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     

Himalayan inverted metamorphism constrained by oxygen isotope thermometry

Inverted metamorphic field gradients are preserved in two amphibolite facies metapelitic sequences forming the crystalline core zone of the Himalayan orogen in the Sutlej valley (NW India). In the High Himalayan Crystalline Sequence (HHCS), metamorphic conditions increase upwards from the staurolite zone at the base, through the kyanite-in and sillimanite-in isograds, finally to reach partial melting conditions at the top. The structurally lower Lesser Himalayan Crystalline Sequence (LHCS) shows a gradual superposition of garnet-in, staurolite-in and kyanite + sillimanite-in isograds. Although phase equilibria constraints imply inverted temperature field gradients in both units, garnet-biotite (GARB) rim thermometry indicates final equilibration at a nearly uniform temperature around T ≈ 600 °C across these sequences. The P-T path and garnet zoning data show that this apparent lack of thermal field gradient is mainly the consequence of a resetting of the GARB equilibria during cooling. In order to constrain peak temperature conditions, 20 samples along the studied section have been analysed for oxygen isotope thermometry. The isotopic fractionations recorded by quartz-garnet and quartz-aluminosilicate mineral pairs indicate temperatures consistent with phase equilibria and P-T path constraints for metamorphic peak conditions. Together with barometry results, based on net transfer continuous reactions, the oxygen isotope thermometry indicates peak conditions characterized by: (1) a temperature increase from T ≈ 570 to 750 °C at a nearly constant pressure around P ≈ 800 MPa, from the base to the top of the HHCS unit; (2) a temperature increase from T ≈ 610 to 700 °C and a pressure decrease from P ≈ 900 to 700 MPa, from the base to the top of the LHCS metapelites. Oxygen isotope thermometry thus provides the first quantitative data demonstrating that the Himalayan inverted metamorphism can be associated with a complete inversion of the thermal field gradient across the crystalline core zone of this orogen. Received: 1 April 1999 / Accepted: 12 July 1999     

Rare earth and trace elements in igneous and high-temperature metamorphic minerals of oceanic gabbros (MARK area, Mid-Atlantic Ridge)

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921–924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge–transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P ≈ 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P ≈ 0.2 GPa); (3) brittle regime (350 ≤ T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show C1-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxene re-equilibrated in amphibole-bearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196–22844 ppm), LREE depleted patterns and La_N/Sm_N=0.10–0.33, La_N/Yb_N=0.10–0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for Ti_N and negative anomalies for Sr_N and Zr_N. Volatiles in amphibole are low, with Cl/F < 1; H₂O% is significantly lower than the stoichiometric ratio (1.33–1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process. Received: 6 September 1999 / Accepted: 6 March 2000     

Thermal expansion and structural transformations of stuffed derivatives of quartz along the LiAlSiO4–SiO2 join: a variable-temperature powder synchrotron XRD study

 The structural behavior of stuffed derivatives of quartz within the Li_{1− x} Al_{1− x} Si_{1+ x} O₄ system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 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     

H2O activity in concentrated KCl and KCl-NaCl solutions at high temperatures and pressures measured by the brucite-periclase equilibrium

H₂O activities in supercritical fluids in the system KCl-H₂O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15  kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase. Measurements spanned the range 550–900 °C. A change of state of solute KCl occurs as pressures increase above 2 kbar, by which H₂O activity becomes very low and, at pressures of 4 kbar and above, nearly coincident with the square of the mole fraction (x _H2O). The effect undoubtedly results primarily from ionic dissociation as H₂O density (ρ_H2O) approaches 1 gm/cm³, and is more pronounced than in the NaCl-H₂O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-x _H2O curves where sylvite saturation occurs. The H₂O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the corresponding temperatures span only 100 °C between 1 and 15 kbar. This remarkable convergence of the isobaric equilibrium curves reflects the great influence of pressure on lowering of both KCl and H₂O activities. The H₂O and KCl activities can be expressed by the formulas: a _H2O = γ_H2O[x _H2O+(1 + (1 + α)x _KCl)], and a _KCL = γ_KCl[(1 + α)x _KCl/(x _H2O +(1 + α)x _KCl)]^(1 + α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γ_i = (1 − x_i)²W. Least squares fitting of our H₂O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρ_H2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρ_H2O in gm/cm³, P in kbar and T in K. The standard deviation from the measured activities is only ± 0.014. The equations define isobaric liquidus curves, which are in perfect agreement with previous DTA liquidus measurements at 0.5–2 kbar, but which depart progressively from their extrapolation to higher pressures because of the pressure-induced dissociation effect. The great similarity of the NaCl-H₂O and KCl-H₂O systems suggests that H₂O activities in the ternary NaCl-KCl-H₂O system can be described with reasonable accuracy by assuming proportionality between the binary systems. This assumption was verified by a few reconnaissance measurements at 10 kbar of the brucite-periclase equilibrium with a Na/(Na + K) ratio of 0.5 and of the saturation temperature for Na/(Na + K) of 0.35 and 0.50. At that pressure the brucite-periclase curves reach a lowest x _H2O of 0.45 and a temperature of 587 °C before salt saturation occurs, values considerably lower than in either binary. This double-salt eutectic effect may have a significant application to natural polyionic hypersaline solutions in the deep crust and upper mantle in that higher solute concentrations and very low H₂O activities may be realized in complex solutions before salt saturation occurs. Concentrated salt solutions seem, from this standpoint, and also because of high mechanical mobility and alkali-exchanging potential, feasible as metasomatic fluids for a variety of deep-crust and upper mantle processes. Received: 9 August 1996 / Accepted: 15 November 1996     

