Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.     

Studies on the spin Hamiltonian parameters and local structure for Rh4+ and Ir4+ in TiO2

The spin Hamiltonian (SH) parameters (g factors g _x , g _y and g _z and the hyperfine structure constants A _x , A _y and A _z ) and local structure for the rhombic Rh⁴⁺ and Ir⁴⁺ centers in TiO₂ (rutile) are theoretically studied from the perturbation formulas of these parameters for a low spin (S = 1/2) d ⁵ ion under rhombically distorted octahedra. In the calculations, the ligand orbital and spin–orbit coupling contributions as well as the influence of the local lattice distortions are taken into account using the cluster approach. The local axial elongation ratios are found to be about 1.7 and 3 times, respectively, larger for the Rh⁴⁺ and Ir⁴⁺ centers than that (≈0.0075) for the host Ti⁴⁺ site in rutile, while the perpendicular distortion angles (≈−0.28° and −0.42°, respectively) are more than one order in magnitude smaller than the host value (≈−9.12°). This means that the impurity centers exhibit further elongations of the oxygen octahedra and much smaller perpendicular rhombic distortions as compared with those of the host Ti⁴⁺ site in TiO₂. The above local lattice distortions can be mainly ascribed to the substitution of the host Ti⁴⁺ by the nd ⁵ impurities, which may induce different physical and chemical properties for the metal–ligand clusters. In addition, the influence of the Jahn–Teller effect on the local structure may not be completely excluded. The calculated SH parameters show reasonable agreement with the observed values.     

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.     

An approach to modeling trace component activities in silicate melts: NiO

This report presents a model predicting activities for NiO in a wide range of silicate melts that include the components SiO₂, TiO₂, Al₂O₃, MgO, FeO, CaO, Na₂O, and K₂O. The conceptual simplicity of this model, combined with its success in modeling complex variations in activity with melt composition, suggests that the approach may provide insight into the character of trace components in the melt. The model presented in this report considers NiO to exist as Ni²⁺ and O^2? in the melt, and predicts the activity of NiO by modeling variations in both aNi²⁺ and aO^2?. Activities of Ni²⁺ are modeled assuming that NiO mixes randomly with a hypothetical ‘mixing pool’ of cations dominated by cations of similar size and charge to Ni²⁺, mainly Fe²⁺, Mg²⁺, Ca²⁺, and Ni²⁺. aO^2? is modeled as a function of total oxygen ? 2·network-forming cations, with the understanding that O^2? in silicate melts exists in equilibrium with bridging and non-bridging oxygens through reactions of the type Si–O–Si + O^2? → 2 Si–O. For illustration, the model is applied to reduced mafic lunar samples that may have equilibrated with a Ni-bearing metal phase.     

Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

Two pumpellyites with the general formula W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH) _n were studied using ⁵⁷Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe²⁺ and two Fe³⁺ doublets for the Mitsu pumpellyite, and one Fe²⁺ and two Fe³⁺ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe²⁺(X):Fe³⁺(X):Fe³⁺(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe²⁺:Fe³⁺-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca₈(Fe _0.88 ²⁺ Mg_0.68Fe _0.77 ³⁺ Al_1.66)_Σ3.99(Al_5.67Fe _2.34 ³⁺ )_Σ8.01Si₁₂O_42.41(OH)_13.59 and Ca₈(Mg_1.24Fe _0.65 ²⁺ Fe _0.46 ³⁺ Al_1.66)_Σ4.01(Al_6.71Fe _1.29 ³⁺ )_Σ8.00Si₁₂O_42.14(OH)_13.86, respectively. Mean Y–O distances and volumes of the YO₆ octahedra increase with increasing mean ionic radii, i.e., the Fe³⁺→Al substitution at the Y site. However, change of the sizes of XO₆ octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO₆ octahedra. Thus, the geometrical change of the YO₆ octahedra with Fe³⁺→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO₆ octahedra by the ionic substitution of Fe³⁺ for Al causes gradual change of the octahedra to more symmetrical and regular forms.     

