METALS IN SEDIMENTS FROM THE SHELF-SLOPE INTERFACE OFF THE POTIGUAR BASIN OFFSHORE OIL EXPLORATION AREA, NE BRAZIL. Marine sediments collected in November 2009 and July 2011 at depths ranging from 150 m to 2,000 m in the Potiguar Basin, northeastern Brazil, were analyzed for their main sedimentological characteristics (contents of carbon, nitrogen and their stable isotopes) and metals (Al, Fe, Mn, As, Cr, Cu, Ni, Pb, V and Zn) concentrations and their spatial distribution. Sediments were relatively rich in organic matter (C-org: 0.21% to 0.56%) and metals concentrations increased with depth, suggesting an accumulation of fine and terrigenous sediments eroded and transported from the continental shelf to the slope region. Metals concentrations were higher than those observed in coarser shelf sediments, because of sorting of fine-grained sediments. Iron (Fe), Cr and Cu distribution, although presenting this general pattern, also suggests some changes along the transport. Fe and Cr, probably in discrete minerals, are less affected by accumulation in deeper sediments. The high enrichment in Cu, however, suggests additional sources directly to slope sediments, probably by biological productivity and deposition through the water column. The concentrations of all metals are lower or fall close to the lowest range of concentrations reported for slope sediments from other marine regions worldwide and no evidence of anthropogenic contribution was evident.

Abstract Elasmobranchs are long-lived predatory fish that show high Hg concentrations generally reflecting environmental levels, notwithstanding they are widely consumed in Brazil increasing Hg exposure to humans. This study reports on Hg concentrations in largely consumed sharks (Rhizoprionodon porosus) and rays (Hypanus guttatus) from the Pernambuco coast, NE Brazil and the risk associated with their consumption. Muscle tissue concentrations of Hg in H. guttatus and R. porosus varied from 40 to 1,020 ng.g-1 w.w. (median = 125; mean = 124 ± 48 ng.g-1 w.w.) in sharks and from 129 to 2,130 ng.g-1 w.w. (median = 976; mean = 919 ± 139 ng.g-1 w.w.) in rays. Concentrations of Hg positively correlated with size in sharks, but not in rays. Concentrations reflect the local environmental contamination of a large urban center and industrial park concentrated in a short extension of mangrove-dominated coastline (50 km) and are higher compared to other Brazilian sites where Hg concentrations in these species have been reported. Sharks had a risk coefficient (HQ) range of 0.04 to 1.1, not surpassing the reference level of exposure. On the other hand, rays’ HQ ranged from 0.14 to 2.3, and exceeds the reference level of exposure and suggests adverse effects to consumers.

Sepetiba Bay, Rio de Janeiro, Brazil, was home to a zinc smelter until its shutdown in 1998, and during 2011 the remains of the smelter were decommissioned. This study investigates the impact of decommissioning on metal concentrations in the bottom sediments of the bay. In addition to Zn and Cd, Cr, Cu, Ni and Pb are also quantified. The results show that over these 15 years, Cd and Zn concentrations have decreased by 100 and 70%, respectively. Temporal effects are also studied by applying five dated 210Pb cores, which are validated using the Zn and Cd profiles. The observed decrease in the Zn concentration in oysters is correlated with its reduction in the sediment. It was possible to verify the impact of Cr, Cu, Ni and Pb on the sediment quality due to the remaining metallurgical industries in the Sepetiba Bay basin.

Abstract This study compares two mangroves with different land uses in the Jaguaribe River estuary, harboring large shrimp farms, and in the more pristine Pacotí River estuary. Normalized Difference Vegetation Index (NDVI) was used to compare the overall health of the forests. Measures of suspended matter (TSS), total (TP), particulate (PartP) and soluble reactive phosphorus (SRP) in the inflow and outflow waters of tidal channels draining the mangroves were performed during tidal cycles. NDVI varied from 0.65 in the Jaguaribe estuary to 0.85 in the Pacotí, suggesting the impact of shrimp farm effluents on mangrove canopy cover. The shrimp farm influenced site showed 10 times larger absolute ∑P (TP + PartP + SRP) = 1.2-5.2 kg.hr-1) flux than the pristine site (∑P = 0.22 kg.hr-1). Tidal balances showed smaller retentions of the total influx: 28-54%; 44-45%; 38-65% and 8-53% for TSS; TP; SRP; and PartP respectively, in the shrimp farm influenced site to over 93% of the total tidal input of TSS and all P fractions in the pristine mangrove. This suggests that mangrove phosphorus accumulation is decreased in the forest with lower NDVI and limits mangrove’s potential as a natural barrier to the nutrient transport to adjacent estuarine and coastal waters.

