Laboratory calibration and field deployment of the polar organic chemical integrative sampler for pharmaceuticals and personal care products in wastewater and surface water.

Aqueous sampling rates for 25 pharmaceuticals and personal care products (PPCPs) were determined on the commercially available passive Polar Organic Chemical Integrative Sampler (POCIS). To date, POCIS calibration has only been carried out for a handful of compounds. Uptake rates were 0.040 to 2.462 L/d under conditions of flowing water; quiescent conditions resulted in uptake rates between 0.016 and 0.223 L/d. The uptake of many PPCPs appears to be boundary-layer controlled, as indicated by higher sampling rates under flowing conditions. Sampling rates were corrected for analyte dissipation rates, and some correlations with octanol-water partition coefficients were noted. Field deployments of POCIS in wastewater effluent and surface waters had time-weighted average concentrations derived from laboratory calibrations that were consistent with regular grab samples. This work indicates that POCIS can be used as a quantitative tool for measuring PPCPs in the aquatic environment.

Solid phase microextraction of macrolide, trimethoprim, and sulfonamide antibiotics in wastewaters.

In this work, we optimize a solid phase microextraction (SPME) method for the simultaneous collection of antibiotics (sulfonamides, macrolides, and trimethoprim) present in wastewaters. The performance of the SPME method is compared to a solid phase extraction (SPE) method. Analytes in both cases were quantified by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) with electrospray ionization. The advantages offered by SPME in this application are: decreased sample volume requirements, ease of sample processing and extraction, decreased cost, and most importantly, elimination of electrospray matrix effects. Despite having higher limits of quantification (16-1380 ng/L in influent and 35-260 ng/L in effluent), nearly all of the compounds found to be present in Edmonton Gold Bar wastewater by SPE were measurable by SPME (i.e., sulfamethoxazole, trimethoprim, erythromycin, and clarithromycin), with values similar to those obtained using the former method. Limits of quantification for the SPE method for the measured compounds were 4.7-15 ng/L and 0.86-6.1 ng/L for influent and effluent, respectively.

Stereoisomer quantification of the beta-blocker drugs atenolol, metoprolol, and propranolol in wastewaters by chiral high-performance liquid chromatography-tandem mass spectrometry.

A chiral liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) method was developed and validated for measuring individual enantiomers of three beta-blocker drugs (atenolol, metoprolol, and propranolol) in wastewater treatment plant (WWTP) influents and effluents. Mean recoveries of the pharmaceuticals ranged from 67 to 106%, and the limits of detection of the analytes were 2-17 ng/L in wastewater effluents. The method was demonstrated by measuring, for the first time, the stereoisomer composition of target analytes in raw and treated wastewaters of two Canadian WWTPs. In these trials, racemic amounts of the three drugs were observed in influent of one wastewater treatment plant, but nonracemic amounts were observed in another. Effluents of the two plants contained nonracemic amounts of the drugs. These results indicate that biologically-mediated stereoselective processes that differ among WWTPs had occurred to eliminate individual enantiomers of the target analytes.