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Gómez, P., Garralón, A., Buil, B., Turrero, M. J., Sánchez, L., & Cruz, B. de la. (2006). Modeling of geochemical processes related to uranium mobilization in the groundwater of a uranium mine. Science of The Total Environment, 366(1), 295–309.
Abstract: This paper describes the processes leading to uranium distribution in the groundwater of five boreholes near a restored uranium mine (dug in granite), and the environmental impact of restoration work in the discharge area. The groundwater uranium content varied from \textless1 μg/L in reduced water far from the area of influence of the uranium ore-containing dyke, to 104 μg/L in a borehole hydraulically connected to the mine. These values, however, fail to reflect a chemical equilibrium between the water and the pure mineral phases. A model for the mobilization of uranium in this groundwater is therefore proposed. This involves the percolation of oxidized waters through the fractured granite, leading to the oxidation of pyrite and arsenopyrite and the precipitation of iron oxyhydroxides. This in turn leads to the dissolution of the primary pitchblende and, subsequently, the release of U(VI) species to the groundwater. These U(VI) species are retained by iron hydroxides. Secondary uranium species are eventually formed as reducing conditions are re-established due to water–rock interactions.
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Holmes, M., Campbell, E. E., Wit, M. de, & Taylor, J. C. (2023). Can diatoms be used as a biomonitoring tool for surface and groundwater?: Towards a baseline for Karoo water. South African Journal of Botany, 161, 211–221.
Abstract: The environmental risks from shale gas extraction through the unconventional method of ‘fracking’ are considerable and impact on water supplies below and above ground. Since 2010 the recovery of natural shale gas through fracking has been proposed in parts of the fragile semi-arid ecosystems that make up the Karoo biome in South Africa. These unique ecosystems are heavily reliant on underground water, intermittent and ephemeral springs, which are at great risk of contamination by fracking processes. Diatoms are present in all water bodies and reflect aspects of the environment in which they are located. As the possibility of fracking has not been removed, the aim of the project was to determine if diatoms could be used for rapid biomonitoring of underground and surface waters in the Karoo. Over a period of 24 months, water samples and diatom species were collected simultaneously from 65 sites. A total of 388 diatom taxa were identified from 290 samples with seasonal and substrate variation affecting species composition but not the environmental information. Species diversity information, on the other hand, often varied significantly between substrates within a single sample. Analysis using CCA established that the diatom composition was affected by lithium, oxidized nitrogen, electrical conductivity, and sulphate levels in the sampled water. We conclude that changes in diatom community composition in the Karoo do reflect the water chemistry and could be useful as bioindicators.
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Moreau, M., & Daughney, C. (2021). Defining natural baselines for rates of change in New Zealand’s groundwater quality: Dealing with incomplete or disparate datasets, accounting for impacted sites, and merging into state of the-environment reporting. Science of The Total Environment, 755, 143292.
Abstract: To effectively manage sustainably groundwater bodies, it is essential to establish what the naturally occurring ranges of chemical concentrations in groundwaters are and how they change over time. We defined baseline trends for New Zealand groundwaters using: 1) pattern recognition techniques to deal with inconsistent monitoring suites between the national (110 sites) and the denser regional network (\textgreater1000 sites), and 2) multivariate statistics to identify and remove impacted sites from the enhanced dataset. Rates of changes were calculated for 13 parameters between January 2005 and December 2014 at more than 1000 groundwater quality monitoring sites. The resulting dataset included 262 complete cases (CC), which was enhanced using Machine-Learning (ML) techniques to a total of 607 sites. Hierarchical cluster analysis was used to identify trend clusters that were consistent between the CC, ML-enhanced datasets and a 2006 study based on solely on the national network. The largest cluster (WR) consisted of low magnitude changes across all parameters and was attributed to water-rock interaction processes. The second largest cluster (I) exhibited fast changes particularly for parameters linked to human-induced impact. The third largest cluster (D) comprised decreases of all parameters and was associated with dilution processes. Trend clusters were further refined using groundwater quality state information, enabling the identification of impacted sites outside of Cluster I in the ML-enhanced and CC datasets. Corresponding trend baselines were subsequently derived at unimpacted sites using univariate quantile distribution (5th and 95th percentile thresholds). Finally, we developed classifications combining baselines (state and trend) and natural variability to enhance state of the environment reporting. This allowed the new identification of deteriorating trends at sites where groundwater quality state is not yet affected in addition to trend reversals. These classifications can be adapted to incorporate new knowledge or align with surface water quality reporting.
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Hofmann, H., Pearce, J. K., Hayes, P., Golding, S. D., Hall, N., Baublys, K. A., et al. (2023). Multi-tracer approach to constrain groundwater flow and geochemical baseline assessments for CO2 sequestration in deep sedimentary basins. International Journal of Coal Geology, , 104438.
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.
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Edmunds, W. M., Shand, P., Hart, P., & Ward, R. S. (2003). The natural (baseline) quality of groundwater: a UK pilot study. Science of The Total Environment, 310(1), 25–35.
Abstract: Knowledge of the natural baseline quality of groundwaters is an essential prerequisite for understanding pollution and for imposing regulatory limits. The natural baseline of groundwaters may show a range of concentrations depending on aquifer mineralogy, facies changes, flow paths and residence time. The geochemical controls on natural concentrations are discussed and an approach to defining baseline concentrations using geochemical and statistical tools is proposed. The approach is illustrated using a flowline from the Chalk aquifer in Berkshire, UK where aerobic and anaerobic sections of the aquifer are separately considered. The baseline concentrations for some elements are close to atmospheric values whereas others evolve through time-dependent water–rock interaction. Certain solutes (K, NH4+), often considered contaminants, reach naturally high concentrations due to geochemical controls; transition metal concentrations are generally low, although their concentrations may be modified by redox controls. It is recommended that the baseline approach be incorporated into future management strategies, notably monitoring.
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