Abstract: The present work tests the use of carapace fragments of the marine turtle Caretta caretta as a tool for environmental biomonitoring of mercury (Hg) and to evaluate the influence of biological and ecological factors in Hg concentrations. Samples of carapace fragments were obtained during the nesting season of 2012 and 2016 and were analyzed for their total-Hg and methyl-Hg concentrations and the isotopic composition of carbon and nitrogen (δ15N and δ13C). Seventy-six females were sampled, with an average size of 87.1 to 107 cm of curved carapace length (CCL). The results showed a wide variation in total Hg concentrations (3.3 – 1,672 ng g-1) and low concentrations of methyl-Hg, not showing any pattern of accumulation among the individuals. The isotopic composition of δ15N and δ13C suggests that the individuals sampled belong to a high trophic level but did not present any relationship with the Hg concentrations. It suggests that, at least with the existing results, and unlike other turtle species, carapace fragments of C. caretta cannot yet be used in environmental monitoring.

Abstract This work reviews the limnology of the largest multi-use reservoir in NE Brazil, the Castanhão Reservoir in Ceará State, during 5 years of an extended drought when the reservoir’s volume decreased from 88% to about 30%. Major physical and chemical parameters of the water column, phytoplankton community, trophic state and sediment geochemistry were monitored, as well as the impact from extensive aquaculture. Water quality of the full reservoir was maintained due to hydrodynamics, which transport nutrients to the hypolimnion of a stratified water column, rendering an oligotrophic state to the reservoir, notwithstanding the large nutrient inputs from aquaculture and irrigated agriculture. However, with the extension of the drought period, the reservoir volume reduced, decreasing water depth leading to breaking of the thermocline due to wind forcing, and mixing the entire water column. This increased turbidity, nutrient availability and primary productivity, also changed phytoplankton functional groups. As a result, at the end of the monitoring period, when the reservoir attained its lowest volume, its trophic state became eutrophic. Under a scenario of climate change, where annual precipitation is decreasing, human uses of reservoirs in the semiarid should be very restricted to maintain water quality proper for human use.

Manguezais funcionam como proteção natural para a linha da costa em casos de erosão e inundação, provendo importantes serviços ambientais. Devido à distribuição geográfica desse habitat na interface continente-oceano, é muito provável que sofra sérios impactos oriundos das mudanças climáticas, potencializados por atividades humanas na zona costeira. Esse trabalho revisa os resul tados de estudos realizados nos últimos 25 anos sobre as respostas observadas dos manguezais às alterações ambientais causadas tanto por alterações climáticas. Foram levados em consideração 104 estudos de caso e de modelagem no mundo todo. A maioria desses estudos foi publicada depois do ano 2000 como um reflexo do relatório publicado pelo IPCC em 1997. Apesar de muitos estudos mostrarem uma diminuição global da área de manguezais no mundo devido à pressão antrópica direta, vários outros mostraram que, localmente, uma variedade de habitats de manguezal está se expandindo como uma resposta à mudança climática global. Em todo o mundo, uma migração em direção aos polos está ampliando os limites latitudinais de manguezais devido a invernos mais quentes, e a diminuição de eventos de baixas temperaturas extremas, enquanto nas baixas planícies costeiras os manguezais estão migrando continente adentro devido ao aumento do nível do mar, como observado para o litoral nordeste brasileiro. Levando em consideração apenas as alterações climáticas globais, os manguezais irão exibir uma resposta positiva na maior parte de sua área de distribuição. Em algumas áreas, no entanto, como ilhas oceânicas baixas, como no oceano pacífico e no Caribe, e zonas costeiras restritas, como no litoral sudeste do Brasil, os manguezais mais provavelmente não sobreviverão.

