Diamond formation during metasomatism of mantle eclogite by chloride-carbonate melt

A xenolith of bimineralic eclogite from the Udachnaya kimberlite pipe provides a snapshot of interaction between mantle rocks and diamond-forming fluids/melts. The major-element composition of the eclogite is similar to that of N-MORB and/or oceanic gabbros, but its trace-element pattern shows the effects of mantle metasomatism, which resulted in diamond formation. The diamonds are clustered in alteration veins that crosscut primary garnet and clinopyroxene. The diamonds contain microinclusions of a fluid/melt dominated by carbonate and KCl. Compared to the worldwide dataset, the microinclusions in these diamonds fall in middle of the range between saline fluids and low-Mg carbonatitic melts. The fluid/melt acted as a metasomatic agent that percolated through ancient eclogitic rocks stored in the mantle. This interaction is consistent with calculated partition coefficients between the rock-forming minerals and diamond-forming fluid/melt, which are similar to experimentally-determined values. Some differences between the calculated and experimental values may be due to the low contents of water and silicates in the chloride-carbonate melt observed in this study, and in particular its high contents of K and LILE. The lack of nitrogen aggregation in the diamonds implies that the diamond-forming metasomatism took place shortly before the eruption of the kimberlite, and that the microinclusions thus represent saline carbonate-rich fluids circulating in the basement of lithospheric mantle (150–170 km depth).     

Mineral inclusions in fibrous diamonds: constraints on cratonic mantle refertilization and diamond formation

We analyzed mineral microinclusions in fibrous diamonds from the Wawa metaconglomerate (Superior craton) and Diavik kimberlites (Slave craton) and compared them with published compositions of large mineral inclusions in non-fibrous diamonds from these localities. The comparison, together with similar datasets available for Ekati and Koffiefontein kimberlites, suggest a general pattern of metasomatic alteration imposed on the ambient mantle by formation of fibrous diamond. Calcium and Fe enrichment of peridotitic garnet and pyroxenes and Fe enrichment of olivine associated with fibrous diamond-forming fluids contributes to refertilization of the cratonic mantle. Saline—carbonatitic—silicic fluid trapped by fibrous diamonds may represent one of the elusive agents of mantle refertilization. Calcium enrichment of peridotitic garnet and pyroxenes is expected in local mantle segments during fibrous diamond production, as Ca in the carbonatitic fluids is deposited into the surrounding mantle when oxidized carbon is reduced to diamond. Harzburgitic garnet evolves towards Ca-rich compositions even when it interacts with Ca-poor saline fluids. An unusual trend of Mg enrichment to Fo_95–98 is observed in some olivine inclusions in Wawa fibrous diamonds. The trend may result from the carbonatitic composition of the fluid that promotes crystallization of magnesian olivine and preferentially oxidizes the fayalite component. We propose a generic model of fibrous and non-fibrous diamond formation from carbonatitic fluids that explains enrichment of the mantle in mafic magmaphile and incompatible elements and accounts for locally metasomatized compositions of diamond inclusions.     

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.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

Mg-Fe云母化学成分的解释和分类(Ⅰ)——基本置换和黑云母平面

中国东部花岗岩类141个Mg-Fe云母的化学成分将近90%的变化属于八面体层内的类质同象置换,置换矢量Mg ₁Fe⁺²和Fe_-3⁺²(R_Ⅵ⁺³)_-2□_Ⅵ组成了天然黑云母平面,大约80%的变化应当解释为基本置换8Mg ₁Fe⁺²+Fe_-3⁺²(R_Ⅵ⁺³)₂□_Ⅵ.这些是Mg-Fe云母在广泛的自然条件下表现出来的最主要的晶体化学关系。文中还提出了置换矢量的长度、分量和以及电价和三个参数,用以识别矿物化学成分变化的类质同象置换特征。     

