Determination of Trace Iodine in Soils, Sediments and Rocks by ICP-MS after Pressurized Acid Digestion-Hydroxylamine Hydrochloride Reduction
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摘要: 碘是活跃元素，价态多，各价态间易相互转化，化学性质不稳定，使用ICP-MS测定土壤、沉积物和岩石样品中的痕量碘，样品前处理和测定结果的稳定性是主要问题。本文采用磷酸-高氯酸高压密闭消解处理样品，提高了样品分解效率，也避免了碘的挥发损失，通过加入0.5mL 20g/L盐酸羟胺溶液将碘还原为I-，提高了碘的稳定性，再于100℃烘箱中保温至少20min，以稀氨水作介质，降低了ICP-MS测定过程中的记忆效应。方法相对标准偏差（RSD）为4.88%~9.19%，相对误差为-6.90%~8.33%，回收率为92.5%~109.6%，检出限（3s）为0.012μg/g。本方法的测定数据与半熔法一致，解决了当前方法存在的分析流程长、空白高、岩石样品提取不完全、提取装置繁多等问题，可以作为土壤、沉积物、岩石中痕量碘测定方法的一种补充，适合批量样品分析。Abstract:
BACKGROUNDIodine is an active element with many valences. It is easy to transform each other between valence states and its chemical properties are unstable. In terms of determination of trace iodine in soil, sediment and rock samples by inductively coupled plasma-mass spectrometry (ICP-MS), sample pretreatment and result stability are the main problems. OBJECTIVESTo obtain stable results, low blank, a short analysis period and complete extraction. METHODSThe sample was digested by phosphoric acid-perchloric acid under high-pressure sealed conditions. The decomposition efficiency of the sample was improved and the volatilization loss of iodine was avoided. The stability of iodine was improved by adding 0.5mL 20g/L hydroxylamine hydrochloride solution to reduce iodine to I-. The iodine was kept in an oven at 10℃ for at least 20 minutes, and the memory effect during ICP-MS analysis was reduced by using dilute ammonia water as the medium. RESULTSThe relative standard deviations of the method were 4.88%-9.19%, the relative errors were -6.90%-8.33%, the recoveries were 92.5%-109.6% and the detection limit (3s) was 0.012μg/g. CONCLUSIONSThe data obtained by this method are in good agreement with those obtained by the semi-melting method. It solves the problems of long analysis process, high blank, incomplete extraction of rock samples and various extraction devices. It can be used as a supplement to the determination of trace iodine in soil, sediment and rock, and is suitable for batch sample analysis. -
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表 1 方法准确度和加标回收率
Table 1. Accuracy and spiked recovery tests of the method
标准物质
编号认定值
(mg/kg)加标前测定值
(mg/kg)加入量
(mg/kg)加标后测定值
(mg/kg)回收率
(%)相对误差
(%)GBW07107
(岩石)0.24±0.06 0.22 0.200 0.41 95.0 8.33 GBW07302a
(沉积物)0.64±0.12 0.65 0.500 1.17 104.4 -3.17 GBW07305a
(沉积物)2.4±0.4 2.4 2.500 5.14 109.6 -6.90 GBW07404
(土壤)9.4±1.1 9.1 5.000 13.8 94.0 1.06 GBW07407
(土壤)19±2 18.2 20.00 36.7 92.5 2.58 
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表 2 半熔法与本法碘测试结果比对
Table 2. Comparison of analytical results of iodine determined by semi-solution method and this study method
样品编号 样品
类型碘(μg/g) 半熔法 本法 HT-1 岩石 0.35 0.38 HT-2 岩石 0.44 0.43 HT-20 岩石 0.38 0.41 HT-21 岩石 0.69 0.68 HT-90 岩石 1.23 1.20 HT-92 岩石 0.54 0.57 HT-150 岩石 1.92 1.89 HT-152 沉积物 3.85 3.77 HT-203 沉积物 15.2 16.4 HT-235 沉积物 14.1 14.1 HT-272 沉积物 6.24 6.33 HT-352 沉积物 5.40 5.40 HT-367 沉积物 8.86 8.78 HT-462 土壤 0.82 0.89 HT-524 土壤 3.27 3.24 HT-685 土壤 7.77 7.65 HT-686 土壤 7.92 8.01 HT-728 土壤 0.88 0.86 HT-791 土壤 11.3 11.7 HT-899 土壤 0.45 0.48 HT-902 土壤 2.73 2.80 HT-1006 土壤 2.45 2.38
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