Kimberlite Melt Research Articles

Subducted carbonates not required: Deep mantle melting explains stable Ca isotopes in kimberlite magmas

Ca isotope geochemistry has great potential for improving our understanding of magmatic systems and for tracing the deep Earth carbon cycle. There are still many open questions, however, regarding the proper application of this relatively novel proxy to the study of mantle-derived magmas, including (i) the possible effects of pressure on mineral-melt Ca isotope fractionation factors, and (ii) the potential for Ca isotopes to be used as tracers of recycled marine carbonates in mantle-derived magmas. Kimberlites are mantle-derived melts that are highly enriched in CO2 and are the deepest-sourced magmas (>200 km depth) known to erupt at Earth’s surface, providing an excellent opportunity to explore these questions. We present Ca isotope data combined with detailed petrographic observations, bulk-carbonate C-O isotope data, and bulk-rock major element analyses, for a suite of 23 well-characterized kimberlite samples from their type-locality (Kimberley, South Africa). These kimberlites have abundant previous evidence for recycled surface materials in their mantle source, including low S isotope and moderately radiogenic Sr isotope compositions, yet display only limited variations in their Ca isotope compositions (δ44CaBSE of −0.08‰ to −0.27‰), with an average of −0.17 ± 0.02‰ (2SE, n = 21). This composition is indistinguishable from average carbonatites [−0.19 ± 0.03‰ (2SE, n = 106)] and OIB from recent studies [−0.16 ± 0.01‰ (2SE, n = 41)], and slightly lower than average MORB [−0.11 ± 0.02‰ (2SE, n = 31)]. Although our samples display a wide range of emplacement styles, alteration conditions, extents of magmatic differentiation, and degrees of mantle-cargo entrainment (i.e., xenocryst accumulation), we find no correlations between Ca isotopes and any of these factors. Instead, we find that low-degree partial melting of the likely kimberlite source lithology (i.e., carbon-bearing garnet lherzolite) yields modelled melt δ44CaBSE values ranging between −0.12‰ and −0.16‰ (at 1400–1500 °C), in agreement with the measured Ca isotope compositions of the Kimberley kimberlites. This observation, and the lack of heavy carbon isotope signatures in the examined samples, indicates that kimberlites do not require subducted carbonates in their mantle sources, despite their very high CO2 contents. Although several recent studies have suggested that equilibrium mineral-melt Ca isotope fractionation factors (e.g., 1000lnαgrt-melt) could be significantly different at higher pressures (i.e., due to pressure-induced changes in CaO bond lengths and coordinations), our models successfully reproduce the kimberlite data using pressure-independent predictions for mineral-melt fractionations. It remains possible, however, that differences in isotopic fractionation due to the peculiar composition of kimberlite melts (e.g., high CO2, low SiO2) are effectively cancelled out by competing pressure effects, and future work independently targeting these factors will be especially important for our understanding of Ca isotope fractionation in mantle-derived melts and the Ca isotope systematics of Earth’s mantle.

Compositions of Kimberlite Melts: A Review of Melt Inclusions in Kimberlite Minerals

This work is a comprehensive review of existing data on melt inclusions entrapped in minerals of kimberlite rocks emplaced in different cratonic settings at different times. The crystallized melt inclusions represent snapshots of kimberlite melts at different stages of their evolution. All inclusions are composed of daughter minerals and shrinkage bubbles, but no aqueous fluids and quenched silicate glasses have been so far found. More than 60 mineral species were identified among the daughter phases in the inclusions, however, such diverse phase assemblages are typical of all kimberlites studied to date. Daughter minerals are represented by various Na-K-Ca-, Na-Ca-, Na-Mg-, K-Ca-, Ca-Mg-, Ca-, Mg-, Na-carbonates, Na-Mg- and Na-carbonates with additional anions Сl–, \({\text{SO}}_{4}^{{2 - }},\) \({\text{PO}}_{4}^{{3 - }},\) alkali- sulfates, chlorides, phosphates, sulfides, oxides and silicates. Alkali carbonates, sulfates, and chlorides are usually absent among groundmass minerals the majority of kimberlites in the world, except the Udachnaya-East kimberlite in Siberia. On the other hand, this paragenesis in association with traditional kimberlite minerals, such as olivine, micas, monticellite, spinel group minerals, perovskite, rutile, ilmenite, calcite, and dolomite, is common in the crystallized melt inclusions in all studied kimberlites. Carbonates (~30 to 85 vol. %) always dominate over silicates (only up to 18 vol. %) within inclusions. All inclusions also contain variable (2 to 55 vol. %.) amounts of chlorides (halite and sylvite). When relatively low abundances of carbonate minerals (30–50 vol. %) are observed in the inclusions, chlorides (18–55 vol. %) appear to take over other minerals, including silicates that are traditionally considered as main components of “ultramafic” kimberlite parental melts. The published results on melt inclusions in the kimberlite minerals strongly imply that parental kimberlite melts were generated and further evolved within the Na2O-K2O-CaO-MgO-CO2-Cl system, that is, they were alkali-rich carbonatite/carbonatite-chloride liquids. According to various estimates, the SiO2 content in kimberlite melts at different stages of their evolution could have varied from the first to 19 wt. %. Obviously, during and after of а kimberlite bodies formation, interaction with external waters leads to serpentinization of kimberlite olivine and dissolution of a significant part of kimberlite igneous minerals, such as alkaline carbonates, sulfates, and chlorides. In the traditional approach to studying kimberlites, the role of components such as Na2O, CO2, Cl, and to a lesser extent K2O and S, F in the petrogenesis of kimberlite magmas and rocks have been largely underestimated, while olivine- and serpentine-forming components, such as of SiO2, MgO and H2O are still overestimated in contemporaneous literature.

