Climate impacts of elevated temperatures and more severe and frequent weather extremes like heatwaves are globally becoming discernible on nature. While a mechanistic understanding is pivotal for ecosystem management, stressors like pesticides may interact with warming, leading to unpredictable effects on freshwater ecosystems. These multiple stressor studies are scarce and experimental designs often lack environmental realism. To investigate the multiple stressor effects, we conducted a microcosm experiment for 48 days comprising benthic macroinvertebrates, zooplankton, phytoplankton, macrophytes, and microbes. The fungicide carbendazim (100 μg/L) was investigated combined with temperature scenarios representing elevated temperatures (+4 °C) or heatwaves (+0 to +8 °C), both applied with similar energy input on a daily fluctuating ambient temperature (18 °C ± 1.5 °C), which served as control. Measurements showed the highest carbendazim dissipation in water under heatwaves followed by elevated and ambient temperatures. Average carbendazim concentrations were about 50% in water and 16% in sediment of the nominal concentration. In both heated cosms, zooplankton community dynamics revealed an unexpected shift from Rotifera to Cladocera and Copepoda nauplii, indicating variations in their thermal sensitivity, tolerance and resilience. Notably, warming and heatwaves shaped community responses similarly, suggesting heat intensity rather than distribution patterns determined the community structure. Heatwaves led to significant early and longer-lasting adverse effects that were exacerbated over time with Cladocera and Copepoda being most sensitive likely due to significant carbendazim interactions. Finally, a structural equation model demonstrated significant relationships between zooplankton and macrophytes and significantly negative carbendazim effects on zooplankton, whereas positive on macroinvertebrate abundances. The relationship between macroinvertebrate feeding and abundance was masked by significantly temperature-affected microbial leaf litter decomposition. Despite the thermal tolerance of zooplankton communities, our study highlights an increased pesticide threat under temperature extremes. More intense heatwaves are thus likely to cause significant alterations in community assemblages which will adversely affect ecosystem's processes and functions.

Fungicides, usually refer to the chemical agents that can effectively control or kill the pathogenic microorganisms. Here, we revealed the effects of three different fungicides, imazalil (IMZ), chlorothalonil (CTL) and carbendazim (CBZ), which are typical broad-spectrum fungicides that are detected at high levels in the natural environment, on heterogeneous human epithelial colorectal cells (Caco-2 cells). All three fungicides had the potential to induce different degrees of toxicity, cause apoptosis, reactive oxygen species (ROS) and even change the cell cycle in the cells. The half maximal inhibitory concentration (IC50) of CTL is the lowest among these three fungicides, suggesting that it may have the highest exposure risk, followed by IMZ, and CBZ. The results of the real-time PCR, Western blotting, and mitochondrial membrane potential (MMP) assays and the activities of key enzymes suggested that CTL induced apoptosis in Caco-2 cells via a mitochondrial-dependent pathway, as indicated by the upregulation of the expression of the apoptotic p53 and bax genes, the increase of the apoptosis marker cytochrome-c, the decrease of mRNA level of bcl-2 gene, and the decrease in the MMP. Exposure to two other fungicides also upregulated the transcriptional level of bax and the expression of cytochrome-c, but the mRNA level of bcl-2 was increased (IMZ) or unchanged (CBZ), suggesting that other pathways may be involved in the induction of cellular apoptosis by these two fungicides. In addition, all three of the fungicides could induce oxidative stress in Caco-2 cells. Our data showed that the three different kinds of fungicides all caused toxic effects in Caco-2 cells through various pathways.

In this study, avoidance response of Enchytraeus albidus to LUFA 2.2 soil contaminated with pesticide carbendazim was investigated. The aim was to clarify minimal test duration and temporal changes in avoidance response due to contamination ageing. Firstly, the concentration causing 50% avoidance (EC50) was determined as 7.6 mg/kg. Then, test duration needed to reach this value (ET50 = approximately 18 h) was identified. Finally, the capability of E. albidus avoidance test to reflect the changes of pollutant bioavailability was tested. The soil was spiked with carbendazim at the EC50 concentration 1, 14, or 28 days before the test started and avoidance effects of fresh versus aged contamination were compared. The results indicated that enchytraeids preferred soil contaminated for 28 days prior to assay where carbendazim was probably less bioavailable than in freshly spiked soil. Our results open an interesting research area of potential use of avoidance tests for contaminant bioavailability assessment.

