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Fish constitutes the main protein source for the Amazonian population. However, the impact of different anthropogenic activities on trace element and metal accumulation in fish and their risks for human health at a regional scale remain largely unexplored. Here we assessed exposure levels of 10 trace elements and metals (Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Pb, and Hg) in 56 samples belonging to 11 different species of fish from the Brazilian Amazon. We studied the relationship between exposure levels, fish origin, and fish feeding habits, and assessed toxicological and carcinogenic risks for the Amazonian population. No significant correlation was found between sampling site and exposure levels to the studied elements, but a significant difference was found between the accumulation of some metals and the position of the fish species in the food chain. The concentrations of Cr and Hg in fish flesh were found to exceed the Brazilian limits for human consumption. This study shows that current fish consumption patterns can lead to estimated daily intakes of Hg, As and Cr that exceed the oral reference dose, thus posing a toxicological concern. Furthermore, carcinogenic risks may be expected due to the continued exposure to Cr and As. The results of this study show that the consumption of wild caught fish in the Amazon region should be controlled. Moreover, continued monitoring of trace element and metal contamination in fish and on the health of the Amazonian population is recommended, particularly for riverine and indigenous communities.

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Imidacloprid is a neonicotinoid insecticide that has received particular attention due to its widespread use and potential adverse effects for aquatic and terrestrial ecosystems. Its toxicity to aquatic organisms has been evaluated in central and southern Europe as well as in (sub-)tropical regions of Africa and Asia, showing high toxic potential for some aquatic insects and zooplankton taxa. However, its toxicity to aquatic organisms representative of tropical regions of Latin America has never been evaluated. To fill this knowledge gap, we carried out a mesocosm experiment to assess the short- and long-term effects of imidacloprid on freshwater invertebrate communities representative of the Ecuadorian Amazon. A mesocosm experiment was conducted with five weekly applications of imidacloprid at four nominal concentrations (0.01 µg/L, 0.1 µg/L, 1 µg/L and 10 µg/L). Toxic effects were evaluated on zooplankton and macroinvertebrate populations and communities, as well as on water quality parameters for 70 days. Given the climatic conditions prevailing in the study area, characterized by a high solar radiation and abundant rainfall that resulted in mesocosm overflow, there was a rapid dissipation of the test compound from the water column (half-life: 4 days). The macroinvertebrate taxa Callibaetis pictus (Ephemeroptera), Chironomus sp. (Diptera), and the zooplankton taxon Macrocyclops sp., showed population declines caused by the imidacloprid treatment, with a 21-d Time Weighted Average No Observed Effect Concentrations (21-d TWA NOEC) of 0.46 µg/L, except for C. pictus which presented a 21-d TWA NOEC of 0.05 µg/L. In general terms, the sensitivity of these taxa to imidacloprid was greater than that reported for surrogate taxa in temperate zones and similar to that reported in other (sub-)tropical regions. These results confirm the high sensitivity of tropical aquatic invertebrates to this compound and suggest the need to establish regulations for the control of imidacloprid contamination in Amazonian freshwater ecosystems.

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Metal contamination associated with mining activities has been considered one of the main environmental pollution problems in the Amazon region. Understanding the levels of metal contamination from mining activities requires a good understanding of background metal concentrations, which may vary notably according to the geology/lithology characteristics of the region, soil type, and predominant biogeochemical processes. This review assessed 50 papers and reports published between 1989 and 2020 describing environmental concentrations of different metals and metalloids (As, Hg, Mn, Fe, Cd, Cu, Cr, Pb, Ni, and Zn) in water and sediments of mining and non-mining areas in five geographic regions of the Amazon basin. Metal enrichment caused by mining activities was calculated and exposure concentrations were compared with sediment and water quality standards set for the protection of aquatic life. Significant enrichments of Cd, Cu, Cr, Fe, Hg, Mn, Ni and Zn were observed in mining areas in both sediment and water. Regarding background levels in the different geographic regions, the highest prevalence of metal enrichment (i.e., concentrations 10 to 100-fold higher than mean background values) in sediment samples was found for Fe (100% of samples), Ni (90%), and Mn (69%). For water, high prevalence of metal enrichment occurred for Zn, Mn, and Fe (100% of samples), and for Hg (86%). Hg, Fe, Pb, Cu, Cd, Ni and Zn exceeded water and/or sediment quality standards in a significant number of samples in the proximity of mining areas. This study indicates that mining activities significantly contribute to water and sediment contamination across the Amazon basin, posing hazards for freshwater ecosystems and potentially having human health implications.

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The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.

