福建东山变质岩中红柱石晶体结构的再测定及顺磁共振的研究

红柱石为铝硅酸盐矿物,在福建沿海低压区域变质作用带的高铝岩石中普遍出现。它经常与石英、白云母、黑云母共生。红柱石为Al_2SiO_5多形之一,属于铝硅酸盐类SiO_4~(-4)四面体。化学式为Al_2SiO_5·Al_2O_3·SiO_2或(AlO)AJSiO_4。红柱石在Al_2SiO_5组成的多形稳定矿物中,     

松嫩平原苏打盐渍土表层土壤黏粒矿物的组成分析

以松嫩平原内的前郭和大安两地苏打盐渍土表层土壤为供试土壤,采用Rigaku RIX 2000型荧光光谱仪和XRD—7000衍射仪,对土壤黏粒矿物组成进行了分析。结果表明:表层土壤黏粒(2μm)化学组成均以SiO_2、Al_2O_3和Fe2O3为主,其SiO_2/Al_2O_3 4,土壤风化脱硅作用较弱;土壤黏粒以2∶1型层状铝硅酸盐矿物为主,含有蒙脱石、伊利石—蒙脱石混层矿物、伊利石、伊利石—白云母混层矿物、蛭石、1∶1型层状铝硅酸盐高岭石以及少量2∶1∶1型绿泥石和石英及1.42 nm间层矿物。苏打盐渍土处于风化脱K作用阶段,土壤中混层及间层矿物较多,以蛭石—绿泥石、蒙脱石—绿泥石过渡矿物为主,为二八面体白云母和二八面体蒙脱石混层矿物。水田利用可使土壤黏粒中绿泥石增加,改善苏打盐渍土不良的结构。     

蛇绿岩地幔岩中自由SiO2的发现及其地质意义

自由SiO_2系指石英及其同质多型物(polymorphs)柯石英、斯石英等。石英广泛分布于地壳中的各种岩石中,柯石英和斯石英只存在于超高压岩石和陨石坑中。由于石英和非饱和SiO_2的橄榄石不能共生,因此在地幔橄榄岩和超镁铁岩中不存在原生石英。最近笔者在西藏罗布莎蛇绿岩的地幔岩(方辉橄榄岩)的豆荚状铬铁矿中发现了自由SiO_2和柯石英相。根据高温高压相平衡实验资料,橄榄石、辉石这样的硅酸盐矿物在地幔深部的压力条件下可以分解成简单氧化物,如FeO(方铁矿)、MgO(方镁石)以及SiO_2(斯石英)等。由此推测,西藏蛇绿岩地幔岩中自由SiO_2可能是来自于下地幔的矿物,是地幔柱作用将其搬运到上地幔浅部。     

钙钛矿型硅酸盐的热膨胀及地幔分层

位于地下670公里深处的地震不连续带是上、下地幔的分界面,其压强为24GPa,温度为2—3千K。在这样的条件下,上地幔的主要矿物——橄榄石〔(Mg、Fe)_2SiO_4〕、辉石〔(Mg、Fe)SiO_3〕和石榴石〔(Mg、Fe、Ca)_3Al_2Si_2O_2〕将转变为斜方畸变的具钙钛矿结构的〔(Mg、Fe)SiO_3〕矿物或以钙钛矿为主的矿物组合。由于钙钛矿型的硅酸盐至少在70GPa压力下还是稳定的,因而它被认为是下地幔(或许是整个地球)中最主要的矿物。尽管钙钛矿型的硅酸盐很重要,但直到1976年才被发现,而且由于合成这种矿物所需的压力和温度条件很难达到,所以对其物理性质还不甚了解。例如,钙钛矿热膨胀系数对下地幔可能存在的成分模式起着重要的制约作用。最近我们合成了足够量的钙钛矿型的(Mg_0.9,Fe_0.1)SiO_2以便用X射线衍射法测定其在温度达840K时的无压热膨胀。在高温下测得的平均热膨胀系数为4×10~(-6)K~(-1)。这么大的热膨胀系数表明:根据土地幔组分(如地幔岩或石榴石橄榄岩,Mg值≈0.89)的标准模式求得的无压密度,要比推断的下地幔在无压条件下的密度低大纣2%。这一结果显示:上地幔与下地幔的化学性质是不同的;这与地幔热对流的分层模式是一致的。     

同安郭山高岭土中 SiO_2与 Al_2O_3、Fe_2O_3与 TiO_2的相关关系的初步探讨

众所周知,在高岭土中 SiO_2与 Al_2O_3之间的比值是确定高岭石矿物含量的一个重要参数,而 Fe_2O_3与 TiO_2的含量则是评价高岭土质量的重要参数。所以 SiO_2、Al_2O_3、Fe_2O_3、TiO_2是高岭土进行化学成分分析的重要分析项目。大量的分析结果表明,高岭土中的 SiO_2含量增高,Al_2O_3含量则相应降低;而 Fe_2O_3     

