Local relaxation around [6]Cr 3+ in synthetic pyrope–knorringite garnets, [8]Mg 3 [6](Al 1-X Cr X 3+) 2 [4]Si 3O 12, from electronic absorption spectra

Pyrope-knorringite garnets, Mg₃(Al_1-X Cr³⁺_X)₂Si₃O₁₂ with X=0.25, 0.50, and 1.00, were synthesized between 9 and 16 GPa and 1300 and 1600 °C, using multianvil high-pressure techniques. The garnets with X=0.25 and 0.50 are fine-grained, pink and violet in color. The end-member knorringites with X=1.00 are black when compact and gray when coarse-grained. The fine powder is greenish gray in natural light and pale pink under a tungsten lamp. Powder remission spectra in the wavenumber range 30 000–10 000 cm^–1 on finely powdered crystals were measured by two different methods: (I.) by the use of a small integrating sphere for small samples or (II.) microscope-spectrometric measurement using diffusely reflected radiation from a 45° illuminated microsample. Both methods yielded similar diffuse reflectance spectra. The following crystal-field parameters of ^[6]Cr³⁺ were determined for garnets with X=0.25, 0.50, 1.00: 10 Dq=17 856, 17 596, 17 286 cm^–1; and B=654, 677, 706 cm^–1; nephelauxetic ratio =(B_field/B_free)= 0.71, 0.74, 0.77. The -values indicate decreasing covalency of the Cr–O bond with increasing Cr content. The 10 Dq value for together with the mean Cr–O distance in end-member knorringite, 1.96 Å (Novak and Gibbs 1971), were used to calculate from the spectral data, local mean Cr–O distances (Langer 2001a) as a function of composition. The results indicate relatively strong local site relaxation with a value of =0.77.     

Fivegite K4Ca2[AlSi7O17(O2 ? xOHx)][(H2O)2 ? xOH]Cl: A new mineral species from the Khibiny alkaline pluton of the Kola Peninsula in Russia

A new mineral fivegite has been identified in a high-potassium hyperalkaline pegmatite at Mt. Rasvumchorr in the Khibiny alkaline complex of the Kola Peninsula in Russia. This mineral is a product of the hydrothermal alteration of delhayelite (homoaxial pseudomorphs after its crystals up to 2 × 3 × 10 cm in size). Hydrodelhayelite, pectolite, and kalborsite are products of fivegite alteration. The associated minerals are aegirine, potassic feldspar, nepheline, sodalite, magnesiumastrophyllite, lamprophyllite, lomonosovite, shcherbakovite, natisite, lovozerite, tisinalite, ershovite, megacyclite, shlykovite, cryptophyllite, etc. Areas of pure unaltered fivegite are up to 2 mm in width. The mineral is transparent and colorless; its luster is vitreous to pearly. Its Cleavage is perfect (100) and distinct (010). Its Mohs hardness is 4, D(meas) = 2.42(2), and D(calc) = 2.449 g/cm³. Fivegite is optically biaxial positive: α 1.540(1), β 1.542(2), γ 1.544(2), and 2V(meas) 60(10)°. Its orientation is X = a, y = c, and Z = b. Its IR spectrum is given. Its chemical composition (wt %; electron microprobe, H₂O determined by selective sorption) is as follows: 1.44 Na₂O, 19.56 K₂O, 14.01 CaO, 0.13 SrO, 0.03 MnO, 0.14 Fe₂O₃, 6.12 Al₂O₃, 50.68 SiO₂, 0.15 SO₃, 0.14 F, 3.52 Cl, 4.59 H₂O; −O = −0.85(Cl,F)2; total 99.66. The empirical formula based on (Si + Al + Fe) = 8 is H_4.22K_3.44Na_0.39Ca_2.07Sr_0.01Fe_0.01Al_1.00Si_6.99O_21.15F_0.06Cl_0.82(SO₄)_0.02. The simplified formula is K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ][(H₂O)_{2 − x} OH _x ]Cl (X = 0−2). Fivegite is orthorhombic: Pm2₁ n, a = 24.335(2), b = 7.0375(5), c = 6.5400(6) ?, V = 1120.0(2) ?³, and Z = 2. The strongest reflections of the X-ray powder pattern are as follows (d, ?, (I, %), [hkl]): 3.517(38) [020], 3.239(28) [102], 3.072(100) [121, 701], 3.040(46) [420, 800, 302], 2.943 (47) [112], 2.983(53) [121], 2.880 (24) [212, 402], 1.759(30) [040, 12.2.0]. The crystal structure was studied using a single crystal: R _hkl = 0.0585. The base of fivegite structure is delhayelite-like two-layer terahedral blocks [(Al,Si)₄Si₁₂O₃₄(O_{4 − x} OH _x )] linked by Ca octahedral chains. K⁺ and Cl⁻ are localized in zeolite-like channels within the terahedral blocks, whereas H₂O and OH occur between the blocks. The mineral is named in memory of the Russian geological and mining engineer Mikhail Pavlovich Fiveg (1899–1986), the pioneering explorer of the Khibiny apatite deposits. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences in Moscow. The series of transformations is discussed: delhayelite K₄Na₂Ca₂[AlSi₇O₁₉]F₂Cl—fivegite K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ]Cl—hydrodelhayelite KCa₂[AlSi₇O₁₇(OH)₂](H₂O)_{6 − x} .     

