Thermodynamic Mixing Models for Muscovite--Paragonite Solutions Based on Solution Calorimetric and Phase Equilibrium Data

Enthalpies of solution have been measured on a series of muscovite—paragonitemicas in 20.1% HF at 50C under isoperibolic conditions. Themolar enthalpy of formation of paragonite at 298 K, for whichno calorimetrically measured value is currently available, hasbeen determined to be –5937.5 (3) kJ. An inversion ofall calorimetric, volumetric and phase equilibrium data hasbeen performed, giving a range of mixing models compatible withmost experimental data. The following expressions of the mixingproperties of 2M₁ micas for enthalpy (H_ex) and volume (V_ex)at pressures up to 10 kbar, forcing excess entropy (S_ex) tobe zero and using a subregular mixing model are favoured: H_ex(kJ) = [10.6+4.45(1–2X_ms)]X_ms(1–X_ms) V_ex(J/bar) = 0.452X_ms(1–X_ms). However, mixing models of higher order with asymmetric negativeS_ex are also possible. KEY WORDS: muscovite; paragonite; solvus; calorimetry; solid solution ^*Corresponding author.     

The Origin of Rapakivi Texture

The mantling of large ovoids of K-feldspar by a rim of plagioclasehas been investigated in the rapakivi granites from the Mid-ProterozoicWiborg batholith of SE Finland. The formation of rapakivi texture,in this the type area, was examined using a variety of techniquesincluding isotopic analyses of mineral separates from specifictextural sites. Cathodoluminescence combined with microprobeanalysis points to the pulsed development of the mantles involvinggrowth of successive plagioclases of composition An₃₀, An₂₅,and An₃, the last being in optical continuity with perthiticplagioclase exsolved from the K-feldspar. Plagioclase mantleshave high ¹⁸O and ⁸⁷Sr/⁸⁶ signatures relative to K-feldspar,which indicate the presence of a late, low-temperature componentthought to represent albite exsolved from the K-feldspar andredistributed onto the ovoid margin. Oligoclase components ofthe mantles are formed by a similar, although higher-temperaturemagmatic process. This involves the subsolvus re-equilibrationof alkali feldspar compositions with evolving melt conditions.Redistribution of the exsolved plagioclase from the alkali feldsparphenocrysts is linked to high fluorine contents of rapakivi-typemagmas, and this major reconstruction of the feldspar phenocrystsgenerates their distinctive ovoidal shape.     

Metamorphism of Calcic Pelitic Schists, Strafford Dome, Vermont: Compositional Zoning and Reaction History

Four assemblages from calcic pelitic schists from South Strafford,Vermont, have been studied in detail to determine the relationshipbetween reaction history and compositional zoning of minerals.The lowest-grade assemblage is garnet + biotite + chlorite +plagioclase + epidote + quartz + muscovite + graphite + fluid.Along a path of isobaric heating, the net reaction is Chl +Ms + Ep + Gr = Grt + Bt + Pl + fluid. Garnet grows with decreasingFe/(Fe + Mg) and X_Spa, (from 0•2 to 0•05), X_Gra staysnearly constant between 0•20 and 0•25, and plagioclasegrows with X_An increasing from peristerite to 0•2–0•5. The subsequent evolution depends on whether chlorite or epidotereacts out first. If chlorite is removed from the assemblagefirst, the net reaction along an isobaric heating path becomesGrt + Ms + Ep + Qtz + Gr = Bt + Pl + fluid. X_An of plagioclaseincreases to 0•20–0•70, depending on the bulk-rockcomposition and changes in pressure and temperature. If epidoteis removed first, the assemblage becomes a simple pelite andthe net reaction becomes Chl + Pl + Ms + Qtz = Grt + Bt + H₂O.Plagioclase is consumed to provide Ca for growing garnet, andX_An, Fe/(Fe + Mg) of garnet, X_Gra, and X_Spa all decrease. Afterboth chlorite and epidote are removed, continued heating upto the metamorphic peak of {small tilde}600C produces littleprogress of the reaction Grt + Ms = Bt + Pl; and X_An increases. The four assemblages have been numerically modeled using theGibbs method starting with measured compositions. The modelssuccessfully predict the observed compositional zoning and trendsof mineral growth and consumption along the computed P–Tpaths. The models also predict the compositional mineral zoningthat would have resulted from other P–T paths. ^* Present address: Department of Geology, University of Alabama, Tuscaloosa, Alabama 35487     

