Standard partial molal properties of aqueous alkylphenols and alkylanilines over a wide range of temperatures and pressures

This article presents methods for predicting the standard partial molar Gibbs energy (standard chemical potential) and related derivative properties of aqueous hydroxy and aminoderivatives of (alkyl)benzenes over a wide range of temperatures and pressures. A thorough literature overview was conducted for collecting all available experimental data resulting from phase equilibrium, calorimetric and volumetric measurements that allow calculation of the thermodynamic properties of hydration. New experimental values are presented for solubility in water of isomeric toluidines and for the partial molal volume of phenol and cresols at high temperatures. Building upon the acquired database several prediction schemes were developed and tested for calculating the standard thermodynamic properties (and namely the Gibbs energy of hydration) of aqueous alkylphenols and alkylanilines as a function of temperature and pressure. First, a simple group contribution method was proposed for estimations at 298.15 K and 0.1 MPa using the simultaneous treatment of all available data on hydration properties at near ambient conditions. Second, this group contribution method allowed re-adjustment of the parameters of the Helgeson-Kirkham-Flowers model (HKF) using a new procedure proposed recently by Plyasunov and Shock [Plyasunov, A.V., Shock, E.L., 2001b. Correlation strategy for determining the parameters of the revised Helgeson-Kirkham-Flowers model for aqueous nonelectrolytes. Geochim. Cosmochim. Acta65, 3879-3900]. Third, using the Sedlbauer-O’Connell-Wood equation of state for aqueous species (SOCW), group contributions were determined for predictions at high temperatures and pressures by simultaneous correlation of all available thermodynamic data on hydration properties. The latter method was constrained by the group contributions at 298.15 K and 0.1 MPa making both group contribution schemes consistent at near ambient conditions. The calculations from the HKF and SOCW equations of state and those from the simple thermodynamic integration of the data at 298.15 K and 0.1 MPa were compared for several alkylphenols and alkylanilines. Equilibrium constants for hydration reactions obtained from the three approaches are in very good agreement at temperatures to at least 400 K. At higher temperatures we assess the accuracy of different predictive schemes and their associated uncertainties. The reliable predictions of the standard chemical potentials to at least 573 K and 100 MPa are possible by the group contribution method using the SOCW equation of state.     

Hydromechanical behaviour of a compacted swelling soil over a wide suction range

A study of the hydromechanical behaviour of a compacted swelling material in the range of suctions comprised between 0 and 40 MPa was performed. This study has required the development of two kinds of suction controlled oedometer devices based on two different suction control techniques. In the range of suctions higher than 8.5 MPa, the saturated salt solutions method was used and a new oedometer using this suction control technique was developed. For suctions lower than 8.5 MPa an osmotic oedometer was used. Despite the differences between the applied suction components (matric and total), the correlation between the two methods was verified for the tested material. The second part of the paper presents a set of oedometer tests conducted under various suctions. The effect of the applied suction on the hydromechanical parameters was studied. First, two swelling phases were highlighted: a low swelling phase above a suction of 4 MPa and a high swelling one below this value. These phases were considered as being related to the microstructure of compacted swelling clays. Secondly, it was shown that the slopes of the elastic part and of the plastic part of the consolidation curves were not influenced significantly by the applied suctions. In opposition, the preconsolidation pressure is affected by the decrease of the applied suctions even in the low swelling phase. Such a behaviour could be explained by the effects of wetting on the microstructure.     

Results of long-term monitoring of 3C 273 over a wide range of wavelengths

The results of long-term monitoring of the quasar 3C 273 at wavelengths from radio to gamma rays between 1963 and 2011 are presented. The variations of the source flux density are studied using harmonic and wavelet analysis techniques. The values and frequency-time localizations of harmonic components in the flux-density variations are determined. The eight-year radio-variability period reported earlier had become gradually reduced and attenuated by 2000. The optical light curve has a component with a quasi-period of approximately 13 years. Cyclic variations whose periodicity gradually increased from approximately one to two years were observed in the X-ray between 1996 and 2006. The relative time delays between the light curves at different radio frequences are determined. The frequency dependence of time delays is approximated by the power law, ΔT(ν) ∝ ν ^?1/k with k = 1.4 ± 0.1, which can be used to infer the corresponding core shift and estimate the core-region magnetic field as B _{1 pc} = 0.5 ± 0.1 G. This approach is preferable to other methods, since it does not require multi-frequency VLBI observations and is a simple and effective tool for studying Active Galactic Nuclei.     

