The issue of diagenetic alteration of carbonate deposits in caves (speleothems) has gained increasing importance in recent years, as this process has serious consequences for speleothembased paleoclimate studies. In this study stable hydrogen and oxygen isotope data of water trapped in fluid inclusions were collected for recently forming stalagmites and flowstones in order to determine how dripwater compositions are reflected and preserved in the inclusion water compositions. Hydrogen isotope compositions were found to reflect dripwater values, whereas the oxygen isotope data were increasingly shifted from the local dripwater compositions with the time elapsed after deposition. The δ 18 O data are correlated with X-Ray diffraction full width at half maximum values (related to crystal domain size and lattice strain),suggesting that the oxygen isotope shift is related to recrystallization of calcite. Transmission electron microscope analyses detected the presence of nanocrystalline (<50 nm) calcite, whose crystallization to coarser-grained calcite crystals (>200 nm) may have induced re-equilibration between the carbonate and the trapped inclusion water. The Ostwald ripening process provides an explanation for unexpectedly low oxygen isotope compositions in the inclusion water. The detected diagenetic alteration and its isotopic effects should be taken into consideration during sampling strategies and data evaluation as speleothems containing nanocrystalline calcite during their deposition are prone to late-stage oxygen isotope water-carbonate re-equilibration, which may shift the oxygen isotope composition of the inclusion water to more depleted values while the hydrogen isotope composition remains intact.

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Abstract:In order to use speleothems in the reconstruction of past climate and environmental changes it is necessary to understand the environmental and hydrological processes that determine the physico-chemical conditions of carbonate precipitation and hence speleothem formation. Therefore, in this study an extended monitoring program was conducted in the Béke and Baradla caves located in the Aggtelek region (Northeastern Hungary). The studied caves are rich in speleothem and flowstone occurrences with great potential for paleoclimatology studies. The monitoring activity included measurements of atmospheric and cave temperatures, CO 2 concentration in cave air, as well as chemical and isotopic compositions of water samples (drip water, precipitation) and in situ carbonate precipitates. The hydrogen and oxygen isotope compositions of drip waters showed no seasonal variation at any of the collection sites, indicating a well-mixed karstic aquifer. This implies that the isotopic compositions of local speleothems were able to record multiannual isotopic changes inherited from stable isotopes in the drip water. CO 2 concentration showed seasonality (high values in summer and low values in winter) in both caves, likely affecting carbonate precipitation or corrosion and consequently stalagmite growth. Systematic variations among Mg/Ca and Sr/Ca, Na/Ca, and Si/Ca element ratios were detected in the drip water suggesting Prior Calcite Precipitation (PCP). As PCP is characteristic of periods of reduced infiltration during drier weather conditions, the variations in drip water chemistry and drip rates indicate that the hydrological conditions also varied significantly during the studied period. This hydrological variability appears to affect not only trace element composition but also the isotopic composition of modern carbonate precipitates. In summary, these findings imply that the speleothems from the studied caves were able to record the hydrological changes resulting from alternating wet and dry periods, and therefore the geochemical data can be used to reconstruct past climate and environmental changes.

γ-Valerolactone-based ionic liquids were successfully used as the catalyst phase for [Rh(cod) 2 ][BF 4 ]/RP(C 6 H 4 -m-SO 3 Na) 2 (R = Me, Pr, Bu, Cp) catalyzed hydrogenation of different olefins. Compared to broadly used ionic liquids e.g. 1-butyl-3-methylimidazolium chloride [bmim][Cl], the turnover frequencies were significantly higher and the reaction was selective for the CvC double bonds in the presence of carbonyl, cyano, and phenyl groups. The catalyst was recycled for ten consecutive runs under regular or biphasic conditions without loss of activity. The vapour pressure and viscosity of γ-valerolactone-based ionic liquids were determined as well. † Electronic supplementary information (ESI) available. See

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