The application of C isotope measurements to the identification of the sources of C in diamonds: a review

In the past decade, the isotopic compositions of C in > 600 inclusion-bearing diamonds have been determined. Such analyses have revealed the following isotopic characteristics: (1) peridotitic diamonds, which typically contain garnet, chromite, olivine and/or orthopyroxene inclusions with refractory compositions (high Mg, Cr), have δ¹³C values predominantly between −10 and −1‰, with a sharp peak in the distribution near −5‰; (2) eclogitic diamonds, which commonly contain inclusions of omphacitic clinopyroxene, Cr-poor pyrope, and/or eclogitic accessory minerals such as rutile, kyanite, coesite or sanidine, have δ¹³C values between −34 and +3‰, with a smaller peak near −5‰; (3) the isotopic compositions obtained for suites of diamonds from individual occurrences are, in general, unique and do not resemble the range and distribution obtained by amalgamating the diamond isotope data from a number of localities; (4) isotopic zoning patterns and heterogeneities are found in some diamonds; cores of coated diamonds tend to be depleted in¹³C relative to the rims, and within single octahedral diamonds δ¹³C variations of nearly 6‰ have been reported.Because expected C isotope fractionations at mantle temperatures are small, attempts to model the full range of diamond isotope values through fractionating a homogeneous mantle C source have been unsuccessful. Nevertheless, fractionation is probably responsible for some of the observed variation in δ¹³C values. Two other models have also been proposed to account for the diamond characteristics outlined above. The “primordial model” suggests that the range and distribution of C isotope compositions are inherited from primordial C in the mantle which has an inhomogeneous isotopic composition, such as that found in meteorites. The “subduction model” suggests that subducted, crustal C is the source of C in diamonds, as organic and inorganic C compounds in the crust exhibit a range of δ¹³C values similar to that observed in diamonds. This paper reviews the C isotope characteristics of diamonds and compares the models which have been proposed to explain the origins of these characteristics.     

Associated chemical and carbon isotopic composition variations in diamonds from Finsch and Premier kimberlite,South Africa

The carbon isotopic composition of 66 inclusion-containing diamonds from the Premier kimberlite, South Africa, 93 inclusion-containing diamonds and four diamonds of two diamond-bearing peridotite xenoliths from the Finsch kimberlite, South Africa was measured. The data suggest a relationship between the carbon isotopic composition of the diamonds and the chemical composition of the associated silicates. For both kimberlites similar trends are noted for diamonds containing peridotite-suite inclusions (P-type) and for diamonds containing eclogite-suite inclusions (E-type): Higher δ¹³C P-type diamonds tend to have inclusions lower in SiO₂ (ol), Al₂O₃ (opx, gt), Cr₂O₃, MgO, $\text{Mg}\text{(Mg + Fe)}$ (ol, opx, gt) and higher in FeO (ol, opx, gt) and CaO (gt). Higher δ¹³C E-type diamonds tend to have inclusions lower in SiO₂, Al₂O₃ (gt, cpx), MgO, $\text{Mg}\text{(Mg + Fe)}$ (gt), Na₂O, K₂O, TiO₂ (cpx) and higher in CaO, $\text{Ca}\text{(Ca + Mg)}$ (gt, cpx).Consideration of a number of different models that have been proposed for the genesis of kimberlites, their xenoliths and diamonds shows that they are all consistent with the conclusion that in the mantle, regions exist that are characterized by different mean carbon isotopic compositions.     

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‰.     

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 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.     

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.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.     

Constraining diamond metasomatic growth using C- and N-stable isotopes: examples from Namibia

The present paper provides C- and N-stable isotope characteristics, N-contents and N-aggregation states for alluvial diamonds of known paragenesis from placers along the Namibian coast. The sample set includes diamonds with typical peridotitic and eclogitic inclusions and the recently reported “undetermined” suite of Leost et al. [Contrib. Mineral. Petrol. 145 (2003) 15] which resulted from infiltration of high temperature, carbonate-rich melts. δ¹³C-values range from −20.3‰ to −0.5‰ (n=48) for peridotitic diamonds and from −38.5‰ to −1.6‰ (n=45) for eclogitic diamonds. Diamonds belonging to the “undetermined” suite span a narrower range in δ¹³C from −8.5‰ to −2.7‰ (n=13). When compared with previous studies, diamonds from Namibia are characterised by unusually low proportions of N-free (i.e. Type II) peridotitic and eclogitic diamonds (3% and 2%, respectively) and an unprecedented high proportion of N-rich diamonds (15% and 73%, respectively, have N-contents >600 ppm). δ¹⁵N-values for diamonds of the peridotitic, eclogitic and “undetermined” suites range from −10‰ to +13‰ without correlations with either N-content or δ¹³C. The similarity in N-isotopic composition and the N-rich character of diamonds belonging to the eclogitic, peridotitic and “undetermined” suites is striking and suggests a close genetic relationship. We propose that a large part of the diamonds mined in Namibia formed during metasomatic events of similar style that introduced carbon and nitrogen into a range of different host lithologies.     

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.