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The Sheahan Diamond Literature Reference Compilation - Scientific and Media Articles based on Major Keyword - Metasomatism
The Sheahan Diamond Literature Reference Compilation is compiled by Patricia Sheahan who publishes on a monthly basis a list of new scientific articles related to diamonds as well as media coverage and corporate announcements called the Sheahan Diamond Literature Service that is distributed as a free pdf to a list of followers. Pat has kindly agreed to allow her work to be made available as an online digital resource at Kaiser Research Online so that a broader community interested in diamonds and related geology can benefit. The references are for personal use information purposes only; when available a link is provided to an online location where the full article can be accessed or purchased directly. Reproduction of this compilation in part or in whole without permission from the Sheahan Diamond Literature Service is strictly prohibited. Return to Diamond Keyword Index
Sheahan Diamond Literature Reference Compilation - Scientific Articles by Author for all years
Each article reference in the SDLRC is tagged with one or more key words assigned by Pat Sheahan to highlight the main topics of the article. In an effort to make it easier for users to track down articles related to a specific topic, KRO has extracted these key words and developed a list of major key words presented in this Key Word Index to which individual key words used in the article reference have been assigned. In most of the individual Key Word Reports the references are in crhonological order, though in some such as Deposits the order is first by key word and then chronological. Only articles classified as "technical" (mainly scientific journal articles) and "media" (independent media articles) are included in the Key Word Index. References that were added in the most recent monthly update are highlighted in yellow.
Metasomatism is the chemical alteration of rock through fluid flow, mainly of a hydrothermal nature, which distinguishes it from metamorphism which changes the minerals without altering the chemical composition. Fluid flow replaces existing minerals with others derived from elements dissolved in the fluids, which in turn makes it a major metal deposit forming mechanism. In this sense metasomatism is not relevant to diamonds, but it is also applied to transformations of the composition of the mantle through the fluid flows created by melting, which provides the magma source for kimberlites and also affects the craton keels where diamonds form in the diamond stability field. These articles are all of a scientific nature and extremely technical.
Relationships between crustal contamination and crystallization in continental flood basalt magmas with special reference to the Deccan Traps Of the Westrn Ghats, In
Earth and Planetary Science Letters, Vol. 84, No. 1, June pp. 59-68
A model of mantle metasom. by carb. alkaline melts:trace element and isotopic compositions of mantle source regions of carbonatite and cont. igneousrocks
Carbonatites -Genesis and Evolution, Ed. K. Bell Unwin Hyman Publ, pp. 464-499
Magmas and metasomites from the Proterozoic Premier kimberlite, SouthAfrica.
Mid-continent diamonds Geological Association of Canada (GAC)-Mineralogical Association of Canada (MAC) Symposium ABSTRACT volume, held Edmonton May, pp. 121-126.
Metasomatism of the southern African lithosphere as recorded by mantlegarnets.
Mid-continent diamonds Geological Association of Canada (GAC)-Mineralogical Association of Canada (MAC) Symposium ABSTRACT volume, held Edmonton May, pp. 127-132.
Cogenetic silica rich and carbonate rich melts trapped in mantle minerals in Kerguelen ultramafic xenoliths -implications for metasomatism in the oceanic upper mantl
Earth Planet. Sci. Letters, Vol. 123, No. 1-2, May pp. 167-178.
Gregoire, M., Tinguely, C., Bell, D.R., Le Roex, A.P.
Spinel lherzolite xenoliths from the Premier kimberlite ( Kaapvaal craton) South Africa: nature and evolution of the shallow upper mantle beneath Bushveld Complex.
Cr Ca and related characteristics of peridotitic garnets from the central Slave and central Kaapvaal craton roots, with implications - carbon in peridotite
GAC Annual Meeting Halifax May 15-19, Abstract 1p.
Phase relations and stability of magnetoplumbite and crichtonite series phases under upper mantle P-T conditions: an experimental study to 15 GPa with LILE
Phase relations and stability of magnetoplumbite and crichtonite series phases under upper mantle P T conditions: an experimental study to 15 GPa. LILE
Roy, A., Sarkar, A., Jeyakumar, S., Aggrawal, S.K., Ebihara, M., Satoh, H.
Late Archean mantle metasomatism below eastern Indian Craton: evidence from trace elements, REE geochemistry and Sr Nd O isotope systematics of ultramafic dykes.
Proceedings National Academy of Sciences India , Vol. 113, 4, pp. 649-666. Ingenta 1045680437
Bonadiman, C., Beccaluva, L., Coltort, M., Siena, F.
Kimberlite like metasomatism and garnet signature in spinel peridotite xenoliths from Sal, Cape Verde Archipelago: relics of subcontinental mantle domain.
Trace element distribution in peridotite xenoliths from Tok, SE Siberian craton: a record of pervasive, multi stage metasomatism in shallow refractory mantle.
Geochimica et Cosmochimica Acta, Vol. 70, 5, pp. 1231-1260.
Os Hf Nd isotope and PGE systematics of spinel peridotite xenoliths from Tok, SE Siberian craton: effects of pervasive metasomatism in shallow refractor
Earth and Planetary Science Letters, Vol. 241, 1-2, pp. 47-64.
The Jungel Valley re-visited: evidence from the lamprophyres for the presence of a Paleoproterozoic carbonate rich metasomatised mantle in Mahakoshal belt
Geological Society of India, Bangalore November Meeting Group Discussion on Kimberlites and Related Rocks India, Abstract p. 123.
India, Madhya Pradesh, Aravalli Bundelkhand Craton
Crystallization of mela-aillikites of the Narsaq region, Gardar alkaline province, south Greenland and relationships to other aillikitic carbonatitic assoc.
Malaspina, N., Hermann, J., Scambelluri, M., Compagnoni, R.
Polyphase inclusions in garnet orthopyroxenite (Dabie Shan, China) as monitors for metasomatism and fluid related trace element transfer in subduction zone.
Geochimica et Cosmochimica Acta, In press available
Moayyed, M., Moazzen, M., Calagari, A.A., Jahangiri, A., Modjarrad, M.
Geochemistry and petrogenesis of lamprophyric dykes and the associated rocks from Eslamy Peninsula, NW Iran: implications for deep mantle metasomatism.
Kohler, J., Schonenberger, J., Upton, B., Markl, G.
Halogen and trace element chemistry in the Gardar Province, South Greenland: subduction related mantle metasomatism and fluid exsolution from alkalic melts.
Buikin, A.I., Trieloff, M., Korochantseeva, E.V., Hopp, J., Kaliwood, M., Meyer, H-P.,Altherr, R.
Distribution of mantle and atmospheric argon in mantle xenoliths from western Arabian Peninsula: constraints on timing and composition of metasomatizing agents....
Characterising modal metasomatic processes in young continental lithospheric mantle: a microsampling isotopic and trace element study on xenoliths from the Middle Atlas Mountains, Morocco.
Contributions to Mineralogy and Petrology, Vol. 162, 2, pp. 289-302.
Deep carbonate recycling and metasomatic enrichment of the sub-continental lithospheric mantle inferred from mantle xenoliths of the East African Rift system.
Mayer, B., Jung, S., Romer, R.,Pfander, J., Klugel, A., Pack, A., Groner, E.
Amphibole in alkaline basalts from intraplate settings: implications for the petrogenesis of alkaline lavas from the metasomatised lithospheric mantle.
Contributions to Mineralogy and Petrology, Vol. 167, 3, pp. 1-22.
Ancient mantle metsomatism recorded in subcalcic garnet xenocrysts: temporal links between mantle metasomatism, diamond growth and crustal tectonomagmatism.
Earth and Planetary Science Letters, Vol. 418, pp. 27-39.
Geological Society of America Special Paper, No. 514, pp. SPE14-17.
Mantle
Melting, metasomatism
Abstract: Various hypotheses for the origin of alkaline sodic mafic magmas have been proposed. This diversity of models is mainly related to the various constraints used to develop them. The goal of this paper is to test these different models using petrological and geochemical constraints in an attempt to understand why alkaline sodic rocks are so similar even while their environment of formation varies from oceanic to continental rift. Incompatible trace-element contents of alkaline basalts from ocean islands and continents show that the sources of these rocks are more enriched than primitive mantle. A fundamental question then is how the sources of alkaline rocks acquire these trace-element enrichments. Recycled oceanic crust, with or without sediment, is often invoked as a source component of alkaline magmas to account for their trace-element and isotopic characteristics. However, the fact that melting of oceanic crust produces silica-rich liquids seems to exclude the direct melting of eclogite derived from mid-ocean-ridge basalt to produce alkaline lavas. Recycling oceanic crust in the source of alkaline magma requires either (1) that the mantle "digests" this component producing metasomatized CO2-rich peridotitic sources or (2) that low-degree melt from recycled oceanic crust reacts with peridotite in the presence of CO2, producing low-silica alkaline melt by olivine dissolution and orthopyroxene precipitation. These two hypotheses are plausible in terms of major elements. However, they have specific implications about the type and proportion of recycled lithologies present in the asthenosphere to explain the specific trace-element pattern of intraplate alkaline lavas. A third hypothesis for the formation of alkaline magmas is the melting of metasomatized lithosphere. In this model, the major- and trace-element signature of alkaline magma is not controlled by the asthenospheric source (i.e., the amount of oceanic crust or CO2 present in the asthenosphere), but by the petrological process that controls the percolation and differentiation of low-degree asthenospheric melts across the lithosphere. This process forms amphibole-bearing metasomatic veins that are a candidate source of alkaline rocks. This hypothesis offers an explanation for the generation of the Na-alkaline lavas with similar major- and trace-element composition that are observed worldwide and for the generation of K- and Na-alkaline magma observed in continental settings. This hypothesis requires the formation of significant amounts of metasomatic veins within the lithosphere. Qualitative analyses of the thermal implication of the potential models for the generation of alkaline rocks demonstrate that such magma requires low potential temperature (Tp: 1320 °C to 1350 °C). If temperatures are higher, melting of the convecting mantle will erase any signature of low-degree melts produced from fertile mantle lithologies. This analysis suggests that a role for hot thermal plumes in the generation of intraplate volcanoes dominated by alkaline magmas is unrealistic.
Abstract: Most kimberlites contain abundant dunitic nodules. These are centimetre-sized, rounded and multi-grained assemblages of xenocrystic olivine with a wide range of compositions (Fo83 to Fo94). The absence of orthopyroxene and other mantle minerals and the range of olivine compositions have been attributed to reaction between mantle peridotite and (proto)kimberlitic fluid or melt, but the timing of the reaction is a subject of debate. In a kimberlite from the Kangamiut region of Greenland, nodule cores are surrounded by fine-grained outer margins with near-constant Fo contents (~Fo88) but highly variable minor element contents (e.g. 500-2500 ppm Ni). These margins crystallized from the kimberlite melt and we show that their compositions can be explained by crystallization of olivine alone, if a high partition coefficient for Ni between melt and olivine (DNi > 20) is assumed. Orthopyroxene assimilation is not required, removing the constraint that its dissolution occurred during ascent of the kimberlite magma. Within some nodules, in addition to the usual core-to-margin gradients, we observe asymmetric compositional changes (variable Fo but near-constant minor element contents) across mobile grain boundaries. These changes document fluid percolation at the grain scale that occurred during dynamic recrystallization in the deforming lithospheric mantle. We note that chemical gradients associated with mobile grain boundaries are observed in olivines that cover the entire compositional range of the nodules, and propose that fluid-assisted dynamic recrystallization took place in dunite that was already compositionally heterogeneous. Reaction between peridotite and protokimberlitic melt or fluid and dissolution of orthopyroxene thus occurred within the lithospheric mantle, immediately (a few days) prior to the ascent of the kimberlite melt and the entrainment of the dunite nodules. We propose that the grain boundary zones probably mimic, at a fine scale, the fluid-peridotite interaction that caused, at a larger scale, orthopyroxene dissolution and formation of compositionally diverse olivine in kimberlites.
Abstract: Canada is host to at least six separate cratons that comprise a significant proportion of its crustal extent. Of these cratons, we possess knowledge of the cratonic lithospheric roots beneath only the Slave craton and, to a lesser extent, the Superior craton, despite the discovery of many new diamond-bearing kimberlites in Canada's North. Here we present the first age, composition and geothermal information for kimberlite-borne peridotite xenoliths from two localities within the central Rae craton: Pelly Bay and Repulse Bay. Our aim is to investigate the nature and evolution of the deep lithosphere in these regions and to examine how events recorded in the mantle may or may not correlate with the complex history of crustal evolution across the craton. Peridotite xenoliths are commonly altered by secondary processes including serpentinization, silicification and carbonation, which have variably affected the major element compositions. These secondary processes, as well as mantle metasomatism recorded in pristine silicate minerals, however, did not significantly modify the relative compositions of platinum-group elements (PGE) and Os isotope ratios in the majority of our samples from Pelly Bay and Repulse Bay, as indicated by the generally high absolute PGE concentrations and mantle-like melt-depleted PGE patterns. The observed PGE signatures are consistent with the low bulk Al2O3 contents (mostly lower than 2.5%) of the peridotites, as well as the compositions of the silicate and oxide minerals. Based on PGE patterns and Os model ages, the peridotites from both localities can be categorized into three age groups: Archean (3.0-2.6 Ga overall; 2.8-2.6 Ga for Pelly Bay and 3.0-2.7 Ga for Repulse Bay), Paleoproterozoic (2.1-1.7 Ga), and "Recent" (<1 Ga, with model ages similar to the ca. 546 Ma kimberlite eruption age). The Archean group provides the first direct evidence of depleted Archean lithospheric mantle forming coevally with the overlying Archean crustal basement, indicating cratonization of the Rae during the Archean. The subtle difference in Os model ages between Pelly Bay and Repulse Bay coincides with the age difference between crustal basement rocks beneath these two areas, supporting the suggestion that the Rae craton was assembled by collision of separate two Archean blocks at 2.7-2.6 Ga. The Paleoproterozoic peridotites are interpreted to represent newly formed lithospheric mantle, most likely associated with regional-scale underplating during the 1.77-1.70 Ga Kivalliq-Nueltin event via removal of the lower portion of Archean lithospheric mantle followed by replacement with juvenile Paleoproterozoic lithospheric mantle. The existence of multiple age clusters in the lithosphere at each locality is consistent with the observation of present-day seismic lithospheric discontinuities (0540 and 0545) that indicate two or more layers of fossil lithospheric mantle fabric beneath this region. Our data define a shallow mantle lithosphere layer dominated by Archean depletion ages underlain by a layer of mixed Archean and Paleoproterozoic ages. This lithospheric mantle structure is probably a response to complex tectonic displacement of portions of the lithospheric mantle during Paleoproterozoic orogeny/underplating. The best equilibrated Archean and Paleoproterozoic peridotites at both Pelly Bay and Repulse Bay define a typical cratonic geotherm at the time of kimberlite eruption, with a ?200 km thick lithospheric root extending well into the diamond stability field, in keeping with the diamondiferous nature of the kimberlites. Such thick lithosphere remains in place to the present day as suggested by seismic and magnetotelluric studies (0540, 0545 and 0550). The metasomatically disturbed peridotites in the Rae lithospheric mantle, yielding model ages indistinguishable from kimberlite eruption, may represent parts of the Rae craton mantle root that show anomalous magnetotelluric signatures.
Abstract: Interaction between carbonatite melt and peridotite is studied experimentally by melting samples of interlayered peridotite-carbonatite-peridotite in graphite containers at 1200-1350 °C and 5.5-7.0 GPa in a split-sphere multianvil apparatus. Starting compositions are lherzolite and harzburgite, as well as carbonatite which may form in the upper part of a slab or in a plume-related source. Most experimental runs were of 150 h duration in order for equilibrium to be achieved. The interaction produced carbonatitic melts with low SiO2 (? 7 wt.%) and high alkalis. At 1200 °C, melt-peridotite interaction occurs through Mg-Ca exchange, resulting in elimination of orthopyroxene and crystallization of magnesite and clinopyroxene. At 1350 °C hybridization of the carbonatite and magnesite-bearing peridotite melts occurred with consumption of clinopyroxene and magnesite, and crystallization of orthopyroxene at MgO/CaO ? 4.3. The resulting peridotite-saturated melt has Ca# (37-50) depending on primary carbonatite composition. Compositions of silicate phases are similar to those of high-temperature peridotite but are different from megacrysts in kimberlites. CaO and Cr2O3 changes in garnet produced from the melt-harzburgite interaction at 1200 and 1350 °C perfectly match the observed trend in garnet from metasomatized peridotite of the Siberian subcontinental lithospheric mantle. K-rich carbonatite melts equilibrated with peridotite at 5.5-7.0 GPa and 1200-1350 °C correspond to high-Mg inclusions in fibrous diamond. Carbonatite melt is a weak solvent of entrained xenoliths and therefore cannot produce kimberlitic magma if temperatures are ~ 1350 °C on separation from the lithospheric peridotite source and ~ 1000 °C on eruption.
Abstract: Mariupolite, aegirine-albite nepheline syenite, outcropping only in the Oktiabrski massif in south-eastern Ukraine, is a potential resource of Nb, Zr and REE for future exploration and development. Some types of this rock can be also used in ceramics, glass and building industry and jewellery. Mariupolite is composed of (1) magmatic and (2) subsolidus and hydrothermal components. The magmatic assemblage includes zircon, aegirine, nepheline, albite, K-feldspar, pyrochlore, fluorapatite, fluorbritholite-(Ce) and magnetite. Alkaline-carbonate-chloride-rich fluids exsolved very early in the history of the rock, in a late stage of, or directly after, its consolidation, induced intensive high-temperature alteration of the primary mariupolite components resulted in formation of cancrinite, calcite, fluorite, REE-bearing minerals such as monazite, parasite-(Ce), bastnäsite-(Ce), as well as sodalite, natrolite and hematite. The genesis of this peculiar mineralization seems to be associated with multistage magmatic and tectonic activity of the Ukrainian Shield and fluids mediated metasomatic processes.
