Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.     

Minerals with Brackebuschite-Like Structures: A Novel Solid Solution System Involving Cr<Superscript>6+</Superscript> and V<Superscript>5+</Superscript>

A novel complex continuous system of solid solutions involving vauquelinite Pb₂Cu(CrO₄)(PO₄)(OH), bushmakinite Pb₂Al(VO₄)(PO₄)(OH), ferribushmakinite Pb2Fe³⁺(VO₄)(PO₄)(OH), and a phase with the endmember formula Pb₂Cu(VO₄)(PO₄)(H₂O) or Pb₂Cu(VO₄)(РО₃ОН)(ОН) is studied based on samples from the oxidation zone of the Berezovskoe, Trebiat, and Pervomaisko-Zverevsky deposits in the Urals, Russia. This is the first natural system in which chromate and vanadate anions show a wide range of substitutions and the most extensive solid solution system involving (CrO₄)^2– found in nature. The major couple substitution is Cr⁶⁺ + Cu²⁺ ? V⁵⁺ + M³⁺, where M = Fe, Al. The correlation coefficients calculated from 125 point analyses are: 0.96 between V and (Fe + Al), 0.96 between Cr and (Cu + Zn),–0.96 between V and (Cu + Zn),–0.97 between Cr and (Fe + Al), and–0.97 between (Fe + Al) and (Cu + Zn). The substitutions V⁵⁺ ? Cr⁶⁺ (correlation coefficient–0.98) and to a lesser extent P⁵⁺ ? As⁵⁺ (correlation coefficient–0.86) occur at two types of tetrahedral sites, whereas the metal–nonmetal/metalloid substitutions, i.e., V or Cr for P or As, are minor. The substitution Fe³⁺ ? Al³⁺ is also negligible in this solid solution system.     

多硅白云母中Fe2+的高压有序效应

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。     

Sapphirine II

The crystal structure of aP2₁/a polymorph of sapphirine (a=11.286(3),b=14.438(2),c=9.957(2) Å, β=125.4(2) °) of composition [Mg_3.7Fe _0.1 ²⁺ Al_4.1- Fe _0.1 ³⁺ ]^IV[Si_1.8Al_4.2]^IVO₂₀ was refined using structure factors determined by both neutron and x-ray diffraction methods to conventionalR factors of 0.067 and 0.031. respectively, forF _obs>2σ. The results of the two refinements agree reasonably well, but a half-normal probability plot (Abrahams, 1974) comparing the two data sets indicates that the pooled standard deviations of the atomic coordinates have been underestimated by a factor of two. The structure of sapphirine, solved initially by Moore (1969), consists of cubic closest packed oxygens with octahedral and predominantly tetrahedral layers alternately stacked along [100]. The layer in which 70% of the octahedral sites are occupied has an Mg-Al distribution characterized by Mg-rich octahedra sharing edges mainly with Al-rich octahedra. Mean octahedral bond lengths correlate well with Al occupancy determined by neutron site refinement if the relative number of shared octahedral edges is taken into account (see Table 1). The predominantly tetrahedral layer has 10% of the octahedral sites occupied by Al and 30% of the tetrahedral sites occupied by Al-Si in the ratio 2.33∶1. There are single chains of Al-Si tetrahedra parallel toz with corner-sharing wing tetrahedra (T5 andT6) on either side in the (100) plane. The meanT-O distance is highly correlated with Al occupancy, X_Al, as determined from the neutron site refinement: $$\langle T - O\rangle = 1.656 + 0.105X_{Al} (r^2 = 0.995).$$ Details of the neutron refinement are summarized below.     

