Combining Polar Organic Chemical Integrative Samplers (POCIS) with Toxicity Testing on Microalgae to Evaluate the Impact of Herbicide Mixtures in Surface Waters.

Pesticide risk assessment within the European Union Water Framework Directive is largely deficient in the assessment of the actual exposure and chemical mixture effects. Pesticide contamination, in particular herbicidal loading, has been shown to exert pressure on surface waters. Such pollution can have direct impact on autotrophic species, as well as indirect impacts on freshwater communities through primary production degradation. The present study proposes a screening method combining polar organic chemical integrative samplers (POCIS) with mode of action-specific toxicity testing on microalgae exposed to POCIS extracts as a standard approach to effectively address the problem of herbicide mixture effects detection. This methodology has been tested using Luxembourgish rivers as a case study and has proven to be a fast and reliable information source that is complementary to chemical analysis, allowing assessment of missing target analytes. Pesticide pressure in the 24 analyzed streams was mainly exerted by flufenacet, terbuthylazine, nicosulfuron, and foramsulfuron, with occasional impacts by the nonagricultural biocide diuron. Algae tests were more sensitive to endpoints affecting photosystem II and reproduction than to growth and could be best predicted with the concentration addition model. In addition, analysis revealed that herbicide mixture toxicity is correlated with macrophyte disappearance in the field, relating mainly to emissions from maize cultures. Combining passive sampler extracts with standard toxicity tests offers promising perspectives for ecological risk assessment. The full implementation of the proposed approach, however, requires adaptation of the legislation to scientific progress. Environ Toxicol Chem 2022;41:2667-2678. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Geochemical matrix differently affects the response of internal standards and target analytes for pesticide transformation products measured in groundwater samples.

Electrospray ionization (ESI) is the most common technique in liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS) allowing for sensitive detection of polar compounds with online water concentration. The technique is popular in groundwater monitoring programs and has permitted great progress in the detection and quantification of polar pesticide transformation products (TP) in recent years. However, ESI is also known to be prone to matrix effects. The common solution to this potential bias is the use of labelled internal standards. Unfortunately, these are not available for all target compounds, which leads to the linkage of target compounds to non-homologue internal standards with unknown consequences for quantification in variable geochemical settings. We investigated these matrix effects for polar TP with a molecular mass range of 225-350 Da and logDpH7 between -0.27 and -1.7 as well as for parent compounds with logDpH3 between 0.84 and 3.22. The acquired internal standards were tested on a gradient of DOC, anions, conductivity and inorganic carbon with a set of ten carefully chosen groundwater samples. Internal standards that were measured in positive ionization mode proved to be insensitive to geochemical variations while those that were measured in negative ionization mode showed reduced response with increasing anion concentration. All pairs of internal standards and target analytes were investigated for deviating matrix effects using standard addition experiments. Positive ionization compounds and target compounds with deuterated homologues showed little deviation while non-homologue pairs in negative mode proved to be strongly biased. Although bias was up to factor five for some compounds it was remarkably stable over the entire gradient studied, suggesting an identical suppression mode at varying matrix levels for different compounds. We advocate the conduct of standard addition experiments if homologue internal standards are not available.

Isotope fractionation of micropollutants during large-volume extraction: heads-up from a critical method evaluation for atrazine, desethylatrazine and 2,6-dichlorobenzamide at low ng/L concentrations in groundwater.

Micropollutants are frequently detected in groundwater. Thus, the question arises whether they are eliminated by natural attenuation so that pesticide degradation would be observed with increasing residence time in groundwater. Conventional analytical approaches rely on parent compound/metabolite ratios. These are difficult to interpret if metabolites are sorbed or further transformed. Compound-specific stable isotope analysis (CSIA) presents an alternative for identifying degradation based on the analysis of natural isotope abundances in pesticides and their changes during degradation. However, CSIA by gas chromatography-isotope ratio mass spectrometry is challenged by the low concentrations (ng/L) of micropollutants in groundwater. Consequently, large amounts of water need to be sampled requiring enrichment and clean-up steps from interfering matrix effects that must not introduce artefacts in measured isotope values. The aim of this study was to evaluate the accuracy of isotope ratio measurements of the frequently detected micropollutants atrazine, desethylatrazine and 2,6-dichlorobenzamide after enrichment from large water volumes (up to 100 L) by solid-phase extraction with consecutive clean-up by HPLC. Associated artefacts of isotope discrimination were found to depend on numerous factors including organic matter content and extraction volume. This emphasizes the necessity to perform a careful method evaluation of sample preparation and sample pre-treatment prior reliable CSIA.

