Biochemical and molecular biomarkers and their association with anthropogenic chemicals in wintering Manx shearwaters (Puffinus puffinus).

Anthropogenic pollution poses a threat to marine conservation by causing chronic toxic effects. Seabirds have contact throughout their lives with pollutants like plastic, metals, polychlorinated biphenyls (PCBs), and organochlorine pesticides such as hexachlorocyclohexanes (HCHs). We assessed 155 Manx shearwaters (Puffinus puffinus) stranded along the Brazilian coast, analyzing associations between organic pollutants, plastic ingestion, biomarkers (transcript levels of aryl hydrocarbon receptor, cytochrome P450-1A-5 [CYP1A5], UDP-glucuronosyl-transferase [UGT1], estrogen receptor alpha-1 [ESR1], and heat shock protein-70 genes) and enzymes activity (ethoxy-resorufin O-deethylase and glutathione S-transferase [GST]). Plastic debris was found in 29 % of the birds. The transcription of UGT1 and CYP1A5 was significantly associated with hexachlorobenzene (HCB) and PCBs levels. ESR1 was associated with HCB and Mirex, and GST was associated with Drins and Mirex. While organic pollutants affected shearwaters more than plastic ingestion, reducing plastic availability remains relevant as xenobiotics are also potentially adsorbed onto plastics.

Persistent organic pollutants and polycyclic aromatic hydrocarbons in livers of stranded Arctocephalus australis in southern Brazilian beaches.

23 livers of South American fur seal (Arctocephalus australis) found stranded in southern Brazilian beaches were evaluated for Persistent Organic Pollutants (POPs) and Polycyclic Aromatic Hydrocarbons (PAHs). POPs (DDTs, mirex, eldrin, dieldrin, aldrin, isodrin, HCHs, chlordanes and PCBs) and PAHs in livers were Soxhlet extracted, analyzed and quantified using Gas Chromatography Tandem Mass Spectrometry (GC-TQMS). The main POPs found were PCBs and DDTs, totaling 81 %. Among pesticides, mirex followed DDTs, possibly due to usage in Uruguay, followed by Σdrins, ΣCHLs and ΣHCHs. Naphthalene was the major PAH found, while heavier compounds did not significantly bioaccumulate. Concentrations of POPs resembled previous findings for A. australis. Considering only juveniles, no POPs showed significant differences between sexes. Lipidic content, weight and length did not show any correlation with POP concentration. This was the first record of PAHs and PBDEs in South American fur seals, and the levels of these pollutants were relatively low.

How does habitat influence metabolism? Clues from biomarker response and contaminant profile in Tursiops truncatus (Montagu, 1821) subspecies living in parapatry.

In western South America (WSA) two subspecies of bottlenose dolphin are recognized: Tursiops truncatus gephyreus, predominantly found in estuaries and river mouths, and Tursiops truncatus truncatus, occurring along the continental shelf. Despite a partial spatial overlap, both subspecies are considered to occupy different habitats and ecological niches. In the present study, chemical analyzes as well as biochemical and molecular biomarkers were used to investigate the influence of niche partitioning over metabolic pathways associated with the detoxification of persistent organic pollutants (POPs), antioxidant metabolism, immune activity and lipid metabolism in Tursiops truncatus subspecies living in parapatry. Overall, the profile and levels of bioaccumulated PCBs, pesticides and PBDEs were similar between groups, with a greater variety of pesticides, such as γ-HCHs, heptachlor, oxychlordane and o,p'DDT, detected in T. truncatus gephyreus. Multivariate analysis of variance (MANOVA) and non-metric multidimensional scaling (NMDS) results indicated that glutathione reductase (GR) and superoxide dismutase (SOD) enzymatic activities were higher in coastal dolphins, as were the mRNA levels of metallothionein 2A (MT2A), interleukin-1α (IL-1α), ceramide synthase 3 (CERS3) and fatty acid elongase (ELOVL4). In parallel, mRNA levels of fatty acid synthase complex 1 (FASN 1) were higher in oceanic dolphins. These findings suggest that, due to their occurrence in coastal habitats, T. truncatus gephyreus is more exposed to environmental pollutants and pathogenic microorganisms. Likewise, niche partitioning may influence lipid biosynthesis, possibly due to differences on feeding habits, reflecting in an enhanced long chain ceramides biosynthesis in T. truncatus gephyreus. Collectively, these data reinforce the need to address habitat specificities in conservation efforts, since distinct groups can be facing different anthropogenic pressures in WSA.

Temporal trends of persistent organic pollutant contamination in Franciscana dolphins from the Southwestern Atlantic.

Persistent organic pollutants (POPs) were analyzed in 136 blubber samples of Franciscana dolphins from Brazil (Pontoporia blainvillei), which is the most threatened dolphin in the Southwestern Atlantic. The dolphins were caught by the fishery fleet and collected from 2000 to 2018 in three regions of São Paulo state: northern São Paulo (SPN), central São Paulo (SPC), and southern São Paulo (SPS). The POPs analyzed in this study were polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), Mirex, hexachlorobenzene (HCB), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and polybrominated diphenyl ethers (PBDEs). The concentrations ranged from 36 to 7200 ng g-1 lipid weight (lw) and 113-42200 ng g-1 lw for predominant compounds DDTs and PCBs, respectively. Similar profiles of PCB congeners were observed with a predominance of hexachlorinated compounds, representing approximately 50% of the total PCB amount; the highest PCB concentrations were observed from Baixada Santista (SPC) proximate to a highly urbanized and industrial coastal area. Significant differences were observed between the sexes and maturity of dolphins, mainly for PCBs, DDTs, and Mirex. In general, POPs other than HCB in Franciscana dolphins showed downward temporal trends, matching the regulatory periods for restricting and/or banning these compounds. Although POP concentrations are declining, PCB levels remain high in small dolphins, suggesting adverse health effects on Franciscanas. As organic contaminants are one of the numerous threats Franciscanas have been vulnerable to along the Brazilian coast, we recommend monitoring POPs levels every five years to check for declining (or stabilizing) trends.

