Ana Paula de Castro Rodrigues

Mass balance in the monitoring of pollutants in tidal rivers of the Guanabara Bay, Rio de Janeiro, Brazil.

This study addressed the identification and monitoring of pollution sources of terrestrial origin in rivers (domestic sewage and industrial effluents) and critical fluvial segments in highly polluted environments under tidal influence (mixing marine and continental sources) from Guanabara Bay Basin, Rio de Janeiro, Brazil. The mass balance of contaminants was determined in conditions of continuous flow (low tide) during dry season (lower dilution capability). The results allowed the evaluation of the potential of contaminant mass generation by the different river segments and the estimation of their natural and anthropogenic components. The water quality of Iguaçú and Sarapuí Rivers were evaluated for metals and biochemical oxygen demand. The method gave an excellent response, including the possibility of sources identification and contaminated river segments ranking. The approach also offers fast execution and data interpretation, being highly efficient.

Using a tiered approach based on ecotoxicological techniques to assess the ecological risks of contamination in a subtropical estuarine protected area

This study sought to assess the ecological risks of sediments from the northern portion of an estuarine protected area (Cananéia-Iguape-Peruíbe Protected Area--CIP-PA). The CIP-PA is located on the southern coast of São Paulo State, Brazil and is influenced by former mining activities along the Ribeira de Iguape River (RIR). We used a tiered approach based on multiple lines of evidence (geochemical analyses, toxicity tests, and whole sediment toxicity identification and evaluation) in order to assess environmental quality. The sediments presented a heterogeneous composition, but the samples collected close to the RIR exhibited higher concentrations of metals (Cd, Cr, Cu, Pb) and toxicity. Multivariate analysis showed that toxicity was associated with metals, mud, organic matter, and CaCO3 quantities. The whole-sediment toxicity identification evaluation approach indicated that ammonia and metals were responsible for sediment toxicity. Overall, we concluded that the sediments collected at depositional areas from the northern portion of the CIP-PA presented high levels of metals, which originated from former mining areas located in the upper RIR basin, and that this contamination had toxic effects on aquatic invertebrates. The tiered approach was useful for identifying the degradation of sediment quality and also for indicating the causes of toxicity. Because the CIP-PA is an important estuarine protected area that is ecologically at risk, large-scale measures are required to control the sources of contamination.

Sediment quality in a metal-contaminated tropical bay assessed with a multiple lines of evidence approach

A sediment quality assessment was performed near to the main industrial source of metal contamination in Sepetiba Bay, Brazil, which represents one of the worst cases of trace metal contamination reported for coastal areas. Acute and chronic toxicity tests, benthic fauna community analysis and metal bioavailability evaluations were applied to identify risks to the benthic community. Significant amphipod mortality was observed close to the major pollution source and lower copepod fertility was observed for all stations. Equilibrium-partitioning and biotic-ligand models to predict pore water metal toxicity, which were based on acid-volatile sulfide (AVS) and organic carbon fraction (fOC) normalization approaches, suggested that metals are not likely to be available in sediment pore water. However, Cd, Pb and Zn concentrations were mainly (>50%) weakly bound to sediments, suggesting high potential bioavailability. Linking the chemical results with ecotoxicological responses, we observed that sediment-feeding organisms presented acute and chronic toxicities that were positively correlated to the metal concentrations in the sediments. Additionally, benthic fauna composition was dominated by tolerant species, revealing a trophic structure response to environmental contamination. These results reinforce the necessity of a multiple lines of evidence approach to establish sediment quality and to support environmental management decisions that are based on observed effects and potential extrapolation scenarios into the future.

