Mineral inclusions in sublithospheric diamonds from Collier 4 kimberlite pipe, Juina, Brazil: subducted protoliths, carbonated melts and primary kimberlite magmatism

We report on a suite of diamonds from the Cretaceous Collier 4 kimberlite pipe, Juina, Brazil, that are predominantly nitrogen-free type II crystals showing complex internal growth structures. Syngenetic mineral inclusions comprise calcium- and titanium-rich phases with perovskite stoichiometry, Ca-rich majoritic-garnet, clinopyroxene, olivine, TAPP phase, minerals with stoichiometries of CAS and K-hollandite phases, SiO₂, FeO, native iron, low-Ni sulfides, and Ca–Mg-carbonate. We divide the diamonds into three groups on the basis of the carbon isotope compositions (δ¹³C) of diamond core zones. Group 1 diamonds have heavy, mantle-like δ¹³C (−5 to −10‰) with mineral inclusions indicating a transition zone origin from mafic protoliths. Group 2 diamonds have intermediate δ¹³C (−12 to −15‰), with inclusion compositions indicating crystallization from near-primary and differentiated carbonated melts derived from oceanic crust in the deep upper mantle or transition zone. A ²⁰⁶Pb/²³⁸U age of 101 ± 7 Ma on a CaTiSi-perovskite inclusion (Group 2) is close to the kimberlite emplacement time (93.1 ± 1.5 Ma). Group 3 diamonds have extremely light δ¹³C (−25‰), and host inclusions have compositions akin to high-pressure–temperature phases expected to be stable in pelagic sediments subducted to transition zone depths. Collectively, the Collier 4 diamonds and their inclusions indicate multi-stage, polybaric growth histories in dynamically changing chemical environments. The young inclusion age, the ubiquitous chemical and isotopic characteristics indicative of subducted materials, and the regional tectonic history, suggest a model in which generation of sublithospheric diamonds and their inclusions, and the proto-kimberlite magmas, are related genetically, temporally and geographically to the interaction of subducted lithosphere and a Cretaceous plume.     

The mineralogy of Ca-rich inclusions in sublithospheric diamonds

This paper discusses mineralogy of Ca-rich inclusions in ultra-deep (sublithospheric) diamonds. It was shown that most of the Ca-rich majoritic garnets are of metabasic (eclogitic) affinity. The observed variation in major and trace element composition is consistent with variations in the composition of the protolith and the degree of enrichment or depletion during interaction with melts. Major and trace element compositions of the inclusions of Ca minerals in ultra-deep diamonds indicate that they crystallized from Ca-carbonatite melts that were derived from partial melting of eclogite bodies in deeply subducted oceanic crust in the transition zone or even the lower mantle. The occurrence of merwinite or CAS inclusions in ultra-deep diamonds can serve as mineralogical indicators of the interaction of metaperidotitic and metabasic mantle lithologies with alkaline carbonatite melts. The discovery of the inclusions of carbonates in association with ultra-deep Ca minerals can not only provide additional support for their role in the diamond formation process but also help to define additional mantle reservoirs involved in global carbon cycle.     

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions ('¹³C: peridotitic -5.4 to -2.2‰; eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side ('¹³C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (̿,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.     

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

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

Enigmatic diamonds in Archean calc-alkaline lamprophyres of Wawa, southern Ontario, Canada