Thermochemistry of the high structural state plagioclases

The enthalpies of solution of a suite of 19 high-structural state synthetic plagioclases were measured in a Pb₂B₂O₅ melt at 970 K. The samples were crystallized from analyzed glasses at 1200°C and 20 kbar pressure in a piston-cylinder apparatus. A number of runs were also made on Amelia albite and Amelia albite synthetically disordered at 1050–1080°C and one bar for one month and at 1200°C and 20 kbar for 10 hr. The component oxides of anorthite, CaO, Al₂O₃ and SiO₂, were remeasured.The ΔH of disorder of albite inferred in the present study from albite crystallized from glass is 3.23 kcal, which agrees with the 3.4 found by Holm and Kleppa (1968). It is not certain whether this value includes the ΔH of a reversible displacive transition to monoclinic symmetry, as suggested by Helgesonet al. (1978) for the Holm-Kleppa results. The enthalpy of solution value for albite accepted for the solid solution series is based on the heat-treated Amelia albite and is 2.86 kcal less than for untreated Amelia albite.The enthalpy of formation from the oxides at 970 K of synthetic anorthite is ?24.06 ± 0.31 kcal, significantly higher than the ?23.16 kcal found by Charluet al. (1978), and in good agreement with the value of ?23.89 ± 0.82 given by Robieet al. (1979), based on acid calorimetry.The excess enthalpy of mixing in high plagioclase can be represented by the expression, valid at 970 K: ΔH^ex(±0.16 kcal) = 6.7461 X_abX²_An + 2.0247 X_AnX²_Ab where X_Ab and X_An are, respectively, the mole fractions of NaAlSi₃O₈ and CaAl₂Si₂O₈. This ΔH^ex, together with the mixing entropy of Kerrick and Darken's (1975) Al-avoidance model, reproduces almost perfectly the free energy of mixing found by Orville (1972) in aqueous cation-exchange experiments at 700°C. It is likely that Al-avoidance is the significant stabilizing factor in the high plagioclase series, at least for X_An≥ 0.3. At high temperatures the plagioclases have nearly the free energies of ideal one-site solid solutions. The Al-avoidance model leads to the following Gibbs energy of mixing for the high plagioclase series: $\text{ΔG}{}^{\mathrm{mix}}\text{= ΔH}{}^{\mathrm{ex}}\text{+ RT X}{}_{\mathrm{Ab}}\text{ln[X}{}^2{}_{\mathrm{Ab}}\text{(2 ? X}{}_{\mathrm{Ab}}\text{)]+ X}{}_{\mathrm{An}}\text{ln}\text{[X}{}_{\mathrm{An}}\text{(1+X}{}_{\mathrm{An}}\text{)}{}^2\text{]}\text{4}$. The entropy and enthalpy of mixing should be very nearly independent of temperature because of the unlikelihood of excess heat capacity in the albite-anorthite join.     

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.     

Thermodynamic data of lawsonite and zoisite in the system CaO–Al2O3–SiO2–H2O based on experimental phase equilibria and calorimetric work

The enthalpy of drop-solution in molten 2PbO·B₂O₃ of synthetic and natural lawsonite, CaAl₂(Si₂O₇)(OH)₂·H₂O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (_fH^Oxides=-168.7Dž.4 kJ mol^-1, or (_fH⁰₂₉₈=-4,872.5dž.0 kJ mol^-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca₂Al₃(SiO₄)(Si₂O₇)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al₂O₃-SiO₂-H₂O (CASH). The following data for lawsonite and zoisite were obtained: (_fH⁰₂₉₈ (lawsonite)=-4,865.68 kJ mol^-1 , S⁰₂₉₈ (lawsonite)=229.27 J K^-1 mol^-1 , (_fH⁰₂₉₈ (zoisite)=-6,888.99 kJ mol^-1 , S⁰₂₉₈ (zoisite)=297.71 J K^-1 mol^-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.     

