Hf isotope compositions and HREE variations in off-craton garnet and spinel peridotite xenoliths from central Asia

Garnet-facies continental mantle is poorly understood because the vast majority of mantle xenoliths in continental basalts are spinel peridotite. Peridotite xenoliths from Vitim (southern Siberia) and Mongolia provide some of the best samples of garnet and garnet-spinel facies off-craton lithospheric mantle. Garnets in those fertile to moderately depleted lherzolites show a surprisingly broad range of HREE abundances, which poorly correlate with modal and major oxide compositions. Some garnets are zoned and have Lu-rich cores. We argue that these features indicate HREE redistribution after the partial melting, possibly related to spinel-garnet phase transition on isobaric cooling. Most peridotites from Vitim have depleted to ultra-depleted Hf isotope compositions (calculated from mineral analyses: ε_Hf(0) = +17 to +45). HREE-rich garnets have the most radiogenic ε_Hf values and plot above the mantle Hf-Nd isotope array while xenoliths with normal HREE abundances usually fall within or near the depleted end of the MORB field. Model Hf isotope ages for the normal peridotites indicate an origin by ancient partial melt extraction from primitive mantle, most likely in the Proterozoic. By contrast, an HREE-rich peridotite yields a Phanerozoic model age, possibly reflecting overprinting of the ancient partial melting record with that related to a recent enrichment in Lu. Clinopyroxene-garnet Lu-Hf isochron ages (31-84 Ma) are higher than the likely eruption age of the host volcanic rocks (∼16 Ma). Garnet-controlled HREE migration during spinel-garnet and garnet-spinel phase transitions may be one explanation for extremely radiogenic ¹⁷⁶Hf/¹⁷⁷Hf reported for some mantle peridotites; it may also contribute to Hf isotope variations in sub-lithospheric source regions of mantle-derived magmas.     

The oxidation state of subcontinental mantle: oxygen thermobarometry of mantle xenoliths from central Asia

The oxygen fugacities of 48 mantle xenoliths from 5 localities in southern Siberia (USSR) and Mongolia have been determined. Ferric iron contents of spinels were measured by ⁵⁷Fe Mössbauer spectroscopy and oxygen fugacities calculated from spinel-olivineorthopyroxene equilibrium. The samples studied represent the major types of upper mantle lithologies including spinel and garnet peridotites and pyroxenites, fertile and depleted peridotites and anhydrous and metasomatized samples which come from diverse tectonic settings. Extensive geochemical and isotope data are also available for these samples. Oxygen fugacity values for most central Asian xenoliths fall within the range observed in peridotite xenoliths from other continental regions at or slightly below the FMQ buffer. However, xenoliths from the Baikal rift zone are the most reduced among xenoliths for which Mössbauer data on spinels are available. They yield fO₂ values similar to those in oceanic peridotites and MORBs, while xenoliths in other occurrences have higher fO₂s. In general, the continental lithosperic mantle is more oxidized than MORB-like oceanic mantle. This difference seems to be due to incorporation of oxidized material into some parts of the subcontinental mantle as a result of subduction of oceanic crust. Garnet- and garnet-spinel lherzolites from the Baikal rift area have slightly higher oxygen fugacities than shallower spinel lherzolites. Oxygen fugacity does not appear to be correlated with the degree of depletion of peridotites, and its values in peridotites and pyroxenites are very much alike, suggesting that partial melting (at least at moderate degrees) takes place at essentially the same fO₂s that are now recorded by the residual material. Modally (amphibole- and phlogopitebearing) and cryptically metasomatized xenoliths from the Baikal rift zone give the same fO₂ values as depleted anhydrous peridotites, suggesting that solid-melt-fluid reactions in the continental rift mantle also take place without substantial change in redox state. This is in contrast to other tectonic environments where metasomatism appears to be associated with oxidation.     

A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle

The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe³⁺ concentrations. Garnet peridotites show a general reduction in log fO₂ (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO₂ (FMQ) with depth that arises from the smaller partial molar volume of Fe³⁺ in garnet, and the observation of distinct slopes of log fO₂ (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.

