Geochemical, Sr–Nd and zircon U–Pb–Hf isotopic studies of Late Carboniferous magmatism in the West Junggar, Xinjiang: Implications for ridge subduction?

Voluminous granitic intrusions are distributed in the West Junggar, NW China, and they can be classified as the dioritic rocks, charnockite and alkali-feldspar granite groups. The dioritic rocks (SiO₂ = 50.4–63.8 wt.%) are calc-alkaline and Mg enriched (average MgO = 4.54 wt.%, Mg^# = 0.39–0.64), with high Sr/Y ratios (average = 21.2), weak negative Eu (average Eu/Eu = 0.80) and pronounced negative Nb–Ta anomalies. Their Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7035–0.7042, ε_Nd(t) = 4.5–7.9, ε_Hf(t) = 14.1–14.5) show a depleted mantle-like signature. These features are compatible with adakites derived from partial melting of subducted oceanic crust that interacted with mantle materials. The charnockites (SiO₂ = 60.0–65.3 wt.%) show transitional geochemical characteristics from calc-alkaline to alkaline, with weak negative Eu (average Eu/Eu = 0.75) but pronounced negative Nb–Ta anomalies. Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7037–0.7039, ε_Nd(t) = 5.2–8.0, ε_Hf(t) = 13.9–14.7) also indicate a depleted source, suggesting melts from a hot, juvenile lower crust. Alkali-feldspar granites (SiO₂ = 70.0–78.4 wt.%) are alkali and Fe-enriched, and have distinct negative Eu and Nb–Ta anomalies (average Eu/Eu = 0.26), low Sr/Y ratios (average = 2.11), and depleted Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7024–0.7045, ε_Nd(t) = 5.1–8.9, ε_Hf(t) = 13.7–14.2). These characteristics are also comparable with those of rocks derived from juvenile lower crust. Despite of the differences in petrology, geochemistry and possibly different origins, zircon ages indicate that these three groups of rocks were coevally emplaced at ~ 305 Ma.A ridge subduction model can account for the geochemical characteristics of these granitoids and coeval mafic rocks. As the “slab window” opened, upwelling asthenosphere provided enhanced heat flux and triggered voluminous magmatisms: partial melting of the subducting slab formed the dioritic rocks; partial melting of the hot juvenile lower crust produced charnockite and alkali-feldspar granite, and partial melting in the mantle wedge generated mafic rocks in the region. These results suggest that subduction was ongoing in the Late Carboniferous and, thus support that the accretion and collision in the Central Asian Orogenic Belt took place in North Xinjiang after 305 Ma, and possibly in the Permian.     

Numerical modeling of three-dimensional contaminant migration from dissolution of multicomponent NAPL pools in saturated porous media

A three-dimensional model for contaminant transport resulting from the dissolution of multicomponent nonaqueous phase liquid (NAPL) pools in three-dimensional saturated subsurface formations is developed. The solution is obtained numerically by a finite-difference scheme, and it is suitable for homogeneous porous media with unidirectional interstitial velocity. Each dissolved component may undergo first-order decay and may sorb under local equilibrium conditions. It is also assumed that the dissolution process is mass transfer limited. The nonaqueous phase activity coefficients of the NAPL pool components are evaluated at each time step. The model behavior is illustrated through a synthetic example with a NAPL pool consisting of a mixture of TCA (1,1,2-trichloroethane) and TCE (trichloroethylene). The numerical solution presented in this work is in good agreement with a recently developed analytical solution for the special case of a single component NAPL pool. The results indicate the importance of accounting for the necessary changes in the organic phase activity which significantly affects the equilibrium aqueous solubility.Notation C liquid phase solute concentration (solute mass/liquid volume) (M L^–3) - C _s single component aqueous saturation concentration (solubility) (M L^–3) - C ^w equilibrium aqueous solubility (M L^–3) - D molecular diffusion coefficient (L² t ^–1) - D _e effective molecular diffusion coefficient (L² t ^–1) - D _x longitudinal hydrodynamic dispersion coefficient (L² t ^–1) - D _y lateral hydrodynamic dispersion coefficient (L² t ^–1) - D _z hydrodynamic dispersion coefficient in the vertical direction (L² t ^–1) - I() integer mode arithmetic operator - k local mass transfer coefficient (Lt ^–1) - k ^* average mass transfer coefficient (Lt ^–1) - L length - l _x ,l _y pool dimensions inx andy directions (L) - ll _x ,l _y x andy Cartesian coordinates of the pool origin (L) - M number of moles remaining in a pool (moles) - M initial number of moles (moles) - n finite-difference scheme time level - R retardation factor (dimensionless) - t time (t) - U _x average interstitial velocity (Lt ^–1) - x, y, z spatial Cartesian coordinates (L) - X dimensionless mole fraction - dimensionless activity coefficient - _w viscosity of water (=0.8904 cp at 25°C) - decay coefficient (t ^–1) - ^* tortuosity ( 1) - i,j, k finite-difference scheme grid indicators - p component number indicator - P total number of components - s pure single component - o nonaqueous phase - w aqueous phase     