Hydromechanical behavior of unsaturated soil with different initial densities over a wide suction range

Acta Geotechnica - Many civil engineering projects are related to hydromechanical behavior of unsaturated soils over a wide suction range, which was investigated by imposing suctions on clayey silt...     

Non-stationary emission of the blazar S4 0954+658 over a wide range of wavelength

Data from long-term multi-frequency monitoring are used to analyze variations in the flux density of the active galactic nucleus S4 0954+658. These data were obtained at the CrimeanAstrophysical Observatory, the Metsähovi Radio Observatory of Aalto University, the University of Michigan Radio Astronomy Observatory, the Cavendish Laboratory of Cambridge University, the Special Astrophysical Observatory, and the National Institute of Astrophysics, Optics, and Electronics; 0.1–300-GeV data from the Fermi space gamma-ray observatory were also used. Radio data at 4.8, 8, 14.5, 15, 22.2, and 36.8 GHz are considered together with optical and near-infrared data in the R, J, H, and K filters.     

Solid solutions of trace Eu(III) in calcite: Thermodynamic evaluation of experimental data over a wide range of pH and pCO2

The thermodynamics of dilute Eu-calcite solid solutions formed under widely different pH-pCO₂ conditions at T = 25°C and p = 1 bar were investigated using three sets of Eu(III) uptake experiments, two of which were taken from the literature: (a) recrystallization in synthetic cement pore water at pH ∼ 13 and pCO₂ ∼ 10⁻¹³ bar (this work); (b) coprecipitation in 0.1 M NaClO₄ at pH ∼ 6 and pCO₂ ∼ 1 bar; (c) coprecipitation in synthetic seawater at pH ∼ 8 and pCO₂ ranging from 3 × 10⁻⁴ to 0.3 bar.Solid solution formation was modeled using the Gibbs energy minimization (GEM) method. In a first step (“forward” modeling), we tested ideal binary solid solution models between calcite and the Eu end-members Eu₂(CO₃)_3, EuNa(CO₃)₂, Eu(OH)CO₃ or Eu(OH)₃, for which solids with independently measured solubility products exist. None of these four binary solid solutions was capable of reproducing all three experimental datasets simultaneously. In a second step (“inverse” modeling), ideal binary solid solutions were constructed between calcite and the candidate Eu end-members EuO(OH), EuH(CO₃)₂ and EuO(CO₃)_0.5, for which no independent solubility products are available. For each single data point and each of these end-members, a free energy of formation with inherent activity coefficient term ( = G_α^o + RT lnγ_α) was estimated from “dual thermodynamic” GEM calculations. The statistical mean of was then calculated for each of the three datasets. A specific end-member was considered to be acceptable if a standard deviation of ± 2 kJ mol⁻¹ or less resulted for each single dataset, and if the mean -values calculated for the three datasets coincided. No binary solid solution with any of the seven above mentioned end-members proved to satisfy these criteria.The third step in our analysis involved consideration of ternary solid solutions with CaCO₃ as the major end-member and any two of the seven considered Eu trace end-members. It was found that the three datasets can only be reproduced simultaneously with the ternary ideal solid solution EuH(CO₃)₂ - EuO(OH) - CaCO₃, setting = −1773 kJ mol⁻¹ and = −955 kJ mol⁻¹, whereas all other end-member combinations failed. Our results are consistent with time-resolved laser fluorescence data for Cm(III) and Eu(III) indicating that two distinct species are incorporated in calcite: one partially hydrated, the other completely dehydrated. In conclusion, our study shows that substitution of trivalent for divalent cations in carbonate crystal structures is a more complex process than the classical isomorphic divalent-divalent substitution and may need consideration of multicomponent solid solution models.     

Analysis of gravity gradients over a thin infinite sheet

A simple method to interpret gravity gradients over a thin infinite dipping sheet is discussed. The Hilbert transform is used to compute the vertical gradient from the horizontal gradient of the gravity field. The method is illustrated with a theoretical example.     

