Occurrence and environmental risk assessment of 22 pesticides in Brazilian freshwaters.

Pesticide contamination in water resources is a global threat. Although usually found at low concentrations, pesticides raise considerable toxicological concerns, mainly when mixtures are considered. The occurrence of 22 pesticides (2,4 D, alachlor, aldicarb, aldrin, atrazine, carbendazim, carbofuran, chlordane, chlorpyrifos, DDT, diuron, glyphosate, lindane, mancozeb, methamidophos, metolachlor, molinate, profenofos, simazine, tebuconazole, terbufos, and trifluralin) was investigated, through consolidated database information, in surface freshwaters of Brazil. Moreover, scenarios of environmental risk assessment considering isolated compounds and mixtures were performed, as well as a meta-analytic approach for toxicity purposes. Pesticides in freshwater have been reported from 719 cities (12.9% of Brazilian cities), where 179 (3.2%) showed pesticide occurrence above the limit of detection or quantification. Considering cities with more than five quantified, 16 cities were prone to environmental risks considering individual risks. However, the number increased to 117 cities when the pesticide mixture was considered. The mixture risk was driven by atrazine, chlorpyrifos, and DDT. The national maximum acceptable concentrations (MAC) for nearly all pesticides are higher than the predicted no-effect concentration (PNEC) for the species evaluated, except aldrin. Our results show the need to consider mixtures in the environmental risk assessment to avoid underestimation and review MAC to protect aquatic ecosystems. The results presented here may guide the revision of the national environmental legislation to ensure the protection of Brazilian aquatic ecosystems.

Sublethal effects of environmental concentrations of caffeine on a neotropical freshwater fish.

Caffeine is a contaminant frequently detected in water bodies. Growth trends in both human population and caffeine consumption per capita are expected to exacerbate the occurrence of caffeine in freshwaters. Yet the effects of caffeine on native fish fauna are poorly understood. We exposed larvae of an endemic Neotropical catfish (Rhamdia quelen) to a range of caffeine concentrations for 30 days. We found that larvae exposed to the highest concentration (16 mg L-1) showed skeletal deformations and reduced growth. We further compiled measured environmental concentrations of caffeine in surface freshwater globally and performed a risk assessment. Our analysis points to a low risk to R. quelen and equally sensitive fish species in ~90% of the freshwater ecosystems considered in our analysis. The risk quotient is higher in freshwater ecosystems of South and Central America, where R. quelen is endemic. Although the ecotoxicological risk is currently low in most places, increased caffeine consumption, exacerbated by the lack of sanitation, is expected to increase caffeine concentrations in many parts of the world, posing a threat of sublethal morphological effects to local fish species.

The link between pharmaceuticals and cyanobacteria: a review regarding ecotoxicological, ecological, and sanitary aspects.

Cyanobacteria are important for ecosystem functioning, but eutrophication may affect the surrounding biome by losing ecosystem services and/or through affecting the cyanotoxins production that threatens ecological and human health. Pollution is an environmental issue that affects aquatic ecosystems worldwide, and the knowledge of the role of synthetic chemicals such as pharmaceuticals is still scarce. Therefore, studies coupling these two relevant issues are essential to better understand the ecological risks and the potential threats to public health. Thus, an overview of ecotoxicological tests performed in the literature exposing cyanobacteria to pharmaceuticals and the possible consequences regarding ecological and sanitary aspects was conducted. Moreover, a risk assessment was performed to enable a better understanding of pharmaceuticals affecting cyanobacteria ecology. Most of the studies found in the literature tested isolated pharmaceuticals in laboratory conditions, while others assessed mixture effects on in situ conditions. The endpoints most assessed were growth, photosynthesis, and antioxidant enzyme activity. The studies also point out that cyanobacteria may present resistance or sensitivity depending on the concentrations and the therapeutic class, which may cause a change in the ecosystem dynamics and/or sanitary implications due to cyanotoxin production. The risk assessment highlighted that antibiotics are among the most relevant substances due to the chemical diversity and higher levels found in the environment than other therapeutic classes. This review highlighted gaps regarding cyanotoxin release into aquatic environments due to the occurrence of pharmaceuticals and the need for more realistic experiments to better understand the potential consequences for human and environmental health.

Glyphosate concentrations in global freshwaters: are aquatic organisms at risk?

Glyphosate is the most used herbicide worldwide. Many studies have reported glyphosate risks to aquatic organisms of different trophic levels. Moreover, evidence suggests flaws in countries' legislation that may imply the non-protection of aquatic species exposed to glyphosate. Therefore, we aimed to investigate glyphosate concentrations in freshwater ecosystems worldwide based on a systematic literature review, to discuss the results considering each country's legislation, and to assess the relative tolerance and risk for aquatic species. Only articles providing in situ concentrations of glyphosate in freshwater systems were included in our study. In total, 73 articles met the inclusion criteria and were used in our analysis. The studies comprised freshwater ecosystems from 21 countries. Most countries evaluated (90%) did not have restrictive legislation for aquatic glyphosate concentrations, resulting in a potential non-protection of aquatic organisms. Glyphosate may pose a moderate to high risk in 95% of the countries investigated, reaching a maximum concentration of 105 mg L-1. Additionally, the risk analysis showed that glyphosate concentrations below 0.1 µg L-1 represent a low risk, whereas glyphosate concentrations above 1 µg L-1, which is below the limit established by some countries' legislation, represent a high risk to aquatic organisms. Therefore, we strongly recommend a revision of the countries' legislation for glyphosate concentration in freshwater systems.

