Crystallographic preferred orientation in wüstite (FeO) through the cubic-to-rhombohedral phase transition

Magnesiowüstite, (Mg_0.08Fe_0.88)O, and wüstite, Fe_0.94O, were compressed to ~36?GPa at ambient temperature in the diamond anvil cell (DAC) at the Advanced Light Source. X-ray diffraction patterns were taken in situ in radial geometry in order to study the evolution of crystallographic preferred orientation through the cubic-to-rhombohedral phase transition. Under uniaxial stress in the DAC, {100}_c planes aligned perpendicular to the compression direction. The {100}_c in cubic became { $\left\{ {10\bar 14} \right\}$ }_r in rhombohedral and remained aligned perpendicular to the compression direction. However, the {101}_c and {111}_c planes in the cubic phase split into { ${10{\bar{1}}4}$ }_r and { ${11{\bar{2}}0}$ }_r, and (0001)_r and { ${10{\bar{1}}1}$ }_r, respectively, in the rhombohedral phase. The { ${11{\bar{2}}0}$ }_r planes preferentially aligned perpendicular to the compression direction while { ${10{\bar{1}}4}$ }_r oriented at a low angle to the compression direction. Similarly, { ${10{\bar{1}}1}$ }_r showed a slight preference to align more closely perpendicular to the compression direction than (0001)_r. This variant selection may occur because the 〈 ${10{\bar{1}}4}$ 〉_r and [0001]_r directions are the softer of the two sets of directions. The rhombohedral texture distortion may also be due to subsequent deformation. Indeed, polycrystal plasticity simulations indicate that for preferred { ${10{\bar{1}}4}$ }〈 ${1{\bar{2}}10}$ 〉_r and { ${11{\bar{2}}0}$ }〈 ${{\bar{1}}101}$ 〉_r slip and slightly less active { ${10{\bar{1}}1}$ }〈 ${{\bar{1}}2{\bar{1}}0}$ 〉_r slip, the observed texture pattern can be obtained.     

Analysis of dislocations in some naturally deformed plagioclase feldspars

Dislocations in intermediate plagioclase feldspars, which were deformed under granulite facies conditions, have been analysed. The study reveals extensive ductile deformation by intracrystalline slip and by twinning. Six out of the seven possible Burgers vectors were identified: \(b = \left[ {001} \right],\tfrac{1}{2}\left[ {110} \right],\tfrac{1}{2}\left[ {1\bar 10} \right],\left[ {101} \right],\tfrac{1}{2}\left[ {112} \right]and\tfrac{1}{2}\left[ {1\bar 12} \right]\) . Most, perhaps all, dislocations are dissociated by up to 200 Å. The microstructure is dominated by [001] screw dislocations, most of which appear to be dissociated in (010). The dominant slip system appears to be (010) [001]. Large grain-to-grain variations in the density of free dislocations indicate that the plastic strain in individual grains depended upon the Schmid factor for (010) [001]. The microstructure suggests that the rate-controlling step for high-temperature creep of plagioclase is cross-slip of extended [001] screw dislocations. The rheological contrast between feldspar and quartz is partly due to a difference in stacking fault energy.     

Experimental study of subsolidus phase relations and mixing properties of pyroxene and plagioclase in the system Na2O-CaO-Al2O3-SiO2

