Occurrence, sources, and ecological risks of polycyclic aromatic hydrocarbons (PAHs) in the Amazon river.

The Amazon is the largest river by discharge volume and one of the most biodiverse biomes in the world. Lately, there has been a rapid increase of the urban population in the region, which has been translated into a growing emission of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) into surface water bodies. This study provides the most comprehensive evaluation of the PAH contamination levels in surface waters of the Amazon basin. We investigated the occurrence and potential sources of 16 priority PAHs and characterised their risks for freshwater ecosystems. For this, we took 40 water samples from different sites along the Brazilian part of the Amazon River, including three major tributaries, and smaller rivers crossing the main urban areas. The results of this study show that PAHs are widespread contaminants in rivers of the Brazilian Amazon. The sum of the total concentration of the 16 priority PAHs reached values of 134 ng L-1 in the Amazon River, and 163 ng L-1 near densely populated areas. On the other hand, the total PAH concentration was generally lower in the monitored tributaries. In most samples, the contamination pattern was dominated by high molecular weight PAHs, suggesting a major contribution of pyrogenic sources, although petrogenic contamination was also present in some locations near urban areas. We assessed ecological risks posed by PAH mixtures using a hazard index. The results indicated that PAH contamination is not likely to pose direct toxic effects for Amazonian freshwater organisms, however continued monitoring is recommended near densely populated areas.

Large-scale monitoring and risk assessment of microplastics in the Amazon River.

Microplastics (MPs) are one of the most widespread contaminants worldwide, yet their risks for freshwater ecosystems have seldom been investigated. In this study, we performed a large monitoring campaign to assess the presence and risks of MPs in Amazonian freshwater ecosystems. We investigated MP pollution in 40 samples collected along 1500 km in the Brazilian Amazon, including the Amazon River, three major tributaries, and several streams next to the most important urban areas. MPs in the 55-5000 µm size range were characterized (size, shape, color) by microscopy and identified (polymer composition) by infrared spectroscopy. Ecotoxicological risks were assessed using chronic Species Sensitivity Distributions for effects triggered by food dilution and tissue translocation using data alignment methods that correct for polydispersity of environmental MPs and bioaccessibility. This study shows that MPs are ubiquitous contaminants in Amazonian freshwater ecosystems, with measured concentrations (55-5000 µm) ranging between 5 and 152 MPs/m3 in the Amazon River and its main tributaries, and between 23 and 74,550 MPs/m3 in urban streams. The calculated Hazardous Concentration for the 5% of species (HC5) derived from the SSDs for the entire MP range (1-5000 µm) were 1.6 × 107 MPs/m3 (95% CI: 1.2 × 106 - 4.0 × 108) for food dilution, and 1.8 × 107 MPs/m3 (95% CI: 1.5 × 106 - 4.3 × 108) for translocation. Rescaled exposure concentrations (1-5000 µm) in the Amazon River and tributaries ranged between 6.0 × 103 and 1.8 × 105 MPs/m3, and were significantly lower than the calculated HC5 values. Rescaled concentrations in urban streams ranged between 1.7 × 105 and 5.7 × 108 MPs/m3, and exceeded both calculated HC5 values in 20% of the locations. This study shows that ecological impacts by MP contamination are not likely to happen in the Amazon River and its major tributaries. However, risks for freshwater organisms may be expected in near densely populated areas, such as the cities of Manaus or Belem, which have limited wastewater treatment facilities.

Ecological risk assessment of pesticides in urban streams of the Brazilian Amazon.

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.

Wide-scope screening of pharmaceuticals, illicit drugs and their metabolites in the Amazon River.

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.

Pharmaceuticals and other urban contaminants threaten Amazonian freshwater ecosystems.

Urban areas in the Brazilian Amazon have grown at an unprecedented rate during the last years. About 90% of the wastewater produced by these urban areas are discharged untreated into Amazonian freshwater ecosystems, constituting a potential environmental pathway for pharmaceuticals and other chemicals consumed by modern societies (e.g. psychostimulants, personal-care products, hormones). The distribution of these chemicals into the Amazon River and their potential risks for freshwater biodiversity have not been evaluated so far. Here, we show the results of the largest chemical monitoring campaign conducted in the Amazon region. We assessed exposure patterns for 43 pharmaceuticals and other urban contaminants in 40 sampling sites distributed along the Amazon River, three major tributaries (Negro, Tapajós and Tocantins Rivers), and four large cities of the Brazilian Amazon (Manaus, Santarém, Macapá, Belém). We assessed risks for freshwater biodiversity using species sensitivity distributions and mixture toxicity approaches. We found that urban areas constitute important hot-spots for chemical contamination, with mixtures containing up to 40 different compounds and exposure concentrations reaching the world's maxima for some of them. We show that chemical pollution can result in long-term effects for up to 50-80% of aquatic species next to urban areas. Moreover, we identified several ubiquitous compounds which can be used as tracers of anthropogenic pressure in the Amazon basin. We conclude that the chemical burden created by urbanization significantly contributes to a biodiversity loss in the region and should be further controlled.

