Finding the needle in a haystack: Evaluation of ecotoxicological effects along the continental shelf break during the Brazilian mysterious oil spill.

Oceanic oil spills present significant ecological risks that have the potential to contaminate extensive areas, including coastal regions. The occurrence of the 2019 oil spill event in Brazil resulted in over 3000 km of contaminated beaches and shorelines. While assessing the impact on benthic and beach ecosystems is relatively straightforward due to direct accessibility, evaluating the ecotoxicological effects of open ocean oil spills on the pelagic community is a complex task. Difficulties are associated with the logistical challenges of responding promptly and, in case of the Brazilian mysterious oil spill, to the subsurface propagation of the oil that impeded remote visual detection. An oceanographic expedition was conducted in order to detect and evaluate the impact of this oil spill event along the north-eastern Brazilian continental shelf. The pursuit of dissolved and dispersed oil compounds was accomplished by standard oceanographic methods including seawater polycyclic aromatic hydrocarbons (PAHs) analysis, biomass stable carbon isotope (δ13C), particulate organic carbon to particulate organic nitrogen (POC:PON) ratios, nutrient analysis and ecotoxicological bioassays using the naupliar phase of the copepod Tisbe biminiensis. Significant ecotoxicological effects, reducing naupliar development by 20-40 %, were indicated to be caused by the presence of dispersed oil in the open ocean. The heterogeneous distribution of oil droplets aggravated the direct detection and biochemical indicators for oil are presented and discussed. Our findings serve as a case study for identifying and tracing subsurface propagation of oil, demonstrating the feasibility of utilizing standard oceanographic and ecotoxicological methods to assess the impacts of oil spill events in the open ocean. Ultimately, it encourages the establishment of appropriate measures and responses regarding the liability and regulation of entities to be held accountable for oil spills in the marine environment.

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.

An integrated assessment to reconstruct the history of changes influenced by multiple anthropogenic activities (City of Fortaleza, Ceará, Brazil).

In this study, the multi-marker approach was used for the first time with a highly urbanized lake located in the city of Fortaleza, Brazil, to provide a comprehensive view of temporal trends in sources of pollutants and evaluate the relation between the influence of anthropogenic activities and socioeconomic development. Total concentrations of the markers analyzed ranged from 21.0 to 103.8 ng g-1, 450.2 to 2390.2 ng g-1, and 233.8 to 9827.3 ng g-1 for ∑PAHs, ∑n-alk, and ∑sterols, respectively. Concentrations and patterns of PAH, AH, and sterol ratio distribution changed over time and may be associated with different episodes in the history of the city of Fortaleza. The marker ratio distribution in the sediment core revealed an overlap of natural and anthropogenic sources, with degraded oil, biogenic inputs, pyrogenic processes, and fecal contamination from humans and animals in the past changing to petroleum fossil inputs and high contamination from sewage in the present day. The distribution of markers and the chronological history of Fortaleza revealed two distinct periods related to human activities during the development of the city. In the first period (prior to the 1950s), the main human activities were animal breeding and the use of biomass for domestic activities, public and cargo transportation, and commercial activities, especially food production. In the second period (after the 1950s), expansion of the city occurred due to the so-called Brazilian economic miracle and the main human activities were industrialization and urbanization processes, involving deforestation, paving, sewage discharge, and petroleum combustion.

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.

Polycyclic aromatic hydrocarbons (PAHs) in fishery resources affected by the 2019 oil spill in Brazil: Short-term environmental health and seafood safety.

We present herein a short-term impact on marketed fisheries and human health safety in the first three months following the 2019 oil spill in Brazil. Total PAHs in the edible tissues of 34 finfish and shellfish species ranged from 8.71 to 418 ng g-1 wet weight, with robust evidence supporting crude oil contamination. A prevalence of low molecular weight PAHs was observed, mainly naphthalenes. A decreasing trend in mean total PAHs from mollusks (134 ng g-1) to crustaceans (73.9 ng g-1) and to fishes (45.3 ng g-1) was noted. The spilled oil caused immediate negative impacts on the local seafood market, despite less than 3% of samples exhibited concentrations above levels of concern, revealing a low probability for human health risks. These findings demonstrate that governments must be prepared to provide not only science-based quick responses but also effective science communication for society upon environmental disasters.

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.

Molecular distribution and isotopic composition (δD and δ13C) of lipids dataset for a sediment core (GeoB16202-2) from the north-eastern Brazilian margin.

The distribution and isotopic composition (δ13C and δD) of lipids are proxies used to determinate paleoenvironmental conditions including precipitation regimes, vegetation changes and sources of organic matter, among others. This data article describes five datasets of distribution (n-alkanes, fatty acids, n-alkanols and sterols) and isotopic composition (n-alkanes and fatty acids) of lipids determined in 50 samples from a gravity core (GeoB16202-2) retrieved on the continental slope off northeastern Brazil. The core site is influenced by the Parnaiba freshwater discharge, the North Brazil Current and by the Intertropical Convergence Zone (ITCZ). Previous work focused on inorganic proxies in this core revealed important clues of climatic conditions during the Heinrich Stadial 1 (HS1). The baseline dataset of molecular and isotopic proxies of the organic matter provided here are additional and/or complimentary evidences to help elucidate past climate change during the Quaternary in the Equatorial Atlantic, where less information is available in comparison to other regions in this ocean.

