Pb diffusion in rutile

Diffusion of Pb was measured in natural and synthetic rutile under dry, 1 atmosphere conditions, using mixtures of Pb titanate or Pb sulfide and TiO₂ as the sources of diffusant. Pb depth profiles were then measured with Rutherford Backscattering Spectrometry (RBS). Over the temperature range 700–1100 °C, the following Arrhenius relation was obtained for the synthetic rutile: D=3.9 × 10⁻¹⁰exp(−250 ± 12 kJ mol⁻¹/RT) m²s⁻¹. Results for diffusion in natural and synthetic rutile were quite similar, despite significant differences in trace element compositions. Mean closure temperatures calculated from the diffusion parameters are around 600 °C for rutile grains of ∼100 μm size. This is about 100 °C higher than rutile closure temperature determinations from past field-based studies, suggesting that rutile is more resistant to Pb loss through volume diffusion than previously thought. Received: 28 June 1999 / Accepted: 29 December 1999     

Oxygen diffusion in anhydrous sanidine feldspar

Oxygen exchange experiments have been performed between single crystals of sanidine feldspar and oxygen gas enriched in ¹⁸O, at temperatures in the range 869–1053 °C, total pressure 1 atmosphere, for times up to 28 days. Oxygen isotope diffusion profiles in a direction perpendicular to (001) were determined with an ion microprobe. The experimental data obey a single Arrhenius relationship of the form D = 8.4 × 10⁻¹¹ exp. (−245 ± 15 kJ mol⁻¹/RT) m²s⁻¹. The results indicate that oxygen diffusion in anhydrous sanidine feldspar is marginally slower than oxygen diffusion in anhydrous anorthite. Comparison with published atomistic simulation studies suggests that oxygen transport in feldspar is by an interstitial mechanism. Received: 17 October 1997 / Accepted: 6 July 1998     

Supercooled diopside melt: confirmation of temperature-dependent expansivity using container-based dilatometry

The expansivity of supercooled diopside liquid has been determined using techniques of container-based dilatometry. Two thermal strategies have been employed, one in which the sample is brought to volumetric equilibrium by long-duration dwells at low temperatures (817 °C) and one in which scanning dilatometry of the sample has been performed at somewhat higher temperatures (890–913 °C). The results of both experiments yield a supercooled liquid expansivity for diopside liquid in the temperature range of 817–913 °C of 84.4 ± 2.8 × 10⁻⁴ cm³/mol K. The expansivity is 65% higher than that obtained for diopside melt obtained at superliquidus temperatures using the double bob Archimedean method. Combined fitting of the new low temperature, volume–temperature data from the present study and the superliquidus data from the literature has been performed. The combined fit yields the following equations for the volume–temperature relationship of diopside liquid (T=temperature in °C):

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996     

Volume and grain boundary diffusion of calcium in natural and hot-pressed calcite aggregates

 Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900° C and 0.1 MPa in a stream of CO₂. Diffusion coefficients (D) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q)=382±37 kJ/mol and pre-exponential factor (D₀)=0.13 m²/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650° to 850° C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700° C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D′) and the effective grain boundary diffusion width (δ) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D′δ values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D^′ ₀δ=1.5×10⁻⁹ m³/s and Q=267±47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks. Received: 19 December 1994/Accepted: 30 June 1995     

Magnesium self-diffusion in orthoenstatite

Magnesium self-diffusion coefficients were determined experimentally for diffusion parallel to each of the three crystallographic directions in natural orthoenstatite (En₈₈Fs₁₂). Experiments were conducted at 1 atm in CO-CO₂ gas mixing furnaces, which provided oxygen fugacities equivalent to the iron-wüstite buffer. Diffusion of ²⁵Mg was induced in polished samples of oriented orthoenstatite using a film of isotopically enriched ²⁵MgO as the source material. Very short (<0.15 μm) diffusional penetration profiles were measured by ion microprobe depth profiling. The diffusion coefficients determined for four temperatures (900, 850, 800, 750 °C) provide the activation energies, E _a , and frequency factors, D _o, where D = D _o exp (−E _a /RT) for Mg self-diffusion parallel to each crystallographic direction: a-axis, E _a  = 360 ± 52 kJ/mole and D _o = 1.10 × 10⁻⁴ m²/s; b-axis, E _a  = 339 ± 77 kJ/mole and D _o = 6.93 × 10⁻⁶ m²/s and c-axis, E _a  = 265 ± 66 kJ/mole and D _o = 4.34 × 10⁻⁹ m²/s. In this temperature range, any possible anisotropy of cation diffusion is very small, however the activation energy for diffusion parallel to the c-axis (001) is the lowest and the activation energies for diffusion parallel to the a-axis (100) and b-axis (010) are higher. Application of these diffusion results to the silicate phases of the Lowicz mesosiderite meteorite provides cooling rates for the silicate portion of the meteorite (4–11 °C/100 years) that are similar, although slower, to previous estimates. These silicate cooling rates are still several orders of magnitude faster than the cooling rates (0.1 °C/10⁶ years) for the metal portions. Received: 22 January 1997 / Accepted: 2 October 1997     