A distribution-free alternative to least-squares regression and its application to Rb/Sr isochron calculations

A distribution-free estimator of the slope of a regression line is introduced. This estimator is designated S_m and is given by the median of the set of n(n – 1)/2 slope estimators, which may be calculated by inserting pairs of points (X _i, Y_i)and (X _j, Y_j)into the slope formula S _i = (Y _i – Y_j)/(X _i – X_j),1 i < j n Once S _m is determined, outliers may be detected by calculating the residuals given by R_i = Y_i – S_mX_i where 1 i n, and chosing the median R_m. Outliers are defined as points for which |R_i – R_m| > k (median {|R _i – R_m|}). If no outliers are found, the Y-intercept is given by R_m. Confidence limits on R_m and S_m can be found from the sets of R_i and S_i, respectively. The distribution-free estimators are compared with the least-squares estimators now in use by utilizing published data. Differences between the least-squares and distribution-free estimates are discussed, as are the drawbacks of the distribution-free techniques.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

Cation diffusion in aluminosilicate garnets: experimental determination in spessartine-almandine diffusion couples,evaluation of effective binary diffusion coefficients,and applications

We present new experimental data on diffusion of divalent cations in almandine-spessartine diffusion couples in graphite capsules in the P-T range of 14–35 kb, 1100–1200° C. The tracer diffusion coefficients of the major divalent cations, viz. Fe, Mg and Mn, retrieved from the multicomponent diffusion profiles, have been combined with earlier data from our laboratory at 29–43 kb, 1300–1480° C (Loomis et al. 1985) to derive expressions of the P-T dependence of the diffusion coefficients at fO₂ approximately corresponding to that defined by equilibrium in the system graphite-O₂. We review the conditions, discussed earlier by Cooper, under which the flux of a component in a multicomponent system becomes proportional to its concentration gradient (Fickian diffusion), as if the entire solvent matrix behaves as a single component, and also suggest a method of incorporating the thermodynamic effect on diffusion in the same spirit. Regardless of the magnitude or sign of the off-diagonal terms of the D matrix, it is always possible to define an effective binary diffusion coefficient (EBDC) of a component in a semi-infinite multicomponent diffusion-couple experiment such that it has the property of the Fickian diffusion coefficient, provided that there is no inflection on the diffusion profiles. It is shown that the success of Elphick et al. in fitting the experimental diffusion profiles of all components over a limited concentration range by a single diffusion coefficient is due to fortuitous similarity of the EBDCs of the components (Fe, Mg, Mn and Ca) in their diffusion couple experiments. In common metapelitic garnets showing compositional zoning, the EBDCs of the divalent cations do not differ from each other by more than a factor of 2.5. However, the EBDC of a component changes from core to rim by a factor of 3 to 12, depending on the composition. We suggest a method of volume averaging of the EBDC which should prove useful in approximate calculations of diffusion flux during relaxation of compositional zoning. The EBDC of Mn is found to reduce essentially to D _MnMn, the main diagonal term of the D matrix, and consequently can be calculated quite easily. Evaluation of EBDC of Fe, Mg and Mn in garnets from a prograde Barrovian sequence did not reveal any significant dependence on the extent of relaxation of garnet. The diffusion data have been applied to calculate the cooling rate of natural biotite-garnet diffusion couple from eastern Finland and diffusional modification of growth zoning in garnet in early Proterozoic Wopmay orogen, Canada. The results are in good agreement with geochronological and other independent constraints.Symbols and abbreviations a Radius of a spherical garnet crystal - BSE Back-scattered electron imaging - C Column vector of (n-1) independent components - D Diffusion coefficient matrix - D _ij An element of the diffusion matrix on the i th row and j th column - D _* ⁱ Tracer diffusion coefficient of component i - D(i) Effective interdiffusion coefficient (EIC) of various components in a multicomponent solution rich in the component i - D(i-j) Interdiffusion coefficient of components i and j in a binary solution - D _i (EB) Effective binary diffusion coefficient of component i in a multicomponent solution - D _i (EB:Ideal) D _i (EB) under condition of ideal thermodynamic mixing of the diffusing species - D _i (EB:thermo) Thermodynamic component of D _i(EB) - D _O ^A Interdiffusion coefficient at peak temperature T ₀ in the phase A - D ₀ Pre-exponential factor in an Arrhenius relation - EBDC Effective binary diffusion coefficient between a solute and a multicomponent solvent matrix - FEC Fixed edge composition model - EIC Effective interdiffusion coefficient - f _i Fugacity of component i - HM Hematite-magnetite oxygen fugacity buffer - kb Kilobars - P Pressure - Q Activation energy (enthalpy) of diffusion - Extent of relaxation defined as the difference between core and rim compositions normalized to the same difference in the initial zoning profile - R Gas constant - s Cooling rate - T ₀, T _Ch Peak temperature and characteristic temperature, respectively - t Time - VEC Variable edge composition model - V ⁺ Activation volume - W _ij Simple mixture interaction parameter between i and j - W _i(EB) Effective simple mixture interaction parameter of a component i in a multicomponent solution - _ij Margules interaction parameter between i and j - X _i Mole fraction of component i - _i Activity coefficient of component i - A dimensionless variable =D t/a ² - _ij Kronecker delta (i=j, _ij =1; ij, _ij =0) - Z_i Charge on the ion i     

