).
Therefore, the Hg/TOC peaks found in the Romualdo Formation influenced by
the volcanism of the Kerguelen plateau and the biostratigraphic dynamics with the OAE
1b event. The increase of CO2 in the atmosphere generated global climate changes and
had a direct impact on the Araripe Basin, causing an increase in biological production,
the burial of large amounts of TOC, enrichment of trace metals, anoxia events, and climate
variations. These processes may have generated biological crises in the Romualdo
Formation, as there are reports of mass fish mortality events, low diversity of organisms,
and forest fires, demonstrating extremely challenging conditions for the survival of local
organisms (Custódio et al., 2017; Martill, 1988; Martill, Brito, Washington-Evans, 2008).

5.7 Conclusion
The results showed the influence of the volcanism events of Ontong Java, Southern
Kerguelen Plateau, and Raajmahal in the Araripe Sedimentary Basin. Trace metal
enrichments found in the Barbalha, Crato, and Romualdo formations characterize the
increase in paleoproductivity and changes in the redox state during Hg/TOC peaks.
Variations of these proxies may be related to the emission of CO2 and other gases into the

67
atmosphere, which directly affect the development of the biological pump and anoxic
conditions.
The Batateira beds (Barbalha Formation) characterized by paleosalinity changes
indicating that the first marine intrusions in the Araripe Basin occurred in the early
Aptian, anticipating the intrusions previously recorded. Paleoredox conditions indicate
that the environment was predominantly anoxic. In addition, the Hg/TOC ratio anomalies
and metal enrichments indicate interference signals from the Ontong Java volcanism,
which was responsible for the oceanic anoxia event 1a. Biostratigraphic correlations point
to a possible depositional system influenced by OAE 1a.
In the Crato Formation, a very heterogeneous environment was identified, with
large variations in salinity, redox state, paleoproductivity, and paleoclimate. In this unit,
the influence of volcanism was also observed, through the enrichment of the
paleoproductivity and paleoredox proxies, being correlated with the Hg/TOC anomalies.
Furthermore, the correlation found between volcanism and trace metal proxies
demonstrates their volcanic source.
The Romualdo Formation, Aptian-Albian transition, was characterized by
presenting a brackish to marine transition environment. Anoxic conditions were observed,
corroborating previous studies. Furthermore, Hg anomalies show the influence of the
Southern Kerguelen Plateau on paleoenvironmental processes, through the enrichment of
paleoproductivity and paleoredox trace metals. Mercury peaks may be related to ocean
anoxia 1b events, responsible for major biological crises.

Acknowledgments
The authors are deeply indebted to the many students at the Regional University of Cariri,
who have helped in the intensive field campaigns in the Araripe Basin. Technicians from
the Marine Biogeochemistry Laboratory (LBC-UFC) helped preparing samples for
chemical analyses. Technicians from the NABISE-UFPE, for isotopes analysis.

68
CAPÍTULO 2
Geochemistry approach to mortality events of autochthonous fauna in
Konservatt-Lagerstätte Crato paleolake (Crato Formation, Araripe
basin, Brazil)
O segundo manuscrito, aborda uma caracterização geoquímica do Konservat -
Laggerstätten do paleolago Crato (Bacia do Araripe). O objetivo principal é caracterizar
as mudanças paleoambientais que podem ter resultado nos eventos de mortalidade
(Dastilbe sp. e ephemerópteras) registrados no sistema lacustre. Este trabalho possibilitou
observar que as mudanças paleoclimáticas no sistema lacustre eram comuns, onde as
variações da profundidade, paleredox e paleoprodutividade do ambiente deposicional
podem ter interferido nos eventos de mortalidade registrados. Além disso, observou-se
uma interferência dos vulcanismos dos platôs Rajmahal- Kerguelen na paleoclimatologia,
podendo ter intensificado a mortandade no Konservat -Lagerstätte do paleolago Crato.
Autorias de Igor Hamid Ribeiro Azevedo *; Luiz Drude de Lacerda, Antônio Álamo
Feitosa Saraiva, Alcides Nobrega Sial, Ana Paula Aquino Benigno, Flaviana Jorge de
Lima, Renan Alfredo Machado Bantim, Mariana Silvestre Martins, Maria Andrea
Ferreira, José Edvar Aguiar.

Keywords: Water level, Volcanism, Paleoclimatic changes, Metals, Enrichment

factor
Highlights
• Changes in paleoproductivity, paleoredox state, paleosalinity and paleoclimate in
the Konservat- Lagerstätte of the Crato paleolake (Araripe Basin- AB).
• Stable isotopes (δ13CVPDB and δ18OVPDB) and trace metal enrichment were
consistent proxies of paleoenvironmental changes.
• Paleoenvironmental changes in the Crato paleolake resulting in cyclical mass
mortality events.

_______________
Hamid, I. R. A.; Martins, M. S.; Saraiva, A. A. F.; Benigno, A. P. A.; De Lima, F. J.; Bantim, R.
A. M.; Sial, A. N.; Aguiar, J. E.; Lacerda, L. D. Geochemistry approach and mortality events of
autochthonous fauna in Konservatt-Lagerstätten Crato paleolake (Crato Formation, Araripe
Basin, Brazil). Submitted to Palaeogeography, Palaeoclimatology, Palaeoecology.

69
 ABSTRACT

Geochemical records from the Konservat-Lagerstätte of the Crato paleolake (Aptian,

Lower Cretaceous) revealed the influence of paleoclimatic variations (wet-dry) on the
lake system. Paleoredox (PbEF, MnEF, and FeEF) and paleoproductivity (CuEF, ZnEF, NiEF,
BaEF, and δ13CVPDB) indexes recorded oscillations in the Crato paleolake, including the
influence of paleodetrital transport (Al and Fe), paleoclimatic conditions (Sr/Cu),
volcanism (Hg/Al and Hg/Fe) and lake level (Fe/Mn and δ18OVPDB). The survival the mass
mortality of organisms present in the Crato paleolake were related to the paleoclimatic
variations experienced by the environment. The Hg anomalies in the Aptian reveal that
volcanism of the Rajmahal-Kerguelen plateaus interfered with the climatic and
depositional processes of the Crato palaeolake, which led to changes in redox conditions
and palaeoproductivity, aridity intensification in the interior of the continent and local
mortality events. Furthermore, wet periods show redox conditions and palaeoproductivity
that can indicate hypoxia in the aquatic system and the mass mortality events recorded in
the Konservat-Lagerstätte of the Crato paleolake.

70
6.1 Introduction
The Araripe Basin (AB), with an area of 9,000 km² and 950 m of thickness (Figure
13), near the borders of the states of Ceará, Piauí and Pernambuco (Northeast Brazil)
(Assine, 1992, 2007). Its origin and evolution are related to the reactivation of faults in
the crystalline basement during fragmentation of the Gondwana supercontinent and the
opening of the Atlantic Ocean (Brito Neves et al., 2000; Neves et al., 1995). As a result,
the Brazilian and African marginal basins were developed due to the mechanical
subsidence during the fragmentation of Africa and South America (Alkmim et al., 2015;
Godot Souza et al., 2022). The Araripe Basin is bounded by the Neoproterozoic
Pernambuco and Patos shear zones, which are associated with the Brazilian-Pan-African
orogeny (Assine, 2007; Brito Neves et al., 2000; Neves et al., 1995).
The ASB shows the highest complexity among all the sedimentary basins in the
Brazilian Northeast, as it presents 5 depositional sequences which are furrowed in two
geomorphological features: the Araripe plateau surface and the Cariri Valley (Assine,
2007; Peulvast, Bétard, 2015). The Araripe plateau has an East-West orientation and
encompasses the Cretaceous (Aptian-Cenomanian) depositional sequences of the post-
rift I (Barbalha, Crato, Ipubi and Romualdo formations) and II (Araripina and Exu
formations) stages of the Atlantic Ocean opening process (Assine, 2007). The Cariri
Valley contains records of the oldest periods of the ASB, including the Paleozoic (Cariri
Formation), the Jurassic pre-rift (Brejo Santo and base of Missão Velha formations) and
the Cretaceous rift (Upper of the Missão Velha and Abaiara formations) sequences from
Gondwana rift event (Fambrini et al., 2020).
The Crato Formation (Aptian, Lower Cretaceous) represents the second lacustrine
phase (Crato paleolake) of the Araripe Basin. It is described as 60 m thick and a
lithostratigraphy composed of six calcific carbonate layers (C1 to C6) intercalated with
green shales and fine sandstones (Assine et al., 2014; Coimbra, Arai, Carreño, 2002;
Neumann, 1999). The presence of calcified coccoid and biofilms of calciferous
filamentous bacteria indicates that the laminated limestones of the Crato Formation are
products of biological mineralization (Catto et al., 2016). The exceptional paleontological
assemblage of the Crato Formation in the carbonate levels has classified such
paleoenvironment as Konservat-Lagerstätte (CKL), due to the remarkable quality of
fauna (pterosaurs, insects, crocodyliforms and fish) and flora (gymnosperms and
angiosperms) (Assine, 2007; Ribeiro et al., 2021; Varejão et al., 2021).

71
 The location of the Crato paleolake, in the Warm Equatorial Tropical belt
(Chumakov et al., 1995), in conjunction with the xerophytic vegetation (Ribeiro et al.,
2021), provides evidence of a depositional paleoenvironment characterized by arid to
semi-arid conditions. Nevertheless, it is important to distinguish the oscillation between
wet and dry periods in the lake system. Such behavior has been observed and documented
through fossil record (do Nascimento et al., 2023; Martill et al., 2005; Mendes et al.,
2020) and geochemistry (Benigno et al., 2018; Hamid et al., 2024; Salgado-Campos et
al., 2021). Previous research has identified that the Crato paleolake exhibits distinct
humidity zones, analogous to modern hypersaline lakes of the Andes (Warren et al., 2017)
or Lake Chad in Sub-Saharan Africa (Ribeiro et al., 2021).
The Crato paleolake exhibited depositional conditions that suggest an
anoxic/dysoxic lacustrine paleoenvironment (Osés et al., 2016), characterized by
extremely arid periods, highlighted by the presence of halite crystals (Martill, Loveridge,
Heimhofer, 2007), and paleo-wildfires (Lima et al., 2019). In this context, cyclical
changes in humidity may have resulted in unfavorable conditions for the survival of
organisms in the Crato paleolake, as the lake system experienced significant fluctuations
in depth, salinity, productivity, and redox state. These oscillations have resulted in the
occurrence of periodical mortality events (Martins-Neto, 2006; Storari et al., 2021).
The present study aims to elucidate the cyclical factors involved in mortality
events recorded by Storari et al. (2021), and other authors in the Crato Formation. To
achieve such goal, the study aims to determine the relationships between the
paleoenvironmental changes of the Crato paleolake, and the consequences that led to the
mass mortality events. The application of multi-proxies (trace metals and ratios between
them and isotopes) will facilitate the interpretation of the evolution and development of
the Konservat -Lagerstätte Crato paleolake, enabling the reconstruction of paleoredox
conditions, paleoproductivity, and paleodetritic inputs variations in the Araripe basin.

72
Figure 13. Location map of the Araripe basin (AB). A) Distribution area and location of lithofacies in the ASB
(Modified from Assine, 2007 and Warren et al., 2017). B) Location of the AB at 120 Ma (Modified from Scotese,
Wright, 2018). S- Stage; T– Tectonostratigraphic; Sand- Sandstone, Silt- Siltstone, Sha- Shale, Gyps- Gypsum.

6.2 Material and methods

6.2.1 Material studied
Samples were collected in the fine-scale profiles of the post-rift I period of the
outcrop of the Crato Formation at the Antônio Finelon Mine (S 7°07’22.5” and W
39°42’01”) in the Nova Olinda municipality, Ceará State, Brazil (Figure 14). The samples
were collected from a layer of the C6 Konservat-Lagerstätten Crato paleolake, more

73
 specifically from the top of the Crato Formation. The controlled excavations were
collected in the quarry’s surface, divided into 5 m² x 5 m², and happened from the base to
the upper part of the outcrop, totaling 3.20 meters in depth (Figure 14). About 84 samples
were collected in the laminated limestones of the Konservat- Lagerstätte, layer and
samples were ground, homogenized and dried (60°C for 12 hours), then preserved in
hermetically closed flasks until analysis. The fossil records indicate the existence of 10
levels of mortality (9 events with Dastilbe sp. and with Ephemeroptera larvae) in the
Crato paleolake. For more information about the fossil content (integrity of the fossils,
type of preservation, length, width, and orientation) of the Crato paleolake consult Storari
et al. (2021).

Figure 14. Profile of the controlled excavation of the Crato Formation at the Antonio Finelon mine (modified from
Storari et al., 2021). The samples come from the C6 layer of the Crato Formation, identifying 10 mortality events
(Dastilbe sp. and Hexagenitidae) in the Crato paleolake.

Figure 27. Profile of the controlled excavation of the Crato Formation at the Antonio Finelon mine (modified from
Storari et al., 2021). The samples come from the C6 layer of the Crato Formation, identifying 10 mortalities events
(Dastilbe sp and Hexagenitidae) in the Crato paleolake.

Figure 15. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies (Al and Fe); volcanism proxies (Hg/Al
and Hg/Fe ratios) and Hg concentration (ng g-1). B) Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation
in the depth of the lake system (Fe/Mn) and δ18OVPDB.Figure 14. Profile of the controlled excavation of the Crato
Formation at the Antonio Finelon mine (modified from Storari et al., 2021). The samples come from the C6 layer of
the Crato Formation, identifying 10 mortalities events (Dastilbe sp and Hexagenitidae) in the Crato paleolake.

Figure 28. Profile of the controlled excavation of the Crato Formation at the Antonio Finelon mine (modified from
Storari et al., 2021). The samples come from the C6 layer of the Crato Formation, identifying 10 mortalities events
(Dastilbe sp and Hexagenitidae) in the Crato paleolake.

74
6.2.2 Metals analysis
The concentrations of Al, Fe, Mn, Sr, Cu, Pb, Ni, Ba, and Zn were measured in 84
samples by Flame Atomic Absorption Spectrometry - FAAS (AA 7000, SHIMADZU).
About 0.7 g of the samples were placed in Teflon tubes closed pressure vessels with 15
mL Aqua Regia 100% v/v (3 HCl:1 HNO3) and were digested in microwaves (1,600 W
and 175 ºC, for 20 min). The extracts were taken in volumetric flasks to 30 mL with HNO3
0.2% v/v. All glassware was previously washed with deionized water in a 10% v/v Extran
detergent solution (10% v/v) for 24 hours, and then in an HCl bath (Sigma-Aldrich) 10%
v/v for 24 hours. Reference standard materials (NIST 1646A), reagent blanks and
duplicated samples were prepared and measured to assess the accuracy (between 84% -
97%), whereas the detection limit of the procedure varied from 0.02 (Ni) to 0.37 µg g-1
(Al). Quantification of the metals used Flame Atomic Absorption Spectrometry - AAS
(AA 6200, SHIMADZU), with calibration curves of each metal constructed from
MERCK standard solutions (1,000 µg mL-1).

