Ferric Iron in CaTiO3 Perovskite as an Oxygen Barometer for Kimberlitic Magmas I: Experimental Calibration

A method to estimate the oxygen fugacity (fO₂) during the crystallizationof kimberlites is developed using the Fe content of CaTiO₃ perovskite(Pv), a common groundmass phase in these rocks. With increasingfO₂, more Fe exists in the kimberlitic liquid as Fe³⁺, and thuspartitions into Pv. Experiments to study the partitioning ofFe between Pv and kimberlite liquid were conducted at 100 kPaon simple and complex anhydrous kimberlite bulk compositionsfrom 1130 to 1300°C over a range of fO₂ from NNO –5 to NNO + 4 (where NNO is the nickel–nickel oxide buffer),and at Nb and rare earth element (REE) contents in the startingmaterials of 0–5 wt % and 1500 ppm, respectively. Thepartitioning of Fe between Pv and kimberlite liquid is influencedmostly by fO₂, although the presence of Nb increases the partitionof Fe³⁺ into perovskite at a given T and fO₂. Multiple linearregression (MLR) of all the experimental data produces a relationshipthat describes the variation of Fe and Nb in Pv with fO₂ relativeto the NNO buffer:

(uncertaintiesat 2, and Nb and Fe as cations per three oxygens). Over therange of conditions of our experiments, this relationship showsno temperature (T) dependence, is not affected by the bulk Fecontent of the kimberlite starting material and reproduces experimentaldata to within 1 log fO₂ unit. KEY WORDS: kimberlites; oxygen fugacity; perovskite; ferric iron; magma     

Continuous Gradations among Primary Carbonatitic, Kimberlitic, Melilititic, Basaltic, Picritic, and Komatiitic Melts in Equilibrium with Garnet Lherzolite at 3-8 GPa

Multianvil melting experiments in the system CaO–MgO–Al₂O₃–SiO₂–CO₂(CMAS–CO₂) at 3–8 GPa, 1340–1800°C, involvingthe garnet lherzolite phase assemblage in equilibrium with CO₂-bearingmelts, yield continuous gradations in melt composition betweencarbonatite, kimberlite, melilitite, komatiite, picrite, andbasalt melts. The phase relations encompass a divariant surfacein P–T space. Comparison of the carbonatitic melts producedat the low-temperature side of this surface with naturally occurringcarbonatites indicates that natural magnesiocarbonatites couldbe generated over a wide range of pressures >2·5 GPa.Melts analogous to kimberlites form at higher temperatures alongthe divariant surface, which suggests that kimberlite genesisrequires more elevated geotherms. However, the amount of waterfound in some kimberlites has the potential to lower temperaturesfor the generation of kimberlitic melts by up to 150°C,provided no hydrous phases are present. Compositions resemblinggroup IB and IA kimberlites are produced at pressures around5–6 GPa and 10 GPa, respectively, whereas the compositionsof some other kimberlites suggest generation at higher pressuresstill. At pressures <4 GPa, an elevated geotherm producesmelilitite-like melt in the CMAS–CO₂ system rather thankimberlite. Even when a relatively CO₂-rich mantle compositioncontaining 0·15 wt % CO₂ is assumed, kimberlites andmelilitites are produced by <1% melting and carbonatitesare generated by even smaller degrees of melting of <0·5%. KEY WORDS: carbonatite; CO₂; kimberlite; melilitite; melt generation     

Similar V/Sc Systematics in MORB and Arc Basalts: Implications for the Oxygen Fugacities of their Mantle Source Regions

