Department of Analytical Chemistry, Faculty of Science and Technology, University of Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
Water Res. 2013 May 15;47(8):2851-62. doi: 10.1016/j.watres.2013.02.049. Epub 2013 Mar 5.
In this work, home-made Polar Organic Chemical Integrative Samplers (POCIS) were studied for passive sampling of 15 endocrine disrupting compounds (4 alkylphenols and steroid hormones) in influent and effluent samples of wastewater treatment plants (WWTPs) as well as up- and downstream of the receiving river water. POCIS calibration at laboratory conditions was carried out using a continuous-flow calibration system. The influence of the exposure position of the POCIS within the calibration device, horizontal or vertical, to the water flow direction was evaluated. While the sampling rates of most of the target substances were not affected by the sampler position, for cis-ADT, E1, E2 and E3, the vertical position provided the highest analyte accumulation. Hence, the POCIS samplers were preferably exposed vertical to the water flow in overall experiments. Using the continuous-flow calibration device, lab-based sampling rates were determined for all the target compounds (RSBPA = 0.0326 L/d; RScisADT = 0.0800 L/d, RSE1 = 0.0398 L/d, RSEQ = 0.0516 L/d, RSTT = 0.0745 L/d, RSE2 = 0.0585 L/d, RSEE2 = 0.0406 L/d, RSNT = 0.0846 L/d, RSPG = 0.0478 L/d and RSE3 = 0.1468 L/d), except for DES, MeEE2, 4tOP, 4OP, 4NPs, where the uptake after 14 days POCIS exposure was found to be insignificant or indicated a no linear behaviour. Recoveries from POCIS extractions were in the range between 71 and 152% for most of the target analytes except for DES and E3 with around 59%. Good precision of the sampling procedure up till 20% was observed and limits of detection were at ng/L level. Two deuterated compounds ([(2)H3]-E2 and [(2)H4]-EQ) were successfully tested as performance reference compounds (PRC, [Formula: see text] = 0.0507 L/d and [Formula: see text] = 0.0543 L/d)). Finally, the POCIS samplers were tested for monitoring EDCs at two wastewater treatment plants, in Halle and Leipzig (Germany). BPA, E1, EQ, E2, MeEE2, NT, EE2, PG and E3 were quantified and their time-weighted average concentrations calculated on the basis of the lab-derived sampling rates were compared with the results based on conventional grab samples. While the influent concentration of BPA, cisADT, E1, TT, PG, EE2 reached the μg/L level, the rest of the target analytes were determined at ng/L. The analyte concentrations in the effluent never exceed ng/L level except for BPA. The concentration determined by spot sampling was partially lower (BPA, E1, TT) or comparable (EQ, E2, EE2, PG, E3) to the concentration obtained by POCIS using performance reference compounds (PRC).
在这项工作中，研究了自制的极性有机化学整合采样器（POCIS），用于被动采样 15 种内分泌干扰化合物（4 种烷基酚和类固醇激素），包括废水处理厂（WWTP）的进水和出水以及受纳河的上下游。在实验室条件下，通过连续流动校准系统进行 POCIS 校准。评估了 POCIS 在校准装置中的暴露位置（水平或垂直）对水流方向的影响。虽然大多数目标物质的采样率不受采样器位置的影响，但对于顺式-ADT、E1、E2 和 E3，垂直位置提供了最高的分析物积累。因此，在总体实验中，POCIS 采样器最好垂直于水流暴露。使用连续流动校准装置，确定了所有目标化合物的实验室采样率（RSBPA = 0.0326 L/d；RScisADT = 0.0800 L/d，RSE1 = 0.0398 L/d，RSEQ = 0.0516 L/d，RSTT = 0.0745 L/d，RSE2 = 0.0585 L/d，RSEE2 = 0.0406 L/d，RSNT = 0.0846 L/d，RSPG = 0.0478 L/d 和 RSE3 = 0.1468 L/d），除了 DES、MeEE2、4tOP、4OP、4NPs，在 14 天 POCIS 暴露后，这些物质的吸收量被发现微不足道或呈非线性。对于大多数目标分析物，POCIS 提取的回收率在 71%至 152%之间，除了 DES 和 E3，回收率约为 59%。采样过程的精密度高达 20%，检测限为 ng/L 水平。两种氘代化合物（[(2)H3]-E2 和 [(2)H4]-EQ）作为性能参考化合物（PRC，[公式：见正文] = 0.0507 L/d 和 [公式：见正文] = 0.0543 L/d）成功进行了测试。最后，在德国哈雷和莱比锡的两个废水处理厂对 POCIS 采样器进行了监测 EDCs 的测试。定量测定了 BPA、E1、EQ、E2、MeEE2、NT、EE2、PG 和 E3，并根据实验室衍生的采样率计算了它们的时间加权平均浓度，并与基于常规点采样的结果进行了比较。虽然 BPA、cisADT、E1、TT、PG、EE2 的进水浓度达到μg/L 水平，但其余目标分析物的浓度为 ng/L。除了 BPA，出水浓度从未超过 ng/L 水平。使用性能参考化合物（PRC）通过点采样确定的浓度部分较低（BPA、E1、TT）或相当（EQ、E2、EE2、PG、E3）。
