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.

Cross-continental importance of CH4 emissions from dry inland-waters.

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO2) emissions. However, methane (CH4) may also be relevant due to its higher Global Warming Potential (GWP). We report CH4 emissions from dry inland water sediments to i) provide a cross-continental estimate of such emissions for different types of aquatic systems (i.e., lakes, ponds, reservoirs, and streams) and climate zones (i.e., tropical, continental, and temperate); and ii) determine the environmental factors that control these emissions. CH4 emissions from dry inland waters were consistently higher than emissions observed in adjacent uphill soils, across climate zones and in all aquatic systems except for streams. However, the CH4 contribution (normalized to CO2 equivalents; CO2-eq) to the total GHG emissions of dry inland waters was similar for all types of aquatic systems and varied from 10 to 21%. Although we discuss multiple controlling factors, dry inland water CH4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO2 and CH4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO2-eq m-2 d-1 from dry inland waters. We argue that increasing droughts likely expand the worldwide surface area of atmosphere-exposed aquatic sediments, thereby increasing global dry inland water CH4 emissions. Hence, CH4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments.

Insights into the factors influencing mercury concentrations in tropical reservoir sediments.

Thousands of dams are currently under construction or planned worldwide to meet the growing need for electricity. The creation of reservoirs could, however, lead to conditions that promote the accumulation of mercury (Hg) in surface sediments and the subsequent production of methylmercury (MeHg). Once produced, MeHg can bioaccumulate to harmful levels in organisms. It is unclear to what extent variations in physical features and biogeochemical factors of the reservoir impact Hg accumulation. The objective of this study was to identify key drivers of the accumulation of total Hg (THg) in tropical reservoir sediments. The concentration of THg in all analyzed depth intervals of 22 sediment cores from the five contrasting reservoirs investigated ranged from 16 to 310 ng g-1 (n = 212, in the different sediment cores, the maximum depth varied from 18 to 96 cm). Our study suggests reservoir size to be an important parameter determining the concentration of THg accumulating in tropical reservoir sediments, with THg ranging up to 50 ng g-1 in reservoirs with an area exceeding 400 km2 and from 100 to 200 ng g-1 in reservoirs with an area less than 80 km2. In addition to the reservoir size, the role of land use, nutrient loading, biome and sediment properties (e.g., organic carbon content) was tested as potential drivers of THg levels. The principal component analysis conducted suggested THg to be related to the properties of the watershed (high degree of forest cover and low degree of agricultural land use), size and age of the reservoir, water residence time and the levels of nutrients in the reservoir. A direct correlation between THg and tested variables was, however, only observed with the area of the reservoir.

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.

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.

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.

Sediment drying-rewetting cycles enhance greenhouse gas emissions, nutrient and trace element release, and promote water cytogenotoxicity.

Increased periods of prolonged droughts followed by severe precipitation events are expected throughout South America due to climate change. Freshwater sediments are especially sensitive to these changing climate conditions. The increased oscillation of water levels in aquatic ecosystems causes enhanced cycles of sediment drying and rewetting. Here we experimentally evaluate the effects of induced drought followed by a rewetting event on the release of carbon dioxide (CO2), methane (CH4), nutrients (nitrogen and phosphorus), and trace elements (iron, manganese, and zinc) from the sediment of a tropical reservoir in southeastern Brazil. Furthermore, we used bulb onions (Allium cepa) to assess the potential cytogenotoxicity of the water overlying sediments after rewetting. We found peaks in CO2 and CH4 emissions when sediments first transitioned from wet to dry, with fluxes declining as sediments dried out. CO2 emissions peaked again upon rewetting, whereas CH4 emissions remained unaltered. Our experiment also revealed average increases by up to a factor of ~5000 in the release rates of nutrients and trace elements in water overlying sediments after rewetting. These increased release rates of potentially toxic compounds likely explain the lower replication of Allium cepa cells (up to 22% reduction) exposed to water overlying sediments after rewetting. Our findings suggest that increased events of drought followed by rewetting may lead to a range of changes in freshwater ecosystems, including nutrient enrichment, increased toxicity following resuspension of contaminants, and higher emission of greenhouse gases to the atmosphere.

