K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

The bearing of the system CaMgSi2O6CaAl2SiO6CaFeAlSiO6 on fassaitic pyroxene

The system CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ has been studied in air at 1 atm. The phase assemblage at subsolidus temperatures in the CaMgSi₂O₆-rich portion is Cpx + An + Mel and that in the CaMgSi₂O₆-poor portion Cpx + An + Mel + Sp. At subsolidus temperatures the sigle-phase field of clinopyroxene increases with an increase in the CaFeAlSiO₆ component of the system. The Al₂O₃ content of clinopyroxene, however, continues to increase beyond the single-phase field and attains at least 16.04 wt.% Al₂O₃ with 3.9 wt.% Fe₂O₃. The stability field of fassaite in the system over a range of pressures and oxygen fugacities has been estimated from data in the literature as well as the present data. The CaFeAlSiO₆ content of fassaite is dependent on oxygen fugacity, but is not influenced by pressure. The stability field is strongly influenced by oxygen fugacity at low and high pressure, and decreases with decreasing oxygen fugacity. Clinopyroxenes in both volcanic and metamorphic rocks from various localities, when plotted on the CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ triangle, show that there is no compositional gap between diopside and fassaitic pyroxene in metamorphic rocks, and that the fassaitic pyroxene in alkalic rocks becomes richer in both CaAl₂SiO₆ and CaFeAlSiO₅ components as crystallization proceeds. These results agree with those obtained in the experimental study.     

Structure of mineral glasses—I. The feldspar glasses NaAlSi3O8, KAlSi3O8, CaAl2Si2O8

The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO₂ glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO₂ glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results.     

Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm³ (meas.) and 3.92 g/cm³ (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ∼ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na₂O, 0.04 K₂O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe₂O₃, 0.27 Al₂O₃, 17.83 SiO₂, 16.88 TiO₂, 0.74 Nb₂O₅, 5.93 P₂O₅, 5.29 SO₃, 0.14 F, −O=F₂ = −0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)₄O₁₄ is (Ba_3.59Sr_0.13K_0.01)_Σ3.73(Na_2.59Mg_0.21Ca_0.04)_Σ3.04(Ti_2.80Fe _0.26 ³⁺ Nb_0.07)_Σ3.13[(Si_3.93Al_0.07)_Σ4O₁₄(P_1.11S_0.87)_Σ1.98O_7.96](O_2.975F_0.10)_Σ3.075. The simplified formula is Ba₄Na₃Ti₃Si₄O₁₄(PO₄,SO₄)₂(O,F)₃. The mineral is triclinic, space group P or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 ?; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 ?³, Z = 1. The strongest lines of the X-ray powder pattern [d, ? in (I)(hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0 2), 2.921(35)(005), 2.810(40)(1 4), 2.683(90)(200, 01), 2.133(80)( 2), 2.059(40)(204, 1 3, 221), 1.772(30)(0 1, 1 7, 2 2, 2 3). The infrared spectrum is demonstrated. An admixture of P substituting S has been detected in the innelite samples from the Inagli pluton (South Yakutia, Russia). An innelite-phosphoinnelite series with a variable S/P ratio has been discovered. The type material of phosphoinnelite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? I.V. Pekov, N.V. Chukanov, I.M. Kulikova, D.I. Belakovsky, 2006, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2006, No. 3, pp. 52–60. Considered and recommended by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, May 9, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 4, 2005 (proposal 2005-022).     

The stability of UO2OH+ and UO2[HPO4]2−2 complexes at 25°C

The cumulative association constant (β₂) for the geochemically important aqueous complex UO₂[HPO₄]^2?₂ has been determined by potentiometric titration in Na₂HPO₄-UO₂(NO₃)₂ solutions in the pH range 3.9–4.7, at ionic strengths below 0.024 molal with the Newton-Raphson method used to compute β₂ from the chemical analytical data. Based on 25 measurements we obtain logβ₂ = 18.3 ± 0.2 at 25°C. From the same experiments we compute that the association constant of UO₂OH⁺ is 8.9 ± 0.1, in disagreement with the value of 8.3 ± 0.3 for this constant given by Baes and Mesmer (1976).     

N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

利用混合气体的标准样品对激光拉曼探针进行标定,可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样,存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置,提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度(纯度99.999%)的N2、CH4以及CO2钢瓶气,经过在线混合增压,在5 MPa和10 MPa条件下制备了N2摩尔分数为30%、50%和70%的N2-CH4以及N2-CO2混合气体在线标样。该方法制备的标样与70%N2+30%CO2的商用钢瓶气标样对比表明,CO2与N2的拉曼相对峰高以及相对峰面积值的误差在4%以内,具有较高的准确度和重现性。通过不同压力和浓度条件下CH4以及CO2的拉曼相对定量因子测定表明,气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明,本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压,为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。     

Rates of oxygen exchange between the Al2O8Al28(OH)56(H2O)26(aq) (Al30) molecule and aqueous solution

