Adeline Charriau

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.

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.

Simultaneous measurement of Cr(III) and Cr(VI) in freshwaters with a single Diffusive Gradients in Thin Films device.

Few attempts have been made to sample labile chromium with the DGT passive sampler (Diffusive Gradients in Thin Films) and, currently, no single device allows the simultaneous determination of both Cr(III) and Cr(VI). In this work, a procedure based on only one device combined with innovative selective elution is evaluated to assess chromium speciation. A zirconium binding gel is used to accumulate both Cr(III) and Cr(VI). Cr(VI) is quantitatively and selectively eluted by NaOH, allowing the subsequent determination of Cr(III). Accurate quantification of both species is demonstrated in synthetic solutions for pH ranging from 4 to 6 and ionic strength ranging from 10(-3) to 5×10(-2)M. Cr(VI) quantification is altered only for [SO4(2-)]≥5×10(-3)M. The method allows successful quantification of labile Cr(III) and Cr(VI) in spiked natural water. The limit of quantification of the procedure is suitable for trace level monitoring (0.03µgL(-1) for Cr(VI) and 1µgL(-1) for Cr(III), for a one-week deployment at 20°C) and the effective capacity of the sampler (∼25µg for each Cr oxidation state) should allow long term deployments. These results highlight the potential of this new procedure for a simple and effective chromium speciation analysis in natural waters.

Efficiency evaluation of an algistatic treatment based on barley straw in a hypertrophic pond

AbstractEutrophication processes were closely examined in a hypertrophic pond that was subjected to a barley straw treatment to inhibit cyanobacteria blooms. A phytoplankton activity was present from February to November 2010 with Chlorophyll a concentrations that ranged between 8 and 83 µg L−1. The good oxygenation of the pond provided by primary production all along the year seems to maintain an oxic layer at the top of the sedimentary column. A high-frequency monitoring of algal development pointed out the end of the diatom bloom at the end of April and the growth of green algae from beginning of May. One month later, the development of cyanobacteria supplanted other algae several times. The implementation of barley straw does not seem to hinder the growth of cyanobacteria in June, August and September and do not promote the development of other algae potentially favoured by such a treatment. As a consequence, a barley straw treatment does not seem to be really appropriate for this kind of ponds in Nor...

Key role of the sorption process in alteration of metal and metalloid quantification by fouling development on DGT passive samplers

The DGT technique (diffusive gradients in thin films) is widely used for passive sampling of labile trace metals and metalloids in natural waters. Although development of fouling on the protective membranes is frequently observed, its effect on DGT sampling has been barely investigated. This study evaluates the influence of fouling on sampling of trace cationic metals Cd(II), Cu(II), Ni(II) and Pb(II) and oxyanions As(V), Cr(VI), Sb(V) and Se(VI). Fouling was developed in situ on polycarbonate membranes in four diverse natural freshwater environments and sampling alteration was assessed in controlled laboratory experiments. Accumulation of oxyanions and Ni was unaltered in the presence of fouling whereas significant alteration occurred in sampling of Cd, Cu and Pb (at pH ∼5.4). Characterization of the fouled membranes highlighted the intervention of sorption phenomenon as sampling alteration was systematically observed alongside element sorption onto fouled membrane. A preliminary flowchart for identifying potentially biased quantifications linked to fouling development during in situ DGT deployment in natural waters is proposed.