Geochimica et Cosmochimica Acta, in press available
Africa, Ethiopia
Metasomatism - picrites
Abstract: The origin of the Ethiopian-Yemeni Oligocene flood basalt province is widely interpreted as representing mafic volcanism associated with the Afar mantle plume head, with minor contributions from the lithospheric mantle. We reinterpret the geochemical compositions of primitive Oligocene basalts and picrites as requiring a far more significant contribution from the metasomatized subcontinental lithospheric mantle than has been recognized previously. This region displays the fingerprints of mantle plume and lithospheric drip magmatism as predicted from numerical models. Metasomatized mantle lithosphere is not dynamically stable, and heating above the upwelling Afar plume caused metasomatized lithosphere with a significant pyroxenite component to drip into the asthenosphere and melt. This process generated the HT2 lavas observed today in restricted portions of Ethiopia and Yemen now separated by the Red Sea, suggesting a fundamental link between drip magmatism and the onset of rifting. Coeval HT1 and LT lavas, in contrast, were not generated by drip melting but instead originated from shallower, dominantly anhydrous peridotite. Looking more broadly across the East African Rift System in time and space, geochemical data support small volume volcanic events in Turkana (N. Kenya), Chyulu Hills (S. Kenya) and the Virunga province (Western Rift) to be derived ultimately from drip melting. The removal of the gravitationally unstable, metasomatized portion of the subcontinental lithospheric mantle via dripping is correlated in each case with periods of rapid uplift. The combined influence of thermo-mechanically thinned lithosphere and the Afar plume together thus controlled the locus of continental rift initiation between Africa and Arabia and provide dynamic support for the Ethiopian plateau.
Progress in Earth and Planetary Science, Vol. 3, 20, 17p.
United States, Colorado Plateau
Metasomatism
Abstract: This is the first report on amphibole exsolution in pyrope from the Colorado Plateau. Pyrope crystals delivered from mantle depths underneath the Colorado Plateau by kimberlitic volcanism at 30 Ma were collected at Garnet Ridge, northern Arizona. The garnet grains analyzed in this study occur as discrete crystals (without adjacent rock matrix) and are classified into two major groups, Cr-rich pyrope and Cr-poor pyrope. The Cr-poor pyrope group is divided into four subgroups based on exsolved phases: amphibole lamella type, ilmenite lamella type, dense lamellae type, and clinopyroxene/amphibole lamellae type. Exsolved amphibole occurs in amphibole lamella type, dense lamellae type, and clinopyroxene/amphibole lamellae type of Cr-poor pyrope. The amphibole crystals tend to have preferred orientations in their garnet hosts and occur as monomineralic hexagonal or rhombic prisms and tablets, and as multimineralic needles or blades with other exsolved phases. Exsolved amphibole has pargasitic compositions (Na2O up to 1.6 apfu based on 23 oxygen). Garnet host crystals that have undergone amphibole exsolution have low OH contents (2-42 ppmw H2O) compared to garnets that do not have amphibole lamellae (up to 115 ppmw H2O). The low OH contents of garnets hosting amphibole lamellae suggest loss of OH from garnet during amphibole exsolution. Amphibole exsolution from pyrope resulted from breakdown of a precursor “hydrous Na-garnet” composition (Mg,Na+ x)3(Al2???x, Mgx)2Si3O12???2x(OH)2x. Exsolution of amphibole and other phases probably occurred during exhumation to depths shallower than 100 km prior to volcanic eruption. Based on the abundance and composition of exsolved clinopyroxene and amphibole lamellae in one garnet, hydrous Na-garnet had excess silicon (Si3.017 apfu, 12 oxygen normalization, vs. X3Y2Si3O12 for typical garnet). Comparison with experimental data suggests crystallization at pressures near 6-8 GPa. Garnet crystals that host exsolved amphibole have compositions (Pyp49-76, 3-10 wt% CaO, and up to 0.6 wt% Cr2O3) similar to garnets reported from pyroxenites, and have pyrope-almandine-grossular compositional ranges that overlap with the Cr-rich pyrope (typical lherzolitic garnet). Hydrous Na-garnet was likely formed by metasomatic reactions between Cr-rich pyrope and Na-rich aqueous fluid in the deep upper mantle. The most likely source of metasomatic Na-rich fluid is ancient oceanic crust that was subducted before subduction of the Farallon Plate beneath the Colorado Plateau.
Abstract: Although trace element concentrations in clinopyroxene serve as a useful tool for assessing the depletion and enrichment history of mantle peridotites, this is not applicable for peridotites in which the clinopyroxene component has been consumed (~ 25% partial melting). Orthopyroxene persists in mantle residues until ~ 40% melting and it is therefore this mineral that offers petrological insights into the evolution of refractory peridotites. Major and trace element concentrations in orthopyroxene ± clinopyroxene from two spinel facies harzburgitic xenolith suites from New Zealand are examined. Samples from Cape L'Evique (CLEV) on Chatham Island contain traces of clinopyroxene (< 2 modal %) but a suite from Lake Moana (MOA) in the South Island is devoid of this mineral. When compared with modelled orthopyroxene trace element budgets, which are constructed from a review of published source modes, melting modes and element/melt partition co-efficients, the measured orthopyroxene rare earth element data in both suites generally indicate minimums of 25-30% partial melting. These results are consistent with co-existing elevated Mg# in olivine (mostly 91.4 to 93.0) and orthopyroxene (mostly 91.3 to 93.6), high spinel Cr# (commonly > 45) and low orthopyroxene Al2O3 (generally < 3.1 wt%). However, comparison of modelled and measured orthopyroxene compositions shows that all samples, even the most refractory, have undergone metasomatism by small volume light rare earth element-bearing agents. Measured orthopyroxene Ti concentrations show that the metasomatic agent that affected the CLEV suite carried Ti, but that the MOA suite metasomatiser was Ti-poor. Orthopyroxene trace elements in the inspected rocks are therefore partly decoupled from the major element abundances, with the results demonstrating that even highly refractory peridotites can record evidence for mantle metasomatism.
Abstract: Construction histories of Archean cratons remain poorly understood; their destruction is even less clear because of its rarity, but metasomatic weakening is an essential precursor. By assembling geophysical and geochemical data in 3-D lithosphere models, a clearer understanding of the geometry of major structures within the Rae, Slave and Wyoming cratons of central North America is now possible. Little evidence exists of subducted slab-like geometries similar to modern oceanic lithosphere in these construction histories. Underthrusting and wedging of proto-continental lithosphere is inferred from multiple dipping discontinuities, emphasizing the role of lateral accretion. Archean continental building blocks may resemble the modern lithosphere of oceanic plateau, but they better match the sort of refractory crust expected to have formed at Archean ocean spreading centres. Radiometric dating of mantle xenoliths provides estimates of rock types and ages at depth beneath sparse kimberlite occurrences, and these ages can be correlated to surface rocks. The 3.6-2.6 Ga Rae, Slave and Wyoming cratons stabilized during a granitic bloom at 2.61-2.55 Ga. This stabilization probably represents the final differentiation of early crust into a relatively homogeneous, uniformly thin (35-42 km), tonalite-trondhjemite-granodiorite crust with pyroxenite layers near the Moho atop depleted lithospheric mantle. Peak thermo-tectonic events at 1.86-1.7 Ga broadly metasomatized, mineralized and recrystallized mantle and lower crustal rocks, apparently making mantle peridotite more ‘fertile’ and more conductive by introducing or concentrating sulfides or graphite at 80-120 km depths. This metasomatism may have also weakened the lithosphere or made it more susceptible to tectonic or chemical erosion. Late Cretaceous flattening of Farallon lithosphere that included the Shatsky Rise conjugate appears to have weakened, eroded and displaced the base of the Wyoming craton below 140-160 km. This process replaced the old re-fertilized continental mantle with relatively young depleted oceanic mantle.
Geochimica et Cosmochimica Acta, Vol. 200, pp. 167-185.
Africa, South Africa, Russia
Metasomatism
Abstract: We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134-186 km beneath the Kaapvaal and Siberian cratons. There is no clear difference in ?26Mg and ?56Fe of garnet peridotites from these two cratons. ?26Mg of whole rocks varies from ?0.243 to ?0.204 with an average of ?0.225 ± 0.037 (2?, n = 19), and ?56Fe from ?0.038‰ o 0.060 with an average of ?0.003 ± 0.068 (2?, n = 19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show ?26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation. The precision of the Mg and Fe isotope data (±0.05 for ?26Mg and ?56Fe, 2?) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest ?26Mg and ?56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy ?26Mg and much lighter ?56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.
Earth and Planetary Science Letters, Vol. 461, pp. 105-118.
Mantle
Metasomatism
Abstract: Peridotite constitutes most of the Earth's upper mantle, and it is therefore unsurprising that most mantle-derived magmas exhibit evidence of past equilibrium with an olivine-dominated source. Although there is mounting evidence for the role of pyroxenite in magma generation within upwelling mantle plumes, a less documented non-peridotite source of melts are metasomatic veins (metasomes) within the lithospheric mantle. Here we present major and trace element analyses of 66 lavas erupted from a small Miocene shield volcano located within the Ethiopian flood basalt province. Erupted lavas are intercalated with lahars and pyroclastic horizons that are overlain by a later stage of activity manifested in small cinder cones and flows. The lavas form two distinctive petrographic and geochemical groups: (A) an olivine-phyric, low Ti group (1.7-2.7 wt.% TiO2; 4.0-13.6 wt.% MgO), which geochemically resembles most of the basalts in the region. These low Ti lavas are the only geochemical units identified in the later cinder cones and associated lava flows; (B) a clinopyroxene-phyric high Ti group (3.1-6.5 wt.% TiO2; 2.8-9.2 wt.% MgO), which resembles the Oligocene HT-2 flood basalts. This unit is found intercalated with low Ti lavas within the Miocene shield. In comparison to the low Ti group, the high Ti lavas exhibit a profound depletion in Ni, Cr, Al, and Si, and significant enrichment in Ca, Fe, V, and the most incompatible trace elements. A characteristic negative K anomaly in primitive-mantle normalized diagrams, and Na2O > K2O, suggests a source rich in amphibole, devoid of olivine, and perhaps containing some carbonate and magnetite. While melt generation during rift development in Ethiopia is strongly correlated with the thermo-chemical anomalies associated with the African Superplume, thermobaric destabilization and melting of mantle metasomes may also contribute to lithospheric thinning. In regions impacted by mantle plumes, such melts may be critical to weakening of the continental lithosphere and the development of rifts.
Abstract: Widespread Miocene (24-8 Ma) ultrapotassic rocks and their entrained xenoliths provide information on the composition, structure, and thermal state of the sub-continental lithospheric mantle in southern Tibet during the India-Asia continental collision. The ultrapotassic rocks along the Lhasa block delineate two distinct lithospheric domains with different histories of depletion and enrichment. The eastern ultrapotassic rocks (89°E-92°E) reveal a depleted, young, and fertile lithospheric mantle (87Sr/86Srt = 0.704-0.707 [t is eruption time]; Hf depleted-mantle model age [TDM] = 377-653 Ma). The western ultrapotassic rocks (79°E-89°E) and their peridotite xenoliths (81°E) reflect a refractory harzburgitic mantle refertilized by ancient metasomatism (lavas: 87Sr/86Srt = 0.714-0.734; peridotites: 87Sr/86Srt = 0.709-0.716). These data integrated with seismic tomography suggest that upwelling asthenosphere was diverted away from the deep continental root beneath the western Lhasa block, but rose to shallower depths beneath a thinner lithosphere in the eastern part. Heating of the lithospheric mantle by the rising asthenosphere ultimately generated the ultrapotassic rocks with regionally distinct geochemical signatures reflecting the different nature of the lithospheric mantle.
Earth and Planetary Science Letters, Vol. 463, pp. 48-55.
Mantle
Metasomatism
Abstract: Following giant impacts the early Hadean Earth was shrouded in a steam atmosphere for durations on the order of 1 Ma. In order to investigate the potential of this atmosphere to fractionate major elements between various silicate reservoirs and influence a planet's geochemical evolution, we performed experiments simulating the interaction of a post-giant-impact steam atmosphere with a bulk silicate Earth (BSE) composition. Our experiments indicate that the composition of the solute in a water-rich atmosphere at 10 MPa and ?727?°C is remarkably similar to that of Earth's modern continental crust and would constitute up to 10% of the solution mass. This solute composition is similar to solute compositions previously measured at higher pressures, but distinct from those of near-solidus peridotite melts. Mass balance calculations based upon the hypothesis that Earth's initial water concentration was similar to that in CI carbonaceous chondrites, and that degassing and metasomatism produced the BSE, indicate that metasomatism could produce from 10 to 300% of the mass of the modern crust. If instead the amount of metasomatism is estimated by the difference between the water concentration in the BSE and in the depleted upper mantle, then a mass of up to approximately 4% of the current crust could be produced by metasomatism. Using results of earlier research we find that the solute is expected to have a smaller Sm/Nd ratio than the residual BSE, and if the solute was formed early in Earth's history its Nd isotopic signatures would be highly enriched. Although we cannot be certain that the metasomatic process created a significant fraction of Earth's crust in the early Hadean, our research indicates that it has the potential to form crustal nuclei and possibly was responsible for the production of incompatible-element enriched reservoirs in the early Earth, as seen in the isotopic signatures of Archean rocks.
Contributions to Mineralogy and Petrology, in press available 22p.
Mantle
Metasomatism, magmatism, carbonatite
Abstract: Hydrous K-rich kimberlite-like systems are studied experimentally at 5.5-7.5 GPa and 1200-1450 °C in terms of phase relations and conditions for formation and stability of phlogopite. The starting samples are phlogopite-carbonatite-phlogopite sandwiches and harzburgite-carbonatite mixtures consisting of Ol + Grt + Cpx + L (±Opx), according to the previous experimental results obtained at the same P-T parameters but in water-free systems. Carbonatite is represented by a K- and Ca-rich composition that may form at the top of a slab. In the presence of carbonatitic melt, phlogopite can partly melt in a peritectic reaction at 5.5 GPa and 1200-1350 °C, as well as at 6.3-7.0 GPa and 1200 °C: 2Phl + CaCO3 (L)?Cpx + Ol + Grt + K2CO3 (L) + 2H2O (L). Synthesis of phlogopite at 5.5 GPa and 1200-1350 °C, with an initial mixture of H2O-bearing harzburgite and carbonatite, demonstrates experimentally that equilibrium in this reaction can be shifted from right to left. Therefore, phlogopite can equilibrate with ultrapotassic carbonate-silicate melts in a ? 150 °C region between 1200 and 1350 °C at 5.5 GPa. On the other hand, it can exist but cannot nucleate spontaneously and crystallize in the presence of such melts in quite a large pressure range in experiments at 6.3-7.0 GPa and 1200 °C. Thus, phlogopite can result from metasomatism of peridotite at the base of continental lithospheric mantle (CLM) by ultrapotassic carbonatite agents at depths shallower than 180-195 km, which creates a mechanism of water retaining in CLM. Kimberlite formation can begin at 5.5 GPa and 1350 °C in a phlogopite-bearing peridotite source generating a hydrous carbonate-silicate melt with 10-15 wt% SiO2, Ca# from 45 to 60, and high K enrichment. Upon further heating to 1450 °C due to the effect of a mantle plume at the CLM base, phlogopite disappears and a kimberlite-like melt forms with SiO2 to 20 wt% and Ca# = 35-40.
Earth and Planetary science Letters, Vol. 466, pp. 152-167.
Mantle
Metasomatism, magma, carbonatite
Abstract: Kimberlite and carbonatite magmas that intrude cratonic lithosphere are among the deepest probes of the terrestrial carbon cycle. Their co-existence on thick continental shields is commonly attributed to continuous partial melting sequences of carbonated peridotite at >150 km depths, possibly as deep as the mantle transition zone. At Tikiusaaq on the North Atlantic craton in West Greenland, approximately 160 Ma old ultrafresh kimberlite dykes and carbonatite sheets provide a rare opportunity to study the origin and evolution of carbonate-rich melts beneath cratons. Although their Sr-Nd-Hf-Pb-Li isotopic compositions suggest a common convecting upper mantle source that includes depleted and recycled oceanic crust components (e.g., negative ??Hf??Hf coupled with View the MathML source>+5‰?7Li), incompatible trace element modelling identifies only the kimberlites as near-primary low-degree partial melts (0.05-3%) of carbonated peridotite. In contrast, the trace element systematics of the carbonatites are difficult to reproduce by partial melting of carbonated peridotite, and the heavy carbon isotopic signatures (?3.6 to View the MathML source?2.4‰?13C for carbonatites versus ?5.7 to View the MathML source?3.6‰?13C for kimberlites) require open-system fractionation at magmatic temperatures.