6.2.3 Mercury analysis

The quantification of mercury (Hg) was performed in duplicates after digestion of
1 g of the samples were placed in Teflon tubes closed pressure vessels with a 10 mL of
concentrated nitric acid (HNO3 65%) for 1 h pre-digestion. Total samples digestion was
carried out in a microwave digestion (at 1,600 W and 175 ºC, for 30 min). The final extract
was quantitatively transferred and diluted in volumetric flasks (100 mL). All glassware
was previously washed with deionized water in an Extran® solution bath (10% v/v) for
24 hours and then in an acid bath of HCl (Sigma-Aldrich) 10% v/v also for 24 hours. The
quantification of Hg was performed using Cold Vapor Generation Atomic Absorption
Spectrometry (CV-AAS), in a NIC-RA-3 (NIPPON®). Furthermore, analyses with
reference material (NIST-1646A) were performed simultaneously with the samples, in
which the mean recovery was 93 ± 6%; the limit of detection of the procedure was 0.04
ng g-1, and the limit of quantification was 0.13 ng g-1.

6.2.4 Stable isotopes (δ13C and δ18OVPDB)

Seventeen samples were selected from the CKL layer of the Crato Formation for
Carbon (δ13C) and Oxygen (δ18O) stable isotopes analysis. Stable isotope analysis was
quantified in the CO2 extracted from the samples by digestion with orthophosphoric acid

75
at 25ºC, using a Thermofinnigan Delta V Advantage mass spectrometer. Results are
expressed in the δ notation (‰) with an accuracy better than ± 0.1‰; Carbon and Oxygen
isotopic data were calibrated to international standards (Vienna Pee Dee Belemnite).

6.2.5 Enrichment Factor (EF)

In order to eliminate the potential impact of sediment sources in the surrounding
area and to mitigate the effects of biogenic components (carbonates, silica and
phosphorites) upon the results, the present study has used Al and Fe as normalizers, with
the objective of discerning abrupt shifts in paleoproductivity (NiEF, CuEF, ZnEF, and BaEF)
and the paleoredox state (PbEF, MnEF, and FeEF) (Sabatino et al., 2015; Soua et al., 2011;
Touati, Haji, 2019; Tribovillard et al., 2006). The application of EF allows for the general
assessment of the enrichment/impoverishment of metals, pertinent paleoenvironmental
alterations, and their essential role in chemostratigraphy (Algeo e Liu, 2020). The
utilization of such metals considers their behavior in a reducing environment, in which
they can adsorb with organic matter, carbonates, and co-precipitate with sulphur (Algeo,
Liu, 2020; Algeo, Maynard, 2004; Herndon et al., 2018).
Al and Fe are constituents of siliciclastic groups and are associated with silt and
clay particles. Furthermore, they are constituents of the major detrital minerals, which
include phyllosilicates, quartz, plagioclase, and k-feldspar. These minerals are
characterized by high stability and low mobility in the environment (Merli et al., 2020;
Montero-Serrano et al., (2015); Rodríguez-Cuicas; Montero-Serrano et al., (2019).
Although the geochemical indicator is for paleoredox conditions (Tribovillard et al.,
2006), the present study has used Fe as an indicator of palaeodetritic input and the
identification of EF anomalies in the calcite limestones of the Crato Formation. The
application of this element is based on a proposal by Heimhofer et al. (2010) for the Crato
palaeolake that indicates that Fe was used as the geochemical standard, which suggests
that the element could originate from rock and soil weathering processes.
The calculation of the enrichment factor (EF) consists of the ratio between the
concentration of the element in limestones and the corresponding average concentration
of the element in the upper middle crust (Cao et al., 2012). However, the present study
uses the concentrations of specific elements found in limestone, as proposed by
Salomons, Förstner (1984). The EF is determined using the equation: EFElement= [(X/Al,
Fe)Sample) /(X/Al, Fe)Limestones], in which (X/Al)(Sample) represents the concentrations of
elements X and Al, Fe measured in the samples, while (X/Al, Fe)(Limestones) corresponds to
76
the concentrations of elements in the "average limestones" of the crust according to the
values proposed by Salomons, Forstner, (1984).

6.2.6 Statistics methodology

The statistical analysis of this study was performed using RStudio software
(version 4.3.1 - © 2009 - 2023 RStudio, Inc.). Homogeneity and normality tests were
carried out for the assessment of the normality of the samples. As a result, it was possible
to determine a non-normal projection of the variables. In this case, Spearman's correlation
coefficient was used (p < 0.05, n= 84). The data provided, known as the correlation index,
varies from -1 to +1 and assesses whether there is a relationship of dependence or
independence between the parameters evaluated (Miller, 2010).
Additionally, Principal Component Analysis (PCA), a multivariate evaluation
method was utilized to investigate the correlation between trace metal concentrations and
observed mortality events in the depositional environment. To apply this method, it was
necessary to classify the mortality events according to the presence or absence of these
events along the stratigraphic column.

77
6.3 Results
6.3.1 Characterization of the Crato paleolake
The aluminum concentration in the Crato paleolake exhibited a range from 0.03%
to 0.69%, with the highest concentration observed at a depth of 160 cm, as illustrated in
Figure 15A. A significant direct correlation (p < 0.05; n = 84) between Al was observed
with Zn (r = 0.61), Fe (r = 0.34), Cu (r = 0.42), Ni (r = 0.40), Pb (r = 0.28), and Hg (r =
0.33). For Iron, concentrations ranged from 0.08 to 1.90% (Figure 15A), were positively
correlated (p < 0.05; n = 84) with Cu (r = 0.55), Zn (r = 0.61), Ni (r = 0.48), Pb (r = 0.39),
Ba (r = 0.32), and Hg (r = 0.34). The highest iron concentrations were observed at depths
of 16 cm (1.69%) and 180 cm (1.90%).
The Sr/Cu ratio, a proxy to paleoclimatic conditions, varied from 0.08 to 13.8
(Figure 15B), while the Sr/Ba ratio, a proxy to paleosalinity, varied from 0.13 to 20
(Figure 15B). Spearman's test (p < 0.05; n= 84) showed significant correlations between
Sr/Cu and Sr/Ba (r = 0.47), and negative with Al (r = -0.32), Fe (r = -0.27), Cu (r = -0.46)
and Zn (r = -0.31). The Sr/Ba ratio was negatively correlated with Al (r = -0.32), Ni (r =
-0.33) and Ba (r = -0.39).
The δ13CVPDB varied from -2.2‰ to +0.3‰ (Figure 16A), with the highest values
at depths of 151.4cm (+0.28‰) and 179.1cm (+0.24‰). δ18OVPDB values varied from -
7.6‰ to -4.9‰ (Figure 15B), being highest at 150 cm and 179.1 cm (-6.25‰). The
δ13Ccarb. and δ18O were positively correlated (r = 0.44; p<0.05).

6.3.2 Volcanism, paleoproductivity and paleoredox conditions in the

Crato paleolake
Mercury (Hg) concentrations exhibited a range from 12 to 355 ng g-1 (Figure
15A), whereas Hg/Al and Hg/Fe ratios, a proxy of volcanic activity, exhibited sharp
positive incursions of 42 to 3,050 and 19 to 882, respectively, as depicted in Figure 15A.
Seven Hg concentrations anomalies were identified in the study, with the highest
concentrations observed at the same depths where mortality events were recorded at the
Crato paleolake. This suggests a potential correlation between Hg concentration and
mortality events. Hg/Al ratio demonstrated a significant, positive correlation with Hg (r
= 0.62; p < 0.05; n = 84) and Sr/Cu (r = 0.37), while Hg/Fe correlated with Hg (r = 0.51),
Sr/Cu (r = 0.42) and Hg/Al (r = 0.54).

78
 The Fe/Mn ratio, a proxy of lake level changes of the Crato paleolake, varied from
0.7 to 13 (Figure 15B). Spearman's test (p < 0.05; n = 84) indicated a direct correlation
between the Fe/Mn ratio and Al (r = 0.35), Fe (r = 0.96), and negative associations
between Hg/Al (r = -0.31), and Hg/Fe (r = -0.40).
Spearman's analysis (p < 0.05; n= 84) revealed a statistically significant negative
correlation between paleoproductivity proxies and Hg/Al (Cu = -0.30, and Zn = -0.30),
and Hg/Fe (Cu = -0.33, and Zn = -0.42). The Fe/Mn ratio was found to be significantly
correlated with Cu (r = 0.51), Zn (r = 0.59) and Ni (r = 0.35). The paleoproductivity
proxies in the Crato Formation were normalized using Al and Fe, respectively, as EF
normalizing elements. It was observed that CuEF values ranged from 15 to 2,545 and 6 to
579; while ZnEF from 39 to 451 and 13 to 331. NiEF varied from 0.2 to 32 and 0.2 to 9,
while those of BaEF from 1 to 24 and 0.5 to 14 (Figure 16).
Spearman's analysis (p < 0.05; n= 84) showed the highest correlations between
the paleoredox proxies and the Fe/Mn ratio (Mn = -0.31 and Pb = 0.38). The EF values
were calculated using normalization with Al and Fe, respectively. In the limestones of the
Crato Formation, the PbEF values ranged from 42 to 937 and 21 to 1,393, while the MnEF
varied from 3 to 59 and 2 to 40; while the FeEF values ranged from 0.3 to 8 (normalized
only for Al) (Figure 16).
A correlation analysis between EF and the volcanism proxies (Hg/Al and Hg/Fe)
showed positive correlations with NiEF, BaEF, MnEF, and FeEF. For more detailed
information on the correlations between the volcanism proxies (e.g., paleosalinity
[Sr/Ba], paleoclimate [Sr/Cu] and depth [Fe/Mn]), the enrichment factors of the
paleoproductivity (Cu, Zn, Ba and Ni) and paleoredox (Pb, Mn and Fe) proxies see the
Supplementary Material.
PCA was applied to evaluate the interference of trace metal enrichment factors
and geochemical ratios (Hg/Al, Hg/Fe, Sr/Cu, Sr/Ba and Fe/Mn) in mortality events
recorded in the Crato paleolake. Note that EF using Al as a normalizer accounted for
69.2% of the total variance, with PC1 and PC2 explaining 35.1% and 34.1% of this
variance, respectively (Figure 17A). For EF using Fe as a normalizer (Figure 17B), we
observed that 52% of the total variance of the data was accounted for, with PC1 and PC2
explaining 31.8% and 20.2% of the total variance, respectively. The PCA suggests that
the mortalities recorded in the Crato Paleolake may be the result of changes in
paleoproductivity and paleoredox in the lacustrine system, which may affect the survival
of organisms.

79
Figure 15. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies (Al and Fe); volcanism proxies (Hg/Al and Hg/Fe ratios) and Hg concentration (ng g-1).
B) Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation in the depth of the lake system (Fe/Mn) and δ18OVPDB.

Figure 29. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies (Al and Fe); volcanism proxies (Hg/Al and Hg/Fe ratios) and Hg concentration (ng g-
1). B) Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation in the depth of the lake system (Fe/Mn) and δ18O VPDB.

Figure 16. Enrichment factor of paleoredox proxies (Pb EF, MnEF and FeEF), and paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13CVPDB) in the Crato paleolake. A) Enrichment
factor using Aluminum (Al) as a normalizer; B) Enrichment factor using Iron (Fe) as a normalizer. Figure 15. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies
(Al and Fe); volcanism proxies (Hg/Al and Hg/Fe ratios) and Hg concentration (ng g -1). B) Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation in the
depth of the lake system (Fe/Mn) and δ18OVPDB.

Figure 30. Chemostratigraphy of the Crato paleolake. A) Paleodetritic proxies (Al and Fe); volcanism proxies (Hg/Al and Hg/Fe ratios) and Hg concentration (ng g-
1). B) Paleoclimatic proxy (Sr/Cu); paleosalinity (Sr/Ba); and variation in the depth of the lake system (Fe/Mn) and δ18O VPDB.

80
Figure 16. Enrichment factor of paleoredox proxies (Pb EF, MnEF and FeEF), and paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13CVPDB) in the Crato paleolake. A) Enrichment factor using
Aluminum (Al) as a normalizer; B) Enrichment factor using Iron (Fe) as a normalizer.

Figure 31. Enrichment factor of paleoredox proxies (Pb EF, MnEF and FeEF), and paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13C VPDB) in the Crato paleolake. A) Enrichment factor using
Aluminum (Al) as a normalizer; B) Enrichment factor using Iron (Fe) as a normalizer.

Figure 32. Principal component analysis with enrichment factor of trace metals (Ba, Cu, Zn, Pb, Fe, Mn, and Ni), volcanism (Hg/Al and Hg/Fe), paleodetritic (Al and Fe), lake lavel
(Fe/Mn), paleoclimate conditions (Sr/Cu), paleosalinity (Sr/Ba) and the correlations with mortality events. A) Enrichment factor using Aluminum as a normalizer; B) Enrichment factor
using Iron as a normalizer.Figure 16. Enrichment factor of paleoredox proxies (PbEF, MnEF and FeEF), and paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13CVPDB) in the Crato paleolake. A)
Enrichment factor using Aluminum (Al) as a normalizer; B) Enrichment factor using Iron (Fe) as a normalizer.

Figure 33. Enrichment factor of paleoredox proxies (Pb EF, MnEF and FeEF), and paleoproductivity proxies (CuEF, ZnEF, NiEF, BaEF, and δ13C VPDB) in the Crato paleolake. A) Enrichment factor using
Aluminum (Al) as a normalizer; B) Enrichment factor using Iron (Fe) as a normalizer.

81
Figure 17. Principal component analysis with enrichment factor of trace metals (Ba, Cu, Zn, Pb, Fe, Mn, and Ni), volcanism (Hg/Al and Hg/Fe), paleodetritic (Al and Fe), lake lavel
(Fe/Mn), paleoclimate conditions (Sr/Cu), paleosalinity (Sr/Ba) and the correlations with mortality events. A) Enrichment factor using Aluminum as a normalizer; B) Enrichment factor
using Iron as a normalizer.

