Compression and amorphization of (Mg,Fe)2SiO4 olivines: An X-ray diffraction study up to 70 GPa

The effect of (Mg,Fe) substitution on the compression and pressure-induced amorphization of olivines has been investigated up to more than 50 GPa in a diamond anvil cell through energy-dispersive X-ray diffraction experiments with synchrotron radiation. For the four (Mg_1–x , Fe _x )₂SiO₄ olivines studied, the compressibility is the highest along the b axis and the smallest along the a axis. For compositions with x = 0, 0.17, 0.66, and 1, the slope of the volume-pressure curves shows a rapid decrease at pressures of around 42, 34, 20 and 10 GPa, respectively. Assuming K₀ = 4, we obtained at lower pressures with a Birch-Murnaghan equation of state essentially the same room-pressure bulk modulus for all olivines, namely K ₀ = 131 ± 6 GPa, in agreement with previous single-crystal compression and ultrasonic measurements. At higher pressures, the compression becomes nearly isotropic and the materials very stiff. These changes could precede partial transformation of olivines to a high-pressure polymorph related to the spinel structure. Only a small fraction of olivines seems to transform actually to this phase, however, because most of the material undergoes instead pressure-induced amorphization which take place at considerably higher pressures for Mg-than for Fe-rich olivines.     

Static and Dynamic Moduli of the Seismogenic Layer in Italy

Summary Static and dynamic elastic moduli of Calcare Massiccio (mudstone-limestone) have been measured as a function of frequency over nine decades, using three different standard methods: uniaxial static compression, dual cantilever forced oscillations, and measurement of ultrasonic velocities. An accurate critical comparison using the same techniques on a poly-methyl-methacrylate (PMMA) material shows that an unresolvable 10 to 20% bias exists in the two low frequency standard techniques, whereas the ultrasonic measurements are more accurate and reproducible within 5%. No significant frequency dependence is found for Calcare Massiccio, which gives a Youngs modulus of (75±7) GPa and a Poisson#x2019;s ratio of (0.28#x2009;#x00B1;#x2009;0.02).     

Inversions in sub-potassic nephelines

Sub-potassic nephelines in the system NaAlSiO₄(Ne)-KAlSiO₄(Ks) were synthesized under a variety of conditions and studied at room temperature and up to 1000 °C using an X-ray powder diffractometer. At low temperatures they do not have the hexagonal structure determined by Hahn and Buerger (1955) for natural nepheline. Samples with 0.7 to 2.5 mole % Ks have an orthorhombic supercell with parameters equivalent to a, 3a, 3c where a and c are Hahn and Buerger structure cell parameters. Nephelines with 0 to 0.7% Ks consist of two phases with different c axes; one of these phases has the orthorhombic supercell.Pure-Na nephelines (NaAlSiO₄) invert to a hexagonal phase with the Hahn and Buerger structure at 190 °±10 °C; this inversion temperature decreases with increasing Ks and a sample with 0.5% Ks inverts at 170 °±5 °C. The inversion is reversible and is displacive. Another reversible inversion begins at 875 °±10 °C in pure-Na nepheline; this inversion increases in temperature with increasing Ks and a sample with 1.8% Ks begins to invert at 960 °±10 °C.Superstructures with anomalous low-temperature cell parameters in sub-potassic nephelines are attributed to reversible collapse of the framework about the larger cation sites which must be occupied by small Na in subpotassic nephelines. Superstructures in natural nephelines are also related to framework collapse at a displacive inversion.     

Self-consistent pressure scales based on the equations of state for ruby,diamond, MgO,B2–NaCl,as well as Au,Pt, and other metals to 4 Mbar and 3000 K

