Cation diffusion in olivine—III. Mn2SiO4 system

The diffusion coefficients of divalent cations, Ni, Co, Mn, Ca, Sr and Ba in Mn-olivine, Mn₂SiO₄, were determined experimentally by the use of ⁶³Ni, ⁶⁰Co, ⁵⁴Mn, ⁴⁵Ca, ⁸⁵Sr and ¹³³Ba radioactive tracers, respectively. The empirical relationship between the diffusion coefficient and ionic size of diffusional species shows a trend of variation which was similar to that observed in Mg-olivine, Mg₂SiO₄. The similarity in the trend of variation of diffusion in various olivine systems strongly suggests that the trend is characteristic to the crystal structure of olivine. However, the diffusion coefficient of each cation in Mn-olivine was higher than that in Mg-olivine by about two orders of magnitude. It is suggested that this is due to the loose structure of Mn-olivine compared with that of Mg-olivine.     

大洋多金属结核中1nm锰矿相的相变及其主要控制因素研究

多金属结核样品在室温中放置或加热干燥后 ,其中的 1nm锰矿相会部分或全部地相变为 0 7nm锰矿相 ,这说明 0 7nm锰矿相可能不是多金属结核的原生锰矿相 ,而仅仅是 1nm锰矿相的相变产物。研究结果表明 :1nm锰矿相结构中的Cu2 + 、Co2 + 、Ni2 + 等金属阳离子的含量与其结构稳定性有正相关关系 ,即金属离子含量越高 ,其结构越稳定 ,1nm锰矿相越不易相变为 0 7nm锰矿相 ,反之亦然 ;另外 ,不同金属阳离子稳定 1nm锰矿相结构的能力也不同 ,结核中几种主要金属阳离子对 1nm锰矿相结构的稳定能力从大到小为 :Ni2 + >Cu2 + >Co2 + >Zn2 + >Ca2 + =Mg2 + 。     

Some Crystallo-chemical Relations of Nephelines and Feldspars on Stjerny, North Norway

Chemical, X-ray, and optical data are given for coexisting nephelinesand potassium feldspars separated from a nepheline syenite,and of nepheline and albite from pegmatites. Li, Rb, Cs (detectedonly in one nepheline), Ba, and Sr were determined, in additionto the major elements. (Pb and Tl were not detected by the spectrographicmethod used.) Some peculiarities of the mineral structures which are consideredto be important for the partition of elements between the coexistingphases are discussed. The importance of vacancies in nephelines,and their probable restriction to the large cavities in thestructure, is emphasized. It is pointed out that since low concentrations of Rb, Cs, Pb,and Tl are found in both nepheline and feldspar, they cannotbe caused by an unfavourable nepheline structure. They are eithera property of the parent magma or are the result of the physicalconditions of crystallization (i.e. escaping gas phase). Thelow concentrations of Sr, and especially of Ba, in nephelinesare in contrast to the high contents of these elements in thecoexisting feldspars. This is explained by considering the nephelinestructure. The unit cell contains eight structural sites forthe large cations (Na, K, Ca), and there are eight valenciesto satisfy. Six of the sites are smaller than the other two,and preferentially incorporate Na (and Ca) ions. The two largersites will tend to remain as vacant sites. Those which haveto be filled in order to satisfy the charge balance, will preferentiallyincorporate the large univalent ions (K and H₃O). The higher-chargedions (Ba² and Sr²) will pull the anions closer together andreduce the size of the site. They are, therefore, rejected fromthese positions. When nephelines coexist with feldspar, theywill incorporate the maximum amount of Si possible at the temperatureof formation. The substitution of Al for Si simultaneously withthe entry of a divalent cation (as in feldpspar) is, therefore,not possible except in non-feldspathic, extremely desilicifiedrocks. Thus, the entry of a divalent cation will not effectivelyclose the vacant sites. The somewhat higher contents of Sr relativeto Ba in the nephelines is because Sr is more easily incorporatedin the small sites (with Na and Ca).     

