Metasomatism in mantle xenoliths from Gees,West Eifel,Germany: evidence for the genesis of calc-alkaline glasses and metasomatic Ca-enrichment

 We have investigated new samples from the Gees mantle xenolith suite (West Eifel), for which metasomatism by carbonatite melt has been suggested. The major metasomatic change is transformation of harzburgites into phlogopite-rich wehrlites. Silicate glasses are associated with all stages of transformation, and can be resolved into two major groups: a strongly undersaturated alkaline basanite similar to the host magma which infiltrated the xenoliths during ascent, and Si-Al-enriched, variably alkaline glass present exclusively within the xenoliths. Si-Al-rich glasses (up to 72 wt% SiO₂ when associated with orthopyroxene (Opx) are usually interpreted in mantle xenoliths as products of decompressional breakdown of hydrous phases like amphibole. In the Gees suite, however, amphibole is not present, nor can the glass be related to phlogopite breakdown. The Si-Al-rich glass is compositionally similar to glasses occurring in many other xenolith suites including those related to carbonatite metasomatism. Petrographically the silicate glass is intimately associated with the metasomatic reactions in Gees, mainly conversion of harzburgite orthopyroxene to olivine + clinopyroxene. Both phases crystallize as microlites from the glass. The chemical composition of the Si-Al-enriched glass shows that it cannot be derived from decompressional melting of the Gees xenoliths, but must have been present prior to their entrainment in the host magma. Simple mass-balance calculations, based on modal analyses, yield a possible composition of the melt prior to ascent of the xenoliths, during which glass + microlite patches were modified by dissolution of olivine, orthopyroxene and spinel. This parental melt is a calc-alkaline andesite (55–60 wt% SiO₂), characterized by high Al₂O₃ (ca. 18 wt%). The obtained composition is very similar to high-alumina, calc-alkaline melts that should form by AFC-type reactions between basalt and harzburgite wall rock according to the model of Kelemen (1990). Thus, we suggest that the Si-Al-enriched glasses of Gees, and possibly of other suites as well, are remnants of upper mantle hybrid melts, and that the Gees suite was metasomatized by silicate and not carbonatite melts. High-Mg, high-Ca composition of metasomatic olivine and clinopyroxene in mantle xenoliths have been explained by carbonatite metasomatism. As these features are also present in the Gees suite, we have calculated the equilibrium Ca contents of olivine and clinopyroxene using the QUI1F thermodynamical model, to show that they are a simple function of silica activity. High-Ca compositions are attained at low a SiO₂ and can thus be produced during metasomatism by any melt that is Opx-undersaturated, irrespective of whether it is a carbonatite or a silicate melt. Such low a SiO₂ is recorded by the microlites in the Gees Si-Al-rich glasses. Our results imply that xenolith suites cannot confidently be related to carbonatite metasomatism if the significance of silicate glasses, when present, is not investigated. Received: 2 March 1995 / Accepted: 12 June 1995     

Calcio-carbonatite melts and metasomatism in the mantle beneath Mt. Vulture (Southern Italy)

At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5–150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2–20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO₂ bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8–5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr–Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate–carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation.     

Melilitite at Fort Portal, Uganda: Another dimension to the carbonate volcanism

Because the calciocarbonatite lavas at Fort Portal were the first ever described they have received great attention, with the pyroclastic rocks being relatively neglected. Volumetrically the lavas are minute, and the major deposit is a 2 m thick blanket of “flaggy” tuffs, long regarded as carbonatite tuff with crustal debris. Fresh examination shows these tuffs to contain melilitite previously unreported from Fort Portal. The rock is a mix of crust and mantle debris with near-isotropic lapilli, set in a matrix composed predominantly of carbonate. The low birefringence parts of the lapilli are devitrified melilitite glass. Compound lapilli are abundant, containing aggregates of globules, together with xenolithic/crystic fragments. In some, there are concentric zones of more carbonate rich material alternating with melilitite: tangential phlogopite flakes mark the outer zones, in marked contrast to their planar distribution through the enclosing rock matrix. Euhedral titano-magnetite (10–15%) is the most obvious cognate mineral. Devitrified melilitite contains abundant small crystals and microlites of melilite, apatite, magnetite, and carbonates, mostly formed during disequilibrium quench crystallisation. Because of this, and widespread fine grained accidental debris, a precise bulk melt composition is hard to obtain, but the average is close to melilitite with high P₂O₅. Mantle debris is largely disaggregated magnetite–phlogopite clinopyroxenite, which could give a bulk composition close to the melt. Low Mg and high Mg calcite are present in the melilitite lapilli, and in the enclosing carbonate rich matrix. Previously, high Mg calcite was reported only as cement in lapilli tuffs, while the lavas contain only low Mg calcite in the assemblage calcite–periclase (consistent with low pressure carbonate melt crystallisation). Carbonatite–melilitite magma left the mantle carrying restite debris. Melt fragmentation took place in the deep crust, with rapidly quenched droplets enclosing crust debris. Chemical covariations within the flaggy tuffs are uniform and explicable as carbonatite–melilitite plus a thoroughly mixed combination of crust and mantle debris. New links are indicated with the alkaline ultramafic-carbonate volcanism to the south, in Uganda, and parallels with that in Italy.     

