Five years after the collapse of the Fundão Dam: lessons from temporal monitoring of chemistry and acute toxicity.

In November 2015, the Fundão Dam break released millions of tons of metal-rich tailings into the Doce River Basin (DRB), causing catastrophic damage and potential ecological effects that reached the Atlantic Ocean. This study aimed to evaluate the geochemistry and toxicity of water and sediments collected in the DRB from 2015 to 2019 and to determine the spatial and temporal trends. Water and sediment samples were analyzed for metals and As by inductively coupled plasma optical emission spectrometry (ICP-OES), and acute toxicity for Daphnia similis or D. magna. Results were explored using geochemical indices and correlation analyzes. Overall, higher concentrations of metals and As in water and sediments were observed immediately after dam breakage, but the levels exhibited a decreasing trend over time, although the levels of some elements such as As and Mn remained high in the upper DRB. The geochemical indices indicated mostly low to moderate contamination, and the enrichment factor (EF) demonstrated a higher enrichment of Mn in the upper DRB. Acute toxicity to water fleas (D. similis and D. magna) was occasionally observed in waters and sediments, but the reference samples were toxic, and the short-term effects were not correlated with metals and As. Overall, the results showed limited bioavailability of metals and As and a decreasing trend in their concentrations, indicating an ongoing recovery process in DRB. These results are important to decision-making regarding the disaster and actions for environmental restoration.

Toxicity of antifouling biocides on planktonic and benthic neotropical species.

Organotin-based (OTs: TBT and TPT) antifouling paints have been banned worldwide, but recent inputs have been detected in tropical coastal areas. However, there is a lack of studies evaluating the toxicity of both legacy and their substitute antifouling booster biocides (e.g., Irgarol and diuron) on neotropical species. Therefore, the acute toxicity of four antifouling biocides (TBT, TPT, Irgarol, and diuron) was investigated using the marine planktonic organisms Acartia tonsa and Mysidopsis juniae, the estuarine tanaid Monokalliapseudes schubarti (water exposure), and the burrowing amphipod Tiburonella viscana (spiked sediment exposure). Results confirmed the high toxicity of the OTs, especially to planktonic species, being about two orders of magnitude higher than Irgarol and diuron. Toxic effects of antifouling compounds were observed at levels currently found in tropical coastal zones, representing a threat to planktonic and benthic invertebrates. Furthermore, deterministic PNECmarine sediment values suggest that environmental hazards in tropical regions may be higher due to the higher sensitivity of tropical organisms. Since regulations on antifouling biocides are still restricted to a few countries, more ecotoxicological studies are needed to derivate environmental quality standards based on realistic scenarios. The present study brings essential contributions regarding the ecological risks of these substances in tropical and subtropical zones.

Ecological risk assessment of metal and hydrocarbon pollution in sediments from an urban tropical estuary: Tijuca lagoon (Rio de Janeiro, Brazil).

Urban tropical lagoons are often impacted by eutrophication, metal, and polycyclic aromatic hydrocarbon (PAH) contamination, but the toxicity of their bottom sediments is still poorly investigated in South America. Aiming to contribute to filling this gap, a sediment quality assessment was conducted in the Tijuca Lagoon (Rio de Janeiro, Brazil) using different lines of evidence (LOEs) including sediment characterization, determination of metals and PAHs, and acute toxicity testing with burrowing amphipods (Tiburonella viscana). Mud and organic matter contents played a crucial role in contaminant distribution along the lagoon. The concentrations of PAH were generally low (mean ΣPAH = 795.42 ± 1146.2 ng/g; n = 23), but a contamination hotspot of light PAH compounds was identified. Such PAHs were mainly pyrolytic, probably related to the deposition of atmospheric pollution, although petrogenic compounds also occur in the lagoon. The data indicated the occurrence of geochemical anomalies of Zn, Cu, Pb, and Hg (mean values = 176.9 ± 91.6, 45.1 ± 21.3, 35.2 ± 15.0, 0.1442 ± 0.0893 mg/kg, respectively; n = 23), probably associated with industrial wastes, garbage deposition, urban runoff, and domestic sewage contributions. The mortality of T. viscana was significant for more than 85% of the samples (mean mortality = 70.3 ± 26.0%; n = 23), but it was not significantly correlated with PAH and metal concentrations. On the other side, domestic sewage contributions and eutrophication seem to play a relevant role in sediment toxicity. Actually, the toxicity observed in the tests seems to be due to the simultaneous influence of multiple toxicants and their combined effects on the organisms. Such stressors may include not only metals, PAH, and eutrophication but also chemicals not evaluated in this study, such as hormones, pharmaceuticals and personal care compounds, perfluorocompounds, detergents, and others.

Effects of mycogenic silver nanoparticles on organisms of different trophic levels.