纤钡锂石 BaMg2LiAl3[Si2O6]2（OH,F）8及其晶体结构

1974年在一水晶矿石英脉晶洞中,发现了一种含Ba、Li的硅酸盐新矿物--纤钡锂石。我们对纤钡锂石进行了光性研究、比重测定、差热及热失重分析、红外光谱分析、X射线单晶结构分析等工作,现分述如下。     

Nanoinclusions of high-pressure hydrous silicate, Mg3Si4O10(OH)2 · n H2O (10?-phase), in mantle olivine: Mechanisms of formation and transformation

The 10?-phase, Mg₃Si₄O₁₀(OH)₂ · nH₂O, where n = 0.65÷2, belongs to the group of dense hydrous magnesium silicates (DHMS), which were produced in experiments and are regarded as hypothetical mineral carriers for H₂O in the mantle. However, DHMS were almost never observed in nature. The only exception is the finding of the 10?-phase as nanoinclusions in olivines from mantle nodules in kimberlites. The inclusions with sizes of a few ten nanometers have a pseudohexagonal habit and are characterized by the presence of voids free of solids. The 10?-phase fills the equatorial parts of the inclusions, and, in the majority of inclusions, it is replaced by the low-pressure serpentine + talc assemblage. Based on the analysis of electron microscope images, a model was proposed for the solid-state formation of inclusions, the precursory material of which was transformed to the 10?-phase with the liberation of a water fluid. According to this model, the formation of hydrous nanoinclusions and their subsequent autoserpentinization occurred without the influx of H₂O from the external medium through the mobilization of intrinsic hydroxyl-bearing point defects trapped during olivine crystallization. The subsequent autoserpentinization of the inclusions occurred during decompression owing to interaction between the inclusion material and the host olivine matrix. The process was accompanied by the partial exhaustion of the fluid phase and the replacement 10?-phase + H₂O = Serp + Tc. The criterion for the credibility of the model is the conservation of the volume of material during the reaction at P = const and T = const. Original Russian Text ? N.R. Khisina, R. Wirth, 2008, published in Geokhimiya, 2008, No. 4, pp. 355–363.     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

我国发现的一种含锂新矿物——纤钡锂石 BaMg2LiAl3[Si2O6]2（OH）8

纤钡锂石产于湖南临武香花岭地区一水晶矿锂云母石英脉晶洞中,与锂云母、石英等矿物共生。矿物为浅黄白色,丝绢光泽,呈针状、纤维状、放射状或平行束状集合体,纤维长达1厘米。经X射线单晶及粉晶衍射测定:该矿物属斜方晶系,空间群Ccca,晶胞参数:a=13.60(?),b=20.24(?),e=5.16(?)。最强衍射线为:10.12(?)(100) 4.05(?)(78) 3.39(?)(91) 2.605(?)(31)2.390(?)(28)。     

Early diagenetic vivianite [Fe3(PO4)2 · 8H2O] in a contaminated freshwater sediment and insights into zinc uptake: A μ-EXAFS, μ-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)₂ · 8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.