Subsolidus Phase Relations in the System MgO-SiO_2-Cr-O and Thermodynamic Properties of Related Cr~(2+)-Containing End-members

Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6)     

Omphacite breakdown reactions and relation to eclogite exhumation rates

Clinopyroxene + plagioclase (±Hbl ± Qtz) symplectites after omphacite are widely cited as evidence for prior eclogite-facies or high-pressure (HP) metamorphism. Precursor omphacite compositions of retrograde eclogites, used for reconstructing retrograde P–T paths, are commonly estimated by reintegrating symplectite phases with the assumption that the symplectite-forming reactions were isochemical. Comparisons of broadbeam symplectite compositions to adjacent unreacted pyroxene from various symplectites after clinopyroxene from the Appalachian Blue Ridge (ABR) and Western Gneiss Region (WGR) suggest that the symplectite forming reactions are largely isochemical. Endmember calculations based on reintegrated symplectite compositions from the ABR and WGR suggest that a minor Ca-Eskola (CaEs) component (X_CaEs = 0.04–0.15) was present in precursor HP clinopyroxene. WGR symplectites consist of fine-grained (∼1 μm-scale), vermicular intergrowths of Pl + Cpx II ± Hbl that occur at grain boundaries or internally. ABR symplectites contain coarser (∼10 μm-scale) planar lamellae and rods of Pl + Cpx II + Qtz + Hbl within clinopyroxene cores. The contrasting textures correlate with decompression and cooling rate, and degree of overstepping of the retrograde reaction (lamellar: slow, erosionally controlled exhumation with slow/low overstepping; fine-grained, grainboundary symplectite: rapid, tectonic exhumation with rapid/high overstepping). Variations in X_CaEs, X_jd, and X_CaTs of precursor HP omphacite are related to the symplectic mineral assemblages that result from decompression. Quartz-normative symplectities indicate quartz-producing retrograde reactions (e.g., breakdown of precursor CaEs); quartz-free symplectities (e.g., diopside + plagioclase after omphacite) indicate quartz-consuming reactions (jd, CaTs breakdown) outpaced quartz-producing reactions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Compositional variation of coexisting olivine,orthopyroxene and Fe/Mg-ferrite as a function of T and f_{O_2 }: a geothermometer and oxygen-barometer

A thermodynamic model is developed that describes the compositional variation of coexisting olivine, orthopyroxene, and ferrite (Fe₃O₄-MgFe₂O₄) as a function of and T. The ferrite phase has a cation distribution which varies from nearly inverse to nearly random with increasing T and is described with a model in which the number of sites per formula unit on which mixing occurs varies from 1.67 to 2.0. Given this model and the equilibrium phase composition data for coexisting olivine and ferrite at 1,300° C of Jamieson and Roeder (1984), the ferrite solution is described to an excellent approximation by a symmetric regular solution model with W _ft =+14.0 ±0.3 kJ/mole. Orthopyroxene and olivine non-ideality are also considered. The T-dependence of the equilibrium constant for the oxidation reaction 6Fs+2Mt=6Fa+O₂ and the two Fe/Mg exchange reactions between olivine-ferrite and olivine-orthopyroxene, are used to calculate the compositional variation of coexisting phases as a function of and T. The results are summarized on an isobaric (1 bar) –1/Tplot with the compositional variation of olivine, ferrite, and orthopyroxene shown by sets of isopleths. The ferrite isopleths intersect those of olivine and orthopyroxene at sufficiently high angles for this assemblage to serve as a sensitive geothermometer and oxygen-barometer. The model is applied to orthopyroxene-ferrite symplectite in coronas around olivine in a metamorphosed gabbro, to olivine-hosted orthopyroxene-ferrite symplectite in unmetamorphosed gabbros and norites and to olivine-hosted orthopyroxene-ferrite symplectites developed within the rims of lherzolite xenoliths.     

