Abstract: Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.

Abstract: Groundwater resources in the crystalline basement complex of India are crucial for supplying drinking water in both rural and urban settings. Groundwater depletion is recognised as a challenge across parts of India due to over-abstraction, but groundwater quality constraints are perhaps even more widespread and often overlooked at the local scale. Uranium contamination in basement aquifers has been reported in many parts of India, locally exceeding WHO drinking water guideline values of 30 μg/L and posing a potential health risk. In this study 130 water samples were collected across three crystalline basement catchments to assess hydrochemical, geological and anthropogenic controls on uranium mobility and occurrence in drinking water sources. Groundwaters with uranium concentrations exceeding 30 μg/L were found in all three study catchments (30% of samples overall), with concentrations up to 589 μg/L detected. There appears to be a geological control on the occurrence of uranium in groundwater with the granitic gneiss of the Halli and Bengaluru study areas having higher mean uranium concentrations (51 and 68 μg/L respectively) compared to the sheared gneiss of the Berambadi catchment (6.4 μg/L). Uranium – nitrate relationships indicate that fertiliser sources are not a major control on uranium occurrence in these case studies which include two catchments with a long legacy of intense agricultural land use. Geochemical modelling confirmed uranium speciation was dominated by uranyl carbonate species, particularly ternary complexes with calcium, consistent with uranium mobility being affected by redox controls and the presence of carbonates. Urban leakage in Bengaluru led to low pH and low bicarbonate groundwater hydrochemistry, reducing uranium mobility and altering uranium speciation. Since the majority of inhabitants in Karnataka depend on groundwater abstraction from basement aquifers for drinking water and domestic use, exposure to elevated uranium is a public health concern. Improved monitoring, understanding and treatment of high uranium drinking water sources in this region is essential to safeguard public health.

Abstract: Reactive transport modeling is known to be computationally intensive when applied to 3D problems. Transforming sequential computing on the computer processor units (CPU) into parallelized computation on the high-performance parallel graphic processor units (GPU) is a classical approach to increasing computational performance. Another complementary approach is to decompose a complex 3D modeling problem into a set of simpler 1D problems using streamline approaches which can be easily parallelized, therefore reducing computation time. This paper investigates solutions to the equations governing dissolution and transport using streamlines coupled with a parallelization approach. In addition, an analytical solution to the dissolution and transfer equations of uranium describing the In-Situ Leaching (ISL) mining recovery is found using an approximation series to the 2nd order. The analytical solution is compared to the 1D numerical resolution along the streamlines and to the 3D simulation results superimposed on the streamline. Both approaches give similar results with a relative error of \textless2 % (2%). The proposed methodology is then applied to a case study in which the classical 3D resolution is compared to the newly suggested streamline solution, demonstrating that the streamline approach increases computational performances by a factor ranging from hundred to thousand depending on the complexity of the grid-block model.