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Garnet and spinel in fertile and depleted mantle: insights from thermodynamic modelling

We performed thermodynamic calculations based on model and natural peridotitic compositions at pressure and temperature conditions relevant to the Earth’s upper mantle, using well-established free energy minimization techniques. The model is consistent with the available experimental data in Cr-bearing peridotitic systems and can therefore be used to predict phase relations and mineral compositions in a wide range of realistic mantle compositions. The generated phase diagrams for six different bulk compositions, representative of fertile, depleted and ultra-depleted peridotitic mantle, shown that the garnet + spinel stability field is always broad at low temperatures and progressively narrows with increasing temperatures. In lithospheric sections with hot geotherms (ca. 60 mW/m²), garnet coexists with spinel across an interval of 10–15 km, at ca. 50–70 km depths. In colder, cratonic, lithospheric sections (e.g. along a 40 mW/m² geotherm), the width of the garnet–spinel transition strongly depends on bulk composition: In fertile mantle, spinel can coexist with garnet to about 120 km depth, while in an ultra-depleted harzburgitic mantle, it can be stable to over 180 km depth. The formation of chromian spinel inclusions in diamonds is restricted to pressures between 4.0 and 6.0 GPa. The modes of spinel decrease rapidly to less than 1 vol % when it coexists with garnet; hence, spinel grains can be easily overlooked during the petrographical characterization of small mantle xenoliths. The very Cr-rich nature of many spinels from xenoliths and diamonds from cratonic settings may be simply a consequence of their low modes in high-pressure assemblages; thus, their composition does not necessarily imply an extremely refractory composition of the source rock. The model also shows that large Ca and Cr variations in lherzolitic garnets in equilibrium with spinel can be explained by variations of pressure and temperature along a continental geotherm and do not necessarily imply variations of bulk composition. The slope of the Cr# [i.e. Cr/(Cr + Al)mol] isopleths in garnet in equilibrium with spinel changes significantly at high temperatures, posing serious limitations to the applicability of empirical geobarometric methods calibrated on cratonic mantle xenoliths in hotter, off-craton, lithospheric mantle sections.     

The characterisation and origin of graphite in cratonic lithospheric mantle: a petrological carbon isotope and Raman spectroscopic study

Graphite-bearing peridotites, pyroxenites and eclogite xenoliths from the Kaapvaal craton of southern Africa and the Siberian craton, Russia, have been studied with the aim of: 1) better characterising the abundance and distribution of elemental carbon in the shallow continental lithospheric mantle; (2) determining the isotopic composition of the graphite; (3) testing for significant metastability of graphite in mantle rocks using mineral thermobarometry. Graphite crystals in peridotie, pyroxenite and eclogite xenoliths have X-ray diffraction patterns and Raman spectra characteristic of highly crystalline graphite of high-temperature origin and are interpreted to have crystallised within the mantle. Thermobarometry on the graphite-peridotite assemblages using a variety of element partitions and formulations yield estimated equilibration conditions that plot at lower temperatures and pressures than diamondiferous assemblages. Moreover, estimated pressures and temperatures for the graphite-peridotites fall almost exclusively within the experimentally determined graphite stability field and thus we find no evidence for substantial graphite metastability. The carbon isotopic composition of graphite in peridotites from this and other studies varies from δ¹³ C_PDB = ? 12.3 to ? ?3.8%o with a mean of-6.7‰, σ=2.1 (n=22) and a mode between-7 and-6‰. This mean is within one standard deviation of the-4‰ mean displayed by diamonds from peridotite xenoliths, and is identical to that of diamonds containing peridotite-suite inclusions. The carbon isotope range of graphite and diamonds in peridotites is more restricted than that observed for either phase in eclogites or pyroxenites. The isotopic range displayed by peridotite-suite graphite and diamond encompasses the carbon isotope range observed in mid-ocean-ridge-basalt (MORB) glasses and ocean-island basalts (OIB). Similarity between the isotopic compositions of carbon associated with cratonic peridotites and the carbon (as CO₂) in oceanic magmas (MORB/OIB) indicates that the source of the fluids that deposited carbon, as graphite or diamond, in catonic peridotites lies within the convecting mantle, below the lithosphere. Textural observations provide evidence that some of graphite in cratonic peridotites is of sub-solidus metasomatic origin, probably deposited from a cooling C-H-O fluid phase permeating the lithosphere along fractures. Macrocrystalline graphite of primary appearance has not been found in mantle xenoliths from kimberlitic or basaltic rocks erupted away from cratonic areas. Hence, graphite in mantle-derived xenoliths appears to be restricted to Archaean cratons and occurs exclusively in low-temperature, coarse peridotites thought to be characteristic of the lithospheric mantle. The tectonic association of graphite within the mantle is very similar to that of diamond. It is unlikely that this restricted occurrence is due solely to unique conditions of oxygen fugacity in the cratonic lithospheric mantle because some peridotite xenoliths from off-craton localities are as reduced as those from within cratons. Radiogenic isotope systematics of peridotite-suite diamond inclusions suggest that diamond crystallisation was not directly related to the melting events that formed lithospheric peridotites. However, some diamond (and graphite?) crystallisation in southern Africa occurred within the time span associated with the stabilisation of the lithospheric mantle (Pearson et al. 1993). The nature of the process causing localisation of carbon in cratonic mantle roots is not yet clearly understood.     

