Cr Spinel Research Articles

Neutron Scattering Studies of the Breathing Pyrochlore Antiferromagnet LiGaCr_{4}O_{8}.

We report neutron scattering measurements of the spinel oxide LiGaCr_{4}O_{8}, in which magnetic ions Cr^{3+} form a breathing pyrochlore lattice. Our experiments reveal the coexistence of a nearly dispersionless resonance mode and dispersive spin-wave excitations in the magnetically ordered state, which can be quantitatively described by a quantum spin model of hexagonal loops and linear spin-wave theory with the same set of exchange parameters, respectively. Comparison to other Cr spinel oxides reveals a linear relationship between the resonance energy and lattice constant across all these materials, which is in agreement with our hexagonal loop calculations. Our results suggest a unified picture for spin resonances in Cr spinel oxides.

Development of a complex arc–back-arc basin system within the South Tianshan Ocean: Insights from the Wuwamen ophiolitic peridotites

Ophiolites within the South Tianshan orogenic belt directly record the nature and tectonic evolution of the South Tianshan Ocean (STO), which is key for understanding the accretionary history of the Central Asian Orogenic Belt. Here we present petrological and Os isotopic data for the Wuwamen mantle peridotites from the South Tianshan orogenic belt, which provide new insights into the tectonic origin of this ophiolite and evolution of the STO. The lherzolites have low spinel Cr# (0.1–0.2), similar to those of fertile oceanic or continental peridotites that have undergone low degrees of melting. However, the extremely high Na2O (1.5–1.8 wt%) and Al2O3 (5.5–6.2 wt%) contents of the clinopyroxenes are atypical of oceanic peridotites, and resemble those of subcontinental peridotites. The harzburgites have more refractory compositions, suggesting higher degrees of melt extraction. Both the lherzolites and harzburgites have low initial 187Os/188Os ratios (< 0.121), which reflect Proterozoic melt depletion and a long-term lithospheric evolution. These data confirm an ancient subcontinental lithospheric mantle origin for the Wuwamen peridotites. The replacive dunites have moderate spinel Cr# (0.3–0.4), reduced Os and enriched 187Os/188Os (0.142–0.160), indicative of reaction between host lherzolites and percolating mid-ocean ridge basalt (MORB)-type melts with radiogenic Os isotopic signatures, presumably in a subduction-related setting. This and the associated back-arc basin basalt (BABB)–type mafic crust suggest the Wuwamen ophiolite formed in a continental margin back-arc setting. A comparison with other ophiolites in the South Tianshan orogenic belt further indicates that a complex arc–back-arc system existed along the southern margin of the Central Tianshan, which was associated with northward subduction within the STO.

Corrosion characteristics of T91 steel in lead–bismuth eutectic with different oxygen concentrations at 500°C

AbstractCorrosion tests of T91 were carried out in the stagnant lead–bismuth eutectic (LBE) containing 10−6, 10−7, and 10−8 wt% oxygen at 500°C for up to 2000 h, respectively. The dependence of corrosion characteristics on oxygen concentrations in LBE was obtained. The results show that the oxide‐scale structure changes from a three‐layer magnetite/spinel/internal oxidation zone (IOZ) scale under the oxygen concentration of 10−6 wt%, to the formation of a two‐layer spinel/IOZ scale under the oxygen concentrations of 10−7 and 10−8 wt%. In addition, with the decrease of the oxygen concentration, the Cr/Fe ratio in the Fe–Cr spinel slightly increases in a linear rule while the thicknesses of the oxide layers gradually decrease.

Chromium speciation, mobility, and Cr(VI) retention-release processes in ultramafic rocks and Fe-Ni lateritic deposits of Greece.

Water contamination by geogenic hexavalent chromium is an emerging issue in areas developed on ultramafic rocks and their weathering products. In this study, samples of serpentinites, soil, and laterites were collected and analyzed for the levels of Cr species, distribution into phases of different mobility, mineralogy, Cr oxidation capacity, and leaching of Cr(VI). Total chromium (2176-21,929mgkg-1) was mainly found in Cr spinels (~ 50% wt as Cr2O3) and Fe (hydr)oxides (2.5% wt). Total Cr(VI) contents (0.49-11.5mgkg-1) increased from the serpentinites to the soil and lateritic deposit, i.e., during the advanced stages of weathering, which were accompanied by increased Cr mobility. Batch experiments of 500-h duration showed that Cr(VI) released in water at rates of 0.25-1.20nMh-1. Rates were higher in water of pH 5.7 rather than pH 8.5, because more Cr(VI) was formed during the experimental period. Asbolane-type Mn oxides and Mn-bearing crystalline Fe oxides were responsible for Cr(III) oxidation. Most of the generated Cr(VI) (52-79% of total Cr(VI)) remained solid-bound by adsorption and/or precipitation processes. Because all samples had a self-capacity to oxidize Cr(III), it seems that retention processes will ultimately define the extent of geogenic Cr(VI) contamination of aquatic systems.