Physicogeochemical Mechanisms of the Genesis of Matryoshka-Type Diamonds on the Basis of the Mantle-Carbonatite Theory

A physicochemical analysis of the genesis of a unique Matryoshka-type diamond from the Nyurbinskaya kimberlite pipe of the Nakyn kimberlite field, Yakutia, Russia, was performed. The specimen consists of a host diamond with a cavity containing a loose diamond inclusion; two through holes with a width of 0.1–0.4 mm emerge from the cavity. The analysis is based on the mantle-carbonatite theory of the genesis of diamonds and associated phases developed on the basis of consistent results of a physicochemical experiment and an analytical study of paragenetic inclusions in natural diamonds from kimberlite deposits. The published data of crystal morphological and physical studies of the Matryoshka diamond were used as well. As a result, the physicogeochemical mechanisms of nucleation and crystallization of the host diamond with a cavity and diamond inclusion under the conditions of mass genesis of diamonds in completely miscible carbonate–eclogite–carbon melts of the upper-mantle diamond-forming chamber are substantiated. The initially closed cavity was filled with a diamond-forming carbonate–silicate melt with dissolved carbon. In addition, an analysis of the conditions of etching and dissolution of the host diamond and diamond inclusion during the kimberlite transport of diamond-bearing material from the mantle chamber to the depths of the Earth’s crust was performed. The reasons for the explosive formation of cone-shaped through holes in the main diamond, which was accompanied by the ejection of the diamond-forming medium and the filling of the cavity with (С–О–Н)-fluid-containing kimberlite melt, are considered. The final episodes of partial dissolution of diamonds from the Matryoshka sample by kimberlite and assimilated melts continued during the formation of a cumulative chamber in the Earth’s crust and its solidification with the release of a highly compressed C–O–H fluid. “Fluid drilling” of the top of the cumulative chamber stimulated the explosive formation of the Nyurbinskaya pipe and its filling with kimberlite and assimilated diamondiferous matter. With prolonged compaction of this substance, the Matryoshka diamond was subjected to atmospheric and hydrothermal factors, as is evidenced by fine-grained sedimentary barite, a mineral of barium sulphate, found in the through holes of the host diamond.

Inverse Modeling to Constrain Composition of CO2-Rich Parental Melt of Kimberlite: Model Development and Application to the Majuagaa Dyke, Southern West Greenland.

Abstract A model is developed to test the hypothesis that kimberlites can form by low-degree melting of asthenospheric mantle followed by entrainment and assimilation of lithospheric mantle. The developed model uses inversion calculations based upon rare earth and compatible trace elements. For kimberlites (s.s.), an equation describing mass balance between a melt of unknown composition and a contaminant end-member of xenocrystic/assimilated material from the lithospheric mantle is inverted. This allows calculation of the mass fraction of xenocrystic minerals from the lithospheric mantle (olivine, orthopyroxene, clinopyroxene, garnet, ilmenite) entrained in the kimberlitic magma, as well as the source mineralogy and melt degree in the source region. The composition of the parental melt prior to interaction with the lithosphere is not assumed a priori but is calculated by the model. The CO2, H2O, K2O and P2O5 contents of the source are estimated assuming batch melting and the inversion models. The range and coupling of the model parameters are found using a non-linear most-squares inversion procedure, and the model space is visualised using a Self-Organising Map approach. Our earlier work supporting assimilation of xenocrystic opx is, however, not a precondition but provides a post-processing constraint, as well as the selection of a more likely set of solutions from the Self-Organising Map. The calculation is applied to a data set from the Majuagaa kimberlite dyke (southern West Greenland) including added whole rock analyses for CO2 and H2O. Major variations in whole rock compositions are related to flow differentiation of olivine macrocrysts. The textures of opx, cpx, gt and ilm megacrysts show evidence for reaction with the transporting melt and physical erosion in the kimberlitic mush. Using the bulk rocks in our inversion scheme results in a silico-carbonatite parental melt with major element concentrations consistent with experimental melts. The ol, opx, and cpx mass fractions in the source are not well-resolved by this calculation, but the proportion of gt in the source is comparatively well defined at 15–22 wt% and cpx is constrained to less than 14 wt%. The source assemblage required is 36–80 wt% ol, 2–49 wt% opx, 0–6 wt% cpx, and 15–19 wt% gt. This suggests a peridotitic rather than an eclogitic source. The inversion model gives an overall mass fraction of xenocrystic material in the Majuagaa kimberlite magma of 41–51 wt% The mass fractions of the xenocryst phases are as follows: 71–85 wt% ol, 0–13 wt% opx, 5 ± 1 wt% gt, and 10–14 wt% ilm. There is less than 3 wt% cpx in the xenocrystic and assimilated assemblage. These results agree with petrographic observations. Processing the model results using the Self-Organising Map clearly displays the extent and coupling within the statistically acceptable region of the model space and leads us to a preferred model of 49 wt% xenocrysts with a xenocryst assemblage of 71–76 wt% ol, 8–13 wt% opx, 4 wt% gt and 12 wt% ilm. A source with a REE pattern similar to that of primitive mantle is sufficient to form the parental melt and consistent with generation of the initial kimberlite melt in the convecting mantle. Calculated CO2 and H2O concentrations in the source of the Majuagaa kimberlite of 230–860 μg/g and 223–741 μg/g, respectively, are within the range of independent convecting mantle estimates. This is equivalent to <0.17 wt% magnesite and the H2O budget of the mantle source can be accommodated via storage in nominally anhydrous silicate phases. When applied to Majuagaa kimberlite, the inversions are consistent with a conceptually simple model of kimberlite formation: (1) low degree melting in carbonated asthenospheric peridotite, (2) melt extraction and concentration, and (3) entrainment and reaction with lithospheric mantle material.