Pd-oxide equilibration: a new experimental method for the direct determination of oxide activities in melts and minerals

We have developed a new technique for the experimental determination of the activities of oxide components in melts and minerals using the equilibrium between Pd alloy, oxygen, and the oxide component in the sample of interest. If a melt or mineral sample is equilibrated with Pd metal at fixed P, T, and f _{O 2}, a small amount of each constituent oxide will reduce to metal and dissolve into the Pd, forming an alloy. Due to the extraordinary stability of dilute alloys of Pd with Mg, Al, and Si, these metals dissolve into the Pd in amounts easily measured with the electron microprobe at f _{O 2} s that can be achieved with conventional gas-mixing techniques. We determined the activity-composition relations for Pd–Mg, –Al, and –Si alloys by equilibrating Pd at fixed f _{O 2}and T with periclase, corundum, and cristobalite (a _oxide1). Because Mg, Al, and Si have constant activity coefficients in Pd at low concentrations, the activity of the oxide of each metal is a simple function of the ratio of the concentration of the metal in Pd in equilibrium with the sample to that in Pd in equilibrium with the pure oxide. Therefore, if Pd plus a melt or mineral and Pd plus pure oxide standards are equilibrated simultaneously at fixed T and f _{O 2}, the precision of the analytical technique is the major limitation on the determination of oxide activities. We used Pd-oxide equilibration to explore activities in silicate melts analogous to Type B Ca–Al-rich inclusions (CAIs) from carbonaceous chondrites; the measured activities deviate systematically from model valves but agree to within 1–30%. The activities imply that Type B CAIs did not condense as liquids from a gas of solar composition, and that only very aluminous compositions are potential liquid condensates from the solar nebula. We also used Pd-oxide equilibration to determine the free energy of formation from the oxides, G _f ^/O , of the spinel end-member MgAl₂O₄ at 1150 to 1400°C to a precision of 2–19% (1). Because the technique reflects equilibration at high temperature, the G _f ^/O _s accurately represent the mineral with equilibrium Mg–Al disorder at temperature, a feature not true of drop calorimetric results because of partial reordering during quenching. Our results indicate more negative G _f ^Emphasis>/O and hence higher entropy of formation, S _f ^Emphasis>/O , than given in most compilations of thermodynamic data for spinel.Division of Geological and Planetary Sciences Contribution #5278     

Petrology of the Chilliwack batholith,North Cascades,Washington: generation of calc-alkaline granitoids by melting of mafic lower crust with variable water fugacity

Calc-alkaline granitoid rocks of the Oligocene-Pliocene Chilliwack batholith, North Cascades, range from quartz diorites to granites (57–78% SiO₂), and are coeval with small gabbroic stocks. Modeling of major element, trace element, and isotopic data for granitoid and mafic rocks suggests that: (1) the granitoids were derived from amphibolitic lower crust having REE (rare-earth-element) and Sr-Nd isotopic characteristics of the exposed gabbros; (2) lithologic diversity among the granitoids is primarily the result of variable water fugacity during melting. The main effect of f_{H 2 O} variation is to change the relative proportions of plagioclase and amphibole in the residuum. The REE data for intermediate granitoids (quartz diorite-granodiorite; Eu/Eu^*=0.84–0.50) are modeled by melting with f_{H 2 O}<1 kbar, leaving a plagioclase + pyroxene residuum. In contrast, data for leucocratic granitoids (leuco-granodiorites and granites; Eu/Eu^* =1.0–0.54) require residual amphibole in the source and are modeled by melting with f_{H 2 O}=2–3 kbar. Consistent with this model, isotopic data for the granitoids show no systematic variation with rock type (⁸⁷Sr/⁸⁶Sr_i =0.7033–0.7043; Nd(0)=+3.3 to +5.5) and overlap significantly with data for the gabbroic rocks (⁸⁷Sr/⁸⁶Sr_i =0.7034–0.7040; Nd(0)=+3.3 to +6.9). The f_{H 2 O} variations during melting may reflect additions of H₂O to the lower crust from crystallizing basaltic magmas having a range of H₂O contents; Chillwack gabbros document the existence of such basalts. One-dimensional conductive heat transfer calculations indicate that underplating of basaltic magmas can provide the heat required for large-scale melting of amphibolitic lower crust, provided that ambient wallrock temperatures exceed 800°C. Based on lithologic and geochemical similarities, this model may be applicable to other Cordilleran batholiths.     