Based on the modified formalism of Dorogokupets and Oganov (2007), we calculated the equation of state for diamond, MgO, Ag, Al, Au, Cu, Mo, Nb, Pt, Ta, and W by simultaneous optimization of the data of shock-wave experiments and ultrasonic, X-ray diffraction, dilatometric, and thermochemical measurements in the temperature range from ~ 100 K to the melting points and pressures of up to several Mbar, depending on the material. The obtained room-temperature isotherms were adjusted with a shift of the R1 luminescence line of ruby, which was measured simultaneously with the unit cell parameters of metals in the helium and argon pressure media. The new ruby scale is expressed as P(GPa) = 1870?Δλ / λ0(1 + 6?Δλ / λ0). It can be used for correction of room-pressure isotherms of metals, diamond, and periclase. New simultaneous measurements of the volumes of Au, Pt, MgO, and B2-NaCl were used for interrelated test of obtained equations of state and calculation of the room-pressure isotherm for B2-NaCl. Therefore, the constructed equations of state for nine metals, diamond, periclase, and B2-NaCl can be considered self-consistent and consistent with the ruby scale and are close to a thermodynamic equilibrium. The calculated PVT relations can be used as self-consistent pressure scales in the study of the PVT properties of minerals using diamond anvil cell in a wide range of temperatures and pressures.     

An elevated temperature X-ray study of synthetic disordered Na-K alkali feldspars

The temperature dependence of cell parameters for three disordered, synthetic alkali feldspars (Or₁₉, Or₃₈, and Or₁₀₀) has been determined up to 1,000 °C. The samples show no change in composition or degree of Si-Al disorder during the experiments. The triclinic-monoclinic inversion in the sample of composition Or₁₉ occurs at 560 °±10 °C and is accompanied by changes in the rates of expansion of a, b and c; the rate for a increases and those for b and c decrease above the inversion. The b and c parameters in Or₁₀₀ show small decreases with increasing temperature and this may be due to thermal motion effects causing a contraction of cell directions that are fully expanded at room temperature. Calculation of the thermal expansion ellipsoids for the monoclinic phases shows that the major expansion coefficients (₁) for all three samples are more than an order of magnitude greater than the intermediate (₂) and minor (₃) coefficients. Thus the thermal expansion of these phases is dominated by that of ₁ which makes an angle of 22 ± 4 ° with+a; this orientation is parallel to that of the short M-OA2 bonds. The thermal expansion mechanism for monoclinic, disordered alkali feldspars may involve tilting within the framework releasing compression along this direction and allowing the M-OA2 bonds to show high expansion rates. The stretching of the crankshaft units, which are parallel to a, may only play a subordinate role in controlling the expansion of the feldspar framework.     

Compression of α-MnS (alabandite) and a new high-pressure phase

The compressibility of -Mns (alabandite) was determined by x-ray analysis using a Mao-Bell type diamond anvil cell. The zero pressure bulk modulus (K₀) is 74±2 GPa with the pressure derivative of the bulk modulus (K_o) fixed at four. Allowing (K_o) to vary yielded a statistically better fit with K₀ = 88±6 GPa and k₀ = 2.2±0.6. Our data combined with the data of McCammon (1991) gave K_o = 73±1 GPa with k_o fixed at four. A fit with k_o allowed to vary yielded k_o = 75±2 GPa and k_o = 3.7±0.4. Alabandite transformed from the B1 structure (NaCl-type) to an unknown high-pressure phase at 26 GPa. The high-pressure phase has lower than hexagonal symmetry and it is stable to at least 46±4 GPa.Also affiliated with the James Franck Institute, University of Chicago     

Chloritoid-bearing pelitic rocks of the Horsethief Creek Group,Southeastern British Columbia

Aluminous pelitic rocks of the Late Precambrian Horsethief Creek Group of southeastern British Columbia contain the assemblage chloritoidmuscovite-paragonite-quartz-chlorite (biotite zone). Additional members of the assemblage may include graphite, Fe-Mg carbonate, rutile, ilmenite and pyrite. No albite was detected. Lower grade pelitic rocks (chlorite zone) contain muscovite-chlorite and rare paragonite.Chloritoids from carbonate-free assemblages show a narrow range of composition (85±5 mol % Fe-chtd) and most porphyroblasts are zoned with higher Mn in cores and higher Mg in rims. For eight chloritoid-chlorite pairs, K _D = (Mg/Fe chtd/Mg/Fe chl) = 0.188±0.0234.Correlation of these mineral assemblages with experimental and computed phase equilibria and oxygen isotope temperatures suggest a minimum pressure near 4.5 Kbar, a minimum temperature near 335 ° C and an upper limit on temperature near 460 ° C. Variation in X _{CO 2} content of fluids attending metamorphism is inferred from the alternate appearance of either Fe-Mg carbonate + rutile or ilmenite-bearing assemblages. The assemblage paragonite-chloritoid-quartz-Fe-Mg carbonate-rutile is inferred to be stable at a T near 360 ° C, an X _{CO 2} near 0.9 and P near 5 Kbar.     