Quantitative use of passive sampling data to derive a complete seasonal sequence of flood event loads: a case study for maize herbicides in Luxembourg.

Pesticides are the class of compounds with the most dynamic behaviour in their surface water occurrence: their episodic release to surface waters is closely related to the date of application and the following weather conditions and poses substantial challenges to monitoring in order to yield accurate mass transfer figures. Moreover, pesticide use, dose and time of application are largely unknown catchment wide and pose an essential problem as to the realism and reliability of pesticide fate modelling as well as accurate farmer counselling. Spatially and temporally highly resolved monitoring establishing pesticide sources was logistically unthinkable until the advent of passive samplers which combine ease of deployment and continuous sampling. However, because research on passive sampler performance has been mainly driven by analytical precision issues, doubts were high as to whether passive samplers could yield accurate time weighted averages in the field, all the more so that the number of field validations is to this day very limited. Here we present a study that used a combination of spatially distributed passive- and autosamplers to capture the runoff dynamics of pesticides used for maize crops in a 82 km2 catchment in Luxembourg. We demonstrate that passive samplers are capable of accurately monitoring episodic emissions of pesticides through a longitudinal profile in a catchment, thus allowing the identification of pesticide source areas. Thanks to the time-proportional nature of the passive sampling it was furthermore possible to calculate event mean concentrations and loads which were behaving temporally according to the physico-chemical properties of the compounds and to the timing and extent of mobilising discharge.

An immission perspective of emerging micropollutant pressure in Luxembourgish surface waters: A simple evaluation scheme for wastewater impact assessment.

While wastewater treatment plants have been identified as the most prominent source of emerging micropollutants in surface waters, prediction of their ambient concentrations remains a challenge. This is due to the variability of loads entering individual treatment plants and of the elimination capacity by the latter as well as potential attenuation in the river network. Although geospatially detailed models exist, they suffer from the same data input uncertainties. Here, we investigated the concentration profiles of 20 emerging pollutants in different river stretches in Luxembourg with variable sanitary pressures. Using carbamazepine as a recalcitrant wastewater indicator, the correlation of the compounds to the latter revealed source and fate variability as well as specific emitters. Relating carbamazepine to sanitary pressure, expressed as the sum of population equivalents in a catchment divided by its surface [PE ha-1] allowed predicting the impact of emerging pollutants on the entire river network. The limited variability of the pollutant profiles allowed for prioritization of impacted stretches depending on the different sanitary pressures at risk quotient exceedance. The main drivers of impact were triclosan, diclofenac, clarithromycine and diuron.

Breakthrough dynamics of s-metolachlor metabolites in drinking water wells: Transport pathways and time to trend reversal.

We present the results of a two years study on the contamination of the Luxembourg Sandstone aquifer by metolachlor-ESA and metolachlor-OXA, two major transformation products of s-metolachlor. The aim of the study was twofold: (i) assess whether elevated concentrations of both transformation products (up to 1000 ng/l) were due to fast flow breakthough events of short duration or the signs of a contamination of the entire aquifer and (ii) estimate the time to trend reversal once the parent compound was withdrawn from the market. These two questions were addressed by a combined use of groundwater monitoring, laboratory experiments and numerical simulations of the fate of the degradation products in the subsurface. Twelve springs were sampled weekly over an eighteen month period, and the degradation rates of both the parent compound and its transformation products were measured on a representative soil in the laboratory using a radiolabeled precursor. Modelling with the numeric code PEARL simulating pesticide fate in soil coupled to a simple transfer function model for the aquifer compartment, and calibrated from the field and laboratory data, predicts a significant damping by the aquifer of the peaks of concentration of both metolachlor-ESA and -OXA leached from the soil. The time to trend reversal following the ban of s-metolachlor in spring protection zones should be observed before the end of the decade, while the return of contaminant concentrations below the drinking water limit of 100 ng/l however is expected to last up to twelve years. The calculated contribution to total water discharge of the fast-flow component from cropland and short-circuiting the aquifer was small in most springs (median of 1.2%), but sufficient to cause additional peaks of concentration of several hundred nanograms per litre in spring water. These peaks are superimposed on the more steady contamination sustained by the base flow, and should cease immediately once application of the parent compound stops.

