Determination of Bromine and Iodine in Rock, Soil, and Sediments by Inductively Coupled Plasma-Mass Spectrometry Using Pyrohydrolysis with Liquid Nitrogen Trap
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摘要: 分析地质样品中的溴碘，目前常用的提取方法有半熔法、稀氨水密封溶样法和热解法，但由于元素含量低、易损失，样品分解和溴碘的提取过程是主要的误差来源。本文改进了传统热解法的吸收装置，用液氮冷凝吸收代替常规的碱溶液吸收，提取地质样品中的溴碘，用电感耦合等离子体质谱法测定其含量。以标准偏差的10倍计算，稀释倍数为50，溴碘的检出限分别为0.06 μg/g、0.01 μg/g，低于传统热解法和半熔法，略高于稀氨水密封溶样法；精密度（RSD）为6.4%～21.0%。本方法相对于传统的碱溶液吸收热解法，减少了碱试剂的引入，降低了基体空白和稀释倍数，提高了精密度，操作较半熔法简便，可作为稀氨水密封溶样法的一种补充方法。因此，对于土壤和水系沉积物，宜采用稀氨水密封溶样法；对于岩石以及采用稀氨水密封溶样法难以完全提取的样品，可采用本方法。Abstract: The available extraction methods for the determination of Br and I in geological samples, include semifusion, aqua ammoniae closed digestion and pyrohydrolysis. The sample digestion and extraction of Br and I are the major error sources, due to the low content and volatization of Br and I. A pyrohydrolysis method with liquid nitrogen trap has been developed and used to extract Br and I in geological samples using liquid nitrogen condensation absorption replacing alkaline solution absorption. Br and I are measured by Inductively Coupled Plasma-Mass Spectrometry. The detection limits of Br and I are 0.06 μg/g and 0.01 μg/g, respectively, calculated as 10 times standard deviation using dilution times of 50. These detection limits are lower than those of traditional pyrohydrolysis and semifusion methods and slightly higher than those of aqua ammoniae closed digestion method. The precision is 6.4%-21.0% RSD. The proposed method reduces the use of alkaline solution, lowers the blank and dilution times, and improves the precision. This method is much simpler than the semifusion method and can serve as a complementary method for aqua ammoniae closed digestion method. For soils and stream sediments, aqua ammoniae closed digestion method is preferred. For rocks and samples that cannot be completely digested by aqua ammoniae closed digestion method, the proposed method may be more suitable.
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表 1 岩石、土壤和水系沉积物标准物质中的Br和I含量分析结果
Table 1. Analytical results of bromine and iodine in standard reference materials
标准物质编号 Br含量 I含量 标准值(μg/g) 本法测定值(μg/g) RSD(%) 标准值(μg/g) 本法测定值(μg/g) RSD(%) GBW07107(岩石) - - - 0.24±0.06 0.22±0.02 7.2 GBW07109(岩石) 1.21±0.39 1.02±0.13 12.0 0.14±0.04 0.16±0.02 13.0 GBW07114(岩石) 0.84±0.15 0.93±0.20 21.0 0.23±0.04 0.26±0.04 17.0 GBW07407(土壤) 5.1±0.5 5.1±0.8 17.0 19±2 18±2 11.0 GBW07451(土壤) 24±2 25±3 10.0 8.6±0.7 8.4±0.6 7.5 GBW07452(土壤) 26±3 24±4 15.0 6.1±0.7 5.6±0.5 9.7 GBW07302(水系沉积物) 3.0±0.6 2.96±0.4 13.5 2.9±0.4 3.1±0.4 12.9 GBW07360(水系沉积物) 3.7±0.5 3.2±0.3 9.6 2.0±0.2 1.9±0.1 6.4 注：GBW07107没有Br含量的标准定值，且测定的不确定度较大。 
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