Formation of clinopyroxene + spinel and amphibole + spinel symplectites in coronitic gabbros from the Sierra de San Luis (Argentina): a key to post-magmatic evolution

The El Arenal metagabbros preserve coronitic shells of orthopyroxene ± Fe‐oxide around olivine, as well as three different types of symplectite consisting of amphibole + spinel, clinopyroxene + spinel and, more rarely, orthopyroxene + spinel. The textural features of the metagabbros can be explained by the breakdown of the olivine + plagioclase pair, producing orthopyroxene coronas and clinopyroxene + spinel symplectites, followed by the formation of amphibole + spinel symplectites, reflecting a decrease in temperature and, possibly, an increase in water activity with respect to the previous stage. The metagabbros underwent a complex P–T history consisting of an igneous stage followed by cooling in granulite, amphibolite and greenschist facies conditions. Although the P–T conditions of emplacement of the igneous protolith are still doubtful, the magmatic assemblage suggests that igneous crystallization occurred at a pressure lower than 6 kbar and at 900–1100 °C. Granulitic P–T conditions have been estimated at about 900 °C and 7–8 kbar combining conventional thermobarometry and pseudosection analysis. Pseudosection calculation has also shown that the formation of the amphibole + spinel symplectite could have been favoured by an increase in water activity during the amphibolite stage, as the temperature of formation of this symplectite strongly depends on aH₂O (<740 °C for aH₂O = 0.5; <790 °C for aH₂O = 1). Furthermore, but not pervasive, re‐equilibration under greenschist facies P–T conditions is documented by retrograde epidote and chlorite. The resulting counterclockwise P–T path consists of progressive, nearly isobaric cooling from the igneous stage down to the granulite, amphibolite and greenschist stage.     

Development of orthopyroxene-Fe/Mg ferrite symplectites by continuous olivine oxidation

The development of orthopyroxene-Fe/Mg ferrite symplectites associated with olivine is discussed with respect to the chemical reactions by which they form. Previously proposed reactions are presented graphically and the differences between them are reviewed. With the exception of exsolution, these are all discontinuous reactions in the sense that olivine is replaced by the two-phase symplectite assemblage.Olivine-hosted symplectites developed in the margins of lherzolite xenoliths from Kauai, Hawaii, demonstrate a reaction mechanism which has not been previously documented from natural samples. Original Fo₉₀ olivine in these samples oxidized to a new assemblage consisting of orthopyroxene (En_92–95)-Fe/Mg ferrite (Mf_35–50) symplectites developed within more magnesian olivine (Fo_92–96) hosts. Thus, by this mechanism, olivine of a different composition persists as part of a final three-phase assemblage. As oxidation advanced, the compositions of all three product phases became continuously more magnesian and the stoichiometric coefficients of the orthopyroxene and Fe/Mg ferrite continuously increased, whereas those of the product olivine decreased in the mass-balance equations. These characteristics demonstrate that the reaction was controlled by oxygen diffusion into the xenoliths from the highly oxidized alkali picrite melt in which they were entrained. Thermodynamic calculations suggest that a gradient in oxygen fugacity of 10^0.9 bars existed across the xenolith rims and resulted in compositional gradients of 4 mol% fayalite and ferrosilite and 15 mol% magnetite.     

