Abstract: The quantification of groundwater resources is essential especially in water scarce countries like Namibia. The chloride mass balance (CMB) method and isotopic composition were used in determining groundwater recharge along a precipitation gradient at three sites, namely: Tsumeb (600 mm/a precipitation); Waterberg (450 mm/a precipitation) and Kuzikus/Ebenhaezer (240 mm/a precipitation). Groundwater and rainwater were collected from year 2016–2017. Rainwater was collected monthly while groundwater was collected before, during and after rainy seasons. Rainwater isotopic values for δ18O and δ2H range from −10.70 to 6.10‰ and from −72.7 to 42.1‰ respectively. Groundwater isotopic values for δ18O range from −9.84 to −5.35‰ for Tsumeb; from −10.85 to −8.60‰ for Waterberg and from −8.24 to −1.56‰ for Kuzikus/Ebenhaezer, while that for δ2H range from −65.6 to −46.7‰ for Tsumeb; −69.4 to −61.2‰ for Waterberg and −54.2 to −22.7‰ for Kuzikus/Ebenhaezer. Rainwater scatters along the GMWL. Rainwater collected in January, February and March are more depleted in heavy isotopes than those in November, December, April and May. Waterberg groundwater plots on the GMWL which indicates absence of evaporation. Tsumeb groundwater plots on/close to the GMWL with an exception of groundwater from the karst Lake Otjikoto which is showing evaporation. Groundwater from Kuzikus/Ebenhaezer shows an evaporation effect, probably evaporation occurs during infiltration since it is observed in all sampling seasons. All groundwater from three sites plot in the same area with rainwater depleted in stable isotopic values, which could indicates that recharge only take place during January, February and March. CMB method revealed that Waterberg has the highest recharge rate ranging between 39.1 mm/a and 51.1 mm/a (8.7% – 11.4% of annual precipitation), Tsumeb with rates ranging from 21.1 mm/a to 48.5 mm/a (3.5% – 8.1% of annual precipitation), and lastly Kuzikus/Ebenhaezer from 3.2 mm/a to 17.5 mm/a (1.4% – 7.3% of annual precipitation). High recharge rates in Waterberg could be related to fast infiltration and absence of evaporation as indicated by the isotopic ratios. Differences in recharge rates cannot only be attributed to the precipitation gradient but also to the evaporation rates and the presence of preferential flow paths. Recharge rates estimated for these three sites can be used in managing the savannah aquifers especially at Kuzikus/Ebenhaezer where evaporation effect is observed that one can consider rain harvesting.

Abstract: Carbon dioxide (CO2) enhanced oil recovery (EOR) provides a pathway for economic reuse and storage of CO2, a greenhouse gas. One challenge with this practice is ensuring CO2 injection does not result in target reservoir fluids migrating into overlying shallow (\textless1000 m) groundwater formations. Effective monitoring for leakage from storage formations could involve measuring sensitive chemical indicators in overlying groundwater units and within the producing formation itself for evidence of deviation from an initial state. In this study, produced waters and overlying groundwaters were monitored over a five-year period to evaluate which geochemical signals may be useful to ensure that oilfield produced waters did not impact overlying groundwaters. During this five-year period, a mature carbonate oil reservoir in the Permian Basin transitioned from a waterflooding operation to a water-alternating-gas injection (WAG), in which the formation was flooded with CO2 and various mixtures of produced water. Significant increases in dissolved inorganic constituents [alkalinity, TDS, Na+, Cl−, SO42−] were observed in produced waters following CO2 injection; however, carbonate reservoir dissolution-precipitation reactions appear to be minimal and injected CO2 appears to be stored via solubility trapping. Although there are statistically significant geochemical variations following CO2 injection, applying isometric log-ratios to certain parameters establishes a narrow range for post-CO2 injection produced waters. This narrow range can be considered a baseline for post-CO2 injection produced waters; this baseline can be utilized to monitor overlying local groundwaters for produced water intrusion. Additionally, certain parameters [Na+, Ca2+, K+, Cl−, alkalinity, and TDS] display large concentration disparities between produced water and overlying groundwaters; these parameters would be sensitive indicators of produced water intrusion into overlying groundwaters.