Analysis of gravity gradients over a thin infinite sheet

Expressions are derived for the horizontal and vertical gradients of the gravity anomaly over a thin dipping sheet of infinite depth extent. The resultant of these two gradients, known as the complex gradient, is also derived and properties of the amplitude and phase responses of the complex gradient are studied. It is shown that the amplitude plot is a symmetric curve whose, shape is independent of the dip (?) of the sheet whereas the phase plot is an antisymmetric curve with an offset value equal to ?-π/2. The depth to top of the sheet is obtained from the amplitude plot. The method is applied on a field example and the results are in good agreement with the results obtained by earlier workers.     

Structural similarity and variety at the tips in a wide range of strike–slip faults: a review

Strike–slip faults are often accompanied by a variety of structures, particularly at their tips. The zones of additional fracturing are classified as tip‐damage zones. These zones can be subdivided into several different damage patterns based on the nature and orientation of faults and fractures developed. Damage zones at the ends of small strike–slip faults (mode II tips) develop wing cracks, horsetail splays, antithetic faults, synthetic branch faults and solution surfaces. Similar tip‐damage patterns are also commonly observed at larger (regional) scales, but with a dominance of faulting over tensile cracks and solution surfaces. Wing cracks and horsetail splays developed at small‐scale faults are replaced by normal faults in large‐scale faults. Antithetic faults and synthetic branch faults are observed at small and large scales. Thrust faults are developed at large scales, in a similar pattern to solution surfaces at a small scale. All these structures may show slightly different angular relationships to the master fault at small and large scale, but develop in response similar stress distribution and mechanics around the fault. Thus, mode II tip‐damage zones show similar patterns over a wide range of fault scales.     

Catalytic oxidation of arsenite and reaction pathways on the surface of CuO nanoparticles at a wide range of pHs

Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O₂ as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~?pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O₂ back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.     

广吸力范围内压实红黏土的强度特性

为了研究广吸力范围内红黏土的强度特性,采用经压力板法饱和,对盐溶液蒸汽平衡法吸力平衡后的非饱和桂林红黏土样进行一系列常含水率直剪试验。高吸力时土–水特征曲线不受土体密度的影响,故等含水率试验可以认为是等吸力试验。试验结果表明,随着平衡吸力的增加,非饱和红黏土的抗剪强度与黏聚力均先增大后减小,吸力为7 MPa左右时出现抗剪强度的最大值;当吸力超过7 MPa后内摩擦角基本保持不变,说明高吸力阶段吸力增大引起的强度变化是由黏聚力的变化引起的;吸力超过70 MPa后随着吸力的增加,强度变化较小。最后结合压汞试验的结果,从孔隙大小分布的角度解释了红黏土在广吸力范围内的强度特性。     

Evaluation of a wide range laser diffraction grain size analyser for use with sediments

The qualities of a laser diffraction grain size analyser, the Coulter LS-100 (range claimed by the manufacturer: 0·4–900 μm in a single measurement), are evaluated on sediments of fluvial and lacustrine origin. Accuracy and resolution of measurement on standard latex spheres are excellent. Reproducibility of the results on natural sediments appears to be satisfactory, but the method underestimates the fraction of clay particles with an efficiency of detection (36–70%) proportional to the clay content determined from pipette analysis. This efficiency is somewhat higher than those reported from other instruments of the same generation. Comparison of the Coulter LS-100 with other sizing techniques shows good agreement with the sieving method but some differences appear with the electroresistance particle technique: median and mean size values measured by the Coulter Counter TA1 are systematically lower than those obtained by the Coulter LS-100. Analyses show good correlation with those of a Malvern Laser particle analyser but a discrepancy appears with very fine silt and clay sized sediments. The Coulter LS-100 detects a higher clay content than that measured with the Malvern Laser Sizer 2600. Except when precise measurements of clay content are needed, the Coulter LS-100 produces precise and accurate results in size ranges required for geological and environmental studies.     