Given that the oxidation state of Earth's mantle at >150 km depth is too reduced to enable larger volumes of ‘pure’ carbonate melt to migrate, it is reasonable to speculate that percolating near-solidus melts of carbonated peridotite must be silicate-dominated with only dilute carbonate contents, similar to the Tikiusaaq kimberlite compositions (e.g., 16-33 wt.% SiO2). This concept is supported by our findings from the North Atlantic craton where kimberlite and other deeply derived carbonated silicate melts, such as aillikites, exsolve their carbonate components within the shallow lithosphere en route to the Earth's surface, thereby producing carbonatite magmas. The relative abundances of trace elements of such highly differentiated ‘cratonic carbonatites’ have only little in common with those of metasomatic agents that act on the deeper lithosphere. Consequently, carbonatite trace element systematics should only be used with caution when constraining carbon mobility and metasomatism at mantle depths. Regardless of the exact nature of carbonate-bearing melts within the mantle lithosphere, they play an important role in enrichment processes, thereby decreasing the stability of buoyant cratons and promoting rift initiation - as exemplified by the Mesozoic-Cenozoic breakup of the North Atlantic craton.
Abstract: Tectonically young, orogenic settings are commonly the sites of post-collisional silica-rich ultrapotassic magmas with extreme K2O-contents of up to 9 wt% and K2O/Na2O > 2. Many experimental studies investigating the generation of these melts have concentrated on melting of homogenous phlogopite bearing peridotites, whereas geochemical signatures indicate the involvement of at least two types of source rocks: ultra-depleted and K and trace elements-enriched ones. We report the results of melting experiments at 1–2 GPa of mixed glimmerite and harzburgite, in which these rock types make up two halves each capsule. Melting begins in the glimmerite, and its metasomatic effects on the harzburgite are apparent at 1100 °C even before melt pools are visible. The first melts are Na-rich, seen in zoning of olivines and as growth of clinopyroxene in the harzburgite, but change at higher degrees of melting to produce a typical lamproite-like melt with K2O > 10 wt%. A major advantage of this study is the preservation of distinct melts in different parts of the capsule, which reflect a process of dynamic metasomatism: within the harzburgite matrix, the infiltrating melt derived from melting of the glimmerite changes consistently with the distance of travel through the harzburgite, enabling quantification of the metasomatic effects as an increase in SiO2 and K2O. This results principally from assimilation of orthopyroxene, which increases the Ol/Opx ratio of the residual harzburgite. The effects of quench olivine growth are recognizable and can be quantified due to a step-change in composition at the glimmerite/harzburgite border: the large total surface area of olivine and small melt fraction mean that the amount of quench olivine is high within the harzburgite, but negligible in the almost completely molten glimmerite. Melts of the glimmerite contain up to 8–10 wt% K2O and 53 wt% SiO2, which increase to 55–56 wt% after interaction with the harzburgite. Mediterranean lamproites resemble melts of glimmerite, whereas melts that have interacted with harzburgite are more similar to less potassic, but more SiO2-rich shoshonites of the Mediterranean region.
Abstract: Most eclogitic mantle xenoliths brought to the surface exhibit a certain degree of enrichment with incompatible elements, usually attributed to the effect of mantle metasomatism by a putative metasomatic fluid. The metasomatic overprint is represented mainly by enrichments in Na, K, Ba, Ti and LREE and the original source of this fluid remains unknown. In this paper, we present a detailed petrological study of a typical eclogitic mantle xenolith from the Roberts Victor kimberlite mine in South Africa. We find that its textural and mineralogical features present strong evidence for incipient melting. The melting assemblage we observe did not necessarily require introduction of additional components, that is: in-situ melting alone could produce highly incompatible element enriched melt without involvement of a hypothetical and speculative “metasomatic event”. Due to the higher abundance in incompatible elements and lower solidus temperature than peridotites, mantle eclogites, some of which represent previously subducted oceanic crust, are much more plausible sources of mantle metasomatism, but on the other hand, they can be considered as highly metasomatised themselves. This brings us to the “chicken or egg” dilemma – was the secondary mineral assemblage in mantle lithologies a result or a source of mantle metasomatism?
Abstract: The LILE-enrichments and radiogenic Sr isotope compositions of lamproites and other alkaline magmas have commonly been attributed to the occurrence of phlogopite-rich rocks such as MARID (Mica-AmphiboleRutile-Ilmenite-Diopside) in their mantle sources. To provide new constraints on the relationship between mantle metasomatism and alkaline magmatism, we have investigated the major and trace element compositions of MARID and PIC (Phlogopite-Ilmenite-Clinopyroxene) xenoliths, hosted in kimberlites and orangeites from the Kimberley area, South Africa. As MARID and PIC xenoliths often do not exhibit their complete mineral assemblages, such phlogopite-rich rocks are better classified using geochemical criteria such as mineral major and trace element compositions (e.g. clinopyroxene chondrite-normalised Ce/Yb; MARID = 16- 60 vs PIC = 10-21). New data indicate that major element compositions of phlogopite and clinopyroxene grains from PIC xenoliths are similar to those in peridotite xenoliths from the Kaapvaal craton; furthermore, MARID minerals exhibit broader compositional ranges than previously reported, and also partly overlap those in peridotites. These results necessitate the reconsideration of a genetic link between MARID/PIC rocks and metasomatised peridotites. Importantly, similarities in the trace element compositions of MARID and other on- and off-craton peridotitic clinopyroxene indicate that MARID-like metasomatic fluids may be a ubiquitous feature of the lithospheric mantle. Comparing bulk-rock and average mineral trace element ratios suggests that melting of the silicate components of MARID rocks may contribute to the trace element enrichments in alkaline magmas (specifically magmas in the “lamproite clan”).
Abstract: In this study, a private collection of diamondiferous eclogite xenoliths has been made available for non-destructive investigation. All samples have at least one diamond visible. The samples are predominantly sourced from the Excelsior and Newlands mines (South Africa), with additional samples from Roberts Victor mine (South Africa) and Orapa (Botswana). 3D volume models of the samples were created using X-ray tomography. The 3D images reveal abundant secondary veining that is clearly younger than the eclogite. Diamonds are located in fluid pathways and occur in both altered garnet and altered clinopyroxene. Most of the veining is unrelated to the spatial positioning of diamond in the samples. In some instances, early veining has annealed or partially annealed, suggesting a range in timing of at least some of the several metasomatic events that have affected the rock. Importantly, in the most graphic examples, a clear distinction can be seen between diamond-bearing and non-diamond-bearing veins, even where sulphide is present in abundance in the non-diamond-bearing veins. The amount of diamond detected in the xenoliths varies from a single crystal to well over 50 diamonds forming more than 9% of the rock. This extreme value contrasts with the diamond recovery from currently viable diamond mines of less than 2ppm or 0.0002%. The morphology of the diamonds includes step-faced flat-faced octahedra, single crystals and aggregates. This is particularly a feature of diamonds in the Excelsior specimens. In the samples from Newlands and Orapa, in contrast, diamond surfaces reflect resorption processes such as rounding and corrosion of the diamonds. The following conclusions can be drawn from this study: Diamonds in this collection, sourced from within the Kalahari craton, appear to have formed by a metasomatic process during which fluids infiltrated pre-existing mantle-derived eclogite; Several metasomatic events have occurred during the residence of the eclogite in the mantle; Some of these metasomatic events have been diamond-friendly, whilst others have been diamond-neutral or diamond-destructive; Diamond can be present at very high concentrations along particular metasomatic fluid pathways in eclogitic mantle rocks; The absolute timing of diamond formation is still to be determined.
Abstract: Mantle metasomatism is a relatively recent concept introduced in the early 1970s when detailed studies of lithospheric mantle rock fragments (xenoliths), brought to the surface of in basaltic to kimberlitic magmas, became widespread. Two main types of metasomatism were defined: modal (or patent) metasomatism describes the introduction of new minerals; cryptic metasomatism describes changes in composition of pre-existing minerals without formation of new phases. A new type of metasomatism is introduced here, stealth metasomatism; this process involves the addition of new phases (e.g. garnet and/or clinopyroxene), but is a “deceptive” metasomatic process that adds phases indistinguishable mineralogically from common mantle peridotite phases. The recognition of stealth metasomatism reflects the increasing awareness of the importance of refertilisation by metasomatic fluid fronts in determining the composition of mantle domains. Tectonically exposed peridotite massifs provide an opportunity to study spatial relationships of metasomatic processes on a metre to kilometre scale. The nature of mantle fluids can be determined from the nature of fluid inclusions in mantle minerals and indirectly from changes in the chemical (especially trace-element) compositions of mantle minerals. Metasomatic fluids in off-craton regions cover a vast spectrum from silicate to carbonate magmas containing varying types and abundances of dissolved fluids and solutes including brines, C-O-H species and sulfur-bearing components. Fluid inclusions in diamond and deep xenoliths reveal the presence of high-density fluids with carbonatitic and hydro-silicic and/or saline-brine end-members. The deep cratonic xenolith data also reinforce the importance of highly mobile melts spanning the kimberlite-carbonatite spectrum and that may become immiscible with changing conditions. A critical conceptual advance in understanding Earth’s geodynamic behaviour is emerging from understanding the linkage between mantle metasomatism and the physical properties of mantle domains recorded by geophysical data. For example, metasomatic refertilisation of cratonic lithospheric mantle increases its density, lowers its seismic velocity and strongly affects its rheology. Introduction of heat-producing elements (U, Th, K) increases heat production, and the key to understanding electromagnetic signals from mantle domains may be closely related to fluid distribution and type (e.g. carbonatitic) and its residence in or between grains. The lithospheric mantle is a palimpsest recording the multiple fluid events that have affected each domain since it formed. These events, involving different fluids and compositions, have repeatedly overprinted variably depleted original mantle wall-rocks. This produces a complex, essentially ubiquitously metasomatised lithospheric mantle, heterogeneous on scales of microns to terranes and perhaps leaving little or no “primary” mantle wall-rock. Decoding this complex record by identifying significant episodes and processes is a key to reconstructing lithosphere evolution and the nature and origin of the volatile flux from the deep Earth through time.
Geochemical Perspectives Letters, Vol. 4, pp. 1-6.
Africa, South Africa, Zimbabwe
metasomatism, geochronology
Abstract: Metasomatism, the chemical alteration of rocks by a variety of melts and fluids, has formed a key concept in studies of the Earth’s mantle for decades. Metasomatic effects are often inferred to be far-reaching and yet the evidence for their occurrence is usually based upon individual hand specimens or suites of rocks that display considerable heterogeneity. In rare cases, however, we are offered insights into larger-scale chemical modifications that occur in the mantle. Here we utilise the Lu–Hf systematics of zircon megacrysts erupted in kimberlite magmas to discern two temporally and compositionally discrete metasomatic events in the mantle beneath southern Africa, each having an influence extending over an area exceeding one million km2. These data provide unambiguous evidence for metasomatic processes operating at continental scales and seemingly unperturbed by the age and composition of the local lithospheric mantle. The most recent of these events may be associated with the major Jurassic-Karoo magmatism in southern Africa.
Abstract: Fluids are important for mass transfer at the slab–mantle interface in subduction zones. However, it is usually difficult to trace fluids from specific sources in a subducting slab, especially those derived from dehydration of serpentinite. Coesite-bearing whiteschist at Dora-Maira in the Western Alps is characterized by strong Mg enrichment relative to the country rocks, which requires infiltration of Mg-rich fluids into the supracrustal rock. In order to constrain the origin of such Mg-rich fluids, we have performed an integrated study of whole-rock Mg and O isotopes, zircon U–Pb ages and O isotopes for the whiteschist and related rocks. Zircons in the whiteschist show two groups of U–Pb ages at ?262 Ma and ?34 Ma, respectively, for relict and newly grown domains. The Permian U–Pb ages of relict magmatic domains are consistent with the protolith age of host metagranite, suggesting that their common protolith is the Permian granite. The Tertiary U–Pb ages occur in coesite-bearing metamorphic domains, consistent with the known age for ultrahigh-pressure metamorphism. The metamorphic domains have ?18O values of
‰5.8–6.8‰, whereas the relict magmatic domains have high ?18O values of ‰?10‰. Such high ?18O values are also characteristic of the metagranite, indicating that the whiteschist protolith underwent metasomatism by metamorphic fluids with low ?18O value of f ‰?2–4‰. The whiteschist mostly has whole-rock ?26Mg values of ?0.07 to 0.72‰, considerably higher than country-rock ?26Mg values of ?0.54 to ‰?0.11‰. Thus, the metamorphic fluids are not only rich in Mg but also heavy in Mg isotopes. They were probably derived from the breakdown of Mg-rich hydrous minerals such as talc and antigorite in serpentinite at the slab–mantle interface in the subduction channel. Therefore, the dehydration of mantle wedge serpentinite during the subduction and exhumation of continental crust can provide the Mg-rich fluids responsible for the metasomatism of crustal rocks at subarc depths.
Abstract: Cratons are strong and their preservation demonstrates that they resist deformation and fragmentation. Yet several cratons are rifting now, or have rifted in the past. We suggest that cratons need to be weakened before they can rift. Specifically, metasomatism of the depleted dehydrated craton mantle lithosphere is a potential weakening mechanism. We use 2D numerical models to test the efficiency of simulated melt metasomatism and coeval rehydration to weaken craton mantle lithosphere roots. These processes effectively increase root density through a parameterized melt-peridotite reaction, and reduce root viscosity by increasing the temperature and rehydrating the cratonic mantle lithosphere. The models are designed to investigate when a craton is sufficiently weakened to undergo rifting and is no longer protected by adjacent standard Phanerozoic lithosphere. We find that cratons only become vulnerable to rifting following large-volume melt metasomatism (~ 30% by volume) and thinning of the gravitationally unstable cratonic lithosphere from > 250 km to ~ 100 km; at which point its residual crustal strength is important. Furthermore, our results indicate that rifting of cratons depends on the timing of extension with respect to metasomatism. An important effect in the large-volume melt models is the melt-induced increase in temperature which must have time to reach peak values in the uppermost mantle lithosphere before rifting. Release of water stored in the transition zone at the base of a big mantle wedge may provide a suitable natural setting for both rehydration and refertilization of an overlying craton and is consistent with evidence from the eastern North China Craton. An additional effect is that cratons subside isostatically to balance the increasing density of craton mantle lithosphere where it is moderately metasomatized. We suggest that this forms intracratonic basins and that their subsidence and subsequent uplift, and cratonic rifting constitute evidence of progressive metasomatism of cratonic mantle lithosphere.
Earth and Planetary Science Letters, Vol. 401, pp. 132-147.
Africa, South Africa
metasomatism
Abstract: The Karoo igneous rocks (174-185 Ma) of southern Africa represent one of the largest continental flood basalt provinces on Earth. Available evidence indicates that Karoo magmas either originated in the asthenosphere and were extensively modified by interaction with the lithospheric mantle prior to emplacement in the upper crust; or were produced by partial melting of enriched mantle lithosphere. However, no direct evidence of interaction by Karoo melts (or their precursors) with lithospheric mantle rocks has yet been identified in the suites of mantle xenoliths sampled by post-Karoo kimberlites in southern Africa. Here we report U-Pb ages for lindsleyite-mathiasite (LIMA) titanate minerals (crichtonite series) from three metasomatised, phlogopite and clinopyroxene-rich peridotite xenoliths from the ?84 Ma Bultfontein kimberlite (Kimberley, South Africa), located in the southern part of the Karoo magmatic province. The LIMA minerals appear to have formed during metasomatism of the lithospheric mantle by fluids enriched in HFSE (Ti, Zr, Hf, Nb), LILE (K, Ba, Ca, Sr) and LREE. LIMA U-Pb elemental and isotopic compositions were measured in situ by LA-ICP-MS methods, and potential matrix effects were evaluated by solution-mode analysis of mineral separates. LIMA minerals from the three samples yielded apparent U-Pb ages of , and (). A single zircon grain extracted from the ?190 Ma LIMA-bearing sample produced a similar U-Pb age of , within uncertainty of the LIMA ages. These data provide the first robust evidence of fluid enrichment in the lithospheric mantle beneath the Kimberley region at ?180-190 Ma, and suggest causation of mantle metasomatism by Karoo melts or their precursor(s). The results further indicate that U-Pb dating of LIMA minerals provides a new, accurate tool for dating metasomatic events in the lithospheric mantle.
Earth and Planetary Science Letters, Vol. 482, pp. 253-264.
Africa, South Africa
metasomatism
Abstract: Radiogenic isotope variations unrelated to radiogenic ingrowth are common between minerals found in metasomatised mantle xenoliths entrained in kimberlite, basalts and related magmas. As the metasomatic minerals are assumed to have been in isotopic equilibrium originally, such variations are typically attributed to contamination by the magma host and/or interaction with mantle fluids during or before xenolith transport to surface. However, the increasing evidence of metasomatism by multiple, compositionally distinct fluids permeating the lithospheric mantle, coeval with specific magmatic events, suggests that isotopic disequilibrium might be a consequence of discrete, though complex, metasomatic events. Here we provide clear evidence of elemental and Sr isotope heterogeneity between coeval Ti-rich LIMA (lindsleyite–mathiasite) minerals at the time of their formation in the mantle. LIMA minerals occur in close textural association with clinopyroxene and phlogopite in low-temperature (?800–900?°C), strongly metasomatised mantle xenoliths from the ?84 Ma Bultfontein kimberlite (South Africa). Previous U/Pb dating of the LIMA phases was used to argue that each xenolith recorded a single event of LIMA crystallisation at ?180–190 Ma, coeval with the emplacement of Karoo magmas. SEM imaging reveals that up to four types of LIMA phases coexist in each xenolith, and occasionally in a single LIMA grain. Major element and in situ Sr isotope analyses of the different LIMA types show that each phase has a distinct elemental composition and initial 87Sr/86Sr ratio (e.g., 0.7068–0.7086 and 0.7115–0.7129 for two LIMA types in a single xenolith; 0.7053-0.7131 across the entire sample suite). These combined age and isotopic constraints require that multiple fluids metasomatised these rocks at broadly the same time (i.e. within a few thousands to millions of years), and produced similar mineralogical features. Elemental and isotopic variations between different LIMA types could be due to interaction between one (or more) Karoo-related Ti-rich silicate melts and previously metasomatised, phlogopite-rich lithospheric mantle. This study demonstrates that mantle metasomatic assemblages seemingly generated in a single event may instead result from the infiltration of broadly coeval fluids with variable compositions. This in turn implies that the isotopic variations recorded in mantle rocks may be an inherent feature of metasomatism, and that hot fluids infiltrating a rock do not necessarily cause equilibration at the cm scale, as has been assumed previously. Simple modelling of solid-state diffusion in mantle minerals shows that isotopic disequilibrium may be preserved for up to hundreds of Myr at mantle lithosphere temperatures (?1100–1200?°C), unless subsequently affected by transient heating and/or fluid infiltration events. Radiogenic isotope disequilibrium associated with mantle metasomatism may therefore be a common feature of mantle xenoliths.
