A systematic review on polycyclic aromatic hydrocarbon contamination in elasmobranchs and associated human health risks.

Polycyclic aromatic hydrocarbon (PAH) contamination is ubiquitous and comprises a significant worldwide concern in ecological and Public Health frameworks. Many aquatic biota representatives have been reported as contaminated by these toxic compounds, including one of the most threatened vertebrate groups, elasmobranchs (sharks and rays). Although elasmobranchs play important ecological roles and provide significant ecosystem services, they are highly consumed and comprise a cheap source of protein for humans globally. Studies concerning elasmobranch PAH contamination are, however, notably lacking. A systematic review was, thus, conducted herein to assess PAH elasmobranch contamination and discuss potential human health risks following the Preferred Reporting Item Statement Guidelines for Systematic Reviews and Meta-analyses (PRISMA) guidelines applying the Population (P), Intervention (I), Comparison I, and Outcome (O) (PICO) strategy. A total of 86 published papers were retrieved by this method and analyzed. Only nine studies of this total concerned PAH elasmobranch contamination, assessed in 10 shark species and one ray species, with only one study calculating human health risks. A significant knowledge gap is, thus, noted for this subject, indicating the need to monitor PAH elasmobranch contamination in consumed shark and ray species worldwide.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) in liver samples of green turtles Chelonia mydas stranded in the Potiguar Basin, northeastern Brazil.

Sea turtles are affected by pollutants worldwide, and the polycyclic aromatic hydrocarbons (PAHs) have been detected in different types of samples and at high levels in some cases. The present study brings concentrations of 37 PAHs in liver samples of 17 green turtles Chelonia mydas stranded in northeastern Brazil [four with cutaneous tumors of fibropapillomatosis (FP), being classified as FP+]. Six PAHs were detected in 100% of the liver samples, and all alkylated PAHs were frequently quantified. High levels of phenanthrene (771.20 and 794.43 ng g-1 d.w.) and fluorene (1882.36 ng g-1 d.w.) were found in three females FP- (without FP cutaneous tumors). On the other hand, one green turtle FP+ had the higher level of naphthalene (531.70 ng g-1 d.w.), compound detected in 82.35 % of the samples. Our study brings additional baseline of organic pollutants in green turtles, improving knowledge on bioaccumulation of these compounds in sea turtles.

Concentration of polycyclic aromatic hydrocarbons (PAHs) and histological changes in Anomalocardia brasiliana and Crassostrea rhizophorae from Pernambuco, Brazil after the 2019 oil spill.

The present study aimed to analyze the concentrations of polycyclic aromatic hydrocarbons (PAHs) in populations of the shellfish Anomalocardia brasiliana and oysters Crassostrea rhizophorae three years after the 2019 oil spill, as well as evaluate histopathological changes on the gill tissues of the bivalves. Individuals of both species were sampled at points along the northern and southern coast of Pernambuco, Brazil. The permanence of oil residues was confirmed, evidenced by the total concentration of PAHs in the shellfish from the northern coast, which was roughly four times higher than the southern one. Among the PAHs analyzed, the low molecular weight compounds naphthalene and anthracene were the main contributors to the total concentration. Histological changes in the gills of the bivalves, were more severe in the specimens sampled on the north coast indicating alterations in the bivalve's health, mainly on the state's northern coast.

Persistent Organic Pollutants (POPs) in Sardine (Sardinella brasiliensis): Biomonitoring and Potential Human Health Effects.

Organochloride (OC) and polychlorinated biphenyl (PCB) concentrations were determined in the muscle tissue of fifty sardine samples (Sardinella brasiliensis) sampled off the south-east Brazilian shelf. The aim herein was to investigate OCs and PCBs composition profile, bioaccumulation potential and human risks. The concentrations of 18 organochlorine pesticides (OCPs) were below the method limit of quantification in most samples (ca. 94%), with few detected, namely δ-HCH, γ-HCH, Endosulfan I and II, Endosulfan Sulphate, DDE, Dieldrin, Endrin, Endrin Aldeide, Endrin Cetone and Metoxyclor. The median concentration for the Σ41 PCBs was 2.32 ng g-1, ranging from values below the limit of quantification (

Human risk assessment of ash soil after 2020 wildfires in Pantanal biome (Brazil).

