Offshore oil spills in Brazil: An extensive review and further development.

The present study offers an extensive overview on the evolution and current state of marine oil spill research in Brazil and then discusses further directions. Given the historical and current relevance of this issue, this paper also aims to summarize the exploration, geological background, design of oil spills timeline and assessment of the most important of them. Moreover, it includes a critical comparison of Brazilian oil spill models in terms of their simulation abilities, real-time field data assimilation, space and time forecasts and uncertainty evaluation. This study also presents the perspectives of the Multi-User System for Detection, Prediction, and Monitoring of Oil Spills at Sea (SisMOM) the largest and most important Brazilian project to face the offshore oil spills.

Sources and temporal patterns of polychlorinated biphenyls around a large South American grain-shipping port (Paranaguá Estuarine System, Brazil).

The Paranaguá Estuarine System (PES) is an important estuarine environment on the Brazilian coast. The economic importance of the PES is mainly related to industries, fuel terminals, and the main South American grain-shipping port. The aim of this work was to determine the vertical distribution of polychlorinated biphenyls (PCBs) in three sediment cores from the PES. The methods included Soxhlet extraction, clean-up, and quantification by gas chromatography with electron capture detection. The concentrations of total PCBs ranged from lower than the detection limit to 6.65 ng g(-1). Low PCB concentrations were detected in P1 and P3, which were collected far away from direct human activities. In P2, the compositional pattern of PCB congeners showed greater concentrations of tetra- and penta-chlorinated congeners associated with urban and port activities near Paranaguá city. The differences in concentrations between the three sediment cores were attributed to the distance of the sampling points in relation to the possible sources of pollution, which are mostly related to Paranaguá city. The vertical distribution of PCBs in the sediment core P2 was related to historical anthropogenic activities. The highest PCB input was from 1970 to the early 1990s, which coincides with a period of greater use of PCBs in Brazil as well as their greater worldwide production.

Persistent organic pollutant patterns in seabirds from marine protected areas in the tropical Atlantic Ocean.

Persistent organic pollutants were investigated in the blood of living seabirds (Pterodroma arminjoniana, Onychoprion fuscatus, Sula dactylatra, Anous minutus, Anous stolidus and Sula leucogaster) from two Brazilian Conservation Units - Trindade Island and São Pedro and São Paulo Archipelago. ∑PCBs (0.55 to 55.09 ng/g wet weight (ww), ∑DDTs (0.01 to 17.36 ng/g ww) and Mirex (0.01 to 5.53 ng/g ww) were predominant in all samples. Trindade petrel Pterodroma arminjoniana presented higher values than other seabirds, which is potentially related to diet and migratory behavior. Fluctuations in the trophic ecology data, through carbon and nitrogen stable isotope ratios, warn of temporal variation in diet and foraging and highlight the importance of using a nondestructive matrix to allow long-term monitoring of POP contamination in seabirds from Brazilian Conservation Units. In addition, the data will fill the gaps in the POP baselines for seabirds from the tropical Atlantic Ocean.

Mobilization of persistent organic pollutants in humpback whales: Insights from feeding areas in the Antarctic peninsula and Strait of Magellan to migration, breeding, and calving grounds along the Brazilian coast.

Southern Hemisphere Megaptera novaeangliae undertake the longest migration, which reflect their exposure to lipophilic contaminants. To assess these changes, persistent organic pollutants were analyzed in blubber samples of humpback whales from three regions: the Antarctic Peninsula (n = 46), the Strait of Magellan, Chile (n = 22), and the Brazilian coast (n = 38). The similarity in PCB and HCB levels between individuals from feeding grounds and breeding grounds suggests contamination during feeding. The whales around the Antarctic Peninsula exhibited a predominance of tetrachlorobiphenyl PCBs. Whales feeding in the Strait of Magellan showed a slight prevalence of 5Cl biphenyls, likely due to their consumption of subantarctic krill species as well as small fishes potentially contaminated by industrial activities in Chile. The dominance of 5-6Cl congeners in whales in Brazil, may be attributed to the extreme physiological changes during fasting when whales utilize blubber reserves and metabolize lighter congeners, or transfer them to their calves.

