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.

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.

Shrimp laccase degrades polycyclic aromatic hydrocarbons from an oil spill disaster in Brazil: A tool for marine environmental bioremediation.

Our work aims to purify, characterize and evaluate a laccase from by-products of the shrimp farming industry (Litopenaeus vannamei) for the degradation of Polycyclic Aromatic Hydrocarbons (PAHs) from 2019 oil spill in Brazilian coast. The enzyme was purified by affinity chromatography and characterized as thermostable, with activity above 90 °C and at alkaline pH. In addition, the laccase was also tolerant to copper, lead, cadmium, zinc, arsenic, hexane and methanol, with significant enzymatic activation in acetone and 10 mM mercury. Concerning PAHs' degradation, the enzyme degraded 42.40 % of the total compounds, degrading >50 % of fluorene, C4-naphthalenes, C3-naphthalenes, C2-naphthalenes, anthracene, acenaphthene, 1-methylnaphthalene and 2-methylnaphthalene. Thus, this laccase demonstrated important characteristics for bioremediation of marine environments contaminated by crude oil spills, representing a viable and ecological alternative for these purposes.

New insights on the role of nitrogen in the resistance to environmental stress in an endosymbiotic dinoflagellate.

Endosymbiotic dinoflagellates provide the nutritional basis for marine invertebrates, especially reef-building corals. These dinoflagellates are sensitive to environmental changes, and understanding the factors that can increase the resistance of the symbionts is crucial for the elucidation of the mechanisms involved with coral bleaching. Here, we demonstrate how the endosymbiotic dinoflagellate Durusdinium glynnii is affected by concentration (1760 vs 440 µM) and source (sodium nitrate vs urea) of nitrogen after light and thermal stress exposure. The effectiveness in the use of the two nitrogen forms was proven by the nitrogen isotopic signature. Overall, high nitrogen concentrations, regardless of source, increased D. glynnii growth, chlorophyll-a, and peridinin levels. During the pre-stress period, the use of urea accelerated the growth of D. glynnii compared to cells grown using sodium nitrate. During the luminous stress, high nitrate conditions increased cell growth, but no changes in pigments composition was observed. On the other hand, during thermal stress, a steep and steady decline in cell densities over time was observed, except for high urea condition, where there is cellular division and peridinin accumulation 72 h after the thermal shock. Our findings suggest peridinin has a protective role during the thermal stress, and the uptake of urea by D. glynnii can alleviate thermal stress responses, eventually mitigating coral bleaching events.

Can the stable isotope variability in a zooplankton time series be explained by its key species?

Stable isotope (SI) analysis is a standard tool to study marine food webs, usually based on the measurement of a few individuals from a small list of subjectively pre-defined species. The main objective of this study was to find out which species are significantly associated with the temporal variability of the SI composition of zooplankton in a tropical marine ecosystem. We investigated this by means of a novel species-biomass-isotopes-mixture (SBIM) approach that uses a relative biomass matrix to explain the SI signature of the zooplankton community. Furthermore, SBIM was applied to detect key taxa that can be considered bioindicators for important descriptors of ecosystem state (e.g., oligotrophy, carbon sources, mean trophic level). Plankton samples (64 µm mesh size) were obtained in Tamandaré Bay (northeastern Brazil) from June 2013 to August 2019. One aliquot of each sample was taken for stable isotope measurements and one for taxonomic identification and estimation of size and relative biomass. Total zooplankton biomass differed significantly between years, seasons and stations. Total zooplankton δ13C values ranged from -21.0 to -18.2‰ (mean ± standard deviation: -19.7 ± 0.7‰ in the dry season, and -19.4 ± 0.8‰ in the rainy season). Total zooplankton δ15N values ranged from 3.8 to 9.0‰ (7.0 ± 1.0‰ in the dry season, and 6.5 ± 1.2‰ rainy season). Total zooplankton C/N ratios ranged from 3.5 to 5.0 (4.2 ± 0.4 in the dry season and 4.2 ± 0.3 in the rainy season). The sparsely abundant and relatively large-sized copepod Pseudodiaptomus acutus was the most important species for explaining the variability in δ15N (22% of the total variability). Relative biomass (%) of P. acutus showed a strong positive correlation with δ15N, indicating a high trophic level (TL). Our results highlight the importance of less abundant taxa for marine food webs. Small-sized invertebrate larvae were negatively correlated with δ15N, indicating a TL below average. The copepod Dioithona oculata was the most important organism in explaining the δ13C of zooplankton (17.7% of the total variability, positive correlation with δ13C), indicating possible selective use of a13C-enriched food source (e.g., diatoms) by this cyclopoid copepod. Oithona spp. juveniles showed a negative relationship with zooplankton C/N ratio, which can be indicators of an oligotrophic ecosystem state and lipid-poor zooplankton. The tintinnid F. ehrenbergii showed a positive correlation with C/N, being an indicator for turbid "green waters'', during the rainy season, when the ecosystem was in a eutrophic state, with high lipid contents in the zooplankton community. The proposed SBIM approach opens up a novel pathway to understanding the factors and species that shape the temporal variability of food webs.