V/Sc systematics in peridotites, mid-ocean ridge basalts andarc basalts are investigated to constrain the variation of fO₂in the asthenospheric mantle. V/Sc ratios are used here to ‘seethrough’ those processes that can modify barometric fO₂determinations in mantle rocks and/or magmas: early fractionalcrystallization, degassing, crustal assimilation and mantlemetasomatism. Melting models are combined here with a literaturedatabase on peridotites, arc lavas and mid-ocean ridge basalts,along with new, more precise data on peridotites and selectedarc lavas. V/Sc ratios in primitive arc lavas from the Cascadesmagmatic arc are correlated with fluid-mobile elements (e.g.Ba and K), indicating that fluids may subtly influence fO₂ duringmelting. However, for the most part, the average V/Sc-inferredfO₂s of arc basalts, MORB and peridotites are remarkably similar(–1·25 to +0·5 log units from the FMQ buffer)and disagree with the observation that the barometric fO₂s ofarc lavas are several orders of magnitude higher. These observationssuggest that the upper part of the Earth's mantle may be stronglybuffered in terms of fO₂. The higher barometric fO₂s of arclavas and some arc-related xenoliths may be due respectivelyto magmatic differentiation processes and to exposure to large,time-integrated fluid fluxes incurred during the long-term stabilityof the lithospheric mantle. KEY WORDS: vanadium; scandium; oxygen fugacity; mantle; arcs     

The Solubility of Sulphur in Hydrous Rhyolitic Melts

Experiments performed at 2 kbar, in the temperature range 800–1000°C,with fO₂ between NNO–2·3 and NNO+2·9 (whereNNO is the nickel–nickel oxide buffer), and varying amountsof sulphur added to hydrous metaluminous rhyolite bulk compositions,were used to constrain the solubility of sulphur in rhyolitemelts. The results show that fS₂ exerts a dominant control onthe sulphur solubility in hydrous silicate melts and that, dependingon fO₂, a rhyolitic melt can reach sulphur contents close to1000 ppm at high fS₂. At fO₂ below NNO+1, the addition of ironto a sulphur-bearing rhyolite magma produces massive crystallizationof pyrrhotite and does not enhance the sulphur solubility ofthe melt. For a given fO₂, the melt-sulphur-content increaseswith fS₂. For fixed fO₂ and fS₂, temperature exerts a positivecontrol on sulphur solubilities, at least for fO₂ below NNO+1.The mole fraction of dissolved sulphur exhibits essentiallylinear dependence on fH₂S at low fO₂ and, although the experimentalevidence is less clear, on fSO₂ at high fO₂. The minimum insulphur solubility corresponds to the redox range where bothfH₂S and fSO₂ are approximately equal. A thermodynamic modelof sulphur solubility in hydrous rhyolite melts is derived assumingthat total dissolved sulphur results from the additive effectsof H₂S and SO₂ dissolution reactions. The model reproduces wellthe minimum of sulphur solubility at around NNO+1, in additionto the variation of the sulphide to sulphate ratio with fO₂.A simple empirical model of sulphur solubility in rhyoliticmelts is derived, and shows good correspondence between modeland observations for high-silica rhyolites. KEY WORDS: sulphur; solubility; rhyolite; thermodynamics; fO₂; fS₂     

Evolution of a Porphyry-Cu Mineralized Magma System at Santa Rita, New Mexico (USA)

The magmatic processes leading to porphyry-Cu mineralizationat Santa Rita are reconstructed on the basis of petrographicstudies, thermobarometry, and laser-ablation inductively-coupled-plasmamass-spectrometry analyses of silicate melt and sulfide inclusionsfrom dikes ranging from basaltic andesite to rhyodacite. Combinedresults suggest that magma evolution at Santa Rita is similarto that of sulfur-rich volcanoes situated above subduction zones,being characterized by repeated injection of hot, mafic magmainto an anhydrite-bearing magma chamber of rhyodacitic composition.The most mafic end-member identified at Santa Rita is a shoshoniticbasaltic andesite that crystallized at 1000–1050°C,1–3 kbar and log f_O2 = NNO + 0·7 to NNO + 1·0,whereas the rhyodacite crystallized at 730–760°C andlog f_O2 = NNO + 1·3 to NNO + 1·9. Mixing betweenthe two magmas caused precipitation of 0·1–0·2wt % magmatic sulfides and an associated decrease in the Cucontent of the silicate melt from 300–500 ppm to lessthan 20 ppm. Quantitative modeling suggests that temporal storageof ore-metals in magmatic sulfides does not significantly enhancethe amount of copper ultimately available to ore-forming hydrothermalfluids. Magmatic sulfides are therefore not vital to the formationof porphyry-Cu deposits, unless a mechanism is required thatholds back ore-forming metals until late in the evolution ofthe volcanic–plutonic system. KEY WORDS: porphyry-Cu; sulfur; sulfides; magma mixing; LA-ICP-MS     

