Mechanism of the olivine-spinel transformation in Co2SiO4

An experiment conducted in a 2000-ton uniaxial split-sphere apparatus (USSA-2000) utilizes large sample volume and a substantial temperature gradient to synthesize intergrowths of the olivine and spinel polymorphs of Co₂SiO₄. The olivine starting material consists of a finegrained fraction (<20μm) which records the stable polymorphs along the length of the sample plus large olivine grains (100–500 μm) which help decipher the mechanism of the phase transformation. At conditions near equilibrium, the olivine-spinel transformation in the large grains occurs by inward growth of a few large single crystals of spinel nucleated on the surfaces of the olivine. The overall rate of transformation is governed by the mobility of the interphase boundary, whose morphology is crystallographically controlled by the spinel. No renucleation of spinel is observed in the host olivine crystal, even in the region immediately adjacent to the olivine/spinel interface; analysis of this region with transmission electron microscopy reveals an extremely high density of dislocations induced by plastic flow accommodating the volume change associated with the phase transformation.     

Spinel inclusions in olivine of peridotite xenoliths from TUBAF seamount (Bismarck Archipelago/Papua New Guinea): evidence for the thermal and tectonic evolution of the oceanic lithosphere

Olivine in spinel peridotite xenoliths from the Bismarck Archipelago northeast of Papua New Guinea, which were transported to the surface by Quaternary basalts, shows spinel inclusions up to 25 μm long and 200 nm wide. These inclusions mainly occur as inhomogeneously distributed needles and subordinately as octahedral grains in olivine of veined metasomatic peridotites as well as peridotites without obvious metasomatism. The needles very often occur in swarms with irregular spacing in between them. Similar spinel inclusions in olivine have only previously been reported from ultramafites of meteoritic origin. Composition and orientation of the spinel inclusions were determined by transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Both the needles and the grains display a uniform crystallographic orientation in the host olivine with [001]^O1//[1ˉ10]_Spl and (100)_Ol// (111)_Spl. The needles eare elongated parallel [010] in olivine, which is the same in all olivine grains. As these needles have no relation to the metasomatic sections in the peridotite, it is concluded that they are primary features of the rock. Although the composition of the spinel needles is often very similar to the large chromian spinel octahedra in the matrix, the small octahedral spinel inclusions in olivine are in part Mg-rich aluminous spinel and sometimes almost pure magnetite. The spinel needles are suggested to have formed by exsolution processes during cooling of Al- and Cr-rich, high-temperature olivine during the initial formation of the lithospheric mantle at the mid-ocean ridge. The Al-rich spinel octahedra probably formed by the breakdown of an Al-rich phase such as phlogopite or by metasomatism, whereas the magnetite was generated by oxidizing fluids. These oxidizing fluids may either have been set free by dehydration of the underlying, subducted plate or by the Quaternary magmatism responsible for the transport of the xenoliths to the seafloor. Received: 25 May 2000 / Accepted: 12 July 2000     

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。     

Crystal structural features of the olivine → spinel transition

Comparisons of structural features of olivine (α phase), spinel (γ phase), and the modified spinel (β phase) lead to predictions of possible mechanisms for the olivine → spinel transitions. In the olivine structure, rigid tetrahedral edges and shared octahedral edges form columns of corner-sharing trigonal dipyramids parallel to the a axis. These rigid columns are separated by weaker, unshared octahedral edges which may be stretched to reduce cation-cation repulsion. As a result, olivine has a relatively loose structure and is stable at low pressure. At elevated pressure, olivine transforms to the more compact spinel structure, in which the rigid tetrahedral edges and shared octahedral edges form a three dimensional network instead of aligned columns. These structural differences explain how compressibility and thermal expansion may be taken up mainly by octahedral sites in olivine, but are evenly distributed over both octahedral and tetrahedral sites in spinel. Because the closest packings of oxygens and interstitial cation distributions differ between olivine (h.c.p.) and spinel (c.c.p.), the olivine structure may have to disintegrate during its transformation to spinel, so that the olivine → spinel transition involves processes of nucleation and growth. The migration of atoms across the olivine-spinel interface is thus a complicated process of random walk without a definite path. In the β phase → spinel transition, however, the diffusion of cations may follow a definite path in restricted regions because oxygen closest packings and cation distributions are similar in the two structures. If the oxygen packing remains intact during the β → γ transition, the transformation will be an intracrystalline process leading to domain structure in the spinel product.     