Mantle-Derived Cargo vs Liquid Line of Descent: Reconstructing the P–T–fO2–X Path of the Udachnaya–East Kimberlite Melts during Ascent in the Siberian Sub-Cratonic Lithosphere

Abstract Disentangling the physico-chemical evolution of the melts that give rise to kimberlites during their genesis, ascent through the sub-cratonic lithosphere and emplacement in the crust is challenging. This is because the extensive entrainment and assimilation of, and reaction with, mantle-derived material makes kimberlites mixtures of xenocrystic, magmatic components and alteration minerals, rarely preserving evidence of their original melt composition. Here, a detailed textural and compositional study of coherent and volcaniclastic kimberlite units from the Udachnaya–East pipe (Siberian craton) was performed to reconstruct the pressure–temperature–oxygen fugacity-compositional (P–T–fO2–X) path of kimberlite melts during their ascent through the sub-cratonic lithosphere. Routine and high-precision electron microprobe analyses of olivine, phlogopite and Fe–Ti oxides enabled to discriminate the mantle-derived cargo from the magmatic components, and thus make inferences on the liquid line of descent (LLD) of proto-kimberlite to kimberlite melts. Most of the olivine cores in Udachnaya–East kimberlite are xenocrystic and record conditions of last equilibration in the Siberian sub-cratonic lithospheric mantle at T–P ranging from 812–1227°C at 3.1–5.4 GPa, to 871–1170°C at 4.6–7.0 GPa, depending on the chosen model geotherm (35 mW/m2 vs 40 mW/m2). Based on their Ni, Cr, Mn, Al and P vs Mg/Fe systematics, olivine core populations were associated to the sheared, granular garnet-bearing or spinel-bearing cratonic peridotites. The occurrence of olivine Internal Zones (I) having the same composition as Fe-rich cores, as well as rare mantle-derived xenocrystic cores of phlogopite, bear witness of mantle metasomatism preceding kimberlite ascent. The assimilation of mantle material by initially H2O- and P-rich proto-kimberlitic melts is recorded by the cotectic formation of magmatic olivine Internal Zones (II) and phlogopite Internal Zones around resorbed xenocrystic cores. The LLD then evolved by inducing cotectic precipitation of olivine, phlogopite rims and Cr-spinel at P of 1.5–3.0 GPa, T of 1120–1250°C and fO2 from −2.8 to −1.6 ΔFMQ. Ilmenite–magnetite pairs in the groundmass record the later conditions of crystallization that occurred at P of ~1.0 GPa, T from 1133°C down to 1000°C and fO2 of +0.3 to +0.9 ΔFMQ. These results confirm the progressive oxidation of the melt that finally led to the formation of calcite, apatite and Mg-rich olivine and phlogopite rinds. The F-enrichment of phlogopite rinds reflects a late decrease of the H2O/CO2 activity of the melt that evolved toward alkali-carbonated composition. Our results showed that the crystal cargo of kimberlites can be used to track all processes acting in between the melt-rock reactions in the mantle and the emplacement in the crust.

Trace Elements in Chromian Spinels from Four Siberian Kimberlites

We analysed the major, minor and trace elements chemistry of forty-two Cr-spinels from four Siberian kimberlites. They showed a wide range in Mg# (Mg/(Mg + Fe2+); 0.42–0.78) and Cr# (Cr/(Cr + Al); 0.32–0.92) and a common trend of increasing Cr# with decreasing Mg#. The major element classification schemes suggested that there were spinels deriving from a peridotitic source (Xen) and spinels crystallised from kimberlitic melts (Chr). Laser-Ablation Inductively Coupled Plasma Mass Spectrometry on both groups showed that the trace elements with the highest abundance were Mn (985–3390 ppm), Ni (531–3162 ppm), V (694–2510 ppm) and Zn (475–2230 ppm). Testing the effectiveness of trace elements in determining the source for Cr-spinels, we found out that Cr-spinels crystallised directly from a kimberlitic melt usually showed higher Mn, Ni, Sc and V concentrations with respect to those of peridotitic origin. In addition, using the available partitioning models, we found that the correlations between major elements and Ni, Co, Sc and Ga in the Xen group could be explained by subsolidus equilibration between spinel, olivine and clinopyroxene at 800–1000 °C, thus supporting a peridotitic source for this group. Finally, we calculated the composition of the possible melts in equilibrium with the Cr-spinels of the Chr group, using a selected set of partition coefficients. Calculated abundances of Cu, Ga and Zr were comparable to those of the kimberlite, while V was never close to the kimberlite composition. This simulation highlighted the need for new data on the trace elements partition coefficients between kimberlitic melts and Cr-spinel.

