A sensitive and accurate method is developed for the simultaneous ultra-trace determination of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), methylmercury (MeHg) and inorganic mercury (iHg) in waters including seawater by dynamic headspace in-tube extraction (dHS-ITEX) and GC-ICPMS detection. Quantitation of TBT, DBT, iHg and MeHg was achieved by isotope dilution mass spectrometry using ¹¹⁷Sn-enriched TBT and DBT, ²⁰¹Hg-enriched iHg and enriched Me¹⁹⁸Hg (NRC CRM EMMS-1), respectively, wherein analyte mass fractions in enriched spikes were determined by reverse isotope dilution at the same time using natural abundance TBT, DBT, iHg and MeHg primary standards by exactly matching the analyte and enriched spikes. Quantitation of MBT was realized by standard addition calibration with ¹¹⁷Sn-enriched DBT serving as the internal standard. The proposed method achieved detection limits of 0.06, 0.08 and 1.1 pg g⁻¹ (as Sn) for TBT, DBT and MBT and 0.08 and 0.4 pg g⁻¹ (as Hg) for MeHg and iHg, respectively. Validation of the proposed method was demonstrated by quantitative spike recoveries of 94–105% at 5 to 50 pg g⁻¹ levels achieved in drinking water, river water and seawater, demonstrating the accuracy of the method. The obtained detection limits are sufficiently low to perform measurements in support of the Water Framework Directive. The developed method was applied for the determination of butyltins, iHg and MeHg in drinking water (AQUA-1), river water (SLRS-6) and seawater (CASS-6 and NASS-7) samples. Values of 0.124 ± 0.041 and 0.157 ± 0.060 pg g⁻¹ (1SD, n = 4) for MeHg in CASS-6 and NASS-7 and values of 1.74 ± 0.61, 22.15 ± 0.13, and 31.42 ± 0.30 pg g⁻¹ (1SD, n = 4) for iHg in SLRS-6, CASS-6 and NASS-7 were obtained, respectively. A value of 2.27 ± 0.45 pg g⁻¹ as Sn for MBT was detected in NASS-7 seawater, whereas other butyltins were below the detection limits in the waters.

中文翻译：

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通过动态顶空管内萃取和GC-ICPMS检测以亚ppt方式测定天然水中的丁基锡，甲基汞和无机汞†

建立了一种灵敏而准确的方法，用于通过动态顶空管同时测定水中（包括海水）中的三丁基锡（TBT），二丁基锡（DBT），单丁基锡（MBT），甲基汞（MeHg）和无机汞（iHg）提取（dHS-ITEX）和GC-ICPMS检测。通过使用¹¹⁷锡富集的TBT和DBT，²⁰¹汞富集的iHg和金属富集的^198的同位素稀释质谱法对TBT，DBT，iHg和MeHg进行定量分别使用Hg（NRC CRM EMMS-1），其中使用自然丰度TBT，DBT，iHg和MeHg一级标准品通过精确匹配分析物和富集的尖峰，同时通过反向同位素稀释来测定富集的尖峰中的分析物质量分数。MBT的定量是通过以¹¹⁷ Sn富集DBT作为内标物的标准添加校准实现的。所提出的方法对于TBT，DBT和MBT分别达到0.06、0.08和1.1 pg g ^-1（作为Sn）的检出限，对于MeHg和iHg分别达到0.08和0.4 pg g ^-1（作为Hg）。在5至50 pg g ^-1时定量加标回收率为94–105％，证明了所提出方法的有效性在饮用水，河水和海水中达到的水平表明了该方法的准确性。所获得的检测限足够低，无法执行支持水框架指令的测量。所开发的方法用于测定饮用水（AQUA-1），河水（SLRS-6）和海水（CASS-6和NASS-7）样品中的丁基锡，iHg和MeHg。在CASS-6和NASS-7中MeHg的值分别为0.124±0.041和0.157±0.060 pg g ^-1（1SD，n = 4），以及1.74±0.61、22.15±0.13和31.42±0.30 pg g ^-1（在SLRS-6，CASS-6和NASS-7中分别获得了iHg的1SD，n = 4）。值为2.27±0.45 pg g ^-1 因为在NASS-7海水中检测到MBT的锡，而其他丁基锡则低于海水中的检出限。