Silicate Inclusions In Diamonds Research Articles

Sulphide survival and diamond genesis during formation and evolution of Archaean subcontinental lithosphere: A comparison between the Slave and Kaapvaal cratons

Sulphide inclusions from 35 eclogitic and 7 peridotitic diamonds from the Diavik kimberlites in the central Slave craton have been characterized to address questions of diamond age and craton formation. Eclogitic sulphide inclusions occur in diamonds with mantle-like δ 13C (− 4.94 ± 0.72 1 σ) and low N aggregation states (%N as B = 8.2 ± 10.0, average N contents of 720 ppm) indicative of relatively low mantle residence temperatures. A 1.86 ± 0.19 Ga Re–Os age array for eclogitic sulphides with suprachondritic initial 187Os/ 188Os of 0.13 (± 0.10) indicates a close temporal link between eclogitic diamond formation, eclogite emplacement and collisional events affecting the Slave craton. Sulphides in peridotitic diamonds plot on older, previously established 3.3 and 3.5 Ga isochrons, consistent with higher average N aggregation states (~ 20%) despite lower N contents (~ 230 ppm) for their host diamonds compared to eclogitic diamonds. Two intriguing observations emerge from a comparison of diamond populations and formation ages between the Slave and Kaapvaal that indicate fundamentally different and common diamond formation mechanisms, respectively: (1) Despite the general abundance of peridotitic silicate inclusions, peridotitic sulphide inclusions are rare in the Kaapvaal and occur in relatively young diamonds whereas in the central Slave there is a sizable Archaean population. (2) Compared to the distribution of silicate inclusions in diamonds, both cratons have an overabundance of eclogitic relative to peridotitic sulphide inclusions. During Kaapvaal lithospheric mantle formation, large melting intervals, as gauged by extremely depleted silicate inclusions in diamonds, led to exhaustion of sulphide in the residue. Formation of peridotitic sulphide inclusion-bearing diamonds occurred only significantly later, after re-sulphidation accompanying metasomatism. By contrast, the less depleted deep lithospheric mantle beneath the central Slave craton may have formed during plume subcretion, leading to smaller melting intervals due to the presence of a pre-existing lithospheric mantle lid, thereby allowing for coeval precipitation of sulphide inclusion-bearing diamonds. Abundant eclogitic sulphide inclusion-bearing diamonds that can be related to accretionary processes along the edges of the Slave and Kaapvaal craton indicate that sulphide-saturated eclogite is a fertile source for diamond formation. Reduced fluids from dehydration of underlying seawater-altered peridotite may react with the overlying oceanic crust to precipitate eclogitic sulphide-bearing diamonds penecontemporaneously with metamorphism and tectonic emplacement of eclogite into the subcratonic lithosphere.

Age, paragenesis and composition of diamonds and evolution of the Precambrian mantle lithosphere of southern Africa

Two decades of diamond research in southern Africa allow the age and average composition (C isotope and N abundance) of diamonds and the dominant paragenesis (peridotitic versus eclogitic) of their syngenetic silicate and sulfide inclusions to be reviewed on a cratonwide scale. Individual eclogitic sulfide inclusions in diamonds from the Kimberley area kimberlites, Koffiefontein, Orapa and Jwaneng have Re-Os isotopic ages that range from ~2.9 Ga to the 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 to 225km). 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 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. The converse is true for diamonds from higher velocity mantle. The oldest formation ages of diamonds support a model whereby mantle that became part of the keel of the oldest continental nuclei was created by middle Archean (~3.3 to ~3.2 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 subduction-accretion events involving an oceanic lithosphere component 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.

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.

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.

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.

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

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

Diamond precipitation and mantle metasomatism - evidence from the trace element chemistry of silicate inclusions in diamonds from Akwatia, Ghana

Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr2O3 diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (LaN/YbN = 0.02–0.06) while harzburgitic garnets have sinusoidal REEN patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr2O3 respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO2-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H2O-rich melts. We therefore favour diamond precipitation by oxidation of CH4-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes.

