Rare and unusual mineral inclusions in diamonds from Mwadui, Tanzania

Syngenetic diamond inclusions from the Mwadui kimberlite reveal that an unusually fertile section of lithospheric mantle beneath the Central African Craton was sampled. This is shown by a very high ratio of lherzolitic to harzburgitic garnet inclusions (1:2) and low Mg/Fe-ratios in olivine and orthopyroxene. Geothermometry applied to the peridotitic inclusions indicates disequilibrium between non-touching inclusion pairs to be common. Disequilibrium between garnet-olivine and garnet-orthopyroxene pairs suggests successive iron enrichment during diamond formation, e.g. leading to the presence of harzburgitic garnet and lherzolitic olivine in the same diamond. Apart from the dominant peridotitic inclusion suite (88%), rare eclogitic inclusions occur (2%) and a number of uncertain paragenesis. Two diamonds, one with eclogitic garnets with moderate pyroxene solid solution and the other with a single ferro-periclase inclusion, suggest the contribution of a small sub-lithospheric component. The finding of the association Fe-FeO-Fe₃O₄ in one single diamond indicates diamond formation over a large range of f _O2 conditions, possibly along redox fronts. Steep compositional gradients may also be reflected by the joint occurrence of harzburgitic garnet and a SiO₂-phase in the same diamond. Alternatively the formation of the SiO₂-phase may be due to extreme carbonation of the peridotitic source. Further unusual findings include the exsolution of a silicate phase from magnetite inclusions, (i.e. primary solution of γ-olivine) and an ilmenite inclusion with an eskolaite (Cr₂O₃) component of 14.5 mol%, the latter together with harzburgitic paragenesis silicate inclusions. Received: 23 August 1997 / Accepted: 7 January 1998     

Diamonds from Jagersfontein (South Africa): messengers from the sublithospheric mantle

The diamond population from the Jagersfontein kimberlite is characterized by a high abundance of eclogitic, besides peridotitic and a small group of websteritic diamonds. The majority of inclusions indicate that the diamonds are formed in the subcratonic lithospheric mantle. Inclusions of the eclogitic paragenesis, which generally have a wide compositional range, include two groups of eclogitic garnets (high and low Ca) which are also distinct in their rare earth element composition. Within the eclogitic and websteritic suite, diamonds with inclusions of majoritic garnets were found, which provide evidence for their formation within the asthenosphere and transition zone. Unlike the lithospheric garnets all majoritic garnet inclusions show negative Eu-anomalies. A narrow range of isotopically light carbon compositions (δ¹³C −17 to −24 ‰) of the host diamonds suggests that diamond formation in the sublithospheric mantle is principally different to that in the lithosphere. Direct conversion from graphite in a subducting slab appears to be the main mechanism responsible for diamond formation in this part of the Earth’s mantle beneath the Kaapvaal Craton. The peridotitic inclusion suite at Jagersfontein is similar to other diamond deposits on the Kaapvaal Craton and characterized by harzburgitic to low-Ca harzburgitic compositions.     