Mangroves function as a natural coastline protection for erosion and inundation, providing important environmental services. Due to their geographical distribution at the continent-ocean interface, the mangrove habitat may suffer heavy impacts from global climate change, maximized by local human activities occurring in a given coastal region. This review analyzed the literature published over the last 25 years, on the documented response of mangroves to environmental change caused by global climate change, taking into consideration 104 case studies and predictive modeling, worldwide. Most studies appeared after the year 2000, as a response to the 1997 IPCC report. Although many reports showed that the world's mangrove area is decreasing due to direct anthropogenic pressure, several others, however, showed that in a variety of habitats mangroves are expanding as a response to global climate change. Worldwide, pole ward migration is extending the latitudinal limits of mangroves due to warmer winters and decreasing the frequency of extreme low temperatures, whereas in low-lying coastal plains, mangroves are migrating landward due to sea level rise, as demonstrated for the NE Brazilian coast. Taking into consideration climate change alone, mangroves in most areas will display a positive response. In some areas however, such as low-lying oceanic islands, such as in the Pacific and the Caribbean, and constrained coastlines, such as the SE Brazilian coast, mangroves will most probably not survive.

Este estudo é uma avaliação das taxas de sedimentação na região do delta do Rio Paraíba do Sul e sua correlação com a forte erosão que ocorre em Atafona, Rio de Janeiro. Os resultados obtidos são baseados 14 testemunhos de sedimentos, com um total de aproximadamente 540 amostras, coletados em janeiro de 2010 e fevereiro de 2011. Os inventários de 210Pb nos pontos de amostragem ao sul da desembocadura do Rio Paraíba do Sul foram maiores do que aqueles observados para os pontos de coleta na região norte e central, o que sugere que os sedimentos são transportados ao longo da costa com as correntes nesta direção. Os resultados da datação 210Pb foram validados com base na variação de concentração elementar ao longo de dois dos testemunhos. Concentrações de Cd e Zn aumentaram significativamente em 1982 e atingindo valores máximos (0,5 mg kg-1 e 139 mg kg-1, respectivamente) em 1984. Estes máximos correspondem ao acidente da indústria Cia Paraibuna de Metais, que ocorreu em 1982.

This study aims to evaluate sedimentation rates in the Paraíba do Sul estuary and its shelf regions. These sedimentation rates were correlated with strong erosion occurring in Atafona, Rio de Janeiro. The results were based on four transects, from which 14 sediment cores with approximately 540 sediment samples were collected in January 2010 and February 2011. At sampling points south of the Paraíba do Sul River (PSR) mouth, 210Pb inventories were higher than those at the northern and central sampling locations, suggesting that sediment is transported southward by the alongshore current. The 210Pb dating results were validated based on the elemental concentration variation throughout two of the sediment cores. Heavy metal concentrations, such as Cd and Zn, increased significantly in 1982 and reached maximum values (0.5 mg kg-1 and 139 mg kg-1, respectively) in 1984. These maxima correspond to the Cia Paraibuna de Metais industry accident, which occurred in 1982.

Fluxos de Hg foram determinados entre 2005 e 2009 nas estações seca e chuvosa no estuário do Rio Jaguaribe, que desagua no Oceano Atlântico Equatorial, NE do Brasil. Na estação chuvosa a massa d'água no estuário apresenta um curto tempo de residência no estuário (0,8 dias), quatro vezes menor que na seca (3,1 dias). As concentrações e fluxos de Hg dissolvido (< 0,7 µm) e particulado foram maiores na interface rio/estuário que na estuário/mar, acumulando Hg particulado na região estuarina. A exportação de Hg particulado (1,8 a 12,6 mg s-1) ao oceano ocorreu sob chuva extrema, enquanto a exportação de Hg dissolvido foi quase zero na estação chuvosa e de até 0,45 mg s-1 na seca. Como a lixiviação continental no semiárido é afetada por mudanças climáticas globais e dos usos da terra, um aumento da acumulação de Hg particulado nos estuários e uma maior exportação de Hg dissolvido para o oceano é esperada.

