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     

Synthesis and Stability Relations of Epidote, Ca2Al2FeSi3O12 (OH)

Hydrothermal investigation of the bulk composition 2CaO·Al₂O₃·l/2Fe₂O₂·3SiO₂+excessH₂O (Ps 33 +excess H₂O) has been conducted using conventionalapparatus and solid oxygen buffer techniques. Coarse-grainedepidotes (over 150 microns in some cases) were readily synthesizedfrom oxide mixtures with a 98 per cent yield as well as fromtheir high temperature equivalents at 600–700 °C and5 kb P_fluid and over a range of oxygen fugacities. Electronmicroprobe analyses show that maximum Fe⁺³ content of syntheticepidotes varies as a function of fo₂. Epidote is most iron-rich(Ps 33 ± 2) at high (HM and CCO) oxygen buffers and becomesprogressively more aluminous (Ps 25 ± 3) with decreasingfo₂ values and temperatures. Such variation is consistent withthe change of refractive indices and cell dimensions. The meanrefractive indices and cell dimensions for synthetic epidote(Ps 33) are N = 1.745 ± 0.005, N = l.786±0.005,a = 8.920±0.005 Å, b = 5.645±0.004 Å,c = 10.190 ű0.006 Å, and ß = 115°31'±4' and for epidote (Ps 25) are N = 1.735±0.005,N = 1.775±0.005, a = 8.891±0.005 Å, b =5.625±0.004 Å, c = 10.177±0.006 Å,and ß = 115° 30'±3'. Mössbauer spectraindicate synthetic epidotes are relatively disordered. Garnets of intermediate composition in the grossular-andraditeseries were synthesized and the cell dimensions and refractiveindices vary linearly with composition. With successive decreasein fo₂, garnet synthesized on the Ps 33 bulk composition movestoward the grossular end member with simultaneously increasingalmandine component; concomitantly the hercynite component ofthe coexistent magnetite increases. The fo₂-T-P_fluid relations were determined by employing mineralmixtures of synthetic epidote and its high temperature equivalentin subequal proportions. Equilibrium was demonstrated for thereactions (1) epidote (Ps 33) = anorthite+grandite+FeO_x+quartz+ fluid, and (2) epidote (Ps 25) (+quartz) = garnet₃₈+anorthite+magnetitc+fluid.With fo₂ defined by the HM buffer, epidote (Ps 33) is stableup to 748 °C, 5 kb, 678 °C, 3 kb, and 635 °C, 2kb P_fluid. With fo₂ defined by the NNO buffer, the epidote (Ps25) high temperature stability limit is reduced about 100 °Cat 5kb P_fluid. At slightly lower fo₂, than defined by the QFMbuffer, epidote is not stable at any temperatures; the assemblagehedenbergite+anorthite+garnet₃₈+fluid replaces epidote in thepresence of excess quartz. Combined with previously determined equilibria for prehnite,andradite, and hedenbergite, isobaric fo,-T relations were furtherinvestigated by chemographic analysis interrelating the phasesprehnite, epidote, grandite, hedenbergite, wollastonite, anorthite,and magnetite in the system CaO-Fe₂O₃-Al₂O₃-SiO₂-H₂0. Such analysisallowed the construction of a semi-quantitative petrogeneticgrid applicable to natural parageneses in low µCO₂ environments,and the delineation of the low temperature stability limit ofepidote as a function of fo₂. Enlargement of the epidote stabilityrange toward both high and low temperatures with increasingfo₂, is consistent with widespread occurrences of epidote inlow- and mediumgrade metamorphic rocks.     