New calibration data for the Fe–Ti oxide thermo-oxybarometers from experiments in the Fe–Ti–O system at 1 bar, 1,000–1,300°C and a large range of oxygen fugacities

The current formulations of the Fe–Ti oxide thermobarometer (titanomagnetite–ilmenite_ss) fail to reproduce experimental results, in particular at the high temperatures that are relevant for basaltic assemblages. With the aim of improving the experimental basis of the calibration in the Fe–Ti–O system, we have synthesised assemblages of titanomagnetite–ilmenite_ss (Tmt–Ilm_ss), ilmenite_ss–pseudobrookite_ss (Ilm_ss–Psb_ss) and single-phase samples under a wide range of fO₂ (fixed with CO/CO₂ mixtures or by solid oxygen buffers) in sub-solidus conditions (1,000–1,300°C) at 1 bar. Runs lasted 24 h at 1,300°C and up to 240 h at 1,000°C and were terminated by quenching in water. All run products are polycrystalline, roughly equigranular aggregates, with grain sizes of 10–50 m. They were examined and analysed with the SEM and EMP. Tmt compositions are broadly in accordance with the current models at moderate fO₂, but significantly richer in Ti at low fO₂ and high T, due to cationic vacancies. Ilm_ss compositions depart from the predicted values practically at all fO₂ and T conditions, which is related to unsatisfactory thermodynamic models for the rhombohedral oxide. For Ilm_ss–Psb_ss assemblages the best agreement between our data and current calculations is at 1,000°C and moderately high fO₂. Otherwise, experimental and calculated data strongly disagree. The experimental data set on the three Fe–Ti oxide solid solutions presented here is intended to support new versions of both the titanomagnetite–ilmenite_ss thermo-oxybarometer and the ilmenite_ss–pseudobrookite_ss oxybarometer.     

Intrinsic and scattering attenuation in western India from aftershocks of the 26 January, 2001 Kachchh earthquake

176 vertical-component, short period observations from aftershocks of the M_w 7.7, 26 January, 2001 Kachchh earthquake are used to estimate seismic wave attenuation in western India using uniform and two layer models. The magnitudes (M_w) of the earthquakes are less than 4.5, with depths less than 46 km and hypocentral distances up to 110 km. The studied frequencies are between 1 and 30 Hz. Two seismic wave attenuation factors, intrinsic absorption (Q_i^− 1) and scattering attenuation (Q_s^− 1) are estimated using the Multiple Lapse Time Window method which compares time integrated seismic wave energies with synthetic coda wave envelopes for a multiple isotropic scattering model. We first assume spatial uniformity of Q_i^− 1, Q_s^− 1 and S wave velocity (β). A second approach extends the multiple scattering hypothesis to media consisting of several layers characterized by vertically varying scattering coefficient (g), intrinsic absorption strength (h), density of the media (ρ) and shear wave velocity structure. The predicted coda envelopes are computed using Monte Carlo simulation. Results show that, under the assumption of spatial uniformity, scattering attenuation is greater than intrinsic absorption only for the lowest frequency band (1 to 2 Hz), whereas intrinsic absorption is predominant in the attenuation process at higher frequencies (2 to 30 Hz). The values of Q obtained range from Q_t = 118, Q_i = 246 and Q_s = 227 at 1.5 Hz to Q_t ≈ 4000, Q_i ≈ 4600 and Q_s ≈ 33,300 at 28 Hz center frequencies, being Q_t^− 1 a measure of total attenuation. Results also show that Q_i^− 1, Q_s^− 1 and Q_t^− 1 decrease proportional to f^−ν. Two rates of decay are clearly observed for the low (1 to 6 Hz) and high (6 to 30 Hz) frequency ranges. Values of ν are estimated as 2.07 ± 0.05 and 0.44 ± 0.09 for total attenuation, 1.52 ± 0.21 and 0.48 ± 0.09 for intrinsic absorption and 3.63 ± 0.07 and 0.06 ± 0.08 for scattering attenuation for the low and high frequency ranges, respectively. Despite the lower resolution in deriving the attenuation parameters for a two layered crust, we find that scattering attenuation is comparable to or smaller than the intrinsic absorption in the crust whereas intrinsic absorption dominates in the mantle. Also, for a crustal layer of thickness 42 km, intrinsic absorption and scattering estimates in the crust are lower and greater than those of the mantle, respectively.     