In the system Na₂O-CaO-Al₂O₃-SiO₂ (NCAS), the equilibrium compositions of pyroxene coexisting with grossular and corundum were experimentally determined at 40 different P-T conditions (1,100–1,400° C and 20.5–38 kbar). Mixing properties of the Ca-Tschermak — Jadeite pyroxene inferred from the data are (J, K): $$\begin{gathered} G_{Px}^{xs} = X_{{\text{CaTs}}} X_{{\text{Jd}}} [14,810 - 7.15T - 5,070(X_{{\text{CaTs}}} - X_{{\text{Jd}}} ) \hfill \\ {\text{ }} - 3,350(X_{{\text{CaTs}}} - X_{{\text{Jd}}} )^2 ] \hfill \\ \end{gathered} $$ The excess entropy is consistent with a complete disorder of cations in the M2 and the T site. Compositions of coexisting pyroxene and plagioclase were obtained in 11 experiments at 1,190–1,300° C/25 kbar. The data were used to infer an entropy difference between low and high anorthite at 1,200° C, corresponding to the enthalpy difference of 9.6 kJ/mol associated with the C \(\bar 1\) =I \(\bar 1\) transition in anorthite as given by Carpenter and McConnell (1984). The resulting entropy difference of 5.0 J/ mol · K places the transition at 1,647° C. Plagioclase is modeled as ideal solutions, C \(\bar 1\) and I \(\bar 1\) , with a non-first order transition between them approximated by an empirical expression (J, bar, K): $$\Delta G_T = \Delta G_{1,473} \left[ {1 - 3X_{Ab} \tfrac{{T^4 - 1,473^4 }}{{\left( {1,920 - 0.004P} \right)^4 - 1,473^4 }}} \right],$$ where $$\Delta G_{1,473} = 9,600 - 5.0T - 0.02P$$ The derived mixing properties of the pyroxene and plagioclase solutions, combined with the thermodynamic properties of other phases, were used to calculate phase relations in the NCAS system. Equilibria involving pyroxene+plagioclase +grossular+corundum and pyroxene+plagioclase +grossular+kyani te are suitable for thermobarometry. Albite is the most stable plagioclase.     

Intergrowth of pyroxene and pyroxenoid; chain periodicity faults in pyroxene

Intergrowth of clinopyroxenes (augite, A) and pyroxenoids (Fe-rhodonite and pyroxferroite, Pxo) was observed by transmission electron microscopy. The following orientation relationship was found: (001)_Pxo is parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)_{\text{A}}\) and \([1\bar 10]_{Pxo}\) is parallel to [011]_A. This relationship can be explained by similarities of the structures of clinopyroxenes and pyroxenoids. It contradicts a suggestion based on structural arguments of Koto et al. (1976). Chain periodicity faults parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)\) are also observed in pure clinopyroxenes.     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

Energetics of hydration of cordierite and water barometry in cordierite-granulites

The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P _total, assuming an ideal one site model for H₂O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H₂O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H₂O and CO₂ in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P_total, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.     

The Activity of H2O,Fugacity of O2 and Variation of Their Chemical Potential During Metamorphic Peak of the Granulite Complex Near Taipingzhai—Louzishan Region,East Hebei Province

The thermodynamic calculation of dehydration reacton suggests very low activity of H2O during metamorphic peak of the Archaean granulite complex in the region studied.The αH2O values for Al-rich gneiss and hypersthene biotite gneiss-granulite in the Taipingzhai region are usually between 0.10 and 0.20,and those in the Louzishan region are 0.15-0.25.The fugacity of O2 in terms of lgf O2 in whole region ranges form-8to-14.The average coefficients of (δμH2O/δHMg^Bt)and(δμO2/δXMg^Bt)in the Taipingzhai region are-0.293 and-1.60 respectively,and those in the Louzishan region are-0.364and-1.420.The activity of H2O is very low in the whole region,but its values and other data mentioned above are considerably constant from place to place within a given region,even in rocks of dirrerent lithological characters.However,they show a certain gradient between different regions.Such characteristics are compatible with the genetic mechanism known as“carbonic metamorphism” put forward by Newton et al.,i.e.,the α H2O during the peak stage is controlled by permeation of pervasive CO2 influx of the mantle source,and shows features of external buffering.     

