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The Water Framework Directive (WFD) demands that good status is to be achieved for all European water bodies. While governmental monitoring under the WFD mostly concludes a good status with regard to pesticide pollution, numerous scientific studies have demonstrated widespread negative ecological impacts of pesticide exposure in surface waters. To identify reasons for this discrepancy, we analysed pesticide concentrations measured in a monitoring campaign of 91 agricultural streams in 2018 and 2019 using methodologies that exceed the requirements of the WFD. This included a sampling strategy that takes into account the periodic occurrence of pesticides and a different analyte spectrum designed to reflect current pesticide use. We found that regulatory acceptable concentrations (RACs) were exceeded for 39 different pesticides at 81% of monitoring sites. In comparison, WFD-compliant monitoring of the same sites would have detected only eleven pesticides as exceeding the WFD-based environmental quality standards (EQS) at 35% of monitoring sites. We suggest three reasons for this underestimation of pesticide risk under the WFD-compliant monitoring: (1) The sampling approach - the timing and site selection are unable to adequately capture the periodic occurrence of pesticides and investigate surface waters particularly susceptible to pesticide risks; (2) the measuring method - a too narrow analyte spectrum (6% of pesticides currently approved in Germany) and insufficient analytical capacities result in risk drivers being overlooked; (3) the assessment method for measured concentrations - the protectivity and availability of regulatory thresholds are not sufficient to ensure a good ecological status. We therefore propose practical and legal refinements to improve the WFD's monitoring and assessment strategy in order to gain a more realistic picture of pesticide surface water pollution. This will enable more rapid identification of risk drivers and suitable risk management measures to ultimately improve the status of European surface waters., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Few studies have examined the exposure of small streams (< 30 km 2 catchment size) to agriculturally used pesticides, compared to large rivers. A total of 105 sites in 103 small agricultural streams were investigated for 76 pesticides (insecticides, herbicides, fungicides) and 32 pesticide metabolites in spring and summer over two years (2018 and 2019) during dry weather and rainfall using event-driven sampling. The median total concentration of the 76 pesticides was 0.18 µg/L, with 9 pesticides per sample on average (n = 815). This is significantly higher than monitoring data for larger streams, reflecting the close proximity to agricultural fields and the limited dilution by non-agricultural waters. The frequency of detection of all pesticides correlated with sales quantity and half-lives in water. Terbuthylazine, MCPA, boscalid, and tebuconazole showed the highest median concentrations. The median of the total concentration of the 32 metabolites exceeded the pesticide concentration by more than an order of magnitude. During dry weather, the median total concentration of the 76 pesticides was 0.07 µg/L, with 5 pesticides per sample on average. Rainfall events increased the median total pesticide concentration by a factor of 10 (to 0.7 µg/L), and the average number of pesticides per sample to 14 (with up to 41 in single samples). The concentration increase was particularly strong for 2,4-D, MCPA, terbuthylazine, and nicosulfuron (75 percentile). Metabolite concentrations were generally less responsive to rainfall, except for those of terbuthylazine, flufenacet, metamitron, and prothioconazole. The frequent and widespread exceedance of the regulatory acceptable concentrations (RAC) of the 76 pesticides during both, dry weather and rainfall, suggests that current plant protection product authorization and risk mitigation methods are not sufficient to protect small streams., (Copyright © 2021. Published by Elsevier Ltd.)

