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Tracking the occurrence of a broad variety of chemicals in the aquatic environment at a high temporal resolution over extended time periods is challenging. Here, we present a transportable platform...

Exposure assessment of pesticides has substantially improved over time, with methods that now include a combination of advanced analytical techniques and fate/transport models to evaluate their spatiotemporal distribution. However, the current regulatory environmental risk assessment considers thresholds from laboratory studies completed under standardized conditions that do not reflect environmental dynamics. Using the General Unified Threshold model for Survival (GUTS) model framework, we predicted the impact of time-varying pesticide exposures on the survival of gammarids in a small agricultural stream. The LP50 values were used as an additional metric for assessing risks (defined in GUTS as a multiplication factor applied to the concentration time series to induce 50% mortality by the end of exposure). Although real-case exposures to individual pesticides were predicted to produce little to no impact on survival, the LP50 values indicate acute (LP50 ≤ 100) and/or chronic (LP50 ≤ 10) toxicities for azoxystrobin, chlorpyrifos, diazinon, and imidacloprid, while risk to propiconazole exposure was considered very low (LP50 ≫ 100). Finally, the model was extended to reflect mixture toxicity via concentration addition. It predicted risks under acute and chronic exposures to organophosphates and neonicotinoids. Given that gammarids are simultaneously exposed to multiple chemicals and other stressors throughout their lifetime, a decline in survival probabilities due to chemical stress can likely influence their overall fitness. We recognize that some assumptions require validation, but our work included a level of realism that can assist risk managers when evaluating the cumulative consequences of chemical exposure. © 2020 American Chemical Society. ISSN:0013-936X ISSN:1520-5851

Tracking the occurrence of a plethora of chemicals in the aquatic environment at high temporal resolution over extended periods is a huge challenge. Here, we present a transportable high-resolution mass spectrometry platform including a fully automated workflow for advanced data processing. It measured several thousand concentration data points at 20-min intervals over several weeks, providing unprecedented insights into pollution dynamics, e.g. acute pesticide toxicity peaks in a small creek, intra-day variation of illicit drugs in raw wastewater and identifying contamination clusters of unknowns. This enabling technology has potential for researching and managing chemicals in natural and technical environments beyond current possibilities, e.g. real-time control in process engineering and sewer operation (water management and environmental toxicology), industrial surveillance (law enforcement) and wastewater-based epidemiology (public health).

The risks associated with pesticides in small streams remain poorly characterized. The challenges reside in understanding the complexities of (1) the highly dynamic concentration profiles of (2) several hundred active substances with (3) differing seasonality. The present study addressed these three challenges simultaneously. Five small streams in catchments under intensive agricultural land use were sampled using half-day composite samples from March to August 2015. Of 213 active substances quantified using liquid chromatography-high resolution mass spectrometry, a total of 128 was detected at least at one of the sites. Ecotoxicological acute and/or chronic quality criteria were exceeded for a total of 32 different active substances. The evaluation of risks over time revealed the necessity to evaluate the sequences of different active substances that are imposed on aquatic organisms. In contrast, a substance-specific perspective provides only a very limited assessment. Scenarios for reduction of either temporal resolution, number of substances or seasonal coverage were defined. It could be shown that risks can be underestimated by more than a factor of 10 in vulnerable catchments and that an increased temporal resolution is essential to cover acute risks but that a focused selection of substances is a possibility to reduce expenditures.

Micropollutants (MPs) as individual compounds or in complex mixtures are relevant for water quality and may trigger unwanted ecological effects. MPs originate from different point and diffuse sources and enter water bodies via different flow paths. Effluents from conventional wastewater treatment plants (WWTPs), in which various MPs are not or not completely removed, is one major source. To improve the water quality and avoid potential negative ecological effects by micropollutants, various measures to reduce the discharge should be taken. In this feature we discuss one of these measures; the benefits of upgrading WWTPs toward reduced MP loads and toxicities from wastewater effluents, using the recently decided Swiss strategy as an example. Based on (i) full-scale case studies using ozonation or powder activated carbon treatment, showing substantial reduction of MP discharges and concomitant reduced toxicities, (ii) social and political acceptance, (iii) technical feasibility and sufficient cost-effectiveness, the Swiss authorities recently decided to implement additional wastewater treatment steps as mitigation strategy to improve water quality. Since MPs are of growing global concern, the concepts and considerations behind the Swiss strategy are explained in this feature, which could be of use for other countries as well. It should be realized that upgrading WWTPs is not the only solution to reduce the discharge of MPs entering the environment, but is part of a broader, multipronged mitigation strategy.