An Experimental Investigation of the Influence of Water and Oxygen Fugacity on Differentiation of MORB at 200 MPa

Crystallization experiments were performed at 200 MPa in thetemperature range 1150–950°C at oxygen fugacitiescorresponding to the quartz–fayalite–magnetite (QFM)and MnO–Mn₃O₄ buffers to assess the role of water andf_O2 on phase relations and differentiation trends in mid-oceanridge basalt (MORB) systems. Starting from a primitive (MgO9·8 wt %) and an evolved MORB (MgO 6·49 wt %),crystallization paths with four different water contents (0·35–4·7wt % H₂O) have been investigated. In primitive MORB, olivineis the liquidus phase followed by plagioclase + clinopyroxene.Amphibole is present only at water-saturated conditions below1000°C, but not all fluid-saturated runs contain amphibole.Magnetite and orthopyroxene are not stable at low f_O2 (QFM buffer).Residual liquids obtained at low f_O2 show a tholeiitic differentiationtrend. The crystallization of magnetite at high f_O2 (MnO–Mn₃O₄buffer) results in a decrease of melt FeO^*/MgO ratio, causinga calc-alkaline differentiation trend. Because the magnetitecrystallization temperature is nearly independent of the H₂Ocontent, in contrast to silicate minerals, the calc-alkalinedifferentiation trend is more pronounced at high water contents.Residual melts at 950°C in a primitive MORB system havecompositions approaching those of oceanic plagiogranites interms of SiO₂ and K₂O, but have Ca/Na ratios and FeO^* contentsthat are too high compared with the natural rocks, implyingthat fractionation processes are necessary to reach typicalcompositions of natural oceanic plagiogranites. KEY WORDS: differentiation; MORB; oxygen fugacity; water activity; oceanic plagiogranite     

High fO2 During Sillimanite Zone Metamorphism of Part of the Barrovian Type Locality, Glen Clova, Scotland

The redox state of sillimanite zone (650–700°C, 5–6kbar) metasediments of the Barrovian type area, Scotland, wasinvestigated using estimates of metamorphic oxygen fugacity(f_O2), sulfur fugacity (f_S2), and fluid chemistry based on newdeterminations of mineral and rock compositions from 33 samples.A total of 94% of the samples lack graphite, contain both ilmenite–hematitesolid solutions (RHOMOX) and magnetite, and had metamorphicf_O2 about 2 log₁₀ units above the quartz–fayalite–magnetite(QFM) buffer. The regional variation in metamorphic f_O2 forthese rocks was minimal, about ±0·3 log₁₀ units,reflecting either a protolith that was homogeneous with respectto redox state, or an initially variable protolith whose redoxstate was homogenized by metamorphic fluid–rock interaction.RHOMOX inclusions in garnet porphyroblasts that become richerin ilmenite from the interior to the edge of the host porphyroblastsuggest that at least some syn-metamorphic reduction of rockoccurred. Significant variations in bulk-rock oxidation ratio(OR) that are probably inherited from sedimentary protolithsare found from one layer to the next; OR ranges mostly between     

Primitive Magma From the Jericho Pipe, N.W.T., Canada: Constraints on Primary Kimberlite Melt Chemistry

