Reactive transport in disordered media: Role of fluctuations in interpretation of laboratory experiments

We review the analysis of the dynamics of reactive transport in disordered media, emphasizing the nature of the chemical reactions and the role of small-scale fluctuations induced by the structure of the porous medium. We are motivated by results and interpretations of laboratory-scale experiments, for which detailed characterization of the system is possible. Modeling approaches based on continuum and particle tracking (PT) schemes are examined critically, highlighting how fluctuations are incorporated. The continuum approach spans a large literature. Traditional formats of reactive transport equations, such as the advection–dispersion–reaction equation (ADRE), are based on a series of assumptions related mainly to scale separation and relative magnitude of time scales involved in the reactive transport setting. These assumptions as well as further developments are assessed in depth. PT methods offer an alternative means of accounting for pore-scale dynamics, wherein space–time transitions are drawn from appropriate probability distributions that have been tested to account for anomalous transport. While PT methods have been employed for many years to describe conservative transport, their application to laboratory-scale reactive transport problems in the context of both Fickian and non-Fickian regimes is relatively recent. We concentrate on experimental observations of different types of reactions in disordered media: (1) the dynamics of a bimolecular reactive transport (A + B → C) in passive (non-reactive) media, and (2) a multi-step chemical reaction, as exemplified in the process of dedolomitization involving both dissolution and precipitation. The fluctuations in a number of the key variables controlling the processes prove to have a dominant role; elucidation of this role forms the basis of the present study and the comparison of methods.