Structural thermal behavior of paragonite and its dehydroxylate: a high-temperature single-crystal study

 The lattice constants of paragonite-2M₁, NaAl₂(AlSi₃)O₁₀(OH)₂, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: α_a = 1.51(8) × 10⁻⁵, α_b = 1.94(6) × 10⁻⁵, α_c = 2.15(7) ×  10⁻⁵ °C⁻¹, and α_V = 5.9(2) × 10⁻⁵ °C⁻¹. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl₂ (AlSi₃)O₁₁, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V ₀ = 1 + 5.9(2) × 10⁻⁵ T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999     

The oxygen isotope fractionation behaviour of kyanite in experiment and nature

The oxygen isotope fractionation between kyanite and calcium carbonate has been investigated experimentally at four temperatures in the range between 625 and 775 °C at 13 kbar. Because of low exchange rates, the isotopic reaction was enhanced by polymorphic transformation of andalusite to kyanite. With this experimental modification a close approach to equilibrium was reached in all runs. The temperature dependence of the equilibrium fractionation is described by the equation 1000 ln _ky-cc=−2.62×10⁶/T ². Application of the experimental results to natural quartz-kyanite-garnet assemblages indicates the preservation of the oxygen isotope composition of kyanite acquired during its formation, reflecting its extremely low oxygen diffusivity. This refractory behaviour restricts the use of kyanite for thermometry but opens the possibility to use its O-isotope composition as an indicator for recognition of polymetamorphic rock histories and reconstruction of the prograde evolution of a metamorphic sequence. Received: 8 June 1998 / Accepted: 24 August 1998     

Diffusion-controlled growth of albite and pyroxene reaction rims

The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H₂O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm²/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H₂O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm²/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′_A, where A = SiO₂, NaAlO₂, or NaAlSi₋₁, and the grain boundary thickness δ in albite. The calculated D′_SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10⁻²³ and 1.4 × 10⁻²² m³ s⁻¹, respectively. Both the rate constants and the calculated D′_Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996     

Pressure–volume–temperature equation of state of andradite and grossular, by high-pressure and -temperature powder diffraction

 The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for andradite K ₀=158.0(±1.5) GPa, (dK/dT )₀=−0.020(3) GPa K⁻¹ and α₀=31.6(2) 10⁻⁶ K⁻¹, and for grossular K ₀=168.2(±1.7) GPa, (dK/dT)₀=−0.016(3) GPa K⁻¹ and α₀=27.8(2) 10⁻⁶ K⁻¹. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out. Received: 7 July 2000 / Accepted: 20 October 2000     

The nature of crystalline silica from the TAG submarine hydrothermal mound, 26°N Mid Atlantic Ridge

Silica occurs in abundance in a variety of hydrothermal samples from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound, 26°N Mid-Atlantic Ridge. The water content, trace element chemistry, and mineralogy of crystalline silica from 15 different samples have been examined by vibrational spectroscopy and probe microanalysis. The samples are from: shallow subsurface ferric iron oxyhydroxide silica deposits (n=4), a fragment of an active white smoker chimney (n=1), anhydrite bearing hydrothermal breccias (n=2), pyrite silica breccias (n=3), and silicified wall rock breccias (n=5). Length-fast chalcedony occurs in association with variable quantities of ferric iron oxyhydroxides in hydrothermal breccias from the mound flanks, within shallower subsurface chert samples, and within white smoker chimney walls. Samples from the anhydrite zone contain textures which are suggestive of an origin involving replacement of anhydrite. Samples taken from TAG 1 and 5 from below the anhydrite zone contain no chalcedony. Instead they contain subhedral quartz crystals which show oscillatory zoning in aluminium. Two types of crystalline silica namely, type A and type B quartz, are defined on the basis of the infrared spectra in the OH region from 3200 cm⁻¹ to 3600 cm⁻¹. The type A quartz occurs beneath the anhydrite zone at TAG 1 and 5. We propose a model that relates specific varieties of crystalline silica to different thermal and chemical environments within the mound interior. Length-fast chalcedony occurs in an outer low temperature envelope across the top and sides of the mound. The common association between length-fast chalcedony and ferric iron oxyhydroxides suggests that chalcedony crystallization is favoured where catalysis by ferric iron can occur. The apparent suppression of fibrous silica at the expense of single quartz crystals with increasing depth is attributed to differing growth rates and degrees of supersaturation of silica-bearing solutions with increasing temperature within the mound. The transition from type A to type B single crystal growth is interpreted to occur at temperatures approaching ˜360 °C due to decreasing solubility of aluminium in quartz, so that aluminium is rendered unavailable for type A valence compensation. Received: 10 September 1998 / Accepted: 6 July 1999     

