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     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

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     

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     

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     

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     

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     

Solubility of Anhydrite, CaSO4, in NaCl-H2O Solutions at High Pressures and Temperatures: Applications to Fluid-Rock Interaction

Anhydrite solubility in H₂O–NaCl solutions was measuredat 6–14 kbar, 600–800°C and NaCl mole fractions(X_NaCl) of 0–0·3 in piston–cylinder apparatus.Solubilities were determined by weight changes of natural anhydritein perforated Pt envelopes confined with fluid in larger Ptcapsules. In initially pure H₂O at 10 kbar and 800°C, CaSO₄concentration is low (0·03 molal), though much largerthan at the same temperature and 1 kbar. Hematite-buffered experimentsshowed slightly lower solubilities than unbuffered runs. CaSO₄solubility increases enormously with NaCl activity: at 800°Cand 10 kbar and X_NaCl of 0·3, CaSO₄ molality is 200 timeshigher than with pure H₂O. Whereas CaSO₄ solubility in pureH₂O decreases with rising T at low T and P, the high-P resultsshow that anhydrite solubility increases with T at constantP at all X_NaCl investigated. The effects of salinity and temperatureare so great at 10 kbar that critical mixing between sulfate-richhydrosaline melts and aqueous salt solutions is probable at900°C at X_NaCl 0·3. Recent experimental evidencethat volatile-laden magmas crystallizing in the deep crust mayevolve concentrated salt solutions could, in light of the presentwork, have important implications regarding such diverse processesas Mount Pinatubo-type S-rich volcanism, high-f O₂ regionalmetamorphism, and emplacement of porphyry Cu–Mo ore bodies,where anhydrite–hematite alteration and fluid inclusionsreveal the action of very oxidized saline solutions rich insulfur. KEY WORDS: anhydrite; sulfur; solubility; metamorphic brines; granulites     

Phase Equilibria of the Lyngdal Granodiorite (Norway): Implications for the Origin of Metaluminous Ferroan Granitoids

The Proterozoic (950 Ma) Lyngdal granodiorite of southern Norwaybelongs to a series of hornblende–biotite metaluminousferroan granitoids (HBG suite) coeval with the post-collisionalRogaland Anorthosite–Mangerite–Charnockite (AMC)suite. This granitoid massif shares many geochemical characteristicswith rapakivi granitoids, yet granodiorites dominate over granites.To constrain both crystallization (P, T, fO₂, H₂O in melt) andmagma generation conditions, we performed crystallization experimentson two samples of the Lyngdal granodiorite (with 60 and 65 wt% SiO₂) at 4–2 kbar, mainly at fO₂ of NNO (nickel–nickeloxide) to NNO + 1, and under fluid-saturated conditions withvarious H₂O–CO₂ ratios for each temperature. Comparisonbetween experimental phase equilibria and the mineral assemblagein the Lyngdal granodiorite indicates that it crystallized between4 and 2 kbar, from a magma with 5–6 wt % H₂O at an fO₂of NNO to NNO + 1. These oxidized and wet conditions sharplycontrast with the dry and reduced conditions inferred for thepetrogenesis of the AMC suite and many other rapakivi granitesworldwide. The high liquidus temperature and H₂O content ofthe Lyngdal granodiorite imply that it is not a primary magmaproduced by the partial melting of the crust but is derivedby the fractionation of a mafic magma. Lyngdal-type magmas appearto have volcanic equivalents in the geological record. In particular,our results show that oxidized high-silica rhyolites, such asthe Bishop Tuff, could be derived via fractionation of oxidizedintermediate magmas and do not necessarily represent primarycrustal melts. This study underlines the great variability ofcrystallization conditions (from anhydrous to hydrous and reducedto oxidized) and petrogenetic processes among the metaluminousferroan magmas of intermediate compositions (granodiorites,quartz mangerites, quartz latites), suggesting that there isnot a single model to explain these rocks. KEY WORDS: ferroan granitoids; crystallization conditions; experiments; Norway; Sveconorwegian; Bishop Tuff     

