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.

Given the many public health and environmental impacts associated with the use of pesticides, comprehensive pesticide application data are a high priority for environmental and health professionals, government agencies, and community groups in Wallonia (Belgium). In that context, geographic information system (GIS) approaches for mapping estimates of agricultural pesticide use were developed in the present study. Data on pesticide application rates and high-resolution annual datasets of the geographic distribution of crops were used to complete this analysis in Wallonia over the period 2015–2017. The method was implemented in Python in order to allow easy update and improvements of maps, or to segment maps by individual pesticides, chemical groups of pesticides (e.g. insecticides, herbicides), etc. Linked databases were created to classify, select, and possibly weight AIs according to specific requests and criteria. The results provide a first map of agricultural pesticide use in Wallonia, which depicts the best picture up to now of their geographic distribution. Maps of fungicides, herbicides, and plant growth regulators showed quite similar spatial patterns as the map of the combination of all pesticides. In contrast, the insecticide map showed a specific pattern related almost exclusively to dwarf-tree orchards in some municipalities in northern Wallonia. This research work is a preliminary result on the spatial characterization of agricultural pesticide use in Wallonia and give a valuable basis for research and environmental health actions in Belgium. Forthcoming developments will focus on exposure characterization to agricultural pesticides using GIS models. Using this information, policymakers will able to detect potential priority zones and take action to check and reduce agricultural pesticide loads in the environment.

Glyphosate is the most popular herbicide used worldwide. This study aimed to investigate the adverse effects of glyphosate on the small intestine and gut microbiota in rats. The rats were gavaged with 0, 5, 50, and 500 mg/kg of body weight glyphosate for 35 continuous days. The different segments of the small intestine were sampled to measure indicators of oxidative stress, ion concentrations and inflammatory responses, and fresh feces were collected for microbiota analysis. The results showed that glyphosate exposure decreased the ratio of villus height to crypt depth in the duodenum and jejunum. Decreased activity of antioxidant enzymes (T-SOD, GSH, GSH-Px) and elevated MDA content were observed in different segments of the small intestine. Furthermore, the concentrations of Fe, Cu, Zn and Mg were significantly decreased or increased. In addition, the mRNA expression levels of IL-1β, IL-6, TNF-α, MAPK3, NF-κB, and Caspase-3 were increased after glyphosate exposure. The 16 S rRNA gene sequencing results indicated that glyphosate exposure significantly increased α-diversity and altered bacterial composition. Glyphosate exposure significantly decreased the relative abundance of the phylum Firmicutes and the genus Lactobacillus, but several potentially pathogenic bacteria were enriched. In conclusion, this study provides important insight to reveal the negative influence of glyphosate exposure on the small intestine, and the altered microbial composition may play a vital role in the process.

Urban-use pesticides present a unique risk to non-target organisms in surface aquatic systems because impervious pavement facilitates runoff that may lead to serious contamination and ensuing aquatic toxicity. Fipronil is an insecticide used at high rates in urban environments, especially in regions such as California. This compound and its biologically active degradation products have been detected in urban runoff drainage and downstream surface water bodies at concentrations exceeding toxicity thresholds for sensitive aquatic invertebrates, necessitating a better understanding of the runoff sources and causes of this contamination at sites of application. In this study, we evaluated sorption of fipronil, fipronil desulfinyl, fipronil sulfide, and fipronil sulfone in urban dust, soil, and concrete, matrices commonly associated with the perimeter of a residential home. Samples were also collected from five single family homes treated with fipronil in Riverside, California, for five months to determine the occurrence of fipronil and its degradates in runoff water, urban dust, soil, and on concrete surfaces. Statistical analysis was performed to determine which urban matrices contributed more significantly to the contaminant levels in runoff water. Freundlich sorption coefficients for fipronil and its degradation products in dust were 3- to 9-fold greater than their values in soil. Fipronil and its degradates were detected in 100% of runoff samples and their presence was observed in dust, soil, and concrete wipe samples for 153 d after the treatment. Linear regression analysis showed that concrete surfaces were a primary source of all four compounds to runoff, and loose dust on concrete pavement also served as an important contributor. This study represents the first comprehensive investigation of the sources and causes for surface runoff contamination by fipronil and its degradation products. Findings highlight the importance to reduce fipronil residues on concrete surfaces through improved application methods and other mitigation practices.

Long-term applications of small concentrations of surfactants in soil via wastewater irrigation or pesticide application may enhance trace metal solubility. Mechanisms by which anionic surfactants (Aerosol 22, SDS and Biopower) affect trace metal solubility were assessed using batch, incubation and column experiments. In batch experiments on seven soils, the concentrations of Cu, Cd, Ni and Zn in the dissolved fraction of soils increased up to 100-fold at the high application rates, but increased less than 1.5-fold below the critical micelle concentration. Dissolved metal concentrations were less than 20% affected by surfactants in long-term incubations (70 days) up to the largest dose of 200 mg C kg⁻¹ soil. Leaching soil columns with A22 (100–1000 mg C L⁻¹) under unsaturated conditions increased trace metal concentrations in the leachates 2–4 fold over the control. Correlation analysis and speciation modelling showed that the increased solubility of metals upon surfactant application was more related to the solubilisation of soil organic matter from soil than to complexation of the metals with the surfactant. Organic matter from soil was solubilised in response to a decrease of solution Ca²⁺ as a result of Ca–surfactant precipitation. At environmentally relevant concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.

Field runoff is an important transport mechanism by which pesticides move into the hydrologic environment of intensive agricultural regions such as California's Central Valley. This study presents a spatially explicit modeling approach to extend Pesticide Root Zone Model (PRZM), a field-scale pesticide transport model, into basin level. The approach was applied to simulate chlorpyrifos use in the Central Valley during 2003-2007. The average value of loading as percent of use (LAPU) is 0.031%. Results of this study provide strong evidence that surface runoff generation and pesticide application timing are the two influencing factors on the spatial and temporal variability of chlorpyrifos sources from agricultural fields. This is one of the first studies in coupling GIS and field-scale models and providing simulations for the dynamics of pesticides over an agriculturally dominated landscape. The demonstrated modeling approach may be useful for implementations of best management practice (BMP) and total maximum daily load (TMDL).