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Gold mining (GM) is a major source of metals and metalloids in rivers, causing severe environmental pollution and increasing the exposure risks to the residents of surrounding areas. Mining in Ecuadorian Amazonia has dramatically increased in recent years, but its impacts on Indigenous local populations that make use of rivers are still unknown. The aim of this study was to assess the risks to adults and children caused by the exposure to metals and metalloids in freshwater ecosystems contaminated with tailings released by GM activities in 11 sites of the upper Napo River basin, Ecuador. We selected a carcinogenic and a noncarcinogenic risk assessment method to estimate the hazard index (HI) and total cancer risk (TCR). The concentration of Ag, Al, As, Cd, Cu, Fe, Mn, Pb, Zn, B, and V in water and sediment samples was considered to assess the risks to human health. The calculated HI was 23-352 times greater than the acceptable limits in all sites for both children and adults. Mn and Fe were the main contributors (75% in water and 99% in sediment) to the total calculated risk based on the HI. The calculated TCR for children and adults exceeded approximately one to three times the permissible threshold in all sites. As and Pb contributed up to 93% of the total calculated risk based on TCR for both children and adults. This study demonstrates that the emission and mobilization of metals and metalloids caused by mining activities increase the risk to human health, to which we recommend further monitoring of freshwater contamination in the area and the implementation of preventive health management measures. Integr Environ Assess Manag 2023;19:706-716. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

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The use of pesticides in households and peri-urban areas of the Amazon has increased notably during the last years. Yet, the presence of these contaminants in Amazonian freshwater ecosystems remains unexplored. Here, we assessed the exposure to 18 pesticides and 5 transformation products in the Amazon River and in the urban streams of Manaus, Santarém, Macapá, and Belém (Brazil). Pesticide concentrations were analyzed by liquid and gas chromatography methods. Ecological risks were assessed following a two-tiered approach. First, hazard quotients and an overall hazard index were calculated using toxicity data for standard test species of primary producers, invertebrates, and fish. Second, the pesticides showing moderate-to-high ecological risks in the first tier were evaluated using Species Sensitivity Distributions (SSDs). Our study shows that pesticides are widespread in urban and peri-urban areas of the Brazilian Amazon. The frequency of detection was higher in urban streams than in the Amazon River, with some samples taken in Manaus, Santarém, and Belém containing up to 8 compounds. Most pesticides were measured at relatively low concentrations (ng L-1), except for malathion, carbendazim and the bulk concentration of chlorpyrifos, which were monitored at concentrations above 100 ng L-1. Based on the first-tier assessment, we found moderate-to-high risks for freshwater invertebrates for malathion, chlorpyrifos, and chlorpyrifos-methyl, and moderate risks for malathion to fish. The risk assessment performed with SSDs indicated high risks of malathion and chlorpyrifos-methyl in urban areas, with up to 15% and 5% of invertebrate species potentially affected, respectively. The bulk concentrations of chlorpyrifos resulted in high risks in some urban areas (14-22% of species affected) and in areas of the main river (32-44%) impacted by agriculture. We conclude that pesticide residues may contribute to a biodiversity impact in the Amazon and should be further monitored in urban and peri-urban areas, particularly after heavy rainfall events.

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As the number of legal and illegal gold mining sites increases in the Andes-Amazonia region, integrative methods to evaluate the effects of mining pollution on freshwater ecosystems are of paramount importance. Here, we sampled water and sediments in 11 sites potentially affected by gold mining activities in the Napo province (Ecuador). The environmental impacts were evaluated using the following lines of evidence (LOEs): water physicochemical parameters, metal exposure concentrations, macroinvertebrate community response (AAMBI), and toxicity by conducting bioassays with Lactuca sativa and Daphnia magna. Dissolved oxygen and total suspended solids were under (<80%) and above (>130 mg/Ls) quality standards 65% of the sites. Ag, Al, As, Cd, Cu, Fe, Mn, Pb, and Zn in water and V, B, and Cr in sediments were detected above quality standards at sampled sites. Nine out of eleven sites were classified as having bad environmental quality based on the AAMBI. L. sativa seed germination in both water (37% to 70%) and sediment (0% to 65%) indicate significant toxicity. In five sites, neonates of D. magna showed a 25% reduction in survival compared to the control. Our integrated LOEs index ranked sites regarding their environmental degradation. We recommend environmental impact monitoring of the mining expansion at the Andes-Amazonia region using multiple LOEs.