This study investigated the occurrence and distribution of pesticides in surface water (lakes, major rivers and tributaries) and potential discharge sources (fish ponds, livestock and poultry farms, and sewage treatment plants) in Wujin District (northwest of Taihu Lake), Jiangsu province, China. An analytical liquid chromatography-tandem mass spectrometry method was developed for 38 pesticides, which was applied in the monitoring of 240 surface water samples and 76 potential discharge source samples. Eleven insecticides and five fungicides with temporal and spatial variation were detected in surface water. The total pesticide concentrations in surface water in different seasons were as follows: March > August > June > November. The two most polluting and widespread pesticides were carbendazim (maximum concentration 508 ng L⁻¹, detection rate 100%) and imidacloprid (maximum concentration 438 ng L⁻¹, detection rate 88%). Gehu Lake (S46) and Sanshangang River (S12) were seriously polluted water bodies. Seven insecticides and four fungicides were detected in the potential discharge sources; and their composition changed significantly with the seasons. The concentrations of detected organophosphorus pesticides and neonicotinoids (e.g. acetamiprid in March and dichlorvos in November) in a few non-agricultural planting sources were far greater than those detected in surface water, and hence a few fish ponds, livestock and poultry farms, and sewage treatment plants might be the potential discharge sources of pesticides in the surrounding surface water. The estimated input flux of the studied pesticides from upstream rivers to Taihu Lake was 141.95 kg a⁻¹. Furthermore, more attention should be paid to the medium or high aquatic ecotoxicological risk presented by the levels of organophosphorus pesticides, carbamates, and benzimidazoles.

The quality of groundwater (GW) resources is decreasing partly due to chemical contaminations from a wide range of activities, such as industrial and agricultural enterprises and changes in land-use. In urban areas, one potential major pathway of GW contamination is associated with urban water management practices based on stormwater runoff infiltration systems (SIS). Data on the performance of the upper layer of soil and the unsaturated zone of infiltration basins to limit the contamination of GW by hydrophilic compounds are lacking. With this aim, the impact of infiltration practices on GW contamination was assessed for 12 pesticides and 4 pharmaceuticals selected according to their ecotoxicological relevance and their likelihood of being present in urban stormwater and GW. For this purpose, 3 campaigns were conducted at 4 SIS during storm events. For each campaign, passive samplers based on the use of Empore™ disk were deployed in GW wells upstream and downstream of SIS, as well as in the stormwater runoff entering the infiltration basins. Upstream and downstream GW contaminations were compared to evaluate the potential effect of SIS on GW contamination and possible relationships with stormwater runoff composition were examined. Our results showed two interesting opposite trends: (i) carbendazim, diuron, fluopyram, imidacloprid and lamotrigine had concentrations significantly increasing in GW impacted by infiltration, indicating a contribution of SIS to GW contamination, (ii) atrazine, simazine and 2 transformation products exhibited concentrations significantly decreasing with infiltration due to a probable dilution of historic GW contaminants with infiltrated stormwater runoff. The other 7 contaminants showed no general trend. This study demonstrates that passive samplers deployed in GW wells enabled the capture of emerging polar pollutants present at very low concentrations and allowed the assessment of infiltration practices on GW quality. New data on GW and urban stormwater are provided for poorly studied hazardous compounds.

Melatonin (Mel) serves as an important signalling molecule in various aspects of stress tolerance in plants. However, the function of Mel in pesticide metabolism remains unknown. Here, selecting the widely used fungicide carbendazim (MBC) as the model, we found that exogenous Mel had the ability to alleviate pesticide phytotoxicity and residues in tomato as well as in some other vegetables. Additionally, overexpression of the Mel biosynthetic gene caffeic acid O-methyltransferase 1 (COMT1) significantly enhanced the capacity of the tomato to reduce MBC phytotoxicity and residue. This outcome was mainly because of the Mel-induced antioxidant capability, as well as the key detoxification process. Indeed, levels of reactive oxygen species (ROS) and lipid peroxides significantly decreased after applying exogenous Mel or overexpressing COMT1, which resulted from direct ROS scavenging, and increased Mel levels significantly enhanced antioxidant enzymatic activity. More importantly, Mel activated the ascorbate-glutathione cycle to participate in glutathione S-transferase-mediated pesticide detoxification. A grafting experiment showed that rootstocks from COMT1 transgenic plants increased the Mel accumulation of wild-type scions, resulting in MBC metabolism in the scions. To our knowledge, this is the first report providing evidence of Mel-induced pesticide metabolism, which provides a novel approach for minimizing pesticide residues in crops by exploiting plant self-detoxification mechanisms.

