Topotaxic relationships between spinel and pyroxene in kelyphite after garnet in mantle-derived peridotites and their implications to reaction mechanism and kinetics

Kelyphite is a reaction product between garnet and olivine, which was formed by subsolidus reactions upon decompression during the ascent of mantle peridotite. We studied crystallographic relationships among constituent (product) phases of kelyphite ?C orthopyroxene, clinopyroxene, spinel and reactant phases, garnet and olivine, using EBSD and found that, for a relatively high temperature sample (from Czech Moldanubian), spinel and pyroxenes are in a topotaxic relationship in such a way that spinel {111} coincides with pyroxene (100) and spinel {110} coincides with pyroxene (010); while the topotaxy is incomplete or non for a lower-temperature sample (from western Norway). On the basis of the observed microstructural and crystallographic relationships, we propose a hypothesis that the topotaxic relationship may be established at nucleation stages of the onset of the kelyphitization and that the degree of topotaxy may be related to the transformation temperature and the degree of supersaturation of the reaction. The lower the temperature, the higher the supersaturation and, therefore, more rapid the nucleation becomes, resulting in a more disordered state in topotaxic relationship.     

Redox state of deep off-craton lithospheric mantle: new data from garnet and spinel peridotites from Vitim, southern Siberia

Oxygen fugacity (fO₂) affects melting, metasomatism, speciation of C–O–H fluids and carbon-rich phases in the upper mantle. fO₂ of deep off-craton mantle is poorly known because garnet-peridotite xenoliths are rare in alkali basalts. We examine the redox and thermal state of the lithospheric mantle between the Siberian and North China cratons using new Fe³⁺/ΣFe ratios in garnet and spinel obtained by M?ssbauer spectroscopy, major element data and P–T estimates for 22 peridotite xenoliths as well as published data for 15 xenoliths from Vitim, Russia. Shallow spinel-facies mantle is more oxidized than deep garnet peridotites (average, ?0.1 vs. ?2.5 ΔlogfO₂(FMQ)). For intermediate garnet–spinel peridotites, fO₂ estimates from spinel-based oxybarometers are 1.5–3.2 ΔlogfO₂(FMQ) lower than those from garnet-based oxybarometers. These rocks may be out of phase and chemical inter-mineral equilibrium because the spinel–garnet reaction and concomitant changes in mineral chemistry do not keep up with P–T changes (e.g., lithospheric heating by recent volcanism) due to slow diffusion of trivalent cations and because gar-, gar-spl and spl-facies rocks may coexist on centimeter–meter scale. The spinel-based fO₂ estimates may not be correct while garnet-based fO₂ values provide conditions before the heating. The T (780–1,100?°C) and fO₂ ranges of the Vitim xenoliths overlap those of coarse garnet and spinel cratonic peridotites. However, because of a higher geothermal gradient, the deepest Vitim garnet peridotites are more reduced (by 0.5–2.0 ΔlogfO₂(FMQ)) than cratonic garnet peridotites at similar depths, and the “water maximum” conditions (>80?% H₂O) in the off-craton mantle exist in a more shallow and narrow depth range (60–85?km) than in cratonic roots (100–170?km). The base of the off-craton lithospheric mantle (≥90?km) at 2.5?GPa and 1,150?°C has fO₂ of ?3.0 ?logfO₂(FMQ), with dominant CH₄ and H₂O and minor H₂ in the fluid. Melting near the base of off-craton mantle lithosphere may be induced by increasing water share in migrating fluids due to oxidation of methane.     

A fertile harzburgite–garnet lherzolite transition: possible inferences for the roles of strain and metasomatism in upper mantle peridotites