Temperature evolution between 50 K and 320 K of the thermal expansion tensor of gypsum derived from neutron powder diffraction data

The unit cell parameters, extracted from Rietveld analysis of neutron powder diffraction data collected between 4.2 K and 320 K, have been used to calculate the temperature evolution of the thermal expansion tensor for gypsum for 50 ≤ T ≤ 320 K. At 300 K the magnitudes of the principal axes are α ₁₁  = 1.2(6) × 10⁻⁶ K⁻¹, α ₂₂  = 36.82(1) × 10⁻⁶ K⁻¹ and α ₃₃  = 25.1(5) × 10⁻⁶ K⁻¹. The maximum axis, α ₂₂ , is parallel to b, and using Institution of Radio Engineers (IRE) convention for the tensor orthonormal basis, the axes α ₁₁ and α ₃₃ have directions equal to (−0.979, 0, 0.201) and (0.201, 0, 0.979) respectively. The orientation and temperature dependent behaviour of the thermal expansion tensor is related to the crystal structure in the I2/a setting. Received 12 February 1998 / Revised, accepted 19 October 1998     

Formation and destruction of periclase by fluid flow in two contact aureoles

Periclase formed in steeply dipping marbles from the Beinn an Dubhaich aureole, Scotland, and the Silver Star aureole, Montana, by the reaction dolomite = periclase + calcite + CO₂. Equilibrium between rock and fluids with X _{CO 2} < 1 requires that reaction was infiltration-driven. Brucite pseudomorphs after periclase occur in the Beinn an Dubhaich aureole either as bed-by-bed replacement of dolomite or in a lens along the contact between dolomite and a pre-metamorphic dike. Transport theory predicts that infiltration drove both periclase reaction and ¹⁸O-depletion fronts which moved at significantly different velocities along the flow path. The distributions of brucite and ¹⁸O-depleted rocks are identical in surface exposures, thus indicating upward flow. Time-integrated flux (q) was <500 mol/cm² and the fluid source was magmatic. Because periclase and its hydrated equivalent brucite are unaltered to dolomite by retrograde reactions, the exposure of brucite marbles accurately images the flow paths of peak metamorphic fluids. In the Silver Star aureole brucite pseudomorphs after periclase exclusively occur in tabular bodies that are beds with elevated Mg/Ca. The spatial pattern of ¹⁸O-depletion requires upward vertical fluid flow. Estimated prograde q ≈ 10³–10⁴ mol/cm² and the fluid source was magmatic. Low Mg/Ca, ¹⁸O-depleted, brucite-free rocks pose a dilemma because the periclase reaction front should have traveled ≈18 times further through them than the isotope alteration front. The dilemma is resolved by reaction textures that indicate periclase and brucite were destroyed in low Mg/Ca rocks by infiltration-driven retrograde carbonation reactions. Values of retrograde q were ≈10³–10⁴ mol/cm². Brucite (after periclase) was preserved only in high Mg/Ca layers where periclase developed in greater abundance. The geometry of brucite marbles at Silver Star thus reflects the location of high Mg/Ca beds rather than the geometry of fluid flow. Retrograde reactions must be considered before the mineralogical record of prograde fluid flow can correctly be interpreted. In both aureoles fluid flow, mineral reaction, and isotope depletion were structurally controlled by bedding and lithologic contacts. Received: 30 July 1996 / Accepted: 21 March 1997     

