Obtaining equilibrium oxygen isotope fractionations from rocks: Theory and examples

A generalized approach for retrieving equilibrium isotope fractionations from natural rocks is proposed in which models of prograde reaction histories and retrograde diffusional exchange are used to identify coexisting minerals with similar isotope closure temperatures. Examples using literature data and new analyses from 32 natural amphibolite-facies schists demonstrate both the feasibility and limitations of obtaining equilibrium oxygen isotope fractionations from minerals in natural rocks. By screening samples according to the theoretical models, natural data are shown to have highly consistent mineral fractionations (±2σ reproducibilities of ±0.16 to 0.54‰) that within uncertainty reproduce experimental determinations among the minerals quartz, biotite, muscovite, and calcic amphibole. This correspondence indicates that the proposed theoretically-based selection criteria improve the likelihood of measuring equilibrium fractionations. The new data further corroborate the expected progressive enrichment of δ¹⁸O in the orthosilicates with increasing Al+Si relative to Fe+ Mg: Δ(Ky-Grt) ∼1.05‰, Δ(St-Grt) ∼0.6‰, and Δ(St-Cld) ∼0.3‰ at 525-575°C. In contrast, typical samples that fail to satisfy screening criteria exhibit fractionations involving quartz, biotite, and amphibole that are strongly disequilibrium because of exchange during cooling. Theoretical screening of samples prior to isotope analysis allows robust, independent assessment of theoretical and experimental determinations of equilibrium isotope fractionations.