ALKALI-CONTAINING MINERALS WITHIN MELT INCLUSIONS IN OLIVINE OF MANTLE XENOLITHS FROM BULTFONTEIN KIMBERLITE PIPE (KAAPVAAL CRATON): EVIDENCE ON HIGH CONCENTRATIONS OF ALKALIS IN KIMBERLITE MELTS

The study reports the mineral assemblage of the crystallized secondary melt inclusions in the olivine of sheared peridotites xenoliths from Bultfontein kimberlite pipe (Kaapvaal Craton, South Africa). In this type of xenoliths, the inclusions may correspond in composition to primitive kimberlite melts related to the magmatism that formed the Bultfontein pipe. Among 32 daughter phases within the inclusions, there are both ordinary rock-forming and minor minerals for kimberlites (silicates, carbonates, oxides) and "exotic" (alkali carbonates, sulfates, and chlorides) for these rocks. In the inclusions, 20 alkali-containing minerals are present, 12 of which are Na-bearing and – 4 Na-K-bearing. For instance, the inclusions contain nyerereite, K-nyerereite, shortite, gregoryite, eitelite, bradleyite, northupite, tychite, burkeite, aphthitalite, arcanite, thenardite, sylvine, and halite. On the basis of these results, the kimberlite melt of the Bultfontein pipe had Na-specification rather than Ca or K ones. The carbonates, sulfates, and chlorides significantly prevail over silicates, which content (serpentine + micas) does not exceed 16 vol. %, in the inclusions.The obtained results pose fundamental questions regarding the petrogenesis of kimberlites: (i) initial sodium concentrations in kimberlite melts and rocks, which are "traditionally" considered as very low; (ii) composition and ratio of volatile components in kimberlite magmas, namely, the initial contents of both CO2 and the components such as Cl, SO3 and H2O; (iii) primary magmatic mineral association of kimberlite rocks, which loses diverse alkali-containing minerals, but mica, due to serpentinization process.

Compositional Variations in Primitive Kimberlite Melts and Entrained Mantle Cargo from a Global Survey of Trace Element Compositions in Kimberlite Olivine

Abstract Olivines are the dominant phase of kimberlites and the majority of grains display distinct compositional zoning with xenocrystic cores surrounded by magmatic rims. Previous work has documented large variations in both core and rim major and minor element compositions in kimberlites globally, which has been related to variable entrainment and assimilation of sub-continental lithospheric mantle (SCLM) material. However, there is limited knowledge of trace element variations in olivine from kimberlites and it is unclear whether mantle assimilation has any effect on the trace element composition of kimberlite melts. To fill this gap, we present a global survey of olivine trace element compositions, along with previously reported major and minor element compositions, for samples representing the full spectrum of olivine compositional variations in kimberlites, including samples from the following: Lac de Gras, Canada (Grizzly, Koala); Kimberley, South Africa (Bultfontein, De Beers, Kimberley Big Hole, Wesselton); Kaalvallei, South Africa (New Robinson, Samada); and Alto Paranaiba, Brazil (Limpeza-18, Tres Ranchos-04). Trace element concentrations of olivine cores can discriminate between those derived from the disaggregation of peridotitic material and those related to the megacryst suite. The megacrystic olivine cores exhibit a negative correlation between Al and Mn, which is absent in peridotite-derived cores, and are characterised by high concentrations of temperature-dependent elements (e.g. Al, Na, V) as well as Zn, Ti, and Mn. Following pre-screening of cores for megacrystic and spinel peridotite-derived grains, we applied the Al-in-olivine thermometer to assess the P–T equilibration conditions of cores in equilibrium with garnet and estimate the sampling depth of kimberlite magmas in the lithospheric mantle. Our results are consistent with predominant entrainment of deep lithosphere xenocrysts in highly diamondiferous compared with diamond-poor kimberlites. Temperature-dependent elements display a gradational increase with depth due to higher T with Ca, Cu and, to a lesser extent, Zn and Ti being higher and Mg# being lower towards the base of the SCLM, which is consistent with melt modification of the lower lithosphere. The Zn, Ti, Co, Mn, Li, Al, Cr, Na, and V concentrations of magmatic olivine rims display systematic variations that have a negative correlation with Mg# (whereas Cr is positively correlated). Lac de Gras olivine feature Mg-rich rims (Mg# >90) and low concentrations of these trace elements, whereas the Fe-rich olivine rims (Mg# ~85) of the Kaalvallei kimberlites have higher concentrations of these elements, with the Kimberley and Alto Paranaiba kimberlites being intermediate. Direct correlations between average Ti, Zn, Co and Li compositions of olivine cores and rims suggests that the olivine rim (i.e. proxy for primitive melt) variations are related to variable assimilation of metasomatised SCLM and can be effectively used to track the composition of the lithospheric column that is traversed by kimberlite magmas. These observations further imply an intimate link between early proto-kimberlite melt, leading to formation of megacrystic olivine at the base of the SCLM, and the composition of kimberlite melts which entrain and assimilate these products. We conclude that lithospheric mantle assimilation has a major and previously overlooked influence on the trace element composition of kimberlite magmas.

