A monitoring network was established in streams within a catchment near the Costa Rican Pacific coast (2008–2011) to estimate the impact of pesticides in surface water (84 samples) and sediments (84 samples) in areas under the influence of melon and watermelon production. A total of 66 (water) and 47 (sediment) pesticides were analyzed, and an environmental risk assessment (ERA) was performed for four taxa (algae, Daphnia magna, fish and Chironomus riparius). One fungicide and seven insecticides were detected in water and/or sediment; the fungicide azoxystrobin (water) and the insecticide cypermethrin (sediments) were the most frequently detected pesticides. The insecticides endosulfan (5.76 μg/L) and cypermethrin (301 μg/kg) presented the highest concentrations in water and sediment, respectively. The ERA revealed acute risk in half of the sampling points of the melon-influenced area and in every sampling point from the watermelon-influenced area. Safety levels were exceeded within and around the crop fields, suggesting that agrochemical contamination was distributed along the catchment, with potential influence of nearby crops. Acute risk was caused by the insecticides chlorpyrifos, cypermethrin and endosulfan to D. magna, fish and C. riparius; the latter was the organism with the overall highest/continuous risk. High chronic risk was determined in all but one sampling point, and revealed a higher number of pesticides of concern. Cypermethrin was the only pesticide to pose chronic risk for all benchmark organisms. The results provide new information on the risk that tropical crops pose to aquatic ecosystems, and highlight the importance of including the analysis of sediment concentrations and chronic exposure in ERA.

Aquatic pollution from emerging organic contaminants (EOCs) is of key environmental importance in India and globally, particularly due to concerns of antimicrobial resistance, ecotoxicity and drinking water supply vulnerability. Here, using a broad screening approach, we characterize the composition and distribution of EOCs in groundwater in the Gangetic Plain around Patna (Bihar), as an exemplar of a rapidly developing urban area in northern India. A total of 73 EOCs were detected in 51 samples, typically at ng.L⁻¹ to low μg.L⁻¹ concentrations, relating to medical and veterinary, agrochemical, industrial and lifestyle usage. Concentrations were often dominated by the lifestyle chemical and artificial sweetener sucralose. Seventeen identified EOCs are flagged as priority compounds by the European Commission, World Health Organisation and/or World Organisation for Animal Health: namely, herbicides diuron and atrazine; insecticides imidacloprid, thiamethoxam, clothianidin and acetamiprid; the surfactant perfluorooctane sulfonate (and related perfluorobutane sulfonate, perfluorohexane sulfonate, perfluorooctanoic acid and perfluoropentane sulfonate); and medical/veterinary compounds sulfamethoxazole, sulfanilamide, dapson, sulfathiazole, sulfamethazine and diclofenac. The spatial distribution of EOCs varies widely, with concentrations declining with depth, consistent with a strong dominant vertical flow control. Groundwater EOC concentrations in Patna were found to peak within ∼10 km distance from the River Ganges, indicating mainly urban inputs with some local pollution hotspots. A heterogeneous relationship between EOCs and population density likely reflects confounding factors including varying input types and controls (e.g. spatial, temporal), wastewater treatment infrastructure and groundwater abstraction. Strong seasonal agreement in EOC concentrations was observed. Co-existence of limited transformation products with associated parent compounds indicate active microbial degradation processes. This study characterizes key controls on the distribution of groundwater EOCs across the urban to rural transition near Patna, as a rapidly developing Indian city, and contributes to the wider understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

Novel stressors introduced by human activities increasingly threaten freshwater ecosystems. The annual application of more than 2.3 billion kg of pesticide active ingredient and 22 billion kg of road salt has led to the contamination of temperate waterways. While pesticides and road salt are known to cause direct and indirect effects in aquatic communities, their possible interactive effects remain widely unknown. Using outdoor mesocosms, we created wetland communities consisting of zooplankton, phytoplankton, periphyton, and leopard frog (Rana pipiens) tadpoles. We evaluated the toxic effects of six broad-spectrum insecticides from three families (neonicotinoids: thiamethoxam, imidacloprid; organophosphates: chlorpyrifos, malathion; pyrethroids: cypermethrin, permethrin), as well as the potentially interactive effects of four of these insecticides with three concentrations of road salt (NaCl; 44, 160, 1600 Cl⁻ mg/L). Organophosphate exposure decreased zooplankton abundance, elevated phytoplankton biomass, and reduced tadpole mass whereas exposure to neonicotinoids and pyrethroids decreased zooplankton abundance but had no significant effect on phytoplankton abundance or tadpole mass. While organophosphates decreased zooplankton abundance at all salt concentrations, effects on phytoplankton abundance and tadpole mass were dependent upon salt concentration. In contrast, while pyrethroids had no effects in the absence of salt, they decreased zooplankton and phytoplankton density under increased salt concentrations. Our results highlight the importance of multiple-stressor research under natural conditions. As human activities continue to imperil freshwater systems, it is vital to move beyond single-stressor experiments that exclude potentially interactive effects of chemical contaminants.