Thermodynamic data from redox reactions at high temperatures. V. Thermodynamic properties of NiO−MnO solid solutions from emf measurements

Divariant oxide plus metal assemblages potentially make useful redox sensors for use in hydrothermal and other high pressure experiments. Here we report the calibration of the (Ni, Mn)O/Ni redox sensor in which the Ni/NiO (NNO) oxygen buffer is displaced to lower oxygen chemical potentials (O₂), by the solid solution of MnO in the oxide phase. This assemblage was chosen because: (1) it covers a useful range of O₂; (2) the system can be calibrated very accurately. Values of O₂ defined by the (Ni, Mn)O/Ni assemblage were determined electrochemically, from 900 to 1300 K, using calcia-stabilized zirconia solid electrolytes. The oxide compositions (8 in total, ranging from 0.1X _NiO0.8) were analysed afterwards by electron microprobe, and were checked for internal consistency by measuring the lattice parameters (a₀), using powder XRD. The accuracies of the measurements, both assessed theoretically and established empirically, are (1): ±80J/mol in O₂, ±0.0002 Å in a₀ and ±0.002 to 0.005 in X _NiO. Activity-composition relations were fitted to the Redlich-Kister formalism. There is a slight asymmetry (corresponding to a subregular model) across the solution with A ₀ ^G =9577(±45) J/mol, and A ₁ ^G =–477(±80) J/mol. The experimental data were also used to derive the parameters V^ex, H^ex and S^ex. There is no obvious relationship between excess volumes and enthalpies of mixing, nor between excess volumes and excess entropies. The experimental data from this study have been used to formulate the (Ni, Mn)O/Ni redox sensor expression: O₂ = ₂(NNO) + 2RTlnX _NiO + 2(1 – X _NiO)²[11483 – 1.697T] – 477(4X _NiO – 1)(900 < T(K) < 1300) where O₂(NNO)=–478967+248.514T–9.7961 T In T, from O'Neill and Pownceby(1993a).     

Seismic hazard of Egypt

Earthquake hazard parameters such as maximum expected magnitude,M _max, annual activity rate,, andb value of the Gutenberg-Richter relation have been evaluated for two regions of Egypt. The applied maximum likelihood method permits the combination of both historical and instrumental data. The catalogue used covers earthquakes with magnitude 3 from the time interval 320–1987. The uncertainties in magnitude estimates and threshold of completeness were taken into account. The hazard parameter determination is performed for two study areas. The first area, Gulf of Suez, has higher seismicity level than the second, all other active zones in Egypt.b-values of 1.2 ± 0.1 and 1.0 ± 0.1 are obtained for the two areas, respectively. The number of annually expected earthquakes with magnitude 3 is much larger in the Gulf of Suez, 39 ± 2 than in the other areas, 6.1 ± 0.5. The maximum expected magnitude is calculated to be 6.5 ± 0.4 for a time span of 209 years for the Gulf of Suez and 6.1 ± 0.3 for a time span of 1667 years for the remaining active areas in Egypt. Respective periods of 10 and 20 years were reported for earthquakes of magnitude 5.0 for the two subareas.     

Paleomagnetic constraints on Zn–Pb ore genesis of the Pillara Mine, Lennard Shelf, Western Australia

