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.

Polycyclic aromatic hydrocarbons in seawater after the mysterious oil spill of 2019 on the Pernambuco coast, northeast Brazil.

In 2019, one of Brazil's most significant environmental disasters occurred, involving an oil spill that directly affected Pernambuco state. Contamination along the coast was evaluated by the quantification of polycyclic aromatic hydrocarbons (PAHs) in fifty seawater samples collected in the summer and winter of 2021. Analysis using fluorescence spectroscopy revealed that for all the samples, levels of dissolved/dispersed petroleum hydrocarbons (DDPHs) were higher than the regional baseline for tropical western shores of the Atlantic Ocean. GC-MS analyses quantified 17 PAHs in the samples, with highest total PAHs concentrations of 234 ng L-1 in summer and 33.3 ng L-1 in winter, which were consistent with the highest risks observed in ecotoxicity assays. The use of diagnostic ratios showed that the coast was impacted by a mixture of PAHs from petrogenic and pyrolytic sources. The results indicated the need for continuous monitoring of the regions affected by the 2019 spill.

A novel in situ method for linear alkylbenzene sulfonate quantification in environmental samples using a digital image-based method.

Surfactants from detergents, when inadequately treated in sewage treatment plants, are carried away into estuaries, resulting in the contamination of aquatic environments. It is thus necessary to develop rapid and efficient techniques that are capable of effectively monitoring these pollutants. In this context, for the first time in the literature, this study reports the development and application of a digital image-based (DIB) method for the in situ quantification of the anionic surfactant linear alkylbenzene sulfonate (LAS) in water bodies using a smartphone. The DIB method is a highly effective modern detection method based on methylene blue, which is employed as a modified alternative technique to the spectrophotometric method and commonly used in environmental studies; in the DIB method, the images of interest are obtained using a smartphone and the analyses are carried out using free software Color grab. The results obtained from the application of the DIB method showed that the method possesses high precision and accuracy, with a linear calibration curve in the range of 0.15 to 4.5 mg L-1, R2 = 0.993, a limit of detection of 6.0 µg L-1, and recovery rates ranging from 82.7% to 114%. The efficacy of the proposed method was evaluated by comparing its results with those of spectrophotometry (used as a reference method) through the analysis of environmental samples obtained from the Capibaribe River Estuary using methylene blue. No statistically significant differences were observed between the results obtained from the DIB and the spectrophotometric method. The innovative method proposed in this study is fast, economical and environmentally friendly; the technique involves the use of only a few microliters of samples and generates little waste compared to spectrophotometry. In addition, the proposed method is applicable for in situ analyses, allowing real-time monitoring of LAS in different types of aquatic environments.

Traces of oil in sea turtle feces.

In 2019, an oil spill hit the Brazilian Northeast coast causing impact to several ecosystems, including sea turtles' breeding and feeding areas. This study aimed to investigate whether sea turtles were impacted by this oil disaster, correlating the oil found inside feces with a sandy-oiled sample collected on the beach some days after the accident. The fecal samples were collected in the upper mid-littoral reef areas during three consecutive days in February 2020. The results suggested that sea turtles consumed algae contaminated by petroleum. Hydrocarbons composition of oil inside feces was similar to the sandy-oiled sample, suggesting they were the same. Lighter aliphatic and polycyclic aromatic compounds were missing, indicating both sandy-oiled and oil inside the feces had experienced significant evaporation prior to collection. Although the long-term damage is still unknown, the data are novel and relevant to support future research and alert authorities about the risks to sea turtles.

PAH residues and toxicity levels two years after an extensive oil spill on the northeast Brazilian coast.

The most extensive oil spill ever recorded in tropical oceans occurred between August 2019 and March 2020, affecting approximately 3000 km of the Brazilian coast. This study assessed the chemical contamination and toxicity of sediments collected from affected reef areas during two sampling surveys conducted 17 and 24 months after the peak of oil slick inputs. Our results indicated that neither PAH levels nor measured toxicity showed a significant contribution from the spilled oil, with concentrations and biological effects indistinguishable from those in unaffected areas. Similarly, no differences were observed between seasons. Furthermore, there was no discernible relationship between sediment toxicity results and the measured PAH concentrations. Therefore, while biological responses indicated toxicity in most assessed areas, these responses are likely related to other local sources. This evidence suggests a natural oil attenuation process contributing to local environmental recovery. Nonetheless, further investigation is needed for other areas affected by oil spills.

