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.     

The Homestead kimberlite, central Montana, USA: mineralogy, xenocrysts, and upper-mantle xenoliths

The Homestead kimberlite was emplaced in lower Cretaceous marine shale and siltstone in the Grassrange area of central Montana. The Grassrange area includes aillikite, alnoite, carbonatite, kimberlite, and monchiquite and is situated within the Archean Wyoming craton. The kimberlite contains 25–30 modal% olivine as xenocrysts and phenocrysts in a matrix of phlogopite, monticellite, diopside, serpentine, chlorite, hydrous Ca–Al–Na silicates, perovskite, and spinel. The rock is kimberlite based on mineralogy, the presence of atoll-textured groundmass spinels, and kimberlitic core-rim zoning of groundmass spinels and groundmass phlogopites.

Garnet xenocrysts are mainly Cr-pyropes, of which 2–12% are G10 compositions, crustal almandines are rare and eclogitic garnets are absent. Spinel xenocrysts have MgO and Cr₂O₃ contents ranging into the diamond inclusion field. Mg-ilmenite xenocrysts contain 7–11 wt.% MgO and 0.8–1.9 wt.% Cr₂O₃, with (Fe⁺³/Fe^tot) from 0.17–0.31. Olivine is the only obvious megacryst mineral present. One microdiamond was recovered from caustic fusion of a 45-kg sample.

Upper-mantle xenoliths up to 70 cm size are abundant and are some of the largest known garnet peridotite xenoliths in North America. The xenolith suite is dominated by dunites, and harzburgites containing garnet and/or spinel. Granulites are rare and eclogites are absent. Among 153 xenoliths, 7% are lherzolites, 61% are harzburgites, 31% are dunites, and 1% are orthopyroxenites. Three of 30 peridotite xenoliths that were analysed are low-Ca garnet–spinel harzburgites containing G10 garnets. Xenolith textures are mainly coarse granular, and only 5% are porphyroclastic.

Xenolith modal mineralogy and mineral compositions indicate ancient major-element depletion as observed in other Wyoming craton xenolith assemblages, followed by younger enrichment events evidenced by tectonized or undeformed veins of orthopyroxenite, clinopyroxenite, websterite, and the presence of phlogopite-bearing veins and disseminated phlogopite. Phlogopite-bearing veins may represent kimberlite-related addition and/or earlier K-metasomatism.

Xenolith thermobarometry using published two-pyroxene and Al-in-opx methods suggest that garnet–spinel peridotites are derived from 1180 to 1390 °C and 3.6 to 4.7 GPa, close to the diamond–graphite boundary and above a 38 mW/m² shield geotherm. Low-Ca garnet–spinel harzburgites with G10 garnets fall in about the same T and P range. Most spinel peridotites with assumed 2.0 GPa pressure are in the same T range, possibly indicating heating of the shallow mantle. Four of 79 Cr diopside xenocrysts have P–T estimates in the diamond stability field using published single-pyroxene P–T calculation methods.     

沅江辰溪地区河流碎屑石榴子石地球化学特征及其对湖南原生金刚石找矿的启示

湖南沅江是我国砂矿金刚石的重要产地,石榴子石和金刚石是砂矿中常见的重矿物,与金刚石相关的石榴子石特征研究,对揭示湖南砂矿金刚石的来源与形成条件有重要意义。本文随机选取湖南沅江辰溪地区金刚石砂矿中160粒碎屑石榴子石和5粒金刚石包裹体中的石榴子石,采用矿物学、地球化学并借鉴统计学方法对它们进行了分析比较。结果显示,碎屑石榴子石主要为铁铝-锰铝榴石系列,其中个别石榴子石含有金刚石包裹体。聚类分析、线性判别、逻辑回归分析计算显示,部分G3榴辉岩型石榴子石与金刚石可能具有成生联系。同时,两个采集地点的石榴子石类型、主微量元素具有一定的差异,其中一个地点的石榴子石样品DJZ-7-1具有与金刚石更强的亲缘性。基于本文碎屑石榴子石Si值大于3.02以及前人对湖南金刚石限定的温压条件进行分析,认为湖南金刚石可能形成于深度小于220 km的橄榄岩-榴辉岩混杂区,该区域系钾镁煌斑岩型金刚石来源的优势区域。据此,建议可在辰溪赤岩村河段上游区域进一步寻找幔源G3型石榴子石以及钾镁煌斑岩,以期发现原生金刚石矿床。     

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.     