Aquatic risk assessment of pesticides in Latin America.

Latin America is anticipated to be a major growth market for agriculture and production is increasing with use of technologies such as pesticides. Reports of contamination of aquatic ecosystems by pesticides in Latin America have raised concerns about potential for adverse ecological effects. In the registration process of pesticides, all countries require significant data packages on aquatic toxicology and environmental fate. However, there are usually no specific requirements to conduct an aquatic risk assessment. To address this issue, the Society of Environmental Toxicology and Chemistry organized a workshop that brought together scientists from academia, government, and industry to review and elaborate on aquatic risk assessment frameworks that can be implemented into regulation of pesticides in Latin America. The workshop concluded that the international framework for risk assessments (protection goals, effects, and exposure assessments, risk characterization, and risk mitigation) is broadly applicable in Latin America but needs further refinement for the use in the region. Some of the challenges associated with these refinements are discussed in the article. It was recognized that there is potential for data sharing both within and outside of the region where conditions are similar. However, there is a need for research to compare local species and environmental conditions to those in other jurisdictions to be able to evaluate the applicability of data used in other countries. Development should also focus on human resources as there is a need to build local capacity and capability, and scientific collaboration and exchange between stakeholders in industry, government, and academia is also important. The meeting also emphasized that, although establishing a regionally relevant risk assessment framework is important, this also needs to be accompanied by enforcement of developed regulations and good management practices to help protect aquatic habitats. Education, training, and communication efforts are needed to achieve this.

Pesticide use and biodiversity conservation in the Amazonian agricultural frontier.

Agricultural frontiers are dynamic environments characterized by the conversion of native habitats to agriculture. Because they are currently concentrated in diverse tropical habitats, agricultural frontiers are areas where the largest number of species is exposed to hazardous land management practices, including pesticide use. Focusing on the Amazonian frontier, we show that producers have varying access to resources, knowledge, control and reward mechanisms to improve land management practices. With poor education and no technical support, pesticide use by smallholders sharply deviated from agronomical recommendations, tending to overutilization of hazardous compounds. By contrast, with higher levels of technical expertise and resources, and aiming at more restrictive markets, large-scale producers adhered more closely to technical recommendations and even voluntarily replaced more hazardous compounds. However, the ecological footprint increased significantly over time because of increased dosage or because formulations that are less toxic to humans may be more toxic to other biodiversity. Frontier regions appear to be unique in terms of the conflicts between production and conservation, and the necessary pesticide risk management and risk reduction can only be achieved through responsibility-sharing by diverse stakeholders, including governmental and intergovernmental organizations, NGOs, financial institutions, pesticide and agricultural industries, producers, academia and consumers.

Effects of malathion and carbendazim on Amazonian freshwater organisms: comparison of tropical and temperate species sensitivity distributions.

The risk assessment of pesticides for freshwater ecosystems in the Amazon has relied on the use of toxicity data and water quality criteria derived for temperate regions due to a lack of ecotoxicological studies performed with indigenous species. This leaves an unknown margin of uncertainty for the protection of Amazonian ecosystems, as differences in environmental conditions and species sensitivity are not taken into account. To address this issue, the acute toxic effects of malathion (an organophosphorus insecticide) and carbendazim (a benzimidazole fungicide) were assessed on five fish and five freshwater invertebrates endemic to the Amazonian region. Subsequently, the intrinsic sensitivity of Amazonian and temperate freshwater species was compared using the species sensitivity distribution (SSD) concept. Amazonian species sensitivity to malathion was found to be similar to that of their temperate counterparts, with LC50 values ranging between 111 and 1507 µg/l for fish species and 2.1-426 µg/l for arthropod species. However, Amazonian fish appeared to be slightly less sensitive for carbendazim than temperate fish with LC50 values ranging between 1648 and 4238 µg/l, and Amazonian invertebrates were found to be significantly more resistant than their temperate counterparts, with LC50 values higher than 16000 µg/l. The results of this study suggest that for these compounds, the use of water quality criteria derived with laboratory toxicity data for temperate species will result in a sufficient protection level for Amazonian freshwater organisms. Recommendations for further research include the validation of threshold concentrations derived with temperate standard test species and with the SSD model with semi-field experiments considering larger assemblages of indigenous species under local environmental conditions.

