Wastewater treatment plants (WWTP) are known to be a source of surface water contamination by organic compounds such as pharmaceuticals. The objective of the present work was to study the suitability of the polar organic chemical integrative sampler (POCIS) to monitor beta-blockers and hormones in effluents and surface waters. Four sampling campaigns were carried out in French rivers (the Saône, the Ardières, the Bourbre, and the Seine) between November 2007 and September 2008. Passive samplers were exposed in surface waters, upstream and downstream of WWTP outflows, and in effluents. Exposures lasted for up to 24 d to study the uptake kinetics directly in situ, and repeatability was assessed by exposure of triplicates. A good agreement was found between POCIS and water samples. With the exception of atenolol, beta-blockers showed a linear uptake during at least three weeks, and their sampling rates could be determined in situ. These sampling rates were then used to calculate time-weighted average concentrations of beta-blockers in the Seine River with an overall good accuracy and repeatability. Such calculations could not be performed for hormones because of their variable occurrences and low concentrations in water and POCIS. Polar organic chemical integrative sampler therefore seems to be a suitable tool for monitoring beta-blockers in surface waters impacted by WWTP effluents. Longer exposure durations would be necessary to determine the suitability of POCIS for monitoring hormones. Finally, preliminary assays on the use of several deuterated compounds as performance reference compounds showed promising results for deuterated atenolol.

In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters.

This study aimed at evaluating and comparing five integrative samplers for the monitoring of indicator and dioxin-like polychlorinated biphenyls (PCBs) in water: semi-permeable membrane device (SPMD), silicone rubber, low-density polyethylene (LDPE) strip, Chemcatcher and a continuous-flow integrative sampler (CFIS). These samplers were spiked with performance reference compounds (PRCs) and then simultaneously exposed under constant agitation and temperature in a 200 L stainless steel tank for periods ranging from one day to three months. A constant PCB concentration of about 1 ng·L(-1) was achieved by immersing a large amount of silicone rubber sheets ("dosing sheets") spiked with the target PCBs. The uptake of PCBs in the five samplers showed overall good repeatability and their accumulation was linear with time. The samplers SPMD, silicone rubber and LDPE strip were the most promising in terms of achieving low limits of quantification. Time-weighted average (TWA) concentrations of PCBs in water were estimated from uptake of PCBs using the sampling rates calculated from the release of PRCs. Except for Chemcatcher, a good agreement was found between the different samplers and TWA concentrations ranged between 0.4 and 2.8 times the nominal water concentration. Finally, the influence of calculation methods (sampler-water partition coefficients, selected PRCs, models) on final TWA concentrations was studied.

Five estrogenic hormones (unconjugated + conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from the WWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.