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Brucite, Mg (OH)2, is an important analog for studying the thermodynamics of hydrous silicate minerals in the deep Earth, as well as H/D isotope fractionation between minerals and water. In this study, we measured in situ Raman and Fourier transform infrared spectra for the natural and deuterated brucite samples, at high temperatures to 650 K, just before the dehydration of brucite at ambient pressure. All of the optical modes systematically shift to lower frequencies at elevated temperature, while deuterium substitution reduces the magnitudes of the temperature dependence. The isobaric mode Grüneisen parameters (γiP), as well as the intrinsic anharmonic parameters (ai), have been evaluated for the vibrational modes between Mg (OH)2 and Mg (OD)2. The anharmonic contribution to the thermodynamic properties (such as internal energy, isochoric and isothermal heat capacities, and entropy) is positive and severe at high temperature. The difference in the heat capacity is up to ~7% at 700 K due to the anharmonic effect. The deuterium isotopic effect on the thermodynamics is positive, and the magnitude of the isotopic effect is comparable to that from the anharmonic effect. On the other hand, the anharmonicity significantly decreases the magnitude of the positive pressure dependence of the D/H fractionation β factor for brucite, and this correction could be more important at elevated temperature. At the temperature of 800 K, 103·(∂lnβ/∂P)T decreases from +0.23 GPa−1 (for quasi‐harmonic approximation) to approaching zero, due to the anharmonic correction.

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The formation of mixed-valent ytterbium and europium complexes L4LnIII 2LnII (Ln = Yb (1), Eu (2)) was observed for the first time in the spontaneous reduction reaction system of quinolinyl aminophenol (H2L) with Ln[N(SiMe3)2]3 (Ln = Yb, Eu) in toluene at 90 °C, whereas the same reaction with Sm[N(SiMe3)2]3 gave the expected monoamido samarium complex LSmN(SiMe3)2(DME) (4). The isolation of the binuclear ytterbium complex L3Yb2 (3) under mild conditions demonstrates that the transformation from a trivalent ytterbium complex to the mixed-valent ytterbium species 1 may involve a ligand redistribution reaction and homolysis of the Yb–N bond.

Medium-low temperature geothermal resources in the Wumishan Formation, which is the geothermal reservoir, are local enrichment resources in Xiong’an New Area, North China. In this study, 35 water samples were collected from the bedrock of Taihang Mountains and Wumishan Formation in Xiong’an New Area and display the chemical compositions of water samples as well as the stable isotope compositions for hydrogen, oxygen, carbon, sulfur, and strontium. Hydrogeochemical characteristics and isotope compositions of water samples are analyzed to understand the origin and circulation processes of these geothermal fluids. Our results of cold groundwaters in the bedrock of Taihang Mountain indicate a more open oxidation environment, and the HCO3-Ca·Mg-type groundwater also indicates a prevailing carbonate dissolution condition. The deep geothermal fluids in the Wumishan Formation beneath Xiong’an New Area indicate a closed reduction condition, and their hydrochemical types are mainly Cl·HCO3-Na type. The diagram of hydrogen vs. oxygen isotope indicates that the recharge for the deep geothermal fluids in the Wumishan Formation of Xiong’an New Area is mainly from atmospheric precipitation. The high δ13C values (-3.4‰−-4.9‰) are notably controlled by the eluviation of the carbonate rock layers. The δ34S values vary from 18.02‰ to 27.01‰; the relatively high values indicate the eluviation of sedimentary rock layers. The high 87Sr/86Sr ratios (0.70806−0.71270) and the high Sr2+ concentrations (0.69−2.92 mg/L) suggest that the Sr in the deep geothermal fluids originates from the eluviation of both silicates and carbonates. According to the multimineral equilibrium diagram, chalcedony is saturated at the measured temperature of geothermal wells; therefore, we chose chalcedony as a geothermal thermometer for the calculation of the reservoir temperature of the Wumishan Formation, and the results vary from 68.63 to 89.10°C. Our study identifies the geothermal type of the deep medium-low temperature hydrothermal systems and also recognizes their water-rock interaction processes. We get a comprehensive understanding that the geothermal resources in the Wumishan Formation beneath Xiong’an New Area is convection-conduction type, for which potential of geothermal development and utilization is enormous.