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     

Ferric Iron in CaTiO3 Perovskite as an Oxygen Barometer for Kimberlite Magmas II: Applications

We apply an oxygen barometer based on the Fe content of CaTiO₃perovskite to estimate the oxygen fugacity (fO₂) during thecrystallization and emplacement of kimberlites in differenteruptive phases of a single pipe, or between different pipes,clusters or provinces. Mineral chemical data for perovskitewere compiled from the literature and obtained in our detailedstudy of perovskites from 11 kimberlites at Somerset Islandand Lac de Gras, Canada. Perovskite compositions in kimberlitesrecord a range in fO₂ of many orders of magnitude from NNO–5to NNO+6 [where log fO₂ is given relative to the nickel–nickeloxide (NNO) buffer]. The range of fO₂ recorded by differentparageneses of perovskite within a single pipe can vary up tothree orders of magnitude with trends toward both oxidationand reduction during crystallization. Kimberlites record someof the greatest ranges, and the highest known fO₂ conditionsfor any terrestrial magma. This is attributed to the presenceof deep and oxidized source regions and the variable interplayof ferric–ferrous vs carbon–fluid equilibria duringascent of kimberlite magmas. Three kimberlite pipes from theLac de Gras field show that higher fO₂ values correlate withhigher proportions of more resorbed diamonds, suggesting thatthis variable has a measurable effect on the physical propertiesof diamonds in a pipe. KEY WORDS: kimberlites; oxygen fugacity; perovskite; diamond; redox; mantle     

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     

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     

Experimentally Determined Conditions in the Fish Canyon Tuff, Colorado, Magma Chamber

The Fish Canyon Tuff, Colorado, forms one of the largest (3000km³ known silicic eruptions in Earth history. The tuff is ahomogeneous quartz latite consisting of 40% phenocrysts (plagioclase,sanidine, biotite, hornblende, quartz, magnetite, apatite, sphene,and ilmenite) in equilibrium with a highly evolved rhyoliticmelt now represented by the matrix glass. Melt inclusions trappedin hornblende and quartz phenocrysts are identical to the newlyanalyzed matrix glass composition indicating that hornblendeand quartz crystallized from a highly evolved magma that subsequentlyexperienced little change. This study presents experimentalphase equilibrium data which are used to deduce the conditions(P, T, f_O2, f_H2O, etc.) in the Fish Canyon magma chamber priorto eruption. These new data indicate that sanidine and quartzare not liquidus phases until 780?C temperatures are achieved,consistent with Fe-Ti oxide geothermometry which implies thatthe magmatic temperature prior to eruption was 760?30?C. NaturalFe-Ti oxide pairs also suggest that log f_O2 was -12.4 (intermediatebetween the Ni-NiO and MnO-Mn₃O₄ oxygen buffers) in the magmachamber. This f_O2.102 is supported by the experimentally determinedvariations in hornblende and melt Mg-numbers as functions off_O2 A new geobarometer based on the aluminum content of hornblendesin equilibrium with the magmatic assemblage hornblende, biotite,plagioclase, quartz, sanidine, sphene, ilmenite or magnetite,and melt is calibrated experimentally, and yields pressuresaccurate to ?0.5 kb. Total pressure in the Fish Canyon magmachamber is inferred to have been 2.4 kb (equivalent to a depthof 7.9 km) based on the Al-content of natural Fish Canyon hornblendesand this new calibration. This depth is much shallower thanhas been proposed previously for the Fish Canyon Tuff. Variationsin experimental glass (melt) composition indicate that the magmawas water-undersaturated prior to eruption. X_H2O in the fluidphase that may have coexisted with the Fish Canyon magma isestimated to have been 0.5 by comparing the An-content of naturalplagioclases to experimental plagioclases synthesized at differentX_H2O and P_totals. This ratio corresponds to about 5 wt.% waterin the melt at depth. The matrix glass chemistry is reproducedexperimentally under these conditions: 760?C, 2.4 kb, X_H2O=0.5,and log f_o2=NNO+2 log units. The fugacity of SO₂ (91 b) is calculatedfrom the coexistence of pyrrhotite and magnetite. Maximum CO₂fugacity (2520 b) is inferred assuming the magma was volatilesaturated at 2.4 kb.     