Wildfires have increased in the last years and, when caused by intentional illegal burnings, are frequently run out of control. Wildfire has been pointed out as an important source of polycyclic aromatic hydrocarbons (PAHs) and trace elements (TEs) - such as, As, Ni, and Pb - to environmental compartments, and thus may pose a risk to human health and to the ecosystem. In 2020, the Brazilian biome, Pantanal, faced the largest losses by wildfires in the last 22 years. Ashes from the topsoil layer in Pantanal were collected after these wildfires at 20 sites divided into the sediment, forest, PF, PS, and degraded sites. Toxicity and associated risks for human health were also evaluated. The areas highly impacted by wildfires and by artisanal gold mining activities showed higher concentrations for TEs and PAHs than the protected areas. Pb varied from 8 ± 4 to 224 ± 81 mg kg-1, and total PAH concentration ranged between 880 ± 314 and 1350 ± 70 ng g-1, at sites impacted by anthropogenic activities. Moreover, health risk assessments for TE and PAH indicated a potentially great risk for children and adults, via ingestion, inhalation, and dermal pathway. The carcinogenic risks exceeded reference values, for both TE and PAH, suggesting harmful conditions, especially for vulnerable groups, such as children and the elderly. Supplementary Information: The online version contains supplementary material available at 10.1007/s11869-022-01248-2.

The novel mangrove environment and composition of the Amazon Delta.

Both freshwater floodplain (várzeas and igapós) forests and brackish-saline mangroves are abundant and well-described ecosystems in Brazil.1 However, an interesting and unique wetland forest exists in the Amazon Delta where extensive mangroves occur in essentially freshwater tidal environments. Unlike the floodplain forests found upriver, the hydrology of these ecosystems is driven largely by large macro-tides of 4-8 m coupled with the significant freshwater discharge from the Amazon River. We explored these mangroves on the Amazon Delta (00°52' N to 01°41' N) and found surface water salinity to be consistently <5; soil pore water salinity in these mangrove forests ranged from 0 nearest the Amazon mouth to only 5-11 at the coastal margins to the north (01°41' N, 49°55' W). We also recorded a unique mix of mangrove-obligate (Avicennia sp., Rhizophora mangle) and facultative-wetland species (Mauritia flexuosa, Pterocarpus sp.) dominating these forests. This unique mix of plant species and soil porewater chemistry exists even along the coastal strands and active coastlines of the Atlantic Ocean. Part of these unique mangroves have escaped current global satellite mapping efforts, and we estimate that they may add over 180 km2 (20% increase in mangrove area) within the Amazon Delta. Despite having a unique structure and function, these freshwater-brackish ecosystems likely provide similar ecosystem services to most mangroves worldwide, such as sequestering large quantities of organic carbon, protection of shoreline ecosystems from erosion, and habitats to many terrestrial and aquatic species (monkeys, birds, crabs, and fish).

Method development and application to sediments for multi-residue analysis of organic contaminants using gas chromatography-tandem mass spectrometry.

A method for the determination of four classes of potentially toxic substances (PTSs) was developed and applied in marine sediments, including (i) polycyclic aromatic hydrocarbons (PAHs), (ii) polychlorinated biphenyls (PCBs), (iii) polybrominated diphenyl ethers (PBDEs), and (iv) organochlorinated pesticides (OCPs). The method is based on ultrasonic extraction with a mixture of dichloromethane:methanol (9:1 v/v) and gas chromatography coupled with tandem mass spectrometry analysis (GC-MS/MS) in multiple reaction monitoring (MRM) mode. A total of 89 compounds were identified using two precursor-product ion standards for each analyte. The method detection limit (MDL; 0.001-0.055 ng g-1 dw) and method quantification limit (MQL; 0.002-0.184 ng g-1 dw) are below the usual thresholds of pollution adopted by international sediment quality guidelines. The method proved to be selective, sensitive, accurate, and linear, with the advantage of reducing sample handling time and consumable expenses (solvent, adsorbents). The developed method was successfully applied to surface sediments of Sepetiba Bay, Rio de Janeiro State, Brazil. Total concentrations of PAH (29.20-209.5 ng g-1 dw), PCB (0.06-2.16 ng g-1 dw), OCP (0.03-0.33 ng g-1 dw), and PBDE (0.06-0.21 ng g-1 dw) represent a baseline for these compounds and revealed mild to low levels of contamination in comparison to other coastal bays in SE Brazil. By using the proposed method, we expect this preliminary dataset can be expanded and include other similar coastal systems from developing countries marked by scarcity of information about levels, risk assessment, and specific sediment quality guidelines encompassing multiple classes of regulated and emerging organic contaminants.

PAHs impacts on aquatic organisms: contamination and risk assessment of seafood following an oil spill accident.

Oil spills, intrinsically related to the petroleum production chain, represent a risk to the marine environment and a potential threat to humans through seafood consumption. We revised the NE Brazil oil spill and other accidents along the Brazilian coast, with a focus on seafood contamination, covering topics such as bioaccumulation, bioaccessibility, and risk analysis. Comprehensive knowledge of the impacts of spills helps in the interpretation of the dynamics of hydrocarbons released into the sea, contributing to actions to control their negative impacts. Currently, no legal limits have been established permanently in Brazil for PAHs in seafood edible tissues.