The Role of Kelvin Number on Bulge Formation from Estuarine Buoyant Outflows

This investigation examines the influence of the Kelvin number (K) and fractional depth (h/D) on bulge formation from buoyant outflows from an estuary or strait perpendicular to the coastline. Here K = W/R is the ratio of the width (W) at the mouth of the estuary to the deformation radius (R), and h and D are the buoyant layer and ambient ocean depths, respectively. Measurements of velocity and lateral shear (≈ relative vorticity ζ) at the baymouth are reported for experiments on a flat-bottomed rotating turntable. The form of the velocity profile across the mouth depends on the value of K. The buoyant outflow flows across the entire width of the estuary for narrow estuaries (i.e., K ≤ 1). In contrast, for wide estuaries (K > 2), dense oceanic water inflows on the left and the buoyant waters outflow on the right (looking seaward). Velocity profiles of the inflowing oceanic waters are laterally uniform with velocities (V/C ≈ −0.4), whereas velocity profiles of the outflowing buoyant waters are laterally sheared with peak velocities of V/C ≈ 1.0 at the right hand exit. The flow pathways when bulges form comprises an anticyclonic turn offshore of the mouth and a downshelf propagating coastal current. Anticyclonic bulges form for surface-advected outflows h/D < 0.25. Anticyclonic bulges do not form for sufficiently large magnitudes of non-dimensional relative vorticity ζ/f (>0.4), and an additional flow pathway is that buoyant waters recirculate back cyclonically into the estuary at the left-hand (upshelf) side of the estuary. The offshore extent of buoyant waters associated with this cyclonic recirculation can be as large as 7R.     

Kink bands in thrust regime: Examples from Srinagar–Garhwal area,Uttarakhand, India

This paper deciphers the late stress systems involved in the development of kink bands in the perspective of thrust regime. In kink bands, the correlation coefficient for α–β plots is positive near thrusts and negative away from thrusts. The plots show nearly linear relationship near thrusts and non-linear relationship away from thrusts. The rotation was prominent mechanism of kink band formation near thrusts and rotation coupled with shearing, along the kink planes away from thrusts. Along thrusts σ ₁ is horizontal E–W trend and it rotates to horizontal N–S trend away from the thrust. The proposed model establishes that (1) the shearing along kink planes led to angular relationship, β < α and (2) the kink planes of conjugate kinks could be used for paleostress analysis even in those cases where shearing along these planes has occurred.     

Structurally controlled fluid flow during contact metamorphism in the Ritter Range pendant, California, USA

The mineralogy and O-isotope geochemistry of siliceous limestones from the Ritter Range pendant constrain the geometry and amount of fluid flow during contact metamorphism associated with emplacement of a pluton of the Sierra Nevada Batholith. Wollastonite (Wo) replaces calcite (Cal) + quartz (Qtz) on a layer-by-layer basis in homoclinal beds that strike NW and dip almost vertically. At the peak of metamorphism (P≈ 1500 bars, T≈ 600 °C) fluid in equilibrium with Cal, Qtz, and Wo has composition XCO₂=0.28, requiring that the Wo-forming reaction was driven by infiltration of reactive H₂O-rich fluid. The spatial distribution of Wo and Cal + Qtz records that peak metamorphic fluid flow was layer-parallel, upward. Bounds on the prograde time-integrated fluid flux associated with formation of Wo are set by: (1) the overlap in O-isotope composition between Wo-bearing and Wo-free rocks (>245 mol fluid/cm² rock); (2) the amount of fluid that would drive the Wo-reaction front upward to the present level of exposure from a point at depth where Cal, Qtz, and Wo would be in equilibrium with pure CO₂ (<1615 mol/cm²). Back-reaction of Wo to Cal + Qtz records an additional time-integrated retrograde fluid flux of ≈ 200–1000 mol/cm². The direction and amount of flow inferred from mineralogical and isotopic data agree with the results of the hydrologic model for metamorphic fluid flow in the area of Hanson et al. (1993). Fingers of Wo-bearing rock that extend farthest from the fluid source along contacts between limestone and more siliceous rocks point to strong control of flow geometry at the 0.1–100 m scale exerted by premetamorphic structures. Studies that neglect structural control at this scale may fail to predict correctly fundamental aspects of contact metamorphic fluid flow. Received: 27 January 1997 / Accepted: 2 October 1997     

Effect of pressure on the thermal expansion of MgO up to 8.2 GPa

Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion data over the experimental pressure range yields the pressure derivative, (∂α/∂P) _T , of −1.04(8) × 10⁻⁶ GPa⁻¹ K⁻¹ and the mean zero-pressure thermal expansion α_{0, T}  = 4.09(6) × 10⁻⁵ K⁻¹. The α_{0, T} value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas (∂α/∂P) _T is determined for the first time on MgO by direct measurements. The cross-derivative (∂α²/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The temperature derivative of the bulk modulus, (∂K _T/∂T) _P , of −0.025(3) GPa K⁻¹, obtained from the measured (∂α/∂P) _T value, is in accord with previous findings. Received: 2 April 1999 / Revised, accepted: 22 June 1999     

