The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995     

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002     

Flow behavior and microstructures of hydrous olivine aggregates at upper mantle pressures and temperatures

Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10^?5 to 7.5 × 10^?5 s^?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm³ mol^?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm³ mol^?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol^?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.     

The effect of Al3+, Fe3+, and Ti4+ on the configurational heat capacities of sodium silicate liquids

The heat capacities of 29 glasses and supercooled liquids in the Na₂O-SiO₂, Na₂O-Al₂O₃-SiO₂, Na₂O-(FeO)-Fe₂O₃-SiO₂, and Na₂O-TiO₂-SiO₂ systems were measured in air from 328 to 998 K with a differential scanning calorimeter. The reproducibility of the data determined from multiple heat capacity runs on a single crystal MgO standard is within ± 1% of the accepted values at temperatures ≤ 800 K and within ± 1.5% between 800 and 1000 K. Within the resolution of the data, the heat capacities of sodium silicate and sodium aluminosilicate liquids are temperature independent. Heat capacity data in the supercooled liquid region for the sodium silicates and sodium aluminosilicates were combined and modelled assuming a linear compositional dependence. The derived values for the partial molar heat capacities of Na₂O, Al₂O₃, and SiO₂ are 112.35 ± 0.42, 153.16 ± 0.82, and 76.38 ± 0.20 J/gfw · K respectively. The partial molar heat capacities of Fe₂O₃ and TiO₂ could not be determined in the same manner because the heat capacities of the Fe₂O₃- and TiO₂-bearing sodium silicate melts showed varying degrees of negative temperature dependence. The negative temperature dependence to the configurational C _P may be related to the occurrence of sub-microscopic domains (relatively polymerized and depolymerized) that break down to a more homogeneous melt structure with increasing temperature. Such an interpretation is consistent with data from in situ Raman, Mössbauer, and X-ray absorption fine structure (XAFS) spectroscopic studies on similar melts.     

The dehydration process in the zeolite laumontite: a real-time synchrotron X-ray powder diffraction study

The dehydration process of the natural zeolite laumontite Ca₄Si₁₆Al₈O₄₈ · 18 H₂O has been studied in situ by means of powder diffraction and X-ray synchrotron radiation. Powder diffraction profiles suitable for Rietveld refinements were accumulated in time intervals of 5 minutes using a position sensitive detector (CPS-120 by INEL), while the temperature increased in steps of about 5 K. The synchronization of accumulation time and temperature plateau allowed collection of 62 temperature-resolved powder patterns in the range 310–584 K, whose analysis produced a dynamic picture of the laumontite structure response to dehydration. The first zeolitic water molecules diffusing out of the channels are those not bonded to the Ca cations and located in the W(1) site, whose occupancy drops smoothly to 10% during heating to 349 K, while the sample in the capillary is still submerged in water. The remaining W(1) and 60% of W(5) water molecules are expelled rather sharply at about 370 K. At this temperature all remaining water submerging the powder crystallites is lost, the structure contains about 13 water molecules/cell, and the crystal structure is that of leonhardite. On continued heating 80% of the water molecules from the W(2) site are lost between 420 and 480 K, while a small amount of the diffusing water is reinserted in the W(5) site. The occupancy factor of the W(8) site decreases starting at 480 K, and reaches a maximum loss of 20% at 584 K. The combined occupancy of the Ca-coordinated W (2) and W (8) water sites never falls much below two, so that the Ca cations in the channels, which are bonded to four framework oxygen atoms, are nearly six-coordinated in the explored temperature range. The water loss is accompanied by large changes in the unit cell dimensions. Except at 367 K, where the excess surrounding water is leaving, all changes in cell dimensions are gradual. The loss of the hydrogen bonded W(1) and W(5) water molecules is related to most of the unit cell volume reduction below 370 K, as shown by the contraction of the a-, b- and c-axes and the increase in the monoclinic angle. Loss of the Ca-coordinated W(2) and W(8) water molecules has a small effect on the unit cell volume as the continued contraction of the a- and c-axes is counter-balanced by a large expansion in the b-axis and a decrease in the monoclinic β angle.     

