Mineralogical criteria for the diamond potential of Upper Triassic placers on the northeastern margin of the Siberian Platform

Representative sampling of a diamond-bearing basal horizon in the Carnian Stage (Upper Triassic) on the northeastern margin of the Siberian Platform revealed a wide spectrum of indicator minerals, first of all, garnets, whose compositions are the same as in the inclusions in the regional diamonds. Of special interest are garnets of potential eclogite paragenesis with an abnormally high impurity of MnO (0.5–3.2 wt.%), which was earlier detected in more than 20% of garnets present as inclusions in diamonds of northern Quaternary placers and recommended as a new mineralogical criterion for diamond presence. Subcalcic Cr-pyropes of dunite–harzburgite paragenesis were also found in variable amounts, from 0.7 to 3.9 rel.%, in the sample of 973 grains of pyropes of lherzolite and websterite parageneses. Three grains contain 11.9, 12.6, and 16 wt.% Cr₂O₃, which corresponds to the presence of 30–34% of Mg–Cr-knorringite component. Such pyropes have been revealed for the first time in the study region. Cr-spinels are a mixture of compositions typical of kimberlites and the regional alkali-ultrabasic rocks. All studied samples contain picroilmenites with a variable content of Cr₂O₃ impurity. Since Mg–Fe–Ca-garnets with Mg# < 35 can be partly hosted in metamorphic rocks of the Anabar Shield, the elevated content of Na₂O impurity (> 0.09 wt.%) was also taken into account. The different contents of indicator minerals in the samples might be due to the variable composition of the diamond orebodies. The Carnian placers call for new systematic sampling. Special attention should be given to estimation of the composition of garnets of presumably eclogite paragenesis with elevated contents of TiO₂, MnO, CaO, and Na₂O and to search for perovskite and Nb-containing rutile. These minerals, together with zircons, are of interest for determining the U–Pb isotopic age of probable diamond orebodies—kimberlites.     

Megacrysts and xenoliths in kimberlite,Elliott County,Kentucky: A mantle sample from beneath the Permian Appalachian Plateau

Two kimberlite pipes in Elliott County contain rare ultramafic xenoliths and abundant megacrysts of olivine (Fo_85–93), garnet (0.21–9.07% Cr₂O₃), picroilmenite, phlogopite, Cr-poor clinopyroxene (0.56–0.88% Cr₂O₃), and Cr-poor orthopyroxene (<0.03–0.34% Cr₂O₃) in a matrix of olivine (Fo_88–92), picroilmenite, Cr-spinel, magnetite, perovskite, pyrrhotite, calcite, and hydrous silicates. Rare clinopyroxene-ilmenite intergrowths also occur. Garnets show correlation of mg (0.79–0.86) and CaO (4.54–7.10%) with Cr₂O₃ content; the more Mg-rich garnets have more uvarovite in solution. Clinopyroxene megacrysts show a general decrease in Cr₂O₃ and increase in TiO₂ (0.38–0.56%) with decreasing mg (0.87–0.91). Clinopyroxene megacrysts are more Cr-rich than clinopyroxene in clinopyroxene-ilmenite intergrowths (0.06–0.38% Cr₂O₃) and less Cr-rich than peridotite clinopyroxenes (1.39–1.46% Cr₂O₃). Orthopyroxene megacrysts and orthopyroxene inclusions in olivine megacrysts form two populations: high-Ca, high-Al (1.09–1.16% CaO and 1.16–1.18% Al₂O₃) and low-Ca, low-Al (0.35–0.46% CaO and 0.67–0.74% Al₂O₃). Three orthopyroxenes belonging to a low-Ca subgroup of the high-Ca, high-Al group were also identified (0.86–0.98% CaO and 0.95–1.01% Al₂O₃). The high-Ca, high-Al group (Group I) has lower mg (0.88–0.90) than low-Ca, low-Al group (Group II) with mg=0.92–0.93; low mg orthopyroxenes (Group Ia) have lower Cr₂O₃ and higher TiO₂ than high mg orthopyroxenes (Group II). The orthopyroxene megacrysts have lower Cr₂O₃ than peridotite orthopyroxenes (0.46–0.57% Cr₂O₃). Diopside solvus temperatures indicate equilibration of clinopyroxene megacrysts at 1,165°–1,390° C and 1,295°–1,335° C for clinopyroxene in clinopyroxene-ilmenite intergrowths. P-T estimates for orthopyroxene megacrysts are bimodal: high-Ca, high-Al (Group I) orthopyroxenes equilibrated at 1,165°–1,255° C and 51–53 kb (± 5kb) and the low-Ca, low-Al (Group II) orthopyroxenes equilibrated at 970°–1,020°C and 46–56 kb (± 5kb). Garnet peridotites equilibrated at 1,240°–1,360° C and 47–49 kb. Spinel peridotites have discordant temperatures of 720°–835° C (using spinel-olivine Fe/Mg) and 865°–1,125° C (Al in orthopyroxene).Megacrysts probably precipitated from a fractionating liquid at >150 km depth. They are not disaggregated peridotite because: (1) of large crystal size (up to 1.5 cm), (2) compositions are distinctly different from peridotite phases, and (3) they display fractionation trends. The high mg, low T orthopyroxenes and the clustering of olivine rims near Fo_89–90 reflect liquid changes to higher MgO contents due to (1) assimilation of wall-rock and/or (2) an increase in Fe³⁺/Fe²⁺ and subsequently MgO/FeO as a result of an increase in f _o.     