The Pillara Zn–Pb deposit is the largest of several known Mississippi Valley-type (MVT) deposits in the Lennard Shelf of the Canning Basin. Paleomagnetic and rock magnetic measurements are reported for 294 specimens from 23 sites in mineralization and its carbonate host rocks from the deposit as well as on 15 artificial specimens of zinc and lead concentrate and of tailings. Pyrrhotite carries the characteristic remanent magnetization (ChRM) in nearly all specimens. The ChRM postdates most faulting as shown by breccia tests and most minor regional tilting as shown by the degraded fit on tilt correction. The mean ChRM direction for all sites is D=20.6°, I=–27.5° (N=23, ₉₅=5.3°, k=34.1), yielding an age of 358±5 Ma (2) that is similar to the comparable age of 354±8 Ma (2) for the Kapok MVT deposit. Host rock diagenesis with attendant secondary remagnetization yields an age of 361±5 Ma (1) and the MVT mineralization with a primary chemical remanent magnetization gives an age of 356±3 Ma (1), co-eval with a published Rb–Sr sphalerite age of 357±3 Ma. Interpretation of this temporal data suggests that the MVT deposits of the southeastern Lennard Shelf originated during extension, probably in response to rift-related topography-driven fluid flow.Editorial handling: C. Brauhart     

Spontaneous strain at the structural phase transition in NaNO3

The temperature dependence of the hexagonal c unit cell parameter of high-purity NaNO₃ shows an anomaly at 553 K corresponding to the orientational ordering transition. The a unit cell parameter is barely influenced by the transition. The single component spontaneous strain for this zone boundary instability is large (55×10^–3 at 295 K), and couples quadratically with the order parameter. The critical exponent is found to have the value 0.22 ± 0.01, which differs from that expected in the classical case. Below ca 450 K, crossover to tricritical behaviour is observed (=1/4). The temperature evolution of the macroscopic order parameter as revealed by the temperature dependence of the spontaneous strain follows a tricritical behaviour between 70 K and 450 K. At temperatures below 70 K order parameter saturation is observed. Combined with recent data from specific heat measurements, the critical exponents suggest that the three-dimensional, three-states Potts model may describe the transition.Precursor spontaneous strain above T _c is consistent with local ordering and may result from fluctuations associated with an antiordered NO₃ group pair configuration.     

Uncertainties in differential thermodynamic (Gibbs' method) P-T paths

A combined analytical and numerical evaluation of the uncertainties in P-T paths is made for three assemblages that propagates errors in the parameters: initial pressure, initial temperature, initial composition, change of composition of monitor parameters, endmember entropy, and endmember volume. Propagated errors along an isobaric heating path (T=77°C) for assemblage 1 (Grt-Bt-Pl-Qtz-Ms-Chl-H₂O), using as monitor parameters the mole fractions of almandine, spessartine, grossular, and anorthite, and ignoring uncertainties in thermodynamic properties, are approximately ±320 bars (1) and ±8.3°C (1) if rim compositional uncertainties of 5% in major cations are assumed, or ±2.5°C (1) and ±50 bars (1) if electron microprobe analytical uncertainties are assumed for compositions. The largest source of uncertainty is from the errors in the monitor parameters, and P-T path uncertainties can depend critically on which monitor parameters are used. If the mole fraction of annite is used as a monitor parameter in place of the anorthite content of plagioclase, then propagated uncertainties are worse than ±29°C (1) and ±5800 bars (1). P-T path uncertainties also depend on assemblage. 1 precisions in assemblages 2 (Grt–Bt–Pl–Qtz–Ms–Sil–H₂O) and 3 (Grt–Bt–Qtz–Kfs–Sil–H₂O) using as monitor parameters the mole fractions of almandine, spessartine, grossular, and anorthite are calculated to be ±267 bars and ±43.4°C and ±372 bars and ±8.2°C respectively. Estimates of the accuracies in P-T paths that include potential errors in endmember entropy of ±1 J/mol·K and in endmember volume of ±1 cm³/mol are: ±324 bars and ±8.5°C (assemblage 1), ±341 bars and ±48.6°C (assemblage 2), and ±388 bars and ±9.7°C (assemblage 3). Use of different garnet, plagioclase, and muscovite activity models can change the length of a P-T path by as much as 15%, but does not typically change directions in P-T space significantly. Models that incorporate changes of fluid composition shorten P-T paths in assemblages 1 and 3 but do not change trajectories significantly. Assemblage 2 is virtually unaffected by fluid phase models. For the mineral assemblages considered here and using appropriate monitor parameters, propagated errors are small compared to the total path length, suggesting that the differential thermodynamic approach is a precise and accurate method for determining amounts of heating or thickening during metamorphism, and hence for interpreting orogenic processes.     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

