Chemical contamination affecting filter-feeding bivalves in no-take marine protected areas from Brazil.

Marine protected areas (MPAs) are zones geographically delimited under pre-defined management goals, seeking to reduce anthropogenic threats to biodiversity. Despite this, in recent years reports of MPAs affected by chemical contamination has grown. Therefore, this study addresses this critical issue assessing legacy and current chemical contamination in filter-feeder bivalves obtained in very restrictive no-take MPAs from Brazil. The detected pollutants encompass polycyclic aromatic hydrocarbons (PAHs), linear alkylbenzenes (LABs), and persistent organic pollutants (POPs) like dichlorodiphenyltrichloroethane (DDTs) and polychlorinated biphenyls (PCBs). Despite protective measures, bivalves from nine MPAs exhibited high LABs (13.2-1139.0 ng g-1) and DDTs levels (0.1-62.3 ng g-1). PAHs were present in low concentrations (3.1-29.03 ng g-1), as PCBs (0.7-6.4 ng g-1), hexachlorobenzene (0.1-0.2 ng g-1), and Mirex (0.1-0.3 ng g-1). Regardless of the sentinel species, MPAs and management categories, similar accumulation patterns were observed for LABs, DDTs, PAHs, and PCBs. Based on the limits proposed by Oslo Paris Commission, the measured levels of PAHs, PCBs and were below the environmental assessment criteria. Such findings indicate the no biological effects are expected to occur. However, they are higher considering background conditions typically measured in remote or pristine areas and potential simultaneous exposure. Such findings indicate an influence of anthropogenic sources, emphasizing the urgency for monitoring programs guiding strategic management efforts to safeguard these areas.

A comprehensive review of polycyclic aromatic hydrocarbons in Brazilian coastal environments.

This study provides an overview of the evaluation of polycyclic aromatic hydrocarbons (PAHs) in the coastal regions of Santos Basin, located in Brazil's Southeast region, the country's most industrialized area. The analysis is based on data compiled from various studies in this area since 2000. A comprehensive literature review was conducted using the SCOPUS database, encompassing peer-reviewed scientific journals from publishers such as Elsevier, Springer, Nature, Wiley, Taylor & Francis, Google Scholar, and ResearchGate. Most of these studies have focused on the sediment compartment due to its role as the primary repository for organic matter and, consequently, PAHs in the marine environment. However, the bioavailability of organic contaminants in sediment is generally lower compared to water and suspended particulate matter, which has received less attention in the context of Santos Basin. The literature search also includes studies evaluating PAH concentrations in organisms to investigate the bioaccumulation rates of these compounds. Data presented in this review primarily originates from coastal and estuarine areas within Santos Basin, with occasional extensions to the continental shelf. The majority of publications are centered on studies conducted in the southeastern Brazilian states of São Paulo and Rio de Janeiro, where the highest levels of PAH contamination across all environmental compartments are typically observed. Santa Catarina, on the other hand, is the coastal region with fewer studies. The regions where most of the studies involving PAHs in the Santos Basin are concentrated in areas where public university research centers are located, a pattern that repeats throughout the Brazilian coast. In areas far from universities, little is known about the environmental status of PAHs.

Navigating the PAH maze: Bioaccumulation, risks, and review of the quality guidelines in marine ecosystems with a spotlight on the Brazilian coastline.

This review delves into the intricate world of Polycyclic Aromatic Hydrocarbons (PAHs) and their bioaccumulation in marine organisms. It explores how physicochemical attributes of individual compounds, along with metabolic oxidation and elimination processes, influence this bioaccumulation. The review further investigates the risks and toxicity associated with PAHs in marine organisms. Subsequently, sediment and water quality guidelines used to assess the potential for adverse effects from PAH exposure are discussed exposing significant differences in the methodological approaches used to establish the guidelines, which can lead to discrepancies in the values used to compare PAH concentrations and limitations to their use. Emphasis is placed on the criteria employed in establishing these guidelines, rooted in adverse effects data linked to PAHs, and efforts to establish local quality guidelines for a tropical area are described. This exploration serves to enhance our understanding of the complex interplay between PAHs and marine ecosystems, informing more effective environmental management strategies.

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.

Remote sensing reveals unprecedented sublethal impacts of a 40-year-old oil spill on mangroves.