Thermochemical and pressure-volume-temperature systematics of data on solids,examples: Tungsten and MgO

Data systematization using the constraints from the equation $$Cp = Cv + \alpha _P {}^2V_T K_T T$$ where C _p, C _v, α _p, K _T and V are respectively heat capacity at constant pressure, heat capacity at constant volume, isobaric thermal expansion, isothermal bulk modulus and molar volume, has been performed for tungsten and MgO. The data are $$K_T (W) = 1E - 5/(3.1575E - 12 + 1.6E - 16T + 3.1E - 20T^2 )$$ $$\alpha _P (W) = 9.386E - 6 + 5.51E - 9T$$ $$C_P (W) = 24.1 + 3.872E - 3T - 12.42E - 7T^2 + 63.96E - 11T^3 - 89000T^{ - 2} $$ $$K_T (MgO) = 1/(0.59506E - 6 + 0.82334E - 10T + 0.32639E - 13T^2 + 0.10179E - 17T^3 $$ $$\alpha _P (MgO) = 0.3754E - 4 + 0.7907E - 8T - 0.7836/T^2 + 0.9148/T^3 $$ $$C_P (MgO) = 43.65 + 0.54303E - 2T - 0.16692E7T^{ - 2} + 0.32903E4T^{ - 1} - 5.34791E - 8T^2 $$ For the calculation of pressure-volume-temperature relation, a high temperature form of the Birch-Murnaghan equation is proposed $$P = 3K_T (1 + 2f)^{5/2} (1 + 2\xi f)$$ Where $$K_T = 1/(b_0 + b_1 T + b_2 T^2 + b_3 T^3 )$$ $$f = (1/2)\{ [V(1,T)/V(P,T)]^{2/3} - 1\} $$ $$\xi = ({3 \mathord{\left/ {\vphantom {3 4}} \right. \kern-\nulldelimiterspace} 4})[K'_0 + K'_1 \ln ({T \mathord{\left/ {\vphantom {T {300}}} \right. \kern-\nulldelimiterspace} {300}}) - 4]$$ where in turn $$V(1,T) = V_0 [\exp (\int\limits_{300}^T {\alpha dT)]} $$ . The temperature dependence of the pressure derivative of the bulk modulus (K′₁) is estimated by using the shock-wave data. For tungsten the data are K′₀ = 3.5434, K′₁ = 0.032; for MgO K′₀ = 4.17 and K′₁ = 0.1667. For calculating the Gibbs free energy of a solid at high pressure and at temperatures beyond that of melting at 1 atmosphere, it is necessary to define a high-temperature reference state for the fictive solid.     

