Abstract: Numerous groundwater analyses from the crystalline bedrock in the Forsmark area have been performed between 2002 and 2019, together with thorough geological, geophysical, and hydrogeological studies, within the site investigations carried out by the Swedish Nuclear Fuel and Waste Management Company. The groundwater samples have been taken from boreholes down to ≈ 1000 m and the analysis include major- and trace-elements, stable and radiogenic isotopes, gases and microbes. The chemical and isotopic composition of these groundwaters evidences the presence of non-marine brackish to saline groundwaters with very long residence times (many hundreds of thousands of years) and a series of complex mixing events resulting from the recharge of different waters over time: glacial meltwaters, probably from different glaciations of which the latest culminated some 20,000 years ago, and marine waters from the Baltic starting some 7000 years ago. Later, meteoric water and present Baltic Sea water have recharged in different parts of the upper 100 m. These mixing events have also triggered chemical and microbial reactions that have conditioned some of the important groundwater parameters and, together with the structural complexity of the area, they have promoted a heterogeneous distribution of groundwater compositions in the bedrock. Due to these evident differences in chemistry, residence time and origin of the groundwater, several groundwater types were defined in order to facilitate the visualisation and communication. The differentiation (linked to the paleohydrological history of the area) was based on Cl concentration, Cl/Mg ratio (marine component), and δ18O value (glacial component). The work presented in this paper increases the understanding of the groundwater evolution in fractured and compartmentalised aquifers where mixing processes are the most important mechanisms. The model proposed to characterise the present groundwater system of the Forsmark area will also help to predict the future hydrogeochemical behaviour of the groundwater system after the construction of the repositories for the nuclear wastes.

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: Acid in situ leaching (AISL) is a subsurface mining approach suitable for low-grade ores which does not generate tailings, and has been adopted widely in uranium mining. However, this technique causes an extremely high concentration of contaminants at post-mining sites and in the surroundings soon after the mining ceases. As a potential AISL remediation strategy, natural attenuation has not been studied in detail. To address this problem, groundwater collected from 26 wells located within, adjacent, upgradient, and downgradient of a post-mining site were chosen to analyze the fate of U(VI), SO42−, δ34S, and δ238U, to reveal the main mechanisms governing the migration and attenuation of the dominant contaminants and the spatio-temporal evolutions of contaminants in the confined aquifer of the post-mining site. The δ238U values vary from −0.07 ‰ to 0.09 ‰ in the post-mining site and from −1.43 ‰ to 0.03 ‰ around the post-mining site. The δ34S values were found to vary from 3.3 ‰ to 6.2 ‰ in the post-mining site and from 6.0 ‰ to 11.0 ‰ around the post-mining site. Detailed analysis suggests that there are large differences between the range of isotopic composition variation and the range of pollutants concentration distribution, and the estimated Rayleigh isotope fractionation factor is 0.9994–0.9997 for uranium and 1.0032–1.0061 for sulfur. The isotope ratio of uranium and sulfur can be used to deduce the migration history of the contaminants and the irreversibility of the natural attenuation process in the anoxic confined aquifer. Combining the isotopic fractionation data for U and S with the concentrations of uranium and sulfate improved the accuracy of understanding of reducing conditions along the flow path. The study also indicated that as long as the geological conditions are favorable for redox reactions, natural attenuation could be used as a cost-effective remediation scheme.