Evidence of subduction and crust–mantle mixing from a single diamond

Cathodoluminescence (CL) imaging of polished sections of a diamond from the Guaniamo region of Venezuela suggests a history of the diamond involving two periods of growth separated by a period of resorption and possibly brittle deformation. In situ electron probe analysis of multiple eclogitic garnet inclusions reveals a correlation between garnet composition and location in the stone. An early-formed garnet in the diamond core has higher Ca/(Ca+Mg) and lower Mg/(Mg+Fe) values than later garnets associated with the second period of diamond growth. This variation conforms to an extensive trend of variation in the suite of eclogitic garnets extracted from Venezuelan diamonds. The diamond is zoned in carbon isotope composition (in situ secondary ion mass spectrometry, SIMS, data). The core compositions (δ¹³C PDB), corresponding to the first stage of growth, average −17.7‰. The second period of growth is apparently in two sub-sets of CL zones with mean values of −13.0‰ and −7.9‰. Nitrogen contents of diamond are low (30–300 atomic ppm) and do not correlate with carbon isotope composition. Oxygen isotope ratios of the garnet inclusions are elevated substantially above those expected for “common mantle”; δ¹⁸O VSMOW of early garnet is approximately +10.5‰ and two late garnets average +8.8‰. The evolutionary trend of magnesium enrichment in garnet is unlikely to represent igneous fractionation. The stable isotope data are consistent with diamond formation in subducted meta-basic rocks that had interacted with sea water at low temperatures at or near the sea floor and contained a substantial biogenic carbon component. During or following subduction, diamonds continued to form in an evolving system that was progressively modified by interaction with mantle material.     

Appraisal of the new occurrence of götzenitess, khibinskite and apophyllite in kalsilite-bearing lavas from San Venanzo and Cupaello (Umbria), Italy

Minerals corresponding in chemical composition to probable götzenite solid solutions, götzenite_ss, ideally (Ca, Na)₃ (Ti, Zr) (Si₂O₇) (F, O, OH)₂, khibinskite (K₄Zr₂Si₄O₁₄) and apophyllite (KCa₄Si₈O₂₀(OH, F)) were first reported in an aphyric, glass-bearing kalsilitite from Cupaello (Umbria), Italy, by Cundari and Ferguson (1991). To the authors knowledge, this occurrence of khibinskite is only the second recorded. Götzenite_ss was also found in a leucite-, melilite-rich pegmatoid in an olivine-melilitite from San Venanzo, S. Venanzo, in the same region.

The S. Venanzo phase, with significant Zr (0.18 atoms per formula unit) is transitional to rosenbuschite, which is the Zr-rich end-member of the isostructural series götzenite-rosenbuschite, while that from Cupaello, virtually Zr free, is close to the ideal götzenite end-member. The S. Venanzo phase crystallized as the preferred Zr phase from the relatively low-Zr (Zr=335 ppm) S. Venanzo lava. This probably inhibited khibinskite crystallization in the S. Venanzo lava, whereas khibinskite is the preferred Zr phase in the Cupaello lava (Zr=760 ppm), coexisting with low-Zr götzenite_ss.

The structural formula of the Cupaello khibinskite, based on 10 cations, yielded: K_3.89[Zr_1.99Mg_0.01Fe_0.04²⁺Ti_0.02]_2.06Si_4.05O_14.1 which is very close to the composition first reported by Khomiakov et al. (1974).

Apophyllite, also occurring in the Cupaello assemblages and in cavities in the lava, yielded a composition close to the ideal formula and supports the important role of alkali-rich fluids in the crystallization history of this lava.

The rare records of these minerals reflect, at least in part, the difficulty in identifying them. Their role as potential acceptors of both large ion lithophile and high field strength elements in peralkaline rock compositions is important in understanding the geochemistry of lamproitic rocks and in detecting possible genetic links with related rocks.     

Diamonds and their mineral inclusions from the A154 South pipe, Diavik Diamond Mine, Northwest territories, Canada

Mineral inclusions recovered from 100 diamonds from the A154 South kimberlite (Diavik Diamond Mines, Central Slave Craton, Canada) indicate largely peridotitic diamond sources (83%), with a minor (12%) eclogitic component. Inclusions of ferropericlase (4%) and diamond in diamond (1%) represent “undetermined” parageneses.

Compared to inclusions in diamonds from the Kaapvaal Craton, overall higher CaO contents (2.6 to 6.0 wt.%) of harzburgitic garnets and lower Mg-numbers (90.6 to 93.6) of olivines indicate diamond formation in a chemically less depleted environment. Peridotitic diamonds at A154 South formed in an exceptionally Zn-rich environment, with olivine inclusions containing more than twice the value (of  52 ppm) established for normal mantle olivine. Harzburgitic garnet inclusions generally have sinusoidal rare earth element (REE_N) patterns, enriched in LREE and depleted in HREE. A single analyzed lherzolitic garnet is re-enriched in middle to heavy REE resulting in a “normal” REE_N pattern. Two of the harzburgitic garnets have “transitional” REE_N patterns, broadly similar to that of the lherzolitic garnet. Eclogitic garnet inclusions have normal REE_N patterns similar to eclogitic garnets worldwide but at lower REE concentrations.

