THE INFLUENCE OF VARIABLE FLUID RESIDENCE TIME DISTRIBUTIONS ON STABLE ISOTOPE FRACTIONATION
We demonstrate this relationship using numerical simulations of δ53Cr fractionation due to abiotic CrO42- reduction by Fe2+, implemented in the reactive transport code CrunchFlow. The chemically homogeneous redox reaction generates Cr3+ with an isotope ratio distinct from the reactant pool, and in turn this product species precipitates as a mineral phase Cr(OH)3(s) through a non-fractionating reaction. The corresponding chromate δ53Cr enrichment across a homogeneous domain varies from a maximum value set by the kinetic fractionation factor (αk) at high mean fluid residence times, to a value <αk as fluid velocity increases, demonstrating a transition from reaction-limited to transport-limited regimes. For physically heterogeneous flow fields, the transition in isotopic fractionation from a reaction-limited to a transport-limited regime becomes variable, and falls between the upper and lower bounds set by the homogeneous simulations at slow and fast precipitation rates, respectively. Our results show that while no variation occurs in the steady-state isotopic profile of the reactant species (δ53Cr of CrO42-), the combined effects of the precipitation rate and the heterogeneous structure of the porous media lead to a wide range in the steady state isotopic composition of the product species (δ53Cr of Cr3+) both in the fluid and mineral phase.