Distribution of mantle-melt interaction zone: A petrological exploration tool for podiform chromitite deposits in the Kalaymyo ophiolite, Myanmar

Podiform chromitite deposits in the Kalaymyo ophiolite, Myanmar, are hosted by replacive dunites and harzburgites with varying degrees of mantle-melt interaction. Combining petrography and spinel and whole-rock compositions of harzburgites from the Bophi-Vum area, one of the ultramafic massifs of the Kalaymyo ophiolite, we investigated petrological and geochemical indicators of the mantle-melt interaction in the harzburgites and their spatial relationship with the location of chromitites.Two end-member types of mantle harzburgites with distinct textures and compositions are recognized in the study area. Low-Cr# (Cr-spinel Cr# < 30; Cr# = molar Cr/(Cr + Al) × 100) harzburgites represent residual mantle peridotites after low degree of partial melting. They are characterized by high whole-rock Al2O3, CaO, and TiO2 contents with a negative correlation between spinel Cr# and TiO2 contents, following the partial melting model trend of the depleted mid-ocean ridge basalt (MORB) mantle. The Cr-spinels from the low-Cr# harzburgites are lobate and vermicular and occur in association with orthopyroxenes, which is typical features of residual harzburgites. On the other hand, the high-Cr# (Cr-spinel Cr# > 30) harzburgites mostly have lower whole-rock Al2O3 (< ~1.4 wt%), CaO (< ~1.3 wt%), and TiO2 (< ~0.04 wt%) contents than the low-Cr# harzburgites, indicating lower modal abundances of pyroxenes. The positive correlation between spinel Cr# and TiO2 contents in the high-Cr# harzburgites suggests their metasomatic origin from the interaction between the low-Cr# harzburgite and island-arc tholeiitic or boninitic melts. The Cr-spinels from the high-Cr# harzburgites, recrystallized during the mantle-melt interaction, are mostly euhedral and associated with olivine.Geochemical maps of the spinel Cr#, whole-rock Al2O3, and CaO contents for the mantle harzburgites show that the distribution of the high-Cr# harzburgites, i.e., the mantle-melt interaction zone, is closely associated with the locations of the dunite and chromitite outcrops. This spatial relationship suggests the potential use of the distribution of mantle-melt interaction zone for podiform chromitite exploration in the study area.

Petrology and geochemistry of ultramafic rocks in the Mogok belt, Myanmar: Cumulates from high‐pressure crystallization of hydrous arc melts

The Mogok metamorphic belt (MMB) in central Myanmar is well known for its complex tectonics, magmatism, and metamorphism in the framework of Tethyan subduction and India–Asia collision. It is also world renowned due to the gemstone‐class rubies and sapphires. Identification and discrimination of those petrological units in this region therefore are important for understanding the gemstone mineralization. Ultramafic massifs also crop out together with the gemstone‐bearing metamorphic rocks in the MMB. It is still poorly constrained about their origin (i.e., mantle peridotites of Jurassic–Cretaceous ophiolites or cumulate rocks) and their relationship with the gemstone generation. Here, we report petrological and geochemical data for the Mogok ultramafic rocks. Petrographic observations show that they have typical cumulate textures, with a crystallization order of olivine/spinel‐orthopyroxene‐clinopyroxene. They have low whole‐rock Al2O3 and CaO, and extremely high spinel Cr# (=Cr/[Cr + Al]; up to 0.86). Clinopyroxenes of these rocks show light rare earth element enriched patterns when normalized to CI chondrite. The results suggest that the Mogok ultramafic rocks have different compositions, both whole‐rock and mineral, from mantle peridotites of Myanmar ophiolites, such as the Kalaymyo and Myitkyina ophiolites, but resemble typical Alaskan‐type ultramafic cumulates. Therefore, the Mogok ultramafic rocks are cumulates generated by high‐pressure crystallization of hydrous arc melts, probably during the subduction of the Tethyan oceanic slab. We argue that the emplacement of these arc melts may have provided additional heat for the earlier magmatic rocks and regional high‐temperature metamorphism, although there is a need to further constrain the ages of these rocks. This, along with magmatism and metamorphism during post‐collisional extension, probably collectively contributed to the generation of world‐class coloured gemstone mineralization.