贵州汇善谷锶-偏硅酸复合型天然饮用矿泉水成因探讨

绥阳汇善谷温泉是贵州省内碳酸盐岩分布区十分少有的锶-偏硅酸复合型天然温矿泉水。通过对研究区水文地质条件、温矿泉水的水文地球化学及环境同位素特征分析,认为汇善谷复合型温矿泉水的形成受水-岩作用和构造作用控制。温矿泉水中δ~(87)Sr/~(86)Sr同位素值0.709 1～0.709 2,指示锶元素来源于碳酸盐岩-蒸发盐岩建造中的含锶矿物,未见幔源锶供给。δD-~(18)O、δ~(34)SO_4~(2-)同位素表明,该温泉矿泉水在区域内接受大气降水后沿构造面向地下深部渗透循环增温,形成较高温度的地热水,并在CO_2参与下与娄山关组天青石(SrSO_4)和蒸发岩(CaSO_4)及类质同象于石膏、文石、方解石等矿物发生水-岩作用形成富Sr-SO_4~(2-)·HCO_3~--Ca·Mg型水。H_2SiO_3形成在热储深度2 172.8～2 811.2m,热储温度68.9～85.4℃的地质条件下石英矿物的水解和地热水沿断裂对流循环过程中溶滤先期形成的硅化碳酸盐岩、石英脉矿物,使SiO_2不断迁移、富集并结合水体中H+形成H_2SiO_3型温矿泉水。     

钴硅锌矿—一个富钴的硅锌矿变种

钴硅锌矿是一种具有特征深蓝紫色、油脂光泽和玻璃光泽的钴锌硅酸盐矿物,属三方晶系。空间群:C_(3j)~2—R3、a=13.9559A,c=9.3364A,c/a=0.6690,V=1574.8104A~3,Z=18。该矿物理论式为(Zn,Co)_2SiO_4,实验式为:(Zn_(1.26),Co_(O.74))SiO_4。据红外光谱以及X射线粉晶分析,其结构与硅锌矿(Zn_2SiO_4)类似。     

关于硅灰石化学分析项目的研究

硅灰石矿物是一种自然产出的偏硅酸钙,其分子式为[CaO·SiO_2]_3,理论组成是CaO48.3％、SiO_251.7％。它作为工业矿物仅有卅年的历史,由于它具有低温快速烧成的窑业性能,近几年来已引起国内外有关行业的重视。其化学分析项目仍沿用了最初规定的SiO_2、CaO、MgO、Fe_2O_3、Al_2O_3和灼减等6项。从吉林省所发现的几处硅灰石产地来看,其主要矿物成份是硅灰石、方解石、尚有少量白云石、透辉石、石榴石和葡萄石伴生。测定SiO_2、CaO是想知道矿物的主要成份;测定MgO想知道矿物中透辉石、白云石的含量;测定Al_2O_3想知道矿物中石榴石的含量;测定Fe_2O_3想了解矿物中的有害成份;测定灼减想知道矿物中CO_2的大概数。一般说来测定这6个项目基本上能判定硅灰石的质量。对硅灰石矿床进行工业评价时,主要以矿石中有益矿物硅灰石和     

一种修正单斜辉石晶体化学式计算的方法——穆斯堡尔谱在计算晶体化学式中的应用

在研究溧水火山岩中次透辉石矿物时,我们利用了化学分析中全铁分析结果和穆斯堡尔谱图中的三对双峰的面积百分比,对矿物晶体中M_1,M_2晶位上的二价铁和三价铁的占位数值进行了计算。用这种方法计算的结果,对按化学成分直接计算的矿物晶体化学式进行了一定的修正。修正后的矿物晶体化学式,无论是阳离子在矿物晶体中所占的位置,还是各阳离子系数的比值,都更加接近于次透辉石矿物的分子式。     

硅酸盐及其矿物的SCF-CNDO/2法研究——硅酸根离子畸变与键性

一、引言七十年代以来,不少人应用量子化学分子轨道法探讨了一些硅酸盐矿物的结构和性能,初步揭示了其内在的某些相互关联。但硅酸盐矿物结构的许多化学键理论问题还有待于深入探讨,例如大多数硅酸盐矿物中(包括石英)SiO_4~(4-)不形成正四面体构型,各个硅-氧键长及氧-硅-氧键角都有差别。     

Internally-Consistent Thermodynamic Data for Minerals in the System Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2

Internally consistent standard state thermodynamic data arepresented for 67 minerals in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-TiO₂-H₂O-CO₂.The method of mathematical programming was used to achieve consistencyof derived properties with phase equilibrium, calorimetric,and volumetric data, utilizing equations that account for thethermodynamic consequences of first and second order phase transitions,and temperature-dependent disorder. Tabulated properties arein good agreement with thermophysical data, as well as beingconsistent with the bulk of phase equilibrium data obtainedin solubility studies, weight change experiments, and reversalsinvolving both single and mixed volatile species. The reliabilityof the thermodynamic data set is documented by extensive comparisons(Figs. 4–45) between computed equilibria and phase equilibriumdata. The high degree of consistency obtained with these diverseexperimental data gives confidence that the refined thermodynamicproperties should allow accurate prediction of phase relationshipsamong stoichiometric minerals in complex chemical systems, andprovide a reasonable basis from which activity models for mineralsmay be derived.     

