We investigated the levels and distribution patterns of α- and β-endosulfan and endosulfan sulfate in air, soil, water, and sediment samples collected from the South Korean persistent organic pollutants (POPs) monitoring networks. In the air samples, the highest concentrations of the total (Σ₃) endosulfan (50.3–611 pg/m³, mean: 274 pg/m³) were observed during summer. Spearman analysis revealed a good correlation between agricultural land area and atmospheric concentrations of Σ₃ endosulfan except during winter. Regardless of the season, the ratio of the two isomers (α/β) was 3.6–4.9 in the air samples, higher than that observed in technical mixtures (2.0–2.3), possibly due to the higher volatility of α-endosulfan, compared to β-endosulfan. Concentrations of Σ₃ endosulfan in the soil samples (n.d.−13.4 ng/g, mean: 0.8 ng/g) were not significantly different except at some stations adjacent to large areas of farmland. The average levels of Σ₃ endosulfan in the water and sediment samples were 2.1 ng/L and 0.1 ng/g dw, respectively. In analyzing the four largest rivers, it was observed that a few water stations during spring and fall and sediment stations in fall had high concentrations of the two isomers and endosulfan sulfate, particularly around the Yeoungsan and Nakdong Rivers near large areas of agricultural land. Endosulfan sulfate was dominant at most water and sediment sampling stations. This study demonstrates that the endosulfan found in most environmental compartments most probably derives from agricultural areas despite its ban as a pesticide. On the other hand, given that it was also detected in industrial and urban areas, in which pesticide application does not occur, it can be conjectured that endosulfan is aerially transported at higher temperatures and continuously circulates within the environment.

The ecological impacts of insecticides in aquatic areas around agricultural lands have long been ignored in the regulation scheme of pesticides in Japan. Upon the scheme, the predicted concentration of an insecticide in the main stream of a river is the only parameter considered, suggesting that the ecological impacts of insecticides on local biodiversity around agricultural fields are underestimated. To fill this knowledge gap, we measured insecticide concentrations in surface water and sediment in aquatic areas around paddy fields at 35 locations across Japan. Among the 18 insecticides considered, 15 were detected somewhere in Japan and their concentrations were generally higher in the southwestern region in Japan (e.g. Hiroshima, Saga, or Kagoshima prefectures). Most insecticides were accumulated at higher concentrations in sediment than in surface water, consistent with previous studies. We also detected insecticides applied to nursery boxes at high concentrations in surrounding aquatic areas, although such application is generally considered to have low environmental risks. In addition, derivatives of fipronil, which have similar toxicity as that of fipronil, were often detected in sediment at higher concentrations than fipronil itself. Concentrations of dinotefuran in water at two sampling points were higher than the 5% hazardous concentration (HC5), indicating a possibility of a risk of acute toxicity to aquatic organisms. Our findings indicate that ecological risk assessments of insecticides and their derivatives should be expanded to include concentrations in sediment and water around paddy fields as well.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of ¹³C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of ¹³C into amino acids (AA). At the end, 25% of ¹³C₆-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the ¹³C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total ¹³C-biogenic NER. About 33% of the total ¹³C-NER could thus be explained by ¹³C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The ¹³C label from ¹³C₆-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The ¹³C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of ¹³C₆-bromoxynil equivalents, respectively, corresponding to total ¹³C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly ¹³C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown ¹³C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

Waterborne exposure towards fungicides is known to trigger negative effects in aquatic leaf-associated microbial decomposers and leaf-shredding macroinvertebrates. We expected similar effects when these organisms use leaf material from terrestrial plants that were treated with systemic fungicides as a food source since the fungicides may remain within the leaves when entering aquatic systems. To test this hypothesis, we treated black alder (Alnus glutinosa) trees with a tap water control or a systemic fungicide mixture (azoxystrobin, cyprodinil, quinoxyfen, and tebuconazole) at two worst-case application rates. Leaves of these trees were used in an experiment targeting alterations in two functions provided by leaf-associated microorganisms, namely the decomposition and conditioning of leaf material. The latter was addressed via the food-choice response of the amphipod shredder Gammarus fossarum. During a second experiment, the potential impact of long-term consumption of leaves from trees treated with systemic fungicides on G. fossarum was assessed. Systemic fungicide treatment altered the resource quality of the leaf material resulting in trends of increased fungal spore production and an altered community composition of leaf-associated fungi. These changes in turn caused a significant preference of Gammarus for microbially conditioned leaves that had received the highest fungicide treatment over control leaves. This higher food quality ultimately resulted in a higher gammarid growth (up to 300% increase) during the long-term feeding assay. Although the underlying mechanisms still need to be addressed, the present study demonstrates a positive indirect response in aquatic organisms due to systemic pesticide application in a terrestrial system. As the effects from the introduction of plant material treated with systemic fungicides strongly differ from those mediated via other pathways (e.g., waterborne exposure), our study provides a novel perspective of fungicide-triggered effects in aquatic detritus-based food webs.