High–μ signature in lavas of Mt. Oku: Implications for lithospheric and asthenospheric contributions to the magmatism of the Cameroon Volcanic Line (West Africa)

This study presents geochemical data for mafic lavas from Mt. Oku to investigate the mantle source for Mt. Oku lavas and regional variations in isotopic ratios along the Cameroon Volcanic Line (CVL). The investigated mafic lavas present trace element and isotope signatures akin to ocean island basalts (OIB) and cover the entire range of the CVL. Major and trace element compositions of the studied lavas indicates that they have undergone fractionation of olivine + clinopyroxene + Fe-Ti oxide ± Cr–spinel with insignificant crustal contamination. The lavas were generated by <2% partial melting from a heterogeneous source containing less than 4% garnet. Major and trace elements abundances indicate the presence of hydrous minerals indicative of modal metasomatism.The highest value of radiogenic 206Pb/204Pb (20.7) so far measured along the CVL is reported in this study. The isotopic features of the lavas suggest that the HIMU signatures are dominantly inherited from the asthenosphere (primary source) and melting of enriched components hosted in the subcontinental lithospheric mantle (SCLM; secondary source). Lavas from Mt. Oku present more comprehensive ranges of Sr–Nd–Pb isotopic composition than those from the continent-ocean-boundary (COB). The isotopic composition of Mt. Oku lavas with 206Pb/204Pb > 19.5 differs from those of the COB but are similar to FOZO.The isotopic composition of Mt. Oku lavas (87Sr/86Sr = 0.7030–0.7036, 143Nd/144Nd = 0.5127–0.5129, 206Pb/204Pb = 17.9–20.7) suggest that the lavas are the result of contributions from the asthenosphere and the SCLM. Using a combination of Sr–Nd–Pb isotope display on a 3D plot and Sm/Yb, we identify four essential components denoted; A, B, C and D involved in the petrogenesis of Mt. Oku lavas and the approximate melting depth. While A and B are from the asthenosphere with HIMU mantle flavour, C and D owe their origin from the SCLM with EM1 and DMM characteristics, respectively. Although depleted in Sr-Nd isotopes, D is radiogenic in 206Pb/204Pb, indicating the influence of metasomatism. Therefore, the petrogenesis of Mt. Oku lavas involves the mixing of at least three mantle end-members: HIMU–DMM–EM1. The “fanning” of samples from”A" towards the other components (B, C and D) indicates a HIMU–like end–member dominance in Mt. Oku magmatism.Considering the geophysical studies on mantle convection and plumes, we have developed a schematic model that explains the petrogenesis of the CVL lavas. The continuous spectrum from relatively depleted to HIMU characteristics of CVL lavas is associated with the progressive change in source components (i) SCLM with ± pockets of enriched metasomes to (ii) SCLM + asthenosphere sources and finally to (iii) typically asthenospheric source material ± pockets of enriched metasomes. Lavas derived from stage (i) exhibit geochemical variability involving DMM–like and EM1–like signatures. The magma generated at Stage (iii) is dominated by the HIMU mantle component and accounts for over 85% of CVL lavas.

Mineral chemistry and geochemistry of serpentinites from the Bianmagou ophiolite in the North Qilian Belt, NW China: Implications for protoliths, melt extractions, and melt/fluid metasomatism

The North Qilian Belt in northwestern China contains a large number of ophiolites. Most ultramafic rocks from the ophiolites have been entirely transformed into serpentinites because of extensive serpentinization, making it difficult to determine their origin and tectonic significance and further hindering advancements in the understanding of the evolutionary history of the Palaeozoic North Qilian Ocean. In this study, we present new mineral chemistry and whole‐rock geochemistry analyses (including rare earth elements, [REE]) for the serpentinites from the Bianmagou ophiolite to discuss their protoliths, geodynamic environment, melt extractions, and melt/fluid interactions. The mineral chemistry of the relic minerals (e.g., olivine, orthopyroxene, and spinel) and the whole‐rock geochemical compositions (e.g., Mg#, Ni, etc.) strongly demonstrate that the protoliths of the serpentinites were refractory mantle residues after melt extractions and probably emplaced into a tectonic regime of mid‐ocean ridge akin to abyssal peridotites. They experienced high degrees of partial melting (15–20%) recorded by spinel Cr# values and bulk incompatible elements (e.g., Ti, heavy rare‐earth element), resulting from multiple episodes of melt depletion in the lithospheric mantle. Moreover, the serpentinites commonly have U‐shaped chondrite‐normalized REE patterns. The significantly elevated LREEs probably reflect the early partial‐melting processes overprinted by later melt‐dominated metasomatism. The medium to strong enrichment of certain fluid‐mobile elements (e.g., U, Pb, Ba, Sr, As, etc.) in the studied serpentinites was a consequence of the fluid/rock interactions during serpentinization. Overall, despite the variable serpentinization they experienced, this study indicates that the mineral chemical and geochemical proxies of serpentinites provide reliable constraints on the petrogenesis and mantle metasomatism of ancient ophiolites.