The restricted stability of osumilite under hydrous conditions in the system K2O-MgO–Al2O3–SiO2–H2O

Osumilite_ss was synthesized as a single phase product in the model system K₂O-MgO-Al₂O₃-SiO₂ at 800° C/ 0.5 Kbar water pressure and at 800° to 840° C/1.0 Kbar total pressure with 0.3 in the gas phase. The experimentally determined solid solubility range of synthetic osumilites can be expressed by the formula KMg₂(Al_3-xMg_x) (Al_2–xSi_10+x)O₃₀ with 0x0.4. A survey of sixteen chemical analyses of natural osumilites from eleven occurrences shows a solid solubility characterized by 0x0.6. Reversed stability experiments for the synthetic osumilite KMg₂(Al_2.75Mg_0.25)(Al_1.75Si_10.25)O₃₀ determined at water pressure equal to total pressure demonstrate its restriction to water pressures below 0.8 Kbar (at 0.5 Kbar, the stability range is between 765° and 800° C). At the lower thermal stability limit osumilite+H₂O vapor break down to cordierite+K feldspar+phlogopite_ss+quartz, at the higher one to cordierite+K feldspar+phlogopite+liquid. Reduction of water fugacity will expand the stability field largely by shifting the lower and higher thermal stability limits to lower and higher temperatures, respectively. The dependence of osumilite stability on water fugacity makes osumilite a sensitive indicator mineral for dry conditions in rocks formed at total pressures higher than about 0.8 Kbar.     

Energy associated with dislocations: A calorimetric study using synthetic quartz

High temperature oxide melt solution calorimetry was used to study the energy associated with dislocations in quartz by comparing undeformed and deformed single crystals of synthetic quartz. Samples were deformed at 698 K, 1000–1500 MPa at a strain rate of 10^–5 sec^–1. Two sets of calorimetric measurements were made: (i) using a Pt capsule as a container for powdered sample, and (ii) using pellets made from sample powder without any container. For the first set of measurements, the undeformed sample with a dislocation density of enthalpy is sum of heat content H ₉₇₃-H ₂₉₅ and enthalpy of solution in molten lead borate at 973 K of 39.22 ± 1.00 kJ mol^–1, while the sample deformed in the dislocation creep regime with a dislocation density of 6 × 10¹⁰ to 1 × 10¹¹ cm^–2 gave an enthalpy of 38.59 ± 0.78 kJ mol^–1. For the second set of measurements the measured enthalpy of the undeformed sample was 38.87 ± 0.31 kJ mol^–1, and that of a deformed sample with a dislocation density of 3 × 10¹⁰ to 1 × 10¹¹ cm^–2 was 38.24 ± 0.58 kJ mol^–1.The present study and previous theoretical calculations and estimates are consistent and suggest that the energy associated with dislocations in quartz is 0.6 ± 0.6 kJ mol^–1 for a dislocation density of 10¹¹ cm^–2; a precise value is difficult to determine because of the overlapping errors. These results indicate that for geologically realistic dislocation densities, the maximum excess energy due to dislocations would be 0.5 kJ mol^–1 for most minerals; the exact value would depend on the Burgers vector as well as the shear modulus.     

An experimental calibration of the “Nickel in Garnet” geothermometer with applications

The partitioning of Ni between olivine and garnet in two multi-component compositions was studied as a function of temperature and pressure in a 6–8 type multi-anvil apparatus. Weighted least squares regression of the experimental results for both compositions give a temperature dependence for Ni partitioning between olivine (Ol) and garnet (Gt) of the form: T=–10210(±114)/[lnD _Gt/Ol ^Ni –3.59(±67)] where DGt/Ol/Ni=Ni content of Gt/Ni content of olivine (by weight) and Tis in Kelvin. The pressure effect on Ni exchange between olivine and garnet is estimated to be 0.13 J/bar, and should therefore have a negligible effect on the geothermometer, as is demonstrated in the experiments. The experimentally derived Ni in Gt geothermometer is in agreement with an extant empirical version between 1100 to 900°C, but the two thermometers produce significantly different results outside of this temperature range.     