A Review on Atmospheric Analysis Focusing on Public Health, Environmental Legislation and Chemical Characterization.

Atmospheric pollution has been considered one of the most important topics in environmental science once it can be related to the incidence of respiratory diseases, climate change, and others. Knowing the composition of this complex and variable mixture of gases and particulate matter is crucial to understand the damages it causes, help establish limit levels, reduce emissions, and mitigate risks. In this work, the current scenario of the legislation and guideline values for indoor and outdoor atmospheric parameters will be reviewed, focusing on the inorganic and organic compositions of particulate matter and on biomonitoring. Considering the concentration level of the contaminants in air and the physical aspects (meteorological conditions) involved in the dispersion of these contaminants, different approaches for air sampling and analysis have been developed in recent years. Finally, this review presents the importance of data analysis, whose main objective is to transform analytical results into reliable information about the significance of anthropic activities in air pollution and its possible sources. This information is a useful tool to help the government implement actions against atmospheric air pollution.

Microbial Succession under Freeze-Thaw Events and Its Potential for Hydrocarbon Degradation in Nutrient-Amended Antarctic Soil.

The polar regions have relatively low richness and diversity of plants and animals, and the basis of the entire ecological chain is supported by microbial diversity. In these regions, understanding the microbial response against environmental factors and anthropogenic disturbances is essential to understand patterns better, prevent isolated events, and apply biotechnology strategies. The Antarctic continent has been increasingly affected by anthropogenic contamination, and its constant temperature fluctuations limit the application of clean recovery strategies, such as bioremediation. We evaluated the bacterial response in oil-contaminated soil through a nutrient-amended microcosm experiment using two temperature regimes: (i) 4 °C and (ii) a freeze-thaw cycle (FTC) alternating between -20 and 4 °C. Bacterial taxa, such as Myxococcales, Chitinophagaceae, and Acidimicrobiales, were strongly related to the FTC. Rhodococcus was positively related to contaminated soils and further stimulated under FTC conditions. Additionally, the nutrient-amended treatment under the FTC regime enhanced bacterial groups with known biodegradation potential and was efficient in removing hydrocarbons of diesel oil. The experimental design, rates of bacterial succession, and level of hydrocarbon transformation can be considered as a baseline for further studies aimed at improving bioremediation strategies in environments affected by FTC regimes.

Polychlorinated biphenyls (PCBs) in water: method development and application to river samples from a populated tropical urban area.

A method for the determination of polychlorinated biphenyls (PCBs) in water from urban rivers was implemented and validated. Extractions of dissolved and particulate PCBs were performed using solid-phase extraction and a pressurized solvent extraction system, respectively, and the analytes were identified and quantified by gas chromatography with tandem mass spectrometry in selected reaction monitoring mode with no further purification. The method was successfully developed for the determination of 41 PCBs with two precursor-product confirmations for each analyte. Low method detection limits (0.06-0.50 ng L-1) and good precision (≤ 20%; n = 8) were obtained, as well a linear response of the calibration curve ranging from 1.0 to 50 ng L-1. Method performance for real samples was tested with water collected weekly in triplicate during April 2018 from a eutrophic river in the city of Rio de Janeiro. The total (dissolved + particulate) PCB concentrations ranged from 2.17 to 5.29 ng L-1, above the threshold for river water quality standards in Brazil. Graphical abstract.

Sedimentary record of hydrocarbons and sewage inputs from a highly populated region in South-Eastern Brazil.

The environmental impacts of the urban expansion in Rio de Janeiro was evaluated based on the historical accumulation of black carbon (BC), aliphatic (AHs) and aromatic hydrocarbons (PAHs) and sterols in a sediment core retrieved from Botafogo Cove. BC related to oil combustion sources increased significantly since the 1990s. AHs were associated with petroleum inputs and revealed a high level of contamination. Multivariate statistical methods (a Principal Component Analysis associated with a linear multiple regression - PCA/LMR) applied to PAHs suggests changes in the sources in recent years. This can be ascribed to a reduction in pyrogenic emissions over the last four decades and to an increase in petrogenic inputs since the 1990s. The sterol dinosterol registered the increased eutrophication over the last three decades, but the sewage marker coprostanol was present at relatively low concentrations (0.40 to 1.16 µg g-1) probably caused by enhanced bacterial activity in the sediment.

Distribution and source apportionment of hydrocarbons in sediments of oil-producing continental margin: a fuzzy logic approach.

