Estimating 42 pesticide sampling rates by POCIS and POCIS-MIP samplers for groundwater monitoring: a pilot-scale calibration.

Pesticides occur in groundwater as a result of agricultural activity. Their monitoring under the Water Framework Directive is based on only a few spot-sampling measurements per year despite their temporal variability. Passive sampling, which was successfully tested in surface water to provide a more representative assessment of contamination, could be applied to groundwater for a better definition of its contamination. However, few reliable calibration data under low water flow are available. The objective of our study thus consisted in determining sampling rates by two types of passive samplers, a POCIS (polar organic chemical integrative sampler) for polar pesticides, and a POCIS-MIP sampler based on a receiving phase of molecular imprinted polymers, specific for AMPA and glyphosate under low flow conditions as exist in groundwater. To our knowledge, this is the first time that sampling rates (sampling rate represents the volume of water from which the analyte is quantitatively extracted by the sampler per unit time) are estimated for groundwater applications. Our calibrations took place in an experimental pilot filled with groundwater and with low water flow (a few metres per day). Pesticide uptake in POCIS showed good linearity, with up to 28 days before reaching equilibrium. Two types of accumulation in POCIS were noted (a linear pattern up to 28 days, and after a time lag of 7 to 14 days). Sampling rates for 38 compounds were calculated and compared with those available in the literature or obtained previously under laboratory conditions. The values obtained were lower by a factor 1 to 14 than those estimated under stirring conditions in the literature, whereas water flow velocity (m s-1) differed by a factor of 2000 to 10,000.

Preliminary recovery study of a commercial molecularly imprinted polymer for the extraction of glyphosate and AMPA in different environmental waters using MS.

A commercial molecularly imprinted polymer (MIP) dedicated to glyphosate (GLY) and its main metabolite, aminomethylphosphonic acid (AMPA), was lately assessed as "POCIS-like" sampler on mineral water. The obtained results were encouraging with 111 and 122 mL day-1 as sampling rates for GLY and AMPA, respectively. Therefore, before applying this passive sampler to environmental waters, the commercial phase was tested on different water matrices as a solid-phase extraction (SPE) device. The SPE protocol was carried on 250 mg of MIP with the following three steps: conditioning by Milli-Q water, loading of the sample (15 mL), and elution of the analytes by 4 mL 0.1 M HCl that were evaporated to dryness and recovered in 15 mL of the suitable solvent for analysis. This protocol was first applied to mineral water spiked by GLY and AMPA at environmental concentration levels (25-750 ng L-1). Analyses were carried out by ultra-performance liquid chromatography hyphenated to tandem mass after derivatization of GLY and AMPA by 9-fluorenylmethylchloroformate. The linear correlation between concentrations measured with and without SPE on MIP was proved.Furthermore, other extractions showed that high concentrations of metal ion interferents (lead(II), cadmium(II), and zinc(II)) in groundwaters did not reduce SPE performance of the MIP.Then, concentration assays were undertaken and brought noteworthy results, such as the recovery of 80% GLY and AMPA from groundwater spiked at 10 ng L-1 and concentrated 100 times. For this purpose, ion exclusion chromatography hyphenated to mass was applied without previous derivatization of the analytes. The same concentration factor and analytical method were applied to 100 ng L-1 spiked sea water with recoveries of 96% for GLY and 121% for AMPA.

Laboratory calibration of a POCIS-like sampler based on molecularly imprinted polymers for glyphosate and AMPA sampling in water.

For more than 15 years, integrative passive sampling has been successfully used for monitoring contaminants in water, but no passive sampling device exists for strongly polar organic compounds, such as glyphosate. We thus propose a polar organic chemical integrative sampler (POCIS)-like tool dedicated to glyphosate and its main degradation product aminomethylphosphonic acid (AMPA), and describe the laboratory calibration of such a tool for calculating the sampling rates of glyphosate and AMPA. This passive sampler consists of a POCIS with molecularly imprinted polymer as a receiving phase and a polyethersulfone diffusion membrane. The calibration experiment for the POCIS was conducted for 35 days in a continuous water-flow-through exposure system. The calibration results show that the sampling rates are 111 and 122 mL day-1 for glyphosate and AMPA respectively, highlighting the potential interest in and the applicability of this method for environmental monitoring. The influence of membrane porosity on the glyphosate sampling rate was also tested. Graphical Abstract ᅟ.