A suite of 80 macrodiamonds recovered from volcaniclastic breccia of Wawa (southern Ontario) was characterized on the basis of morphology, nitrogen content and aggregation, cathodoluminescence (CL), and mineral inclusions. The host calc-alkaline lamprophyric breccias were emplaced at 2.68–2.74 Ga, contemporaneously with voluminous bimodal volcanism of the Michipicoten greenstone belt. The studied suite of diamonds differs from the vast majority of diamond suites found worldwide. First, the suite is hosted by calc-alkaline lamprophyric volcanics rather than by kimberlite or lamproite. Second, the host volcanic rock is amongst the oldest known diamondiferous rocks on Earth, and has experienced regional metamorphism and deformation. Finally, most diamonds show yellow-orange-red CL and contain mineral inclusions not in equilibrium with each other or their host diamond. The majority of the diamonds in the Wawa suite are colorless, weakly resorbed, octahedral single crystals and aggregates. The diamonds contain 0–740 ppm N and show two modes of N aggregation at 0–30 and 60–95% B-centers suggesting mantle storage at 1,100–1,170°C. Cathodoluminescence and FTIR spectroscopy shows that emission peaks present in orange CL stones do not likely result from irradiation or single substitutional N, in contrast to other diamonds with red CL. The diamonds contain primary inclusions of olivine (Fo₉₂ and Fo₈₉), omphacite, orthopyroxene (En₉₃), pentlandite, albite, and An-rich plagioclase. These peridotitic and eclogitic minerals are commonly found within single diamonds in a mixed paragenesis which also combines shallow and deep phases. This apparent disequilibrium can be explained by effective small-scale mixing of subducted oceanic crust and mantle rocks in fast “cold” plumes ascending from the top of the slabs in convergent margins. Alternatively, the diamonds could have formed in the pre-2.7–2.9 Ga cratonic mantle and experienced subsequent alteration of syngenetic inclusions related to host magmatism and ensuing metamorphism. Neither orogenic nor cratonic model of the diamond origin fully explains all of the observed characteristics of the diamonds and their host rocks. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Superdeep diamonds from the Juina area, Mato Grosso State, Brazil

Alluvial diamonds from the Juina area in Mato Grosso, Brazil, have been characterized in terms of their morphology, syngenetic mineral inclusions, carbon isotopes and nitrogen contents. Morphologically, they are similar to other Brazilian diamonds, showing a strong predominance of rounded dodecahedral crystals. However, other characteristics of the Juina diamonds make them unique. The inclusion parageneses of Juina diamonds are dominated by ultra-high-pressure ("superdeep") phases that differ both from "traditional" syngenetic minerals associated with diamonds and, in detail, from most other superdeep assemblages. Ferropericlase is the dominant inclusion in the Juina diamonds. It coexists with ilmenite, Cr-Ti spinel, a phase with the major-element composition of olivine, and SiO₂. CaSi-perovskite inclusions coexist with titanite (sphene), "olivine" and native Ni. MgSi-perovskite coexists with TAPP (tetragonal almandine-pyrope phase). Majoritic garnet occurs in one diamond, associated with CaTi-perovskite, Mn-ilmenite and an unidentified Si-Mg phase. Neither Cr-pyrope nor Mg-chromite was found as inclusions. The spinel inclusions are low in Cr and Mg, and high in Ti (Cr₂O₃<36.5 wt%, and TiO₂>10 wt%). Most ilmenite inclusions have low MgO contents, and some have very high (up to 11.5 wt%) MnO contents. The rare "olivine" inclusions coexisting with ferropericlase have low Mg# (87-89), and higher Ca, Cr and Zn contents than typical diamond-inclusion olivines. They are interpreted as inverted from spinel-structured (Mg, Fe)₂Si₂O₄. This suite of inclusions is consistent with derivation of most of the diamonds from depths near 670 km, and adds ilmenite and relatively low-Cr, high-Ti spinel to the known phases of the superdeep paragenesis. Diamonds from the Juina area are characterized by a narrow range of carbon isotopic composition ('¹³C=-7.8 to -2.5‰), except for the one majorite-bearing diamond ('¹³C=-11.4‰). There are high proportions of nitrogen-free and low-nitrogen diamonds, and the aggregated B center is predominant in nitrogen-containing diamonds. These observations have practical consequences for diamond exploration: Low-Mg olivine, low-Mg and high-Mn ilmenite, and low-Cr spinel should be included in the list of diamond indicator minerals, and the role of high-Cr, low-Ti spinel as the only spinel associated with diamond, and hence as a criterion of diamond grade in kimberlites, should be reconsidered.     

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr₂O₃ = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr₂O₃ = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ¹³C_PDB = −6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ¹³C_PDB = −5.5‰) to somewhat low (δ¹³C_PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.     

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.     