Figure 34. Scheme demonstrating the paleoenvironmental variations (wet-dry) of the Konservat -Laggerstätten of the Crato paleolake. A) Arid paleoclimatic conditions and mortality of
Ephemeroptera; B) Humid paleoclimatic conditions and mortality of Dastilbe sp.Figure 35. Principal component analysis with enrichment factor of trace metals (Ba, Cu, Zn, Pb, Fe,
Mn, and Ni), volcanism (Hg/Al and Hg/Fe), paleodetritic (Al and Fe), lake lavel (Fe/Mn), paleoclimate conditions (Sr/Cu), paleosalinity (Sr/Ba) and the correlations with mortality
events. A) Enrichment factor using Aluminum as a normalizer; B) Enrichment factor using Iron as a normalizer.

82
6.4 Discussion
6.4.1 Characterization of the Crato paleolake
6.4.1.1 Paleosalinity
The Sr/Ba ratio was used to determine the paleosalinity of the Crato Formation.
Values of the Sr/Ba lower than 0.2 indicate a freshwater environment, whereas from 0.2
to 0.5 indicate brackish waters. Higher values (> 0.5) indicate marine characteristics (Wei,
Algeo, 2020). The Sr/Ba ratio concentrations observed in this study indicate that the Crato
Formation showed characteristics of a marine depositional environment (Sr/Ba > 0.5).
The samples collected for this study were obtained from the C6 layer of the Crato
Formation, situated in proximity to the upper portion of the Crato Formation, which is
characterized by short events of marine input (Goldberg et al., 2019; Salgado-Campos et
al., 2021). In the present context, it is hypothesized that the elevated Sr/Ba ratio observed
in the studied samples may be attributed to two potential factors: i) the geochemical
behavior of Strontium (Sr) in carbonates must be considered; Sr can replace calcium
(Ca2+) in calcite and is a product of the chemical weathering of minerals rich in Sr-
plagioclase, gypsum, calcite and strontianite (Roden et al., 2002; Wei, Algeo, 2020). ii)
the intensification of aridity in conjunction with marine intrusions and/ or stratified water
column in the lacustrine system may have contributed the observed increase in salinity in
the Crato paleolake.
Previous studies indicated that the Crato paleolake exhibited stratification in the
water column. The upper surface waters were characterized as freshwater and oxic, while
the bottom waters were classified as brackish to hypersaline and anoxic (Heimhofer et
al., 2010; Nascimento, Silva Filho, Erthal, 2023). The presence of a stratified water
column influenced by climatic oscillations has been previously reported for other Aptian
carbonate lake systems (Codó Formation - Parnaíba basin, Serra do Tonã Formation -
Tucano basin, and Serra Negra Formation - Jatobá basin) (Gratzer et al., 2013; Heimhofer,
Martill, 2007; Silveira et al., 2014).
Furthermore, the presence of palynomorphs (Chagas, 2017), microforaminifera
(Goldberg et al., 2019), marine dinocysts, and tidal geological structures (Varejão et al.,
2019, 2021) suggest the occurrence of short pulses of marine intrusion in the upper layers
of the Crato paleolake. In this scenario, the entry of marine waters into the lake system,
brought about by arid conditions, is thought to have resulted in hypersalinity in the Crato
paleolake and the precipitation of halite crystals.

83
 Geochemical proxies (Hamid et al., 2024; Salgado-Campos et al., 2021), the
presence of halite crystals (Martill, Loveridge, Heimhofer, 2007; Storari et al., 2021), the
absence of bioturbation (Warren et al., 2017), along with the development of microbial
mats (Catto et al., 2016) corroborate the occurrence of hypersaline periods in the bottom
of the Crato paleolake. Nevertheless, the oscillations in the Sr/Ba ratio indicate that,
despite the hypersalinity, the Crato paleolake exhibited fluctuations in salinity. Previous
reports have documented episodes of high humidity (Neumann et al., 2003; Santos et al.,
2020; Varejão et al., 2019) in the Konservat-Lagerstätten Crato paleolake, which may
have contributed to a decrease in salinity in the lake system. This behavior is corroborated
by the positive correlation between Sr/Cu (paleoclimatic proxy) and Sr/Ba, which
indicates that salinity variations in the Crato paleolake are linked to the paleoclimatic
oscillations that occurred during the Aptian. During arid periods, salinity increased, while
during humid events, salinity decreased.

6.4.1.2 Palaeoclimatology conditions

Paleoclimatic variations were established by means of the Sr/Cu ratio, whose
application relies on the capacity of these elements to reflect hydrological alterations in
the environment. In general, the ratio classifies the environment as humid/semi-humid
when values are lower than 5; semi-arid conditions (5 to 10); and arid/hot conditions when
the values are higher than 10 (Cao et al., 2023; Fan et al., 2021).
The CKL level of the Crato Formation is composed of evaporites (Assine, 2007),
paleo-wildfire records (Lima et al., 2019), and xerophytic vegetation (drought-resistant)
(Ribeiro et al., 2021), indicating that the Crato paleolake was in a dry environment. In
more precise terms, this environment can be identified as the Arid Hot Tropical Equatorial
Belt (Chumakov et al., 1995). However, the Sr/Cu ratio values recorded at the CKL level
of the Crato Formation are not consistent with a predominantly arid paleoenvironment,
as would be suggested by the occurrence of a humid episode.
The correlation observed between Sr/Cu and Sr/Ba (paleosalinity) indicates
alternating periods of wet and dry environments. This suggests that the Crato paleolake
experienced fluctuations in salinity, in agreement with paleoclimatic oscillations.
Furthermore, the presence of wetlands in the Crato paleolake indicates periods of higher
precipitation levels, greater freshwater inputs, and lower salinity levels in the lake system
(Heimhofer et al., 2010; Ribeiro et al., 2021).

84
 Paleontological, sedimentological, and geochemical records also indicate the
alternation of wet and dry cycles at the CKL level (Guerra-Sommer et al., 2021; Neumann
et al., 2003; Ribeiro et al., 2021). This is evidenced by the analysis of plant biodiversity
(Souza-Lima e Silva, 2018), their growth rings (irregular and/or absent) (Guerra-Sommer
et al., 2021; Santos et al., 2021), and fungus-plant interaction (Santos et al., 2020).
Furthermore, previous geochemical evidence registered high kaolinite values in the Crato
Formation, which suggests the occurrence of wet periods (Salgado-Campos et al., 2021).

6.4.1.3 Paleodetrital input and depth oscillation

Al, Fe, Ti, and K are used to assess the contributions of paleodetrital inputs to
aquatic systems, as they are constituents of siliciclastic minerals and are products of
weathering of soils and rocks adjacent to waterbodies (Calvert, Pedersen, 1993;
Tribovillard et al., 2006). The present study has indicated that the contribution of
paleodetritus in the Crato Formation relatively small. This suggests a reduced input of
allochthonous material from the surrounding environment, particularly in terms of iron
and aluminum. These observations can be linked to the paleoclimatic conditions in the
region, which have been described as arid or semi-arid with low precipitation (less than
250 mm) (Heimhofer et al., 2010; Salgado-Campos et al., 2021). Furthermore, the low
abundance of these elements to the size of the detrital material found in the laminated
limestones, which is composed of subangular silty quartz and insignificant amounts of k-
feldspar grains (Heimhofer et al., 2010).
The positive correlation observed between paleodetrital proxies and Fe/Mn (lake
level) and the negative correlation with Sr/Cu (paleoclimate) suggest that detrital inputs
to the Crato paleolake are influenced by wet-arid cycles. At the CKL level of the Crato
Formation, oscillations in precipitation were recorded (Neumann et al., 2003), resulting
in variations in paleodetrital inputs (Heimhofer et al., 2010). Wet periods are
characterized by the input of continental material to the lake system, which, through
weathering, results in the formation of Fe3+ oxyhydroxides and the availability of
nutrients for the biotic development of the Crato paleolake (Heimhofer, Martill, 2007;
Osés et al., 2017).
The oscillation levels of the Crato paleolake were determined by measuring the
Fe/Mn ratio, which has been shown to be sensitive to changes in the redox state and the
paleodetrital contributions (Tribovillard et al., 2006). Fe is an element susceptible to
redox state fluctuations, which vary according to the conditions of oxidation and
85
reduction. Under these conditions, Fe2+ adsorbs to H2S (hydrogen sulfide) and precipitates
in the sediment (Algeo, Li, 2020). In the case of Mn, when exposed to aerobic conditions,
Mn oxides are formed and precipitate, whereas dissolution of Mn occurs under anoxic
conditions (Robbins et al., 2023). Therefore, the increase in the Fe/Mn ratio is conditioned
by a decrease in the oxygenation of the environment and an increase in the depth of the
lake system (Evans et al., 2021; Zou et al., 2022).
The positive correlations between Fe/Mn and Al and Fe indicate an increase in
water depth during wet periods, while in the dry periods, it is observed a decrease in water
level of the Crato paleolake. Weathering is sensitive to climatic conditions, in warm
periods, there is an increase in paleodetritic contributions, whereas dry-cold climates are
characterized by a reduction in weathering (Nesbitt, Young, 1982). Consequently, the
humid episodes of the Crato paleolake are characterized by an increase in the
contributions of terrigenous materials (increased rainfall and depth), while the reductions
in paleodetrital transport indicate the predominance of an arid environment.

6.4.1.4 Stable isotopes (δ13CVPDB and δ18OVPDB)

The isotopic variations of δ13CVPDB and δ18OVPDB observed in the limestones of
the Crato Formation can be attributed to the balance between precipitation and
evaporation, which directly influences paleoclimatic oscillations. The positive correlation
between δ13CVPDB and δ18OVPDB indicates that the level of the Crato paleolake experienced
periods in which the lake environment was closed (Heimhofer et al., 2010), under
conditions of a hot and dry paleoclimate with elevated evaporation (Neumann, 1999). The
δ13C isotope data reveals a similar pattern of change, indicating enrichment of δ13CVPDB
isotope when the lake system was isolated from external fresh-water sources. Negative
values of δ13CVPDB indicate the input of fresh water from outside the system, which
resulted in the dilution of paleoproductivity signals (Nascimento et al., 2023).
The Codó (Parnaíba Basin) and Serra do Tonã (Tucano Basin) formations (also
located in the northeastern Brazil) are stratigraphically correlated with the Crato
Formation (Araripe Basin) (Lima Barros et al., 2022; Varejão et al., 2016, 2021). These
formations are characterized by laminated limestones typical of a lacustrine system with
depth oscillation (Lindoso, Maisey, Carvalho, 2016; Pradel et al., 2021; Silveira et al.,
2014; Varejão et al., 2021). The isotopic signals for carbon and oxygen of these
sedimentary basins, located in the Northeast region of Brazil, exhibited values like those
reported for the Crato paleolake. The oscillations observed in these isotopic signals are
86
associated with changes in the hydrological cycle (precipitation-evaporation) (Bobco et
al., 2023; Silveira et al., 2014). Consequently, the fluctuations observed in the
depletion/enrichment of δ13CVPDB and δ18OVPDB in the Crato paleolake are similar from
those observed in trace metals. This indicates that the variations in the lake system may
have influenced not only the redox state and paleoproductivity but also the mortality
events in the lake system.

6.4.2 Paleoproductivity
The application of Cu, Zn, Ni, and Ba as proxies for paleoproductivity is based on
their capacity to form organometallic complexes with organic matter and to act as
micronutrients for the development of trophic webs (Tribovillard et al., 2006). The
presence of diagenetic barite (BaSO4) at the CKL level (Osés et al., 2017) demonstrates
that paleoproductivity in the lake system was high. This mineral is known to show a
correlation with the carbon flow in aquatic ecosystems (House, Norris, 2020; Liguori,
Almeida, Rezende, 2016).
The Spearman analysis and anomalies of the paleoproductivity proxies suggest
that proximal sources, such as detrital inputs and distal processes, including volcanism,
influenced the Crato paleolake. The paleoproductivity proxies exhibited a positive
correlation with detrital inputs and lake level, indicating that during humid periods there
was an increase in freshwater input and nutrient, which led to an increase in primary
productivity in the lacustrine system. Previous studies in the Crato paleolake have
demonstrated a correlation between the increase in productivity in the algal horizons of
Crato Formation and the rise in nutrient load during humid periods. This phenomenon has
been shown to facilitate the proliferation of phytoplankton activity (Heimhofer et al.,
2010; Martins-Neto, 2006; Osés et al., 2017).
The stratification of the water column in the Crato paleolake suggests the presence
of surface waters with high primary productivity and anoxic conditions at the bottom of
the lake (Heimhofer, Martill, 2007). In environments with high salinity, drought, and
elevated pH levels, cyanobacteria tend to prevail (Brehm et al., 2002; Kifumbi et al.,
2022). The record of Spirulina, filamentous cells, well-preserved coccoid, extracellular
polymers (Catto et al., 2016), 14 species of algae (abundant chlorophyte Botryococcus
sp.) (Martine, 2013), and the development of stromatolites (Warren et al., 2017) attest to
a productive lake paleoenvironment.

87
6.4.3 Paleoredox conditions of the Crato paleolake
The application of Pb, Mn and Fe as paleoredox proxies is related to their
precipitation with oxyhydroxides of Al, Fe and Mn (oxic conditions) and hydrogen
sulfides- H2S (anoxic conditions) (Algeo, Li, 2020; Algeo, Liu, 2020). Despite the high
paleoproductivity of the lacustrine system, the occurrence of framboidal pyrites in the
fossil records of the Crato Formation indicates the possibility that these elements were
also enriched through bacterial sulfate reduction. The pyritization of soft tissues in the
fossils, the absence of bioturbation and the presence of microbial mats indicate anoxic
depositional conditions at the CKL level of the Crato Formation (Barling et al., 2020;
Hamid et al., 2024; Heimhofer, Martill, 2007).
The precipitation of pyrite (FeS2) in anaerobic environments can be attributed to
the reduction of iron (Fe2+) in the presence of sulfide (H2S) and mediated by sulfate-
reducing bacteria influence (Wilkin, Barnes, Brantley, 1996). Negative values of δ13CVPDB
and high values of amorphous organic matter (AOM) are indicative of an anoxic
paleoenvironment, likely influenced by sulfate bacterial reduction in the lacustrine system
(Catto et al., 2016; Swart, 2015; Varejão et al., 2021). The presence of galena and
sphalerite in the fossil record (Barling et al., 2015; Martill et al., 2007), in conjunction
with framboidal pyrite and marcasite (FeS2) (Cabral et al., 2019), provides evidence that
Zn, Cu and Pb may have co-precipitated with the reduced forms of iron (Heimhofer,
Martill, 2007). Consequently, the positive correlations observed between CuEF, PbEF, and
ZnEF and FeEF suggest that anoxic conditions and elevated productivity were conducive
to bacterial sulfate reduction. This process made the reduced forms of iron available in
the Crato paleolake and in the enrichment of these elements.