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

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

High-temperature study and thermal expansion of phlogopite

 Unit-cell dimensions of a natural phlogopite from Pargas, Finland, have been determined in the temperature interval of 27–1050 °C by X-ray powder diffraction technique. Expansion rates vary discontinuously with temperature with a break at 412 °C. Below this temperature, the linear expansions (α) for a, b and c axis lengths are 3.74 × 10⁻⁵ K⁻¹, 1.09 × 10⁻⁵ K⁻¹, and 1.19 × 10⁻⁵ K⁻¹, respectively, and above that they are 0.86 × 10⁻⁵ K⁻¹, 0.80 × 10⁻⁵ K⁻¹, and 1.93 × 10⁻⁵ K⁻¹. The volume thermal expansion coefficients are 6.26 × 10⁻⁵ K⁻¹ and 3.71 × 10⁻⁵ K⁻¹ for low-temperature and high-temperature intervals, respectively. The observed kink in the rate of thermal expansions with temperature could be due to the different mode of structural changes. Thermogravimetric analysis of the sample indicates the oxidation of iron in the temperature range of 500–600 °C and dehydroxylation as well as decomposition of phlogopite in the temperature range of 900–1200 °C. Received: 8 September 1998 / Accepted: 28 February 2000     

Retrograde fluids in the Archean Shawmere anorthosite, Kapuskasing Structural Zone, Ontario, Canada

The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO₂ < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO₂ < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO₂ > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H₂O-rich to CO₂-rich. The calcite in the retrograde veins has δ¹⁸O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ¹³C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO₂-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO₂ ≈ 1.13 to 1.05 g/cm³). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO₂-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO₂-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO₂-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996     

Stability of phlogopite in granitic melts, an experimental investigation

Water-saturated and water-undersaturated experiments (a _{H2 O} = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a _{H2 O} = 1.0 and up to 780°C at a _{H2 O} = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a _{H2 O} = 1.0) and there is a temperature interval of 80°C at a _{H2 O} = 1.0, and 90–100°C at a _{H2 O} = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopite_ss breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a _{H2 O} = 1.0 ranges between 0.4 and 1.7 wt % and at a _{H2 O} = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996     

Calcium self-diffusion in diopside at high temperature: implications for transport properties

We have investigated ⁴⁴Ca self-diffusion in natural diopside single crystals (containing ∼2 atomic % Fe) at temperatures up to 1320 °C (i.e. 30 °C below the nominal melting point). Oxygen fugacity was controlled by gaseous mixtures. Diffusion profiles ranging from ∼50 to 500 nm were analysed by Rutherford Back-Scattering Spectrometry (RBS). The present results are complementary to previous studies, and show that in both synthetic (Fe-poor) and natural (Fe-rich) diopside, there are two different diffusion regimes for Ca with a transition at ∼1230±15 °C. Below this temperature diffusion is characterised by an activation enthalpy of ∼284±10 kJ/mol, while at higher temperatures it increases up to ∼1006±75 kJ/mol. These regimes are proposed to be respectively extrinsic and intrinsic. For the intrinsic regime Ca self-diffusion may involve Ca-Frenkel point defects. These are pairs of a vacancy on a M₂ site and a calcium cation on an interstitial (normally unoccupied) site. The concentration of such point defects depends only on temperature, and it is especially important at very high temperatures. The activation enthalpy for intrinsic diffusion may represent the half defect formation enthalpy plus the migration enthalpy for movement through interstitial sites. For the extrinsic regime we propose Ca self-diffusion to involve extrinsic interstitial point defects with concentration proportional to ()^{–0.19±0.03}. We suggest that for both regimes, Ca diffusion involves the well known M₃ sites in the octahedral layers, as well as sites in the tetrahedral layers, that we call M_4. These sites are especially convenient to explain the observed isotropic diffusion. Increasing concentration of Ca-Frenkel point defects may be related to the onset of premelting, which affects the thermodynamic properties of Fe-“free” diopside above 1250 °C. In the light of the present results, premelting is also expected to occur in natural Fe-bearing diopside and it could strongly influence its thermodynamic and transport properties. Subsequently, in deep upper mantle conditions (T≈1250 °C–1300 °C) where premelting could occur, diffusional cation exchanges with surrounding phases and diffusion controlled creep might be facilitated. Finally, our diffusion data support a previous suggestion that electrical conductivity may be electronic rather than ionic. Received: 17 December 1997 / Revised, accepted: 17 April 1998     