南极月球陨石MIL05035矿物学、岩石学及演化历史

月球陨石MIL05035岩石类型上属于普通辉石低钛玄武岩,粗粒辉长结构,无角砾化。主要矿物为辉石(60.2%)、斜长石(27.3%)和橄榄石(6.05%),次要矿物为石英(4.36%)、钛铁矿(1.25%)和陨硫铁(0.84%),含极少量富Ti、Fe尖晶石和磷灰石,广泛发育由钙铁辉石+铁橄榄石+石英组成的后成合晶三相集合体。辉石颗粒具有明显的化学成分不均匀性和出溶片晶,核部相对贫铁钙富镁(Fs30.2-60.8Wo14.2-35.0),边部富铁钙贫镁(Fs47.5-64.9Wo22.8-44.3)。熔长石化斜长石具有微弱的成分环带,边部相对富碱金属元素(Ab9.3-12.3,Or0.31-1.03),核部则相反(Ab7.6-10.6,Or0.12-0.36),含有未熔长石化的残留斜长石。橄榄石具有粗晶橄榄石(Fa95.5-96.6)和后成合晶中细粒橄榄石(Fa88.9-93.5)两种产状。石英具有脉状、团块状和蠕虫状等产状:脉状石英大部分转变为二氧化硅玻璃,核部石英具有较宽的拉曼谱特征峰(448~502cm-1),证明其经历了冲击变质与退变质作用;团块状石英分布于粗粒橄榄石颗粒间或橄榄石与斜长石和辉石接触边界上,与斜长石构成充填结构;蠕虫状石英分布于细粒后成合晶中。粗粒辉石边部铁辉石和后成合晶中辉石成分的继承性、结构上的延续性、光学特征上的冲击暗化现象、与冲击熔脉结构上的相关性和后成合晶中发育与粗粒辉石方向几乎一致的解理等方面的证据,认为后成合晶可能由于铁辉石在冲击压力释放与温度降低后的退变质作用下分解形成。根据岩石矿物结构观察、成分分析和MELTS模拟表明该陨石母岩的岩浆演化过程可能为:母岩浆在温度降低后首先产生极少量钛铁尖晶石、其次是普通辉石和钙长石先后结晶;随着温度下降,贫钙铁普通辉石、铁钙铁辉石和铁普通辉石等在普通辉石边部大量结晶,钙长石边部分异结晶少量培长石或拉长石;随着温度继续下降,早期结晶的普通辉石析出易变辉石等出溶片晶,橄榄石在辉石和斜长石边部结晶;其后,钛铁矿和陨硫铁析出,石英沿橄榄石和钙长石等先结晶矿物裂隙充填。出露月表后强烈的冲击变质作用使斜长石几乎全部转变为熔长石、石英大部分转变为二氧化硅玻璃,并具有一系列面状变形,冲击熔脉发育,冲击变质程度至少为S5。本研究为月球的岩浆演化和冲击变质过程提供了重要证据。     

Occurrence of low-Ca clinopyroxene and the role of deformation in the formation of pyroxene-Fe−Ti oxide symplectites

Pyroxene-Fe−Ti oxide symplectites in a norite from the leuconoritic phase of the Bjerkreim-Sokndal lopolith, SW Norway, have been studied using EMPA (electron microprobe analysis) and TEM (transmission electron microscopy) techniques. Textural and mineralchemical data indicate that the symplectites formed under subsolidus conditions at T=720–736°C and f_{o 2}=10^-17 bars. Solidus temperatures are estimated as 981–1060° C. Two models of formation are proposed: non-isochemical replacement of olivine, and growth at boundaries between exsolving grains of orthomagmatic high-Ca pyroxene and Fe−Ti oxide. TEM reveals the presence of low-Ca clinopyroxene and this formed in response to strain and/or shear stress. Comparison with published experimental data indicates that strain rates of up to 10^-12 s^-1 are necessary to explain the occurrence of low-Ca clinopyroxene. The transition from orthopyroxene to low-Ca clinopyroxene may be related to deformation which accompanied intrusion of the leuconoritic phase of the Bjerkreim-Sokndal lopolith or to local post-intrusive faulting and/or shearing. Selected-area diffraction shows that the Fe−Ti oxide lamellae are oriented with respect to the pyroxene such that (111)_oxide/(100)_pyroxene. the planes of closest oxygen packing in the constituent phases are thus adjacent to one another which leads to minimal misfit between the structures and to low interfacial strain energy. The same topotactic relationship exists in both lamellar and vermicular parts of symplectites (but is not continuous along the total length of the interface), indicating that the form of the intergrowths is a primary growth feature that to some extent can be explained in terms of growth models for duplex cells. Deformation during growth is probably necessary to account for the lattice distortion observed in the symplectites. Supercooling is necessary for nucleation and growth of the symplectites. A period of cooling under static, fluid-absent conditions allows substantial overstepping of equilibrium reaction boundaries. Nucleation and growth is triggered by local deformation accompanied by influx of fluid or, possibly, melt. Under these conditions growth can be rapid (≈1 year), and low-Ca clinopyroxene forms during or after growth. The proportions of pyroxene and Fe−Ti oxide in symplectites from a variety of rocks fall in a narrow range (70.5:29.5–74.8:25.3) which suggests a common growth mechanism. The interlamellar spacing is related to the amount of supercooling prior to growth, but the effects of fluid on growth rate must be studied before this relationship can be quqntified. Symplectites provide evidence for the development of retrograde mineral assemblages in relatively short time intervals under transitory fluid-present conditions. The models for symplectite formation in the intrusives of southwestern Norway may be applicable to pyroxene-Fe−Ti oxide intergrowths in other slowly cooled basic igneous rocks.     