6.4.4 Volcanism
Mercury (Hg) of natural origin is emitted into the atmosphere in the elemental
form (Hg0), through processes such as volcanism and wildfires (Percival et al., 2015).
Subsequently, Hg is oxidized in the atmosphere to the ionized form (Hg2+) and transferred
to terrestrial and aquatic compartments through precipitation (Benigno et al., 2018; Font;
Bond, 2021). In the sediment, Hg is preferentially stored over geologic time complexed
with total organic carbon (TOC) (Grasby et al., 2019), clay minerals (aluminum and iron),
and Hg sulfides in anoxic environments (Krupp, 1988). Due to the low concentration of
TOC observed in the calcitic limestone layers of the Crato Formation, the present study
utilized the Hg/Al and Hg/Fe ratios as volcanism proxies. Previous studies have

88
demonstrated that the application of Hg/paleodetritic proxy’s ratios (Al, Fe, Zr, Ti and
phyllosilicates) enables the identification of the activation periods of large LIPs
throughout geological time (Font et al., 2016; Sabatino et al., 2018; Sanei, Grasby,
Beauchamp, 2012; Sial et al., 2013). The role of clay minerals as geochemical carriers of
Hg was validated by observing a positive correlation between paleodetritic proxies (Al
and Fe) and Hg, indicating a mineral influence on the Hg burial process.
Considering the depositional age of the Crato paleolake, the presence of non-
marine ostracods (Pattersoncypris micropapilosa), OST-11 biozone (Guzmán et al.,
2023) suggests a deposition period at the Alagoas level (Assine, 2007), specifically during
the transition between the Upper Aptian and the end of the Aptian. The record observed
in OST 11 biozone was also documented in other sedimentary basins in Brazil (Campos,
Parnaíba, Sergipe-Alagoas) and Africa (Gabon, Congo, Kwanza) (Guzmán et al., 2023;
Lima Barros et al., 2022; Poropat, Colin, 2012). Despite the limited biostratigraphic
resolution at the CKL level of the Crato Formation, the Hg anomalies identified in the
present study suggest the presence of volcanic episodes originating from the Rajmahal-
Kerguelen plateaus (~118-110 Ma) (Coffin et al., 2006, 2002; Hamid et al., 2024).

6.4.4.1 Volcanism as a driver of the environmental changes

During periods of volcanism, the injection of CO₂ and other gases into the
atmosphere (including HS, HCl, and HF) induces a series of alterations of the
hydrological cycles in aquatic and terrestrial ecosystems (Bom et al., 2023; Grasby, Bond,
2023). In addition, the injection of gases has been linked to ocean acidification, acid rain,
elevated primary productivity, and sediments enrichment of organic matter, and trace
metals (Davis, 2023; Wang et al., 2022). The Hg peaks found in the Crato paleolake
demonstrated a positive correlation with Sr/Cu ratio (paleoclimate), indicating that
volcanic processes may have modified the hydrological cycle (increasing and/or
decreasing the precipitation).
The negative correlations observed between Hg anomalies with the detrital inputs,
and Fe/Mn ratio (lake level), provide further evidence that volcanic events may have
limited precipitation, resulting in a decrease in the transport of terrigenous material and
the depth of the lagoon system. The intensification of arid conditions in the Crato
paleolake can be observed through the presence of paleo-wildfires (Lima et al., 2019) and
halite crystals (Martill et al., 2007; Storari et al., 2021). The correlation between Hg
anomalies and an increased frequency of paleo-wildfires and salinity in terrestrial
89
ecosystems has been recorded during the activation of LIPs, indicating that climate
change is caused by perturbations in the carbon cycle (Fan et al., 2021; Xu et al., 2022;
Xu et al., 2022).
Although there are records indicating that volcanism can result in increased
precipitation, the present study has found a different behavior. In this case, the
intensification of arid conditions in the Crato paleolake may be attributed to the location
of the lacustrine system (the interior of the supercontinent Gondwana). These
circumstances were attributable to the limited impact of the proto-Atlantic Ocean and the
Intertropical Convergence Zone (ITCZ), which were still in a state of development
(Araripe et al., 2022; Burgener et al., 2023; Santos et al., 2022; Heimhofer, Hochuli,
2010; Varejão et al., 2021). It is crucial to emphasize that, despite the presence of humid
windows in the Crato Formation, arid conditions were the prevailing environmental
setting in the sedimentary basins of the equatorial margin. However, there was a notable
increase in humidity during the Aptian-Albian transition (Bobco et al., 2023; Carvalho et
al., 2019; Giannerini et al., 2023; Souza-Lima, Silva, 2018).
Enrichment factors of the paleoproductivity (Ni and Ba) and paleoredox (Mn and
Fe) proxies exhibited a positive correlation with the anomalies from volcanism. These
results suggest that the activation of LIPs may have affected the depositional processes
of the Crato paleolake. This could have resulted in an increase in primary productivity
and a change in redox conditions. Trace metal anomalies and isotopic changes were
reported during the activation of the Rajmahal-Kerguelen plateaus, which demonstrated
the interference of these events in aquatic ecosystems (Cai et al., 2023; Erba et al., 2015;
Hamid et al., 2024; Leandro et al., 2022). Although the aridity is intensified during the
occurrence of magmatic pulses, the increasing of productivity proxies may be linked to
the increase in the atmospheric concentration of CO2, which, in turn, contributes to the
enhancement of the autochthonous productivity of the lake system (phytoplankton and
cyanobacteria).
Moreover, increasing productivity in aquatic ecosystems can be achieved through
the deposition of pyroclastic material emitted into the atmosphere (including dust,
volcanic ash, and sulfides) derived from volcanic events (Mason et al., 2021). In this
scenario, the dispersal of a plume from LIPs to the stratosphere results in the global
distribution of aerosols and other compounds, which can generate the fertilization of
aquatic environments (Robock, 2000; Wu et al., 2023). An example of this fertilization
process associated with explosive volcanism can be observed during the activation of

90
Krakatau (1883), El Chicón (1982), and Pinatubo (1991), when an increase in
productivity was observed, thereby establishing a correlation between the global
distribution of aerosol clouds and the deposition of the essential elements necessary for
primary productivity (phosphorus and iron) (Glasspool et al., 2015; Manfroi et al., 2015).

6.4.5 Mortality events and paleoenvironmental changes

The limestones of the Crato Formation are classified as Konservat-Lagerstätten,
due to their rich collection of fossils, including insects, pterosaurs, dinosaurs, fish, plants,
birds, crocodyliforms, and arachnids (Assine, 2007; Fambrini et al., 2020; Ribeiro et al.,
2021). The exceptional condition of preservation of the fossils in the Crato paleolake can
be attributed to anoxic conditions, the absence of bioturbation, and the development of
microbial mats (Osés et al., 2016; Varejão et al., 2019). The composition of the fossils in
the Crato Formation is the result of biogeochemical mediation of the preservation process,
which is composed of framboidal micropyrites and hydroxyapatite (Barling, Martill,
Heads, 2020; Osés et al., 2016; Varejão et al., 2019).
The geochemical records presented in this study indicate that the depositional
conditions of siliciclastic limestones were characterized by large shifts in wet-dry periods,
accompanied by changes in paleoproductivity and redox conditions. The substantial
fluctuations observed in the Crato paleolake may have created an environment that was
highly stressful for the development of organisms, resulting in mortality events (Martill,
Loveridge, Heimhofer, 2007; Menon, Martill, 2007; Salgado, Carvalho, 2023). Martins-
Neto, (2006) identified that cyclical mortality events of Ephemeroptera species were the
result of an intensification in arid conditions, which resulted in a significant reduction in
the depth of the lake. The earliest record of mortality we observed occurring between 280
and 290 cm, was observed to be accompanied by the occurrence of halite crystals and
anomalies in geochemical proxies (paleosalinity and paleoclimate). In this case, the
intensification of aridity concomitant with the reduction in the depth of the lake system
evinces that this taxon was susceptible to paleoenvironmental alterations (reduction in
organism size and failure to reach larval maturity), which resulted in the mortality of these
organisms in the Crato paleolake (Bezerra, Mendes, 2024; Chadwick et al., 2002;
Martins-Neto, 2006; Storari et al., 2021). Dastilbe distribution did not suggest mass
mortality; instead, it exhibited the presence of smaller fish—up to 5 cm in length—when
compared to Dastilbe in the upper layer, which reached up to 21 cm in length (Storari et
al., 2021). This suggests that Dastilbe can tolerate the harsh conditions of the

91
paleoenvironment despite the hypersalinity of the lacustrine system (Davis, Martill,
1999).
The occurrence of Hg anomalies in the 285 cm and the geochemical correlations
previously characterized for the Crato paleolake the observation of a possible interference
of magmatic pulses in the mass mortality of Ephemeroptera. Volcanism is an important
driver of climate change and major biological crises, the increase in greenhouse gas
emissions into the atmosphere modifies the hydrological cycle (Font, Bond, 2021; Zhou
et al., 2024). The elevation in pCO2 brought about by volcanism gives rise to a chain of
events in the interior of the continent. These events include an increased rate of
evapotranspiration, a decline in soil moisture, and the occurrence of convective
transpiration, frequent paleo-wildfires, an elevated salinity, and, consequently, a
widespread aridity (Bos et al., 2023; Liu et al., 2024; Peyser, Poulsen, 2008; Zhang et al.,
2023). Consequently, the volcanism of the Rajmahal-Kerguelen plateau may have
indirectly caused the mass mortality of the Ephemeroptera in the Crato paleolake through
the intensification of aridity, the reduction in depth and the salinization of the lacustrine
system (Figure 18A).
Towards the top of the CKL level, nine mass mortality events of Dastilbe were
recorded, suggesting the existence of greater cyclical mortality events of these fish. The
characterization of the ontogenetic stages of Dastilbe permitted the establishment that
adults were more mobile than juveniles (Storari et al., 2021). Juveniles, in contrast, feed
on plankton and inhabit lake systems, being more susceptible to mortality events (Davis,
Martill, 1999; Ribeiro et al., 2020). Storari et al. (2021) observed that the Dastilbe
identified were primarily juveniles. This evidence indicates that these organisms were
susceptible to the paleoenvironmental fluctuations that occurred within the Crato
paleolake.
An increase in the enrichment factor of the geochemical proxies for
paleoproductivity, paleoredox, and a decrease of paleoclimatic proxy (Sr/Cu) has been
observed in the layers where mass mortality events of Dastilbe have been identified.
Previous studies reported that the Dastilbe mortality horizons were highly productive
(Davis, Martill, 1999; Martins-Neto, 2006). Considering the mechanisms responsible for
the high productivity in the Crato paleolake, it can be suggested that inputs derived from
proximal (detrital inputs) and distal (volcanism) sources may have contributed to the
supply of nutrients and other chemical compounds for the lacustrine system.

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 During periods of elevated precipitation and volcanic activity at the Rajmahal-
Kerguelen plateaus, there was an influx of nutrients into the Crato paleolake, which led
to an intensification of primary productivity. Consequently, eutrophication of the lake
ecosystem occurred, resulting in an increase in organic matter at the lake system.
Consequently, bacterial decomposition of organic matter resulted in the depletion of
oxygen in the water column (hypoxia), and in the cyclic mortality events of the Dastilbe
fish population in the lake system (Figure 18B). The presence of cyanobacteria and green
sulfur bacteria (Chlorobiaceae) in the Crato paleolake corroborates the hypothesis that it
as a stratified productive lacustrine system, with the bottom waters saturated with little
hydrogen sulfide and low oxygen (Catto et al., 2016; Heimhofer, Martill, 2007).

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Figure 18. Scheme demonstrating the paleoenvironmental variations (wet-dry) of the Konservat -Laggerstätte of the
Crato paleolake. A) Arid paleoclimatic conditions and mortality of Ephemeroptera; B) Humid paleoclimatic conditions
and mortality of Dastilbe sp.

Figure 36. Scheme demonstrating the paleoenvironmental variations (wet-dry) of the Konservat -Laggerstätten of the
Crato paleolake. A) Arid paleoclimatic conditions and mortality of Ephemeroptera; B) Humid paleoclimatic conditions
and mortality of Dastilbe sp.

Figure 19. Map of the Araripe Basin, northeastern Brazil, highlighting the geographic distribution of the Santana Group
(including the Romualdo Formation).Figure 37. Scheme demonstrating the paleoenvironmental variations (wet-dry) of
the Konservat -Laggerstätten of the Crato paleolake. A) Arid paleoclimatic conditions and mortality of Ephemeroptera;
B) Humid paleoclimatic conditions and mortality of Dastilbe sp.

Figure 38. Scheme demonstrating the paleoenvironmental variations (wet-dry) of the Konservat -Laggerstätten of the
Crato paleolake. A) Arid paleoclimatic conditions and mortality of Ephemeroptera; B) Humid paleoclimatic conditions
and mortality of Dastilbe sp.

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6.4.6 Exceptional fossil preservation in the Crato paleolake
The evolution of Konservat-Lagerstätten is contingent on the exceptional
condition of their fossils (presence of soft tissues and articulated organisms) (Allison,
1988; Parry et al., 2018). The condition of fossils preservation is influenced by the type
of mineralization (silicification, phosphatization, pyritization, aluminosilification,
carbonate preservation) and the depositional conditions of the paleoenvironment
(anaerobic, euxinic conditions, rapid burial, microbial activity, minerals precipitation, and
early diagenesis) (Grice et al., 2019).
The Konservat-Lagerstätte of the Crato paleolake generated by favorable
depositional conditions conducive to preserving the lacustrine system. The high
concentrations of microframboidal pyrites and phosphorus in the fossils indicate that
mineralization of soft tissues occurred during early diagenesis, through sulfate-mediated
bacterial reduction (Barling et al., 2015; Barling, Martill, Heads, 2020).
The production of framboidal pyrites requires high concentrations of iron, organic
carbon, and sulfate, which allows sulfides to be fixed during the mineralization of the
organisms (Allison, 1988). Nevertheless, the Crato Formation is predominantly
composed of limestone sediments, which implies low concentrations of iron, thus limiting
the formation of framboidal pyrite (Berner, 1984; Osés et al., 2017). In this context, it is
essential to acknowledge the potential contribution of allochthonous sources, including
proximal and distal sources, to the increase in iron and other element concentrations in
the Konservat- Lagerstätte of the Crato paleolake. Then, periods of elevated humidity
may have facilitated enhanced iron transport to the lacustrine system. This, in turn, has
led to the development of bacterial reduction of sulfate and, subsequently, the generation
of framboidal pyrites (Osés et al., 2016, 2017).
Moreover, the Hg anomalies recorded in the Crato paleolake indicate that distal
(volcanic) contributions may have assisted in the preservation and formation of the
Konservat-Lagerstätten of the Crato paleolake. Additionally, other Konservat-
Lagerstätten- Romualdo Formation (Araripe basin, Brazil, early Cretaceous), and Fernie
and Jehol Formation (Chaoyan basin, early Cretaceous, China); Fernie Formation
(Canada), Posidonia shale (Germany), and Strawberry bank (United Kingdom), all in the
Lower Jurassic - demonstrated the potential of volcanism to generate fossil preservation
(Bom et al., 2023; Cai et al., 2023; Muscente et al., 2019; Sinha et al., 2021).