Insecticide resistance is one of the major obstacles for controlling agricultural pests. There have been a lot of studies on insecticides stimulating the development of insect resistance. Herbicides account for the largest sector in the agrochemical market and are often co-applied with insecticides to control insect pests and weeds in the same cropland ecosystem. However, whether and how herbicides exposure will affect insecticide resistance in insect pests is largely unexplored. Here we reported that after exposure to herbicide butachlor, the lepidopteran Spodoptera litura larvae reduced susceptibility to the insecticide chlorpyrifos. Docking simulation studies suggested that general odorant-binding protein 2 (GOBP2) could bind to butachlor with high binding affinity, and silencing SlGOBP2 by RNA interference (RNAi) decreased larval tolerance to chlorpyrifos. Butachlor exposure induced ecdysone biosynthesis, whose function on increasing chlorpyrifos tolerance was supported in synergism experiments and confirmed by silencing the key gene (SlCYP307A1) for ecdysone synthesis. Butachlor exposure also activated the expression of detoxification enzyme genes. Silencing the genes with the highest herbicide-induced expression among the three detoxification enzyme genes led to increased larval susceptibility to chlorpyrifos. Collectively, we proposed a new mechanism that olfactory recognition of herbicides by GOBP2 triggers insect hormone biosynthesis and leads to high metabolic tolerance against insecticides. These findings provide valuable information for the dissection of mechanisms of herbicide-induced resistance to insecticides and also supplements the development of reduced-risk strategies for pest control.

One of the causes of the global decline of amphibians is agricultural activity, responsible for causing habitat fragmentation and bringing a range of agrochemicals and fertilizers in the environment, compounds with a potential disrupting effect on non-target organisms, such as frogs. Exposure to these compounds has numerous harmful effects on the testes of these animals, which can compromise reproduction and, consequently, the maintenance of their communities. In this context, we compared the morphology and morphometry of the testes of three species of neotropical anurans (Physalaemus cuvieri, Dendropsophus minutus, and Boana albopunctata) from an agricultural area and a conservation unit. Histologically, the testicular morphology of the species was similar for both environments; however, morphometrically, there was a difference in the measured testicular parameters (locular area and area of spermatogenic cysts). Physalaemus cuvieri presented higher averages of locular and spermatogonial area in the agricultural environment, whereas the area occupied by the spermatozoa was smaller. Additionally, the testicular pigmentation, which is only present in this species, was greater in animal from the agricultural area. In D. minutus, the locular, spermatogonial, and sperm areas showed lower values in the agricultural area, whereas in B. albopunctata, the opposite pattern was found, with the area of the locule, spermatocytes, and spermatozoids being higher. Agricultural activities influence the testicular metric parameters in different species, and our results suggest that D. minutus is most sensitive to anthropic pressures. The least sensitive species is B. albopunctata. We highlight the importance of evaluating different species, since each species responds differently to agricultural activities.

As agriculture expands to provide food and wellbeing to the world’s growing population, there is a simultaneous increasing concern about the use of agrochemicals, which can harm non-target organisms, mainly in the aquatic environment. The fungicide Mancozeb (MZ) has been used on a large-scale and is a potent inducer of oxidative stress. Therefore, there is an urgent need for the development of more sensitive biomarkers designed to earlier biomonitoring of this compound. Here we tested the hypothesis that behavioral changes induced by sublethal MZ concentrations would occur first as compared to biochemical oxidative stress markers. Embryos at 4 h post-fertilization (hpf) were exposed to Mancozeb at 5, 10 and 20 μg/L. Controls were kept in embryo water only. Behavioral and biochemical parameters were evaluated at 24, 28, 72, and 168 hpf after MZ exposure. The results showed that MZ significantly altered spontaneous movement, escape responses, swimming capacity, and exploratory behavior at all exposure times. However, changes in ROS steady-stead levels and the activity of antioxidant enzymes were observable only at 72 and 168 hpf. In conclusion, behavioral changes occurred earlier than biochemical alterations in zebrafish embryos exposed to MZ, highlighting the potential of behavioral biomarkers as sensitive tools for biomonitoring programs.

Commercial beekeepers in many locations are experiencing increased annual colony losses of honey bees (Apis mellifera), but the causes, including the role of agrochemicals in colony losses, remain unclear. In this study, we investigated the effects of chronic consumption of pollen containing a widely-used fungicide (Pristine®), known to inhibit bee mitochondria in vitro, which has recently been shown to reduce honey bee worker lifespan when field-colonies are provided with pollen containing field-realistic levels of Pristine®. We fed field colonies pollen with a field-realistic concentration of Pristine® (2.3 ppm) and a concentration two orders of magnitude higher (230 ppm). To challenge flight behavior and elicit near-maximal metabolic rate, we measured flight quality and metabolic rates of bees in two lower-than-normal air densities. Chronic consumption of 230 but not 2.3 ppm Pristine® reduced maximal flight performance and metabolic rates, suggesting that the observed decrease in lifespans of workers reared on field-realistic doses of Pristine®-laced pollen is not due to inhibition of flight muscle mitochondria. However, consumption of either the 230 or 2.3 ppm dose reduced thorax mass (but not body mass), providing the first evidence of morphological effects of Pristine®, and supporting the hypothesis that Pristine® reduces forager longevity by negatively impacting digestive or nutritional processes.

