A Reactive Transport Model for the Distribution and Age of Carbon in Soils and Sediments Through Direct Simulation of the Stable and Radiogenic Isotopologues

Abstract:

We present a reactive transport (RT) approach to link hydrologic transport, geochemical transformations and microbial activity influencing the magnitude and residence time of different carbon pools under variably saturated conditions. This model explicitly simulates the simultaneous transport, transformation, fractionation and decay of the three isotopes of carbon (¹²C, ¹³C and ¹⁴C) through a mechanistic framework. This is demonstrated with a modification of the CrunchTope multi-component RT software to extend the isotope-specific versions of both microbially-mediated and transition state theory (TST) rate laws to accommodate a three-isotope system. In addition both aqueous and solid phase decay of ¹⁴C are tracked, yielding in an implicit means of accounting for the ¹³C/¹²C correction in normalized radiocarbon ages.

The capacity of this approach to quantify the storage and flux of carbon through subsurface compartments is demonstrated using two examples distinguished by timescale. The first considers a simplified flow path in which an influent containing labile organic carbon is distributed by biogenic reduction and mineralization into a suite of reaction products. The residence time of these pools and their characteristic stable isotope ratios are tracked through a variety of transient processes occurring at short timescales (e.g. months). These include a change in fluid flow rate, a limitation of ammonium supporting anabolic growth and an influx of oxygenated fluid. The second example considers the distribution of carbon over the timescale of soil development (e.g., millennia), using a dataset of stable isotope ratios and radiocarbon ages of organic and inorganic carbon present in both dissolved and solid phases from a soil chronosequence near Santa Cruz, CA. The results of these model simulations suggest the promise of this tool for improving our understanding of coupling between hydrologic transport and biogeochemical reactions in soils.