Recalibration of mutually consistent garnet–biotite and garnet–cordierite geothermometers

Garnet–biotite and garnet–cordierite geothermometers have been consistently calibrated, using the results of Fe²⁺–Mg cation exchange experiments and utilizing recently evaluated nonideal mixing properties of garnet. Nonideal mixing parameters of biotite (including Fe, Mg, Al^VI, and Ti) and of cordierite (involving Fe and Mg) are evaluated in terms of iterative multiple least-square regressions of the experimental results. Assuming the presence of ferric Fe in biotite in relation to the coexisting Fe-oxide phases (Case A), and assuming the absence of ferric Fe in biotite (Case B), two formulae of garnet–biotite thermometer have been derived. The garnet–cordierite geothermometer was constructed using Margules parameters of garnet adopted in the garnet–biotite geothermometers. The newly calibrated garnet–biotite and garnet–cordierite thermometers clearly show improved conformity in the calculated temperatures. The thermometers give temperatures that are consistent with each other using natural garnet–biotite–cordierite assemblages within ±50 °C. The effects of ferric Fe in biotite on garnet–biotite thermometry have been evaluated comparing the two calibrations of the thermometer. The effects are significant; it is clarified that taking ferric Fe content in biotite into account leads to less dispersion of thermometric results.     

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.     

Origins of subcalcic garnets and their relation to diamond forming fluids—Case studies from Ekati (NWT-Canada) and Murowa (Zimbabwe)

Subcalcic, high-Cr (G10) garnets are found as inclusions within diamonds and in peridotitic xenoliths. The strong spatial associations between G10 garnets and diamond make them an important tool in the investigation of diamond genesis. We present an integrated study of the major and trace element composition and oxygen-Sr-Nd-Hf isotopic ratios of eight G10 garnets from the Ekati mine (NWT-Canada) and four from the Murowa mine (Zimbabwe) in an attempt to determine their petrogenetic evolution and to further examine a possible relationship between the metasomatic agents responsible for G10 garnet signatures and diamond forming fluids.All garnets display sinusoidal to mildly sinusoidal REE patterns and have negative Ti, Sr and positive U anomalies. They have variably radiogenic ⁸⁷Sr/⁸⁶Sr (0.703261-0.731191) and non-radiogenic ε_Nd values (−8.1 to −27.1), except for one sample from Murowa that has a positive ε_Nd of 2.5. One Ekati sample has an extremely low ε_Hf value of −61.6. The Ekati garnets we have studied all appear to come from a single depth in the Slave lithospheric mantle. On the base of Cr-Ca relations they have crystallized at 4.9 GPa and display dunitic Ca intercept values. Their δ¹⁸O values range between +5.23‰ and +5.42‰.The Ekati G10 garnets record a complex, multi-stage metasomatic history involving the interaction of several components during their genesis. One metasomatic agent was enriched in HFSE, LREE, Sr, and depleted in Nb. This agent had the least radiogenic Sr. Another metasomatic agent had highly radiogenic Sr, and was enriched in LREE, Sr, Nb, Th and U.The G10 garnets have very low ε_Nd and ε_Hf values combined with radiogenic Sr, thus, they require an early lithospheric mantle enrichment event at some stage during their genesis or during the evolution of any precursor material that they formed from. The only Hf isotope composition measurable from the Ekati suite is so unradiogenic (ε_Hf = −61) that it yields a Lu/Hf model age of 3521 Ma. This indicates that the lithospheric enrichment event seen by the Ekati garnets or their precursors may have occurred in the early stages of the craton stabilization, during the diamond forming event [Westerlund K., Shirey S., Richardson S., Carlson R., Gurney J. and Harris J. (2006) A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics. Contrib. Mineral. Petrol.152(3), 275-294]. Although our data cannot unequivocally discriminate between a variety of models for the genesis of subcalcic garnets it is clear that the host peridotite originated via melting at shallow depths followed by subduction and that the observed geochemical fingerprint of the garnets is strongly influenced by diamond forming fluids. Diamond forming fluids sampled from fibrous diamonds, have steep REE patterns, negative Ti and Sr anomalies and very low Sm/Nd ratios that are very similar to G10 garnet characteristics. These diamond forming fluids have been recently shown to have extreme Sr and Nd isotopic compositions [Klein-BenDavid O., Pearson D. G., Nowell G. M. and Cantigny P. (2008) Origins of diamond forming fluids—constraints from a coupled Sr-Nd isotope and trace element approach. Extended abstracts to the 9th International Kimberlite Conference, Frankfurt, Germany, 9IKC-A-00118.] that are closely concordant with G10 garnets. The fluids are also rich in LREE, P, K and water, sharing these features with mica-rich metasomes. These similarities suggest that ancient lithospheric metasomes could either provide a source region for, or be a product of diamond forming fluids. Diamond forming fluids appear to be intimately involved in the evolution of G10 garnets in the lithospheric mantle, either acting as a metasomatic agent, or being integral to triggering or enhancing garnet growth in a Cr-rich protolith. Such a link explains the strong association between G10 garnets and diamonds.     

