Molecular dynamics (MD) modeling of the 10-Å phase, Mg3Si4O10(OH)2·xH2O, with x=2/3, 1.0 and 2.0 shows complex structural changes with pressure, temperature and water content and provides new insight into the structures and stabilization of these phases under subduction zone conditions. The structure(s) of this phase and its role as a reservoir of water in the mantle have been controversial, and these calculations provide specific predictions that can be tested by in situ diffraction studies. At ambient conditions, the computed structures of talc (x=0) and the 10-Å phases with x=2/3 and 1.0 are stable over the 350-ps period of the MD simulations. Under these conditions, the 10-Å phases show phlogopite-like layer stacking in good agreement with previously published structures based on powder X-ray diffraction data for samples quenched from high-pressure and high-temperature experiments. The calculations show that the 10-Å phase with x=2.0 is unstable at ambient conditions. The computed structures at P=5.5 GPa and T=750 K, well within the known stability field of the 10-Å phase, change significantly with water content, reflecting changing H-bonding configurations. For x=2/3, the layer stacking is talc-like, and for x=1.0, it is phlogopite-like. The calculations show that transformation between these two stackings occurs readily, and that the talc-like stacking for the x=2/3 composition is unlikely to be quenchable to ambient conditions. For x=2.0, the layer stacking at P=5.5 GPa and T=750 K is different than any previously proposed structure for a 10-Å phase. In this structure, the neighboring basal oxygens of adjacent magnesium silicate layers are displaced by b/3 (about 3 Å) resulting in the Si atoms of one siloxane sheet being located above the center of the six-member ring across the interlayer. The water molecules are located 1.2 Å above the center of all six-member rings and accept H-bonds from the OH groups located below the rings. The b/3-displaced structure does not readily transform to either the talc-like or phlogopite-like structure, because neither of these stackings can accommodate two water molecules per formula unit. There is likely to be a compositional discontinuity and phase transition between the b/3-displaced phase and the phase with phlogopite-like stacking. The simulations reported here are the first to use the recently developed CLAYFF force field to calculate mineral structures at elevated pressures and temperatures. 相似文献
了解全新世的温度变化能为理解目前日益突出的全球变暖、评估未来全球气候变化给出重要的参考。在这项研究中,基于长江下游南漪湖沉积岩芯深度为0~450cm中161个样品的brGDGTs代用指标,对过去12.0ka的大气温度进行重建,以进一步深化对全新世温度变化的理解。发现湖泊周边土壤与湖泊沉积物brGDGTs分子组成存在显著差异:土壤以brGDGTs-Ⅰ系列为主,占到总比重的80%以上,计算得的MBT'5ME平均值为0.81;湖泊表层和柱状沉积物的brGDGTs分子组成更相似,其brGDGT-Ⅰ和brGDGT-Ⅱ分别为43%、48%和62%、35%,对应的MBT'5ME平均值分别为0.44和0.62,因此认为湖泊沉积物brGDGTs主要为自生来源,进而选用基于MBT'5ME的湖泊温度经验计算式进行古温度的重建。重建的南漪湖年均大气温度自12.0 ka B.P.以来变化范围为13.8~22.4℃,根据变化趋势,可以分为4个阶段:①阶段,早全新世(约12.0~8.2 ka B.P.),温度变化范围为15.1~20.6℃,属低温阶段;②阶段,中全新世(约8.2~6.0 ka B.P.),温度为16.8~20.0℃,为稳定高温阶段;③阶段,中晚全新世(约6.0~3.0 ka B.P.),温度为13.8~19.4℃,快速降温阶段;④阶段,晚全新世(约3.0 ka B.P.以来),温度在17.4~22.4℃,快速升温阶段。通过对比其他古气候记录,可以得到以下结论:长江下游地区在约12.0~8.2 ka B.P.时期温度变化主要受高纬度冰川残留的影响,为低温时期;在约8.2~6.0 ka B.P.时期的温度变化主要受到较强的太阳辐射量控制,属稳定高温期,对应全新世大暖期;约6.0 ka B.P.后,温度受到6.0~3.0 ka B.P.中低纬度冷事件以及上升温室气体辐射强迫共同影响,呈现先降后升的"V"型变化趋势。本研究表明长江下游地区自12.0 ka B.P.以来温度变化主要受全球温度变化控制,自晚全新世以来温室气体辐射强迫是影响其温度变化的主要因素。