Phase Relations of Peralkaline Silicic Magmas and Petrogenetic Implications

The phase relationships of three peralkaline rhyolites fromthe Kenya Rift have been established at 150 and 50 MPa, at oxygenfugacities of NNO - 1·6 and NNO + 3·6 (log fO₂relative to the Ni–NiO solid buffer), between 800 and660°C and for melt H₂O contents ranging between saturationand nominally anhydrous. The stability fields of fayalite, sodicamphiboles, chevkinite and fluorite in natural hydrous silicicmagmas are established. Additional phases include quartz, alkalifeldspar, ferrohedenbergite, biotite, aegirine, titanite, montdoriteand oxides. Ferrohedenbergite crystallization is restrictedto the least peralkaline rock, together with fayalite; it isreplaced at low melt water contents by ferrorichterite. Riebeckite–arfvedsoniteappears only in the more peralkaline rocks, at temperaturesbelow 750°C (dry) and below 670°C at H₂O saturation.Under oxidizing conditions, it breaks down to aegirine. In themore peralkaline rocks, biotite is restricted to temperaturesbelow 700°C and conditions close to H₂O saturation. At 50MPa, the tectosilicate liquidus temperatures are raised by 50–60°C,and that of amphibole by 30°C. Riebeckite–arfvedsonitestability extends down nearly to atmospheric pressure, as aresult of its F-rich character. The solidi of all three rocksare depressed by 40–100°C compared with the solidusof the metaluminous granite system, as a result of the abundanceof F and Cl. Low fO₂ lowers solidus temperatures by at least30°C. Comparison with studies of metaluminous and peraluminousfelsic magmas shows that plagioclase crystallization is suppressedas soon as the melt becomes peralkaline, whatever its CaO orvolatile contents. In contrast, at 100 MPa and H₂O saturation,the liquidus temperatures of quartz and alkali feldspar arenot significantly affected by changes in rock peralkalinity,showing that the incorporation of water in peralkaline meltsdiminishes the depression of liquidus temperatures in dry peralkalinesilicic melts compared with dry metaluminous or peraluminousvarieties. At 150 MPa, pre-eruptive melt H₂O contents rangefrom 4 wt % in the least peralkaline rock to nearly 6 wt % inthe two more peralkaline compositions, in broad agreement withprevious melt inclusion data. The experimental results implymagmatic fO₂ at or below the fayalite–quartz–magnetitesolid buffer, temperatures between 740 and 660°C, and meltevolution under near H₂O saturation conditions. KEY WORDS: peralkaline; rhyolite; phase equilibria     

Experimental Investigation and Optimization of Thermodynamic Properties and Phase Diagrams in the Systems CaO-SiO2, MgO-SiO2, CaMgSi2O6-SiO2 and CaMgSi2O6-Mg2SiO4 to 1{middle dot}0 GPa

Using experimental results at 1·0 GPa for the systemsCaO–SiO₂, MgO–SiO₂, CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄,and all the currently available phase equilibria and thermodynamicdata at 1 bar, we have optimized the thermodynamic propertiesof the liquid phase at 1·0 GPa. The new optimized thermodynamicparameters indicate that pressure has little effect on the topologyof the CaO–SiO₂, CaMgSi₂O₆–SiO₂, and CaMgSi₂O₆–Mg₂SiO₄systems but a pronounced one on the MgO–SiO₂ binary. Themost striking change concerns passage of the MgSiO₃ phase fromperitectic melting at 1 bar to eutectic melting at 1·0GPa. This transition is estimated to occur at 0·41 GPa.For the CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄ pseudo-binaries,the size of the field clinopyroxene + liquid increases withincreasing pressure. This change is related to the shift ofthe piercing points clinopyroxene + silica + liquid (from 0·375mol fraction SiO₂ at 1 bar to 0·414 at 1·0 GPa)and clinopyroxene + olivine + liquid (from 0·191 molfraction SiO₂ at 1 bar to 0·331 at 1·0 GPa) thatbound the clinopyroxene + liquid field in the CaMgSi₂O₆·SiO₂and CaMgSi₂O₆·Mg₂SiO₄ pseudo-binaries, respectively. KEY WORDS: CaO–SiO₂; CaMgSi₂O₆–Mg₂SiO₄; CaMgSi₂O₆–SiO₂; experiments; MgO–SiO₂     

Experimental Phase Relations of Water- and Sulfur-Saturated Arc Magmas and the 1982 Eruptions of El Chich?n Volcano

