Effects of Spin Transition and Cation Substitution on the Optical Properties and Iron Partitioning in Carbonate Minerals

The high-pressure behavior of deep carbonate dictates the state and dynamics of oxidized carbon in the Earth's mantle,playing a vital role in the global carbon cycle and potentially influencing long-term climate change.Optical absorption and Raman spectroscopic measurements were carried out on two natural carbonate samples in diamond-anvil cells up to 60 GPa.Mg-substitution in high-spin siderite FeCO_(3)increases the crystal field absorption band position by approximately 1000 cm^(-1),but such an effect is marginal at>40 GPa when entering the low-spin state.The crystal field absorption band of dolomite cannot be recognized upon compression to 45.8 GPa at room temperature but,in contrast,the high-pressure polymorph of dolomite exhibits a strong absorption band at frequencies higher than(Mg,Fe)CO_(3)in the lowspin state by 2000–2500 cm^(-1).Additionally,these carbonate minerals show more complicated features for the absorption edge,decreasing with pressure and undergoing a dramatic change through the spin crossover.The optical and vibrational properties of carbonate minerals are highly correlated with iron content and spin transition,indicating that iron is preferentially partitioned into low-spin carbonates.These results shed new light on how carbonate minerals evolve in the mantle,which is crucial to decode the deep carbon cycle.

Ocean Chemistry Revealed by Mineralogical and Geochemical Evidence at the Permian——Triassic Mass Extinction,Offshore the Persian Gulf,Iran

The Upper Permian Dalan Formation and the Lower Triassic Kangan Formation in the Persian Gulf area are mainly composed of shallow marine facies limestone and dolomite.Two subsurface-cored intervals were investigated in order to understand the original mineralogy and paleoceanic conditions.The decreasing trend of Sr concentration in these deposits shows that aragonite was precipitated during the Late Permian and then gradually changed to calcite toward the Permian-Triassic boundary（PTB）.The dissolution rate of aragonite decreased from 60 m below the PTB toward the boundary,with the only exception at 10 m below the Permian-Triassic Boundary（PTB） due to the Permian-Triassic unconformity in this region.The increasing trend of Mg/Ca ratio in a global scale at the end-Permian time shows that the interpreted variation of mineralogy does not result from the change of this ratio.The increasing p（CO2） and decreasing pH are considered to be the main controlling factors.The increase of Ca2＋ at the end-Permian time due to the input of meteoric waters is too little to fully compensate this effect.A local maximum of the Si content just at the PTB confirms the input of runoff waters.

Mineralogical characteristics of soil dust from source regions in northern China

Mineral compositions of aerosol particles were investigated at four sites （Aksu, Dunhuang, Zhenbeitai, and Tongliao） in desert regions of northern China from March to May in 2001 and 2002 during the intensive field campaign period of ACE-Asia （Aerosol Characterization Experiments-Asia）. The X-ray diffraction （XRD） results show the main minerals for Asian dust are illite, chlorite, kaolinite, quartz, feldspar, calcite, and dolomite. Gypsum, hornblende, and halite are also detected in several samples. Semi-quantitative mineralogical data of aerosol samples show that carbonate content decreases from western to eastern source areas; that is, soil dust collected at western source area sites of Dunhuang and Aksu are enriched with carbonate, while northeastern source area site of Tongliao is associated with low carbonate content. But the spatial distribution of feldspar exhibits a different pattern as compared to carbonate, increasing from the western to the eastern sources. The total clay content is significantly higher （73% in average） at the deposition site of Changwu than those at source areas. Air-mass back trajectory studies for the three dust storm events observed at Changwu, showed that soil dust transport pathways were as expected from carbonate content for the source identification, further demonstrating that carbonate was a useful tracer for eolian dust on regional scale in northern China.