Diagenetic transformations and silcrete–calcrete intergrade duricrust formation in palaeo‐estuary sediments

The Boteti palaeo‐estuary in northern Botswana is located where the endoreic Boteti river, an overflow from the regional Okavango river system, enters the Makgadikgadi pans. The present work considers diagenetic silica and calcium carbonate dominated transformations. The aims are to help identify precursor conditions for the origin of microcrystalline silcrete–calcrete intergrade deposits while developing insight into pene‐contemporaneous silica and calcite matrix formation. General precursor conditions require the presence of cyclical endoreic freshwater inflow into a saline pan. The pan should be deep enough to sustain a permanent watertable under climatic conditions sufficient to cause carbonate fractionation within the groundwater. Freshwater inflow into a saline pan drives the geochemistry of the system (from freshwater to saline, from neutral to high pH). The geochemistry is controlled by the periodicity of inflow relative to salinity levels of phreatic groundwater in the receptor saline pan. The source of most silica and localized CaCO₃ is derived from the dissolution and precipitation of micro‐fossils, while more general CaCO₃ enrichment stems from saline pan based carbonate fractionation. Diagenetic change leads to colloidal then more consolidated bSiO₂/CaO aggregate formation (amorphous silica) followed by transformations into opaline silica over time. Irregular zones of siliceous sediment forming in otherwise calcareous deposits may relate to the irregular occurrence of biogenic silica in the source sediments, inferring a source for local silica mobilization in intergrade deposits. The distribution of calcareous micro‐fossils may have a similar converse effect. Diagenetic evidence from an intergrade deposit with a low SiO₂/CaO ratio suggests that transformation occurred more into the pan, while an intergrade deposit with a high SiO₂/CaO ratio more likely formed closer to a land margin and was frequently inundated by freshwater. Pene‐contemporaneous silcrete–calcrete intergrade formation under the above conditions may take place where dissolved silica crystallizes out in the vicinity of calcite crystals due to local decreases in pH. The continuing consolidation of bSiO₂/CaO aggregates may be facilitated by the presence of increasing amounts of calcite. It appears that CaCO₃ may act as a catalyst leading to pene‐contemporaneous bSiO₂/CaO aggregate formation. However the processes involved require further work. Copyright © 2013 John Wiley & Sons, Ltd.     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃     

Calculation of <Superscript>17</Superscript>O NMR shieldings in molecular models for crystalline MO,M=Mg,Ca, Sr,and in models for alkaline earth silicates

¹⁷O NMR shieldings are calculated for the central O in the molecular model OM₆(OH)₁₂ ^–2, for crystalline alkaline earth oxides, MO, where M=Mg, Ca, and Sr, using both Hartree–Fock and hybrid Hartree–Fock density-functional theory. Agreement of calculated and experimental NMR shifts of CaO and SrO compared to MgO is good, but only if the basis set on the M atoms has sufficient tight d polarization functions. Preliminary results are also presented for nonbridging O in the silicate Si(OH)₃O^– anion, perturbed by alkaline earth cations, giving trends which agree qualitatively with experiment.     

CaO对钙矾石固化/稳定化重金属铅污染土的影响

为研究CaO的赋存形态及含量对钙矾石固化/稳定化重金属铅污染土效果的影响,采用高铝水泥提供AlO2-,纯石膏或磷石膏提供SO42-,高铝水泥、石膏、普通硅酸盐水泥或生石灰提供CaO,制备不同组分固化剂配比的固化土,测试试样强度和孔隙溶液pH值等宏观物理力学指标,通过醋酸缓冲溶液法测试试样的铅溶出量,对比分析不同固化剂固化土的矿物成分与微观结构特征。结果表明,钙矾石固化/稳定化重金属铅污染土效果显著;钙矾石对孔隙的填充作用带来的增强效果不能代替水化硅酸钙胶结土颗粒的胶结作用,普通硅酸盐水泥对试样的强度更有利,但其后期强度增幅不大,而生石灰有利于固化土强度的持续增长;生石灰较普通硅酸盐水泥对钙矾石的形成、稳定和重金属Pb2+的固化/稳定化更有利;磷石膏和纯石膏对试样的pH值、无侧限抗压强度及钙矾石固化/稳定化重金属Pb2+的效果影响较小;固化土体微观结构特征表明,CaO含量对钙矾石生成形态及作用效果影响显著。当CaO含量较低时,早期生成的钙矾石将向单硫型硫铝酸钙转化。研究成果可丰富重金属污染场地原位处理技术,具有重要的理论意义和工程应用价值。     

CaO/MgO比对固硫剂固硫率的影响

通过对不同燃烧温度和固硫剂添加量下CaO/MgO之比与固硫率之间关系的研究发现,燃烧温度相同而CaO/MgO之比不同时,固硫率不同;燃烧温度不同时,最佳CaO/MgO之比也不同,而且随温度升高而向CaO增多、MgO减少的方向变化。最佳固硫温度以及固硫剂添加量均和CaO/MgO之比与固硫率之间的关系无关。     

矿物光电子能量在地球早期生命起源与进化中的作用

地球早期生命起源的第一步是合成简单的有机化合物，但合成有机物所需能量来源问题长期困扰着学术界。早期地球上丰富的硫化物半导体矿物可将太阳光子转化为光电子，提供持续的能量来源。也正是由于矿物光电子能量较高，在非生物途径合成小分子有机物方面具有优势。其中半导体矿物自然硫转化太阳能产生的光电子能量，是目前所发现的最高的矿物光电子能量，不仅能直接还原CO2分子为甲酸物质，还可催化其他生命基础物质的合成。在全球陆地系统中暴露在阳光下的岩石/土壤表面普遍被一层铁锰氧化物“矿物膜”所覆盖，光照下含半导体矿物水钠锰矿的“矿物膜”产生原位、灵敏、长效的光电流，显示出优异的光电效应。生物光合作用中心Mn4CaO5在裂解水产氧过程中产生成分和结构类似水钠锰矿的结构中间体，地球早期“矿物膜”中水钠锰矿可能促进了锰簇Mn4CaO5与生物光合作用的起源与进化。早期地球半导体矿物为生命起源基本物质的合成提供直接能量来源，矿物光电子能量在地球早期生命起源与进化中起到了重要作用。