层间阳离子对水黑云母层间水赋存状态的影响

水黑云是云母－蛭石的１：１规则间层矿物。本文通过阳郭了交换方法得到多种单离子型（Ｎａ＾＋、Ｋ＾＋、Ｃａ＾２＋、Ｍｇ＾２＋、Ｂａ＾２＋、Ｃｕ＾２＋、Ｚｎ＾２＋、Ｃｏ＾２＋和Ａｌ＾３＋）水黑云母。利用Ｘ射线衍射分析和热分析,探讨了层间阳郭了类型对水黑云母间水赋存状态的影响。     

Effect of Natural Organic Acids on Mobilization of Macro- and Microelements from Rocks

Doklady Earth Sciences - Experimental study of leaching of the main cations (Na, K, Mg, and Ca), alkaline and alkali-earth microelements (Li, Rb, Cs, Be, Sr, and Ba), heavy metals (Mn, Fe, Co, Ni,...     

The interaction of metal ions at the manganese dioxide-solution interface

The adsorption of metal ions was measured and alkalimetric titrations were performed on a synthetic sample of hydrous manganese dioxide. The principal characteristics of this phase, its stoichiometry, X-ray diffraction pattern and surface area, resemble closely naturally occurring manganese minerals.Both sets of experiments indicate that the affinity of the metals for the surface followed the order: Mg < Ca < Sr < Ba < Ni < Zn < Mn <-Co, and that the interaction can be characterized by its pH dependence. A comparison of the amount of metal absorbed with the amount of acid released by the surface showed that the interaction of metals with the hydrous manganese dioxide surface involves (1) the separation of a proton from the covalent bond at the surface, and (2) the association of a solute cation with this site. Mg < Ca < Sr < Ba < Ni < Zn < Mn <-Co, The relative degree of the bond strength is reflected by the specific adsorption potentials, which are determined from the amount of metal that is absorbed by the surface, in the absence of any electrostatic attraction, at the pH of zero point of charge.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

含蛭石晶层间层矿物的可交换性阳离子及交换容量研究

对采自新疆尉犁蛭石矿、河南灵宝-陕西潼关蛭石矿的工业蛭石矿物样品进行了可交换性阳离子与交换容量研究，发现新疆尉犁蛭石矿金云母-蛭石中可交换性阳离子主要为Na^ 和Ca^2 ，其次为Mg^2 、K^ 、Ba^2 和Sr^2 ；而河南灵宝-陕西潼关蛭石矿工业蛭石样品的可交换性阳离子主要为Ca^2 和Mg^2 ，其次为Na^ 、K^ 等。金云母-蛭石和绿泥石-蛭石间层矿物的阳离子交换容量随间层结构中蛭石晶层的含量增加而增大，一般在56．92～98．95mmol／100g之间，仅为蛭石最大阳离子交换容量的一半。金云母-蛭石样品阳离子交换容量大小与K2O含量呈负相关关系，与(Na2O CaO)含量呈正相关关系。     

Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux

 Ni-saturated montmorillonite from Camp-Bertaux heated at different temperatures has been studied by X-ray powder diffraction, X-ray absorption (EXAFS) and vibration IR spectroscopy. Analysis of the experimental data has shown that heating of samples at temperatures higher than 150° C was accompanied by migration of Ni cations into vacant cis-octahedra of 2:1 layers. In the octahedral sheet the Ni cation has two “heavy” (Fe) and four “light” (Al and Mg) nearest octahedral cations. A model for the octahedral cation distribution in Camp-Bertaux montmorillonite was proposed in which Fe and Mg octahedral cations are segregated in small clusters. Received July 7, 1996 / Revised, accepted August 23, 1996     

新矿物——汉江石

新矿物汉江石的理想分子式为Ba2CaV23＋[（Si3AlO10）（OH）2]F（CO3）2。矿物呈黄绿色、深绿色,显微镜下呈浅绿色、淡绿色;单斜晶系,空间群为C2,a=0.52050（12）nm,b=0.9033（2）nm,c=3.2077（8）nm,β=93.49（8）°,V=1.5054（8）nm3,Z=4;二轴晶,正延性,负光性,一组完全解理,干涉色为三级绿,多色性明显,浅绿色-黄绿-深绿色;折射率α=1.615,β=1.655,γ=1.700（589 nm）,2Vobs=114°～115°,2Vcalc=88.8°;显微硬度平均值203 kg/mm2,相当于莫氏硬度4;实测密度平均3.69 g/cm3,计算密度3.78 g/cm3。X射线粉晶衍射的强谱线有1.5866 nm（7）（002）、0.5340 nm（91）（006）、0.4010 nm（10）（ī14）、0.3209 nm（23）（027）、0.2676 nm（100）（ī110）、0.2294 nm（29）（ī37）和0.2008 nm（11）（228）。汉江石的晶体结构由硅酸盐结构单元TOT（二八面体型）和碳酸盐结构单元Ba2Ca（CO3）2F交替组成,可能有3个多型,即1M型,2M型和3T型。     