Relaxation mechanisms and effects of motion in albite (NaAlSi3O8) liquid and glass: A high temperature NMR study

The nuclear magnetic relaxation of ²³Na and ²⁹Si in albite glass and liquid has been studied from 800 K to 1400 K. The dominant spin-lattice relaxation mechanism for ²³Na is found to be nuclear quadrupole interaction arising from the Na⁺ diffusion. The activation energy of the Na diffusion is found to be 71±3 kJ/mol, in close agreement with the results on electrical conductivity and on Na self-diffusion from radio-tracer experiments. The correlation time of the Na motion is estimated to be about 8.5×10^?11 s near the melting point (～1390 K). Both nuclear dipole-dipole interaction and chemical shift anisotropy interaction are large enough to contribute to the ²⁹Si relaxation. However, calculations based on a simplified model which employ single correlation time and exponential correlation function, with interactions typical of crystalline silicates, cannot completely account for the experimental data. NMR relaxation data also reveal that the Si motion is correlated to the Na motion and that the Si is relatively immobile. Several possible motions of SiO₄ tetrahedra that can cause ²⁹Si relaxation are suggested. The motion responsible for ²⁹Si relaxation differs from that which is responsible for viscosity: the apparent activation energy for the former is much lower. Measurements of spin-spin relaxation times and linewidths are also presented and the significance of their temperature dependence is discussed.     

Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Growth kinetics of enstatite reaction rims studied on nano-scale,Part I: Methodology,microscopic observations and the role of water

The kinetics of (Mg, Fe)SiO₃ pyroxene layer growth within silicate thin films with total thickness <1 μm was studied experimentally at 0.1 MPa total pressure, controlled fO₂ and temperatures from 1,000 to 1,300°C. The starting samples were produced by pulsed laser deposition. Layer thickness before and after the experiments and layer composition as well as microstructures, grain size and shape of the interfaces were determined by Rutherford back scattering and transmission electron microscopy assisted by focused ion beam milling. Due to the miniaturization of the starting samples and the use of high resolution analytical methods the experimentally accessible temperature range for rim growth experiments was extended by about 300°C towards lower temperatures. The thickness of the layers at a given temperature increases proprotional to the square root of time, indicating a diffusion-controlled growth mechanism. The temperature dependence of rim growth yields an apparent activation energy of 426 ± 34 kJ/mol. The small grain size in the orthopyroxene rims implies a significant contribution of grain boundary diffusion to the bulk diffusion properties of the polycrystalline rims. Based on microstructural observations diffusion scenarios are discussed for which the SiO₂ component behaves immobile relative to the MgO component. Volume diffusion data for Mg in orthopyroxene from the literature indicate that the measured diffusivity is probably controlled by the mobility of oxygen. The observed reaction rates are consistent with earlier results from dry high-temperature experiments on orthopyroxene rim growth. Compared to high pressure experiments at 1,000°C and low water fugacities, reaction rates are 3–4 orders of magnitude smaller. This observation is taken as direct evidence for a strong effect of small amounts of water on diffusion in silicate polycrystals. In particular SiO₂ changes from an immobile component at dry conditions to an extremely mobile component even at very low water fugacities.     

Biogeochemical implications of the isotopic equilibrium fractionation factor between the oxygen atoms of acetone and water

Carbonyl oxygens of organic molecules undergo isotopic exchange with water during reversible hydration reactions. The equilibrium isotopic fractionation factors between the carbonyl oxygen of acetone and water at 15°, 25°, and 35°C are 1.028, 1.028, and 1.026 respectively. The differences between the δ¹⁸O values of the carbonyl oxygen of acetone and of the water with which it is in equilibrium are similar to the differences that have been observed between the δ¹⁸O values of cellulose and the water used in its synthesis by a variety of aquatic plants and animals. Additionally, the identity of the acetone-water fractionation factors at 15° and 25°C parallels the observation that the difference between the δ¹⁸O values of cellulose and water shows no temperature dependence for individual species of plants grown over the same temperature range. These results are discussed in relation to the proposal that the oxygen isotopic relationship between cellulose and water is established by isotopic exchange occurring during the hydration of carbonyl groups of the intermediates of cellulose synthesis.     