Mineral inclusions in pyrope crystals from Garnet Ridge, Arizona, USA: implications for processes in the upper mantle

Mineral inclusions in pyrope crystals from Garnet Ridge in the Navajo Volcanic Field on the Colorado Plateau are investigated in this study with emphasis on the oxide minerals. Each pyrope crystal is roughly uniform in composition except for diffusion halos surrounding some inclusions. The pyrope crystals have near constant Ca:Fe:Mg ratios, 0.3 to 5.7 wt% Cr₂O_3, and 20 to 220 ppm H₂O. Thermobarometric calculations show that pyrope crystals with different Cr contents formed at different depths ranging from 50 km (where T ≈ 600 °C and P = 15 kbar) to 95 km (where T ≈ 800 °C and P = 30 kbar) along the local geotherm. In addition to previously reported inclusions of rutile, spinel and ilmenite, we discovered crichtonite series minerals (AM₂₁O₃₈, where A = Sr, Ca, Ba and LREE, and M mainly includes Ti, Cr, Fe and Zr), srilankite (ZrTi₂O₆), and a new oxide mineral, carmichaelite (MO_2−x(OH)_x, where M = Ti, Cr, Fe, Al and Mg). Relatively large rutile inclusions contain a significant Nb (up to 2.7 wt% Nb₂O₅), Cr (up to ∼6 wt% Cr₂O₃), and OH (up to ∼0.9 wt% H₂O). The Cr and OH contents of rutile inclusions are positively related to those of pyrope hosts, respectively. Needle- and blade-like oxide inclusions are commonly preferentially oriented. Composite inclusions consisting mainly of carbonate, amphibole, phlogopite, chlorapatite, spinel and rutile are interpreted to have crystallized from trapped fluid/melt. These minerals in composite inclusions commonly occur at the boundaries between garnet host and large silicate inclusions of peridotitic origin, such as olivine, enstatite and diopside. The Ti-rich oxide minerals may constitute a potential repository for high field strength elements (HFSE), large ion lithophile elements and light rare earth elements (LREE) in the upper mantle. The composite and exotic oxide inclusions strongly suggest an episode of metasomatism in the depleted upper mantle beneath the Colorado Plateau, contemporaneous with the formation of pyrope crystals. Our observations show that mantle metasomatism may deplete HFSE in metasomatic fluids/melts. Such fluids/melts may subsequently contribute substantial trace elements to island arc basalts, providing a possible mechanism for HFSE depletion in these rocks. Received: 20 December 1997 / Accepted: 15 October 1998     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Geochemistry and mineralization age of magnesian skarn-type iron deposits of the Janggun mine, Republic of Korea

The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs₂ and −log fo₂ values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO₂ during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H⁺ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo₂ and fs₂. The δ³⁴S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated ³⁴SH_{2 S} values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ¹³C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ¹⁸OH_{2 O} and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997     

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

Summary We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes “fassaitic” clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (T_HOM = 1000–1050 °C), b) CO₂ ± H₂S-rich fluid inclusions (T_HOM = 20–31.3 °C into the vapor phase), c) multiphase aqueous brine inclusions (T_HOM = 720–820 °C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (T_HOM = 870–890 °C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt – aqueous chloride-rich liquid – carbonate/sulfate melt?) during heating and cooling below 870 °C. There is no evidence for fluid circulation below 700 °C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable ²⁰⁶Pb/²⁰⁴Pb (19.047–19.202), ²⁰⁷Pb/²⁰⁴Pb (15.655–15.670), and ²⁰⁸Pb/²⁰⁴Pb (38.915–39.069) and relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51211–0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (δ¹³C_V-PDB = −5.4 to −1.1‰; δ18O_V-SMOW = 11.7 to 16.4‰) indicate formation from a ¹⁸O- and ¹³C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO₂-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns. Received March 1, 2000; revised version accepted November 2, 2000