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

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

Decompression and unmixing of crystals included in diamonds from the mantle transition zone

A suite of exceptional mineral inclusions in diamonds from the São Luiz river, Juina province, Brazil, shows a wide range of garnet/majorite mineral compositions co-existing with clinopyroxene; the overall bulk compositions are eclogitic. The inclusions have a wide variety of textural arrangements, but crystallographic data obtained by EBSD shows that each inclusion consists of a single garnet with constant crystallographic orientation whilst clinopyroxene grains have preferred orientation with relation to garnet {110} and <111>. This suggests that the inclusions were originally single phase majoritic garnets, and that they preserve various states of progressive unmixing (exsolution) into lower pressure garnet and clinopyroxene compositions during transport of the host diamonds towards the Earth’s surface. On the basis of high pressure–temperature experimental data some of the original majoritic garnets must have come from depths of 450 km or more, and therefore resided in the transition zone and asthenospheric upper mantle. Particularly extensive re-equilibration of many inclusions took place at depths of ca 180–200 km (probably close to the base of the continental lithosphere). The partially unmixed state of the inclusions provides a unique opportunity for using mineral diffusion data to roughly estimate the rate of transport through the asthenospheric upper mantle, and within error this rate is found to be broadly compatible with expected transport rates by upper mantle convection or plume flow.     

Integrated models of diamond formation and craton evolution

Two decades of diamond research in southern Africa allow the age, average N content and carbon composition of diamonds, and the dominant paragenesis of their syngenetic silicate and sulfide inclusions to be integrated on a cratonwide scale with a model of craton formation. Individual eclogitic sulfide inclusions in diamonds from the Kimberley area kimberlites, Koffiefontein, Orapa and Jwaneng have Re–Os isotopic ages that range from circa 2.9 Ga to the mid-Proterozoic and display little correspondence with the prominent variations in the P-wave velocity (±1%) that the mantle lithosphere shows at depths within the diamond stability field (150–225 km). Silicate inclusions in diamonds and their host diamond compositions for the above kimberlites, Finsch, Jagersfontein, Roberts Victor, Premier, Venetia, and Letlhakane show a regional relationship to the seismic velocity of the lithosphere. Mantle lithosphere with slower P-wave velocity relative to the craton average correlates with a greater proportion of eclogitic vs. peridotitic silicate inclusions in diamond, a greater incidence of younger Sm–Nd ages of silicate inclusions, a greater proportion of diamonds with lighter C isotopic composition, and a lower percentage of low-N diamonds. The oldest formation ages of diamonds support a model whereby mantle that became part of the continental keel of cratonic nuclei first was created by middle Archean (3.2–3.3 Ga or older) mantle depletion events with high degrees of melting and early harzburgite formation. The predominance of eclogitic sulfide inclusions in the 2.9 Ga age population links late Archean (2.9 Ga) subduction–accretion events to craton stabilization. These events resulted in a widely distributed, late Archean generation of eclogitic diamonds in an amalgamated craton. Subsequent Proterozoic tectonic and magmatic events altered the composition of the continental lithosphere and added new lherzolitic and eclogitic diamonds to the already extensive Archean diamond suite. Similar age/paragenesis systematics are seen for the more limited data sets from the Slave and Siberian cratons.     

Regional patterns in the paragenesis and age of inclusions in diamond, diamond composition, and the lithospheric seismic structure of Southern Africa