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6.5 Conclusion
The Konservat- Lagerstätte Crato paleolake exhibited considerable fluctuations in
the water cycle, which resulted in pronounced alterations in paleodetritic input, salinity,
depth, oxygenation, and productivity. The Hg anomalies observed in the lake system
indicated a potential interference of the volcanic pulses from the Rajmahal-Kerguelen
plateaus on the paleoclimate conditions of the lake ecosystem. The increase in CO₂
emissions into the atmosphere may have intensified aridity in the Araripe basin, thereby
generating changes in the depositional process in the Crato paleolake.
Paleoclimatic alternations (wet-dry cycles) had a hostile impact on the resilience
capacity of organisms, resulting in cyclical mortality events that have been recorded in
the Crato paleolake. The mortality of Ephemeroptera was influenced by the aridity of the
lake system, which became hypersaline, and the lake system became saline and alkaline,
which in impeded larval development and the maturation of the larvae of these organisms.
Nevertheless, it has been demonstrated that Dastilbe displays tolerances to elevated
salinity levels. The enrichment of paleoproductivity and redox proxies observed in
Dastilbe mortality levels indicates that intensification of the biological pump in the lake
system generates conducive conditions for bacterial activity. In this case, the occurrence
of hypoxia in the Konservat-Lagerstätten of the Crato paleolake was found to be
responsible for the observed mortality events in Dastilbe.
Acknowledgments
The authors are deeply indebted to the many students at the Regional University of Cariri,
who have helped in the intensive field campaigns in the Araripe Basin. Technicians from
the Marine Biogeochemistry Laboratory (LBC-UFC) helped preparing samples for
chemical analyses. Technicians from the NABISE-UFPE, for isotopes analysis.
Funding
This study was funded by the Fundação Cearense de Apoio ao Desenvolvimento
Científico e Tecnológico (FUNCAP), Proc. No. INT-0159-00009.01.00/19, and by grants
to L.D. Lacerda from the Brazilian Council for Scientific and Technological Development
(CNPq), Proc. No. 405.765/2022-3 (INCTTMC-Ocean). This study was financed in part
by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior- Brasil (CAPES)-
Finance code 001.

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CAPÍTULO 3

Insights into the palaeo-trophic food web of the Brazilian Romualdo

Formation (Cretaceous, Aptian–Albian) based on fossil mercury
bioaccumulation

O terceiro manuscrito é uma participação no artigo intitulado “Insights into the

palaeo-trophic food web of the Brazilian Romualdo Formation (Cretaceous, Aptian–
Albian) based on fossil mercury bioaccumulation”, com autorias de Lucas Silveira
Antonietto, Igor Hamid Ribeiro Azevedo, Borja Holgado, Antonio Leite Rocha, Maria A.
Ferreira, Antônio Álamo Feitosa Saraiva, Luiz Drude de Lacerda.
Este manuscrito tem o objetivo de caracterizar a cadeia paleotrófica do Konservatt
Lagerstätte da Formação Romualdo através da aplicação do Hg. Este trabalho possibilitou
demonstrar o desenvolvimento da cadeia paleotrófica da paleoictiofauna da Formação
Romualdo, sendo possível estabelecer os organismos representantes da base- Rhacolepis
buccalis- até os maiores níveis tróficos- Calamopleurus cylindricus. Além disso, pode-se
inferir sobre o comportamento alimentar dos pterossauros (Ornithocheiriformes and
Thalassodrominae), organismos de grande debate na comunidade científica a respeito da
sua capacidade de predação.

_______________
Antonietto, L. C.; Azevedo, I. H. R.; Borja, H.; Rocha, A. L.; Ferreira, M. A.; Saraiva, A. A. F.;
Lacerda, L. D. Insights into the palaeo-trophic food web of the Brazilian Romualdo Formation
(Cretaceous, Aptian–Albian) based on fossil mercury bioaccumulation. In revision to Nature
Communications.

97
 ABSTRACT

In aquatic environments, mercury (Hg) bioaccumulation rates tend to reflect the

organism’s position in the food web – the larger the rate, the higher their position. Here
we present the first attempt to reconstruct such web for the Romualdo Formation of the
Araripe Basin (Northeastern Brazil), based on Hg bioaccumulation of its fossil record;
the aim is to understand possible trophic relationships between vertebrate/invertebrate
species inhabiting its paleoenvironments. Observed ratios between Hg concentrations
[Hg] in fossils and their surrounding concretions ([Hg]sample) suggest bioaccumulation
increases with the change in feeding habits and size of the fish taxa analysed, being lowest
in Rhacolepis to a maximum peak in the large predator genera Cladocyclus and
Calamopleurus. Feeding habits of Vinctifer were also reviewed, and the genus was
reinterpreted from filter feeder to mesopredator; durophage bottom-feeding taxa recorded
values compatible with their predicted feeding habits. Low [Hg]sample ratios were observed
in ornithocheiriform pterosaurs, suggesting mesopredators specialized in the smaller fish
species, while Thalassodrominae presented intermediate to high [Hg]sample, pointing out
to a unique trophic role as a terrestrial opportunistic generalist, ranging from predator to
scavenger.

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7.1 Introduction
Mercury (Hg) is a chemical element widely distributed through different
compartments of the biosphere, because of major emission being to the atmosphere
through volcanism and forest fires (Beckers, Rinklebe, 2017) . Volcanism emits Hg in its
elementary form (Hg0), which undergoes oxidation in the atmosphere generating Hg2+
(reactive ionic form, soluble in water). Subsequently, Hg2+ is incorporated into aquatic
ecosystems, forming stable organic complexes, and/or precipitating into sulphides in
bottom sediments (Beckers, Rinklebe, 2017; Gamboa Ruiz, Tomiyasu, 2015). The Hg can
undergo methylation mediated by sulphate-reducing bacteria, generating monomethyl-
([CH3Hg] +) and dimethylmercury ([CH3]2Hg) – both bioavailable forms of Hg (Outridge
et al., 2002). High bioaccumulation and biomagnification rates of Hg increase Hg
concentrations ([Hg]) in organisms, amplified through the trophic web highest levels
concentrations in top carnivores.
Bioaccumulated Hg can be preserved in mineralized tissues (hydroxyapatite,
calcite, and aragonite) of fossil and subfossil specimens from different geological periods.
That allows for a wide range of ecological and paleoecological studies-based [Hg],
ranging from the relation between mammal teeth Hg increase and the onset of the
Industrial Revolution, or [Hg] peaks in Pacific Cod (Gadus microcephalus) and Holocene
glaciations (Murray et al., 2015), to the ontogeny of Late Cretaceous baurusuchid
crocodyliforms from Brazil (Cardia et al., 2018). Therefore, Hg can become an excellent
tool to assess trophic relations in both recent and fossil assemblages.
The assessment of [Hg] is also favored by exceptional fossil preservation, as
observed in the Konservat-Lagerstätte of the Romualdo Formation of Brazil. This unit is
the result of a regional-scale late Aptian-early Albian (Araripe et al., 2022) transgression
set during the earliest stages of the opening of the South Atlantic Ocean; it then reached
many interior regions of northeastern Brazil including areas where the Araripe Basin is
presently recorded (Figure 19) (Custódio et al., 2017). The 120 m-thick succession
(Assine, 2007) comprises organic-rich black shales deposited under great saline variation
(Fürsich et al., 2019), and anoxic to dysoxic conditions related to the Oceanic Anoxia
Event (OAE) 1b (Bom et al., 2023; Hamid et al., 2024). Such conditions resulted in the
deposition throughout the unit of stratigraphic horizons abundant in carbonate
concretions, some of them yielding finely preserved plant, vertebrate (mostly fish),
ostracod (Fara et al., 2005) and insect fossils (Freitas, Moura, Saraiva, 2016).

99
 Romualdo concretions preserve not only hard parts but also soft ones (Maldanis
et al., 2016), while at the same time protecting these records from composition-altering
effects from diagenesis (Heimhofer et al., 2017). This excellent fossil preservation,
especially of the ichthyofauna, has already resulted in studies of trophic relations of the
Romualdo assemblage, either through dietary analysis of stomach contents (Maisey,
1994) and/or tooth morphology assessment (Lopes, Barreto, 2021). They are also
abundant: numerous specimens are available for research at scientific collections of
Brazilian institutions such as the Museu de Paleontologia Plácido Cidade Nuvens
(MPPCN), the Laboratório de Paleontologia da URCA (LPU) and the Museu de Ciências
Naturais e História de Barra do Jardim (MCNHBJ) (Coutinho et al., 2021). The present
study is an attempt to contribute, through [Hg] analyses, to the reconstruction of the
trophic relations between part of the highly diverse fossil assemblage of the Romualdo
Formation; we emphasize analyses of its paleoichthyofauna, due to the amount and
variability of taxa preserved, while results on pterosaur taxa are considered preliminary,
although relevant for its relations with fish species that might have been (or not) part of
their diet.

Figure 19. Map of the Araripe Basin, northeastern Brazil, highlighting the geographic distribution of the Santana Group
(including the Romualdo Formation).

Figure 39. Map of the Araripe Basin, northeastern Brazil, highlighting the geographic distribution of the Santana Group
(including the Romualdo Formation).

Figure 20. Average results of (Hg)sample in fossil taxa of the Romualdo Formation analyzed in the present work.Figure 19.
Map of the Araripe Basin, northeastern Brazil, highlighting the geographic distribution of the Santana Group (including the
Romualdo Formation).

Figure 40. Map of the Araripe Basin, northeastern Brazil, highlighting the geographic distribution of the Santana Group
(including the Romualdo Formation).

7.2 Methodology
Romualdo fossils utilized in the present work came from the scientific collections
of the Museu de Paleontologia Plácido Cidade Nuvens (MPPCN) at the municipality of

100
Santana do Cariri, as well as the Laboratório de Paleontologia da URCA (LPU) at Crato
and the Museu de Ciências Naturais e História de Barra do Jardim (MCNHBJ) at Jardim;
all these cities are in the Cariri Valley, southernmost region of the State of Ceará, Brazil.
Specimens belonging to the MPPCN and housed either at the MPPCN or the LPU were
done so under codes “MPPCN P” (for fish) and “MPPCN R” (for reptiles) and respective
numeration; materials from the MCNHBJ are coded with “MCNHBJ”, followed by their
number (Coutinho et al., 2021). Taxa evaluated herein were chosen based on both their
large availability and presumed role in the Romualdo paleo-trophic web, considering 25
organisms (Lopes, Barreto, 2021): Rhacolepis buccalis (n= 5), Vinctifer comptoni (n= 5),
Cladocyclus gardneri (n= 3), Calamopleurus cylindricus (n= 3), Tharrhias araripis (n=
2) and Neoproscinetes penalvai (Actinopterygii) (n= 2) and unidentified species of
Batoidea (Chondrichthyes, n= 2), Ornithocheiriformes and Thalassodrominae
(Pterosauria, n= 3), along with an unidentified ornithocheiroid specimen, were included.
Museum specimens were first processed in the LPU, where parts of them,
approximately 7 cm3, in volume were sawed off with a Makita M0400B circular saw.
Resulting slabs were sent as separate samples to the Marine Science Institute (Labomar)
of the Federal University of Ceará at Fortaleza, Brazil, for analysis of mercury (Hg)
content. The following steps present some modifications in relation to previously
published Hg concentration ([Hg]) analyses (Benigno et al., 2021; Hamid et al., 2024);
after separating the fossil from its carbonate concretion, either were slowly ground into
powder with mortar and pistil, homogenized and sealed in hermetically closed flasks.
Further digestion was carried out by initially placing 1 g of each sample fraction
(concretion and fossil) in polytetrafluoroethylene (Teflon™) tubes containing 10 mL of
concentrated (65%) nitric acid (HNO3) for 1 h. These were then placed in a CEM
MARSXpress vessel and heated at 175 °C for 20 min in a 1,600 W MARS 240/50
synthesis microwave oven. Once heated, we transferred the resulting extracts to
volumetric flasks (previously bathed in Extran® 300 [Merck] detergent at 10%, for 24 h,
then latter in hydrochloric acid at 10% for another 24 h), and the volume of each extract
was adjusted to 100 mL volume with Milli-Q® water. Four additional blank tubes were
prepared specifically to evaluate Hg contamination in the HNO3 reagent used during
digestion.
Quantification was carried out in a NIC RA-3 (Nippon®) cold vapor generation
atomic absorption spectrometer (CVV-AAS), coupled with an RD-3 dispenser. Each
sample was quantified twice, showing reproducibility within 4.6%. The precision and

101
accuracy of fossil results was controlled by simultaneous quantification of a reference
material (NIST-1646A Estuarine Sediments), to which the average recovery was 98 ± 8%
(n = 12). The linearity coefficient of the calibration of curves (R2) was 0.9998 ± 0.0001;
limits of quantification and detection (calculated as three times the standard deviation of
the reagent blank, divided by the slope of the calibration curve) were, respectively, 0.02
± 0.02 ng×g-1 and 0.08 ± 0.07 ng g-1. Measurements were taken both in fossils and the
calcite matrix of their surrounding concretions; because environmental factors can
dramatically enhance [Hg] in living individuals, we used [Hg] in concretions ([Hg]Rock)
as a normalizer for environmental effect over [Hg] in fossils ([Hg]Fossil), applying the
following ratio (Fang et al., 2017) to quantify bioaccumulation ([Hg]Sample):
[Hg]Sample = [Hg]Fossil/[Hg]Rock
This procedure removes interference from nearby sources of sedimentation, while
also compensating for the potential diagenetic effect over biochemical compounds
(carbonates, silica, phosphorite and organic matter in general) (Soua et al., 2011; Touati,
Haji, 2019).