Porphyroclastic enstatite in a garnet lherzolite xenolith from the Monastery Mine kimberlite, South Africa, has exsolved pyrope garnet, Cr-diopside and Al-chromite, and the specimen is interpreted as representing a transition from fertile harzburgite, (containing high Ca-Al-Cr enstatite) to granular garnet lherzolite. Although the exsolved phases occur in morphologically different forms (fine and coarse lamellae; equant, ripened grains), indicating textural disequilibrium, the exsolved grains are very constant in composition, indicating chemical equilibrium. Theoretically, the exsolution could have been due to a fall in temperature, but the close association of exsolution and deformation of the host enstatite suggests that exsolution was also aided by straining of the enstatite lattice. The phase compositions can be broadly matched with those in other mantle peridotites, except that all phases are characterised by a virtual absence of Ti. In the garnet and diopside Ti, Co, Zr and most of the REE are lower than in published analyses of garnet and diopside in both granular and sheared garnet lherzolites from Southern African kimberlites, and diopside/garnet partitioning for Sr and the REE is higher. Comparison with the trace element chemistry of an enstatite from a fertile harzburgite indicates that, except for Nb, the trace element content and distribution found in the Monastery phases could arise by isochemical exsolution from such an enstatite. On the assumption that (a) the Monastery specimen represents a transition from harzburgite to garnet lherzolite, and (b) many garnet lherzolites are of exsolution origin (as suggested by their modal compositions), the inference is that most garnet lherzolites, and not just the sheared variety, have been subject to varying degrees of Ti, Zr, Sr and REE metasomatism.     

Abundance and distribution of gold,palladium and iridium in some spinel and garnet lherzolites: implications for the nature and origin of precious metal-rich intergranular components in the upper mantle

The abundance and distribution of Au, Pd, Ir, Cu, Co and Cr has been determined in mantle-derived spinel lherzolite xenoliths in basanites from Mt Porndon (Victoria, Australia) and Kilbourne Hole (New Mexico, U.S.A.) and in garnet lherzolites from the Matsoku and Thaba Putsoa kimberlites (Lesotho). Minerals in the lherzolites concentrate Au, Pd and Ir in the following sequence of increasing platinum group element (PGE) content; garnet, olivine, orthopyroxene, clinopyroxene, spinel. and demonstrate that there exists a real crystallochemical control on the distribution of PGE. Whole rock PGE abundances calculated from the modal mineralogy are less than actually determined and indicate that the bulk of the PGE (60–80%) occur in a sulphide-rich intergranular component. A metasomatic origin for this component is considered to be unlikely and it is proposed that it represents an immiscible sulphide melt which has been retained in the mantle after extraction of a sulphur saturated basic partial melt. This component may in the case of garnet lherzolites have been modified by metasomatic events in the mantle leading to Au depletion and rare earth element addition. Spinel lherzolites are relatively homogeneous at a given locality but differ in their PGE content regionally. The weighted average abundances of PGE in a spinel lherzolite upper mantle are 0.6 ppb. Au, 4.0 ppb Pd. 3.6 ppb Ir. Garnet lherzolites are very heterogeneous and insufficient data is available to allow calculation of geochemically meaningful averages. Spinel lherzolite-basalt based pyrolite contains 0.9 ppb Au, 4.3 ppb Pd, 3.0 ppb Ir, and indicates that the mantle contains an apparent excess of Au over a calculated abundance based upon the siderophilic equilibrium distribution of Au between core and mantle. This excess is considered to be due to failure to consider the chalcophilic nature of Au in the mantle and not to the addition of a meteoritic component to a mantle equilibrated with the core.     

A crustal origin for eclogites and a mantle origin for garnet peridotites: Strontium isotopic evidence from clinopyroxenes

Strontium isotopic data suggest that the classic eclogite-facies rocks of western south Norway described by Eskola (1921) formed from several parental materials in a variety of environments. Mineral separates from essentially basic, bi-minerallic (clinopyroxene and garnet) eclogites that occur as lens-shaped masses within high grade gneisses (country rock eclogites) have Sr⁸⁷/Sr⁸⁶ values that range from 0.704 for fine-grained varieties to 0.716 for coarse-grained, orthopyroxene-bearing varieties. These high, varied ratios contrast with the very low, restricted ratios (0.701 to 0.704) of similar minerals from ultrabasic, garnet-clinopyroxene-orthopyroxene-olivine assemblages (garnet peridotites) that occur as lenses within large peridotite bodies. The eclogite-facies metamorphism that generated the garnet peridotites may have occurred in the mantle. However, the metamorphism that generated at least the more radiogenic country-rock eclogites must have occurred in the crust. The high Sr⁸⁷/Sr⁸⁶ ratios of these eclogites could be generated either by forming them from crustal parental rocks or by contaminating mantle-derived parental rocks with radiogenic strontium from the country rocks. If this contamination occurred after intrusion and before eclogite-facies metamorphism, a rather contrived history must be postulated that involves intrusion, contamination accompanied by hydration, subsequent dehydration, and finally eclogite-facies metamorphism. These processes could have occurred within the long, complicated history of the enclosing country rocks. Alternatively, if the contamination occurred during eclogite-facies metamorphism, the presence of some hydrous fluid appears to be required to transport the radiogenic strontium from the enclosing country rocks. The eclogites with the highest Sr⁸⁷/Sr⁸⁶ ratios are also the most coarse-grained and it is possible that the presence of some intergranular fluid enabled these eclogites to recrystallize to a much larger grain size than would have been possible in a totally anhydrous environment. The garnet peridotites and fine-grained country rock eclogites may have formed from mantle material in the crust but escaped contamination by radiogenic strontium as a result of their position in a dry environment in the crust.Lamont-Doherty Geological Observatory Contribution No. 2443     