Liquid immiscibility between silicate,carbonate and sulfide melts in melt inclusions hosted in co-precipitated minerals from Kerimasi volcano (Tanzania): evolution of carbonated nephelinitic magma

The evolution of a carbonated nephelinitic magma can be followed by the study of a statistically significant number of melt inclusions, entrapped in co-precipitated perovskite, nepheline and magnetite in a clinopyroxene- and nepheline-rich rock (afrikandite) from Kerimasi volcano (Tanzania). Temperatures are estimated to be 1,100°C for the early stage of the melt evolution of the magma, which formed the rock. During evolution, the magma became enriched in CaO, depleted in SiO₂ and Al₂O₃, resulting in immiscibility at ~1,050°C and crustal pressures (0.5–1 GPa) with the formation of three fluid-saturated melts: an alkali- and MgO-bearing, CaO- and FeO-rich silicate melt; an alkali- and F-bearing, CaO- and P₂O₅-rich carbonate melt; and a Cu–Fe sulfide melt. The sulfide and the carbonate melt could be physically separated from their silicate parent and form a Cu–Fe–S ore and a carbonatite rock. The separated carbonate melt could initially crystallize calciocarbonatite and ultimately become alkali rich in composition and similar to natrocarbonatite, demonstrating an evolution from nephelinite to natrocarbonatite through Ca-rich carbonatite magma. The distribution of major elements between perovskite-hosted coexisting immiscible silicate and carbonate melts shows strong partitioning of Ca, P and F relative to Fe_T, Si, Al, Mn, Ti and Mg in the carbonate melt, suggesting that immiscibility occurred at crustal pressures and plays a significant role in explaining the dominance of calciocarbonatites (sövites) relative to dolomitic or sideritic carbonatites. Our data suggest that Cu–Fe–S compositions are characteristic of immiscible sulfide melts originating from the parental silicate melts of alkaline silicate–carbonatite complexes.     

Carbonatite melt inclusions in coexisting magnetite,apatite and monticellite in Kerimasi calciocarbonatite,Tanzania: melt evolution and petrogenesis

Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na–K–Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite–monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900–1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C–O–H–S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na₂O + K₂O) that is at least 5–10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.     

Experiments on melt–rock reaction in the shallow mantle wedge

This experimental study simulates the interaction of hotter, deeper hydrous mantle melts with shallower, cooler depleted mantle, a process that is expected to occur in the upper part of the mantle wedge. Hydrous reaction experiments (~6 wt% H₂O in the melt) were conducted on three different ratios of a 1.6 GPa mantle melt and an overlying 1.2 GPa harzburgite from 1060 to 1260 °C. Reaction coefficients were calculated for each experiment to determine the effect of temperature and starting bulk composition on final melt compositions and crystallizing assemblages. The experiments used to construct the melt–wall rock model closely approached equilibrium and experienced <5% Fe loss or gain. Experiments that experienced higher extents of Fe loss were used to critically evaluate the practice of “correcting” for Fe loss by adding iron. At low ratios of melt/mantle (20:80 and 5:95), the crystallizing assemblages are dunites, harzburgites, and lherzolites (as a function of temperature). When the ratio of deeper melt to overlying mantle is 70:30, the crystallizing assemblage is a wehrlite. This shows that wehrlites, which are observed in ophiolites and mantle xenoliths, can be formed by large amounts of deeper melt fluxing though the mantle wedge during ascent. In all cases, orthopyroxene dissolves in the melt, and olivine crystallizes along with pyroxenes and spinel. The amount of reaction between deeper melts and overlying mantle, simulated here by the three starting compositions, imposes a strong influence on final melt compositions, particularly in terms of depletion. At the lowest melt/mantle ratios, the resulting melt is an extremely depleted Al-poor, high-Si andesite. As the fraction of melt to mantle increases, final melts resemble primitive basaltic andesites found in arcs globally. An important element ratio in mantle lherzolite composition, the Ca/Al ratio, can be significantly elevated through shallow mantle melt–wall rock reaction. Wall rock temperature is a key variable; over a span of <80 °C, reaction with deeper melt creates the entire range of mantle lithologies from a depleted dunite to a harzburgite to a refertilized lherzolite. Together, the experimental phase equilibria, melt compositions, and reaction coefficients provide a framework for understanding how melt–wall rock reaction occurs in the natural system during melt ascent in the mantle wedge.     