Abstract: The origin of groundwater recharge and subsequent flow paths are often difficult to establish in fractured, multi-lithological, and highly compartmentalized aquifers such as the Troodos Fractured Aquifer (TFA). As the conjunctive use of stable isotopes and hydrogeochemical data provides additional information, we established a monitoring network for stable isotopes in precipitation in Cyprus. The local meteoric water line, altitude effect and seasonal variation of stable isotopes in precipitation are derived from monitoring data. Stable isotopes and hydrogeochemical data are combined to model water-rock interactions and groundwater evolution along a complete ophiolite sequence. As a result a generic hydrogeologic description for the observed water types is developed. Isotope hydrology was applied in conjunction with hydrogeochemical modelling in Kargiotis Watershed, a major north-south transect of the TFA. PHREEQC was used for hydrogeochemical modelling to establish generic descriptions for observed water types. Mean precipitation-weighted values from 16 monitoring stations were used to calculate the Local Meteoric Water Line (LMWL), which was found to be equal to δ2H = (6.58 ± 0.13)*δ18O + (12.64 ± 0.91). A general decrease of 1.22‰ for δ2H and 0.20‰ for δ18O in precipitation was calculated per 100 m altitude. A generic groundwater evolution path was established: 1. Na/MgClHCO3, 2. MgHCO3, 3. Ca/MgHCO3, 4. Ca/MgNaHCO3, 4a. MgNa/CaHCO3/Cl, 5. NaMg/CaHCO3/Cl, 6. NaHCO3, 7. Na/MgHCO3SO4, 8. NaSO4Cl/HCO3. Hydrogeologic descriptions, consisting of groundwater origin, flow path and possible active water-rock processes, have been realised for the observed water types. The first two water types occur in serpentine and ultramafic-gabbro springs. Type 3 waters represent early stages of recharge and/or short flow paths, in gabbro whereas types 4 and 5 are typical for further percolating waters in gabbro and diabase. Water types 6 and 7 occur both in diabase and in the basal group and represent the regional flow. Water type 8 is the end member of regional, upwelling groundwater in the basal group. The presented descriptions and methods have practical applications in groundwater exploration, characterization, and protection. The methodology can be applied in other complex aquifer systems.

Abstract: The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S=−43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into depositional conditions and sources of both sulfide and uranium mineralization and an improved understanding of pyrite geochemistry can also underpin an effective vector for uranium exploration at Beverley North and other sedimentary systems of the Lake Eyre Basin, as well as in comparable geological environments elsewhere.

Abstract: The Nalinggou–Daying uranium metallogenic belt is situated at the northern Ordos Basin, China. Petrographical, mineralogical and geochemical techniques were used to study the ore-bearing sandstones and host rocks in the Nalinggou–Daying uranium metallogenic belt. The present study shows that uranium minerals, i.e., coffinite, pitchblende, and brannerite, are mostly disseminated around pyrite and detrital particles. The ore-bearing sandstones are enriched in organic matter, with which this reductive environment influenced uranium leaching. The carbonate concentration of the uranium ores is markedly higher than that of the host rocks, and intense carbonatization occurs in the ore-bearing sandstones. In this case, the usage of the classical in-situ leach uranium mining technique by injecting H2SO4 + H2O2 solution produces calcium sulfate precipitate, which can lead to blocking of the ore-bearing strata. For this reason, laboratory and field uranium mining tests were conducted using CO2 + O2 in-situ leaching technology and were demonstrated to be successful, illustrating that this approach is technically feasible. Inhibiting ore bed blockage and increasing the amount of injected O2 are important for uranium leaching in this setting.