Vanadium in peridotites as a proxy for paleo-fO2 during partial melting : prospects, limitations, and implications

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO₂): at high fO₂’s, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO₂ at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO₂. V-MgO and V-Al₂O₃ systematics were found to be sensitive to fO₂ variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO₂ differences greater than ∼2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al₂O₃ systematics that can be modeled by 1.5 GPa melting between FMQ − 3 and FMQ − 1. This is consistent with fO₂’s of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe³⁺ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO₂’s as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO₂’s in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO₂ during partial melting, whereas the activity of Fe³⁺ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively.Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ∼FMQ − 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO₂’s. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO₂ content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO₂’s significantly greater than that of modern oceanic mantle. Instead, the fO₂’s inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.     

Experimental tests of garnet peridotite oxygen barometry

We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe?Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO₂ was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for ⁵⁷Fe Mössbauer spectroscopy. The latter gave the Fe³⁺ content of the garnet at the measured P-T-fO₂ conditions. Approach to equilibrium was checked by observed shifts in Fe³⁺ content and by the approach of garnet-olivine Fe?Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO₂ from two possible garnet oxybarometers:- (1) $\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $ and (2) $\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $ Comparison of calculated fO₂s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO₂ units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO₂ recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990).     

Chemical Variations in Peridotite Xenoliths from Vitim, Siberia: Inferences for REE and Hf Behaviour in the Garnet-Facies Upper Mantle

Peridotite xenoliths in a Miocene picrite tuff from the Vitimvolcanic province east of Lake Baikal, Siberia, are samplesof the off-craton lithospheric mantle that span a depth rangefrom the spinel to garnet facies in a mainly fertile domain.Their major and trace element compositions show some scatter(unrelated to sampling or analytical problems), which is notconsistent with different degrees of partial melting or metasomatism.Some spinel peridotites and, to a lesser degree, garnet-bearingperidotites are depleted in heavy rare earth elements (HREE)relative to middle REE (MREE), whereas some garnet peridotitesare enriched in HREE relative to MREE, with Lu abundances muchhigher than in primitive mantle estimates. Clinopyroxenes fromseveral spinel peridotites have HREE-depleted patterns, whichare normally seen only in clinopyroxenes coexisting with garnet.Garnets in peridotites with similar modal and major elementcompositions have a broad range of Lu and Yb abundances. Overall,HREE are decoupled from MREE and Hf and are poorly correlatedwith partial melting indices. It appears that elements withhigh affinity to garnet were partially redistributed in theVitim peridotite series following partial melting, with feweffects for other elements. The Lu–Hf decoupling may disturbHf-isotope depletion ages and their correlations with meltingindices. KEY WORDS: garnet peridotite; lithospheric mantle; Lu–Hf isotope system; Siberia; trace elements     

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.     

Behavior of Siderophile and Chalcophile Elements in the Subcontinental Lithospheric Mantle beneath the Changbaishan Volcano,NE China

The mantle xenoliths in the Quaternary ChangbaishanVolcano in southern Jilin Province contain spinel-facies lherzolites. The equilibration temperatures for these samples range from 902oC to 1064oC based on the two-pyroxene thermometer of Brey and K?hler (1990), and using the oxybarometry of Nell and Wood (1991), the oxidation state was estimated from FMQ-1.32 to -0.38 with an average value of FMQ-0.81 (n?=?8), which is comparable to that of abyssal peridotites and the asthenospheric mantle. The fO2 values of peridotites, together with their bulk rock compositions (e.g., Mg#, Al2O3, CaO, Ni, Co, Cr) and mineral compositions (e.g., Mg# of olivine and pyroxene, Cr# [=Cr/[Cr+Al]] and Mg# [=Mg/[Mg+Fe2+] of spinel), suggest that the present-day subcontinental lithospheric mantle (SCLM) beneath the Changbaishan Volcano most likely formed from an upwelling asthenosphere at some time after the late Mesozoic and has undergone a low degree of partial melting. The studied lherzolite xenoliths show low concentrations of S, Cu, and platinum group elements (PGE), which plot a flat pattern on primitive-mantle normalized diagram. Very low concentrations in our samples suggest that PGEs occur as alloys or hosted by silicate and oxide minerals. The compositions of the studied samples are similar to those of peridotite xenoliths in the Longgang volcanic field (LVF) in their mineralogy and bulk rock compositions including the abundance of chalcophile and siderophile elements. However, they are distinctly different from those of peridotite xenoliths in other areas of the North China Craton (NCC) in terms of Cu, S and PGE. Our data suggest that the SCLM underlying the northeastern part of the NCC may represent a distinct unit of the newly formed lithospheric mantle.     