Subduction initiation-induced rapid emplacement of garnet-bearing peridotites at a nascent forearc: Petrological and Os-Li isotopic evidence from the Purang ophiolite, Tibet

Abstract Garnet-bearing peridotites commonly occur in the deeper parts of mature or thickened oceanic lithosphere, and are rarely exhumed and emplaced onto the seafloor. The Purang ophiolitic peridotites in south Tibet contain rare symplectite pseudomorphs after garnet, offering a unique window into the still poorly understood evolution of the deep oceanic lithosphere. Here, integrated petrologic and Os-Li isotopic data are used to constrain the evolution and dynamics of emplacement for these garnet peridotite protoliths. The Purang peridotites show wide variations of chemical compositions (spinel Cr#: 0.2–0.8) and Os model ages (up to 2.0 Ga), thus representing a piece of heterogeneous oceanic mantle lithosphere. Dunite channels show two distinctive groups of Cr# of spinels and Os-isotope compositions, with the low- to medium-Cr# (0.2–0.6) and high-Cr# (0.7–0.8) dunites reflecting the reaction of host lherzolites/harzburgites with percolating mid-ocean ridge basalt–like and boninitic melts, respectively. This confirms recent subduction initiation-related melt percolation in the Purang peridotites. Coexisting olivines and pyroxenes in the peridotites show systematic Li elemental and isotopic disequilibrium, suggesting fast cooling of the peridotites to Li closure temperature shortly after the melt percolations, likely during exhumation of the peridotites onto the seafloor. This supports a close link between subduction initiation and tectonic emplacement of the Purang peridotites. Combined with other geological evidence, we suggest the Purang peridotites may originate from the deep part of old, thick oceanic lithosphere of the Neo-Tethys. This thick oceanic lithosphere was progressively weakened and thinned likely during widespread plume-lithosphere interaction, triggering the transformation of garnet peridotite protoliths to spinel peridotites. Subsequently, initiation of a new subduction zone along the lithospheric weakness caused rapid ascent and emplacement of the Purang peridotites at a nascent forearc.

Mechanical and Corrosion Response of 316SS in Supercritical CO2

The supercritical carbon dioxide (s-CO2) Brayton cycle is currently being explored as a replacement for the steam Rankine cycle due to its potential for higher efficiency and lower cycle cost. 316 stainless steel is a candidate alloy for use in s-CO2 up to roughly 600 °C, but the mechanical effects of prolonged exposure of base and welded material in s-CO2 have not been analyzed. The potential for carburization makes this an important concern for the implementation of 316 and similar austenitic stainless steels in the s-CO2 environment. In this study, welded and base material of two types of 316–316L and 316H–were exposed in either s-CO2 or argon at 550 °C or 750 °C for 1000 h. 550 °C s-CO2 exposure yielded a thin (< 1 µm) Cr oxide with occasional nodules of duplex Fe oxide and Fe–Cr spinel that were up to 5 microns thick. However, tensile results from s-CO−2 exposure matched those of 550 °C thermal aging in Ar, indicating that no mechanically detrimental carburization occurred in either 316 variant after 1000 h exposure. Conversely, 750 °C s-CO2 exposure produced roughly 10 × the oxide thickness, with a more substantial Fe oxide (3–5 µm) on the majority of the surface and nodules of up to 40 µm thick. In comparison to aged samples, tensile testing of 750 °C CO2-exposed samples revealed ductility loss attributed to carburization. Projections of 316L performance in s-CO2 indicate that mechanically detrimental carburization—equal to that shown here for 750 °C, 1000 h—will likely be present after 7–14 years of service at 550 °C.

Melt addition to mid-ocean ridge peridotites increases spinel Cr# with no significant effect on recorded oxygen fugacity

Mid-ocean ridge peridotites record significantly greater variability in major and trace elements, isotopic compositions, and thermodynamic properties such as oxygen fugacity (fO2) than do their basaltic counterparts. This variability may derive from modern ridge processes related to melting and melt-rock interaction or from long-lived source heterogeneity related to recycled material or ancient melting events. In this study, we investigate variations in spinel geochemistry as well as silicate major and trace element chemistry and oxygen fugacity of a suite of peridotites from a single segment of the Southwest Indian Ridge (SWIR). We present new petrographic analysis and trace element data for samples with previously-published fO2 results and combine this with new data for a suite of SWIR gabbro-veined peridotites. We find that SWIR residual lherzolites record low spinel Cr# (Cr# = 100*Cr/(Cr+Al) < 30) and represent low to moderate degrees of melting (∼5-8%) beneath the ridge axis, with no change in oxygen fugacity during melting. In contrast, a subset of SWIR peridotites with high spinel Cr# (Cr#>30) record both melt extraction as well as melt-rock interaction. In these samples, spinel Cr# has been substantially elevated by reaction of spinel to form plagioclase during melt addition, complicating the use of spinel Cr# in mid-ocean ridge peridotites as a proxy for degree of melt extraction alone. While spinel Cr# remains a robust proxy for melt extraction within residual, non-melt-influenced samples, mid-ocean ridge peridotites must first be evaluated to ensure that modification by melt-rock reaction has not occurred. Although addition of MORB melt to a peridotite residue modifies spinel Cr#, this melt addition does not result in significant changes to the fO2 recorded by the peridotite. Residual SWIR lherzolites record fO2 of 0.66±0.39 relative to the quartz-fayalite-magnetite buffer (QFM), statistically indistinguishable from melt-influenced and veined SWIR samples (QFM+1.13±0.61). In contrast to other tectonic settings, such as subduction zones, ocean islands, and continental cratons—locations where peridotite is oxidized by petrogenetically unrelated, presumably high-fO2 melts/fluids—ridge peridotites interact with MORB, which has little to no oxidizing power over its own mantle residues. Thus, modern processes beneath the ridge modify peridotite major and trace elements, but do not generate variability in oxygen fugacity.