Kinetics of high-pressure phase transformations: Implications to the evolution of the olivine → spinel transition in the downgoing lithosphere and its consequences on the dynamics of the mantle

The rate of a high-pressure phase transition increases exponentially with temperature (T) and overpressure or pressure beyond equilibrium (ΔP). It is also greatly promoted by introducing shear stress, diminishing grain size, and adding water or other catalysts to the reactants. For an isothermal and isobaric transition with no compositional change, if steady state of nucleation on grain surfaces is attained, the rate equation can be expressed: (1) before site saturation by: X = 1 − exp(−Kt⁴), where

Full-size image (2K)

and (2) after site saturation by: X = 1 − exp(−K′T), where

Full-size image (1K)

, where X is volume fraction of completion of transformation, t is time, and the C's are characteristic constants. C₁ and C₉ are functions of grain size, C₃ and C₆ are functions of shear stress. All the C's are almost independent of temperature and pressure. Thus, if X as a function of T, ΔP, and t over a narrow P-T range can be experimentally determined, the C's can be calculated and the effect of grain size and shear stress on the rate of transformation can be evaluated. The isothermal and isobaric rate equations for a given composition, shear stress, and grain size are then experimentally determinable. The non-isothermal and non-isobaric rate equation can be calculated from the isothermal and isobaric ones if the rate of penetration into the metastability field is known. The important feature of the kinetics of high-pressure phase transitions predicted by these rate equations is that for a given rate of penetration into the metastability field, there can be defined a characteristic temperature, T_ch, below which the rate of the transition is virtually zero no matter how metastable the material is. For the olivine → spinel transition in the mantle, this characteristic temperature may be as high as 700° C. Thus, in a fast moving downgoing slab, the temperature at its cold center may remain below T_ch even down to depths in excess of 600 km, thereby greatly depressing the olivine—spinel phase boundary.At an early stage in the development of a downgoing slab, the plunging speed is slow. This allows the interior of the slab to heat up and the olivine → spinel transition to proceed rapidly and near equilibrium. As a result, the olivine—spinel phase boundary in the slab will be distorted upwards. The rising of the denser spinel phase then provides an additional driving force which accelerates the plate. Since the upper portion of the slab is pulled from below and the lower portion pushed from above, earthquakes of down-dip extension will occur in the upper mantle while those of down-dip compression will originate in the transition zone. Because the transformation occurs close to equilibrium, there will be an aseismic region separating the two seismic zones. When the plate velocity exceeds a certain limit, the temperature in the cold interior becomes low enough to depress the olivine → spinel transition. The phase boundary is then distorted downwards. The buoyant force thereby created will reduce the driving force, and the plunging speed of the plate will approach a steady state. In addition, the buoyant force will compress the slab from below and result in earthquakes of down-dip compression throughout the length of the slab. Now the olivine → spinel transition is so far from equilibrium that the reaction becomes implosive. A rise in frequency of deep earthquakes towards the implosion region in the lower transition zone is thus predicted. Therefore, as well as stabilizing the plate velocity, the olivine → spinel transition may also control earthquake distributions throughout the downgoing slab.     

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.     

