When laboratory-measured chemical reaction rates are used in simulations at the field-scale, the models typically overpredict the apparent reaction rates. The discrepancy is primarily due to poorer mixing of chemically distinct waters at the larger scale. As a result, realistic field-scale predictions require accurate simulation of the degree of mixing between fluids. The Lagrangian particle-tracking (PT) method is a now-standard way to simulate the transport of conservative or sorbing solutes. The method's main advantage is the absence of numerical dispersion (and its artificial mixing) when simulating advection. New algorithms allow particles of different species to interact in nonlinear (e.g., bimolecular) reactions. Therefore, the PT methods hold a promise of more accurate field-scale simulation of reactive transport because they eliminate the masking effects of spurious mixing due to advection errors inherent in grid-based methods. A hypothetical field-scale reaction scenario

Unsaturated porous media, where liquid and gas phases coexist, play a central role in a broad range of environmental and industrial applications, including contaminant transport (Lahav et al., 2010;Sebilo et al., 2013), artificial groundwater recharge (Bouwer, 2002), underground gas storage (Panfilov, 2010), radioactive waste disposal (Winograd, 1981), and energy storage (Barbier, 2002), among others. Previous studies have shown that under saturated conditions, that is, for single-phase flow, structural heterogeneity in the solid phase is sufficient to induce anomalous transport (de

Kinetic Monte Carlo methods such as the Gillespie algorithm model chemical reactions as random walks in particle number space. The interreaction times are exponentially distributed under the assumption that the system is well mixed. We introduce an arbitrary interreaction time distribution, which may account for the impact of incomplete mixing on chemical reactions, and in general stochastic reaction delay, which may represent the impact of extrinsic noise. This process defines an inhomogeneous continuous time random walk in particle number space, from which we derive a generalized chemical master equation. This leads naturally to a generalization of the Gillespie algorithm. Based on this formalism, we determine the modified chemical rate laws for different interreaction time distributions. This framework traces Michaelis-Menten-type kinetics back to finite-mean delay times, and predicts time-nonlocal macroscopic reaction kinetics as a consequence of broadly distributed delays. Non-Markovian kinetics exhibit weak ergodicity breaking and show key features of reactions under local nonequilibrium.

Abstract