We couple current findings of pesticides in surface and groundwater to the history of pesticide usage, focusing on the potential contribution of legacy pesticides to the predicted ecotoxicological impact on benthic macroinvertebrates in headwater streams. Results suggest that groundwater, in addition to precipitation and surface runoff, is an important source of pesticides (particularly legacy herbicides) entering surface water. In addition to current-use active ingredients, legacy pesticides, metabolites and impurities are important for explaining the estimated total toxicity attributable to pesticides. Sediment-bound insecticides were identified as the primary source for predicted ecotoxicity. Our results support recent studies indicating that highly sorbing chemicals contribute and even drive impacts on aquatic ecosystems. They further indicate that groundwater contaminated by legacy and contemporary pesticides may impact adjoining streams. Stream observations of soluble and sediment-bound pesticides are valuable for understanding the long-term fate of pesticides in aquifers, and should be included in stream monitoring programs.

Dioecious plants show sexual differences in resistance traits to abiotic stresses. However, the effects of exogenous pesticide application on female and male plant growth and their associated adaptation mechanisms are unclear. Our study investigated the effects of the broad-spectrum pesticide lambda-cyhalothrin (λ-CY) on dioecious Populus cathayana growth and explored the factors through which λ-CY changed the rhizosphere bacterial community and physicochemical soil properties via sex-specific metabolomics. The sequential application of λ-CY significantly suppressed male shoot- and root biomass, with little effect on the growth of females. Females possessed a higher intrinsic chemo-diversity within their root exudates, and their levels of various metabolites (sugars, fatty acids, and small organic acids) increased after exposure to λ-CY with consequences on bacterial community composition. Maintaining high bacterial alpha diversity and recruiting specific bacterial groups slowed down the loss of rhizosphere nutrients in females. In contrast, the reduction in bacterial alpha diversity and network structure stability in males was associated with lower rhizosphere nutrient availability. Spearman's correlation analysis revealed that several bacterial groups were positively correlated with the root secretion of lipids and organic acids, suggesting that these metabolites can affect the soil bacterial groups actively involved in the nutrient pool. This study provided novel insights that root exudates and soil microbial interactions may mediate sex-specific differences in response to pesticide application.

Global climate change (GCC) significantly affects aquatic ecosystems. Continual use of pyrethroid insecticides results in contamination of these ecosystems and concurrent GCC raises the potential for synergistic effects. Resistance to pyrethroids has been documented in Hyalella azteca, a common epibenthic amphipod and model organism. Resistant H. azteca can bioconcentrate elevated amounts of pyrethroids and represent a threat to consumers via trophic transfer. In the present study, a predator of H. azteca, the inland silverside (Menidia beryllina), was used to examine the impacts of GCC on pyrethroid bioaccumulation via trophic transfer from resistant prey organisms. M. beryllina were fed ¹⁴C-permethrin dosed pyrethroid-resistant H. azteca for 14 days at three salinities (6, 13 and 20 practical salinity units (PSU)) and two temperatures (18 and 23 °C). Fish were analyzed for total body residues, percent parent compound and percent metabolites. Gene expression in liver and brain tissue were evaluated to assess whether dietary bioaccumulation of permethrin would impact detoxification processes, metabolism, and general stress responses. M. beryllina bioaccumulated significant amounts of permethrin across all treatments, ranging from 39 to 557 ng g⁻¹ lipid. No statistically significant effect of temperature was found on total bioaccumulation. Salinity had a significant effect on total bioaccumulation, owing to greater bioaccumulation at 6 PSU compared to 13 and 20 PSU, which may be due to alterations to xenobiotic elimination. Permethrin bioaccumulation and the interaction with temperature and salinity elicited significant transcriptional responses in genes relating to detoxification, growth, development, and immune response. Given the increased prevalence of pesticide-resistant aquatic invertebrates, GCC-induced alterations to temperature and salinity, and the predicted increase in pesticide usage, these findings suggest trophic transfer may play an important role in pesticide bioaccumulation and effects in predatory fish.