The Stability of Andradite, Hedenbergite, and Related Minerals in the System Ca--Fe--Si--O--H

Phase relations for the bulk compositions 3CaO·2FeO_x·3SiO₂+excessH₂O and CaO·FeO_x·2SiO₂+excess H₂O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO₂. Andradite, Ca₃Fe³⁺₂Si₃O₁₂, synthesized above 550 °C hasan average unit cell edge, a_o, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, a_o increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars P_fluid andradite is stable above an f_O2of 10¹⁵ bar at 800 °C and 10-³² bar at 400 °C. At lowerf_O2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe²⁺SiO₄)+ wollastonite and kirschsteinite+xonotlite (Ca₆Si₆O₁₇(OH)₂). Synthetic hedenbergite, CaFe²⁺Si₂O₆, has average unit cell dimensionsof a_o = 9.857± 0.004 Å, b_o = 9.033±0.002Å, c_o = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars P_fiuid, hedenbergite is stable below an f_O2 of10-¹³ bar at 800 °C and 10-²⁸ bar at 400 °C. Above thesef_O2 values, hedenbergite+O₂ breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the f_O2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H₂O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.     

An Experimental Study of the Influence of Oxygen Fugacity on Fe-Ti Oxide Stability, Phase Relations, and Mineral--Melt Equilibria in Ferro-Basaltic Systems

Equilibrium crystallization experiments at atmospheric pressureand over a range of oxygen fugacity (fO₂) have been carriedout on a ferro-basaltic composition similar to liquids proposedto have been parental to much of the exposed portion of theSkaergaard intrusion. Before Fe-Ti oxide saturation the liquidline of descent is little affected by fO₂. However, the appearancetemperatures of the magnetite-ulvspinel solid solution (Mt)and the ilmenite-haematite solid solution (Ilm) depend stronglyon fO₂. Above the fayalite-magnetite-quartz (FMQ) buffer Mtis the first oxide phase to appear on the liquidus, but belowthe FMQ buffer Ilm is the first oxide to crystallize. The appearancetemperature of Mt is 1100C at FMQ and the Mt liquidus slopeis 30C/log fO₂ unit between FMQ–;2 and FMQJ+1. The Ilmliquidus is at 1100C between FMQ and FMQ–2, but movesto lower temperature at higher fO₂ where Mt is the first oxidephase. The results indicate that the ferric iron content ofMt-saturated melts varies linearly with inverse temperature,and that Ilm saturation is closely related to melt TiO₂ content.Mt saturation produces an immediate enrichment of SiO₂ and depletionin FeO^* in the melt phase, whereas Ilm saturation produces similarenrichment in SiO², but inn enrichment may continue for 10Cbelow the ilmenite liquidus. The experimental liquids reacha maximum of 18 wt% FeO^*, at 48 wt% SiO₂ for ilmenite-saturatedmelts at low f_O2, more differentiated melts having lower ironand higher silica. Cotectic proportions, derived from mass balancecalculations, are in good agreement with data from natural samplesand other experimental studies. Olivine resorption is inferredat all fO₂, with the onset of resorption occurring 10C higherthan the appearance of magnetite. The effect of fO₂ on silicatemineral compositions, and partitioning of elements between coexistingmineral-melt pairs, is small. Thermodynamic considerations suggestthat variations of Fe-Mg partitioning between the iron-richolivines, pyroxenes and melts produced in this study may beexplained by known non-idealities of Fe-Mg mixing in the crystallinephases, rather than nonidealities in the coexisting melts. Theseexperiments also provide insights into many features commonto natural tholeiitic series of volcanic and plutonic rocks,and provide experimental data required for modelling of fractionalcrystallization and crystallization closed to oxygen, processeswhich are not easily investigated experimentally. KEY WORDS: ferro-basalt; Fe-Ti oxides; oxygen fugacity; Skaergaard intrusion; iron enrichment ^*Corresponding author. Present address: Bayerisches Geoinstitut, Univerritt Bayreuth, D-95440 Bayreuth, Germany     

Quantification of Magmatic and Hydrothermal Processes in a Peralkaline Syenite-Alkali Granite Complex Based on Textures, Phase Equilibria, and Stable and Radiogenic Isotopes