The concept of residual stress in rock

The purpose of this paper is to clarify the concept of residual stress in rock. Residual stress is stress near a point in a body subjected to zero external tractions and to zero temperature gradients, excluding body forces. Thus, residual stresses can develop in rock if there are local phase transformations, inelastic strains, or differences in thermal or elastic properties. In these cases, residual stresses can result from changes in temperature, applied stress or configuration of the body.Analysis of residual stresses at the scale of mineral grains within a polycrystalline aggregate such as rock is virtually intractable. One can, however, obtain important insights into residual stresses within bodies with widely spaced sources of residual stress, such as inclusions, and within bodies comprised of multilayers. The analyses indicate that patterns of residual stress in rock can be expected to be extremely complicated. For example, study of residual stresses in a body containing a circular inclusion indicates that:

1. (1) There is a single state of residual stress within an inclusion but the state within the surrounding medium is variable. Thus, values of residual stress within rocks reported in the literature generally are of minor value because the sizes and shapes of the sources and the positions of the measurements relative to the positions of sources of residual stresses in the bodies have not been determined.

2. (2) Residual stresses within an inclusion can be tensile or compressive, even though the applied stresses were compressive, depending upon the source of residual stress.

3. (3) The magnitudes and orientations of residual stresses in an isolated body of rock containing one or more inclusions depends upon the size and shape of the body. The same general conclusions are derived from an analysis of residual stresses in a simple multilayered body.

4. (4) In addition, however, the anisotropy of a multilayered body tends to cause principal residual stresses to parallel the layers rather than to parallel the applied stresses that were responsible for inducing the residual stresses. Thus, without identifying the sources of residual stresses in a body, one cannot infer the directions of principal tectonic stresses that might have been responsible for the residual stresses.

Comparison of the theoretical results with measurements of change of residual stress in blocks of granite, with maximum dimensions of 2.5 m in the field and 0.2 m in the lab oratory, suggests that sources of residual stress are inhomogeneous elements or elements of inelastic deformation within the blocks that are smaller than the blocks themselves, but larger than individual mineral grains. The sources of residual stress are unknown in these granites.     

The rheology of olivine and spinel magnesium germanate (Mg2GeO4): TEM study of the defect microstructures

Synthetic polycrystals of α-Mg₂GeO₄ (with the olivine structure) and γ-Mg₂GeO₄ (with the spinel structure) deformed at high temperature and pressure in their respective stability fields were investigated by analytical transmission electron microscopy. Specimens with a mean grain size of 20–30 µm deform by dislocation glide and/or climb. The predominance of glide versus climb depends on stress and grain orientation. The defect microstructures of both polymorphs are very similar to those observed in their respective silicate analogues, α- and γ-(Mg,Fe)₂SiO₄, and, in the case of the spinel phase, very similar to those observed in magnesium aluminate spinels. These observations suggest that Mg₂GeO₄ is a good rheological analogue for the Earth’s upper mantle. A spinel specimen deformed under the same conditions of temperature and strain rate as an olivine specimen was approximately three times stronger than olivine. In specimens of both phases deformed at or above 1400 K, a thin amorphous film composed of Mg, Ge, and O was detected along some grain boundaries. Grains ≤10 µm diameter surrounded by a film of amorphous phase (>10 nm thick) exhibited low dislocation densities, and deformation appeared to have occurred by grain boundary sliding.     

Experimental investigation of the α-β transformation of San Carlos olivine single crystal

Single crystalline San Carlos olivine (1 mm cube) was transformed to (Mg,Fe)₂SiO₄β-phase at 13.5–15 GPa, 1030–1330 °C for 0–600 min using a multi-anvil high pressure apparatus. The α-β transformation occurred by incoherent surface nucleation and interface-controlled growth and recovered partially transformed samples showed sharply defined reaction rim. The growth rate of the β-phase rim significantly decreased with time and the growth eventually ceased. TEM observations revealed that many dislocations were created in both the relict olivine just near the α-β interface and the β-phase in the rim, which show evidence for deformation caused by interfacial stresses associated with the misfit elastic strain of the transformation. The observed tangled dislocation texture in β-phase suggested that the β-phase rim was hardened and relaxation of the interfacial stress was retarded. This probably caused a localized pressure drop in the relict olivine and decreased the growth rate. Time-dependent growth rates of β-phase is possibly controlled by the rheology of β-phase, which must be considered for the prediction of the olivine metastability in the subducting slabs. Received: 24 January 1997 / Revised, accepted: 24 July 1998     