安徽栏杆含金刚石基性岩中石榴子石矿物学特征

在中国东部皖北地区分布着新元古代镁铁质岩,其中一些碱性基性岩为金刚石的赋矿岩石。为了确定安徽栏杆金刚石矿区的石榴子石种类,对矿区内不同类型的石榴子石进行系统采样,测定了62件石榴子石微区化学成分。结果显示,安徽栏杆石榴子石矿物化学式A_3~(2+)B_2~(3+)(SiO_4)_3中的A组阳离子由Mg~(2+)、Fe~(2+)和Ca~(2+)离子占位,B主要由Al~(3+)、Fe~(3+)、Mn~(3+)和Cr~(3+)离子占位,三价阳离子主要为Al~(3+),二价阳离子主要为Ca~(2+),表明研究区石榴子石主要为钙铝-钙铁-镁铝石榴子石系列。在62个样品中,发现了超硅石榴子石。经过计算其形成的压力范围为12.1～12.8GPa,深度可达300km。     

An internally consistent model for the thermodynamic properties of Fe−Mg-titanomagnetite-aluminate spinels

A model is developed for the thermodynamic properties of Fe²⁺–Mg²⁺-aluminate-titanate-ferrite spinels of space group Fd3m. The model incorporates an expression for the configurational entropy of mixing which accounts for long-range order over tetrahedral and octahedral sites. Short-range order or departures from cubic symmetry are not considered. The non-configurational Gibbs energy is formulated as a second degree Taylor expansion in six linearly independent composition and ordering variables. The model parameters are calibrated to reproduce miscibility gap constraints, order-disorder phenomena in MgAl₂O₄ and MgFe₂O₄, and Fe²⁺–Mg²⁺ partitioning data between olivine and: (1) aluminate spinels; (2) ferrite spinels; (3) titanate spinels; (4) mixed aluminate-ferrite spinels. This calibration is achieved without invoking non-configurational excess entropies of mixing. The model predicts that the ordering state of FeAl₂O₄ is more normal than that of MgAl₂O₄. It also successfully accounts for heat of solution measurements and activity-composition relations in the constituent binaries. Phase equilibrium constraints require that the structure of Fe₃O₄ is more inverse than random at all temperatures and that Mg²⁺ has a strong tetrahedral site preference with respect to that of Fe²⁺. The analysis suggests that in the titanates short range order on octahedral sites may be significant at temperatures as high as 1300° C. Constraints developed from calibrating the thermodynamic properties of Fe²⁺–Mg²⁺-aluminatetitanate-ferrite spinel solid solutions permit extension of the database of Berman (1988) to include estimates of the end-member properties of hercynite (FeAl₂O₄), ulvöspinel (Fe₂TiO₄), MgFe₂O₄ and cubic Mg₂TiO₄. In constructing these estimates, provision is made for low-temperature magnetic entropy contributions and the energetic consequences of disordering the aluminates and the ferrites. These estimates are consistent with all of the available low-temperature adiabatic calorimetry, high-temperature heat content, and heat of solution measurements on the end-members. The analysis implies that there is a substantial heat capacity anomaly in the range 300°–900° C associated with disordering of the MgAl₂O₄ structure while that in FeAl₂O₄ becomes significant at temperatures above 700° C. The same heat capacity response in the ferrites indicates that the order/disorder transformation is coupled to the antiferromagnetic-paramagnetic transition in MgFe₂O₄ but takes place well above the ferrimagnetic-paramagnetic transition in magnetite. The proposed model is internally consistent with solution theory reported elsewhere for Fe²⁺–Mg²⁺ olivines and orthopyroxenes (Sack and Ghiorso 1989), rhombohedral oxides (Ghiorso 1990a) and the remaining end-member properties of Berman (1988).     