Investigation were carried out targeting distribution and source apportioning of hydrocarbons in surface sediments from shallow to deep waters in the Campos Basin, one of the most important oil-producing provinces in Brazil. The observed levels of aliphatic (≤ 124 µg g-1) and polycyclic aromatic hydrocarbons (PAHs ≤ 599 ng g-1) are lower than those considered relevant for environmental risk to the benthic habitats. Higher median concentrations of aliphatic hydrocarbons (8.49 µg g-1) and PAHs (84.8 ng g-1) in the middle slope sediments (700-1000-m water depths) showed the influence of hydrodynamics upon hydrocarbon accumulation in the sediments. Diagnostic ratios and conventional statistical analysis applied to hydrocarbon data produced insufficient information on the contribution of different sources. These traditional approaches do not consider the potential changes affecting source assignment and therefore cannot deal with the uncertainties. The fuzzy logic applied as an alternative method for data treatment successfully incorporated the uncertainties in the differentiation between petrogenic and pyrolytic sources, including those due to degradation. Moreover, by using fuzzy logic, it was possible to identify that water circulation patterns, mass transport, deposition, and degradation processes are more relevant factors in determining hydrocarbon composition than source proximity.

Distribution, sources and toxicity potential of hydrocarbons in harbor sediments: A regional assessment in SE Brazil.

Aliphatic and polycyclic aromatic hydrocarbons (PAHs) were quantified in harbors sediments from SE Brazil. The aims were to (i) compare harbors with distinct sizes and under the influence of different environmental pressures with respect to the sources and level of hydrocarbon contamination and (ii) evaluate the potential of adverse biological effects of sediment contamination by PAHs, based on sediment quality guidelines and toxicity equivalence quotient. The concentrations of total aliphatics (39.9µgg-1; 22.9-113µgg-1) and total PAHs (727ngg-1; 366-1760ngg-1) varied according to the size of and urban development around each harbor. Mixed contamination by petrogenic and pyrolytic hydrocarbons, and input of biogenic compounds, indicated the influence of both harbor activities and a myriad of urban, industrial and atmospheric inputs. The quality of sediment poses a risk to benthic biological communities, and, if dredged, this material may cause environmental damage in the waste disposal area.

Occurrence and Source Appraisal of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Waters of the Almendares River, Cuba.

In this work, 14 polycyclic aromatic hydrocarbons (PAHs) included in the United States Environmental Protection Agency pollutant priority list were analyzed in the surface water of the upper urbanized part of Almendares River, the most important water course in Havana, Cuba. Surface water from five sampling sites was collected at the end of dry season and analyzed by high-performance liquid chromatography-fluorescence detection method after solid phase extraction procedure. Total PAHs concentrations varied from 836 to 15 811 ng L(-1) with a geometric mean value of 2512 ng L(-1). PAH typology was dominated by low molecular-weight PAHs (2- to 3-ring components). Pollutant source appraisal was determined by diagnostic ratios method in five sampling sites. Factor analysis of normalized samples was used to concentration identified two factors as the main significant pollutant sources and to cluster similar sampling sites corresponding to petrogenic and combustion inputs, respectively. Ecological risks were considered. For animal aquatic life, acute toxicity values exceed the permissible values in the more-polluted sampling sites.

Urban rivers as conveyors of hydrocarbons to sediments of estuarine areas: source characterization, flow rates and mass accumulation.

Aliphatic (n-C12-n-C40, unresolved complex mixture, resolved peaks) and aromatic hydrocarbons (46 PAH) were investigated in suspended particulate matter (SPM) sampled over eleven months in six of the major rivers and two channels of the Guanabara Bay Basin. PAH flow rates of the most contaminated rivers, the contribution to the PAH sediment load of the receiving bay, and the main sources of hydrocarbons were determined. PAH (38) ranged from 28 ng L(-1) to 11,514 ng L(-1). Hydrocarbon typology and statistical evaluation demonstrated contribution of distinct sources in different regions and allowed quantification of these contributions. Total flow rate for the five major rivers amounts to 3 t year(-1) and responds for 30% of the total PAH annual input into the northern area of the Guanabara Bay. For the first time PAH mass deposited in the bay sediments has been estimated and shall serve as base for decision making and source abatement.

Revisiting hydrocarbons source appraisal in sediments exposed to multiple inputs.

The aim of this work was to test the efficiency of statistical methods as compared to the traditional diagnostic ratios to improve hydrocarbon source identification in sediments subjected to multiple inputs. Hydrocarbon determination in Guanabara Bay sediments pointed out high degradation and ubiquitous petrogenic pollution through the presence of high unresolved complex mixture. Polycyclic aromatic hydrocarbon (PAHs) ratios suggested pervasive contamination derived from combustion in all sediments and failed discriminating samples despite the specificity of sources in different sampling sites. Principal component analysis (PCA) effectively distinguished the petrogenic imprint superimposed to the ubiquitous combustion contamination, since this technique reduces the influence of PAHs distribution which is common to all samples. PCA associated to multivariate linear regression (MLR) allowed a quantitative assessment of sources confirming predominance of the pervasive contaminant component superimposed to a generalized petrogenic imprint. The pervasive component derives from combustion contributions as well as from differential PAHs degradation.