The buffering capacity of lithospheric mantle: implications for diamond formation

Current models for the formation of natural diamond involve either oxidation of a methane-bearing fluid by reaction with oxidized mantle, or reduction of a carbonate-bearing fluid (or melt) by reaction with reduced mantle. Implicit in both models is the ability of the mantle with which the fluid equilibrates to act as an oxidizing or reducing agent, or more simply, to act as a source or sink of O₂. If only redox reactions involving iron are operating, the ability of mantle peridotite to fulfill this role in diamond formation may not be sufficient for either model to be viable. Using the recent experimental recalibration of olivine–orthopyroxene–garnet oxybarometers of Stagno et al. (2013), we re-evaluated the global database of ~200 garnet peridotite samples for which the requisite Fe³⁺/Fe²⁺ data for garnet exist. Relative to the previous calibration of Gudmundsson and Wood (1995), the new calibration yields somewhat more oxidized values of Δlog fO₂ (FMQ), with the divergence increasing from <0.5 units of log fO₂ at ~3 GPa to as much as 1.5 units at 5–6.5 GPa. Globally, there is a range of ~4 log units fO₂ for samples from the diamond stability field at any given pressure. Most samples are sufficiently reduced such that diamond, rather than carbonate, would be stable, and CHO fluids at these conditions would be H₂O-rich (>60 mol%), with CH₄ being the next most abundant species. To ascertain the capacity for mantle peridotite to act as a source or sink of O₂, we developed a new model to calculate the fO₂ for a peridotite at a given P, T, and Fe³⁺/Fe²⁺. The results from this model predict 50 ppm or less O₂ is required to shift a depleted mantle peridotite the observed four log units of fO₂. Coupled with the observed distribution of samples at values of fO₂ intermediate between the most reduced (metal-saturated) and most oxidized (carbonate-saturated) possible values for diamond stability, these results demonstrate that peridotites are very poor sinks or sources of O₂ for possible redox reactions to form diamond. A corollary of the poor redox buffering capacity of cratonic peridotites is that they can be employed as faithful indicators of the redox state of the last metasomatic fluid that passed through them. We propose that diamond formation from CHO fluids is a predictable consequence either of isobaric cooling or of combined cooling and decompression of the fluid as it migrates upward in the lithosphere. This establishes a petrological basis for the observed close connection between subcalcic garnet and diamond: based on high solidus temperatures of harzburgite and dunite effectively precluding dilution of CHO fluids through incipient melts, such highly depleted cratonic peridotites are the preferred locus of diamond formation. Due to a rapid increase in solidus temperature with increasing CH₄ content of the fluid, diamond formation related to reduced CHO fluids may also occur in some cratonic lherzolites.     

Ultra-depleted, shallow cratonic mantle beneath West Greenland: dunitic xenoliths from Ubekendt Ejland

Dunitic xenoliths from late Palaeogene, alkaline basalt flows on Ubekendt Ejland, West Greenland contain olivine with 100 × Mg/(Mg + Fe), or Mg#, between 92.0 and 93.7. Orthopyroxene has very low Al₂O₃ and CaO contents (0.024–1.639 and 0.062–0.275 wt%, respectively). Spinel has 100 × Cr/(Cr + Al), or Cr#, between 46.98 and 95.67. Clinopyroxene is absent. The osmium isotopic composition of olivine and spinel mineral separates shows a considerable span of ¹⁸⁷Os/¹⁸⁸Os values. The most unradiogenic ¹⁸⁷Os/¹⁸⁸Os value of 0.1046 corresponds to a Re-depletion age of ca. 3.3 Gy, while the most radiogenic value of 0.1336 is higher than present-day chondrite. The Os isotopic composition of the xenoliths is consistent with their origin as restites from a melt extraction event in the Archaean, followed by one or more subsequent metasomatic event(s). The high Cr# in spinel and low modal pyroxene of the Ubekendt Ejland xenoliths are similar to values of some highly depleted mantle peridotites from arc settings. However, highly depleted, arc-related peridotites have higher Cr# in spinel for a given proportion of modal olivine, compared to cratonic xenolith suites from Greenland, which instead form coherent trends with abyssal peridotites, dredged from modern mid-ocean ridges. This suggests that depleted cratonic harzburgites and dunites from shallow lithospheric mantle represent the residue from dry melting in the Archaean.     

