Sophie Lissalde

Evaluation of the Use of Performance Reference Compounds in an Oasis-HLB Adsorbent Based Passive Sampler for Improving Water Concentration Estimates of Polar Herbicides in Freshwater

Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5 was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling rates from a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS.

Liquid chromatography coupled with tandem mass spectrometry method for thirty-three pesticides in natural water and comparison of performance between classical solid phase extraction and passive sampling approaches.

The aim of this study is to propose an analytical method for determining different classes of pesticides in water using LC-ESI-MS/MS. Two techniques of field-sampling and analyte extraction were used: solid phase extraction (SPE) of water samples from active sampling and field exposure of Polar Organic Chemical Integrative Samplers (POCIS). We have worked with thirty-three molecules representing eight pesticide classes: carbamates, chloroacetanilides, dicarboximides, morpholines, organophosphorous, phenylureas, strobilurines and triazines. First, liquid chromatography separation protocols and the optimization of the ESI-MS/MS parameters were developed. Then, the SPE step was optimized to obtain acceptable levels of recovery for the various classes of molecules. The matrix effect that may significantly lower the ionization efficiency with ESI interfaces was evaluated and minimized. The performances (limits of quantification, accuracy and precision) of the SPE and POCIS techniques were evaluated, and a comparison between the active and passive sampling techniques was carried out with a field application.

Evaluation of single and joint toxic effects of diuron and its main metabolites on natural phototrophic biofilms using a pollution-induced community tolerance (PICT) approach

This study assessed the single and joint acute toxicity of diuron and two of its metabolites (DCPMU and 3,4-DCA) on natural phototrophic biofilms using a PICT approach with photosynthesis bioassays. River biofilm communities were collected at three sampling stations exhibiting increasing concentrations of diuron, DCPMU and 3,4-DCA from upstream to downstream. Applied individually, the parent compound was more toxic than its metabolites, with DCPMU being more toxic than 3,4-DCA which only inhibited photosynthesis at very high concentrations (EC25 at about 5 mg/l). Sensitivity of biofilm communities to diuron and DCPMU decreased from upstream to downstream, revealing tolerance induction in contaminated sections of the river, as expected from the PICT concept. Nevertheless, PICT was not applicable for 3,4-DCA, which similarly affected upstream, intermediate and downstream biofilm communities. Chemical mixtures of diuron and DCPMU demonstrated additive effects whereas combinations with 3,4-DCA enhanced the observed effects. Our results reveal that the individual and combined presence of diuron and DCPMU in lotic ecosystems can have both short-term effects (as shown with bioassays) and long-term effects (as shown through the PICT approach) on phototrophic biofilms, whereas environmental concentrations of 3,4-DCA may not affect biofilm photosynthetic activity.

Can POCIS be used in Water Framework Directive (2000/60/EC) monitoring networks? A study focusing on pesticides in a French agricultural watershed.

In this study, the main current limitations in the application of the Polar Organic Chemical Integrative Sampler (POCIS) in regulatory monitoring programmes were evaluated. POCIS were exposed from March to December by successive periods of 14 days in the River Trec (Lot et Garonne, France) and analysed for 34 pesticides. The study of the uncertainty related to the POCIS data was performed and we concluded that it might be up to 138%, which is higher than European Union requirements but this issue was adequately counterbalanced by the gain of temporal representativeness. Comparison with data from the official monitoring programme from the French Water Agency showed that the POCIS is already suitable for both operational and investigative monitoring. The sampled fraction issue, and then compliance with Environmental Quality Standards, was also addressed. It was confirmed that POCIS samples only the dissolved fraction of dimethenamid and showed that for compounds like atrazine, desethylatrazine and metolachlor, the POCIS concentration is equivalent to the whole water concentration. For dimethenamid, which exhibited a tendency to adsorb on suspended matter, a method was suggested to assess the raw water concentration from the POCIS measure. Finally, an innovative procedure for using passive sampler data for compliance checks in the framework of surveillance monitoring is proposed.

Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms

Polar organic chemical integrative samplers (POCIS) are valuable tools in passive sampling methods for monitoring polar organic pesticides in freshwaters. Pesticides extracted from the environment using such methods can be used to toxicity tests. This study evaluated the acute effects of POCIS extracts on natural phototrophic biofilm communities. Our results demonstrate an effect of POCIS pesticide mixtures on chlorophyll a fluorescence, photosynthetic efficiency and community structure. Nevertheless, the range of biofilm responses differs according to origin of the biofilms tested, revealing spatial variations in the sensitivity of natural communities in the studied stream. Combining passive sampler extracts with community-level toxicity tests offers promising perspectives for ecological risk assessment.

Polar organic chemical integrative samplers for pesticides monitoring: impacts of field exposure conditions.

This study focuses on how Polar Organic Chemical Integrative Samplers (POCIS) work in real environmental conditions. A selection of 23 polar pesticides and 8 metabolites were investigated by exposure of triplicates of integrative samplers in two rivers in France for successive 14-day periods. The pesticides and metabolites were trapped not only in Oasis HLB sorbent but also in the polyethersulfone (PES) membrane of the POCIS. The distribution of pesticides depended on the molecular structure. The use of the Performance Reference Compound (PRC) is also discussed here. The impact of some environmental parameters and exposure setup on the transfer of pesticides in POCIS sorbent was studied: river flow rate, biofouling on membranes, sampler holding design and position in the stream. Results show a significant impact of river flow velocity on PRC desorption, especially for values higher than 4 cm·s(-1). Some fouling was observed on the PES membrane which could potentially have an impact on molecule accumulation in the POCIS. Finally, the positioning of the sampler in the river did not have significant effects on pesticide accumulation, when perpendicular exposures were used (sampler positioning in front of the water flow). The POCIS with PRC correction seems to be a suitable tool for estimating time-weighted average (TWA) concentrations, for all the molecules except for one of the nine pesticides analyzed in these two French rivers.