Cation distribution and structure modelling of spinel solid solutions

 This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and unpublished data. Selected compositions include the following cations: Mg²⁺, Al³⁺, Si⁴⁺, Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe³⁺ or Ni²⁺ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and for identifying inconsistencies and inaccuracies in experimental data. Received: 19 February 2001 / Accepted: 1 June 2001     

Effect of the Si/Al ordering on structural parameters and the energetic stabilization of vermiculites – a theoretical study

The effect of the Si/Al distribution in the tetrahedral sheets of the vermiculite mineral has been investigated employing density functional theory. The structures of six models for vermiculite with the structural formula (Mg₄)(Mg₁₂)(Si₈Al₈)O₄₀(OH)₈·24(H₂O) per unit cell were fully optimized. The models differ by the T···Mg²⁺···T coordination of the interlayer Mg²⁺ cations by two central cations from the adjacent tetrahedral sheets of the 2:1 vermiculite layers (T,T=Si,Al). We observed the formation of very strong hydrogen bonds between water molecules solvating the interlayer Mg²⁺ cations and the surface basal oxygen atoms of the 2:1 layers. The directionality of hydrogen bonds is the major factor determining the layer stacking in the vermiculite structure. Results showed that the most stable model is that where only silicon atoms in the tetrahedral sheets coordinate all interlayer Mg²⁺ cations.     

High-<Emphasis Type="Italic">T</Emphasis> behaviour of gedrite: thermoelasticity,cation ordering and dehydrogenation

The thermoelastic behaviour of a natural gedrite having the crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.05 Fe_0.86²⁺ Mn_0.02 Ca_0.04) ^C(Mg_3.44 Fe_0.36²⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69)O₂₂ ^W(OH)₂ has been studied by single-crystal X-ray diffraction to 973 K (Stage 1). After data collection at 973 K, the crystal was heated to 1,173 K to induce dehydrogenation, which was registered by significant changes in unit-cell parameters, M1–O3 and M3–O3 bond lengths and refined site-scattering values of M1 and M4 sites. These changes and the crystal-chemical formula calculated from structure refinement show that all Fe²⁺ originally at M4 migrates into the ribbon of octahedrally coordinated sites, where most of it oxidises to Fe³⁺, and there is a corresponding exchange of Mg from the ribbon into M4. The resulting composition is that of an oxo-gedrite with an inferred crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.93 Ca_0.04) ^C(Mg_2.56 Mn_0.02²⁺ Fe_0.10²⁺ Fe_1.22³⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69) O₂₂ ^W[O_1.12²⁻ (OH)_0.88]. This marked redistribution of Mg and Fe is interpreted as being driven by rapid dehydrogenation at the H3A and H3B sites, such that all available Fe in the structure orders at M1 and M3 sites and is oxidised to Fe³⁺. Thermoelastic data are reported for gedrite and oxo-gedrite; the latter was measured during cooling from 1,173 to 298 K (Stage 2) and checked after further heating to 1,273 K (Stage 3). The thermoelastic properties of gedrite and oxo-gedrite are compared with each other and those of anthophyllite.     

Fe-rich Li-bearing magnesionigerite-6N6S from Xianghualing tin-polymetallic orefield, Hunan Province, P.R. China

The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn_1.81Li_0.67(Fe_1.43Zn_1.19 Mn_0.41)_Σ3.03(Al_14.89Mg_1.46 Ti_0.11Si_0.01)_Σ16.47O₃₀(OH)₂. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) ų, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn_1.80Li_0.97(Fe_1.89Zn_0.91) _Σ2.80 (Al_14.60Mg_1.63 Ti_0.20)_Σ16.43O₃₀(OH)₂ with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li₂O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg²⁺)₄(Al³⁺)₁₈O₃₀(OH)₂. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A _x B_18-x O₃₀(OH)₂, x?=?~4, where A?=?Mg²⁺, Fe²⁺, Zn²⁺; B?=?Al³⁺, Sn⁴⁺, Ti⁴⁺, Li⁺, □.     

Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

OH in zoned amphiboles of eclogite from the western Tianshan,NW-China

Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( ^B Na₂ ^C M²⁺ ₃ M³⁺ ₂ ^T Si₈(OH)₂) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( ^A _0.5 ^B Ca_1.5Na_0.5 ^C M ²⁺ _4.5 M _0.5^{3+ T} Si_7.5Al_0.5(OH)₂) (A = Na and/or K; M ²⁺ = Mg and Fe²⁺; M ³⁺ = Fe³⁺ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm⁻¹) which can be attributed to a local O(3)-H dipole surrounded by ^{M(1) M(3)}Mg₃, ^{M(1) M(3)}Mg₂Fe²⁺ and ^{M(1) M(3)} Fe²⁺ ₃, respectively, an empty A site and ^T Si₈ environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm⁻¹) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.     

