Reactive transport (RT) couples bio-geo-chemical reactions and transport. RT is important to understand numerous scientific questions and solve some engineering problems. RT is highly multidisciplinary, which hinders the development of a body of knowledge shared by RT modelers and developers. The goal of this paper is to review the basic conceptual issues shared by all RT problems, so as to facilitate advancement along the current frontier: biochemical reactions. To this end, we review the basic equations to indicate that chemical systems are controlled by the set of equilibrium reactions, which are easy to model, but whose rate is controlled by mixing. Since mixing is not properly represented by the standard advection-dispersion equation (ADE), we conclude that this equation is poor for RT. This leads us to review alternative transport formulations, and the methods to solve RT problems using both the ADE and alternative equations. Since equilibrium is easy, difficulties arise for kinetic reactions, which is especially true for biochemistry, where numerous challenges are open (how to represent microbial communities, impact of genomics, effect of biofilms on flow and transport, etc.). We conclude with the basic eleven conceptual issues that we consider fundamental for any conceptually sound RT effort.

Heterogeneity of subsurface environments and insufficient site characterization are some of the reasons why decisions about groundwater exploitation and remediation have to be made under uncertainty. A typical decision maker chooses between several alternative remediation strategies by balancing their respective costs with the probability of their success or failure. We conduct a probabilistic risk assessment (PRA) to determine the likelihood of the success of a permeable reactive barrier, one of the leading approaches to groundwater remediation. While PRA is used extensively in many engineering fields, its applications in hydrogeology are scarce. This is because rigorous PRA requires one to quantify structural and parametric uncertainties inherent in predictions of subsurface flow and transport. We demonstrate how PRA can facilitate a comprehensive uncertainty quantification for complex subsurface phenomena by identifying key transport processes contributing to a barrier's failure, each of which is amenable to uncertainty analysis. Probability of failure of a remediation strategy is computed by combining independent and conditional probabilities of failure of each process. Individual probabilities can be evaluated either analytically or numerically or, barring both, can be inferred from expert opinion.

The processes that control water quality improvement during artificial recharge (filtering, degradation, and adsorption) can be enhanced by adding a reactive barrier containing different types of sorption sites and promoting diverse redox states along the flow path, which increases the range of pollutants degraded. While this option looks attractive for renaturazing reclaimed water, three issues have to be analyzed prior to broad scale application: (1) a fair comparison between the system with and without reactive barrier; (2) the role of plants in prevention of clogging and addition of organic carbon; and (3) the removal of pathogens. Here, we describe a pilot installation built to address these issues within a waste water treatment plant that feeds on water reclaimed from the secondary outflow. The installation consists of six systems of recharge basin and aquifer with some variations in the design of the reactive barrier and the heterogeneity of the aquifer. We report preliminary results after one year of operation. We find that (1) the systems are efficient in obtaining a broad range of redox conditions (at least iron and manganese reducing), (2) contaminants of emerging concern are significantly removed (around 80% removal, but very sensitive to the compound), (3) pathogen indicators (E. coli and Enterococci) drop by some 3-5 log units, and (4) the recharge systems maintained infiltration capacity after one year of operation (only the system without plants and the one without reactive barrier displayed some clogging). Overall, the reactive barrier enhances somewhat the performance of the system, but the gain is not dramatic, which suggests that barrier composition needs to be improved.