Phase Equilibria in the Pyroxene Quadrilateral

Experimental phase equilibrium data on compositions of coexistingpyroxenes in the quadrilateral enstatite-diopside-ferrosilite-hedenbergitehave been used to model pyroxene solid solutions and to formulatepyroxene geothermometers. Each pyroxene is treated as a solidsolution of four quad-components using the Kohler formulation where G_ij^* is the excess free energy of mixing in a binary solutioncalculated with binary mole fractions (e.g. X_i^o = X_i/(X_i+X_j))and X_i is the mole fraction in a multicomponent solution. Thefit to the experimental data is achieved by minimizing the totalGibbs free energy of the assemblage. The following set of thermochemicaldata and simple mixture parameters (W_ij) are found to be bestsuited. Standard (T = 298?15 K) enthalpy and entropy of formationfrom elements for fictive orthohedenbergite are –1416?8kJ and 84?88 J K^–1 mol ^–1 respectively. The heatcapacity is given by 114?67+17?09E-3T–31?40E5T^–2.The W_ij data are: Opx: W₁₂ = W₂₁ = 25 W₁₃ = (13?1–0-015T),W₃₁ = (3?37–0?005T), W₂₃ = 20, W₃₂ = 16, W₂₄ = 5, W₄₂= 7, W₃₄ = 15, W₄₃ = 15; Cpx: W₁₂ = (25?484+0?0812P), W₂₁ =(31?216–0?0061P),W₃₁ = W₁₃ = 0W₁₄ = (93?3–0?045T), W₄₁ = (–20?0+0?028T),W₂₃ = 24, W₃₂ = 15, W₂₄ = 12, W₄₂ = 12, W₃₄ = (16?941+0?00592P),W₄₃ = (20?697–0?00235P). Coexisting pyroxene compositionshave been computed in the temperature range of 700 to 1400?C. Two geothermometers have been constructed, one based on atomicfraction of iron (Fe/(Fe + Mg)) in orthopyroxene and the Fe-Mgdistribution coefficient and the other, based on wollastonitecontent of clinopyroxene. The two scales yield different temperatureswhen applied to the same rock. In igneous pyroxenes, the Catransfer ceased at 150 to 200?C above the closure temperatureof the Fe-Mg ion-exchange. In metamorphic rocks an oppositeeffect seems to have prevailed.     

Fractionation and Liquid Immiscibility in an Anorthositic Pluton of the Nain Complex, Labrador

Fine-grained anorthositic dikes are associated with a massiveleuconorite pluton (Cl = 15) which is exposed over an area ofabout 200 km². Internally, the pluton shows little compositionalvariation; average plagioclase composition ranges from An₅₂to An₄₈. The dikes are nearly uniform in composition and similarto the estimated bulk composition of the pluton (55 per centSiO₂). They therefore appear to represent the parental magmaof the leuconorite pluton. A small body of granite (10 km²) was emplaced within and priorto the complete solidification of the leuconorite. The graniticintrusion caused local deformation of the leuconorite and filter-pressingof its late stage interstitial liquids. These liquids occurin the younger hydrous granite as very finegrained, chilledpillows of nearly anhydrous Fe-rich diorite and granite. Mostof the pillows are diorites with approximately 55 per cent SiO₂.On oxide plots these lie approximately on a plagioclase controlline passing through the composition of the leuconorite dikes.The entire group of chilled pillows ranges in composition from45 to 71 per cent SiO₂ with a gap between 57 and 63 per centSiO₂. On oxide plots they produce a smooth trend which is obliqueto and truncates the plagioclase control line. Variation inthe pillows can best be explained by late-stage liquid immiscibility. Fractionation in the interstitial magma was controlled earlyby crystallization of plagioclase and later by plagioclase pluspyroxene. Very late stage differentiation was controlled mainlyby liquid immiscibility and produced FeO- and SiO₂-rich liquids.     

