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采用光化学蒸气发生电容耦合等离子体微炬光学发射光谱法测定海产品中的甲基汞。

Methylmercury determination in seafood by photochemical vapor generation capacitively coupled plasma microtorch optical emission spectrometry.

机构信息

Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, Arany Janos 11, 400028 Cluj-Napoca, Romania.

National Institute for Research and Development of Optoelectronics Bucharest, Research Institute for Analytical Instrumentation, Donath 67, 400293 Cluj-Napoca, Romania.

出版信息

Talanta. 2017 Aug 1;170:464-472. doi: 10.1016/j.talanta.2017.04.036. Epub 2017 Apr 17.

Abstract

A non-chromatographic method based on double liquid-liquid extraction and measurements by UV photochemical vapor generation capacitively coupled plasma microtorch optical emission spectrometry was developed and characterized for methylmercury determination in seafood. Samples were prepared following the procedure recommended in JRC Technical Report of European Commission formerly proposed for the determination of methylmercury in seafood by thermal decomposition atomic absorption spectrometry, namely confinement of Hg species in 47% HBr solution, extraction of CHHg in toluene and back-extraction in 1% l-cysteine aqueous solution. Mercury cold vapor was generated by flow injection UV photo-reduction from CHHg in 0.6molL HCOOH, while quantification was performed against external Hg aqueous standards and measuring Hg 253.652nm emission using a low power/Ar consumption plasma microtorch (15W, 100mLmin) and a low resolution microspectrometer (Ocean Optics). The figures of merit and analytical capability were assessed by analyzing certified reference materials and test samples of fish fillet and discussed in relation with requirements for Hg determination in seafood in European legislation (Decisions 2007/333/EC and 2002/657/EC) as well as compared to performances achieved in thermal decomposition atomic absorption spectrometry. The limit of detection and quantification of 2µgkg and 6µgkg respectively, precision of 2.7-9.4% and accuracy of 99±8% of the proposed method for the determination of CHHg fulfill the demands of European legislation for Hg quantification. The limit of detection and quantification were better than those in the used reference method or other non-/chromatographic methods taken for comparison. The analysis of certified reference materials and the Bland and Altman test performed on 12 test samples confirmed trueness of the proposed method and its reliability for the determination of traces of CHHg with 95% confidence level. The proposed method fulfills several demands of the eco-scale concept, is sensitive, simple and safe related to sample preparation through elimination of classical, harmful reductants and attractive by using economical miniaturized instrumentation incorporating a low power and low Ar consumption plasma.

摘要

建立并表征了一种非色谱法,基于双液-液萃取和紫外光化学蒸气发生电容耦合等离子体微炬原子发射光谱法测量,用于海产品中甲基汞的测定。样品按照 JRC 技术报告中推荐的程序进行制备,该程序最初是为了通过热分解原子吸收光谱法测定海产品中的甲基汞而提出的,即 47%氢溴酸溶液中 Hg 物种的封闭、甲苯中 CHHg 的萃取和 1%巯基丙氨酸水溶液中的反萃取。Hg 冷蒸气通过 CHHg 在 0.6mol/L 甲酸中的流动注射紫外光还原生成,同时通过外部 Hg 水溶液标准品进行定量,并使用低功率/低氩气消耗等离子体微炬(15W,100mL/min)和低分辨率微光谱仪(Ocean Optics)测量 Hg 253.652nm 发射。通过分析认证参考物质和鱼片测试样品,评估了该方法的优点和分析能力,并与欧洲法规(2007/333/EC 和 2002/657/EC 号决定)中对海产品中 Hg 测定的要求进行了讨论,并与热分解原子吸收光谱法的性能进行了比较。对于 CHHg 的测定,该方法的检出限和定量限分别为 2μg/kg 和 6μg/kg,精密度为 2.7-9.4%,准确度为 99±8%,满足欧洲法规对 Hg 定量的要求。检出限和定量限优于所使用的参考方法或其他非色谱/色谱方法。对认证参考物质的分析和对 12 个测试样品进行的 Bland 和 Altman 检验证实了该方法的准确性和可靠性,可在 95%置信水平下测定痕量的 CHHg。该方法满足生态标度概念的几个要求,通过消除经典的有害还原剂,与样品制备相关,具有较高的灵敏度、简单性和安全性,并且使用经济的小型化仪器,结合低功率和低氩气消耗等离子体,具有吸引力。

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