The Blosseville Coast basalts of East Greenland: Their occurrence,composition and temporal variations

In the system CaO-MgO-A1₂O₃-SiO₂ the tie lines connecting anorthite with other phases are sequentially broken down with increasing pressure according to the following univariant reactions: anorthite+ enstatite_ss+sillimanite pyrope-grossular_ss+quartz (3), anorthite+enstatite_ss pyrope-grossular_ss+diopside_ss+quartz (2), anorthite+pyrope-grossular_ss+ quartz diopside_ss+kyanite (4) and anorthite+diopside_ss grossular-pyrope_ss +kyanite+quartz (8). At 1,200 ° C these reactions occur at 14.5± 0.5, 15.5±0.5, 19.5±0.5 and 26.4±1 kilobar and have positive slopes (dP/dT) of 1±0.5, 2.8±0.5, 13.3±0.5 and 24±2bars/°C respectively. An invariant point involving kyanite rather than sillimanite, occurs at 850 °C±25 °C and 14.5±0.5kbar at the intersection of reactions (3), (2) and (4). Reaction(4) exhibits significant curvature with an increase in dP/dT from 13.3±0.5 to 18.5± 0.5 bars/°C between 1,050° and 850° C. The pressure at which the complete grossular-pyrope join is stable with quartz is estimated at 41 ± 1 kbar at 1,200 ° C. The pressure at which garnet appears according to reaction (2) is lowered by 5 kbar for a composition with anorthite and orthopyroxene (En_0.5Fs_0.5). Enstatite and plagioclase (An_0.5Ab_0.5) first produce garnet at 2 kbar higher pressure than enstatite and pure anorthite (reaction (2)). The calcium content of garnet in various divariant assemblages is relatively insensitive to temperature but very sensitive to pressure, it is therefore a useful geobarometer. At metamorphic temperatures of 700–850 °C pressures of 8–10 kbar are required for the formation of quartz-bearing garnet granulites containing calcic plagioclase and with (Mg/Mg+Fe) bulk = 0.5.     

Determination of the principal reflectances of an absorbing uniaxial mineral,ilmenite, from measurements on random sections

We show the steps followed for obtaining the principal reflectances of an absorbing uniaxial mineral, ilmenite, by use of the inference method derived from statistical reflectance parameters of the sample. The values obtained in air, at 580 nm, with this method are: R =19.6±0.3 and R =17.8±0.3.     

Annite stability revised. 1. Hydrogen-sensor data for the reaction annite = sanidine + magnetite + H2

In P - T - logfO₂ space, the stability of annite (ideally KFe ₃ ²⁺ (OH)₂AlSi₃O₁₀) at high fO₂ (low fH₂) is limited by the reaction: annite = sanidine + magnetite + H₂. Using the hydrogen-sensor technique, the equilibrium fH₂ of this reaction was measured between 500 and 800° C at 2.8 kbar in 50° C intervals. Microbrobe analyses of the reacted annite+sanidine+magnetite mixtures show that tetrahedral positions of annite have a lower Si/Al ratio than the ideal value of 3/1. Silicon decreases from 2.9 per formula unit at low temperatures to 2.76 at high temperatures. As determined by Mössbauer spectroscopy in three experimental runs, the Fe³⁺ content of annite in the equilibrium assemblage is 11%±3. A least squares fit to the hydrogensensor data gives H _R ⁰ = 50.269 ± 3.987 kJ and S _R ⁰ = 83.01 ± 4.35 J/K for equilibrium (1). The hydrogene-sensor data are consistent with temperature half brackets determined in the classical way along the nickel-nickel oxide (NNO) and quartz-fayalite-magnetite (QFM) buffers with a mixture of annite+sanidine+magnetite for control. Compared to published oxygen buffer reversals, agreement is only found at high temperature and possible reasons for that discrepancy are discussed. The resulting slope of equilibrium (1) in logfO₂ – T dimensions is considerably steeper than previously determined and between 400 and 800°C only intersects with the QFM buffer curve. Based on the hydrogen-sensor data and on the thermodynamic dataset of Berman (1988, and TWEEQ data base) for sanidine, magnetite and H₂, the deduced standard-state properties of annite are: H _f ⁰ =-5127.376±5.279 kJ and S ⁰=422.84±5.29 J/(mol K). From the recently published unit cell refinements of annites and their Fe³⁺ contents, determined by Mössbauer spectroscopy (Redhammer et al. 1993), the molar volume of pure annite was constrained as 15.568±0.030 J/bar. A revised stability field for annite is presented, calculated between 400 and 800°C.     