Tar balls as a floating substrate for long-distance species dispersal.

Recent arrivals of tar balls have been observed in several tropical beaches associated with the oceanic circulation that flows to the Brazilian continental shelf. Between August and September 2022, tar balls were collected in the northeastern coast of Brazil and analyzed. Nearly 90 % of the oils were colonized by barnacles, polychaetes, decapods, and algae. Most rafting organisms were Lepas anserifera with capitulum measuring 0.32 to 22.21 mm. Based on the growth rate of barnacles and the speed of the SEC it was estimated that tar balls were floating since July and August 2022 and traveled a maximum of 1938.82 km. The organisms and tar balls' possible origin is in the international waters, near to the meso-Atlantic ridge, known for oil tanker traffic. The tar balls, in addition to the oil-related impacts, can act as a vector of long-distance species dispersion, and it needs to raise an alert, considering the possible ecological impacts.

Zebrafish as a biological model for assessing water quality along tropical hydrographic river basins in Northeast Brazil.

Tropical rivers are the main destinations for tailings from urban, industrial and agricultural activities in the region studied. The present study aimed to investigate if early stages of zebrafish (Danio rerio) development is a viable biological model to assess the toxicity of surface waters of tropical rivers, and whether that toxicity could be correlated to standard water quality indexes. Embryos were exposed to samples from 55 sites from 10 hydrographic basins of rivers in Pernambuco State, northeastern Brazil. Lethality rates, sublethal toxicity based on the general morphology score (GMS) and frequencies of abnormalities were analyzed. Significant mortality was observed in samples of 7 basins. The GMS indicated significant delay in embryo-larval development in 50% of the samples. The highest toxicity was detected in basins within Recife metropolitan area, where 61% of the samples caused sublethal toxicity. Most frequent developmental abnormalities included non-inflation of the swim bladder, delayed hatching and blood stasis. The highest frequencies of blood stasis were detected in samples with highest NH3 concentrations, corroborated by a positive correlation suggesting the existence of a causal relationship. A significant correlation was detected between water quality indexes and GMS with a greater toxic effect being observed in samples collected in areas of greater urban density and greater contamination by domestic sewage. This study demonstrates that the early stages of the zebrafish is a viable ecotoxicological model to assess the toxicity of surface waters and can contribute to a better understanding between the chemical composition and the adverse effects suffered by fish early life stage fish in tropical rivers.

Antifouling booster biocides in Latin America and the Caribbean: A 20-year review.

This review summarized booster biocides studies from Latin America and the Caribbean during the last two decades. Studies were focused on six countries, with most of them in Brazil. In water and sediment, diuron and Irgarol were the most abundant and frequent biocides, probably due to their former intense use. Antifouling paint particles were also reported and had mainly DCOIT, which is currently the most used booster biocide. Toxicity of individual booster biocides was tested in laboratory, and most effects were related to chlorothalonil, DCOIT, dichlofluanid, and Irgarol, including, but not limited to DNA damage, fertility decrease, and mortality at different trophic levels. This review highlighted the need for further studies on environmental occurrence of booster biocides in Latin America and Caribbean associated to ecotoxicological studies. Such information is essential to determine the potential ecological risks and to create directives regarding safe limits of booster biocides in aquatic systems.

Sewage contamination assessment in an urbanized tropical estuary in Northeast Brazil using elemental, isotopic and molecular proxies.

