The Sangdong W (tungsten)-deposit is known as one of the world’s largest W-deposits, a magmatic–hydrothermal ore deposit including both skarn and hydrothermal alteration zones. The strata-bound characteristic of the deposit resulted in three major orebodies (hanging wall, main, footwall). The main ore mineral is a scheelite (CaWO4)–powellite (CaMoO4) solid solution. We examined the fluid evolution and scheelite formation process of the quartz–scheelite veins of the ore deposit, based on the microtextures and geochemical characteristics of the scheelite. After the initial magmatic–hydrothermal fluid release from the granitic body, prograde skarn is formed. In the later prograde stage, secondary fluid rises and precipitates stage I scheelite. Well-developed oscillatory zoning with the highest Mo content indicates continuous fluid infiltration under an open system. Pressure rises as mineralization occurs, generating the pressure release of the retrograde fluid. Fluid migrates downward by the gravitational backflow mechanism, forming stage II to IV scheelites. Dented oscillatory zoning of stage II scheelite is strong evidence of this pressure release. Stage III and IV scheelite do not show specific internal structures with pure scheelite composition. Retrograde scheelites are formed by fractional crystallization under a closed system. The observation of systematical fractional crystallization in the quartz–scheelite vein system is a meaningful result of our research. The geochemical characteristics and microtextural evidence imprinted in scheelites from each stage provide crucial evidence for the understanding of sequential scheelite mineralization of the quartz–scheelite vein system of the Sangdong W-deposit.
In this study, we propose a revised structural model for highly ordered synthetic Ge-akaganéite, a stable analogue of tunnel-type Fe-oxyhydroxide, based on the Rietveld refinement of synchrotron X-ray diffraction data and density functional theory with dispersion correction (DFT-D) calculations. In the proposed crystal structure of Ge-akaganéite, Ge is found not only in the tunnel sites as GeO(OH)3− tetrahedra, but also 4/5 of total Ge atoms are in the octahedral sites substituting 1/10 of Fe. In addition, the tunnel structures are stabilized by the presence of hydrogen bonds between the framework OH and Cl− species, forming a twisted cube structure and the GeO(OH)3− tetrahedra corner oxygen, forming a conjugation bond. The chemical formula of the synthetic Ge-akaganéite was determined to be (Fe7.2Ge0.8)O8.8(OH)7.2Cl0.8(Ge(OH)4)0.2.