Determination of Tungsten, Molybdenum, Tin, Germanium, Selenium and Tellurium in Lead-Zinc Ore by Inductively Coupled Plasma-Mass Spectrometry with Resin Exchange Separation
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摘要: 铅锌矿常与硫化矿共生形成复合多金属矿床，其中伴生有益元素的含量对矿床的综合利用评估有重要的参考意义。在目前常用方法中，钨钼锡锗硒碲主要采用分组或单独熔矿和测试的方法，操作强度大、分析效率低，且高含量铜、铅和含量高于1 μg/g的硒分别干扰钨钼和碲的测定。本文采用过氧化钠碱熔，提取后加入0.8%柠檬酸溶液络合钨、钼、锡形成金属复合物，以8~9 g阳离子树脂交换分离高含量钠盐和铜、铅、锌、铁等主量元素，采用动能歧视模式以铼、硼为内标用电感耦合等离子体质谱仪同时测定钨钼锡锗硒碲的含量。经树脂处理后，铜铅锌铁的去除率均高于96%，在测定介质中实际浓度为0.192 ng/mL~1.28 μg/mL，基本消除了主量元素的干扰。各待测元素工作曲线相关系数为0.9994~0.9999，优于阳离子树脂处理前的0.9923~0.9992。经标准物质验证，各元素测定相对误差为-8.33%~7.00%，加标回收率为94.9%~107.5%，相对标准偏差（RSD，n=8）小于8%。该方法在样品前处理环节将主量干扰元素从溶液体系中分离，优化了测定介质，实现了铅锌矿中多元素的准确快速测定。
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关键词:
- 铅锌矿 /
- 过氧化钠熔融 /
- 阳离子树脂分离 /
- 电感耦合等离子体质谱法
Abstract:BACKGROUNDLead-zinc ore often co-exists with sulfide ore to form polymetallic deposits. The content of the associated beneficial elements can provide an important reference for the comprehensive utilization evaluation of the mineral deposits. Using current methods, tungsten, molybdenum, tin, germanium, selenium, and tellurium were analyzed by grouping or separate melting and analytical methods with strong operation and low analysis efficiency were employed. Moreover, copper and lead with high content, and selenium with the content higher than 1 μg/g interferes with the determination of tungsten and tellurium, respectively, when using current methods. OBJECTIVESTo establish a method for the determination of tungsten, molybdenum, tin, germanium, selenium, and tellurium in lead-zinc ore by ICP-MS. METHODSThe samples were melted with sodium peroxide. After extraction, 0.8% citric acid solution was added to complex tungsten, molybdenum and tin to form metal complexes. 8-9 g cation resin was used to exchange sodium, copper, lead, zinc, iron and other major elements. The content of tungsten, molybdenum, tin, germanium, selenium and tellurium was determined by ICP-MS using a kinetic discrimination model with rhenium and boron as the internal standard. RESULTSAfter the resin treatment, the removal rate of copper, lead, zinc and iron is higher than 96%, the actual concentrations in the measuring medium are 0.192 ng/mL-1.28 μg/mL, which effectively eliminates the interference of the main elements. The correlation coefficients of the working curve are 0.9994-0.9999, better than 0.9923-0.9992 before cation resin treatment. The method is verified by standard material, the relative errors are -8.33%-7.00%, the standard addition recoveries are 94.9%-107.5%, and the relative standard deviation (RSD, n=8) is less than 8%. CONCLUSIONSThis method can be used effectively to separate the main interference elements from the solution by sample pretreatment, optimizing the measuring medium and determining the accurate and rapid values of multiple elements in lead-zinc ore. -
