Assessment of metallic element contamination in sediments from the Santos - São Vicente Estuarine System

Three approaches were applied to evaluate metal contamination in 41 sediment samples from the Santos - São Vicente Estuarine System: normalization to Al, statistical analysis and sediment quality guidelines (SQGs). The results showed increases in the concentrations of Zn, Ni, Pb, Cd, Cr and Hg, which seemed to be associated with human activities. The levels of Al, Fe and Co probably were associated with crustal material or natural weathering processes. About 45% of the samples presented concentrations exceeding TEL-ERL, levels occasionally associated with adverse biological effects. Four of these samples presented concentrations above PEL-ERM, levels frequently associated with adverse biological effects.FAPES

Assessing legacy contaminants in sediments from marine protected areas of the central coast of São Paulo (Brazil)

The presence of legacy contaminants in sediments from three Marine Protected Areas (MPAs) of the coast of São Paulo State was evaluated. Four sampling surveys were conducted between 2013 and 2015 in 10 sites, distributed along the Laje de Santos Marine and Xixova-Japui State Parks (PEMLS and XJSP, respectively) and Central Coast Marine Protection Area (APAMLC). Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb and Zn), aliphatic and polycyclic aromatic hydrocarbons (AH and PAH). Sediments were generally sandy (excepting muddy samples from APAMLC), with variable amounts of TOC, OM and CaCO3. Most of the sediments exhibited low to moderate concentrations of metals, except APAMLC. Low contamination of sediments by hydrocarbons was found but samples from XLSP and APAMLC exhibited the highest concentrations of biogenic AH and PAH from pyrogenic sources. In APAMLC and PEMLS, the levels of metals can be considered as background levels according to geochemical indices (Igeo and EF). In XJSP and especially in APAMLC data indicated poor sediment quality, probably due to the effect of anthropic activities.A contaminação dos sedimentos superficiais foi avaliada neste estudo em amostras de áreas marinhas protegidas (AMP) da costa central de São Paulo. Quatro campanhas de amostragem foram feitas entre 2013 e 2015 em 10 sítios localizados nos Parques Estaduais Marinho da Laje de Santos e Xixová-Japuí (PEMLS e PEXJ, respectivamente), e Área de Proteção Ambiental Litoral Centro (APAMLC). As amostras foram analisadas quanto granulometria, carbono orgânico total, CaCO3, metais (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb e Zn) e hidrocarbonetos alifáticos(AHs) e policíclicos aromáticos (PAHs). Em geral os sedimentos foram arenosos (exceto aqueles de APAMLC, que foram lamosos) e com quantidades variáveis de COT, MO e CaCO3. A maioria das amostras apresentaram baixas concentrações de metais de acordo com índices geoquímicos (Igeo e fatores de enriquecimento - FE). Baixa contaminação por hidrocarbonetos foi encontrada e em APAMLC os sedimentos apresentaram as maiores concentrações de AHs de origem biogênica e PAHs de pirogênicos. Nos sedimentos de APAMLC e PEMLS, os níveis de metais podem ser considerados como valores de referência. Já em PEXJ, os dados indicaram baixa qualidade de sedimentos, possivelmente devido às fontes antrópicas

Assessing the sediment quality of the Laje de Santos marine state park and other marine protected areas of the central coast of São Paulo (Brazil)

Este estudo analisou a qualidade dos sedimentos de três Áreas Marinhas Protegidas (AMP) situadas na porção central do litoral paulista (Parque Estadual Marinho da Laje de Santos - PEMLS; Parque Estadual Xixová-Japuí- PEXJ; Área de Proteção Ambiental Marinha do Litoral Centro - APAMLC). Quatro campanhas de coleta foram organizadas (Setembro/Outobro-2013; Janeiro-2014; Julho-2014; Janeiro-2015). Amostras de sedimento foram coletadas em 10 pontos ao longo das 3 AMP. As amostras foram analisadas para granulometria, carbono orgânico total, CaCO3, metais, hidrocarbonetos alifáticos e policíclico aromáticos, e toxicidade de sedimento integral e interface sedimento-água. Análise de Componentes Principais foi utilizada na integração dos dados. A maioria das amostras exibiu baixa contaminação, exceto a amostra de P2 (APAMLC) onde níveis moderados de contaminantes foram detectados. Sedimentos de P7 e P9 (PEMLS) eventualmente apresentaram sinais de hidrocarbonetos de petróleo. As demais amostras não apresentaram contaminação relevante, mas tiveram toxicidades variáveis, especialmente os sedimentos predominantemente bioclásticos. A PCA indicou forte contribuição das propriedades do sedimento, principalmente CaCO3 e amônia, na geração da toxicidade, indicando que fatores naturais e/ou antrópicos podem estar induzindo a toxicidade nas AMP estudadas.In this study, the quality of sediments from three Marine Protected Areas (MPAs) located on the coast of São Paulo (Laje de Santos Marine State Park - PEMLS; Xixova-Japui State Park - XJSP; and Central Coast Marine Protection Area - APAMLC) was assessed. Four sampling surveys were conducted (September/October 2013; January 2014; July 2014; January 2015). Sediment samples were collected at10 sites, distributed along the 3 MPAs. Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals, aliphatic and polycyclic aromatic hydrocarbons, and for whole-sediment and sediment-water interface toxicities. Principal component analysis (PCA) was used to integrate data. Most of the sediments exhibited low concentrations of chemicals, with the exception of those from P2 (APAMLC) where moderate levels of contaminants were detected. Sediments from P7 and P9 (PEMLS) occasionally showed signs of petroleum hydrocarbons. The other sediments showed no relevant contamination but presented variable toxicity, especially those of bioclastic composition. The PCA indicated a contribution of the sediment properties to the toxicities, especially the CaCO3. In bioclastic sediments, toxicity might be due to physical causes by or any indirect factor such as the presence of ammonia. It was concluded that both natural and anthropic factors are causing toxicity in sediments from the MPAs studied