Atomic-scale investigation of Lithiation/Delithiation mechanism in High-entropy spinel oxide with superior electrochemical performance

• The cycling microstructure evolution of spinel (CrMnFeCoNi) 3 O 4 HEO was precisely demonstrated at atomic scale. • The detailed information of HEO cycling electrochemistry was firstly revealed by EELS. • The lithiated nano grains enhanced the diffusion mobility of spinel oxides and Mn, contributing to the reversible capacity. • The in-depth understanding of the fundamental science influences future development of HEOs in lithium energy storage systems. Transition-metal high-entropy oxides (HEOs) are promising electrode materials for lithium-ion batteries (LIBs) due to their superior electrochemical properties and excellent long-term cycling stability. The performance of HEOs for LIBs is highly correlated with their microstructures, especially their evolution during charging/discharging. However, there is limited information regarding this topic in the literature. In this study, the unique transition behavior of a spinel HEO, (CrMnFeCoNi) 3 O 4 , at various states of charge and cycle numbers is examined in detail for the first time. Although the elemental segregation of lithiated HEO particles is observed, the crystal structure remains spinel, leading to great cyclability. Mn nanocrystals form at 0.5 V lithiation and metallic Cr, Fe, Ni, and Co particles form at 0.01 V lithiation. The spinel Cr x Fe 3-x O 4 and LiNi x Co 1-x O 2 phases act as seeds that grow by devouring surrounding metal nanoparticles during delithiation. The Mn can reversibly move at least dozens of nanometers across the oxide during lithiation/delithiation. The detailed cycling mechanism is examined using electron energy-loss spectroscopy. The reversible valence state variations of the constituent elements are observed. The results provide an in-depth understanding of the fundamental lithiation/delithiation mechanism of HEO, which will facilitate the development of better multi-element HEOs for Li + storage applications.

Abiotic Methane Generation via CO2 Hydrogenation With Natural Chromitite Under Hydrothermal Conditions

AbstractIn modern continental serpentinization systems and ultramafic rock‐hosted sub‐seafloor hydrothermal systems, it is believed that chromitite plays an important role in abiotic hydrocarbon generation. Previous experiments have suggested that chromite acts as a catalyst of CH4 generation, but the composition of chromite used in the previous experiment is unrealistic on Earth. On the other hand, other studies have suggested that natural chromite including Mg and Al cannot function as a catalyst for CH4 generation. Consequently, it still remains uncertain whether naturally occurring Cr‐rich minerals promote CH4 generation. We monitored the reaction between naturally occurring chromitite and CO2‐rich fluid at 300°C, 500 bars. We performed two experiments in different initial CO2/H2 ratios. In both experiments, CH4 was generated immediately after the beginning of experiments. When CO2 was more abundant than H2, the CH4 concentration in the fluid decreased below the detection limit value. On the other hand, when H2 was more abundant than CO2, the CH4 concentration in the fluid was maintained above 0.01 mmol/kg. This is the first report to demonstrate that naturally occurring Cr‐rich minerals act as a promotor of CH4 generation. Cr‐rich minerals such as Cr spinel are common accessory mineral in ultramafic rock. Therefore, on the early Earth, a certain level (on the order of 0.01 mmol/kg) of CH4 was likely produced through reactions between ultramafic rock and CO2‐bearing fluid. To produce more abundant CH4, more favorable conditions featuring greater quantities of Cr spinel and much higher H2 concentration (H2/CO2 ratio) must be necessary.