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表 1 钨钼锡锗硒碲标准工作溶液
Table 1. Standard working solution of tungsten, molybdenum, tin, germanium, selenium and tellurium
混合标准溶液系列 浓度(ng/mL) W Mo Sn Ge Se Te S0 0.0 0.0 0.0 0.0 0.0 0.0 S1 4.0 10.0 4.0 2.0 2.0 1.0 S2 8.0 20.0 8.0 4.0 4.0 2.0 S3 20.0 50.0 20.0 10.0 10.0 5.0 S4 40.0 100.0 40.0 20.0 20.0 10.0 S5 80.0 200.0 80.0 40.0 40.0 20.0 S6 120.0 400.0 120.0 60.0 60.0 30.0 S7 200.0 1000.0 200.0 100.0 100.0 50.0 
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表 2 主量元素去除试验
Table 2. Removal tests of the principal components
标准物质编号 Cu Pb Zn Fe 认定值(%) 实测含量(%) 去除率(%) 认定值(%) 实测含量(%) 去除率(%) 认定值(%) 实测含量(%) 去除率(%) 认定值(%) 实测含量(%) 去除率(%) GBW07170 12.59 1.28×10-3 99.99 2.24 8×10-5 99.99 1.21 8×10-5 99.99 - 8×10-3 - GBW07167 0.028 9.6×10-4 96.57 57.1 8×10-2 99.86 3.3 1.84×10-3 99.94 12 0.16 98.67 BY0110-1 0.135 2.4×10-5 99.98 0.35 3.44×10-3 99.02 42.98 8.24×10-4 99.99 - 7.2×10-3 - 注：“-”表示该元素无定值或其去除率无法计算。
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表 3 内标元素选择试验
Table 3. Selection tests of internal standards
内标元素 对应待测元素 RSD(%) 各类样品中内标元素含量范围 Re W、Mo、Sn、Ge 0.92~2.20 铅锌矿石：0.24~3.5 μg/g
土壤样品：0.074~0.53 ng/gRh W、Mo、Sn、Ge 1.03~3.55 贵金属矿石：0.017~22 ng/g B Se、Te 1.66~2.43 土壤样品：4.6~155 μg/g P Se、Te 3.68~4.94 土壤样品：140~1490 μg/g I Se、Te 3.93~5.81 土壤样品：0.3~2.9 μg/g 注：各元素大致含量范围参考国家一级标准物质定值。
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表 4 同位素、相关系数、质谱干扰扣除及方法检出限
Table 4. Isotope, correlation coefficient, mass spectrum interference deduction and detection limits
元素 同位素 相关系数 干扰校正 方法检出限(μg/g) 树脂处理前 树脂处理后 W 182W 0.9981 0.9995 - 0.50 Mo 95Mo 0.9990 0.9999 - 0.15 Sn 118Sn 0.9954 0.9994 - 0.29 Ge 74Ge 0.9992 0.9997 -0.0407×78Se 0.15 Se 82Se 0.9989 0.9995 -1.0010×83Kr 0.05 Te 128Te 0.9923 0.9995 - 0.03 注：“-”表示元素无干扰或存在的干扰极小，可忽略。
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表 5 准确度和精密度试验
Table 5. Accuracy and precision tests of the method
标准物质编号 元素 参考值(μg/g) 测定值(μg/g) 相对误差(%) 加标量(μg/g) 测定值(μg/g) 回收率(%) RSD(%) GBW07234 W 3.9 3.88 -0.51 5.0 8.69 95.8 4.7 Mo 2.4 2.32 -3.33 2.0 4.51 105.5 2.2 Sn 3.8 4.05 6.58 5.0 8.93 102.6 3.5 Ge 0.93 0.94 1.08 1.0 1.91 98.0 2.7 Se 0.89 0.86 -3.37 1.0 1.84 95.0 6.1 Te 0.13 0.12 -7.69 0.2 0.34 105.0 7.6 GBW07164 W 56 54.5 -2.68 50.0 105.5 99.5 2.2 Mo 137 137.6 0.44 150.0 282.3 98.3 1.5 Sn 9.7 9.2 -5.15 10.0 18.7 94.9 4.6 Ge 3.3 3.1 -6.06 5.0 8.90 107.2 2.6 Se 24 25.1 4.58 30.0 55.3 102.4 1.8 Te 1.8 1.65 -8.33 2.0 3.71 95.0 5.7 GBW07235 W 17.6 18.35 4.26 20.0 38.22 103.1 3.2 Mo 1.6 1.65 3.12 2.0 3.63 101.5 4.8 Sn 3.0 3.21 7.00 5.0 7.97 99.4 5.6 Ge 0.90 0.88 -2.22 1.0 1.91 101.0 3.1 Se 1.7 1.66 -2.35 2.0 3.85 107.5 5.3 Te 3.9 4.09 4.87 5.0 8.88 99.6 2.2
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