The system Fe-Si-O: Oxygen buffer calibrations to 1,500K

The five solid-phase oxygen buffers of the system Fe-Si-O, iron-wuestite (IW), wuestite-magnetite (WM), magnetite-hematite (MH), quartz-iron-fayalite (QIF) and fayalite-magnetite-quartz (FMQ) have been recalibrated at 1 atm pressure and temperatures from 800°–1,300° C, using a thermogravimetric gas mixing furnace. The oxygen fugacity, \(f_{{\text{O}}_{\text{2}} }\) was measured with a CaO-doped ZrO₂ electrode. Measurements were made also for wuestite solid solutions in order to determine the redox behavior of wuestites with O/Fe ratios varying from 1.05 to 1.17. For FMQ, additional determinations were carried out at 1 kb over a temperature range of 600° to 800° C, using a modified Shaw membrane. Results agree reasonably well with published data and extrapolations. The reaction parameters K, ΔG _r ^o , ΔH _r ^o , and ΔS _r ^o were calculated from the following log \(f_{{\text{O}}_{\text{2}} }\) /T relations (T in K): $$\begin{gathered} {\text{IW }}\log f_{{\text{O}}_{\text{2}} } = - 26,834.7/T + 6.471\left( { \pm 0.058} \right) \hfill \\ {\text{ }}\left( {{\text{800}} - 1,260{\text{ C}}} \right), \hfill \\ {\text{WM }}\log f_{{\text{O}}_{\text{2}} } = - 36,951.3/T + 16.092\left( { \pm 0.045} \right) \hfill \\ {\text{ }}\left( {{\text{1,000}} - 1,300{\text{ C}}} \right), \hfill \\ {\text{MH }}\log f_{{\text{O}}_{\text{2}} } = - 23,847.6/T + 13.480\left( { \pm 0.055} \right) \hfill \\ {\text{ }}\left( {{\text{1,040}} - 1,270{\text{ C}}} \right), \hfill \\ {\text{QIF }}\log f_{{\text{O}}_{\text{2}} } = - 27,517.5/T + 6.396\left( { \pm 0.049} \right) \hfill \\ {\text{ }}\left( {{\text{960}} - 1,140{\text{ C}}} \right), \hfill \\ {\text{FMQ }}\log f_{{\text{O}}_{\text{2}} } = - 24,441.9/T + 8.290\left( { \pm 0.167} \right) \hfill \\ {\text{ }}\left( {{\text{600}} - 1,140{\text{ C}}} \right). \hfill \\ \end{gathered}$$ These experimentally determined reaction parameters were combined with published 298 K data to determine the parameters G_f, H_f, and S_f for the phases wuestite, magnetite, hematite, and fayalite from 298 K to the temperatures of the experiments. The T? \(f_{{\text{O}}_{\text{2}} }\) data for wuestite solid solutions were used to obtain activities, excess free energies and Margules mixing parameters. The new data provide a more reliable, consistent and complete reference set for the interpretation of redox reactions at elevated temperatures in experiments and field settings encompassing the crust, mantle and core as well as extraterrestrial environments.     

High temperature calorimetry of sulfide systems

The standard enthalpies of formation of FeS (troilite), FeS₂ (pyrite), Co_0.9342S, Co₃S₄ (linnaeite), Co₉S₈ (cobalt pentlandite), CoS₂ (cattierite), CuS (covellite), and Cu₂S (chalcocite) have been determined by high temperature direct reaction calorimetry at temperatures between 700 K and 1021 K. The following results are reported: $$\Delta {\rm H}_{f,FeS}^{tr} = - 102.59 \pm 0.20kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,FeS}^{py} = - 171.64 \pm 0.93kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_{0.934} S} = - 99.42 \pm 1.52kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_9 S_8 }^{ptl} = - 885.66 \pm 16.83kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_3 S_4 }^{In} = - 347.47 \pm 7.27kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,CoS_2 }^{ct} = - 150.94 \pm 4.85kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Cu_2 S}^{cc} = - 80.21 \pm 1.51kJ mol^{ - 1} ,$$ and $$\Delta {\rm H}_{f,CuS}^{cv} = - 53.14 \pm 2.28kJ mol^{ - 1} ,$$ The enthalpy of formation of CuFeS₂ (chalcopyrite) from (CuS+FeS) and from (Cu+FeS₂) was determined by solution calorimetry in a liquid Ni_0.60S_0.40 melt at 1100 K. The results of these measurements were combined with the standard enthalpies of formation of CuS, FeS, and FeS₂, to calculate the standard enthalpy of formation of CuFeS₂. We found \(\Delta {\rm H}_{f,CuFeS_2 }^{ccp} = - 194.93 \pm 4.84kJ mol^{ - 1}\) . Our results are compared with earlier data given in the literature; generally the agreement is good and our values agree with previous estimates within the uncertainties present in both.     

Cation stacking faults in magnesium germanate spinel

Widely extended, cation stacking faults in experimentally deformed Mg₂GeO₄ spinel have been studied using transmission electron microscopy (TEM). The faults lie on {110} planes. The displacement vector is of the form \(\frac{1}{4}\left\langle {1\bar 10} \right\rangle \) and is normal to the fault plane. The partial dislocations which bound the stacking fault have colinear Burgers vectors of the form \(\frac{1}{4}\left\langle {1\bar 10} \right\rangle \) which are normal to the fault plane.     

