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: Analyses of satellite data mainly over the world’s ocean surfaces have shown that during 1986–2006 global average values of atmospheric water vapor, precipitation and evaporation have increased at a relative rate of 0.0013a−1; this is roughly in accordance with the Clausius-Clapeyron equation for the average temperature trend during this period, and amounts to 0.065K−1 at the average temperature of T=14∘C. Application of this concept over the world’s land surfaces yields an average global evaporation trend during the past half century of around 0.4 to 0.5 mma−2; this confirms the values obtained in previous studies with totally different methods.

Abstract: This paper presents the first continuous pollen record from the southern Namib Desert spanning the last 50,000years. Obtained from rock hyrax middens found near the town of Pella, South Africa, these data are used to reconstruct vegetation change and quantitative estimates of temperature and aridity. Results indicate that the last glacial period was characterised by increased water availability at the site relative to the Holocene. Changes in temperature and potential evapotranspiration appear to have played a significant role in determining the hydrologic balance. The record can be considered in two sections: 1) the last glacial period, when low temperatures favoured the development of more mesic Nama-Karoo vegetation at the site, with periods of increased humidity concurrent with increased coastal upwelling, both responding to lower global/regional temperatures; and 2) the Holocene, during which time high temperatures and potential evapotranspiration resulted in increased aridity and an expansion of the Desert Biome. During this latter period, increases in upwelling intensity created drier conditions at the site. Considered in the context of discussions of forcing mechanisms of regional climate change and environmental dynamics, the results from Pella stand in clear contrast with many inferences of terrestrial environmental change derived from regional marine records. Observations of a strong precessional signal and interpretations of increased humidity during phases of high local summer insolation in the marine records are not consistent with the data from Pella. Similarly, while high percentages of Restionaceae pollen has been observed in marine sediments during the last glacial period, they do not exceed 1% of the assemblage from Pella, indicating that no significant expansion of the Fynbos Biome has occurred during the last 50,000years. These findings pose interesting questions regarding the nature of environmental change in southwestern Africa, and the significance of the diverse records that have been obtained from the region.

Abstract: This paper reviews critical features of basin-related uranium mineral systems in Australia. These mineral systems include Proterozoic unconformity-related uranium systems formed predominantly from diagenetic fluids expelled from sandstones overlying the unconformity, sandstone-hosted uranium systems formed from the influx of oxidised groundwaters through sandstone aquifers, and calcrete uranium systems formed from oxidised groundwaters flowing through palaeochannel aquifers (sand and calcrete). The review uses the so-called ‘source-pathway-trap’ paradigm to summarise critical features of fertile mineral systems. However, the scheme is expanded to include information on the geological setting, age and relative timing of mineralisation, and preservation of mineral systems. The critical features are also summarised in three separate tables. These features can provide the basis to conduct mineral potential and prospectivity analysis in an area. Such analysis requires identification of mappable signatures of above-mentioned critical features in geological, geophysical and geochemical datasets. The review of fertile basin-related systems shows that these systems require the presence of at least four ingredients: a source of leachable uranium (and vanadium and potassium for calcrete-uranium deposits); suitable hydrological architecture enabling connection between the source and the sink (site of accumulation); physical and chemical sinks or traps; and a post-mineralisation setting favourable for preservation. The review also discusses factors that may control the efficiency of mineral systems, assuming that world-class deposits result from more efficient mineral systems. The review presents a brief discussion of factors which may have controlled the formation of large deposits in the Lake Frome region in South Australia, the Chu-Sarysu and Syrdarya Basins in Kazakhstan and calcrete uranium deposits in the Yilgarn region, Western Australia.