The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

Zircon U–Pb geochronological and geochemical constraints on the petrogenesis of the Taishan sanukitoids (Shandong): Implications for Neoarchean subduction in the Eastern Block, North China Craton

Elemental, Sr–Nd–Pb isotopic and geochronological data are presented for the Taishan high-mg dioritic rocks (western Shandong) from the Eastern Block of the North China Craton in order to better understand the Archean tectonic evolution and crustal growth of the Craton. The rocks gave the zircon U–Pb age of 2536–2540 Ma. They show low SiO₂ and Al₂O₃ contents, high MgO, mg-number, Cr, Ni, Y, Yb, Sr and Ba, enriched LILEs and LREEs, depleted HFSEs and HREEs with (Nb/La)_N of 0.07–0.12. They exhibit _Nd(t) values of 1.53–3.30, (²⁰⁶Pb/²⁰⁴Pb)_i of 11.20–15.30, (²⁰⁷Pb/²⁰⁴Pb)_i of 14.14–14.83 and (²⁰⁸Pb/²⁰⁴Pb)_I of 31.10–33.93. Such geochemical features with an affinity to both a mantle- and crust-like source for the Taishan dioritic rocks are similar to those of the typical Archean sanukitoids, suggesting an origination from a sub-arc mantle wedge variably metasomatized by the slab-derived dehydration fluids and melts before 50–100 Ma of the emplacement of the Taishan sanukitoid plutons. It is proposed that the Taishan sanukitoids resulted from the sudden change of the downgoing slab from a flat subduction to subsequently steeper subduction in an active continental margin regime during Neoarchean time.     

Petrogenesis of the Mesozoic intrusive complexes from the southern Taihang Orogen,North China Craton: elemental and Sr–Nd–Pb isotopic constraints

A geochemical and isotopic study was carried out for three Mesozoic intrusive suites (the Xishu, Wuan and Hongshan suites) from the North China Craton (NCC) to understand their genesis and geodynamic implications. The Xishu and Wuan suites are gabbroic to monzonitic in composition. They share many common geochemical features like high Mg# and minor to positive Eu anomalies in REE patterns. Initial Nd–Sr isotopic compositions for Xishu suite are _Nd(135 Ma)=–12.3 to –16.9 and mostly I_Sr = 0.7056–0.7071; whereas those for Wuan suite are slightly different. Pb isotopic ratios for Xishu suite are (²⁰⁶Pb/²⁰⁴Pb)_i = 16.92–17.3, (²⁰⁷Pb/²⁰⁴Pb)_i=15.32–15.42, (²⁰⁸Pb/²⁰⁴Pb)_i=37.16–37.63, which are slightly higher than for Wuan suite. The Xishu–Wuan complexes are considered to originate from partial melting of an EM1-type mantle source, followed by significant contamination of lower crustal components. The Hongshan suite (mainly syenite and granite) shows distinctly higher _Nd(135 Ma) values (–8 to –11) and slightly higher Pb isotopic ratios than the Xishu–Wuan suites. It was formed via fractionation of a separate parental magma that also originated from the EM1-type mantle source, with incorporation of a small amount of lower crustal components. Partial melting of the mantle sources took place in a back-arc extensional regime that is related to the subduction of the paleo-Pacific slab beneath the NCC.     

Kinetics and mechanisms of the reaction of zoisite to anorthite under hydrothermal conditions: reaction phenomenology away from the equilibrium region

The kinetics and mechanisms of the dehydration reactions of zoisite have been studied at 635°–792° C, 1–2 kbar. The equilibrium reaction does not occur and is replaced by metastable reactions involving the formation of gehlenite and a calcium tri-octahedral mica, instead of corundum: zoisite anorthite+grossular+gehlenite +calcium 3T mica+H₂O.The experimental data can be interpreted by zero-order equations dX _An/dt=k (X _An=fractional extent of reaction, t=time, k=zero-order rate constant). These relations hold for variations in P, T, A _initial(the initial surface area of zoisite) and also in the presence of seed crystals, which enhance the reaction rate. No induction period is evident and only at advanced stages of reaction are sharp decreases observed in the rate, which are attributed to physical affects (shrinking particles, armouring). SEM studies show that dissolution of zoisite is anisotropic, occurring preferentially parallel to the crystallographic b-axis, with the result that a characteristic sawtooth etch structure develops. Garnet grows as euhedral crystals located in cavities or on teeth of dissolving zoisite, whereas anorthite forms as clusters of coalescing grains which spread over and enclose the zoisite. In seeded runs, garnet growth initiates on both seeds and on zoisite surfaces whereas anorthite growth is more closely tied to the seeds, resulting in the development of clusters of smaller grains.The experimental evidence favours dissolution and nucleation-controlled growth as rate-determining processes. The preservation of zero-order kinetics in the face of shrinking particles is attributed to the anisotropic dissolution mechanism, which effectively preserves a constant reaction interface. The rate effects of nucleation appear to accord with the classic model in which growth of crystal layers is initiated by the formation of coherent nuclei.The temperature dependence of rate constants reflects both thermally activated Arrhenius-type behaviour and the rate-depressing influences of approach to equilibrium. Similarly pressure affects on reaction rate can be interpreted in terms of competition between rate enhancement due to pressure increase and rate-depression accompanying the approach to equilibrium. Although the equilibrium-approach effects accord with current treatments of reaction kinetics, a problem exists in deriving an exact relation coupling dissolution and nucleation rate control. Consequently an overall-reaction rate equation, such as that of Fisher and Lasaga (1981), is only partially successful in interpreting the temperature dependence of rates. The data suggest that the surface reaction equation of Wood and Walther (1983) only applies when nuclei are present.     