Remarkably fresh abyssal peridotites from Sibuyan island, Romblon Island Group, Philippines: Markers of young arc-continent collision

The bulk of Sibuyan island in the Romblon Island Group, Philippines is underlain by remarkably fresh spinel lherzolites, harzburgites and dunites collectively called as the Sibuyan Ultramafics. Based on petrographic and geochemical characteristics, the Sibuyan Ultramafics can be classified into: (1) Group I peridotites composed of spinel lherzolites and harzburgites with spinel Cr# < 0.35, (2) Group II harzburgites and dunites with intermediate spinel Cr# = 0.40–0.65, and (3) Group III dunites with very high spinel Cr# (>0.75). Increase in spinel Cr# is accompanied by decreasing Al2O3 contents and increasing Mg# in the pyroxenes from the Group I to Group II and Group III peridotites. Chondrite-normalized clinopyroxene data revealed various trace-element patterns for the three groups suggestive of different processes (e.g. anhydrous and hydrous melting, mantle-melt interaction) involved in their formation. The Sibuyan Ultramafics is closely associated with the similarly fresh Calaton Hill metamorphic/plutonic complex in Tablas island which is thought to be representative of the lower crust of the Philippine island arc. At a more regional context, the Sibuyan Ultramafics and the Calaton Hill metamorphic/plutonic complex can be used as markers for the young arc-continent collision in western Philippines. Rapid uplift and emplacement due to the collision of the Philippine Mobile Belt and the Palawan Microcontinental Block during the Miocene or even later may have led to the remarkably fresh state of these lithologies. This occurrence is similar to the Horoman peridotite complex in the Hidaka metamorphic belt in Northern Japan. The Sibuyan Ultramafics and the Calaton Hill metamorphic/plutonic complex therefore provide a rare and fresh glimpse into the upper mantle and lower crust in the Philippines due to their young ages of emplacement.

Melt Migration and Interaction in a Dunite Channel System within Oceanic Forearc Mantle: the Yushigou Harzburgite–Dunite Associations, North Qilian Ophiolite (NW China)

AbstractHarzburgite–dunite associations in the Yushigou ophiolitic complex (North Qilian suture, NW China) offer insights into melt migration and melt–rock interaction above a subduction zone. Based on detailed petrographic and in situ analyses, we propose a three-stage model to describe the history of melt channel formation in oceanic arc mantle. In the first stage, high-degree melt extraction was followed by widespread infiltration of small-volume melts, which formed the harzburgite that makes up most of the Yushigou complex. The Yushigou harzburgites thus have highly refractory major-element compositions (olivine Fo = 91·1–93·2, spinel Cr# [atomic 100 × Cr/(Cr + Al)] = 55·2–62·9, whole-rock Mg# = 90·5–92·0, Al2O3 = 0·29–0·74 wt%, CaO = 0·35–0·54 wt%, and low Na2O = 0·02–0·05 wt%) but slight enrichment in the light rare earth elements (LREE). In the second stage, high-volume focused melts infiltrated into the mantle wedge and produced two types of dunite, with high-Cr# (mainly 63·1–73·6) versus low-Cr# (23·6–33·7) spinel. In the low-Cr# dunites, spinels have significantly fewer inclusions and lower Fo values (88·7–90·1) in olivine than in the high-Cr# dunite (Fo = 89·9–90·5), together with higher modal abundances of interstitial sulfides. The two groups of dunite show similar extremely low TiO2 (&amp;lt;0·01 wt%) but different igneous clinopyroxene trace-element patterns (ΣLREE/ΣHREE ≈ 1 in low-Cr# dunite versus ΣLREE/ΣHREE &amp;gt;10 in high-Cr# dunite), indicating distinct differences in the infiltrating melts. The low-Cr# dunite is a cumulate from an anhydrous Al- and S-enriched basaltic melt, whereas the high-Cr# dunite was produced by reaction of harzburgite with a carbon-bearing, alkaline hydrous silicate magma. The confluence of these melt migrations finally formed a channelized dunite network, and later magmatic activity was restricted to these channels. Pulsated melt supply after chromite crystallization formed pervasive sieve-textured rims around spinel in both kinds of dunite, but these are rare in the harzburgite. The third stage was marked by fluid-dominated metasomatism recorded by millimeter-scale veined conduits, which contain carbonate (dolomite and magnesite), amphibole, phlogopite and compound crystal assemblages in both kinds of dunite. CH4–N2–graphite-dominated fluid inclusions are widespread in all lithologies, recording the volatiles transported during the last metasomatic event. The Yushigou complex thus provides a detailed example of interaction between multiple batches of melt or fluid and a lithospheric mantle wedge dunitic channel system. The results of this study further suggest that the formation of podiform chromite requires melt participation, and the nature and origins of the melts can be diverse.