A global trend of caffeine consumption over time and related-environmental impacts.

Caffeine is one of the most consumed substances, and it has been largely detected in aquatic ecosystems. We investigated the trends in caffeine consumption over three decades and its relationships with gross domestic product (GDP) and human development index (HDI) to understand global patterns and to identify potential hotspots of contamination. The total caffeine consumption is increasing mainly due to population growth. Moreover, caffeine consumption per capita is also increasing in some countries, such as Brazil, Italy, and Ethiopia. A high positive correlation between caffeine consumption per capita with HDI and GDP was found for coffee-importing countries in Europe, while a high negative correlation was found for coffee-exporting countries in Africa. The literature review showed that the highest caffeine concentrations coincide with countries that present an increasing caffeine consumption per capita. Also, approximately 35% of the caffeine concentrations reported in the literature were above the predicted no-effect concentration in the environment and, again, overlaps with countries with increasing per capita consumption. Despite the high degradation rate, caffeine consumption tends to increase in a near future, which may also increase the overall amount of caffeine that comes into the environment, possibly exceeding the thresholds of several species described as tolerant to the current environmental concentrations. Therefore, it is essential to prevent caffeine from reaching aquatic ecosystems, implementing sewage treatment systems, and improving their efficiency.

Environmental Risk of Metal Contamination in Sediments of Tropical Reservoirs.

Reservoir sediment can work as both sink and source for contaminants. Once released into the water column, contaminants can be toxic to biota and humans. We investigate potential ecological risk to benthic organisms by metals contamination in six reservoirs in Southeast Brazil. Results of the bioavailable fraction of copper (Cu), chromium (Cr), cadmium (Cd), lead (Pb), zinc (Zn), and iron (Fe) in sediment samples are presented. Considering Cu, Cd, and Zn concentrations, about 6% of the samples exceeded the threshold effect levels of sediment quality guidelines. The comparison to sediment quality guidelines is conservative because we used a moderate metal extraction. Control of contaminant sources in these reservoirs is key because they are sources of water and food. The mixture toxicity assessment showed an increased incidence of toxicity to aquatic organisms showing that mixture toxicity should be taken into account in sediment assessment criteria.

Investigation of medicines consumption and disposal in Brazil: A study case in a developing country.

The incorrect disposal of medicines can be harmful to the environment. Here, we aim to understand the consumption and disposal of medicines in Brazil using online forms. 64% of the respondents have the habit to self-medicate. 66% of respondents dispose the disused or expired medicines in the garbage. 71.9% of respondents never receive any information about correct disposal of medicines. 95.2% of respondents believe that residues of medicines can be harmful to the environment. Environmental education can provide information to the population and help to mitigate pharmaceuticals pollution.

Far-reaching cytogenotoxic effects of mine waste from the Fundão dam disaster in Brazil.

On November 2015, one of Brazil's most important watersheds was impacted by the mine waste from Fundão dam collapse in Mariana. The mine waste traveled over 600 km along the Doce River before reaching the sea, causing severe devastation along its way. Here we assessed trace element concentrations and cytogenotoxic effects of the released mine waste. Water samples were collected along the Doce River ten days after the disaster in two impacted sites and one non-impacted site. Sampling points were located hundreds of kilometers downstream of the collapsed dam. Water samples were used for trace element quantification and to run an experiment using Allium cepa to test cytogenotoxicity. We found extremely high concentrations of particulate Fe, Al, and Mn in the impacted sites. We observed cytogenotoxic effects such as alterations in mitotic and phase indexes, and enhanced frequency of chromosomal aberrations. Our results indicate interferences in the cell cycle in impacted sites located hundreds of kilometers downstream of the disaster. The environmental impacts of the dam collapse may not only be far-reaching but also very likely long-lasting, because the mine waste may persist in the Doce River sediment for decades.

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.