Carbon isotopic values (δ¹³C) range from − 10.5‰ to + 0.7‰, with 94% of diamonds falling between − 6.3‰ and − 4.0‰. Nitrogen concentrations range from below detection (< 10 ppm) to 3800 ppm and aggregation states cover the entire spectrum from poorly aggregated (Type IaA) to fully aggregated (Type IaB). Diamonds without evidence of previous plastic deformation (which may have accelerated nitrogen aggregation) typically have < 25% of their nitrogen in the fully aggregated B-centres. Assuming diamond formation beneath the Central Slave to have occurred in the Archean [Westerlund, K.J., Shirey, S.B., Richardson, S.H., Gurney, J.J., Harris, J.W., 2003b. Re–Os systematics of diamond inclusion sulfides from the Panda kimberlite, Slave craton. VIIIth International Kimberlite Conference, Victoria, Canada, Extended Abstracts, 5p.], such low aggregation states indicate mantle residence at fairly low temperatures (< 1100 °C). Geothermometry based on non-touching inclusion pairs, however, indicates diamond formation at temperatures around 1200 °C. To reconcile inclusion and nitrogen based temperature estimates, cooling by about 100–200 °C shortly after diamond formation is required.     

Multiple-mineral inclusions in diamonds from the Snap Lake/King Lake kimberlite dike, Slave craton, Canada: a trace-element perspective

Multiple inclusions of minerals in diamonds from the Snap Lake/King Lake kimberlites of the southeastern Slave craton in Canada have been analyzed for trace elements to elucidate the petrogenetic history of these inclusions, and of their host diamonds. As observed worldwide, the harzburgitic-garnet diamond inclusions (DIs) possess sinusoidal REE patterns that indicate an early depletion event, followed by metasomatism by LREE-enriched, HREE-depleted fluids. Furthermore, these fluids appear to contain appreciable concentrations of LILE and HFSE, based on the increasing abundances of these elements in the olivine inclusion that occurs at the outer portion of a diamond compared to that near the core. The compositions of these fluids are probably a mixture of hydrous-silicic melt, carbonatitic melt, and brine, similar to the compositions of micro-inclusions in diamonds reported by Navon et al. (2003). Comparison between the compositions of majoritic and normal harzburgitic garnets shows that the former are more depleted in terms of major/minor elements (higher Cr#) but significantly more enriched in the REE (up to 10×). This characteristic may indicate the higher susceptibility for metasomatic enrichment of previously more depleted garnets. Garnets of eclogitic paragenesis show strong LREE-depleted patterns, whereas the coexisting omphacite inclusion has relatively flat light- and middle-REE but depleted HREE. Whole-rock reconstruction from coexisting garnet and omphacite inclusions indicates that the protolith of these inclusions was probably the extrusive section of an oceanic crust, subducted beneath the Slave craton.     

New insights into the occurrence of C-depleted carbon in the mantle from two closely associated kimberlites: Letlhakane and Orapa, Botswana

Carbon isotope measurements on diamonds from the Letlhakane kimberlite, and the analyses of their inclusions, permit the examination of km-scale mantle-composition variations by comparing the results with those for the nearby Orapa kimberlite. Diamonds from Letlhakane have a wide range in carbon isotopic composition (−3‰ to −21‰); however, the relative abundance of diamonds depleted in ¹³C is significantly lower than in the Orapa kimberlite. Most of the ¹³C-depleted diamonds belong to the eclogictic or websteritic paragenesis. The relative abundance of inclusions in diamonds and their composition indicate that there are significant differences in petrology in the mantle below the two locations. At Letlhakane, peridotitic compositions are more prevalent than at Orapa and the protolith of P-Type inclusions in diamonds may have experienced a higher degree of partial melting at Letlhakane compared to Orapa. P/T estimates for both W- and E-Type diamonds indicate that a region of ¹³C-depletion may exist beneath the two kimberlites. The relationships between carbon isotopic composition of the host diamond and the Al₂O₃/Cr₂O₃ ratios of their websteritic and eclogitic garnet inclusions indicate that the low δ¹³C regions may represent a primary mantle feature, unrelated to a crustal component.     

