硅酸盐玻璃中的Na和K含量电子探针分析条件设定探讨

含Ti硅酸盐玻璃在基础科学研究和应用技术开发上均有重要价值,亟需对其进行准确的成分分析,为进一步的科研工作提供重要的数据支撑.对玻璃进行电子探针分析时,由于样品的易损性和其中(Na和K)阳离子在电子束轰击下极易发生迁移和扩散,因此往往需要经过条件实验来确定合适的分析条件,确保样品在该条件下能够保持尽量稳定的状态,才能获...     

Na2O对高铝粉煤灰合成莫来石的影响

本文研究了Na2O添加量和烧结温度对粉煤灰合成莫来石材料性能、晶体结构和显微形貌的影响。结果表明,Na2O可较大辐度降低粉煤灰合成莫来石的温度。在1300℃,Na2O添加至2%时,生成的莫来石细小,含量较高,但试样强度不高;Na2O添至4%时,莫来石发育为长柱状,长径比约8～12,并且相互交错成网状,材料的机械强度较高,抗折强度为97.71MPa,莫来石相对含量为76.1%;Na2O添加至8%时,莫来石含量明显减少,晶形变为不规则状。在一定范围内,材料的体积密度、烧成线收缩率和抗折强度均随温度的升高而增大,莫来石含量也相应增多。     

K和Na在深俯冲板块中的元素化学行为

放射性钾元素(40 K)是地球演化过程中重要的热源之一,钠(Na)则是俯冲带岩石中的重要组成元素之一。俯冲板块是地壳物质运输到深部地幔的载体,而石榴石和单斜辉石是其中常见的矿物,因此K和Na在单斜辉石和石榴石中行为的研究具有重要意义。本文分以下3个方面总结了近50年来自然界以及高温高压实验中K和Na在石榴石和单斜辉石中行为的研究进展:1含Na、K石榴石的发现及其形成机制,以及Na、K进入石榴石对其晶格所产生的影响;2含K单斜辉石的发现及其形成机制,以及K进入单斜辉石对其晶格所产生的影响;3含K基性岩体系的实验岩石学研究现状。K作为大离子亲石元素,在高温高压下能够分别以KX+Si Y=(Ca,Mg)X+Al Y和MgM1+CaM2=Al M1+KM2的机制进入石榴石和单斜辉石晶格中,对其从地表到深部地幔中的循环具有重要贡献;而在持续俯冲板块中,Na元素在单斜辉石消失后以NaX+Si Y=(Ca,Mg)X+Al Y的机制进入石榴石晶格中,继续被运输到更深的地幔中去。前人在模拟地幔温压条件下对含K玄武岩和单斜辉石体系的高温高压实验研究结果表明,单斜辉石中K2O含量及石榴石中的Na2O含量与压力呈正相关。然而,到目前为止,K和Na在俯冲带温压条件下的富K基性岩(如榴辉岩)体系中的行为仍有待进一步深入研究。     

红外光谱法定量测定石灰岩中游离二氧化硅

采用红外光谱定量测定石灰岩中游离SiO_2可以克服化学分析中硅酸盐(高岭石族矿物例外)中SiO_2的干扰以及X衍射法不能测定非晶质SiO_2相的不足。在样品不含高岭石族矿物时分析的绝对误差小于0.5％。方法具有快速、准确、样品用量少、消耗低等优点。     

粉煤灰的矿物学研究及其成因分析

粉煤灰是燃煤热电厂的废尘。为扩大其综合利用途径,作者应用了多种方法研究其矿物成份、结构特征及共生组合,并探讨了它的形成条件。粉煤灰的化学成份变化比较大,一般为SiO_2 45～60％,Al_2O_3 20～30％,Fe_2O_3 2～25％,及少量K、Na、Ca、Mg、Ti、Mn等。矿物成份可分晶质和非晶质二类。晶质组份有原生的粉屑矿物和新生成的微晶矿物。非晶质组份以新生成的碳粒为主。这二类矿物相由于高温熔融极少呈单独产出,多呈离析共生或粘连成以Si—Al质为主的玻璃体、铁质玻璃、碳粒和石英四类。     