The Capibaribe Estuarine System (CES) is a tropical estuary located within a densely populated metropolitan region in the Brazilian Northeast, providing multiple ecosystem services including artisanal fisheries, tourism, and navigation. A significant load of domestic and industrial effluents is causing visible environmental degradation that needs to be characterized. This study evaluated the degree of contamination by domestic sewage and the relative contribution of organic carbon (OC) sources in sediments, measuring carbon-to-nitrogen atomic (C/N)a ratios, δ13C of OC, and linear alkylbenzene concentrations (LAB). The SIAR mixing model indicated that estuarine phytoplankton and sewage contribute 73% and 22% to OC, respectively, based on sedimentary (C/N)a ratios that varied from 8.5 to 13, and δ13C ranging from -25.21 to -21.63‰. This suggests that eutrophication of CES is triggered by sewage inflow. The CES was moderately contaminated by LAB, and the highest concentrations observed in the inner portion, from 287 to 1349 ng g-1 dry weight, suggests the retention of sewage. The mixing isotopic model indicated a significant dilution process of sewage-derived OC by estuarine phytoplankton. The lowest LAB in the lower estuary (317-320 ng g-1 dw) probably resulted from marine dilution. Principal component analysis demonstrated that mud regulates sedimentary OC content, and that the sewage plume regulates sedimentary LAB. High degradation of LAB isomers probably reflects the net heterotrophic condition of this system, also suggesting these compounds are introduced into CES partially degraded. Our results pointed out that degraded OM is a result of chronic and long-term sewage input. Considering the implications of sewage pollution to environmental and public health, there is an urgent need of better policies to improve domestic effluent treatment capacity, reducing contamination of estuarine environments.

Effects of PAHs on meiofauna from three estuaries with different levels of urbanization in the South Atlantic.

Estuarine environments are suggested to be the final receivers of human pollution and are impacted by surrounding urbanization and compounds carried by the river waters that flow from the continent. Polycyclic aromatic hydrocarbons (PAHs) are among the contaminants that can reach estuaries and can directly affect marine conservation, being considered highly deleterious to organisms living in these environments. This research investigated the meiofauna of three estuaries exposed to different levels of urbanization and consequently different levels of PAH concentrations, in order to assess how these compounds and environmental factors affect the distribution, structure and diversity of these interstitial invertebrates. A total of 15 major meiofauna groups were identified, with Nematoda being the dominant taxon (74.64%), followed by Copepoda (9.55%) and Polychaeta (8.56%). It was possible to observe significant differences in all diversity indices studied in the estuaries. With the exception of average density, the diversity indices (richness, Shannon index and evenness) were higher in the reference estuary, Goiana estuarine system (GES). On the other hand, the Timbó estuarine system (TES) had the lowest Shannon index value and richness, while the Capibaribe estuarine system (CES) had the lowest evenness value. The latter two estuaries (TES and CES) presented intermediate and high levels of urbanization, respectively. The ecological quality assessment (EcoQ) in the studied estuaries was classified from Poor to Moderate and the estuary with the lowest demographic density in its surroundings, GES, showed a better ecological quality (Moderate EcoQ). A significant distance-based multivariate linear modelling regression (DistLM) was observed between the environmental variables and the density of the meiobenthic community, where PAHs and pH were the main contributors to organism variation. The sediments were characterized by predominance of very fine sand and silt-clay in the most polluted environments, while the control site environment (GES) was dominated by medium grains. The highest concentrations of PAHs were found in the most urbanized estuaries, and directly affected the structure of the interstitial benthic community. The metrics used in the present study proved to be adequate for assessing the environmental quality of the investigated estuaries.

Reef crab population changes after oil spill disaster reach Brazilian tropical environments.

The oil spill that reached Brazilian Coast in 2019 was one of the most extensive disasters and its effects on distinct species are still under investigation. This study evaluated the effects of the oil spill on the crab Pachygrapsus transversus in four reef areas in Northeast of Brazil that are also under different levels of chronic anthropogenic impacts. Changes in population aspects were investigated including maturity, sex ratio, and relative growth considering periods before and after the oil spill. An acute decrease in the number of females captured in areas most affected by oil spill was evident and may be associated with the closure of burrows used for protection. Crabs from the most touristic area presented a decrease in the medium size of carapace and maturation compared to crabs from other less visited areas, which highlights the importance of studying the effects of impacts on marine fauna.

Cellular accumulation of crude oil compounds reduces the competitive fitness of the coral symbiont Symbiodinium glynnii.