The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

Mineral equilibria of diamond-forming carbonate-silicate systems

Based on experimental and mineralogical data, the model of mantle carbonate-silicate (carbonatite) melts as dominating parental media for natural diamonds was substantiated. It was demonstrated that the compositions of silicate constituents of parental melts were variable and saturated with respect to mantle rocks, namely pyrope peridotite, garnet pyroxenite, and eclogite. Based on concentration contributions and role in diamond genesis, major (carbonate and silicate) and minor (admixture) components were distinguished. The latter components may be both soluble (oxides, phosphates, chlorides, carbon dioxide, and water) and insoluble (sulfides, metals, and carbides) in silicate-carbonate melts. This paper presents the results of a study of diamond crystallization in multicomponent melts of variable composition with carbonate components (K₂CO₃, CaCO₃ · MgCO₃, and K-Na-Ca-Mg-Fe carbonatite) and silicate components represented by model peridotite (60 wt % olivine, 16 wt % orthopyroxene, 12 wt % clinopyroxene, and 12 wt % garnet) and eclogite (50 wt % garnet and 50 wt % clinopyroxene). Carbonate-silicate melts behave like completely miscible liquid phases in experiments performed under the P-T conditions of diamond stability. The concentration barriers of diamond nucleation (CBDN) in melts with variable proportions of silicates and carbonates were determined at 8.5 GPa. In the peridotite system with K₂CO₃, CaCO₃ · MgCO₃, and carbonatite, they correspond to 30, 25, and 30 wt % silicates, respectively, and in the eclogite system, the CBDN is shifted to 45, 30, and 35 wt % silicates. In the silicate-carbonate melts with higher silicate contents, diamond grows on seeds, which is accompanied by the crystallization of thermodynamically unstable graphite. At P = 7.0 GPa and T = 1200−1800°C, we studied and constructed phase diagrams for the multicomponent peridotite-carbonate and eclogite-carbonate systems as a physicochemical basis for revealing the syngenetic relationships between diamond and its silicate (olivine, ortho- and clinopyroxene, and garnet) and carbonate (aragonite and magnesite) inclusions depending on the physicochemical conditions of growth media. The results obtained allowed us to reconstruct the evolution of diamond-forming systems. The experiments revealed similarity between the compositions of synthetic silicate minerals and inclusions in natural diamonds (high concentrations of Na in garnets and K in clinopyroxenes). It was experimentally demonstrated that the formation of Na-bearing majoritic garnets is controlled by the P-T parameters and melt alkalinity. Diamonds with inclusions of such garnets can be formed in alkalic carbonate-silicate (aluminosilicate) melts. A mechanism was suggested for sodic end-member dissolution in majoritic garnets, and garnet with the composition Na₂MgSi₅O₁₂ and tetragonal symmetry was synthesized for the first time.     

Experimental investigation of the origin of majoritic garnet inclusions in diamonds

 Multianvil experiments were carried out at 10–15 GPa and 1600–1700 °C to match the compositions of majoritic garnet inclusions from diamonds, and to determine the compositions of other phases potentially coexisting with these inclusions in the source. Most experiments produced coexisting majoritic garnet, diopsidic clinopyroxene, one or more (Mg,Fe)₂SiO₄ polymorphs, and quenched carbonatic melt. The experimental garnets had relatively high Ca and Fe contents similar to the observed Ca and Fe contents of the inclusions. The resulting Si contents confirmed that the depth of origin of the inclusion with the highest Si content did not exceed 410 km, thus none of the majoritic garnet inclusions found so far originated in the transition zone (410–660 km). The evidence from inclusions and experiments is consistent with the presence of an eclogite layer occurring globally between 200 and 410 km. Compositional variations observed among more than 100 majoritic garnet inclusions with their Si content, which is a measure of pressure and depth, are consistent with the origin of the eclogite layer by crystal fractionation in a magma ocean. The compositions of olivine coexisting with majoritic garnet in the experimental products had the average Fe/(Fe + Mg) ratios between 0.16 and 0.28. Inclusions with such high Fe contents have not been found; the Fe/(Fe + Mg) ratio of the olivine inclusions in diamonds usually varies between 0.05 and 0.09. Hence, the mantle between 200 and 410 km may not contain olivine. In the absence of olivine, the discontinuity at 410 km is most likely a chemical boundary between the 200-km-thick eclogite layer and a more mafic transition zone. Received: 15 March 2001 / Accepted: 14 September 2001     

Trace element partitioning between carbonatitic melts and mantle transition zone minerals: Implications for the source of carbonatites

The occurrence of CO₂-rich lavas (carbonatites, kimberlites) and carbonate-rich xenoliths provide evidence for the existence of carbonatitic melts in the mantle. To model the chemical composition of such melts in the deep mantle, we experimentally determined partition coefficients for 23 trace elements (including REE, U-Th, HFSE, LILE) between deep mantle minerals and carbonatite liquids at 20 and 25 GPa and 1600 °C. Under these conditions, majoritic garnet and CaSiO₃ perovskite are the main reservoirs for trace elements. This study used both femtosecond LA-ICP-MS and SIMS techniques to measure reliable trace element concentrations. Comparison of the two techniques shows a general agreement, except for Sc and Ba. Our experimentally determined partition coefficients are consistent with the lattice strain model. The data suggest an effect of melt structure on partition coefficients in this pressure range. For instance, strain-free partition coefficient (D₀) for majorite-carbonatite melts do not follow the order of cation valence, , observed for majorite-CO₂-free silicate melts. The newly determined partition coefficients were combined with trace element composition of majoritic garnets found as inclusions in diamond to model trace element patterns of deep-seated carbonatites. The result compares favorably with natural carbonatites. This suggests that carbonatites can originate from the mantle transition zone.     