Grain growth in porous olivine aggregates

Grain growth experiments have been performed at 1 atm on fine grain size (<10 μm) synthetic olivine (Fo₉₁) aggregates at various temperatures (1200° to 1400° C), oxygen fugacities (10^-4 to 10^-11 atm) and total anneal times (10, 30, 60, 100 and 200 h). The rate of grain growth increased with increasing temperature and with increasing oxygen fugacity. The presence of a second phase (residual porosity), introduced during sample fabrication, has a significant effect on grain growth, with evolution in grain size paralleled by changes in the size and frequency of the pores. When the grain growth data were fit to a growth law G ⁿ ?G _O ⁿ =κ₀ tf ₀ ^m ₂e^?Q/RT, the growth exponents fall in the range of n=4 to 5, suggesting that grain growth may be controlled by the coalescence of the second phase. The evolution in pore size and frequency may occur either by the transport of the ionic species constituting olivine between the pores or by the movement of the pores themselves along the grain boundaries and edges. Thus, the rate of growth of the pores and grains is probably limited by diffusion of the slowest ionic species constituting olivine (magnesium, iron, silicon, or oxygen) moving along the fastest path for that species (through the lattice, along the grain boundaries, around the surface of the moving pores, or through the vapor phase in the pores). Activation energies for grain growth of Q=290 ± 20 kJ/mol and 345 ± 25 kJ/mol were calculated from our results for n=4 and 5, respectively. These activation energies preclude vapor-phase transport and iron diffusion along grain boundaries but do not otherwise permit a discrimination between the rate limiting species or path. The oxygen fugacity exponent of m ≈0.12 suggests that lattice diffusion does not control the grain growth. However, the lack of data for magnesium, iron, silicon and oxygen surface and grain boundary diffusion in olivine makes definitive determination of the mechanism controlling grain growth difficult.     

Oxygen isotopic distribution in an amoeboid olivine aggregate from the Allende CV chondrite: Primary and secondary processes

The oxygen isotopic distribution in an amoeboid olivine aggregate (AOA), TTA1-02, from the Allende CV3 chondrite has been determined by secondary ion mass spectrometry. The irregular shaped TTA1- 02 (5×3mm) consists mostly of olivine grains of ca. 5μm in diameter. Olivine grains of Mg-rich (Fo₉₅) and Fe-rich (Fo₆₀) composition are in direct contact with each other, with a sharp compositional boundary. Oxygen isotopic compositions of Fe-rich olivine grains are ¹⁶O-poor (Δ¹⁷O ≅ −5‰), whereas Mg-rich olivine is ¹⁶O-rich (Δ¹⁷O ≅ −25‰). Several Al-rich inclusions (<ca. 500 μm in diameter) are enclosed by olivine grains in the AOA. Oxygen isotopic compositions of spinel and fassaite in Al-rich inclusions are ¹⁶O-rich (Δ¹⁷O ≅ −20‰), whereas those of anorthite, nepheline and phyllosilicate are ¹⁶O-poor (Δ¹⁷O ≅ −5‰). We propose the following sequence of events during the formation of AOAs in the Allende meteorite: 1) Formation of Al-rich inclusions with ¹⁶O-rich oxygen isotopic composition; 2) Accretion of Mg-rich olivine grains with ¹⁶O-rich oxygen isotopic composition around Al-rich inclusions; 3) Accretion into parent body; and 4) Aqueous alteration in the parent body, which led to crystallization of ¹⁶O-poor minerals, Fe-rich olivine, anorthite, nepheline, and phyllosilicate. This is reflecting reactions among primary ¹⁶O-rich AOA minerals and aqueous fluid having ¹⁶O-poor oxygen isotopic composition. Fe-rich olivine grains precipitated from aqueous fluids, which partially dissolved pre-existing Mg-rich olivine grains. Sintering and Mg-Fe diffusion occurred during thermal metamorphism. Anorthite, nepheline and phyllosilicate in Al-rich inclusions replaced primary anorthite or melilite during the aqueous alteration stage.     