Olivine in Kimberlites: Magma Evolution from Deep Mantle to Eruption

Abstract Elucidating the origin, composition and physical properties of primary kimberlite melts is crucial to our understanding of their source, petrogenesis, ascent mechanisms and ultimately the origin of diamonds. Recently, there has been a growing interest in the study of olivine, which is one of the most abundant minerals in kimberlites with xenocrystic, metamorphic (mantle) and magmatic origins. Olivine is one of the earliest minerals to crystallise in kimberlite magmas, and the presence of ubiquitous zoning (e.g. cores, internal zones, transitional zones, rims, rinds, outmost rinds) and different generations (i.e. primary, pseudosecondary and secondary) of crystal/melt/fluid inclusions in euhedral olivine grains has been shown to provide fundamental insights into the composition and evolution of kimberlite melts. In this contribution, we review and evaluate the following: (1) the widely accepted notion that kimberlite olivine has two distinct origins—xenocrystic and magmatic. We present detailed electron microprobeX-ray element maps of well-preserved and zoned euhedral olivine microcrysts from the Koala and Mark (Lac de Gras, Canada) and Udachnaya-East (Siberia, Russia) kimberlites to show that the cores of olivine occasionally adopt euhedral shapes, which is commonly defined by the distribution of Ni. We present a scenario in which mantle olivine was recrystallised by the early (or proto-) kimberlite melt/fluid infiltrating through the lithospheric mantle to form euhedral ‘pyrocrysts’ (i.e. olivine that formed via re-crystallisation in the mantle in the presence of a melt), which in turn become cores for the subsequent crystallisation of magmatic olivine during kimberlite magma ascent and emplacement. (2) The evolution of ideas using different geochemical, petrological, experimental and melt inclusion approaches to constrain the composition of the primary/parental kimberlite melt. Based on our assessment of available data, in particular using melt inclusions, we propose that kimberlites originated from melts that were initially Si-poor, and Na-K-F-Cl-P-S-bearing and Ca-Mg-carbonate-rich. With this model composition for the primary/parental kimberlite melt considered, we emphasise the implications for the evolution of olivine and its role in the kimberlite petrogenesis. Furthermore, we present a comprehensive model outlining the key stages involved in the petrogenesis of kimberlites, ranging from the generation of the proto kimberlite melt in the mantle, its interaction with mantle silicates during ascent, the role of liquid immiscibility in driving magma differentiation and CO2 degassing and its emplacement and modification in the crust. Finally, we discuss prospective directions that may further guide the future of kimberlite petrological research.

Genetic Link between Ilmenite and Kimberlite: Constrain from Ilmenite Compositions of Majhgawan Kimberlite Pipe, Panna, Madhya Pradesh

We present, major element geochemical data for ilmenite grains obtained from heavy mineral concentrate of diamondiferous Majhgawan kimberlite clan diatreme in Central Indian Diamond Province (CIDP) in Panna District of Madhya Pradesh, India. The chemical composition of 148 ilmenite grains suggests different compositional trends when plotted over “Haggerty's parabola” and as seen in MgO-Cr2O3 bivariant plots. The study indicates that the ilmenite crystallized in three stages: the first stage where Cr - poor ilmenite is crystallized from protokimberlitic or kimberlitic melt and forms the base of Haggerty's parabola on MgO-Cr2O3 plots; the second stage ilmenite is rich in MgO and Cr2O3 -represented by left branch of Haggerty’s parabola-might have formed by interaction between melt and lithosphere; the third stage ilmenite is formed by sub-solidus recrystallization in an evolved kimberlite melt due to oxidation and is reflected in the right branch of Haggerty’s parabola in MgO-Cr2O3 plots. The various trends in the ilmenite composition from Majhgawan pipe are attributed to conditions prevailing during ilmenite crystallization in a kimberlite melt ascending through the lithospheric mantle. These geochemical features indicate a genetic link between ilmenite and the host kimberlite melt.

Experimental Study of the Multicomponent Chemical Diffusion of Major Components (SiO2, Al2O3, Na2O, CaO, MgO, and FeO) and the $$\text{CO}_{3}^{2-}$$ Anion at Interaction between Basalt and Kimberlite Melts under a Moderate Pressure

Experimental Study of the Multicomponent Chemical Diffusion of Major Components (SiO2, Al2O3, Na2O, CaO, MgO, and FeO) and the $$\text{CO}_{3}^{2-}$$ Anion at Interaction between Basalt and Kimberlite Melts under a Moderate Pressure

Towards composition of carbonatite melts in peridotitic mantle

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.