The Archean lithospheric mantle beneath the Kaapvaal–Zimbabwe craton of Southern Africa shows ±1% variations in seismic P-wave velocity at depths within the diamond stability field (150–250 km) that correlate regionally with differences in the composition of diamonds and their syngenetic inclusions. Seismically slower mantle trends from the mantle below Swaziland to that below southeastern Botswana, roughly following the surface outcrop pattern of the Bushveld-Molopo Farms Complex. Seismically slower mantle also is evident under the southwestern side of the Zimbabwe craton below crust metamorphosed around 2 Ga. Individual eclogitic sulfide inclusions in diamonds from the Kimberley area kimberlites, Koffiefontein, Orapa, and Jwaneng have Re–Os isotopic ages that range from circa 2.9 Ga to the Proterozoic and show little correspondence with these lithospheric variations. However, silicate inclusions in diamonds and their host diamond compositions for the above kimberlites, Finsch, Jagersfontein, Roberts Victor, Premier, Venetia, and Letlhakane do show some regional relationship to the seismic velocity of the lithosphere. Mantle lithosphere with slower P-wave velocity correlates with a greater proportion of eclogitic versus peridotitic silicate inclusions in diamond, a greater incidence of younger Sm–Nd ages of silicate inclusions, a greater proportion of diamonds with lighter C isotopic composition, and a lower percentage of low-N diamonds whereas the converse is true for diamonds from higher velocity mantle. The oldest formation ages of diamonds indicate that the mantle keels which became continental nuclei were created by middle Archean (3.2–3.3 Ga) mantle depletion events with high degrees of melting and early harzburgite formation. The predominance of sulfide inclusions that are eclogitic in the 2.9 Ga age population links late Archean (2.9 Ga) subduction-accretion events involving an oceanic lithosphere component to craton stabilization. These events resulted in a widely distributed younger Archean generation of eclogitic diamonds in the lithospheric mantle. Subsequent Proterozoic tectonic and magmatic events altered the composition of the continental lithosphere and added new lherzolitic and eclogitic diamonds to the already extensive Archean diamond suite.     

Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ¹³C ~ ?25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (?5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth’s deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are intimately related to subducted material and record a polybaric growth history across a depth interval stretching from the lower mantle to the base of the lithosphere. It is suggested that the interaction of slab-derived melts and mantle material combined with subsequent upward transport in channelised networks or a buoyant diapir explains the formation of Juina-5 diamonds. We conclude that these samples, despite originating at great mantle depths, do not provide direct information about the ambient mantle, instead, providing a snapshot of the Earth’s deep carbon cycle.     

Petrology and Geochemistry of Post-Collisional Early Miocene Volcanism in the Karacada? Area (Central Anatolia, Turkey)

Early Miocene (ca.?21–18 Ma) volcanism in the Karacada? area comprises three groups of volcanic rocks: (1) calcalkaline suite (andesitic to rhyolitic lavas and their pyroclastics), (2) mildly-alkaline suite (alkali basalt, hawaiite, mugearite, benmoreite and trachydacite), and (3) a single trachyandesitic flow unit. Field observations, 40Ar/39Ar ages and geochemical data show that there was a progressive temporal transition from group 1 to 3 in a post-collisional tectonic setting. The calcalkaline suite rocks with medium-K in composition resemble those of subduction-related lavas, whereas the mildly-alkaline suite rocks having a sodic tendency (Na2O/K2O=1.5–3.2) resemble those of within-plate lavas. Incompatible element and Sr-Nd isotopic characteristics of the suites suggest that the lithospheric mantle beneath the Karacada? area was heterogeneously enriched by two processes before collision: (1) enrichment by subduction-related processes, which is important in the genesis of the calcalkaline volcanism, (2) enrichment by small degree melts from the astenosphere, which dominates the mildly alkaline volcanism. Perturbation of the enriched lithosphere by either delamination following collision and uplift or removal of the subducted slab following subduction and collision (i.e., slab breakoff) is the likely mechanism for the initiation of the post-collision volcanism.     

Peridotitic diamonds from the Slave and the Kaapvaal cratons—similarities and differences based on a preliminary data set

A comparison of the diamond productions from Panda (Ekati Mine) and Snap Lake with those from southern Africa shows significant differences: diamonds from the Slave typically are un-resorbed octahedrals or macles, often with opaque coats, and yellow colours are very rare. Diamonds from the Kaapvaal are dominated by resorbed, dodecahedral shapes, coats are absent and yellow colours are common. The first two features suggest exposure to oxidizing fluids/melts during mantle storage and/or transport to the Earth's surface, for the Kaapvaal diamond population.

Comparing peridotitic inclusions in diamonds from the central and southern Slave (Panda, DO27 and Snap Lake kimberlites) and the Kaapvaal indicates that the diamondiferous mantle lithosphere beneath the Slave is chemically less depleted. Most notable are the almost complete absence of garnet inclusions derived from low-Ca harzburgites and a generally lower Mg-number of Slave inclusions.