We report the first estimates of primary kimberlite melt compositionfrom the Slave craton, based on samples of aphanitic kimberlitefrom the Jericho kimberlite pipe, N.W.T., Canada. Three samplesderive from the margins of dykes where kimberlite chilled againstwall rock (JD51, JD69 and JD82) and are shown to be texturallyconsistent with crystallization from a melt. Samples JD69 andJD82 have geochemical characteristics of primitive melts: theyhave high MgO (20–25 wt %), high mg-numbers (86–88),and high Cr (1300–1900 ppm) and Ni (800–1400 ppm)contents. They also have high contents of CO₂ (10–17 wt%). Relative to bulk macrocrystal kimberlite, they have lowermg-numbers and lower MgO but are enriched in incompatible elements(e.g. Zr, Nb and Y), because the bulk kimberlite compositionsare strongly controlled by accumulation of mantle olivine andother macrocrysts. The compositions of aphanitic kimberlitefrom Jericho are similar to melts produced experimentally bypartial melting of a carbonate-bearing garnet lherzolite. Onthe basis of these experimental data, we show that the primarymagmas from the Jericho kimberlite could represent 0·7–0·9%melting of a carbonated lherzolitic mantle source at pressuresand temperatures found in the uppermost asthenosphere to theSlave craton. The measured CO₂ contents for samples JD69 andJD82 are only slightly lower than the CO₂ contents of the correspondingexperimental melts; this suggests that the earliest hypabyssalphase of the Jericho kimberlite retained most of its originalvolatile content. As such these samples provide a minimum CO₂content for the primary kimberlite magmas from the Slave craton. KEY WORDS: kimberlite; melt; primitive; primary magma; Slave craton     

Experimental and Thermodynamic Constraints on the Sulphur Yield of Peralkaline and Metaluminous Silicic Flood Eruptions

Many basaltic flood provinces are characterized by the existenceof voluminous amounts of silicic magmas, yet the role of thesilicic component in sulphur emissions associated with trapactivity remains poorly known. We have performed experimentsand theoretical calculations to address this issue. The meltsulphur content and fluid/melt partitioning at saturation witheither sulphide or sulphate or both have been experimentallydetermined in three peralkaline rhyolites, which are a majorcomponent of some flood provinces. Experiments were performedat 150 MPa, 800–900°C, fO₂ in the range NNO –2 to NNO + 3 and under water-rich conditions. The sulphur contentis strongly dependent on the peralkalinity of the melt, in additionto fO₂, and reaches 1000 ppm at NNO + 1 in the most stronglyperalkaline composition at 800°C. At all values of fO₂,peralkaline melts can carry 5–20 times more sulphur thantheir metaluminous equivalents. Mildly peralkaline compositionsshow little variation in fluid/melt sulphur partitioning withchanging fO₂ (D_S 270). In the most peralkaline melt, D_S risessharply at fO₂ > NNO + 1 to values of >500. The partitioncoefficient increases steadily for S_bulk between 1 and 6 wt% but remains about constant for S_bulk between 0·5 and1 wt %. At bulk sulphur contents lower than 4 wt %, a temperatureincrease from 800 to 900°C decreases D_S by 10%. These results,along with (1) thermodynamic calculations on the behaviour ofsulphur during the crystallization of basalt and partial meltingof the crust and (2) recent experimental constraints on sulphursolubility in metaluminous rhyolites, show that basalt fractionationcan produce rhyolitic magmas having much more sulphur than rhyolitesderived from crustal anatexis. In particular, hot and dry metaluminoussilicic magmas produced by melting of dehydrated lower crustare virtually devoid of sulphur. In contrast, peralkaline rhyolitesformed by crystal fractionation of alkali basalt can concentrateup to 90% of the original sulphur content of the parental magmas,especially when the basalt is CO₂-rich. On this basis, we estimatethe amounts of sulphur potentially released to the atmosphereby the silicic component of flood eruptive sequences. The peralkalineEthiopian and Deccan rhyolites could have produced 10¹⁷ and10¹⁸ g of S, respectively, which are comparable amounts to publishedestimates for the basaltic activity of each province. In contrast,despite similar erupted volumes, the metaluminous Paraná–Etendekasilicic eruptives could have injected only 4·6 x 10¹⁵g of S in the atmosphere. Peralkaline flood sequences may thushave greater environmental effects than those of metaluminousaffinity, in agreement with evidence available from mass extinctionsand oceanic anoxic events. KEY WORDS: silicic flood eruptions; sulphur; experiment; Ethiopia; Deccan     

Cr-Saturation Arrays in Concentrate Garnet Compositions from Kimberlite and their Use in Mantle Barometry

