Federal Institute of Hydrology (BfG), Am Mainzer Tor 1, D-56068 Koblenz, Germany.
J Chromatogr A. 2010 Apr 2;1217(14):2088-103. doi: 10.1016/j.chroma.2010.01.079. Epub 2010 Feb 4.
This paper describes the development of a multi-residue method for the determination of 36 emerging organic pollutants (26 biocides, 5 UV-filters and 5 benzothiazoles) in raw and treated wastewater, activated sludge and surface water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The target analytes were enriched from water samples adjusted to pH 6 by solid-phase extraction (SPE) on Oasis HLB 200mg cartridges and eluted with a mixture of methanol and acetone (60/40, v/v). Extraction of freeze-dried sludge samples was accomplished by pressurized liquid extraction (PLE) using a mixture of methanol and water (50/50, v/v) as extraction solvent followed by SPE. LC-tandem MS detection was compared using electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) in positive and negative ionization mode. ESI exhibited strong ion suppression for most target analytes, while APCI was generally less susceptible to ion suppression but partially leading to ion enhancement of up to a factor of 10. In general, matrix effects could be compensated using stable isotope-labeled surrogate standards, indicated by relative recoveries ranging from 70% to 130%. In wastewater, activated sludge and surface water up to 33 analytes were detected. Maximum concentrations up to 5.1 and 3.9mugL(-1) were found in raw wastewater for the water-soluble UV-filters benzophenone-4 (BZP-4) and phenylbenz-imidazole sulfonic acid (PBSA), respectively. For the first time, the anti-dandruff climbazole was detected in raw wastewater and in activated sludge with concentrations as high as 1.4 microg L(-1) and 1.2 microg gTSS(-1), respectively. Activated sludge is obviously a sink for four benzothiazoles and two isothiazolones, as concentrations were detected in activated sludge between 120 ng gTSS(-1) (2-n-octyl-4-isothiazolin-3-one, OIT) to 330 ng gTSS(-1) (benzothiazole-2-sulfonic acid, BTSA).
本文描述了一种用于测定原始和处理废水中 36 种新兴有机污染物（26 种杀生物剂、5 种紫外线滤光剂和 5 种苯并噻唑）的多残留方法的开发，使用液相色谱-串联质谱法（LC-MS/MS）。目标分析物通过固相萃取（SPE）在 Oasis HLB 200mg 小柱上从 pH 6 的水样中富集，并以甲醇和丙酮（60/40，v/v）的混合物洗脱。冷冻干燥污泥样品的提取通过加压液体提取（PLE）完成，使用甲醇和水（50/50，v/v）作为提取溶剂，然后进行 SPE。LC-串联 MS 检测比较了电喷雾电离（ESI）和大气压化学电离（APCI）在正离子和负离子模式下的效果。ESI 对大多数目标分析物表现出强烈的离子抑制，而 APCI 一般不易受到离子抑制的影响，但部分导致离子增强高达 10 倍。通常，基质效应可以通过使用稳定同位素标记的替代标准品进行补偿，相对回收率在 70%至 130%之间。在废水中、活性污泥中和地表水中，检测到多达 33 种分析物。在原始废水中，水溶性紫外线滤光剂二苯甲酮-4（BZP-4）和苯并咪唑磺酸（PBSA）的浓度高达 5.1 和 3.9mugL(-1)。首次在原始废水中和活性污泥中检测到去屑剂克霉唑，浓度分别高达 1.4 microg L(-1)和 1.2 microg gTSS(-1)。活性污泥显然是四种苯并噻唑和两种异噻唑啉酮的汇，因为在活性污泥中检测到的浓度在 120ng gTSS(-1)（2-正辛基-4-异噻唑啉-3-酮，OIT）到 330ng gTSS(-1)（苯并噻唑-2-磺酸，BTSA）之间。
