Federal Institute of Hydrology (BfG), Am Mainzer Tor 1, 56068 Koblenz, Germany.
Federal Institute of Hydrology (BfG), Am Mainzer Tor 1, 56068 Koblenz, Germany.
J Chromatogr A. 2018 Feb 2;1535:27-43. doi: 10.1016/j.chroma.2017.12.023. Epub 2017 Dec 11.
Benefits and limitations of HILIC were studied for the analysis of extreme polar organic contaminants in aqueous environmental matrices. A sensitive analytical method was developed and validated for the detection of 11 pharmaceuticals, 15 pharmaceutical metabolites and transformation products and the artificial sweetener acesulfame in aqueous environmental samples. The analytical method consisted of a simple and non-specific sample preparation based on freeze-drying followed by detection with large injection volume (70 μL) zwitterionic HILIC-ESI-MS/MS. Robustness studies showed a high sensitivity of the retention times and peak shapes to variations of the acetonitrile/water ratio of both the eluent and the diluent. Thus, a thorough sample and eluent preparation is required to obtain reproducible results. Extreme matrix effects of >200% were observed for emtricitabine and acyclovir, which could be traced to the co-elution of nitrate and chloride, respectively. These matrix effects and those of other analytes could be efficiently compensated by using deuterated, C and N-labeled internal standards. The developed method was able to detect the selected 27 analytes in treated wastewater, surface water and groundwater down to limit of quantification (LOQ) in the lower ng/L range. Appreciable concentrations were detected, ranging up to 110 μg/L (guanyl urea) in treated wastewater, up to 5.1 μg/L (oxipurinol) in surface water and up to 6.1 μg/L (acesulfame) in groundwater. In a German drinking water, only the X-ray contrast medium diatrizoate and the artificial sweetener acesulfame were quantified above LOQ with 0.19 μg/L and 0.35 μg/L, respectively.
亲水作用色谱法（HILIC）在分析水环境极端极性有机污染物方面的优缺点进行了研究。开发并验证了一种用于检测水环境样品中 11 种药物、15 种药物代谢物和转化产物以及人工甜味剂乙酰磺胺酸的灵敏分析方法。该分析方法基于冷冻干燥进行简单且非特异性的样品制备，然后使用大进样量（70μL）的两性离子亲水作用色谱-电喷雾串联质谱法（ESI-MS/MS）进行检测。稳健性研究表明，保留时间和峰形对洗脱液和稀释剂中乙腈/水比例的变化具有很高的灵敏度。因此，需要彻底的样品和洗脱液制备才能获得可重复的结果。恩曲他滨和阿昔洛韦的极端基质效应>200%，这可以追溯到分别与硝酸盐和氯化物共洗脱。可以通过使用氘代、C 和 N 标记的内标有效地补偿这些基质效应和其他分析物的基质效应。所开发的方法能够检测处理后的废水中、地表水中和地下水中选定的 27 种分析物，其定量下限（LOQ）在较低的 ng/L 范围内。检测到明显的浓度，在处理过的废水中高达 110μg/L（鸟嘌呤脲），在地表水中高达 5.1μg/L（氧吡咯烷），在地下水中高达 6.1μg/L（乙酰磺胺酸）。在德国饮用水中，只有 X 射线造影剂 diatrizoate 和人工甜味剂乙酰磺胺酸的浓度高于 LOQ，分别为 0.19μg/L 和 0.35μg/L。
