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A strong anomaly was found in the heat capacity of Co3O4 between 1000 K and the decomposition temperature. This anomaly is not related to the decomposition of Co3O4 to CoO. The measured entropy of transition, S=46±4 J mol-1 K-1 of Co3O4, supports the interpretation that this anomaly reflects a spin unpairing transition in octahedrally coordinated Co3+ cations. Experimental values of heat capacity, heat content and entropy of Co3O4 in the high temperature region are provided. The enthalpy of the spin unpairing transition is 53±4 kJ mol-1 of Co3O4.  相似文献   
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This experimental study simulates the interaction of hotter, deeper hydrous mantle melts with shallower, cooler depleted mantle, a process that is expected to occur in the upper part of the mantle wedge. Hydrous reaction experiments (~6 wt% H2O in the melt) were conducted on three different ratios of a 1.6 GPa mantle melt and an overlying 1.2 GPa harzburgite from 1060 to 1260 °C. Reaction coefficients were calculated for each experiment to determine the effect of temperature and starting bulk composition on final melt compositions and crystallizing assemblages. The experiments used to construct the melt–wall rock model closely approached equilibrium and experienced <5% Fe loss or gain. Experiments that experienced higher extents of Fe loss were used to critically evaluate the practice of “correcting” for Fe loss by adding iron. At low ratios of melt/mantle (20:80 and 5:95), the crystallizing assemblages are dunites, harzburgites, and lherzolites (as a function of temperature). When the ratio of deeper melt to overlying mantle is 70:30, the crystallizing assemblage is a wehrlite. This shows that wehrlites, which are observed in ophiolites and mantle xenoliths, can be formed by large amounts of deeper melt fluxing though the mantle wedge during ascent. In all cases, orthopyroxene dissolves in the melt, and olivine crystallizes along with pyroxenes and spinel. The amount of reaction between deeper melts and overlying mantle, simulated here by the three starting compositions, imposes a strong influence on final melt compositions, particularly in terms of depletion. At the lowest melt/mantle ratios, the resulting melt is an extremely depleted Al-poor, high-Si andesite. As the fraction of melt to mantle increases, final melts resemble primitive basaltic andesites found in arcs globally. An important element ratio in mantle lherzolite composition, the Ca/Al ratio, can be significantly elevated through shallow mantle melt–wall rock reaction. Wall rock temperature is a key variable; over a span of <80 °C, reaction with deeper melt creates the entire range of mantle lithologies from a depleted dunite to a harzburgite to a refertilized lherzolite. Together, the experimental phase equilibria, melt compositions, and reaction coefficients provide a framework for understanding how melt–wall rock reaction occurs in the natural system during melt ascent in the mantle wedge.  相似文献   
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Previous research has shown that the Kaapvaal lithospheric mantle is generally reduced and characterised by a decreasing redox state with increasing depth. As a consequence, C-O-H fluids in the Kaapvaal lithospheric mantle are dominated by H2O, CH4, and C2H6. Thermodynamic calculations demonstrate that diamond precipitation from such a fluid during ascend is possible as it is exposed to a more oxidised environment and both CH4 and C2H6 are oxidised. However, the calculations also demonstrate that the diamond precipitation potential from such a fluid decreases when: (1) the mantle is either more reduced or oxidised compared to the Kaapvaal mantle, or (2) the change in temperature with pressure is smaller compared to that of the Kaapvaal mantle. Therefore, the presence of reduced mantle fluid species and a generally decreasing oxygen fugacity with increasing depth do not necessarily warrant diamond precipitation from a rising reduced fluid.  相似文献   
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Paleoproterozoic mafic igneous rocks (2450–1970 Ma) are exposed in the form of layered intrusions, dykes, and volcanic rocks in the Karelian, Kola and Murmansk provinces and in the form of dykes and small intrusions in the Belomorian Province, Eastern Fennoscandian Shield. The age and sequence of mafic dyke emplacement during the Paleoproterozoic are very similar in these regions. Further comparisons of geochemical characteristics of mafic dyke swarms in the Belomorian Province and neighboring cratons show considerable similarities.  相似文献   
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