Environmental monitoring of metals from platinum group elements (Pt, Pd e Rh), in road dust samples collected in high traffic routes of the São Paulo city

Na poeira acumulada nas ruas das cidades (\"road dust\"), encontra-se a presença de platina, paládio e ródio (Elementos do Grupo da Platina, os EGPs) liberados, devido aos desgastes com o uso, pelos catalisadores automobilísticos utilizados nos escapamentos, para controle das emissões de gases poluentes. Amostras de \"road dust\" de algumas das principais vias de tráfego intenso da cidade de São Paulo foram avaliadas quanto aos EPGs em 18 (dezoito) locais estrategicamente escolhidos e amostradas em 3 (três) campanhas de coleta (julho de 2008, julho - agosto de 2016 e julho de 2018). Para a realização deste trabalho foi utilizada metodologia para amostragem, preparação das amostras, digestão, separação dos interferentes da matriz por cromatográfica por troca iônica e a análise dos íons dos EGPs por espectrometria de massa com fonte de plasma, ICP-MS. A separação cromatográfica foi otimizada pelo acompanhamento da manutenção da razão isotópica natural, comprovando-se a eliminação dos íons interferentes durante a separação. A validação da metodologia proposta foi realizada utilizando-se os parâmetros de seletividade, efeito matriz, faixa de trabalho, linearidade, limites de detecção (LD) e de quantificação (LQ), precisão, exatidão e recuperação. Foi estimada a incerteza da medida, composta pela combinação da incerteza analítica e a incerteza de amostragem. Foi calculado o índice de poluição por metais, MPI, e o fator de enriquecimento, EF, dos EGPs. Nessas amostras foram quantificados os elementos nos intervalos: Pt (2,6 - 227 ng g-1), Pd (16,3 - 1875 ng g-1) e Rh (2,02 - 257 ng g-1). Os pontos de coleta das poeiras localizados na Av. da Consolação, na Av. Paulista e na Av. Rebouças, próximo às avenidas Consolação e Paulista, todas regiões com tráfego intenso e lento de veículos, apresentaram os valores mais elevados das concentrações dos EGPs e, portanto, também os maiores índices de poluição, \"metal pollution index\" (MPI), e dos fatores de enriquecimento \"EF\", evidenciando que esses EGPs são originários do desgaste dos catalisadores automotivos. Foram verificadas alterações nas razões entre os EGPs de 2008, 2016 e 2018, principalmente o aumento na concentração de paládio e diminuição na concentração da platina, diferenças essas ocorridas de acordo com as alterações feitas pela indústria automobilística nos catalisadores devido ao alto custo da platina.The presence of platinum, palladium and rhodium (Platinum Group Elements, PGEs) in the road dust comes from the direct release of the automobile catalysts used in the exhausts, to control pollutant gas emissions, due abrasion. Road dust samples from some of the main highways from São Paulo city were evaluated in 18 (eighteen) strategically chosen locations and sampled in 3 (three) collection campaigns (July 2008, July - August 2016 and July 2018). To perform this work, methodology was used for sampling, sample preparation, digestion, separation of matrix interferents by ion exchange chromatography and analysis of the PGEs by mass spectrometry, ICP-MS. The chromatographic separation was optimized by monitoring the maintenance of the natural isotope ratio, proving the elimination of the interfering ions during the separation. The validation of the proposed methodology was performed using the parameters of selectivity, matrix effect, working range, linearity, limits of detection (LD) and quantification (LQ), precision, accuracy and recovery. The measurement uncertainty, compounded by the combination of analytical uncertainty and sampling uncertainty, was estimated. The metal pollution index, MPI, and the enrichment factor, EF, of the PGEs were calculated. In these samples the range quantified of the elements were: Pt (2.6 - 227 ng g-1), Pd (16.3 - 1875 ng g -1) and Rh (2.02 - 257 ng g-1). The dust collection points located on Av. Consolação, Av. Paulista and Av. Rebouças close to Consolação and Paulista avenues, all regions with intense and slow vehicle traffic, presented the highest values of PGEs and therefore, also the highest metal pollution index (MPI) and enrichment factors (EF), showing that these PGEs originate from the wear of automotive catalysts. Changes in the PGEs ratios were observed between the road dust samples from 2008, 2016 and 2018, mainly the increase in the palladium concentration and decrease in the platinum concentration. Differences that occurred according to the changes made by the automotive industry in the catalysts due to the high cost of platinum