Evaluation of tropical water sources and mollusks in southern Brazil using microbiological, biochemical, and chemical parameters.

Florianópolis, a city located in the Santa Catarina State in southern Brazil, is the national leading producer of bivalve mollusks. The quality of bivalve mollusks is closely related to the sanitary conditions of surrounding waters where they are cultivated. Presently, cultivation areas receive large amounts of effluents derived mainly from treated and non-treated domestic, rural, and urban sewage. This contributes to the contamination of mollusks with trace metals, pesticides, other organic compounds, and human pathogens such as viruses, bacteria, and protozoan. The aim of this study was to perform a thorough diagnosis of the shellfish growing areas in Florianópolis, on the coast of Santa Catarina. The contamination levels of seawater, sediments, and oysters were evaluated for their microbiological, biochemical, and chemical parameters at five sea sites in Florianópolis, namely three regular oyster cultivation areas (Sites 1, 2, and oyster supplier), a polluted site (Site 3), and a heavily polluted site (Site 4). Samples were evaluated at day zero and after 14 days. Seawater and sediment samples were collected just once, at the end of the experiment. Antioxidant defenses, which may occur in contaminated environments in response to the increased production of reactive oxygen species (ROS) by organisms, were analyzed in oysters, as well as organic compounds (in oysters and sediment samples) and microbiological contamination (in oysters and seawater samples). The results showed the presence of the following contaminants: fecal coliforms in seawater samples (four sites), human adenovirus (all sites), human noroviruses GI and GII (two sites), Hepatitis A viruses (one site), JC Polyomavirus in an oyster sample from the oyster supplier, Giardia duodenalis cysts, and Cryptosporidium sp oocysts (one site). Among organochlorine pesticides, only DDT (dichlorodiphenyltrichloroethane) and HCH (hexachlorocyclohexane) were detected in some sediment and oysters samples in very low levels; site 4 had the highest concentrations of total aliphatic hydrocarbons, PAHs, and linear alkylbenzenes (LABs) found either in oysters or in sediment samples. The major concentration of fecal sterol coprostanol was found at site 4, followed by site 3. After 14 days of allocation in the four selected sites, there was a significant difference in the enzymes analyzed at the monitored spots. The detection of different contaminants in oysters, seawater, and sediment samples in the present study shows the impact untreated or inadequately treated effluents have on coastal areas. These results highlight the need for public investment in adequate wastewater treatment and adequate treatment of oysters, ensuring safe areas for shellfish production as well as healthier bivalve mollusks for consumption.

Persistent organic pollutants and contaminants of emerging concern in spinner dolphins (Stenella longirostris) from the Western Atlantic Ocean.

The presence and distribution of persistent organic pollutants (POPs) and contaminants of emerging concern (CECs) were evaluated in spinner dolphins (Stenella longirostris) from the Fernando de Noronha Archipelago (Western Atlantic Ocean). Blubber samples (n = 37) were Soxhlet extracted and analyzed using gas chromatography tandem mass spectrometry. The levels of POPs reported in this study are far below those previously reported in spinner dolphins from the Indian and Pacific Oceans. Despite relatively low levels of contaminants, the presence of chemicals represents an additional stressor to these marine mammals, which are subject to increasing anthropogenic pressures, especially regarding tourism activities, in Fernando de Noronha.

Assessment of crabs from Trindade, a Brazilian remote island: Support to marine studies.

Trindade is a remote island far from 1170 km of the Brazilian coast in the Atlantic Ocean, between South America and South Africa. The island has great biodiversity and scientific studies on the fauna and flora of Trindade are still scarce. Accordingly, since crustacean species of the island are also little known, this research features an unprecedented data set, which provides information on the level of potential toxic elements in two crab species: the Grapsus grapsus (herbivore) and the endemic species Gecarcinus lagostoma (omnivorous) which is in threatened status. Although Trindade has experienced contamination from human activities, mainly plastic debris, the element levels found in the samples suggest that there are no relevant inorganic sources into the island. Since minor and trace elements accumulated by marine invertebrates does not present a pattern behavior, our results can support other studies focused on the impact of global warming to the marine ecosystem.