Abstract: he meta-analysis of about 13,000 analyses of scandium content in garnet grains shows that, below the spinel-garnet transition, this phase carries about three-quarters of the Sc budget of the mantle, indicating its control on Sc mobility. The Sc content of garnets in mafic rocks is low, due to a dilution effect resulting from their high modal content in garnet. Garnets from ultramafic rocks exhibit a wider range of Sc concentrations. We assess the relative influence of thermobarometry, crystal chemistry and fluid-related events on the distribution of Sc in garnet from such rocks to improve the tracking of geochemical processes in the mantle. Pressure and temperature of equilibration in the mantle are second-order factors influencing the Sc content of garnet, while crystal-chemistry, in particular and , is the main parameter controlling the compatibility of Sc. Scandium is incorporated in both X and Y sites of Cr-Ca-rich garnets, resulting in a behaviour intermediate between rare-earth elements, incorporated in the X site, and trivalent transition elements, occupying the Y site. This affinity for both sites results in a mild compatibility of Sc in the garnet stability field of the mantle; hence Sc concentration in garnet increases with melt extraction and can be reduced by silicate-melt metasomatism. In contrast, metasomatism by volatile-rich fluids increases the Sc concentration in garnet. The control of garnet on the compatibility of Sc in deep lithospheric rocks demonstrates the potential of using Sc to track the conditions of formation of magmas and their residual rocks, as well as the origin and nature of metasomatic fluids.
Mineralogy and Petrology, in press available, 14p.
Europe, Israel
metasomatism
Abstract: Oxygen fugacity (fO2) is a key parameter of Earth’s mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping fO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low fO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of ?13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing fO2 with depth (e.g. Yaxley et al. in Lithos 140:142-151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism.
Mineralogy and Petrology, 10.1007/ s00710-018- 0577-8, 19p.
Africa
metasomatism, subduction, geobarometry
Abstract: The Kaapvaal craton and its underlying mantle is probably one of the best studied Archean entity in the world. Despite that, discussion is still vivid on important aspects. A major debate over the last few decades is the depth of melting that generated the mantle nuclei of cratons. Our new evaluation of melting parameters in peridotite residues shows that the Cr2O3/Al2O3 ratio is the most useful pressure sensitive melting barometer. It irrevocably constrains the pressure of melting (melt separation) to less than 2 GPa with olivine (ol), orthopyroxene (opx) and spinel (sp) as residual phases. Garnet (grt) grows at increasing pressure during lithosphere thickening and subduction via the reaction opx?+?sp ? grt?+?ol. The time of partial melting is constrained by Re-depletion model ages (TRD) mainly to the Archean (Pearson and Wittig 2008). However, only 3% of the ages are older than 3.1 Ga while crustal ages lie mainly between 3.1 to 2.8 Ga for the W- and 3.7 to 2.8 Ga for the E-block. Many TRD-ages are probably falsified by metasomatism and the main partial melting period was older than 3.1 Ga. Also, Nd- and Hf- model ages of peridotitic lithologies from the W-block are 3.2 to 3.6 Ga old. The corresponding very negative ?Nd (?40) and ?Hf values (?65) signal the presence of subducted crustal components in these old mantle portions. Subducted components diversify the mantle in its chemistry and thermal structure. Adjustment towards a stable configuration occurs by fluid transfer, metasomatism, partial melting and heat transfer. Ages of metasomatism from the Lu-Hf isotope system are 3.2 Ga (Lace), 2.9 Ga (Roberts Victor) and 2.62 Ga (Finsch) coinciding with the collision of cratonic blocks, the growth of diamonds, metamorphism of eclogites and of Ventersdoorp magmatism. The cratonic lithosphere was stabilized thermally by the end of the Archean and cooled since then with a rate of 0.07 °C/Ma.
Earth and Planetary Science Letters, Vol. 499, pp. 219-229.
United States, Colorado Plateau
metasomatism
Abstract: In magmatic settings, water behaves as an incompatible species and should be depleted during melting and enriched during metasomatism. Previous studies have identified correlations between nominally anhydrous mineral (NAM) water content ([H2O]) and indices of metasomatism or melt extraction, seemingly confirming this behavior in the mantle. However in detail, these correlations are ambiguous and do not reflect robust controls on NAM [H2O]. We measured orthopyroxene (opx) and clinopyroxene (cpx) [H2O] in variably hydrated and metasomatized peridotite xenoliths from the Navajo volcanic field (NVF) that sample the Colorado Plateau subcontinental lithospheric mantle (SCLM), an endmember of SCLM hydration and metasomatism. These xenoliths span a wide range of pyroxene [H2O] (opx from 50 to 588 ppm wt. H2O; cpx from 38 to 581 ppm wt. H2O), but NAM [H2O] does not correlate with either indices of melt depletion or metasomatism. Growth of hydrous minerals suggests higher water activity than in anhydrous peridotites, and therefore hydrous-mineral-bearing xenoliths and anhydrous xenoliths should have different NAM [H2O] and water activities. However, when the two groups are compared no significant differences can be found in either NAM [H2O] or water activity. We propose that the high diffusivity of hydrogen in the mantle allows for equilibration of water activity in the mantle over sub-kilometer length scales over geologic time. Such diffusive equilibration reduces water activity variability and results in the blurring and destruction of correlations between NAM [H2O] and indices of metasomatism or melt extraction. As a result of diffusive equilibration of water, there is a large difference in the variability of concentration between NAM [H2O] (spanning ?2 orders of magnitude) and similarly incompatible elements such as Ce in the same peridotites (spanning ?4 orders of magnitude). This difference in behavior explains why H2O/Ce ratios in mantle peridotites are highly variable relative to those of basalts.
Earth and Planetary Science Letters, Vol. 497, 1, pp. 181-192.
Mantle
metasomatism
Abstract: At convergent margins fluids liberated from subducting slabs metasomatise the overlying mantle wedge, enriching it in volatiles, incompatible elements and possibly ore-forming metals. Despite the genetic link between this process, the genesis of arc magmas, and formation of porphyry Cu-Au deposits, there is currently little understanding of the behaviour of chalcophile and siderophile elements during subduction-related mantle metasomatism. In this study, we report sulfur isotopic compositions and PGE concentrations of sulfides in a suite of garnet peridotites from the Western Gneiss Region of Norway, sampling mantle wedge from ?100 to ?250 km depth. Sulfides hosted in metasomatised samples have deviated from typical mantle values, ranging between ?10.0 and +5.4‰, indicating derivation of sulfur from subducted crust. Sulfides in pervasively metasomatised samples have atypical PGE signatures, with strong enrichment in Os and Ru relative to Ir, whereas channelised fluid flow produced sulfides extremely enriched in Pd, up to 700 times the concentration found in non-metasomatised samples. These signatures are reconcilable with a high oxidation state of the metasomatising agents and demonstrate that subduction can recycle chalcophile and siderophile elements into and within the mantle, along with sulfur. We further show that because the solubility of Os and Ru in fluids is redox sensitive, and Pd is more soluble than the I-PGE, ratios such as Os/Ir, Ru/Ir plotted against Pd/Ir can be used to trace the metasomatic oxidation of mantle samples, mantle-derived magmas and porphyry Cu±Au deposits. This geochemical insight is used to show that Au-rich porphyry Cu deposits are derived from more oxidised mantle wedge than Au-poor porphyry deposits.
Journal of the Geological Society, doi.org/10.1144/jgs20`8-046 10p.
Mantle
metasomatism
Abstract: The valence of carbon is governed by the oxidation state of the host system. The subducted oceanic lithosphere contains considerable amounts of iron so that Fe3+/Fe2+ equilibria in mineral assemblages are able to buffer the (intensive) fO2 and the valence of carbon. Alternatively, carbon itself can be a carrier of (extensive) ‘excess oxygen’ when transferred from the slab to the mantle, prompting the oxidation of the sub-arc mantle. Therefore, the correct use of intensive and extensive variables to define the slab-to-mantle oxidation by C-bearing fluids is of primary importance when considering different fluid/rock ratios. Fluid-mediated processes at the slab-mantle interface can also be investigated experimentally. The presence of CO2 (or CH4 at highly reduced conditions) in aqueous COH fluids in peridotitic systems affects the positions of carbonation or decarbonation reactions and of the solidus. Some methods to produce and analyse COH fluid-saturated experiments in model systems are introduced, together with the measurement of experimental COH fluids composition in terms of volatiles and dissolved solutes. The role of COH fluids in the stability of hydrous and carbonate minerals is discussed comparing experimental results with thermodynamic models and the message of nature. The investigation of redox processes and the role of volatiles especially at the slab-mantle interface are crucial for depicting the framework of Earth carbon cycling. During the early stages of the Earth's history, the abundances of carbon and other volatiles in the different reservoirs were determined by the coupled evolution of the terrestrial magma ocean and the primitive atmosphere (Hier-Majumder & Hirschmann 2017). Since the Archean, the efficient deep subduction of organic carbon produced by photosynthesis could have promoted carbon burial in the mantle and an increase of atmospheric levels of oxygen through time (Duncan & Dasgupta 2017). In this picture the oxidation state of the mantle, mainly governed by Fe0 and Fe2+/Fe3+ ratios, and its dynamics played a key role in modulating the fO2 of the Earth's surface, leading to the precipitation of minerals in their oxidized forms such as carbonates (Sverjensky & Lee 2010; Andrault et al. 2018). Carbon at the modern terrestrial surface is largely divided between carbonates and organic deposits, with a total budget of 1?×?1023 g C, corresponding to about 100 ppm in the upper mantle (Porcelli & Pepin 2014). Recent estimates from volcanic degassing suggest that the carbon content in the modern deep mantle is even higher (c. 263 ppm; Anderson & Poland 2017; Barry 2017). In fact, the fate of carbonates and organic carbon in modern subduction zones is still largely unconstrained, although recent studies suggest that most of the subducted carbon, in the form of carbonates and organic matter, could be recycled back to the surface (Kelemen & Manning 2015). In this contribution we aim to introduce some basic principles regarding the importance of the use of intensive and extensive variables to define the ‘oxidation transfer’ from the slab to the overlying mantle by C-bearing fluids, and the buffering capacity of the mantle in the carbon speciation at subduction zones, both from the natural and experimental point of view.
Abstract: Phase relations are studied experimentally in the harzburgite-hydrous carbonate melt system, the bulk composition of which represents primary kimberlite. Experiments were carried out at 5.5 and 7.5 GPa, 1200-1350°?, and \({{X}_{{{\text{C}}{{{\text{O}}}_{2}}}}}\) = 0.39-0.57, and lasted 60 hours. It is established that olivine-orthopyroxene-garnet-magnesite-melt assemblage is stable within the entire range of the studied parameters. With increase of temperature and \({{X}_{{{\text{C}}{{{\text{O}}}_{2}}}}}\) in the system, Ca# in the melt and the olivine fraction in the peridotite matrix significantly decrease. The composition of silicate phases in run products is close to those of high-temperature mantle peridotite. Analysis of obtained data suggest that magnesite at the base of subcontinental lithosphere could be derived by metasomatic alteration of peridotite by asthenospheric hydrous carbonate melts. The process is possible in the temperature range typical of heat flux of 40-45 mW/m², which corresponds to the conditions of formation of the deepest peridotite xenoliths. Crystallization of magnesite during interaction with peridotite matrix can be considered as experimentally substantiated mechanism of CO2 accumulation in subcratonic lithosphere.
Abstract: This paper reports the results of high-pressure experimental modeling of interaction between glaucophane schist and harzburgite or websterite for the evaluation of the influence of mantle material on the input-output of components and character of metasomatic transformations at the crust-mantle boundary in the subduction zone. In all experiments, glaucophane schist (proxy for oceanic crust) containing volatile components (H2O and CO2) incorporated in hydrous minerals (amphiboles, phengite, and epidote) and calcite was loaded into the bottom of each capsule and overlain by mantle material. During the experiments at a temperature of 800°C and a pressure of 2.9 GPa, which correspond to the conditions of a hot subduction zone, the schist underwent partial (up to 10%) eclogitization with the formation of the anhydrous assemblage omphacite + garnet + quartz ± magnesite ± potassic phase. Carbonate and a potassic phase were formed only in the experiments with websterite in the upper layer. A reaction zone was formed at the base of the websterite layer, where newly formed omphacite, quartz, and orthopyroxene replaced in part initial pyroxenes. Orthopyroxene and phlogopite (or an unidentified potassic phase) were formed in the reaction zone at the base of the harzburgite layer; among the initial minerals, only orthopyroxene relicts were preserved. Above the reaction zones produced by diffusion metasomatism, new phases developed locally, mainly at grain boundaries: newly formed orthopyroxene and magnesite were observed in harzburgite, and omphacite and quartz, in websterite. Alterations along grain boundaries extended much further than the reaction zones, which indicates that fluid infiltration dominated over diffusion in the experiments. The experiments demonstrated that the H2O-CO2 fluid with dissolved major components released from the glaucophane schist can produce mineral assemblages of different chemical compositions in mantle materials: Na-bearing in websterite and K-bearing in harzburgite. The complementary components, K2O and CO2 for the websterite layer and Na2O for the harzburgite layer, are fixed in the initial glaucophane schist layer. The distinguished separation of alkalis and CO2 at the crust-mantle boundary can affect the character of metasomatism in the mantle wedge, primary magma compositions, and the chemical evolution of the rocks of the subducting slab.
Abstract: Of great importance in the problem of redox evolution of mantle rocks is the reconstruction of scenarios of alteration of Fe?- or Fe3C-bearing rocks by oxidizing mantle metasomatic agents and the evaluation of stability of these phases under the influence of fluids and melts of different compositions. Original results of high-temperature high-pressure experiments (P = 6.3 GPa, T = 1300-1500°?) in the carbide-oxide-carbonate systems (Fe3C-SiO2-(Mg,Ca)CO3 and Fe3C-SiO2-Al2O3-(Mg,Ca)CO3) are reported. Conditions of formation of mantle silicates with metallic or metal-carbon melt inclusions are determined and their stability in the presence of CO2-fluid representing the potential mantle oxidizing metasomatic agent are estimated. It is established that garnet or orthopyroxene and CO2-fluid are formed in the carbide-oxide-carbonate system through decarbonation, with subsequent redox interaction between CO2 and iron carbide. This results in the formation of assemblage of Fe-rich silicates and graphite. Garnet and orthopyroxene contain inclusions of a Fe-C melt, as well as graphite, fayalite, and ferrosilite. It is experimentally demonstrated that the presence of CO2-fluid in interstices does not affect on the preservation of metallic inclusions, as well as graphite inclusions in silicates. Selective capture of Fe-C melt inclusions by mantle silicates is one of the potential scenarios for the conservation of metallic iron in mantle domains altered by mantle oxidizing metasomatic agents.
Contributions to Mineralogy and Petrology, Vol. 173, 12, pp. 106-
Mantle
metasomatism
Abstract: Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg3(Si3Al)O10(OH)2, kinoshitalite BaMg3(Al2Si2)O10(OH)2 and ferrokinoshitalite BaFe3(Al2Si2)O10(OH)2. In addition to Ba (0.24-0.67 apfu), mica is significantly enriched in Mg ( X Mg 0.85 to 0.95), Cr (0.03-0.43 apfu) and Cl (0.04-0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFeIVAlClK-1Mg-1Si-1(OH)-1. A minor amount of Cr and VIAl enters octahedral sites following a substitution vector VI(Cr,Al)2?VI(Mg,Fe)-3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP-UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.
Earth and Planetary Science Letters, Vol. 506, pp. 493-506.