Crystal chemistry of amphiboles: implications for oxygen fugacity and water activity in lithospheric mantle beneath Victoria Land,Antarctica

Amphibole is the hydrous metasomatic phase in spinel-bearing mantle xenoliths from Baker Rocks, Northern Victoria Land, Antarctica. It occurs in veins or in disseminated form in spinel lherzolites. Both types derive from reaction between metasomatic melts and the pristine paragenesis of the continental lithospheric mantle beneath Northern Victoria Land. To determine the effective role of water circulation during the metasomatic process and amphibole formation, six amphibole samples were fully characterized. Accurate determination of the site population and the state of dehydrogenation in each of these amphiboles was carried out using single-crystal X-ray diffraction, electron microprobe and secondary ion mass spectroscopy on the same single crystal. The Fe³⁺/ΣFe ratio was determined by X-ray absorption near edge spectroscopy on amphibole powder. The degree of dehydrogenation determined by SIMS is 0.870–0.994 O3(O^2?) a.p.f.u., primary and ascribed to the Ti-oxy component of the amphibole, as indicated by atom site populations; post-crystallization H loss is negligible. Estimates of aH₂O (0.014–0.054) were determined from the dehydration equilibrium among end-member components assuming that amphiboles are in equilibrium with the anhydrous peridotitic phases. A difference up to 58 % in determination of aH₂O can be introduced if the chemical formula of the amphiboles is calculated based on 23 O a.p.f.u. without knowing the effective amount of dehydrogenation. The oxygen fugacity of the Baker Rocks amphibole-bearing mantle xenoliths calculated based upon the dissociation constant of water (by oxy-amphibole equilibrium) is between ?2.52 and ?1.32 log units below the fayalite–magnetite–quartz (FMQ) buffer. These results are systematically lower and in a narrow range of values relative to those obtained from anhydrous olivine–orthopyroxene–spinel equilibria (fO₂ between ?1.98 and ?0.30 log units). A comparative evaluation of the two methods suggests that when amphibole is present in mantle peridotites, the application of oxy-amphibole equilibrium is preferred, because ol–opx–sp oxy-calibrations are not “sensitive” enough in recording the effects (if any) of amphibole in the peridotite matrix. Amphibole acts as the main H acceptor among the peridotite minerals and may prevent fluid circulation and buffer oxygen fugacity. The important conclusion of this study is that amphibole within the lithospheric mantle does not always means high water activity and oxidizing conditions.     

Oxidation state of lithospheric mantle along the northeastern margin of the North China Craton: implications for geodynamic processes

Quaternary volcanic rocks in the Kuandian (KD), Longgang (LG), Changbaishan (CBS), Wangqing (WQ), and Jilin (JL) volcanic centres in eastern Liaoning and southern Jilin provinces contain mantle xenoliths of spinel-facies lherzolites and minor harzburgites. Among the study sites, the KD, LG, and CBS volcanic fields are located on the northeastern margin of the North China Craton (NCC), whereas the WQ and JL fields lie on the southern margin of the Xing'an–Mongolia Orogenic Belt (XMOB). The (Fo) components of olivine (Ol) and Cr# (=Cr/(Cr + Al)) of spinel, together with trace element abundance of clinopyroxene, suggest that the subcontinental lithospheric mantle (SCLM) in the study area has undergone a low degree (4–6%) of partial melting. The rocks do not show modal metasomatism, but clinopyroxene grains in selected samples show elevated large ion lithophile element compositions, suggesting that the mantle xenoliths underwent minor cryptic metasomatism by exchange with a silicate melt. Two-pyroxene thermometry yielded equilibration temperatures ranging from 740°C to 1210°C. The corresponding oxygen fugacity (fO₂) was calculated to range from FMQ –2.64 to +0.39 with an average of –0.59 (n?=?53). The oxidation state is comparable to that of abyssal peridotites and the asthenospheric mantle. We failed to discover differences in equilibration temperatures and oxidation state between lherzolites and harzburgites, suggesting that partial melting did not affect fO₂ values. In addition, similar fO₂ of non-metasomatized and metasomatized samples suggest that metasomatism in the region did not affect fO₂. Our data suggest that the present SCLM beneath the northeastern margin of the NCC and the southern margin of the XMOB are very similar and likely formed from a fertile asthenosphere after delamination of an old lithospheric keel below the NCC in response to the west-dipping subduction of the Pacific oceanic plate since early to middle Mesozoic time.     

