A preliminary stable isotope study on Mogok Ruby, Myanmar

The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ¹³C–δ¹⁸O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ¹⁸O depletion trend with relatively constant δ¹³C values. Ruby formation might have resulted from CO₂-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO₂-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.     

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 A database of 295 spinels was prepared from the literature and unpublished data.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     

Cryptic crustal contamination of MORB primitive melts recorded in olivine-hosted glass and mineral inclusions

The origin of compositional heterogeneities among the magmas parental to mid-ocean ridge basalts (MORB) was investigated using a single rock piece of the olivine-phyric basalt from 43°N, Mid-Atlantic Ridge (AII D11-177). The exceptional feature of this sample is presence of very primitive olivine crystals (90–91 mol% Fo) that are significantly variable in terms of CaO (0.15–0.35 wt%). A population of low-Ca olivine (0.15–0.25 wt% CaO) is also notably distinct from high-Ca olivine population in AII D11-177, and primitive MORB olivine in general, in having unusual assemblage of trapped mineral and glass inclusions. Mineral inclusions are represented by high-magnesian (Mg# 90.7–91.1 mol%) orthopyroxene and Cr-spinel, distinctly enriched in TiO₂ (up to 5 wt%, c.f. <1 wt% in common MORB spinel). Glass inclusions associated with orthopyroxene and high-Ti Cr-spinel have andesitic compositions (53–58 wt% SiO₂). Compared to the pillow-rim glass and “normal” MORB inclusions, the Si-rich glass inclusions in low-Ca olivine have strongly reduced Ca and elevated concentrations of Ti, Na, K, P, Cl, and highly incompatible trace elements. Strong variability is recorded among glass inclusions within a single olivine phenocrysts. We argue that the observed compositional anomalies are mineralogically controlled, and thus may arise from the interaction between hot MORB magmas and crystal cumulates in the oceanic crust or magma chamber.     

High-temperature creep in a Ni2GeO4: a contribution to creep systematics in spinel

 High-temperature creep behavior in Ni₂GeO₄ spinel was investigated using synthetic polycrystalline aggregates with average grain sizes ranging from submicron to 7.4 microns. Cylindrical samples were deformed at constant load in a gas-medium apparatus at temperatures ranging from 1223 to 1523 K and stresses ranging from 40 to 320 MPa. Two deformation mechanisms were identified, characterized by the following flow laws: where σ is in MPa, d is in μm and T is in Kelvin. These flow laws suggest that deformation was accommodated by dislocation creep and grain-boundary diffusion (Coble) creep, respectively. A comparison with other spinels shows that an isomechanical group can be defined for spinels although some differences between normal and inverse spinels can be identified. When creep data for olivine and spinel are normalized and extrapolated to Earth-like conditions, spinel (ringwoodite) has a strength similar to olivine in the dislocation creep regime and is considerably stronger than olivine in the diffusion creep regime at coarse grain size. However, when grain-size reduction occurs, spinel can become weaker than olivine due to its high grain-size sensitivity (Coble creep behavior). Analysis of normalized diffusion creep data for olivine and spinel indicate that spinel is weaker than olivine at grain sizes less than 2 μm. Received: 18 June 2000 / Accepted: 3 April 2001     

Crystal chemistry of some Mg,Cr, V normal spinels from Sludyanka (Lake Baikal,Russia): the influence of V<Superscript>3+</Superscript> on structural stability

A suite of vanadian magnesiochromites from the Sludyanka metamorphic complex (South Lake Baikal, Russia) were investigated by means of X-ray single-crystal structural refinements and microprobe analyses. Various morphological types of Cr–V-bearing Mg spinels are located in calc–silicate metamorphic rocks, in an assemblage that also contains other Cr–V minerals such as escolaite–karelianite, uvarovite–goldmanite, Cr–V-bearing clinopyroxene, tourmaline, amphibole, mica, etc. Along the suite there is widespread V–Cr substitution (0.14 V³⁺ 0.95 afu, 1.02 Cr³⁺ 1.80 afu), and minor, variable Al contents. The Mg content of slightly lesser than 1 afu, is almost constant. Cell parameters and octahedral bond distances increase with V³⁺. Unexpectedly, the Mg–O tetrahedral bond distance also increases slowly with V³⁺. This weak dragging effect contributes towards maintaining distortion of the oxygen array with respect to the ideal CCP, thus providing a shielding effect, which reduces V³⁺–V³⁺ repulsion. This leads to the energetic stabilization of the structure, in spite of the increase of bond strain with increasing V³⁺ contents.     