Mantle
metasomatism
Abstract: Most diamonds found in kimberlites show complex patterns of growth and dissolution (resorption) surface features. Populations of diamonds from within single kimberlite bodies commonly contain a large diversity of diamond surface forms, some of which are a result of dissolution in kimberlite magma and others are inherited from the mantle. Morphological studies of natural diamonds differentiated features produced during dissolution in kimberlite magma and during mantle metasomatism. The former features were experimentally reproduced at 1 3 GPa and used to infer the presence and composition of magmatic fluid in different kimberlites. However, the mantle-derived resorption features have not been reproduced experimentally and the composition and origins of their formative solvents are unknown. Here we report the results of diamond dissolution experiments conducted in a multi-anvil apparatus at 6 GPa and 1200 to 1500 °C in synthetic CaO MgO SiO2 CO2 H2O system. The experiments produced very different diamond resorption morphologies in COH fluid, in silicate-saturated fluid, and in silicate and carbonate melts. Dissolution in SiO2-free COH fluid developed rounded crystal forms with shallow negative trigons, striations and hillocks, which are commonly observed on natural diamonds and are similar in 6 GPa and in 1 3 GPa experiments. However, silicate-saturated fluid produced very different resorption features that are rarely observed on natural diamonds. This result confirms that natural, SiO2-poor fluid-induced resorption develops under the comparatively low-pressures of kimberlite ascent, because at mantle pressures the high content of SiO2 in fluids would produce features like those from the silicate-saturated experiments. Comparison of the experimental products from this study to natural diamond resorption features from the literature suggests that natural diamonds show no record of dissolution by fluids during mantle metasomatism. Diamond resorption morphologies developed in experiments with silicate carbonate melts closely resemble many of the mantle-derived resorption features of natural diamonds, whose diversity can result from variable SiO2 concentration in carbonatitic melts and temperature variation. The experimental results imply that metasomatism by fluids does not dissolve diamond, whereas metasomatism by melts is diamond-destructive. The repetitive growth-dissolution patterns of natural diamonds could be due to diamond growth from fluids in harzburgitic lithologies followed by its dissolution in partial melts.
Abstract: The interaction of hydrous fluids and melts with dry rocks of the lithospheric mantle inevitably modifies their viscoelastic and chemical properties due to the formation of compositionally distinct secondary phases. In addition, melt percolation and the associated metasomatic alteration of mantle rocks may also facilitate modification of the pre-existing rock texture and olivine crystallographic preferred orientation (CPO) and thus seismic properties. Here we explore the relationship between mantle metasomatism, deformation and seismic anisotropy using subduction-related mantle xenoliths from the Penghu Islands, western Taiwan. The investigated xenoliths have equilibrated at upper lithospheric mantle conditions (879?°C to 1127?°C) based on pyroxene geothermometry and show distinct variations in clinopyroxene chemical composition, texture and olivine CPO allowing for the classification of two distinct groups. Group 1 xenoliths contain rare earth element (REE) depleted clinopyroxene, show a porphyroclastic texture and olivine grains are mostly characterized by [100]-axial pattern symmetries. In contrast, REE-enriched clinopyroxene from Group 2 xenoliths occur in a fine-grained equigranular texture and coexisting olivine frequently displays [010]-axial pattern symmetries. The clinopyroxene compositions are indicative of cryptic and modal to stealth metasomatic alteration of Group 1 and Group 2 xenoliths, respectively. Furthermore, the observed olivine [100]-axial pattern of Group 1 xenoliths reflects deformation by dislocation creep at high temperature, low pressure and dry conditions, whereas olivine [010]-axial patterns of Group 2 xenoliths imply activation of olivine [001] glide planes along preferentially wet (010) grain boundaries. This correlation indicates that the variation in olivine CPO symmetry from [100]- to [010]-axial pattern in Penghu xenoliths results from deformation and intra-crystalline recovery by subgrain rotation during metasomatic alteration induced by melt percolation. The microstructural observations and olivine CPO combined with petrological and geochemical data suggest that Group 1 xenoliths preserve microstructural and chemical characteristics of an old, probably Proterozoic lithosphere, while Group 2 xenoliths record localized Miocene deformation associated with wall-rock heating and metasomatism related to melt circulation. Furthermore, the observed transition of olivine CPO from [100]-axial pattern to [010]-axial pattern by deformation in the presence of variable melt fractions and associated metasomatic alteration can be inferred to modify the physical properties of mantle rocks.
Contributions to Mineralogy and Petrology, Vol. 174, 23p.
Europe, Greenland
metasomatism
Abstract: We report highly siderophile element (HSE) abundances and Re-Os isotope compositions, obtained by isotope dilution induc-tively coupled plasma mass spectrometry, of olivine separates from a suite of multiply metasomatised peridotite xenoliths entrained in kimberlites from SW Greenland. Combined with petrographic and compositional observations on accessory base metal sulphides (BMS), the results reveal new insights into the chemical, physical and mineralogical effects of multi-stage rifting and associated melt percolation on the Archaean lithospheric mantle. Refertilised lherzolites are dominated by rare to frequent small (tens of µm) BMS inclusions in olivine, whereas modally metasomatised phlogopite-bearing lherzolite and wehrlites have higher proportions of more Ni-rich BMS, including abundant large interstitial grains (hundreds of µm). The olivine separates display depleted HSE systematics with Primitive Upper Mantle (PUM)-normalised Pd/Ir of 0.014-0.62, and have both depleted and enriched 187 Os/ 188 Os (0.1139-0.2724) relative to chondrite that are not correlated with 187 Re/ 188 Os. Four out of ten olivine separates retain similarly depleted Os corresponding to Re-depletion model ages of 2.1-1.8 Ga. They may reflect Palaeoproterozoic refertilisation (lherzolitisation) during Laurentia plate assembly, with re-introduction of clinopyroxene and Os-rich BMS into the originally refractory mantle lithosphere by asthenosphere-derived basaltic melts, followed by recrystallisation and occlusion in olivine. Unradiogenic Os is observed regardless of lithology, including from peridotites that contain abundant interstitial BMS. This reflects addition of Os-poor BMS (<< 1 ppm) during more recent wehrlitisation and phlogopite-introduction, and control of the Os isotopic signature by older Os-rich BMS that precipitated from the basaltic melt. Depletions in compatible HSE (< 0.5 × PUM for Ru, Ir, Os) in all, but one olivine separate reflect nugget effects (amount of depleted vs. metasomatic BMS inclusions) and/or loss due to sulphide dissolution into oxidising small-volume melts that invaded the lithosphere during recurrent rifting, the latter supported by similar depletions in published bulk peridotite data. Combined, these multiple metasomatic events destroyed all vestiges of Mesoarchaean or older inheritance in the olivine separates investigated here, and highlight that caution is needed when interpreting Proterozoic Os model ages in terms of Proterozoic lithosphere stabilisation.
Geochimica et Cosmochimica Acta, Vol. 248, pp. 1-13.
Mantle, Asia, Mongolia, Russia, Siberia
metasomatism
Abstract: Ca isotopes can be strongly fractionated at the Earth’s surface and thus may be tracers of subducted carbonates and other Ca-rich surface materials in mantle rocks, magmas and fluids. However, the ?44/40Ca range in the mantle and the scope of intra-mantle isotope fractionation are poorly constrained. We report Ca isotope analyses for 22 mantle xenoliths: four basalt-hosted refractory peridotites from Tariat in Mongolia and 18 samples from the Obnazhennaya (Obn) kimberlite on the NE Siberian craton. Obn peridotites are Paleoproterozoic to Archean melting residues metasomatised by carbonate-rich and/or silicate melts including unique xenoliths that contain texturally equilibrated carbonates. ?44/40Ca in 15 Obn xenoliths shows limited variation (0.74-0.97‰) that overlaps the value (0.94?±?0.05‰) inferred for the bulk silicate Earth from data on fertile lherzolites, but is lower than ?44/40Ca for non-metasomatised refractory peridotites from Mongolia (1.10?±?0.03‰). Bulk ?44/40Ca in four Obn peridotites containing metasomatic carbonates ranges from 0.81?±?0.08‰ to 0.83?±?0.06‰, with similar values in acid-leachates and leaching residues, indicating isotopic equilibration of the carbonates with host rocks. We infer that (a) metasomatism tends to decrease ?44/40Ca values of the mantle, but its effects are usually limited (?0.3‰); (b) Ca isotopes cannot distinguish “carbonatite” and “silicate” types of mantle metasomatism. The lowest ?44/40Ca value (0.56‰) was obtained for a phlogopite-bearing Obn peridotite with a very high Ca/Al of 8 suggesting that the greatest metasomatism-induced Ca isotope shifts may be seen in rocks initially low in Ca that experienced significant Ca input leading to high Ca/Al. Two Obn peridotites, a dunite (melt channel material) and a veined spinel wehrlite, have high ?44/40Ca values (1.22‰ and 1.38‰), which may be due to isotope fractionation by diffusion during silicate melt intrusion and percolation in the host mantle. Overall, we find no evidence that recycling of crustal carbonates may greatly affect Ca isotope values in the global mantle or on a regional scale.
Geochimica et Cosmochimica Acta, in press available, 93p.
Mantle
metasomatism
Abstract: Fluids in the deep crust and upper mantle appear to have played roles in the long-term evolution of the subcratonic lithospheric mantle and the stabilities of the continents, in the geochemical cycles of the elements from subduction zones to Earth’s surface environment, and in the formation of diamonds. Much evidence of the chemistry of deep fluids has accumulated from studies of fluid inclusions in diamonds and xenoliths. But the origins of the fluids and their behavior are still unclear. In part, this is due to the lack of a comprehensive theoretical model of aqueous, high-pressure fluids. Traditional models have used a C-O-H-type of model, which contains no major rock-forming elements or aqueous ions or metal-complexes. In the present study, we use experimentally measured solubility data for multicomponent K-free eclogite, K-free peridotite and K-bearing peridotite rocks at upper mantle conditions from the literature to construct aqueous speciation solubility models that enabled calibration of the thermodynamic properties of ions and metal-complex species involving the elements Na, K, Mg, Ca, Fe, Al, Si, and C in an extended Deep Earth Water (DEW) model. New equilibrium constants were retrieved for the aqueous bisilicate anion, a silica trimer, silicate complexes of Ca, Fe, and Al, a silicate complex of Mg and bicarbonate, and formate complexes of Fe and Ca. The aqueous speciation and solubility model also took account of decreases in the activity of water and aqueous activity coefficients of neutral dissolved gases and included consideration of. Based on the temperature and pressure dependences of the equilibrium constants, and supporting data covering a wide range of conditions, we then developed aqueous equation of state characterizations of the ions and metal-complex species. Overall, the results form a basis for modeling fluid-rock interactions under upper mantle conditions consistent with experimental solubility measurements.
Abstract: The interaction of hydrous fluids and melts with dry rocks of the lithospheric mantle inevitably modifies their viscoelastic and chemical properties due to the formation of compositionally distinct secondary phases. In addition, melt percolation and the associated metasomatic alteration of mantle rocks may also facilitate modification of the pre-existing rock texture and olivine crystallographic preferred orientation (CPO) and thus seismic properties. Here we explore the relationship between mantle metasomatism, deformation and seismic anisotropy using subduction-related mantle xenoliths from the Penghu Islands, western Taiwan. The investigated xenoliths have equilibrated at upper lithospheric mantle conditions (879?°C to 1127?°C) based on pyroxene geothermometry and show distinct variations in clinopyroxene chemical composition, texture and olivine CPO allowing for the classification of two distinct groups. Group 1 xenoliths contain rare earth element (REE) depleted clinopyroxene, show a porphyroclastic texture and olivine grains are mostly characterized by [100]-axial pattern symmetries. In contrast, REE-enriched clinopyroxene from Group 2 xenoliths occur in a fine-grained equigranular texture and coexisting olivine frequently displays [010]-axial pattern symmetries. The clinopyroxene compositions are indicative of cryptic and modal to stealth metasomatic alteration of Group 1 and Group 2 xenoliths, respectively. Furthermore, the observed olivine [100]-axial pattern of Group 1 xenoliths reflects deformation by dislocation creep at high temperature, low pressure and dry conditions, whereas olivine [010]-axial patterns of Group 2 xenoliths imply activation of olivine [001] glide planes along preferentially wet (010) grain boundaries. This correlation indicates that the variation in olivine CPO symmetry from [100]- to [010]-axial pattern in Penghu xenoliths results from deformation and intra-crystalline recovery by subgrain rotation during metasomatic alteration induced by melt percolation. The microstructural observations and olivine CPO combined with petrological and geochemical data suggest that Group 1 xenoliths preserve microstructural and chemical characteristics of an old, probably Proterozoic lithosphere, while Group 2 xenoliths record localized Miocene deformation associated with wall-rock heating and metasomatism related to melt circulation. Furthermore, the observed transition of olivine CPO from [100]-axial pattern to [010]-axial pattern by deformation in the presence of variable melt fractions and associated metasomatic alteration can be inferred to modify the physical properties of mantle rocks.
Geochimica et Cosmochimica Acta, Vol. 254, pp. 21-39.
New Zealand
metasomatism
Abstract: Megacrystic zircon grains from alkaline basaltic fields are rare but can provide fundamental insights into mantle metasomatic processes. Here, we report in-situ U-Pb ages, trace element concentrations and hafnium and oxygen isotopes for fourteen zircon megacrysts from two intraplate alkaline basalt locations in New Zealand. U-Pb ages indicate the zircons crystallised between 12.1 and 19.8 Ma. Zircon oxygen isotopic compositions range from low to mantle-like compositions (grain average ? ¹? O = 3.8-5.1‰). Hafnium isotopes (?Hf (t) = +3.3 to +10.4) mostly overlap with intraplate mafic rocks and clinopyroxene in metasomatized peridotitic mantle xenoliths but show no correlation with most trace element parameters or oxygen isotopes. The zircons are interpreted to have formed by the reaction between low-degree melts derived from pre-existing mantle metasomes and the depleted mantle lithosphere prior to eruption and transport to the surface. The low Hf concentration, an absence of Eu anomalies, and elevated U/Yb compared to Nb/Yb in the megacrystic zircons are interpreted to show that the source metasomes comprised subduction- and carbonatite-metasomatised lithospheric mantle. As these trace element characteristics are common for megacrystic zircon in intra-plate basaltic fields globally, they suggest the prevalence of subduction- and carbonatite-metsasomatised mantle under these intraplate volcanic regions. The unusually low ? ¹? O was likely present prior to metasomatic enrichment and may have resulted from high-temperature hydrothermal alteration during initial mantle lithosphere formation at a mid ocean ridge or, possibly, during subduction-related processes associated with continent formation. The combination of proportionally varied contributions from carbonatite- and subduction-metasomatised lithospheric melts with asthenospheric melts may explain the variety of primitive intraplate basalt compositions, including low ? ¹? O reported for some local intraplate lavas.
Abstract: Saline (Cl-rich) fluids potentially play an important role as metasomatic agents in the lithospheric mantle. Natural evidence for deep saline fluids exists as inclusions within diamonds and within groundmass minerals in kimberlites. Previous experimental studies have investigated melting relations in the chloride-carbonate-silicate system at upper mantle conditions, but a systematic experimental study of how saline fluids react with the lithospheric mantle is still lacking. Here, we present high-pressure, high-temperature (HP-HT) reaction experiments between a saline fluid and different mantle rocks (lherzolite, harzburgite, eclogite) at conditions corresponding to the lower cratonic lithosphere. Experiments were performed over a P-T range of 3-6 GPa and 1050-1300 °C using a multi-anvil apparatus. Preliminary results show that the interaction between saline fluid and mantle rocks is very reactive, compared to reactions with silico-carbonate melts. The reaction between saline fluid and lherzolite at 4 GPa and 1200 °C leads to extensive melting. The restite consists mainly of olivine and garnet, whereas pyroxenes are only observed as rare inclusions within garnet. In contrast, reactions between saline fluid and eclogite at 4 GPa and 1200 °C also lead to melting, but the melt is more enriched in Si. The restite consists exclusively of garnet. The experimental results demonstrate how saline fluids react with different components of the lithospheric mantle and support evolutionary models of high density fluids within diamonds.
Abstract: The results of experiments on the synthesis of exotic titanates (priderite and yimengite) simulating metasomatic conditions of alteration of the mantle minerals (chromite and ilmenite) are reported. Ba-free Cr-bearing priderite was synthesized for the first time. Experiments showed the possibility of crystallization of this mineral as a product of the reaction of high-Cr spinel and rutile with hydrous-carbonate fluid (melt) under the conditions of the upper mantle. In particular, the experimental data obtained provide an interpretation of the relationships between K?Cr priderite and carbonate-silicate inclusions in chromites from garnet peridotite of the Bohemian massif. Experimental study of the reaction of chromite and ilmenite with potassic hydrous-carbonate fluid (melt) shows the presence of both titanate phases (priderite and yimengite), the mineral indicators of mantle metasomatism. This provides direct evidence for the formation of yimengite and K?Cr priderite, as well as other titanates, due to mantle metasomatism of the upper mantle peridotite under the conditions of the highest activities of potassium.
Abstract: The subduction of sediment connects the surface nitrogen cycle to that of the deep Earth. To understand the evolution of nitrogen in the atmosphere, the behavior of nitrogen during the subduction and melting of subducted sediments has to be estimated. This study presents high-pressure experimental measurements of the partitioning of nitrogen during the melting of sediments at sub-arc depths. For quantitative analysis of nitrogen in minerals and glasses, we calibrated the electron probe micro-analyzer on synthetic ammonium feldspar to measure nitrogen concentrations as low as 500??g?g?1. Nitrogen abundances in melt and mica are used together with mass balance calculations to determine DN(Mica/Melt), DN(Fluid/Mica), and DN(Fluid/Melt). Calculated partition coefficients correspond to expected values for NH4+, which behaves similarly to Rb+ due to its nearly identical size. Nitrogen partitioning between fluid and melt (DN(Fluid/Melt)) and fluid and bulk residue (melt+mica) (DN(Fluid/Bulk)) increase linearly with temperature normalized to pressure. This linear relationship can be used to calculate DN(Fluid/Melt) and DN(Fluid/Bulk) for slab melts from 800 to 1200?°C following: and [nasty equation that did not copy]. We used these partition coefficients to quantify the amount of N recycled into the mantle as 50?±?6% of today's atmospheric N. Depending on the rate of mantle N degassing we calculated 4 different scenarios for atmospheric pN2 evolution. All 4 scenarios estimate pN2 to be 8-12% higher at the beginning of the Phanerozoic. These estimates diverge towards the past due to uncertainties in the mechanism and magnitude of N degassing from the mantle. Assuming degassing of N in the past was close to modern degassing rates from MORB, pN2 was up to 40% higher at the onset of plate tectonics at 3-4?Ga. However, degassing rates were probably higher than this: assuming 10× and 20× times higher rates at the onset of plate tectonics leads to pN2 within 20% of modern values. If N degassing from the mantle is increased to 40× the modern MORB rate, pN2 in the Archean would have been 50% lower than today's, which is in accordance with observations from paleoatmospheric studies.