The Puklen complex of the Mid-Proterozoic Gardar Province, SouthGreenland, consists of various silica-saturated to quartz-bearingsyenites, which are intruded by a peralkaline granite. The primarymafic minerals in the syenites are augite ± olivine +Fe–Ti oxide + amphibole. Ternary feldspar thermometryand phase equilibria among mafic silicates yield T = 950–750°C,a_SiO2 = 0·7–1 and an f_O2 of 1–3 log unitsbelow the fayalite–magnetite–quartz (FMQ) bufferat 1 kbar. In the granites, the primary mafic minerals are ilmeniteand Li-bearing arfvedsonite, which crystallized at temperaturesbelow 750°C and at f_O2 values around the FMQ buffer. Inboth rock types, a secondary post-magmatic assemblage overprintsthe primary magmatic phases. In syenites, primary Ca-bearingminerals are replaced by Na-rich minerals such as aegirine–augiteand albite, resulting in the release of Ca. Accordingly, secondaryminerals include ferro-actinolite, (calcite–siderite)_ss,titanite and andradite in equilibrium with the Na-rich minerals.Phase equilibria indicate that formation of these minerals tookplace over a long temperature interval from near-magmatic temperaturesdown to     

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     

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.     

The Stability of Igneous Anhydrite: Experimental Results and Implications for Sulfur Behavior in the 1982 El Chichon Trachyandesite and Other Evolved Magmas

Hydrothermal experiments on natural samples of trachyandesiteand dacite bulk composition show that anhydrite (CaSO₄) mayoccur as a stable phenocryst phase at oxygen fugacities greaterthan or equal to 1.0 to 1.5 log f_O2 units above the Ni–NiOequilibrium. The dissolved sulfur concentration in anhydritesaturated melts from MnO–Mn₃O₄ buffered experiments decreaseswith decreasing temperature, from approximately 2300 p.p.m.Sat 1025?C to 250 p.p.m.S at 850?C (all at 2 kb P_fluid = P_total).In FeS-saturated melts equilibrated at the Ni–NiO bufferand 2 kb pressure, the concentration of dissolved sulfur alsodecreases with decreasing temperature, varying from approximately400 p.p.m. S at 1025?C to less than 100 p.p.m. S at 850?C. AtNNO or lowerf_O2s, decreasing melt FeO content due to crystalfractionation may explain the observed decrease in sulfur solubilitywith decreasing temperature. Sulfur solubility values equivalent to the approximately 0.6wt. per cent S present in fresh bulk pumice samples from the1982 eruptions of El Chichon volcano are not readily achievedunder any reasonable combinations of pressure, temperature,and oxidation state. Dissolved sulfur contents approaching 0.6wt. per cent might occur if the source regions of melts parentalto the El Chichon trachyandesite were at an f_O2 several logunits above the Ni–NiO equilibrium. Because such elevatedoxidation states are far greater than the generally acceptedvalues for mantle-derived partial melts we believe the highsulfur content of the El Chichon pumices is not a primary feature;it reflects reaction with sulfur enriched material at some unknowndepth beneath the volcano. Published sulfur isotopic and petrologicdata suggest that hydrothermally altered rocks similar to thepyrite- and anydritebearing lithic fragments found in the 1982pumices could have provided a source of sulfur for crystallizationof magmatic anhydrite. The anhydrite was an important sourceof sulfur for evolution of a sulfur-rich vapor phase duringeruption of the magma. Although many calc-alkaline dacites and rhyolites appear toattain oxidation states high enough to stabilize anhydrite,the characteristically low bulk sulfur contents of these rockswill limit anhydrite abundances to less than approximately 0.1wt. per cent, assuming sufficient sulfur is present to achievesaturation. Such small amounts of a water soluble mineral couldbe easily removed by subaerial weathering processes, dissolvedduring vapor exsolution from a magma, or simply overlooked duringroutine petrographic examination.     

Subduction Influence on Oxygen Fugacity and Trace and Volatile Elements in Basalts Across the Cascade Volcanic Arc