Zircon megacrysts from Devonian kimberlites of the Azov Domain, Eastern part of the Ukrainian Shield: Implications for the origin and evolution of kimberlite melts

Zircon megacrysts are commonly found in kimberlites and, together with olivine, low-Cr garnet, pyroxene, phlogopite, and ilmenite megacrysts, they constitute a mineral assemblage known as the “low-Cr suite”. The generally close similarity of ages and similar isotope geochemical characteristics of megacrysts and matrix minerals in the host kimberlites support a cognate origin. However, alteration rims commonly develop on zircon and ilmenite megacrysts, providing evidence for a lack of chemical equilibrium between the megacrysts and kimberlitic melts. Here, we report results of a detailed geochronological and geochemical study of zircon megacrysts found in the Middle Devonian Novolaspa kimberlite pipe and dyke located in the Azov Domain of the Ukrainian Shield. The concordia age of zircons is 397.0 ± 2.0 Ma, and it is 14 m.y. older than the age of kimberlite emplacement as defined by a Rb-Sr isochron on phlogopite. The average εHf(397) value for unaltered zircon megacrysts is 6.8 ± 0.14, with the alteration rims having similar Hf isotope systematics. These hafnium isotope data indicate a moderately depleted mantle source for zircon. Unaltered megacrystic zircons have low abundances of trace elements and fractionated REE, with pronounced positive Ce/Ce* anomalies and almost no Eu/Eu* anomalies. In contrast, alteration rims have very high and variable concentrations of trace elements, indicating a reaction between zircon and kimberlite melt. The melt or fluid responsible for zircon and ilmenite megacryst formation, in contrast to kimberlitic melt, was poor in incompatible trace elements, except for the HFSE (Zr, Hf, Nb, Ta, and Ti). The oxygen fugacity during crystallization of the megacryst suite was close to the FMQ buffer.Azov zircon megacrysts do not demonstrate close geochronological and isotope-geochemical similarities with their host kimberlites. They are cognate in the broad sense of being related to the same plume event, but their direct affinity is not clearly defined. The megacryst suite may have crystallized from the earliest melts/fluids that separated from the ascending mantle plume, whereas kimberlite magmas were emplaced 14 m.y. after this event.

Unaltered kimberlite of Internationalnaya pipe (Mirny field)

The porphyry kimberlite block (intrusive coherent kimberlite, after Scott-Smith, 2013) on the deep horizons of the Internationalnaya pipe is characterized by the lack of olivine macrocryst serpentinization, and the minimum degree of postmagmatic alteration in the matrix minerals. Garnet keliphitization and the composition of olivine and phlogopite outer zones are due to the interaction of deep minerals and the surrounding kimberlite melt at depth. The rapid melt crystallization contributed to the heterogeneous magma structure represented by the macrocryst (porphyry) and aphyric schlieren.

Tectonic setting of kimberlites in the Vilyui-Markhinsky fault zone according to modern data

The lateral heterogeneity of the Vilyui-Markha fault zone was determined, the central and western subzones were identified. The high-grade diamondiferous Mir and Nakyn kimberlite fields are confined to the central subzone. The low-grade diamondiferous Syuldyukar kimberlite field is confined to the western subzone of the VilyuiMarkha zone. The analysis of the fault network density in the research area was carried out. It was found that the fault network density increases within the subzones, which characterizes them as increased permeability areas favorable for kimberlite melts uprising. This fact can be another tectonic criterion for setting up diamond prospecting operations.

An exotic Cretaceous kimberlite linked to metasomatized lithospheric mantle beneath the southwestern margin of the São Francisco Craton, Brazil

We present major and trace element compositions of mineral concentrates comprising garnet xenocrysts, ilmenite, phlogopite, spinel, zircon, and uncommon minerals (titanite, calzirtite, anatase, baddeleyite and pyrochlore) of a newly discovered Late Cretaceous kimberlite (U-Pb zircon age 90.0 ± 1.3 Ma; 2σ) named Osvaldo França 1, located in the Alto Paranaíba Igneous Province (APIP), southeastern Brazil. Pyrope grains are lherzolitic (Lherz-1, Lherz-2 and Lherz-3), harzburgitic (Harz-3) and wehrlitic (Wehr-2). The pyrope xenocrysts cover a wide mantle column in the subcratonic lithosphere (66–143 km; 20–43 kbar) at relatively low temperatures (811–875 °C). The shallowest part of this mantle is represented by Lherz-1 pyropes (20–32 kbar), which have low-Cr (Cr2O3 = 1.74–6.89 wt.%) and fractionated middle to heavy rare earth elements (MREE-HREE) pattern. The deepest samples are represented by Lherz-2, Lherz-3, Harz-3, and Wehr-2 pyropes (36–43 kbar). They contain high-Cr contents (Cr2O3 = 7.36–11.19 wt.%) and are characterized by sinusoidal (Lherz-2 and Wehr-2) and spoon-like (Lherz-3 and Harz-3) REE patterns. According to their REE and trace elements, pyrope xenocrysts have enriched nature (e.g., Ce and Yb vs. Cr2O3), indicating that the cratonic lithosphere has been affected by a silicate melt with subalkaline/tholeiite composition due to their low Zr, Ti and Y concentrations. Besides minerals with typical kimberlitic signatures, such as ilmenite and zircon, the exotic compositions of phlogopite and ulvöspinel suggest an enriched component in the magma source. The formation of rare mineral phases with strong enrichment of light-REE (LREE) and high field strength elements (HFSE) is attributed to the late-stage kimberlitic melt. We propose a tectonic model where a thermal anomaly, represented by the low-velocity seismic anomaly observed in P-wave seismic tomography images, supplied heat to activate the alkaline magmatism from a metasomatized cratonic mantle source during the late-stages of Gondwana fragmentation and consequent South Atlantic Ocean opening. The metasomatism recorded by mineral phases is a product of long-lived recycling of subducted oceanic plates since the Neoproterozoic (Brasiliano Orogeny) or even older collisional events, contributing to the exotic character of the Osvaldo França 1 kimberlite, as well as to the cratonic lithospheric mantle.