Chemical Evolution of Intercumulus Liquid, as Recorded in Plagioclase Overgrowth Rims from the Skaergaard Intrusion

The intercumulus liquid of a crystal mush fills pore spaces,and typically solidifies to form overgrowths on cumulus grainsand poikilitic post-cumulus minerals. If the liquid is immobile,solidification produces zoned intercumulus minerals, as a resultof progressive fractionation of the residual liquid. Convectionwithin the mush results in buffering of the liquid composition,and thus limits mineral zonation. For fully solidified cumulates,‘fossil’ changes in liquid composition or porosityare difficult to identify. However, detailed study of immobileminor components of plagioclase overgrowth rims can provideinformation about the progressive solidification of intercumulusmaterial. Ti contents of plagioclase overgrowths, in samplesfrom the lowermost parts of the Skaergaard Intrusion, show strongvariations with anorthite content. With decreasing X_An, Ti concentrationsfirst rise and then fall, consistent with changing TiO₂ contentsof the intercumulus liquid during solidification. TiO₂ in plagioclasedecreases sharply at An₅₅, reflecting local saturation of Fe–Tioxides. Ti in clinopyroxene oikocrysts also falls rimward, butzoning in faster diffusing species (Fe, Mg) is limited. Otherthan slight reverse zones that may occur on the plagioclasemargins, X_An falls continuously during crystallization. Thereverse zoning is interpreted as the result of compaction-drivendissolution and reprecipitation of plagioclase. The continualdecrease in X_An is exploited, together with back-scattered electronimages of the cumulates, to produce calibrated images showingregions of progressive crystallization. This allows the regionscrystallizing at each stage of solidification to be visualized.These images show that the final remnants of interstitial meltwere present in triangular pockets and as thin grain-boundarymelt films. This approach can provide information about theprogressive reduction of porosity during cumulate solidification. KEY WORDS: residual liquid; cumulate; plagioclase; porosity; Skaergaard     

Experimental Constraints on the Conditions of Formation of Highly Calcic Plagioclase Microlites at the Soufrire Hills Volcano, Montserrat

High-pressure and -temperature experiments on a bulk-rock compositionrepresentative of the groundmass of the Soufrière HillsVolcano andesite have allowed the phase equilibria of the systemto be determined; these are then compared with the natural samples.Experimental conditions varied from 825 to 1100°C and from5 to 225 MPa; the main phases observed were clinopyroxene, crystallinesilica, amphibole and plagioclase. A relationship between plagioclasemicrolite size and anorthite content is identified in samplesof the natural andesite. Large crystals (>60 µm² inarea) have cores of An_60–75, whereas small crystals (<60µm² in area) have cores of An_40–60. Experimentalresults show that if the magma is heated to >950°C thehigh-anorthite microlite crystals can form at magma chamberpressures without any need for a change in bulk composition.It is proposed that convective self-mixing occurs within themagma chamber. Geothermometry of coexisting plagioclase–amphibolepairs confirms the complex crystallization history of the naturalsamples. Analysis of natural glass samples has identified compositionalvariations that can be related to the crystallinity of the sampleand also the groundmass plagioclase composition. Rapidly eruptedpumice samples have high glass contents, lower SiO₂ glass compositionsand plagioclase microlites that are large in size (>60 µm²)and have a high anorthite content (>An₆₀). Slowly erupteddome samples are highly crystalline and contain numerous plagioclasemicrolites of variable size and composition. KEY WORDS: glass evolution; experiment; Montserrat; plagioclase; self-mixing     

Geochemical and isotopic zoning patterns of plagioclase megacrysts in gabbroic dykes from the Gardar Province, South Greenland: implications for crystallisation processes in anorthositic magmas