Electronic absorption spectra of chromium-bearing sapphirine

Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg_3.40Fe_0.23Al_3.25Cr_0.16)^[6] Al _1.00 ^[6] [O₂/Al_4.53Si_1.47O₁₈] (N) and (Mg_2.53Fe_0.55 Mn_0.04Ti _0.03 ⁴⁺ Al_3.55Cr _0.08 ³⁺ )^[6]Al _1.00 ^[16] [O₂/Al_4.28Si_1.73O₁₈] (Sl). Single crystal spectra in the range 35000–6000 cm^1- showed a slightly polarization dependent absorption edge near 3200 cm^1- (N) or 30000 cm^1- (Sl) and unpolarized bands at 25300 and 17300 cm^1-, typical of spin-allowed transitions, derived from ⁴A_2g→⁴T_1g and ⁴A_2g→⁴T_2g, of Cr³⁺ in octahedral sites, with point symmetry C₁, of the structure. Another weak band at 23000 cm^?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited ⁴T₁ (F)-State of Cr³⁺. These assignments lead to crystal field parameters Dq=1730cm^?1 and B= 685cm^?1 of Cr³⁺ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr³⁺ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr³⁺-transitions, spectra of Sl exhibit weak dd-bands of Fe²⁺ at 10000 and 7700 cm^1-, which are unpolarized in consistency with the C₁ site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv_1/2～-5000 cm^1-) at 15000 and 11000 cm^1-, which occur in E//Y(//b) and E//Z(//_c=12°) only and exhibit an intensity ratio α_Y∶α_z close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe^2+[6]-Fe^3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe²⁺-Fe³⁺ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.     

Ellenbergerite,a new high-pressure Mg-Al-(Ti,Zr)-silicate with a novel structure based on face-sharing octahedra

Ellenbergerite occurs as purple millimetre-size grains associated with talc, kyanite, clinochlore, rutile, and zircon in composite inclusions within decimetre-large pyrope crystals (90–98 mole percent end-member) in the quartzite layer of the Dora Maira massif, Western Alps, from which coesite has been recently reported (Chopin 1984). It is hexagonal, a=12.255(8), c=4.932(4) Å, Z=1, space group P6₃. Mohs hardness 6.5; D_mes 3.15, D_cal 3.10; no cleavage. Uniaxial negative and vividly pleochroic, colourless, colourless to deep lilac with colour zoning. The intensely coloured variety has 1.6789(5), 1.670(1); microprobe analysis yields SiO₂ 39.1, P₂O₅ 0.45, Al₂O₃ 25.1, TiO₂ 4.0, MgO 22.2, FeO 0.20, sum 99.05 wt.% including H₂O 8.0 (coulometrically). The formula calculated on a O₂₈(OH)₁₀ basis (implying 7.5 wt.% H₂O) is Mg_6.71 Fe_0.03 Ti_0.61 Al_6.00 Si_7.92 P_0.08 O₂₈(OH)₁₀ The colour zoning is due to nearly complete TiZr substitution. In addition ellenbergerite may contain more than 8 wt.% P₂O₅ with strictly correlated changes of Si, Mg, Al and Ti+Zr contents, over 80% of which represent the SiAlPMg substitution.The structure has been determined from 1049 observed independent reflections and refined to R=0.034, R_w=0.031, including six of ten protons. It consists of single chains of face-sharing octahedra with one third vacancies extending along the six-fold screw axes, and of pairs of fully occupied face-sharing octahedra linked by edge-sharing to form octahedral double chains parallel to the twofold screw axes, all interconnected by SiO₄ tetrahedra. It may be compared with the dumortierite polymorph with space group P6₃mc derived hypothetically by Moore and Araki (1978). The structural formula is (Mg,Ti,Zr,)₂ Mg₆(Al,Mg)₆ (Si,P)₂ Si₆ O₂₈(OH)₁₀ Face-sharing octahedra are an unusual feature in silicates which results in a dense structure and reflects, considering the common bulk composition, the uncommon high-pressure formation conditions (about 25–30 kbar, 700–800° C). Ti⁴⁺-Fe²⁺ charge transfer between face-sharing octahedra on the six-fold screw axes most likely accounts for the absorption scheme.     