川东南—黔中及其周边地区下组合烃源岩元素地球化学特征及沉积环境意义

笔者采用ICP-MS测试分析技术,对川东南-黔中及其周边地区震旦-志留纪地层28件样品进行了B、V、Ni、Sr、Ba、Th、U等指示沉积环境的敏感微量元素做了系统测试分析,采用GB/T14506.28-93硅酸盐岩石化学分析方法和X射线荧光光谱法测定主要元素和微量元素含量,并探讨了Sr/Ba、V/Ni、V/(V+Ni)、Sr/Ca、Ca/Mg、Th/U比值与沉积环境的对应关系.分析结果表明,本区下组合沉积环境主要为半深海、深海及浅海滞流环境.元素空间分布的差异性反映了沉积环境的区域性变化.     

膨润土的交换性阳离子组成及其属性分析

系统考察了我国不同产地膨润土的可交换阳离子组成、pH值以及碱性系数，根据层间阳离子组成对各地膨润土进行了属性分析。研究表明，所选矿区膨润土大多是钙基土，矿样的层间阳离子组成存在差异。讨论了膨润土层间阳离子种类、pH值、碱性系数以及其属性之间的关系。对比不同属性划分法后发现，离子比率法是一种全面反映膨润土层间阳离子种类及数量的属性分类方法。     

Dehydration dynamics of Ba-phillipsite: an in situ synchrotron powder diffraction study

 The stepwise dehydration process of the Ba-exchanged form of the zeolite phillipsite was studied by in situ synchrotron X-ray powder diffraction. A series of structure refinements were performed using the Rietveld method on powder diffraction data measured in the interval between 332 and 712 K. At 482 K, more than half of the water molecules were lost. The continuous water loss causes the Ba cations to migrate inside the zeolite channels in order to achieve a stable coordination with the framework oxygens. The dehydration process was completed at 663 K, where a new, completely dehydrated stable phase was detected. The temperature range of stability of this phase was more than 100 K, thanks to the stable coordination of the Ba cations with the framework oxygens. This phase is the first example of completely dehydrated zeolite containing divalent (barium) cations. Received: 8 January 2001 / Accepted: 1 November 2001     

含铬蒙脱石中铬离子占位位置研究

采用提纯后的蒙脱石在不同浓度硫酸铬溶液中进行交换吸附制备了含铬蒙脱石,并利用包括粉末X射线衍射术 （XRD）、电子自旋共振谱术（ESR） 和傅里叶变换红外吸收光谱术（FTIR） 等分析测试手段对铬在蒙脱石中的吸附位置进 行了探索研究。研究结果显示铬离子不仅置换了层间域中的Ca2+,K+和Na+等,而且置换了位于八面体位的Mn2+ 和少量 Al3+,并较大量的进入硅氧四面体的六边形孔洞、甚至有可能置换极少量的四面体位的Al3+和Fe3+等。此外,根据X射线衍 射分析可知,在0.2 mol/L硫酸铬溶液中充分交换吸附后的蒙脱石存在两层水型和单层水型两种含铬蒙脱石,其水合阳离子 分别为[Cr(H2O)6]3+和[Cr(H2O)3O3]3+,当吸附量增大至一定程度后水合铬离子借助TOT结构片的硅氧四面体的底氧形成配位多 面体。     