Origin of xenoliths in the trachyte at Puu Waawaa,Hualalai Volcano,Hawaii

Rare dunite and 2-pyroxene gabbro xenoliths occur in banded trachyte at Puu Waawaa on Hualalai Volcano, Hawaii. Mineral compositions suggest that these xenoliths formed as cumulates of tholeiitic basalt at shallow depth in a subcaldera magma reservoir. Subsequently, the minerals in the xenoliths underwent subsolidus reequilibration that particularly affected chromite compositions by decreasing their Mg numbers. In addition, olivine lost CaO and plagioclase lost MgO and Fe₂O₃ during subsolidus reequilibration. The xenoliths also reacted with the host trachyte to form secondary mica, amphibole, and orthopyroxene, and to further modify the compositions of some olivine, clinopyroxene, and spinel grains. The reaction products indicate that the host trachyte melt was hydrous. Clinopyroxene in one dunite sample and olivine in most dunite samples have undergone partial melting, apparently in response to addition of water to the xenolith. These xenoliths do not contain CO₂ fluid inclusions, so common in xenoliths from other localities on Hualalai, which suggests that CO₂ was introduced from alkalic basalt magma between the time CO₂-inclusion-free xenoliths erupted at 106±6 ka and the time CO₂-inclusion-rich xenoliths erupted within the last 15 ka.     

Titanium solubility in olivine in the system TiO<Subscript>2</Subscript>–MgO–SiO<Subscript>2</Subscript>: no evidence for an ultra-deep origin of Ti-bearing olivine

The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO₂–MgO–SiO₂ system. Experiments at atmospheric pressure in the temperature range 1,200–1,500°C showed that the highest concentration of TiO₂ is obtained when olivine coexists with spinel (Mg₂TiO₄). The amount of TiO₂ in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi₂O₅) and a Ti–Si-rich melt at 1,500°C displays a fourfold lower TiO₂ content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg₂TiO₄. The unit cell volume of olivine increases systematically with increasing TiO₂ content demonstrating that the measured TiO₂ contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (ų)=290.12(1) + 23.67(85) N_Ti. The partial molar volume of end-member Mg₂TiO₄ olivine (N_Ti=1) is thus 47.24±0.13 cm³. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO₂ contents with pressure and in all the experiments olivine contains ~0.2 wt.% TiO₂. Moreover, a thermodynamic analysis indicates that Ti contents of olivine coexisting with rutile and orthopyroxene should decrease rather than increase with increasing pressure. These data indicate that the ilmenite exsolution observed in some natural olivine does not signify an ultra-deep origin of peridotite massifs.     

Mineralogy and petrology of xenoliths in a diatreme from south Westland,New Zealand

Xenoliths up to a metre in length occur in a carbonatitic diatreme member of a lamprophyric dike swarm at Moeraki River, south Westland, New Zealand. The xenoliths reported here consist of Iherzolite (chromite, orthopyroxene, clinopyroxene and olivine) and harzburgite (chromite, olivine and orthopyroxene). A clinopyroxene xenocryst is also reported. Analyses of these phases are presented. The chemistry, low CaO and high Al₂O₃ and Na₂O content of the clinopyroxenes; low CaO and high forsterite content of the olivine, suggests that these phases were in equilibrium under high pressures within the spinel Iherzolite field. An orthopyroxene-chromite intergrowth is described and is interpreted as the product of the re-equilibration of garnet in passing from the garnet Iherzolite field to the spinel Iherzolite field.     

Relict chromian spinels in Tulu Dimtu serpentinites and listvenite,Western Ethiopia: implications for the timing of listvenite formation