Characteristics and chronology of fracture — fluid infiltration in the Archean,Eye Dashwa Lakes pluton,Superior Province: evidence from H,C, O-isotopes and fluid inclusions

The Archean Eye Dashwa Lakes pluton (2672±24 Ma) has domains of mineralogically fresh isotropic granite, domains that have undergone bulk hydrothermal alteration, and at least eleven sets of sequential fracture arrays, each with distinctive mineral assemblages. Fresh granite is characterized by whole rock ¹⁸O=8.1 to 8.6 and primary magmatic quartz-feldspar (+1.3), quartz-biotite (5.2 to 5.4) and quartz-magnetite (+9.8) fractionations. Magmatic fluids had a calculated isotopic composition of ¹⁸O=7.9±0.5, and D=–80±5. These isotropic volumes of the granite have not experienced significant incursion of external thermal waters. Pegmatites, quartz-molybdenite veins, and phlogopite-muscovite coated fractures are sporadically distributed in the granite, and were precipitated from high-temperature magmatic fluids where ¹⁸O=8.0 to 10.3 and D=–80±5.The most abundant variety of fracture filling assemblage is epidote-quartz-chlorite±muscovite: fractures are bounded by domains of mineralogically similar bulk hydrothermal alteration of the granite. These minerals formed at 160 to 280° C, in the presence of NaCl, and NaCl-MgCl₂ brines (up to 25 wt% NaCl equivalent) of probable evolved marine water origin ( ¹⁸O=+0.4 to +3.8, D=–10 to –35) undergoing transient boiling. Upper plateau ⁴⁰Ar/³⁹Ar ages for the muscovite are 2650±15 Ma. Sequentially in the chronology of fracture-infiltration events, calcite-fluorite veins were deposited from boiling fluids at 340 to 390° C, isotopically characterized by ¹⁸O=4.7 and ¹³C=–5; and rare prehnite-chlorite lined fractures formed at 250 to 290° C. A generation of adularia-bearing veins precipitated at 140 to 230° C, from CaCl₂-NaCl brines, where ¹⁸O=0 to –6.5 and D=–10 to –30. Incremental ⁴⁰Ar/³⁹Ar age spectra on the K-feldspar yield an upper plateau of 1100 Ma. Subsequently, hematite developed during reactivation of earlier fractures, at 140 to 210° C in the presence of fluids characterized by ¹⁸O=–0.4 to –5.4 and D=–15 to –25. Arrays of open fractures partially occupied by gypsum and goethite reflect a fluid infiltration event at temperatures <50° C. Many of the earlier generations of fracture minerals have transgranular fracture infillings which record the presence of low temperature (88–190° C), hypersaline CaCl₂-NaCl brines. Narrow fractures lined with clays±calcite are sites for seepage of modern ground-waters. The isotopic signature of clay ( ¹⁸O=12 to 20, D=–80±5) plots near the line for modern kaolinites, confirming its formation in the presence of recent surface waters. Calcites coexisting with the clay minerals, and in fractured pegmatite show a common isotopic signature ( ¹⁸O=23±0.5, ¹³C=–13.6), indicating precipitation from modern groundwaters, where reactivated fractures have acted as conduits for infiltration of surface waters to depths of 200 m. Intermittent fracture-infiltration has occurred over 2.7 Ga. The early sequences of fracture-related fluid flow are interpreted in terms of devolatilization of the granite, followed by thermal contraction fracturing, incursion of marine water and convective cooling in the Archean. Hematite and adularia fracture fillings correspond to a stage when meteoric water infiltrated the volcanicplutonic terrain during Proterozoic and later times. Episodic fracture-fluid expulsion events may have been driven by seismic pumping, in response to magmatically and tectonically induced stresses within the Shield, with surface waters penetrating to depths of 15 km in the crust.