Overview of the Chemcatcher® for the passive sampling of various pollutants in aquatic environments Part A: Principles, calibration, preparation and analysis of the sampler.

The passive sampler Chemcatcher(®), which was developed in 2000, can be adapted for various types of water contaminants (e.g., trace metals, polycyclic aromatic hydrocarbons, pesticides and pharmaceutical residues) depending on the materials chosen for the receiving phase and the membrane. The Chemcatcher(®) has been used in numerous research articles in both laboratory experiments and field exposures, and here we review the state-of-the-art in applying this passive sampler. Part A of this review covers (1) the theory upon which the sampler is based (i.e., brief theory, calculation of water concentration, Performance and Reference Compounds), (2) the preparation of the device (i.e., sampler design, choice of the membrane and disk, mounting of the tool), and (3) calibration procedures (i.e., design of the calibration tank, tested parameters, sampling rates).

Overview of the Chemcatcher® for the passive sampling of various pollutants in aquatic environments Part B: Field handling and environmental applications for the monitoring of pollutants and their biological effects.

The Chemcatcher(®) has been used for a wide range of environmental applications in various media (river water, seawater, sewage water, and treated wastewater). The aim of part B of this review is to compile and discuss the results obtained during these applications, from a screening or quantitative monitoring of water contamination, to a comparison with biomonitoring and bioassays. Special attention will also be paid to, firstly, the influence of environmental factors on analyte uptake and, secondly, the use of Performance and Reference Compounds for the in situ correction of sampling rates.

Improvement of POCIS ability to quantify pesticides in natural water by reducing polyethylene glycol matrix effects from polyethersulfone membranes

The presence of polyethylene glycol compounds (PEG) in extracts from polar organic chemical integrative samplers (POCIS) was shown by high resolution time-of-flight mass spectrometry. PEG compounds, which are released by polyethersulfone (PES) membranes used to build POCIS, can induce matrix effects during quantification of performance reference compounds (PRC, DIA-d5) and target pesticides by mass detection, even after chromatographic separation. Dilution of POCIS extracts can reduce this matrix effect, but dilution may induce a decrease in POCIS performance, primarily for quantification limits. To reduce PEG interference during chromatographic analysis, a simple non-damaging washing protocol for PES membranes is proposed. The method consists of 2 successive baths of washing solution (140 mL per membrane) of ultrapure water (UPW) and methanol (50/50), stirred at 300 rotations per minute (rpm), followed by a final membrane rinse with UPW (140 mL). The signal from PEG compounds was significantly decreased for washed membranes (between 4 and 6 fold lower). After field deployment, total ion current chromatograms of extracts from POCIS built with washed PES membranes did not display a significant PEG fingerprint. This led to improved quantification accuracy for compounds co-eluting with PEG, i.e. PRC (performance and reference compound, DIA-d5) and some pesticides and metabolites. With washed membranes, an accurate quantification of PRC and pesticides sampled by POCIS was indeed possible without a large extract dilution; 10 times instead of the 25 times needed in unwashed conditions. Assuming that the PRC approach corrects for environmental conditions and sampling rates (Rs), a proper PRC (DIA-d5) quantification significantly improved pesticide time weighted average concentration (TWAC) determination in natural water after field deployment.

Coupling passive sampling and time of flight mass spectrometry for a better estimation of polar pesticide freshwater contamination: Simultaneous target quantification and screening analysis

The aim of this study was first to develop and validate an analytical method for the quantification of 35 polar pesticides and 9 metabolites by ultra-high-performance-liquid chromatography combined with a high resolution time-of-flight mass spectrometer detector (UHPLC-(Q)-TOF). Various analytical conditions were investigated (eluent composition and mass parameters) to optimize analyte responses. Analytical performance (linearity, limit of quantification, and accuracy) was then evaluated and interference in the extract of a passive sampler exposed in freshwater (POCIS: Polar Organic Chemical Integrative Sampler) was studied. The proposed quantification method was validated for 43 compounds with variation of calibration slopes below 10% in environmental matrix. For the unvalidated compound DIA (atrazine-desisopropyl: an atrazine metabolite), interference increased the error of concentration determination (50%). The limits of quantification obtained by combining POCIS and UHPLC-(Q)-TOF for 43 target compounds were between 0.1 (terbuthylazine) and 10.7 ng/L (acetochlor). Secondly, the method was successfully applied during a 14-day POCIS river exposure, and gave concentration values similar to a more commonly used triple quadrupole detector regarding concentration, but allowed for the detection of more compounds. Additionally with the targeted compound quantification, the (Q)-TOF mass spectrometer was also used for screening non-target compounds (other pesticides and pharmaceuticals) in POCIS extracts. Moreover, the acquisition of full scan MS data allowed the identification of the polyethylene glycol (PEG) compounds which gave unresolvable interference to DIA, and thus questions the ability of DIA to be used as performance reference compound (PRC) to determine sampling rates in situ. This study therefore illustrates the potential, and proposes a pathway, of UHPLC-(Q)-TOF combined with POCIS in situ pre-concentration for both quantitative and screening analyses of organic contaminants in water.