Subseabed disposal of radioactive waste: effects of consolidational fluid flow

Subseabed disposal of radioactive waste applies a multiple-barrier concept with the sediment being the most important barrier for preventing a release of nuclides into the biosphere. While many investigations have been carried out to analyze the risk potential in this type of disposal, the effects of sediment consolidation and associated fluid flow have not fully been taken into consideration. Here, possible effects of consolidational fluid flow in the penetrator disposal option and possible consequences to the transport of nuclides in the sediment are analyzed. Results of numerical experiments demonstrate that consolidation contributes to the transport of radioactive nuclides released from containers buried in the sediment and to the release of nuclides at the sediment-water interface. Both depend on geological conditions and to a large extent on possible alterations of hydraulic conductivity i of the sediment in the vicinity of the entry path of a penetrator.Symbols c concentration ml m^–3 - c _a concentration of adsorbed solute mg kg^–1 (relative to dry weight of sorbing substance) - c _in solute concentration of source q mg m^–3 - c ₀ initial concentration mg m^–3 - ID dispersion tensorm ²s^–1 - ID ^* diffusion tensor m²s^–1 - D coefficient of dispersion m²s^–1 - d ₀ coefficient of molecular diffusion m²s^–1 - d coefficient of effective diffusion m²s^–1 - g gravity m²s^–1 - h piezometric pressure m - k hydraulic conductivity m²s^–1 - m mass kg - p pressure Pa - q source/sink m³s^–1 - S ₀ specific surface m²m^–3 - t time s - v velocity m s^–1 - x, z cartesian coordinates m - compressibiliy of sediment m²N^–1 - _L longitudinal dispersivity m - effective porosity (decimal fraction) - density kg m^–3 - _s density of sediment kg m^–3 - _w density of water kg m^–3 - decay constant per s - kinematic viscosity m²s^–1     

Ground failure around buried tubes

Summary The hoop forces which develop in circular tubes buried in elastic-plastic ground are investigated. A closed form solution is used to determine the hoop forces which develop when the field stresses in the elastic-plastic ground are initially uniform. The finite element method is used to solve the problem for biaxial field stress. A parametric study is undertaken to assess the influence of tube stiffness and ground strength on the hoop forces, and use is made of elastic stress contours to predict the likely extent of material failure around tubes buried in ground with biaxial prestress.Notation a tube radius - c cohesion - D flexural stiffness of the structure - E _i Young's modulus of structure - E _s Young's modulus of ground - F hoop force (compression positive) - G _s shear modulus of ground - H hoop stiffness of the structure - K coefficient of lateral pressure - N tan²(45+/2) - q ( ₁– ₁)/2 - S _f relative flexural stiffness of the structure - S _h relative hoop stiffness of the structure - t structural thickness - v circumferential displacement - w radial displacement - v _l Poisson's ratio of structure - v _s Poisson's ratio of ground - normal traction acting on the structure - _d deviatoric component of field stress - _h horizontal field stress - _m uniform component of field stress - _v vertical field stress - ₁ major principal stress - ₃ minor principal stress - tangential traction acting on the structure - angle of internal friction of the ground - angle of dilation of the ground     

F-OH exchange equilibria between mica-amphibole mineral pairs

Fluoride-hydroxyl exchange equilibria between phlogopite-pargasite and phlogopite-tremolite mineral pairs were experimentally determined at 1,173K, 500 bars and 1,073–1,173 K, 500 bars respectively. The distribution of fluorine between phlogopite and pargasite was found to favor phlogopite slightly, G _ex ^. (1,173 K)=–1.71 kJ anion^–1, while in the case of phlogopite-tremolite, fluorine was preferentially incorporated in the mica, G _ex ^. (1,073)=– 5.67 kJ anion^–1 and G _ex ^. (1,173K)=–5.84 kJ anion^–1. These results have yielded new values of entropy and Gibbs energy of formation for fluortremolite, S _f =–2,293.4±16.0JK^–1 mol^–1 and G _f = –11,779.3±25.0 kJ mol^–1, respectively. In addition, F-OH mineral exchange equilibria support a recent molten oxide calorimetric value for the Gibbs energy of fluorphlogopite, G _f =–6,014.0±7.0 kJ mol^–1, which is approximately 40 kJ mol^–1 more exothermic than the tabulated value.This work performed in part at Sandia National Laboratories supported by the U.S. Department of Energy, DOE, under contract number DE-AC04-76DP00789     