Magnetic properties of the clinopyroxenes aegirine and hedenbergite: a magnetic susceptibility study on single crystals

Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T _N =7.5(5)?K, Θ _P =?19(1)?K for AEG, and T _N =31(1)?K, Θ _P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.     

Measurements of the scattering of pulsar radio emission

Measurements of the broadening of pulsar pulses by scattering in the interstellar medium are presented for a complete sample of 100 pulsars with Galactic longitudes from 6° to 311° and distances to three kiloparsec. The dependences of the scattering on the dispersion measure (τ _sc(DM) ∝ DM^α), frequency (τ _sc(v) ∝ v ^?γ ), Galactic longitude, and distance to the pulsar are analyzed. The dependence of the scattering on the dispersion measure in the near-solar neighbourhood can be represented by the power law τ _sc(DM) ∝ DM^2.2±0.1). Measurements at the low frequencies 111, 60, and 40 MHz and literature data are used to derive the frequency dependence of the scattering (τ _sc(v) ∝ V ^?γ ) over a wide frequency interval (covering a range of less than 10: 1) with no fewer than five frequencies. The index for the frequency dependence, γ = 4.1 ± 0.3, corresponds to a normal distribution for inhomogeneities in the turbulence in the scattering medium. Based on an analysis of the dependence of the scattering on the distance to the pulsar and on Galactic longitude, on average, the turbulence level C _n ² is the same in all directions and at all distances out to about three kpc, testifying to the statistical homogeneity of the turbulence of the scattering medium in the near-solar region of the Galaxy.     

Thermochemistry of the new silica polymorph moganite

Samples of microcrystalline silica varieties containing variable amounts of the new silica polymorph moganite (up to R~82 wt.%) have been studied by a combination of high temperature solution calorimetry using lead borate (2 PbO · B₂O₃) solvent and transposed temperature drop calorimetry near 977 K, in order to investigate the thermochemical stability of this new silica mineral. The enthalpy of solution at 977 K and the heat content (H₉₇₇ — H₂₉₈) of “pure” moganite phase were estimated to be -7.16 ± 0.35 kJ/mol and 43.62 ± 0.50 kJ/mol, respectively. The standard molar enthalpy of formation is-907.3 ± 1.2 kJ/mol. Thus, calorimetry strongly supports results of previous X-ray and Raman spectroscopic studies that moganite is a distinct silica polymorph. Its thermochemical instability relative to quartz at 298 K of 3.4 ± 0.7 kJ/mol is marginally higher than those of cristobalite and tridymite. Structurally, this instability may be related to the presence of distorted 4-membered rings of SiO₄ tetrahedra, which are not found in the quartz structure. The metastability relative to quartz may also explain the apparent scarcity of moganite in altered rocks and in rocks that are older than 130 my.     

Experimental study of 2,4,6-Trichlorophenol and pentachlorophenol solubilities in aqueous solutions: derivation of a speciation-based Chlorophenol solubility model

Despite the widespread occurrence of chlorophenols as groundwater contaminants, the aqueous solubilities of the chlorophenols are not well-characterized. In this study, the authors report the solubility of 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP) based on experiments conducted as a function of pH, ionic strength and temperature, and a speciation-based model for estimating the solubilities of other chlorophenols is derived.Narrow constraints on the aqueous solubility of both chlorophenols were made possible by conducting experiments in pure water and in 0.1 NaCl at 25°C and 55°C, from both under- and over-saturation. The solubility of the chlorophenols is pH-independent under low pH conditions, but at higher pH values it increases with increasing pH. The concentration of the protonated chlorophenol species determines the low pH solubility and, at 25°C, the log molality of the protonated species of 2,4,6-TCP is −2.8±0.1, whereas for PCP the value is −5.1±0.3. Two other properties were used to model the solubility as a function of pH: the acidity constant (K_a) and the stability constant for a Na-chlorophenolate complex. The pK_a and Na-chlorophenolate log stability constant values that best fit the solubility data for 2,4,6-TCP are 6.1±0.3 and 1.0±0.5, respectively; the values for PCP are 4.5±0.3 and 1.0±0.5, respectively. At 55°C, the log molality of protonated PCP increases to −4.7±0.2 and the pK_a and log stability constant value are 4.1±0.3 and 0.9±0.5, respectively. The log stability constant for NaPCP° at 55°C is equal to 0.9±0.5.The experimental solubility measurements are used to construct a theoretical model which defines the solubility of a chlorophenol in terms of its acidity constant and its low pH minimum solubility. This approach enables estimations of the aqueous solubility of other chlorophenol molecules as a function of pH, ionic strength and temperature. In order to facilitate application of this model to other chlorophenol molecules, the authors compile and critically review the solubility data for 20 chlorophenols from the literature. The results of the experiments and review enable estimations of chlorophenol solubilities under a wide range of conditions of environmental interest.     