Slab‐fluid metasomatism in the Early Paleozoic forearc mantle deduced from the Motai serpentinites, South Kitakami Belt, northeast Japan

AbstractThe present study examines the petrology and geochemistry of the Early Paleozoic Motai serpentinites, the South Kitakami Belt, northeast Japan, to reveal the subduction processes and tectonics in the convergent margin of the Early Paleozoic proto‐East Asian continent. Protoliths of the serpentinites are estimated to be harzburgite to dunite based on the observed amounts of bastite (orthopyroxene pseudomorph). Relic chromian spinel Cr# [=Cr/(Cr + Al)] increases with decreasing amount of bastite. The compositional range of chromian spinel is similar to that found in the Mariana forearc serpentinites. This fact suggests that the protoliths of the serpentinites are depleted mantle peridotites developed beneath the forearc regions of a subduction zone. The Motai serpentinites are divided into two types, namely, Types 1 and 2 serpentinites; the former are characterized by fine‐grained antigorite and lack of olivine, and the latter have coarse‐grained antigorite and inclusion‐rich olivine. Ca‐amphibole occurs as isolated crystals or vein‐like aggregates in the Type 1 serpentinites and as needle‐shaped minerals in the Type 2 serpentinites. Ca‐amphibole of the Type 1 serpentinites is more enriched in LILEs and LREEs, suggesting the influence of hydrous fluids derived from slabs. By contrast, the mineral assemblage, mineral chemistry, and field distribution of the Type 2 serpentinites reflect the thermal effect of contact metamorphism by Cretaceous granite. The Ca‐amphibole of the Type 1 serpentinites is different from that of the Hayachine–Miyamori Ophiolite in terms of origin; the latter was formed by the infiltration of melts produced in an Early Paleozoic arc–backarc system. Chemical characteristics of the Ca‐amphibole in the ultramafic rocks in the South Kitakami Belt reflect the tectonics of an Early Paleozoic mantle wedge, and the formation of the Motai metamorphic rocks in the forearc region of the Hayachine–Miyamori subduction zone system, which occurred at the Early Paleozoic proto‐East Asian continental margin.

Petrogenesis of heterogeneous mantle peridotites with Ni-rich olivine from the Pujada Ophiolite, Philippines

Nickel (Ni) enrichment (>0.40 wt%) in olivine was previously recognized in mantle xenoliths and volcanic rocks. Though this enrichment is often attributed to subarc metasomatic processes, the occurrence of Ni rich olivines in mantle peridotites remains to be established. We found peridotites that randomly contain unusually high-Ni olivines (up to Ni = 0.53 wt%) from the mantle section of the Pujada Ophiolite, Philippines. The Pujada mantle peridotites can be classified into three groups based on their occurrence and spinel Cr#: Group I - massive lherzolites and harzburgites with Cr# = 0.10–0.40, Group II - lherzolite-dunite and harzburgite-dunite interlayers with Cr# = 0.10–0.40, and Group III - interlayered harzburgites and dunites with Cr# >0.40. Rare earth element composition of clinopyroxenes shows general light rare earth element (LREE) depletion and relatively flat heavy rare earth element (HREE) with minor LREE enrichment. The high-Ni olivines are associated to the occurrence of secondary orthopyroxenes, high modal abundance of orthopyroxenes (>30%) and LREE enrichment. The Ni enrichment in olivine is the result of the diffusion of Ni from a pyroxenitic melt. The crystallization of a hybridized melt formed by the combination of pyroxenite melt, primitive MORB melt and siliceous slab-derived melt, shows the same case of formation for the high Ni-olivine phenocrysts in alkali basalts from Hawaii, Kamchatka and the Mexican Volcanic Belt.

Geochemical evidence for forearc metasomatism of peridotite in the Xigaze ophiolite during subduction initiation in Neo-Tethyan Ocean, south to Tibet

Subduction initiation is one of the key processes in the operation of plate tectonics. Our understanding of this process is largely derived from geochemical studies of basaltic rocks in ophiolites at continental margins. Because of the petrological inheritance in forearc basalts, it is important to acquire geochemical signatures for fluid metasomatism of the nascent mantle wedge at forearc depths. This may be provided by the study of peridotite in ophiolites, which is least affected by tectonic emplacement of the ophiolites onto continental margins. For this purpose, we have carried out a comprehensive study of whole-rock and mineral geochemical compositions for harzburgites from the Xigaze ophiolites in the Yarlung Zangbo suture zone, southern Tibet. The results provide insights into the forearc metasomatism during subduction initiation before the closure of Neo-Tethyan Ocean for the India-Asia continental collision in the Cenozoic. The harzburgites show high spinel Cr# values and strong whole-rock depletion in CaO, Al2O3 and REE, suggesting high degrees of melt extraction (~10–20%) during seafloor spreading to form the Neo-Tethyan mid-ocean ridge basalts. They exhibit positive LILE anomalies in trace element distribution patterns, indicating metasomatism by subduction zone fluids. This is supported by the occurrence of tremolite and dolomite in some of the harzburgites. Based on the presence or absence of carbonate minerals, two types of metasomatic fluids are distinguished. One is the aqueous solutions, leading to the formation of tremolite and the enrichment of LILE in clinopyroxene. The other is the carbonate-bearing fluids, resulting in the formation of dolomites, tremolite and low Mg# (79–82) olivine. The metasomatism also results in the high contents of structural hydroxyl in pyroxenes and elevated δ18O values for the harzburgites. It is inferred that the fluid metasomatism was induced by incipient subduction of the juvenile Neo-Tethyan oceanic slab to forearc depths shortly after conversion of the Neo-Tethyan mid-ocean ridge into the trench. During this period of subduction initiation, the fluids were produced by heating dehydration of the sinking ridge crust to the forearc depths. It is these fluids that would metasomatize the overlying nascent mantle wedge, leading to superimposition of the geochemically enriched signature on the lithochemically depleted harzburgites in the ophiolites. Therefore, the forearc metasomatism of peridotite in ophiolite can be used as a geochemical proxy for subduction initiation. Furthermore, the Xigaze ophiolites were produced by the ridge-trench conversion for subduction initiation in the Mesozoic and they were emplaced onto the southern margin of the Asian continent in the Cenozoic.