Precipitation of pyroxenes and Mg2SiO4 from majoritic garnet: simulation of peridotite exhumation from great depth

Our experimental simulations of the exhumation path of mantle peridotites show that high‐temperature (1400 °C) decompression of lherzolite from 14 to 13 and 12 GPa results in exsolution of interstitial blebs of diopside and Mg₂SiO₄ (wadsleyite) lamellae from majoritic garnet. At lower pressures (from 8 to 5 GPa, at T = 1400 °C) only enstatite exsolves as blebs at garnet boundaries. Continuous high‐temperature decompression from 14 to 7 GPa produces zoned majoritic garnet containing blebs of exsolved pyroxenes inside garnet rims. No intracrystalline precipitation of pyroxene was observed in garnet, although such lamellae are found in some natural garnet peridotites. The explanation appears to be the three orders of magnitude difference in grain size between experimental and natural specimens. Our data suggest that Mg₂SiO₄ and diopside exsolutions reflect the deepest point of the exhumation path of garnet peridotites, whereas enstatite precipitation may be restricted to garnets with less majoritic component at shallower depths.     

Comment on “Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing” by Qiu and Wijbrans (2006)

Qiu and Wijbrans [Qiu H.-N. and Wijbrans J. R. (2006) Paleozoic ages and excess ⁴⁰Ar in garnets from the Bixiling eclogite in Dabieshan, China: new insights from ⁴⁰Ar/³⁹Ar dating by stepwise crushing. Geochim. Cosmochim. Acta70, 2354-2370] present three Ar-Ar age spectra for fluid inclusions in garnet from eclogite at Bixiling in the Dabie orogen, east-central China. These Paleozoic ages of 427 ± 20 to 444 ± 10 Ma are interpreted to represent the first formation of Dabie ultrahigh-pressure (UHP) eclogite and thus require subduction of Yangtze crust to have started much earlier than previously accepted. However, no petrographic evidence, such as mineral inclusions in the garnet relating to the particular metamorphic conditions, is presented to substantiate the proposed UHP metamorphic event. Because garnet growth is not uniquely responsible for UHP eclogite-facies metamorphism, a distinction between UHP and high-pressure (HP) metamorphic events must be made in the interpretation of geochronological results. Available data from mineral Sm-Nd and zircon U-Pb dating of eclogites from the same area have firmly established that the UHP eclogite-facies metamorphism took place at Triassic. Neither the age of UHP metamorphism nor the timing of continental collision is reliably constrained by their presented data; the fluid inclusions in garnet must contain inherited ⁴⁰Ar from UHP eclogite precursor, without considerable resetting of the Ar-Ar isotopic system during Triassic UHP metamorphism. Therefore, their data are either meaningless, or at best viewed as the age of garnet growth by low-T/HP blueschist/eclogite-facies metamorphism of the UHP eclogite precursor during arc-continent collision in the early Paleozoic. Furthermore, it is critical for metamorphic geochronology to substantiate the timing of UHP metamorphic event by means of zircon U-Pb in situ dating on coesite-bearing domains of metamorphically grown zircon.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Oxygen isotopic compositions of chondrules from the metal-rich chondrites Isheyevo (CH/CBb), MAC 02675 (CBb) and QUE 94627 (CBb)