7.3 Trophic relations between fish species

Absolute [Hg]Fossil and [Hg]Rock, as well as [Hg]Sample values, are presented in Table
1, while [Hg]Sample averages are summarized in Figure 20. The lower the trophic level of
Romualdo taxa (represented by smaller species with villiform dentition) (Lopes e Barreto,
2021), presented the lower (< 1.00) [Hg]sample, respectively: R. buccalis (0.27); T. araripis
(0.87) and V. comptoni (0.92). The position of V. comptoni in the Romualdo food web is
still dubious. It was inferred as a predatory species that fed on small fish, based on
stomach content analysis of some specimens (Coutinho et al., 2021; Wilby e Martill,
1992) –although there are no published images detailing this record. Similar studies
(Maisey, 1994), on the other hand, found no small fish fragments while performing
stomach content analysis, and linked V. comptoni’s reduced dentition and well-developed
gill apparatus to morphologies observed in recent filter-feeding taxa, such as paddlefishes
(genus Polyodon).

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Figure 20. Average results of (Hg)sample in fossil taxa of the Romualdo Formation analyzed in the present work.

Figure 41. Average results of (Hg)sample in fossil taxa of the Romualdo Formation analyzed in the present work.

The observed average [Hg]sample in V. comptoni is higher than those observed in

the lower trophic levels represented by R. buccalis and T. araripis, indicating piscivore
feeding habits based in consumption of the latter taxa – and possibly even smaller ones,
such as Santanichthys diasii (Santos, 1995). However, it is important to note that these
ratios show large variability per specimen (0.45–2.01), compared to other fish species
currently analysed – possible evidence of foraging variation that could either be tied to
geographical (Azad et al., 2019) and/or ontogenetic factors (Beneditto et al., 2013). Thus,
this broad range of [Hg]sample values in V. comptoni might be caused either by occupying
different ecological niches through life, or simply presenting less Hg accumulation at a
different ontogenic stage at time of death.
With the increase in trophic level (transition from villiform to molariform
dentition, and from the latter to conical teeth, accompanied by increase in overall size of
species), [Hg]sample becomes higher, indicating shifts to higher levels of the trophic web.
Molariform, mid-tying level species interpreted as durophagous taxa, which fed on larger,
opportunistic invertebrates (Lopes, Barreto, 2021), presented [Hg]sample of ~1.00, as in
Batoidea indet. (1.02) and N. penalvai (1.12). Values of [Hg]Sample around 1.00 were also
found in individuals of Cl. gardneri, along with others up to 1.31, which is expected for
upper ties of the trophic web, occupied by the largest fish taxa, with conical dentition, of

103
the Araripe. The highest [Hg]sample (1.52–21.08) are observed in specimens of Ca.
cylindricus; these might have acted as apex predators in the aquatic environments of the
Romualdo, being able to feed on whatever fit into their mouths – including delving into
cannibalism (Mulder, 2013).

7.4 The role of pterosaurs as mesopredators and opportunists

As in V. comptoni and C. cylindricus, [Hg]samples in pterosaurs varied greatly
between specimens. Specimens attributed to the Ornithocheiriformes showed very low
[Hg]sample (0.27 and 0.30), but slightly higher, in average, than those observed for R.
buccalis. Representatives of this clade were commonly interpreted as highly capable
piscivores, based on dental morphology and geochemistry, as well as digestive tract
content (Bestwick et al., 2018). However, the low bioaccumulation ratios observed in the
present specimens suggest a foraging habit typical of mesopredators specialized in small
epipelagic species of the Romualdo fish fauna, such as R. buccalis and S. diasii, or even
in smaller, plankton-feeding invertebrates (Lopes, Barreto, 2021; Maisey, 1994). The
presence of an air-sac system inferred from an extremely extended skeletal pneumaticity
in ornithocheiriforms also indicates they used to plunge after their prey like modern
pelicans (Shoop, Tilson, 2022).
Regarding the only examined specimen of Thalassodrominae, the [Hg]sample of the
specimen is significantly higher (2.6) than in ornithocheiriforms. It is important, however,
to highlight the possible role of vital effect in the present results, as the number of sampled
specimens is very small (the observed value, nonetheless, is identical to that found in the
indeterminate ornithocheiroid). Thalassodromines were first suggested as piscivores with
skim-feeding habits, but posterior studies proposed they were terrestrially foraging
opportunists, because of the robust hind limbs observed in some thalassodromine
specimens (Pêgas, Costa, Kellner, 2021; Witton, Witton, 2013). Present [Hg]sample results
strengthen the opportunistic diet hypothesis, since higher ratios would be attainable only
by a combination of varied predatory (small to mid-size prey) and scavenging behaviours,
as already suggested for all known thalassodromine taxa so far (Pêgas, Costa, Kellner,
2021).

7.5 An integrative analysis of the Romualdo vertebrate assemblage

Present inferences based on [Hg] quantified in vertebrate species of the Aptian–

104
Albian Romualdo Formation help reconstruct trophic relationships occurring in
paleoenvironments of the Brazilian Romualdo Formation (Figure 21). Bioaccumulation
ratios increased along specific chains of the Romualdo food web based on taxon size and
diet, as observed from small, filiform-toothed fish specialized in smaller prey, to, large,
conical-toothed fish which fed on the former. In such a scenario, bioaccumulation ratios
of V. comptoni favour an interpretation of its feeding habits as of a predatory species,
despite the absence of conical teeth. Low bioaccumulation ratios observed in
ornithocheiriform pterosaurs indicate they were also part of the studied trophic web,
acting as mesopredators specialized in the smaller fish species observed in the Romualdo.
Molariform fish taxa fell slightly apart in the food web, as they probable tended to
consume typically filtering bottom invertebrates, but at the same time might have been
consumed by C. cylindricus – the apex predator of Romualdo aquatic paleoenvironments
(and probably a scavenger as well). Meanwhile, the Thalassodrominae presented
intermediate to high [Hg]samples that put them in a more separate trophic role compared
to aquatic and water-dependent species, as a terrestrial generalist that not only predated
small terrestrial taxa but could also have engaged in scavenging of both terrestrial and
aquatic taxa inhabiting the Romualdo paleoenvironments. However, further investigation
is required to comprehend the behavioural characteristics of the Thalassodrominae. The
availability of a larger number of specimens would facilitate the elucidation of both the
ontogenetic behaviour of these organisms as well as their feeding habits.

105
Figure 21. A summary of the Romualdo Formation trophic web based on literature and present Hg sample results, including the following
groups or taxa: 1) Phytoplankton; 2) Zooplankton; 3) Santanichthys diasii; 4) Rhacolepis buccalis; 5) Tharrhias araripis; 6) Vinctifer
comptoni; 7) Neoproscinetes penalvai; 8) Batoidea indet.; 9) Benthic invertebrates; 10) Cladocyclus gardneri; 11) Calamopleurus
cylindricus; 12) Ornithocheiriformes; 13) Thalassodrominae; and 14) Other terrestrial Tetrapoda.

Funding
The authors acknowledge FUNCAP (PV1-0187-00042.01.00/21 to LSA; PV1-0187-
00054.01.00/21 to BH; BP5-0197-00172.01.02/23 to ALR). This study was financed in
part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior- Brasil
(CAPES)- Finance code 001. We are also indebted to the MCNHBJ staff (DLC Coutinho,
JA Coutinho Júnior and CC Coutinho) for all the support providing fossil specimens for
analyses in the present work.

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8. Considerações finais
Compreender o processo de formação, incluindo as diversas crises biológicas
envolvidas da Bacia do Araripe, oportuniza conhecer as condições pretéritas do planeta,
sendo possível estabelecer relações com o comportamento atual da vida e das
transformações dos ambientes naturais. Estudos anteriores demonstraram uma grande
variedade dos registros fossilíferos (fauna e flora) e estratigráficos na Bacia do Araripe,
demonstrando grande heterogeneidade dos paleoambientes durante o seu
desenvolvimento. Essas mudanças também foram refletidas no Quimioestratigrafia da
Bacia do Araripe, sendo possível estabelecer mudanças climáticas, na
paleoprodutividade, estado redox, salinidade e eventos cíclicos de mortalidade.
A Quimioestratigrafia da Bacia do Araripe demonstrou a presença de anomalias
de Hg, indicando a influência das Grandes Províncias Ígneas (LIPs) na deposição desta
bacia sedimentar. Considerando a idade bioestratigráfica, foi possível estabelecer uma
correlação com os vulcanismos dos platôs Ontong- Java (OJP, ~120 Ma) e o Rajmahal-
Kerguelen Sul (SKP, ~113 Ma). Como resultado do magmatismo dessas LIPs observou-
se a intensificação da produtividade primária, o maior soterramento do carbono e metais-
traço e o desenvolvimento da anoxia nos ecossistemas aquáticos. Dentro desse contexto,
foi possível estabelecer o impacto dos Eventos Anóxicos Oceânicos (OAE 1a e 1b) nas
formações Barbalha e Romualdo, respectivamente. Além disso, constatou-se que os
eventos magmáticos foram responsáveis por mudanças paleoambientais no sistema
deposicional, influenciado pelas mudanças da salinidade, umidade, paleoprodutividade e
estado paleoredox.
Como resultado das grandes mudanças paleoclimáticas globais, houve um
impacto direto nas condições paleoambientais, podendo ter sido este o fator principal para
os eventos de mortalidade cíclicos encontrados no Konservat-Lagerstätte do paleolago
Crato. A partir da química das rochas foi possível estabelecer que a alternância dos
períodos úmidos-secos e da baixa oxigenação das águas desse sistema lacustre
ocasionaram a mortandade dos Dastilbe sp. e Ephemeropteras. Entretanto, são
necessários mais estudos voltados para a entender as variações de salinidade e clima no
sistema lacustre. Além disso, será importante estabelecer uma correlação
quimioestratigráfica com outras bacias sedimentares para entender o desenvolvimento
dos sistemas lacustres carbonáticos do Aptiano. Vale destacar que o estabelecimento da
geoquímica isotópica forense (δ13CVPDB e δ18OVPDB) dessas bacias sedimentares podem

107
auxiliar a entender as diferenças deposicionais entre dos sistemas lacustres carbonáticos,
vir a reduzir impacto do tráfico de fósseis, proteger a geodiversidade e o patrimônio
paleontológico do Brasil.
Considerando o desenvolvimento da pesquisa a respeito da química dos fósseis da
Bacia do Araripe, observou-se que através da determinação das concentrações do Hg nos
fósseis e nas concreções calcárias possível estabelecer o desenvolvimento da cadeia
trófica no Konservat-Lagerstätte da Formação Romualdo. Este ambiente é caracterizado
por apresentar grande biodiversidade da paleoictiofauna e pterossauros. Neste caso,
observou-se a evolução dos níveis tróficos de acordo com o aumento dos valores das
razões do Hg (fóssil/rocha), demonstrando que o Hg possui uma grande aplicabilidade.
Futuros estudos voltados para a uma integração entre as análises de morfometria,
osteohistológicos e geoquímicos (δ13CVPDB, δ18OVPDB e Hg) podem auxiliar no
estabelecimento da cadeia trófica dos Konservat-Lagerstätten globais e na compreensão
do comportamento dos vertebrados do passado.

108
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Material Suplementar- CAPÍTULO 1
Tabela 1. Valores dos indicadores geoquímicos de aportes detríticos, vulcanismo, paleosalinidade, estado redox e paleoprodutividade na Formação Barbalha.
Hg Al
Formação Amostra TOC (%) Hg/TOC Sr/Ba V/Cr V/V+Ni V/Ni PbEF MnEF VEF CrEF FeEF CuEF NiEF ZnEF BaEF
(ng g-1) (%)
8.1A 12.4 1,9 6,9 6,5 0,05 6,4 0,82 4,6 0,62 0,27 2,1 0,25 1,1 2,3 0,79 0,91 0,32
(camada Batateira)

8.1B 3.9 1,6 5,3 2,5 0,05 5,7 0,82 4,7 0,42 0,37 1,9 0,26 1,2 1,7 0,71 1,0 0,29
8.2A 10.4 2,4 7,1 4,3 0,06 5,2 0,79 3,9 2,0 0,58 2,0 0,29 1,1 3,4 0,88 1,5 0,26
8.2B 11.0 2,1 6,2 5,4 0,08 6,5 0,81 4,1 1,7 0,37 2,3 0,28 1,2 3,6 0,99 1,3 0,19
Barbalha

17B 16.6 1,7 8,9 9,6 0,06 5,5 0,80 3,9 0,87 0,43 1,3 0,18 0,68 2,1 0,56 0,79 0,16
17A 43.6 3,3 0,72 13,3 1,4 8,2 0,75 3,0 59,9 34 5,5 0,52 2,9 44 3,2 59 1,2
18 13,3 1,4 4,1 9,3 0,07 5,4 0,78 3,5 1,3 0,90 2,4 0,35 1,9 5,0 1,2 2,4 0,44
19B 5,1 0,9 3,7 5,3 0,39 3,6 0,67 2,0 2,9 0,27 0,48 0,10 0,28 0,74 0,41 7,2 0,04
19A 30,6 1,5 6,4 20,2 0,03 4,7 0,80 4,0 0,62 0,38 1,9 0,31 1,0 2,4 0,82 1,0 0,19
20 3,5 0,4 4,2 8,1 0,04 2,2 0,67 2,0 0,65 0,49 1,3 0,44 2,2 1,6 1,08 1,4 0,35
21B 3,9 0,3 2,5 12,2 0,50 2,9 0,83 4,7 0,69 3,1 2,1 0,54 0,92 0,91 0,75 1,1 0,12
21A 2,7 0,4 5,5 6,4 0,09 5,5 0,75 2,9 0,33 0,34 1,6 0,23 1,6 1,4 0,94 1,2 0,17
22 3,6 0,3 3,0 11,9 0,19 2,3 0,78 3,5 1,3 0,03 0,47 0,16 0,22 0,60 0,23 0,45 0,05

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Tabela 2. Matriz de correlação de Spearman para os metais estudados na Formação Barbalha. Os valores em negrito são significativos (p< 0,05;
n=13).
Al Fe Mn Cu Zn Ni Pb Cr Sr V Ba Hg TOC Hg/TOC Sr/Ba
Al 1 0,62 -0,58 0,17 -0,50 0,76 -0,42 0,81 -0,57 0,79 0,58 -0,18 0,12 -0,58 -0,74
Fe 1 -0,35 0,29 -0,41 0,91 -0,35 0,77 -0,33 0,75 0,82 -0,18 0,54 -0,46 -0,62
Mn 1 0,55 0,77 -0,27 0,87 -0,39 0,98 -0,27 -0,13 0,76 0,58 0,24 0,93
Cu 1 0,47 0,52 0,68 0,26 0,59 0,52 0,54 0,72 0,91 -0,10 0,31
Zn 1 -0,30 0,9 -0,57 0,83 -0,35 -0,2 0,63 0,65 -0,04 0,83
Ni 1 -0,18 0,83 -0,26 0,92 0,81 0,03 0,66 -0,41 -0,55
Pb 1 -0,41 0,93 -0,19 -0,09 0,75 0,76 0,06 0,85
Cr 1 -0,46 0,81 0,70 -0,09 0,09 -0,19 -0,65
Sr 1 -0,26 -0,01 0,76 0,64 0,17 0,92
V 1 0,79 0,07 0,72 -0,35 -0,52
Ba 1 0,09 0,70 -0,43 -0,42
Hg 1 0,72 0,47 0,62
TOC 1 -0,19 0,42
Hg/TOC 1 0,26
Sr/Ba 1

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Tabela 3. Valores dos indicadores geoquímicos de aportes detríticos, vulcanismo, paleosalinidade, estado redox e paleoprodutividade na Formação
Barbalha.