Abstract:
We report new U-Pb zircon age data, zircon in situ oxygen isotope, mineral chemistry, whole-rock geochemistry and Sr-Nd isotopic compositions from the Early Devonian ultrapotassic Gucheng pluton in the North China Craton, and discuss its petrogenesis. The Gucheng pluton is exposed in the northern part of the North China Craton and forms a composite intrusion, consisting of K-feldspar-bearing clinopyroxenite, clinopyroxene-bearing syenite and alkali-feldspar syenite. Mineral phases in these lithologies include clinopyroxene (Wo43-48En19-35Fs18-38), sanidine (An0Ab3-11Or89-97), and subordinate titanite, andradite and Na-feldspar. These rocks show homogeneous Sr but variable Nd isotopic compositions, and have relatively high zircon in situ oxygen isotopes (?18O = 5.2-6.7). The Gucheng plutonic rocks formed through fractional crystallization and accumulation from ultrapotassic magmas, which were originated from partial melting of metasomatic vein systems in the subcontinental lithospheric mantle of the North China Craton. These vein networks developed as a result of the reactions of fluids derived from subducted pelitic sediments on the downgoing Palaeo-Asian ocean floor with the enriched, subcontinental lithospheric mantle peridotites. Sensitive high-resolution ion microprobe (SHRIMP) U-Pb zircon dating has revealed a crystallization age of 415 Ma for the timing of the emplacement of the Gucheng pluton that marks the early stages of alkaline magmatism associated with the Andean-type continental margin evolution along the northern edge of the North China Craton facing the Palaeo-Asian Ocean.
Abstract: MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) and PIC (Phlogopite-Ilmenite-Clinopyroxene) rocks occur as mantle-derived xenoliths in kimberlites and other alkaline volcanic rocks. Both rock types are alkaline and ultramafic in composition. The H2O and alkali metal enrichments in MARID and PIC rocks, reflected in abundant phlogopite, have been suggested to be caused by extreme mantle metasomatism. Radiogenic (Sr-Nd-Hf-Pb) isotope and trace element compositions for mineral separates from MARID (clinopyroxene and amphibole) and PIC (clinopyroxene only) samples derived from Cretaceous kimberlites (Kimberley) and orangeites (Newlands) from South Africa are used here to examine the source(s) of mantle metasomatism. PIC clinopyroxene ( n = 4 ) is relatively homogeneous, with narrow ranges in initial isotopic composition (calculated to the emplacement age of the host Bultfontein kimberlite; 87Sr/86Sri: 0.7037-0.7041; ?Ndi: +3.0 to +3.6; ?Hfi: +2.2 to +2.5; 206Pb/204Pbi: 19.72-19.94) similar to kimberlite values. This is consistent with PIC rocks representing peridotites modified by intense metasomatic interaction with kimberlite melts. The MARID clinopyroxene ( n = 9 ) and amphibole separates ( n = 11 ) studied here display broader ranges in isotope composition (e.g., 87Sr/86Sri: 0.705-0.711; ?Ndi: ?11.0 to ?1.0; ?Hfi: ?17.9 to ?8.5; 206Pb/204Pbi: 17.33-18.72) than observed in previous studies of MARID rocks. The Nd-Hf isotope compositions of kimberlite-derived MARID samples fall below the mantle array (??Hfi between ?13.0 and ?2.4), a feature reported widely for kimberlites and other alkaline magmas. We propose that such displacements in MARID minerals result from metasomatic alteration of an initial “enriched mantle” MARID composition (i.e., 87Sr/86Sri = 0.711; ?Ndi = ?11.0; ?Hfi = ?17.9; and 206Pb/204Pbi = 17.3) by the entraining kimberlite magma (87Sr/86Sr ? i 0.704 ; ?Nd ? i + 3.3 ; ?Hf ? i + 2.3 ; 206Pb/204Pb ? i 19.7 ). A model simulating the flow of kimberlite magma through a mantle column, thereby gradually equilibrating the isotopic and chemical compositions of the MARID wall-rock with those of the kimberlite magma, broadly reproduces the Sr-Nd-Hf-Pb isotope compositions of the MARID minerals analysed here. This model also suggests that assimilation of MARID components could be responsible for negative ??Hfi values in kimberlites. The isotopic composition of the inferred initial MARID end-member, with high 87Sr/86Sr and low ?Nd, ?Hf, and 206Pb/204Pb, resembles those found in orangeites, supporting previous inferences of a genetic link between MARID-veined mantle and orangeites. The metasomatic agent that produced such compositions in MARID rocks must be more extreme than the EM-II mantle component and may relate to recycled material that experienced long-term storage in the lithospheric mantle.
Abstract: The interaction between hydrous fluids and melts with dry pre-existing mantle rocks alters the physocochemical porperties of the deep lithosphere. Here we present new insight into mantle metasomatism based on petrology, geochemistry, and Rare Earth Element (REE) distribution modelling using mantle xenoliths from various eruption centres in the Cenozoic Tariat volcanic field, Mongolia. These centres include the Horgo, Tsagan, Zala, Haer and Shavaryn-Tsaram lava flows that vary in composition and age between alkali basalts to trachybasalts to tephrite basanites and 4 ka to 1.5 Ma, respectively. Our sample suite contains xenolith from the lower crust and underlying mantle with a size range of individual xenoliths between 3 cm and 8 cm. Based on the clinopyroxene REE concentration pattern, the investigated xenoliths can be divided in two groups, characterized by LREE depletion (Group 1) and enrichment (Group 2) relative to primitive mantle. Group 1 xenoliths display well-preserved deformation textures and are considered to represent the sub-continental lithosphere prior to Cenozoic rejuvenation. In contrast, Group 2 samples are marked by partial annealing of pre-existing textures. REE distribution modelling between clinopyroxene and inferred chemically enriched basaltic melt suggests that the observed REE pattern do not reconcile with a simple mixing model but reflect chromatographic fractionation during reactive melt flow. In addition, the clinopyroxene core-rim REE variation in some of the xenoliths suggests interaction with at least one other melt of distinct chemical composition.
Geochimica et Cosmochimica Acta, Vol. 266, pp. 307-311.
United States, California, Africa, Morocco
metasomatism
Abstract: We investigate the potential to use concentrations and zoning patterns of phosphorus (P) in clinopyroxene as indicators of the rates of igneous and metasomatic processes, comparable to recent applications of P in olivine but applicable to more evolved rocks and lower temperatures of crystallization. Few high-P pyroxenes have been previously reported, and none have been analyzed in detail for the mechanism of P enrichment or the implications for mineral growth kinetics. Here, we report the discovery and characteristics of exotic phosphorus-rich secondary clinopyroxene in glassy pockets and veins in composite mantle xenoliths from the Cima Volcanic Field (California, USA) and the Middle Atlas Mountains (Morocco, West Africa). These glass-bearing xenoliths preserve evidence of melt infiltration events and the contrasting behavior of P in their pyroxene crystals constrains the different rates of reaction and extents of equilibration that characterized infiltration in each setting. We report optical petrography and chemical analysis of glasses and minerals for major elements by electron microprobe microanalyzer and trace elements by laser-ablation Inductively Coupled Plasma Mass Spectrometry. The Cima Volcanic Field specimen shows one end-member behavior, with unzoned P-rich clinopyroxene in a melt pocket. We attribute this occurrence to a slow crystallization process that occurred after the melt temperature reached near-equilibrium with the host rock and during which the P concentration in the melt was buffered by apatite saturation. In the Morocco xenolith, by contrast, clinopyroxene exhibits zonation with P increasing all the way to the rim, in contact with the glass. We ascribe this feature to a rapid growth process in which excess P was incorporated into the growing clinopyroxene from a diffusive boundary layer. We demonstrate quantitative agreement between the enrichment of P and other trace elements and their expected diffusion and partitioning behavior during rapid growth. We suggest that P has not been widely reported in clinopyroxene in large part because it has rarely been looked for and that its analysis offers considerable promise as a kinetic indicator both in xenoliths and volcanic rocks.
Abstract: MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) and PIC (Phlogopite-Ilmenite-Clinopyroxene) rocks are rare mantle xenoliths entrained by kimberlites. Their high phlogopite modes (15 to ?100 vol.%) and consequent enrichments in alkali metals and H2O suggest a metasomatic origin. Phlogopite also has high concentrations (>0.2 ?g/g) of thallium (Tl) relative to mantle abundances (<3 ng/g). Thallium isotope ratios have proven useful in tracing the input of Tl-rich materials, such as pelagic sediments and altered oceanic crust, to mantle sources because of their distinct isotopic compositions compared to the peridotitic mantle. This study presents the first Tl isotopic compositions of well-characterised phlogopite separates from MARID and PIC samples to further our understanding of their genesis. The PIC rocks in this study were previously interpreted as the products of kimberlite melt metasomatism, whereas the radiogenic and stable N-O isotope systematics of MARID rocks suggest a parental metasomatic agent containing a recycled component. The ?205Tl values of phlogopite in both PIC (-2.7 ± 0.8; 2 s.d., n = 4) and MARID samples (-2.5 ± 1.3; 2 s.d., n = 21) overlap with the estimated mantle composition (-2.0 ± 1.0). PIC phlogopite Tl contents (?0.4 ?g/g) are suggestive of equilibrium with kimberlite melts (0.1-0.6 ?g/g Tl), based on partitioning experiments in other silica-undersaturated melts. Kimberlite Tl-?205Tl systematics suggest their genesis does not require a recycled contribution: however, high temperature-altered oceanic crust cannot be ruled out as a component of the Kimberley kimberlites’ source. Mantle-like ?205Tl values in MARID samples also seem to contradict previous suggestions of a recycled contribution towards their genesis. Recycled components with isotopic compositions close to mantle values (e.g., high temperature-altered oceanic crust) are still permitted. Moreover, mass balance mixing models indicate that incorporation into the primitive mantle of 1-30% of a low temperature-altered oceanic crust + continental crust recycled component or 1-50% of continental crust alone could be accommodated by the Tl-?205Tl systematics of the MARID parental melt. This scenario is consistent with experimental evidence and existing isotopic data. One PIC phlogopite separate has an extremely light Tl isotopic composition of -9.9, interpreted to result from kinetic isotopic fractionation. Overall, phlogopite is the main host mineral for Tl in metasomatised mantle and shows a very restricted range in Tl isotopic composition, which overlaps with estimates of the mantle composition. These results strongly suggest that negligible high temperature equilibrium Tl isotopic fractionation occurs during metasomatism and reinforces previous estimates of the mantle’s Tl isotopic composition.
Journal of Asian Earth Sciences, Vol. 177, pp. 76-88.
Mantle
metasomatism
Abstract: Potassium-rich lavas with K/Na of >2 are common in orogenic and anorogenic intraplate magmatic provinces. However, in the primitive mantle, the concentration of Na exceeds that of K by 10 times. The source of K-rich lavas thus needs to be either K-enriched or Na-depleted to account for high K/Na ratios. The geochemical and isotopic compositions of high 87Sr/86Sr post-collisional lavas show that their mantle source contains a recycled crustal component. These highly K-enriched lavas with crustal like trace element patterns are termed “orogenic lamproites” and are compositionally distinct from K-rich “anorogenic lamproites” that show lower 87Sr/86Sr and a trace element pattern that resembles that of primary mantle melts. For both groups the processes of K-enrichment within their source are uncertain and are thought to be linked to melts of sedimentary rocks for “orogenic lamproites” and low-degree melts of ultramafic mantle rocks for “anorogenic lamproites”. In both cases, metasomatism of the mantle lithosphere is the precursor to K-rich magmatism. In this study we experimentally determine the effects of mantle metasomatism by sediment- and hydrous mantle melts. The experiments simulate the interaction of refractory lithospheric mantle and metasomatizing melt in a 2-layer reaction experiment. The sediment/dunite reaction experiments lead to formation of a strongly K-enriched phlogopite-pyroxenite layer sandwiched between the two starting materials. The low temperature of the sediment/dunite reaction runs at <1000?°C simulates a fore-arc subduction environment, in which the melts of sediment are consumed during interaction with dunite as the temperature is below the solidus of the produced phlogopite-pyroxenites. The hydrous mantle melt/dunite reaction run is simulated by reacting a hydrated basanite with dunite. Since the temperature of the reaction is higher than the solidus of the resulting phlogopite-pyroxenites (1200?°C), the hydrous melt is not consumed but flows further, increasing in K2O and K/Na as it reacts with the refractory peridotite. In both cases, melts are enriched in K and K/Na increases by crystallizing a low K and low K/Na eclogitic residue. Compositions of glass and phlogopite from both types of reactions are comparable to glasses and phlogopites found within post-collisional lavas. Since the enrichment of K within the reaction zone is strongly controlled by the formation of low K/Na and low-K residues, metasomatic enrichment of the mantle lithosphere in K does not need a highly K-enriched metasomatic agent.
Geochimica et Cosmochimica Acta, Vol. 270, pp. 95-111.
China, Russia
metasomatism, melting
Abstract: The eastern part of Asia between the North China and Siberian cratons contains orogenic belts formed by the Paleo-Asian and Pacific subduction and older continental blocks. A fundamental question regarding these and all mobile belts is the fate of the continental lithospheric mantle (CLM) during their formation, i.e. whether, or to what extent the CLM may be formed, replaced or affected during orogeny. Insights into these processes can be obtained from mantle xenoliths hosted by Cenozoic basalts in the Proterozoic Khanka block in the far eastern Russia between NE China and the Pacific coast of Asia. We report petrographic, chemical, and Os-Sr-Nd isotope data for spinel peridotite xenoliths at two Khanka sites: Sviyagin and Podgelban. The modal abundances and chemical compositions suggest that the peridotites are residues of low to moderate degrees of melt extraction from fertile mantle. They show an 187Os/188Os vs. 187Re/188Os correlation with an apparent 1.9?Ga age; the 187Os/188Os ratios are positively correlated with Al2O3 and other melt extraction indices. These results provide the first robust CLM age constraints for the eastern Central Asian Orogenic Belt (CAOB). The ages suggest that the ancient CLM of the Khanka block may be roughly coeval with reworked CLM at Hannuoba (North China craton), and that it persisted through the Phanerozoic orogenies. Moreover, despite the proximity to Phanerozoic subduction zones, the Khanka CLM shows little post-melting enrichment, e.g. the clinopyroxenes are typically LREE-depleted and have Sr-Nd isotope ratios typical of the MORB mantle. We posit that the metasomatism of the CLM, earlier proposed for North China xenolith suites and ascribed to the effects of Pacific or older subduction and related mantle upwelling, may not be widespread in the CAOB. In general, Proterozoic blocks composed of residual peridotites may be more common in the CLM of the SE Siberia and northern China, and possibly other orogenic belts, than previously thought.
Abstract: In total, subduction zones span 40,000 km across Earth’s surface and recycle an average thickness of 500 m of sediment. During burial and heating these sediments eventually start melting at T >675 °C, following which Si-rich hydrous melts infiltrate the peridotites of the mantle wedge above the subducting slab. In this thesis, a high-pressure experimental approach is used to examine the reaction of sediments and peridotites at 2-6 GPa in subduction zones and its consequences on the generation of K-rich magmatism and on deep nitrogen cycling. All experiments are conducted in a layered arrangement, where the depleted peridotite is placed above the sediments in a 1:1 ratio. At 2-3 GPa, the reaction of melts of sediment with depleted peridotite, simulating the fore-arc of a subduction zone, leads to the formation of layered phlogopite pyroxenites and selective incorporation of major and trace elements in these metasomatic layers. Partial melting of these phlogopite pyroxenites produces melts rich in K2O (>9 wt%) with K/Na >>2 and a trace element pattern comparable to “orogenic lamproites”. At similar pressures, the reaction of hydrous mantle melts with depleted peridotites produces metasomatic layers that show K/Na ~1 and a trace element pattern that closely resembles “anorogenic lamproites”. In both cases, K-enrichment is facilitated by the crystallization of an eclogitic residue rich in Na, poor in K, and consequently with low K/Na. At 4-6 GPa, the reaction of melts of sediment with depleted peridotite is does not produce mica, instead resulting in alkali chlorides with K/Na ratios similar to saline fluid inclusions in diamonds. Besides the chlorides, magnesite also crystallises in the peridotite. Both phases are important ingredients for the generation of salty kimberlites such as Udachnaya East. The change in metasomatic style from mica- to chloride formation between 3 to 4 GPa corresponds to the depth of the mid-lithospheric discontinuity, a zone of low seismic velocities that is found intermittently beneath all continents at a depth of 80-100 km. The subduction of sediment is the main mechanism that recycles nitrogen back to Earth’s mantle. The partitioning of nitrogen between fluid and melt (DN(Fluid/Melt)) and fluid and bulk residue (melt+mica) (DN(Fluid/Bulk)) was found to increase linearly with temperature normalized to pressure. Using the new partition coefficients, the amount of N recycled to Earth’s mantle since the onset of subduction is calculated as 50 ±6 %.