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.

Acetylcholinesterase from the charru mussel Mytella charruana: kinetic characterization, physicochemical properties and potential as in vitro biomarker in environmental monitoring of mollusk extraction areas.

Acetylcholinesterase (AChE; EC 3.1.1.7) from aquatic organisms have been used to evaluate the exposure of specimens to pesticides and heavy metals at sublethal levels in environmental samples. AChE of Mytella charruana was extracted to characterize its physicochemical and kinetic properties as well as the effect of organophosphate (dichlorvos, diazinon, chlorpyrifos, methyl-parathion and temephos), carbamates (carbaryl, carbofuran and aldicarb), benzoylureas (diflubenzuron and novaluron), pyrethroid (cypermethrin) and juvenile hormone analog - JHA (pyriproxyfen) and the effect of metal ions: Hg2+, Cd2+, Pb2+, As3+, Cu2+ and Zn2+, in order to evaluate the potential of the enzyme as biomarker. The optimum pH of M. charruana AChE was 8.5 and the maximum activity peak occurred at 48 °C, being highly thermostable maintaining 97.8% of its activity after incubation at 60 °C. The Michaelis-Menten constants (km) for the substrates acetylthiocholine and propionylthiocholine were 2.8 ± 1.26 and 4.94 ± 6.9 mmol·L-1, respectively. The Vmax values for the same substrates were 22.6 ± 0.90 and 10.2 ± 4.94 mU·mg-1, respectively. Specific inhibition results suggest an AChE presenting active site with dimensions between those of AChE and butyrylcholinesterase (BChE). The IC20 values related to the effect of the pesticides on the enzyme showed higher inhibitory power of temephos (0.17 µmol·L-1), followed by aldicarb (0.19 µmol·L-1) and diflubenzuron (0.23 µmol·L-1). Metal ions inhibited M. charruana enzyme in the following order: Hg2+ > Pb2+ > Cd2+ > As3+ > Cu2+ > Zn2+. These data suggest that the enzyme showed potential as in vitro biomarker of the exposure to temephos, mercury, zinc and copper.

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.

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.

Use of Tisbe biminiensis nauplii in ecotoxicological tests and geochemical analyses to assess the sediment quality of a tropical urban estuary in northeastern Brazil.

An approach pooling geochemical analyses and ecotoxicological tests has been applied to assess the sediment quality of the Capibaribe River Estuary, Brazil. Toxicity tests were performed to compare a well-established, labor-intensive protocol using ovigerous females to a new, easier and faster protocol using nauplii of the epibenthic marine copepod Tisbe biminiensis. The endpoints of the nauplii toxicity test were comparable to those of the female test. Nauplii proved to be more sensitive than females as a biological model for indicating sediment toxicity. All sediments collected had at least one contaminant above the threshold effects level (TEL) proposed in the literature. Furthermore, more than one-third of samples exhibited contaminants above the probable effects level (PEL). The PCA revealed that nauplii mortality was associated with metals in October 2014, which was confirmed by the Spearman correlation factor. In contrast, no strong association among contaminants and toxicological endpoints in May 2015 was found.

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

Sources and distribution of aromatic hydrocarbons in a tropical marine protected area estuary under influence of sugarcane cultivation.

