Abstract: Most of the World’s germanium (Ge) is mined from Ge-rich lignite, where it is commonly associated with elevated arsenic (As), tungsten (W) and beryllium (Be) contents. Over the past decade, new evidence showing that World-class Ge deposits result from the interaction of hydrothermal fluids with organic matter in coal seams has emerged. Yet, the chemical state of Ge and associated metals in lignite remains poorly understood. We used Mega-pixel Synchrotron X-ray Fluorescence (MSXRF), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) to characterize the oxidation states and chemical bonding environment of Ge, As, and W in two world-class Mesozoic Ge-in-lignite deposits (Lincang, Yunnan, southwestern China; Wulantuga, Inner Mongolia, northeastern China); in lignite-bearing uranium (U) ores from the Beverley deposit (South Australia) hosted in Eocene sandstones; and in lignite and preserved wood in late Oligocene-Miocene fluviatile sediments (Gore, Southland, New Zealand). The aim was to improve our understanding of the enrichment mechanism of Ge in lignite and better evaluate the environmental mobility of Ge and some of the associated metals (specifically As and W) in lignite ores. In all samples, chemical maps show that Ge is distributed homogeneously (down to 2μm) within the organic matter. XANES and EXAFS data show that Ge exists in the tetravalent oxidation state and in a distorted octahedral coordination with O, consistent with complexing of Ge by organic ligands. In some pyrite-bearing samples, a minor fraction of Ge is also present as Ge(IV) in association with pyrite. In contrast, As displays a more complex speciation pattern, sometimes even in a single sample, including As(III), As(V), and As(−I/+II) in solid solution in sulfides. Arsenic in sulfides occurs in anionic and cationic forms, i.e., it shows both the common substitution for S22− and the substitution for Fe recently discovered in some hydrothermal pyrites. Tungsten was present as W(VI) in distorted octahedral (3+3) coordination. The EXAFS data confirm the absence or minor contribution of individual W-rich minerals such as scheelite or ferberite to W mass balance in the studied samples. These data show that Ge, W, and probably some As are scavenged via formation of insoluble, oxygen-bridged metal organic complexes in lignite. Destruction of the organic ligands responsible for fixing Ge and W (As) in these lignites is required for liberating the metals, e.g. from waste materials. Geochemical modelling suggests that Ge, W, Be and As all can be extracted from granitic rocks by dilute, low temperature hydrothermal fluids. Germanium is transported mainly as the tetrahedral Ge(OH)4(aq) complex, but fixed as an octahedral oxy-bridged organic complex. The same situation is valid for W, which is transported at the tetrahedral tungstate ion, but most likely scavenged via formation of a 6-coordinated metal-organic species. The Ge-Be-W±As association in Ge-rich coals reflects the source of the metals as well as related scavenging mechanisms.

Abstract: It is proposed that a geothermal artesian karstic system at the central part of the Yarkon–Taninim aquifer creates the ‘Ayalon Saline Anomaly’ (ASA), whose mechanism has been under debate for several decades. A 4-year-long detailed groundwater monitoring was carried out at 68 new shallow boreholes in the Ayalon region, accompanied by a comprehensive survey of karstic voids. Results indicate the rising of warm-brackish groundwater through highly permeable swarms of karstic shafts, serving as an outflow of the artesian geothermal system. The ASA area contains ‘hot spots’, where groundwater contrasts with ‘normal’ water hundreds of meters away. The ASA temperature reaches 30°C (∼5°C warmer than its surroundings), chloride concentration reaches 528mg/l (50–100mg/l in the surrounding), H2S concentration reaches 5.6mg/l (zero all around) and pH value is 7.0 (compared with 7.8 around). Subsequently, the hydrothermal water flows laterally of at the watertable horizon through horizontal conduits, mixing with ‘normal’ fresh water which had circulated at shallow depth. Following rainy seasons, maximal watertable rise is observed in the ASA compared to its surroundings. Regional hydrogeology considerations suggest that the replenishment area for the ASA water is at the Samaria Mountains, east of the ASA. The water circulates to a great depth while flowing westward, and a cross-formational upward flow is then favored close the upper sub-aquifer’s confinement border.