It has been recently suggested that (1) CH chondrites and the CB_b/CH-like chondrite Isheyevo contain two populations of chondrules formed by different processes: (i) magnesian non-porphyritic (cryptocrystalline and barred) chondrules, which are similar to those in the CB chondrites and formed in an impact-generated plume of melt and gas resulted from large-scale asteroidal collision, and (ii) porphyritic chondrules formed by melting of solid precursors in the solar nebula. (2) Porphyritic chondrules in Isheyevo and CH chondrites are different from porphyritic chondrules in other carbonaceous chondrites ( [Krot et al., 2005], [Krot et al., 2008a] and [Krot et al., 2008b]). In order to test these hypotheses, we measured in situ oxygen isotopic compositions of porphyritic (magnesian, Type I and ferroan, Type II) and non-porphyritic (magnesian and ferroan cryptocrystalline) chondrules from Isheyevo and CB_b chondrites MAC 02675 and QUE 94627, paired with QUE 94611, using a Cameca ims-1280 ion microprobe.On a three-isotope oxygen diagram (δ¹⁷O vs. δ¹⁸O), compositions of chondrules measured follow approximately slope-1 line. Data for 19 magnesian cryptocrystalline chondrules from Isheyevo, 24 magnesian cryptocrystalline chondrules and 6 magnesian cryptocrystalline silicate inclusions inside chemically-zoned Fe,Ni-metal condensates from CB_b chondrites have nearly identical compositions: Δ¹⁷O = −2.2 ± 0.9‰, −2.3 ± 0.6‰ and −2.2 ± 1.0‰ (2σ), respectively. These observations and isotopically light magnesium compositions of cryptocrystalline magnesian chondrules in CB_b chondrites (Gounelle et al., 2007) are consistent with their single-stage origin, possibly as gas-melt condensates in an impact-generated plume. In contrast, Δ¹⁷O values for 11 Type I and 9 Type II chondrules from Isheyevo range from −5‰ to +4‰ and from −17‰ to +3‰, respectively. In contrast to typical chondrules from carbonaceous chondrites, seven out of 11 Type I chondrules from Isheyevo plot above the terrestrial fractionation line. We conclude that (i) porphyritic chondrules in Isheyevo belong to a unique population of objects, suggesting formation either in a different nebular region or at a different time than chondrules from other carbonaceous chondrites; (ii) Isheyevo, CB and CH chondrites are genetically related meteorites: they contain non-porphyritic chondrules produced during the same highly-energetic event, probably large-scale asteroidal collision; (iii) the differences in mineralogy, petrography, chemical and whole-rock oxygen isotopic compositions between CH and CB chondrites are due to various proportions of the nebular and the impact-produced materials.     

Diamonds from the Buffalo Head Hills,Alberta: Formation in a non-conventional setting

Kimberlite pipes K11, K91 and K252 in the Buffalo Head Hills, northern Alberta show an unusually large abundance (20%) of Type II (no detectable nitrogen) diamonds. Type I diamonds range in nitrogen content from 6 ppm to 3300 ppm and in aggregation states from low (IaA) to complete (IaB). The Type IaB diamonds extend to the lowest nitrogen concentrations yet observed at such high aggregation states, implying that mantle residence occurred at temperatures well above normal lithospheric conditions. Syngenetic mineral inclusions indicate lherzolitic, harzburgitic, wehrlitic and eclogitic sources. Pyropic garnet and forsteritic olivine characterize the peridotitic paragenesis from these pipes. One lherzolitic garnet inclusion has a moderately majoritic composition indicating a formation depth of ∼ 400 km. A wehrlitic paragenesis is documented by a Ca-rich, high-chromium garnet and very CaO-rich (0.11–0.14 wt.%) olivine. Omphacitic pyroxene and almandine-rich garnet are characteristic of the eclogitic paragenesis. A bimodal δ¹³C distribution with peaks at − 5‰ and − 17‰ is observed for diamonds from all three kimberlite pipes. A large proportion (∼ 40%) of isotopically light diamonds (δ¹³C < −10‰) indicates a predominantly eclogitic paragenesis.The Buffalo Head Terrane is of Lower Proterozoic metamorphic age (2.3–2.0 Ga) and hence an unconventional setting for diamond exploration. Buffalo Hills diamonds formed during multiple events in an atypical mantle setting. The presence of majorite and abundance of Type II and Type IaB diamonds suggests formation under sublithospheric conditions, possibly in a subducting slab and resulting megalith. Type IaA to IaAB diamonds indicate formation and storage under lower temperature in normal lithospheric conditions.     

