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.