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We investigated the occurrence and the environmental risk of eight contaminants of emerging concern (CECs; acetaminophen, naproxen, diclofenac, methylparaben, 17ß-estradiol, sulfathiazole, sulfadimethoxine, and sulfamethazine) in three Brazilian water bodies, namely, the Monjolinho River Basin (São Paulo State), the Mogi Guaçu River (São Paulo State), and the Itapecuru River (Maranhão State) in three sampling campaigns. The CECs were only quantified in surface water samples collected at the Monjolinho River Basin. Acetaminophen, naproxen, and methylparaben were detected in the range of <200 to 575.9 ng L-1, <200 to 224.7 ng L-1, and <200 to 303.6 ng L-1, respectively. The detection frequencies of the three measured compounds were between 33% and 67%. The highest concentrations of CECs were associated with intense urbanization and untreated sewage discharge. Furthermore, CEC concentrations were significantly correlated with total organic carbon, electrical conductivity, and dissolved oxygen levels, suggesting that domestic pollution from urban areas is an important source in the distribution of CECs in the Monjolinho River Basin. The environmental risk assessment indicated a high risk for acetaminophen (risk quotient [RQ] values between 2.1 and 5.8), a medium risk for naproxen (RQs between 0.6 and 0.7), and a low risk for methylparaben (RQs < 0.1) to the freshwater biota of the Monjolinho River Basin. Our findings show potential threats of CECs in Brazilian water bodies, especially in vulnerable areas, and reinforce the need for improvements in environmental regulations to include monitoring and control of these compounds in aquatic systems. Environ Toxicol Chem 2024;43:2199-2210. © 2024 SETAC.

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Diuron and Irgarol are common antifouling biocides used in paints to prevent the attachment and growth of fouling organisms on ship hulls and other submerged structures. Concerns about their toxicity to non-target aquatic organisms have led to various restrictions on their use in antifouling paints worldwide. Previous studies have shown the widespread presence of these substances in port areas along the Brazilian coast, with a concentration primarily in the southern part of the country. In this study, we conducted six sampling campaigns over the course of 1 year to assess the presence and associated risks of Diuron and Irgarol in water collected from areas under the influence of the Maranhão Port Complex in the Brazilian Northeast. Our results revealed the absence of Irgarol in the study area, irrespective of the sampling season and site. In contrast, the mean concentrations of Diuron varied between 2.0 ng L-1 and 34.1 ng L-1 and were detected at least once at each sampling site. We conducted a risk assessment of Diuron levels in this area using the risk quotient (RQ) method. Our findings indicated that Diuron levels at all sampling sites during at least one campaign yielded an RQ greater than 1, with a maximum of 22.7, classifying the risk as "high" based on the proposed risk classification. This study underscores the continued concern regarding the presence of antifouling biocides in significant ports and marinas in Brazilian ports, despite international bans.

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The diffusive gradients in thin films (DGT) technique pre-concentrates labile species of trace elements, giving time-integrated in situ information about their labile concentrations. All previous DGT approaches for simultaneous uptake of cations and anions have used the hazardous polyacrylamide reagent to immobilize the binding phase. The present work proposes a diffusive layer of agarose and a mixed binding layer of ZrO2 and Chelex 100 immobilized in an agarose hydrogel to simultaneously determine the labile concentration of cations (Mn, Co, Ni, Cu, Zn and Cd) and anions (V, As, Se, Mo and Sb) in aquatic systems. The use of both layers using agarose instead of carcinogenic polyacrylamide as the hydrogel significantly reduces the costs and simplifies the manufacturing process. The proposed device was evaluated through recovery tests, deployment curves and pH/ionic strength tests. The mixed binding layer was compared with commercially available DGT devices for in situ deployment in river water. The relationships between accumulated mass and time (24 h) was linear (r2 > 0.9) for all analytes. The diffusion coefficients obtained were consistent with the literature, ranging from 3.98 to 8.43 × 10-6 cm2 s-1. Except for Zn at pH 8.0, the obtained values of CDGT/Cbulk were within the range of 1.00 ± 0.2 for the studied range of pH and for most ionic strengths. However, at low ionic strength, the concentrations of Mn, Co, Ni, Zn, V and Mo were underestimated. The concentrations of trace elements determined in river water using the proposed devices agreed with the labile concentrations determined by using commercial devices.