Confocal Raman spectroscopic study of melt inclusions in olivine of mantle xenoliths from the Bultfontein kimberlite pipe (Kimberley cluster, South Africa): Evidence for alkali‐rich carbonate melt in the mantle beneath Kaapvaal Craton

AbstractIdentifying the composition of primary/primitive mantle melts is crucial for understanding the mantle's evolution and mantle‐derived magmatism. Melt inclusions in mantle xenoliths provide key information about such melts. This study used confocal Raman spectroscopy to characterize mineral assemblage of unexposed crystallized secondary melt inclusions in the olivine from the xenoliths of the sheared garnet peridotites from the Bultfontein kimberlite pipe (Kimberley cluster, Kaapvaal Craton, South Africa). The studied peridotites originated from 112‐ to 146‐km mantle depths. In total, 16 minerals were identified among daughter crysatls, which include carbonates (calcite, magnesite, dolomite), alkali carbonates (eitelite, nyerereite, gregoryite/natrite, K–Na–Ca–carbonate (K,Na)2Ca(CO3)2 (K analogue of nyerereite), alkali carbonates with additional anions (northupite, bradleyite, burkeite), alkali sulfates (glauberite, thenardite, aphthitalite), apatite, tetraferriphlogopite, and magnetite. Several more daughter minerals gave distinct Raman spectra, but they were not determined due to the lack of similar spectra in the databases. Carbonates are predominant among the daughter minerals in the melt inclusions. Many daughter minerals are rich in alkalis. These facts indicate that melt(s), parental for the inclusions, is alkali‐rich carbonate in composition. Two possible models were suggested for the origin of these melt inclusions: (1) in situ fracturing of olivine and the mantle melt infiltration shortly before the sheared peridotites were entrained by the ascending kimberlitic magma; (2) infiltration of the transporting kimberlite melt into xenoliths during ascent. Both models imply that the alkali‐rich carbonate melt(s) that interacted with peridotites originated at a greater depth than the entrapment level of studied xenoliths (&gt;150 km), that is, at the base of the lithosphere or in the asthenosphere. This melt is genetically related to the kimberlite magmatism that formed the Bultfontein pipe and points at the alkali‐rich carbonate composition of primary kimberlite melt.

Dissolution of mantle orthopyroxene in kimberlitic melts: Petrographic, geochemical and melt inclusion constraints from an orthopyroxenite xenolith from the Udachnaya-East kimberlite (Siberian Craton, Russia)

Reconstructing the original composition of kimberlite melts in the mantle and delineating the processes that modify them during magmatic ascent and emplacement in the crust remains a significant challenge in kimberlite petrology. One of the most significant processes commonly cited to drive initial kimberlite melts towards more Si-Mg-rich compositions and decrease the solubility of CO2 is the assimilation of mantle orthopyroxene. However, there is limited direct evidence to show the types of reactions that may occur between mantle orthopyroxene and the host kimberlite melt.To provide new constraints on the interaction between orthopyroxene and parental kimberlite melts, we examined a fresh (i.e. unmodified by secondary/post-magmatic alteration) orthopyroxenite xenolith, which was recovered from the serpentine-free units of the Udachnaya-East kimberlite (Siberian Craton, Russia). This xenolith is composed largely of orthopyroxene (~ 90%), along with lesser olivine and clinopyroxene and rare aluminous magnesian chromite. We can show that this xenolith was invaded by the host kimberlite melt along grain interstices and fractures, where it partially reacted with orthopyroxene along the grain boundaries and replaced it with aggregates of compositionally distinct clinopyroxene, olivine and phlogopite, along with subordinate Fe-Cr-Mg spinel, FeNi sulphides and djerfisherite (K6(Fe,Ni,Cu)25S26Cl).Primary melt inclusions in clinopyroxene replacing xenolith-forming orthopyroxene, as well as secondary melt inclusion trails in xenolith orthopyroxene, clinopyroxene and olivine are composed of similar daughter mineral assemblages that consist largely of: NaK chlorides, along with varying proportions of phlogopite, Fe-Cu-Ni sulphides, djerfisherite, rasvumite (KFe2S3), Cr-Fe-Mg spinel, nepheline and apatite, and rare rutile, sodalite, barite, olivine, Ca-K-Na carbonates and NaK sulphates. The melt entrapped by these inclusions likely represent the hybrid products produced by the invading kimberlite melt reacting with orthopyroxene in the xenolith.The mechanism that could explain the partial replacement of orthopyroxene in this xenolith by clinopyroxene, olivine and phlogopite could be attributed to the following reaction:Orthopyroxene + Carbonatitic (melt) ➔ Olivine + Clinopyroxene + Phlogopite + CO2.This reaction is supported by theoretical and experimental studies that advocate the dissolution of mantle orthopyroxene within an initially silica-poor and carbonate-rich kimberlite melt. The mineral assemblages replacing orthopyroxene in the xenolith, together with hosted melt inclusions, suggests that the kimberlitic melt prior to reaction with orthopyroxene was likely carbonate-rich and Na-K-Cl-S bearing. The paucity of carbonate in the reaction zones around orthopyroxene and in melt inclusions in clinopyroxene replacing xenolith-forming orthopyroxene and xenolith minerals (orthopyroxene, clinopyroxene and olivine) is attributed to the consumption of carbonates and subsequent exsolution of CO2 by the proposed decarbonation reaction.Concluding, we propose that this orthopyroxenite xenolith provides a rare example of the types of reactions that can occur between mantle orthopyroxene and the host kimberlite melt. The preservation of this xenolith and zones around orthopyroxene present new insights into the composition and evolution of parental kimberlite melts and CO2 exsolution.