Fluids or melts derived from a subducting plate are often citedas a mechanism for the oxidation of arc magmas. What remainsunclear is the link between the fluid, oxygen fugacity, andother major and trace components, as well as the spatial distributionof the impact of those fluids. To test the potential effectsof addition of a subduction-derived fluid or melt to the sub-arcmantle, olivine-hosted melt inclusions from primitive basalticlavas sampled from across the central Oregon Cascades (43°–45°N)have been analyzed for major, trace and volatile elements andfO₂. Oxygen fugacity was determined in melt inclusions fromsulfur speciation determined by electron microprobe and fromolivine–chromite oxygen geobarometry. The overall rangein fO₂ based on sulfur speciation measurements is from <–0·25log units to + 1·9 log units (FMQ, where FMQ is fayalite–magnetite–quartzbuffer). Oxygen fugacity is positively correlated with fluid-mobiletrace element and light rare earth element contents in basaltsgenerated by relatively low-degree partial melting. Establishinga further correlation between fO₂ and fluid-mobile trace elementabundances with position along the arc requires the basaltsto be subdivided into shoshonitic, calc-alkaline, low-K tholeiiteand enriched intraplate basalt groups. Melt inclusions fromenriched intraplate and shoshonitic lavas show increasing fO₂and trace element abundances closer to the trench, whereas calc-alkalinemelt inclusions exhibit no significant across-arc variations.Low-K tholeiitic melt inclusions record an increase in incompatibletrace elements closer to the trench; however, there is no correlatedincrease in fO₂. The correlation observed in enriched intraplateand shoshonitic melt inclusions is interpreted to reflect aprogressively greater proportion of a fluid-rich, oxidized subductioncomponent in magmas generated nearer the subduction zone. Significantly,calc-alkaline melt inclusions with high ratios of large ionlithophile elements to high field strength elements, characteristicof ‘typical’ arc magmas, have oxidation states indistinguishablefrom low-K tholeiite and enriched intraplate basalt melt inclusions.The lack of across-arc geochemical variation in calc-alkalinemelt inclusions may suggest that these basalts are not necessarilythe most appropriate magmas for examining recent addition ofa subduction component to the sub-arc mantle. Flux and batchmelt model results produce a wide range of predicted amountsof melting and subduction component added to the mantle source;however, general trends characterized by increased melting andproportion of the subduction component from enriched intraplate,to low-K tholeiite, to calc-alkaline are robust. The model resultsdo not require enriched intraplate, low-K tholeiite and calc-alkalinemagmas to be produced from the same more fertile mantle source.However, enriched intraplate magmas, in contrast to calc-alkalineand low-K tholeiite magmas, cannot be generated from a depletedmantle source. Flux or batch melting of either the more fertileor depleted mantle sources used to generate the low-K tholeiite,calc-alkaline, and enriched intraplate magmas cannot reproduceshoshonitic compositions, which require a significantly depletedmantle source strongly metasomatized by a subduction component.The potential mantle source for shoshonitic basalts has a predictedfO₂ (after oxidation) from + 0·3 to + 2·4 logunits (FMQ) whereas the mantle source for low-K tholeiite, calc-alkaline,and enriched intraplate magmas may range from –1·1to + 0·7 log units (FMQ). KEY WORDS: basalt; Cascades; melt inclusions; oxidation state; volatiles     

The Klokken Gabbro-Syenite Complex, South Greenland: Quantitative Interpretation of Mineral Chemistry

The layered syenite series in the Klokken stock formed by continuousin situ fractionation of a trachytic magma in a chamber linedby gabbro with 3000 m of cover rocks. The following mineralsand reactions are assessed as geothermometers and barometers:two feldspars; hypersolvus ternary feldspars; ferrohedenbergite-ß-wollastonite;clinopyroxene-olivine Fe-Mg exchange; Fe-Ti oxides; sanidine-magnetite-annite;ferroedenite stability. Estimates of silica activity are obtainedfrom the silica-magnetite-fayalite assemblage. The gabbros ended magmatic crystallization at > 1000–1050°C.The less fractionated members of the syenite range probablycrystallized with P_H2O < P_total, at T > 870°C and,P_H2O 800 bars. In the more fractionated syenites P_H2O = P_totalduring intercumulus feldspar growth, and all magmatic phasescrystallized within the interval 940–830°C and P_H2O< 1100 bars. Magmatic f_O2 (bars) was 1 log unit below theQFM buffer. a_SIO2 in gabbros was slightly above the albite-nephelinebuffer, but rose suddenly to just <1 in the syenites, a jumpmirrored by minor elements in pyroxenes and opaque oxides. Biotitegrew subsolidus in most rocks, at f_O2 < QFM, except in intermediaterocks when f_O2 > QFM and was defined by the sanidine-magnetite-biotiteassemblage. In these rocks P_H2O of 450 bars at 760°C isobtained using existing experimental data, but application ofthis data to Fe-rich biotites in the layered series (where biotiteis an intercumulus phase) requires P > 10 kb at magmatictemperatures. High TiO₂ or F: OH probably accounts for increasedT stability of natural annites at low P. The syenitic liquid fractionated down a low temperature zonein a multicomponent system precipitating alk fsp + ol + cpx+ mt and the more fractionated members of the layered serieshad a negligible crystallization interval, a prerequisite forthe development of the unique Klokken-type inversely gradedmineral layering.     

