Implications of Sediment Geochemistry and Diet Habits in Fish Metal Levels and Human Health Risk

In this study the concentration of Cd, Cu, Fe, Ni, Pb, and Zn in muscle and liver tissues was compared between four estuarine fish species (Centropomus parallelus, Genidens genidens, Diapterus rhombeus, and Mugil liza) to assess contamination levels and the influence of eating habits on metal distribution and human health risk by consumption. In general, liver tissue showed higher metal contents than muscle. Between metals, Fe and Zn contents were relatively higher for both tissues in all analyzed populations. Based on the observations, the variability of metal levels between species is associated with their transfer from the contaminated sediments, where diet habits associated with the substrate result in higher metal accumulation in fish, exerting great influence than bioaccumulation by trophic level. The estimated daily intake (EDI), target hazard quotients (THQ) and the total target hazard quotients (TTHQ), below 1 for all metals on muscle tissues, are suggested the absence of health hazard for the human population. However, high levels of Pb and Zn in liver tissue may endanger predators

Concentrations of chemical elements in liver and muscle of demersal fish of Santos - Cubatão estuarine system (SP) : spatial and temporal aspects

Orientador: Wanilson Luiz SilvaDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de GeociênciasResumo: A região de Cubatão (SP) abriga o maior polo industrial da América Latina e nos anos de 1980 ficou internacionalmente conhecida como um dos lugares mais seriamente poluídos do planeta por consequência de atividades industriais que ocasionaram grandes perturbações ambientais locais. Desde então, a contaminação da biota do sistema estuarino de Santos-Cubatão vem sendo monitorada e tem apresentado níveis elevados de elementos químicos nos organismos. Entretanto, ainda não foram realizados estudos que levem em consideração amostragens sazonais, que poderiam refletir as consequências das variações físico-químicas do ambiente na transferência de elementos químicos para a biota. No presente estudo, concentrações de As, Se e metais (Cd, Cr, Cu, Fe, Mn, Ni, Pb e Zn) foram determinadas em tecidos hepático e muscular de quatro espécies de peixes demersais do sistema estuarino em foco. No inverno/2010 e verão/2011, exemplares de Diapterus rhombeus, Genidens genidens, Centropomus parallelus e Mugil Liza foram coletados nos rios Morrão, Casqueiro e Cubatão. As amostras foram liofilizadas e os elementos químicos extraídos por digestão ácida com posterior análise por ICP-MS. Os resultados foram comparados ao LMT (limite máximo de tolerância) determinado pelo Ministério da Saúde do Brasil. Concentrações de As, Cr, Cu, Fe, Mn, Pb, Se e Zn foram, em geral, acima do LMT estabelecido pela legislação brasileira, e o tecido hepático apresentou concentrações químicas muito superiores às registradas no tecido muscular. Mugil Liza foi a espécie que acumulou mais elementos químicos em ambos os tecidos e é a melhor bioindicadora da área de estudo. As associações com o substrato e o hábito alimentar mostraram-se fatores decisivos na absorção de elementos químicos pelos organismos. Variabilidades sazonais foram observadas para as concentrações de Cd, Cr, Cu, Fe, Mn e Zn nos tecidos dos organismos analisados. Apesar de o rio Morrão ser considerado um dos cenários mais impactados do sistema estuarino de Santos-Cubatão, a biodisponibilidade de elementos químicos naquele ambiente não parece diferente de ambientes historicamente menos impactados, como os rios Casqueiro e CubatãoAbstract: The city of Cubatão (SP) holds the largest industrial center in Latin America. During the 1980s, this region became internationally known as one of the most polluted cities in the world. This was a result of local industrial activities that caused large local environmental disturbances. Since then, biota contamination along the Santos-Cubatão estuarine system has been monitored, and high levels of contamination amongst organisms have been found. Environmental monitoring of the biota, taking into account the importance of seasonal variability, has not been considered. Concentrations of As, Se and metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were determined in liver and muscle tissue of four species of demersal fishes of the Santos-Cubatão estuarine system. Specimens of Diapterus rhombeus, Genidens genidens, Centropomus parallelus and Mugil Liza were collected in summer and winter, in the Morrão, Casqueiro and Cubatão rivers. The samples were freeze-dried, underwent acid digestion and subsequently were analyzed using an ICP-MS. The results were compared to the LMT (maximum allowable) guidelines determined by the Brazilian Ministry of Health. Concentrations of As, Cr, Cu, Fe, Mn, Pb, Se, and Zn were generally above the LMT, as established by Brazilian legislation. Specific organs were analyzed and compared, for instance, liver tissue had contaminant concentrations much higher than those recorded in the muscle tissue. Mugil Liza was the species that accumulated more chemical elements in both tissues. The association with the substrate and eating habits proved to be decisive factors in the absorption of specific contaminants by the organisms. Seasonal variability was observed for concentrations of Cd, Cr, Cu, Fe, Mn, and Zn in the tissues of organisms analyzed. Although the Morrão river is considered one of the scenarios most impacted of the Santos-Cubatão estuarine system, the bioavailability of specific chemical pollutants in this work does not support this scenario, as indicated by the results found in the less impacted environments, such as Cubatão and Casqueiro riversMestradoGeologia e Recursos NaturaisMestre em Geociência