Despite elaborate regulation of agricultural pesticides, their occurrence in non-target areas has been linked to adverse ecological effects on insects in several field investigations. Their quantitative role in contributing to the biodiversity crisis is, however, still not known. In a large-scale study across 101 sites of small lowland streams in Central Europe, Germany we revealed that 83% of agricultural streams did not meet the pesticide-related ecological targets. For the first time we identified that agricultural nonpoint-source pesticide pollution was the major driver in reducing vulnerable insect populations in aquatic invertebrate communities, exceeding the relevance of other anthropogenic stressors such as poor hydro-morphological structure and nutrients. We identified that the current authorisation of pesticides, which aims to prevent unacceptable adverse effects, underestimates the actual ecological risk as (i) measured pesticide concentrations exceeded current regulatory acceptable concentrations in 81% of the agricultural streams investigated, (ii) for several pesticides the inertia of the authorisation process impedes the incorporation of new scientific knowledge and (iii) existing thresholds of invertebrate toxicity drivers are not protective by a factor of 5.3 to 40. To provide adequate environmental quality objectives, the authorisation process needs to include monitoring-derived information on pesticide effects at the ecosystem level. Here, we derive such thresholds that ensure a protection of the invertebrate stream community., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Pesticide contamination of agricultural streams has widely been analysed in regions of high intensity agriculture such as in Western Europe or North America. The situation of streams subject to low intensity agriculture relying on human and animal labour, as in parts of Romania, remains unknown. To close this gap, we determined concentrations of 244 pesticides and metabolites at 19 low-order streams, covering sites from low to high intensity agriculture in a region of Romania. Pesticides were sampled with two passive sampling methods (styrene-divinylbenzene (SDB) disks and polydimethylsiloxane (PDMS) sheets) during three rainfall events and at base flow. Using the toxic unit approach, we assessed the toxicity towards algae and invertebrates. Up to 50 pesticides were detected simultaneously, resulting in sum concentrations between 0.02 and 37 µg L -1 . Both, the sum concentration as well as the toxicities were in a similar range as in high intensity agricultural streams of Western Europe. Different proxies of agricultural intensity did not relate to in-stream pesticide toxicity, contradicting the assumption of previous studies. The toxicity towards invertebrates was positively related to large scale variables such as the catchment size and the agricultural land use in the upstream catchment and small scale variables including riparian plant height, whereas the toxicity to algae showed no relationship to any of the variables. Our results suggest that streams in low intensity agriculture, despite a minor reported use of agrochemicals, exhibit similar levels of pesticide pollution as in regions of high intensity agriculture., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Silicone rubber passive samplers spiked with 4 deuterated performance reference compounds were deployed for 29-33 days to estimate the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in 9 streams in Victoria, Australia, following a wildfire. Silicone rubber strips of 2 thicknesses were used to obtain information on the status of uptake of the chemicals of interest at retrieval. In addition, we monitored the stream macroinvertebrate community for potential effects of PAHs or other fire organics. All selected PAHs were detected in the passive samplers and the sampling rates ranged from 0.5 to 50 L/day significantly varying between sites but not compounds, presumably due to differences in current velocity. The estimated water concentrations were 0.1-10 ng/L for total PAHs with phenanthrene, pyrene and fluoranthene accounting for 91% of the total concentration. All PAHs were a factor of 1000 or more below the reported 48-h median lethal concentrations (48-h LC50) for Daphnia magna. Two sites located closest to the fires exhibited elevated concentrations compared to the other sites and the passive samplers in these sites remained in the integrative uptake regime for all compounds, suggesting precipitation-associated PAH input. No acute toxic effects of PAHs or other fire organics on the invertebrate community were detected using a biotic index for organic toxicants (SPEAR), whereas a non-specific biotic index (SIGNAL) decreased in two sites indicating impacts from changes in other environmental parameters. We conclude (1) that silicone-based passive samplers with two different area-to-volume ratios represent a promising tool for determining organic toxicants and (2) that PAHs from wildfires are unlikely to be a common main cause for fire-related ecological effects in streams adjacent to burnt regions., ((c) 2010 Elsevier Ltd. All rights reserved.)

We investigated the performance of the Chemcatcher, an aquatic passive sampling device consisting of a sampler body and an Empore disk as receiving phase, when used to monitor acetochlor, alachlor, carbofuran, chlorfenvinphos, alpha-endosulfan, fenpropidin, linuron, oxadiazon, pirimicarb and tebuconazole in 16 Central European streams. The Chemcatcher, equipped with an SDB-XC Empore disk, detected seven of the aforementioned pesticides with a total of 54 detections. The time-weighted average (TWA) concentrations reached up to 1 microg/L for acetochlor and alachlor. Toxic units derived from these concentrations explained reasonably well the observed ecological effects of pesticide stress, measured with the SPEAR index. In a follow-up analysis, we compared the Chemcatcher performance with those of two other sampling systems. The results obtained with the Chemcatcher closely matched those of the event-driven water sampler. By contrast, the TWA concentrations were not significantly correlated with concentrations on suspended particles. We conclude that the Chemcatcher is suitable for the monitoring of polar organic toxicants and presents an alternative to conventional spot sampling in the monitoring of episodically occurring pollutants.