Incidence of anthropogenic material in Sula leucogaster nests in a distant archipelago of Brazil.

Anthropogenic debris has been affecting fauna in different ways. We investigate the frequency of anthropogenic material in nests of a brown booby (Sula leucogaster) colony in the Saint Peter and Saint Paul Archipelago (SPSPA), Rio Grande do Norte, Brazil in February 2015 and November 2016. The items were classified according to type (threadlike plastic, sheet plastics, hard fragments, foamed synthetics and miscellaneous) and color. In 2015, a total of 30 anthropogenic items were found in 20.4% of the nests. In nests containing debris, miscellaneous items were found in 73.6% of nests. White/clear was the most common color, 52.6% of nests containing debris had items of this color. In 2016, 45 anthropogenic items were observed in 13.3% of the nests. Threadlike plastic was found in 59.2% of nests. Blue/purple was the most common color (55.5%). Even far from the Brazilian coast, the S. leucogaster colony has been affected by marine pollution.

Bioavailability of polycyclic aromatic hydrocarbons to penguins on the coast of southeastern Brazil.

Bioavailability of polycyclic aromatic hydrocarbons on São Paulo state coast (southeastern Brazil) was evaluated through the analysis of biliary metabolites in Spheniscus magellanicus (n = 79). The animals analyzed in present study were either found dead during beach monitoring procedures or died at rehabilitation centers. Analyses of naphthalene (NAP), phenanthrene (PHE) and benzo[a]pyrene (BaP) metabolites were performed using a high-performance liquid chromatograph equipped with fluorescence detectors. Total metabolite (TM) concentrations ranged from below the method quantification limit to 270 µg g-1 of bile. TM concentrations were mainly composed of NAP metabolites, followed by PHE metabolites. BaP metabolites were detected in only two samples. This is the first study using PAHs metabolites in S. magellanicus to assess the bioavailability of these compounds in coastal regions.

Biochemical and molecular biomarkers in integument biopsies of free-ranging coastal bottlenose dolphins from southern Brazil.

Adverse effects of exposure to persistent organic pollutants (POPs) threaten the maintenance of odontocete populations. In southern Brazil, coastal bottlenose dolphins from the Laguna Estuarine System (LES) and Patos Lagoon Estuary (PLE) were sampled using remote biopsies during the winter and summer months. Levels of bioaccumulated POPs were measured in the blubber. The activities of glutathione S-transferase (GST), glutathione reductase (GR), glutathione peroxidase (GPx), and superoxide dismutase (SOD) were also quantified, as were the mRNA transcript levels of aryl hydrocarbon receptor (AhR), AhR nuclear translocator (ARNT), cytochrome P450 1A1-like (CYP1A1), metallothionein 2A (MT2A), GST-π, GPx-4, GR, interleukin 1 alpha (IL-1α), and major histocompatibility complex II (MHCII) in the skin. In general, levels of POPs were similar among sites, sexes, ages and seasons. For most animals, total polychlorinated biphenyl (ΣPCBs) levels were above the threshold level have physiological effects and pose risks to cetaceans. The best-fitting generalized linear models (GLMs) found significant associations between GR, IL-1α and GPx-4 transcript levels, SOD and GST activities, and total polybrominated diphenyl ether (ΣPBDEs) and pesticide levels. GLMs and Kruskal-Wallis analyses also indicated that there were higher transcript levels for most genes and lower GST activity in the winter. These results reinforce the need to consider the influence of environmental traits on biomarker values in wildlife assessments.

Transplacental transfer of persistent organic pollutants in La Plata dolphins (Pontoporia blainvillei; Cetartiodactyla, Pontoporiidae).