Goiana estuary is a well preserved marine protected area (MPA) located on the northeastern coast of Brazil. Despite its current state, human activities in the watershed represent a potential threat to long term local preservation. Dissolved/dispersed aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were investigated in water and sediments across the estuarine salt gradient. Concentration of aromatic hydrocarbons was low in all samples. According to results, aromatic hydrocarbons are associated to suspended particulate matter (SPM) carried to the estuary by river waters. An estuarine turbidity maximum (ETM) was identified in the upper estuary, indicating that both sediments and contaminants are trapped prior to an occasional export to the adjacent sea. PAHs distribution in sediments were associated with organic matter and mud content. Diagnostic ratios indicated pyrolytic processes as the main local source of PAHs that are probably associated with sugarcane burning and combustion engines. Low PAH concentrations probably do not cause adverse biological effects to the local biota although their presence indicate anthropogenic contamination and pressure on the Goiana estuary MPA.

Shell alterations in limpets as putative biomarkers for multi-impacted coastal areas.

During the last years, shell alterations in gastropods have been proposed as tools to be used in monitoring programs. However, no studies were so far performed investigating the relationships among shell parameters and classical biomarkers of damage. The relationship between shell alterations (biometrics, shape and elemental composition) and biomarkers (LPO and DNA strand break) was evaluated in the limpet L. subrugosa sampled along a contamination gradient in a multi-impacted coastal zone from southeastern Brazil. Statistically significant differences were detected among sites under different pollution levels. The occurrence of shell malformations was consistent with environmental levels of several hazardous substances reported for the studied area and related to lipid peroxidation and DNA damage. In addition, considering the low mobility, wide geographic distribution, ease of collection and abundance of limpets in coastal zones, this putative tool may be a cost-effective alternative to traditional biomarkers. Thus, shell alterations in limpets seem to be good proxies for assessing biological adverse effects in multi-impacted coastal zones.

Organic pollutants and their correlation with stable isotopes in vegetation from King George Island, Antarctica.

Vegetation samples from King George Island, Antarctica (62°05'S, 058°23'W) were collected in the austral summer of 2004-2005. Lichens (Usnea aurantiaco-atra and Usnea antarctica), mosses (Sanionia uncinata, Syntrichia princeps and Brachytecium sp.), and one angiosperm (Colobanthus quitensis) species were analyzed for persistent organic pollutants as well as δ(13)C and δ(15)N stable isotopes. The following contaminants were found above the method detection limit (MDL): HCB (0.141-1.06 ng g(-1) dry weight), HCHs (

Chlorinated pesticides and polychlorinated biphenyls in marine tucuxi dolphins (Sotalia fluviatilis) from the Cananéia estuary, southeastern Brazil.

The Cananéia estuary is an important biological area on the southeast coast of Brazil. In the past, it was impacted by both chlorinated pesticides and polychlorinated biphenyls (PCBs) due to its natural location. The marine tucuxi dolphin (Sotalia fluviatilis) is a top predator in this ecosystem and can be found year round in Cananéia estuarine waters that represent an important nursing area for the species. This work investigated chlorinated compounds in the blubber of nine individuals from the Cananéia estuary. Residue levels of DDTs (0.541-125 microg g(-1) lipid wt.) were the highest, followed by PCBs (0.2-9.22 microg g(-1) lipid wt.), mirex (0.014-0.312 microg g(-1) lipid wt.), chlordanes (0.001-0.047 microg g(-1) lipid wt.), HCHs (<0.003-0.044 microg g(-1) lipid wt.), and HCB (n.d.-0.024 microg g(-1) lipid wt.). The mean p,p'-DDE/Sigma DDT ratio was approximately 0.8 and is indicative of the former DDT application in the study area. PCB contamination is suggested to be associated with atmospheric transport and relative proximity to the Cubatão industrial complex-the most important along the Brazilian coast. Low levels of HCHs and HCB can be attributed to their high volatility in tropical environments. Concentrations of organochlorines in the blubber of marine tucuxis from the Cananéia estuary were lower than levels found in small cetacean species from developed countries, where the input of these compounds was considerably greater than in Brazil. At extremes, male dolphins can present DDT burden several orders of magnitude higher than females. Despite the high levels of total DDT found in males, the major detected compound was p,p'-DDE which is considered to be of low toxicity.