Abstract: Geological storage of gases will be necessary in the push to net zero and the energy transition to reduce carbon emissions to atmosphere. These include CO2 geological storage in suitable sandstone reservoirs. Understanding groundwater flow, connectivity and hydrogeochemical processes in aquifer and storage systems is vital to prevent risk and protect important water resources, such as the Great Artesian Basin. Here, we provide a ‘tool-box’ of geochemical assessment methods to provide information on flow patterns through the basin’s aquifers (changes in chemistry along flow path), stagnant versus flowing conditions (cosmogenic isotopes and noble gases), inter-aquifer connectivity and seal properties (major ions, Sr and stable isotopes), water quality (major ions and metals) and general assessments on residence times of groundwater (cosmogenic isotopes and noble gases). This information can be used with reservoir and groundwater models to inform on possible changes in the above-mentioned processes and serve as input parameters for CO2 injection impact modelling. We demonstrate the use and interpretation on an example of a potential CO2 storage geological sequestration site in the Surat Basin, part of the Great Artesian Basin, and the aquifers that overly the reservoir. The stable water isotopes are depleted compared to average rainfall and most likely indicate greater contributions from monsoonal rain events from the northern monsoonal troughs, where amount and rainout effects lead to the depletion rather than colder recharge climates. This is supported by the modern recharge temperatures from noble gases. Inter-aquifer mixing between the Precipice Sandstone reservoir and the Hutton Sandstone aquifer seems unlikely as the Sr isotope ratios are distinctly different suggesting that the Evergreen Formation is a seal in the locations sampled. Mixing, however, occurs on the edges of the basin, especially in the south-east and east where the Surat Basin transitions into the Clarence-Moreton Basin. Groundwater flow appears to be to the south in the Precipice Sandstone, with a component of flow east to the Clarence-Morton Basin. The cosmogenic isotopes and noble gases strongly indicate very long residence times of groundwater in the central south Precipice Sandstone around a proposed storage site. 14C values below analytical uncertainty, R36Cl ratios at secular equilibrium as well as high He concentrations and high 40Ar/36Ar ratios support the argument that groundwater flow in this area is extremely slow or groundwater is stagnant. The results of this study reflect the geological and hydrogeological complexities of sedimentary basins and that baseline studies, such as this one, are paramount for management strategies.

Abstract: In the southern San Joaquin Valley (SJV) of California, an agriculturally productive region that relies on groundwater for irrigation and domestic water supply, the infiltration of produced water from oil reservoirs is known to impact groundwater due to percolation from unlined disposal ponds. However, previously documented impacts almost exclusively focus on salinity, while contaminant loadings commonly associated with produced water (e.g., radionuclides) are poorly constrained. For example, the infiltration of bicarbonate-rich produced waters can react with sediment-bound uranium (U), leading to U mobilization and subsequent transport to nearby groundwater. Specifically, produced water infiltration poses a particular concern for SJV groundwater, as valley-fill sediments are well documented to be enriched in geogenic, reduced U. Here, we analyzed monitoring well data from two SJV produced water pond facilities to characterize U mobilization and subsequent groundwater contamination. Groundwater wells installed within 2 km of the facilities contained produced water and elevated levels of uranium. There are \textgreater400 produced water disposal pond facilities in the southern SJV. If our observations occur at even a fraction of these facilities, there is the potential for widespread U contamination in the groundwaters of one of the most productive agricultural regions in the world.

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.

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: 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.