Biogenic silver nanoparticles (AgNPs) are considered a promising alternative to their synthetic versions. However, the environmental impact of such nanomaterials is still scarcely understood. Thus, the present study aims at assessing the antimicrobial action and ecotoxicity of AgNPs biosynthesized by the fungus Aspergillus niger IBCLP20 towards three freshwater organisms: Chlorella vulgaris, Daphnia similis, and Danio rerio (zebrafish). AgNPs IBCLP20 showed antibacterial action against Klebsiella pneumoniae between 5 and 100 µg mL-1, and antifungal action against Trichophyton mentagrophytes in concentrations ranging from 20 to 100 µg mL-1. The cell density of the microalgae Chlorella vulgaris decreased 40% after 96 h of exposure to AgNPs IBCLP20, at the highest concentration analysed (100 µg L-1). The 48 h median lethal concentration for Daphnia similis was estimated as 4.06 µg L-1 (2.29-6.42 µg L-1). AgNPs IBCLP20 and silver nitrate (AgNO3) caused no acute toxicity on adult zebrafish, although they did induce several physiological changes. Mycosynthetized AgNPs caused a significant increase (p < 0.05) in oxygen consumption at the highest concentration studied (75 µg L-1) and an increase in the excretion of ammonia at the lower concentrations, followed by a reduction at the higher concentrations. Such findings are comparable with AgNO3, which increased the oxygen consumption on low exposure concentrations, followed by a decrease at the high tested concentrations, while impairing the excretion of ammonia in all tested concentrations. The present results show that AgNPs IBCLP20 have biocidal properties. Mycogenic AgNPs induce adverse effects on organisms of different trophic levels and understanding their impact is detrimental to developing countermeasures aimed at preventing any negative environmental effects of such novel materials.

Levels of hydrocarbons and toxicity of water-soluble fractions of maritime fuels on neotropical invertebrates.

Accidents involving fuels and oil spills are among the main sources of hydrocarbons to the marine ecosystems and often damage the biota. Diesel and bunker oil are two examples of fuels with broad application that release hydrocarbons to the aquatic environment and little is known about their toxicity on tropical organisms. This study aimed to assess the toxicity of the water-soluble fraction (WSF) of diesel and bunker oils to neotropical marine invertebrates. Commercial fuels were purchased for WSF extraction, analyzed for total petroleum hydrocarbons (TPH), and polycyclic aromatic hydrocarbons (PAHs), and acute and chronic toxicity determined. The WSF analyzed contained varied levels of TPH and PAHs mixtures, especially low molecular weight PAHs; bunker WSF presented higher amounts of TPH and PAHs. Both WSFs tested produced significant mortality of the brine shrimp Artemia salina, affected the reproduction rate of the copepod Nitokra sp, and impaired the embryo-larval development of the mussel Perna perna and of the sea urchin Lytechinus variegatus. In general WSF from diesel was more toxic to the organisms tested, but bunker WSF was more toxic to embryos of L. variegatus. Toxicity started from concentrations of 3% WSF, which can be environmentally relevant after an oil spill, indicating that marine biota may be adversely affected in short term.

Metal pollution in surface sediments from Rodrigo de Freitas Lagoon (Rio de Janeiro, Brazil): Toxic effects on marine organisms.

The Rodrigo de Freitas Lagoon (RFL - Rio de Janeiro, RJ, Brazil) is a highly polluted and eutrophic lacustrine system, which has been often used for the practice of aquatic sports, including during the 2016 Summer Olympic Games. This study proposes the evaluation of metal concentrations in surface sediments from the RFL before and after urban interventions performed for the 2016 Olympics, as well as their toxicity to the benthic amphipod Tiburonella viscana and embryos of the sea-urchin Echinometra lucunter. Metal concentrations determined in 2017 were significantly higher than those obtained in 2015 (especially Cu, Cd and Ni), suggesting that the interventions performed to fulfill the requirements of the Olympics increased metal contents in sediments. The sediments from the northern sector of the RFL were muddier, more organically enriched, exhibited higher metal concentrations and were more toxic to T. viscana when compared to the sediments collected in the southern sector. This fact is particularly important since the practice of sports, including during the 2016 Olympics, has been preferably performed in the northern sector. Metal distribution was strongly correlated with organic matter and mud contents. The toxicity to E. lucunter embryos was high for both northern and southern sediments; most of the samples led to 100% lack or abnormal embryonic development. The integration of physical, chemical and ecotoxicological data indicates that the mortality to T. viscana was correlated with metal contents, whereas the toxicity to E. lucunter was apparently related to the release of ammonia from the sediment to water column. Finally, high metal concentrations and the toxicity to aquatic organisms evidence the ecological risks to the biota from RFL.

