Selection of performance reference compound (PRC) for passive sampling of pharmaceutical residues in an effluent dominated river.

A passive sampling device, a polar organic chemical integrative sampler (POCIS), was used to monitor 13 pharmaceuticals and 8 transformation products in upstream and downstream wastewater treatment plant effluent. A POCIS laboratory calibration study was performed to determine uptake behavior and the effect of water flow on the sampling rate. Most compounds showed a linear accumulation, and the sampling rate values ranged from 0.031 to 0.559 L/day. The developed POCIS samplers were used in field experiments in a wastewater-impacted river. Using the calculated sampling rates, the time-weighted average concentration values were measured by three different approaches: (1) laboratory calibration sampling rates (2) performance reference compound (PRC) correction sampling rates and (3) field calibration sampling rates. Nine deuterated compounds (acetaminophen-d, antipyrine-d, sulfamethoxazole-d, carbamazepine-d, diclofenac acid-d, clofibric acid-d, bezafibrate-d, ibuprofen-d and naproxen-d) were studied as PRCs. Antipyrine-d was successfully tested as a PRC for sulfamethoxazole, ibuprofen, 2-hydroxy ibuprofen, diclofenac acid, 4-hydroxydiclofenac acid, carbamazepin, carbamazepin 10,11-epoxide, sulfadiazine, 1-naphthol, antipyrine, naproxen and 4-chlorobenzoic acid. Finally, the POCIS was used to monitor target compounds in river water and measure their attenuation. For most compounds, the POCIS attenuation results were not significantly different from those of the spot samples, which demonstrated that a POCIS with a PRC correction can determine the attenuation of organic micropollutants in rivers.