Sulfur isotope fractionation factors between sulfate and sulfide at 600 to 1, 000°C were experimentally determined by decomposing anhydrous Na
2SO
3 in melts of NaCl and LiCl-KCl mixture (6 : 4 molar ratio). Sulfur isotope exchange equilibrium was attained between sulfate and sulfide formed by decomposition of sodium sulfite within 120 minutes at 600°C in the LiCl-KCl melt and within 30 minutes at 810°C in the NaCl melt. The observed fractionation factors (α) obey the relationship in the experimental temperature range: 1000 lnα
sulfate-sulfide = 7.4 × 10
6/T
2 − 0.19. In alkali chloride melts, sulfide would exist as HS
-, S
2-, NaHS and NaS
-, and sulfate as SO
42- and NaSO
4-, respectively, in an analogy with aqueous sodium chloride solution. The observed fractionation factors are considered to represent those between bulk sulfate and sulfide ions. The fractionation factor between gaseous H
2S and dissolved sulfate in melt at 600 and 700°C is about 1 and 0.7‰ smaller than those between dissolved sulfide and sulfate in melt, respectively, and may be approximated by the following equation in the experimental temperature range: 1000 lnα
sulfate-H2S = (6.5 ± 0.3) × 10
6/T
2.
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