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.

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.

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.

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.

Low levels of persistent organic pollutants in sediments of the Doce River mouth, South Atlantic, before the Fundão dam failure.

The Doce River mouth (DRM) was severely impacted by the rupture of the Fundão Dam in 2015, considered the greatest Brazilian environmental tragedy in terms of tailings volume released (>40 million m3) and traveled distance (~600 km until the Atlantic Ocean). Environmental monitoring has been performed since then, but background levels are scarce or absent to Persistent Organic Pollutants (POPs), making impact assessments difficult. In the current study, we presented the baseline levels, inventories, and risk assessment of the POPs polychlorinated biphenyl (PCBs) and organochlorinated pesticides (OCPs), in surface sediment of the DRM. Samples were collected in December 2010 and July 2011, i.e., four years before the Fundão dam failure. The total PCBs and the OCPs (Aldrin, HCHs, and Chlordanes) were detected in both sampling campaigns, with levels up to 9.50 and 1.64, 0.28, and 0.63 ng g-1, respectively. The decrease of the Doce River flow was the main factor contributing to seasonal variations in the spatial distribution, and to a slight decline in the levels and frequency of the analyzed POPs in sediments collected in the dry season (July 2011). Environmental risk assessment, inventories, and total mass results suggest a low potential of PCBs and OCPs accumulation before the dam failure. This is the first POPs assessment in the study area that helped identify some unexpected impacts of the Fundão dam failure and contributed to the understanding of POPs cycles in the Southern Atlantic, data that are still scarce in the region.

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.

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.

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.

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.

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.

Persistent organic pollutants in blubber of fin whales (Balaenoptera physalus) from the Southern Ocean.

Persistent organic pollutants (POPs) were analyzed in eighteen blubber samples biopsied from fin whales (Balaenoptera physalus) during the feeding season near the Antarctic Peninsula in the summer of 2013. POP content (in ng g-1 lipid weight) ranged from 46.4 to 708 for polychlorinated biphenyls (∑PCBs), 6.77 to 123 for hexachlorobenzene (HCB), 10.1 to 489 for dichlorodiphenyltrichloroethane and derivatives (∑DDTs), 5.38 to 52.8 for hexachlorocyclohexanes (∑HCH) and <0.40 to 2.54 for polybrominated diphenyl ethers (∑PBDEs). The presence of those compounds in Southern Ocean fin whales is related to long-range transport and their diet based mainly on euphausiids (krill). Their contents were much lower compared to the same species in other locations, especially in the Northern Hemisphere, presumably due to differences in trophic position and the proximity of POP sources and contamination of prey items.

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.

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.

Occurrence of halogenated organic contaminants in estuarine sediments from a biosphere reserve in Southern Atlantic.

The occurrence, distribution, and the total mass of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in surficial sediments of the Paranaguá Estuarine System (PES), a subtropical estuary in Southern Atlantic. Altogether, concentrations and inventories of contaminants ranged from <0.06 to 4.78 ng g-1 and < 0.13 to 10.47 ng cm-2, respectively. OCPs presented the higher total mass (10.85 kg) and a decreasing trend from the inner estuary towards the adjoining shallow shelf. The occurrence of PCBs was restricted to sites nearby urban and industrial areas, which accumulated ~80% of the total mass of PCBs. Although the level of contamination is low, the results refer to recent years, which mean that the actual values could be greater if sediments from periods of higher usage were analyzed. This study provides the first estimates of POPs (persistent organic pollutants) total mass in the PES, contributing to data for the Southern American inventories.

What Factors Guide the Selection of Medicinal Plants in a Local Pharmacopoeia? A Case Study in a Rural Community from a Historically Transformed Atlantic Forest Landscape.

The criteria that local people use for selecting medicinal plants have been a recurrent topic in pharmacology and ethnobotany. Two of the current hypotheses regarding this phenomenon, ecological apparency and diversification, attempt to explain the inclusion of "apparent" and "non-apparent" and native and exotic taxa, respectively, in local pharmacopoeia. This study addresses the following questions: Do "apparent" and "non-apparent" medicinal plants have the same importance in local pharmacopoeia? Do "non-apparent" plants occupy more local categories of diseases than "apparent" plants? Do native and exotic medicinal plants have the same importance? Do exotic and native plants occupy different local categories of diseases? This study was conducted with householders of a community from Northeastern Brazil. Out of the 66 plant species cited, most were herbs (39 species), followed by trees and shrubs (27). Herbaceous species also occupied more local categories of diseases (51) than tree and shrub species (28). Furthermore, most of the species cited by the informants were exotic (42). Out of the 94 therapeutic applications cited in this research, 65 were treated with exotic species and 29 with native species, distributed among 13 body systems. These results support both the hypotheses of ecological apparency and diversification.

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.

Persistent organic pollutants and polycyclic aromatic hydrocarbons in penguins of the genus Pygoscelis in Admiralty Bay - An Antarctic specially managed area.

Persistent organic pollutants were assessed in fat samples of the Gentoo (Pygoscelis papua), Chinstrap (Pygoscelis antarcticus) and Adélie (Pygoscelis adeliae) penguins collected during the austral summers of 2005/06 and 2006/07 in Admiralty Bay, King George Island, Antarctica. The predominant organic pollutants were PCB (114 to 1115), polycyclic aromatic hydrocarbons (PAHs) (60.1 to 238.7), HCB (<0.3 to 132.2) and BDE-47 (<1.0 to 10.7) in ng g(-1) wet weight. The mean concentrations of the majority of organic pollutants were similar among the three species of penguins. Chicks of all three species showed similar profiles of PCB congeners, with predominance of lower chlorinated compounds. The distribution of PAHs was similar in all birds, with a predominance of naphthalene and alkyl-naphthalene, which are the main constituents of arctic diesel fuel. These data contribute to the monitoring of the continued exposure to organic pollutants in the Antarctic biota.

Persistent organic pollutants and polycyclic aromatic hydrocarbons in mosses after fire at the Brazilian Antarctic Station.

A fire at the Brazilian Antarctic Station on February 25th, 2012 led to the burning of material that produced organic pollutants. To evaluate the impact in the surrounding area, polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs) were analyzed in moss samples collected in the vicinities of the station before and after the incident and compared to findings from previous studies in the same region. PCBs were on the same magnitude as that reported in previous studies, which could be associated to the global dispersion of these compounds and may not be related to the local fire. In contrast, concentrations of HCB and PAHs were higher than those reported in previous studies. No PBDEs were found above the method detection limit. Organic contaminant concentrations in mosses decreased a few months after the fire, which is an important characteristic when considering the use of mosses for monitoring recent exposure.