Statistical approaches to the discrimination of mantle- and crust-derived low-Cr garnets using major and trace element data

Diamond exploration focuses on geochemical analysis of indicator minerals that are more abundant than diamond itself. Among such indicators, low-Cr (Cr₂O₃ < 1 wt%) garnets from mantle eclogites are problematic since they overlap compositionally with many lower-crust-derived garnets also transported by kimberlite. Misclassification of these garnets may create “false positive” mantle signatures and possible misdirection of exploration efforts. Statistical solutions using major elements in low-Cr garnet (Hardman et al. in J Geochem Explor 186:24–35, 2018) provide improved error rates for the discrimination of low-Cr crustal and mantle garnets recovered from kimberlite. In this study we analysed a large suite of garnets (n = 571) from both crustal and mantle settings, already characterised for major elements, for a wide range of trace elements by laser ablation inductively-coupled plasma mass spectrometry and use these new data along with literature data (n = 169) to evaluate the effectiveness of adding trace elements to garnet-based diamond exploration programs. A new garnet classification scheme, initially using a major-element based filter, uses garnet Sr contents and Eu anomalies to help identify low-Cr garnets that are misclassified using major element methods. Combined with existing methods, our new trace element classifiers offer improvement in classification error rates for low-Cr, crustal and mantle garnets to as low as 4.7% for calibration data.

     

辽宁瓦房店金伯利岩中石榴石特征及种类鉴定

辽宁瓦房店金刚石矿区金伯利岩中的石榴石一直被当作镁铝榴石。为了确定矿区颜色复杂的石榴石种类,本文对矿区的石榴石进行了系统的采样分析,测定了112件石榴石样品的晶胞参数、50件样品的微区化学成分和40件样品的红外光谱。利用石榴石晶胞参数、红外光谱、化学成分和化学分子式方法对矿区石榴石进行分类,结果显示:晶胞参数分类法误差大,容易得出错误结论;红外图谱分类法准确度不高,只能作为参考方法;化学成分分类法太过笼统,达不到详细划分石榴石种类的目的;化学分子式分类法可把矿区的石榴石详细划分6个矿种:镁钙铁-铝铬铁榴石、镁铁钙-铝铬铁榴石、镁钙铁-铝铬榴石、镁钙-铝铬铁镁榴石、镁铁钙-铝铬榴石、镁铁钙-铝铁铬榴石,每种石榴石都充分反映了A、B离子的种类及占位特征,是4种分类方法中最为科学的方法。研究认为瓦房店金刚石矿区金伯利岩中石榴石A端元成分以Mg²⁺离子占位为主;B端元成分以Al³⁺离子占位为主。由于阳离子替代普遍,A、B端元成分复杂,瓦房店金伯利岩中不存在单纯意义上的镁铝榴石。     