The spinel–garnet transition in Cr/Al-enriched peridotiticbulk compositions is known from experimental investigationsto occur at 20–70 kbar, within the pressure range sampledby kimberlites. We show that the Cr₂O₃–CaO compositionsof concentrate garnets from kimberlite have maximum Cr/Ca arrayscharacterized by Cr₂O₃/CaO 0·96–0·81, andinterpret the arrays as primary evidence of chromite–garnetcoexistence in Cr-rich harzburgitic or lherzolitic bulk compositionsderived from depth within the lithosphere. Under Cr-saturatedconditions on a known geotherm, each Cr/Ca array implicitlydelineates an isobar inside a garnet Cr₂O₃–CaO diagram.This simplification invites a graphical approach to calibratean empirical Cr/Ca-in-pyrope barometer. Carbonaceous chromite–garnetharzburgite xenoliths from the Roberts Victor kimberlite tightlybracket a graphite–diamond constraint (GDC) located atCr₂O₃ = 0·94CaO + 5·0 (wt %), representing a pivotalcalibration corresponding to 43 kbar on a 38 mW/m² conductivegeotherm. Additional calibration points are established at 14,17·4 and 59·1 kbar by judiciously projecting garnetcompositions from simple-system experiments onto the same geotherm.The garnet Cr/Ca barometer is then simply formulated as follows(in wt %):

if Cr₂O₃ 0·94CaO + 5, then P₃₈ (kbar) = 26·9+ 3·22Cr₂O₃ – 3·03CaO, or

if Cr₂O₃ <0·94CaO + 5, then P₃₈ (kbar) = 9·2+ 36[(Cr₂O₃+ 1·6)/(CaO + 7·02)].

A small correction to P₃₈ values, applicable for 35–48mW/m² conductive geotherms, is derived empirically by requiringconventional thermobarometry results and garnet concentratecompositions to be consistent with the presence of diamondsin the Kyle Lake kimberlite and their absence in the Zero kimberlite.We discuss application of the P₃₈ barometer to estimate (1)real pressures in the special case where chromite–garnetcoexistence is known, (2) minimum pressures in the general casewhere Cr saturation is unknown, and (3) the maximum depth ofdepleted lithospheres, particularly those underlying Archaeancratons. A comparison with the P_Cr barometer of Ryan et al.(1996, Journal of Geophysical Research 101, 5611–5625)shows agreement with P₃₈ at 55 ± 2 kbar, and 6–12%higher P_Cr values at lower P₃₈. Because the P_Cr formulationsystematically overestimates the 43 kbar value of the GDC by2–6 kbar, we conclude that the empirical Cr/Ca-in-garnetbarometer is preferred for all situations where conductive geothermsintersect the graphite–diamond equilibrium. KEY WORDS: Cr-pyrope; chromite; P₃₈ barometer; mantle petrology; lithosphere thickness     

Intensive Variables in Kimberlite Magmas, Lac de Gras, Canada and Implications for Diamond Survival

Crystallization temperatures (T) and oxygen fugacities (fO₂)of kimberlite magma are estimated from oxides included in olivinephenocrysts from the Leslie, Aaron, Grizzly and Torrie kimberlitepipes in the central Slave Province, Canada. Crystallizationtemperatures recorded by olivine–chromite pairs at anassumed pressure of 1·0 GPa are 1030–1170°C± 50°C, with a mean of     

Empirical Solution Model for Alkalic to Tholeiitic Basic Magmas

Currently available models to simulate naturally occurring mineral–meltequilibria use mineral components limited to tholeiitic basaltcompositions and thus they cannot be used for alkali-rick basaltsand basanites. To expand mineral–melt equilibria calculationsto alkali-rich composition space at low pressures, we have derivedequations that describe chemical equilibria between olivine–melt,pyroxene–melt, plagioclase–melt, nepheline–meltand leucite–melt components. Excess free energies of reactionsbetween the end-member mineral and melt components at equilibriumhave been expressed as a function of melt composition, temperatureand fo₂. The database used to calculate the mineral–meltexpressions consists of a total of >350 anhydrous experimentsconducted under controlled oxygen fugacity defined by the quartz–fayalite–magnetite(QFM) oxygen buffer. Rocks used in these experiments range frombasanites, nephelinites and alkali olivine basalts, to tholeiiticbasalts and basaltic andesites. Using bulk compositions of startingmaterials both in this experimental database and in others thatwere not incorporated into the regression of modeled parameters,modeled equations successfully predict, at a given temperatureand fo₂, compositions of multiply saturated melts as well asthe compositions of coexisting minerals. Standard deviationsof the calculated mole fractions of mineral components () areas follows: anorthite 002; forsterite 002; clinoenstatite002; enstatite 0003; nepheline 002; and leucite 001. Standarddeviations () of the calculated melt compositions in terms ofweight percent of oxides are: SiO₂ 0•96; Al₂O₃ 132; Fe₂O₃023; FeO 121; MgO 084; CaO 079; Na₂O 058; and K₂O 069.All calculations were carried out using a non-linear Newton–Raphsonnumerical procedure. KEY WORDS: mineral–melt equilibria; alkalic–tholeiitic basalts; equilibrium thermodynamics ^*Corresponding author     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.     