Persistent organic pollutants (POPs) accumulate in the fat tissue of living organisms and are found in relatively high concentrations in animals at the top of the food chain, such as dolphins. The ability of these compounds to interact with the endocrine system of marine mammals constitutes a risk for the reproduction and conservation of species. The La Plata dolphin, Pontoporia blainvillei, is exclusive to the southwestern Atlantic Ocean and is classified on the IUCN red list as a vulnerable species. Blubber, liver, kidney and muscle samples from four P. blainvillei mother-fetus pairs were analyzed to evaluate the transfer of POPs to fetal tissues through the placenta. The presence of POPs in fetal tissues indicates the maternal transfer of compounds. In the pregnant females, blubber was the tissue with POP highest concentration, followed by the liver, kidneys and muscles. In the fetuses, POP accumulation mainly occurred in the blubber followed by the muscles, liver and kidneys. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) were found in all tissues analyzed and had the highest concentrations among all compounds. The main PCB congeners in the fetal samples had five to seven chlorine atoms. The only polybrominated diphenyl ether (PBDE) in the fetal samples was 47 and was found only in blubber. The main DDT metabolite in the fetuses was p,p'-DDE. POP transfer via the placenta occurs in the first months of gestation and increases with fetal development, according to fetus/mother (F/M) ratio: HCB>DDT>PCB>PBDE>Mirex, which may follow the order of the octanol/water partition coefficient (Kow) values.

Historical records and spatial distribution of high hazard PCBs levels in sediments around a large South American industrial coastal area (Santos Estuary, Brazil).

The depositional history of polychlorinated biphenyls (PCBs) was studied from surficial sediments and three sediment cores sampled in the Santos Estuary, an important industrial and urban centre in South America. The maximum concentration (190.7 ng g-1 dry weight) and inventory (295.50 ng cm-2) were detected in sediments related to the 1980s, representing a ten-year delay of the emission peak in Brazil. PCB consumption, the congener patterns, and multivariate statistical analyses indicated that the levels started to increase with the intensification of regional urban and industrial development that continued to interfere in the magnitude of input during the past 50 years. In addition, the risk assessment indicates that levels observed in most of the samples are in a range capable of producing ecological risks to the marine biota. This study provides the first estimates of historic sediments PCB inventories in the Southwestern Atlantic, contributing data for regional and global management and highlighting the role of sediment as a compartment for permanently storing POPs and the risks involved in their resuspension, especially in regions that are constantly dredged such as the Santos Estuary.

Biochemical and molecular responses in oysters Crassostrea brasiliana collected from estuarine aquaculture areas in Southern Brazil.

Biochemical and molecular responses were evaluated in oysters Crassostrea brasiliana collected from three oyster farms, at Guaratuba Bay, southern Brazil, forming a pollutant gradient: Farm 1 (reference site - farther from the urban area), Farm 2 (intermediate site) and Farm 3 (nearest to the urban area). Oxidative stress markers, DNA damage and transcript levels of CYP2AU1, CYP2-like1, CYP2-like2, SULT-like, GPx-like, SOD-like, CAT-like, GSTmicrosomal-like, GSTomega-like, FABP-like and ALAd-like genes were analyzed in the gills. The levels of polycyclic aromatic hydrocarbons, linear alkylbenzenes and polychlorinated biphenyls were also evaluated in the soft tissues of the oysters and in the sediment of the Farms. Higher GSTomega-like, CYP2AU1 and FABP-like transcript levels, GR and G6PDH activities and lipid peroxidation levels were observed in oysters from Farms 2 and 3, suggesting pollutant effects on oysters. Alterations in oxidative stress markers also suggest a response against a prooxidant condition in C. brasiliana due to pollutant effects.

Depositional history and inventories of polychlorinated biphenyls (PCBs) in sediment cores from an Antarctic Specially Managed Area (Admiralty Bay, King George Island).