Spatial and multivariate analysis of geochemical data from metavolcanic rocks in the Ben Nevis area, Ontario

A study of the lithogeochemistry of metavolcanics in the Ben Nevis area of Ontario, Canada has shown that factor analysis methods can distinguish lithogeochemical trends related to different geological processes, most notably, the principal compositional variation related to the volcanic stratigraphy and zones of carbonate alteration associated with the presence of sulphides and gold. Auto- and cross-correlation functions have been estimated for the two-dimensional distribution of various elements in the area. These functions allow computation of spatial factors in which patterns of multivariate relationships are dependent upon the spatial auto- and cross-correlation of the components. Because of the anisotropy of primary compositions of the volcanics, some spatial factor patterns are difficult to interpret. Isotropically distributed variables such as CO ₂ are delineated clearly in spatial factor maps. For anisotropically distributed variables (SiO ₂ ), as the neighborhood becomes smaller, the spacial factor maps becomes better. Interpretation of spatial factors requires computation of the corresponding amplitude vectors from the eigenvalue solution. This vector reflects relative amplitudes by which the variables follow the spatial factors. Instability of some eigenvalue solutions requires that caution be used in interpreting the resulting factor patterns. A measure of the predictive power of the spatial factors can be determined from autocorrelation coefficients and squared multiple correlation coefficients that indicate which variables are significant in any given factor. The spatial factor approach utilizes spatial relationships of variables in conjunction with systematic variation of variables representing geological processes. This approach can yield potential exploration targets based on the spatial continuity of alteration haloes that reflect mineralization.List of symbols c _i Scalar factor that minimizes the discrepancy between andU _i - D Radius of circular neighborhood used for estimating auto- and cross-correlation coefficients - d Distance for which transition matrixU is estimated - d _ij Distance between observed valuesi andj - E Expected value - E _i Row vector of residuals in the standardized model - F(d _ij) Quadratic function of distanced _ij F(d _ij)=a+bd _ij+cd _ij ² - L Diagonal matrix of the eigenvalues ofU - _i Eigenvalue of the matrixU;ith diagonal element ofL - N Number of observations - p Number of variables - Q Total predictive power ofU - R Correlation matrix of the variables - R _0j Variance-covariance signal matrix of the standardized variables at origin;j is the index related tod andD (e.g.,j=1 ford=500 m,D=1000 m) - R _1j Matrix of auto- and cross-correlation coefficients evaluated at a given distance within the neighborhood - R _m ² Multiple correlation coefficient squared for themth variable - S _i Column vectori of the signal values - s _k ² Residual variance for variablek - T _i Amplitude vector corresponding toV _i;ith row ofT=V ^–1 - T Total variation in the system - U Nonsymmetric transition matrix formed by post-multiplyingR ₀₁ ^–1 byR _ij - U _i Componenti of the matrixU, corresponding to theith eigenvectorV _i;U _i= _iV_iT_i - U* _i ComponentU _i multiplied byc _i - U _ij Sum of componentsU _i+U _j - V _i Eigenvector of the matrixU;ith column ofV withUV=VL - w Weighting factor; equal to the ratio of two eigenvalues - X _i Random variable at pointi - x _i Value of random variable at pointi - y _i Residual ofx _i - Z _i Row vectori for the standardized variables - z _i Standardized value of variable     

Solid inclusions of magmatic halite and sylvite in felsic granitoids, Sierra Norte, Córdoba, Argentina