Activation energies of the self-diffusion of HTO, 22Na+ and 36Cl− in a highly compacted argillaceous rock (Opalinus Clay)

The temperature dependence of the self-diffusion of HTO, ²²Na⁺ and ³⁶Cl⁻ in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol⁻¹, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol⁻¹ for ²²Na⁺ and ³⁶Cl⁻, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol⁻¹). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na⁺ and Cl⁻, slightly higher values than in bulk liquid water (Na⁺: 18.4 kJ mol⁻¹; Cl⁻: 17.4 kJ mol⁻¹) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA.     

Heat capacity and thermodynamic functions of pretulite ScPO<Subscript>4</Subscript>(c) at 0–1600 K

The heat capacity of synthetic pretulite ScPO₄(c) was measured by adiabatic calorimetry within a temperature range of 12.13–345.31 K, and the temperature dependence of the pretulite heat capacity at 0–1600 K was derived from experimental and literature data on H ⁰(T)-H ⁰(298.15 K) for Sc orthophosphate. This dependence was used to calculate the values of the following thermodynamic functions: entropy, enthalpy change, and reduced Gibbs energy. They have the following values at 298.15 K: C _p ⁰ (298.15 K) = 97.45 ± 0.06 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 84.82 ± 0.18 J K⁻¹ mol⁻¹, H ⁰(298.15 K)-H ⁰(0) = 14.934 ± 0.016 kJ mol⁻¹, and Φ ⁰(298.15 K) = 34.73 ± 0.19 J K⁻¹mol⁻¹. The enthalpy of formation Δ _f H ⁰(ScPO₄, 298.15 K) = − 1893.6 ± 8.4 kJ mol⁻¹.     

A revised model for the density and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liquids from 700 to 1900 K: extension to crustal magmatic temperatures

A revised model for the volume and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids, which can be applied at crustal magmatic temperatures, has been derived from new low temperature (701–1092 K) density measurements on sixteen supercooled liquids, for which high temperature (1421–1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium aluminosilicate samples, for which high temperature density measurements are also available. Compositions (in mol%) range from 37 to 75% SiO₂, 0 to 27% Al₂O₃, 0 to 38% MgO, 0 to 43% CaO, 0 to 33% Na₂O and 0 to 29% K₂O. The strategy employed for the low temperature density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T _f ^′. The volume of the glass and liquid at T _f ^′ was obtained from the glass density at 298 K and the glass thermal expansion coefficient from 298 K to T _f ^′. The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767–1127 degrees) with a fitted 1 error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of Vˉ _i ±1 (cc/mol) at 1373 K for SiO₂ (26.86 ± 0.03), Al₂O₃ (37.42±0.09), MgO (10.71±0.08), CaO (15.41±0.06), Na₂O (26.57±0.06), K₂O (42.45 ± 0.09), and fitted values of dVˉ _i /dT (10⁻³ cc/mol-K) for MgO (3.27±0.17), CaO (3.74±0.12), Na₂O (7.68±0.10) and K₂O (12.08±0.20). The results indicate that neither SiO₂ nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT ^liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contributions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively. Received: 2 August 1996 / Accepted: 12 June 1997     

The Thermal History of the Huangmeijian Granite Intrusion in Anhiii and Its Relation to Mineralization: Isotopic Evidence