Chemical and Sr isotopic zoning patterns in plagioclase megacrysts from gabbroic dykes in the Gardar Province can be used to elucidate magma-chamber and emplacement processes. The megacrysts occur either as single crystals or assembled as anorthosite xenoliths. The size of the megacrysts varies from <1 cm to 1 m. They consist of a large core with variable zonation (An_58-39) and a relatively small (<600 µm), normally zoned rim (An_62-27). The contact between core and rim is sharp and marked by a sharp increase in anorthite content which can reach 11 mol% An. This gap is interpreted as having formed during dyke emplacement due to a sudden pressure release. Some of the megacryst cores show a fairly constant composition whereas others exhibit an unusual wavy-oscillatory zoning which has not been reported elsewhere to our knowledge. The oscillatory zoning has wavelengths of up to 2,500 µm and a maximum amplitude of 7 mol% An. It is interpreted as reflecting movements of the crystals in the magma reservoir. The Sr isotopic composition of one crystal shows a radiogenic inner core ((⁸⁷Sr/⁸⁶Sr)_i=0.7044) and a less radiogenic outer core ((⁸⁷Sr/⁸⁶Sr)_i=0.7039-0.7036). The lack of a significant change between outer core and rim ((⁸⁷Sr/⁸⁶Sr)_i=0.7037) is consistent with formation of the more An-rich rim due to pressure release. Variations in the core may be related to movements of the crystal and/or magma mixing. A trace-element profile across a megacryst shows a small increase in Sr and small decreases in Ba and La contents of the recalculated melt composition across the core-rim boundary, whereas P, Ce, Nd and Eu remain constant. Melt compositional changes upon emplacement are therefore considered to be of minor importance. Constant ratios of incompatible trace elements in the megacryst cores indicate a dominant influence of a lower crustal source on trace-element budgets.     

Structural characterization of labradorite-bytownite plagioclase from volcanic,plutonic and metamorphic environments

The transmission electron microscope and the electron microprobe are used to characterize calcic plagioclase (An₆₅ to An₈₅) from a variety of geological environments. The cooling histories of samples from volcanic, plutonic and metamorphic environments are estimated and the transformation and exsolution sequence is inferred from observations in the transmission electron microscope. Several distinctive textural modifications occur depending both on bulk composition and cooling history. (1) Exsolution occurs in increasingly calcic bulk compositions upon slower cooling, and the coexisting phases are An₆₆ intermediate plagioclase and An_85–90 P¯1, c=14 Å plagioclase in the sample from the metamorphic environment, (2) the morphology of b antiphase boundaries (APBs) in An₇₅ to An₈₅ plagioclase changes from smoothly curving (rapid cooling and calcic compositions) to zig-zag (slower cooling or sodic compositions). (3) The concentration of defects in the intermediate plagioclase superstructure changes from a high density in rapidly cooled plagioclase to a lower density in slowly cooled plagioclase. In all plagioclases except for the rapidly cooled, volcanic specimens there is evidence in images and diffraction patterns for short-range ordered domains with P¯1 symmetry. The observations allow the microstructure of a single zoned plagioclase to be used as an indication of the geologic environment under which it cooled.     