The equilibrium phase relations of two volcanic rocks from thesubduction-related Mexican Volcanic Belt have been determinedwith an argon-pressurized internally heated vessel. One rockis the trachyandesite erupted from El Chich?n Volcano in 1982;the other is a primitive basalt erupted from Jorullo Volcanoin 1759. A simplified synthetic equivalent to the trachyandesitewas also investigated in lesser detail. All charges were saturatedwith hydrous vapor and a sulfur-bearing mineral. Temperatureranged from 800 to 1000?C, pressure from 1 to 4 kb, and f_o2was controlled by four different solid oxygen buffers in a doublegold capsule configuration: fayalite-magnetite-quartz (FMQ),Ni-NiO (NNO), manganosite-hausmanite (MNH), and magnetite-hematite(MTH). Pyrrhotite was the only sulfur-bearing mineral observed in chargesbuffered under FMQ and NNO, whereas anhydrite crystallized underthe more oxidizing MNH or MTH; both of these observations areconsistent with those of earlier workers. With increasing temperatureand pressure, SiO₂ and K₂O decreased in the experimental melts,whereas Al₂O₃ and CaO increased. Sulfur solubility in silicatemelts was low (<0?1 wt% equivalent SO^t₃) for pyrrhotite-saturatedcharges, but significantly greater (to 1?3 wt.% SO^t₃) when anhydritewas present. Sulfur solubility in anhydrite-saturated meltsshowed strong positive dependence on both temperature and P_vapor. Sulfur amounted to some 2?5 wt.% (SO^t₃) of the total ejectaduring the 1982 El Chich?n eruptions, and the original magmaticsulfur content was in the range 1?25–2–5 wt% SO^t₃.Extrapolations of experimental temperature and pressure dependencesfor sulfur solubility indicate that such concentrations couldbe contained in a hydrous, oxidized, basaltic parent melt generatedunder Benioff zone conditions. During ascent through the uppermantle and crust, the sulfur solubility limit of the melt wouldcontinuously decrease; in response, most of the sulfur wouldbe transferred from the melt to anhydrite crystals and a separategas phase. Trachyandesite pumices erupted from El Chich?n in1982 contained both pyrrhotite and anhydrite at a temperatureof 800?C. The composition of the natural pyrrhotite yieldedan f_o2 estimate 1 log unit above the NNO buffer. Based on compositionalvariations in the experimental melts with temperature and pressure,the composition of the matrix glass in the 1982 pumices indicatesequilibration of the magmatic liquid at about P_total=P_vapor=2kb just before eruption. At that time, sulfur in El Chich?ntrachyandesite was about equally partitioned between anhydritemicrophenocrysts and some 20 vol.% gas phase in which H₂S wasprobably the dominant sulfur-bearing species. The melt thencontained only 0?05 wt.% SO^t₃, consistent with experimentalsolubility limits at 800?C and P_vapor=2 kb.     

Volcan Popocatepetl, Mexico. Petrology, Magma Mixing, and Immediate Sources of Volatiles for the 1994-Present Eruption

Volcán Popocatépetl has been the site of voluminousdegassing accompanied by minor eruptive activity from late 1994until the time of writing (August 2002). This contribution presentspetrological investigations of magma erupted in 1997 and 1998,including major-element and volatile (S, Cl, F, and H₂O) datafrom glass inclusions and matrix glasses. Magma erupted fromPopocatépetl is a mixture of dacite (65 wt % SiO₂, two-pyroxenes+ plagioclase + Fe–Ti oxides + apatite, 3 wt % H₂O, P= 1·5 kbar, f_O2 = NNO + 0·5 log units) and basalticandesite (53 wt % SiO₂, olivine + two-pyroxenes, 3 wt % H₂O,P = 1–4 kbar). Magma mixed at 4–6 km depth in proportionsbetween 45:55 and 85:15 wt % silicic:mafic magma. The pre-eruptivevolatile content of the basaltic andesite is 1980 ppm S, 1060ppm Cl, 950 ppm F, and 3·3 wt % H₂O. The pre-eruptivevolatile content of the dacite is 130 ± 50 ppm S, 880± 70 ppm Cl, 570 ± 100 ppm F, and 2·9 ±0·2 wt % H₂O. Degassing from 0·031 km³ of eruptedmagma accounts for only 0·7 wt % of the observed SO₂emission. Circulation of magma in the volcanic conduit in thepresence of a modest bubble phase is a possible mechanism toexplain the high rates of degassing and limited magma productionat Popocatépetl. KEY WORDS: glass inclusions; igneous petrology; Mexico; Popocatépetl; volatiles     

Monazite-Xenotime Thermochronometry and Al2SiO5 Reaction Textures in the Picuris Range, Northern New Mexico, USA: New Evidence for a 1450-1400 Ma Orogenic Event