Abstract Whole—rock Rb—Sr, zircon U—Pb and hornblende, biotite and K—feldspar K—Ar ages are used to reconstruct the cooling history of the Huangmeijian intrusion in the Anqing—Lujiang quartz—syenite belt in Anhui. Oxygen isotope geothermometry of mineral pairs demonstrates that diffusion is a dominant factor controlling the closure of isotopic systems. Assuming the cooling of the intrusion is synchronous with a dicrease in local geothermal gradients, an emplacement depth of about 8 km and the magma crystallization temperature of 800 ± 50°C are estimated. The Huangmeijian intrusion experienced a rapid cooling process and uplifted after its emplacement and crystallization at 133 Ma B.P. with a cooling rate of 34.5°C / Ma and an uplifting rate of 0.35 mm/ a. The intrusion was rising until it rested at a depth of 3 km at a temperature of 300 ± 50°C about 14 Ma later. Then the intrusion was in slow cooling and uplifting with a cooling rate of 4.4°C / Ma and an uplifting rate of 0.04 mm/ a. U—Pb dating of pitchblende is done for the hydrothermal uranium deposit formed in the contact zone of the Huangmeijian intrusion. The result shows that the mineralization age is close to the closing time of the K—Ar system in biotite. The fluid inclusion thermometry indicates that the mineralization temperature is in agreement with the closure temperature of the biotite K—Ar system. This suggests a close relationship between the slow cooling of the intrusion and the hydrothermal uranium mineralization process.     

Aluminous hematite: A mössbauer study

Aluminous hematites prepared in three different ways have been examined at 300K and 4.2K using the Mössbauer technique. The results indicate significant differences between the behaviour of aluminous hematites that have been subjected to high temperatures (>600° C) and those which have not. The magnitude of the room temperature quadrupole splitting of the former increases with aluminium content, approaching at ～16 mole percent substitution the value (?0.22 mm/s) exhibited by all of the low temperature specimens. This variation may be explained qualitatively in terms of a preferential c-axis contraction of the lattice upon incorporation of aluminium, which does not occur unless a c-axis defect structure is removed by subjection of the hematite to high temperatures. The solid solubility limits of high and low temperature hematites (～15 mol % and ≥19 mol % respectively) also differ, as do the room temperature decreases in hyperfine splitting (?0.82 kOe/mol % Al and ?0.86 kOe/mol % Al). At 4.2 K only low temperature hematite exhibits a decrease in hyperfine splitting with increasing Al content (?0.40 kOe/mol % Al). The absolute values of the recoil free fractions of hydrothermally prepared aluminous hematites have been determined at 4.2 K (0.70±0.02 — pure hematite, 0.82±0.02, 14±2 mol % Al substitution) and exhibit a similar increase with Al content to that previously observed for aluminous goethites. The room temperature recoil free fraction of pure hematite has been measured to be 0.64±0.02. The effects of particle size on both hyperfine splitting and recoil free fraction have been investigated.     

Aquifer residence times for recycled water estimated using chemical tracers and the propagation of temperature signals at a managed aquifer recharge site in Australia

A prerequisite for minimizing contamination risk whilst conducting managed aquifer recharge (MAR) with recycled water is estimating the residence time in the zone where pathogen inactivation and biodegradation processes occur. MAR in Western Australia’s coastal aquifers is a potential major water source. As MAR with recycled water becomes increasingly considered in this region, better knowledge of applied and incidental tracer-based options from case studies is needed. Tracer data were collected at a MAR site in Floreat, Western Australia, under a controlled pumping regime over a distance of 50 m. Travel times for bromide-spiked groundwater were compared with two incidental tracers in recycled water: chloride and water temperature. The average travel time using bromide was 87?±?6 days, whereas the estimates were longer based on water temperature (102?±?17 days) and chloride (98?±?60 days). The estimate of average flow velocity based on water temperature data was identical to the estimate based on bromide within a 25-m section of the aquifer (0.57?±?0.04 m day^?1). This case study offers insights into the advantages, challenges and limitations of using incidental tracers in recycled water as a supplement to a controlled tracer test for estimating aquifer residence times.