Marmara Research Center, Environment and Cleaner Production Institute, TÜBİTAK, 41470, Kocaeli, Turkey.
Marine Science and Management Institute, Istanbul University, 34134, Istanbul, Turkey.
Anal Bioanal Chem. 2020 Aug;412(21):5169-5178. doi: 10.1007/s00216-020-02553-4. Epub 2020 Mar 16.
The aim of this work is the highly sensitive determination of 117 contaminants in surface waters at very low concentrations. Gas chromatography-amenable priority compounds from the European Water Framework Directive (EWFD, 45 priority substances) and substances from the Turkish Regulation on the Management of Surface Water Quality (TRMSWQ, 250 substances) were analyzed. Almost a third to one half of the compounds in the TRMSWQ list were successfully detected in a single gas chromatography-tandem mass spectrometry (GC-MS/MS) injection. Analyzing these pollutants in water samples is difficult with conventional extraction methods. An efficient, easy and fast method for both extraction and analysis is thus important. Here, the stir bar sorptive extraction (SBSE) approach employing Twister was used for analyte enrichment from 100 mL water samples. The Twister apparatus was used for thermal desorption. Compounds were separated via gas chromatography (GC) and detected by tandem mass spectrometry (MS/MS) utilizing an Agilent 7000D MS instrument. The analysis method was comprehensively validated, and complied with the requirements of the EWFD and Turkish regulation for surface water quality for inland surface water. The method includes various endocrine disruptor compounds listed in the EWFD, such as polychlorinated biphenyls, polycyclic aromatics hydrocarbons, polybrominated diphenyl ethers, phenols, phthalates and pesticides. The method is also applicable for the analysis of similar contaminants that are not on this list. The analyzed pollutants have varying polarities based on octanol-water coefficients and are extracted by SBSE. This method may be preferred for the analysis of pollutants with an octanol-water partition coefficient (log Ko/w) higher than 2. The SBSE method, which is easy, lab-friendly and quick, taking a total of only 2 h for parameter analysis, was optimized to reduce time and chemical usage. The entire extraction and analysis was completed in virtually 3 h. The limits of quantification (LOQs) ranged from 0.12 to 50 ng/L and complied with the requirements for analytical methods to be used in the analysis of the compounds included in the directives. Several quality parameters including linearity, trueness and precision were studied, with good results, and uncertainty was also estimated. Precision (in terms of relative standard deviation [RSD]) was lower than 40%, recoveries ranged from 60 to 120%, and determination coefficients were higher than 0.990 for all analytes. Graphical abstract.
本工作的目的是在非常低的浓度下高度灵敏地测定地表水中的 117 种污染物。分析了来自欧洲水框架指令(EWFD,45 种优先物质)的气相色谱可分析的优先化合物和来自土耳其地表水质量管理条例(TRMSWQ,250 种物质)的物质。在单次气相色谱-串联质谱(GC-MS/MS)进样中,成功检测到 TRMSWQ 清单中近三分之一到一半的化合物。用常规提取方法分析这些水样中的污染物非常困难。因此,一种高效、简单、快速的提取和分析方法非常重要。在这里,采用 Twister 的搅拌棒吸附萃取(SBSE)方法用于从 100 mL 水样中富集分析物。Twister 装置用于热解吸。通过气相色谱(GC)分离化合物,并利用安捷伦 7000D MS 仪器通过串联质谱(MS/MS)进行检测。该分析方法进行了全面验证,符合 EWFD 和土耳其内陆地表水水质法规的要求。该方法包括 EWFD 中列出的各种内分泌干扰物化合物,如多氯联苯、多环芳烃、多溴二苯醚、酚类、邻苯二甲酸酯和农药。该方法也适用于分析不在此列表中的类似污染物。分析的污染物根据辛醇-水系数具有不同的极性,并通过 SBSE 萃取。对于辛醇-水分配系数(log Ko/w)高于 2 的污染物,这种方法可能更具优势。SBSE 方法简单、实验室友好且快速,参数分析总共只需 2 小时,通过优化可减少时间和化学物质的使用。整个萃取和分析在大约 3 小时内完成。定量限(LOQ)范围为 0.12 至 50 ng/L,符合指令中包含的化合物分析方法的要求。研究了包括线性、准确性和精密度在内的多个质量参数,结果良好,并对不确定度进行了评估。所有分析物的精密度(以相对标准偏差 [RSD] 表示)均低于 40%,回收率在 60%至 120%之间,测定系数均高于 0.990。