Simulated conservative tracer as a proxy for S-metolachlor concentration predictions compared to POCIS measurements in Arcachon Bay.

The work presented here aims at comparing monitoring of S-metolachlor, the major pesticide in use in the Arcachon Bay (South West of France, transitional coastal area), by chemical analysis (monthly passive sampling) and contaminant dissipation modeling from sources (Mars-2D model). The global strategy consisted in i) identifying the major sources of S-metolachlor to the Bay, ii) monitoring these sources for 12 months, and iii) comparing modeled data in the Bay based on measured inputs, to chemical measurements made inside the Bay along with the 12-month source monitoring. Results first showed that the major S-metolachlor surface inputs to the Arcachon Bay are mainly from one single source. Modeled and measured data were in good agreement at 5 sites in the Bay, both in terms of concentration range and seasonal trends. Modeling thus offers a cost-effective solution for monitoring contaminants in transitional waters, overcoming in addition the technical limitations for measuring pg L-1 or lower levels in coastal waters. However, we highlighted that secondary sources may affect accuracy at local level.

Analyzing the uncertainty of diffusive gel-based passive samplers as tools for evaluating the averaged contamination of surface water by organic pollutants.

Agarose gel-based passive samplers are nowadays one of the most effective sampling devices able to provide a quantitative evaluation of water contamination level for a broad range of organic contaminants. These devices show significant improvements in comparison to the previous passive samplers dedicated to hydrophilic compounds because they tend to reduce the effect of hydrodynamic flow conditions on the uptake rate of compounds and thus subsequently to improve their accuracy. However, albeit their effects minimized, hydrodynamic water flow and temperature are reported as variables likely to change the uptake rate of compounds that may lead to some inaccuracy if they are not adequately taken into account. This work aims to investigate the magnitude of effects of such uncorrected variables on the bias of the deduced water contamination level. The analysis of the error structure shows that the uncertainty on the diffusivity of contaminants in agarose gel and its dependency on temperature are the most inferring factors. At 8 °C, these factors are, respectively, responsible of 34 and 33% of the squared uncertainty on the final deduced contamination level. The overall uncertainty for a single exposed passive sampler is in the order of 39% and drops to 23% if threesamplers are co-exposed (at 8 °C). Despite this uncertainty, we present results for a set of pesticides and personal care products throughout a field monitoring conducted over a 4-month period, which show the potential of passive samplers to allow assessing the temporal trend of water contamination.

Understanding and predicting the diffusivity of organic compounds in polydimethylsiloxane material for passive sampler applications using a simple quantitative structure-property relationship model.

The diffusivity of 145 compounds in polydimethylsiloxane (PDMS) material was determined in the laboratory using a film stacking technique. The results were pooled with available literature data, providing a final data set of 198 compounds with diffusivity (DPDMS ) spanning over approximately 5 log units. The principal variables controlling the diffusivity of penetrants were investigated by comparing DPDMS within and between different homologous series. The dipole moment, molecular size, and flexibility of penetrants appear to be the most prevalent factors controlling a compound's diffusivity. A nonlinear quantitative structure-property relationship is proposed using as predicting variables the molecular volume, the number of rotatable bonds, the topological polar surface area, and the number of O and N atoms. The final relationship has a correlation coefficient of R2 = 0.81 and a mean absolute error of 0.26 m2 s-1 (log unit), approaching the average error for the experimentally determined values (0.12 m2 s-1 ). The model, based on a heuristic approach, is ready for use by analytical chemists with no specific background in theoretical chemistry (notably for passive sampler development). Environ Toxicol Chem 2018;37:1291-1300. © 2018 SETAC.

Can pesticides, copper and seasonal water temperature explain the seagrass Zostera noltei decline in the Arcachon bay?

Dwarf eelgrasses (Zostera noltei) populations have decreased since 2005 in Arcachon Bay (southwest France). Various stressors have been pointed out, however the role of xenobiotics like pesticides or copper (Cu) and of parameters like water temperature warming have not yet been explored. To determine their impact, Z. noltei individuals were collected in a pollution-free site and transferred to the laboratory in seawater microcosms. This dwarf eelgrass was exposed to a pesticide cocktail and copper, alone or simultaneously, at temperatures (10°C, 20°C, 28°C) representative of different seasons. After a two-week contamination, leaf growth, leaf bioaccumulation of Cu, and differential expression of target genes were studied. Eelgrasses bioaccumulated Cu regardless of the temperature, with reduced efficiency in the presence of the Cu and pesticide cocktail at the two higher temperatures. High temperature also exacerbated the effect of contaminants, leading to growth inhibition and differential gene expression. Mitochondrial activity was strongly impacted and higher mortality rates occurred. Experimental results have been confirmed during field survey. This is the first report on the impacts on Z. noltei of pesticides and Cu associate to temperature.