An Experimentally Constrained Petrogenetic Grid in the Silica-Saturated Portion of the System KFMASH at High Temperatures and Pressures

Experiments in the quartz-saturated part of the system KFMASHunder fO₂ conditions of the haematite–magnetite bufferand using bulk compositions with X_Mg of 0·81, 0·72,0·53 define the stability limits of several mineral assemblageswithin the P–T field 9–12 kbar, 850–1100°C.The stability limits of the mineral assemblages orthopyroxene+ spinel + cordierite ± sapphirine, orthopyroxene + garnet+ sapphirine, sapphirine + cordierite + orthopyroxene and garnet+ orthopyroxene + spinel have been delineated on the basis ofP–T and T–X pseudosections. Sapphirine did not appearin the bulk composition of X_Mg = 0·53. A partial petrogeneticgrid applicable to high Mg–Al granulites metamorphosedat high fO₂, developed in our earlier work, was extended tohigher pressures. The experimental results were successfullyapplied to several high-grade terranes to estimate P–Tconditions and retrograde P–T trajectories. KEY WORDS: KFMASH equilibria; experimental petrogenetic grid at high fO₂     

Origin of Grandite Garnet in Calc-Silicate Granulites: Mineral-Fluid Equilibria and Petrogenetic Grids

The role of clinopyroxene in producing grandite garnet is evaluatedusing data from an ultrahigh-temperature metamorphosed calc-silicategranulite occurrence in the Eastern Ghats Belt, India. ‘Peak’pressure–temperature conditions of metamorphism were previouslyconstrained from associated high Mg–Al granulites as c.0·9 GPa, >950°C, and the rocks were near-isobaricallycooled to c. 750°C. Grandite garnet of variable compositionwas produced by a number of reactions involving phases suchas clinopyroxene, scapolite, plagioclase, wollastonite and calcite,in closely spaced domains. Compositional heterogeneity is preservedeven on a microscale. This precludes pervasive fluid fluxingduring either the peak or the retrograde stage of metamorphism,and is further corroborated by computation of fluid–rockratios. With the help of detailed textural and mineral compositionalstudies leading to formulation of balanced reactions, and usingan internally consistent thermodynamic dataset and relevantactivity–composition relationships, new petrogenetic gridsare developed involving clinopyroxene in the system CaO–Al₂O₃–FeO–SiO₂–CO₂–O₂in T–aCO₂–fO₂ space to demonstrate the importanceof these factors in the formation of grandite garnet. Two singularcompositions in garnet-producing reactions in this system arededuced, which explain apparently anomalous textural relations.The possible role of an esseneite component in clinopyroxenein the production of grandite garnet is evaluated. It is concludedthat temperature and fO₂ are the most crucial variables controllinggarnet composition in calc-silicate granulites. fO₂, however,behaves as a dependent variable of CO₂ in the fluid phase. Externalfluid fluxing of any composition is not necessary to producechemical heterogeneity of garnet solid solution. KEY WORDS: grandite garnet; role of clinopyroxene; internal buffering; oxidation–decarbonation equilibria     

Olivine in the Udachnaya-East Kimberlite (Yakutia, Russia): Types, Compositions and Origins

