Role of membrane porosity in passive sampling of aquatic contaminants for stable isotope analysis: enhancement of analyte accumulation rates and selectivity

Compound-specific isotope analysis (CSIA) is a potent method for illustrating the in situ degradation of aquatic contaminants. However, its application to surface and groundwater is hindered by low contaminant concentrations, typically in the nanogram-per-litre range, requiring the processing of large water volumes. Polar organic chemical integrative samplers (POCIS) have shown promising results when combined with CSIA, yet their extended deployment time to accumulate sufficient analyte mass remains a major limitation. In our study, we addressed this issue by increasing the pore size of the polyethersulfone membrane (PES) from 0.1 to 8 \(\upmu \)m. This resulted in significant increases in the mass accumulation rates of atrazine (3.5-fold), S-metolachlor (3.4-fold), and boscalid (3.0-fold). Importantly, the larger pore sizes did not compromise isotopic integrity, with \(\Delta \delta ^{13}\)C\(\le +0.4\pm 0.1\)‰ and \(\Delta \delta ^{15}\)N\(\le -0.6\pm 0.4\)‰, both within accepted uncertainties. Additionally, we observed an enhanced selectivity of the larger pores towards the target analytes over humic acids, whereas no significant increase in (bio)fouling potential was detected for the 8 \(\upmu \)m membrane, as demonstrated by gravimetric analysis, SEM measurements, mass accumulation rates, and isotope ratios of fouled and unfouled POCIS. Our findings show that increasing the membrane pore size from 0.1 to 8 \(\upmu \)m reduces deployment time and expedites the accumulation of analyte mass required for gas chromatography isotope ratio mass spectrometry, offering a promising method to expand CSIA for low-concentration pesticide analysis in the field.