Near-surface distribution of pollutants in coastal waters as assessed by novel polyethylene passive samplers.

We report a novel and inexpensive method to provide high resolution vertical measurements of temporally integrated organic contaminants in surface and sub-surface waters in polluted coastal environments. It employs a strip of polyethylene deployed as a passive sampler. Verifications are confirmed via conventional spot sample analyses and against Performance Reference Compound (PRC) calibration methods. Analytes targeted include 16 Polycyclic Aromatic Hydrocarbons, 15 personal care products, 8 organophosphorus flame retardants, 4 antifouling 'booster' biocides and 15 n-alkanes. Whilst all contaminants typically revealed homogeneous concentrations from 10 cm to 3 m depth in the selected harbour (<30% variations), many increased sharply at the air-sea interface. The passive sampler was shown to afford better resolution than could be achieved using conventional analytical techniques at the surface microlayer (SML). Whilst hydrophobicity appeared to be a key factor for the enrichment of many determinants, less correlation was found for the emerging contaminants.

Calibration and response of an agarose gel based passive sampler to record short pulses of aquatic organic pollutants.

A passive sampler inspired from previous devices was developed for the integrative sampling of a broad range of contaminants in the water column. Our primary objective was to improve the performance of the device to provide accurate and averaged pollutant water concentrations. For this purpose, an agarose diffusive gel was used as the boundary layer that drives the analyte uptake rate. Contrary to conventional passive samplers, the developed device does not require the sampling rates to be corrected for exposure conditions (e.g. hydrodynamic flow) because the diffusive gel boundary layer selected was sufficiently large to control the pollutant diffusion rate from the aqueous phase. The compounds diffusion coefficients in agarose gel and the gel thickness are the only required data to accurately calculate the time weighted averaged water concentration of pollutants. The performance of the developed sampler was evaluated in the laboratory under two contamination scenarios and in the field in 8 contrasting exposure sites for a selection of 16 emerging pollutants and pesticides. The results show that detection limits of this method are environmentally relevant and allow the determination of the averaged pollutant concentrations. Additionally, the ability of the device to sense very short contamination pulses (5-320min) was evaluated through a theoretical approach and laboratory tests. Results show that the device is suitable for sampling contamination pulses as short as 5min without deviation from the actual average concentrations of pollutants.

Assessing the transport of PAH in the surficial sediment layer by passive sampler approach.

A new method based on passive samplers has been developed to assess the diffusive flux of fluorene, fluoranthene and pyrene in the sediment bed and across the sediment-water interface. The dissolved compound concentration gradient in the sediment in the vertical direction was measured at the outlet of a storm water pond by using polyethylene strips as passive samplers. Simultaneously, the dissipation of a set of tracer compounds preloaded in the passive samplers was measured to estimate the effective diffusion coefficients of the pollutants in the sediment. Both measurements were used to evaluate the diffusive flux of the compounds according to Fick's first law. The diffusive fluxes of the 3 studied compounds have been estimated with a centimetre-scale resolution in the upper 44cm of the sediment. According to the higher compound diffusion coefficient and the steeper concentration gradient in the surficial sediment layer, the results show that the net flux of compounds near the sediment interface (1cm depth) is on average 500 times higher than in the deep sediment, with average fluxes at 1cm depth on the order of 5, 0.1 and 0.1ng/m2/y for fluorene, fluoranthene and pyrene, respectively.

A new application of passive samplers as indicators of in-situ biodegradation processes.

In this paper, a method for evaluating the in-situ degradation of nitro polycyclic aromatic hydrocarbons (nitro-PAH) in sediments is presented. The methodology is adapted from the passive sampler technique, which commonly uses the dissipation rate of labeled compounds loaded in passive sampler devices to sense the environmental conditions of exposure. In the present study, polymeric passive samplers (made of polyethylene strips) loaded with a set of labeled polycyclic aromatic hydrocarbons (PAH) and nitro-PAH were immersed in sediments (in field and laboratory conditions) to track the degradation processes. This approach is theoretically based on the fact that a degradation process induces a steeper concentration gradient of the labeled compounds in the surrounding sediment, thereby increasing their compound dissipation rates compared with their dissipation in abiotic conditions. Postulating that the degradation magnitude is the same for the labeled compounds loaded in polyethylene strips and for their native homologs that are potentially present in the sediment, the field degradation of 3 nitro-PAH (2-nitro-fluorene, 1-nitro-pyrene, 6-nitro-chrysene) was semi-quantitatively analyzed using the developed method.