Field setting,mineralogy, chemistry,and genesis of arc picrites,New Georgia,Solomon Islands

The field setting, petrography, mineralogy, and geochemistry of a suite of picrite basalts and related magnesian olivine tholeiites (New Georgia arc picrites) from the New Georgia Volcanics, Kolo caldera in the active ensimatic Solomon Islands arc are presented. These lavas, with an areal extent in the order of 100² km and almost 1 km thick in places, are located close to the intersection of the Woodlark spreading zone with the Pacific plate margin. They contain abundant olivine (Fo_94-75) and diopside (Cr₂O₃ 1.1-0.4%, Al₂O₃ 1–3%), and spinels characterised by a large range in Cr/(Cr+Al) (0.85–0.46) and Mg/(Mg+ Fe⁺⁺) (0.65–0.1). The spinels are Fe⁺⁺⁺ rich, with Fe⁺⁺⁺/ (Fe⁺⁺⁺+Cr+Al) varying from 0.06 to 1.0. A discrete group of spinels with the highest Cr/(Cr+Al) (0.83–0.86) and lowest Fe⁺⁺⁺ contents are included in the most Mg-rich olivine (Fo_91–94) and both may be xenocrystal in origin.The lavas, which range between 10–28% MgO, define linear trends on oxide (element) — MgO diagrams and these trends are interpreted as olivine (0.9) clinopyroxene (0.1) control lines. For the reconstructed parent magma composition of these arc picrites, ratios involving CaO, Al₂O₃, TiO₂, Zr, V and Sc are very close to chondritic. REE patterns are slightly LREE — enriched ((La/Sm)^N 1.3–1.43) and HREE are flat. All lavas show marked enrichments in K, Rb, Sr, Ba, and LREE relative to MORB with similar MgO contents, but the TiO₂ content of the proposed parent magma is close to those of postulated primary MORB liquids. It is proposed that the arc parent magma was produced by partial melting of sub-oceanic upper mantle induced by the introduction of LILE — enriched hydrous fluids derived by dehydration and/or partial melting of subducted ocean crust and possibly minor sediments.     

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.     

Refractory- and metallurgical-type chromite ores,Zambales ophiolite,Luzon, Philippines

The Zambales ophiolite is the major source of chromite ore in the Philippines. The chromitites are concordant cumulates and are associated with distinct chromitite-bearing sequences within the mantle peridotites. Refractory and metallurgical chromite deposits are spatially separated and related to different lithologic associations, which crystallized from different parental magmas. — Refractory chromite ores (30–44 wt% Cr₂O₃; 20–30 wt% Al₂O₃) are linked with the peridotite-troctolite-olivine gabbro lineage. Two main types were found: (1) Al-rich refractory ores associated with harzburgites and feldspathic periodotites and (2) more Cr-rich varieties associated with lherzolites. — Metallurgical chromite ores (45–53 wt% Cr₂O₃; 12–18 wt% Al₂O₃) are linked with the peridotite-pyroxenite-norite lineage. Two main types were also found: (1) Cr-rich metallurgical ores associated with orthopyroxenites and (2) more Al-rich varieties related to clinopyroxenites. — The chemical composition of chromite within the deposits varies depending on the chromite/silicate ratios of the ore types and grades continuously into accessory chrome spinels in the wall-rock peridotites. — The geochemistry of accessory chrome spinels in various peridotites and mafic cumulates depends on the mineralogical composition and the stratigraphic position of their host rocks.New address: BEB Erdgas und Erdöl GmbH, Riethorst 12, D-3000 Hannover 51The terms chrome-spinels and chromite are used as follows: 1. Chrome-spinel is only used for those occuring as accessory minerals in various ultramafic and mafic rocks (= accessory chrome-spinels). Their chemical composition has been determined only by microprobe analysis. — 2. Chromite is used for ore and ore deposits (=chromitites); the chemical composition has been determined by wet chemistry (AAS) or by microprobe analysis     

Isomorphic sodium admixture in garnets formed at high pressures

Na₂O contents were determined by electron microprobe analysis in 124 garnets from diamonds, xenoliths of peridotites, eclogites from kimberlitic pipes and metamorphic complexes. Na₂O content ranges between 0.01 and 0.22% with the limit of detection at about 0.01%. In the garnets of diamond-bearing eclogites and orange garnets from diamonds a regular increase in the Na₂O content has been established, varying from 0.09 to 0.22, as compared to garnets from eclogites of metamorphic complexes (range 0.01 to 0.06). It is assumed that the increased Na₂O content in the garnets of eclogites is mainly connected with higher pressure, whereas isomorphism of sodium is connected with the initial stages of the transition from Si⁴ to Si⁶ in the garnet structure: CaAlNaSi.The study of the sodium content of garnets has shown that all the orange-coloured garnets from diamonds so far studied are related to eclogite assemblage. Determination of the Na₂O content of individual inclusions of chrome pyropes from diamonds permits a conclusion on the type of assemblage (with or without clinopyroxene). Proceeding from these data, the importance of garnet-olivine paragenesis within the stability field of diamond has been revealed.Some clear distinctions in the sodium content of the garnets from xenoliths of the kyanite eclogites from the Zagadochnaya pipe in Yakutia and the Roberts Victor mine in South Africa confirm the relation of these eclogites to different subfacies.A conclusion is drawn as to the possibility of utilizing the Na/Na+Ca distribution in the garnets and pyroxenes of eclogites of especially deep-seated origin as a pressure indicator and to the necessity for experimental testing of the dependence of the distribution of these elements in garnets and pyroxenes on pressure, presumably in the range of 30–100 kbars.     

On the origin of silicate-bearing diamondites

Garnets and clinopyroxenes, intergrown with diamonds in 37 diamondites (“bort”, “polycrystalline diamond aggregates”, “polycrystalline diamond”, “framesite”), presumably from southern Africa, were analyzed for trace element contents by LA-ICP-MS. The intimate diamond-silicate intergrowths suggest that both precipitated from the same fluids during the same crystallization events. In this study we distinguish 5 chemical garnet groups: “peridotitic” (P), intermediate (I) and 3 “eclogitic” groups (E1, E2 and E3). Chondrite-normalized trace element patterns for the garnet groups roughly correlate with major element abundances. Most of P garnets show complex, mildly sinusoidal REE_N patterns with relatively flat HREE_N-MREE_N, a small hump at Sm-Nd and depleted LREE_N, and have relatively high contents of Nb, Ta, U, and Th. The REE_N abundance patterns of E garnets differ by showing a continuous increase from LREE to HREE and depletion in LREE and highly incompatible elements relative to the P garnets. Of all garnet groups, E3 garnets are the poorest in highly incompatible trace elements and in Mg. Model equilibrium fluids for P garnets suggest crystallization from magnesian carbonate-bearing fluids/melts, which were very rich in incompatible trace elements — similar to kimberlites. Hypothetical equilibrium melts for E1 and E2 garnets are also magnesian and poorer in LREE and highly incompatible elements relative to typical kimberlitic or carbonatitic melts. Fluids that crystallized the P and most of the E garnets have similar mg numbers indicating a peridotitic source for both. The differences in Cr and highly incompatible element contents can be the result of differences in fluid formation and/or evolution rather than different source rock. The positive correlation of Cr₂O₃ and mg with the abundances of highly incompatible elements in garnets indicate fluid-rock fractionation processes rather than igneous fractional crystallization processes being responsible for the evolution of the diamondite-forming fluids.     

Pyrope–knorringite garnets: overview of experimental data and natural parageneses

This paper gives an analytical overview of the experimental data obtained by different authors at high P and T in the model system MgO–Al₂O₃–SiO₂–Cr₂O₃ (MASCr). A set of four simple polynomial equations is proposed for the temperature and pressure dependence of chromium content in garnet and spinel in the assemblage Gar + Opx + Es and Gar + Fo + Opx + Sp.From the first equation, one can estimate the minimum pressure at a given temperature which is required for the formation of peridotite garnets of uncertain paragenesis with a known knorringite content. A combination of the second and third equations helps estimate P and T from the chromium content of garnet and spinel from assemblages containing both minerals. If the spinel composition is unknown, but there is reason to assign garnet to a spinel-bearing paragenesis, the fourth equation is applicable for estimating pressure at given temperature.Originally, the proposed garnet–spinel geothermobarometer was developed for a harzburgite paragenesis. However, it is applicable to garnets with CaO/Cr₂O₃ < 0.903 (including lherzolitic ones), that is, those within the Pyr–Kn–Uv triangle of the reciprocal quaternary diagram Pyr–Cros–Uv–Kn.Using the above equations and an empirical P_CG geobarometer (Grütter et al., 2006), comparative geothermobarometric estimates were obtained for a set of garnet and garnet–spinel inclusions in diamonds and intergrowths with diamond, as well as garnet inclusions in spinel. If garnet has CaO/Cr₂O₃ = 0.35–0.40, the results are in good accord. For Cr-richest and Ca-poorest garnets, the P_CG barometer shows pressures 10–15% higher compared with our estimates.     

Diamondiferous peridotite xenoliths from the Argyle (AK1) lamproite pipe,Western Australia

This paper describes a suite of peridotite xenoliths. some carrying diamonds at high grades, from the richly diamondiferous early Proterozoic (1180 Ma) Argyle (AK1) lamproite pipe, in northwestern Australia. The peridotites are mostly coarse garnet lherzolites but also include garnet harzburgite, chromite — garnet peridotite, a garnet wehrlite, and an altered spinel peridotite with extremely Cr-rich chromite. In all cases the garnet has been replaced by a kelyphite-like, symplectic intergrowth of Alrich pyroxenes, Al-spinel and secondary silicates. The peridotites have refractory compositions characterized by high Mg/(Mg+Fe) and depletion in lithophile elements (Al₂O₃ and CaO < 1%, Na₂O0.03%) and high field strength cations such as Ti, Zr, Y, and Yb. Olivines have high Mg/(Mg+Fe) (Mg ^91–93 ) and, like olivine inclusions in diamonds from the Argyle pipe, contain detectable amounts of Cr₂O₃ (0.03%–0.07%) but have very low CaO contents (typically 0.04%–0.05%). Enstatites (Mg ^92–94 ) have comparatively high Cr₂O₃ (0.2%–0.45%) and Na₂O (up to 0.18%) but very low Al₂O₃ contents (0.5%–0.7%). Diopsides (Mg ^92–94 , Ca/(Ca+Mg+Fe)=0.37–0.43) are Cr-rich (0.7%–1.9% Cr₂O₃) and have low Al₂O₃ (0.7%–2.2%) and Na₂O (0.5%–1.6%) contents. Many have high K₂O contents, typically 0.1%–0.4% but up to 1.3% K₂O in one xenolith. The chromite coexisting with former garnet is Mg-and Cr-rich [Mg/(Mg+Fe²⁺)=0.68–0.72, Cr/(Cr+Al)=0.72–0.79] whereas chromite in the spinel peridotite is even more Cr-rich (65% Cr₂O₃, Cr/(Cr+Al)=0.85, resembling inclusions in diamond. One highly serpentinized former garnet peridotite contains a Cr-rich (up to 13% Cr₂O₃) titanate resembling armalcolite but containing significant K₂O (1%–2.5%), CaO (0.6%–2.2%), ZrO₂ (0.1%–0.8%), SrO (0.1%–0.3%), and BaO (up to 0.58%): this appears to have formed as an overprint of the primary mineralogy. Temperatures and pressures estimated from coexisting pyroxenes and reconstructed garnet compositions indicate that the garnet lherzolites equilibrated at 1140°–1290° C and 5.0–5.9 GPa (160–190 km depth), within the stability field of diamond. Oxygen fugacties within the diamond forming environment are estimated from spinel-bearing assemblages to be reducing, with f _O2 between MW and IW. The presence of significant K in the diopsides from the peridotite xenoliths and in diopsides from heavy mineral concentrate from the Argyle pipe implies metasomatic enrichment of the subcontinental lithosphere within the diamond stability field. The P-T conditions estimated for the Argyle peridotites demonstrate that diamondiferous lamproite magmas incorporate mantle xenoliths from similar depths to kimberlites in cratonic settings, and imply that Proterozoic cratonized orogenic belts can have lithospheric roots of comparable thickness to beneath Archaean cratons. These roots lie at the base of the lithosphere within the stability field of diamond. The xenoliths, the calcic nature of chrome pyropes from heavy mineral concentrate, and the diamond inclusion assemblage indicate that the lighosphere beneath the Western Australian lamproites is mostly depleted lherozolite rather than the harzburgite commonly found beneath Archaean cratons. Nevertheless, the dominance of eclogitic paragenesis inclusions in Argyle diamonds indicates a significant proportion of diamondiferous eclogite is also present. The form, mineral inclusion assemblage, and the C-isotopic composition of diamonds in the peridotite xenoliths suggest that disaggregated diamondiferous peridotites are the source of the planar octahedral diamonds which constitute a minor component of the Argyle production. These diamonds are believed to have formed from mantle carbon in reduced, refractory peridotite (Iherzolite-harzburgite) in contrast to the predominant strongly ¹³C-depleted eclogitic suite diamonds which contain a recycled crustal carbon component. The source region of the lamproites has undergone long-term (2 Ga) enrichment in incompatible elements.     

Petrochemistry of eclogites from the Koidu Kimberlite Complex,Sierra Leone

Petrography, mineral and bulk chemistry of upper mantle-derived eclogites (garnet and clinopyroxene) from the Koidu Kimberlite Complex, Sierra Leone, are presented in the first comprehensive study of these xenoliths from West Africa. Although peridotite-suite xenoliths are generally more common in kimberlites, the upper mantle sample preserved in Pipe Number 1 at Koidu is exclusively eclogitic, making this the fifth locality in which eclogite is the sole polymineralic xenolith in kimberlite. Over 2000 xenoliths were collected, of which 47 are described in detail that include diamond, graphite, kyanite, corundum, quartz after coesite, and amphibole eclogites. Grossular-pyrope-almandine garnets are chromium-poor (<0.72 wt% Cr₂O₃) and fall into two distinct groups based on magnesium content. High-MgO garnets have an average composition of Pyr₆₇Alm₂₂Gross₁₁, low-MgO garnets are grossular- and almandine-rich with an average composition of Gross₃₄Pyr₃₃Alm₃₃. Clinopyroxenes are omphacitic with a range in jadeite contents from 7.7 to 70.1 mol%. Three eclogites contain zoned and mantled garnets with almandine-rich cores and pyrope-rich rims, and zoned clinopyroxenes with diopside-rich cores and jadeite-rich rims, and are among a very rare group of eclogites reported on a world-wide basis. The bulk compositions of eclogites have ranges comparable to that of basalts. High-MgO eclogites (16–20 wt% MgO) have close chemical affinities to picrites, whereas low-MgO eclogites (6–13 wt% MgO) are similar to alkali basalts. High-MgO eclogites contain high-MgO garnets and jadeiterich clinopyroxenes. Low-MgO eclogites contain low-MgO garnets, diopside and omphacite, and the group of primary accessory phases (diamond, graphite, quartz after coesite, kyanite, and corundum); grospydites are peraluminous. Estimated temperatures and pressures of equilibration of diamond-bearing eclogites, using the diamond-graphite stability curve and the Ellis and Green (1979) geothermometer, are 1031°–1363° C at 45–50 kb.K _D values of Fe-Mg in garnet and clinopyroxene range from 2.3 to 12.2. Diamonds in eclogites are green, yellow, and clear, and range from cube to octahedral morphologies; the entire spectrum in color and morphology is present in a single metasomatized eclogite with zoned garnet and clinopyroxene. Ages estimated from Sm-Nd mineral isochrons range from 92–247 Ma. _Nd values range from +4.05 to 5.23. Values of specific gravity range from 3.06–3.60 g/cc, with calculated seismic Vp of 7.4–8.7 km/s. Petrographie, mineral, and bulk chemical data demonstrate an overall close similarity between the Koidu xenolith suite and upper mantle eclogites from other districts in Africa, Siberia and the United States. At least two origins are implied byP-T, bulk chemistry and mineral compositions: low-MgO eclogites, with diamond and other accessory minerals, are considered to have formed from melts trapped and metamorphically equilibrated in the lithosphere; high-MgO eclogites are picritic and are the products of large degrees of partial melting, with equilibration in the asthenosphere. Fluid or diluted melt metasomatism is pervasive and contributed here and elsewhere to the LIL and refractory silicate incompatible element signature in kimberlites and lamproites, and to secondary diamond growth.     

The system diopside-ureyite at 20 Kb

The join diopside (CaMgSi₂O₆) — ureyite (NaCrSi₂O₆) was studied at pressures of 1 atm, 1 kb, 5 kb, and 20 kb using gel mixtures as starting materials. All runs except those at 1 atm were made under hydrous conditions. The data show that the solubility of ureyite in diopside decreases with increasing pressure. At 20 kb the maximum ureyite content of diopside is 13 weight percent (4.6% Cr₂O₃) as compared to 24 weight percent at 1 atm. It is predicted that pyroxenes that have equilibrated at depths >140 km will not contain a ureyite component; rather Cr will enter diopside in the form of a CaCr(CrSi)O₆ component. Pyroxenes containing this component were found as metastable phases at 20 kb.     

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

Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr₂O₃ diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (La_N/Yb_N = 0.02–0.06) while harzburgitic garnets have sinusoidal REE_N patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr₂O₃ respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO₂-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H₂O-rich melts. We therefore favour diamond precipitation by oxidation of CH₄-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes. Received: 27 January 1996 / Accepted: 5 May 1997     

Minor element abundances in olivines of the Sharps (H-3) chondrite

Olivine crystals in 21 chondrules from the Sharps (H-3) chondrite were analyzed for CaO, Al₂O₃, Cr₂O₃, MnO, TiO₂, NiO, and Na₂O. The chondrules studied include representatives of all major types found in Sharps, and the mean fayalite contents of their olivine range from 1 to 28 %. Those olivines which contain less than 18 mol.% fayalite typically contain or occur with metallic nickel-iron; the others are metal-free.Na₂O is below detectability (0.01 wt.%) in all cases, and the abundances of Al₂O₃, NiO and TiO₂ are also typically very low. MnO varies simply and directly with FeO.Cr₂O₃ varies widely (0.03–0.21%) and several lines of evidence suggest that Cr is dominantly trivalent. It is concluded that F_{O 2} was rarely less than 10^–11 atm. during the crystallization of the chondrules in Sharps.     

Crystallization of high-Ca chromium garnet upon interaction of serpentine,chromite, and Ca-bearing hydrous fluid

The results of experimental modeling of the conditions of crystallization of high-Ca chromium garnets in the system serpentine–chromite–Ca-Cr-bearing hydrous fluid at a pressure of 5 GPa and temperature of 1300°С are reported. The mineral association including quantitatively predominant high-Mg olivine and diopside-rich clinopyroxene, bright-green garnet, and newly formed chrome spinel was formed. Garnet mostly crystallized around primary chromite grains and was characterized by a high concentration of CaO and Cr₂O₃. According to the chemical composition, garnets obtained are close to the uvarovite–pyrope varieties, which enter the composition of relatively rare natural paragenesis of garnet wehrlite. The experimental data obtained clearly show that high-Ca chromium garnets are formed in the reaction of chromite-bearing peridotite and Ca-rich fluid at high P–T parameters.

     

Single crystal Raman spectrum of uvarovite, Ca3Cr2Si3O12

Single-crystal Raman spectra of synthetic end-member uvarovite (Ca₃Cr₂Si₃O₁₂) and of a binary solution (59% uvarovite, 41% andradite) have been measured using single crystal techniques. For each of these garnets, 22 and 21 of the 25 Raman modes were located, respectively. The spectra for uvarovite garnets closely resemble those of the other calcic garnets, grossular, and andradite. The modes for uvarovites do not fit into the same trends as established by the other five anhydrous end-member garnets: the high energy “internal” Si–O modes do not depend on lattice constant in uvarovite. They exceed frequencies for both andradite and grossular. This is likely due to the large crystal field stabilization energy of trivalent chromium. The low energy and midrange modes are at similar frequencies to the other calcic garnets.     

Constraints on the origin of mantle-derived low Ca garnets

Current hypotheses for the source rock of low Ca garnets hosted in mantle-derived diamonds and xenoliths range from residues of komatiite generation, to subducted serpentinite, to subducted mid-ocean ridge (MORB) harzburgite. Experiments designed to test these hypotheses were undertaken. The stability and compositional variation of garnets at pressures above 4 GPa through the melting interval of hydrous peridotite, in the subsolidus of depleted harzburgite and peridotite compositions, and along the liquidus of aluminium-undepleted and aluminium-depleted komatiites were examined, and compared with petrological data for natural low Ca garnets. Partitioning of Cr between garnet and ultramafic liquid along the liquidus of komatiites and within the melting interval of peridotite, indicates that garnets in mantle residues after single stage Archean ultramafic liquid removal would contain 2 to 4 wt% Cr₂O₃. Thus, the more Cr-poor population of mantle-derived low Ca garnets, with Cr₂O₃ less than 4 wt%, could have originated by such a process. Experimental results for other compositions indicate that average cratonic peridotite or its hydrated equivalent is typically too Cr-poor to be the protolith from which low Ca garnets containing greater than 4 wt% Cr₂O₃ could have crystallized in the upper mantle. Experiments on a spinel harzburgite composition indicate that an extremely Cr-rich protolith (Cr/Cr+Al>0.3) is required to crystallize spinel and Cr-rich low Ca garnets, at pressures deduced for the ultramafic inclusion suite in diamonds (5 to 7 GPa). Natural examples of such Cr-rich protoliths are represented in some ophiolite harzburgites. All the experimental data taken together require that low Ca garnets with greater than 4 wt% Cr₂O₃ originated from residues that underwent multiple melt extraction. Whether such multi-stage events formed protoliths for low Ca garnets at shallow (i.e. MORB source region) or deep (i.e. komatiite source region) levels in the Precambrian mantle is not completely resolvable. The former environment can better account for the abundance of spinel in many diamonds hosting low Ca garnets, but the latter scenario best explains the presence of low Ca garnets in harzburgite xenoliths with cratonic bulk compositions well removed from typical MORB residues.     

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.     

Metasomatic origin of garnet xenocrysts from the V. Grib kimberlite pipe,Arkhangelsk region,NW Russia

This paper presents new major and trace element data from 150 garnet xenocrysts from the V. Grib kimberlite pipe located in the central part of the Arkhangelsk diamondiferous province (ADP). Based on the concentrations of Cr₂O₃, CaO, TiO₂ and rare earth elements (REE) the garnets were divided into seven groups: (1) lherzolitic “depleted” garnets (“Lz 1”), (2) lherzolitic garnets with normal REE patterns (“Lz 2”), (3) lherzolitic garnets with weakly sinusoidal REE patterns (“Lz 3”), (4) lherzolitic garnets with strongly sinusoidal REE patterns (“Lz 4”), (5) harzburgitic garnets with sinusoidal REE patterns (“Hz”), (6) wehrlitic garnets with weakly sinusoidal REE patterns (“W”), (7) garnets of megacryst paragenesis with normal REE patterns (“Meg”). Detailed mineralogical and geochemical garnet studies and modeling results suggest several stages of mantle metasomatism influenced by carbonatite and silicate melts. Carbonatitic metasomatism at the first stage resulted in refertilization of the lithospheric mantle, which is evidenced by a nearly vertical CaO-Cr₂O₃ trend from harzburgitic (“Hz”) to lherzolitic (“Lz 4”) garnet composition. Harzburgitic garnets (“Hz”) have probably been formed by interactions between carbonatite melts and exsolved garnets in high-degree melt extraction residues. At the second stage of metasomatism, garnets with weakly sinusoidal REE patterns (“Lz 3”, “W”) were affected by a silicate melt possessing a REE composition similar to that of ADP alkaline mica-poor picrites. At the last stage, the garnets interacted with basaltic melts, which resulted in the decrease CaO-Cr₂O₃ trend of “Lz 2” garnet composition. Cr-poor garnets of megacryst paragenesis (“Meg”) could crystallize directly from the silicate melt which has a REE composition close to that of ADP alkaline mica-poor picrites. P-T estimates of the garnet xenocrysts indicate that the interval of ～60–110 km of the lithospheric mantle beneath the V. Grib pipe was predominantly affected by the silicate melts, whereas the lithospheric mantle deeper than 150 km was influenced by the carbonatite melts.     

Crystallization of titaniferous chromite,magnesian ilmenite and armalcolite in tholeiitic suites in the Karoo Igneous Province

Titaniferous chromite (up to 8 wt% TiO₂) and magnesian ilmenite (up to 10 wt% MgO) coexist at the base of the differentiated tholeiitic Mount Ayliff Intrusion in the Karoo Province of southern Africa, suggesting that the original magma was TiO₂-rich. Picritic lavas with 3% TiO₂ from the Lebombo monocline of the Karoo Province also contain microphenocrysts of magnesian ilmenite (up to 6 wt% mgO) and armalcolite (up to 7 wt% MgO). These oxide mineral associations and compositions are atypical of tholeiitic magmas, in which chromite usually has less than 1 wt% TiO₂, ilmenite less than 3 wt% MgO and armalcolite is rarely a primary mineral. Experiments have been conducted at one atmosphere pressure on a range of compositions to determine the effect of TiO₂ on the crystallization and composition of chromite, ilmenite and armalcolite. The results indicate that increasing the TiO₂ content of picritic magmas increases the TiO₂ content of the spinel, mainly at the expense of Al₂O₃, whereas Cr₂O₃ is not affected. Spinel compositions in the Mount Ayliff Intrusion (with over 45 wt% Cr₂O₃, less than 10 wt% Al₂O₃ and 8 wt% TiO₂) were duplicated in experiments on a picrite at temperatures of about 1,200°C at the Ni/NiO buffer. Increasing fO₂ from fayalite-magnetite-quartz to Ni/NiO buffer is shown to increase the crystallization temperature of armalcolite and to decrease that of ilmenite. The total FeO content of the liquid has little influence on the crystallization temperature of these phases. The TiO₂ content of the liquid, when either ilmenite or armalcolite crystallizes, varies inversely with SiO₂ content. The MgO content of the liquid at which ilmenite or armalcolite crystallizes depends upon the TiO₂ content of the starting composition, with naturally occurring and experimetally determined saturation being demonstrated for liquids with 5 wt% MgO and 5.5 wt% TiO₂. The partition coefficent for MgO between armalcolite or ilmenite and liquid is about 1.5. Observed magnesian armalcolite and ilmenite compositions in picrite lavas (both minerals) and in the Mount Ayliff Intrusion (ilmenite only) are consistent with crystallization from a TiO₂-rich magma with approximately 5 wt% MgO. The Fe ₂ ³⁺ TiO₅ component of armalcolite in the picrite lavas matches those formed experimentally at temperatures of 1,150–1,110°C and fO₂ of the Ni/NiO to Ni/NiO+1 log unit. Similarities also exist between the compositions of chromite, ilmenite and armalcolite and liquid fraction-ation trends of some Hawaiian high-TiO₂ lavas and the experimental studies presented here.     

Ti-poor hoegbomite in kornerupine-cordierite-sillimanite rocks from Ellammankovilpatti,Tamil Nadu,India

Hoegbomite occurs sparingly in minute (mostly 0.1 mm) grains with fine-grained hercynite, magnetite, and rutile in two coarse-grained kornerupine-cordierite-sillimanite rocks from Ellammankovilpatti, Tamil Nadu, India. The hoegbomite is Ti-poor (2.5 wt% TiO₂), Fe-rich (25–26% Fe as FeO), and contains 6.2–6.8% MgO, 59.8–60.1% Al₂O₃, 1.0–1.3% ZnO, 0.3–0.7% Cr₂O₃ and 0.02% Li₂O. Minor amounts (estimated not to exceed 0.2 wt% oxide) of V, Co, Ni, Ga, and Sn were detected on the electron microprobe, but Be, Nb, and Zr were not detected with the ion microprobe mass analyser. Assuming the crystal structure refined by Gatehouse and Grey (1982) to be applicable to the Ellammankovilpatti hoegbomite, the analyses were recalculated on a basis of 22 cations, 30 oxygens, and two hydroxyls, resulting in 49 to 53% of the iron being ferric. Identification of hoegbomite was confirmed by X-ray powder diffraction. Associated cordierite (Fe/(Fe+Mg)=0.14) and kornerupine (Fe/(Fe+Mg)= 0.27) contain 0.02 weight % Li₂O and 0.05–0.07% BeO, while only the kornerupine contains B₂O₃ — 1.57% (ion microprobe analyses). Hoegbomite and the other oxides may have crystallized at temperatures between 680 and 720° C (P6.5 kbar) following attainment of peak conditions by the reaction: kornerupine+sillimanite±rutile+ZnO+H₂O+O₂ =cordierite+chlorite+hercynite+hoegbomite +magnetite+B₂O₃.The conditions for hoegbomite formation at Ellammankovilpatti appear to be characteristic of many hoegbomite parageneses. Critical for hoegbomite are silica undersaturation and relatively high oxygen and water activities at fairly high temperatures, conditions which are most commonly attained in later phases of a metamorphic cycle in upper amphibolite- and granulite-facies terrains.