Geochemical syntheses among the cratonic,off-cratonic and orogenic garnet peridotites and their tectonic implications

Garnet-bearing mantle peridotites, occurring as either xenoliths in volcanic rocks or lenses/massifs in high-pressure and ultrahigh-pressure terrenes within orogens, preserve a record of deep lithospheric mantle processes. The garnet peridotite xenoliths record chemical equilibrium conditions of garnet-bearing mineral assemblage at temperatures (T) ranging from ~700 to 1,400°C and pressures (P) > 1.6–8.9 GPa, corresponding to depths of ~52–270 km. A characteristic mineral paragenesis includes Cr-bearing pyropic garnet (64–86 mol% pyrope; 0–10 wt% Cr₂O₃), Cr-rich diopside (0.5–3.5 wt% Cr₂O₃), Al-poor orthopyroxene (0–5 wt% Al₂O₃), high-Cr spinel (Cr/(Cr + Al) × 100 atomic ratio = 2–86) and olivine (88–94 mol% forsterite). In some cases, partial melting, re-equilibration involving garnet-breakdown, deformation, and mantle metasomatism by kimberlitic and/or carbonatitic melt percolations are documented. Isotope model ages of Archean and Proterozoic are ubiquitous, but Phanerozoic model ages are less common. In contrast, the orogenic peridotites were subjected to ultrahigh-pressure (UHP) metamorphism at temperature ranging from ~700 to 950°C and pressure >3.5–5.0 GPa, corresponding to depths of >110–150 km. The petrologic comparisons between 231 garnet peridotite xenoliths and 198 orogenic garnet peridotites revealed that (1) bulk-rock REE (rare earth element) concentrations in xenoliths are relatively high, (2) clinopyroxene and garnet in orogenic garnet peridotites show a highly fractionated REE pattern and Ce-negative anomaly, respectively, (3) Fo contents of olivines for off-cratonic xenolith are in turn lower than those of orogenic garnet and cratonic xenolith but mg-number of garnet for orogenic is less than that of off-cratonic and on-cratonic xenolith, (4) Al₂O₃, Cr₂O₃, CaO and Cr# of pyroxenes and chemical compositions of whole rocks are very different between these garnet peridotites, (5) orogenic garnet peridotites are characterized by low T and high P, off-cratonic by high T and low P, and cratonic by medium T and high P and (6) garnet peridotite xenoliths are of Archean or Proterozoic origin, whereas most of orogenic garnet peridotites are of Phanerozoic origin. Taking account of tectonic settings, a new orogenic garnet peridotite exhumation model, crust-mantle material mixing process, is proposed. The composition of lithospheric mantle is additionally constrained by comparisons and compiling of the off-cratonic, on-cratonic and orogenic garnet peridotite.     

Geochemistry of peridotites from the Yap Trench,Western Pacific: implications for subduction zone mantle evolution