Effect of parathion-methyl on Amazonian fish and freshwater invertebrates: a comparison of sensitivity with temperate data.

Parathion-methyl is an organophosphorous insecticide that is widely used in agricultural production sites in the Amazon. The use of this pesticide might pose a potential risk for the biodiversity and abundance of fish and invertebrate species inhabiting aquatic ecosystems adjacent to the agricultural fields. Due to a lack of toxicity data for Amazonian species, safe environmental concentrations used to predict the ecological risks of parathion-methyl in the Amazon are based on tests performed with temperate species, although it is unknown whether the sensitivity of temperate species is representative for those of Amazonian endemic species. To address this issue, the acute toxic effect (LC(50)-96 h) of parathion-methyl was assessed on seven fish and five freshwater invertebrate species endemic to the Amazon. These data were used to compare their pesticide sensitivity with toxicity data for temperate species collected from the literature. The interspecies sensitivity was compared using the Species Sensitivity Distribution (SSD) concept. The results of this study suggest that Amazonian species are no more, or less, sensitive to parathion-methyl than their temperate counterparts, with LC(50) values ranging from 2900 to 7270 microg/L for fish and from 0.3 to 319 microg/L for freshwater arthropods. Consequently, this evaluation supports the initial use of toxicity data of temperate fish and freshwater invertebrate species for assessing the effects of parathion-methyl on Amazonian freshwater ecosystems.

Risk assessment of pesticides for soils of the Central Amazon, Brazil: comparing outcomes with temperate and tropical data.

The risk of 11 pesticides to the soil environment was assessed in a 3-tiered approach at 4 sites located in Central Amazon, near Manaus, the capital of the Amazonas State in Brazil. Toxicity-exposure ratios (TERs), as routinely used for the registration of pesticides in the European Union, were calculated. First, the predicted environmental concentration (PEC) values in soil on the basis of real application rates and soil properties but temperate DT50 (degradation time of 50%) values were compared with temperate effect values (earthworm LC50s; median lethal concentrations), both gained from literature. Second, the risk assessment was refined by the use of DT50 values from tropical soils (measured for 7 compounds and estimated for 4) but still with temperate effect values because only a few results from tests performed under tropical conditions are available. Third, the outcome of this exercise was evaluated in a plausibility check with the use of the few results of effect tests, which were performed under tropical conditions. However, the lack of such data allowed this check only for 6 of 11 pesticides. The results are discussed in light of pesticide use in the Amazon in general, as well as compared with the registration status of these pesticides in other countries. Finally, suggestions are given for which kinds of studies are needed to improve the environmental risk assessment of pesticides in tropical regions.

Uma proposta de avaliação integrada de risco do uso de agrotóxicos no estado do Amazonas, Brasil / A proposal for integrated risk assessment of pesticide use in Amazon State, Brasil

Durante os últimos 30 anos, o aumento da população humana no Amazonas introduziu a necessidade de produção adicional de alimentos e levou o governo do estado a desenvolver programas para aumentar e melhorar a produção agrícola. A produção de hortaliças não tradicionais apresentou vários problemas desconhecidos para os agricultores da região, uma vez que estas culturas não são bem adaptadas às condições locais. A suscetibilidade a insetos, fungos e outras pragas, e a competição com vegetação nativa vem forçando os agricultores a usar intensivamente os agrotóxicos. Os agricultores não estavam preparados para o uso adequado desta tecnologia ignorando os riscos dos agrotóxicos para saúde humana e o ambiente. Os agricultores não usam equipamento de proteção individual, porque é caro, desconfortável e inadequado para o clima quente da região. A falta treinamento e o escasso conhecimento sobre os perigos dos agrotóxicos contribuem para a manipulação incorreta durante a preparação, aplicação e disposição das embalagens vazias. Nestas condições, a exposição dos agricultores, suas famílias, consumidores e ambiente é alta. Como um primeiro passo para o entendimento deste problema e a proposição de soluções é proposta a realização de uma avaliação integrada de risco. As três fases do processo, formulação de problema, avaliação da exposição, e caracterização de risco são detalhadas. Programas de educação, treinamento e informação fazem parte das estratégias para a redução do risco do uso de agrotóxicos permitindo o desenvolvimento de uma agricultura ambientalmente sustentável.