Petrology of the Vandfaldsdalen Macrodike, Skaergaard Region, East Greenland

The Vandfaldsdalen macrodike is a layered and differentiatedgabbroic dike approximately 3?5 km long and from 200 to 500m wide. It appears to cut the eastern margin of the Skaergaardintrusion and may have served as a feeder for the Basistoppensill. The macrodike can be divided into three series of rocks:a marginal series of differentiated gabbros adjacent to thewalls of the dike; a central series of differentiated and subhorizontallylayered gabbros and ferrodiorites in the interior of the dike;and an upper felsic series of granophyric rocks with abundantquartzo-feldspathic xenoliths. The mineral and bulk-rock compositionsthrough both the marginal series and central series show progressiveiron enrichment. The most Ca-rich plagioclase (An₆₉) and mostmagnesian pyroxene (Wo₄₂ En₄₆ Fs₁₂) occur in olivine-bearingrocks of the marginal series about 5 m from the contact withwall rocks. The most Na-rich plagioclase (An₃₉) and Fe-richpyroxene (Wo₃₈ En₂₄ Fs₃₈) are in olivine-free ferrodiorite ofthe central series, about 20 m below the contact with the felsicseries. Evidence from field observations, bulk-rock chemical compositions,and Sr and Nd isotopic data indicate the felsic series formedas a mixture of the initial macrodike magma and granitic countryrock. ⁸⁷Sr/⁸⁶Sr ratios of specimens from the felsic series rangebetween 0?7129 and 0?7294. ¹⁴³Nd/¹⁴⁴Nd ratios vary between 0?51208and 0?51118. Both ratios vary serially with the SiO₂ contentsof the specimens. We suggest that the felsic series evolvedas a separate body of low density liquid which floated on thedenser gabbroic magma of the central series. Heat from crystallizationof the gabbroic magma must have diffused into the felsic layer,enabling extensive assimilation of the granitic xenoliths, butour data indicate there was very little exchange of chemicalcomponents between the two liquids.     

Rare earth element diffusion in diopside: influence of temperature, pressure, and ionic radius, and an elastic model for diffusion in silicates

Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to1,450 °C. Polished, pre-annealed crystals were coated with a thin film of rare earth element oxides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At 1 atm pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (001) (diffusion coefficient D in m²/s): log₁₀D_Yb=(-4.64ǂ.42)-(411ᆠ kJ/mol/2.303RT); log₁₀D_Dy=(-3.31ǃ.44)-(461ᆽ kJ/mol/2.303RT); log₁₀D_Nd=(-2.95DŽ.64)-(496ᇡ kJ/mol/2.303RT); log₁₀D_Ce=(-4.10ǃ.08)-(463ᆳ kJ/mol/2.303RT); log₁₀D_Lu=(-4.22DŽ.66)-(466ᇢ kJ/mol/2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with La a factor of ~35 slower than Yb. The relationship between diffusivity and ionic radius is consistent with a model in which elastic strain plays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperature and oxygen fugacity, are 9.0DŽ.0 cm³/mol and 8.9Dž.2 cm³/mol, respectively, corresponding to an order of magnitude decrease in diffusivity as pressure is increased from 0 to 3 GPa at 1,200 °C. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achieved in ~1 My under conditions near the peridotite solidus (~1,450 °C at 2.5 GPa). The equilibration time is much longer under P, T conditions of the lithospheric mantle or at the eclogite solidus (~1 Gy at 1.5 GPa and 1,150 °C). Because of the relatively strong decrease in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, on time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium uptake of REE by growing clinopyroxene phenocrysts may be preserved under natural conditions of basalt crystallization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.     

Thermodynamic properties and stability of AlF-bearing titanite CaTiOSiO4–CaAlFSiO4

Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO₄, as well as activity-composition relations of binary titanite CaTiOSiO₄-CaAlFSiO₄. The heat capacity of synthetic CaAlFSiO₄ was measured with differential scanning calorimetry between 170 and 850 K: C_P=689.96-0.38647T+2911300T^-2-8356.1T^-0.5+0.00016179T² Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO₄ can be expected to lie between 104.7 and 118.1 J mol^-1 K^-1. The temperature of the P2₁/a to A2/a phase change was determined calorimetrically for a titanite with X_Al=0.09 (T_transition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO₄ is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO₄ in the presence of CaTiOSiO₄ was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO₄ consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!

