Experimental quantification of the effect of Mg on calcite–aqueous fluid oxygen isotope fractionation

Magnesium calcites were synthesized from aqueous solutions supersaturated with respect to calcite at 25, 40, 60, and 80 °C in gas tight batch reactors for up to 35 days. Any amorphous material still present in the precipitates was removed using a partial dissolution treatment. Resulting purified Mg-calcite had Mg contents ranging from 6 to 32 mol% MgCO3. An isotopic steady-state was attained between the fluid and the precipitated solids within two weeks at 25 °C. δ18O values derived from the experiments at steady-state, depend on both temperature and the Mg content of the calcite in accord with: 1000 ln α Mg-calcite – H 2 O = 18 , 030 / T − 32.42 + 6 × 10 8 / T 3 – 5.47 × 10 6 / T 2 + 16 , 780 / T − 17.21 × C Mg where α Mg-calcite – H 2 O represents the calcite–water oxygen isotope fractionation factor, T refers to the temperature in °K and CMg denotes the mole percent of MgCO3 in the calcite. These results indicate that the addition of 5 mol% MgCO3 into the calcite increases 1000 ln α Mg-calcite – H 2 O by 0.88 as compared to that of pure calcite at 25 °C. This difference could lead to a 4.2 °C decrease in estimated formation temperature estimates. These results demonstrate that the accurate interpretation of oxygen isotope fractionation in magnesium calcites requires explicit provision for the effect of magnesium on oxygen isotope fractionation factors.