Diamondiferous peridotitic microxenoliths from the Diavik Diamond Mine, NT

Twenty-five diamonds recovered from 21 diamondiferous peridotitic micro-xenoliths from the A154 South and North kimberlite pipes at Diavik (Slave Craton) match the general peridotitic diamond production at this mine with respect to colour, carbon isotopic composition, and nitrogen concentrations and aggregation states. Based on garnet compositions, the majority of the diamondiferous microxenoliths is lherzolitic (G9) in paragenesis, in stark contrast to a predominantly harzburgitic (G10) inclusion paragenesis for the general diamond production. For garnet inclusions in diamonds from A154 South, the lherzolitic paragenesis, compared to the harzburgitic paragenesis, is distinctly lower in Cr content. For microxenolith garnets, however, Cr contents for garnets of both the parageneses are similar and match those of the harzburgitic inclusion garnets. Assuming that the microxenolith diamonds reflect a sample of the general diamond population, the abundant Cr-rich lherzolitic garnets formed via metasomatic overprinting of original harzburgitic diamond sources subsequent to diamond formation, conversion of original harzburgitic diamond sources occurred in the course of metasomatic overprint re-fertilization. Metasomatic overprinting after diamond formation is supported by the finding of a highly magnesian olivine inclusion (Fo₉₅) in a microxenolith diamond that clearly formed in a much more depleted environment than indicated by the composition of its microxenolith host. Chondrite normalized REE patterns of microxenolith garnets are predominantly sinusoidal, similar to observations for inclusion garnets. Sinusoidal REE_N patterns are interpreted to indicate a relatively mild metasomatic overprint through a highly fractionated (very high LREE/HREE) fluid. The predominance of such patterns may explain why the proposed metasomatic conversion of harzburgite to lherzolite appears to have had no destructive effect on diamond content. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mineral chemistry and thermobarometry of inclusions from De Beers Pool diamonds, Kimberley, South Africa

Silicate and oxide mineral inclusions in diamonds from the geologically and historically important De Beers Pool kimberlites in Kimberley, South Africa, are characterised by harzburgitic compositions (>90%), with lesser abundances from eclogitic and websteritic parageneses. The De Beers Pool diamonds contain unusually high numbers of inclusion intergrowths, with garnet+orthopyroxene±chromite±olivine and chromite+olivine assemblages dominant. More unusual intergrowths include garnet+olivine+magnesite and an eclogitic assemblage comprising garnet+clinopyroxene+rutile. The mineral chemistry of the De Beers Pool inclusions overlaps that of most worldwide localities. Peridotitic garnet inclusions exhibit variable CaO (<5.8 wt.%) and Cr₂O₃ contents (3.0–15.0 wt.%), although the majority are harzburgitic with very low calcium concentrations (<2 wt.% CaO). Eclogitic garnet inclusions are characterised by a wide range in CaO (3.3–21.1 wt.%) with low Cr₂O₃ (<1 wt.%). Websteritic garnets exhibit intermediate compositions. Most chromite inclusions contain 63–67 wt.% Cr₂O₃ and <0.5 wt.% TiO₂. Olivine and orthopyroxene inclusions are magnesium-rich with Mg-numbers of 93–97. Olivine inclusions in chromite exhibit the highest Mg-numbers and also contain elevated Cr₂O₃ contents up to 1.0 wt.%. Peridotitic clinopyroxene inclusions are Cr-diopsides with up to 0.8 wt.% K₂O. Eclogitic and websteritic clinopyroxene inclusions exhibit overlapping compositions with a wide range in Mg-numbers (66–86).

Calculated temperatures for non-touching inclusion pairs from individual diamonds range from 1082 to 1320 °C (average=1197 °C), whereas pressures vary from 4.6 to 7.7 GPa (average=6.3 GPa). Touching inclusion assemblages are characterised by equilibration temperatures of 995 to 1182 °C (average=1079 °C) and pressures of 4.2–6.8 GPa (average=5.4 GPa). Provided that the non-touching inclusions represent equilibrium assemblages, it is suggested that these inclusions record the conditions at the time of diamond crystallisation (1200 °C; 3.0 Ga). The lower average temperatures for touching inclusions are attributed to re-equilibration in a cooling mantle (1050 °C) prior to kimberlite eruption at 85 Ma. Pressure estimates for touching garnet–orthopyroxene inclusions are also skewed towards lower values than most non-touching inclusions. This apparent difference may be an artefact of the Al-exchange geobarometer and/or the result of sampling bias, due to limited numbers of non-touching garnet–orthopyroxene inclusions. Alternatively pressure differences could be caused by differential uplift in the mantle or possibly variations in thermal compressibility between diamond and silicate inclusions. However, thermodynamic modelling suggests that thermal compressibility differences would cause only minor changes in internal inclusion pressures (<0.2 GPa/100 °C).     

