RESUMO
L'Albufera Natural Park (Valencia, Spain) is a protected wetland of international significance that provides critical habitats to endemic and threatened bird and plant species. This study aims to use multiple cross-validation techniques to generate an accurate estimation of the environmental risk of organic contaminants (OCs) in an internationally important coastal wetland, to identify compounds of concern and their potential sources and risk factors. Microporous polyethylene tube (MPT) passive samplers were deployed at 12 locations across L'Albufera Natural Park with concurrent grab samples collected. A subset of MPT samplers were also analysed by an additional laboratory in Australia to widen the range of contaminants and assess interlaboratory reproducibility of results. Forty-three pesticides, 20 pharmaceuticals and personal care products (PPCPs), 20 per-and polyfluoroalkyl substances (PFAS) and 4 organophosphorus flame retardants (OPFRs) were detected in the MPT samplers. The fungicides tebuconazole and difenoconazole were detected at the highest concentrations in passive samplers (maximum concentrations, 153 ng sampler-1 and 106 ng sampler-1, respectively). Several other pesticides were detected in all locations (mean concentrations >1 ng sampler-1). The compounds fenamiphos, propyzamide, difenoconazole, propiconazole, metsulfuron methyl, sodium bis (perfluorohexyl) phosphinate (6:6 PFPiA), 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), 6:2 fluorotelomersulfonate (6:2 FTS), citalopram desmethyl and citalopram were reported in the wetland for the first time. Spatial distribution analysis revealed higher pesticide concentrations in the North of L'Albufera. A risk quotient (RQ) analysis showed that ibuprofen is of concern in the area. Overall, the MPT sampling approach is promising as a risk assessment tool for better understanding the transport and fate of OCs in protected areas.
RESUMO
Water resources are vulnerable to contamination from polar organic compounds (POCs) originating from sources such as wastewater effluent. Two configurations of a microporous polyethylene tube (MPT) passive sampler were investigated for the time-integrative detection and quantification of POCs in effluent. One configuration contained the polymeric reversed phase sorbent Strata-X (SX) and the other Strata-X suspended in agarose gel (SX-Gel). These were deployed for up to 29 days and analysed for forty-nine POCs including pesticides, pharmaceuticals and personal care products (PPCPs) together with illicit drugs. Complementary composite samples were collected on days 6, 12, 20 and 26 representing the previous 24 h. Thirty-eight contaminants were detected in composite samples and MPT extracts, with MPT sampling rates (Rs) for 11 pesticides and 9 PPCPs/drugs ranging from 0.81 to 10.32 mL d-1 in SX and 1.35-32.83 mL d-1 in SX-Gel. Half-times to equilibrium of contaminants with the SX and SX-Gel equipped samplers ranged from two days to >29 days. MPT (SX) samplers were also deployed at 10 wastewater treatment effluent discharge sites across Australia for 7 days (again with complementary composite samples), to validate the sampler performance under varying conditions. Extracts from these MPTs detected 48 contaminants in comparison with 46 in composite samples, with concentrations ranging from 0.1 to 138 ng mL-1. An advantage of the MPT was preconcentration of contaminants, resulting in extract levels often markedly above instrument analytical detection limits. The validation study demonstrated a high correlation between accumulated contaminant mass in the MPTs and wastewater concentrations from composite samples (r2 > 0.70, where concentrations in composite samples were > 3× LOD). The MPT sampler shows promise as a sensitive tool for detecting POCs at trace levels in wastewater effluent and also quantifying these levels if temporal concentration variations are not significant.