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The occurrence of high arsenic concentrations (up to 3000 µg L-1) in water of soda lakes of the Pantanal wetland is a remarkable case of natural arsenic contamination in South America. However, little is known about arsenic speciation in this environment, particularly regarding speciation changes related to lake trophic status and seasonal variations. To fill this gap, arsenic speciation analysis was carried out in surface (SW) and subsurface (SSW) waters sampled in five soda lakes with different eutrophication status, in two dry and one wet season. As(V) was the dominant species in these waters, while As(III), DMA, MMA and likely complex organic species were present in lower amounts. The results allow to conclude that the arsenic speciation in SW and SSW varies seasonally according to the regional wet or dry periods and lake water levels. In eutrophic turbid and in oligotrophic vegetated soda lakes, arsenic speciation was also characterized by spatial differences between edge and center or between the SW and SSW. Cyanobacteria or macrophytes/algae are involved in arsenic biotransformation in soda lakes through its metabolic and detoxification processes. Significant variation in surface water arsenic speciation occurs as a result of seasonal primary production fluctuation or water arsenic concentration changes in the soda lakes, increasing organoarsenics in dry periods, whereas in flood periods, As(V) prevails. Spatial distribution of arsenic species is significantly impacted by biogeochemical conditions at the water/sediment interface in soda lakes.

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Methylmercury (MeHg) is highly toxic to the human brain. Although much is known about MeHg neurotoxic effects, less is known about how chronic MeHg affects hippocampal amino acids and other neurochemical markers in adult mice. In this study, we evaluated the MeHg effects on systemic lipids and inflammation, hippocampal oxidative stress, amino acid levels, neuroinflammation, and behavior in adult male mice. Challenged mice received MeHg in drinking water (2 mg/L) for 30 days. We assessed weight gain, total plasma cholesterol (TC), triglycerides (TG), endotoxin, and TNF levels. Hippocampal myeloperoxidase (MPO), malondialdehyde (MDA), acetylcholinesterase (AChE), amino acid levels, and cytokine transcripts were evaluated. Mice underwent open field, object recognition, Y, and Barnes maze tests. MeHg-intoxicated mice had higher weight gain and increased the TG and TC plasma levels. Elevated circulating TNF and LPS confirmed systemic inflammation. Higher levels of MPO and MDA and a reduction in IL-4 transcripts were found in the hippocampus. MeHg-intoxication led to increased GABA and glycine, reduced hippocampal taurine levels, delayed acquisition in the Barnes maze, and poor locomotor activity. No significant changes were found in AChE activity and object recognition. Altogether, our findings highlight chronic MeHg-induced effects that may have long-term mental health consequences in prolonged exposed human populations.

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In situ fractionation and redox speciation of As in three different saline-alkaline lakes (green, black and crystalline lakes) in the Pantanal of Nhecolândia (Brazil) were performed by using Diffusive Gradients in Thin films (DGT). The results indicated that As is present mainly in dissolved form. Total As concentration was similar when using different filter membranes, demonstrating that the species adsorbed by DGT devices were <10 kDa. Higher concentrations of labile total As were observed in the center of the lakes, indicating that the nature of the organic matter influences the formation of As complexes. Total As concentrations determined by using ZrO2 DGT were consistent with As concentration in ultrafiltered water samples collected in the black lake. However, part of the data about As(III) obtained in grab samples contrasted with DGT results. The differences observed may indicate that alterations in the species occur during the storage period before analysis by ultrafiltration. As(III) concentrations measured by DGT in the black and crystalline lakes were 1-3 µg L-1 and 4-7 µg L-1, respectively, accounting for only 4%-8% of the total DGT inorganic As. In the green lake, As(III) concentrations were significantly higher at the center (217 µg L-1). Both the phytoplankton community and the dissolved organic carbon influence the As speciation and bioavailability in the lakes of Nhecolândia. The DGT approach used in the present work was able to perform As speciation and demonstrates that in situ sampling analytical techniques are essential in understanding As speciation and its behavior in complex natural aquatic systems.