LA-ICP-MS微区原位准确分析含水硅酸盐矿物主量和微量元素

通过描述一种利用LA-ICP-MS准确测定含水硅酸盐矿物主量元素和微量元素含量的多外标、无内标分析方法.总结出该方法基于矿物化学计量式计算含水硅酸盐矿物中挥发分的相对含量,再将全部分析元素归一化到总金属氧化物含量(100%减含水量)的原理,利用多种天然成分的岩石标准玻璃(如MPI-DING玻璃和USGS玻璃)作为外标进行校正计算.利用该方法对角闪石、绿帘石、电气石和透闪石等含水硅酸盐矿物进行了分析,并与利用电子探针和微钻(直径300 μm)取样溶液-ICP-MS分析的结果进行了对比研究.研究结果表明:对于组成均一的主量元素的分析结果与电子探针分析数据一致,相对偏差集中在5%以内.除了那些分布异常不均一的元素(在300 μm尺度上),对微量元素的分析结果与溶液-ICP-MS分析结果具有很好的一致性,二者之间的相对偏差大部分集中在10%以内.研究结论为采用归一化校正策略,选择MPI-DING和USGS玻璃作为外标,利用LA-ICP-MS微区分析方法可以准确测定含水硅酸盐矿物中的主、微量元素含量.      

微生物影响硅酸盐矿物风化作用的模拟试验

研究了硅酸盐细菌对矿物的风化作用。选用土壤中常见的钾长石、伊利石等矿物作为细菌风化作用的对象,通过在含有矿物颗粒的无氮培养基中培养硅酸盐细菌,使其在培养液中与矿物颗粒发生相互作用,再取样并处理后进行电镜观察和X-射线衍射分析。电镜观察结果表明细菌对矿物试样表面确实发生了溶蚀作用,被细菌作用后的矿粉,颗粒浑圆,边缘模糊不清,表面呈凹凸不平状,矿物颗粒被大量的菌体物质所覆盖。用X-射线衍射分析检测到细菌对具不同晶体结构矿物的“选择性”破坏作用,在有多种矿物同时存在的情况下,细菌对较易分解的矿物破坏作用速度较快。结合矿物学与微生物学相关知识,初步分析了细菌培养液中细菌与矿物界面之间的相互作用以及土壤生态系统中矿物的生物风化作用过程。     

柳林泉域滞流区岩溶水的热源及其Na+、Cl-来源探讨

柳林泉域滞流区岩溶水以高温、高Na+和Cl-浓度为主要特征。文章在区域地质及水文地质条件分析基础上,采用化学计量学原理,判断了该区岩溶水的热源及Na+和Cl-的来源。结果显示:在泉域的补给区、径流区和排泄区的上青龙、龙门会、杨家港和寨东泉组,岩溶水中的Na+和Cl-主要来源于岩盐的溶解,其中多余的Na+可能来自于阳离子交换、黄土中含Na+矿物的溶解及城市污水的排放;滞流区和排泄区的刘家疙瘩泉组岩溶水中高浓度的Na+和Cl-也主要来自于岩盐的溶解,而多余的Cl-可能由岩溶水中的Na+交换吸附介质中的Ca2+或Mg2+所致。西部滞流区岩溶水的热源主要包括地温梯度增热、当地正常地温、岩石中放射性元素产热和石膏的溶解放热,其贡献率分别为45%、28%、20%和7%。      