Crystalline inclusions and C isotope ratios in diamonds from the Snap Lake/King Lake kimberlite dyke system: evidence of ultradeep and enriched lithospheric mantle

U-type paragenesis inclusions predominate (94.7%) among the crystalline inclusion suite of 115 diamonds (−4+2 mm) obtained from the recently discovered Snap Lake/King Lake (SKL) kimberlite dyke system, Southern Slave, Canada. The most common inclusions are olivine (90) and enstatite (22). Sulfide, Cr-pyrope, chromite and Cr-diopside inclusion are less abundant (15, 10, 5 and 1, respectively). Results of the inclusion composition study demonstrate the following. (a) The relatively enriched character of the mantle parent rocks of the U-type diamonds. The average Mg# of olivine inclusions is 92.1, and of enstatite inclusions average 93.3. CaO content in Cr-pyrope inclusions is relatively high (3.73–5.75 wt.%). (b) Four of ten U-type Cr-rich pyrope inclusions contain a majoritic component up to 16.8 mol.% which requires pressures of 110 kbar. Carbon isotopes compositions for 34 diamonds with U-type inclusions have a δ¹³C range from −3.2‰ to −9‰ with a strong peak around −3.5‰. This is much heavier than the ratios of U-type diamonds from Siberia and South Africa (4.5‰). Diamonds with olivine inclusions can be divided into two groups based on their δ¹³C values as well as the Mg# and Ni/Fe ratio in the olivines. Most show a narrow range of δ¹³C values from −3.2‰ to −4.8‰ (average −3.72‰) and have olivine inclusions with Mg# less than 92.3 and relatively high Fe/Ni ratios. A second group is characterized by a much wider variation of C isotope composition (δ¹³C varies from −3.8‰ to −9.0‰, average −5.97‰), and the olivine inclusions having a higher Mg# (up to 93.6) and relatively low Fe/Ni ratios. This difference in the C isotope composition may have several explanations: (a) peculiarities of asthenosphere degassing coupled with an abnormal thickness of lithosphere; (b) the abnormal thickness and enriched character of lithospheric mantle; (c) involvement of subducted C of crustal origin in the processes of the diamond formation. The presence of subcalcic Cr-rich majorite (up to 17 mol.%) pyropes of low-Ca harzburgite paragenesis among the crystalline inclusion suite of SKL diamonds is strong evidence for the existence of diamondiferous depleted peridotite in lithospheric mantle at depth near 300 km beneath Southern Slave area and is postulated to be one of the main reasons for the much heavier C isotope composition of SKL U-type diamonds in comparison with those from Siberian and South African kimberlites.     

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.     

Distribution of structural impurities and fluid microinclusions in cubic and coated diamond crystals from the Udachnaya pipe,Yakutia, Russia

FTIR microspectroscopic data were used to construct two-dimension maps showing the distribution of structural impurities and mineral microinclusions in cubic and coated octahedral diamond crystals from the Udachnaya kimberlite pipe in Yakutia. Elevated concentrations of hydrogen and total nitrogen are detected in parts corresponding to the early growth of single-episode growth regions of diamond crystals. These concentrations decrease toward the peripheral portions of these regions. The microinclusions contain water and polyphase mineral associations that preserve a high residual pressure. Microinclusions in the coats of octahedral diamond crystals are dominated by silicates, in which the intensity of IR spectral bands increases toward the peripheries, whereas the cubes posses irregularly distributed domains rich in these phases. The carbonate phases of the microinclusions are distributed according to growth zones of the crystals, and their distribution is often not correlated with the concentrations of structural impurities. The facts that microinclusions in the diamond cuboids are dominated by carbonates and that the rims of the octahedra are dominated by silicates suggest that the diamonds crystallized from dominantly carbonate and silicate fluids/ melts, respectively. The chemical composition of the microinclusions point to an eclogitic paragenesis of the crystals. Facts are obtained that provide support for the earlier hypothesis that cubic diamond crystals and coated octahedral crystals grow at metasomatic interaction between deep fluids and eclogitic rocks in the lithospheric mantle.     

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.     

