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: Groundwater overexploitation has resulted in huge scarcity and increase in the demand for water and food security in India. Groundwater in India has been observed to have experienced various water quality issues like arsenic, fluoride, and Uranium (U) contamination, leading to risk in human health. Markedly, the health risk of higher U in drinking water, as well as its chemical toxicity in groundwater have adverse effects on human. This study has reported occurrence of U as an emerging and widespread phenomenon in South Indian groundwater. Data on U in groundwater were generated from 284 samples along the Cretaceous Tertiary boundary within 4 seasons viz. pre-monsoon (PRM), southwest monsoon (SWM), northeast monsoon (NEM), and post-monsoon (POM). High U concentrations (74 μgL−1) showed to be above the World Health Organization’s provisional guideline value of 30 μgL−1. The geochemical, stable isotope and geophysical studies suggested that U in groundwater could vary with respect to season and was noted to be highest during NEM. The bicarbonate (HCO3) released by weathering process during monsoon could affect the saturation index (SI)Calcite and carbonate species of U. However, the primary source of U was found to be due to geogenic factors, like weathering, dissolution, and groundwater level fluctuation, and that, U mobilization could be enhanced due to anthropogenic activities. The findings further indicated that groundwater in the study area has reached the alarming stage of chemical toxicity. Hence, it is urgent and imperative that workable management strategies for sustainable drinking water source be developed and preventive measures be undertaken, relative to these water quality concerns to mitigate their disconcerting effect on human health.

Abstract: Study Region: Bandung groundwater basin, Indonesia. Study focus: Groundwater abstraction of various magnitudes, pumped out from numerous depths in a multitude of layers of aquifers, stimulates different changes in hydraulic head distribution, including ones under vertical cross-sections. This generates groundwater flow in the vertical direction, where groundwater flows within its storage from the shallow to the underlying confined aquifers. In the Bandung groundwater basin, previous studies have identified such processes, but quantitative evaluations have never been conducted, with data scarcity mainly standing as one of the major challenges. In this study, we utilize the collated (1) environmental water tracer data, including major ion elements (Na+/K+, Ca2＋, Mg2+, Cl−, SO42−,HCO3−), stable isotope data (2H and δ18O), and groundwater age determination (14C), in conjunction with (2) groundwater flow modeling to quantify the aquifer interaction, driven mainly by the multi-layer groundwater abstraction in the Bandung groundwater basin, and demonstrate their correspondence. In addition, we also use the model to quantify the impact of multi-layer groundwater abstraction on the spatial distribution of the groundwater level changes. New hydrological insights for the region: In response to the limited calibration data availability, we expand the typical model calibration that makes use of the groundwater level observations, with in-situ measurement and a novel qualitative approach using the collated environmental water tracers (EWT) data for the model evaluation. The analysis in the study area using EWT data and quantitative methods of numerical groundwater flow modeling is found to collaborate with each other. Both methods show agreement in their assessment of (1) the groundwater recharge spatial distribution, (2) the regional groundwater flow direction, (3) the groundwater age estimates, and (4) the identification of aquifer interaction. On average, the downwelling to the deeper aquifer is quantified at 0.110 m/year, which stands out as a significant component compared to other groundwater fluxes in the system. We also determine the unconfined aquifer storage volume decrease, calculated from the change in the groundwater table, resulting in an average declining rate of 51 Mm3/year. This number shows that the upper aquifer storage is dwindling at a rate disproportionate to its groundwater abstraction, hugely influenced by losses to the deeper aquifer. The outflow to the deeper aquifer contributes to 60.3% of the total groundwater storage lost, despite representing only 32.3% of the total groundwater abstraction. This study shows the possibility of quantification of aquifer interaction and groundwater level change dynamics driven by multi-layer groundwater abstraction in a multi-layer hydrogeological setting, even in a data-scarce environment. Applying such methods can assist in deriving basin-scale groundwater policies and management strategies under the changing anthropogenic and climatic factors, thereby ensuring sustainable groundwater management.