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand

The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial ¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (D_Zr = 0.220 ± 0.007 and D_Hf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (D_Nb = 0.0007 ± 0.0001 and D_Ta = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating D_Nb/D_Ta by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet D_Hf/D_W = 17 and D_Nb/D_Zr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived ¹⁸²Hf-¹⁸²W and ⁹²Nb-⁹²Zr isotopic systems in Hadean time.     

Ultra-high pressure (P > 6 GPa) garnet peridotites in Western Norway: exhumation of mantle rocks from > 185 km depth

We report here for the first time the occurrence of relics of majoritic garnet within orogenic garnet peridotites from Otrøy, Western Gneiss Region, Norway. The microstructural evidence consists of two-pyroxene exsolution from garnet. Majoritic garnets are only stable at depths greater than 150 km. Estimates of the initial composition of the majoritic garnets imply pressures of 6–6.5 GPa indicating that the Otrøy peridotites were derived from depths > 185 km.
  Mineral-chemical data indicate that the present mineral compositions equilibrated at mantle conditions around 805 ± 40 °C and 3.2 ± 0.2 GPa.
  Estimates of the initial pressure temperature (PT) conditions and PTtime ( t ) path are consistent with a multistage, multiorogenic exhumation history with upwelling of hot asthenosphere up to ≈ 100 km in the Pre-Cambrian followed by subsequent crustal emplacement and exhumation during the Caledonian orogeny.     

Origins of subcalcic garnets and their relation to diamond forming fluids—Case studies from Ekati (NWT-Canada) and Murowa (Zimbabwe)

Subcalcic, high-Cr (G10) garnets are found as inclusions within diamonds and in peridotitic xenoliths. The strong spatial associations between G10 garnets and diamond make them an important tool in the investigation of diamond genesis. We present an integrated study of the major and trace element composition and oxygen-Sr-Nd-Hf isotopic ratios of eight G10 garnets from the Ekati mine (NWT-Canada) and four from the Murowa mine (Zimbabwe) in an attempt to determine their petrogenetic evolution and to further examine a possible relationship between the metasomatic agents responsible for G10 garnet signatures and diamond forming fluids.All garnets display sinusoidal to mildly sinusoidal REE patterns and have negative Ti, Sr and positive U anomalies. They have variably radiogenic ⁸⁷Sr/⁸⁶Sr (0.703261-0.731191) and non-radiogenic ε_Nd values (−8.1 to −27.1), except for one sample from Murowa that has a positive ε_Nd of 2.5. One Ekati sample has an extremely low ε_Hf value of −61.6. The Ekati garnets we have studied all appear to come from a single depth in the Slave lithospheric mantle. On the base of Cr-Ca relations they have crystallized at 4.9 GPa and display dunitic Ca intercept values. Their δ¹⁸O values range between +5.23‰ and +5.42‰.The Ekati G10 garnets record a complex, multi-stage metasomatic history involving the interaction of several components during their genesis. One metasomatic agent was enriched in HFSE, LREE, Sr, and depleted in Nb. This agent had the least radiogenic Sr. Another metasomatic agent had highly radiogenic Sr, and was enriched in LREE, Sr, Nb, Th and U.The G10 garnets have very low ε_Nd and ε_Hf values combined with radiogenic Sr, thus, they require an early lithospheric mantle enrichment event at some stage during their genesis or during the evolution of any precursor material that they formed from. The only Hf isotope composition measurable from the Ekati suite is so unradiogenic (ε_Hf = −61) that it yields a Lu/Hf model age of 3521 Ma. This indicates that the lithospheric enrichment event seen by the Ekati garnets or their precursors may have occurred in the early stages of the craton stabilization, during the diamond forming event [Westerlund K., Shirey S., Richardson S., Carlson R., Gurney J. and Harris J. (2006) A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics. Contrib. Mineral. Petrol.152(3), 275-294]. Although our data cannot unequivocally discriminate between a variety of models for the genesis of subcalcic garnets it is clear that the host peridotite originated via melting at shallow depths followed by subduction and that the observed geochemical fingerprint of the garnets is strongly influenced by diamond forming fluids. Diamond forming fluids sampled from fibrous diamonds, have steep REE patterns, negative Ti and Sr anomalies and very low Sm/Nd ratios that are very similar to G10 garnet characteristics. These diamond forming fluids have been recently shown to have extreme Sr and Nd isotopic compositions [Klein-BenDavid O., Pearson D. G., Nowell G. M. and Cantigny P. (2008) Origins of diamond forming fluids—constraints from a coupled Sr-Nd isotope and trace element approach. Extended abstracts to the 9th International Kimberlite Conference, Frankfurt, Germany, 9IKC-A-00118.] that are closely concordant with G10 garnets. The fluids are also rich in LREE, P, K and water, sharing these features with mica-rich metasomes. These similarities suggest that ancient lithospheric metasomes could either provide a source region for, or be a product of diamond forming fluids. Diamond forming fluids appear to be intimately involved in the evolution of G10 garnets in the lithospheric mantle, either acting as a metasomatic agent, or being integral to triggering or enhancing garnet growth in a Cr-rich protolith. Such a link explains the strong association between G10 garnets and diamonds.     