ABSTRACT

This study examines the major and trace elements of peridotites from the Yap Trench in the western Pacific to investigate mantle evolution beneath a subduction zone. Major element results show that the peridotites are low in Al₂O₃ (0.31–0.65 wt.%) and CaO (0.04–0.07 wt.%) contents and high in Mg# (Mg/(Mg+Fe)) (0.91–0.92) and have spinels with Cr# (Cr/(Cr+Al)) higher than 0.6 (0.61–0.73). Trace element results show that the peridotites have extremely low heavy rare earth element (HREE) contents compared with abyssal peridotites but have U-shaped chondrite-normalized rare earth element (REE) patterns. The degree of mantle melting estimated based on the major elements, HREEs, and spinel Cr# range from 19% to 25%, indicating that the Yap Trench peridotites may be residues of melting associated with the presence of water in the mantle source. In addition to light rare earth element (LREE) enrichment, the peridotites are characterized by high contents of highly incompatible elements, positive U and Sr anomalies, negative Ti anomalies, and high Zr/Hf ratios. The correlations between these elements and both the degree of serpentinization and high field strength element (HFSE) contents suggest that fluid alteration alone cannot account for the enrichment of the peridotites and that at least the enrichment of LREEs was likely caused by melt–mantle interaction. Comparison between the peridotites and the depletion trend defined by the primitive mantle (PM) and the depleted mantle (DM) suggests that the Yap Trench mantle was modified by subduction-related melt characterized by high contents of incompatible elements, high Zr/Hf ratios, and low HFSE contents. Hydrous melting may have been enhanced by tectonic erosion of the subducting Caroline Plate with complex tectonic morphostructures at the earliest stages of subduction initiation.     

Pressure-temperature dependent compositional variation of phlogopitic micas in upper mantle peridotites

Compositional variation of phlogopitic micas in upper mantle peridotites is reviewed. Phlogopitic micas in garnet peridotites are systematically lower in Al (or eastonite component) than those in spinel peridotites. The core of phlogopite megacryst and phenocryst of kimberlite is always lower in Al than the rim. It is apparent that Al/(Al + Si) ratio or eastonite component in phlogopitic micas in ultramafic rocks is controlled by the equilibrium pressure and temperature. In the upper mantle peridotites containing garnet or spinel, the Al/(Al + Si) ratio of phlogopitic mica decreases with increasing pressure at constant temperature. Phlogopitic mica is a potential thermo-barometer in both garnet- and spinel-peridotite facies.     

华北东部大陆地幔橄榄岩组成、年龄与岩石圈减薄

对比分析了华北东部地块陆下岩石圈地幔橄榄石Mg#值和单斜辉石的REE配分形式。报道了汉诺坝和鹤壁橄榄岩中不同产状硫化物的激光MC-ICPMS原位Re-Os年龄和信阳橄榄岩中锆石的U-Pb年龄和信阳橄榄岩锆石的U-Pb年龄。在这些资料基础上,进一步讨论了华北东部岩石圈中、新生代时的减薄机制。原位分析在揭示岩石圈深部过程的细节上,有比全岩分析更大的优越性,并揭示出了在华北深部有中元古代(14亿年)和新元古代(7～8亿年)热活动的记录。岩石圈拆沉作用不能很好地解释古老难熔地幔、过渡型地幔和新生饱满地幔并存的事实;同时,单纯的熔体-橄榄岩相互作用也难以解释中、新生代岩石圈的减薄过程和新生地幔单斜辉石中出现强烈LREE亏损现象,即历史复杂的克拉通岩石圈向历史明显简单的“大洋型”地幔的转换。因此,华北东部岩石圈减薄包括地幔伸展、熔-岩作用、侵蚀置换等复杂过程。这些过程可能包括:(1)早中生代时,扬子地块向北俯冲碰撞所引起华北岩石圈的熔/流体交代富集作用、地幔伸展和受扰动软流圈物质上涌并侵蚀被改造了的岩石圈;(2)晚中生代—古近纪,因太平洋俯冲的热扰动致使软流圈物质进一步的强烈侵蚀作用引起岩石圈的巨大减薄;(3)晚第三纪以来的软流圈热沉降作用所带来的小幅度岩石圈增厚过程。岩石圈先大幅减薄、后小幅增厚实现了最终的地幔置换和岩石圈整体的减薄过程。喷发时代为100Ma的阜新玄武岩所捕获的橄榄岩主体是饱满的,说明华北东部部分地区在此之前曾有过地幔置换作用。     

Water in the structure of minerals from mantle peridotites as controlled bythermal and redox conditions in the upper mantle

Hydrous species and the amount of water (OH^? ions and crystal hydrate H₂O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH^? and H₂O (3800–3000 cm^?1) and deformation vibrations of H₂O (1850–1450 cm^?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe²⁺ and Fe³⁺ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH^? + H₂O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.     