Raman spectroscopic investigation of the order parameter behaviour in hypersolvus alkali feldspar: Displacive phase transition and evidence for Na-K site ordering

Hard mode Raman spectroscopy (HMRS) on hypersolvus alkali feldspar shows a temperature dependence of the order parameter of the displacive \({{C2} \mathord{\left/ {\vphantom {{C2} {m{\text{ - }}C\bar 1}}} \right. \kern-0em} {m{\text{ - }}C\bar 1}}\) phase transition following mean-field behaviour: $$Q \sim \sqrt {T_c - T;} 300 {\text{K}} \lesssim T< T_c $$ At lower temperatures, a spontaneous saturation sets in, which is attributed to site-ordering effects of the alkali atoms even in hypersolvus anorthoclase. Fluctuational line broadening of Si-O viration bands is explained by strong lattice distortions around alkali positions and local deformation of the Al,Si,O network. The thermodynamic relevance of these distortions is discussed in relation to the possibility of an additional diffuse phase transition occurring atT _d =302 K. The experimental results of HMRS are compared with those on Al,Si ordered and disordered albite, where no fluctuation broadening occurs.     

Interaction of B(OH)_3^0 and HCO_3^ - in Seawater: Formation of B(OH)_2 CO_3^ -

Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)₂L^-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$ The formation constant for this reaction at 25 °C and 0.7 molkg^-1 ionic strength is $K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)₂ $CO_3^ - $ concentration inseawater at 25 °C is on the order of 2 μmol kg^-1. Dueto the presence of B(OH)₂ $CO_3^ - $ , theboric acid dissociation constant ( $K\prime _B $ ) in natural seawaterdiffers from $K\prime _B $ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO₂ fugacity, pH, totalcarbon and alkalinity in seawater.     

Multiple-pumped-well aquifer test to determine the anisotropic properties of a karst limestone aquifer in Pasco County, Florida, USA

Groundwater-level data from an aquifer test utilizing four pumped wells conducted in the South Pasco wellfield in Pasco County, Florida, USA, were analyzed to determine the anisotropic transmissivity tensor, storativity, and leakance in the vicinity of the wellfield. A weighted least-squares procedure was used to analyze drawdowns measured at eight observation wells, and it was determined that the major axis of transmissivity extends approximately from north to south and the minor axis extends approximately from west to east with an angle of anisotropy equal to N4.54°W. The transmissivity along the major axis ${\left( {T_{{\xi \xi }} } \right)}$ is 14,019 m² day^–1, and the transmissivity along the minor axis ${\left( {T_{{\eta \eta }} } \right)}$ is 4,303 m² day^–1. The equivalent transmissivity $T_{e} = {\left( {T_{{\xi \xi }} T_{{\eta \eta }} } \right)}^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} = 7,767{{\text{m}}^{2} } \mathord{\left/ {\vphantom {{{\text{m}}^{2} } {{\text{day}}^{{ - {\text{1}}}} }}} \right. \kern-0em} {{\text{day}}^{{ - {\text{1}}}} }$ , and the ratio of anisotropy is 3.26. The storativity of the aquifer is 7.52?×?10^?4, and the leakance of the overlying confining unit is 1.37?×?10^?4 day^?1. The anisotropic properties determined for the South Pasco wellfield in this investigation confirm the results of previous aquifer tests conducted in the wellfield and help to quantify the NW–SE to NE–SW trends for regional fracture patterns and inferred solution-enhanced flow zones in west-central Florida.     