Biomagnification of mercury through the food web of the Santos continental shelf, subtropical Brazil

This study was conducted on the continental shelf surrounding a large metropolitan\ud region on the coast of São Paulo State, Southeast Brazil. This region harbours a large industrial plant and the largest port in Latin America, both of which release pollutants into the Santos−São Vicente estuarine system. High levels of Hg have been reported in sediments and fish from the estuaries and Santos Bay; however, data for the biota in offshore waters are scarce, and the biomagnification of Hg across the food web here has never been assessed. In this study, the trophic structure of the Santos shelf was addressed through the carbon and nitrogen stable isotope compositions of different species across a trophic gradient. We determined the total Hg levels (THg, dry weight) of invertebrates and fish to estimate the rate of biomagnification of this metal in the benthic and pelagic food webs. The lowest mean THg levels were found in zooplankton (0.006 μg g−1)\ud and surface-depositivore polychaetes (0.011 μg g−1); the highest THg levels were found in the largest fishes: Patagonian flounder (0.825 μg g−1), fat snook (0.714 μg g−1), and lesser guitarfish (0.639 μg g−1). Overall, the Hg concentration in fish was below the recommended limit for human consumption. The THg and δ15N were positively correlated in both food webs; however, the rate of biomagnification was higher and the basal Hg was lower in the pelagic food web. These differences may be related to the differing bioavailability of mercury in water and sediment, the higher diversity of prey and more complex feeding interactions in the benthic food web, and metabolic differences among different taxa

Uso do bivalve límnico Anodontites tenebricosus (LEA, 1834) no biomonitoramento de metais do Rio Ribeira de Iguape

This study investigated the contamination of the Ribeira de Iguape River - RIR by Cd, Zn, Cr and Pb, using the bivalve Anodontites tenebricosus as a biomonitor. Metal concentrations in tissue samples were measured by HR-ICPMS. Bivalve tissues exhibited mean levels of 1.00 µg/g Cd; 152.89 µg/g Zn; 14.79 µg/g Cr and 4.40 µg/g Pb. Lead concentrations were comparable to those reported for moderately contaminated sites. The results showed that Pb is bioavailable to the bivalves, exhibiting high concentrations and exceeding both natural and reference values for human consumption. The freshwater bivalve Anodontites tenebricosus is a suitable biomonitor of contamination by metals

Assessing legacy contaminants in sediments from marine protected areas of the central coast of São Paulo (Brazil)

Abstract The presence of legacy contaminants in sediments from three Marine Protected Areas (MPAs) of the coast of São Paulo State was evaluated. Four sampling surveys were conducted between 2013 and 2015 in 10 sites, distributed along the Laje de Santos Marine and Xixova-Japui State Parks (PEMLS and XJSP, respectively) and Central Coast Marine Protection Area (APAMLC). Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb and Zn), aliphatic and polycyclic aromatic hydrocarbons (AH and PAH). Sediments were generally sandy (excepting muddy samples from APAMLC), with variable amounts of TOC, OM and CaCO3. Most of the sediments exhibited low to moderate concentrations of metals, except APAMLC. Low contamination of sediments by hydrocarbons was found but samples from XLSP and APAMLC exhibited the highest concentrations of biogenic AH and PAH from pyrogenic sources. In APAMLC and PEMLS, the levels of metals can be considered as background levels according to geochemical indices (Igeo and EF). In XJSP and especially in APAMLC data indicated poor sediment quality, probably due to the effect of anthropic activities

Assessing the sediment quality of the Laje de Santos marine state park and other marine protected areas of the central coast of São Paulo (Brazil)

Abstract In this study, the quality of sediments from three Marine Protected Areas (MPAs) located on the coast of São Paulo (Laje de Santos Marine State Park - PEMLS; Xixova-Japui State Park - XJSP; and Central Coast Marine Protection Area - APAMLC) was assessed. Four sampling surveys were conducted (September/October 2013; January 2014; July 2014; January 2015). Sediment samples were collected at10 sites, distributed along the 3 MPAs. Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals, aliphatic and polycyclic aromatic hydrocarbons, and for whole-sediment and sediment-water interface toxicities. Principal component analysis (PCA) was used to integrate data. Most of the sediments exhibited low concentrations of chemicals, with the exception of those from P2 (APAMLC) where moderate levels of contaminants were detected. Sediments from P7 and P9 (PEMLS) occasionally showed signs of petroleum hydrocarbons. The other sediments showed no relevant contamination but presented variable toxicity, especially those of bioclastic composition. The PCA indicated a contribution of the sediment properties to the toxicities, especially the CaCO3. In bioclastic sediments, toxicity might be due to physical causes by or any indirect factor such as the presence of ammonia. It was concluded that both natural and anthropic factors are causing toxicity in sediments from the MPAs studied