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle,and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg₂SiO₄ (olivine)?+?6CaCO₃ (liquid)?=?Ca₃MgSi₂O₈ (merwinite)?+?3CaMg(CO₃)₂ (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.     

Carbonate metasomatism of the oceanic mantle beneath Fernando de Noronha Island, Brazil

Evidence is presented for a carbonate-immiscibility phenomena in the upper mantle based on data from a set of strongly metasomatized xenoliths in a basanitic lava flow from Fernando de Noronha Island (southwest Atlantic). A petrological and geochemical study of lherzolitic and harzburgitic xenoliths reveals that the oceanic mantle of this region has been affected by very strong carbonate metasomatism. The metasomatism led to wehrlitization of the primary mantle mineral assemblage (ol, opx, sp). The wehrlitization was the result of interaction between a possibly ephemeral sodic dolomitic melt or fluid with the mantle peridotite according to the following reactions, which include sodic components: 4MgSiO₃+CaMg(CO₃)₂=2Mg₂SiO₄+CaMgSi₂O₆+2CO2 3CaMg(CO₃)₂+CaMgSi₂O₆=4CaCO₃+2Mg₂SiO₄+2CO₂ The olivine has abundant micro-inclusions consisting of Na-Al-Si-rich glass, Fe, Ni and Cu-monosulfide, Ca-rich carbonate and dense CO₂. The interrelationships between the glass, sulfide and carbonate inclusions permit speculation that silicate, sulfide, and Ca-rich carbonatite melts were in equilibrium with each other and originated from partial melting of metasomatized and wehrlitized peridotite underneath Fernando de Noronha Island. These results support a two-stage model of Ca-rich carbonatite formation: first stage - metasomatic wehrlitization and carbonatization of mantle rocks; second stage - partial melting of the carbonate-bearing wehrlitic rock resulting in the formation of immiscible silicate, sodic carbonate and sulfide liquids and the ultimately generation of calciocarbonatites.     

The brevity of carbonatite sources in the mantle: evidence from Hf isotopes

Hf, Zr and Ti in carbonatites primarily reside in their non-carbonate fraction while the carbonate fraction dominates the Nd and Sr elemental budget of the whole rock. A detailed investigation of the Hf, Nd and Sr isotopic compositions shows frequent isotopic disequilibrium between the carbonate and non-carbonate fractions. We suggest that the trace element and isotopic composition of the carbonate fraction better represents that of the carbonatite magma, which in turn better reflects the composition of the carbonatitic source. Experimental partitioning data between carbonatite melt and peridotitic mineralogy suggest that the Lu/Hf ratio of the carbonatite source will be equal to or greater than the Lu/Hf ratio of the carbonatite. This, combined with the Hf isotope systematics of carbonatites, suggests that, if carbonatites are primary mantle melts, then their sources must be short-lived features in the mantle (maximum age of 10–30 Ma), otherwise they would develop extremely radiogenic Hf compositions. Alternatively, if carbonatites are products of extreme crystal fractionation or liquid immiscibility then the lack of radiogenic initial Hf isotope compositions also suggests that their sources do not have long-lived Hf depletions. We present a model in which the carbonatite source is created in the sublithospheric mantle by the crystallization of earlier carbonatitic melts from a mantle plume. This new source melts shortly after its formation by the excess heat provided by the approaching hotter center of the plume and/or the subsequent ascending silicate melts. This model explains the HIMU-EMI isotope characteristics of the East African carbonatites, their high LREE/HREE ratios as well as the rarity of carbonatites in the oceanic lithosphere.     

