Equilibrium Oxygen, Hydrogen and Carbon Isotope Fractionation Factors Applicable to Geologic Systems

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Abstract
As demonstrated by the chapters in this short course, stable isotope techniques are an important tool in almost every branch of the earth sciences. Central to many of these applications is a quantitative understanding of equilibrium isotope partitioning between substances. Indeed, it was Harold Urey’s (1947) thermodynamically based estimate of the temperature-dependence of 18O/16O fractionation between calcium carbonate and water, and a recognition of how this information might be used to determine the temperatures of ancient oceans, that launched the science of stable isotope geochemistry. The approach pioneered by Urey has since been used to estimate temperatures for a wide range of geological processes (e.g. Emiliani 1955; Anderson et al. 1971; Clayton 1986; Valley, this volume). In addition to their geothermometric applications, equilibrium fractionation data are also important in the study of fluid-rock interactions, including those associated with diagenetic, hydrothermal, and metamorphic processes (Baumgartner and Valley, this volume; Shanks, this volume). Finally, a knowledge of equilibrium fractionation is a necessary first step in evaluating isotopic disequilibrium, a widespread phenomenon that is increasingly being used to study temporal relationships in geological systems (Cole and Chakraborty, this volume). In the fifty-four years since the publication of Urey’s paper, equilibrium fractionation data have been reported for many minerals and fluids of geological interest. These data were derived from: (1) theoretical calculations following the methods developed by Urey (1947) and Bigeleisen and Mayer (1947); (2) direct laboratory experiments; (3) semi-empirical bond-strength models; and (4) measurement of fractionations in natural samples. Each of these methods has its advantages and disadvantages. However, the availability of a variety of methods for calibrating fractionation factors has led to a plethora of calibrations, not all of which are in agreement. In this chapter, we evaluate the major methods for determining fractionation factors. …