Multiphase solid inclusions reveal the origin and fate of carbonate-silicate melts in metasomatised peridotite

Orogenic peridotite in ultrahigh-pressure ultrahigh-temperature terranes provides increasingly strong evidence of material transfer in a subduction-zone setting, causing the metasomatism and melting of mantle rocks. Multiphase solid inclusions (MSI) trapped in garnet can provide clues to these processes occurring at great depth. The MSI enclosed in garnet in pyroxenite, lherzolite and harzburgite from a drillcore in the Saxothuringian basement in the Variscan Bohemian Massif are dominated by hornblende, barian mica and carbonate (dolomite and magnesite), and they contain a large variety of other phases, including spinel, clinopyroxene, orthopyroxene, garnet II, apatite, monazite, thorianite, graphite, norsethite and barian feldspar, scheelite and sulfides (e.g., pentlandite). We demonstrate, that the bulk chemical composition of the MSI evolves from the MSI trapped in garnet pyroxenite, which was the source of the metasomatising liquids, to the MSI in the host peridotite. Garnet pyroxenite has a carbonate-silicate composition comparable to kimberlite, and represents a rare example of a low-degree supercritical melt derived from a mixed crust-mantle source frozen in the mantle. Its high-pressure fractional crystallization produced a residual melt, enriched in alkalies (Na, K), highly incompatible elements (LILE – Ba, Sr; Th, U), LREE, Ti, W and volatiles (CO2, Cl, F, P), which is now trapped in the MSI in pyroxenite garnet. The MSI in peridotite reflect changes in the physical and chemical characteristics of the metasomatising medium during its reactive infiltration into peridotite through silicate crystallization and interaction with mantle minerals reflecting the type of rock (lherzolite vs. harzburgite). A change from a more silicic, solute-rich melt to a more diluted carbonate-rich liquid gradually enriched in LILE (K, Ba) and volatiles (CO2, Cl) and LREE fractionation with an increasing degree of fluid evolution coincides with the evolution of kimberlitic melts to carbonatitic melts. The low-viscosity carbonate-rich liquids can migrate far and metasomatise a considerable volume of the rock. Our work demonstrates that the MSI trapped in garnet represent a unique tool to trace the chemical and physical characteristics of the liquids that metasomatise the mantle wedge and their evolution.

Ultramafic Alkaline Rocks of Kepino Cluster, Arkhangelsk, Russia: Different Evolution of Kimberlite Melts in Sills and Pipes

To provide new insights into the evolution of kimberlitic magmas, we have undertaken a detailed petrographic and mineralogical investigation of highly evolved carbonate–phlogopite-bearing kimberlites of the Kepino cluster, Arkhangelsk kimberlite province, Russia. The Kepino kimberlites are represented by volcanoclastic breccias and massive macrocrystic units within pipes as well as coherent porphyritic kimberlites within sills. The volcanoclastic units from pipes are similar in petrography and mineral composition to archetypal (Group 1) kimberlite, whereas the sills represent evolved kimberlites that exhibit a wide variation in amounts of carbonate and phlogopite. The late-stage evolution of kimberlitic melts involves increasing oxygen fugacity and fluid-phase evolution (forming carbonate segregations by exsolution, etc.). These processes are accompanied by the transformation of primary Al- and Ti-bearing phlogopite toward tetraferriphlogopite and the transition of spinel compositions from magmatic chromite to magnesian ulvöspinel and titanomagnetite. Similar primary kimberlitic melts emplaced as sills and pipes may be transitional to carbonatite melts in the shallow crust. The kimberlitic pipes are characterised by low carbonate amounts that may reflect the fluid degassing process during an explosive emplacement of the pipes. The Kepino kimberlite age, determined as 397.3 ± 1.2 Ma, indicates two episodes of ultramafic alkaline magmatism in the Arkhangelsk province, the first producing non-economic evolved kimberlites of the Kepino cluster and the second producing economic-grade diamondiferous kimberlites.