Assessment of the contribution of surfactants to mixture toxicity in French surface waters.

Surfactants are widely used 'down-the-drain' chemicals with the potential to occur at high concentrations in local water bodies and to be part of unintentional environmental mixtures. Recently, increased regulatory focus has been placed on the impacts of complex mixtures in aquatic environments and the substances that are likely to drive mixture risk. This study assessed the contribution of surfactants to the total mixture pressure in freshwater ecosystems. Environmental concentrations, collated from existing French monitoring data, were combined with estimated ecotoxicological thresholds to calculate hazard quotients (HQ) for each substance, and hazard indices (HI) for each mixture. Two scenarios were investigated to correct for concentrations below the limit of quantification (LOQ) in the dataset. The first (best-case) scenario assumed all values

Assessment of exposure to pesticide mixtures in five European countries by a harmonized urinary suspect screening approach.

Humans are exposed to a mixture of pesticides through diet as well as through the environment. We conducted a suspect-screening based study to describe the probability of (concomitant) exposure to a set of pesticide profiles in five European countries (Latvia, Hungary, Czech Republic, Spain and the Netherlands). We explored whether living in an agricultural area (compared to living in a peri-urban area), being a a child (compared to being an adult), and the season in which the urine sample was collected had an impact on the probability of detection of pesticides (-metabolites). In total 2088 urine samples were collected from 1050 participants (525 parent-child pairs) and analyzed through harmonized suspect screening by five different laboratories. Fourty pesticide biomarkers (either pesticide metabolites or the parent pesticides as such) relating to 29 pesticides were identified at high levels of confidence in samples across all study sites. Most frequently detected were biomarkers related to the parent pesticides acetamiprid and chlorpropham. Other biomarkers with high detection rates in at least four countries related to the parent pesticides boscalid, fludioxonil, pirimiphos-methyl, pyrimethanil, clothianidin, fluazifop and propamocarb. In 84% of the samples at least two different pesticides were detected. The median number of detected pesticides in the urine samples was 3, and the maximum was 13 pesticides detected in a single sample. The most frequently co-occurring substances were acetamiprid with chlorpropham (in 62 urine samples), and acetamiprid with tebuconazole (30 samples). Some variation in the probability of detection of pesticides (-metabolites) was observed with living in an agricultural area or season of urine sampling, though no consistent patterns were observed. We did observe differences in the probability of detection of a pesticide (metabolite) among children compared to adults, suggesting a different exposure and/or elimination patterns between adults and children. This survey demonstrates the feasibility of conducting a harmonized pan-European sample collection, combined with suspect screening to provide insight in the presence of exposure to pesticide mixtures in the European population, including agricultural areas. Future improvements could come from improved (harmonized) quantification of pesticide levels.

Harmonized Quality Assurance/Quality Control Provisions for Nontargeted Measurement of Urinary Pesticide Biomarkers in the HBM4EU Multisite SPECIMEn Study.

A set of quality assurance/quality control (QA/QC) criteria for nontargeted measurement of pesticide exposure markers in a large-scale study of human urine has been proposed and applied across five laboratories within the HBM4EU project. Quality control material, including reference standards and fortified pooled urine samples (QC urine) were prepared in a centralized way and distributed across participants to monitor analytical performance and consistency of the liquid chromatography coupled to high-resolution mass spectrometry data generated with a harmonized workflow. Signal intensities, mass accuracy, and retention times of selected QA/QC markers covering a broad range of physicochemical properties were monitored across QC solvent standards, QC urine samples, study urine samples, and procedural blanks, setting acceptance thresholds for repeatability and accuracy. Overall, results showed high repeatability of the collected data. The RSDs of the signal intensities were typically below 20-30% in QC and study samples, with good stability of the chromatographic separation (retention time drift within 2-4 s intrabatch and 5 s interbatch) and excellent mass accuracy (average error < 2 ppm). The use of the proposed criteria allowed for the identification of handling errors, instrumental issues, and potential batch effects. This is the first elaboration of harmonized QA/QC criteria applied across multiple laboratories to assess the quality of data generated by nontargeted analysis of human samples.

Open, High-Resolution EI+ Spectral Library of Anthropogenic Compounds.

