Anion-Exchange Chromatographic Separation of Hg for Isotope Ratio Measurements by Multicollector ICPMS

A procedure is described for precise Hg isotope ratio measurements by solution nebulization multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Hg was released from geological samples using aqua regia extraction and then separated from other matrix elements with the aid of anion-exchange chromatography using strongly basic Dowex 1-X8 anion-exchange resin. Performance of the chromatographic procedure was evaluated using various types of replacement anions for elution of mercury, including l-cysteine, thiourea, NO3 -, and SO4 2-. A solution of 0.15% l-cysteine in 0.06 M HCl was found to be the most convenient eluent for subsequent MC-ICPMS measurements. The optimized procedure provides separation of Hg from virtually all concomitant matrix elements while maintaining quantitative (>95%) recovery. In addition, band displacement chromatographic experiments were conducted to assess whether the anion-exchange purification can produce Hg isotope fractionation artifacts. No isotope fractionation between the Hg(II)−l-cysteine complex in aqueous solution and Hg ions in the anion-exchange resin was observed. Hg isotope ratio measurements were performed using the bracketing standards approach and on-line correction for instrumental mass discrimination using Tl spiking and normalization to the 205Tl/203Tl ratio. The absence of spectral interference during Hg isotope ratio measurements was verified using a three-isotope plot. Uncertainties of Hg isotope ratio measurements for replication of the entire procedure, expressed as two standard deviations, are better than ±0.08‰/amu. The described procedure facilitates study of variations in the isotopic composition of Hg in nature.