MDPI Minerals, Vol. 10, 41;doe.10.3390/min10010041 21p. Pdf
Mantle
metasomatism
Abstract: The generation of strongly potassic melts in the mantle requires the presence of phlogopite in the melting assemblage, while isotopic and trace element analyses of ultrapotassic rocks frequently indicate the involvement of subducted crustal lithologies in the source. However, phlogopite-free experiments that focus on melting of sedimentary rocks and subsequent hybridization with mantle rocks at pressures of 1-3 GPa have not successfully produced melts with K2O >5 wt%-6 wt%, while ultrapotassic igneous rocks reach up to 12 wt% K2O. Accordingly, a two-stage process that enriches K2O and increases K/Na in intermediary assemblages in the source prior to ultrapotassic magmatism seems likely. Here, we simulate this two-stage formation of ultrapotassic magmas using an experimental approach that involves re-melting of parts of an experimental product in a second experiment. In the first stage, reaction experiments containing layered sediment and dunite produced a modally metasomatized reaction zone at the border of a depleted peridotite. For the second-stage experiment, the metasomatized dunite was separated from the residue of the sedimentary rock and transferred to a smaller capsule, and melts were produced with 8 wt%-8.5 wt% K2O and K/Na of 6-7. This is the first time that extremely K-enriched ultrapotassic melts have been generated experimentally from sediments at low pressure applicable to a post-collisional setting.
Abstract: Eclogite mantle xenoliths from various kimberlite occurrences on the Kaapvaal craton show evidence for depth- and redox-dependent metasomatic events that led to variable base metal sulphide and incompatible element enrichments. Eclogite xenoliths from the Roberts Victor, Jagersfontein, Kimberley (Kamfersdam) and Premier kimberlites were investigated for their silicate and base metal sulphide geochemistry, stable oxygen isotope compositions and oxybarometry. The variably metasomatised eclogites had basaltic, picritic and gabbroic protolith compositions and have garnet ?18O values that range from +3.3 to +7.9‰, which, when coupled with the trace element characteristics, indicate oceanic lithosphere protoliths that had undergone variable degrees of seawater alteration. The deepest equilibrated eclogites (175220?km depth) from near the base of the Kaapvaal craton lithosphere are the most refractory and feature significant light rare earth element (LREE) depletions. They show the most oxidised redox compositions with ?logƒO2 values of FMQ-3.9 to FMQ-1.5. Subtle metasomatic overprinting of these eclogites resulted in base metal sulphide formation with relatively depleted and highly fractionated HSE compositions. These deepest eclogites and their included base metal sulphides suggest interaction with relatively oxidised melts or fluids, which, based on their HSE characteristics, could be related to precursor kimberlite metasomatism that was widespread within the Kaapvaal craton mantle lithosphere. In contrast, eclogites that reside at shallower, “mid-lithospheric” depths (140180?km) have been enriched in LREE and secondary diopside/phlogopite. Importantly, they host abundant metasomatic base metal sulphides, which have higher HSE contents than those in the deeper eclogites at the lithosphere base. The mid-lithospheric eclogites have more reducing redox compositions (?logfO2?=?FMQ-5.3 ? FMQ-3.3) than the eclogites from the lowermost Kaapvaal lithosphere. The compositional overprint of the shallower mantle eclogites resembles basaltic rather than kimberlitic/carbonatitic metasomatism, which is also supported by their relatively reducing redox state. Base metal sulphides from the mid-lithospheric eclogites have HSE abundances and distributions that are similar to Karoo flood basalts from southern Africa, suggesting a link between the identified shallow mantle metasomatism of the Kaapvaal cratonic lithosphere and the Karoo large igneous event during the Mesozoic. The sulphide-hosted platinum group element abundances of the mid-lithospheric eclogites are higher compared with their analogues from the deeper lithospheric eclogites, which in combination with their contrasting oxidation states, may imply redox-controlled HSE mobility during sulphur-rich metasomatism of continental mantle lithosphere.
Abstract: Phlogopite is widely accepted as a major mineral indicator of the modal metasomatism in the upper mantle within a very wide P-T range. The paper reviews data on various phlogopite-forming reactions in upper-mantle peridotites. The review includes both descriptions of naturally occurring reactions and results of experiments that model some of these reactions. Relations of phlogopite with other potassic phases, such as K-richterite, sanidine and K-titanates, are discussed. These data are taken as a basis for thermodynamic modeling of the phlogopite-forming reactions for specific mantle rocks in terms of log(aH2O) ? log(aK2O) diagrams (pseudosections) using the Gibbs free energy minimization. These diagrams allow estimation of potassium-water activity relations during metasomatic transformations of mantle rocks, prediction sequences of mineral assemblages with respect to these parameters and comparison of metasomatic processes in the rocks of different composition. This approach is illustrated by examples from peridotite xenoliths from kimberlites.
Abstract: The ~545 Ma-old syn-collisional Otjimbingwe alkaline complex is composed of pyroxene-amphibole-biotite-bearing, mildly nepheline-normative to quartz-normative rocks ranging in composition from monzogabbro to monzonite, syenite and granite. The alkaline rocks have moderate to high SiO2 (50.5-73.0 wt%) and Na2O + K2O (5.1-11.5 wt%) and moderate to low MgO (6.6-0.2 wt%) concentrations. All samples have high large ion lithophile element (LILE: Ba up to 4600 ppm) and high-field-strength element contents (HFSE; Zr: 155-1328 ppm; Nb: 16-110 ppm; Ta: 1.4-7.1 ppm and Hf: 4-24 ppm) and have strongly fractionated LREE patterns ((La/Yb)N = 14-51). The most primitive members lack significant negative Eu anomalies. Mantle-normalized multi-element diagrams show depletion in Ba, Rb, Nb (Ta), P and Ti. The alkaline rocks have moderate radiogenic initial 87Sr/86Sr ratios (0.7061-0.7087) and unradiogenic initial ?Nd values (?3.9 to ?6.1). This isotope signature, associated with high LREE/HFSE ratios indicates that the parental melts were generated in enriched portions of the shallow lithospheric mantle, which was probably affected by previous subduction zone processes. In addition, correlations between Sr and Nd isotopes indicate that some of these variations result from combined crustal assimilation and fractional crystallization (AFC) processes. A new model of flat subduction is presented that explains most of the unsolved problems in the orogenic evolution of the Damara orogen, namely (i) the absence of early intrusive rocks with a clear subduction zone setting, (ii) the absence of high-pressure rocks such as blueschists and eclogites, (iii) the unusual distribution of igneous rocks with a clear predominance of granite and granodiorite and (iv) the need for a asthenospheric window during a classical subduction to explain the high T/moderate P granulite facies conditions in the overriding plate.
Abstract:
This study reports halogen contents (F and Cl) of amphibole and phlogopite derived from mantle xenoliths and one peridotite massif, for amphibole and phlogopite megacrysts and ultramafic magmatic cumulates (hornblendites) found in alkaline volcanic rocks from 12 localities in Europe and Africa. Amphibole and phlogopite contain more F than Cl with F/Cl ratios reaching about 160 in phlogopites and 50 in amphiboles. Phlogopites are higher in F (median of 3400 ?g/g) than amphibole (median of 1000 ?g/g), while median Cl contents are higher in amphibole (290 ?g/g) compared to phlogopite (180 ?g/g). The Cl contents and the F/Cl ratios in amphibole and phlogopite from mantle xenoliths exhibit large differences between samples of the same region, recording very large variations of halogen contents in the continental lithosphere. We suggest that the halogen content in such samples largely depends on the initial composition of percolating melts and fluids in the continental lithosphere. During reaction of these agents with peridotitic wall-rocks, Cl is preferentially retained in the fluid as it is much more incompatible compared to water and F. This desiccation effect continuously increases salinity (Cl content) and decreases the F/Cl ratio in the agent with time, causing variable Cl contents and F/Cl ratios in amphibole and phlogopite at a specific locality. Subsequent partial melting processes may then sequester and re-distribute, especially Cl among amphibole, phlogopite and melts/fluids as a result of its strong incompatibility, whereas F is much less affected as it behaves slightly compatible. The impact of even small amounts of amphibole and mica on the total halogen budget in the continental lithosphere is significant and both minerals can effectively contribute to the high halogen contents typical of alkaline melts.
Abstract: The range of carbonatite melts in equilibrium with the subcontinental lithospheric mantle (SCLM) under geothermal conditions is limited by alkali-rich near-eutectic compositions. Therefore, here we employed eutectic Na/K-Ca-Mg-Fe carbonate mixtures to model the interaction of a metasomatic carbonatite melt with natural garnet lherzolite. The experiments were performed at 1100 and 1200 °C and 6 GPa in graphite capsules using a multianvil press. The run duration was 111 and 86 h, respectively. To verify achieving an equilibrium, a synthetic mixture identical to natural lherzolite was also employed. We have found that both Na- and K-bearing carbonatite melts cause wehrlitization accompanying by the elimination of orthopyroxene and an increase of CaO in garnet at a constant Cr2O3. Interaction with the K?carbonatite melt alters clinopyroxene composition toward lower Na2O (0.2-0.3 wt%), and higher K2O (0.5-1.0 wt%), whereas the Na?carbonatite melt revealed the opposite effect. The resulting melts have a following approximate composition [40(Na, K)2CO3?60Ca0.5Mg0.4Fe0.1CO2 + 0.6-1.4 wt% SiO2] displaying a decrease in Ca# at a nearly constant alkali content relative to the initial composition, where Ca# = 100?Ca/(Ca + Mg + Fe). We have also found that alkali-poor (? 20 mol% (Na, K)2CO3) carbonate mixtures do not melt completely but yield magnesite and alkali- and Ca-rich melts like those in the systems with eutectic mixtures. Under SCLM P-T conditions the range of carbonatite melt compositions is restricted by the full melting field of alkali-rich carbonates in the corresponding Na/K-Ca-Mg carbonate systems. Infiltration of less alkaline higher-temperature carbonatite melt in SCLM and its subsequent cooling to the ambient mantle temperature, 1100-1200 °C at 6 GPa, should cause crystallization of magnesite and shift the melt composition to [30(Na, K)2CO3?70Ca0.6Mg0.3Fe0.1CO3]. Owing to its high Ca#, this melt is not stable in equilibrium with orthopyroxene yielding its disappearance by CaMg exchange reaction producing clinopyroxene, magnesite, and shifting the melt composition toward higher alkali content. The melts containing 40-45 mol% of alkaline carbonates have no limitation in Ca# because the corresponding binary NaMg and KMg carbonate eutectics are located near 1200 °C. Therefore, these melts can achieve Ca# ? 30-40 and, be in equilibrium with garnet lherzolites and harzburgites under the geothermal condition of SCLM. Considering the present results and previous experimental data the following ranges of carbonatite melt compositions can be expected in equilibrium with garnet peridotites at the base of SCLM: Ca# < 30 and > 30 mol% (K, Na)2CO3 in equilibrium with harzburgite; Ca# 30-40, >25 mol% (K, Na)2CO3 in equilibrium with lherzolite; and Ca# 40-60 and >20 mol% (K, Na)2CO3 in equilibrium with wehrlite.
Abstract: The results of experimental studies are presented for reactions in the orthopyroxene-garnet-phlogopite system in the presence of H2O-KCl fluid at 3-5 GPa and 900-1000°C, which model the processes of phlogopite formation in garnet peridotites and pyroxenites during alkaline metasomatism of the upper mantle. The experiments demonstrated regular variations in the composition of garnet, pyroxenes, and phlogopite depending on the KCl content of the fluid. With increasing KCl content of the fluid, enstatite and garnet become unstable, the Al2O3 content of enstatite decreases, and the amount of grossular and knorringite components in garnet are maximum at a KCl content of ~10 mol %. Our results illustrate well the regular variations in the compositions of the coexisting minerals and their zoning in phlogopite-bearing peridotites of the lithospheric mantle.
Geochimica et Cosmochimica Acta, in press availabe 38p. Pdf
China
metasomatism
Abstract: Water is key to many geodynamical processes in the Earth's upper mantle, yet its preservation in mantle minerals is still debated. To throw some light on this problem, we here carried out an integrated study of whole-rock and mineral chemistry, and hydrogen concentrations in olivine, orthopyroxene, and clinopyroxene within 18 spinel lherzolite samples from three localities (Lianshan, Panshishan, and Tashan) in the Nanjing area, eastern China. Whole-rock and mineral compositions suggest that the studied peridotite samples interacted with melt at different melt/rock ratios following various degrees of partial melting (up to 11%). Fourier transform infrared (FTIR) measurements show that olivine is almost dry (<1 wt ppm H2O) while the cores of orthopyroxene and clinopyroxene contain 14-151 wt ppm H2O and 41-218 wt ppm H2O, respectively. Profile analyses of >70 orthopyroxene grains, which are homogeneous in major-element compositions, covering all the studied samples show hydrogen-depleted rims, indicative of hydrogen diffusional loss. This hydrogen zonation is probably caused by hydrogen chemical diffusion controlled by the mobility of trivalent cations (most likely Al3+) in response to magma degassing or partial melting of peridotite during ascent, or interactions of peridotite with melt, or a combination of these processes. By contrast, no hydrogen zonation is observed in clinopyroxene. Based upon the comparison of chemical compositions (especially Fe and AlIV contents) of clinopyroxene within our samples with those in diffusion experiments, it is inferred that the hydrogen diffusivity in clinopyroxene should be larger than that in orthopyroxene from our samples. This inference points to that clinopyroxene within the studied samples must have experienced diffusional loss of hydrogen as well, suggesting that water concentrations in the lithospheric mantle beneath the study area are probably underestimated. Furthermore, it also implies that orthopyroxene instead of clinopyroxene most likely preserves the in-situ water concentrations at depth, at least at its core. The absence of hydrogen zonation in clinopyroxene can be attributed to its fine-grained nature and fast hydrogen diffusivity. Our FTIR data also show that Lianshan and Tashan samples have water concentration ratio between clinopyroxene and orthopyroxene (RCpx/Opx) of ?2, similar to mantle xenoliths from eastern China and other localities worldwide, yet Panshishan samples have higher RCpx/Opx values (2.3-5.9). Since hydrogen loss is suggested for both pyroxenes, RCpx/Opx of ?2 thus cannot be taken as a reliable indicator of preservation of original water concentration of mantle source and equilibrium partitioning of hydrogen between pyroxene, as opposed to previous suggestions.
Nature Scientific Reports, 10.1038/s41598-021-83261-6 11p. Pdf
Canada, Northwest Territories
metasomatism
Abstract: We present the first oxidation state measurements for the subcontinental lithospheric mantle (SCLM) beneath the Rae craton, northern Canada, one of the largest components of the Canadian shield. In combination with major and trace element compositions for garnet and clinopyroxene, we assess the relationship between oxidation state and metasomatic overprinting. The sample suite comprises peridotite xenoliths from the central part (Pelly Bay) and the craton margin (Somerset Island) providing insights into lateral and vertical variations in lithospheric character. Our suite contains spinel, garnet-spinel and garnet peridotites, with most samples originating from 100 to 140 km depth. Within this narrow depth range we observe strong chemical gradients, including variations in oxygen fugacity (ƒO2) of over 4 log units. Both Pelly Bay and Somerset Island peridotites reveal a change in metasomatic type with depth. Observed geochemical systematics and textural evidence support the notion that Rae SCLM developed through amalgamation of different local domains, establishing chemical gradients from the start. These gradients were subsequently modified by migrating melts that drove further development of different types of metasomatic overprinting and variable oxidation at a range of length scales. This oxidation already apparent at ~?100 km depth could have locally destabilised any pre-existing diamond or graphite.
Abstract: Many Cenozoic basaltic rocks in Eastern Australia exhibit an age-progressive trend from north to south, leading to the suggestion that one or more mantle plumes passed beneath the Australian plate. Trace element patterns indicate that the source regions have been metasomatised by infiltrating melts, but the source rock assemblages have never been closely identified. Here, trace element analyses of olivine and whole rock geochemistry for several occurrences in New South Wales (Bingara-Inverell, Dubbo, Barrington and Ebor) are combined to characterize the mineralogy of the source and identify the nature of the melts that caused the metasomatic enrichment. According to Ni/Mg against Mn/Fe and Zn/Fe ratios in olivines, Zn/Fe and FC3MS (FeOT/CaO-3*MgO/SiO2) parameters in whole rocks, tholeiite, alkali basalt, and basanite rich in olivine xenocrysts from Dubbo were derived from pyroxenite-dominated mixed source, mixed pyroxenite+peridotite source, and peridotite-dominated source, respectively. Similarly, basalts from Ebor and Bingara/Inverell are suggested to originate from a mixed pyroxenite+peridotite source based on their high FC3MS values. In contrast, the source of basanite and picrobasalt from Barrington was peridotite with little pyroxenite. High Li and Zn in olivines, high P2O5/TiO2 and Zr/Hf at low Ti/Eu in whole rocks illustrate that the pyroxenite sources of basanites from Bingara/Inverell, Barrington and Dubbo resulted from variable degrees of carbonatitic metasomatism. Partial melting of peridotite metasomatised by carbonatite melts at around the spinel-garnet peridotite transition depth produced basalts and basanites from Dubbo, Barrington, Ebor, Bingara/Inverell and Buckland (Queensland). Carbonatitic metasomatism is widespread in the eastern Australian mantle lithosphere, occurring seaboard of a ledge between thick lithosphere beneath the Australian continent that stretches from Queensland, through New South Wales to Victoria.