Unusual natural polycyclic aromatic hydrocarbons in sediment cores of an Amazon estuary.

Polycyclic aromatic hydrocarbons (PAHs) most likely derived from natural sources were observed in two sediment cores covering the last 100 years in an Amazon estuarine region. A considerable change in the PAHs main source was observed in the 1960s. Before the 1960s, the sources of PAHs seem to be related to biogenic and/or early-diagenetic processes. Concentrations of perylene were higher before the 1960s and suggest that its primary source to the sediments in the Amazon region is linked to a short-term diagenetic transformation of their biogenic precursors. The natural formation of alkylated PAHs in sediments was linked to the methylation of the parental aromatic hydrocarbons due to sediment maturation processes and the dehydrogenation of sterols in the sediments. The relatively rapid reaction occurring in recent sediments of the Amazon region suggests the importance of the microbial community in the transformation of biogenic precursors to alkylated-PAHs in the sediments.

Anthropogenic and natural inputs of polycyclic aromatic hydrocarbons in the sediment of three coastal systems of the Brazilian Amazon.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 32 surface sediment samples collected around three cities (Barcarena, Belém, and Santana) located on the coast of the Brazilian Amazon. The concentration of total PAHs ranged from lower than detection limit to 33,101 ng g-1 in a sample from Barcarena and was related to a large aluminum industrial complex and port activities. In Belém, which is the most populated area in the Amazon region, PAHs were probably derived from untreated sewage discharge and inputs from a large municipal landfill. Pyrogenic PAHs were predominant in both cities, with a smaller contribution of petrogenic PAHs. Low alkylated PAH levels may be associated with small boats and ship traffic. Santana had low total PAH concentrations, with a predominance of unusual alkylated PAHs, probably related to diagenetic transformations of organic matter in the sediment. In general, PAH concentrations in the samples were low and may reflect baseline levels for this Amazon estuarine system.

Organic contaminants and trace metals in the western South Atlantic upper continental margin: Anthropogenic influence on mud depocenters.

Trace metals, dichloro-diphenyl-trichloroethane (DDTs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) were quantified in surface sediments from mud depocenters located in the western South Atlantic upper continental margin. There was no anthropogenic trace metal pollution observed, and the higher As values were attributed to high CaCO3 content in the area. The results indicate PCB sources associated with long-range atmospheric transport in addition to past DDT use for agriculture and pest control. PAHs were mainly originated from biomass and fossil fuel combustion, and their distribution is in alignment with the riverine runoff influence in southern region, which is transported towards the northern regions by coastal currents. Higher concentrations of 2-3 ring PAHs and DDTs in shallow and northern stations indicate a coastal influence. This work presents baseline information on the extent of anthropogenic influence in mud depocenters located in the western South Atlantic upper continental margin, showing these locations as potential source to sink of anthropogenic contaminants.

Spatial variability in persistent organic pollutants and polycyclic aromatic hydrocarbons found in beach-stranded pellets along the coast of the state of São Paulo, southeastern Brazil.

High spatial variability in polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides, such as DDTs, and polybrominated diphenylethers was observed in plastic pellets collected randomly from 41 beaches (15 cities) in 2010 from the coast of state of São Paulo, southeastern Brazil. The highest concentrations ranged, in ng g(-1), from 192 to 13,708, 3.41 to 7554 and <0.11 to 840 for PAHs, PCBs and DDTs, respectively. Similar distribution pattern was presented, with lower concentrations on the relatively less urbanized and industrialized southern coast, and the highest values in the central portion of the coastline, which is affected by both waste disposal and large port and industrial complex. Additional samples were collected in this central area and PCB concentrations, in ngg(-)(1), were much higher in 2012 (1569 to 10,504) than in 2009/2010 (173 to 309) and 2014 (411), which is likely related to leakages of the PCB commercial mixture.

Historical record of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in marine sediment cores from Admiralty Bay, King George Island, Antarctica.

This paper describes the first results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used to assess the local input of anthropogenic materials (particulate and organic compounds) as a result of the influence of human occupation in a sub-Antarctic region and a possible long-range atmospheric transport of combustion products from sources in South America. The highest SCPs and PAHs concentrations were observed during the last 30 years, when three research stations were built in the area and industrial activities in South America increased. The concentrations of SCPs and PAHs were much lower than those of other regions in the northern hemisphere and other reported data for the southern hemisphere. The PAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustion and sewage contribution generally close to the Brazilian scientific station.

Sedimentary changes on the Southeastern Brazilian upper slope during the last 35,000 years.

A first evaluation of the sedimentary changes, including accumulation of inorganic and organic carbon on the upper slope off Southeastern Brazil under different climatic conditions, based on the analysis of a sedimentary core, is here presented. Results indicate that sedimentation rate as well sedimentary characteristics, including the nature of the organic carbon deposited during the LGM (Last Glacial Maximum), were different from the present deposition, indicating higher primary productivity during the LGM, to be accounted for by the higher values of marine organic carbon. Nevertheless, the higher values of Accumulation Rate of calcium carbonate and organic carbon can be credited to the higher values of the sedimentation rates. Conditions prevailing during Isotope Stage 3 may be considered intermediate as between the LGM and the present day. The conditions for a higher primary productivity associated with the deposition of finer terrigenous sediments may be explained as a response to the off shoreward displacement of the main flow of the Brazil Current.