Reactions of iron with calcium carbonate at 6 GPa and 1273–1873 K: implications for carbonate reduction in the deep mantle

Experimental data on Fe-CaCO₃ interaction at 6 GPa and 1273–1873 K are presented. The system models the hypothetical redox interaction in subducting slabs at the contact with the reduced mantle and a putative process at the core-mantle boundary. The reaction is accompanied by carbonatite melt formation. It also produces Fe3C and calcium wustite, which form solid or liquid phases depending on experimental conditions. In iron-containing systems at 6 GPa, calcium carbonate melts in the range 1473–1573 K, which is consistent with aragonite disappearance from complex carbonate systems. The composition of calcium carbonate liquid is not influenced by metallic Fe. It corresponds to nearly pure CaCO₃. Along the mantle adiabat or at slightly higher temperatures, nearly pure CaCO₃ coexists with metallic iron or calcium wustite. This hypothesis explains the coexistence of metallic iron and carbonate inclusions in lithospheric and superdeep diamonds.     

Entrained Macrocryst Minerals as a Key to the Source Region of Olivine Nephelinites: Humberg, Kaiserstuhl, Germany

Olivine nephelinites commonly contain macrocrysts of olivineand clinopyroxene. Some of these macrocrysts might representfragments of the source region of the host magma transportedto the Earth's surface. If this hypothesis is correct thesefragments can be used to characterize the composition of thesource region and to put constraints on the magma generationprocess. In this study, we investigate the origin of macrocrystsand mineral aggregates from an olivine nephelinite from theKaiserstuhl, Germany. We focus on clinopyroxenes (Cpx), whichcan be divided into three groups. Cpx I is relict Cpx from aggregateswith deformed olivine that is depleted in Ca and characterizedby strong light rare earth element (LREE) fractionation, lowTi/Eu and negative high field strength element (HFSE) anomalies.Its geochemical signature is consistent with formation by carbonatitemetasomatism and with equilibration in the presence of orthopyroxene.Cpx II is Ca-rich Cpx, forming both aggregates with deformedolivine and individual macrocrysts. The LREE, as for Cpx I,are strongly fractionated. Convex REE patterns may be present.The depletion in HFSE is less pronounced. Cpx III is oscillatoryzoned Cpx phenocrysts showing enrichment in Ca, convex REE patternsand no HFSE anomalies. The transition in the trace element abundancesbetween the Cpx of the three groups is gradual. However, CpxI and II did not crystallize from the host magma, as demonstratedby the presence of kink-bands and undulose extinction in theassociated olivine and by the composition of alkali aluminosilicateglass inclusions in Cpx II. Based on the Cpx relationships,we interpret the studied suite of macrocrysts and mineral aggregatesas a mixture of disintegrated fragments of the source regionof the host olivine nephelinite. The process of melt generationwas multi-stage. A primary carbonatite melt ascending from deeperlevels in the mantle, probably from the dolomite–garnetperidotite stability field, reacted with mantle peridotite alongthe solidus ledge in the system lherzolite–CO₂ (< 20–22kbar) and started to crystallize carbonate minerals. Becauseof its low solidus temperature, the resulting carbonate-wehrliteassemblage melted incongruently with the formation of additionalclinopyroxene. The carbonatite melt evolved during crystallizationof carbonate minerals and concomitant incongruent melting ofthe carbonate-wehrlite, accompanied by the segregation of incipientalkali aluminosilicate melts. As a consequence of fast reactionrates in the presence of a carbonatite melt, this process probablytook place under disequilibrium conditions. Further meltingof the assemblage wehrlite + alkali aluminosilicate melt ledto the generation of the olivine nephelinite magma. It entrainedfragments of the wehrlite and brought them to the surface. KEY WORDS: carbonatite; metasomatism; source region; clinopyroxene macrocrysts; wehrlite; olivine nephelinite; Kaiserstuhl     

A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

Magmatic graphite in dolomite carbonatite at Pogranichnoe,North Transbaikalia,Russia