烟曲霉对蛇纹石和橄榄石风化作用的试验研究

含镁硅酸盐矿物是重要自然资源,国内外大都采用传统的化学方法进行开发利用,而微生物法释放含镁硅酸盐矿物中镁和硅的研究还未见报道。试验采用摇瓶培养与对照结合的方法研究烟曲霉(Aspergillusfumigatus)对含镁硅酸盐矿物——蛇纹石和橄榄石的风化作用。试验采用ICP-OES测定第5、10、20、30 d培养液滤液中Mg2+和Si的含量,同时对相应试样的pH值和代谢产物进行分析测定,采用SEM和TEM观察作用后的微生物-矿物聚集体。结果表明,烟曲霉作用蛇纹石和橄榄石试样滤液中的Mg2+和Si含量变化不仅与烟曲霉生长状况有关,而且与矿物的晶体结构相关,蛇纹石较橄榄石更易被烟曲霉风化;另外烟曲霉在生长过程中产生的酸性代谢产物有助于对矿物的风化;SEM和TEM观察结果直观地显示出烟曲霉对蛇纹石和橄榄石的风化作用痕迹。综合分析认为,烟曲霉对蛇纹石和橄榄石的风化作用应该是酸溶作用、菌丝对矿物的穿插包裹和菌丝体对养分的吸收等方式协同作用的综合效果。研究结果为探讨真菌与矿物相互作用的过程与机理以及为微生物法开发蛇纹石和橄榄石矿产资源提供了基础资料。     

地幔岩中不同产状的流体-熔体包裹体及地幔流体交代作用

地幔捕虏体中存在不同产状的熔体包裹体和各种硅酸盐玻璃相,包括主矿物内部的蠕虫状、长圆形、圆形、不规则状包裹体(I型)、边部的连通的管状包裹体(T型)、主矿物边部和粒间的片状熔融体——“浆胞”(C型),三者可见明显过渡关系,它们是地幔流体交代地幔岩石过程中由交代重熔形成的,是研究地幔流体的特征和地幔交代作用的对象之一,从I型、T型到C型,其成分呈规律变化,其中S、Cu、Ni,K、Na含量呈明显的降低趋势．包裹体中玻璃相的成分较主矿物富Si、Al、S、Cu、Ni、K和Na,再加上C02包裹体的发现,表明地幔流体的成分富碱金属、Si、Al、S、Cu、Ni和CO2,地幔交代作用可以使交代产物中Si、Al含量升高而形成中酸性岩浆,也可由于硫化物熔体聚集而形成矿浆．不同地区的地幔流体性质可能存在差异,这些不同性质的地幔流体町能与不同类型的地幔成矿作用有关．     

星叶石族矿物的晶体化学

星叶石是碱性岩中分布较广泛的副矿物,成分富含碱金属K、Na及Ti,随其产出的地球化学条件,类质同象代换情况较复杂,形成许多成分异种。本工作之前对其组成和性质都不十分清楚,前人虽进行了一般矿物学研究,但未能确定所属晶系,B.C.索波列夫曾推断星叶石中Ti呈四面体配位,并与硅氧四面体组成复杂构造。     

A Practical Method for Accurate Measurement of Trace Level Fluorine in Mg‐ and Fe‐Bearing Minerals and Glasses Using Electron Probe Microanalysis

Fluorine plays an important role in magmatic and hydrothermal processes, but due to its low abundance in geological samples determining F is difficult by electron probe microanalysis. By using a W‐Si multi‐layered pseudocrystal as the diffraction crystal instead of thallium acid phthalate (TAP), count rates were considerably higher, which however introduced spectral interferences between FKα and FeLα and MgKβ lines when normal integral mode is applied. In this study, we developed a protocol using a W‐Si multi‐layered pseudocrystal for measuring accurately trace level F in both minerals and glasses. First, we used differential mode with an optimised PHA (pulse height analysis) setting in signal processing, instead of normal integral mode, which completely eliminated the second‐order MgKβ line. Second, the overlap of the first‐order FeLα on FKα peak, which cannot be filtered by modifying the PHA setting, was calibrated quantitatively using F‐free minerals and silicate glasses. Applying this two‐step method, F was determined in a number of reference glasses, as well as in glasses synthesised from powders of the rock reference materials AC‐E, GS‐N and DR‐N. Our data are consistent within error with F concentrations determined by other methods, demonstrating the reliability of this method.     

