Comment on the studies of oxygen isotope fractionation between calcium carbonates and water at low temperatures by Zhou and Zheng (2003; 2005)

Experimental and theoretical aspects of oxygen isotope fractionation in the system calcite–water at low temperatures were critically examined. Contrary to the claim made by Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta67, 387–399], there is excellent agreement between fractionation factors that were experimentally determined by means of slow, inorganic precipitation of calcite from solutions and those obtained largely from theoretical, statistical–mechanical calculations of the reduced partition function ratios. This agreement strongly suggests that calcite was precipitated from a solution very close to isotopic equilibrium. However, recently Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Miner.90, 1121–1130] presented, without any explanation, conclusions on these major aspects that contradict the previous statements of Zhou and Zheng (2003). The apparent discrepancy in calcite–water oxygen isotope fractionation between experimental and theoretical studies discussed by Zhou and Zheng (2003) originates from the “mineral–water interaction” term in the modified increment method, which was developed by one of the authors (Y.-F. Zheng). We call for evidence for the theoretical nature of the modified increment method, which has never been presented in any of Zheng’s papers. Without such evidence, great caution must be exercised in using fractionation factors derived from the modified increment method.