Rare earth elements and isotopic tracers in subtropical estuaries : a geochemistry approach of metal transfer to biota

Orientador: Wanilson Luiz-SilvaTese (doutorado) - Universidade Estadual de Campinas, Instituto de GeociênciasResumo: O presente trabalho explora a geoquímica dos elementos terras raras (REE) em sedimentos de diferentes profundidades, sua solubilidade em águas intersticiais e consequências na biota exposta (musculatura e carapaças de caranguejos Ucides cordatus) em três ambientes estuarinos subtropicais no sudeste do Brasil. Estes ambientes contrastam em termos de impactos antrópicos industrial e urbano e esta investigação propõe a utilização de assinaturas de REE, elementares e isotópicas como ferramentas para realizar diagnóstico ambiental da transferência destes contaminantes entre o meio físico e biótico. Foram testadas as razões isotópicas 143Nd/144Nd e 147Sm/144Nd como potenciais traçadores desde a fonte (produto mineral utilizado em um processo industrial) até o organismo vivo exposto no ambiente natural. Os resultados sugerem duas assinaturas de REE diferentes nos sedimentos da área, uma natural (background geoquímico sedimentar e água do mar) e outra do contaminante (foscoritos ligados à indústria de fertilizantes e sedimentos superficiais). Essas assinaturas ajudam a compreender o histórico de acumulação de REE e outros elementos nos sedimentos do estuário. Baixa solubilidade de REE foi encontrada como consequência das condições redox do ambiente, sugerindo que os níveis destes elementos presentes na água não colocam em risco a biota exposta. Entretanto, indícios da transferência da assinatura de REE aos organismos analisados foram observados, cujos seus tecidos assimilam assinaturas isotópicas diferentes. Esse comportamento é um resultado de hábitos alimentares de Ucides cordatus e do processo de troca de exoesqueleto destes organismos que conferem vias diferentes de incorporação de REE. A utilização das razões 143Nd/144Nd e 147Sm/144Nd, juntamente com outras ferramentas testadas (R(M/L), R(H/M), (La/Yb)n, (Sm/La)n, (Yb/Sm)n, e correspondência do padrão de REE), mostrou-se como conspícuos traçadores e eficazes ferramentas diagnósticas que liga o substrato sedimentar contaminado à biotaAbstract: This research explores the geochemistry of rare earth elements (REE) in sediments from different depths, their solubility in pore water, and their effects on exposed biota (crabs, Ucides cordatus muscles, and shells) in three subtropical estuarine environments located in southeastern Brazil. These environments are contrasting in terms of industrial and urban human impacts. This novel research proposes the use of REE signatures, elemental and isotopic, as a tool to assess the environmental impacts of these contaminants and the possibility of a transfer between the physical and biotic environment. The isotopic ratio of 143Nd/ 144Nd and 147Sm /144Nd were tested as potential tracers from the source (mineral product used in an industrial process) to the exposed living organism in the natural environment. The results suggested two different REE signatures in the sediments; a natural signature (from the geochemical background and sea water), and a contaminant signature (phoscorites connected to the fertilizer industry and the surface sediments). These signatures helped understand the accumulation history of REEs and other elements in the estuary sediments. Low solubility of REEs were found to be related to the redox environmental conditions, suggesting that present level of these elements in the water does not pose any risk to the exposed biota. However, it was observed that the REE signature could transfer to the analyzed organisms, with each tissue assimilating different isotopic signatures. This behavior is a result of Ucides cordatus eating habits and exoskeleton exchange process, which confer different routes of REE incorporation. The use of 143Nd/144Nd and 147Sm/144Nd, along with other ratios including R(M/L), R(H/M), (La/Yb)n, (Sm/La)n, (Yb/Sm)n and REE pattern matching proved to be conspicuous tracers and effective diagnostic tools connecting the contaminated substrate to biotaDoutoradoGeologia e Recursos NaturaisDoutora em Ciências152059/2011-308-11511-8CNPQFAPES

