Determination of Tin in Primary Ores by Inductively Coupled Plasma-Mass Spectrometry with Sodium Peroxide Alkali Fusion
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摘要: 原生锡矿石主要存在的矿床类型有矽卡岩型锡矿、斑岩型锡矿、锡石硅酸盐脉型锡矿、锡石硫化物脉型锡矿、石英脉及云英岩型锡矿。锡矿石一般不溶于盐酸、硝酸及王水体系，采用硫酸、氢氟酸处理时无法全部溶解。苯芴铜分光光度法和碘量法等传统测试方法存在受样品中伴生元素干扰大、稳定性差、检出限高、分析效率低等不足。本文建立了电感耦合等离子体质谱法测定原生矿石中锡元素含量的分析方法，用过氧化钠对样品进行熔融分解处理，热水浸取后用酒石酸-盐酸酸化，采用铑作为内标进行仪器信号漂移校正，同时用高倍稀释的方式来克服基体干扰。方法检出限为0.1μg/g，精密度小于5%，最低检出浓度为0.4μg/g，测试范围为12.5~12700μg/g。本方法操作简便，分析速度和数据质量都优于传统分析方法。
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关键词:
- 锡矿石 /
- 电感耦合等离子体质谱法 /
- 过氧化钠 /
- 酒石酸-盐酸酸化
Abstract:BACKGROUNDThe main types of primary tin ore occur in skarn, porphyry, cassiterite silicate vein, cassiterite sulfide vein, quartz vein and greisen tin deposits. Tin ores are generally insoluble in hydrochloric acid, nitric acid and aqua regia, and tin ores cannot be dissolved completely when treated with sulfuric acid or hydrofluoric acid. Traditional measurement methods such as phenylfluorone-cetyltrimethyl ammonium bromide spectrophotometry and iodometry have disadvantages, such as the serious interference of the associated elements in the sample, poor stability, high detection limit and low analysis efficiency. OBJECTIVESTo establish a method for the determination of tin in primary ore by Inductively Coupled Plasma-Mass Spectrometry. METHODSThe sample was melted and decomposed by sodium oxide, and leached by hot water, followed by tartaric acid and hydrochloric acid acidification. 103Rh was used as the internal standard element to correct instrument signal drift, and the matrix effect was overcome by high-dilution factors. RESULTSThe detection limit of the method was 0.1μg/g for tin, the precision was less than 5%, the minimum detection concentration was 0.4μg/g, and the measurement range was 12.5-12700μg/g. CONCLUSIONSThe method has simple pretreatment and operation. The analysis efficiency and data quality are an improvement over traditional methods. -
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表 1 稀释倍数的影响s
Table 1. Effects of dilution rate
标准物质编号 Sn认定值
(μg/g)Sn测定值(μg/g) 稀释
1000倍稀释
5000倍稀释
8000倍稀释
10000倍稀释
12000倍GBW07103 12.5 11.75 12.07 12.33 12.63 13.16 GBW07184 152 136.8 138.9 141.6 149.9 165 GBW07238 86.7 78.8 80.9 84.3 87.1 90.2 GBW07240 1400 1163 1256 1347 1412 1463 GBW07282 12700 10350 11986 12130 12650 13102 
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表 2 方法精密度
Table 2. Precision tests of the method
标准物质编号 Sn含量(μg/g) RSD
(%)认定值 12次分次测定值 平均值 GBW07103 12.5 13.89 12.36 12.08 12.99
11.92 12.73 13.20 12.84
12.74 11.88 12.65 12.3112.63 4.57 GBW07184 152 141.2 151.0 145.2 151.1
149.8 148.4 151.8 149.9
148.2 155.2 158.3 148.2149.9 2.92 GBW07241 1700 1625 1723 1734 1718
1722 1702 1706 1719
1698 1689 1723 17091706 1.67
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表 3 方法准确度
Table 3. Accuracy tests of the method
标准物质编号 Sn认定值
(μg/g)本方法Sn测定值
(μg/g)本方法的相对误差
(%)其他方法Sn测定值
(μg/g)其他方法的相对误差
(%)GBW07239 33.20 32.39 2.44 31.52 5.06 GBW07238 86.70 88.20 1.73 84.82 2.17 GBW07311 370 366.20 1.03 365.76 1.15 GBW07240 1400 1413 0.93 1382 1.29 GBW07282 12700 12481 1.72 12470 1.81
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