Evaluation of hydrogeochemistry and water quality in Bist-Doab region,Punjab, India

Agricultural activities act as dominant polluter of groundwater due to increased fertilizers and pesticides usage. Bist-Doab region, Punjab, India, is one such region facing deterioration of groundwater quality due to usage of fertilizers. This study aims in delineating and evaluating the groundwater quality in the region. Water samples are collected from canals, reservoir, and shallow and deep groundwater. Water types in canal and reservoir in Kandi region are Mg²⁺HCO₃ ^? and Mg²⁺Ca²⁺Na⁺HCO₃ ^?, respectively. While water types of shallow and deep groundwaters are found to be of two types: Na⁺Mg²⁺Ca²⁺HCO₃ ^? and Ca²⁺Mg²⁺Na⁺HCO₃ ^?. Presence of Mg²⁺ in groundwater at locations adjoining canals indicates recharge due to canal. The major ion (Na⁺, Mg²⁺, Ca²⁺, HCO₃ ^?) chemistry of the region is due to weathering of rocks that are rich in sodic minerals and kankar. Deep groundwater quality in the region meets BIS and WHO standards for drinking purpose, unlike shallow groundwater which is of poor quality at many locations. Both shallow and deep groundwater with high sodium concentration (>1.5 meq/l) affect cropping yield and permeability of soil matrix. High concentration of SO₄ ^2? and NO₃ ^2? (>1 meq/l) in shallow groundwater at few locations indicates influence of anthropogenic (fertilizer) activity. Factor analysis indicates that the major cations, bicarbonate and chloride are derived from weathering/dissolution of source rocks. Higher concentration of nitrate and presence of sulphate in shallow groundwater at few locations is due to usage of fertilizers and pesticides.     

High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

The enthalpies of solution of La₂O₃, TiO₂, HfO₂, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La₂O₃ in these silicate solvents is strongly exothermic and varies little with La₂O₃ concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO₂ is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti⁴⁺ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na⁺ by addition of Ni²⁺ or Cu²⁺. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.     

Pyroxene mineral chemistry of the Jinchuan intrusion,China

Summary Chemical compositions of orthopyroxene and clinopyroxene from the Jinchuan ultramafic intrusion have been obtained by electron microprobe analysis. The Mg number (MgO/(MgO + FeO)) for both pyroxenes falls within narrow ranges, 82–87 for clinopyroxene and 81–85.5 for orthopyroxene, suggesting limited magma differentiation in regard to the present igneous body. The Al₂O₃ content ranges from 2.44 wt.% to 4.43 wt.% and increases with decreasing Mg of the pyroxenes, i.e., with the more evolved magma. This is attributed to the relatively greater effects of Al₂O₃, TiO₂, Cr₂O₃ and Fe₂O₃ than that of SiO₂ on pyroxene crystallization.Negative linear relationships between Ti⁴⁺ and Si⁴⁺, and Al³⁺ and Si⁴⁺ characterize the pyroxenes. In clinopyroxene, regression of Si⁴⁺ versus Al³⁺ results in a straight line with a slope of –1.012, indicating that the decrease of Si⁴⁺ in the crystal structure is matched by an increase only in tetrahedral Al³⁺; octahedral Al³⁺ has remained relatively constant. The negative linear relationship between Ti⁴⁺ and Si⁴⁺ in clinopyroxene reflects either a greater tendency of Ti⁴⁺ to occupy octahedral sites than Al³⁺, or that replacement of Al³⁺ for Si⁴⁺ demands a more efficient charge balance. The scatter in plots of Ti⁴⁺ versus Si⁴⁺ for orthopyroxene indicates that charge balance is not as critical as structure symmetry.The crystallization temperature of pyroxene is calculated to be 1108–1229°C usingWood andBanno's (1973) two pyroxene thermometer, and is within 40°C of that calculated fromWells's (1977) thermometer. The distribution coefficient (Kd) for Mg²⁺ and Fe²⁺ between clinopyroxene and orthopyroxene is estimated to be 0.86, which is higher than that of the other intrusions and lower than that of mantle nodules, but still falls within their Kd-1/T trend. This suggests that the Kd value of pyroxene is controlled mainly by temperature.