An alternative approach to bioaccumulation assessment of methyl-Hg, total-Hg, Cd, Pb, Zn in bivalve Anomalocardia brasiliana from Rio de Janeiro bays

We present an alternative approach for establishing in situ bioaccumulation assessment of methyl-Hg (MeHg), total-Hg, Cd, Pb and Zn in bivalve Anomalocardia brasiliana from four bays of Rio de Janeiro presenting varying degrees of eutrophication, acid volatile sulfides (2-55 μmol g-1), simultaneously extracted metals (SEM) and total metals (TM) in sediments. Using metal concentrations of composite samples from three size classes of bivalve and their incorporation rates (IR = metal concentration / total length), which depend on exposure time, we calculated asymptotic IR and respective consequent metal concentrations. Both IR and the metal concentration presented inverse relationships with total length (excepting MeHg) and bay contamination. Lead and zinc concentrations were above Brazilian legal criteria in the most anoxic and contaminated bay, suggesting significant metal bioavailability (SEM/TM between 8% and 63%).

Spatial variability and seasonal toxicity of dredged sediments from Guanabara Bay (Rio de Janeiro, Brazil): acute effects on earthworms

The toxicity of dredged sediments from Guanabara Bay (Rio de Janeiro, Brazil) was evaluated using acute bioassays with Eisenia andrei and metal determination. The sediments were collected in August 2014 (winter) and February 2015 (summer) and in five areas distributed along the Bay: Port of Rio de Janeiro, Port of Niterói, Meriti River mouth, Iguaçu River mouth, and the Environmental Protection Area (APA) of Guapimirim. The sediments were mixed with a ferralsol (a representative Brazilian tropical soil) in proportions varying between 0 (pure soil) and 30%. The acute bioassays with E. andrei followed a standard protocol (ISO 11268-2:2012). Total metal determination in the sediments was performed by ICP-OES. The medium lethal earthworm concentration (LC50) was estimated through PriProbit analysis. The sediments from the APA of Guapimirim, which is a control area at the Guanabara Bay, were the only ones whose total metal concentrations were in agreement with the limits established by Brazilian law for land disposal of dredged sediments. However, the sediments collected in the APA of Guapimirim were the most toxic ones among the study areas due to very high contents of salts in these materials. Winter sediments were generally more toxic compared to the summer ones due to the increase of metal concentrations and salt precipitation to bottom sediments during the winter. The exceptions were (i) the sediments from APA of Guapimirim, where the toxicity in the summer (LC50 = 3.99%) and winter (LC50 = 4.60%) were relatively similar to each other, since the toxicity is linked to salt in excess; and (ii) the Iguaçu River mouth, where the presence of mangrove areas might be associated with the filtering of pollution sources (winter LC50 = 12.67%; summer LC50 = 11.58%). In the Port of Rio de Janeiro, LC50 obtained in the winter (7.30%) was almost three times lower than that found in the summer (19.64%). The sediments from Meriti River mouth showed the highest total metal concentrations, were the most toxic sediments among the study areas (excluding the APA of Guapimirim), and its winter LC50 (6.64%) was almost twice lower than that obtained in the summer (12.55%). By following the same tendency, summer LC50 (17.52%) found for the sediment collected in the Port of Niterói was also higher than the value found in the winter (12.34%). Finally, the dredged sediments from Guanabara Bay were toxic to earthworms in mixtures with pure ferralsol and winter samples were generally more toxic than the summer ones, in agreement with the increase of metal and salt concentrations during the winter.

Metal Bioavailability in Contaminated Estuarine Sediments from a Highly-Impacted Tropical Bay

The aim of this study is to assess possible spatial variability of trace metal (Cd, Cu, Pb and Zn) bioavailability along the main channel of a highly eutrophic tropical estuary (Iguaçu River estuary, Guanabara Bay, Brazil). Metal potentially-bioavailable concentrations (soluble in 1 mol L -1 HCl) and strongly-bound concentrations (soluble in concentrated HNO3) were sequentially extracted and determined by a Coupled Plasma Optical Emission Spectrometry (ICP OES). These sediments generally have high trace metal contents associated to weakly-bound fractions, while Zn was the most bioavailable metal (approximately 83% of Zn concentrations were weakly-bound to sediments) while Cu showed the greatest heterogeneity of proportion between weaklyand strongly-bound fractions. The employed sampling strategy combined results from sediments taken along and across the estuarine channel, evidencing that care is required when using only a single sampling transect along estuarine channels, particularly for metals sensitive to changes in geochemical partitioning during sediment transport and redistribution, as evidenced by the Cu concentrations in this work.