Siderit-Magnesit-Mischkristallbildung im system Mg2+-Fe2+-CO 3 2− -Cl 2 2− -H2O

The formation of the solid solution series MgCO₃-FeCO₃ in the system Mg²⁺-Fe²⁺-CO ₃ ^2? -Cl ₂ ^2? -H₂O has been investigstad between 200° C and 500° C. The experimental results show that the composition of any of these carbonates strongly depends on the temperature: At high temperatures mixed crystals rich in MgCO₃ are formed and low temperatures lead to the formation of FeCO₃-rich carbonates. Thus, at 200° C a Fe-poor (Mg-rich) solution is in equilibrium with a Fe-rich carbonate. At temperatures higher than 350° C a Fe-rich (Mg-poor) solution coexists with a Fe-poor (Mg-rich) solid phase; see Fig. 1. At 350° C a solution with a mole fraction^mFe²⁺/(^mFe²⁺+^mMg²⁺) of 0.20 leads to the formation of magnesite very poor in Fe, whereas at 250° C the same solution is in equilibrium with sideroplesit, containing 80 Mol-% FeCO₃, see Figs. 2 and 3. The importance of the experimental results for the formation of deposits of magnesite and siderite is discussed.     

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Single crystal Raman spectra of pyrite-type RuS₂, RuSe₂, OsS₂, OsSe₂, PtP₂, and PtAs₂ are presented and discussed with reference to the energies of the X-X stretching modes _x-x (A _g, F _g) and the X₂ librations (E, 2F_g). The main results obtained are (i) strong Raman resonance effects, (ii) different sequences for _x-x (A _g) and (E _g), i.e., R_{x_2 } $$ " align="middle" border="0"> for PtP₂ and PtAs₂ and R_{x_2 } $$ " align="middle" border="0"> for OsS₂, owing to the interplay of intraionic and interionic lattice forces, (iii) greater strengths for the intraionic P-P and As-As bonds compared to the S-S and Se-Se bonds, respectively, and (iv) a strong influe_gnce of the metal ions on the strength of the X-X bonds.This is contribution LXI of a series of papers on lattice vibration spectra     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation,estimation, and high temperature extrapolation

A revised equation is proposed to represent and extrapolate the heat capacity of minerals as a function of temperature: C _P=k₀+k₁ T ^–0.5+k₂ T ^–2+k₃ T ^–3 (where k₁, k₂0).This equation reproduces calorimetric data within the estimated precision of the measurements, and results in residuals for most minerals that are randomly distributed as a function of temperature. Regression residuals are generally slightly greater than those calculated with the five parameter equation proposed by Haas and Fisher (1976), but are significantly lower than those calculated with the three parameter equation of Maier and Kelley (1932).The revised equation ensures that heat capacity approaches the high temperature limit predicted by lattice vibrational theory (C _P=3R+²VT/). For 16 minerals for which and have been measured, the average C _Pat 3,000 K calculated with the theoretically derived equation ranges from 26.8±0.8 to 29.3±1.9 J/(afu·K) (afu = atoms per formula unit), depending on the assumed temperature dependence of . For 91 minerals for which calorimetric data above 400 K are available, the average C _Pat 3,000 K calculated with our equation is 28.3±2.0 J/(afu·K). This agreement suggests that heat capacity extrapolations should be reliable to considerably higher temperatures than those at which calorimetric data are available, so that thermodynamic calculations can be applied with confidence to a variety of high temperature petrologic problems.Available calorimetric data above 250 K are fit with the revised equation, and derived coefficients are presented for 99 minerals of geologic interest. The heat capacity of other minerals can be estimated (generally within 2%) by summation of tabulated oxide component C _Pcoefficients which were obtained by least squares regression of this data base.     

Studies in the system KAlSiO4-BaAl2Si2O8-SiO2-H2O

Various members of the KAlSi₃O₈-BaAl₂Si₂O₈ feldspar series are hydrothermally synthesized. Cellparameters of these are calculated from diffractometer patterns and found to be similar to those of Gay and Roy. A variation diagram is constructed correlating Cn-content and values of Δ_FeKα(2θ₍₁₁₁₎CaF₂—2θ₍₀₀₄₎Fs_ss), which gives $${\text{Mol}}\% {\text{ Cn = 229}}{\text{.83}}\Delta {\text{2}}\theta ---{\text{190}}{\text{.81}}$$ by a least square regression fitting. Phase equilibria relation in the solidus-liquidus-region for the KAlSi₃O₈-BaAl₂Si₂O₈-H₂O system at 1000 kg/cm² are investigated. It is found to be a case of simple solid solution in a binary system, with reservations at the potassium-rich side of the system. Goranson (1938) gives a temperature of about 1000°C at 1000 kg/cm² \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) for the incongruent melting of sanidine, but the authors prefer a value around 930°C at the same \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) . Reaction products of starting materials on the join KAlSi₂O₆-BaAl₂Si₂O₈ and KAlSiO₄-BaAl₂Si₂O₈ gave no experimental hint for replacement of K⁺ by Ba⁺⁺.