During the last 30 years, the increase of the human population in the Amazon introduced the need for additional food production and caused the state government to implement programs to increase and improve agricultural production. The production of nontraditional crops introduced several problems unknown to traditional farmers, since they are not well adapted to tropical conditions. Their susceptibility to insects, fungi and other plagues, and the competition with native vegetation forced farmers to use pesticides intensively. Amazonian farmers were not adequately prepared for the use of this new technology and they ignored the risk of pesticides to human health and the environment. Farmers do not use protective clothing or equipment because they are expensive and not suitable for a tropical climate in which they prove to be very uncomfortable. The lack in training and poor knowledge of pesticide hazards contribute to careless handling during preparation, application and disposal of empty packages. Under such circumstances, exposure of farmers, their families, consumers and the environment is high. As a first step to solve this problem, an integrated risk assessment is proposed. The three stages of the process, problem formulation, exposure assessment, and risk characterization are explained. Training and information programs are part of the strategies risk-reduction in order to build up environmentally sustainable agriculture.

Use and fate of pesticides in the Amazon State, Brazil: risk to human health and the environment.

During the last 30 years, the increase of the human population in the Amazon introduced the need for additional food production and caused the state government to implement programs to increase and improve agricultural production. The production of nontraditional crops introduced several problems unknown to traditional farmers, since they are not well adapted to tropical conditions. Their susceptibility to insects, fungi and other plagues, and the competition with native vegetation forced farmers to use pesticides intensively. Amazonian farmers were not adequately prepared for the use of this new technology; they ignored the risk of pesticides to human health and the environment. Using the region of the state capital Manaus as an example, the characteristics of the pesticide use are described (e.g. the increased use and the lack of personal protective equipment, as well as the legal situation). In detail, the registration status of pesticides used in the State of Amazonas and the state of their registration in the European Union is compared. Finally, it is concluded that the use and the fate of pesticides in the Amazon region has to be monitored. Data of the effects on humans and on the environment have to be collected from the literature or have to be produced in standardized tests, so that an environmental risk assessment becomes possible. Training and information programs are urgently needed in order to build up environmentally sustainable agriculture. Finally, the enforcement of Brazilian laws concerning pesticide registration has to be improved.

Composição do Zooplâncton em diferentes ambientes do lago Camaleão, na ilha da Marchantaria, Amazonas, Brasil

This study aims to verify occurrence and distribution of the major zooplankton groups in three different sub-habitats at Lago Camaleão: channel, aquatic macrophytes and flooded forest, during the high water period (August, 1996). Cladocera, Copepoda and Rotifera occurred with different relative abundances within the three studied environments. In the channel, Cladocera occurred with a high number of species and individuals, Bosminopsis deitersi being the dominant species (89%). Cladocera and Copepoda were equally dominant in the flooded forest, even thought only copepods, nauplius and copepodites immature forms were found. On the macrophytes, Rotifera was the group with the largest occurrence, with the dominance of Lecane quadridentata, Keratella Americana and Brachionus patulus followed by copepods (immature forms) and cladoceres, the latter mostly of the Chydoridae family (21.4%).

Este trabalho teve o objetivo de verificar a ocorrência e a distribuição dos principais grupos de zooplâncton em três diferentes sub-habitats do lago Camaleão: canal, macrófitas aquáticas e floresta alagada, no período de cheia (agosto de 1996). Nos três ambientes estudados, Cladocera, Copepoda e Rotifera ocorreram com abundância relativa diferentes. No canal, Cladocera ocorreu com maior número de espécies e de indivíduos, sendo dominante a espécie Bosminopsis deitersi (89%). Na floresta alagada Cladocera e Copepoda foram igualmente dominantes, ressaltando-se que somente ocorreram as formas imaturas de copépodes, náuplios e copepoditos. Nas macrófitas, o grupo de maior ocorrência foi Rotifera, com a dominância de Lecane quadrídentata, Keratella americana e Brachionus patulus seguido de copépodes (formas imaturas) e de cladóceros, estes na maioria da família Chydoridae (21.4%).