Temporal patterns, fluxes and inventories of polychlorinated biphenyls (PCBs) were assessed in nine sediment cores collected from selected areas of Admiralty Bay off the Antarctic Peninsula. Concentrations of total PCBs were low, but slightly higher in comparison to low-impacted, remote environments in the world, ranging from below the detection limit to 11.9ngg-1 in dry weight. PCB concentrations and inventories suggest a possible minor influence related to the nearby logistic activities, especially in the sediment core collected close to the Ferraz Station. Despite being the most remote and protected area on the planet, the Antarctic continent is no longer a pristine environment.

Distribution and evolution of sterols and aliphatic hydrocarbons in dated marine sediment cores from the Cabo Frio upwelling region, SW Atlantic, Brazil.

We report the distribution of selected lipid biomarkers specifically sterols and aliphatic hydrocarbons in sediment cores from Cabo Frio, SW Atlantic continental shelf, Brazil, corresponding approximately to the last 700 years. In the Cabo Frio region, a costal upwelling occurs as a quasi-seasonal phenomenon characterized by nutrient-rich bottom waters that intrude on the continental shelf and promote relatively high biological productivity compared to other Brazilian continental shelf areas. The results for sterols indicate the predominance of organic matter (OM) inputs related to marine organisms, mainly plankton, in all of the cores along the time scale studied. Principal component analyses show three different groups of variables, which may be associated with (i) the more effective intrusion of the nutrient-rich South Atlantic Central Water, resulting in the increase of marine lipid biomarkers such as sterols and short-chain n-alkanes; (ii) the influence of the Coastal Water with higher surface water temperature and subsequently lower primary productivity; and (iii) OM characterized by high total organic carbon and long-chain n-alkanes related to an allochthonous source. Relatively high concentrations of sterols and n-alkanes between 1450 and 1700 AD, chronologically associated with the Little Ice Age, suggest a period associated with changes in the local input of specific sources of these compounds. The concentrations of lipid biomarkers vary over core depth, but this does not suggest a notably high or low intensity of upwelling processes. It is possible that the climatic and sea surface temperature changes reported in previous studies did not affect the input of the sedimentary lipid biomarkers analyzed here.

Occurrence of organochlorines in the green sea turtle (Chelonia mydas) on the northern coast of the state of São Paulo, Brazil.

Organochlorines (OCs), such as pesticides and polychlorinated biphenyls (PCBs), are persistent, toxic and widely distributed through atmospheric transport and ocean currents. Few studies have been conducted on OCs in sea turtles, especially on the coast of Brazil. Chelonia mydas is the largest hard-shell sea turtle and is found tropical and subtropical regions in all oceans. The aim of the present study was to determine the occurrence of OCs in the green sea turtle (C. mydas). Fat, liver, kidney and muscle samples were collected from 27 juveniles found on the beach of the city of Ubatuba on the northern coast of the state of São Paulo, Brazil. OCs were extracted with organic solvents and the extract was purified with concentrated acid. Gas chromatography-mass spectrometry and electron capture detection were used for the identification and quantification of PCBs and pesticides, respectively. No organochlorine pesticides were detected in any of the samples. Concentrations of total PCBs in wet weight were <1.6 to 48.9ng/g in fat tissue, <1.6 to 17.4ng/g in liver tissue and <1.6 to 37.7ng/g in kidney tissue. The low levels found are mainly related to diet, as the green sea turtle is basically herbivorous and lower PCB contamination compared to other regions.

Distribution of butyltin compounds in Brazil's southern and southeastern estuarine ecosystems: assessment of spatial scale and compartments.