Stability Relations of the Ferruginous Biotite, Annite

Annite, KFe₃AISi₃O₁₀(OH)₂ a member of the iron biotites andthe ferrous analogue of phlogopite, has been synthesized andits phase relations have been determined as functions of temperature,fugacity of oxygen (fo₂), and total pressure (P_totalPH₂O+PH₂).A method for controlling fo₂at high total pressures is described,and data for the ‘oxygen buffers’ used are given.Buffers range from quartz+iron+fayalite assemblages (low fo₂)to magnetite-hematite assemblages (high fo₂). Optical propertiesand unit-cell dimensions of synthetic annites depend on theconditions of synthesis. By recalculating published analyses of natural iron-rich biotitesit can be shown that one cannot assume a constant hydrogen contentfor such biotites. Oxidation may have occurred by drying at115?C. Octahedral occupancy therefore cannot be calculated fromsuch data. Phase relations of annite are presented in 2,070 and 1,035 barsections. Depending on fo₂-T values annite was found to decomposeto one of the following assemblages: hematite+ sanidine, magnetite+sanidine,fayalite+leucite+kalsilite, iron+sanidine. All decompositionsare dehydration and redox reactions and are sensitive to changesin fH₂0 and fo₂ (or fH₂0 and fH₂). At 2, 070 bars total pressureannite+magnetite+sanidine can coexist between 425?C and 825?C, depending upon the magnitude of fo₂. In the presence of quartz the stability field of annite is morerestricted. Phase equilibria in the system KAlSiO₄–SiO₂–Fe–O₂–H₂have been summarized schematically. Wherever possible, thermodynamic extrapolations are made totest the internal consistency of the data. Enthalpies of formationare calculated for both annite and phlogopite. Ranges of fo₂values in nature as well as mechanisms for changes in fo₂ areinvestigated. It is useful to distinguish between assemblageswhich are internally buffered with respect to fo₂changes andthose which are not buffered. The applications of individualreactions involving annite to specific geologic problems arediscussed with respect to igneous, metamorphic, and sedimentaryrocks.     

