Abstract: The prospect of unconventional shale gas development in the semi-arid Karoo Basin (South Africa) has created the prerequisite to temporally characterise the natural radioactivity in associated groundwater which is solely depended on for drinking and agriculture purposes. Radon (222Rn) was the primary natural radionuclide of interest in this study; however, supplementary radium (226Ra and 228Ra) in-water measurements were also conducted. A total of 53 aquifers spanning three provinces were studied during three separate measurement campaigns from 2014 to 2016. The Karoo Basin’s natural radon-in-water levels can be characterised by a minimum of 1 ± 1 Bq/L (consistent with zero or below LLD), a maximum of 183 ± 18 Bq/L and mean of 41 ± 5 Bq/L. The mean radon-in-water levels for shallow aquifers were systematically higher (55 ± 10 Bq/L) compared to deep (14 ± 3 Bq/L) or mixed aquifers (20 ± 6 Bq/L). Radon-in-water activity concentration fluctuations were predominantly observed from shallow aquifers compared to the generally steady levels of deep aquifers. A collective seasonal mean radon-in-water levels increase from the winter of 2014 (44 ± 8 Bq/L) to winter of 2016 (61 ± 16 Bq/L) was noticed which could be related to the extreme national drought experienced in 2015. Radium-in-water (228Ra and 226Ra) levels ranged from below detection level to a maximum of 0.008 Bq/L (226Ra) and 0.015 Bq/L (228Ra). The 228Ra/226Ra ratio was characterised by a minimum of 0.93, a maximum of 6.5 and a mean value of 3.3 ± 1.3. Developing and improving baseline naturally occurring radionuclide groundwater databases is vital to study potential radiological environmental impacts attributed to industrial processes such as hydraulic fracturing or mining.

Abstract: Complex pyrite textures associated with large changes in isotopic and trace element compositions are routinely assumed to be indicative of multi-faceted processes involving multiple fluid and sulfur sources. We propose that the features of ore-stage pyrite from roll front deposits across the world, revealed in exquisite detail via high-resolution trace element mapping by LA-ICP-MS, reflect the dynamic internal evolution of the biogeochemical processes responsible for sulfate reduction, rather than externally driven changes in fluid or sulfur sources through time. Upon percolation of oxidizing fluids into the reduced host-sandstones, roll front systems become self-organized, with a systematic reset of their activity cycle after each translation stage of the redox interface down dip of the aquifer. Dominantly reducing conditions at the redox interface favor the formation of biogenic framboidal pyrite (δ34S from −30.5 to −12.5‰) by bacterial sulfate reduction and the genesis of the U mineralization. As the oxidation front advances, oxidation of reduced sulfur minerals induces an increased supply of sulfate and metals in solution to the bacterial sulfate reduction zone that has similarly advanced down the flow gradient. Hence, this stage is marked by increased rates of the bacterial sulfate reduction associated with the crystallization of variably As-Co-Ni-Mo-enriched concentric pyrite (up to 10,000′s of ppm total trace contents) with moderately negative δ34S values (from −13.7 to −7.5‰). A final stage of pyrite cement with low trace element contents and heavier δ34S signature (from −6.9 to +18.8‰) marks the end of the roll front activity cycle and the transition from an open to a predominantly closed system behavior (negligible advection of fresh sulfate). Blocky pyrite cement is formed using the remaining sulfate, which now becomes quickly heavy according to a Rayleigh isotope fractionation process. This ends the cycle by depleting the nutrient supplies for the sulfate-reducing bacteria and cementing pore spaces within the host sandstone, effectively restricting fluid infiltration. This internally-driven roll front activity cycle results in systematic, large S isotope and trace element fractionation. Ultimately, the long-time evolution of the basin and fluid sources control the metal endowment and evolution of the system; these events, however, are unlikely to be preserved by the roll front, as a direct result of its hydrodynamic nature.

