Polar organic chemical integrative samplers (POCIS) are useful in monitoring for a wide range of chemicals in aquatic systems; however, a lack of available uptake rate data for compounds of environmental interest is one limitation in the application of these samplers to environmental studies. In this study, laboratory calibration experiments were conducted with POCIS for 65 compounds at 25°C under flowing conditions to determine chemical-specific uptake rates (R(s)). Experimental uptake rates measured in this study ranged from 0.034 to 1.33 L/d, and uptake rates were determined for 36 compounds with no previously reported values. Experimentally determined uptake rates were applied to data obtained from POCIS samplers deployed downstream of three wastewater treatment plant (WWTP) effluent discharges and in four surface waters influenced by agricultural runoff. Time-weighted average concentrations for atrazine and metolachlor determined using uptake rates generated in this study compare well with results from composited grab sampling previously conducted in agricultural watersheds in Nebraska, USA.
Analytical methods for the determination of several natural and synthetic steroids in water and solid samples were developed using liquid chromatography tandem mass spectrometry. Atmospheric pressure photoionization (APPI) in positive mode was used as the source which appeared to reduce background and interferences as compared to electrospray ionization. Toluene was identified as the most appropriate dopant and its concentration optimized to enhance ionization efficiency. Method detection limits were in the low-nanogram-per-liter range for water samples using on-line solid-phase extraction and near 0.2 ng/g using microwave-assisted solvent extraction for solid samples. This on-line method, using APPI as a source and toluene as a dopant, is beneficial as it saves time due to on-line extraction and reduces interference and matrix effects using gas-phase photoionization. Groundwater, wastewater, runoff, and soil samples were collected and analyzed using the method indicating that traces of several androgens, estrogens, and other steroid-like compounds do occur in samples impacted by animal waste.
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