Hg TOC Al
FORMAÇÃO Amostra Hg/TOC Sr/Ba V/Cr V/V+Ni V/Ni PbEF MnEF VEF CrEF FeEF CuEF NiEF ZnEF BaEF
(ng g-1) (%) (%)
12 19,8 0,63 31,5 6,7 0,08 2,6 0,58 1,4 1,05 0,30 0,64 0,19 0,93 2,1 0,80 2,6 0,12
11E 12,5 0,45 27,7 0,02 0,31 2,3 0,86 6,4 572 1,989 229 76,4 44,6 348 63,1 816 138
11D 9,7 0,42 23,2 2,5 0,24 8,8 0,83 5,0 3,73 3,4 2,7 0,24 0,82 5,9 0,94 88,7 0,89
11C 34,2 0,32 107 0,04 0,68 5,3 0,86 5,9 4,245 889 168 24,7 164 679 49,8 1,359 29,7
11B 9,9 0,26 38,1 0,69 0,50 6,4 0,87 6,4 7,93 172 7,3 0,88 1,1 22,7 1,9 348 2,1
11A 8,1 0,59 13,7 6,3 0,36 3,4 0,73 2,7 1,01 0,50 1,5 0,34 1,0 4,2 0,96 30,1 0,10
5A 2,5 0,8 3,1 6,1 0,20 2,8 0,68 2,1 1,20 0,93 0,76 0,21 0,64 1,0 0,63 4,3 0,15
5B 1,6 0,78 1,9 4,5 0,25 10,8 0,80 4,0 0,84 5,7 1,2 0,08 1,2 0,69 0,51 8,6 0,64
FORMAÇÃO CRATO

5C 1,2 0,95 1,2 8,3 0,07 3,5 0,68 2,1 0,50 0,51 0,59 0,13 0,52 0,76 0,49 4,4 0,15
5D 3,8 1,01 3,8 2,6 0,17 4,4 0,72 2,5 1,66 10,2 0,92 0,17 2,1 0,92 0,64 24,4 0,50
5E 2,2 0,9 2,4 4,9 0,20 5,3 0,80 3,9 0,88 8,0 1,7 0,24 0,85 1,1 0,75 13,7 0,23
10D 23 0,25 92 0,11 0,47 2,0 0,84 5,2 132 311 29,2 11,4 10,6 54,3 9,9 232,8 14,2
10C 5,2 0,77 6,8 6,6 0,18 2,8 0,78 3,6 1,36 0,38 1,6 0,44 0,78 2,8 0,75 1,8 0,25
10B 2,5 0,39 6,3 4,9 0,26 5,8 0,76 3,2 1,25 0,53 1,1 0,15 0,70 0,85 2,3 2,3 0,14
10A 6,1 0,16 37,8 2,4 0,42 5,4 0,82 4,7 2,73 17,6 1,8 0,26 3,2 1,0 0,76 7,4 0,49
1B 31 1,44 21,6 6,1 0,08 4,2 0,71 2,4 4,12 2,0 1,1 0,20 1,0 4,8 0,62 8,0 0,49
1C 19 1,67 11,7 4,2 0,15 3,1 0,73 2,7 2,93 2,9 0,94 0,24 0,9 3,0 0,55 7,6 0,34
1D 34 1,84 18,9 6,3 0,02 4,3 0,67 2,1 5,17 3,0 0,65 0,12 0,64 4,1 7,6 6,9 0,40
1E 44 0,54 81,6 0,24 2,4 5,4 0,82 4,7 395 211 19,6 2,8 4,2 901 15,3 286 8,3
13 21 1,16 17,7 0,02 3,5 4,2 0,91 10,1 568 1,939 87,9 16,4 170 130 15,3 98,9 75,3
14 7,6 0,35 21,7 0,04 3,9 10,9 0,86 6,4 148 606 56,1 4,0 29,2 109 0,76 87,4 34,1

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Tabela 4. Matriz de correlação de Spearman para os metais estudados na Formação Barbalha. Os valores em negrito são significativos (p< 0,05;
n=21).

Al Fe Mn Cu Zn Ni Pb Cr Sr V Ba Hg TOC Hg/TOC Sr/Ba

Al 1 0,33 -0,59 -0,11 -0,32 0,90 -0,31 0,50 -0,56 0,52 -0,04 -0,30 0,47 -0,62 -0,59
Fe 1 -0,30 -0,15 0,03 0,50 0,08 0,67 -0,30 0,52 -0,15 -0,07 -0,05 0,77 -0,33
Mn 1 -0,08 0,26 -0,57 0,01 -0,36 0,26 -0,25 0,10 0,03 -0,26 0,32 0,23
Cu 1 0,12 0,02 0,42 -0,04 -0,02 -0,05 -0,13 0,72 0,04 0,72 0,18
Zn 1 -0,08 0,71 0,02 -0,18 0,29 -0,05 0,21 -0,32 0,49 -0,16
Ni 1 -0,16 0,71 -0,57 0,71 -0,14 -0,19 0,30 -0,42 -0,58
Pb 1 -0,09 -0,02 0,01 -0,06 0,66 -0,04 0,71 0,06
Cr 1 -0,43 0,75 -0,12 -0,17 0,04 -0,14 -0,45
Sr 1 -0,47 0,05 0,11 -0,09 0,08 0,97
V 1 0,01 -0,30 -0,04 0,43 -0,50
Ba 1 0,14 0,38 -0,16 -0,08
Hg 1 0,25 0,68 0,21
TOC 1 -0,44 -0,15
Hg/TOC 1 0,19
Sr/Ba 1

139
Tabela 5. Valores dos indicadores geoquímicos de aportes detríticos, vulcanismo, paleosalinidade, estado redox e paleoprodutividade na Formação Barbalha.

Hg TOC Al
FORMAÇÃO Amostra Hg/TOC Sr/Ba V/Cr V/V+Ni V/Ni PbEF MnEF VEF CrEF FeEF CuEF NiEF ZnEF BaEF
(ng g-1) (%) (%)
23 2,5 0,6 4,5 1,05 0,65 4,2 0,8 4,7 2,3 9,8 1,8 0,3 1,0 2,1 2,1 1,2 1,2
4.1 5,6 1,4 3,9 6,93 0,48 3,9 0,8 4,9 1,4 0,3 1,9 0,4 1,9 2,5 2,2 2,3 0,3
4.1.1 5,1 1,4 3,6 6,72 0,37 4,1 0,8 3,0 1,6 1,1 2,2 0,4 1,5 3,4 4,0 4,3 0,1
4.2.1 11,7 1,2 9,7 1,48 0,42 11,0 0,9 8,3 3,2 31,4 4,7 0,3 1,3 6,5 3,1 4,2 0,7
Romualdo
Formação

15 D 1,5 0,8 1,8 5,72 0,21 3,4 0,7 2,6 0,7 0,7 1,4 0,3 2,1 1,5 2,9 2,7 0,1
15C 2,0 0,6 3,2 2,07 0,64 1,6 0,8 4,8 2,5 3,7 0,6 0,3 0,4 0,4 0,7 0,4 0,3
15B 2,3 0,7 3,1 6,58 0,76 1,6 0,6 1,6 0,6 0,4 0,8 0,4 1,8 0,7 2,7 2,3 0,0
15A 6,9 1,0 6,9 3,85 0,23 1,3 0,8 3,2 1,2 0,6 1,2 0,7 3,2 1,7 2,1 2,4 0,1
3A 1,1 0,5 2,2 2,18 0,41 12,8 0,9 12,7 4,6 2,8 2,0 0,1 0,4 0,4 0,9 0,5 0,3
3B 26,3 0,7 39,3 3,70 0,06 1,4 0,6 1,5 9,0 0,9 1,4 0,7 2,2 6,7 5,1 4,7 0,9
3C 6,8 0,8 8,1 1,97 0,58 6,5 0,8 3,5 2,7 11,6 2,0 0,2 2,1 3,6 3,2 0,3 0,5
3D 2,8 0,7 4,1 1,86 0,72 12,8 0,9 6,8 1,8 10,8 1,3 0,1 0,2 1,9 1,1 1,4 0,6
3E 2,0 0,5 4,1 5,06 0,18 1,5 0,7 1,9 2,5 0,3 0,4 0,2 1,0 0,7 1,1 0,8 0,3

140
Tabela 6. Matriz de correlação de Spearman para os metais estudados na Formação Barbalha. Os valores em negrito são significativos (p< 0,05;
n=13).

Al Fe Mn Cu Zn Ni Pb Cr Sr V Ba Hg TOC Hg/TOC Sr/Ba

Al 1 0,87 −0,58 0,53 0,84 0,84 0,3 0,84 −0,29 0,68 −0,08 −0,08 0,46 −0,11 -0,53
Fe 1 −0,51 0,52 0,69 0,79 0,17 0,93 −0,29 0,64 −0,12 0,07 0,54 0,00 −0,31
Mn 1 −0,08 −0,10 −0,36 −0,24 −0,55 0,37 −0,06 0,12 0,14 0,22 −0,01 0,31
Cu 1 0,56 0,79 0,69 0,66 −0,05 0,76 0,33 0,63 0,70 0,52 −0,42
Zn 1 0,8 0,1 0,61 0,04 0,82 −0,09 −0,17 0,73 −0,29 0,06
Ni 1 0,39 0,84 −0,31 0,77 −0,10 0,24 0,57 0,18 −0,27
Pb 1 0,35 0,09 0,46 0,39 0,51 0,3 0,5 −0,24
Cr 1 −0,40 0,63 −0,13 0,27 0,55 0,21 −0,37
Sr 1 0,08 0,70 −0,19 0,21 −0,24 0,53
V 1 0,16 0,05 0,89 −0,11 −0,15
Ba 1 0,29 0,72 0,26 −0,14
Hg 1 0,15 0,97 −0,49
TOC 1 −0,08 −0,04
Hg/TOC 1 −0,49
Sr/Ba 1

141
 Material Suplementar- CAPÍTULO 2

Tabela 7. Valores dos indicadores geoquímicos de aportes detríticos, vulcanismo, paleoprodutividade, paleoredox, paleosalinidade, paleoclima e
paleosalinidade no Konservat-Lagerstätte do paleolago Crato.

Aportes Fator de Enriquecimento com o Alumínio Fator de Enriquecimento com o Ferro Nível
Vulcanismo Clima Salin.
Altura
(cm)

detríticos Paleoprodutividade Paleoredox Paleoprodutividade Paleoredox Lago

Al Fe Hg Hg/Al Hg/Fe Cu Zn Ni Ba Pb Mn Fe Cu Zn Ni Ba Pb Mn Sr/Cu Sr/Ba Fe/Mn
1,72 0,1 0,2 18 273 90 149 79 8 3 166 27 1 118 63 6 3 132 22 1 4 1
1,73 0,1 0,6 42 433 76 15 112 5 2 203 17 2 6 48 2 1 86 7 11 5 4
1,74 0,1 0,1 54 521 377 17 67 1 3 137 17 1 30 117 1 5 241 30 8 3 1
1,83 0,1 0,7 24 256 35 98 39 2 3 320 20 3 32 13 1 1 105 6 1 3 4
2,05 0,1 0,3 54 782 175 217 93 7 2 128 25 2 118 50 4 1 69 14 1 5 2
2,17 0,1 0,3 77 1.048 271 141 53 7 1 204 21 2 88 33 4 1 128 13 1 8 2
2,5 0,1 0,9 124 1.515 145 173 92 6 2 136 20 4 40 21 1 0,5 32 5 1 3 6
10 0,0 0,5 57 1.719 124 1399 197 19 12 412 45 6 245 34 3 2 72 8 1 5 3
11,2 0,0 0,4 57 1.753 130 1377 214 32 9 260 46 6 248 39 6 2 47 8 0,2 2 3
14 0,1 0,9 28 528 32 570 151 10 8 188 41 7 83 22 1 1 27 6 0,3 1 5
16 0,3 1,7 355 1.154 210 183 52 4 9 211 8 2 81 23 2 4 93 3 0,1 0,1 8
17 0,1 0,3 160 2.485 502 34 64 8 19 229 28 2 16 31 4 9 112 14 4 0,4 2
19,5 0,0 0,4 135 3.050 356 42 141 14 24 316 48 4 12 40 4 7 90 14 6 1 2
20 0,1 0,1 130 1.862 882 15 288 6 6 100 33 1 17 331 7 7 115 38 11 1 1
25,2 0,0 0,2 58 1.750 265 26 128 12 14 301 59 3 9 47 4 5 111 22 11 1 1
28 0,1 0,5 81 888 170 151 141 1 7 201 17 2 70 66 0,5 3 93 8 1 1 4
35 0,3 0,8 122 478 152 102 48 3 4 66 8 1 79 37 3 3 51 6 2 3 5
55 0,1 1,0 47 689 47 36 166 6 7 289 31 6 6 27 1 1 47 5 4 1 5
67,2 0,1 1,3 56 617 43 109 335 13 5 181 23 6 18 57 2 1 31 4 1 1 7
69,2 0,1 0,7 28 209 39 105 153 4 4 45 15 2 48 70 2 2 21 7 1 1 4
75 0,1 0,3 20 201 57 309 155 2 5 134 33 1 212 106 2 3 92 23 1 4 1