Cyclicity in the Main and Upper Zones of the Bushveld Complex, South Africa: Crystallization from a Zoned Magma Sheet

The major element composition of plagioclase, pyroxene, olivine,and magnetite, and whole-rock ⁸⁷Sr/⁸⁶Sr data are presented forthe uppermost 2·1 km of the layered mafic rocks (upperMain Zone and Upper Zone) at Bierkraal in the western BushveldComplex. Initial ⁸⁷Sr/⁸⁶Sr ratios are near-constant (0·7073± 0·0001) for 24 samples and imply crystallizationfrom a homogeneous magma sheet without major magma rechargeor assimilation. The 2125 m thick section investigated in drillcore comprises 26 magnetitite and six nelsonite (magnetite–ilmenite–apatite)layers and changes up-section from gabbronorite (An₇₂ plagioclase;Mg# 74 clinopyroxene) to magnetite–ilmenite–apatite–fayaliteferrodiorite (An₄₃; Mg# 5 clinopyroxene; Fo₁ olivine). The overallfractionation trend is, however, interrupted by reversals characterizedby higher An% of plagioclase, higher Mg# of pyroxene and olivine,and higher V₂O₅ of magnetite. In the upper half of the successionthere is also the intermittent presence of cumulus olivine andapatite. These reversals in normal fractionation trends definethe bases of at least nine major cycles. We have calculateda plausible composition for the magma from which this entiresuccession formed. Forward fractional crystallization modelingof this composition predicts an initial increase in total iron,near-constant SiO₂ and an increasing density of the residualmagma before magnetite crystallizes. After magnetite beginsto crystallize the residual magma shows a near-constant totaliron, an increase in SiO₂ and decrease in density. We explainthe observed cyclicity by bottom crystallization. Initiallymagma stratification developed during crystallization of thebasal gabbronorites. Once magnetite began to crystallize, periodicdensity inversion led to mixing with the overlying magma layer,producing mineralogical breaks between fractionation cycles.The magnetitite and nelsonite layers mainly occur within fractionationcycles, not at their bases. In at least two cases, crystallizationof thick magnetitite layers may have lowered the density ofthe basal layer of melt dramatically, and triggered the proposeddensity inversion, resulting in close, but not perfect, coincidenceof mineralogical breaks and packages of magnetitite layers. KEY WORDS: layered intrusion; mineral chemistry; isotopes; magma; convection; differentiation     

Experimental Reversal of the Na-K Exchange Reaction Between Muscovite-Paragonite Crystalline Solutions and a 2 Molal Aqueous (Na,K)Cl Fluid

Single-phase 2M₁ muscovite-paragonite crystalline solutionsin the range 0?00–0?10 and 0?70–1?00 X_ms have beensynthesized by hydrothermal treatment of gels of appropriatecompositions at 600–700?C, and 7 to 18 kb P_H2O. The molarvolumes of these micas may be expressed as V(J/b?mol) = 13?1845+1?463X_ms+0?0160 X_ms²–0?1679 X_ms³ (?0?005), which translateto a substantial positive excess molar volume of mixing. Na-K ion exchange experiments between presynthesized 2M₁ micacrystalline solutions and 2 molal aqueous (Na,K)Cl fluids failedto proceed to completion despite 98 day runs at 500–600?C,6 kb P_total. Results of analogous exchange experiments provedencouraging however, when a much finer-grained 1M mica was usedas starting material. Applying the tie line rotation technique,reversal of ion exchange experiments could be achieved in the2-phase fields, not, however, in the 3-phase field of the ms-pg-NaCl-KClreciprocal ternary. Using gels as starting material, reversalexperiments were eventually successful both in the 2-phase andthe 3-phase fields; the results of reversal experiments withinthe two-phase fields being identical to those obtained earlierusing 1M micas. Four isobaric-isothermal sections through the ms-pg-NaCl-KClternary were reversibly determined at 450?C/5 kb, 550?C/6 kb,550?C/15 kb, and 620?C/7 kb. At 450?C, the coexisting mica compositionsin the 3-phase field (2 micas plus 1 fluid) are 0?10 and 0?77X_ms, at 550?C they are 0?10 and 0?60 X_ms, and finally, at 620?Cthese are 0?12 and 0?51 X_ms. To the extent that internal equilibriumwas accomplished between the coexisting micas, these data wouldindicate a wide solvus at 450?C, narrowing gradually with increasingtemperature to 620?C. The critical temperature will be wellin excess of 620?C, although the mica at the critical conditionwill prove to be metastable with respect to the assemblage alkalifeldspars+corundum+H₂O. The companion paper by Chatterjee & Flux (1986) presentsa thermodynamic analysis of the above experimental data.     