Chromium-bearing olivine in the St. Mesmin chondrite

Olivine phenocrysts in microporphyritic xenoliths in the St. Mesmin chondrite (LL-breccia) show parallel rimward variations of FeO (10 to > -30wt.%), CaO (0·1–0·4%), MnO (0·2–0·8%) and Cr₂O₃ (0·2–0·7%). Aluminum is near background levels and does not vary systematically with iron. Titanium, sodium and nickel are below the limit of detection. Covariation of Fe and Cr in this olivine distinguishes it from the olivines in lunar mare basalts, in which Cr varies inversely with Fe.Transmission electron microscopy of the St. Mesmin olivine suggests that it is free of submicroscopic inclusions and exsolution lamellae and that the chromium present occurs in solid solution in the olivine. Charge balance and ionic radius considerations suggest that it occurs as Cr²⁺, whose effective ionic radius is nearly identical to that of Mn²⁺.The different Fe-Cr relationships observed in the lunar basaltic and St. Mesmin olivines reflect different crystallization sequences. Chromian spinel coprecipitated with olivine in the lunar basalts, reducing the activity of chromium in the melt and leading to the observed anticorrelation of Fe and Cr in olivine (butler, 1972). By contrast, olivine precipitated first in the St. Mesmin microporphyry and was the only solid phase present until more than half of the rock had crystallized. Parallel variation of Fe and Cr reflects crystallization from a melt in which the activity of chromium was increasing.     

On the origin of multi‐layer coronas between olivine and plagioclase at the gabbro–granulite transition,Valle Fértil–La Huerta Ranges,San Juan Province,Argentina