Temporal and Spatial Variability of Micropollutants in a Brazilian Urban River.

In Brazil, environmental occurrence of micropollutants, such as pharmaceuticals, is rarely studied, and these compounds are not part of national water quality guidelines. In this study, we evaluated the occurrence of micropollutants in the Paraibuna River, located in the southeast region of Brazil, which is the most populated region of the country. Surface water samples were taken every 3 months for 1.5 years at four different sites downstream the city of Juiz de Fora. A total of 28 compounds were analyzed on an UHPLC-Orbitrap-MS/MS using a direct injection method. Nine substances were found in at least one water sample, with concentrations ranging from 11 to 4471 ng L-1. The micropollutants found in the river were not detected at the reference site upstream of the city, except for caffeine, which was present at low concentrations in the reference site. Additionally, a nontarget screening of the river samples was applied, which resulted in the identification of 116 chemicals, most of which were pharmaceuticals. Concentrations of most of the micropollutants varied with season and correlated significantly with rainfall events, which caused dilution in the river. The highest observed concentrations were for pharmaceuticals used for treating chronic diseases, such as metformin, which is used to treat diabetes, and were among the most consumed in Juiz de Fora during the study period. Moderate ecotoxicological risks were found for metformin, oxazepam, triclosan, and tramadol. Considering the complex mixture of micropollutants in the environment, more knowledge is needed to elucidate their ecological risk in aquatic ecosystems.

Three-bestseller pesticides in Brazil: Freshwater concentrations and potential environmental risks.

Agricultural production in Brazil is favored by weather conditions and by the large amount of available land. Therefore, currently, Brazil is the second largest exporter of agricultural products globally. Pesticides are widely used in Brazilian crops due to their high efficiency, their low cost, and permissive legislation. However, pesticides tend to reach water resources threatening organisms and the water quality. Thereby, we aimed to review the surface freshwater concentrations of the three-bestseller pesticides in Brazil (glyphosate, 2,4D, and atrazine), and discuss the results with sales, legislation, toxicity and potential risks. For that, we performed a systematic review of quantitative studies of glyphosate, atrazine, and 2,4D in Brazilian freshwater and included monitoring data provided by the Brazilian Ministry of Health in our analysis. Finally, we calculated the risk assessment for the three pesticides. Only a few scientific studies reported concentrations of either of the three-bestseller pesticides in Brazilian freshwaters. Between 2009 and 2018, an increase in the sales of 2,4D, atrazine, and glyphosate was observed. It was not possible to evaluate the relation between concentrations and sales, due to limited number of studies, lack of standard criteria for sampling, individual environmental properties, and type of pesticide. Atrazine showed a higher toxicity compared to 2,4D and glyphosate. Regarding the environmental risks, 65%, 72%, and 94% of the Brazilian states had a medium to high risk to 2,4D, atrazine, and glyphosate, respectively. Finally, 80% of the Brazilian states evaluated showed a high environmental risk considering a mixture of the three pesticides. Although most of the environmental concentrations registered were below the allowed limits according to the Brazilian legislation, they are already enough to pose a high risk for the aquatic ecosystems. We, therefore, strongly recommend a revaluation of the maximum allowed values in the national surface freshwater Brazilian legislation.

Do pharmaceuticals reach and affect the aquatic ecosystems in Brazil? A critical review of current studies in a developing country.

Pharmaceutical residues are not completely removed in wastewater treatment plants (WWTPs) becoming contaminants in aquatic ecosystems. Thereby, it is important to investigate their concentrations in the environment and the possible consequences of their occurrence, including for human health. Here, we briefly reviewed the paths of pharmaceuticals to reach the environment, their behavior and fate in the environment, and the possible consequences of their occurrence. Moreover, we synthetized all the studies about the detection of pharmaceuticals in Brazilian water bodies and the available ecotoxicological knowledge on their effects. In this study, when we compare the data found on these compounds worldwide, we observed that Brazilian surface waters present considerable concentrations of 17α-ethinylestradiol, 17ß-estradiol, and caffeine. In general, concentrations found in aquatic systems worldwide seems to be low; however, ecotoxicological tests showed that even these low concentrations can cause sublethal effects in biota. The knowledge about the effects of continuous exposure and mixtures is sparse. In summary, new research is urgently required about the effects of these compounds in biota-including long-term exposition and mixture tests-and on specific technologies to remove these compounds in water bodies and WWTPs, besides the introduction of new policies for pharmaceutical use.