下扬子南京地区早寒武世幕府山组海平面相对升降的地球化学和碳、氧同位素记录

本文对南京地区早寒武世幕府山组沉积环境及地球化学特征进行了研究,利用元素地球化学和碳、氧同位素特征对古盐度、古水深及古环境的记录,分析幕府山组时期发生的海平面相对升降。结果表明：下扬子南京地区下寒武统幕府山组Mg²⁺/Ca²⁺值与古水深呈负相关,Sr/Ba值、1000Sr/Ca值和V/Ni值与古盐度、古水深呈正相关,Sr/Ba值、1000Sr/Ca值和V/Ni值反映的古盐度、古水深曲线可以指示海平面相对升降。幕府山组样品碳、氧同位素保留了原始海洋的同位素组成：δ¹³C_PDB值分布于0.8‰~3.5‰之间,均值为2.55‰;δ¹⁸O_PDB值分布于-6.9‰~-2.2‰之间,均值为-4.18‰。幕府山组样品的δ¹³C_PDB值大小可以反映海平面的相对升降,两者呈正相关。根据Sr/Ba值、1000Sr/Ca值、V/Ni值、δ¹³C_PDB值和沉积环境演化,绘制了幕府山组海平面相对升降曲线。幕府山组经历了一次海侵-海退旋回,海平面相对升降曲线反映了幕府山组海平面波动频繁,由3次海平面相对上升和3次海平面相对下降组成。     

Local structure of (Ca, Sr)2 (Mg, Co, Zn) Si2O7 melilite solid-solution with modulated structure

The local structure around Co, Zn and Sr atoms in incommensurately modulated, melilite-type X₂T¹ T ₂ ² O₇ (X=Ca and Sr, T¹=Mg, Co and Zn, T²=Si) solid-solutions has been investigated by EXAFS analyses. The modulated structure was confirmed in Ca_2-xSr_xCoSi₂O₇ solid-solutions with X=0.0 to 0.6 and for both Ca₂Mg_1-YCo_YSi₂O₇ and Ca₂Mg_1-YZn_YSi₂O₇ solid-solutions over the whole compositional range at room temperature. The actual bond-distances determined by the EXAFS method for the T¹ site (Co-, Zn-O) in the modulated structure are longer than the mean bond-distances obtained from the X-ray diffraction method. This is attributable to the libration of the T¹ tetrahedra. In the Ca_1-XSr_XCoSi₂O₇ solid-solution both the Sr-O and Co-O distances by the EXAFS method for the X-site increase from Ca end-member to Sr end-member. These increases are respectively 0.8% and 0.6%. This means the local expansions of the tetrahedral sheets and of the XO polyhedra are well matched. In the modulated Ca₂Co_1-YMg_YSi₂O₇ and Ca₂Zn_1-YMg_YSi₂O₇ solid-solutions, the actual Co-O and Zn-O distances for the T¹-sites are nearly constant in the whole compositional range. The compositional variations of the local structure around the cations in the solid-solution are different for the X and T¹ sites. It is concluded that the local geometric restriction for the size of substituted cation in X site is larger than that in T¹ site. The dimension of the tetrahedral sheet puts restriction on the size of the cations situated at the interlayer X sites. In other words, the different behavior of the local geometric restriction between the X and T¹ sites is an important feature of the melilite structure and is also related to the modulated structure.     

Simultaneous flow of water and solutes through geological membranes—I. Experimental investigation

The relative retardation by geological membranes of cations and anions generally present in subsurface waters was investigated using a high pressure and high temperature ‘filtration cell’. The solutions were forced through different clays and a disaggregated shale subjected to compaction pressures up to 9500 psi and to temperatures from 20 to 70°C.The overall efficiences measured increased with increase of exchange capacity of the material used and with decrease in concentration of the input solution. The efficiency of a given membrane increased with increasing compaction pressure but decreased slightly at higher temperatures for solutions of the same ionic concentration.The results further show that geological membranes are specific for different dissolved species. The retardation sequences varied depending on the material used and on experimental conditions. The sequences for monovalent and divalent cations at laboratory temperatures were generally as follows: Li < Na < NH₃ < K < Rb < Cs Mg < Ca < Sr < Ba.The sequences for anions at room temperature were variable, but at 70°C, the sequence was: HCO₃ < I < B < SO₄ < Cl < Br.Monovalent cations contrary to some field data were generally retarded with respect to divalent cations. The differences in the filtration ratios among the divalent cations were smaller than those between the monovalent cations. The passage rate of B, HCO₃, I and NH₃ was greatly increased at 70°C.     

