Laurence Y. Yeung and Justin A. Hayles
Rev. Mineral. Geochem. 86 (2021) 97-137
Are current theoretical methods sufficiently accurate to benchmark oxygen triple-isotope
geochemistry? In this review and synthesis article, we first cover basic concepts and notation relevant to oxygen triple-isotope geochemistry. Second, we examine what theory predicts for oxygen triple-isotope variability in chemical processes. Third, we examine the systematic biases that may be present in theoretical approaches, with special attention paid to first-principles electronic structure calculations. Fourth, we will consider the current limits of analytical accuracy and the complications introduced by physical effects in real systems. Finally, we revisit the triple-isotope mass dependence of carbonate acid digestion as a case study of how theory and experiment can work together to improve both each other and ultimately also our understanding of a process that is vital for the emerging area of carbonate-based paleohydrology.