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Only a limited number of households in the Amazon are served by sewage collection or treatment facilities, suggesting that there might be a significant emission of pharmaceuticals and other wastewater contaminants into freshwater ecosystems. In this work, we performed a wide-scope screening to assess the occurrence of pharmaceuticals, illicit drugs and their metabolites in freshwater ecosystems of the Brazilian Amazon. Our study included 40 samples taken along the Amazon River, in three of its major tributaries, and in small tributaries crossing four important urban areas (Manaus, Santarém, Macapá, Belém). More than 900 compounds were investigated making use of target and suspect screening approaches, based on liquid chromatography coupled to high-resolution mass spectrometry with ion mobility separation. Empirical collision-cross section (CCS) values were used to help and confirm identifications in target screening, while in the suspect screening approach CCS values were predicted using Artificial Neural Networks to increase the confidence of the tentative identification. In this way, 51 compounds and metabolites were identified. The highest prevalence was found in streams crossing the urban areas of Manaus, Macapá and Belém, with some samples containing up to 30 - 40 compounds, while samples taken in Santarém showed a lower number (8 - 11), and the samples taken in the main course of the Amazon River and its tributaries contained between 1 and 7 compounds. Most compounds identified in areas with significant urban impact belonged to the analgesics and antihypertensive categories, followed by stimulants and antibiotics. Compounds such as caffeine, cocaine and its metabolite benzoylecgonine, and cotinine (the metabolite of nicotine), were also detected in areas with relatively low anthropogenic impact and showed the highest total prevalence. This study supports the need to improve the sanitation system of urban areas in the Brazilian Amazon and the development of follow-up studies aimed at quantifying exposure levels and risks for Amazonian freshwater biodiversity.

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Temperature increase, salinity intrusion and pesticide pollution have been suggested to be among the main stressors affecting the biodiversity of coastal wetland ecosystems. Here we assessed the single and combined effects of these stressors on zooplankton communities collected from a Mediterranean coastal lagoon. An indoor microcosm experiment was designed with temperature variation (20 °C and 30 °C), salinity (no addition, 2.5 g/L NaCl) and the insecticide chlorpyrifos (no addition, 1 µg/L) as treatments. The impact of these stressors was evaluated on water quality variables and on the zooplankton comunity (structure, diversity, abundance and taxa responses) for 28 days. This study shows that temperature is the main driver for zooplankton community change, followed by salinity and chlorpyrifos. The three stressors contributed to a decrease on zooplankton diversity. The increase of temperature contributed to an increase of zooplankton abundance. Salinity generally affected Cladocera, which resulted in a Copepoda increase at 20 °C, and a reduction in the abundance of all major zooplankton groups at 30 °C. The insecticide chlorpyrifos affected primarily Cladocera, altough the magnitude and duration of the direct and indirect effects caused by the insecticide substantially differed between the two temperature scenarios. Chlorpyrifos and salinity resulted in antagonistic effects on sensitive taxa (Cladocera) at 20 °C and 30 °C. This study shows that temperature can influence the direct and indirect effects of salinity and pesticides on zooplankton communities in Mediterranean coastal wetlands, and highlights vulnerable taxa and ecological responses that are expected to dominate under future global change scenarios.

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Pharmaceuticals are biologically active molecules that may exert toxic effects to a wide range of aquatic organisms. They are considered contaminants of emerging concern due to their common presence in wastewaters and in the receiving surface waters, and the lack of specific regulations to monitor their environmental occurrence and risks. In this work, the environmental exposure and risks of pharmaceuticals have been studied in the Mijares River, Eastern Mediterranean coast (Spain). A total of 57 surface water samples from 19 sampling points were collected in three monitoring campaigns between June 2018 and February 2019. A list of 40 compounds was investigated using a quantitative target UHPLC-MS/MS method. In order to complement the data obtained, a wide-scope screening of pharmaceuticals and metabolites was also performed by UHPLC-HRMS. The ecological risks posed by the pharmaceutical mixtures were evaluated using species sensitivity distributions built with chronic toxicity data for aquatic organisms. In this study, up to 69 pharmaceuticals and 9 metabolites were identified, out of which 35 compounds were assessed using the quantitative method. The highest concentrations in water corresponded to acetaminophen, gabapentin, venlafaxine, valsartan, ciprofloxacin and diclofenac. The compounds that were found to exert the highest toxic pressure on the aquatic ecosystems were principally analgesic/anti-inflammatory drugs and antibiotics. These were: phenazone > azithromycin > diclofenac, and to a lower extent norfloxacin > ciprofloxacin > clarithromycin. The monitored pharmaceutical mixtures are expected to exert severe ecological risks in areas downstream of WWTP discharges, with the percentage of aquatic species affected ranging between 65% and 82% in 3 out of the 19 evaluated sites. In addition, five antibiotics were found to exceed antibiotic resistance thresholds, thus potentially contributing to resistance gene enrichment in environmental bacteria. This work illustrates the wide use and impact of pharmaceuticals in the area under study, and the vulnerability of surface waters if only conventional wastewater treatments are applied. Several compounds included in this study should be incorporated in future water monitoring programs to help in the development of future regulations, due to their potential risk to the aquatic environment.

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