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（WO₄ ^2‒）和4种硫代钨酸盐（WO₃S^2‒、WO₂S₂ ^2‒、WOS₃ ^2‒、WS₄ ^2‒）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R ²>0.999），WO₄ ^2‒、WO₃S^2‒、WO₂S₂ ^2‒、WOS₃ ^2‒、WS₄ ^2‒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.

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 (WO₄ ^2‒) and four thiotungstates (including WO₃S^2‒, WO₂S₂ ^2‒, WOS₃ ^2‒ and WS₄ ^2‒). 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 °C 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 R ²>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.