Determination of Iodine in Geochemical Samples by ICP-MS with Sodium Carbonate-Zinc Oxide Semi-melting
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摘要:
应用电感耦合等离子体质谱法(ICP-MS)测定地球化学调查样品中的碘，主要采用封闭溶样、混合酸溶、碱熔和半熔法进行样品处理，但由于碘在土壤和沉积物中的存在形态较为复杂，有高碘酸根、碘酸根、碘离子，且碘为卤族元素，第一电离能较高，在样品处理及上机测定环节中存在溶出不彻底、记忆效应强、稳定性较差等问题。本文采用碳酸钠-氧化锌半熔法处理样品，乙醇-沸水提取后用732型阳离子交换树脂将溶液中大量阳离子分离，采用内标法ICP-MS测定样品溶液中的碘。通过优化溶样程序提升了样品溶出效果，优化测定介质及内标元素消除记忆效应，提升了结果稳定性，建立了一套完善的ICP-MS测定碘的方法。使用土壤和沉积物国家一级标准物质进行方法验证，方法检出限为0.045μg/g，方法检测下限为0.15μg/g，方法精密度(RSD，n=12)≤5.93%，方法准确度△logC≤0.01，符合地球化学调查样品分析测试要求，可推广应用于地球化学调查中大批量土壤和沉积物样品的分析测试。
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关键词:
- 电感耦合等离子体质谱法 /
- 地球化学样品 /
- 碳酸钠-氧化锌 /
- 阳离子交换树脂 /
- 碘
Abstract:BACKGROUND The determination of iodine in geochemical samples by inductively coupled plasma-mass spectrometry (ICP-MS) is treated mainly by closed sample melting, mixed acid solution, alkali fusion and semi-melting method. However, due to the complex existent morphology of iodine in soil and sediment samples, including periodate, iodate and iodide ions, and the first ionization energy of iodine being high as a halogen group element, there are problems such as incomplete dissolution, strong memory effect and poor precision during sample processing and measurement.
OBJECTIVES To improve the determination of iodine in geochemical samples by ICP-MS.
METHODS The samples were treated by sodium carbonate-zinc oxide semi-melting method, extracted with boiling water-ethanol, and separated by 732 cation exchange resin. Following this, iodine in the solution was determined by ICP-MS using an internal standard method.
RESULTS The optimized detection limit of iodine was 0.045μg/g, the lower limit of detection was 0.15μg/g. The precision (RSD, n=12) and the accuracy (△logC) of the method were ≤5.93% and ≤0.01, respectively, which satisfied the analysis standards of geochemical survey sample.
CONCLUSIONS This method meets the requirements of sample analysis for geochemical investigation, and can be used for the analysis of iodine in large quantities of soil and sediment samples.
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表 1 ICP-MS工作参数
Table 1. Working parameters for ICP-MS instrument
工作参数 数值 工作参数 数值 RF发射功率 1550W 扫描方式 跳峰 冷却气(Ar)流速 13L/min 通道数 3 载气(Ar)流速 0.85L/min 扫描次数 30 采样锥(Ni)孔径 1.0mm 驻留时间 20ms 截取锥(Ni)孔径 0.4mm 质量分辨率 0.6~0.75u 采样深度 100mm 氧化物产率 ＜2.5% 蠕动泵泵速 40r/min 双电荷产率 ＜2% 
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表 2 溶样程序的影响
Table 2. Effect of sample melting program
标准物质编号 碘含量标准值(μg/g) 程序1碘含量测量值(μg/g) 程序2碘含量测量值(μg/g) GBW07407 19±2 17.1 19.2 17.5 19.2 17.4 18.1 17.7 18.3 GBW07305a 2.4±0.4 2.17 2.45 2.27 2.39 2.06 2.38 2.13 2.41 GBW07358 0.47±0.08 0.41 0.48 0.41 0.49 0.39 0.46 0.43 0.45 GBW07451 8.6±0.7 8.13 8.88 8.15 8.83 8.09 8.72 8.09 8.69
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表 3 还原剂实验(标准物质)
Table 3. Effect of reducing agent (reference materials)
标准物质编号 碘含量标准值(μg/g) 加入抗坏血酸碘含量测定值(μg/g) 未加入抗坏血酸碘含量测定值(μg/g) GBW07407 19±2 17.6 19.2 17.4 19.2 18.4 18.8 17.7 19.3 GBW07305a 2.4±0.4 2.27 2.45 2.13 2.39 2.21 2.38 2.06 2.41 GBW07358 0.47±0.08 0.40 0.46 0.41 0.49 0.41 0.47 0.43 0.46 GBW07451 8.6±0.7 8.07 8.88 8.17 8.83 7.94 8.72 7.82 8.69
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表 4 方法精密度和准确度
Table 4. Precision and accuracy tests of the method (n=12)
样品序号 GBW07407 GBW07305a GBW07358 GBW07451 1 18.8 2.36 0.49 8.57 2 19.1 2.41 0.49 8.98 3 18.9 2.37 0.45 8.84 4 19.7 2.33 0.46 8.97 5 19.5 2.45 0.51 8.67 6 18.9 2.52 0.48 8.68 7 19.0 2.38 0.43 8.86 8 19.4 2.38 0.47 9.02 9 19.4 2.46 0.47 9.12 10 19.0 2.34 0.53 8.53 11 20.3 2.51 0.51 9.03 12 18.4 2.48 0.46 8.83 碘含量测定平均值(μg/g) 19.2 2.42 0.48 8.84 碘含量标准值(μg/g) 19 2.4 0.47 8.6 相对标准偏差RSD(%) 2.46 2.73 5.93 2.17 准确度(△logC) 0.005 0.003 0.01 0.01
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表 5 实际样品测试结果比对
Table 5. Comparison of analytical results in actual samples
样品检测编号 样品类型 碘含量测定值(μg/g) 样品检测编号 样品类型 碘含量测定值(μg/g) 本文方法 分光光度法 封闭酸溶法 本文方法 分光光度法 封闭酸溶法 21T002-022 土壤 3.80 3.51 3.75 20C011-031 沉积物 2.67 2.25 2.66 21T002-035 土壤 1.13 1.25 1.13 20C011-086 沉积物 1.85 1.21 1.83 21T002-046 土壤 1.01 0.83 1.06 20C011-121 沉积物 1.63 1.97 1.66 21T002-052 土壤 6.43 6.38 6.51 20C011-154 沉积物 0.72 0.55 0.77 21T002-088 土壤 3.99 3.52 3.89 20C011-182 沉积物 0.51 0.73 0.52 21T002-102 土壤 0.74 0.57 0.78 20C011-243 沉积物 2.28 1.92 2.24 21T002-115 土壤 1.05 0.94 1.01 20C011-244 沉积物 6.19 6.28 6.21 21T002-154 土壤 12.4 12.68 12.3 20C011-280 沉积物 1.20 1.03 1.24 21T002-199 土壤 0.45 0.27 0.49 20C011-311 沉积物 8.33 8.25 8.24 21T002-348 土壤 2.02 2.28 2.01 20C011-315 沉积物 4.47 4.10 4.54 21T002-412 土壤 9.83 10.06 9.76 20C011-343 沉积物 3.55 3.14 3.61 21T002-424 土壤 12.7 13.15 12.6 20C011-380 沉积物 0.84 0.93 0.89
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