Garnet Peridotite Xenoliths from the Vitim Volcanic Field, Baikal Region: the Nature of the Garnet--Spinel Peridotite Transition Zone in the Continental Mantle

A suite of large and fresh peridotite xenoliths from a picritetuff deposit in the Cenozoic Vitim volcanic field, {small tilde}200km east of Lake Baikal, shows a continuous gradation from protogranularspinel through garnet–spinel to very abundant garnet peridotites.This includes composite nodules in which all these lithologiescoexist on the scale of a few centimeters. Garnet and many spinellherzolites are remarkably fertile in terms of their ‘basaltic’major element contents (CaO 30–37%, MgO 37–40%,Ca/Al=11, Cr/Al<013), whereas some garnet–spineland spinel peridotites are moderately depleted (Cr/Al 014–045).T estimates are 850–880C for the fertile spinel lherzolitesapparently brought up from shallow depths of 40–50 km.This contrasts with 980–1030C for depleted spinel peridotitesand 1000–1150C for the garnet-bearing peridotites forwhich equilibration pressures between 16 and 23 kbar are inferred.The data suggest that garnet and spinel peridotites coexistin the sub-Vitim mantle at a pressure of {small tilde}18 kbarover an interval of {small tilde}2 kbar, with the appearanceof garnet, and with the garnetto-spinel ratio in this transitionalzone primarily being controlled by bulk rock contents of Ca,Al, Cr, and Cr/Al ratios, in addition to P–T conditions. The Vitim peridotites show little evidence for metasomatic enrichment:they commonly show depletion of LREE compared with intermediateREE; this includes also rare amphibole-bearing veins. The fertilespinel and garnet lherzolites have very similar bulk rock majoroxide contents and REE distribution patterns; these featuresindicate a lack of significant chemical vertical mantle stratificationin that region. Garnet peridotites from Vitim show large differencesin modal and chemical composition from garnet peridotite xenolithsfrom Yakutian and South African kimberlites, suggesting distinctlithospheric mantle structure and composition in Archean cratonsand post-Archean mobile belts. ^* Present address: School of Earth Sciences, Macquarie University, N.S.W. 2109, Australia     

Constraints on the origin of the oxidation state of mantle overlying subduction zones: An example from Simcoe,Washington, USA

Type I spinel peridotite xenoliths from Simcoe Volcano, southern Washington (USA), are from lithospheric mantle approximately 65 km inboard from the axis of the subduction-related Cascade Range. Oxygen fugacities calculated from contents of Fe³⁺/ΣFe in Simcoe spinels, determined by Mössbauer spectroscopy, are up to 1.4 log units more oxidizing than the FMQ buffer. These are among the most oxidized mantle xenoliths reported, with fugacities substantially higher than those calculated for mantle beneath most of western North America. These results, together with those from amphibole-bearing spinel peridotites from Ichinomegata, Japan (Wood and Virgo, 1989), provide evidence that the mantle above subduction zones is more oxidized than is oceanic or ancient cratonic mantle. We suggest that oxidation was accomplished by an agent ranging in composition from solute-rich hydrous fluid to water-bearing silicate melt. A qualitative model relating extent of oxidation, duration of the oxidation process, and proportion of the available water (derived from subducting slabs) that oxidizes Fe in subarc mantle peridotite, suggests that such an agent can easily produce the observed extents of oxidation over timescales similar to the typical lifespans of subduction zones. For the Cascade arc with a duration of 50 Ma, the observed oxidation in the Simcoe peridotites can be achieved by reacting about 6–11 % of the available water with the mantle. These results demonstrate that water can make an efficient oxidizing agent, and because of the comparatively low ferric iron contents reported for mantle peridotites from other tectonic settings, oxidation of the mantle by water is mostly restricted to subduction zones where water is recycled from the surface and transferred into the mantle wedge.     