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.

Spatial distribution of organic and inorganic contaminants in Ria de Aveiro Lagoon: A fundamental baseline dataset.

This paper presents baseline data of sediments characterization from Ria de Aveiro lagoon (Portugal). Twenty-two intertidal surface sediments were collected and analysed for their pseudo-total content of 25 major and trace elements and for their total content of PAHs (Sum16) and PCBs (Sum13). The fine fraction percentage and total organic carbon content were also determined. Ria de Aveiro Lagoon has been the target of several studies during the last decades, and it has been pointed out as a hot spot in terms of contamination García-Seoane et al., 2016. Nevertheless, data about sediments contamination is mostly focused on Hg Lillebø et al.,2011, and in a specific area of the lagoon Grilo et al., 2013, and there is not a clear and global picture about the spatial distribution of other elements, and especially of organic contaminants. Thus, this baseline dataset is of utmost importance for researchers and planners and it can be used to monitor the effect of disturbances, such as: dredging activities; hydrodynamic changes (either due to human activities or extreme events); external inputs (new discharges from industries and wastewater plants, etc).

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.

Microplastic contamination in surface waters in Guanabara Bay, Rio de Janeiro, Brazil.

Microplastics (MPs) are contaminants of environmental concern that represent a threat to marine systems. Here we report data on the abundance and characteristics of MPs collected from surface waters of the urban Guanabara Bay. Samples were collected, by horizontal trawling of a plankton net on two occasions (summer of 2016). The MPs were obtained from samples by sieving and particles were manually sorted with microscope. Characterization of MPs was accomplished by gravimetry and digital image processing (for quantification and morphology categorization), and chemical composition identified by infrared spectroscopy and elemental analyses. Total MPs ranged from 1.40 to 21.3 particles/m3, which places Guanabara Bay amongst the most contaminated coastal systems worldwide by microplastics. Polyethylene and polypropylene polymers ≤1 mm were the most abundant particles. Therefore, the occurrence of MPs in Guanabara Bay is relevant to understand ecological hazards of exposition to marine biota and merits further investigation.

Effects of hydrocarbon pollution in the structure of macrobenthic assemblages from two large estuaries in Brazil.

Changes in the structure of benthic macrofauna and its relationship with hydrocarbon contamination were determined at different spatial scales in sublittoral sediments of two large estuaries in Brazil. Guanabara Bay (GB) is a heavily polluted estuary due to the presence of a large industrial complex and high demographic density. Laranjeiras Bay (LB) lies in an Environmental Protection Area and can still be considered as preserved from human activities. Despite some spatial differences within each bay, the PAHs concentrations were significantly and consistently higher in GB, with values generally above the threshold effect levels. No signs of hydrocarbon contamination were observed in LB. Macrofauna abundance, diversity and overall assemblage structure were largely different between bays. Canonical analysis of principal coordinates (CAP), used to model the relationship between macrofauna and PAHs levels, indicated that this class of hydrocarbons is the main structuring factor of soft-bottom assemblages in both bays.

Structural signatures of water-soluble organic aerosols in contrasting environments in South America and Western Europe.

This study describes and compares the key structural units present in water-soluble organic carbon (WSOC) fraction of atmospheric aerosols collected in different South American (Colombia - Medellín and Bogotá, Peru - Lima, Argentina - Buenos Aires, and Brazil - Rio de Janeiro, São Paulo, and Porto Velho, during moderate (MBB) and intense (IBB) biomass burning) and Western European (Portugal - Aveiro and Lisbon) locations. Proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to assess the relative distribution of non-exchangeable proton functional groups in aerosol WSOC of diverse origin, for the first time to the authors' knowledge in South America. The relative contribution of the proton functional groups was in the order H-C > H-C-C= > H-C-O > Ar-H, except in Porto Velho during MBB, Medellín, Bogotá, and Buenos Aires, for which the relative contribution of H-C-O was higher than that of H-C-C=. The 1H NMR source attribution confirmed differences in aging processes or regional sources between the two geographic regions, allowing the differentiation between urban combustion-related aerosol and biological particles. The aerosol WSOC in Aveiro, Lisbon, and Rio de Janeiro during summer are more oxidized than those from the remaining locations, indicating the predominance of secondary organic aerosols. Fresh emissions, namely of smoke particles, becomes important during winter in Aveiro and São Paulo, and in Porto Velho during IBB. The biosphere is an important source altering the chemical composition of aerosol WSOC in South America locations. The source attribution in Medellín, Bogotá, Buenos Aires, and Lima confirmed the mixed contributions of biological material, secondary formation, as well as urban and biomass burning emissions. Overall, the information and knowledge acquired in this study provide important diagnostic tools for future studies aiming at understanding the water-soluble organic aerosol problem, their sources and impact at a wider geographic scale.

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.