Abstract: Generic hydrochemical modelling of a grantoid-groundwater system, using the Russian software “HydroGeo”, has been carried out with an emphasis on simulating the accumulation of uranium in the aqueous phase. The baseline model run simulates shallow granitoid aquifers (U content 5 ppm) under conditions broadly representative of southern Norway and southwestern Siberia: i.e. temperature 10 °C, equilibrated with a soil gas partial CO2 pressure (PCO2, open system) of 10−2.5 atm. and a mildly oxidising redox environment (Eh = +50 mV). Modelling indicates that aqueous uranium accumulates in parallel with total dissolved solids (or groundwater mineralisation M – regarded as an indicator of degree of hydrochemical evolution), accumulating most rapidly when M = 550–1000 mg L−1. Accumulation slows at the onset of saturation and precipitation of secondary uranium minerals at M = c. 1000 mg L−1 (which, under baseline modelling conditions, also corresponds approximately to calcite saturation and transition to Na-HCO3 hydrofacies). The secondary minerals are typically “black” uranium oxides of mixed oxidation state (e.g. U3O7 and U4O9). For rock U content of 5–50 ppm, it is possible to generate a wide variety of aqueous uranium concentrations, up to a maximum of just over 1 mg L−1, but with typical concentrations of up to 10 μg L−1 for modest degrees of hydrochemical maturity (as indicated by M). These observations correspond extremely well with real groundwater analyses from the Altai-Sayan region of Russia and Norwegian crystalline bedrock aquifers. The timing (with respect to M) and degree of aqueous uranium accumulation are also sensitive to Eh (greater mobilisation at higher Eh), uranium content of rocks (aqueous concentration increases as rock content increases) and PCO2 (low PCO2 favours higher pH, rapid accumulation of aqueous U and earlier saturation with respect to uranium minerals).

Abstract: Quantifying evapotranspiration and drainage losses is essential for improving irrigation efficiency. The FAO-56 is the most popular method for computing crop evapotranspiration. There is, however, a need for locally derived crop coefficients (Kc) with a high temporal resolution to reduce errors in the water balance. The aim of this paper is to introduce a dynamic Kc approach, based on Leaf Area Index (LAI) observations, for improving water balance computations. Soil moisture and meteorological data were collected in a terraced nectarine (Prunus persica var. nucipersica) orchard in Cyprus, from 22 March 2019 to 18 November 2021. The Kc was derived as a function of the canopy cover fraction (c), from biweekly in situ LAI measurements. The use of a dynamic Kc resulted in Kc estimates with a bias of 17 mm and a mean absolute error of 0.8 mm. Evapotranspiration (ET) ranged from 41% of the rainfall (P) and irrigation (I) in the wet year (2019) to 57% of P + I in the dry year (2021). Drainage losses from irrigation (DR_I) were 44% of the total irrigation. The irrigation efficiency in the nectarine field could be improved by reducing irrigation amounts and increasing the irrigation frequency. Future studies should focus on improving the dynamic Kc approach by linking LAI field observations with remote sensing observations and by adding ground cover observations.

Abstract: Quantifying evapotranspiration and drainage losses is essential for improving irrigation efficiency. The FAO-56 is the most popular method for computing crop evapotranspiration. There is, however, a need for locally derived crop coefficients (Kc) with a high temporal resolution to reduce errors in the water balance. The aim of this paper is to introduce a dynamic Kc approach, based on Leaf Area Index (LAI) observations, for improving water balance computations. Soil moisture and meteorological data were collected in a terraced nectarine (Prunus persica var. nucipersica) orchard in Cyprus, from 22 March 2019 to 18 November 2021. The Kc was derived as a function of the canopy cover fraction (c), from biweekly in situ LAI measurements. The use of a dynamic Kc resulted in Kc estimates with a bias of 17 mm and a mean absolute error of 0.8 mm. Evapotranspiration (ET) ranged from 41% of the rainfall (P) and irrigation (I) in the wet year (2019) to 57% of P + I in the dry year (2021). Drainage losses from irrigation (DR_I) were 44% of the total irrigation. The irrigation efficiency in the nectarine field could be improved by reducing irrigation amounts and increasing the irrigation frequency. Future studies should focus on improving the dynamic Kc approach by linking LAI field observations with remote sensing observations and by adding ground cover observations.

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.