Oil spill events in the marine environment can have a deleterious impact on the affected ecosystems, such as coral reefs, with direct consequences for their socioeconomic value. The mutualistic relationship between tropical corals and their dinoflagellate symbionts (Symbiodiniaceae) provide structural and nutritional basis for a high local biodiversity in oligotrophic waters. Here, we investigated effects of crude oil water-accommodated fraction on the competitive fitness of the model zooxanthellae species Symbiodinium glynnii. Results of laboratory essays demonstrate that crude oil carbon is incorporated into the cellular biomass with a concomitant change of δ13C isotopic value. Carcinogenic/mutagenic polycyclic aromatic hydrocarbons were identified in the culture media and were responsible for a linear reduction in population growth of S. glynnii, presumably related to energy relocation for DNA repair. Additionally, the experiments revealed that physiological effects induced by crude oil compounds are genetically inherited by the following generations under non-contaminated growth conditions, and induce a reduction in the competitive fitness to cope with other environmental parameters, such as low salinity. We suggest that the effects of crude oil contamination represent an imparing factor for S. glynnii coping with anthropogenic drivers (e.g. warming and acidification) and interfere with the delicate symbiont-host relationship of tropical corals. This is especially relevant in the coastal areas of northeastern Brazil where an oil spill event deposited crude oil on shallow water sediments with the potential to be resuspended to the water column by physical and/or biological activity, enhancing the risk of future coral bleaching events.

Contamination and Toxicity of Surface Waters Along Rural and Urban Regions of the Capibaribe River in Tropical Northeastern Brazil.

The Capibaribe River provides water to a population of 1.7 million people in the Brazilian northeast, while receiving agricultural runoff and industrial and domestic effluents along its 280 km. The present study evaluated the ecotoxicity of surface waters along ten sites in rural and urban areas using zebrafish (Danio rerio) early-life stages and related it to water quality indices and chemical abiotic variables. Lethality rates, delays in embryo-larval development quantified by the general morphology score (GMS), and frequencies of developmental abnormalities were analyzed. A correlation was detected between zebrafish GMS and water quality index (WQI), sensitivity to domestic sewage contamination, and trophic state index, focused on eutrophication. These indices agreed in identifying a spatial pattern of smaller impact in terms of ecotoxicity, domestic sewage contamination, and eutrophication risk at three sites in rural areas (mean GMS 16.9), an intermediate impact at four sites with urban and agricultural influence (mean GMS 16.4), and greatest impacts at three more urbanized sites (mean GMS 14.9). Most frequent developmental abnormalities included noninflation of the swim bladder, delayed hatching, nonprotrusion of the mouth, blood stasis, and nondevelopment of pectoral fins. Toxic NH3 concentrations varied spatially, with higher concentrations in urban sites; and blood stasis correlated positively with NH3 , suggesting a causal relationship. Polycyclic aromatic hydrocarbons were detected in both rural and urbanized sites, contributing to detected toxicity. The present study demonstrates the potential of zebrafish early-life stages as an ecotoxicological model that may contribute to a better understanding of surface water quality and ecotoxicity in tropical river systems. Environ Toxicol Chem 2021;40:3063-3077. © 2021 SETAC.

Morphological abnormalities in Acartia lilljeborgii Giesbrecht (1889) (Copepoda, Calanoida) in a tropical estuary under industrial development.

Morphological abnormalities in crustaceans have been registered and several are attributed to pollution and others anthropogenic activities. This study reports for the first time a temporal record of the amount and variety of morphological abnormalities in Acartia lilljeborgii, in an impacted neotropical estuary. The specimens were obtained from Suape port area, Northeast Brazil, between May 2009 and September 2010 using a 300 µm plankton net. Seven types of abnormalities were observed in one of the terminal spines of the prosome, but no temporal variation of abnormalities was found in our study. The deformities were registered in 85.7% of samples and they were found in up to 10% of the individuals (3.2 ± 2.9%). The proportion of females with abnormalities was greater than for males, in opposite to most previous reports. Due to its high distribution and abundance in part of the neotropical Atlantic coastal area, A. lilljeborgii has the potential to be used as a bioindicator of environmental conditions, although the reasons of the abnormality occurrences should be accurately investigated.

Effects of substances released from a coal tar-based coating used to protect harbor structures on oysters.

Products coal tar-based are largely used as concrete structures as protective coatings but some questions about leaching and potential toxic effects remain unclear. A laboratory experiment exposing oysters to miniaturized concrete pillars painted with Lackpoxi N1761 over time was performed and trace elements and 17 PAH were monitored in seawater exposure media, and oyster tissues. The original paint composition was also analyzed, and high concentrations of trace elements and PAH were detected. Sharp increases in PAH concentrations were observed after 6-96 h in exposure media and oyster tissues, suggesting that these compounds were leached from the painted structures. In parallel, the integrity of the hemocytes lysosomal membranes of exposed organisms has been damaged. Based on the response of this biomarker, the use of Lackpoxi N1761 is potentially harmful to the environment and it is required that coal tar-based paints be evaluated according to the environmental risk assessment protocols.