Troctolitic gabbros from Valle Fértil and La Huerta Ranges, San Juan Province, NW‐Argentina exhibit multi‐layer corona textures between cumulus olivine and plagioclase. The corona mineral sequence, which varies in the total thickness from 0.5 to 1 mm, comprises either an anhydrous corona type I with olivine|orthopyroxene|clinopyroxene+spinel symplectite|plagioclase or a hydrous corona type II with olivine|orthopyroxene|amphibole|amphibole+spinel symplectite|plagioclase. The anhydrous corona type I formed by metamorphic replacement of primary olivine and plagioclase, in the absence of any fluid/melt phase at <840 °C. Diffusion controlled metamorphic solid‐state replacement is mainly governed by the chemical potential gradients at the interface of reactant olivine and plagioclase and orthopyroxene and plagioclase. Thus, the thermodynamic incompatibility of the reactant minerals at the gabbro–granulite transition and the phase equilibria of the coronitic assemblage during subsequent cooling were modelled using quantitative μMgO–μCaO phase diagrams. Mineral reaction textures of the anhydrous corona type I indicate an inward migration of orthopyroxene on the expense of olivine, while clinopyroxene+spinel symplectite grows outward to replace plagioclase. Mineral textures of the hydrous corona type II indicate the presence of an interstitial liquid trapped between cumulus olivine and plagioclase that reacts with olivine to produce a rim of peritectic orthopyroxene around olivine. Two amphibole types are distinguished: an inclusion free, brownish amphibole I is enriched in trace elements and REEs relative to green amphibole II. Amphibole I evolves from an intercumulus liquid between peritectic orthopyroxene and plagioclase. Discrete layers of green amphibole II occur as inclusion‐free rims and amphibole II+spinel symplectites. Mineral textures and geochemical patterns indicate a metamorphic origin for amphibole II, where orthopyroxene was replaced to form an inner inclusion‐free amphibole II layer, while clinopyroxene and plagioclase were replaced to form an outer amphibole+spinel symplectite layer, at <770 °C. Calculation of the possible net reactions by considering NCKFMASH components indicates that the layer bulk composition cannot be modelled as a ‘closed’ system although in all cases the gain and loss of elements within the multi‐layer coronas (except H₂O, Na₂O) is very small and the main uncertainties may arise from slight chemical zoning of the respective minerals. Local oxidizing conditions led to the formation of orthopyroxene+magnetite symplectite enveloping and/or replacing olivine. The sequence of corona reaction textures indicates a counter clockwise P–T path at the gabbro–granulite transition at 5–6.5 kbar and temperatures below 900 °C.     

Symplectites in upper mantle peridotites: Development and implications for the growth of subsolidus garnet,pyroxene and spinel

Silicate-oxide symplectites in complex mineral intergrowths are relatively common in upper mantle xenoliths and in xenoliths in the Jagersfontein Kimberlite, South Africa.Harzburgites of olivine and high-Al (1.9–3.6 wt%), Ca (0.6–0.9 wt%) and Cr (0.3–0.9 wt%) enstatite contain symplectites of spinel and diopside, or spinel, diopside and lower-Al (0.8–2.2 wt%), Ca (0.1–0.4 wt%) and Cr (0.02–0.8 wt%) enstatite. From textures and mineral chemistries these symplectites are interpreted to have formed by mineral unmixing and migration from Al–Ca–Cr discrete enstatite to adjoining mineral interfaces.Garnet harzburgites are composed of large (0.5–1 cm) olivine, equally large discrete low-Al (0.6–1.1 wt%), Ca (0.1–0.5 wt%), and Cr (0.1–0.3 wt%) enstatite and smaller interstitial garnet, diopside, and high-Cr and low-Al spinel. Symplectites are composed of either spinel+diopside+garnet, or garnet+spinel. Spinel diopside garnet symplectites have cores of spinel+diopside, resembling symplectites inharzburgites, but surrounded by rims of garnet or garnet+undigested globular spinel. From textures and chemistries we suggest that the spinel+diopside cores formed from Ca-Al-Cr-rich orthopyroxene initially as a nonstoichiometric homogeneous single phase clinopyroxene enriched in Fe, Cr and Al. This was followed by decomposition of the clinopyroxene to diopside+spinel, and subsequent garnet formation in a prograde reaction with olivine or enstatite. In bothharzburgites andgarnet harzburgites the metastable cellular structures may also have formed by the simultaneous precipitation of pyroxene and spinel. In all cases there is a strongly preferred embayment of symplectite bodies into olivine. Olivine appears to have activated adjacent     

Fluid inclusions as petrogenetic indicators in granulite xenoliths,Pali-Aike volcanic field,Chile

Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO₂ fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO₂ during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm³. Higher density (=0.90–1.02 g/cm³) IIb inclusions occur only in symplectite phases. Secondary Type III CO₂+glass inclusions with =0.47–0.78 g/cm³ occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO₂ from the host basalt during its ascent to the surface. These data suggest that CO₂ is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO₂ from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.     