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Arsenic (As) is a naturally occurring element in the Earth's crust, exhibiting toxicity towards a wide range of living organisms. Its properties and environmental dynamics are strongly regulated by its speciation, and the species As(III) and As(V) are the most commonly found in environmental systems. Recently, high concentrations of As were found in saline-alkaline lakes of the Pantanal (Brazil), which is the largest wetland area in the world. Therefore, we evaluated As contamination and its redox speciation (As(III) and As(V)) at the soil/water interface of biogeochemically distinct saline-alkaline lakes of Pantanal wetlands (Brazil). Both conventional sampling and in situ diffusive gradients in thin films (DGT) technique were employed. Zirconium oxide and 3-mercaptopropyl were used as ligand phases in DGT to selectively bind As species. High concentrations of total dissolved As in a shallow water table were found (<2337.5 µg L-1), whereas levels in soils were up to 2.4 µg g-1. Distinct scenarios were observed when comparing speciation analysis through spot sampling and DGT. Considering spot sampling, As(V) was the main species detected, whereas As(III) was only detected in only a few samples (<4.2 µg L-1). Conversely, results obtained by DGT showed that labile As(III) dominated arsenic speciation at the soil/water interface with levels up to 203.0 µg L-1. Coupling DGT data and DGT induced fluxes in sediments and soils model allowed obtaining kinetic data, showing that the soil barely participated in the arsenic dynamics on the shore of the lakes, and that this participation depends on the evapoconcentration process occurring in the region. Therefore, soil acts like a nonreactive matrix depending on the natural concentration process. In addition, our results reinforced the different geochemical characteristics of the studied saline-alkaline lakes and highlights the importance of robust passive sampling techniques in the context of metal/metalloid speciation in environmental analysis.

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Antifouling biocides, such as irgarol and diuron, are commonly used in antifouling paints. Recently, studies carried out in a Brazilian region of ecological concern have warned for extremely high levels of these biocides. So, this work focused on a 4-year (2015-2018) evaluation considering the occurrence, environmental fate, seasonal variations and ecological risk assessment of irgarol and diuron in water and sediment from São Marcos Bay, Brazil, which is an area of international relevance located in the Amazon region. The results showed the ubiquitous presence of antifouling biocides, as well as their wide distribution along the bay. The concentration range of irgarol was between <0.8 and 89.4 ng L-1 in water and between <0.5 and 9.2 ng g-1dw in sediments, whereas diuron showed a range between <1.4 and 22.0 ng L-1 in water and between <2.0 and 15.0 ng g-1dw in sediments. The distribution of the biocides was mainly related to the intense Bay hydrodynamics. The environmental risk assessment showed that irgarol and diuron posed "high risk" to the aquatic biota of São Marcos Bay, exceeding international Environmental Quality Guidelines. The results represent a robust study on the environmental fate of such biocides and intend to be a useful data source for eventual legislation since regulation concerning antifouling substances is necessary for Brazil.

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Fouling organisms attach and grow on submerged surfaces causing several economic losses. Thus, biocides have been introduced in antifouling paints in order to avoid this phenomenon, but their widespread use became a global problem, mainly in ports, leisure and fishing boat harbors, since these substances can be highly toxic to non-target organisms. The occurrence and environmental behavior of antifouling biocides are especially unknown in some peculiar regions, such as Amazon areas. Thus, the aim of this work was to evaluate, for the first time, levels and the partitioning behavior of the antifouling organic biocides irgarol, diuron and also stable degradation products of dichlofluanid and diuron (DMSA and DCPMU, respectively) in sediments and porewaters from a high boat traffic area located in the Northeast of Brazil, a pre-Amazon region. Our results showed high concentrations of irgarol (<1.0-89.7 µg kg-1) and diuron (<5.0-55.2 µg kg-1) in sediments. In porewater, DCPMU (<0.03-0.67 µg L-1) and DMSA (<0.008-0.263 µg L-1) were the mainly substances detected. High Kd and Koc obtained for both irgarol and diuron showed a partitioning preference in the solid phase. This work represents one of the few registers of contamination by antifouling substances in Amazonian areas, despite their environmental relevance.

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