Olivine is the principal mineral of kimberlite magmas, and isthe main contributor to the ultramafic composition of kimberliterocks. Olivine is partly or completely altered in common kimberlites,and thus unavailable for studies of the origin and evolutionof kimberlite magmas. The masking effects of alteration, commonin kimberlites worldwide, are overcome in this study of theexceptionally fresh diamondiferous kimberlites of the Udachnaya-Eastpipe from the Daldyn–Alakit province, Yakutia, northernSiberia. These serpentine-free kimberlites contain large amountsof olivine (50 vol.%) in a chloride–carbonate groundmass.Olivine is represented by two populations (olivine-I and groundmassolivine-II) differing in morphology, colour and grain size,and trapped mineral and melt inclusions. The large fragmentalolivine-I is compositionally variable in terms of major (Fo_85–94)and trace element concentrations, including H₂O content (10–136ppm). Multiple sources of olivine-I, such as convecting andlithospheric mantle, are suggested. The groundmass olivine-IIis recognized by smaller grain sizes and perfect crystallographicshapes that indicate crystallization during magma ascent andemplacement. However, a simple crystallization history for olivine-IIis complicated by complex zoning in terms of Fo values and traceelement contents. The cores of olivine-II are compositionallysimilar to olivine-I, which suggests a genetic link betweenthese two types of olivine. Olivine-I and olivine-II have oxygenisotope values (+ 5·6 ± 0·1 VSMOW, 1 SD)that are indistinguishable from one another, but higher thanvalues (+ 5·18 ± 0·28) in ‘typical’mantle olivine. These elevated values probably reflect equilibriumwith the Udachnaya carbonate melt at low temperatures and ¹⁸O-enrichedmantle source. The volumetrically significant rims of olivine-IIhave constant Fo values (89·0 ± 0·2 mol%),but variable trace element compositions. The uniform Fo compositionsof the rims imply an absence of fractionation of the melt'sFe²⁺/Mg, which is possible in the carbonatite melt–olivinesystem. The kimberlite melt is argued to have originated inthe mantle as a chloride–carbonate liquid, devoid of ‘ultramafic’or ‘basaltic’ aluminosilicate components, but becameolivine-laden and olivine-saturated by scavenging olivine crystalsfrom the pathway rocks and dissolving them en route to the surface.During emplacement the kimberlite magma changed progressivelytowards an original alkali-rich chloride–carbonate meltby extensively crystallizing groundmass olivine and gravitationalseparation of solids in the pipe. KEY WORDS: kimberlite; olivine; partial melting; carbonatitic melt; oxygen isotopes; H₂O     

The Range of Spinel Compositions in Terrestrial Mafic and Ultramafic Rocks

Compositional fields for spinels from a wide variety of mafic–ultramaficigneous rock types and tectonic environments have been determinedfrom a global database of over 26 000 analyses. These fieldsare defined using contoured data density plots based on thespinel prism, and plots of T iO₂ vs ferric iron, for mantlexenoliths, ophiolitic rocks, continental layered intrusions,alkalic and lamprophyric rocks, tholeiitic basalts, Alaskanultramafic complexes and komatiites. Several trends appear regularlyin the various environments: a trend of widely variable Cr/(Cr+ Al) at low Fe²⁺/(Mg + Fe²⁺) (the Cr–Al trend); increasingFe³⁺, Fe²⁺/(Mg + Fe²⁺) and T iO₂ at constant Cr/(Cr + Al) (Fe–Ti trend); a trend found primarily in kimberlites, similar toFe–T i but at constant Fe²⁺/(Mg + Fe²⁺); and an unusualtrend of increasing Al found only in layered intrusions. TheCr–Al and Fe–T i trends are both found to varyingdegrees in tholeiitic basalts. The Cr–Al trend is prevalentin rocks that have equilibrated over a range of pressures, whereasthe Fe–T i trend is dominantly due to low-pressure fractionation.The most Cr-rich chromites found in nature occur in boninites,diamond-bearing kimberlites, some komatiites and ophioliticchromitites. Exceptionally reduced chromites are found in somekomatiites and in ophiolitic chromitites. Detrital chromitesfrom the Witwatersrand conglomerates are of komatiitic provenance. KEY WORDS: basalt; chromite; kimberlite; ophiolite; spinel     

Petrological and Experimental Constraints on the Pre-eruption Conditions of Holocene Dacite from Volcan San Pedro (36{degrees}S, Chilean Andes) and the Importance of Sulphur in Silicic Subduction-related Magmas