Redox potential of mantle magmatic systems

A new variant of the olivine-clinopyroxene-spinel oxygen barometer was developed on the basis of the equilibrium 3CaMgSi₂O₆(Cpx) + 2Fe₃O₄(Spl) = 3CaMgSiO₄(Ol) + 3Fe₂SiO₄(Ol) + O₂. Oxygen fugacity was estimated for the mineral assemblages of meymechites, olivine-bearing rocks of the Guli intrusion, and olivine and clinopyroxene microphenocrysts from interstitial glasses in mantle xenoliths containing metal alloys from Sal Island, Cape Verde Archipelago. It was shown that oxygen fugacity may vary in mantlederived magmatic systems by 7–8 orders of magnitude. Thermodynamic analysis showed that the low water activity in the lower part of the subcratonic lithosphere prevents the formation of hydrocarbons even at the presence of elemental carbon and low oxygen fugacity. The most probable mechanism of diamond formation is the reduction of carbonate components in the composition of near-solidus melts coming into the lithosphere from ascending mantle plumes.     

Vermicular orthopyroxene-magnetite symplectites from the Wateranga layered mafic intrusion,Queensland, Australia

Orthopyroxene-magnetite intergrowths (symplectites), partly or completely surrounding olivine, are described from the Wateranga layered mafic intrusion, Queensland, Australia. The texture occurs in unmetamorphosed plagioclase-rich norites, olivine gabbros and troctolites in which the primary minerals are olivine (Fo_63–69) orthopyroxene (En_66–72), clinopyroxene (Wo₄₂En₄₂Fs₁₆), plagioclase (An_49–65), hornblende, ilmenite, magnetite and sulphides. Symplectites range from incipient fine grained developments around corroded olivine grains to intricately formed pseudomorphs after olivine and slow a consistent orthopyroxene/magnetite ratio. Orthopyroxene in symplectites is commonly in optical continuity with surrounding magnetite-free orthopyroxene rims. Later intercumulus hornblended has replaced orthopyroxene. There is marked chemical similarity between primary and simplectite, orthopyroxenes and magnetites. Textures similar to those described here are considered elsewhere to have formed at a late magmatic stage or by solid state reactions involving subsolidus oxidation of olivine. In the Wateranga intrusion textural relations, the chemical similarity between primary and symplectite phases, and the consistent volume proportions of magnetite and orthopyroxene in the intergrowths suggest that they developed during late magmatic crystallization.     

Petrogenesis of sapphirine-bearing metatroctolites from the Buck Creek ultramafic body,southern Appalachians

The Buck Creek ultramafic body, North Carolina, includes aluminous lenses that have been described as troctolites. These lenses preserve mineral assemblages which record several different stages of metamorphism. The first stage is characterized by anhydrous reactions between olivine and plagioclase to produce coronas of orthopyroxene+ clinopyroxene/spinel symplectite. Thermo barometric results indicate minimum pressures of c. 6 kbar and c. 800 ^oC. Sapphirine replaces spinel in some clinopyroxene symplectites, and occurs as anhedral grains within amphibole, observations which in combination suggest peak metamorphic conditions of c. 9-10 kbar and c. 850 ^oC. Sapphirine-bearing hydrous assemblages formed at the expense of the coronas, indicating a second metamorphic episode involving deeper burial, deformation and hydration. Schistose rocks from the margins of the lenses are composed of anorthite+amphibole+margarite+corundum, and probably record a later, lower P-T event. Whole rock analyses for the Buck Creek lenses suggest an accumulate protolith of magnesian olivine and calcic plagioclase. Trace element data for the troctolites are consistent with data for adjacent amphibolites in suggesting that the Buck Creek mafic and ultramafic cumulates crystallized from magmas derived from a mantle source similar to that which produces modern intraplate or rift-related basalts. We propose that the Buck Creek ultramafics represent basal cumulates(± uppermost mantle) from ocean crust formed in a marginal basin in the latest Precambrian. Subduction-induced burial to at least 18 km under dry conditions induced corona formation. Collisional events of the Taconic orogeny thrust the Buck Creek rocks into the orogenic pile to at least 30 km depth and hydrated them along zones of weakness, locally producing P-T -P_H2O conditions appropriate for formation of sapphirine and hydrated assemblages, but still preserving some dry symplectites.     