Abstract: Conventional continental geoarchives are rarely available in arid southern Africa. Therefore, palaeoclimate data in this area are still patchy and late Quaternary climate development is only poorly understood. In the western Kalahari, salt pans (playas, ephemeral lakes) are common and can feature quasi-continuous sedimentation. This study presents the first climate-related biomarker record using sediments from the Omongwa Pan, a Kalahari salt pan located in eastern Namibia. Our approach to reconstruct vegetation and hydrology focuses on biogeochemical bulk parameters and plant wax-derived lipid biomarkers (n-alkanes, n-alkanols, and fatty acids) and their compound-specific carbon and hydrogen isotopic compositions. The presented record reaches back to 27 ka. During the glacial, rather low δ2H values of n-alkanes and low sediment input exclude a strong influence of winter rainfall. n-Alkane and n-alkanol distributions and δ13C values of n-hentriacontane (n-C31) indicate a shift to a vegetation with a higher proportion of C4 plants at the end of the Last Glacial Maximum until the end of Heinrich Stadial I (ca. 18–14.8 ka), which we interpret to indicate an abrupt excursion to a short wetter period likely to be caused by a temporary southward shift of the Intertropical Convergence Zone. Shifts in δ2H values of n-C31 and plant wax parameters give evidence for changes to drier conditions during early Holocene. Comparison of this dataset with representative continental records from the region points to a major influence of summer rainfall at Omongwa Pan during the regarded time span and demonstrates the potential of southern African salt pans as archives for biomarker-based climate proxies.

Abstract: The rapid rate of urban expansion with its associated physical development in recent years conflicts with the urban ecosystem and the services it provides. In most Sub-Saharan African cities, rapid urban expansion often does not conform to existing spatial plans. Physical developments are sometimes carried out in unauthorized areas, contributing to urban floods. The Sub-Saharan African regions’ flood management strategies mainly focus on engineering solutions but have not been fully functional in mitigating urban floods. There is a scarcity of knowledge on how urban flood-related NBS measures can be part of the spatial development in Sub-Saharan African cities for effective flood management. In order to address this gap, this study employed content and text analysis of policy documents and interviews to understand how current spatial and flood mitigation schemes in Accra, Ghana reflect possible NBS applicability and identify possible approaches to integrating NBS into existing planning schemes to prevent urban floods. The study found that Accra’s spatial plans and flood mitigation schemes reflect a possibility of NBS integration. Additionally, the study unveiled techniques for integrating NBS measures and possible implementation barriers and facilitation in the Ghanaian context, which can be linked to combating the challenges that the Ghanaian spatial planning and flood management authorities face. The research, therefore, contributes to knowledge of how NBS can be integrated into spatial planning systems and flood mitigation schemes in Sub-Saharan African regions.

Abstract: The Complexe Terminal (CT) multi-layer aquifer is formed by Neogene/Paleogene sand deposits, Upper Senonian (Campanian-Maastrichtian limestones) and Turonian carbonates. The chemical composition and isotopes of carbon and uranium were investigated in groundwater sampled from the main hydrogeological units of the (CT) aquifer in southern Tunisia. We paid special attention to the variability of uranium contents and isotopes ratio (234U/238U) to provide a better understanding of the evolution of the groundwater system. Uranium concentrations range from 1.5 to 19.5 ppb, typical of oxic or mildly reducing conditions in groundwaters. The lowest concentrations are found southeast of the study area, where active recharge is supposed to take place. When looking at the isotope composition, it appears that all the samples, including those from carbonate levels, are in radioactive disequilibrium with significant 234U excess. A clear-cut distinction is observed between Turonian and Senonian carbonate aquifers on the one hand, with 234U/238U activity ratios between 1.1 and 1.8, and the sandy aquifer on the other hand, showing higher ratios from 1.8 to 3.2. The distribution of uranium in this complex aquifer system seems to be in agreement with the lithological variability and are ultimately a function of a number of physical and chemical factors including the uranium content of the hosting geological formation, water-rock interaction and mixing between waters having different isotopic signatures. Significant relationships also appear when comparing the uranium distribution with the major ions composition. It is noticeable that uranium is better correlated with sulfate, calcium and magnesium than with other major ions as chloride or bicarbonate. The 14C activities and δ13C values of DIC cover a wide range of values, from 1.1 pmc to 30.2 pmc and from −3.6‰ to −10.7‰, respectively. 14C model ages estimated by the Fontes and Garnier model are all younger than 22 Ka and indicate that the recharge of CT groundwater occurred mainly during the end of the last Glacial and throughout the Holocene.