Abstract: Aillikites are carbonate-rich ultramafic lamprophyres, and although they are volumetrically minor components of large igneous province (LIP), these rocks provide important clues to melting and meta-somatism in the deep mantle domain during the initial stages of LIPs. In this study, we investigate the Wajilitag “kimberlites” in the northwestern part of the Tarim LIP that we redefine as hypabyssal aillikites based on the following features: (1) micro-phenocrystic clinopyroxene and Ti-rich andradite garnet occurring in abundance in the carbonate-rich matrix; (2) Cr-spinel exhibiting typical Fe-Ti enrichment trend also known as titanomagnetite trend; and (3) olivine showing dominantly low Mg values (Fo < 90). To constrain the magma source and evolution, the major, minor, and trace element abundance in olivine grains from these rocks were analyzed using electron microprobe and laser ablation-inductively coupled plasma-mass spectrometry. Olivine in the aillikites occurs as two textural types: (1) groundmass olivines, as sub-rounded grains in matrix, and (2) macrocrysts, as euhedral-anhedral crystals in nodules. The groundmass olivines show varying Mg (Fo89-80) with high-Ni (1606-3418 ppm) and Mn (1424-2860 ppm) and low-Ca (571-896 ppm) contents. In contrast, the macrocrysts exhibit a restricted Fo range but a wide range in Ni and Mn. The former occurs as phenocrysts, whereas the latter are cognate cumulates that formed from earlier, evolved aillikite melt. The two olivine populations can be further divided into sub-groups, indicating a multi-stage crystallization history of the aillikite melt. The crystallization temperatures of groundmass olivines and macrocrysts in dunite nodules as computed from the spinel-olivine thermometers are 1005-1136 and 906-1041 °C, respectively. The coupled enrichment of Ca and Ti and lack of correlation between Ni and Sc and Co in the olivine grains suggest a carbonate-silicate metasomatized mantle source. Moreover, the high 100•Mn/Fe (average 1.67) at high Ni (up to 3418 ppm), overlapping with OIB olivine, and the 100•Ni/Mg (~1) of primitive Mg-Ni-rich groundmass olivines suggest a mixed source that involved phlogopite- and carbonate-rich metasomatic veins within mantle peridotite.
Contributions to Mineralogy and Petrology, Vol. 177, 2, 21p.pdf
Mantle
metasomatism
Abstract: Melting experiments on a carbonated pelite were performed at 5.5-15.5 GPa, 800-1875 °C using multi-anvil apparatuses to determine the melting phase relations and the P-T stability fields of various phases, which may shed some light on the source of silica-undersaturated magmas and the deep Earth carbon and water cycles. The subsolidus assemblages contain garnet, clinopyroxene, coesite/stishovite at all investigated pressures. Phengite, aragonite or magnesite, and topaz-OH occur below 9.5 GPa. Phase egg, K-hollandite, Ti-oxide, and CAS phase appear at 12-15.5 GPa. Phengite is stable up to 6 GPa and 800 °C, with the phengite-out boundary overlapping with the carbonate-out curve. Thus, the initial melt is carbonatitic and extremely potassium-rich, with K2O/Na2O weight-ratios larger than 40 at fluid-present conditions. The melting reaction phase egg?+?magnesite?+?aragonite?+?(clinopyroxene)?+?stishovite???melt?+?garnet?+?kyanite defines the solidus at 9.5 GPa, 1000-1100 °C. With increasing pressure, the composition of the near-solidus melts gradually evolves from potassium-rich to sodium-rich due to the formation of K-hollandite and the destabilization of clinopyroxene, and as a result of the clinopyroxene-out, the near-solidus melt has the lowest K2O/Na2O value and partitioning coefficient of sodium between clinopyroxene and melt (Dcpx/meltNa) at 15.5 GPa. In addition, phase egg remains stable up to 1400 °C at 15.5 GPa. Thus, phase egg is a good candidate as a deep-water carrier during subduction of pelitic sediments. This study concludes that low degree partial melting of carbonated pelite produces alkali-rich carbonatite melts evolving from potassium-rich (6-12 GPa) to sodium-rich (above 12 GPa) with increasing pressure, and if a slab stagnates at depth, and/or subduction slows down, the produced carbonatite melts will be more silicate-rich with increasing temperature. Moreover, the produced melts generally evolve from relatively silicate-rich to carbonatite-rich with increasing pressure. These alkali-rich carbonatite melts are compositionally similar to those in diamond inclusions, which provides strong evidence for the origin of deep-seated silica-undersaturated carbonatitic magma. Such magma is an ideal metasomatic agent that can give rise to mantle heterogeneity.
Africa, South Africa, Europe, Greenland, China, Russia, Siberia, Canada, South America, Brazil
subduction, metasomatism
Abstract: To investigate halogen heterogeneity in the subcontinental lithospheric mantle (SCLM), we measured the concentrations of Cl, Br, and I in kimberlites and their mantle xenoliths from South Africa, Greenland, China, Siberia, Canada, and Brazil. The samples can be classified into two groups based on halogen ratios: a high-I/Br group (South Africa, Greenland, Brazil, and Canada) and a low-I/Br group (China and Siberia). The halogen compositions were examined with the indices of crustal contamination using Sr and Nd isotopes and incompatible trace elements. The results indicate that the difference between the two groups was not due to different degrees of crustal contamination but from the contributions of different mantle sources. The low-I/Br group has a similar halogen composition to seawater-influenced materials such as fluids in altered oceanic basalts and eclogites and fluids associated with halite precipitation from seawater. We conclude that the halogens of the high-I/Br group are most likely derived from a SCLM source metasomatized by a fluid derived from subducted serpentinite, whereas those of the low-I/Br group are derived from a SCLM source metasomatized by a fluid derived from seawater-altered oceanic crust. The SCLM beneath Siberia and China could be an important reservoir of subducted, seawater-derived halogens, while such role of SCLM beneath South Africa, Greenland, Canada, and Brazil seems limited.
Abstract: The interaction of natural eclogite (Ecl) with synthetic hydrous carbonate melts with Na:K = 0:1 (KH2) and 1:1 (NKH2) was studied in multianvil experiments at 3-6 GPa and 850-1250 °C. The interaction with KH2 consumes garnet and clinopyroxene producing phlogopite and calcite-dolomite solid solution. Besides, the interaction yields a decrease in the jadeite component of clinopyroxene, evolving eclogite toward pyroxenite. This is consistent with a metasomatic alteration of eclogite xenoliths, manifested as Na-poor “spongy” clinopyroxene, replacing primary omphacite, and kelyphitic rims around garnet, containing phlogopite and carbonates. The interaction with NKH2 also produces phlogopite and carbonate, but the latter is more magnesian and represented by magnesite, above the solidus, and magnesite + dolomite below the solidus. The interaction with NKH2 increases the jadeite component in clinopyroxene and grossular component in garnet, evolving eclogite Group A to eclogite Group B. The studied systems have H2O/K2O = 2, like that in phlogopite, and therefore correspond to carbonated phlogopite eclogite under fluid-absent conditions. Based on the obtained results its solidus is situated near 1050 °C at 3 GPa and decreases to 950 °C at 6 GPa. Thus, hydrous K- and Na-K-carbonatite melts can coexist with eclogite in SCLM at depths exceeding 120-170 km, and solidify as temperature decreases below 950-1050 °C according to the following solidus reactions: pyrope + diopside + melt ? phlogopite + dolomite, below 6 GPa, and pyrope + diopside + melt ? phlogopite + magnesite + grossular, at 6 GPa. The melting reaction, involving phlogopite and dolomite, suggests the partial melting at the peak of ultrahigh-pressure metamorphism (UHPM) during continent-continent plate collision. The prograde P-T path of UHPM crosses the solidus of clinopyroxene + garnet + phlogopite + dolomite assemblage at 4.7-5.2 GPa and 970-990 °C and yields the formation of hydrous K-carbonatite melt-fluid in situ. This melt could be responsible for the formation of K-bearing clinopyroxenes and microdiamonds in the UHPM marbles in the Kokchetav massif, Kazakhstan. The retrograde P-T path intersects the solidus that has a negative Clapeyron slope in the diamond stability field. Thus, the hydrous K-carbonatite melt should disappear soon after the peak of metamorphism reacting with garnet to produce Ca-Mg carbonates and phlogopite.
Abstract: Metasomatic processes modify the composition of the subcratonic lithospheric mantle and can either form or destroy diamonds. The composition of these metasomatic agents is uncertain and has been mostly deduced from chemical zonation and overprints recorded by associated mantle silicates. Diamonds experience partial dissolution (resorption) during their residence in the mantle due to mantle metasomatism and later during their ascent in kimberlite magma. Diamonds, enclosed inside mantle xenoliths during the whole duration of ascent in kimberlite magma, can preserve their pre-kimberlite surface features, which record the last diamond-destructive metasomatic event to have occurred in the mantle. The geometry of diamond dissolution features acquired during mantle storage can provide information about diamond-destructive metasomatic events in the mantle. Diamond samples recovered from inside mantle xenoliths are extremely rare and mostly limited to eclogitic lithology, which suggests that variable resistance of different mantle lithologies to disintegration in kimberlite magma may affect representativity of these sample. Here we use whole diamond populations from exploration parcels and apply our earlier developed set of criteria to distinguish between kimberlitic and pre-kimberlitic surface features on diamonds. The study used diamonds (<1 to 4.5 mm size) from eight kimberlites in three localities: Orapa cluster, Botswana (BK1, AK15, and AK1 kimberlites), Ekati Mine, Northwest Territories, Canada (Grizzly, Leslie, Koala, and Misery kimberlites), and Snap Lake kimberlite dyke, Northwest Territories, Canada. The host kimberlites cover seven different volcaniclastic and coherent kimberlite lithologies, and our previous studies demonstrated a correlation between the style of kimberlitic resorption on diamonds and the host kimberlite lithology for these samples. From the total of 3256 studied diamonds, we identified 534 diamonds with pre-kimberlite surface textures. These pre-kimberlite surface textures display six distinct types, which are present in all the studied diamond parcels regardless of their geographic locality and host kimberlite lithology. The relative proportions of these types depend on the geographic locality showing linkage to a specific mantle source. We examined the relationship between the surface features on diamonds, their growth patterns revealed in cathodoluminescence (CL) images, the content and aggregation of nitrogen defects using Fourier transform infrared spectroscopy (FTIR), and nitrogen content in specific growth zones of diamonds obtained using secondary ion mass spectrometry (SIMS) for 82 Ekati diamonds. Our data show that growth step-faces develop on diamonds with complex multi-crystal cores, whereas flat-faced octahedra with simple oscillatory-zoned growth patterns derive from single growth events. Initial stages of dissolution affecting only outer growth zones develop simple serrate laminae on diamonds, while more extensive dissolution exposes more complex growth zones developing various shapes of laminae and etch features (trigons and irregular asperities). The effect of internal growth patterns on dissolution features is more profound during pre-kimberlitic than kimberlite-related resorption likely due to the greater role of defects in diamond dissolution at mantle conditions. Comparison with the results of diamond dissolution experiments shows that metasomatism by C-O-H fluid is not destructive to diamond, while carbonate-silicate melt-driven metasomatism causes diamond dissolution. Continuous change in the silicate content of silicate?carbonate melts and temperature variations within 200 °C can explain all pre-kimberlite dissolution features observed in this study. Similar pre-kimberlite dissolution features on diamonds from both the Zimbabwe and Slave cratons suggests that these metasomatic processes are widespread and affected the mantle below the eight studied kimberlites.
Earth and Planetary Science Letters, Vol. 581, 11p.
Mantle
metasomatism
Abstract: It is generally accepted that carbonatite metasomatism in the subcontinental lithospheric mantle (SCLM) inevitably causes wehrlitization of the primary lherzolite substrate. However, the K-rich carbonatite inclusions in kimberlitic diamonds containing orthopyroxene indicate that this is not always the case. In the present study, we equilibrated natural garnet lherzolite with carbonate melts containing 33-38 wt% K2O with various Ca# = 10, 20, 30, and 40 at 6 GPa and 1200-1500 °C, where Ca# = 100?Ca/(Ca+Mg+Fe). The original ratio of peridotite to carbonate was 58 to 42 by weight. In the studied temperature range, the melt retains essentially carbonate composition with silica content increasing from 1 to 11-12 wt%. The melt with Ca# 10 alters lherzolite to harzburgite, replacing clinopyroxene by orthopyroxene and decreasing CaO content in garnet below 4 wt%. The melts with Ca# 20-30 also consume clinopyroxene; although CaO content in garnet remains in the range of lherzolitic compositions. The melt with Ca# 40 yields wehrlitization, consuming orthopyroxene, increasing clinopyroxene fraction, and increasing CaO content in garnet above 6 wt%. After the interaction, the Ca# of the melt changes as follows 10 ? 16-28, 20 ? 20-33, 30 ? 27-34, and 40 ? 30-34. The olivine + orthopyroxene + clinopyroxene + garnet assemblage was found in equilibrium with carbonatite melt with Ca# 34 at 1200 °C and Ca# 30 at 1400 °C. Thus, K-rich (26-35 wt% K2O) carbonatite melts with Ca# = 30-34 can appear in equilibrium with garnet lherzolite, while the melts with Ca# < 30 and > 34 can be in equilibrium with harzburgite and wehrlite, respectively, at 6 GPa and 1200-1400 °C. Considering that Ca-Mg-Fe carbonates do not melt at the geothermal conditions of the SCLM, while sodic, dolomitic melt causes wehrlitization, high-Mg (Ca# < 35) K-rich dolomitic melt is the only possible carbonatite fluids that are thermodynamically stable in equilibrium with garnet harzburgites and lherzolites in the SCLM at a depth of about 200 km. At higher temperatures corresponding to the underlying asthenosphere, the high alkalinity ceases to be a requirement for the stability of the carbonate melt. Nevertheless, the regularities established here for the K-rich melts remain valid for less alkaline (4-15 wt% Na2O+K2O) primary kimberlite (i.e., mantle carbonatite) melts in the sublithospheric mantle.
Abstract: A plausible origin of the seismically observed mid-lithospheric discontinuity (MLD) in the subcontinental lithosphere is mantle metasomatism. The metasomatized mantle is likely to stabilize hydrous phases such as amphiboles. The existing electrical conductivity data on amphiboles vary significantly. The electrical conductivity of hornblendite is much higher than that of tremolite. Thus, if hornblendite truly represents the amphibole varieties in MLD regions, then it is likely that amphibole will cause high electrical conductivity anomalies at MLD depths. However, this is inconsistent with the magnetotelluric observations across MLD depths. Hence, to better understand this discrepancy in electrical conductivity data of amphiboles and to evaluate whether MLD could be caused by metasomatism, we determined the electrical conductivity of a natural metasomatized rock sample. The metasomatized rock sample consists of ~87% diopside pyroxene, ~9% sodium-bearing tremolite amphibole, and ~3% albite feldspar. We collected the electrical conductivity data at ~3.0 GPa, i.e., the depth relevant to MLD. We also spanned a temperature range between 400 to 1000 K. We found that the electrical conductivity of this metasomatized rock sample increases with temperature. The temperature dependence of the electrical conductivity exhibits two distinct regimes. At low temperatures <700 K, the electrical conductivity is dominated by the conduction in the solid state. At temperatures >775 K, the conductivity increases, and it is likely to be dominated by the conduction of aqueous fluids due to partial dehydration. The main distinction between the current study and the prior studies on the electrical conductivity of amphiboles or amphibole-bearing rocks is the sodium (Na) content in amphiboles of the assemblage. Moreover, it is likely that the higher Na content in amphiboles leads to higher electrical conductivity. Pargasite and edenite amphiboles are the most common amphibole varieties in the metasomatized mantle, and our study on Na-bearing tremolite is the closest analog of these amphiboles. Comparison of the electrical conductivity results with the magnetotelluric observations constrains the amphibole abundance at MLD depths to <1.5%. Such a low-modal proportion of amphiboles could only reduce the seismic shear wave velocity by 0.4-0.5%, which is significantly lower than the observed velocity reduction of 2-6%. Thus, it might be challenging to explain both seismic and magnetotelluric observations at MLD simultaneously.
Abstract: The morphology of resorbed diamond crystals is a valuable source of information on the composition and ascent rate of kimberlite magmas, as well as on possible redox conditions in protolith. Previously, diamond resorption was thoroughly investigated at P-T-fO2 parameters of the kimberlite magma ascent. In this study, we investigated diamond resorption using unaltered group I kimberlite and model carbonatite at P-T-fO2 parameters that are typical of the peridotite source of kimberlite magmas in the subcontinental lithospheric mantle. An analysis of previous studies made it possible to determine the rate of diamond octahedron transformation into a spherical tetrahexahedron depending on the composition of the carbonate-silicate melt. It was shown that the rate of diamond resorption at 6.3 GPa increases in all the investigated systems as fO2 and temperature rise. There is a steady decrease in the diamond resorption rate as pressure increases from 1 GPa to 6.3 GPa. The morphology comparison of the experimentally produced samples with natural diamonds is indicative of the significant contribution of metasomatic alteration of protolith by the oxidized agent and at the initial stages of kimberlite magma ascent to the resorption of natural diamonds.