Marine protected areas in Latin America and Caribbean threatened by polycyclic aromatic hydrocarbons.

The present study is a literature-based analysis investigating occurrence and the possible consequences of polycyclic aromatic hydrocarbons (PAH) in marine protected areas (MPAs) of Latin America and Caribbean. The approach using overlapping of georeferenced MPA polygons with data compiled from peer-reviewed literature, published during the last 15 years, showed 341 records of PAH in 9 countries. PAH was reported to occur within the boundaries of 36 MPAs located in Argentina, Brazil, Colombia, Mexico, Nicaragua and Uruguay. According to quality guidelines, low to moderate impacts are expected in MPAs categorized in different management classes. Considering sediment samples, 13% of the records presented concentrations enough to cause occasional toxicity. Such level of risk was also seen in Ramsar sites and in Amazonian MPAs. In addition, based on concentrations reported in biota, occasional deleterious effects on organisms from Biosphere Reserves might occur. Diagnostic ratios pointed out petrogenic and pyrolytic processes as PAH predominant sources, and were mainly attributed to the proximity to ports, industries and urban areas. MPAs located in the vicinity of impact-generating areas may be under threat and require government attention and action, mainly through implementation of contamination monitoring programs.

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.

Distribution and sources of organic contaminants in surface sediments of Hooghly river estuary and Sundarban mangrove, eastern coast of India.

This study investigated polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds such as polychlorinated biphenyls (PCBs) and DDT-related pesticides in surface sediments of Hooghly estuary and the Sundarban mangrove wetlands. Concentrations of ∑17PAH, ∑182PCB and ∑6DDT ranged from 15.4 to 1731, not detected (nd) to 13.5 and nd to 8.97 ng g-1 dry weight, respectively. Low levels of PCBs and low to moderate concentrations of DDTs and PAHs reflected recent development in West Bengal, which was dominated by agriculture and multifarious industries in the past. Diagnostic ratios suggested that major sources of PAHs are combustion processes, DDTs are input by agriculture, antifouling paints and public health campaigns, and organochlorines are predominantly from industrial origin. Heavier PCB congeners suggest local sources and short-range transport of such chemicals. Decision makers may use these findings for managing the Hooghly River watershed in order to promote a sustainable development on the eastern coast of India.

Aquatic organic matter: Classification and interaction with organic microcontaminants.

Organic matter (OM) in aquatic system is originated from autochthonous and allochthonous natural sources as well as anthropogenic inputs, and can be found in dissolved, particulate or colloidal form. According to the type/composition, OM can be divided in non-humic substances (NHS) or humic substances (HS). The present review focuses on the main groups that constitute the NHS (carbohydrates, proteins, lipids, and lignin) and their role as chemical biomarkers, as well as the main characteristics of HS are presented. HS functions, properties and mechanisms are discussed, in addition to their association to the fate, bioavailability, and toxicity of organic microcontaminants in the aquatic systems. Despite the growing diversity and potential impacts of organic microcontaminants to the aquatic environment, limited information is available about their association with OM. A protective effect is, however, normally seen since the presence of OM (HS mainly) may reduce bioavailability and, consequently, the concentration of organic microcontaminants within the organism. It may also affect the toxicity by either absorbing ultraviolet radiation incidence and, then, reducing the formation of phototoxic compounds, or by increasing the oxygen reactive species and, thus, affecting the decomposition of natural and anthropogenic organic compounds. In addition, the outcome data is hard to compare since each study follows unique experimental protocols. The often use of commercial humic acid (Aldrich) as a generic source of OM in studies can also hinder comparisons since differences in composition makes this type of OM not representative of any aquatic environment. Thus, the current challenge is find out how this clear fragmentation can be overcome.

Assessment of organotins and imposex in two estuaries of the northeastern Brazilian coast.

Butyltin compounds (BTs) were used worldwide, especially because of their properties as biocides. Due to its high toxicity, the use of tributyltin (TBT) in antifouling paints has been prohibited in most countries. The occurrence and impact of BTs were assessed in surface sediments and in Stramonita rustica populations of two tropical estuaries that host major ports in northeastern Brazil. ΣBT concentrations ranged from