Oil spills cause long-lasting mangrove loss, threatening their conservation and ecosystem services worldwide. Oil spills impact mangrove forests at various spatial and temporal scales. Yet, their long-term sublethal effects on trees remain poorly documented. Here, we explore these effects based on one of the largest oil spills ever recorded, the Baixada Santista pipeline leak, which hit the mangroves of the Brazilian southeastern coast in 1983. Historical, Landsat-derived normalized difference vegetation index (NDVI) maps over the spilled mangrove reveal a large dieback of trees within a year following the oil spill, followed by a eight-year recolonization period and a stabilization of the canopy cover, however 20-30% lower than initially observed. We explain this permanent loss by an unexpected persistence of oil pollution in the sediments based on visual and geochemical evidence. Using field spectroscopy and cutting-edge drone hyperspectral imaging, we demonstrate how the continuous exposure of mangrove trees to high levels of pollution affects their health and productivity in the long term, by imposing permanent stressful conditions. Our study also reveals that tree species differ in their sensitivity to oil, giving the most tolerant ones a competitive advantage to recolonize spilled mangroves. By leveraging drone laser scanning, we estimate the loss of forest biomass caused by the oil spill to be 9.8-91.2 t ha-1, corresponding to 4.3-40.1 t C ha-1. Based on our findings, we encourage environmental agencies and lawmakers to consider the sublethal effects of oil spills on mangroves in the environmental cost of these accidents. We also encourage petroleum companies to use drone remote sensing in monitoring routines and oil spill response planning to improve mangrove preservation and impact assessment.

Chemical contamination in coastal areas alters shape, resistance and composition of carnivorous gastropod shells.

Morphological, structural and compositional alterations in shells of molluscs have been proposed as putative biomarkers of chemical contamination in coastal zones. Despite this, few studies were carried out using top predator gastropods which tend to be more susceptible to contamination exposure. Thus, the present study assessed disturbances on shells of Stramonita brasiliensis considering compression resistance and organic and mineralogical matrix composition, related to morphometric alterations. Results showed reductions in compression resistance and organic matrix content associated with higher contaminated sites. In addition, a predominance of calcite polymorphs was seen in shells obtained in polluted areas. Such outputs were consistent with local contamination levels which may have induced the observed alterations. Thus, changes in mollusc shells showed good performance as potential biomarkers of coastal contamination, being probably observed in other species of carnivorous gastropods around the world.

Mollusc shell shape as pollution biomarkers: Which is the best biological model?

Alterations in mollusc shells have been proposed contamination biomarkers. We used geometric morphometrics analyses associated with analytical determinations of contaminants to select suitable biological models among species widely distributed on coastal zones. The study was carried out using Lottia subrugosa (herbivore limpet), Crassostrea brasiliana (filter-feeder bivalve), and Stramonita brasiliensis (carnivore gastropod) obtained along a marked contamination gradient at Santos Estuarine System (Brazil). L. subrugosa and S. brasiliensis presented distinct shapes along the gradient, while no significant differences in shell form were seen for C. brasiliana. Indeed, limpets and snails presented morphometric parameters consistent with measured contamination levels hazardous substances. Based on cross-validation models, the reliability of morphometric responses was over 75% for the herbivore and carnivore species. In addition, for S. brasiliensis, a 95.2% confidence was detected in most contaminated sites. Therefore, shell alterations on carnivorous gastropods should be further investigated, seeking to be effectively employed as pollution biomarkers.

Persistent organic pollutants and stable isotopes in the liver of Chelonia mydas stranded on the southeastern Brazilian coast.

Among the various pollutants released into the environment, there are persistent organic pollutants (POPs). Chelonia mydas are one of the species that can be exposed to these pollutants and it is classified in the IUCN Red List as "endangered". The present study evaluated the occurrence of POPs in 49liver tissue samples of C. mydas juveniles collected on the southeastern Brazilian coast. Furthermore, the concentrations were correlated with carbon and nitrogen isotopic ratio, biometrics, and ecological factors. The main POPs found were Æ´-HCH and PCBs. Overall, the concentrations found were low and there were no significant correlations among POPs, isotopic ratios, size and weight, which may be related to the fact that the studied individuals are juveniles and occupy similar trophic positions despite the individual variations found. Despite the low concentrations, the presence of POPs, mainly PCBs, in the sea turtles' liver indicates their exposure to these compounds.