Crystal-chemistry and cation ordering in the system diopside-jadeite: A detailed study by crystal structure refinement

The Nybö eclogite pod in Norway is characterized by a great variety of clinopyroxene compositions with Jd contents ranging from less than 5% up to nearly 80%, whilst Ac+Hd contents remain almost constant (mostly within 10±5%).Unconstrained X-ray structure refinement has been carried out on 16 pyroxene crystals (8 with C2/c and 8 with P2/n space group) from the Nybö eclogite, and also on one omphacite crystal (from Lago Mucrone in the Sesia-Lanzo Zone, Western Alps) which displays the highest degree of cation ordering yet described. The final discrepancy factors range from 0.014 to 0.029. The population of the sites has been determined on the basis of bond length considerations and of the results of the site occupancy refinement. Six of these crystals were subsequently analysed by electron microprobe.The tetrahedral sites are occupied by Si with negligible amounts of Al. Al, Mg, Fe³⁺ and Fe²⁺ occur at the octahedral sites; in the ordered P2/n crystals Al and Fe³⁺ are concentrated at the M11 site, whilst Mg and Fe²⁺ are concentrated and the M1 site. The eight-coordinated sites contain Ca and Na with negligible amounts of Fe and/or Mg. Ordering of Ca and Na takes place in the P2/n samples in such a way that in the most ordered crystal the M2 site contains almost exactly 0.75 Na+0.25 Ca and the M21 site 0.25 Na+0.75 Ca.Some geometrical features of the tetrahedra as well as of the octahedra (e.g. tetrahedral quadratic elongation and TILT angle) are not a simple linear function of composition, even when no change in space group occurs. The crystals evidently do not behave like a binary system of the two components, Di and Jd, but behave rather as if the composition Di_0.50 Jd_0.50 was a distinct end member.The boundaries between disordered and ordered phases in the Nybö pyroxenes fall at about 0.35 and 0.65 Jd/(Di+ Jd), in close agreement with the previous TEM investigations.The degree of order varies with composition following a bell-shaped curve: different coaxial bell-shaped curves can be drawn for crystals which have similar compositions but come from different metamorphic environments. The order vs composition diagrams may be useful for the interpretation of the P-T-t histories of the host rocks.     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg₂Li)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg²⁺ → Fe²⁺, 2Mg²⁺ → Li⁺ + Al³⁺, and Mg²⁺ + OH → Al³⁺ + O²⁻. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al_1.5Li_1.5)Al₆(Si₆O₁₈)(BO₃)₃ (OH₂O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.     

Crystal chemistry, surface morphology and X-ray photoelectron spectroscopy of Fe-rich osumilite from Mt. Arci, Sardinia (Italy)

Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K_0.729)_C (Na_0.029)_B (Si_10.498 Al_1.502)_T1 (Al_2.706 Fe _0.294 ²⁺ )_T2 (Mg_0.735 Mn_0.091 Fe _1.184 ²⁺ )_AO₃₀. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe²⁺ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si_2p, Al_2p, Mg_1s and Fe_2p core levels, suggests that Fe presents Fe²⁺ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si⁴⁺ and Si¹⁺ components, respectively, both in tetrahedral coordination. The binding energy of Al_2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L_2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.     

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

A clinopyroxene geobarometer for basaltic systems based on crystal-structure modeling

 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅Al_T−26.826⋅Fe²⁺ _M1−3.764⋅Fe³⁺ +53.989⋅Al_M1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅Mg_M2−691.138⋅Fe²⁺ _M2−688.384⋅Mn−6.267⋅(Mg_M2)²−4.144⋅(Fe²⁺ _M2 where: (Fe²⁺ _M1⋅Mg_M2)/(Fe²⁺ _M2⋅Mg_M1)=e^**(0.238⋅R³⁺+0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R³⁺=Al_M1+Fe³⁺+Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al₂O₃ basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a _CaO and a _SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al₂O₃ (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995     

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.     