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 element compositions of submicroscopic inclusions in coated diamond: A tool for understanding diamond petrogenesis

Trace element compositions of submicroscopic inclusions in both the core and the coat of five coated diamonds from the Democratic Republic of Congo (DRC, formerly Zaire) have been analyzed by Laser Ablation Inductively Coupled Mass Plasma Spectrometry (LA-ICP-MS). Both the diamond core and coat inclusions show a general 2-4-fold enrichment in incompatible elements relative to major elements. This level of enrichment is unlikely to be explained by the entrapment of silicate mantle minerals (olivine, garnet, clinopyroxene, phlogopite) alone and thus submicroscopic fluid or glass inclusions are inferred in both the diamond coat and in the gem quality diamond core. The diamond core fluids have elevated High Field Strength Element (Ti, Ta, Zr, Nb) concentrations and are enriched in U relative to inclusions in the diamond coats and relative to chondrite. The core fluids are also moderately enriched in LILE (Ba, Sr, K). Therefore, we suggest that the diamond cores contain inclusions of silicate melt. However, the Ni content and Ni/Fe ratio of the trapped fluid are very high for a silicate melt in equilibrium with mantle minerals; high Ni and Co concentrations in the diamond cores are attributed to the presence of a sulfide phase coexisting with silicate melt in the diamond core inclusions. Inclusions in the diamond coat are enriched in LILE (U, Ba, Sr, K) and La over the diamond core fluids and to chondrite. The coats have incompatible element ratios similar to natural carbonatite (coat fluid: Na/Ba ≈0.66, La/Ta≈130). The coat fluid is also moderately enriched in HFSE (Ta, Nb, Zr) when normalized to chondritic Al. LILE and La enrichment is related to the presence of a carbonatitic fluid in the diamond coat inclusions, which is mixed with a HFSE-rich hydrous silicate fluid similar to that in the core. The composition of the coat fluid is consistent with a genetic link to group 1 kimberlite.     

Ar–Ar age determinations of eclogitic clinopyroxene and garnet inclusions in diamonds from the Venetia and Orapa kimberlites

Ar–Ar age measurements are reported for selected eclogitic clinopyroxene and garnet inclusions in Orapa diamonds and clinopyroxene inclusions in Venetia diamonds. Laser drilling of encapsulated clinopyroxene inclusions within Venetia diamonds released a maximum of 3% of the total ⁴⁰Ar, indicating little diffusive transfer and storage of radiogenic ⁴⁰Ar at the diamond–inclusion boundary. Apparent ages obtained during stepped heating of three diamonds are consistent with diamond crystallisation occurring just prior to the kimberlite eruption 520 Ma ago. Stepped heating of three clinopyroxene-bearing Orapa diamonds gave ages of 906–1032 Ma, significantly above the eruption age, but consistent with previously determined isotopic ages. A few higher apparent ages hint at the presence an older generation of Orapa diamonds that formed >2500 Ma ago. Orapa garnets also contain measurable K contents, and record a range of ages between 1000 and 2500 Ma. The old apparent ages and lack of significant interface ⁴⁰Ar released by the laser probe, suggests that pre-eruption radiogenic ⁴⁰Ar and mantle-derived ⁴⁰Ar components are trapped in microinclusions within the pyroxene and garnet inclusions.     

Petrology of the Hopen mangerite-charnockite intrusion, Lofoten, north Norway

The Hopen massif, intrusive age 1900 m.y., exposed area 15 km², in the Lofoten-Vesterålen granulite facies province has the mineral assemblages: (1) mesoperthite+plagioclase (An_7–20)+quartz+clinopyroxene (Di_20–25)+orthopyroxene En_15–25+opaques±minor amphibole±minor biotite; (2) mesoperthite+plagioclase (An <2)+quartz+clinopyroxene (Di <10)+olivine Fe lt;5)+opaques. By using mineral and whole rock analyses, the crystallization conditions were estimated to be 1000°C, 12 kb load pressure and an oxygen fugacity approximately corresponding to the WM buffer. Rocks with the assemblage of type (2) contain secondary orthoferrosilite (Fe_0.90–0.95Mn_0.04–0.07Mg_0.01Ca_0.01)₂Si₂O₆, generated by reactions involving fayalite, magnetite and quartz at 800°C, 10kb load pressure and at oxygen fugacities approaching QFM buffer conditions. Subsequent to a crustal thickening, the mangeritic rocks in Lofoten-Vesterålen were emplaced in a tensional environment comparable with modern continental rifts. A ‘gabbro pillow’ magma chamber at the crustal base is proposed as parental magma for the mangeritic rocks, of which the Hopen massif represents a late differentiation.