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During the Variscan orogeny in Central Europe, partial melting in the lower continental crust formed granitic magmas, which intruded into the upper crust and left compounds of Ca (plus Eu2+), Mg, etc. in the lower crust. From the late Paleozoic decomposition of the tonalitic upper crust, sedimentary graywackes were produced reflecting the composition of this crust. The repeated reworking of the sedimentary cover caused the formation of sands. Sandstones as their products of consolidation contain increasing fractions of quartz and decreasing feldspar from Carboniferous and Triassic to Cretaceous age. A distinct negative Eu anomaly characterizes the majority of these rocks. The latter is imprinted by the Variscan magmatism. Quartz as used for numerous Medieval wood ash glasses is marked for its Central European origin by a distinct negative Eu anomaly in contrast to many soda glasses produced outside Germany mostly with a small or none Eu anomaly.

In order to better understand the role of fluids during subduction and subsequent exhumation, we have investigated whole-rock and mineral chemistry (major and trace elements) and Li, B as well as O, Sr, Nd, Pb isotopes on selected continuous drill-core profiles through contrasting lithological boundaries from the Chinese Continental Scientific Drilling Program (CCSD) in Sulu, China. Four carefully selected sample sets have been chosen to investigate geochemical changes as a result of fluid mobilization during dehydration, peak metamorphism, and exhumation of deeply subducted continental crust. Our data reveal that while O and Sr-Nd-Pb isotopic compositions remain more or less unchanged, significant Li and/or B isotope fractionations occur between different lithologies that are in close contact during various metamorphic stages. Samples that are supposed to represent prograde dehydration as indicated by veins formed at high pressures (HP) are characterized by element patterns of highly fluid-mobile elements in the veins that are complementary to those of the host eclogite. A second sample set represents a UHP metamorphic crustal eclogite that is separated from a garnet peridotite by a thin transitional interface. Garnet peridotite and eclogite are characterized by a >10% difference in MgO, which, together with the presence of abundant hydroxyl-bearing minerals and compositionally different clinopyroxene grains demonstrate that both rocks have been derived from different sources that have been tectonically juxtaposed during subduction, and that hydrous silicate-rich fluids have been added from the subducting slab to the mantle. Two additional sample sets, comprising retrograde amphibolite and relatively fresh eclogite, demonstrate that besides external fluids, internal fluids can be responsible for the formation of amphibolite. Li and B concentrations and isotopic compositions point to losses and isotopic fractionation during progressive dehydration. On the other hand, fluids with isotopically heavier Li and B are added during retrogression. On a small scale, mantle-derived rocks may be significantly metasomatized by fluids derived from the subducted slab. Our study indicates that during high-grade metamorphism, Li and B may show different patterns of enrichment and of isotopic fractionation.

Decay of trachyte used as building stone in urban environment was investigated through the analysis of crusts and patinas found on trachyte of the Euganean Hills in the Renaissance city walls of Padua, northeastern Italy. Mineralogical and microstructural characteristics of the alteration products, as well as major- and trace-element chemical composition, were determined by optical microscopy, SEM–EDS and X-ray mapping, XRPD, and LA-ICPMS. The results are discussed referring to environmental parameters, in particular concerning air quality and anthropic pollution sources. The influence of composition of the stone and other neighboring materials on specific weathering processes is also debated. The formation of crusts and patinas turns out to be mainly due to exogenous processes. Enrichment in heavy metals and carbonaceous matter derives from the deposition of particulate emitted during fuel combustion by road vehicles, domestic heating and, secondarily, industrial activities. The particulate is typically cemented by calcite, mainly mobilized after dissolution from nearby mortar joints, or iron, released by leaching from iron-bearing minerals, reprecipitated according to pH fluctuations. Gypsum layers were rarely observed. Generally, composition of the weathering crusts and patinas of Euganean trachyte proves to be an informative marker for the relevant environmental conditions and their evolution.

Aquifer Storage and Recovery (ASR) was a pilot project for solving flood and drought problem in the northern part of Chao Phraya River basin, Thailand. This part of Thailand always faces flooding in rainy season and drought during dry season every year. The overexploitation of groundwater during dry season leads to continuously decline of water level in this area. In this project, the excessive surface water during rainy season was stored by injection of this treated surface water through recharge wells into the underground aquifers. This would serve to raise the water level, which can be extracted for use during the dry season. To assess the efficiency of the ASR process some tracers are required. The aim of this study is to prove the suitability of natural tracers to follow up the artificial recharge process; emphasis will be placed on Strontium (Sr) isotopic composition. The results showed that the change in 87Sr/86Sr ratios could be observed during an artificial recharge due to the different isotopic fingerprint of surface water and groundwater. However, the flow direction of the injected water cannot be clearly interpreted because of the limited number of monitoring wells, small distance between each monitoring well and the short duration of injection., Open-Access-Publikationsfonds 2016

Microbial iron oxyhydroxides are common deposits in natural waters, recent sediments, and mine drainage systems. Along with these minerals, trace and rare earth elements (TREE) are being accumulated within the mineralizing microbial mats. TREE patterns are widely used to characterize minerals and rocks, and to elucidate their evolution and origin. However, whether and which characteristic TREE signatures distinguish between a biological and an abiological origin of iron minerals is still not well-understood. Here we report on long-term flow reactor studies performed in the Tunnel of Äspö (Äspö Hard Rock Laboratory, Sweden). The development of microbial mats dominated by iron-oxidizing bacteria (FeOB), namely Mariprofundus sp. and Gallionella sp were investigated. The feeder fluids of the flow reactors were tapped at 183 and 290 m below sea-level from two brackish, but chemically different aquifers within the surrounding, ~1.8 Ga old, granodioritic rocks. The experiments investigated the accumulation and fractionation of TREE under controlled conditions of the subsurface continental biosphere, and enabled us to assess potential biosignatures evolving within the microbial iron oxyhydroxides. After 2 and 9 months, concentrations of Be, Y, Zn, Zr, Hf, W, Th, Pb, and U in the microbial mats were 103- to 105-fold higher than in the feeder fluids whereas the rare earth elements and Y (REE+Y) contents were 104- and 106-fold enriched. Except for a hydrothermally induced Eu anomaly, the normalized REE+Y patterns of the microbial iron oxyhydroxides were very similar to published REE+Y distributions of Archaean Banded Iron Formations (BIFs). The microbial iron oxyhydroxides from the flow reactors were compared to iron oxyhydroxides that were artificially precipitated from the same feeder fluid. Remarkably, these abiotic and inorganic iron oxyhydroxides show the same REE+Y distribution patterns. Our results indicate that the REE+Y mirror closely the water chemistry, but they do not allow to distinguish microbially mediated from inorganic iron precipitates. Likewise, all TREE studied showed an overall similar fractionation behavior in biogenic, abiotic, and inorganic iron oxyhydroxides. Exceptions are Ni and Tl, which were only accumulated in the microbial iron oxyhydroxides and may point to a potential utility of these elements as microbial biosignatures.