A pesticide monitoring study including 80 and 60 active ingredients (in surface waters and sediments, respectively) was carried out in a river basin in Costa Rica during 2007–2012. A special emphasis was given on the exceptional ecological conditions of the tropical agro-ecosystem and the pesticide application strategies in order to establish a reliable monitoring network. A total of 135 water samples and 129 sediment samples were collected and analyzed. Long-term aquatic ecotoxicological risk assessment based on risk quotient in three trophic levels was conducted. Short-term risk assessment was used to calculate the toxic unit and prioritization of sampling sites was conducted by the sum of toxic units in both aquatic and sediment compartments. Dimethoate (61.2 μg/L), propanil (30.6 μg/L), diuron (22.8 μg/L) and terbutryn (4.8 μg/L) were detected at the highest concentrations in water samples. Carbendazim and endosulfan were the most frequently detected pesticides in water and sediment samples, respectively. Triazophos (491 μg/kg), cypermethrin (71.5 μg/kg), permethrin (47.8 μg/kg), terbutryn (38.7 μg/kg), chlorpyrifos (18.2 μg/kg) and diuron (11.75 μg/kg) were detected at the highest concentrations in sediment samples. The pesticides carbendazim, diuron, endosulfan, epoxyconazole, propanil, triazophos and terbutryn showed non-acceptable risk even when a conservative scenario was considered. Sum TUsite higher than 1 was found for one and two sampling sites in water and sediment compartments, respectively, suggesting high acute toxicity for the ecosystem.Exceptional ecological conditions of the tropical agro-ecosystem affect the fate of pesticides in water and sediment environment differently than the temperate one.

The increased use of pesticides during recent years necessitates a reevaluation of the effect of those compounds by extending the range of nontarget species commonly used in risk assessment. In the present work, we thus determined the impact of the pesticides glyphosate, carbendazim, and malathion on the parasite Chordodes nobilii in both natural and reconstituted freshwater as the assay medium and tested the sensitivity of three of this species's ecologically relevant parameters—e. g., embryo nonviablity and the infective capability of larvae exposed for 48 or 96 h either in ovo or after hatching via the infection index mean abundance—to compare those parameters to data from previous trials with reconstituted freshwater. In natural-freshwater assays, at environmentally relevant concentrations, all three pesticides inhibited the preparasitic-stage endpoints; with carbendazim being the most toxic pesticide and the subsequent infectivity of larvae exposed in ovo the most sensitive endpoint. In general, the 50%-inhibitory concentrations assayed in reconstituted freshwater were higher than those obtained in natural freshwater, indicating a certain protective effect; whereas the maximal toxicity of the three pesticides in both aqueous environments was essentially similar. The sensitivity of C. nobilii to these agents demonstrated that this species is one of the most susceptible to toxicity by all three pesticides. These findings with the assay methodology provide relevant information for a future assessment of the risk of toxicity to aquatic ecosystems and furthermore underscore the need to include parasitic organisms among the nontarget species canvassed. We also recommend that in the bioassays in which the risk assessment is carried out, water from a nontarget species's natural environment be used in parallel in order to obtain more conclusive results.

Carbendazim is a fungicide commonly used as active substance in plant protection products and biocidal products, for instance to protect facades of buildings against fungi. However, the subsequent occurrence of this fungicide and potential endocrine disruptor in the aqueous environment is a major concern. In this study, high resolution mass spectrometry shows that carbendazim can be detected with an increasing abundance from the source to the mouth of the River Rhine. Unexpectedly, the abundance of carbendazim correlates poorly with that of other fungicides used as active ingredients in plant protection products (r² of 0.32 for cyproconazole and r² of 0.57 for propiconazole) but it correlates linearly with that of pharmaceuticals (r² of 0.86 for carbamazepine and r² of 0.89 for lamotrigine). These results suggest that the occurrence of carbendazim in surface water comes mainly from the discharge of treated domestic wastewater. This hypothesis is further confirmed by the detection of carbendazim in wastewater effluents (n = 22). In fact, bench-scale leaching tests of textiles and papers revealed that these materials commonly found in households could be a source of carbendazim in domestic wastewater. Moreover, additional river samples collected nearby two paper industries indicate that the discharge of their treated process effluents is also a source of carbendazim in the environment. While characterizing paper and textile as overlooked sources of carbendazim, this study also shows the biocide as a possible ubiquitous wastewater contaminant that would require further systematic and worldwide monitoring due to its toxicological properties.

Nineteen biocides were investigated in the Yangtze River to understand their spatiotemporal distribution, mass loads and ecological risks. Fourteen biocides were detected, with the highest concentrations up to 166 ng/L for DEET in surface water, and 54.3 ng/g dry weight (dw) for triclocarban in sediment. The dominant biocides were DEET and methylparaben, with their detection frequencies of 100% in both phases. An estimate of 152 t/y of 14 biocides was carried by the Yangtze River to the East China Sea. The distribution of biocides in the aquatic environments was significantly correlated to Gross Domestic Product (GDP), total phosphorus (TP) and total nitrogen (TN), suggesting dominant input sources from domestic wastewater of the cities along the river. Risk assessment showed high ecological risks posed by carbendazim in both phases and by triclosan in sediment. Therefore, proper measures should be taken to reduce the input of biocides into the river systems.