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.
The following provides a short overview of the important topics arising from the 6(th) International Passive Sampling Workshop and Symposium (IPSW 2013) held in Bordeaux, France between 26 and 29(th) June, 2013. Most of the discussions focussed on monitoring non-polar and polar organic pollutants in water with less coverage on air (probably already seen as a mature technology for this medium) and sediments. The use of passive sampling devices within regulatory water monitoring programmes was also a major theme of the Workshop.
Acidic herbicides are increasingly monitored in freshwater, since their high solubility favors their rapid transfer to the water phase. Therefore, contaminant levels in the water can vary rapidly and passive sampling would be preferred over spot sampling to integrate all pollution events over a given exposure time. In this work, we propose to compare the conventional pharmaceutical polar organic chemical integrative sampler (POCIS) with modified POCISs containing two different receiving phases: a standard polystyrene divinylbenzene polymer with a higher specific surface area (Chromabond HR-X) and a mixed-mode anion exchange sorbent providing additional strong anion exchange interaction sites (Oasis MAX). Due to its hydrophobic character, Chromabond HR-X had little interaction with water (no sampling of acidic herbicides); whereas Oasis MAX provided acceptable sampling parameters (longer kinetic regime together with higher sampling rates). Additional experiments with POCIS-MAX showed no influence of nitrates on analyte uptakes, and linear isotherms reaching 10 μg L⁻¹, supporting the applicability of this device for the sampling of organic acids in continental water. The performance and reference compound (PRC) approach would be then applicable for POCIS-MAX if no competition is observed with other anions, especially organic acids (e.g., humic acids).
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