We present an experimental and petrological study aimed at estimatingthe pre-eruptive conditions of a Holocene dacitic lava fromVolcán San Pedro (36°S, Chilean Andes). Phase-equilibriumexperiments were performed at temperatures (T) from 800 to 950°C,and mainly at 200 MPa, but also at 55, 150, and 406 MPa. Oxygenfugacity (fO₂) ranged from the Ni–NiO buffer (NNO) to3·5 log units above (NNO + 3·5), and water contentsfrom     

Selected Phase Relationships in the System Al-Mn-Fe-Si-O-H: A Model for Garnet Equilibria

The bulk compositions 3FeO_x.Al₂O₃.3SiO₂ $ excess H₂O and 3MnO.Al₂O₃.3SiO₂$ excess H₂O were investigated employing conventional hydrothermaltechniques. Almandine and spessartine were synthesized and stabilityrelationships determined in terms of temperature, fluid pressure,and oxygen fugacity. Synthetic almandine has unit cell edge, a₀ = 11.528 0.001 index of refraction, N_D = 1.829 0.003. No systematic variationsof these values with respect to temperature, fluid pressure,and oxygen fugacity were observed. Spessartine, synthesizedat high temperatures, has average values of a₀ = 11.614 0.001 and N_D = 1.799 0.003. However, below about 600 C a₀ graduallyincreases to 11.635 0.001 and N_D decreases to 1.772 0.003with decreasing temperature, irrespective of fluid pressureand oxygen fugacity. These changes appear to reflect the productionof hydrospessartine below about 600 C. The stability of almandine strongly depends on the oxygen fugacity.It is stable up to the vicinity of oxygen fugacities definedby the fayalite–magnetite$quartz buffer; the low f_o2,range has not been determined, but lies at oxygen fugacitiesless than those defined by the ironquartz–fayalite buffer.The stability field of almandine$fluid is bounded by the followingP_fluid-T values. At low oxidation states, the low temperature hydrous assemblageof equivalent composition consists of quartz$iron chlorite ($magnetite)$fluidand the high temperature equivalent assemblage consists of fayalite$ironcordierite$hercynite₈₈$fluid. Where f_O2 approximates or is inexcess of that defined by the fayalite–magnetite$quartzbuffer the low temperature hydrous assemblages consist of quartz$ironchlorite$magnetite$fluid, iron chlorite$pyrophyllite$magnetite$fluid,magnetite$mullite$pyrophyllite$fluid, and hematite$mullite$pyrophyllite$fluid;the anhydrous equivalent assemblages consist of quartz$hercynite₈₈,$magnetite₈₈$fluid, quartz$mullite$magnetite$fluid, and quartz$mullite$hematite$fluid,both in order of increasing oxygen fugacity. The stability of spessartine, in contrast to that of almandine,is essentially independent of oxygen fugacity at least up tothat defined by the magnetite-hematite buffer. Spessartine isstable up to the highest temperature, 930 C, employed in thisinvestigation at P_fluid = 500 bars. However, it decomposes toa hydrous assemblage consisting of quartz$manganese chlorite$fluidat the following P_fluid-T values: 414 5 C and 3000 bars;405 5C and 2000 bars; 386 10 C and 1000 bars; 3645C and 500 bars. Garnets are rare constituents of igneous rocks; those whichdo occur are predominantly spessartine-rich, and are virtuallyconfined to felsic magmas. Garnets are absent from mafic igneousrocks because the thermal stability ranges of iron-rich membersare below the solidus. The near absence of almandine in contactmetamorphosed pelitic rocks may reflect a relatively high oxidationstate in the aureoles rather than inappropriate P-T conditions.It is argued that the compositions of pyralspite garnets inpelitic schists are subject to various physical and chemicalfactors, including f_O2. With appropriate provisions, the Mn/Feratios of garnet coexisting with chlorite and quartz might beused as a temperature indicator. The rarity of spessartine in igneous and metamorphic rocks apparentlystems from the departure of rock bulk composition from Mn-richvalues rather than from the absence of appropriate physicalconditions.