Butyltin compounds (BTs), including tributyltin (TBT) and its degradation products, dibutyltin and monobutyltin, have been found in a diversity of aquatic systems and causing toxic effects in target and nontarget organisms. They enter in coastal systems through different sources (as antifouling paints, industrial effluents, etc.) where they interact with biotic and abiotic components, and their distribution is commonly determined by the morphological and hydrodynamic conditions of the coastal systems. In this study, we discuss the contamination by BTs on a spatial scale (eight estuaries with three subareas each) and in different compartments of the estuaries (sediments, suspended particulate matter (SPM), and estuarine catfish tissues (liver and gills). Lower concentrations of BTs were found in the sediments (n.d. to 338 ng g(-1)) in comparison to studies before a ban of TBT in antifouling paints was enacted, mostly indicating an old input or preservation related with sediment properties and composition. For SPM samples (n.d. to 175 ng L(-1)) as well as in fish tissues (n.d. to 1426 ng g(-1)), the presence of these compounds was frequent, especially in the fish due to their movement throughout the estuaries and the potential to assess point sources of BTs. These results indicate that BTs persist in the environment, with variation in amounts between investigated estuaries and even at locations inside the same estuary, because of ideal preservation conditions, transport to remote areas, and input from different sources.

Incidence of plastic debris in Sooty Tern nests: A preliminary study on Trindade Island, a remote area of Brazil.

Plastic is abundant in the oceans, reaching pelagic zones away from continents. Here we present the first recordings of plastic used as nest material in Sooty Tern nests, on a remote oceanic island. We describe our findings in terms of quantity, size and color of plastic debris. A total of 78 plastics were noted in 54 nests. Four color categories were found: Blue, White, Green and Red. Blue fragments were the most frequent color, present three times as much as white debris. This pattern was present despite blue fragments being smaller and lighter. The plastic debris of lowest frequency were the larger and heavier pieces (red). To our knowledge this is the first record of plastic in Sooty Tern nests. Trindade Island is on an oceanic zone expected to accumulate garbage due to the dynamic ocean currents. Such findings call for a closer inspection of pollution in the Atlantic Ocean.

Bioaccumulation of heavy metals in marine organisms and sediments from Admiralty Bay, King George Island, Antarctica.

The Antarctic continent is considered a low-impact environment; however, there is a tendency to increase the contaminants' levels due to human activities in the research stations. In this study, As, Cd, Cr, Cu, Hg, Ni, Pb and Zn levels in sediment and biota were determined in the environmental samples from Admiralty Bay (King George Island, Antarctica) collected in 2003. The results demonstrated high concentrations of Cu and Zn in the sediments. There was bioaccumulation of As in the biota from Admiralty Bay and bioaccumulation of Zn specifically in the biota from Martel Inlet. In addition, the results were useful in order to understand the heavy metal levels for the pre-accident condition of Comandante Ferraz Antarctic Station, where an accident occurred in 2012, and also for the comparison with current conditions within the monitoring work developed by INCT-APA (National Institute of Science and Technology for Environmental Research Antarctic).

Yeasts from macroalgae and lichens that inhabit the South Shetland Islands, Antarctica.

Antarctic terrestrial ecosystems are largely dominated by lichens, while shallow coastal environments are mainly covered by macroalgae. The aim of this study was to isolate and to evaluate the diversity of yeasts in different species of macroalgae and lichens collected in South Shetland Islands, Antarctica. A total of 405 yeasts were recovered (205 from macroalgae and 200 from lichens). The yeast community from macroalgae was most diversity than the yeast community from lichen. The dominance index was similar for both substrates. A total of 24 taxa from macroalgae and 18 from lichens were identified, and only 5 were common to both substrates. Metschnikowia australis, Mrakia sp., Rhodotorula glacialis and Glaciozyma litorale were the most abundant yeasts in macroalgae and Cryptococcus victoriae, Rhodotorula laryngis, Rhodotorula arctica, Trichosporon sp. 1 and Mrakia sp. were the most abundant in lichens. Based on molecular and phylogenetic analyses, four yeast from macroalgae and six from lichens were considered potential new species. This is the first study to report the yeast communities from the Antarctic macroalgae Himantothallus grandifolius and lichen Ramalina terebrata. Results suggest that Antarctic phyco and lichensphere represent a huge substrate for cold-adapted yeasts and enhanced the knowledge of the microbiota from extreme environments.