Lattice-preferred orientation of olivine found in diamond-bearing garnet peridotites in Finsch,South Africa and implications for seismic anisotropy

Seismic anisotropy in the upper mantle provides important constraints on mantle dynamics, continental evolution and global tectonics and is believed to be produced by the flow-induced lattice-preferred orientation (LPO) of olivine. Recent experimental studies at high pressure and temperature have suggested that the LPO of olivine is affected by pressure in addition to water and stress. However, there has been no report yet for the pressure-induced LPO of natural olivine because samples from the deep upper mantle are rare and often unsuitable for study due to ambiguous foliation and lineation. Here we show evidence of the pressure-induced LPO of natural olivine in diamond-bearing garnet peridotites from Finsch, South Africa. We found that the [010] axes of olivine are aligned subnormal to foliation and that the [001] axes are aligned subparallel to lineation, which is known as B-type LPO of olivine. The equilibrium pressure of the samples, as estimated using geobarometer, was greater than 4 GPa, indicating that the samples originated from a depth greater than ∼120 km. In addition, FTIR spectroscopy of the olivine showed that the samples are dry, with a water content of less than 90 ± 20 ppm H/Si (5.5 ± 1.2 ppm wt. H₂O). These data suggest that the samples are the first natural examples of olivine displaying B-type LPOs produced due to high pressure under dry condition. Our data indicate that the trench-parallel seismic anisotropy observed in many subduction zones in and below subducting slabs at depths greater than ∼90 km under dry condition may be attributed to the pressure-induced olivine fabrics (B-type LPO) and may be interpreted as the entrainment of the sub-lithospheric mantle in the direction of subduction rather than anomalous trench-parallel flow.     

The trapped fluid phase in upper mantle xenoliths from Victoria,Australia: implications for mantle metasomatism

Mantle-derived xenoliths of spinel lherzolite, spinel pyroxenite, garnet pyroxenite and wehrlite from Bullenmerri and Gnotuk maars, southwestern Victoria, Australia contain up to 3 vol.% of fluids trapped at high pressures. The fluid-filled cavities range in size from fluid inclusions (1–100 m) up to vugs 11/2 cm across, lined with euhedral high-pressure phases. The larger cavities form an integral part of the mosaic microstructure. Microthermometry and Raman laser microprobe analysis show that the fluids are dominantly CO₂. Small isolated inclusions may have densities 1.19 g/cm³, but most inclusions show microstructural evidence of partial decrepitation during eruption, and these have lower fluid densities. Mass-spectrometric analysis of gases released by crushing or heating shows the presence of He, N₂, Ar, H₂S, CO_s and SO₂ in small quantities; these may explain the small freezing-point depressions observed in some inclusions. Petrographic, SEM and microprobe studies show that the trapped fluids have reacted with the cavity walls (in clinopyroxene grains) to produce secondary amphiboles and carbonates. The trapped CO₂ thus represents only a small residual proportion of an original volatile phase, which has undergone at least two stages of modification — first by equilibration with spinel lherzolite to form amphibole (±mica±apatite), then by limited reaction with the walls of the fluid inclusions. The inferred original fluid was a CO₂-H₂O mixture, with significant contents of (at least) Cl and sulfur species. Generation of this fluid phase in the garnet-peridotite stability field, followed by its migration to the spinel peridotite stability field, would provide an efficient mechanism for metasomatic enrichment of the upper mantle in LIL elements. This migration could involve either a volatile flux or transport in small volumes of silicate melt that crystallize in the spinel peridotite field. These observations suggest that some portions of the subcontinental upper mantle contain large reservoirs of free fluid CO₂, which may be liberated during episodes of rifting or magmatism, to induce granulite-facies metamorphism of the lower crust.     