Lherzolite xenoliths in kimberlites and basalts: petrogenetic and crystallochemical significance of some minor and trace elements in olivine, pyroxenes, garnet and spinel

ABSTRACTElectron and ion microprobe analyses for P, Si, Ti, Al, Cr, V, Sc, Fe, Mn, Mg, Ni, Co, Ca, Sr, Na, K and Li in olivine, pyroxenes and garnet in forty-two cold and twelve hot garnet lherzolites from kimberlites, nine spinel lherzolites from kimberlites and eighteen from alkali basalts, and one cold garnet lherzolite from the Malaita alnöite, are compared with published data for minerals occurring in lherzolite, harzburgite and eclogite xenoliths, for silicate megacrysts in kimberlites, and for silicate inclusions in diamonds. Despite wide ranges in the chemistry of minerals from garnet and spinel lherzolites, there are distinct regions in composition space that would enable determination of the parent lithology of disaggregated minerals in kimberlites and alkali basalts. Titanium correlates with Fe3+ in garnets. Chromium, Al, V and Sc are distributed similarly between silicates in lherzolites. Sodium correlates with trivalent ions in olivine, and increases with temperature. The distribution of Na, but not of K and Li, between olivine and clinopyroxene correlates with temperature. The regular partitioning of Ti, Mn and Ni places constraints on crystal-liquid partition coefficients. Above the stability temperature of mica, ‘metasomatising fluids’ may scavenge Cr and other trivalent ions as they increase Ti in silicates.

Lead, uranium, strontium, potassium and rubidium in inclusion-bearing diamonds and mantle-derived xenoliths from Southern Africa

Measurements are reported of K, Rb and Sr levels and Sr isotopic compositions in silicate inclusions in diamonds, and of U, Th and Pb levels and Pb isotopic compositions in sulphide inclusions in diamonds. Samples are from the Premier Mine (Transvaal), the Finsch Mine (northern Cape Province) and the Kimberley mines (northern Cape Province). The isotopic composition of Pb in sulphide inclusions indicates that the diamonds containing these inclusions are xenocrysts in the host kimberlite. Model Pb ages for the sulphide inclusions in the diamonds from Finsch and Kimberley are in excess of 2 b.y., although the host kimberlites are Cretaceous. The sulphide inclusions from Premier, however, have a model age similar to the emplacement age of the Premier kimberlites (approximately 1.2 b.y.). In addition, K, Rb, Sr, U and Pb concentrations and Sr and Pb isotopic compositions in clinopyroxenes from 14 mantle-derived xenoliths were measured. Samples were eclogites from the Roberts Victor Mine (Orange Free State), peridotites from the Matsoku Pipe (Lesotho) and diopside megacrysts from the four mines in Kimberley. The samples from the Roberts Victor Mine define a large spread in Sr and Pb isotopic composition. The slope of a regression line through the Pb data in the 207/204 vs. 206/204 plot defines an age of roughly 2.5 b.y. The Matsoku samples have 87Sr/ 86Sr ratios around 0.704. One group of samples (“fertile peridotites”) shows uniform, anomalously radiogenic Pb isotopic compositions, and bears evidence of a young event involving isotopic homogenisation. Lead isotopic heterogeneity, indicating an old age, has persisted in another group (“common peridotites”). The megacrysts from the four Kimberley mines have 87Sr/ 86Sr ratios around 0.704 and uniform, anomalously radiogenic Pb isotopic compositions, indicating a young age. Their Pb isotopic uniformity contrasts with the spread shown by kimberlites in Kimberley, and shows that the megacrysts did not crystallise in equilibrium with their host kimberlites. The similarity between the Pb isotopic data obtained on clinopyroxenes from xenoliths and the data obtained on sulphide inclusions in diamonds from Finsch and Kimberley suggests that these diamonds might be cogenetic with old rock provinces in the subcontinental mantle.