Melt extraction and reaction in the forearc mantle: Constraints from trace elements and isotope geochemistry of ultra-refractory peridotites of the New Caledonia Peridotite Nappe

The forearc mantle has generally experienced high degrees of partial melting and pervasive melt-rock reactions. Large ultramafic massifs of the New Caledonia ophiolite (Peridotite Nappe) provide opportunities for studying processes within the forearc mantle. Samples of harzburgite, dunite and websterite from three massifs (i.e., Me Maoya, Ouassë Bay, Massif du Sud) have been selected in this study. The peridotites have low contents of Al2O3 (0.10–0.78 wt%) and CaO (0.21–0.58 wt%), but high olivine Fo (90.8–92.5) and spinel Cr# (0.55–0.74) values. This indicates that they have experienced high degrees of partial melting, resulting in the complete consumption of primary clinopyroxene. Trace elements of orthopyroxenes have been measured to constrain the evolution of the New Caledonia harzburgites. Results show that orthopyroxenes have low contents of heavy rare earth element (HREE); their Yb contents are 0.04–0.39 times of chondrites, which can be modeled by ~25–30% of fractional melting of a depleted MORB mantle (DMM) source. The orthopyroxenes also show variable enrichment of light and middle rare earth elements (LREEs and MREEs) and large ion lithophile elements (LILEs), implying late-stage metasomatism. The websterites have high CaO (9.02–9.75 wt%) but low Al2O3 (1.59–1.60 wt%) contents. They have depleted Sr-Nd-Hf isotope compositions similar to that of New Caledonia CE-boninites and plot within the MORB field. Both websterites and dunites have 187Os/188Os ratios (0.12348–0.13067) comparable to that of abyssal peridotites and the New Caledonia harzburgites (0.1203–0.1534). Geochemical compositions and modeling of whole-rock and minerals of harzburgites, dunites and websterites suggest that the New Caledonia peridotites have experienced at least two-stage partial melting and reactions with various migrating melts. Moreover, we also demonstrated that trace element of orthopyroxenes can be applied to discriminate ultra-refractory harzburgites from different tectonic settings.

WITHDRAWN: Petrogenesis of heterogeneous mantle peridotites with Ni-rich olivine from the Pujada Ophiolite, Philippines

Abstract Nickel (Ni) enrichment (>0.40 wt%) in olivine was previously recognized in mantle xenoliths and volcanic rocks. Though this enrichment is often attributed to subarc metasomatic processes, the occurrence of Ni rich olivines in mantle peridotites remains to be established. We found peridotites that randomly contain unusually high-Ni olivines (up to Ni = 0.53 wt%) from the mantle section of the Pujada Ophiolite, Philippines. The Pujada mantle peridotites can be classified into three groups based on their occurrence and spinel Cr#: Group I - massive lherzolites and harzburgites with Cr# = 0.10–0.40, Group II - lherzolite-dunite and harzburgite-dunite interlayers with Cr# = 0.10–0.40, and Group III - interlayered harzburgites and dunites with Cr# >0.40. Rare earth element composition of clinopyroxenes shows general light rare earth element (LREE) depletion and relatively flat heavy rare earth element (HREE) with minor LREE enrichment. The high-Ni olivines are associated to the occurrence of secondary orthopyroxenes, high modal abundance of orthopyroxenes (>30%) and LREE enrichment. The Ni enrichment in olivine is the result of the diffusion of Ni from a pyroxenitic melt. The crystallization of a hybridized melt formed by the combination of pyroxenite melt, primitive MORB melt and siliceous slab-derived melt, shows the same case of formation for the high Ni-olivine phenocrysts in alkali basalts from Hawaii, Kamchatka and the Mexican Volcanic Belt.