Kimberlite AT-56: a mantle sample from the north central Superior craton, Canada

Kimberlite AT-56, discovered in February 2001, represents the most recent addition to the Attawapiskat kimberlite cluster, located in the James Bay Lowlands of Ontario, Canada. AT-56 is a small kimberlite body with a surface diameter of approximately 40 m and a steep southeastern plunge. It consists of a medium to coarse-grained matrix supported kimberlite with abundant olivine, clinopyroxene, garnet, ilmenite and mica macrocrysts in a green-black to orange-black matrix. The kimberlite is classified as a hypabyssal facies sparsely macrocrystic calcite kimberlite. Heavy mineral concentrates from two representative samples of AT-56 have been analyzed to characterize the mantle sampled by the kimberlite. Both samples yielded large heavy mineral concentrates comprised of roughly equal proportions of Mg-ilmenite, Cr-diopside, high-Cr garnet and low-Cr garnet. Mg-chromite is also present in quantities an order of magnitude less than the other constituents.

The high-Cr peridotitic garnet macrocrysts are only slightly more abundant than the low-Cr varieties, the population being dominated by G9 (lherzolitic) types with only a few (less than 10%) weakly sub-calcic G10 (probable harzburgitic) garnets present. Ni thermometry results for a representative selection of G9 and G10 garnets indicate that the majority equilibrated at temperatures ranging from 1000 to 1250 °C. A significant proportion of the low-Cr garnet population derived from AT-56 is characterized by relatively low-Ti (0.2 to 0.4 wt.% TiO₂) and elevated Na (0.07 to 0.13 wt.% Na₂O) contents characteristic of Group 1, diamond inclusion type eclogite garnets. These sodic garnets have elevated Cr₂O₃ contents (typically 1 to 2 wt.% Cr₂O₃), suggesting they may be websteritic in origin rather than eclogitic. Comparison of AT-56 garnet compositions with published data available for other Attawapiskat kimberlites suggests websteritic mantle has also been sampled by kimberlite bodies elsewhere in the Attawapiskat cluster and it may be an important diamond reservoir in this area.     

Mineral inclusions in microdiamonds and macrodiamonds from kimberlites of Yakutia: a comparative study

Chemical compositions were determined on mineral inclusions recovered from 290 microdiamonds (<1 mm) from 8 operating diamond mines in Yakutia. The sampled diamond mines include Mir, Udachnaya, Internatsionalnaya, Aykhal, Sytykanskaya, Yubileynaya, Komsomolskaya and Krasnopresnenskaya. The mineral inclusions include both ultramafic (peridotitic) suite (U-type) and eclogitic suite (E-type) examples. Olivines, chromites, Cr-pyropes, Cr-diopsides and enstatite were studied from U-type diamonds. Mg–Ca–Fe-garnets and omphacitic clinopyroxenes were studied from E-type microdiamonds. Abundances and compositions of these inclusions were compared with published and unpublished data on inclusions available from approximately 2000 macrodiamonds (>1 mm) from the same sources, and worldwide data for olivines and chromites. Although there are general similarities, notable exceptions were detected in about 10% of the inclusions from microdiamonds. For each of the pipes, anomalous compositions occur between the micro- and macrodiamond inclusions, but in different proportions, sometimes as high as 50% of the inclusions. Our study has demonstrated that mineral inclusions in microdiamonds are considerably more variable in their compositions and parageneses compared with inclusions in macrodiamonds.

Significant compositional anomalies in inclusions from microdiamonds include: (1) garnets containing pyroxene solid solution (majoritic component) both in U- and E-type microdiamonds from three pipes: Yubileynaya, Komsomolskaya and Krasnopresnenskaya. The moles of Si (pfu) in these garnets range from 3.07 to 3.13 and as high as 3.29, on the basis of 12 oxygens, along with a notable contents of Na₂O in two eclogitic garnets (0.43 and 0.93 wt.%) and uniquely high Cr₂O₃ and CaO contents in an ultramafic garnet of wehrlitic paragenesis; (2) coexisting wehrlitic garnets in a single microdiamond, one majoritic, the other normal, both with distinct +Eu anomalies, considered as signatures of crustal protoliths for the precursors to these garnets; (3) olivines with relatively low Fo (86–89) and high-NiO contents (0.46–0.64 wt.%), from Yubileynaya and Sytykanskaya microdiamonds; (4) chromites containing high-TiO₂ (up to 4.7 wt.%) and some extremely rich in MgO (Mg# 80). It is concluded that many of these compositional features observed may be related to a deeper origin for the microdiamond source region (>300 km), for at least a 10–30% portion of microdiamonds from each Yakutian pipe.     