Organic contaminants in marine environment - Let us not forget the shallow areas.

The evaluation of anthropogenic pressures in marine environments commonly involves sediments, water and marine biota. However, the evaluation of the quality of the beach sediment and sediments from shallow areas are scarce compared to sediments from deeper areas in environmental assessment studies. In this study polycyclic aromatic hydrocarbons and linear alkylbenzenes were assessed in sediments from shallow areas of the São Sebastião channel, southeastern Brazil. The channel is part of the Marine Protected Area of the Northern Coast of São Paulo State besides holds the largest petroleum terminal in South America further than three sewage outfalls. Despite the concentrations of these contaminants in the sediments were relatively low compared to those found in the sediments from deeper areas of the channel, suggesting low toxicity of the beach sediments, the contamination reflected the pattern of the sediments of the São Sebastião channel.

Levels of hydrocarbons and toxicity of water-soluble fractions of maritime fuels on neotropical invertebrates.

Accidents involving fuels and oil spills are among the main sources of hydrocarbons to the marine ecosystems and often damage the biota. Diesel and bunker oil are two examples of fuels with broad application that release hydrocarbons to the aquatic environment and little is known about their toxicity on tropical organisms. This study aimed to assess the toxicity of the water-soluble fraction (WSF) of diesel and bunker oils to neotropical marine invertebrates. Commercial fuels were purchased for WSF extraction, analyzed for total petroleum hydrocarbons (TPH), and polycyclic aromatic hydrocarbons (PAHs), and acute and chronic toxicity determined. The WSF analyzed contained varied levels of TPH and PAHs mixtures, especially low molecular weight PAHs; bunker WSF presented higher amounts of TPH and PAHs. Both WSFs tested produced significant mortality of the brine shrimp Artemia salina, affected the reproduction rate of the copepod Nitokra sp, and impaired the embryo-larval development of the mussel Perna perna and of the sea urchin Lytechinus variegatus. In general WSF from diesel was more toxic to the organisms tested, but bunker WSF was more toxic to embryos of L. variegatus. Toxicity started from concentrations of 3% WSF, which can be environmentally relevant after an oil spill, indicating that marine biota may be adversely affected in short term.

Polycyclic aromatic hydrocarbons in marine mammals: A review and synthesis.

Most marine mammal species and populations are listed as endangered, threatened, or depleted under the Endangered Species Act and the Marine Mammal Protection Act. Organic contaminants such as polycyclic aromatic hydrocarbons from anthropogenic activities are part of the threat to marine mammals. The evaluation of the potential bioaccumulation of these compounds by marine mammals is a tool for adoption of policies to reduce polycyclic aromatic hydrocarbons discharges to the marine environment, where important players such as the oil and gas industries, maritime transport and sewage companies operate. This review seeks to present a bibliographic survey covering all published peer reviewed works of the contents of polycyclic aromatic hydrocarbons in biological tissues of marine mammals. It intended to compare the sampling protocols, procedures for preservation of the tissues, and the analytical method applied to quantify the polycyclic aromatic hydrocarbons, no to criticize any of them but to review the data and discuss how they can be compared.

Sources and depositional changes of aliphatic hydrocarbons recorded in sedimentary cores from Admiralty Bay, South Shetland Archipelago, Antarctica during last decades.

Organic biomarkers, as aliphatic hydrocarbons, are present in sedimentary organic matter and have been largely applied to the evaluation of recent environmental changes in the marine environment around the globe, including the Antarctic continent. Five sediment cores were taken in the Admiralty Bay, South Shetland Archipelago, Antarctica to evaluate changes in the signature of aliphatic hydrocarbons such as n-alkanes (n-C10 to n-C40) and isoprenoids as pristane and phytane, over the last decades. The total n-alkanes concentration ranged from 0.17 to 1.67 µg g-1 (mean = 0.74 ± 0.42) which is considered low and similar to pristine sediments. Aliphatic hydrocarbons present in the sedimentary pool came mostly from terrestrial sources as Antarctic lichens and mosses, and from marine sources as the macroalgae forest debris and emergent macrophytes. Anthropogenic inputs of aliphatic hydrocarbons (e.g., petroleum and their by-products) may be neglected based on the multi-proxy approach used to distinct sources of these organic compounds. In general, no significant changes in the sources of aliphatic hydrocarbons were observed along the sediment cores; however, an increased aliphatic hydrocarbons input registered between 1975 and 1992 may be related to the increase in meltwater runoff and the relatively high abundance of marine producers more adapted to increased sea temperatures.