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si−O bond distances, coordination numbers and Debye-Waller factors). The mean Si−O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R≈0.172 nm and N≈5) to R≈0.167 nm and N≈4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced. Received: 18 December 1996 / Revised, accepted: 20 June 1997     

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

Summary The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47′S Lat., 70°43′W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06−0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21−0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ¹⁸O and δD for the hydrothermal fluids were between 3 and 10‰ and between −95 and −75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit. Author’s present address: J. Carrillo-Rosúa, Dpto. de Didáctica de las Ciencias Experimentales, Universidad de Granada, Campus de Cartuja, 18071, Granada, Spain     

Crystal orbital contributions to the pyrrhotite valence band with XPS evidence for weak Fe–Fe π bond formation

 Synchrotron excited X-ray photoelectron spectra (SXPS) of hexagonal pyrrhotite reveal three distinct Fe 3d-derived photopeaks within its outer valence band. The t _2gα band (majority spin) is centered at about 2.5 eV, the e _g α band at about 1.0 eV and the t _2gβ (minority spin) contribution at about 0.25 eV. From these data the ligand field splitting energy is 1.5 (±0.2) eV and the majority spin pairing energy is 2.25 (±0.2) eV. These are the first such XPS measurements for this mineral. S 3p-derived bonding and non-bonding bands are identified, with the former centred at about 6.5 eV and the latter near 4.5 eV. The XPS results are remarkably consistent with SCF-Xα scattered wave molecular orbital calculations. Although the calculations and the collected spectra are consistent, they differ from a recent interpretation of the pyrrhotite valence band. An explanation for the discrepant results is provided. Auger resonant enhancement of Fe 3d photopeaks at 60 eV photon energy results in the t _2gα emission (at 2.5 eV) being strongly enhanced and broader than the t _2gβ emission (0.25 eV). The explanation of these observations requires the presence of weak Fe–Fe π and π^* crystal (molecular) orbitals located near 2.5 eV, and separated by no more than about 0.5 eV. The π-bonded crystal orbitals are derived from weak mixing of adjacent Fe t _2g atomic orbitals along the c crystallographic axis. Received: 15 June 2000 / Accepted: 11 June 2001     

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     

X-ray powder diffraction study on the modulated high temperature forms of SiO2 tridymite between 110 and 220 °C

 The crystal structure of intermediate incommensurate tridymite was refined at 150 °C from powder data. Upon cooling from above 220 °C, the basic structure with space group symmetry C222₁ is gradually distorted from orthorhombic to monoclinic symmetry. With decreasing temperature, the monoclinic angle γ smoothly opens up to 90.3°, while a displacive modulation with temperature-dependent wavelength develops. The 3 + 1 dimensional superspace group of the incommensurate phase is C112₁(αβ0). The modulation mainly consists of two sinusoidal transverse displacement waves for the silicon atoms coupled to rotations of the rigid SiO_4/2 tetrahedra. The wave vector is r=0.1192(1)a* − 0.0043(1)b* at 150 °C. Below 150 °C tridymite discontinuously transforms to another orthorhombic phase and the modulation partially locks in at the wave vector r ₁=1/3a*. Simultaneously, an additional incommensurate modulation with r ₂= 0.0395(1)b* − 0.3882(1)c* is formed. The two-dimensional modulation does not vary significantly with the temperature. Received: 13 September 2000 / Accepted: 29 January 2001     

Volcanogenic-related origin of sulfide-rich quartz veins: evidence from O and S isotopes at the Géant Dormant gold mine, Abitibi belt, Canada

The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ¹⁸O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ¹⁸O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ¹⁸O value of 4.7‰ calculated at 275 °C. The δ³⁴S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ¹⁸O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ¹⁸O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

High-temperature thermal expansion of lime, periclase, corundum and spinel

The high-temperature cell parameters of lime (CaO), periclase (MgO), corundum (Al₂O₃), and spinel (MgAl₂O₄) have been determined from 300 up to 3000 K through X-ray diffraction experiments with synchrotron radiation. The good agreement found with dilatometric results suggests that vacancy-type defects do not make a large contribution to thermal expansion for these oxides, even near the melting point, justifying the use of X-ray diffraction for determining volume properties up to very high temperatures. Thermal expansion coefficients were determined from the measured cell volumes with equations of the form α=α₀ + α₁ T + α₂/T ². Along with available isobaric heat capacity and compressibility data, these derived coefficients clearly show that anharmonic effects contribute little to the isochoric heat capacities (C _v ) of CaO, MgO, and Al₂O₃, which do not depart appreciably from the 3nR Dulong and Petit limit. Received: 31 March 1999 / Revised, accepted: 23 June 1999