The heavy use of veterinary antibiotics in modern animal production causes concern about risks of spreading antibiotic resistance after manure applications to agricultural fields. We report on a field study aiming at elucidating the fate of sulfonamide (SA) antibiotics in grassland soils and their transport to surface water. Two controlled manure applications were carried out under different weather conditions. After both applications, the SA concentrations in pore water and the total soil content declined rapidly. This stage of fast decline was followed by a second one during which the SA were rather persistent. More than 15% of the SAs applied were still present in the soil 3 months after application, always exceeding 100 microg/kg topsoil. The apparent SA sorption increased strongly with time. Accordingly, the risk for SA losses to water bodies decreased within 2 weeks to very low values. In contrast to SA concentrations in the soil, losses to the brook were strongly influenced by the weather conditions after the two manure applications. The overall losses were 15 times larger (about 0.5% of applied SA) during the wet conditions of May 2003 compared to the dry conditions following the first application (March 2003).

Monitoring programs throughout America and Europe have demonstrated the common occurrence of herbicides in surface water. Nevertheless, mixtures are rarely taken into account in water quality regulation. Taking mixtures into account is only feasible if the water quality criteria (WQC) of the single compounds are derived by a common and consistent methodology, which overcomes differences in data quality without settling on the lowest common denominator but making best use of all available data. In this paper, we present a method of defining a risk quotient for mixtures of herbicides with a similar mode of action (RQm). Consistent and comparable WQC are defined for single herbicides as a basis for the calculation of the RQm. Derived from the concentration addition model, the RQm can be expressed as the sum of the ratios of the measured environmental concentration and the WQC for each herbicide. The RQm should be less than one to ensure an acceptable risk to aquatic life. This approach has the advantage of being easy to calculate and communicate, and is proposed as a replacement for the current limit of 0.1 microg/L for herbicides in Switzerland. We illustrate the proposed approach on the example of five commonly applied herbicides (atrazine, simazine, terbuthylazine, isoproturon, and diuron). Their risk profile, i.e., the RQm as a function of time for one exemplary river, clearly shows that the single compounds rarely exceeded their individual WQC. However, the contribution of peaks of different seasonally applied herbicides, whose application periods partially overlap, together with the continuously emitted herbicides from nonagricultural use, results in the exceedance of the RQm threshold value of one upon several occasions.

Diffuse losses from agricultural fields are a major input source for herbicides in surface waters. In this and in a companion paper, we present the results of a comprehensive field study aimed at assessing the overall loss dynamics of three model herbicides (i.e., atrazine, dimethenamid, and metolachlor) from a small agricultural catchment (2.1 km2) and evaluating the relative contributions of various fields having different soil and topographical characteristics. An identical mixture of the three model herbicides as well as an additional pesticide for identification of a given field were applied within 12 h on 13 cornfields (total area approximately 12 ha), thus ensuring that the herbicides were exposed to identical meteorological conditions. After the simultaneous application, the concentrations of the compounds were monitored in the soils and at the outlets of three subcatchments containing between 4 and 5 cornfields each. Particular emphasis was placed on the two rain events that led to the major losses of the herbicides. The rank orders of herbicide dissipation in the soils and of the compound-specific mobilization into runoff were the same in all three subcatchments and were independent of the field characteristics. In contrast, the field properties caused the relative losses from two subcatchments to differ by up to a factor of 56 during the most important event, whereas compound-specific differences of the three neutral herbicides caused the losses to vary only by a factor of 2 during the same event. The enormous spatial variability was mainly caused by factors influencing the fraction of rain that was lost to surface water by fast transport mechanisms. Thus, the key factors determining the spatially variable herbicide losses were the permeability of the soils, the topography, and the location of subsurface drainage systems. These results illustrate the large potential to reduce herbicide losses by avoiding application on risk areas.

To take appropriate measures to minimize agricultural herbicide inputs into surface waters, detailed knowledge is required about all the factors that control the losses of a given compound from point sources (i.e., farmyards) as well as from the diffuse sources (i.e., the fields) within a given catchment. In this and in a companion paper, we present the results of a comprehensive field study, in which the temporal and spatial variability of the losses of three herbicides (atrazine, dimethenamid, and metolachlor) into the surface waters within a small catchment (2.1 km2) were investigated on different scales (i.e., field scale to whole catchment) after a controlled application of the compounds. In this paper, we discuss the loss dynamics of the three herbicides (and some of their metabolites) from the whole catchment over a period of 67 d after application. An identical mixture of the three herbicides was applied on 13 cornfields within 12 h, allowing for a comparison of their losses under identical meteorological conditions. Thanks to a high temporal sampling resolution, it was possible to distinguish between losses from a farmyard and losses from the fields. Farmyard losses contributed less than 20% to the total loads but caused the highest concentrations. The major herbicide losses from the agricultural fields occurred during the first two rain events after application that led to significant surface runoff and preferential flow into tile drains. In the soils of all fields, dimethenamid declined somewhat faster than atrazine and metolachlor, whereas atrazine was mobilized most effectively to runoff water. Relative losses of the three compounds did not vary by more than a factor of 3 (0.82, 0.27, and 0.41% of the mass applied for atrazine, dimethenamid, and metolachlor, respectively). Highest peak concentrations at the outlet of the catchment were found for atrazine (i.e., approximately 8 microg L(-1) for a short period (2 h) due to point source losses and between 1 and 3.5 microg L(-1) during more than 24 h due to diffuse losses).