Archean-Paleoproterozoic Lithospheric Mantle at the Northern Margin of the North China Craton Represented by Tectonically Exhumed Peridotites

Tectonically emplaced peridotites from North Hebei Province, North China Craton, have retained an original harzburgite mineral assemblage of olivine(54%–58%) + orthopyroxene(40%–46%)+minor clinopyroxene(1%)+spinel. Samples with boninite-like chemical compositions also coexist with these peridotites. The spinels within the peridotites have high-Al end-members with Al_2O_3 content of 30 wt % –50 wt %, typical of mantle spinels. When compared with experimentally determined melt extraction trajectories, the harzburgites display a high degree of melting and enrichment of SiO_2, which is typical of cratonic mantle peridotites. The peridotites display variably enriched light rare earth elements(REEs), relatively depleted middle REEs and weakly fractionated heavy REEs, which suggest a melt extraction of over 25% in the spinel stability field. The occurrence of arc-and SSZ-type chromian spinels in the peridotites suggests that melt extraction and metasomatism occurred mostly in a subduction-related setting. This is also supported by the geochemical data of the coexisting boninite-like samples. The peridotites have ~(187)Os/~(188)Os ratios ranging from 0.113–0.122, which is typical of cratonic lithospheric mantle. These ~(187)Os/~(188)Os ratios yield model melt extraction ages(TRD) ranging from 981 Ma to 2054 Ma, which may represent the minimum estimation of the melt extraction age. The Al_2O_3-~(187)Os/~(188)Os-proxy isochron ages of 2.4 Ga–2.7 Ga suggest a mantle melt depletion age between the Late Achaean and Early Paleoproterozoic. Both the peridotites and boninite-like rocks are therefore interpreted as tectonically exhumed continental lithospheric mantle of the North China Craton, which has experienced mantle melt depletion and subduction-related mantle metasomatism during the Neoarchean-Paleoproterozoic.     

The redox state of the continental lithospheric mantle of the Baikal-Mongolia region

The thermal and redox state of the upper mantle beneath the Baikal-Mongolia region was estimated on the basis of the investigation of the chemical composition (including iron oxidation state) of major minerals (olivine, orthopyroxene, clinopyroxene, and spinel) in spinel and garnet-spinel peridotite xenoliths from the Cenozoic alkali basalts of the volcanic fields of the Dariganga Plateau, Tariat Depression, and Vitim Plateau. At temperatures of 1030–1500°C and pressures of 29–47 kbar, the Δlog$ f_{O_2 } $ f_{O_2 } values relative to the FMQ buffer (calculated using the olivine-spinel oxygen barometer) range from −0.9 to −1.7 for the xenoliths of the Dariganga Plateau, from −0.9 to −1.8 for the Tariat Depression, and from −0.8 to −0.1 for the Vitim Plateau. The oxygen fugacity of peridotites from all of the areas is, in general, lower than that of the WM buffer. Oxygen fugacity is usually below the CCO and EMOD/G buffers in the peridotites of the Dariganga Plateau and the Tariat Depression and higher than these buffers in the peridotites of the Vitim Plateau. The T-PΔlog$ f_{O_2 } $ f_{O_2 } relationships in the xenoliths suggest the existence of spatial heterogeneity in the thermal and redox state of the upper mantle of the Baikal-Mongolia region. This heterogeneity is probably related to the influence of the plume that was responsible for the Late Mesozoic-Cenozoic intraplate magmatism of this region and reflects the different distance of the respective mantle domains from the plume head. The C-O-H fluids in equilibrium with the upper mantle peridotites are composed mainly of water and carbon dioxide. The mantle of the Dariganga Plateau and the Tariat Depression (Δlog$ f_{O_2 } $ f_{O_2 } < −0.9) is characterized by the dominance of H₂O, whereas CO₂-rich fluids are characteristic of the more oxidized mantle of the Vitim Plateau (Δlog$ f_{O_2 } $ f_{O_2 } is mostly higher than −0.8).     