23Na NMR chemical shifts and local Na coordination environments in silicate crystals,melts and glasses

In order to decipher information about the local coordination environments of Na in anhydrous silicates from ²³Na nuclear magnetic resonance spectroscopy (NMR), we have collected ²³Na magic angle spinning (MAS) NMR spectra on several sodium-bearing silicate and aluminosilicate crystals with known structures. These data, together with those from the literature, suggest that the ²³Na isotropic chemical shift correlates well with both the Na coordination and the degree of polymerization (characterized by NBO/T) of the material. The presence of a dissimilar network modifier also affects the ²³Na isotropic chemical shift. From these relations, we found that the average Na coordinations in sodium silicate and aluminosilicate liquids of a range of compositions at 1 bar are nearly constant at around 6–7. The average Na coordinations in glasses of similar compositions also vary little with Na content (degree of polymerization). However, limited data on ternary alkali silicate and aluminosilicate glasses seem to suggest that the introduction of another network-modifier, such as K or Cs, does cause variations in the average local Na coordination. Thus it appears that the average Na coordination environments in silicate glasses are more sensitive to the presence of other network-modifiers than to the variations in the topology of the silicate tetrahedral network. Further studies on silicate glasses containing mixed cations are necessary to confirm this conclusion.     

Quantum mechanical calculation of 23Na NMR shieldings in silicates and aluminosilicates

To assist in the assignment and interpretation of ²³Na NMR spectra in silicate and aluminosilicate minerals and glasses we have calculated the ²³Na NMR shieldings and the electric field gradients (EFG) at the Na for a number of Na-containing species. Included are Na(OH₂) _n ⁺, n = 1, 2, 4, 5, 6 and 8, and Na⁺ complexes with SiH₃OH, SiH₃ONa and O(SiH₃)₂. We have also evaluated shieldings and EFGs for Na-centered clusters extracted from crystalline Na₂SiO₃ and anhydrous sodalite, Na₆[AlSiO₄]₆. Using 6-31G* SCF optimized geometries and the GIAO method with a 6-31G* basis set [and 6-311(2d,p) bases for the smaller clusters] we find a calculated increase in shielding with coordination number (CN) for the Na(OH₂) _n ⁺, n = 4, 6, 8 series that agrees reasonably well with experimental trends. Calculated changes in the Na shielding as water is replaced by bridging or nonbridging silicate O atoms are also consistent with experimental observations. The deshielding of Na (with respect to gas-phase Na⁺) which is produced by an O-containing ligand is a strongly decreasing function of the R(Na–O) and a weakly decreasing function of the underbonding or free valence of the O. Deshielding contributions to the isotropic shielding from different ligands are additive to good approximation for low CN species, so that the total deshielding can be calculated accurately by summing the contributions from the individual ligands. However for the larger CN species the directly calculated deshieldings are substantially smaller than those obtained using such an additivity approximation. We further test this approximation by calculating the deshieldings for Na in 12 different sites in silicate and aluminosilicate minerals which have recently been studied experimentally, using our calculated deshielding contributions for individual O-containing ligands and experimental values for the Na–O distances. Correlation coefficients between the experimental shifts and the calculated deshieldings are around 0.9 and the slope of the correlation is almost 1.0 . Calculations on large Na-centered clusters extracted from the crystal structures of Na₂SiO₃ and anhydrous sodalite reproduce the experimental values for both NMR shieldings and electric field gradients but at considerable computational cost. Comparison with recent ²³Na NMR studies on hydrous albite glasses indicates that coordination of either H₂O or OH⁻ to the Na could give the magnitude of deshielding observed, depending upon the detailed Na–O distances within the hydrous glass. Received: 31 December 1998 / Revised, accepted: 11 May 1999     

矿物和玻璃中NaK—边的同步辐射XANES研究

本文利用同步辐射的NaK-边X射线近边结构谱（XANES）研究了含Na矿物NaK-边的特征谱，其谱的能量位置随着配位数垢增加而增大，同时建立了含磷（P）的钠玻璃中NaK-边的能量，随着P的含量增加而增大，由此表明本方法可以作为研究含Na矿物和Na玻璃的配位与局部结构的新方法。     