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

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

Magma storage prior to the 1912 eruption at Novarupta, Alaska

New analytical and experimental data constrain the storage and equilibration conditions of the magmas erupted in 1912 from Novarupta in the 20th century's largest volcanic event. Phase relations at H₂O+CO₂ fluid saturation were determined for an andesite (58.7 wt% SiO₂) and a dacite (67.7 wt%) from the compositional extremes of intermediate magmas erupted. The phase assemblages, matrix melt composition and modes of natural andesite were reproduced experimentally under H₂O-saturated conditions (i.e., P_H2O=P_TOT) in a negatively sloping region in T-P space from 930 °C/100 MPa to 960 °C/75 MPa with fO₂~NNO+1. The H₂O-saturated equilibration conditions of the dacite are constrained to a T-P region from 850 °C/50 MPa to 880 °C/25 MPa. If H₂O-saturated, these magmas equilibrated at (and above) the level where co-erupted rhyolite equilibrated (~100 MPa), suggesting that the andesite-dacite magma reservoir was displaced laterally rather than vertically from the rhyolite magma body. Natural mineral and melt compositions of intermediate magmas were also reproduced experimentally under saturation conditions with a mixed (H₂O + CO₂) fluid for the same range in P_H2O. Thus, a storage model in which vertically stratified mafic to silicic intermediate magmas underlay H₂O-saturated rhyolite is consistent with experimental findings only if the intermediates have X_H2O^fl=0.7 and 0.9 for the extreme compositions, respectively. Disequilibrium features in natural pumice and scoria include pristine minerals existing outside their stability fields, and compositional zoning of titanomagnetite in contact with ilmenite. Variable rates of chemical equilibration which would eliminate these features constrain the apparent thermal excursion and re-distribution of minerals to the time scale of days.     

Carbonate Assimilation at Merapi Volcano, Java, Indonesia: Insights from Crystal Isotope Stratigraphy

Recent basaltic andesite lavas from Merapi volcano contain abundant,complexly zoned, plagioclase phenocrysts, analysed here fortheir petrographic textures, major element composition and Srisotope composition. Anorthite (An) content in individual crystalscan vary by as much as 55 mol% (An_40–95) across internalresorption surfaces with a negative correlation between highAn mol% (>70), MgO wt% and FeO wt%. In situ Sr isotope analysesof zoned plagioclase phenocrysts show that the ⁸⁷Sr/⁸⁶Sr ratiosof individual zones range from 0·70568 to 0·70627.The upper end of this range is notably more radiogenic thanthe host basaltic andesite whole-rocks (< 0·70574).Crystal zones with the highest An content have the highest ⁸⁷Sr/⁸⁶Srvalues, requiring a source or melt with elevated radiogenicSr, rich in Ca and with lower Mg and Fe. Recent Merapi eruptiverocks contain abundant xenoliths, including metamorphosed volcanoclasticsediment and carbonate country rock (calc-silicate skarns) analysedhere for petrographic textures, mineralogy, major element compositionand Sr isotope composition. The xenoliths contain extremelycalcic plagioclase (up to An₁₀₀) and have whole-rock ⁸⁷Sr/⁸⁶Srratios of 0·70584 to 0·70786. The presence ofthese xenoliths and their mineralogy and geochemistry, coupledwith the ⁸⁷Sr/⁸⁶Sr ratios observed in different zones of individualphenocrysts, indicate that magma–crust interaction atMerapi is potentially more significant than previously thought,as numerous crystal cores in the phenocrysts appear to be inheritedfrom a metamorphosed sedimentary crustal source. This has potentiallysignificant consequences for geochemical mass-balance calculations,volatile saturation and flux and eruptive behaviour at Merapiand similar island arc volcanic systems elsewhere. KEY WORDS: assimilation; isotopes; Merapi; xenolith; calc-silicate