Serpentinites (massive and schistose) and listvenite occur as tectonic sheets and lenses within a calcareous metasedimentary mélange of the Tulu Dimtu, western Ethiopia. The massive serpentinite contains high-magnesian metamorphic olivine (forsterite [fo] ~96 mol%) and rare relict primary mantle olivine (Fo_90–93). Both massive and schistose serpentinites contain zoned chromian spinel; the cores with the ferritchromite rims preserve a pristine Cr/(Cr+Al) atomic ratio (Cr# = 0.79–0.87), suggesting a highly depleted residual mantle peridotite, likely formed in a suprasubduction zone setting. Listvenite associated with serpentinites of smaller ultramafic lenses also contain relict chromian spinel having identical Cr# to those observed in serpentinites. However, the relict chromian spinel in listvenite has significantly higher Mg/(Mg+Fe²⁺) atomic ratios. This suggests that a nearly complete metasomatic replacement of ultramafic rocks by magnesite, talc, and quartz to prevent Mg–Fe²⁺ redistribution between relict chromian spinel and the host, that is, listvenite formation, took place prior to re-equilibration between chromian spinel and the surrounding mafic minerals in serpentinites. Considering together with the regional geological context, low-temperature CO₂-rich hydrothermal fluids would have infiltrated into ultramafic rocks from host calcareous sedimentary rocks at a shallow level of accretionary prism before a continental collision to form the East African Orogen (EAO).     

The formation of eclogite facies metatroctolites and a general petrogenetic grid in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH)

Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐M_H2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐M_H2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐M_H2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.     

High-pressure Raman spectroscopic study of Mn2GeO4, Ca2GeO4, Ca2SiO4, and CaMgGeO4 olivines

We present a Raman spectroscopic study of the structural modifications of several olivines at high pressures and ambient temperature. At high pressures, the following modifications in the Raman spectra are observed: 1)?in Mn₂GeO₄, between 6.7 and 8.6?GPa the appearance of weak bands at 560 and 860?cm^?1; between 10.6 and 23?GPa, the progressive replacement of the olivine spectrum by the spectrum of a crystalline high pressure phase; upon decompression, the inverse sequence of transformations is observed with some hysteresis in the transformation pressures; this sequence may be interpreted as the progressive transformation of the olivine to a spinelloid where Ge tetrahedra are polymerized, and then to a partially inverse spinel; 2)?in Ca₂SiO₄, the olivine transforms to larnite between 1.9 and 2.1?GPa; larnite is observed up to the maximum pressure of 24?GPa and it can partially back-transform to olivine during decompression; 3)?in Ca₂GeO₄, the olivine transforms to a new structure between 6.8 and 8?GPa; the vibrational frequencies of the new phase suggest that the phase transition involves an increase of the Ca coordination number and that Ge tetrahedra are isolated; this high pressure phase is observed up to the maximum pressure of 11?GPa; during decompression, it transforms to a disordered phase below 5?GPa; 4)?in CaMgGeO₄, no significant modification of the olivine spectrum is observed up to 15?GPa; between 16 and 26?GPa, broadening of some peaks and the appearance of a weak broad feature at 700–900?cm^?1 suggests a progressive amorphization of the structure; near 27?GPa, amorphization is complete and an amorphous phase is quenched down to ambient pressure; this unique behaviour is interpreted as the result of the incompatibilities in the high pressure behaviour of the Ca and Mg sublattices in the olivine structure.     

Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros,Adirondack Mountains,New York

Olivine metagabbros from the Adirondacks usually contain both clear and spinel-clouded plagioclase, as well as garnet. The latter occurs primarily as the outer rim of coronas surrounding olivine and pyroxene, and less commonly as lamellae or isolated grains within plagioclase. The formation of garnet and metamorphic spinel is dependent upon the anorthite content of the plagioclase. Plagioclase more sodic than An_38±2 does not exhibit spinel clouding, and garnet rarely occurs in contact with plagioclase more albitic than An_36±4. As a result of these compositional controls, the distribution of spinel and garnet mimics and visually enhances original igneous zoning in plagioclase. Most features of the arrangement of clear (unclouded) plagioclase, including the shells or moats of clear plagioclase which frequently occur inside the garnet rims of coronas, can be explained on the basis of igneous zoning. The form and distribution of the clear zones may also be affected by the metamorphic reactions which have produced the coronas, and by redistribution of plagioclase in response to local volume changes during metamorphism.Authors listed alphabeticallyPublished by permission of the Director, New York State Museum, Journal Series Number 299