An Analysis Method of Thiotungstates in Natural Water
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摘要: 天然水中硫代钨酸盐的分析对钨的环境地球化学研究具有重要意义. 建立了利用反相离子对色谱‒电感耦合等离子质谱同时测定天然水中钨酸盐（WO42‒）和4种硫代钨酸盐（WO3S2‒、WO2S22‒、WOS32‒、WS42‒）的方法，并采用电喷雾‒高分辨质谱对这5种钨化合物进行鉴定. 采集富硫化物地热水样品经干冰速冻并在-20 ℃冷冻保存运输至实验室后，在厌氧环境下解冻后，利用优化的色谱及质谱条件在30 min内完成5种钨化合物的分离和测定. 以钨酸盐作为其他钨化合物的标准建立工作曲线，在0.001~20 mg/L浓度范围内具有良好线性关系（相关系数R2 > 0.999），WO42‒、WO3S2‒、WO2S22‒、WOS32‒、WS42‒检出限分别为0.82、0.34、0.22、0.79和0.62 µg/L. 本方法具有灵敏度高、重现性好等优点，为天然水中硫代钨酸盐的检测和研究提供了一种有效途径.
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关键词:
- 硫代钨酸盐 /
- 天然水 /
- 反相离子对色谱-电感耦合等离子质谱 /
- 同时检测 /
- 分析化学
Abstract: Analysis of thiotungstates in natural water is of great importance for systematically investigating the environmental geochemistry of tungsten. In this paper, a method based on a system combining reversed-phase ion pair chromatography and inductively coupled plasma mass spectrometry is proposed to simultaneously determine the concentrations of tungstate (WO42‒) and four thiotungstates (including WO3S2‒, WO2S22‒, WOS32‒ and WS42‒). The speciation analyses of these five tungsten compounds were performed by a high-resolution electrospray ionization mass spectrometer. Sulfide-rich geothermal water samples were snap frozen at -20 ℃ and transported to the laboratory. After thawing under anaerobic conditions, the five tungsten compounds were separated and determined within 30 min using optimized chromatographic and mass spectrometric conditions. The working curves were established using tungstate as the standards for the other tungsten compounds, with good linear relation (correlation coefficient R2 > 0.999) in the concentration range of 0.001-20 mg/L. The limits of detection (LOD) for tungstate, monothiotungstate, dithiotungstate, trithiotungstate and tetrathiotungstate were 0.82 µg/L, 0.34 µg/L, 0.22 µg/L, 0.79 µg/L and 0.62 µg/L, respectively. This method has the advantages of high sensitivity and good reproducibility, and provides an effective way for the detection and research of thiotungstates in natural water. -
图 1 负离子模式下钨酸盐‒硫化物混合溶液质谱图
Fig. 1. Mass spectrum of a tungstate-sulfide mixed solution obtained using a high-resolution electrospray ionization mass spectrometer (ESI-HRMS) in negative mode
图 2 实验室配制钨相关溶液的RP-IPC-ICP-MS图
a、b. 100 µM Na2WO4与4 mM Na2S混合溶液，盐酸调pH=5，其中定量环分别为500 µL（图a）、200 µL（图b）；c. 100 µM Na2WO4溶液，定量环=200 µL；d. 100 µM（NH4）2WS4溶液，定量环=200 µL. “0”代表钨酸盐，“1~4”代表一至四硫代钨酸盐
Fig. 2. RP-IPC-ICP-MS chromatograms of the tungsten-bearing solutions prepared in the laboratory
图 3 硫代钨形态测试标准曲线
a. 测试实验室配制溶液时钨标液浓度梯度为1、5、10、20 mg/L，定量环=200 µL；b. 测试天然水样品时钨标液浓度梯度为1、5、10、20、50、100、300 µg/L，定量环=500 µL
Fig. 3. Calibration curves for quantitative analysis of thiotungstates
图 4 天然水样品硫代钨酸盐的RP-IPC-ICP-MS图
Fig. 4. RP-IPC-ICP-MS chromatograms of thiotungstates in natural water samples
图 5 天然水样LL10解冻后置于空气中硫代钨形态随时间变化的RP-IPC-ICP-MS图
Fig. 5. RP-IPC-ICP-MS chromatograms reflecting the thiotungstates speciation change with time in a natural water sample (LL10) which was stored at room temperature and under oxic condition after thawing
表 1 反相色谱法常用溶剂的强度因子
Table 1. Intensity factors of common solvents used in reversed-phase chromatography
试剂 水 甲醇 乙腈 乙醇 异丙醇 溶剂强度因子 0.0 3.0 3.2 3.6 4.2 
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表 2 RP⁃IPC⁃ICP⁃MS联用法测试实验室配制硫代钨溶液色谱峰结果
Table 2. Analytical RP-IPC-ICP-MS results of the thiotungstates solutions prepared in the laboratory
峰 钨形态 化学式a 保留时间（s） 结果 0 钨酸盐 HnWO42‒n 620 单峰(200 µL)/驼峰(500 µL) 1 一硫代钨酸盐 HnWO3S2‒n 790 单峰 2 二硫代钨酸盐 HnWO2S22‒n 1 045 单峰 3 三硫代钨酸盐 HnWOS32‒n 1 335 单峰 4 四硫代钨酸盐 HnWS42‒n 1 545 单峰 注：a.实际水溶液中受pH值的影响存在多种质子化形式(n=0~2), 为方便文中均写为脱质子形式即n=0.
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表 3 实验室配制溶液硫代钨测试结果
Table 3. Quantitative analysis of thiotungstates in the solutions prepared in the laboratory
表 4 热泉样品的硫代钨和相关水化学指标分析结果
Table 4. Analysis results of thiotungstates and relevant hydrogeochemical parameters in representative hot spring samples
泉名 地热区 T
(℃)pH Eh
(mV)硫化物
(mg/L)WO42‒
(µg/L)WO3S2‒
(µg/L)WO2S22‒
(µg/L)WOS32‒
(µg/L)WS42‒
(µg/L)钨形态之和
(µg/L)总钨
(µg/L)回收率
(%)WGQ 热海 41 5.52 -41 1.4 2.4
(RSD=
4.46%)0
(RSD=
2.57%)0
(RSD=
0.81%)0
(RSD=
1.22%)0
(RSD=
4.41%)2.4 2.2 109.09 LL10 邦腊掌 91 8.36 -306 8.0 15.0
(RSD=
4.20%)7.7
(RSD=
2.35)13.2
(RSD=
2.13%)175.7
(RSD=
3.54%)62.5
(RSD=
3.79%)274.2 267.8 102.35
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表 5 天然水样LL10解冻后置于空气中硫代钨形态相对含量结果
Table 5. Change of relative contents of various thiotungstates in a natural water sample (LL10) which was stored at room temperature and under oxic condition after thawing
接触空气时间 WO42‒
(%)WO3S2‒
(%)WO2S22‒
(%)WOS32‒
(%)WS42‒
(%)< 5 min 5 3 5 64 23 2 h 8 5 6 57 23 24 h 22 2 9 47 20 2 d 36 2 10 34 18 5 d 57 2 8 20 13
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