Iron isotope variations in spinel peridotite xenoliths from North China Craton: implications for mantle metasomatism

Iron isotopes, together with mineral elemental compositions of spinel peridotite xenoliths and clinopyroxenites from Hannuoba and Hebi Cenozoic alkaline basalts, were analyzed to investigate iron isotopic features of the lithospheric mantle beneath the North China Craton. The results show that the Hannuoba spinel peridotite xenoliths have small but distinguishable Fe isotopic variations. Overall variations in δ⁵⁷Fe are in a range of ?0.25 to 0.14‰ for olivine, ?0.17 to 0.17‰ for orthopyroxene, ?0.21 to 0.27‰ for clinopyroxene, and ?0.16 to 0.26‰ for spinel, respectively. Clinopyroxene has the heaviest iron isotopic ratio and olivine the lightest within individual sample. No clear linear relationships between the mineral pairs on “δ-δ” plot suggest that iron isotopes of mineral separates analyzed have been affected largely by some open system processes. The broadly negative correlations between mineral iron isotopes and metasomatic indexes such as spinel Cr#, (La/Yb)_N ratios of clinopyroxenes suggest that iron isotopic variations in different minerals and peridotites were probably produced by mantle metasomatism. The Hebi phlogopite-bearing lherzolite, which is significantly modified by metasomatic events, appears to be much heavier isotopically than clinopyroxene-poor lherzolite. This study further confirms previous conclusions that the lithospheric mantle has distinguishable and heterogeneous iron isotopic variations at the xenoliths scale. Mantle metasomatism is the most likely cause for the iron isotope variations in mantle peridotites.     

Ultramafic Xenoliths from the Bearpaw Mountains, Montana, USA: Evidence for Multiple Metasomatic Events in the Lithospheric Mantle beneath the Wyoming Craton

Ultramafic xenoliths in Eocene minettes of the Bearpaw Mountainsvolcanic field (Montana, USA), derived from the lower lithosphereof the Wyoming craton, can be divided based on textural criteriainto tectonite and cumulate groups. The tectonites consist ofstrongly depleted spinel lherzolites, harzburgites and dunites.Although their mineralogical compositions are generally similarto those of spinel peridotites in off-craton settings, somecontain pyroxenes and spinels that have unusually low Al₂O₃contents more akin to those found in cratonic spinel peridotites.Furthermore, the tectonite peridotites have whole-rock majorelement compositions that tend to be significantly more depletedthan non-cratonic mantle spinel peridotites (high MgO, low CaO,Al₂O₃ and TiO₂) and resemble those of cratonic mantle. Thesecompositions could have been generated by up to 30% partialmelting of an undepleted mantle source. Petrographic evidencesuggests that the mantle beneath the Wyoming craton was re-enrichedin three ways: (1) by silicate melts that formed mica websteriteand clinopyroxenite veins; (2) by growth of phlogopite fromK-rich hydrous fluids; (3) by interaction with aqueous fluidsto form orthopyroxene porphyroblasts and orthopyroxenite veins.In contrast to their depleted major element compositions, thetectonite peridotites are mostly light rare earth element (LREE)-enrichedand show enrichment in fluid-mobile elements such as Cs, Rb,U and Pb on mantle-normalized diagrams. Lack of enrichment inhigh field strength elements (HFSE; e.g. Nb, Ta, Zr and Hf)suggests that the tectonite peridotites have been metasomatizedby a subduction-related fluid. Clinopyroxenes from the tectoniteperidotites have distinct U-shaped REE patterns with strongLREE enrichment. They have ¹⁴³Nd/¹⁴⁴Nd values that range from0·5121 (close to the host minette values) to 0·5107,similar to those of xenoliths from the nearby Highwood Mountains.Foliated mica websterites also have low ¹⁴³Nd/¹⁴⁴Nd values (0·5113)and extremely high ⁸⁷Sr/⁸⁶Sr ratios in their constituent phlogopite,indicating an ancient (probably mid-Proterozoic) enrichment.This enriched mantle lithosphere later contributed to the formationof the high-K Eocene host magmas. The cumulate group rangesfrom clinopyroxene-rich mica peridotites (including abundantmica wehrlites) to mica clinopyroxenites. Most contain >30%phlogopite. Their mineral compositions are similar to thoseof phenocrysts in the host minettes. Their whole-rock compositionsare generally poorer in MgO but richer in incompatible traceelements than those of the tectonite peridotites. Whole-rocktrace element patterns are enriched in large ion lithophileelements (LILE; Rb, Cs, U and Pb) and depleted in HFSE (Nb,Ta Zr and Hf) as in the host minettes, and their Sr–Ndisotopic compositions are also identical to those of the minettes.Their clinopyroxenes are LREE-enriched and formed in equilibriumwith a LREE-enriched melt closely resembling the minettes. Thecumulates therefore represent a much younger magmatic event,related to crystallization at mantle depths of minette magmasin Eocene times, that caused further metasomatic enrichmentof the lithosphere. KEY WORDS: ultramafic xenoliths; Montana; Wyoming craton; metasomatism; cumulates; minette