Thermodynamics of multicomponent pyroxenes: I. Formulation of a general model

A model is proposed for the thermodynamic properties of multicomponent pyroxenes in the composition space defined by the end-member component CaMgSi₂O₆ and the exchange components Fe(Mg)_-1, TiAl₂(MgSi₂)_-1, Fe³⁺(Al)_-1, Fe³⁺Al(MgSi)_-1, and Mg(Ca)_-1. It is formulated for the simplifying assumptions that: (1) a molecular mixing type approximation describes changes in the molar configurational entropy associated with the coupled exchange substitutions TiAl₂MgSi₂, Fe³⁺AlMgSi, and Al₂MgSi (and their ferroan equivalents), and (2) Fe²⁺ and Mg²⁺, and Al³⁺ and Fe³⁺ display long-range non-convergent ordering between M2 and octahedral M1 sites, and octahedral M1 and tetrahedral sites, respectively. The molar vibrational Gibbs energy is described by a Taylor expansion of second degree in seven linearly independent composition and ordering variables, which is extended to third degree to account for asymmetry in the mixing of Ca and Mg, and Ca and Fe on the M2 site, and is further modified for the assumption that the standard state properties of Ca end-member components of clinopyroxenes are linearly dependent on the coordination number of Ca²⁺ on the M2 site. The model is shown to be consistent with miscibility gap feaures of pyroxenes in the system CaMgSi₂O₆–CaTiAl₂O₆–CaAl₂SiO₆. In subsequent papers, the model is calibrated for the simplifying assumptions that: (1) all regular-solution-type parameters are constants independent of temperature, (2) Pbca and C2/c end-members have identical heat capacities and coefficients of thermal expansion and compressibility, and (3) the heat capacities and coefficients of thermal expansion and compressibility are zero for all reciprocal reactions relating Pbca and pigeonite or high-calcium pyroxene C2/c endmember components.     

The molar volume of FeO–MgO–Fe2O3–Cr2O3–Al2O3–TiO2 spinels

We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe²⁺)(Al, Cr, Fe³⁺)₂O₄ ? (Mg, Fe²⁺)₂TiO₄. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg²⁺, Al³⁺, and Fe³⁺ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.     

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.     

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.     

Mössbauer and infrared spectrometry of lizardite-1T from Monte Fico, Elba

A well crystallized and homogeneous specimen of lizardite from Monte Fico, Elba, Italy, has been studied by Mössbauer and Fourier transform infrared (FTIR) spectrometries. One of the aims was the determination of the oxidation state and the distribution of iron in the structure of this reference sample. Mössbauer data indicate the presence of octahedral ferrous iron, octahedral ferric iron and tetrahedral ferric iron (59.9, 31.3 and 8.8% of total iron, respectively). The existence of only one octahedral site, previously suggested by X-ray structure refinement, is confirmed. The occurrence of tetrahedrally coordinated iron is indicated also by FTIR spectrometry, in particular by the presence of an absorption band at 790 cm^–1. Based also on new electron microprobe data, the improved crystal chemical formula for lizardite from Monte Fico is: (Mg_2.74Fe²⁺ _0.10Fe³⁺ _0.05Al_0.11)_Σ=3.00 ?· (Si_1.94Al_0.05Fe³⁺ _0.01)_Σ=2.00O_5.05(OH)_3.95.     

An analytical electron microscopic study of a pyroxene-amphibole intergrowth

Samples of a garnet granulite from the mafic border units of the Lake Chatuge, Georgia alpine peridotite body were found to contain lamellar intergrowths of a pargastic amphibole in augite having the typical appearance of an exsolution feature. Single crystal X-ray diffraction, optical, electron microprobe and conventional and analytical electron microscopic studies have provided data limiting the compositions and structures of the coexisting phases. Individual lamellae of both materials are from 0.5 to 2.0 m in width with the lamellar interface parallel to {0 1 0}. The formulae of the minerals, as determined by a combination of electron microprobe and analytical electron microscopy, are (Na_0.1Ca_1.0Mg_0.6Fe³⁺ _0.3)(Si_1.8Al_0.2)O₆ for the pyroxene and Na_0.7Ca_1.9(Mg_2.1Fe²⁺ _1.4Fe³⁺ _0.5Ti_0.1Cr_0.1Al_0.8)(Si_5.9Al_2.1) O₂₂(OH)₂ for the amphibole. Several other studies have described intergrowths similar to those observed in this work, in general favoring exsolution as the formation mechanism for the intergrowths. In the Lake Chatuge samples however, replacement of pyroxene by amphibole is in part indicated by continuous gradation of amphibole lamellae into amphiboles rimming the clinopyroxenes.Contribution No. 368 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan     