阴离子捕获剂及其在污染防治与环境修复领域中的应用

综述了阴离子捕获剂的结构、性能、制备与表征方法、吸附专属性及其在环境修复方面的应用。阴离子捕获剂是一种具有层状结构的阴离子粘土，由于其特殊的结构和性能，可通过层间阴离子交换、层状结构重建等机制来吸附环境中的阴离子，从而清除环境中的污染物。大量研究表明。阴离子捕获剂对环境中以络阴离子形式存在的重金属污染物有很强的吸附能力，并能有效吸附水体中的N、P、As、Se和放射性元素。此外，阴离子捕获剂还能吸附有机污染物，如农药、酚类化合物、洗涤剂和腐殖质等。从环境中除去不同类型的有毒有害组分。需使用不同类型的阴离子捕获剂。其吸附能力主要由捕获剂本身的特点和外部理化条件所决定。阴离子捕获剂的研究已成为当前环境保护工程和技术研究的一个新热点。     

Energy minimum criteria in modeling structures and properties of minerals

The leading principle in modeling procedures is the minimization of structural energy. It is assumed that the calculated minimal energy has to be compared with the experimental estimate of cohesion energy of a crystal. The reference state for structure energy depends on bonding type: the lattice energy for purely ionic crystals consisting of cations and anions, the atomization energy for covalent and metallic crystals consisting of atoms, the sublimation energy for molecular crystals consisting of molecules etc.As is well-known, a majority of minerals can not be correctly described as purely ionic crystals. Moreover, for these crystals lattice energy cannot be determined empirically because free anions, such as O^2-, S^2-, As^3-, etc., do not exist. In order to describe crystal structures and properties in a better approximation it is usually proposed that the bonding character of such crystals is intermediate between ionic and covalent, so that effective charges instead of formal ones, and an appropriate covalent contribution, are involved in energy calculations. However, the corresponding calculated structure energies are not comparable to any experimental values. Moreover, they decrease with increasing effective charges and a purely ionic structure seems, as before, to be most stable from energetic point of view.     

Petrographic and mineralogical features of amblygonite- and spodumene-carrying granites

Granites carrying amblygonite and spodumene are characterized by 1) little if any, biotite; 2) strong alteration of rock-forming minerals; 3) development of potash feldspar over plagioclase in amblygonite granites; 4) development of plagioclase over potash feldspar + an epidote-garnet accessory mineral association in spodumene granite; 5) concentration of rubidium in amblygonite granites rich in potash feldspar. Amplygonite granite is most typical of greisenized granites and spodumene, of albitized granites. Chemically spodumene granites are of sodium type (Na/K>1), the amblygonite varieties are of potassium type (Na/K<1), and accessory epidote and tourmaline of spodumene and amblygonite granites are richer in lithium than those in common granites. Fluorine in the greisenizing solutions promoted transfer and deposition of lithium as amblygonite. Altered leucocratic granites are most likely to contain lithium minerals. The criterion for lithium presence is its higher content in pneumatolytic and hydrothermal minerals, tourmaline and epidote. — R.M. Hutchinson     

哈密尾亚地区花岗岩类副矿物特征对比

壳－幔混合源型、壳源高铝型、深源碱性型等不同成因的花岗岩类，在演化过程中，其副矿物组合特征是不同的。主要表现在磁铁矿与钛铁矿，锆石与磷灰石之间的含量及比值，以及花岗岩形成演化到中－晚期时，褐帘石、萤石、独居石、石榴石等的出现及其含量多少，在副矿物组合图上表现出不同的曲线形态。尤其锆石晶体形态（在皮藩“ｐｕｐｉｎ”群型图上）的分布位置，与花岗岩成因类型密切相关。锆石的晶面、晶棱特点，可直接反映花岗岩时代的新老。而锆石晶体的长短轴之比、包裹体特征和磷灰石的晶面、晶棱特点、包裹体特征等，在不同代，不同成因类型的花岗岩中都有区别，均具有对比意义。