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

Abstract

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 (140mL 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 (140mL). 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.