Abstract: Paleohydrological data from the African tropics and subtropics, including lake, groundwater and speleothem records, are reviewed to show how environments and climates from both hemispheres are inter-related. Although orbitally induced changes in the monsoon strength account for a large part of long-term climatic changes in tropical Africa, the Late Pleistocene–Holocene hydrological fluctuations rather appear to have been a series of abrupt events that reflect complex interactions between orbital forcing, atmosphere, ocean and land surface conditions. During the Last Glacial Maximum (23–18ka BP), most records indicate that generally dry conditions have prevailed in both hemispheres, associated with lower tropical land- and sea-surface temperatures. This agrees with simulations using coupled ocean–atmosphere models, which predict cooling and reduced summer precipitation in tropical Africa; the global hydrological cycle was weaker than today when the extent of large polar ice-sheets and sea-ice was a prominent forcing factor of the Earth’s climate. Glacial-interglacial climatic changes started early: a first wetting/warming phase at ca. 17–16ka BP took place during a period of rapid temperature increase in Antarctica. Next, two drastic arid-humid transitions in equatorial and northern Africa occurred around 15–14.5ka BP and 11.5–11ka BP. Both are thought to match the major Greenland warming events, in concert with the switching of the oceanic thermohaline circulation to modern mode. However, part of the climatic signal after 15 ka BP also seems related to the Antarctica climate. During the Holocene, Africa has also experienced rapid hydrological fluctuations of dramatic magnitude compared to the climatic changes at high latitudes. In particular, major dry spells occurred around 8.4–8ka and 4.2–4ka BP in the northern monsoon domain. Comparison with other parts of the world indicates that these events have a worldwide distribution but different regional expressions. In the absence of large polar ice sheets, changes in the continental hydrological cycles in the tropics may have a significant impact on the global climate system. Climate information gathered here allows to identify geographical and methodological gaps, and raise some scientific questions that remain to be solved to better understand how the tropics respond to changes in major climate-forcing factors, and how they influence climate globally.

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: Uranium reserve estimates in ore deposits can be significantly impacted by 226Ra/238U disequilibria arising from the differential mobility of uranium and radium during groundwater transport. 1D reactive transport models were developed to investigate the long-term effects of retention processes (UO2(am) precipitation, U(VI) and Ra sorption on smectite, Ra co-precipitation with barite) on the repartitioning of 238U and 226Ra during formation of roll-front type deposits. Analytical solutions to radioactive decay chains were used in complement to examine the influence of geochemical parameters, including fluid 234U/238U activity ratios and α-recoil loss, on 226Ra/238U disequilibria in uranium ores. Model results demonstrate that smectite and barite can produce 226Ra/238U ratios \textgreater1 at low uranium contents and may explain 226Ra/238U disequilibria occurring in altered rock up- and downstream of roll-front deposits. The capacity of these phases to take up Ra and generate 226Ra/238U disequilibria depends on both mineral contents and groundwater compositions, and is thus expected to be site-specific. Simulations of ore deposits that advance downstream with time demonstrate the formation of stronger 226Ra/238U disequilibria, as expected, in the downgradient side or nose of the ore, reflecting both younger mineralization ages and the presence of active uranium precipitation. Whether disequilibria are positive or negative with respect to secular equilibrium, however, depends on the 234U/238U activity ratio in the fluid from which uranium minerals precipitate. Smaller hydraulic conductivities are shown to generate a narrower range in 226Ra/238U activity ratios with distance, and may explain the occurrence of disequilibria in the limb ore that are less pronounced than those in the nose. Furthermore, the ability of α-recoil loss to decrease 226Ra/238U activity ratios at secular equilibrium may account for negative disequilibria in high grade ores. The South Tortkuduk uranium deposits (Kazakhstan) are subsequently used as a case study to identify the processes and parameters that may contribute to 226Ra/238U disequilibria at this site. Variations in multiple parameters, including clay contents, barite contents, and mineralization ages, are found to reproduce measured 226Ra/238U activity ratios in the roll-front ore. Prioritization of these parameters will necessitate field measurements targeting both groundwater fluids and the host rock. Results from this study will ultimately aid geologists in building appropriate hydrogeochemical data sets to more efficiently locate and exploit uranium ore deposits.