Toxicidade de águas e sedimentos em um rio afetado por atividades mineradoras pretéritas / Water and sediment toxicity in a river affected by formermining residues

bacia do Rio Ribeira de Iguape foi palco de intensa atividade de mineração de chumbo e, como resultado, estima-se que o rio Ribeira de Iguape tenha recebido a descarga de aproximadamente 5,5 t/mês de materiais ricos em As, Ba, Cd, Pb, Cu, Cr e Zn. No presente trabalho, foi analisada a toxicidade de sedimentos e águas coletados ao longo do rio com o intuito de avaliara qualidade ambiental, tendo sido realizadas 3 campanhas de coleta, entre 2009 e 2010. Os testes de toxicidade aguda foram conduzidos com o cladócero Daphnia similis, utilizando as amostras brutas de água e a exposição aos sedimentos pela interface sedimento-água. Os resultados indicaram, em geral, ausência de toxicidade, tanto para sedimentos quanto para águas, com efeitos tóxicos agudos registrados apenas episodicamente (toxicidade marginal). Tais resultados são coerentes com as baixas concentrações de metais em águas e sedimentos indicadas na literatura, porém diferem do monitoramento feito pela agência ambiental estadual, que tem registrado toxicidade crônica. Essa toxicidade aguda eventual indica, ainda, que embora a qualidade do Rio Ribeira de Iguape esteja sendo recuperada, as condições ainda não estão totalmente controladas.

The Ribeira de Iguape River basin received intense mining activities for lead exploiting and, as a result, the river received the discharges of estimated amounts of 5.5 tons/month of material rich in As, Ba, Cd, Pb, Cu, Cr and Zn. In this article, the toxicity of waters and sediments collected in Ribeira de Iguape River was assessed aiming to estimate environmental quality. Three sampling campaigns were conducted, from 2009 to 2010. Toxicity tests with the cladoceran Daphnia similis were done for water samples and for sediments, in this case using sediment-water interface exposure. Results showed in general absence of toxicity for sediments and waters, and only eventually were acute effects registered (marginal toxicity). Results are consistent with the conditions indicated by the literature, of low concentrations of metals in waters and sediments; however they differ from the monitoring made by the state environmental agency, which registered chronic toxicity. The occurrence of eventual acute toxicity indicates that although Ribeira de Iguape River quality is being restored, conditions still are not totally under control.

Organotin contamination in South American coastal areas.

Organotin compounds (OTs) were used in antifouling paints for more than four decades. However, due to their widespread intensive use and high toxicity, undesirable effects in non-target marine organisms have been detected since the early 1980s. Consequently, the International Maritime Organization banned new maritime applications of these products on January 1, 2003 and their presence on ship hulls from January 1, 2008. Although extensively studied in Europe, North America, Oceania, and Asia, environmental levels and effects of organotin contamination are still poorly known for South America. Thus, the current review aimed to present the actual status of this problem in South America by summarizing and comparing the available data in the literature. An overview of the OTs concentrations in sediment and biota and their effects, mainly imposex in marine gastropods, are presented. This work showed that in Atlantic coastal areas of South America there are "hot spots" of OTs contamination, similar to that observed in industrialized countries of Northern Hemisphere. On the other hand, the number of accomplished studies in the Pacific coast is extremely low. Despite the limitation on studies about OTs environmental levels and their related effects, the available data pointed out for a widespread TBT contamination along the South American coastal areas. Therefore, the establishment of baselines of organotin contamination in the Pacific coast and the implementation of temporal trend studies in the South American coastal areas is crucial to verify the effectiveness of local regulations and OTs global ban, and to map the most sensitive areas related to present and future antifouling impacts.

Comparative toxicity of antifouling compounds on the development of sea urchin.

In the present study, embryotoxicity experiments using the sea urchin Lytechinus variegatus were carried out to better clarify the ecotoxicological effects of tributyltin (TBT) and triphenyltin (TPT) (the recently banned antifouling agents), and Irgarol and Diuron (two of the new commonly used booster biocides). Organisms were individually examined to evaluate the intensity and type of effects on embryo-larval development, this procedure has not been commonly used, however it showed to be a potentially suitable approach for toxicity assessment. NOEC and LOEC were similar for compounds of same chemical class, and IC10 values were very close and showed overlapping of confidence intervals between TBT and TPT, and between Diuron and Irgarol. In addition, IC10 were similar to NOEC values. Regardless of this, the observed effects were different. Embryo development was interrupted at the gastrula and blastula stages at 1.25 and 2.5 µg l(-1) of TBT, respectively, whereas pluteus stage was reached with the corresponding concentrations of TPT. Furthermore, embryos reached the prism and morula stages at 5 µg l(-1) of TPT and TBT, respectively. The effects induced by Irgarol were also more pronounced than those caused by Diuron. Pluteus stage was always reached at any tested Diuron concentration, while embryogenesis was interrupted at blastula/gastrula stages at the highest concentrations of Irgarol. Therefore, this study proposes a complementary approach for interpreting embryo-larval responses that may be employed together with the traditional way of analysis. Consequently, this application leads to a more powerful ecotoxicological assessment tool focused on embryotoxicity.