Compositional evolution of grossular garnet from leucotonalitic pegmatite at Ruda nad Moravou, Czech Republic; a complex EMPA, LA-ICP-MS, IR and CL study

Five distinct paragenetic, morphological and compositional types of grossular garnet (G1, G2, G3, G4, G5) were distinguished within the individual (sub)units of the zoned leucotonalitic pegmatite cutting serpentinized lherzolite with rodingite dikes at ??ár near Ruda nad Moravou, Staré Město Unit, Northern Moravia. Detailed study using Electron Microprobe Analysis, Laser Ablation Inductively Coupled Plasma Mass Spectrometry, Cathodoluminiscence and Infrared Spectroscopy revealed distinct compositional trends in major, minor and trace elements. The contents of Fe³⁺, Mn, Mg and Ti increase from early garnet (G1) in the outermost grossular subunit through the interstitial garnet (G2) in the leucocratic subunit to graphic intergrowths of quartz+garnet (G3) in the coarse-grained unit. Then these constituents decrease in inclusions of garnet (G4) from the blocky unit and large crystals of garnet (G5) from the quartz core. Some trace elements (V, Ni, Y) exhibit the same trends, only Be evidently increases in garnet from border zone to the centre. Fluorine has negative correlation with Fe³⁺ as well as some trace elements (Ta, Pb). Concentrations of H₂O in garnets, up to 0.22 wt.% H₂O, are comparable with spessartine-almandine garnets from the Rutherford No. 2 pegmatite, Virginia, and grossular garnets from high-temperature calc-silicate rocks (skarns). Water contents correlate positively with Fe³⁺, but inversely with F. The use of water contents in garnet to elucidate the fluctuations of activity of H₂O during the pegmatite formation is only limited; the incorporation of hydrous defects seems to be controlled instead by crystal-structural constraints. However, the sum of all volatile components (H₂O + F) increases about twice from the outermost subunit to the centre of the pegmatite body.     

Compositional zonation in garnets in peridotite xenoliths

Garnets in 42 peridotite xenoliths, most from southern Africa, have been analyzed by electron probe to seek correlations between compositional zonation and rock history. Xenoliths have been placed into the following 6 groups, based primarily upon zonation in garnet: I (12 rocks)-zonation dominated by enrichment of Ti and other incompatible elements in garnet rims; II (10 rocks)-garnet nearly homogeneous; III (8 rocks)-rims depleted in Cr, with little or no related zonation of Ti; IV (3 rocks)-slight Ti zonation sympathetic to that of Cr; V (3 rocks)-garnet rims depleted or enriched in Cr, and chromite included in garnet; VI (6 rocks)-garnets with other characteristics. Element partitioning between olivine, pyroxene, and garnet rims generally is consistent with the assumption of equilibrium before eruption. Although one analyzed rock contains olivine and pyroxene that may have non-equilibrated oxygen isotopes, no corresponding departures from chemical equilibrium were noted. Causes of zoning include melt infiltration and changes in temperature and pressure. Zonation was caused or heavily influenced by melt infiltration in garnets of Group I. In Groups III, IV, and V, most compositional gradients in garnets are attributed to changes in temperature, pressure, or both, and gradients of Cr are characteristic. There are no simple relationships among wt% Cr₂O₃ in garnet, calculated temperature, and the presence of compositional gradients. Rather, garnets nearly homogeneous in Cr are present in rocks with calculated equilibration temperatures that span the range 800–1500 °C. Although the most prominent Cr gradients are found in relatively Cr-rich garnets of rocks for which calculated temperatures are below 1050 °C, gradients are well-defined in a Group IV rock with T1300 °C. The variety of Cr gradients in garnets erupted from a range of temperatures indicates that the zonations record diverse histories. Petrologic histories have been investigated by simulated cooling of model rock compositions in the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃. Proportions and compositions of pyroxene and garnet were calculated as functions of P and T. The most common pattern of zonation in Groups III and IV, a decrease of less than 1 wt% Cr₂O₃ core-to-rim, can be simulated by cooling of less than 200 °C or pressure decreases of less than 1 GPa. The preservation of growth zonation in garnets with calculated temperatures near 1300 °C implies that these garnets grew within a geologically short time before eruption, probably in response to fast cooling after crystallization of a small intrusion nearby. Progress in interpreting garnet zonations in part will depend upon determinations of diffusion rates for Cr. Zonation formed by diffusion within garnet cannot always be distinguished from that formed by growth, but Ca–Cr correlations unlike those typical of peridotite suite garnets may document diffusion.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