The reversed alumina contents of orthopyroxene in equilibrium with spinel and forsterite in the system MgO-Al2O3-SiO2

Equilibrium alumina contents of orthopyroxene coexisting with spinel and forsterite in the system MgO-Al₂O₃-SiO₂ have been reversed at 15 different P-T conditions, in the range 1,030–1,600° C and 10–28 kbar. The present data and three reversals of Danckwerth and Newton (1978) have been modeled assuming an ideal pyroxene solid solution with components Mg₂Si₂O₆ (En) and MgAl₂SiO₆ (MgTs), to yield the following equilibrium condition (J, bar, K): $$\begin{gathered} RT{\text{ln(}}X_{{\text{MgTs}}} {\text{/}}X_{{\text{En}}} {\text{) + 29,190}} - {\text{13}}{\text{.42 }}T + 0.18{\text{ }}T + 0.18{\text{ }}T^{1.5} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [0.013 + 3.34 \times 10^{ - 5} (T - 298) - 6.6 \times 10^{ - 7} P]P. \hfill \\ \end{gathered} $$ The data of Perkins et al. (1981) for the equilibrium of orthopyroxene with pyrope have been similarly fitted with the result: $$\begin{gathered} - RT{\text{ln(}}X_{{\text{MgTs}}} \cdot X_{{\text{En}}} {\text{) + 5,510}} - 88.91{\text{ }}T + 19{\text{ }}T^{1.2} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [ - 0.832 - 8.78{\text{ }} \times {\text{ 10}}^{ - {\text{5}}} (T - 298) + 16.6{\text{ }} \times {\text{ 10}}^{ - 7} P]{\text{ }}P. \hfill \\ \end{gathered} $$ The new parameters are in excellent agreement with measured thermochemical data and give the following properties of the Mg-Tschermak endmember: $$H_{f,970}^0 = - 4.77{\text{ kJ/mol, }}S_{298}^0 = 129.44{\text{ J/mol}} \cdot {\text{K,}}$$ and $$V_{298,1}^0 = 58.88{\text{ cm}}^{\text{3}} .$$ The assemblage orthopyroxene+spinel+olivine can be used as a geothermometer for spinel lherzolites, subject to a choice of thermodynamic mixing models for multicomponent orthopyroxene and spinel. An ideal two-site mixing model for pyroxene and Sack's (1982) expressions for spinel activities provide, with the present experimental calibration, a geothermometer which yields temperatures of 800° C to 1,350° C for various alpine peridotites and 850° C to 1,130° C for various volcanic inclusions of upper mantle origin.     

Transmission electron microscopy of experimentally deformed chalcopyrite single crystals

Two crystals of natural chalcopyrite, CuFeS₂, experimentally deformed at 200° C have been studied by means of transmission electron microscopy (TEM). The activated glide planes are (001) and {112}. The dislocations in (001) have the Burgers vector [110] and a predominating edge character. They are split into two colinear partials b=1/2[110] and can cross split into {112}. The dislocations in {112} consist of straight segments along low index lattice lines. They are often arranged in dipoles generating trails of loops. Few dislocations with b=1/2[ \(\overline {11} \) 1] and [1 \(\bar 1\) 0] are present and dislocations with b=[0 \(\bar 2\) 1] occur in low angle subgrain boundaries. From weak beam contrasts it is presumed that most of the dislocations gliding in {112} have b=1/2〈3 \(\overline {11} \) 〉. They are dissociated into up to four partials. Microtwins and different types of stacking faults in {112} also occur. Models of the dissociation of dislocations are discussed.     

Transmission electron microscope study of experimentally deformed K-Feldspar single crystals

Single crystals of sanidine which were experimentally deformed so as to introduce the (010)[100] slip system were examined by transmission electron microscopy (tem). Dislocation glide is mainly manifested in the samples deformed at 700° C, with a strain rate \(\dot \varepsilon = 1 - 2 \times 10^{ - 6} s^{ - 1} \) . In addition to the expected slip system another more important one, (12 \(\bar 1\) )[101], was found. The dislocations lying in (010) present a glissile dissociation. These observations have been discussed in term of the feldspar structure. Models for glissile dissociation in (010) are proposed: [100]=1/2[100]+1/2[100] or 1/2[101]+1/2[10 \(\bar 1\) ] and [101]=1/2[101]+1/2[101].     