Majoritic garnet grains within shock-induced melt veins in amphibolites from the Ries impact crater suggest ultrahigh crystallization pressures between 18 and 9 GPa

Shock-induced melt veins in amphibolites from the Nördlinger Ries often have chemical compositions that are similar to bulk rock (i.e., basaltic), but there are other veins that are confined to chlorite-rich cracks that formed before the impact and these are poor in Ca and Na. Majoritic garnets within the shock veins show a broad chemical variation between three endmembers: (1) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}{\text{Al}}_{2} ({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (normal garnet, Grt), (2) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}[{\text{M}}^{2 + } ({\text{Si,Ti}})]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\)  (majorite, Maj), and (3) \({}^{\text{VIII}}({{\text {Na} {\text M}^{2+}}_2}) {}^{\text{VI}}[ ({\text{Si,Ti}}){\text {Al}}]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (Na-majorite₅₀Grt₅₀), whereby M²⁺ = Mg²⁺, Fe²⁺, Mn²⁺, Ca²⁺. In particular, we observed a broad variation in ^VI(Si,Ti) which ranges from 0.12 to 0.58 cations per formula unit (cpfu). All these majoritic garnets crystallized during shock pressure release at different ultrahigh pressures. Those with high ^VI(Si,Ti) (0.36–0.58 cpfu) formed at high pressures and temperatures from amphibole-rich melts, while majoritic garnets with lower ^VI(Si,Ti) of 0.12–0.27 cpfu formed at lower pressures and temperatures from chlorite-rich melts. Furthermore, majoritic garnets with intermediate values of ^VI(Si,Ti) (0.24–0.39) crystallized from melts with intermediate contents of Ca and Na. To the best of our knowledge the ‘MORB-type’ Ca–Na-rich majoritic garnets with maximum contents of 2.99 wt% Na₂O and calculated crystallisation pressures of 16–18 GPa are the most extreme representatives ever found in terrestrial shocked materials. At the Ries, the duration of the initial contact and compression stage at the central location of impact is estimated to only ~ 0.1 s. We used a ~ 200-µm-thick shock-induced vein in a moderately shocked amphibolite to model its pressure–temperature–time (P–T–t) path. The graphic model manifests a peak temperature of ~ 2600 °C for the vein, continuum pressure lasting for ~ 0.02 s, a quench duration of ~ 0.02 s and a shock pulse of ~ 0.038 s. The small difference between the continuum pressure and the pressure of majoritic garnet crystallization underlines the usefulness of applying crystallisation pressures of majoritic garnets from metabasites for calculation of dynamic shock pressures of host rocks. Majoritic garnets of chlorite provenance, however, are not suitable for the determination of continuum pressure since they crystallized relatively late during shock release. An extraordinary glass- and majorite-bearing amphibole fragment in a shock-vein of one amphibolite documents the whole unloading path.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