A recently discovered dolomite carbonatite at Pogranichnoe, North Transbaikalia, Russia, dated at 624 ± 3 Ma, contains xenoliths of calcite-bearing dolomite carbonatite with graphite spherulites. Apatite and aegirine are the other rock-forming minerals. Chemically the carbonatites are ferrocarbonatite and ferruginous calciocarbonatite. The graphite forms <1 mm up to 1.5 mm diameter spherulites, with Raman spectra similar to published spectra of microcrystalline, amorphous carbon and disordered graphite, with G and D bands at 1,580−1,600 cm⁻¹ and at around 1,350 cm⁻¹. Alteration has formed Fe-bearing calcite to Ca-bearing siderite compositions not previously reported in nature around the graphite along cracks and fractures. Mineral and stable isotope geothermometers and melt inclusion measurements for the carbonatite all give temperatures of 700°–900°. It is concluded that the graphite precipitated from the ferrocarbonatite magma. There are three candidates to control the precipitation of graphite (a) a redox reaction with Fe^II in the magma, (b) potential presence of organics in the magma (c) seeding of, or dissolution in, the magma of graphite/diamond from the mantle, and further work is required to identify the most important mechanism(s). Graphite in carbonatite is rare, with no substantial published accounts since the 1960s but graphite at other localities seems also to have precipitated from carbonatite magma. The precipitation of reduced carbon from carbonatite provides further evidence that diamond formation in carbonate melts at high mantle pressures is feasible.     

Stability of phlogopite in ultrapotassic kimberlite-like systems at 5.5–7.5 GPa

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.     

Compositions of magmas,formation conditions,and genesis of carbonate-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex,eastern Sayan

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas responsible for the calcite-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex (eastern Sayan, Russia). Primary melt and coexisting crystalline inclusions were found in the nepheline and calcite of these rocks. Diopside, amphibole (?), perovskite, potassium feldspar, apatite, calcite, pyrrhotite, and titanomagnetite were identified among the crystalline inclusions. The melt inclusions in nepheline from the ijolites are completely crystallized. The crystalline daughter phases of these inclusions are diopside, phlogopite, apatite, calcite, magnetite, and cuspidine. During thermometric experiments with melt inclusions in nepheline, the complete homogenization of the inclusions was attained through the dissolution of a gas bubble at temperatures of 1120–1130°C. The chemical analysis of glasses from the homogenized melt inclusions in nepheline of the ijolites revealed significant variations in the content of components: from 36 to 48 wt % SiO₂, from 9 to 21 wt % Al₂O₃, from 8 to 25 wt % CaO, and from 0.6 to 7 wt % MgO. All the melts show very high contents of alkalis, especially sodium. According to the results of ion microprobe analysis, the average content of water in the melts is no higher than a few tenths of a percent. The most salient feature of the melt inclusions is the extremely high content of Nb and Zr. The glasses of melt inclusions are also enriched in Ta, Th, and light rare earth elements but depleted in Ti and Hf. Primary melt inclusions in calcite from the carbonatites contain a colorless glass and daughter phlogopite, garnet, and diopside. The silicate glass from the melt inclusions in calcite of the carbonatite is chemically similar to the glasses of homogenized melt inclusions in nepheline from the ijolites. An important feature of melt inclusions in calcite of the carbonatites is the presence in the glass of carbonate globules corresponding to calcite in composition. The investigation of melt inclusions in minerals of the ijolites and carbonatites and the analysis of the alkaline and ore-bearing rocks of the Belaya Zima Massif provided evidence for the contribution of crystallization differentiation and silicate-carbonate liquid immiscibility to the formation of these rocks. Using the obtained trace-element compositions of glasses of homogenized melt inclusions and various alkaline rocks and carbonatites, we determined to a first approximation the compositions of mantle sources responsible for the formation of the rock association of the Belaya Zima alkaline-carbonatite complex. The alkaline rocks and carbonatites were derived from the depleted mantle affected by extensive metasomatism. It is supposed that carbonate melts enriched in sodium and calcium were the main agents of mantle metasomatism.     