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Mineralchemie der Pyroxene der Jinchuan-Intrusion, China

Zusammenfassung Die chemische Zusammensetzung von Orthopyroxenen und Klinopyroxenen aus der ultramafischen Jinchuan Intrusion wurden mit der Mikrosonde bestimmt. Die Mg-Zahl (MgO/(MgO + FeO)) beider Pyroxene liegt innerhalb enger Grenzen, 82–87 für Klinopyroxen und 81–85.5 für Orthopyroxen. Dies weist auf beschränkte magmatische Differentiation der Intrusion hin. Der Al₂O₃-Gehalt liegt zwischen 2.44 Gew.%. und 4.43 Gew.%. und nimmt mit der abnehmenden Mg-Zahl der Pyroxene ab, d.h. mit dem mehr entwickelten Magma. Dies wird damit erklärt, daß Al₂O₃, TiO₂, Cr₂O₃ und Fe₂O₃ einen größeren Einfluß auf die Kristallisation der Pyroxene ausüben als SiO₂.Die Pyroxene werden durch negative lineare Beziehungen zwischen Ti⁴⁺ und Si⁴⁺, sowie Al³⁺ und Si⁴⁺ charakterisiert. In Klinopyroxenen resultiert die Regression von Si⁴⁺ gegen Al³⁺ in einer geraden Linie mit einer Neigung von –1.012. Dies weist darauf hin, daß die Abnahme der Si⁴⁺ Gehalte in die Kristallstruktur durch Zunahme von ausschliesslich tetraedrischem Al³⁺ kompensiert wird; oktaedrisches Al³⁺ ist relativ konstant geblieben. Die negative lineare Beziehung zwischen Ti⁴⁺ und Si⁴⁺ in Klinopyroxenen geht entweder auf eine stärkere Tendenz des Ti₄O₂, oktaedrische Plätze zu besetzen zurück, oder darauf daß ein Ersatz von Al³⁺ für Si⁴⁺ einen effizienteren Ladungsausgleich verlangt. Die unregelmäßige Verteilung der Plots von Ti⁴⁺ gegen Si⁴⁺ in Orthopyroxenen läßt erkennen, daß Ladungsausgleich hier nicht so kritisch ist wie die Symmetrie der Struktur.Die Kristallisationstemperatur der Pyroxene wurde mit dem Zwei Pyroxenthermometer nachWood undBanno (1973) mit 1108–1229°C bestimmt. Diese Werte liegen innerhalb von 40°C des vonWells (1977) berechneten. Der Verteilungskoeffizient (Kd) für Mg²⁺ und Fe²⁺ zwischen Klinopyroxen und Orthopyroxen wird auf 0.86 berechnet; das ist höher als der aus anderen Intrusionen und niedriger als der von Mantelxenolithen, fällt aber immer noch innerhalb des Kd-1/T Trends derselben. Dies legt den Gedanken nahe, daß der Kd Wert der Pyroxene hauptsächlich durch Temperatur bestimmt wird.

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With 6 Figures     

Olivine/melt transition metal partitioning, melt composition, and melt structure—Melt polymerization and Q-speciation in alkaline earth silicate systems

The two most abundant network-modifying cations in magmatic liquids are Ca²⁺ and Mg²⁺. To evaluate the influence of melt structure on exchange of Ca²⁺ and Mg²⁺ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg₂SiO₄-CaMgSi₂O₆-SiO₂ with ?1 wt% m-cations (Mn²⁺, Co²⁺, and Ni²⁺) substituting for Ca²⁺ and Mg²⁺. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca²⁺, Ca²⁺-NBO) is linearly related to NBO/Si, whereas fraction of Mg²⁺-NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of K_D(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, m^melt + Mg^olivine ? m^olivine + Mg^melt, is linear. K_D(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r² (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r² [ΔH = 261(9)-81(3)·Z/r² (Å⁻²)]. From existing information on (Ca,Mg)O-SiO₂ melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qⁿ-species in the melts. The negative ∂K_D(m−Mg)/∂(Z/r²) and ∂(ΔH)/∂(Z/r²) is because increasing Z/r² is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qⁿ-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.