To address the lack of high-resolution electron ionisation mass spectral libraries (HR-[EI+]-MS) for environmental chemicals, a retention-indexed HR-[EI+]-MS library has been constructed following analysis of authentic compounds via GC-Orbitrap MS. The library is freely provided alongside a compound database of predicted physicochemical properties. Currently, the library contains over 350 compounds from 56 compound classes and includes a range of legacy and emerging contaminants. The RECETOX Exposome HR-[EI+]-MS library expands the number of freely available resources for use in full-scan chemical exposure studies and is available at: https://doi.org/10.5281/zenodo.4471217.

Plants radically change the mobility of PCBs in soil: Role of different species and soil conditions.

The mobility of Polychlorinated Biphenyls (PCBs) in soil cultivated with different plant species was evaluated by means of a column experiment to investigate the specific plant influence on PCB environmental fate and the potential for leaching. The soil was collected at a National Relevance Site for remediation located in Northern Italy (SIN Brescia-Caffaro) and underwent a rhizoremediation treatment for 18 months with different plant species (Festuca arundinacea, Cucurbita pepo ssp pepo and Medicago sativa). The same but unplanted soil was also considered as control for comparison. The columns were leached with tap water and PCB concentrations were measured in the leachate after 7 days of soil/water contact. Soil previously cultivated with different plant species exhibited statistically different behavior in terms of chemical leaching among the different fractions. Total PCB bulk concentrations ranged from 24 to 219 ng/L. Leachate samples were enriched in tetra- to hepta-PCBs. While PCB concentrations in the dissolved phases varied within a factor of 2 between controls and treatments, PCB associated to particulate organic carbon (POC) differed by more than one order of magnitude. More specifically, Medicago sativa enriched the soil with POC doubling PCB leaching with respect to the other plant species and the unplanted controls.

Accelerated equilibrium sampling of hydrophobic organic chemicals in solid matrices: A proof of concept on how to reach equilibrium for PCBs within 1 day.

Equilibrium sampling of hydrophobic organic chemicals (HOCs) is increasingly used to measure freely dissolved concentrations and chemical activities in sediments and soils. However, for the most hydrophobic chemicals (Log Kow > 6) such equilibrium sampling requires often very long sampling times in the order of weeks to months. The aim of the present study was to explore two strategies for markedly increasing the HOC mass transfer from matrix to sampler with the overall goal to shorten equilibration times down to a few hours. Two Solid Phase Microextraction (SPME) approaches were thus developed and tested in sediment and soil contaminated by polychlorinated biphenyls (PCBs). In the first method, the SPME fiber was immersed directly in the aqueous suspension of the sample under vigorous agitation. In the second method equilibration took place via the headspace and was accelerated by elevating the temperature. Headspace-SPME at 80 °C provided fast equilibration within approximately 2 h without contacting the sample and thus avoiding fiber fouling. Both SPME methods were calibrated by passive dosing from preloaded silicone rods and yielded similar results, supporting the validity of HS-SPME at elevated temperatures on a proof of principle level. Finally, by using 13C labelled PCB standards, total concentrations were simultaneously measured, which in turn allowed calculation of matrix-water distribution coefficients.

A review of the predictive models estimating association of neutral and ionizable organic chemicals with dissolved organic carbon.

Dissolved organic carbon (DOC) plays a key role in environmental transport, fate and bioavailability of organic chemicals in terrestrial and aquatic ecosystems. Predicting the association of contaminants to DOC is therefore crucial in modelling chemical exposure and risk assessment. The models proposed so far to describe interaction mechanisms between chemicals and DOC and the most influential variables have been reviewed. The single-parameter linear free energy relationships (sp-LFERs) and the poly-parameter linear free energy relationships (pp-LFERs) in the form of linear solvation energy relationships (LSERs) currently available in literature for estimating dissolved organic carbon/water partition (KDOC) and distribution (DDOC) coefficients for organic chemicals were discussed, and limits of the existing approaches explored. For neutral chemicals many predictive equations are currently available in literature, but the quality of the input data on which they are based is often questionable, due to the lack of an unequivocal definition of DOC among different references and to the different and often unreliable KDOC measurement method. For ionizable chemicals instead there is a substantial lack of predictive approaches that need to be fulfilled since just few models are nowadays available to predict DDOC of ionized species. This paper reviews the current approaches for neutral and ionizable chemicals proposing guidelines to select conditions for obtaining reliable data and predictive equations for an improved estimation of KDOC and DDOC.

Predicting dissolved organic carbon partition and distribution coefficients of neutral and ionizable organic chemicals.