This study provides evidence for the existence of halite and sylvite solid inclusions in igneous quartz and feldspars, the first to be reported in intrusive rocks, and to partially constrain the physicochemical environment that lets halides crystallize under magmatic conditions.Halite and sylvite solid inclusions were found included in quartz and feldspars from a micrographic–granophyric assemblage in a miarolitic aplite and, rarer, in alkali-feldspar from a miarolitic monzogranite. Monzogranite and aplite represent I-type, K-enriched postcollisional rocks of the Late Cambrian–Early Ordovician Sierra Norte–Ambargasta batholith in the Eastern Sierras Pampeanas. Both granitoids fall among the most evolved felsic rocks of the batholith, with aplite approaching haplogranitic compositions. Halite is far more common than sylvite and the presence and distribution of one or both halides are erratic within the felsic intrusive bodies. Halides occur as small skeletal grains, commonly in cross-shaped aggregates of less than 50 μm. No K or Na was found at the detection limits of EDS in either halite or sylvite respectively. Textural relationships suggest that the alkali-chlorides separated from the melt near the minima along the quartz–feldspar cotectics of P_H2O > 160 < 200 MPa in a silica-, and potassium-rich magmatic system at approximately 750–700 °C, prior to the H₂O-vapor saturated miarole-forming stage.Computed ratios for the magmatic volatile phase (MVP) coexisting with melt at the early stage of aplite crystallization are: NaCl/HCl = 0.11–0.97 and KCl/HCl = 0.24–1.62, being the highest range of values (0.79–0.97 and 1.45–1.62, respectively) found in those alkali-chloride-bearing samples. Maximum HCl/ΣCl_(MVP) (0.28 to 0.31) indicates higher total Cl concentration in the MVP of alkali-chloride-bearing aplites, which is much higher in the halite-free aplite samples (HCl/ΣCl_(MVP) = 0.59 to 0.74). One miarolitic monzogranite sample, where halite solid inclusions are present, also yielded the highest ratios for NaCl/HCl_(MVP) (0.91) and KCl/HCl_(MVP) (1.46), and the HCl/ΣCl_(MVP) is 0.30. A high HCl concentration in the fluid phase is suggested by the log f(HF)/f(H₂O) = − 4.75 to − 4.95, log f(HCl)/f(H₂O) = − 3.73 to − 3.86, and log f(HF)/f(HCl) = − 0.88 to − 1.22, computed at 750 °C after biotite composition. The Cl concentrations at 800 °C, computed with a D^v/l_Cl = 0.84 + 26.6P (P at 200 MPa), yielded values within the range of  70 to 700 ppm Cl in the melt and  4000 to 40 000 ppm Cl in the coexisting MVP. The preferential partitioning of Cl in the vapor phase is controlled by the D^v/l_Cl; however, the low concentration of Cl in the melt suggests that high concentrations of Cl are not necessary to saturate the melt in NaCl or KCl.Cl-saturation of the melt and coexisting MVP might have been produced by a drop in Cl solubility due to the near-haplogranitic composition of the granitoids after extreme fractionation, probably enhanced by fluctuating reductions of the emplacement pressure in the brittle monzogranite host. Liquid immiscibility, based in the differential viscosity and density among alkali-chloride saturated hydrosaline melt, aluminosilicate felsic melt, and H₂O-rich volatiles is likely to have crystallized halite and sylvite from exsolved hydrosaline melt. High degrees of undercooling might have been important at the time of alkali-chloride exsolution. The effectiveness of alkali-chloride separation from the melt at magmatic temperatures is in line with the interpretation of “halite subtraction” as a necessary process to understand the origin of the “halite trend” in highly saline fluid inclusions from porphyry copper and other hydrothermal mineralizations, despite the absence of the latter in the Cerro Baritina aplites, where this process preceded the exsolution of halite-undersaturated fluids.Pervasive alteration of the monzogranite country rock as alkali-metasomatic mineral assemblages, the mineral chemistry of some species, and the association of weak molybdenite mineralization are compatible with the activity of alkaline hypersaline fluids, most likely exsolved during the earliest stages of aplite consolidation.     

Three-dimensional graphic display of disconnected bodies

Lett= (x, y, z) be an ore grade function sampled at the nodes of a three dimensional regular grid. Ift ₀ is a given cut-off, the ore deposit may be considered to be constituted by all the points (x, y, z) such that (x, y, z)>t ₀. In fact, the ore deposit may be constituted by one or several disconnected bodies and two algorithms to display these bodies may be considered. The first consists in drawing intersections of the bodies with a series of equidistant parallel planes. The second consists in covering their surface with painted triangles. In both cases, how to remove hidden parts of the drawing is shown. An interactive approach of the problem also is considered.This paper presented at Emerging Concepts, MGUS-87 conference, Redwood City, California, 13–15 April 1987.     

Coexisting zoisite and clinozoisite in biotite schists from the Hohe Tauern,Austria

Coexisting zoisite and clinozoisite assemblages in biotite schists from the western Hohe Tauern, Austria, have been investigated with the electron microprobe, polarization optics, and X-ray diffractometer. Zoisite and clinozoisite show slight compositional zoning, ranging from the core to the rim from about 1.8 to 1.0 wt. % Fe in zoisite, and 4.0 to 3.0 wt. % Fe in clinozoisite. The results suggest a gap of composition between coexisting zoisite and clinozoisite under greenschist-amphibolite transition facies conditions.The optical orientation and 2V of zoisite vary considerably within single grains. Lamellar structures have been detected which may be produced by unmixing of zoisite. The Fe-poor lamellae have 2V _z=20–50°, a dispersion r>v, and relatively low refringence, the Fe-rich lamellae have 2V _z =90–100°, rv, and higher refringence. The optic axial planes of both lamellae systems deviate from the (100) cleavage by up to 15°, and suggest a deviation from orthorombic symmetry. The lattice constants of coexisting zoisite and clinozoisite are given.