Intrinsic oxygen fugacity measurements: techniques and results for spinels from upper mantle peridotites and megacryst assemblages

A new technique for the determination of intrinsic oxygen fugacities () of single and polyphase geological samples with solid ZrO₂, oxygen-specific electrolytes is described. Essentially the procedure involves isolating the emf signal from the sample from that unavoidably imposed by the residual atmosphere inside the sample-bearing sensor. By varying the of the residual atmosphere, it is possible to determine a ‘plateau’ value of constant recorded from the sensor which represents a reversed intrinsic measurement for the sample alone, and where the extent of the plateau reflects the innate buffering capability of the sample. A measure of the precision and accuracy of the data obtained is the fact that identical values are obtained whether on a heating or cooling cycle of the sample + compatible atmosphere system.These techniques have been applied to measurements of the intrinsic of spinels from peridotites and megacryst assemblages from Australia, West Germany and the U.S.A. Oxidation states range from ～- 0.25 log₁₀ units more oxidized to 1 log₁₀ unit more reduced than the iron-wüstite (IW) buffer. The overall reduced nature of the spinels and the range of 's obtained are striking features of the data. One implication of the results is that the majority of mantle-derived magmas are initially highly reduced, and the relatively oxidized values observed at surface (～- 4–5 log₁₀ orders more oxidized than IW) reflect late-stage alteration, perhaps by H₂ loss (Sato, 1978).     

Nitrogen-rich fluid in the upper mantle: fluid inclusions in spinel dunite from Lanzarote,Canary Islands

Fluid inclusions, ranging from pure N₂ to pure CO₂, occur in olivine porphyroclasts in spinel dunite xenoliths (chrome-diopside suite) from two localities within the Quaternary to Historic alkaline lavas of Lanzarote, Canary Islands. This is the first report of fluid inclusions containing major amounts of N₂ in mantle xenoliths. The nitrogen-rich fluid inclusions predate at least one generation of nitrogen-free carbon dioxide inclusions; textural evidence indicates that the inclusions were trapped within the upper mantle. Some of the nitrogen-rich fluid inclusions are intimately associated with solid inclusions of spinel. The nitrogen-rich fluid was most likely produced in-situ, by oxidation-dehydration reactions destabilizing ammonium-bearing silicate minerals (phlogopite, amphibole), increasing oxygen fugacity or, possibly, increasing temperature of the mantle. This process could be related to an event of CO₂ and silicate melt injection at 6–8 kbar (Neumann et al., in press), or to some earlier event in the evolution of the mantle beneath Lanzarote. The existence of a N₂-rich fluid phase in at least some mantle lithology(ies) at certain conditions is demonstrated by these data. This discovery has consequences for the understanding of the evolution of the mantle below the Canary Islands, as well as for the global nitrogen budget.     

Single-crystal elastic properties of chondrodite: implications for water in the upper mantle

Chondrodite, a member of the humite group of minerals, forms by hydration of olivine and is stable over a range of temperatures and pressures that includes a portion of the uppermost mantle. We have measured the single crystal elastic properties of a natural chondrodite specimen at ambient conditions using Brillouin spectroscopy. The isotropic aggregate bulk (K) and shear (μ) moduli calculated from the single-crystal elastic moduli, C_ij, are: K_S=118.4(16) GPa and μ=75.6(7) GPa. A comparison of the structures and elasticity of olivine and chondrodite indicate that the replacement of O with (OH,F) in M²⁺O₆ octahedra has a small effect on the elasticity of humite-group minerals. The slightly diminished elastic moduli of humite-group minerals (as compared to olivine) are likely caused by a smaller ratio of strong structural elements (SiO₄ tetrahedra) to weaker octahedra, and perhaps a more flexible geometry of edge-sharing MO₄(O,OH,F)₂ octahedra. In contrast to the humite-olivine group minerals, the incorporation of water into garnets and spineloids leads to a more substantial decrease in the elastic properties of these minerals. This contrasting behavior is due to formation of O₄H₄ tetrahedra and vacant hydroxyl-bearing octahedra in the garnets and spineloids, respectively. Therefore, the mechanism of incorporation of H/OH into mineral phases, not only degree of hydration, should be taken into account when estimating the effect of water on the elastic properties of minerals. The bulk elastic wave velocities of chondrodite and olivine are very similar. If humite-like incorporation of OH is predominant in the upper mantle, then the reaction of OH with olivine will have a minor or possibly no detectable effect on seismic velocities. Thus, it may be difficult to distinguish chondrodite-bearing rocks from “anhydrous” mantle on the basis of seismically determined velocities for the Earth. Received: 25 February 1998 / Revised, accepted: 18 August 1998     

Zoned minerals in garnet peridotite nodules from the Colorado Plateau: implications for mantle metasomatism and kinetics

