Historical deposition of PAHs in mud depocenters from the Southwestern Atlantic continental shelf: The influence of socio-economic development and coal consumption in the last century.

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in four dated sediment cores collected in mud depocenters of the southern Brazilian continental shelf. Core dating results covered the interval between 1925 and 2017. The total PAH concentrations (ΣPAHs) ranged from 44.69 ng g-1 to 305.43 ng g-1 and were similar between the analysed cores. Fine-grained sediments and total organic carbon (TOC) results did not correlate with the ΣPAHs, indicating that the variations in PAH concentrations are mostly related to variations in sources and emissions. PAH source appointment indicated a high input of a natural compound (perylene) and the predominance of anthropogenic PAHs from coal, biomass, and fuel combustion. Alkylated PAHs presented high contributions throughout all cores. The historical deposition of PAHs was associated with different periods of the socio-economic and industrial development of near coastal cities and reflected very well the history of coal production and consumption in the southern region of Brazil. The low levels of ΣPAHs before 1945 in all analysed cores may be related to the beginning of the industrialization process and the lower urbanization degree in the region. Between 1945 and 1965, the gradual ΣPAHs increase reflects the establishment and enlargement of the southern Brazilian industrial sector. The interval between 1965 and 1990 corresponded to the highest ΣPAHs in three of the four analysed cores. After 1990, a relative decrease in the ΣPAHs was observed in most cores and may be related the multiple cuts of incentives to the industrial usage of coal, as well as to Brazil's efforts in environmental regulation for coal extraction and consumption.

Environmental quality survey of an industrialized estuary and an Atlantic Forest Biosphere Reserve through a comparative appraisal of organic pollutants.

An evaluation of the concentrations, bioavailability and sources of polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs) was performed in the industrialized estuary of Santos-São Vicente and in the Cananéia-Iguape estuarine lagoon system, considered an Atlantic forest biosphere reserve, using different approaches. Semipermeable membrane devices (SPMDs) and bivalves (Crassostrea brasiliana) were deployed in both estuarine systems. Samples of water, suspended particulate material (PM), and sediments were also collected in these regions. The concentrations of PAHs in the water and in the PM from both estuarine systems were similar. In the sediment, the concentrations of PAHs and POPs were higher in the estuary of Santos-São Vicente than in the Cananéia-Iguape estuarine lagoon system. The accumulation of PAHs and POPs by the SPMD and C. brasiliana revealed that in both regions the bioavailability of contaminants was similar. Because of the hydrophobicity of the organic compounds, each matrix responded in a different manner to the source of the contaminants; C. brasiliana and sediment were primarily associated with 4-5 ring-PAHs that represent pyrolytic sources of hydrocarbons, whereas water and the SPMDs were correlated with the 2-3 ring-PAHs, which represent petrogenic sources. The PM produced an intermediated concentration among these compartments and was related to the concentration of POPs. Because no significant differences between the mean concentrations of contaminants in both studied regions were observed, anthropogenic effects currently impact the Cananéia-Iguape lagoon system, which was initially considered a pristine area.

From banana fields to the deep blue: Assessment of chlordecone contamination of oceanic cetaceans in the eastern Caribbean.

In the French West Indies (Caribbean), the insecticide Chlordecone (CLD) has been extensively used to reduce banana weevil (Cosmopolites sordidus) infestations in banana plantations. Previous studies have shown high CLD concentrations in freshwater and coastal communities of the region. CLD concentrations, however, have not yet been assessed in marine top predators. We investigated CLD concentrations in cetacean blubber tissues from Guadeloupe, including Physeter macrocephalus, Lagenodelphis hosei, Stenella attenuata and Pseudorca crassidens. Chlordecone was detected in all blubber samples analysed, with the exception of four P. macrocephalus. Concentrations (range: 1 to 329 ng·g-1 of lipid weight) were, however, lower than those found in species from fresh and brackish water. Ecological factors (open ocean habitat), CLD kinetics, and cetacean metabolism (high or specific enzymatic activity) might explain low concentrations found in cetacean blubber. Future analyses that include internal organ sampling would help to confirm CLD levels observed in this study.

Validating the use of biopsy sampling in contamination assessment studies of small cetaceans.

