Kinetic O effects in the hydrologic cycle: Indirect evidence and implications

The abundances of ¹⁸O and deuterium in the present and past hydrologic cycle have proven to be an important tool in Earth systems science. In contrast, the abundance of ¹⁷O in precipitation has thus far been assumed to carry no additional information to that of ¹⁸O. Here, we demonstrate, using known constraints on oxygen isotope abundances from the O₂ cycle and existing data about the natural abundance of ¹⁷O in water, that the relationship between the discrimination against ¹⁷O and ¹⁸O in water may vary. This relationship, presented here as θ = ln (¹⁷α)/ln (¹⁸α), is found to be 0.511 ± 0.005 for kinetic transport effects and 0.526 ± 0.001 for equilibrium effects, with very low temperature sensitivity. As a result, the ¹⁷Δ of precipitation is controlled primarily by kinetic effects during evaporation of the initial vapor and, in contrast to the deuterium excess, is independent of the temperature at the evaporation (and condensation) site. This makes ¹⁷Δ a unique tracer that complements ¹⁸O and deuterium, and may allow for a decoupling of changes in the temperature of the ocean, that serves as the vapor source, from changes in the relative humidity above it. In addition, the ¹⁷Δ of ice caps is influenced by the kinetic effects in ice formation, and therefore measurement of ice ¹⁷Δ can be used as an additional constraint for better understanding and parameterization of these effects.