Enrichment processes at the base of the Archean lithospheric mantle: observations from trace element characteristics of pyropic garnet inclusions in diamonds

Trace element concentrations of peridotitic garnet inclusions in diamonds from two Chinese kimberlite pipes were determined using the ion microprobe. Garnet xenocrysts from the same two kimberlite pipes were also analyzed for comparison. In contrast to their extremely refractory major element compositions, all harzburgitic garnets showed enrichment in light rare earth elements (REE) relative to chondrite, resulting in sinuous REE patterns. Both normal and sinuous REE patterns were observed from the lherzolitic garnets. Concentrations of REE in garnets changed significantly from diamond to diamond and no specific correlations were observed with their major element compositions. Analyses of randomly selected two to three points within every grain of a large number of garnet inclusions by the ion microprobe demonstrated that there was no evident compositional heterogeneity, and multiple grains of one phase from a single diamond host also exhibit very similar compositions. This implies that the trace element heterogeneity within one grain or among multiple inclusions from the same diamond host, as reported from Siberian diamonds, is not a common feature for these Chinese diamonds. Concentrations of Na, Ti, and Zr tend to decrease when garnets become more refractory, but variations of Sr and Li are more complex. Compositions rich in light REE and relatively poor in high field strength elements (HFSE) of the harzburgitic garnet inclusions in diamonds are generally consistent with metasomatism by carbonatite melts. The trace element features observed from the garnet inclusions in Chinese diamonds may be caused by carbonatite melt infiltration and partial melt extraction. Spatial and temporal gradients in melt/rock ratio and temperature are the main reasons for the large variations of REE patterns and other trace element concentrations. Received: 27 April 1999 / Accepted: 1 March 2000     

The discovery of garnets closely related to diamonds in the Finsch pipe,South Africa

Magnesium-rich, calcium-poor, lilac coloured garnets have been found in the heavy mineral concentrate of the Finsch kimberlite pipe. Some of these garnets contain sufficient chromium to place them within the compositional field of the garnets previously only reported as inclusions in diamonds.These lilac garnets are considered to have formed in equilibrium with the minerals found as inclusions in diamond and hence with the diamond itself. Their presence in the kimberlite should be diagnostic of the presence of diamond, but it is not known if there is any quantitative relationship. The garnets are considered to have a deeper provenance than the magnesian garnets commonly found as xenocrysts in kimberlite and in garnet peridotite xenoliths. The mantle composition at their depths of origin must be more refractory in nature than the peridotite xenoliths. The garnets having a higher magnesium and chromium content, a higher Mg/Fe ratio and lower calcium, aluminium and titanium than those found in the xenoliths.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

Garnets from diamond deposits in China and in the Arkhangelsk diamondiferous province

The morphology and chemical composition of garnets from principal deposits in China and in the Arkhangelsk Province consisting of kimberlites of various mineral types have been examined. The morphology of garnets (300 specimens) from the V. Grib pipe was examined, in which crystal fragments and irregular grains predominate, and dissolution traces are common. Distribution of types of garnet coloration is typical of kimberlites: lilac-violet and red garnets of ultramafic rock association are preponderant, and the proportion of yellow-orange garnets is rather high, while brown garnets are very rare. The garnet preservation degree is very low, which is related to their high primary fracturing due to cataclasis. Grains with finely matted surfaces are preponderant (90%) reflecting their high corrosion alterations. The chemical composition was determined in 56 garnet speciments from the Grib pipe. Garnets from lherzolitic and eclogitic rock types were found and garnets from magnesium and ilmenite ultramafics are present; there are no garnets from eclogites, but garnets from diamondiferous rock associations occur. The investigations demonstrated that garnets from lherzolite rock association are preponderant in kimberlites from China, as well as from other regions, while garnets from the harzburgite-dunite and from diamondiferous rock associations are rare. Garnets belonging to the graphitepyrope depth facies were also found.