Rates of steady exchange of oxygens between bulk solution and the largest known aluminum polyoxocation: Al₂O₈Al₂₈(OH)₅₆(H₂O)₂₆¹⁸⁺(aq) (Al₃₀) are reported at pH≈4.7 and 32-40°C. The Al₃₀ molecule is a useful model for geochemists because it is ≈2 nm in length, comparable to the smallest colloidal solids, and it has structural complexity greater than the surfaces of most aluminum (hydr)oxide minerals. The Al₃₀ molecule has 15 distinct hydroxyl sites and eight symmetrically distinct bound waters. Among the hydroxyl bridges are two sets of μ₃-OH, which are not present in any of the other aluminum polyoxocations that have yet been studied by NMR methods. Rates of isotopic equilibration of the μ₂-OH and μ₃-OH hydroxyls and bound water molecules fall within the same range as we have determined for other aluminum solutes, although it is impossible to determine rate laws for exchange at the large number of individual oxygen sites. After injection of ¹⁷O-enriched water, growth of the ¹⁷O-NMR peak near 37 ppm, which is assigned to μ₂-OH and μ₃-OH hydroxyl bridges, indicates that these bridges equilibrate within two weeks at temperatures near 35°C. The peak at +22 ppm in the ¹⁷O-NMR spectra, assigned to bound water molecules (η-OH₂), varies in width with temperature in a similar fashion as for other aluminum solutes, suggesting that most of the η-OH₂ sites exchange with bulk solution at rates that fall within the range observed for other aluminum complexes. Signal from one anomalous group of four η-OH₂ sites is not observed, indicating that these sites exchange at least a factor of ten more rapidly than the other η-OH₂ sites on the Al₃₀.     

The kinetics of oxygen exchange between the GeO4Al12(OH)24(OH2)12(aq) molecule and aqueous solutions

We report rates of oxygen exchange with bulk solution for an aqueous complex, ^IVGeO₄Al₁₂(OH)₂₄(OH₂)₁₂⁸⁺(aq) (GeAl₁₂), that is similar in structure to both the ^IVAlO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (Al₁₃) and ^IVGaO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (GaAl₁₂) molecules studied previously. All of these molecules have ε-Keggin-like structures, but in the GeAl₁₂ molecule, occupancy of the central tetrahedral metal site by Ge(IV) results in a molecular charge of +8, rather than +7, as in the Al₁₃ and GaAl₁₂. Rates of exchange between oxygen sites in this molecule and bulk solution were measured over a temperature range of 274.5 to 289.5 K and 2.95 < pH < 4.58 using ¹⁷O-NMR.Apparent rate parameters for exchange of the bound water molecules (η-OH₂) are k_ex²⁹⁸ = 200 (±100) s⁻¹, ΔH^‡ = 46 (±8) kJ · mol⁻¹, and ΔS^‡ = −46 (±24) J · mol⁻¹ K⁻¹ and are similar to those we measured previously for the GaAl₁₂ and Al₁₃ complexes. In contrast to the Al₁₃ and GaAl₁₂ molecules, we observe a small but significant pH dependence on rates of solvolysis that is not yet fully constrained and that indicates a contribution from the partly deprotonated GeAl₁₂ species.The two topologically distinct μ₂-OH sites in the GeAl₁₂ molecule exchange at greatly differing rates. The more labile set of μ₂-OH sites in the GeAl₁₂ molecule exchange at a rate that is faster than can be measured by the ¹⁷O-NMR isotopic-equilibration technique. The second set of μ₂-OH sites have rate parameters of k_ex²⁹⁸ = 6.6 (±0.2) · 10⁻⁴ s⁻¹, ΔH^‡ = 82 (±2) kJ · mol⁻¹, and ΔS^‡ = −29 (±7) J · mol⁻¹ · K⁻¹, corresponding to exchanges ≈40 and ≈1550 times, respectively, more rapid than the less labile μ₂-OH sites in the Al₁₃ and GaAl₁₂ molecules. We find evidence of nearly first-order pH dependence on the rate of exchange of this μ₂-OH site with bulk solution for the GeAl₁₂ molecule, which contrasts with Al₁₃ and GaAl₁₂ molecules.     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

异构比φiC4 /φnC4 和φiC5 /φnC5 的石油地质意义

同分子量的正构烷烃和异构烷烃存在着物理化学性质差异,在运移过程中受围岩的物理化学性质及其它外部因素的影响必然产生分异效应,从而使二者在空间分布上具有一定的特征和规律,异构比指标可以在一定程度上反映出这种特征和规律性。用异构比φ_iC4 /φ_nC4 和φ_iC5 /φ_nC5 指标可以判断有机质的成熟度,研究轻烃运移的途径、方向、生成环境及轻烃的生物降解。     

低硅埃达克岩和高硅埃达克岩问题

低硅埃达克岩(low-SiO2adakites,LSA,SiO2<60%)和高硅埃达克岩(high-SiO2adakites,HSA,SiO2>60%)的术语是Martin等(2005)提出来的。本文不赞同上述分类,因为,他们的低硅埃达克岩是赞岐岩而不是埃达克岩。赞岐岩是幔源的,埃达克岩是壳源的,虽然埃达克岩可以与地幔混合形成高镁的埃达克岩,但仍然是壳源的。不应当把壳源的岩浆和幔源的岩浆混淆起来。     

Solubility of Fe-ettringite (Ca6[Fe(OH)6]2(SO4)3 · 26H2O)

The solubility of Fe-ettringite (Ca₆[Fe(OH)₆]₂(SO₄)₃ · 26H₂O) was measured in a series of precipitation and dissolution experiments at 20 °C and at pH-values between 11.0 and 14.0 using synthesised material. A time-series study showed that equilibrium was reached within 180 days of ageing. After equilibrating, the solid phases were analysed by XRD and TGA while the aqueous solutions were analysed by ICP-OES (calcium, sulphur) and ICP-MS (iron). Fe-ettringite was found to be stable up to pH 13.0. At higher pH-values Fe-monosulphate (Ca₄[Fe(OH)₆]₂(SO₄) · 6H₂O) and Fe-monocarbonate (Ca₄[Fe(OH)₆]₂(CO₃) · 6H₂O) are formed. The solubilities of these hydrates at 25 °C are: