Temperature-dependent distribution of Cr between olivine and pyroxenes in lherzolite xenoliths

The temperature effect on the exchange reaction Cr₂O₃(ol)=Cr₂O₃(px) was studied for coexisting olivine and both clino and ortho pyroxenes. The distribution of Cr between olivine and clinopyroxene in 31 coarse garnet lherzolites and 10 porphyroclastic garnet lherzolites from kinberlites, and in 17 coarse spinel lherzolites from basalts, obeys a van't Hoff relation (c.f. Stosch 1981) with the Wells two-pyroxene temperature: T(Kelvin)=8,787 (In D _Cr+ 2.87) where D _Cr(opx/ol)=wt.% Cr(clinopyroxene)/Cr(olivine). An analogous exchange for olivine and orthopyroxene with 0.7–1.6 wt.% Al₂O₃ in 41 garnet lherzolites from kimberlites shows considerable scatter about the following relation: T(Kelvin)=5,540/(ln D _cr+1.86) where D _cr(opx/ol)= wt.% Cr(orthopyroxene)/Cr(olivine). Spinel lherzolites and a garnet lherzolite from the Malaita alnöite do not obey the second relation. For orthopyroxene with 2.5–5.1 wt.% Al₂O₃, D _cr(opx/ol) is 1.7 to 3 times higher, and for 0.1 wt.% Al₂O₃ is 2 times lower than for the garnet lherzolites. Experimental calibration is needed, especially to check the possible effect of Al on D _cr(opx/ol).     

Exsolved garnet-bearing pyroxene megacrysts from some South African kimberlites

Clinopyroxene and orthopyroxene megacrysts containing garnet lamellae up to 1.2 mm thick as an exsolved phase are found rarely in kimberlites from Frank Smith and Bellsbank. Chemically the clinopyroxenes are characteristically subcalcic, being within the range of 100 Ca/Ca + Mg + Fe = 27 to 36, and the orthopyroxenes are characterized by high Al₂O₃ and Cr₂O₃. Immediately after crystallization during very slow cooling, clinopyroxene and orthopyroxene exsolve wide-spaced orthopyroxene and clinopyroxene phases parallel to (100) of the host phases, respectively, then both host and exsolved phases exsolve garnet lamellae. Topotactic relations between pyroxenes and garnet are determined by X-ray for the first time. Partitioning of major and minor elements among the coexisting clinopyroxene, orthopyroxene and garnet in pyroxene megacrysts is the same as that of the granular-type garnet peridotite xenoliths in Lesotho and South African kimberlies. Mineralogy and chemistry indicate that subcalcic clinopyroxene and orthopyroxene megacrysts contain respectively about 10 and 3 mole % of the garnet molecule in solid solution.     

Macrocryst Fe - Ti oxides in olivine melilitites from Namaqualand-Bushmanland South Africa

Ilmenite macrocrysts in olivine melilitites from Namaqualand-Bushmanland, South Africa, have decomposed by subsolidus reduction to form oriented Mg-titanomagnetite along {0001} ilmenite planes. Residual ilmenite contains 10–11 wt% MgO, 1 wt% MnO, and 0.1 wt% Cr₂O₃. This macrocryst assemblage is mantled by an annulus of Mg-titanomagnetite, followed by an overgrowth of radiating magnetite + perovskite. Terminal compositions of these magnetites are similar to groundmass spinels, and to the outermost margins of magnetite macrocrysts that have very high Fe³⁺ core contents. The assemblages are remarkably similar to oxide intergrowths in kimberlites and an upper mantle derivation is proposed for ilmenite macrocrysts in these melilitites. Oxidation states in the source regions are also very similar, whether on-or off-craton, being slightly above FMQ (NNO), but reduced to FMQWM with the onset of decompression, volatile loss, and carbonate immiscibility. In the case of the melilitites, late stage, low pressure crystallization above NNO precipated abundant magnetite + perovskite. The oxide fO₂ data are consistent with, and refine the fO₂ estimates obtained previously for the behavior of Fe/Mg and Ni contents in olivine from the same suite of samples.     

The alleged kimberlite-carbonatite relationship: evidence from ilmenite and spinel from Premier and Wesselton mines and the Benfontein sill,South Africa

Carbonate-rich, SiO₂-poor residua are developed in some kimberlites solidifying as ocelli, layers, or discrete dikes which satisfy petrographic definitions of carbonatite. Arguments that these rocks have mineralogies, antecedents, and comagmatic rocks differing from those of the carbonatites in alkaline rock complexes, including the specific observation that kimberlites and carbonatites contain ilmenites and spinels of different composition, have been used to refute the alleged kimberlite-carbonatite relationship. New microprobe analyses of ilmenites and spinels from carbonate-rich rocks associated with kimberlites in three South African localities correspond to spinels and ilmenites of carbonatites from alkalic complexes, or have characteristics intermediate between those of carbonatites and kimberlites. The ilmenites are distinguished from kimberlite ilmenites by higher MnO, FeTiO₃, and Nb₂O₅, and by negligible Cr₂O₃. The spinels are distinguished from kimberlite spinels by their Al₂O₃ and Cr₂O₃ contents. There is clearly a genetic relationship between the kimberlites and the carbonate-rich rocks, despite the observation that their ilmenites and spinels are distinctly different, which indicates that the same observation is not a valid argument against a petrogenetic relationship between kimberlites and carbonatites. These rocks are among the diverse products from mantle processes influenced by CO₂, and we believe that the petrogenetic links among them are forged in the upper mantle. We see insufficient justification to deny the name carbonatite to carbonate-rich rocks associated with kimberlites if they satisfy the petrographic definition in terms of major mineralogy.     

Granny Smith diopside megacrysts from the kimberlites of the Kimberley area and Jagersfontein,South Africa

Calcic diopside megacrysts, called Granny Smith nodules, in the Kimberley area and Jagersfontein kimberlites are sheared, commonly contain lenticles of ilmenite and intergrowths of phlogopite, and have a distinctive apple-green color. These diopsides have $\text{Ca}\text{(Ca + Mg)}\text{> 0.45,}\text{Mg}\text{(Mg + Fe)}\text{> 0.90, 0.2?0.4}$ wt% TiO₂ and 0.5–3 wt% Cr₂O₃. They have Na > (Al + Cr), in contrast to diopsides in peridotite xenoliths and those that form subcalcic discrete nodules, but in this respect are similar to diopsides in amphibole-bearing MARID nodules and mica-rich glimmerites. Granny Smith megacrysts are not cognate (Kramers, 1979); their parental magmas (in an igneous or metasomatic sense) may have been parts of the spectrum between kimberlites and lamproites.     

Mineralogy, Chemical Characteristics and Upgrading of Beach Ilmenite of the Top Meter of Black Sand Deposits of the Kafr Al-Sheikh Governorate, Northern Egypt

Egyptian beach ilmenite occurs in a relatively high content in the naturally highly concentrated superficial black sand deposits at specific beach zones in the northern parts of the Nile Delta at Rosetta. Microscopic study shows that the ilmenite occurs as fresh homogeneous black or heterogeneous multicoloured altered grains and exhibits three types (homogeneous, exsolved and altered) of ilmenite varieties. XRD data of ilmenite indicates their association with minor hematite and quartz, whereas leucoxene shows its association with Nb‐rutile, pseudorutile and hematite. Grain size distribution suggests a very fine sand size of >89% and 80% and a fine sand size of 10.5% and 18.3% for fresh and altered ilmenites, respectively. The density of fresh, altered ilmenite and leucoxene concentrates varies from 2.70, 2.50 to 2.40 ton/m³, suggesting a gradual decrease from high grade fresh to leucoxene and consistent with variation in magnetic susceptibility as a consequence of the leaching of iron. Mass magnetic susceptibility reveals 97.6% of ilmenite and 92% of the altered form are obtained at 0.20 and 0.48 ampere. Fresh ilmenite exhibits variable TiO₂ (47.18%) and Fe₂O₃^T (46.10%) with minor MnO, MgO and Cr₂O₃ (1.22, 1.10 and 0.51%). The altered ilmenite is higher in TiO₂ (76.16%) and SiO₂ (4.68%) and lower in Fe₂O₃^T (14.45%), MnO, MgO and Cr₂O₃ (0.39, 0.52 and 0.11%) compared with the fresh form. Three concentrates of ilmenites (G1, G2 and G3) were prepared from crude ore using a Reading cross belt magnetic separator under different conditions, revealing a gradual increase of TiO₂, SiO₂, Al₂O₃ and CaO accompanied by a decrease of Fe₂O₃^T, MgO and Cr₂O₃ with repetition of the separation processes. Several ore dressing techniques were carried out to upgrade the ilmenite concentrate.     

Experimental calibration of the partitioning of Fe and Mg between biotite and garnet

The cation exchange reaction Fe₃Al₂Si₃O₁₂ +KMg₃AlSi₃O₁₀(OH)₂ = Mg₃Al₂Si₃O₁₂+KFe₃-AlSi₃ O₁₀(OH)₂ has been investigated by determining the partitioning of Fe and Mg between synthetic garnet, (Fe, Mg)₃Al₂Si₃O₁₂, and synthetic biotite, K(Fe, Mg)₃AlSi₃O₁₀(OH)₂. Experimental results at 2.07 kbar and 550 °–800 ° C are consistent with In [(Mg/Fe) garnet/(Mg/Fe) biotite] = -2109/T(°K) +0.782. The preferred estimates for ¯H and ¯S of the exchange reaction are 12,454 cal and 4.662 e.u., respectively. Mixtures of garnet and biotite in which the ratio garnet/biotite=49/1 were used in the cation exchange experiments. Consequently the composition of garnet-biotite pairs could approach equilibrium values in the experiments with minimal change in garnet composition (few tenths of a mole percent). Equilibrium was demonstrated at each temperature by reversal of the exchange reaction. Numerical analysis of the experimental data yields a geothermometer for rocks containing biotite and garnet that are close to binary Fe-Mg compounds.     

Experimental tests of garnet peridotite oxygen barometry

We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe?Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO₂ was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for ⁵⁷Fe Mössbauer spectroscopy. The latter gave the Fe³⁺ content of the garnet at the measured P-T-fO₂ conditions. Approach to equilibrium was checked by observed shifts in Fe³⁺ content and by the approach of garnet-olivine Fe?Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO₂ from two possible garnet oxybarometers:- (1) $\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $ and (2) $\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $ Comparison of calculated fO₂s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO₂ units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO₂ recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990).     

The MARID (mica-amphibole-rutile-ilmenite-diopside) suite of xenoliths in kimberlite

Within the ‘glimmerite’ nodules occurring within kimberlite pipes we recognize the MARID suite consisting of varying proportions of mica, amphibole, rutile, ilmenite and diopside. Banding of some specimens is interpreted as cumulate layering. All specimens were deformed either before incorporation into the host kimberlite or during intrusion. Compared with minerals in peridotite xenoliths, the MARID ones are lower in Al₂O₃ and Cr₂O₃, but richer in total iron. The MARID micas, amphiboles, diopsides, ilmenites and probably rutiles contain substantial Fe₂O₃ indicative of oxidizing conditions. The amphibole is potassic richterite. Micas of the megacryst suite in kimberlite have less total iron and Fe₂O₃ than micas of the MARID suite. We suggest that the rocks of the MARID suite crystallized under oxidizing conditions from a magma, chemically similar to kimberlite, within the higher parts of the upper mantle: the presence of amphibole restricts the depth to less than ~ 100 km. A xenolith containing olivine and orthopyroxene as well as minerals similar to but not the same compositionally as MARID-types is interpreted as a metasomite, possibly representing wall-rock of a magma body from which MARID-suite rocks crystallized.     

An experimental study of Ca-(Fe,Mg) interdiffusion in silicate garnets

Ca-(Fe,Mg) interdiffusion experiments between natural single crystals of grossular (Ca_2.74Mg_0.15 Fe_0.23Al_1.76Cr_0.04Si_3.05O₁₂) and almandine (Ca_0.21Mg_0.40 Fe_2.23Mn_0.13Al_2.00Cr_0.08Si_2.99O₁₂ or Ca_0.43Mg_0.36Fe_2.11 Al_1.95Si_3.04O₁₂), were undertaken at 900–1100 °C and 30 kbar, and pressures of 15.0–32.5 kbar at 1000 °C. Samples were buffered by Fe/FeO in most cases. Diffusion profiles were determined by electron microprobe. Across the experimental couples the interdiffusion coefficients (D˜) were almost independent of composition. The diffusion rates in an unbuffered sample were significantly faster than in buffered samples. The temperature dependence of the D˜ (Ca-Fe,Mg) interdiffusion coefficients may be described by

The influence of low aluminum concentrations on the composition and conditions of crystallization of majorite–knorringite garnets: Experiment at 7.0 GPa and 1500–1700°C

Crystallization of garnet in high-chromium restite formed under the conditions of partial melting in the spinel facies and subsequently subducted into the garnet depth facies was studied experimentally in the MgO–Al₂O₃–Cr₂O₃–SiO₂ system. The crystallization of garnet and the dependence of its composition on the temperature and bulk composition of the system with low Al concentration were studied as well. Experiments in the knorringite–majorite–pyrope system with 5, 10, and 20 mol % Prp were carried out at 7 GPa. The phase associations for the starting composition of pure knorringite Mg₃Cr₂Si₃O₁₂ included chromiumbearing enstatite MgSiO₃ (up to 3.2 wt % Cr₂O₃) and eskolaite Cr₂O₃. Addition of Al resulted in crystallization of high-chromium majoritic garnet. The portion of garnet in the samples always exceeded the concentration of pyrope in the starting composition owing to the formation of the complex majorite–knorringite–pyrope series of solid solutions. With increasing content of pyrope (from 5 to 20 mol %) and increasing temperature, the modal concentration of garnet increased significantly (from 6–12 to 22–37%). The garnet was characterized by high concentrations of the pyrope (23–80 mol %) and knorringite (22–70 mol %) components. The excess of Si (>3 f.u.) with decreasing Cr concentration provided evidence for the contribution of the majorite–knorringite trend to the variation in garnet composition. On the basis of the natural data, most of the garnets composing xenoliths of ultrabasic rocks in kimberlites and occurring as inclusions in diamonds are low-chromium; i.e., their protolith was not subjected to partial melting, at least in the spinel depth facies.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Petrochemical characteristics of kimberlites and identification of their diamond-bearing potentiality

There has been found a distinct directional trend of kimberlites differing in ore-bearing potentiality with changing chemical composition. The contents of MgO, NiO and Cr₂O₃ decrease gradualy while Na₂O, K₂O, Al₂O₃ and P₂O₅ increase considerably in the order of diamond-rich—diamond-poor—diamond-barren kimberlites. In general Fe₂O₃, FeO and TiO₂ also show an increasing tendency. Therefore, the variations in chemical composition may be used as petrochemical indexes for calculating the ore-bearing potentiality of kimberlites. Based on discriminant analysis, it is possible to make a distinction between diamond-bearing and diamond-barren, or between diamond-rich and diamond-poor kimberlites.     

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.     

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

 Solid solutions of (Fe,Mn)TiO₃ were synthesized, mostly at 0.10 X_Mn intervals, at 1 bar, 900°C and log f _{O 2} = –17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with X_Mn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700–900°C and fixed f _{O 2} in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO₂ and H₂ gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO₃ ilmenite, which is well described by an asymmetric Margules model with W^H _FeFeMn = –9.703 and W^H _FeMnMn = –23.234 kJ/mol, W^S _FeFeMn = –19.65 and W^S _FeMnMn = –22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (W^G _FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite. Received: 10 January 1996 / Accepted: 11 July 1996     

Superdeep diamonds from the Juina area, Mato Grosso State, Brazil

Alluvial diamonds from the Juina area in Mato Grosso, Brazil, have been characterized in terms of their morphology, syngenetic mineral inclusions, carbon isotopes and nitrogen contents. Morphologically, they are similar to other Brazilian diamonds, showing a strong predominance of rounded dodecahedral crystals. However, other characteristics of the Juina diamonds make them unique. The inclusion parageneses of Juina diamonds are dominated by ultra-high-pressure ("superdeep") phases that differ both from "traditional" syngenetic minerals associated with diamonds and, in detail, from most other superdeep assemblages. Ferropericlase is the dominant inclusion in the Juina diamonds. It coexists with ilmenite, Cr-Ti spinel, a phase with the major-element composition of olivine, and SiO₂. CaSi-perovskite inclusions coexist with titanite (sphene), "olivine" and native Ni. MgSi-perovskite coexists with TAPP (tetragonal almandine-pyrope phase). Majoritic garnet occurs in one diamond, associated with CaTi-perovskite, Mn-ilmenite and an unidentified Si-Mg phase. Neither Cr-pyrope nor Mg-chromite was found as inclusions. The spinel inclusions are low in Cr and Mg, and high in Ti (Cr₂O₃<36.5 wt%, and TiO₂>10 wt%). Most ilmenite inclusions have low MgO contents, and some have very high (up to 11.5 wt%) MnO contents. The rare "olivine" inclusions coexisting with ferropericlase have low Mg# (87-89), and higher Ca, Cr and Zn contents than typical diamond-inclusion olivines. They are interpreted as inverted from spinel-structured (Mg, Fe)₂Si₂O₄. This suite of inclusions is consistent with derivation of most of the diamonds from depths near 670 km, and adds ilmenite and relatively low-Cr, high-Ti spinel to the known phases of the superdeep paragenesis. Diamonds from the Juina area are characterized by a narrow range of carbon isotopic composition ('¹³C=-7.8 to -2.5‰), except for the one majorite-bearing diamond ('¹³C=-11.4‰). There are high proportions of nitrogen-free and low-nitrogen diamonds, and the aggregated B center is predominant in nitrogen-containing diamonds. These observations have practical consequences for diamond exploration: Low-Mg olivine, low-Mg and high-Mn ilmenite, and low-Cr spinel should be included in the list of diamond indicator minerals, and the role of high-Cr, low-Ti spinel as the only spinel associated with diamond, and hence as a criterion of diamond grade in kimberlites, should be reconsidered.     

Exsolutions of Diopside and Magnetite in Olivine from Mantle Dunite, Luobusa Ophiolite, Tibet, China

The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature d     

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

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

Origin of zoned spinel by coupled dissolution–precipitation and inter-crystalline diffusion: evidence from serpentinized wehrlite, Bangriposi, Eastern India

Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe³⁺ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr₂O₃, Al₂O₃ and MgO and complementary increase in Fe₂O₃ at constant FeO. In diffusion profiles, Fe₂O₃–Cr₂O₃ crossover coincides with Al₂O₃ decrease to values <0.5 wt% in ferritchromite zone, with Cr₂O₃ continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O₂): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.