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: Study Region: Bandung groundwater basin, Indonesia. Study focus: Groundwater abstraction of various magnitudes, pumped out from numerous depths in a multitude of layers of aquifers, stimulates different changes in hydraulic head distribution, including ones under vertical cross-sections. This generates groundwater flow in the vertical direction, where groundwater flows within its storage from the shallow to the underlying confined aquifers. In the Bandung groundwater basin, previous studies have identified such processes, but quantitative evaluations have never been conducted, with data scarcity mainly standing as one of the major challenges. In this study, we utilize the collated (1) environmental water tracer data, including major ion elements (Na+/K+, Ca2＋, Mg2+, Cl−, SO42−,HCO3−), stable isotope data (2H and δ18O), and groundwater age determination (14C), in conjunction with (2) groundwater flow modeling to quantify the aquifer interaction, driven mainly by the multi-layer groundwater abstraction in the Bandung groundwater basin, and demonstrate their correspondence. In addition, we also use the model to quantify the impact of multi-layer groundwater abstraction on the spatial distribution of the groundwater level changes. New hydrological insights for the region: In response to the limited calibration data availability, we expand the typical model calibration that makes use of the groundwater level observations, with in-situ measurement and a novel qualitative approach using the collated environmental water tracers (EWT) data for the model evaluation. The analysis in the study area using EWT data and quantitative methods of numerical groundwater flow modeling is found to collaborate with each other. Both methods show agreement in their assessment of (1) the groundwater recharge spatial distribution, (2) the regional groundwater flow direction, (3) the groundwater age estimates, and (4) the identification of aquifer interaction. On average, the downwelling to the deeper aquifer is quantified at 0.110 m/year, which stands out as a significant component compared to other groundwater fluxes in the system. We also determine the unconfined aquifer storage volume decrease, calculated from the change in the groundwater table, resulting in an average declining rate of 51 Mm3/year. This number shows that the upper aquifer storage is dwindling at a rate disproportionate to its groundwater abstraction, hugely influenced by losses to the deeper aquifer. The outflow to the deeper aquifer contributes to 60.3% of the total groundwater storage lost, despite representing only 32.3% of the total groundwater abstraction. This study shows the possibility of quantification of aquifer interaction and groundwater level change dynamics driven by multi-layer groundwater abstraction in a multi-layer hydrogeological setting, even in a data-scarce environment. Applying such methods can assist in deriving basin-scale groundwater policies and management strategies under the changing anthropogenic and climatic factors, thereby ensuring sustainable groundwater management.