Relationship between the water-exchangeable fraction of PAH and the organic matter composition of sediments.

The sorption of PAH on 12 different sediments was investigated and was correlated to their corresponding organic matter (OM) content and quality. For this purpose, the OM was precisely characterized using thermal analysis consisting in the successive combustion and quantification of the increasingly thermostable fractions of the OM. Simultaneously, the water-exchangeable fraction of the sorbed PAH defined as the amount of PAH freely exchanged between the water and the sediment (by opposition to the PAH harshly sorbed to the sediments particles) was determined using a passive sampler methodology recently developed. The water concentrations, when the sediment-water system is equilibrated, were also assessed which allows the determination of the sediment-water distribution coefficients without artifacts introduced by the non water-exchangeable fraction of PAH. Hence, the present study provides the distribution coefficients of PAH between the water and 4 different OM fractions combusted at a specific temperature range. The calculated distribution coefficients demonstrate that the sedimentary OM combusted at the intermediate temperature range (between 300 °C and 450 °C) drives the reversible sorption of PAH while the inferred sorption to the OM combusted at a lower and higher temperature range does not dominate the partitioning process.

Simulation of aromatic polycyclic hydrocarbons remobilization from a river sediment using laboratory experiments supported by passive sampling techniques.

Resuspension of bedded sediments was simulated under laboratory-controlled conditions in order to assess the amount of polycyclic aromatic hydrocarbons (PAH) remobilized in the dissolved fraction during one short and vigorous mixing. The desorbed amount of PAH was compared to the exchangeable fraction, the total amount of PAH sorbed on the sediment particles, and the dissolved PAH amount contained in the interstitial pore waters in order to evaluate the contribution of each fraction to the total amount of PAH released. To monitor the desorption of PAH and measure low trace level concentrations, passive samplers were used in an experimental open flow through exposure simulator. Results show that for the selected sediment, a substantial fraction of sorbed PAH (69 % of the total amount) is not available for remobilization in a depleted medium. Obtained data pinpoint that over 9 days, only 0.007 % of PAH are desorbed by passive diffusion through a water-sediment interface area of 415 cm(2) and that an intense resuspension event of 15 min induces desorption of 0.015 % of PAH during the following 9 days. Results also highlight that during resuspension simulation, modifications of the sediment and the water body occurred since partitioning constants of some pollutants between sediment and water have significantly decreased.

Thickness and material selection of polymeric passive samplers for polycyclic aromatic hydrocarbons in water: Which more strongly affects sampler properties?

Three configurations of single-phase polymer passive samplers made of polyoxymethylene (POM), silicone rubber, and polyethylene (PE) were simultaneously calibrated in laboratory experiments by determining their partitioning coefficients and the POM diffusion coefficients and by validating a kinetic accumulation model. In addition, the performance of each device was evaluated under field conditions. With the support of the developed model, the device properties are discussed with regard to material selection and polymer thickness. The results show that a sampler's properties, such as its concentration-averaging period and ability to sample a large amount of polycyclic aromatic hydrocarbons, are widely affected by material selection. Sampler thickness also allows modulation of the properties of the device but with a much lower magnitude. Selection of the appropriate polymer and/or thickness allows samplers to be adapted either for quick equilibration or for the kinetic accumulation regime and promotes either membrane or water boundary layer control of the kinetic accumulation. In addition, membrane-controlled or equilibrated compounds are quantified with greater accuracy because they are not corrected by the performance reference compounds approach. However, the averaged concentrations cannot be assessed when compounds reach equilibrium in the sampler, whereas membrane-controlled devices remaining in the kinetic accumulation regime provide averaged concentrations without requiring performance reference compound correction; detection limits are then increased because of the higher mass transfer resistance of the membrane. Environ Toxicol Chem 2016;35:1708-1717. © 2015 SETAC.

Optimization of the polar organic chemical integrative sampler for the sampling of acidic and polar herbicides.