Estimating KDOC (dissolved organic carbon/water partition coefficient) and DDOC (dissolved organic carbon/water distribution coefficient) of neutral and ionizable organic chemicals is a crucial task for assessing mobility, modelling transport, environmental fate of a variety of chemicals and for evaluating their bioavailability in terrestrial and aquatic environments. A critical literature search of reliability-selected KDOC and DDOC values was performed to setup novel predictive relationships for KDOC and DDOC of neutral and ionizable organic chemicals. This goal was pursued by using: 1) LSER (linear solvation energy relationship) models to predict KDOC for neutral chemicals using Abraham solute parameters calculated for different DOC sources (all DOC sources together, soil porewater, surface water, wastewater and Aldrich humic acid (HA)); 2) linear regressions for predicting DDOC of organic acids from the octanol/water partition coefficient (Log KOW or Log P) and the dissociation constant (pKa), accounting separately for the contribution of the neutral and ionic fraction. The proposed models predicted Log KDOC and DDOC values within a root mean square deviation (RMSD) generally smaller than 0.3 log units.

How good are the predictions of mobility of aged polychlorinated biphenyls (PCBs) in soil? Insights from a soil column experiment.

A column leaching experiment was performed to evaluate the influence of some relevant environmental factors (soil/water contact time, temperature, saturation) on mobility of aged polychlorinated biphenyls (PCBs) in soil together with transport mediated by dissolved organic carbon (DOC) and mobile organic carbon (OC) coated fine particles/colloids. Consecutive fractions of leachates were collected after a variable pre-equilibration time (2, 5, 7, 48 days), using leaching solutions with different DOC content (tap water vs. Aldrich humic acid), in saturated vs. field capacity conditions and at different temperatures (25 °C vs. 15 °C). The data obtained were compared to the predicted values using a multimedia model (SoilPlusVeg) to evaluate model behaviour. Contact time and temperature determined a relevant effect on DOC and particle/colloid availability, with significant variations in leachate concentrations (up to 1 order of magnitude), typically overlooked by most environmental fate models. Results obtained at different temperatures show a modulation of the DOC/particles production with temperature and therefore the role of temperature changes in the environmental scenarios (e.g. seasonal variations). Transport of PCBs enhanced by Aldrich DOC was not linearly correlated to chemical hydrophobicity but revealed a threshold to ~Log KOW 6.5, likely because of the slow sorption kinetics of more hydrophobic chemicals. Additionally, variation of the saturation conditions (e.g. drying-wetting cycles) can determine contamination peaks at the beginning of an irrigation/rainfall event because of the soil/water equilibration. Model simulations, even when including DOC in the water phase, but not accounting for the particle/colloidal transport and sorption/desorption kinetics, mismatched the ratio of dissolved vs. DOC-associated and particle-associated PCBs and substantially underpredicted concentrations, especially for the high chlorinated congeners. The results indicated that some of the common assumptions and paradigms in fate modelling of such hydrophobic compounds should be revisited and models updated.

Predicting pesticide fate in small cultivated mountain watersheds using the DynAPlus model: Toward improved assessment of peak exposure.

The use of plant protection products (PPPs) in agricultural areas implies potential chemical loadings to surface waters, which can pose a risk to aquatic ecosystems and human health. Due to the spatio-temporal variability of PPP applications and of the processes regulating their transport to surface waters, aquatic organisms are typically exposed to pulses of contaminants. In small mountain watersheds, where runoff fluxes are more rapid due to the steep slopes, such exposure peaks are particularly likely to occur. In this work, a spatially explicit, dynamic model for predicting pesticide exposure in surface waters of cultivated mountain basins (DynAPlus) has been developed. The model has been applied to a small mountain watershed (133km2) located in the Italian Eastern Alps and characterized by intensive agriculture (apple orchards) around the main river and its tributaries. DynAPlus performance was evaluated for chlorpyrifos through experimental monitoring, using samples collected during the 2011 and 2012 productive seasons. The comparison between predictions and measurements resulted in a good agreement (R2=0.49, efficiency factor 0.60), although a more accurate spatial information in the input scenario (e.g., field-specific applications, rainfall amount, soil properties) would dramatically improve model performance. A set of illustrative simulations performed for three PPPs highlighted the potential role of DynAPlus in improving exposure predictions for ecological risk assessment and pesticide management practices (e.g., for active ingredient and application rate selection), as well as for planning efficient monitoring campaigns and/or interpreting monitoring data. However, some model improvements (e.g., solid erosion and transport) and a more thorough model validation are desirable to enlarge the applicability domain.