Mercury fluxes were measured during the dry and rainy seasons (2005 to 2009) at the Jaguaribe River estuary, which discharges into the Equatorial Atlantic Ocean in NE Brazil. During rainy periods, the water masses exhibited a short residence time within the estuary (0.8 days). During dry periods, seawater choked the fluvial discharge, resulting in longer residence times (3.1 days). Dissolved (< 0.7 µm) and particulate Hg concentrations and fluxes were greater from the river to the estuary than from the estuary to the sea, producing accumulated particulate Hg in the estuary. Particulate Hg export (1.8 to 12.6 mg s-1) to the ocean occurred during extremely rainy periods, while dissolved Hg export was practically nonexistent during rainy periods and increased up to 0.45 mg s-1 during dry periods. Because continental runoff in semi-arid regions is affected by land use and global climate changes, the increasing accumulation of particulate Hg in the estuaries and increasing export of dissolved Hg to the ocean are expected.

As concentrações de Hg em fragmentos de carapaça de Chelonia mydas no litoral do Ceará, nordeste do Brasil, são reportadas. Concentrações variaram de <0,34 a 856,6 ng.g -1 em peso seco, e foram maiores (média de 154,8 ng.g -1 em peso seco) em indivíduos juvenis (n = 22), enquanto que as menores concentrações (média de 2,5 ng.g -1 em peso seco) foram observadas em indivíduos adultos/sub-adultos (n = 3). Houve uma correlação negativa significativa entre tamanho do animal e concentração de Hg provavelmente devido a diferença de dieta entre juvenis e sub-adultos/adultos. Fragmentos de carapaça, que constituem substratos não-invasivos e não letais, podem ser importantes para fins de monitoramento ambiental dessas espécies ameaçadas de extinção.

Mercury concentrations in carapace fragments of the green turtle Chelonia mydas from the Ceará coast in NE Brazil are reported. Concentrations varied from <0.34 to 856.6 ng.g -1 d.w., and were highest (average of 154.8 ng.g -1 d.w.) in juveniles (n = 22), whereas lowest concentrations (average of 2.5 ng.g -1 d.w.) were observed in adult/sub-adult animals (n = 3). There was a significant negative correlation between animal size and Hg concentration probably due to different diets between juveniles and sub-adults/adults. Carapace fragments, which are non-invasive, non-lethal substrates, may be of importance for monitoring purposes of these generally endangered species.

Foram estudadas as alterações na hidroquímica e na distribuição de Hg em águas do Rio Madeira entre Porto Velho (RO) e a confluência com o Rio Amazonas (AM) em dois cruzeiros realizados em 1997 e 2002. A condutividade da água foi similar nos dois períodos, porém o pH foi significativamente maior em 2002, principalmente ao longo da porção média do curso do rio. A concentração do material suspenso total também aumentou de 1997 a 2002, nesta mesma porção do rio, o que é um resultado da conversão de florestas para outros usos, principalmente pastos e agricultura, que foi intensificada no intervalo entre os dois cruzeiros. As concentrações de Hg dissolvido foram similares ao longo do rio nos dois cruzeiros, mas as concentrações de Hg particulado aumentaram significativamente ao longo da porção média de seu curso, embora em 2002 a concentração de Hg no material particulado fosse menor que aquela verificada em 1997. Uma vez que o Hg particulado representou mais de 90% do total do Hg presente na água, ocorreu um aumento significativo no transporte de Hg total pelo Rio Madeira. Embora o garimpo de ouro tenha praticamente cessado na região, a remobilização de Hg pela conversão de solos florestais para ouros usos é responsável pela manutenção de níveis relativamente elevados de Hg no meio ambiente do Rio Madeira.