Tracing rare earth element sources in ucides cordatus crabs by means of Sm-147/Nd-144 and Nd-143/Nd-144 isotopic systematics

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOThis study tested for the first time Sm-147/Nd-144 and Nd-143/Nd-144 ratios as tracers of rare earth element (REE) sources in semi-terrestrial organisms from a subtropical estuary affected by fertilizer industry activities. The isotopic composition of cla22936519FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO08-11511-8,432922/2016-

Fractionation Of Rare Earth And Other Trace Elements In Crabs, Ucides Cordatus, From A Subtropical Mangrove Affected By Fertilizer Industry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms, and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers (contamination source), which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint. (C) 2016 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.546976State of Sao Paulo Research Foundation (FAPESP) [08-11511-8]National Council for Scientific and Technological Development [CNPq- 152059/2011-3]Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Paleoproterozoic manganese oxide precipitation in oxic seawater surface and reductive enrichment in anoxic seafloor

Accelerated precipitation of Mn-rich rocks in the early Paleoproterozoic ocean is considered to reflect the irreversible rise of oxygen in the atmosphere during the Great Oxidation Event (GOE), 2.501–2.220 billion years ago. But the precipitation conditions, pathways, mechanisms, and linkages to ocean redox, broadly remain unresolved. The Lagoa do Riacho Mn deposit in Borborema Province, northeastern Brazil, Ceará state, consists mainly of manganese-rich and manganese-poor silicates deposited during the GOE epoch. Negative Ce anomalies in the manganese-poor silicates point to the scavenging of Ce3+ onto Mn-oxyhydroxide reactive surfaces in the oxygenated surface waters. In contrast, samples with positive Ce anomalies, predominantly associated with the manganese-rich silicates, indicate a reductive dissolution of Mn-oxyhydroxides across a redoxcline, enriching the anoxic bottom water with Ce and Mn2+. A paleoredox reconstruction based on couple Mn, Mo, and U systematics supports the existence of the proposed Mn-oxide redox shuttle that enriched the anoxic sediment pile with Mn precipitated from the oxygenated shallow surface waters. This study uncovers a unique pathway in Paleoproterozoic Mn mineralization involving the transfer of Mn oxides from an oxygenated upper ocean reservoir to a predominantly deep anoxic silicate reservoir that was subsequently metamorphosed. The proposed Mn oxide sink switch mechanism is different from the commonly reported reductive transfer of Mn to a diagenetic carbonate sink during the Paleoproterozoic

Viruses of sulfur oxidizing phototrophs encode genes for pigment, carbon, and sulfur metabolisms

Abstract Viral infections modulate bacterial metabolism and ecology. Here, we investigated the hypothesis that viruses influence the ecology of purple and green sulfur bacteria in anoxic and sulfidic lakes, analogs of euxinic oceans in the geologic past. By screening metagenomes from lake sediments and water column, in addition to publicly-available genomes of cultured purple and green sulfur bacteria, we identified almost 300 high and medium-quality viral genomes. Viruses carrying the gene psbA, encoding the small subunit of photosystem II protein D1, were ubiquitous, suggesting viral interference with the light reactions of sulfur oxidizing autotrophs. Viruses predicted to infect these autotrophs also encoded auxiliary metabolic genes for reductive sulfur assimilation as cysteine, pigment production, and carbon fixation. These observations show that viruses have the genomic potential to modulate the production of metabolic markers of phototrophic sulfur bacteria that are used to identify photic zone euxinia in the geologic past

Fractionation of rare earth and other trace elements in crabs, Ucides cordatus, from a subtropical mangrove affected by fertilizer industry

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertil546976FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO08-11511-8,152059/2011-