Gala Lake is an internationally important lake due to its location on one of the world's most important bird migration routes. For this reason, water quality of the lake is of great concern. However, the lake surrounded by paddy fields may face eutrophication and toxic metal contamination due to excessive use of fertilizers and pesticides. In this study, impact of paddy fields on water quality of the Gala Lake was investigated. The concentrations of metal(loid)s and physico-chemical parameters in surface water samples taken from the lake were measured and compared with water quality guidelines. Also, human health risks and contamination status of metal(loid)s were assessed. The mean NO₂, SRP and BOD concentrations in the lake exceeded the permissible levels for both salmonid and cyprinid waters. The mean BOD value indicated contaminated water quality in the lake, while mean COD and SRP values indicated lightly contaminated water quality. The mean As, Cr and Pb values in the winter exceeded the drinking water limits set by WHO and EC, while the mean Cr and Zn values exceeded the limit values for the protection of freshwater aquatic organisms set by USEPA. Similarly, heavy metal pollution index and the degree of contamination values in the winter indicated that the lake water is moderately polluted. Health risk assessment results revealed that As and Cr in the lake water via ingestion exposure pathway may pose both non-carcinogenic and carcinogenic health risks to the residents. The results of this study indicated that paddy fields are a major source of nutrients, organic matter and toxic metal(loid)s to the Gala Lake. To improve the water quality of the lake, we suggest that excessive use of fertilizers and pesticides should be controlled to reduce metal(loid) and nutrient loads from the paddy fields.

Pyraclostrobin is a widely used and highly efficient fungicide that also has high toxicity to aquatic organisms, especially fish. Although some research has reported the toxic effects of pyraclostrobin on fish, the main toxic pathways of pyraclostrobin in fish remain unclear. The present study has integrated histopathological, biochemical and hematological techniques to reveal the main toxic pathways and mechanisms of pyraclostrobin under different exposure routes. Our results indicated that pyraclostrobin entered fish mainly through the gills. The highest accumulation of pyraclostrobin was observed in the gills and heart compared with accumulation in other tissues and gill tissue showed the most severe damage. Hypoxia symptoms (water jacking, tummy turning and cartwheel formation) in fish were observed throughout the experiment. Taken together, our results suggested that the gills are important target organs. The high pyraclostrobin toxicity to gills might be associated with oxidative damage to the gills, inducing alterations in ventilation frequency, oxygen-carrying substances in blood and disorders of energy metabolism. Our research facilitates a better understanding of the toxic mechanisms of pyraclostrobin in fish, which can promote the ecotoxicological research of agrochemicals on aquatic organisms.

Cavity nesting bees are proficient and important pollinators that can augment or replace honey bee pollination services for some crops. Relatively little is known about specific pesticide concentrations present in cavity nesting insect reed matrices and associated potential risks to cavity nesting bees. Nesting substrates (Phragmites australis reeds in bundles) were deployed in an agriculturally intensive landscape to evaluate colonization and agrochemical exposure among cavity nesting pollinators over two consecutive field seasons. Composition of insect species colonizing reeds within nest bundles varied considerably; those placed near beef cattle feed yards were dominated by wasps (93% of the total number of individuals occupying reed nest bundles), whereas nest bundles deployed in cropland-dominated landscapes were colonized primarily by leaf cutter bees (71%). All nesting/brood matrices in reeds (mud, leaves, brood, pollen) contained agrochemicals. Mud used in brood chamber construction at feed yard sites contained 21 of 23 agrochemicals included in analysis and >70% of leaf substrate stored in reeds contained at least one agrochemical. Moxidectin was most frequently detected across all reed matrices from feed yard sites, and moxidectin concentrations in nonviable larvae were more than four times higher than those quantified in viable larvae. Agrochemical concentrations in leaf material and pollen were also quantified at levels that may have induced toxic effects among developing larvae. To our knowledge, this is the first study to characterize agrochemical concentrations in multiple reed matrices provisioned by cavity-nesting insects. Use of nest bundles revealed that cavity nesting pollinators in agriculturally intensive regions are exposed to agrochemicals during all life stages, at relatively high frequencies, and at potentially lethal concentrations. These results demonstrate the utility of nest bundles for characterizing risks to cavity nesting insects inhabiting agriculturally intensive regions.