Exsolution Lamellae in Olivine Grains of Dunite Units from Different Types of Mafic‐Ultramafic Complexes

Exsolution microstructures in olivine grains from dunite units in a few selected tectonic environments are reported here. They include lamellae of clinopyroxene and clinopyroxene-magnetite intergrowth in the Gaositai and Yellow Hill Alaskan-type complexes, clinopyroxene-magnetite intergrowth in the K?z?lda? ophiolite, and chromite lamellae in the Hongshishan mafic-ultramafic intrusive complex. These lamellae commonly occur as needle-or rod-like features and are oriented in olivine grains. The host olivine grains have Fo contents of 92.5–92.6 in the Gaositai complex, 86.5–90.1 in the Yellow Hill complex, 93.2–93.4 in the K?z?lda? ophiolite and 86.9–88.3 in the Hongshishan complex. Clinopyroxene in the rod-like intergrowth exsolved in olivine grains in the Gaositai and Yellow Hill is diopside with similar major element compositions of Ca O(23.6–24.3 wt%), SiO_2(52.2–54.0 wt%), Al_2O_3(0.67–2.15 wt%), Cr_2O_3(0.10–0.42 wt%) and Na_2O(0.14–0.26 wt%). It falls into the compositional field of hydrothermal clinopyroxene and its origin is thus probably related to reaction between dunite and fluids. The enrichment of the fluids in Ca~(2+), Fe~(3+), Cr~(3+) and Na+, resulted in elevated concentrations of these cations in olivine solid solutions via the reaction. With decreasing temperature, the olivine solid solutions altered to an intergrowth of magnetite and clinopyroxene. The Fe~(3+) and Cr~(3+) preferentially partitioned into magnetite, while Ca~(2+) and Na+ entered clinopyroxene. Since the studied Alaskan-type complexes and ophiolite formed in a subduction environment, the fluids were probably released from the subducted slab. In contrast, the exsolved chromite in olivine grains from the Hongshishan complex that formed in post-orogenic extension setting can be related to olivine equilibrated with Cr-bearing liquid. Similarly, these lamellae have all been observed in serpentine surrounding olivine grains, indicating genetic relations with serpentinization.     

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     

Multistage reaction textures in xenolithic high-MgAl granulites at Anakapalle, Eastern Ghats Belt, India: examples of contact polymetamorphism and infiltration-driven metasomatism

High‐MgAl rocks occur as xenoliths (up to 2 m in diameter) in mafic granulites at a newly discovered locality near Anakapalle. Following an early phase of deformation, ultrahigh‐temperature (UHT) metamorphism and near‐isothermal decompression, the rocks were intruded in a lit‐par‐lit manner by felsic melts (charnockite), which caused local‐scale metasomatism. A subsequent deformation produced isoclinal folds and the distinct gneissic foliation of the charnockite still at granulite facies conditions. The sequence of multiphase reaction textures in the high‐MgAl xenoliths reflects the changes of physico‐chemical conditions during the polyphase evolution of the terrane; UHT metamorphism (stage 1, > 1000°C, c. 10 kbar) is documented by relics of extremely coarse grained domains with the assemblage orthopyroxene (opx)₁ + garnet (grt)₁ + sapphirine (spr)₁ + spinel (spl)₁ + rutile (rt). A subsequent phase of near‐isothermal decompression in the order of 1–2 kbar (stage 2) resulted in extensive replacement of grt₁ and opx₁ megacrysts by lamellar (opx₂ + spr₂) symplectites. The intrusion of felsic melt (stage 3) led to the development of a narrow metasomatic black wall reaction zone (bt + sil + plg₃ + opx_2,3 + rt) at the immediate contact of the xenoliths and in melt infiltration zones to the partial replacement of (opx₂ + spr₂) symplectites by biotite and sillimanite and/or plg₃, mainly at the expense of orthopyroxene, with concomitant coarsening of the intergrowth texture. The subsequent deformation (stage 4) further modified the symplectite textures through polygonization, recrystallization and grain‐size coarsening. The deformation was followed by a period of cooling and decompression (stage 5, c. 800°C, 4–7 kbar) as indicated by local growth of late garnet (grt₅) at the expense of (opx + spr + plg) domains at static conditions. Recently published isotope data suggest that the multistage evolution of the high‐MgAl granulites at Anakapalle followed a discontinuous P–T trajectory that may be related to heating of the crust through magmatic accretion culminating in deep‐crustal UHT metamorphism at 1.4 Ga (stage 1), fast uplift of the UHT granulites into mid‐crustal levels as a consequence of extensional tectonics (stage 2), emplacement of felsic magmas in the Grenvillian (at c. 1 Ga, stage 3) resulting in reheating of the crust to high–T conditions followed by a phase of compressional tectonics (stage 4) and a period of cooling to the stable geotherm (stage 5) still in the Grenvillian.     