Changes in hydrochemistry and Hg distribution in the Madeira River from Porto Velho to the confluence with the Amazon River were studied in two cruises in 1997 and 2002. Water conductivity was similar in both periods, but the pH was significantly higher in 2002, in particular along the middle reaches of the river. Total suspended matter concentrations also increased from 1997 to 2002 along the same river portion, which is a result of forest conversion to other land uses, in particular pastures and agriculture accelerated during the interval between the cruises. Dissolved Hg concentrations were similar along the river in both cruises, but particulate Hg concentrations increased significantly along the middle portion of the river, although the suspended matter from 2002 was relatively poorer in Hg compared to that from 1997. Since particulate Hg represents more than 90% of the total Hg present in the river water, there was a significant increase in the total Hg transport in the Madeira River. Although gold mining has nearly ceased to exist in the region, the remobilization of Hg from forest soils through conversion to other land uses is responsible for maintaining relatively high Hg content in the Madeira River environment.

O objetivo desse trabalho foi otimizar uma metodologia semi-automática utilizando cartuchos comerciais preenchidos com ouro puro (Tekran Inc.) para a quantificação de mercúrio gasoso elementar em atmosfera tropical. O limite de detecção foi 0,020 ± 0,006 ng de Hg. Isso corresponde a limites de detecção variando entre 0,2 e 0,4 ng m-3, para volumes de amostragem entre 0,1 e 0,05 m³. A similaridade entre os 9 cartuchos foi avaliada. A avaliação do efeito da vazão de amostragem entre 0,4 e 2,0 L min-1 não representou diferença. A capacidade máxima de retenção dos cartuchos (breakthrough) não foi alcançada nos experimentos com vazão de 1 ou 2 L min-1, concentração de Hg de 25 ng m-3 e volume máximo de 150 L. A condensação de água na superfície do ouro mostrou ser um problema, mas isso foi solucionado com o aquecimento do cartucho de amostragem a 60 ºC.

The aim of this study was to optimize a semi-automatic methodology using commercial pure gold cartridges (Tekran Inc.) to quantify gaseous elemental mercury (GEM) in the Amazon atmosphere. The detection limit was 0.020 ± 0.006 ng Hg. This corresponds to detection limits varying from 0.2 to 0.4 ng Hg m-3, for field sample volumes ranging between 0.1 and 0.05 m³. The similarity between the 9 tested cartridges was evaluated. Under sampling flow rates varying between 0.4 and 2.0 L min-1 no difference among cartridges was observed. The maximum retention capacity of the cartridge (breakthrough) was not reached in experiments with flow rates of 1 or 2 L min-1, and with Hg concentration of 25 ng m-3 and maximum air volume of 150 L. Water condensation on the gold surface showed to be a problem, but that was solved by heating the sample cartridge at 60 ºC during sampling.

A acumulação de Hg foi investigada em testemunhos sedimentares da Baía de Guanabara, Rio de Janeiro, Brasil, amostrados ao longo de um gradiente de eutrofização, que se refletiu na qualidade física dos sedimentos e na distribuição de carbono orgânico total (COT). Sedimentos da área oeste da baía foram fortemente afetados por aportes de efluentes domésticos e industriais, apresentando concentrações de Hg de até 7500 ng g-1 e inventários de Hg de até 786 mg m-2, em contraste com valores próximos aos de background encontrados na área nordeste (< 65 ng g-1 e 10,6 mg m-2). Uma mudança de uma relação negativa para uma positiva entre Hg e COT ocorreu no estuário mais eutrofizado, no qual um aumento nos níveis de Hg no sentido do topo foi observado. Este aumento pode ser atribuído a (i) um crescente aporte fluvial de Hg e (ii) um impacto da eutrofização sobre a qualidade dos sedimentos, que pode aumentar a sua capacidade de acumular Hg associado à matéria orgânica.

The accumulation of Hg was investigated in sediment cores from Guanabara Bay, Rio de Janeiro, Brazil, sampled along an eutrophication gradient, which was reflected in the sediment physical quality and total organic carbon (TOC) distribution. Sediments from the western bay area are strongly affected by inputs of urban and industrial effluents, showing Hg concentrations up to 7500 ng g-1 and Hg inventories up to 786 mg m-2, in contrast with near-background values found in the northwestern bay area (< 65 ng g-1 and 10.6 mg m-2). A shift from a negative to a positive relationship between Hg and TOC occurred in the most eutrophicated estuary, in which an upward increase in the recorded Hg levels was observed. This increase may be attributed to (i) an increasing riverine Hg input and (ii) an impact of eutrophication on the sediment quality, which may enhance the sediment capacity to accumulate organic matter-bound Hg.