Al₂SiO₅ reaction textures in aluminous schist and quartziteof the northern Picuris range, north-central New Mexico, recorda paragenetic sequence of kyanite to sillimanite to andalusite,consistent with a clockwise P–T loop, with minor decompressionnear the Al₂SiO₅ triple-point. Peak metamorphic temperaturesare estimated at 510–525°C, at 4·0–4·2kbar. Kyanite and fibrolite are strongly deformed; some prismaticsillimanite, and all andalusite are relatively undeformed. Monaziteoccurs as inclusions within kyanite, mats of sillimanite andcentimetre-scale porphyroblasts of andalusite, and is typicallyaligned subparallel to the dominant regional foliation (S₀/S₁or S₂) and extension lineation (L₁). Back-scatter electron imagesand X-ray maps of monazite reveal distinct core, intermediateand rim compositional domains. Monazite–xenotime thermometryfrom the intermediate and rim domains yields temperatures of405–470°C (±50°C) and 500–520°C(±50°C), respectively, consistent with the progradeto peak metamorphic growth of monazite. In situ, ion microprobeanalyses from five monazites yield an upper intercept age of1417 ± 9 Ma. Near-concordant to concordant analyses yield²⁰⁷Pb–²⁰⁶Pb ages from 1434 ± 12 Ma (core) to 1390± 20 Ma (rim). We find no evidence of older regionalmetamorphism related to the 1650 Ma Mazatzal Orogeny. KEY WORDS: Al₂SiO₅; metamorphism; monazite; thermochronometry; triple-point     

The Role of Advective Fluid Flow and Diffusion during Localized, Solid-State Dehydration: Sondrum Stenhuggeriet, Halmstad, SW Sweden

A localized dehydration zone, Söndrum stone quarry, Halmstad,SW Sweden, consists of a central, 1 m wide granitic pegmatoiddyke, on either side of which extends a 2·5–3 mwide dehydration zone (650–700°C; 800 MPa; orthopyroxene–clinopyroxene–biotite–amphibole–garnet)overprinting a local migmatized granitic gneiss (amphibole–biotite–garnet).Whole-rock chemistry indicates that dehydration of the graniticgneiss was predominantly isochemical. Exceptions include [Y+ heavy rare earth elements (HREE)], Ba, Sr, and F, which aremarkedly depleted throughout the dehydration zone. Systematictrends in the silicate and fluorapatite mineral chemistry acrossthe dehydration zone include depletion in Fe, (Y + HREE), Na,K, F, and Cl, and enrichment in Mg, Mn, Ca, and Ti. Fluid inclusionchemistry is similar in all three zones and indicates the presenceof a fluid containing CO₂, NaCl, and H₂O components. Water activitiesin the dehydration zone average 0·36, or X_H2O = 0·25.All lines of evidence suggest that the formation of the dehydrationzone was due to advective transport of a CO₂-rich fluid witha minor NaCl brine component originating from a tectonic fracture.Fluid infiltration resulted in the localized partial breakdownof biotite and amphiboles to pyroxenes releasing Ti and Ca,which were partitioned into the remaining biotite and amphibole,as well as uniform depletion in (Y + HREE), Ba, Sr, Cl, andF. At some later stage, H₂O-rich fluids (H₂O activity >0·8)gave rise to localized partial melting and the probable injectionof a granitic melt into the tectonic fracture, which resultedin the biotite and amphibole recording a diffusion profile forF across the dehydration zone into the granitic gneiss as wellas a diffusion profile in Fe, Mn, and Mg for all Fe–Mgsilicate minerals within 100 cm of the pegmatoid dyke. KEY WORDS: charnockite; fluids; CO₂; brines; localized dehydration; Söndrum     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃     

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     

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     

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     

Formation of Carbon and Hydrogen Species in Magmas at Low Oxygen Fugacity

Studies of iron-bearing silicate melt (ferrobasalt) + iron metallicphase + graphite + hydrogen equilibria show that carbon andhydrogen solubilities in melts are important for the evolutionof the upper mantle. In a series of experiments conducted at3·7 GPa and 1520–1600°C, we have characterizedthe nature (oxidized vs reduced) and quantified the abundancesof C- and H-compounds dissolved in iron-bearing silicate melts.Experiments were carried out in an anvil-with-hole apparatuspermitting the achievement of equal chemical potentials of H₂in the inner Pt capsule and outer furnace assembly. The fO₂for silicate melt–iron equilibrium was 2·32 ±0·04 log units below iron–wüstite (IW). Theferrobasalt used as starting material experienced a reductionof its iron oxides and silicate network. The counterpart wasa liberation of oxygen reacting with the hydrogen entering thecapsule. The amount of H₂O dissolved in the glasses was measuredby ion microprobe and by step-heating and was found to be between1 and 2 wt %. The dissolved carbon content was found to be 1600ppm C by step-heating. The speciation of C and H componentswas determined by IR and Raman spectroscopy. It was establishedthat the main part of the liberated oxygen was used to formOH^– and to a much lesser extent H₂O, and only traces ofH₂, CO₂ and