Remote biopsy sampling is the most common technique for acquiring samples from free-ranging marine mammals. However, such techniques may result in variable sampling being sometimes superficial skin and blubber biopsies. For decades, blubber has been used to monitor the exposure of marine mammals to persistent organic pollutants (POPs), but little is known regarding the variability of POPs as a function of blubber depth in small cetaceans and the available literature offers variable results. Thus, the aim of the present study was to validate biopsy sampling for monitoring contaminant concentrations in small, free-ranging cetaceans. Samples from the dorsal blubber of 10 incidentally captured Atlantic spotted dolphins (Stenella frontalis) were separated into two different layers (outer and inner) to investigate the influence of sampling depth on POP concentrations. POP concentrations were compared to those of the full blubber layer. The results revealed no significant differences in lipid content between males and females or among the inner, outer and full blubber layers (p>0.05). Moreover, the wet and lipid weight concentrations of all POP classes analysed [i.e. polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs), polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), chlordanes (CHLs) and mirex] did not differ significantly with blubber depth (p>0.05). POP classes followed the same decreasing order of wet weight concentrations in blubber layers and full blubber: PCBs>DDTs>PBDEs>mirex>HCB>HCHs>CHLs. Moreover, there was a low degree of differentiation in the accumulation of POP congeners. The present findings indicated that the distribution of contaminants was homogenous with blubber depth, which validates the use of biopsy sampling for the assessment of contaminants in small cetaceans.

An assessment of PCB and PBDE contamination in two tropical dolphin species from the Southeastern Brazilian coast.

PCBs and PBDEs were determined in two dolphin species, Sotalia guianensis and Steno bredanensis, from an upwelling system off the Central-northern coast of Rio de Janeiro, Brazil. PCB levels varied from 0.040 to 0.75 µg g(-1) lw in muscles and from 0.022 to 1.32 µg g(-1)lw in liver samples from S. guianensis. In S. bredanensis, values varied from 0.085 to 11.3 µg g(-1) lw in muscles and from 0.024 to 18.6 µg g(-1) lw in livers. PCB-138, -153 and -180 were the major PCB congeners detected in both species, while BDE-47 was the predominant PBDE congener found in both species. Higher concentrations in S. bredanensis were possibly related to the different feeding habits for both delphinid species. These results contribute to extend the database on organic contamination in cetaceans from the southern hemisphere, understanding their distribution and environmental fate in Southeastern Brazil.

A multi-molecular marker assessment of organic pollution in shore sediments from the Río de la Plata Estuary, SW Atlantic.

Organic pollution was evaluated in surface sediments along the middle portion of the Río de la Plata Estuary, SW Atlantic. A multi-molecular marker approach was performed to identify major sources of organic compounds using diagnostic indices. The relative contribution of different sources of hydrocarbons was quantified by source apportionment employing Principal Component Analysis/Multiple Linear Regression (PCA/MLR) as chemometric technique. All molecular markers indicated high chronic organic pollution in the stations of Montevideo Bay. Main sources of aliphatic and polycyclic aromatic hydrocarbons were petroleum inputs and combustion, due to oil transport and refinement, harbour activities and vehicular emissions. Major sources of linear alkylbenzenes and steroids were industrial and domestic sewage. Although, significant anthropogenic inputs, a natural footprint of terrestrial higher plants contribution was recognized. Multi-molecular marker and comprehensive assessments can improve the establishment of more precise regulation actions to reduce pollution levels.

Integrated assessment of multilevel biomarker responses and chemical analysis in mussels from São Sebastião, São Paulo, Brazil.

The aim of the present study was to investigate the presence of contaminants in the mussel Perna perna from São Sebastião Channel, São Paulo, Brazil, and to evaluate the effects of these contaminants on these organisms at biochemical (catalase [CAT], glutathione-S-transferase [GST], and cholinesterase [ChE]), cellular (neutral red retention time [NRRT] assay), and physiological (cardiac monitoring) levels. Two sampling surveys were performed (winter of 2001 and summer of 2002) at six stations along the channel: Cigarras, station 1; Iate Clube de Ilhabela, station 2; Oil Terminal, station 3; Toque Toque, station 4; Ponta da Sela, station 5 (reference station); and Taubaté, station 6. Differences in CAT activity were observed between mussels from stations 3 and 5 during the winter, but no differences were detected in the summer. No differences in GST activity were found among stations during the winter, although animals from station 3 showed higher activity during the summer. The ChE activity was significantly higher in the mussels from stations 1 and 2 during the winter and from stations 1 and 3 during the summer. Organisms from stations 1 through 4 showed statistically lower NRRT in both seasons. Similar heart rates were observed in the mussels from all stations. Hydrocarbons were detected in organisms from all the stations in both seasons. During the winter, higher polycyclic aromatic hydrocarbon (PAH) levels were observed in organisms from station 3, whereas during the summer, higher levels of metals were found in organisms from stations 1, 3, and 4. The multivariate analyses showed a strong influence of PAHs on the winter biological results, but metals showed higher influence on these responses in the summer, indicating multiple contaminant sources.