Genesis of melilitolite from Colle Fabbri: inferences from melt inclusions

Melilite and wollastonite from the Colle Fabbri stock contain silicate melt and silicate-carbonate inclusions. The homogenization temperatures of silicate inclusions are within the magmatic temperature range of mantle ultrabasic melts: about 1,320?±?15 °С. Their composition is melilititic and evolves to the composition of leucite tephrite and phonolite. The composition of silicate-carbonate inclusions are high SiO₂, Ca-rich, enriched in alkalies and are similar to that of inclusions of carbonatite melts in the minerals of melilitolites of other intrusive ultramafic complexes. They are also similar to the compositions of metasomatized travertine covering the melilitolite stock. The presence of primary silicate and silicate-carbonate inclusions evidences that the melilitite magma from which melilitolites of Colle Fabbri crystallized was associated with carbonatite liquid. This liquid was highly fluidized, mobile and aggressive. Actively interacting with overlying travertine, the liquid enriched them with alkalies, aluminosilicates and incompatible elements, which resulted in the equalization of their compositions. Heterogeneous compositional dominions were formed at the contact between melilitolite and wall pelites. In the minerals of these contact facies high-Si melt inclusions of varying composition have been observed. Their occurrence is related to the local assimilation by the high-temperature melilitite magma of pelitic country rocks. The content of incompatible elements in melilitite melts and melilitolites is higher than the mantle norm and they have peculiar indicator ratios, spectra, Eu/Eu^* ratio, which suggest a peculiar mantle source.     

Magmatism and fenitization in the Cretaceous potassium-alkaline-carbonatitic complex of Ipanema S?o Paulo State, Brazil

The Ipanema alkaline-carbonatitic complex is part of the Meso-Cenozoic alkaline magmatism located within the southeastern part of the Brazilian Platform. Drill-core and field sampling have indicated the occurrence of glimmerites, with subordinate shonkinites (mela-syenites), clinopyroxene-bearing glimmerites, diorites and syenites. The glimmerites are cross-cut by lamprophyric dykes and calciocarbonatites. Fenitization has deeply affected the country rocks, originating dioritic and syenitic rocks. The Ipanema rocks show a distinct potassic affinity. The initial Sr-Nd- isotopic composition of the Ipanema rocks (⁸⁷Sr/⁸⁶Sr?=?0.70661–0.70754 and ¹⁴³Nd/¹⁴⁴Nd?=?0.51169–0.51181) is similar to that of tholeiitic and potassium-rich-alkaline rocks of the Eastern Paraguay. Stable isotope data for the Ipanema calciocarbonatite suggest interaction with fluids at temperatures typical of hydrothermal stages, as hypothesized for other carbonatite complexes from southeastern Brazil. The chemical differences between the lamprophyre, glimmerites, carbonatites, apatitites and magnetitites, and the absence of marked REE enrichment in the evolved lithologies, all indicate that fractional crystallization and accumulus of liquidus phases in a magma reservoir, likely coupled with liquid immiscibility processes, may have played an important role in the genesis of the Ipanema rocks.     

Carbonate-rich melt infiltration in peridotite xenoliths from the Eurasian–North American modern plate boundary (Chersky Range,Yakutia)

A suite of mainly spinel peridotite and subordinate pyroxenite xenoliths and megacrysts were studied in detail, enabling us to characterize upper mantle conditions and processes beneath the modern North American–Eurasian continental plate boundary. The samples were collected from 37-Ma-old basanites cropping out in the Main Collision Belt of the Chersky Range, Yakutia Republic (Russian Far East). The spinel lherzolites reflect a mantle sequence, equilibrated at temperatures of 890–1,025 °C at pressures of 1.1–2 GPa, with melt extraction estimated to be around 2–6 %. The spinel harzburgites are characterized by lower P–T equilibration conditions and estimated melt extraction up to 12 %. Minor cryptic metasomatic processes are recorded in the clinopyroxene trace elements, revealing that percolating hydrous fluid-rich melts and basaltic melts affected the peridotites. One of the lherzolites preserves a unique melt droplet with primary dolomite in perfect phase contact with Na-rich aluminosilicate glass and sodalite. On the basis of the well-constrained P–T frame of the xenolith suite, as well as the rigorously documented melt extraction and metasomatic history of this upper mantle section, we discuss how a carbonated silicate melt infiltrated the lherzolite at depth and differentiated into an immiscible carbonate and silicate liquid shortly before the xenolith was transported to the surface by the host basalt. Decreasing temperatures triggered crystallization of primary dolomite from the carbonate melt fraction and sodalite as well as quenched glass from the Na-rich aluminosilicate melt fraction. Rapid entrainment and transport to the Earth’s surface prevented decarbonatization processes as well as reaction phenomena with the host lherzolite, preserving this exceptional snapshot of upper mantle carbonatization and liquid immiscibility.     