142
 83,2 0,1 0,5 13 148 28 398 139 3 6 62 22 2 179 62 1 3 28 10 1 5 3
88,6 0,1 0,3 58 836 168 766 237 13 6 414 55 2 374 116 6 3 202 27 1 6 1
95,7 0,2 0,2 34 211 160 94 45 1 2 58 17 1 173 83 2 4 106 31 3 8 1
103 0,1 0,4 25 229 55 411 180 8 6 123 25 2 239 105 5 3 71 15 0,4 2 2
110 0,2 0,3 22 122 68 173 74 1 2 76 14 1 231 100 1 3 102 19 3 14 1
115 0,5 1,2 22 42 19 322 98 3 1 67 3 1 348 106 3 1 73 4 0,1 1 8
125 0,1 0,4 90 714 213 440 183 6 5 133 15 1 319 133 5 3 97 11 1 4 2
138 0,2 0,9 57 362 65 715 252 9 3 118 12 2 312 110 4 1 51 5 0,2 3 5
138,1 0,1 0,5 32 391 64 595 180 8 2 221 35 3 237 72 3 1 88 14 1 10 2
144,9 0,2 0,7 26 130 35 422 134 3 1 99 9 2 274 87 2 1 64 6 0,2 5 5
148,1 0,1 0,1 20 192 151 259 124 5 2 123 18 1 496 238 9 3 236 34 2 14 1
150 0,1 0,3 40 29 126 314 94 4 1 445 13 1 323 97 4 1 458 13 0,4 6 2
151,4 0,1 0,1 23 341 172 268 118 5 2 521 32 1 328 145 6 3 638 39 2 15 1
151,8 0,1 0,2 35 245 221 173 68 2 2 86 18 0,5 379 150 4 5 188 40 1 3 1
152,3 0,1 0,3 26 443 76 678 232 13 3 288 33 2 281 96 6 1 119 14 1 11 2
155,8 0,1 0,1 32 396 243 272 104 4 2 937 23 1 405 155 5 3 1393 34 2 14 1
156 0,1 0,1 28 232 211 192 97 1 3 129 17 0,5 424 215 2 7 286 38 3 8 1
158,1 0,1 0,3 30 305 98 379 355 2 5 145 19 1 296 278 1 4 114 15 2 8 2
158,6 0,1 0,7 31 281 44 1128 249 4 4 162 21 3 424 94 1 2 61 8 0,1 2 4
158,8 0,1 0,2 12 195 53 635 136 <LD 15 184 35 2 416 89 <LD 10 121 23 2 4 1
159 0,1 0,2 26 336 116 467 72 6 7 209 27 1 392 60 5 5 175 23 0,4 1 1
160 0,7 0,7 149 217 218 131 76 1 1 42 3 0,4 319 184 3 2 101 7 1 7 4
162,7 0,2 0,1 50 327 425 121 51 2 3 93 8 0,3 382 160 7 8 292 25 4 12 1
165,6 0,1 0,7 39 341 53 637 172 2 3 143 18 3 238 64 1 1 53 7 1 10 4
176,3 0,2 0,8 69 306 87 527 123 2 2 90 8 1 366 86 1 1 62 6 1 11 5
176,6 0,1 1,0 23 190 23 1107 264 6 3 156 17 3 325 78 2 1 46 5 0,1 2 6
179,1 0,3 0,8 52 167 68 275 61 2 2 94 5 1 271 60 2 2 93 5 1 5 5
179,2 0,1 0,4 21 211 57 476 111 2 3 141 19 2 313 73 2 2 93 12 0,2 2 2
180 0,1 1,9 58 618 31 2545 451 9 5 477 17 8 308 55 1 1 58 2 0,2 5 13
180,5 0,1 0,2 31 245 127 328 99 2 4 140 15 1 414 125 2 5 176 19 0,3 2 1
180,9 0,1 0,4 31 229 88 307 100 3 5 94 13 1 287 93 3 5 88 12 1 3 2
181,7 0,1 0,1 38 301 470 133 52 2 4 99 8 0 505 196 8 14 376 29 1 1 1

143
 182 0,1 0,3 32 340 105 366 128 1 13 143 20 1 274 96 1 10 107 15 1 2 2
183,1 0,1 0,3 25 259 80 433 144 2 3 131 20 1 324 108 2 3 98 15 0,3 2 2
186,3 0,1 0,3 34 390 133 697 263 2 <LD 151 20 1 579 218 2 <LD 126 16 1 <LD 2
189,3 0,1 0,5 33 498 69 612 107 6 11 338 28 3 205 36 2 4 113 9 1 4 3
191 0,1 0,4 28 375 70 635 243 2 6 434 23 2 286 110 1 3 196 10 1 4 3
191,3 0,1 0,2 20 282 83 586 157 3 5 380 29 1 418 111 2 3 270 20 0,3 2 1
191,7 0,1 0,3 44 475 159 485 153 1 5 111 16 1 394 124 1 4 90 13 2 10 2
192 0,1 0,4 47 437 130 413 145 3 4 145 20 1 299 105 2 3 105 14 1 7 2
193 0,1 0,4 40 452 105 385 124 2 6 157 21 2 218 70 1 3 89 12 1 5 2
193,4 0,1 0,3 31 348 91 400 142 2 5 121 26 2 253 90 1 3 76 16 2 7 2
194 0,1 0,9 54 601 61 939 230 3 5 213 20 4 231 56 1 1 52 5 1 6 6
195 0,1 0,7 82 572 121 472 182 4 3 190 13 2 243 94 2 1 98 6 0,2 2 4
197 0,1 0,9 168 2.388 197 881 341 5 8 467 27 5 176 68 1 2 94 5 1 9 5
199 0,1 0,4 49 830 115 332 195 4 8 337 31 3 111 65 1 3 113 11 5 12 3
201 0,0 0,3 69 1.800 248 461 219 3 7 246 46 3 154 73 1 2 82 15 5 20 2
205 0,1 0,7 60 590 91 259 201 1 4 306 14 3 97 75 0,5 2 114 5 4 13 5
214 0,1 0,5 74 604 138 121 149 1 2 170 12 2 67 82 1 1 94 7 7 20 4
217 0,1 0,7 146 1.329 217 173 203 2 5 243 15 3 68 80 1 2 96 6 5 11 5
224 0,2 0,5 102 579 190 123 70 0,2 2 115 7 1 98 56 0,2 1 92 6 5 20 5
226 0,1 0,3 235 1.715 696 72 77 1 3 212 13 1 71 76 1 3 209 13 11 13 2
229,5 0,1 0,8 109 1.158 129 317 148 2 5 357 16 4 85 40 1 1 96 4 4 13 6
235 0,1 0,4 62 792 156 168 97 <LD 10 206 23 2 80 46 <LD 5 98 11 7 6 2
242 0,1 0,8 117 996 152 179 129 <LD 5 312 12 3 66 48 <LD 2 116 4 6 11 6
255 0,2 1,6 46 187 29 211 142 1 2 136 6 3 80 54 0,5 1 51 2 2 13 13
258 0,1 0,8 75 960 96 227 272 <LD 5 224 20 4 55 66 <LD 1 54 5 5 13 6
265 0,1 0,4 68 1.236 165 418 302 <LD 8 230 32 3 135 98 <LD 3 75 11 4 12 3
274,5 0,1 0,4 118 1272 301 219 124 <LD 5 78 17 2 126 71 <LD 3 45 10 4 10 3
284,5 0,0 0,5 88 1943 174 239 239 3 10 641 35 5 52 52 1 2 139 8 13 17 4
285 0,1 0,6 93 806 148 95 118 <LD 5 273 13 2 42 52 <LD 2 121 6 10 10 5
288 0,1 0,5 49 890 101 184 187 4 15 272 31 4 50 51 1 4 74 8 11 8 3
295 0,1 0,5 61 834 121 246 412 <LD 12 164 21 3 87 145 <LD 4 58 7 6 7 4

144
Tabela 8. Matriz de correlação de Spearman para os metais estudados no Konservat-Lagerstätte do paleolago Crato. Os valores em negrito são
significativos (p< 0,05; n=84).

Al Fe Mn Cu Pb Zn Ni Hg Ba Sr/Cu Sr/Ba Hg/Al Hg/Fe Fe/Mn

Al 1 0.34 -0,02 0.42 0.28 0.61 0.40 0.33 0.20 -0,32 -0,34 -0,33 -0,08 0.35
Fe 1 -0,11 0.55 0.39 0.61 0.48 0.34 0.32 -0,27 -0,17 0.06 -0,38 0.96
Mn 1 0.05 -0,07 -0,04 0.25 0.03 0.08 -0,07 -0,09 -0,1 -0,12 -0,31
Cu 1 0.27 0.71 0.39 -0,1 0.03 -0,46 -0,07 -0,30 -0,33 0.51
Pb 1 0.25 0.20 0.29 0.21 -0,15 0.22 -0,05 -0,09 0.38
Zn 1 0.43 -0,03 0.13 -0,31 -0,02 -0,30 -0,42 0.59
Ni 1 0.29 0.25 -0,08 -0,33 0.04 -0,05 0.35
Hg 1 0.56 0.03 -0,13 0.62 0.51 0.25
Ba 1 0.03 -0,39 0.21 0.07 0.21
Sr/Cu 1 0.47 0.37 0.42 -0,1
Sr/Ba 1 -0,18 -0,05 -0,09
Hg/Al 1 0.54 -0,31
Hg/Fe 1 -0,4
Fe/Mn 1
Mortality

145
Tabela 9. Matriz de correlação de Spearman para o Fator de Enriquecimento do Alumínio (Al) no Konservat-Lagerstätte do paleolago Crato. Os valores
em negrito são significativos (p< 0,05; n=84).

CuEF ZnEF NiEF BaEF PbEF MnEF FeEF Hg Hg/Al Hg/Fe Sr/Ba Sr/Cu Fe/Mn Mortality
CuEF 1 0.58 0.19 0.02 0.27 0.24 0.51 -0,19 -0,03 -0,34 -0,05 -0,45 0.32 0.33
ZnEF 1 0.23 0.21 0.29 0.25 0.61 -0,2 0.12 -0,41 0.03 -0,13 0.34 0.07
NiEF 1 0.30 0.19 0.57 0.44 0.11 0.41 0.10 -0,25 0.21 0.06 0.03
BaEF 1 0.28 0.57 0.34 0.22 0.62 0.17 -0,38 0.30 -0,1 0.18
PbEF 1 0.41 0.36 0.05 0.33 -0,04 0.25 0.10 0.04 0.18
MnEF 1 0.40 -0,14 0.49 0.11 -0,11 0.24 -0,36 0.14
FeEF 1 0.06 0.41 -0,29 -0,16 -0,02 0.57 -0,06
Hg 1 0.62 0.51 -0,06 0.23 0.21 -0,09
Hg/Al 1 0.54 -0,09 0.44 -0,31 0.11
Hg/Fe 1 -0,03 0.54 -0,4 0.13
Sr/Ba 1 0.28 -0,08 -0,25
Sr/Cu 1 -0,05 -0,31
Fe/Mn 1 0.28
Mortality 1

146
Tabela 10. Matriz de correlação de Spearman para o Fator de Enriquecimento com o Ferro (Fe) no Konservat-Lagerstätte do paleolago Crato. Os valores
em negrito são significativos (p< 0,05; n=84).

CuEF ZnEF NiEF BaEF PbEF MnEF Hg Hg/Al Hg/Fe Sr/Ba Sr/Cu Fe/Mn Mortality
CuEF 1 0.68 0.18 0.23 0.33 0.40 -0,43 -0,51 -0,17 0.15 -0,55 -0,30 0.49
ZnEF 1 0.33 0.45 0.37 0.53 -0,3 -0,41 0.07 0.29 -0,17 -0,41 0.29
NiEF 1 0.36 0.38 0.64 -0,1 -0,04 0.43 0.02 0.24 -0,44 0.06
BaEF 1 0.19 0.55 0.02 0.10 0.51 -0,24 0.20 -0,49 0.27
PbEF 1 0.55 -0,11 -0,04 0.22 0.37 0.12 -0,33 0.21
MnEF 1 -0,27 -0,13 0.43 0.18 0.17 -0,73 0.26
Hg 1 0.64 0.51 -0,06 0.23 0.28 -0,09
Hg/Al 1 0.58 -0,06 0.44 -0,31 -0,04
Hg/Fe 1 -0,04 0.54 -0,4 0.13
Sr/Ba 1 0.28 -0,08 -0,25
Sr/Cu 1 -0,1 -0,31
Fe/Mn 1 0.28
Mortality 1

147
Material Suplementar- CAPÍTULO 3
Tabela 11. Concentração de mercúrio (ng g-1) em espécimes de vertebrados fósseis (Hgfossil),
das concreções (Hgrocha), a razão de bioacumulação (Hgamostra) na Formação Romualdo, Bacia
do Araripe, Nordeste do Brasil.

Hg fóssil Hg rocha
Amostra Táxon (ng g-1) (ng g-1)
Hgrazão

MPPCN P 5319 20,73 13,53 1,53

Calamopleurus
MPPCN P 5320 26,95 17,74 1,52
MPPCN P 5354 cylindrius 202,16 9,59 21,08
Média 8,04
MPPCN P 2425 22,90 22,99 1,00
Cladocyclus
MPPCN P 2448 20,93 16,89 1,24
MPPCN P 2436 gardneri 10,83 8,29 1,31
Média táxon 1,18
MCNHBJ 134 Neoproscinetes 34,29 29,59 1,16
MCNHBJ 364 panalvai 31,22 28,89 1,08
Média táxon 1,12
MCNHBJ 353 45,31 41,83 1,08
MCNHBJ 043
Baitodea 41,13 42,93 0,96
Média táxon 1,02
MPPCN P 5311 10,13 22,55 0,45
MPPCN P 5313 111,29 125,68 0,89
Vinctifer
MPPCN P 5314 6,73 12,29 0,55
MPPCN P 5317 comptoni 18,64 25,96 0,72
MPPCN P 5309 112,02 55,80 2,01
Média táxon 0,92
MPPCN P 5356 157,16 1,330 0,12
MPPCN P 5358 105,25 304,62 0,35
Rhacolepis
MPPCN P 5359 41,25 95,68 0,43
MPPCN P 5360 buccalis 298,59 808,80 0,37
MPPCN P 5357 34,65 482,67 0,07
Média táxon 0,43
Pterosauria
MCNHBJ 5038 10,72 4,19 2,56
(Thalassodrominae)
Pterosauria
MCNHBJ 1434 10,91 4,14 2,64
(Ornithocheiroidea ind,)
MCNHBJ 105 Pterosauria 1,46 4,45 0,33
MCNHBJ 345 (Ornithocheiriforme) 3,85 17,92 0,21
Média táxon 0,27
TR1 17,72 20,11 0,88
TR2
Tharrhias araripis 8,28 9,72 0,85
Média táxon 0,87

148