Estimating Pesticide Attenuation From Water Dating and the Ratio of Metabolite to Parent Compound.

Although pesticides are primarily degraded in the topsoil, significant attenuation can be expected in groundwater systems where the transit time of pesticides usually are orders of magnitude longer than in the soil. Because degradation and transport processes in the subsurface take place at time scales of months to years or even decades, direct measurements of natural attenuation are hampered by practical and logistical limitations (for instance the limited duration of sampling or a correct estimation of the pesticide flux into groundwater). Indirect methods such as measuring the changes in the ratio of degradation product to parent compound as a function of transit time in the aquifer, along a flow line provide a possible alternative. This paper presents a simple mathematical formulation of the relationship between transit time in the subsurface and changes in that ratio, and allows estimating the transformation rate of both parent compound and degradation product. The applicability of the method is illustrated in a case study investigating atrazine attenuation in a fractured sandstone aquifer.

A case-study on the accuracy of mass balances for xenobiotics in full-scale wastewater treatment plants.

Removal efficiencies of micropollutants in wastewater treatment plants (WWTPs) are usually evaluated from mass balance calculations using a small number of observations drawn from short sampling campaigns. Since micropollutant loads can vary greatly in both influent and effluent and reactor tanks exhibit specific hydraulic residence times, these short-term approaches are particularly prone to yield erroneous removal values. A detailed investigation of micropollutant transit times at full-scale and on how this affects mass balancing results was still lacking. The present study used hydraulic residence time distributions to scrutinize the match of influent loads to effluent loads of 10 polar micropollutants with different influent dynamics in a full-scale WWTP. Prior hydraulic modeling indicated that a load sampled over one day in the effluent is composed of influent load fractions of five preceding days. Results showed that the error of the mass balance can be reduced with increasing influent sampling duration. The approach presented leads to a more reliable estimation of the removal efficiencies of those micropollutants which can be constantly detected in influents, such as pharmaceuticals, but provides no advantage for pesticides due to their sporadic occurrence. The mismatch between sampled influent and effluent loads was identified as a major error source and an explanation was provided for the occurrence of negative mass balances regularly reported. This study indicates that the accurate determination of global removal values is only feasible in full-scale investigations with sampling durations much longer than 1 day. In any case, the uncertainty of these values needs to be reported when used in removal assessment, model selection or validation.

Xenobiotic removal efficiencies in wastewater treatment plants: residence time distributions as a guiding principle for sampling strategies.

The effect of mixing regimes and residence time distribution (RTD) on solute transport in wastewater treatment plants (WWTPs) is well understood in environmental engineering. Nevertheless, it is frequently neglected in sampling design and data analysis for the investigation of polar xenobiotic removal efficiencies in WWTPs. Most studies on the latter use 24-h composite samples in influent and effluent. The effluent sampling period is often shifted by the mean hydraulic retention time assuming that this allows a total coverage of the influent load. However, this assumption disregards mixing regime characteristics as well as flow and concentration variability in evaluating xenobiotic removal performances and may consequently lead to biased estimates or even negative elimination efficiencies. The present study aims at developing a modeling approach to estimate xenobiotic removal efficiencies from monitoring data taking the hydraulic RTD in WWTPs into consideration. For this purpose, completely mixed tanks-in-series were applied to address hydraulic mixing regimes in a Luxembourg WWTP. Hydraulic calibration for this WWTP was performed using wastewater conductivity as a tracer. The RTD mixing approach was coupled with first-order biodegradation kinetics for xenobiotics covering three classes of biodegradability during aerobic treatment. Model simulations showed that a daily influent load is distributed over more than one day in the effluent. A 24-h sampling period with an optimal time offset between influent and effluent covers less than the half of the influent load in a dry weather scenario. According to RTD calculations, an optimized sampling strategy covering four consecutive measuring days in the influent would be necessary to estimate the full-scale elimination efficiencies with sufficient accuracy. Daily variations of influent flow and concentrations can substantially affect the reliability of these sampling results. Commonly reported negative removal efficiencies for xenobiotics might therefore be a consequence of biased sampling schemes. In this regard, the present study aims at contributing to bridge the gap between environmental chemistry and engineering practices.