Kinetic analysis of cation exchange in birnessite using time-resolved synchrotron X-ray diffraction

In this study, we applied time-resolved synchrotron X-ray diffraction (TRXRD) to develop kinetic models that test a proposed two-stage reaction pathway for cation exchange in birnessite. These represent the first rate equations calculated for cation exchange in layered manganates. Our previous work has shown that the substitution of K, Cs, and Ba for interlayer Na in synthetic triclinic birnessite induces measurable changes in unit-cell parameters. New kinetic modeling of this crystallographic data supports our previously postulated two-stage reaction pathway for cation exchange, and we can correlate the kinetic steps with changes in crystal structure. In addition, the initial rates of cation exchange, R (ų min⁻¹), were determined from changes in unit-cell volume to follow these rate laws: R = 1.75[]^0.56, R = 41.1[]^1.10, R = 1.15[]^0.50. Thus, the exchange rates for Na in triclinic birnessite decreased in the order: Cs ? K > Ba. These results are likely a function of hydration energy differences of the cations and the preference of the solution phase for the more readily hydrated cation.     

渤海湾盆地石炭-二叠系微量元素特征及其指相意义

本文采用ICP-MS测试分析技术,对渤海湾盆地4口钻井42件石炭—二叠系岩心样进行了Sr、Ba、Ga、V、Ni、Co等沉积环境敏感元素的系统测试分析,讨论6种元素含量及Sr/Ba、Ba/Ga、Ni/Co等比值的变化特征。除去5件样品中的异常点,测试元素大多数集中的变化范围:Sr(100~200)×10-6,Ba(100~700)×10-6,Ga(10~40)×10-6,V(80~200)×10-6,Co(5~30)×10-6,Ni(15~45)×10-6,Sr/Ba 0.2~0.9,Ba/Ga 2~20,Ni/Co 1~4。根据微量元素指标特点结合岩相资料,认为渤海湾盆地本溪组发育海相沉积,太原组发育过渡相沉积,山西组及其以上地层发育陆相沉积。元素指标中,Ba、Sr/Ba和Ba/Ga沉积环境指示意义显著,在判断渤海湾盆地石炭—二叠纪沉积相方面具有实用价值。     

广东三水盆地古近系心组生油层的元素地球化学特征

沉积物的元素地球化学特征是对沉积盆地水体环境以及古气候条件变化的响应。本文根据元素（Al、Fe、Mg、Ca、K、Na、P、V、Ni、Co、Cr、Cu、Zn、Sr、Ba、Cd、Li、Mn、Pb、Ti）的含量及其比值（Al/Ti、Fe/Mn、Sr/Ba、Mg/Ca、Sr/Ca、Na/Ca、V/Cr、Ni/Co、Ni/V）的变化，对三水盆地古近系心组红岗段生油层的沉积条件进行了系统分析。心组红岗段下部（亚段A）表现为较稳定的地球化学特征。各元素丰度及其比值指示这一时期陆源输入持续较高、且物源组成变化不大。由于海水入侵的影响，湖盆水体盐度相对较高，底部水体以弱氧化条件为主，O₂-H₂S界面位于水/沉积物界面附近。红岗段中上部（亚段B、C）的元素地球化学特征变化较为频繁且幅度很大，反映古气候和湖盆沉积条件的迅速变迁。在潮湿气候条件下，沉积物的地球化学特征表现为以Al、Ti为代表的外源元素含量及其比值较高，而Mg、Ca等盆内化学沉积元素含量较低。古氧气指标指示底部水体为还原环境，有利于有机质保存。因而，相应于较高的有机碳含量。在间歇性干旱时期，陆源输入减少，外源元素含量及其比值显著降低。随着蒸发作用的加强，水体盐度加大，内源元素丰度以及Mg/Ca、Sr/Ba、Sr/Ca和Na/Ca比值大幅度上升。底部水体为氧化环境，O₂-H₂S界面多位于水/沉积物界面或沉积物中。上述两种气候条件在红岗段中上部沉积时期交替出现。红岗段沉积后期由于淡水的长期输入，湖水出现逐渐淡化趋势。