Acidities of confined water in interlayer space of clay minerals

The acid chemistry of confined waters in smectite interlayers have been investigated with first principles molecular dynamics (FPMD) simulations. Aiming at a systematic picture, we establish the model systems to take account of the three possible controlling factors: layer charge densities (0 e, 0.5 e and 1.0 e per cell), layer charge locations (tetrahedral and octahedral) and interlayer counterions (Na⁺ and Mg²⁺). For all models, the interlayer structures are characterized in detail. Na⁺ and Mg²⁺ show significantly different hydration characteristics: Mg²⁺ forms a rigid octahedral hydration shell and resides around the midplane, whereas Na⁺ binds to a basal oxygen atom and forms a very flexible hydration shell, which consists of five waters on average and shows very fast water exchanges. The method of constraint is employed to enforce the water dissociation reactions and the thermodynamic integration approach is used to derive the free-energy values and the acidity constants. Based on the simulations, the following points have been gained. (1) The layer charge is found to be the direct origin of water acidity enhancement in smectites because the neutral pore almost does not have influences on water dissociations but all charged pores do. (2) With a moderate charge density of 0.5 e per cell, the interlayer water shows a pKa value around 11.5. While increasing layer charge density to 1.0 e, no obvious difference is found for the free water molecules. Since 1.0 e is at the upper limit of smectites’ layer charge, it is proposed that the calculated acidity of free water in octahedrally substituted Mg²⁺-smectite, 11.3, can be taken as the lower limit of acidities of free waters. (3) In octahedrally and tetrahedrally substituted models, the bound waters of Mg²⁺ show very low pKa values: 10.1 vs 10.4. This evidences that smectites can also promote the dissociations of the coordinated waters of metal cations. The comparison between the two Mg²⁺-smectites reveals that different layer charge locations do not lead to obvious differences for bound and free water acidities.     

最近11万年来东亚季风轨道与千年尺度气候变率在南京下蜀黄土中的记录

对南京李家岗下蜀黄土剖面上部的近20 m地层进行野外观察和室内研究,划分出5层黄土和5层古土壤,按5 cm间距采集了Rb/Sr、色度、磁化率和粒度样品,并在剖面和可追索的相邻剖面上采集了13个光释光测年样品。分析结果显示,Rb/Sr、色度和磁化率等夏季风代用指标曲线所表现的4次岁差变率振荡具有高度的一致性,依据气候地层...     

末次冰消期以来东海内陆架沉积速率及其气候环境响应

对位于东海内陆架浙-闽沿岸泥质带的EC2005孔岩性、粒度以及AMS14C年代进行了分析,着重探讨了研究区自末次冰消期以来的沉积速率变化,划分出4个大的沉积阶段和4次快速沉积事件.千年时间尺度上大的沉积阶段主要受控于物源供应、海平面变化以及可容空间的大小.百年时间尺度上揭示的4次快速沉积事件主要受控于东亚冬季风的增强或...     

古沙漠记录的沉积体系及层序地层研究进展——以鄂尔多斯盆地白垩系为例

鄂尔多斯盆地白垩纪古沙漠沉积地层主要为冲积扇、湖泊、河流、三角洲及沙漠沉积体系.风成沉积和沙漠沉积、风成沉积体系和沙漠沉积体系等概念有必要予以区分.基准面变化是沙漠和河流、湖泊等其他陆相地层对比的基础.鄂尔多斯盆地志丹群划分为上下两个三级层序单元,反映了两期古沙漠由风成沉积强盛期到衰退期的演化,且每个层序可划分为低位、...     

鄂西地区长阳组的时代问题

对长阳组命名剖面的重新观察和研究表明,原认定的长阳组层位不存在误认的问题.来自长阳组命名剖面和相邻剖面长阳组的两件牙形石样品的分析结果显示:长阳组的牙形石化石组合以Siphonodella levis大量发育为特征,兼有少量的Polygnathus inormatus、P.cf.symmetricus、Bispatho...     

内蒙古固阳盆地东北缘更新统洪积物地层的发现及研究意义

关于内蒙古高原的隆升,长期以来研究较少,从更新世的冲、洪积物分布在现今1600～1700m海拔高程的山顶上出发,发现固阳盆地东北缘更新统的洪积物的沉积类型、沉积特点和粗碎屑岩系的组分以及孢粉的资料,无不与内蒙古高原隆升紧密相关.内蒙古高原隆升不是孤立的,而是受青藏高原隆升的控制,它们几乎是同步的或者说紧密相连的.     

聚油古地貌成因类型及其有利成藏条件分析——以鄂尔多斯盆地上里塬地区前侏罗纪古地貌为例

运用地层厚度印模法（延9＋延10＋富县组地层厚度）恢复出了陇东上里塬地区前侏罗纪古地貌形态,其形态为一级甘陕古河呈近东西向分布,二级庆西古河位于研究区南部向北注入甘陕古河,研究区的北部和南部分别发育姬塬和演武高地,在高地和河谷的过度带分别发育姬塬南斜坡和演武北斜坡,此外,在一级河谷中央还发育有河间丘,在斜坡上发育残丘、...     

青藏高原地面有效辐射变化及其对表层土温的影响

利用青藏高原格尔木、狮泉河、昌都日射站及中国科学院冰冻圈观测研究站的观测资料,分析了高原有效辐射的变化,在此基础上结合土壤温度资料讨论了高原北部有效辐射的变化对表层土壤热状况的影响.结果显示：1）青藏高原有效辐射变化因所处的区域不同而异,高原东北部、西部及高原腹地有效辐射总体呈减小的趋势,高原东南部有效辐射呈增大的趋势...     

Influence of Uneven Trace Spacing on Rayleigh Wave Dispersion

Rayleigh wave dispersion signals are significant to underground investigation.Tradition-ally,uniformed trace spacing is employed in surface wave surveys.In some cases,however,uneven trace spacing is often encountered because of the limitations of the site condition.In order to study the influence of uneven trace spacing on the dispersion data construction of Rayleigh waves,data acquisi-tion is performed based on a 2.5D field layout with a linear array of geophones fixed and a mobile source.The observation d...     

Comparison of Results of Recent Seismic Profiles with Tectonic Models of the North China Craton

The geometry and timing of amalgamation of the North China craton(NCC) have been controversial,with three main models with significantly different interpretations of regional structure,geochronology,and geological relationships.The model of Zhao G C et al.suggests that the eastern and western blocks of the NCC formed separately in the Archean,and an active margin was developed on the eastern block between 2.5 and 1.85 Ga,when the two blocks collided above an east dipping subduc-tion zone.The model of Kusky ...