An experimental study of the partitioning of Fe and Mg between garnet and orthopyroxene

The partitioning of Fe and Mg between garnet and aluminous orthopyroxene has been experimentally investigated in the pressure-temperature range 5–30 kbar and 800–1,200° C in the FeO-MgO-Al₂O₃-SiO₂ (FMAS) and CaO-FeO-MgO-Al₂O₃-SiO₂ (CFMAS) systems. Within the errors of the experimental data, orthopyroxene can be regarded as macroscopically ideal. The effects of Calcium on Fe-Mg partitioning between garnet and orthopyroxene can be attributed to non-ideal Ca-Mg interactions in the garnet, described by the interaction term:W _CaMg ^ga -W _CaFe ^ga =1,400±500 cal/mol site. Reduction of the experimental data, combined with molar volume data for the end-member phases, permits the calibration of a geothermometer which is applicable to garnet peridotites and granulites: $$T(^\circ C) = \left\{ {\frac{{3,740 + 1,400X_{gr}^{ga} + 22.86P(kb)}}{{R\ln K_D + 1.96}}} \right\} - 273$$ with $$K_D = {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } \mathord{\left/ {\vphantom {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}} \right. \kern-\nulldelimiterspace} {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}$$ and $$X_{gr}^{ga} = (Ca/Ca + Mg + Fe)^{ga} .$$ The accuracy and precision of this geothermometer are limited by largerelative errors in the experimental and natural-rock data and by the modest absolute variation inK _D with temperature. Nevertheless, the geothermometer is shown to yield reasonable temperature estimates for a variety of natural samples.     

Light scattering in jadeite melt: Strain relaxation measurements by photon correlation spectroscopy

Photon correlation spectroscopy has been applied to the study of longitudinal strain relaxation of vitreous Jadeite (NaAlSi₂O₆) in the temperature range 811–1014° C. The correlation function $\left| {g^{\left( 1 \right)} \left. {\left( t \right)} \right|^2 \propto \exp \left( {\left( { - 2t/\tau _\beta } \right)^\beta } \right)} \right.$ obeys a Kohlrausch type function with β=0.64±0.01. Individual correlation functions fit altogether a master relaxation curve, thus demonstrating thermorheological simplicity (TRS). The temperature dependence of the measured relaxation times shows Arrhenian behaviour with $\log \left( \tau \right) = - 21.4 \pm 0.3{\text{s}} {\text{ + }} {\text{471}}{\text{.6}} \pm {\text{22}} {\text{kJmol}}^{{\text{ - 1}}} /RT$ . The time scale of longitudinal strain relaxation is consistent with the existing data on shear relaxation derived from shear viscosity and structural relaxation calculated from calorimetric C _pmeasurements. Comparison with oxygen diffusion indicates that network forming elements relax at about the same time scale as viscoelastic properties. On the other hand, Na⁺ relaxation times derived from impedance spectroscopy are short compared to viscoelastic relaxation times at low temperatures. This difference is decreasing with increasing temperature and possibly disappearing at approximately 1100° C.     

The origin of mafic rocks in the Naqadeh intrusive complex, Sanandaj-Sirjan Zone, NW Iran

The Naqadeh mafic plutonic rocks are located on a plutonic assemblage and include different granitoid rocks related to ～40 Ma. U-Pb SHRIMP data shows different ages of 96?±?2.3 Ma for mafic rocks. Naqadeh mafic plutonic rocks consist of diorite to diorite-gabbros with relatively high contents of incompatible elements, low Na2O, and $ {\hbox{Mg\# }} = \left[ {{\hbox{molar}}\;{100} \times {\hbox{MgO/}}\left( {{\hbox{MgO}} + {\hbox{FeO}}} \right)} \right] > 44.0 $ . These features suggest that the Naqadeh mafic rocks originate from enriched lithospheric mantle above subducted slab during Neotethys subduction under Iranian plate.