Geothermobarometric calculations suggest that Slave diamonds originally formed at very similar thermal conditions as observed beneath the Kaapvaal (geothermal gradients corresponding to 40–42 mW/m² surface heat flow), but the diamond source regions subsequently cooled by about 100–150 °C to fall on a 37–38 mW/m² (surface heat flow) conductive geotherm, as is evidenced from touching (re-equilibrated) inclusions in diamonds, and from xenocrysts and xenoliths. In the Kaapvaal, a similar thermal evolution has previously been recognized for diamonds from the De Beers Pool kimberlites. In part very low aggregation levels of nitrogen impurities in Slave diamonds imply that cooling occurred soon after diamond formation. This may relate elevated temperatures during diamond formation to short-lived magmatic perturbations.

Generally high Cr-contents of pyrope garnets (inside and outside of diamonds) indicate that the mantle lithosphere beneath the Slave originally formed as a residue of melt extraction at relatively low pressures (within the stability field of spinelperidotites), possibly during the extraction of oceanic crust. After emplacement of this depleted, oceanic mantle lithosphere into the Slave lithosphere during a subduction event, secondary metasomatic enrichment occurred leading to strong re-enrichment of the deeper (>140 km) lithosphere. Because of the extent of this event and the occurrence of lower mantle diamonds, this may be related to an upwelling plume, but it may equally just reflect a long term evolution with lower mantle diamonds being transported upwards in the course of “normal” mantle convection.     

Trace elements in sulfide inclusions from Yakutian diamonds

 Sulfide inclusions in diamonds may provide the only pristine samples of mantle sulfides, and they carry important information on the distribution and abundances of chalcophile elements in the deep lithosphere. Trace-element abundances were measured by proton microprobe in >50 sulfide inclusions (SDI) from Yakutian diamonds; about half of these were measured in situ in polished plates of diamonds, providing information on the spatial distribution of compositional variations. Many of the diamonds were identified as peridotitic or eclogitic from the nature of coexisting silicate or oxide inclusions. Known peridotitic diamonds contain SDIs with Ni contents of 22–36%, consistent with equilibration between olivine, monosulfide solid solution (MSS) and sulfide melt, whereas SDIs in eclogitic diamonds contain 0–12% Ni. A group of diamonds without silicate or oxide inclusions has SDIs with 11–18% Ni, and may be derived from pyroxenitic parageneses. Eclogitic SDIs have lower Ni, Cu and Te than peridotitic SDIs; the ranges of the two parageneses overlap for Se, As and Mo. The Mo and Se contents range up to 700 and 300 ppm, respectively; the highest levels are found in peridotitic diamonds. Among the in-situ SDIs, significant Zn and Pb levels are found in those connected by cracks to diamond surfaces, and these elements reflect interaction with kimberlitic melt. Significant levels of Ru (30–1300 ppm) and Rh (10–170 ppm) are found in many peridotitic SDIs; SDIs in one diamond with wustite and olivine inclusions and complex internal structures have high levels of other platinum-group elements (PGEs) as well, and high chondrite-normalized Ir/Pd. Comparison with experimental data on element partitioning between crystals of monosulfide solid solution (MSS) and sulfide melts suggests that most of the inclusions in both parageneses were trapped as MSS, while some high-Cu SDIs with high Pd±Rh may represent fractionated sulfide melts. Spatial variations of SDI composition within single diamonds are consistent with growth histories shown by cathodoluminescence images, in which several stages of growth and resorption have occurred within magmatic environments that evolved during diamond formation. Received: 5 July 1995 / Accepted: 21 February 1996     

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

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

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

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

Architecture and composition of ocean floor subducted beneath northern Gondwana during Neoproterozoic to Cambrian: A palinspastic reconstruction based on Ocean Plate Stratigraphy (OPS)