The occurrence, spatiotemporal variations, influence factors and environmental risks of eight common neonicotinoids (NEOs), fipronil, and three fipronil metabolites (fipronil and its metabolites are collectively referred to as FIPs) in different seasons from the estuary to the inner area of Jiaozhou Bay, China were comprehensively investigated. First- and second-generation NEOs were found to be the predominant pesticides in this area. The average contents of ∑NEOs and ∑FIPs from the estuary to the inner bay decreased from 12.99 ng/L to 0.82 ng/L and from 1.10 ng/L to 0.17 ng/L, respectively. NEO and FIP concentrations were higher in summer and autumn. High ∑NEO content is distributed in main inflow rivers, such as Dagu River and Licun River, which are influenced by pesticide application. NEO concentrations in all rivers were high upstream and low downstream because of the influence of heavy rainfall and seawater dilution in summer. NEO concentrations were high along the coast and low at the mouth and center of Jiaozhou Bay in summer and autumn and evenly distributed in winter and spring. Temperature has a great influence on most NEOs and FIPs owing to its effect on their degradation. Nitrogen-containing nutrients have an important influence on the distribution of fipronil and acetamiprid, which may be due to the activity of nitrogen-containing functional groups in their structure. Only Licun River, Dagu River and Haibo river sewage treatment plant in summer posed a certain risk of chronic toxicity for NEOs using the new threshold established by the species sensitive distribution (SSD) method for Chinese native aquatic lives. These findings should arouse people's attention.

Pesticides are widely and intensively used in the world for crops protection. High pesticide loadings can potentially pollute the water resource. However, little is known about the usage, environmental emission and fate of pesticides in river basins. Here, we firstly established a pesticide emission estimation method, and investigated the environmental fate of three commonly used pesticides (chlorpyrifos, triazophos, and isoprothiolane) in Dongjiang River basin, southern China using mathematical modelling approach in combination with field monitoring. The distributed hydrological model SWAT (Soil and Water Assessment Tool) was applied to model the emission of the target pesticides from farmland to stream water, and their fate in the basin. A satisfactory model calibration for flow and suspended sediment was obtained based on eight-year observation data of four hydrological monitoring stations in Dongjiang River basin. The differences between the simulation and observation of pesticides were almost within an order of magnitude, including more than 53% differences within 0.5 order of magnitude. In the river basin, 78860 kg of chlorpyrifos, 54990 kg of triazophos and 35320 kg of isoprothiolane were sprayed onto the crops, the estimated annual emissions of the basin come up to 1801 kg, 3779 kg, and 2330 kg under the conditions of rainfall, surface runoff and percolation. After a series of environmental processes including settlement and degradation within the channels, the predicted export masses for chlorpyrifos, triazophos and isoprothiolane were reduced to 266 kg, 1858 kg, 1350 kg, respectively. Successful prediction suggests that the reliable estimation method combing the SWAT modelling can help us understand the source, concentration levels and fate of pesticides in river basin in different scales. Combing the method of emission and fate modelling method we proposed, countries and regions lacking pesticide-application database can facilitate better management of pesticides.

Thiamethoxam is a widely used pesticide applied to different field crops. To inform risk assessment for this pesticide across relevant crops, we usually rely on field trials, which require time, costs and energy. For providing reliable data across crops and reduce experimental efforts, field trials should be complemented with dynamic modelling. In the present work, we hence focused on combining field trials with dynamic modelling to simulate mass evolutions of the pesticide-plant-system for thiamethoxam applied to wheat, lettuce and tomato as three major food crops. Field trials were conducted with QuEChERS (quick, easy, cheap, effective, rugged and safe) liquid chromatography-mass spectrometry, which gave consistent maximum residue concentrations for thiamethoxam in wheat, lettuce and tomato. We used these residues to evaluate the related dietary risk of humans consuming these food crops. Our results indicated that thiamethoxam did not provide any unacceptable dietary risk for humans across these three food crops, which is in line with findings from previous studies. Results for the studied crops could be extrapolated to other crops and with that, our study constitutes a cost- and time-efficient way of providing reliable input for risk assessment of pesticides across crops, which is relevant for both practitioners and regulators.