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.

Can the environmental health of urban centers be assessed through pollutants trapped in lakes? A study case in the biggest city of the southern hemisphere.

Air and water quality in urban centers are summited to pollution from different sources, such as industrial activities, traffic, and wastewater effluents. A great number of chemicals can be spread by wind throughout the city, exposing the inhabitants to the health risks associated to them. Atmospheric analysis provides punctual data and represents the timing of the air sampling. A long-term evaluation of the atmospheric air quality can be assessed through the evaluation of pollutants that reach the soil by atmospheric deposition; however, they also can be redistributed and desorbed. The evaluation of pollutants in lakes could be a practical solution, given that lakes may act as traps to these compounds. In this context, organic pollutants were assessed in sediment and water from a lake located in the urban area of São Paulo, Brazil, the biggest city of the southern hemisphere. There were no evidences of sewage input to the lake and pyrogenic compounds reached the lake through atmospheric deposition. The content of pyrogenic PAH exposed the large amount of PAH emitted to the atmosphere by the multiple sources of PAH, mainly vehicular emission and diesel combustion. The PAH trapped in the lake highlighted the impact of all burning process in the air quality in which 12.3 million people are exposed.

Mysterious oil spill along Brazil's northeast and southeast seaboard (2019-2020): Trying to find answers and filling data gaps.

Large amounts of crude oil were found along Brazil's northeast and southeast seaboard from August 2019 to January 2020. Petroleum companies and oil tankers reported no accidents previously or during this period. The stranded oil on Brazilian beaches looks like tar; it has solid aspect and is denser than seawater. Chemical characterization of this oil showed that light hydrocarbons were still present, increasing the probability of negative effects to coastal organisms and ecosystems upon release in the water column. Diagnostic ratios, chromatogram pattern, and percentage-weathering plots proved that the oil samples share the same oil source. This work provides data for future comparison with oil samples that will likely be found stranded along the Brazilian shoreline in the years to come, helping to understand long term issues associated with the mysterious oil spill that made landfall in late 2019.

Evaluation of macroalgae and amphipods as bioindicators of petroleum hydrocarbons input into the marine environment.

The brown alga Sargassum furcatum and three families of amphipods (Ampithoidae, Caprellidae and Hyalidae) associated to that algae were evaluated as bioindicators of petroleum hydrocarbons input into the marine environment of São Sebastião Channel, in southeastern region of Brazil. The n-alkanes pattern were mainly associated with the natural composition of the macroalgae and amphipods, although some indicatives of petroleum hydrocarbons such as unresolved complex mixture and the no predominance of odd over even n-alkanes have been observed in some samples. Total PAHs ranged from 33.4 to 2010 ng g-1 dry weight with the predominance of low molecular weight PAHs, mostly of naphthalene and alkyl-naphthalenes, which also suggested petroleum input. Even in low concentration, Sargassum furcatum and amphipods species studied seems to be good indicators of the introduction of petroleum hydrocarbons.

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.

Bioaccumulation Study of Produced Water Discharges from Southeastern Brazilian Offshore Petroleum Industry Using Feral Fishes.

The main effluent of oil and gas production is the discharge of produced water (PW). Despite the potential environmental impact, the structure of oil and gas platforms can act as artificial reefs. Two species of fish, Caranx crysos and Tylosurus acus, were captured under two discharging platforms at Campos Basin, P19 and P40. A nondischarging platform, P25, was taken as reference. The highest median concentration of PAH in muscle tissue was observed for C. Crysos at P40 (219.38 ng g-1) followed by P19 (68.26 ng g-1). For T. acus, the highest median concentrations were 40.07 and 42.21 ng g-1 from P19 and P40 respectively. P25 presented the smallest recorded concentrations. The results of PAH in the muscle tissue of C. crysos enabled to distinguish the platforms with PW discharge from the platform without discharge. Trace elements concentrations reflected the background levels and were not influenced by the PW release.

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.

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.