The Blovice accretionary complex, Bohemian Massif, hosts well-preserved basaltic blocks derived from an oceanic plate subducted beneath the northern active margin of Gondwana during late Neoproterozoic to early Cambrian. The major and trace element and Hf–Nd isotope systematics revealed two different suites, tholeiitic and alkaline, whose composition reflects different sources of melts within a back-arc basin setting. The former suite has composition similar to mid-ocean ridge basalts (MORB), yet with striking enrichment in large-ion lithophile elements (LILE) and Pb paralleled by depletion in Nb, in agreement with its derivation from depleted mantle fluxed by subduction-related fluids. In contrast, the latter suite has composition similar to ocean island basalts (OIB) with variable contribution of ancient, recycled crustal material. We argue that both suites represent volcanic members of Ocean Plate Stratigraphy (OPS) and indicate that the oceanic realm consumed by the Cadomian subduction was a complex mosaic of intra-oceanic subduction zones, volcanic island arcs, and back-arc basins with mantle plume impinging the spreading centre. Hence, the basalt geochemistry implies that two distinct domains of oceanic lithosphere may have existed off the Gondwana’s continental edge: an outboard domain, made up of old and less buoyant oceanic lithosphere (remnants of the Mirovoi Ocean surrounding former Rodinia?) that was steeply subducted and generated the back-arcs, and young, hot, and more buoyant oceanic lithosphere generated in the back-arcs and later involved in accretionary complexes as dismembered OPS. Perhaps the best recent analogy of this setting is the Izu Bonin–Mariana arc–Philippine Sea in the western Pacific.     

Magmatic evolution of the material of the Earth’s lower mantle: Stishovite paradox and origin of superdeep diamonds (Experiments at 24–26 GPa)

The ultrabasic–basic magmatic evolution of the lower mantle material includes important physicochemical phenomena, such as the stishovite paradox and the genesis of superdeep diamonds. Stishovite SiO₂ and periclase–wüstite solid solutions, (MgO · FeO)_ss, associate paradoxically in primary inclusions of superdeep lower mantle diamonds. Under the conditions of the Earth’s crust and upper mantle, such oxide assemblages are chemically impossible (forbidden), because the oxides MgO and FeO and SiO₂ react to produce intermediate silicate compounds, enstatite and ferrosilite. Experimental and physicochemical investigations of melting phase relations in the MgO–FeO–SiO₂–CaSiO₃ system at 24 GPa revealed a peritectic mechanism of the stishovite paradox, (Mg, Fe)SiO₃ (bridgmanite) + L = SiO₂ + (Mg, Fe)O during the ultrabasic–basic magmatic evolution of the primitive oxide–silicate lower mantle material. Experiments at 26 GPa with oxide–silicate–carbonate–carbon melts, parental for diamonds and primary inclusions in them, demonstrated the equilibrium formation of superdeep diamonds in association with ultrabasic, (Mg, Fe)SiO₃ (bridgmanite) + (MgO · FeO)_ss (ferropericlase), and basic minerals, (FeO · MgO)_ss (magnesiowüstite) + SiO₂ (stishovite). This leads to the conclusion that a peritectic mechanism, similar to that responsible for the stishovite paradox in the pristine lower mantle material, operates also in the parental media of superdeep diamonds. Thus, this mechanism promotes both the ultrabasic–basic evolution of primitive oxide–silicate magmas in the lower mantle and oxide–silicate–carbonate melts parental for superdeep diamonds and their paradoxical primary inclusions.     

Geochemical evolution of Middle—Late Cenozoic magmatism in the northern part of the Rio Grande Rift,Western United States

Geochemical studies of the Middle—Late Cenozoic succession of volcanic rocks from the northern part of the Rio Grande Rift were conducted. The initial activation of the rift structure was coeval with voluminous eruptions of lava and pyroclastic material of mainly intermediate and acid compositions in the San Juan volcanic field 35–27 Ma. The composition of the volcanic products after the rifting was dominated by basic and intermediate lavas. It is shown that the basanites and alkali basalts of the territory had geochemical characteristics of sublithospheric slab and above–sl ab sources. The processes of the riftogenic thinning of lithosphere are expressed by geochemical parameters that reflect the interaction between the liquids from the sublithospheric mantle and the rocks from different levels of both the lithospheric mantle and lower crust. In the 35–18 Ma interval, melts of different–depth sublithospheric and lithospheric sources erupted simultaneously in the northern part of the rift. However, the products of interaction between the sublithospheric and lithospheric materials dominated later in the past 15 Ma, although the sublithospheric magmatic liquids erupted at the northern structural termination of the rift within the Yampa volcanic field at about 10 Ma.