This paper presents an optimization of the pharmaceutical Polar Organic Chemical Integrative Sampler (POCIS-200) under controlled laboratory conditions for the sampling of acidic (2,4-dichlorophenoxyacetic acid (2,4-D), acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid, bentazon, dicamba, mesotrione, and metsulfuron) and polar (atrazine, diuron, and desisopropylatrazine) herbicides in water. Indeed, the conventional configuration of the POCIS-200 (46 cm(2) exposure window, 200 mg of Oasis® hydrophilic lipophilic balance (HLB) receiving phase) is not appropriate for the sampling of very polar and acidic compounds because they rapidly reach a thermodynamic equilibrium with the Oasis HLB receiving phase. Thus, we investigated several ways to extend the initial linear accumulation. On the one hand, increasing the mass of sorbent to 600 mg resulted in sampling rates (R s s) twice as high as those observed with 200 mg (e.g., 287 vs. 157 mL day(-1) for acetochlor ESA). Although detection limits could thereby be reduced, most acidic analytes followed a biphasic uptake, proscribing the use of the conventional first-order model and preventing us from estimating time-weighted average concentrations. On the other hand, reducing the exposure window (3.1 vs. 46 cm(2)) allowed linear accumulations of all analytes over 35 days, but R s s were dramatically reduced (e.g., 157 vs. 11 mL day(-1) for acetochlor ESA). Otherwise, the observation of biphasic releases of performance reference compounds (PRC), though mirroring acidic herbicide biphasic uptake, might complicate the implementation of the PRC approach to correct for environmental exposure conditions.

Development of an adapted version of polar organic chemical integrative samplers (POCIS-Nylon).

POCIS (polar organic chemical integrative samplers) are increasingly used for sampling polar compounds. Although very efficient for a wide range of pollutants, the classic configuration of the device has a number of limitations, in particular for the sampling of highly polar analytes and hydrophobic compounds. This study presents a new version of the POCIS passive sampler which uses a highly porous Nylon membrane of 30 µm pore size, enabling the sampling of hydrophobic pollutants and improving the accumulation rate of other pollutants. This newly designed tool and the classic POCIS were both tested during a laboratory experiment to evaluate the accumulation kinetics of a selection of pesticides and pharmaceuticals. The observed results show unexpected accumulation kinetics for the new version of POCIS. To explain the data, the use of an intraparticulate diffusion model was required, which also enabled us to propose another explanation of the burst effect observed with the classic POCIS, primarily related to the potential wetting of the device as the first step in the accumulation of compounds.

Development of the performance reference compound approach for the calibration of "polar organic chemical integrative sampler" (POCIS).

The purpose of the Water Framework Directive is to ensure the quality of the natural water across Europe. In this context, passive samplers have shown interesting capacities for the monitoring of contaminants in aqueous ecosystems. They allow the measurement of time-weighted average concentrations, overcoming many drawbacks of the spot-sampling techniques known to be expensive and time consuming. However, application of passive samplers such as polar organic chemical integrative samplers (POCIS) for the monitoring of hydrophilic contaminants requires calibration to define compound sampling rates; key parameters to deduce the pollutant water concentrations from the amounts of pollutants accumulated by the device. Unfortunately, sampling rates are influenced by a range of environmental factors; in that respect, a question remains: is it not evident to know to what extent the sampling rates obtained in laboratory experiments can be used in field conditions? The problem can be solved for hydrophobic samplers by using performance reference compounds (PRCs), and an ongoing challenge for POCIS is focused on the improvement of the quantitative aspect of this family of samplers. In this study, potential PRCs have been selected during a specific experiment and their performance was tested in the laboratory under two hydrodynamic conditions. Results revealed a good proportionality between elimination rates of PRCs and sampling rates of chemicals. Afterwards, the application of the approach under environmental conditions was assessed by deploying POCIS in the Arcachon Bay (France) where POCIS-PRC-derived water concentrations appear to be close to the simultaneous grab-sampling results.

Embryotoxic and genotoxic effects of heavy metals and pesticides on early life stages of Pacific oyster (Crassostrea gigas).

This study evaluated embryotoxicity and genotoxicity of two dissolved metals copper and cadmium (Cu and Cd) and two pesticides (metolachlor and irgarol) occurring in Arcachon Bay (SW France) in Pacific oyster (Crassostrea gigas) larvae and investigated the relationship between those two endpoints. Embryotoxicity was measured by calculating the percentage of abnormal D-shaped larvae and genotoxicity was evaluated with DNA strand breaks using the comet assay. After 24h exposure, significant increases of the percentage of abnormal D-larvae and the DNA strand breaks were observed from 0.1 µg L⁻¹ for Cu, 10 µg L⁻¹ for Cd and 0.01 µg L⁻¹ for both irgarol and metolachlor in comparison with the controls. A strong positive relationship between embryotoxicity and genotoxicity was recorded for Cu, Cd and metolachlor. The current study suggests that copper, irgarol and metolachlor can induce larval abnormalities and DNA damage in a population of exposed oysters at environmentally relevant concentrations.