Generation and differentiation of group II kimberlites: constraints from a high-pressure experimental study to 10 GPa

Experiments have been performed in the multicomponent (natural) bulk system to constrain the conditions of generation and differentiation of a K-rich group II kimberlite (now also referred to as orangeite). The group II composition examined was saturated in olivine, orthopyroxene, and garnet at near liquidus conditions in the pressure range 4 to 10 GPa. In the range 2 to 3 GPa, the liquidus phase was olivine only. The potassic nature of the melts in the bulk compositions studied was ensured by the absence of any K-bearing phase in the residual assemblage at P > 4 GPa. Phlogopite is destabilized toward higher pressures by a carbonation reaction of the type phlogopite + CO₂ = enstatite + garnet + K₂CO₃ (liquid) + H₂O leading to alkalic, carbonatitic liquids coexisting with a garnet-peridotite (harzburgite or lherzolite) residue over a wide pressure-temperature space at pressures in excess of 4 GPa. Evidently, CO₂-bearing systems do not favor the stability of phlogopite and/or K-richterite amphibole at pressures in excess of 4 to 5 GPa, and it is suggested that the carbonate-bearing and potassic character of any mantle melt originating from this depth is most likely the product of a two-stage process: either a carbonate-bearing protolith is invaded by a potassic melt or fluid (probably supercritical), or a potassic protolith (after metasomatism) has been invaded by a carbonatite melt.     

Genetic link between saline and carbonatitic mantle fluids: The system NaCl-CaCO3-MgCO3 ± H2O ± Fe0 at 6 GPa

Melt inclusions in kimberlitic minerals and diamonds indicate that chlorides are important constituents of mantle carbonatite melts. Besides, alkaline chlorides are important constituents of saline high-density fluids (HDFs) found in diamonds from kimberlites and placers around the world. Continuous compositional variations suggest that saline and carbonatitic HDFs could be genetically linked. However, the essence of this link remains unclear owing to the lack of data on phase relations in the chloride-carbonate systems under pressure. Here we studied subsolidus and melting phase relations in the system NaCl–CaCO₃–MgCO₃ at 6 GPa and 1000–1600 °C using a Kawai-type multianvil press. We found that at 1000 °C, subsolidus assemblage consists of halite, magnesite, and aragonite. At higher temperatures, the stabilization of dolomite splits the subsolidus area into two partial ternary fields: halite + magnesite + dolomite and halite + dolomite + aragonite. The minimum on the liquidus surface corresponds to the halite-dolomite-aragonite ternary eutectic, situated at 1100 °C. The eutectic melt has Ca# 89 and contains 30 wt.% NaCl (26 mol% 2NaCl). The system has two ternary peritectics: halite + dolomite = magnesite + liquid located near the ternary eutectic and magnesite + dolomite = Mg-dolomite + liquid situated between 1300 and 1400 °C. Although under dry conditions incipient melting yields carbonate-dominated melt, the addition of water facilitates the fusion of NaCl and expands the liquid field to NaCl-rich compositions with up to 70 wt.% NaCl. The obtained results favor the idea that hydrous saline melts/fluids (brines) found as inclusions in diamonds could be a lower temperature derivative of mantle carbonatite melts and disagree with the hypothesis on chloride melt generation owing to the chloride-carbonate liquid immiscibility since no such immiscibility was established. We also studied the interaction of the NaCl–CaCO₃–MgCO₃ system with iron metal and found that carbonate reduction produces C-bearing species (Fe⁰, Fe-C melt, Fe₃C, Fe₇C₃, C⁰) and wüstite containing Na₂O, CaO, and MgO. Besides, a carbonate chloride compound, Ca₂Cl₂CO₃, was established among the reaction products. The interaction between NaCl-bearing carbonate melt shifts its composition toward Mg-poor and NaCl-rich. Given the above, an alternative hypothesis can be proposed, according to which the interaction of alkaline chloride-bearing carbonate melts formed in the subduction zones with the reduced mantle should be accompanied by diamond crystallization and shift the composition of the melt from carbonatitic to alkali-rich saline.