Crystal Structure and Chemical Composition of Ludwigite from Vranovac Ore Deposit (Boranja Mountain,Serbia)

The crystal structure of ludwigite from Vranovac ore deposit (Boranja Mt., Serbia) was refined using the X-ray powder diffraction (XRPD) Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It has the unit cell dimensions of: a=9.2515(2) ?; b=12.3109(2) ?; c=3.03712(7) ?; and V=345.91(1) ?3. The calculated distances and angles are mostly in good agreement with the Mg2+-Fe2+ substitutions across the M(1) and M(3) sites, as well as with the Fe3+-Al3+ replacement in the M(4) site. However, the mean observed M(2)-O distance is considerably shorter than prescribed, due to a slight increase of the Fe3+ content in the M(2) site. Such replacement was compensated by slight increase of the Fe2+ content in the M(4) site, resulting in the (Mg1.48Fe2+0.46Fe3+0.05Mn0.02)2.01(Fe3+0.94Fe2+0.04Al0.02)1.00B1.00O5 composition. The formation temperature was estimated to be about 500–600°C. The influences of the various chemical compositions to the crystallographic parameters, M-O distances, M(3) and M(4) sites shift, distortion parameters and estimated valences, were also studied and compared with other reference samples.     

Multiple origins of clinopyroxenes in alkali basaltic rocks

Geochemical and textural data on clinopyroxenes in individual alkali basaltic flows from provinces in eastern Australia and the Massif Central can be used to differentiate four different modes of origin (three at high pressure) for these clinopyroxenes. Many single flows from the two provinces contain clinopyroxenes of three, or even four, of these origins. Rare flows contain core clinopyroxene with overgrowths of clinopyroxenes of two distinct generation. Each of the overgrowth is compositionally analogous to clinopyroxenes occurring in xenoliths or as discrete crystals in the same host lava. Such rimming relationships provide evidence that the host magma has undergone high pressure crystallisation and confirm that some xenoliths and megacrysts are cognate. With decreasing pressure the major changes in clinopyroxene chemistry are an increase in the ratio Al^lv/Al^vi, a linear increase of atomic proportions of Ti and Al with decreasing Si, and an increase in the Ti: (100 Mg/(Mg + Σ Fe)) ratio of the pyroxenes. Al₂O₂ wt, % is an unreliable potential geobarometric indicator; consideration of tetrahedral and octahedral site occupancies by Al (Al^lv/Al^vl ratio) is necessary. High-pressure fractionation dominated by clinopyroxene is postulated for some basaltic-composition, resulting in SiO₂ depletion, alkali enrichment and decrease in the Mg/(Mg + Fe²⁺) value of the host magma.     

Structure analysis on synthetic emerald crystals

Single crystals of emerald synthesized by means of the flux method were adopted for crystallographic analyses. Emerald crystals with a wide range of Cr³⁺-doping content up to 3.16 wt% Cr₂O₃ were examined by X-ray single crystal diffraction refinement method. The crystal structures of the emerald crystals were refined to R ₁ (all data) of 0.019–0.024 and wR ₂ (all data) of 0.061–0.073. When Cr³⁺ substitutes for Al³⁺, the main adjustment takes place in the Al-octahedron and Be-tetrahedron. The effect of substitution of Cr³⁺ for Al³⁺ in the beryl structure results in progressively lengthening of the Al–O distance, while the length of the other bonds remains nearly unchanged. The substitution of Cr³⁺ for Al³⁺ may have caused the expansion of a axis, while keeping the c axis unchanged in the emerald lattice. As a consequence, the Al–O–Si and Al–O–Be bonding angles are found to decrease, while the angle of Si–O–Be increases as the Al–O distance increases during the Cr replacement.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.