Native niobium in the regolith from the Mare Crisium

A new mineral phase was discovered in the course of studies at the Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry (IGEM) of fine-grained fractions of the lunar regolith delivered to the Earth by the Luna 16, Luna 20, and Luna 24 automatic stations. The grain of native niobium was identified in the regolith sample from the Mare Crisium. Presumably, this phase was formed during the fractioning process in a gas–plasma cloud under an impact event on the Moon.     

Effect of the disproportionation reaction of ferrous iron in impact-evaporation processes

Evidence for the disproportionation of iron was found in model experiments imitating impact melting, evaporation, and condensation. The experiments were carried out using a laser system at a characteristic temperature of ～3000–4000 K and a pulse duration of ～10^?3 s in a He atmosphere (P = 1 atm). Augite and mixtures of peridotite with MnO₂ and WO₃ were used as starting target materials. Experimental products (condensed vapor phase) were analyzed by X-ray photoelectron spectroscopy. The results of condensate analysis provided compelling evidence for the presence of iron in three oxidation states (Fe⁰, Fe²⁺, and Fe³⁺). In an experiment with augite, the proportions of iron species of different valences were similar to the stoichiometry of the disproportionation reaction. Similar evidence for this reaction was first found in a condensate from the samples of the fine fraction of the Luna 16 regolith. In the layers of the lunar condensate, the proportions of the valence states of iron were on average Fe⁰:Fe²⁺:Fe³⁺ = 1.2: 1.9: 0.7.     

Valence state of iron in a condensate from the Luna 16 regolith

This paper reports the results of an X-ray photoelectron spectroscopic study of the condensate phase of regolith sample L1639 returned by the Luna 16 mission. The reduced Si⁰, Si²⁺, Al⁰, Ti²⁺, and Ti³⁺ forms were detected in the sample. Iron occurs in all valence states, and Fe³⁺ species were detected for the first time in the condensate. Minor Fe³⁺ concentrations were observed in the upper layers of the sample containing the maximum amounts of condensate products. The fraction of ferric Fe is 22%, and the Fe⁰: Fe²⁺: Fe³⁺ proportion is 33: 45: 22. The appearance of ferric Fe in the lunar condensate is explained by the reaction of FeO disproportionation occurring either at the stage of the expansion and cooling of impact-related vapor or directly in the condensed phase on the surface of regolith particles. This interpretation is supported by the results of a model experiment on augite vaporization and condensation. The experiment simulating impact vaporization was carried out on a laser set-up at a temperature of ∼3000–4000 K and a pulse duration of ∼10⁻³ s in a He atmosphere (P = 1 atm). The results of analyses provided compelling evidence that the condensate produced after augite vaporization contains Fe in all oxidation states, and the proportions of different valence forms approach the stoichiometry of the disproportionation reaction.