High-pressure phase equilibria and element partitioning experiments on Apollo 15 green C picritic glass: Implications for the role of garnet in the deep lunar interior

We report results of nominally anhydrous near-liquidus experiments on a synthetic analog to very low-titanium Apollo 15 green C lunar picritic glass from ∼2 to 5 GPa. Apollo 15 green C glass (A15C) is saturated with garnet and pyroxene on the liquidus at ∼3 GPa. However, such an assemblage is unlikely to represent the lunar-mantle source region for this glass, and instead an olivine + orthopyroxene-dominated source is favored, in accord with earlier lower-pressure experiments on A15C. Near-liquidus garnet has a slight but significant majorite component at ∼5 GPa in this iron-rich bulk composition, as expected from our previous work in ordinary-chondritic bulk compositions. Ion microprobe measurements of partitioning of Sr, Ba, Sc, Nd, Sm, Dy, Yb, Y, Zr, Hf, and Th between garnet and coexisting melt in these experiments are the first garnet partition coefficients (D values) available that are directly relevant to lunar compositions. D values for these garnets differ significantly compared to D values for garnets grown in more magnesian, terrestrial bulk compositions, which until now are all that have been available in modeling the possible role of garnet in the lunar interior. For example, D values for heavy rare earth elements are lower than are those from terrestrial basaltic systems. These partitioning values are well-described by the lattice-strain partitioning model, but predictive relationships for garnet partitioning using that model fail to match the measured values, as was the case in our earlier work on chondritic compositions. Using our new D values in place of the “terrestrial” values in a variety of models of lunar petrogenesis, we suggest that garnet is unlikely to be present in the source regions for very titanium-poor lunar liquids despite its appearance on the liquidus of A15C.     

SHRIMP U-Pb dating, trace elements and the Lu-Hf isotope system of coesite-bearing zircon from amphibolite in the SW Sulu UHP terrane, eastern China

In this study, we link mineral inclusion data, trace element analyses, U-Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732-839 °C and P = 3.0-4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612-698 °C and P = 0.70-1.05 GPa). Inherited zircons from both samples yield SHRIMP ²⁰⁶Pb/²³⁸U ages of 695-520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236-225 and 239-225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give ²⁰⁶Pb/²³⁸U ages around 219-210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar-Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively. Thus, early exhumation from a mantle depth of 120-100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2-3 cm/y).Based on similar P-T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The εHf₍₈₀₀₎ of +8 implies a significant input from the depleted mantle to the Sulu-Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher ¹⁷⁶Hf/¹⁷⁷Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu-Hf system during UHP metamorphism. The combined dataset suggests homogenization of the ¹⁷⁶Hf/¹⁷⁷Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.     

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Comment on ‘Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing by Hua-Ning Qiu and J.R. Wijbrans’

In a recent study, Qiu and Wijbrans (2006) [Qiu, H.-N. and Wijbrans, J. R. (2006). Paleozoic ages and excess ⁴⁰Ar in garnets from the Bixiling eclogite in Dabieshan, China: new insights from ⁴⁰Ar/³⁹Ar dating by stepwise crushing. Geochimica et Cosmochimica Acta70, 2354-2370.] analyzed Ar-isotopes extracted by crushing garnets from the Dabie Shan Bixiling eclogite and claimed to have constrained a pre-Triassic (∼450 Ma) episode of UHP metamorphism from primary fluid inclusions.However, in the absence of careful sample characterization and stepped heating analyses, the reported ages are more easily explained as experimental artifacts related to Ar extracted from either mineral inclusions or the interface sites between mineral inclusions and the garnet matrix: Dabie Shan garnets commonly contain mineral impurities such as K-rich omphacite and/or K-feldspar.If Dabie Shan UHP metamorphism is of the generally accepted Triassic age (210-240 Ma), the apparent age of a phengite sample in equilibrium with the garnet can be explained by the presence of an extraneous ⁴⁰Ar^∗ component with mean ⁴⁰Ar/³⁶Ar value of ∼5000. This value is similar to the composition of extraneous ⁴⁰Ar^∗ in other eclogite facies terrane.