Experimental studies of alunite: I. ¹⁸O-¹⁶O and D-H fractionation factors between alunite and water at 250-450°C

We have determined oxygen and hydrogen isotope fractionation factors between alunite and water over a temperature range of 250-450??C by reacting synthetic natroalunite with 0.7 m K2SO4 -0.1 to 0.65 m H2SO4 solutions to produce K-rich alunite. From 88 to 95% alkali and isotope exchange were observed in most of these experiments, and the partial equilibrium method was used to compute equilibrium fractionation factors. Least-squares fits of the data give 103 In ??alunite(so4)-H2O = 3.09 ( 106 T2 (K)) - 2.94 and 103 In ??alunite(OH)-H2O = 2.28 ( 106 T2 (K)) - 3.90. The intramineral 18O- 16O fractionation factor 103 In ??alunite(so4-OH site) is given by the expression 0.8 ( 106 T2 (K)) + 0.96. The alunite-water D-H fractionation factor ranges from -19 at 450??C to -6 at 250??C and does not appear to be strongly dependent on temperature. Runs with alkali exchange in the opposite direction were used to obtain 18O- 16O and D-H fractionation factors between natroalunite (mol% Na = 70-75) and water at 350-450??C. These indicate that mol% Na has negligible effect on the fractionation factors over this temperature range. Measured 18O-16O and D-H fractionation factors between alunite and 1.0 m KCl -0.5 m H2SO4 fluids also agree within 2?? with the values obtained from the K2SO4-H2SO4 fluids. However, experiments with alunite and distilled water at 400??C gave a value of 103 In ??alunite(SO4)-H2O of 0.0, compared with a value of 3.9 obtained at this temperature with K2SO4- and H2SO4-bearing fluids. This suggests that changes in fluid composition can affect alunite-water 18O-16O fractionation factors. Reconnaissance experiments with fine-grained natural natroalunite demonstrate that alunite-water D-H exchange can occur by hydrogen diffusion, although this process is generally not significant in the experiments with coarser grained synthetic alunites. ?? 1994.