中国大陆科学钻探CCSD-PP3钻孔地幔岩的尖晶石相部分熔融证据

CCSD PP3超镁铁岩表现为高 Mg 和 Cr,低 Ca 和 Al 特征,是中国东部和超高压变质带上极其罕见的亏损地幔岩,通过地球化学和矿物学和 Re-Os 同位素研究发现岩石来自古元古代岩石圈地幔,并在地幔浅部尖晶石相条件下发生部分熔融,最近一次部分熔融作用发生在中-晚元古代,后经岩石圈厚度加大、拆沉或深俯冲过程,岩石转变为石榴石橄榄岩。     

Structure modelling and cation partitioning of spinel solid solutions at high <Emphasis Type="Italic">T</Emphasis>,<Emphasis Type="Italic">P</Emphasis> conditions

This paper presents evaluation of cation distributions from diffraction data collected at high T, P, and is an extension of the spinel structure modelling procedure by Lavina et al. (2002). Optimised cation-to-oxygen distances are modified for thermal expansion and compressibility at T and P of interest following Hazen and Prewitt (1977) and Hazen and Yang (1999). The procedure is applied to literature data concerning hercynite, spinel s.s., Zn aluminate, Zn ferrite, magnetite and the (Fe₃O₄)_{1– x} (MgAl₂O₄) _x join. Calculated cation distribution is strongly affected by standard deviations in cell parameters and oxygen coordinates. The underestimated values often reported in the literature for powder profile refinements may strongly affect the cation distribution; however, if standard deviations are increased to physically realistic values, consistent results are obtained. For P up to 10 GPa, reasonable evaluations of cation distribution are obtained for spinel s.s., Zn aluminate and magnetite, whereas for Zn ferrite they are limited to 1.8 GPa. For P beyond 10 GPa, compressibility cannot be assumed to be linear; the relationship between cell parameter and pressure is well-defined, but the inaccuracy of oxygen coordinate prevents simple modelling of bond distances with pressure.     

碱性玄武岩中幔源岩石包体内尖晶石成分特征及其岩石学成因意义

通过对我国东部北起黑龙江省南至海南省３１个产地的新生代碱性玄武岩中橄榄岩类 （纯橄岩、方辉橄榄岩及二辉橄榄岩） 包体和辉石岩类包体中的１６０ 多个尖晶石电子探针分析数据, 论述了尖晶石的Ｃｒ－Ａｌ, Ｆｅ－Ｍｇ, Ｎｉ－Ｍｇ 主元素及有关比值和端员组分之间的关系, 分析研究了不同岩类包体中尖晶石的颜色、成分及成因之间的联系。并利用所分析的有关橄榄石、斜方辉石、单斜辉石共生矿物的电子探针分析数据, 采用新的、较合理的Ｂｒｅｙ－Ｋｏｈｌｅｒ温度计及Ｋｏｈｌｅｒ－Ｂｒｅｙ 压力计和Ｂａｌｌｈａｕｓ ｅｔａｌ． 氧逸度计算方法进行了计算, 探讨了尖晶石成分与其形成温度、压力和氧逸度状态的关系, 指出了尖晶石成分所反映的地幔亏损程度及部分熔融程度的变化规律及尖晶石 （相） 稳定的温度、压力和氧逸度范围。     

不同Ni原料对固相法合成MnCoNiO固溶体的反应机理影响研究

以Mn、Co、Ni的无机盐为反应原料,采用固相法制备粉体材料Mn1.8Co0.2NiO4。利用XRD、差热-热失重表征了粉体的晶相及晶型的转化。实验结果表明,不同的Ni原料均可以合成具有单一尖晶石结构的金属氧化物,其中间的反应过程存在差异,差异是由固相反应的拓扑学特征决定的。     

Synthetic MgGa2O4-Mg2GeO4 spinel solid solution and β-Mg3Ga2GeO8: chemistry, crystal structures, cation ordering, and comparison to Mg2GeO4 olivine

 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa₂O₄-Mg₂GeO₄ spinel solid solution (0, 8, 15 and 23 mol% Mg₂GeO₄; 1400 °C, 1 bar) and for spinelloid β-Mg₃Ga₂GeO₈ (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg₂GeO₄ causes the cation distribution of the MgGa₂O₄ component to change from a disordered inverse distribution in end member MgGa₂O₄, ^[4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg₂GeO₄. An increase in a_o with increasing Mg₂GeO₄ component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga³⁺⇄ Mg²⁺+Ge⁴⁺. The spinel exhibits high configurational entropy, reaching 20.2 J mol⁻¹ (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH _D  = αx + βx ², α = 22(3), β = −21(3) kJ mol⁻¹. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg₃Ga₂GeO₈ has cation distribution ^M1[Mg_0.50(2)Ga_0.50(2)] ^M2[Mg_0.96(2)Ga_0.04(2)] ^M3[Mg_0.77(2) Ga_0.23(2)]₂ (Ge_0.5Ga_0.5)₂O₈ (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol⁻¹; eight oxygen basis). Comparison of the crystal structures of Mg_{1+ N} Ga_{2−2 N} Ge _N O₄ spinel, β-Mg₃Ga₂GeO₈, and Mg₂GeO₄ olivine reveals β-Mg₃Ga₂GeO₈ to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg₂GeO₄ component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg₃Ga₂GeO₈ to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999