Contribution of a sewage sludge application to the short-term carbon sequestration across a wide range of agricultural soils

The atmospheric levels of carbon dioxide (CO₂) and other greenhouse gases (GHGs) have increased dramatically since the industrial revolution. The atmospheric enrichment with CO₂ and other GHGs has resulted in multiple negative consequences: such as the increase in the average temperature and the rise of the sea level. Hence, there is a growing interest in developing feasible methods to reduce the atmospheric levels of these gases. One of these strategies is to enhance C sequestration through the increase of soil organic carbon (SOC) pool by the amendment of agricultural soils with sewage sludge. However, there is considerable uncertainty about the effects (positive or negative) of sewage sludge applications on the SOC pool. Thus, a simple approach developed under laboratory conditions is presented to discern the effect of a single sewage sludge application of 50 t ha⁻¹ on the short-term SOC pool in 60 contrasting agricultural soils. The role of soil factors in the C sequestration of the recently added carbon was also studied. The application of sewage sludge supposed a mean increase of 1.7 ± 1.6 g SOC kg⁻¹, with peak increases of up to 3.8 g SOC kg⁻¹ and decreases of up to 4.6 g SOC kg⁻¹. The initial SOC contents conditioned the C sequestration after sewage sludge application, and no other soil property was related.     

Quantifying the tectono-metamorphic evolution of pelitic rocks from a wide range of tectonic settings: mineral compositions in equilibrium

Commonly used thermometer and barometer calibrations are sensitive to mineral assemblage and, thus, bulk-rock composition. Calculated mineral stabilities for an average pelitic rock over a pressure–temperature (PT) range appropriate for normal, thickened, heated and shallowly subducted continental crust (400–900°C at 0.1–3.0 GPa) reveal more than one hundred possible assemblages. Individual phase compositions are dependent on the assemblage in which they belong and combining isopleth sets to represent and reveals several PT-ranges where commonly used mineral thermobarometers are less effective. For example, the garnet-biotite thermometer becomes increasingly P dependent in the absence of muscovite in high T melt-bearing assemblages, and biotite and plagioclase are not stable at pressures appropriate for lower thickened continental crust. Compositional thermobarometers involving equilibration between alternative phases (namely garnet, phengite and omphacite) are presented. Although the equilibrium compositions of phases at any P and T may change significantly as a function of bulk-rock composition, compositional-ratio thermobarometers are typically insensitive to this, unless a pseudo-univariant reaction is crossed and the buffering assemblage is altered. Quantification of the limits of efficacy of various thermobarometers allows the mineralogy of metapelites to be used to precisely determine segments of PT paths and infer their likely tectonic controls. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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A systematic field-based testing program of hydraulic conductivity and dispersivity over a range in scale

In a small watershed underlain by relatively homogeneous (nonlayered), sandy, glacial outwash, hydraulic conductivity (K) and longitudinal dispersivity (α _L) were systematically measured over a range in scale. Test methods employed in the investigation are conventional and/or based on accepted principles, measurement scales are those typically encountered in applied field problems, and the hydrogeologic setting is typical of large areas within the northern hemisphere and similar to many alluvial environments worldwide. The results show that K measured under radial flow is scale-dependent up to a radius of influence (r _i) of approximately 15 m but reaches an asymptotic value above this threshold. This asymptotic value of K is consistent with results obtained at the regional scale (～10⁴ m) for the same aquifer using non-radial three-dimensional techniques; the initial increase appears to reflect increasing dimensionality of the radial tests with larger r _i. Although α _L was evaluated over a much smaller interval relative to K, α _L proved to be independent of scale over the full range tested, from 2 to 29 m, an unexpected result. The findings support the idea that there is, as yet, no predictable relationship between scale effects in K and α _L at scales normally encountered in applied field hydrogeology.     

Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m² on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange process appears to be a significant subsystem within macroscopic pH-dependent Fe(II) adsorption.     

Analysis of the steady‐state flow of a compressible viscoplastic medium over a wedge

A new model for calculating the resistance to penetration into geological or geologically derived materials is proposed. We assume steady‐state flow of the target material over the penetrator. The target medium is described by a rate dependent constitutive equation that accounts for combined effects of strain rate and compaction on yielding. The wedge‐shaped penetrator is considered to be rigid. The influence of the characteristics of the penetrator/target interface, impact velocity, target mechanical properties and nose geometry on the resistance to penetration is investigated. It is found that for low to intermediate impact velocities, accounting for friction results in a blunter optimal wedge geometry for optimal penetration performance. Copyright © 2005 John Wiley & Sons, Ltd.