Este estudo descreve as mudanças na especiação de Hg nas águas da Baía de Sepetiba, SE, Brasil, ao longo do gradiente estuarino, durante eventos de maré em diferentes estações. A avaliação química das águas da baía indicou uma exportação de material particulado em suspensão (MPS) pobre em carbono orgânico para a plataforma continental adjacente, principalmente durante a estação chuvosa e uma importação de MPS oceânico rico em carbono orgânico, provavelmente de origem fitoplanctônica, durante a estação seca. A especiação química do Hg demonstrou que a produção de Hg0 na Baía de Sepetiba pode ser controlada pela produtividade primária, e que a baía atua como produtora e exportadora de formas orgânicas de Hg para as áreas adjacentes, já que as maiores concentrações de Hg não-reativo foram encontradas durante a maré vazante. Não foram observadas correlações significantes entre as concentrações de Hg não-reativo e carbono orgânico dissolvido ou particulado. Em geral, as frações de Hg particulado, Hg não-reativo e Hg reativo representam 55%, 35% e 9,5% do conteúdo total de Hg nas águas da Baía de Sepetiba, respectivamente.

This work describes changes in Hg speciation in water along the transport from Sepetiba Bay, SE Brazil, to the adjacent continental platform during tide events and in different seasons. The chemical evaluation of Sepetiba Bay waters showed that the bay exports suspended particulate material (SPM) impoverish in organic carbon to adjacent continental platform areas, mainly during the wet season and imports SPM enriched in organic carbon from the ocean, probably of phytoplanktonic origin, during the dry season. The chemical speciation of Hg during the study period showed that Hg0 production can be controlled by primary productivity and that the bay acts as a producer and exporter of organic species of Hg to adjacent areas, since the highest non-reactive Hg concentrations were observed during the ebb tide. No significant correlations were found between non-reactive Hg and dissolved or particulate organic matter concentrations. In general the particulate Hg, non-reactive Hg and reactive Hg fractions represents 55%, 35.5% and 9.5% of the total Hg content in Sepetiba Bay waters, respectively.

As concentrações totais de Hg foram medidas em amostras de deposição atmosférica total coletadas em três regiões costeiras do Estado do Rio de Janeiro, sudeste do Brasil entre Outubro de 1998 e Dezembro de 1999. Amostras foram coletadas em Campos dos Goytacazes, área agrícola no norte do estado, em Niterói, região urbanizada e industrializada, e em Itacuruçá, um pólo turístico no litoral sul. As concentrações de Hg em Campos apresentaram uma média de 0,51 ng L-1, variando de 0,07 a 1,01 ng L-1, e mostraram uma tendência sazonal aparentemente afetada pela queima da cana de açúcar no inverno. Em Niterói, foram medidas as maiores concentrações, com média de 0,73 ng L-1 e variando de 0,06 a 2,95 ng L-1, sem padrão de distribuição sazonal definido. Em Itacuruçá, 35% das amostras apresentaram concentrações menores que o limite de detecção do método (<0,02 ng L-1), com média de 0,24 ng L-1 e variando entre <0,02 a 1,04 ng L-1.

Total Hg concentrations were measured in bulk atmospheric deposition from three sampling stations along the Rio de Janeiro State coast, Southeast, Brazil, from October 1998 to December 1999. Samples were collected at Campos dos Goytacazes, an agriculture center at the North coast; Niterói, an industrialized metropolitan area and at Itacuruçá, a tourist town at the South. Concentrations at Campos average 0.51 ng L-1, ranging from 0.07 to 1.01 ng L-1, and showed a seasonal trend, probably affected by burning of sugar cane plantations in winter. At Niterói, concentrations were highest, averaging 0.73 ng L-1 andranging from 0.06 to 2.95 ng L-1. No pattern of temporal variation was observed and concentration peaks are probably related to industrial emissions. At Itacuruçá, Hg concentrations were below the detection limit of the method (0.02 ng L-1) in 35% of the samples, with an average of 0.24 ng L-1 and ranging from <0.02 to 1.04 ng L-1.