Some garnet peridotite nodules from The Thumb, a minette neck on the Colorado Plateau in the southwestern United States, contain zoned minerals. Zoning does not exceed 1.5 wt.% for any oxide, but some relative changes are large: in one garnet TiO₂ and Cr₂O₃ ranges are 0.05–0.65 and 3.5–5.0 wt.%, respectively. In two porphyroclastic nodules, garnet rims are depleted in Mg and enriched in Fe, Ti, and Na compared to cores, and one garnet is irregularly zoned in Ti and Cr. Olivine crystals in these rocks are unzoned, and pyroxene zoning is slight, yet matrix olivine and pyroxene contain more Fe and Ti and less Mg and Cr than inclusions of these phases in garnet. In three coarse nodules, garnet rims are Ti-rich compared to cores, and Ca, Fe, Mg, and Cr zoning patterns are complex. Several nodules appear to have partially equilibrated near 1200° C and 35 kb, and under these conditions cation mobility in pyroxene was greater than in garnet. The zoning partly reflects Fe and Ti metasomatism in the mantle. Calculations indicate that Fe-Mg gradients in garnet could have persisted for only a short time in the mantle, perhaps thousands of years or less, so the metasomatism occurred shortly before eruption. The minette host, a likely source of the Fe and Ti, is rich in light rare earth elements: since the nodules are much poorer in these elements, little or no infiltrated minette was trapped in them. Diffusion is a possible mechanism for nodule metasomatism. Some fertile peridotite nodules from kimberlites may have been affected by similar events. Compositional differences between inclusions in garnet and matrix phases are intriguingly similar to some of the differences between most peridotite inclusions in diamonds and common lherzolite phases.     

Partition of magnesium and iron between Olivine and spinel,and between pyroxene and spinel

Partition of Fe²⁺ and Mg between coexisting (Mg, Fe)₂SiO₄ spinel and (Mg, Fe)SiO₃ pyroxene was investigated at pressures 80 and 90 kbar and at temperatures 840 and 1050° C, using tetrahedral-anvil type of high pressure apparatus. Olivine-spinel solid solution equilibria in the system Mg₂SiO₄-Fe₂SiO₄ were discussed in the light of the partition reaction. Partition of Fe²⁺ and Mg in both olivine-spinel and pyroxene-spinel systems can not be regarded as that between ideal solid solutions. By applying the simple solution model for the partition of Fe²⁺ and Mg, sign of the heat of mixing was estimated to be positive for all olivine, spinel and pyroxene. Relative concentration of Fe²⁺ in spinel in the pyroxene-spinel system is likely to cause some change in the chemical composition of modified spinel () or spinel () in the transition zone of the mantle. A considerable change is also expected in the transition pressure of to ( + ) and ( + ) to .Presented at the symposium Recent Advances in the Studies of Rocks and Minerals at High Pressures and Temperatures held in Montreal, 1972. Jointly sponsored by the International Mineralogical Association and the Commission on Experimental Petrology.     

Storage of F and Cl in the upper mantle: geochemical implications

Electron microprobe analyses yielded mean values of $\text{F}\text{0.43}\text{and}\text{Cl}\text{0.08}\text{wt.}\text{\%}$ for primary-textured phlogopites in coarse, depleted garnet-lherzolite xenoliths from kimberlites. Most secondary-textured phlogopites have too low Cl (0.01–0.08 wt.%) to be metamorphic precursors of primary-textured phlogopites. MARID-suite phlogopites and many megacrysts in kimberlites have low Cl ($\text{～ 0.02}\text{wt.}\text{\%}$), and some but not necessarily all secondary micas may result from infiltration of kimberlite into peridotite xenoliths. A good correlation between P and F in some oceanic basalts and gabbros might suggest that these elements are derived mainly from F-rich apatite inthe mantle, and that whitlockite is not present in the source region. Mantle-derived mica and amphibole have such low Cl that it is necessary to attribute Cl in oceanic basalts and gabbros either to substantial Cl in the source apatite, or to Cl from invading solutions, or both: three apatites from the mantle contain 0.8–1.0 wt.% Cl, and others contain lower amounts. The halogen contents of kimberlitic magmas can be explained by incorporation of Cl-bearing mica and F-rich apatite during melting of peridotites, but compositional constraints are weak.