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     

Synthesis and Stability Relations of Mg--Al Pumpellyite, Ca4Al5MgSi6O21(OH)7

Hydrothermal synthesis and investigations of stability relationsof Mg—Al pumpellyite were conducted using high-pressurecold-seal apparatus over the temperature range 250–600°C and 2–8 kb P_fluid. Mg—Al pumpellyite Ca₄Al₅MgSi₆O₂₁(OH)₇was synthesized from partially crystalline gel mixtures of stoichiometriccomposition at 275–410 °C, 6–9 kb P_fluid, andruns of 7–90 days. Pure monomineralic synthetic Mg—Alpumpellyite has refractive index n_ß = 1.624 (2) andcell dimensions = 8.825 (8) Á, b = 5.875 (5) Á,c = 19.10 (1) Á, and ß = 97.39 (7)°. The high temperature assemblage of the equivalent bulk compositionconsists of clinozoisite, hydrogrossular/grossular, aluminousseptechlorite/chlorite, quartz, and H₂O. Hydrogrossular wassynthesized in the presence of quartz at 8 kb from 400–500°C, and hydrogrossular + quartz are unstable with respectto grossular + H₂O at 400 °C and 8 kb P_fluid. At 8 kb P_fluid,aluminous septechlorite forms at temperatures below 500 °Cwhereas aluminous 14 Á chlorite crystallizes at 500–600°C. The equilibrium relations of Mg—Al pumpellyite were determinedusing subequal mixtures of synthetic Mg—Al pumpellyiteand its high temperature assemblage. The reaction 9 Mg—Alpumpellyite = 9 clinozoisite + 6 grossular + 2 chlorite + 4quartz + 19 H₂O occurs at temperatures of 390 °C at 8 kb,368 °C at 5 kb, and near 325 °C at 2 kb P_fluid. Thereversal data yield an approximate value of –3141 joules/mole°K for the standard entropy of formation for the syntheticMg—Al pumpellyite. The Schreinemakers' relations for pumpellyite, prehnite, clinozoisite,tremolite, grossular, and amesite in the presence of excessquartz and fluid were constructed in the pseudo-ternary systemCaO–Al₂O₃–MgO(SiO₂–H₂O). The results, togetherwith reconnaissance experiments on the reaction 4 Mg—Alpumpellyite + 2 quartz = 8 prehnite + aluminous septechlorite+ 2 H₂O, locate the invariant point [TR] at approximately 5.7kb P_fluid and 375 °C. The results of the present study arenot compatible with previous experimental data on the invariantpoint [GR]. The P–T oriented phase relations are used to interpretsome natural parageneses developed in low-grade metabasalticrocks recrystallized under conditions of low _co2. The high-temperaturestability relations of Mg—Al pumpellyite are useful todenote the onset of greenschist facies metamorphism in rocksof basaltic composition.     

Petrological significance of manganese carbonate inclusions in spessartine garnet and relation to the stability of spessartine in metamorphosed manganese-rich rocks

Idioblastic spessartine garnet pervasively developed in Mn-rich rocks and impure manganese carbonate ore at the Lower Proterozoic Nsuta manganese deposit, Western Ghana, contains abundant inclusions of micritic and microconcretionary carbonates and, to a lesser extent, quartz. Detailed mineralogical and microprobe studies indicate all the carbonate phases (i.e. carbonate inclusions in garnet, carbonates coexisting with garnet and carbonates not directly in contact with garnet, the latter hereafter referred to as matrix carbonates) lie within the rhodochrosite-kutnahorite solid solution series, i.e. ~Mn_55-80(Ca + Mg)_20-45CO₃ to Ca₄₂(Mn + Mg)₅₈(CO₃)₂. Minor compositional differences occur in the various carbonate phases, but partition of major elements among coexisting phases indicate most carbonate minerals strongly fractionate Ca and Mg over coexisting spessartine. The nature, composition and textural relationship of coexisting minerals and inclusions in porphyroblastic spessartine indicate that the latter formed from metamorphic reactions in which rhodochrosite and/or kutnahorite and quartz were consumed, in part corroborating earlier observations on a rhodochrosite precursor for spessartine. Spessartine formation is thus envisaged to have taken place when the predominantly Mn carbonate-quartz assemblage became unstable in the presence of minor amounts of an unknown aluminous phase. Because all the carbonates appear to be low-temperature phases with no indications of significant recrystallisation or homogenisation, it could be argued that the spessartine + rhodochrosite - kutnahorite - quartz - pyrite assemblage stabilised during very low-grade greenschist facies metamorphism under relatively low but uniform f_O2 conditions. These observations also suggest the stability field of spessartine could extend to relatively lower temperatures than currently envisaged.     

The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400{degrees}C and 1 bar

The solubility of sulfur as S^2– has been experimentallydetermined for 19 silicate melt compositions in the system CaO–MgO–Al₂O₃–SiO₂(CMAS)± TiO₂ ± FeO, at 1400°C and 1 bar, using CO–CO₂–SO₂gas mixtures to vary oxygen fugacity (fO₂) and sulfur fugacity(fS₂). For all compositions, the S solubility is confirmed tobe proportional to (fS₂/fO₂)^1/2, allowing the definition ofthe sulfide capacity (C_S) of a silicate melt as C_S = [S](fO₂/fS₂)^1/2.Additional experiments covering over 150 melt compositions,including some with Na and K, were then used to determine C_Sas a function of melt composition at 1400°C. The resultswere fitted to the equation