Silicate melts at magmatic temperatures: in-situ structure determination to 1651°C and effect of temperature and bulk composition on the mixing behavior of structural units

The abundance of coexisting structural units in K-, Na-, and Li-silicate melts and glasses from 25° to 1654°C has been determined with in-situ micro-Raman spectroscopy. From these data an equilibrium constant, K_x, for the disproportionation reaction among the structural units coexisting in the melts, Si₂O₅(2Q³)SiO₃(Q²)+SiO₂(Q⁴), was calculated (K_x is the equilibrium constant derived by using mol fractions rather than activities of the structural units). From ln K_x vs l/T relationships the enthalpy (H_x) for the disproportionation reaction is in the range of-30 to 30 kJ/mol with systematic compositional dependence. In the potassium and sodium systems, where the disproportionation reaction shifts to the right with increasing temperature, the H_x increases with silica content (M/Si decreases, M=Na, K). For melts and supercooled liquids of composition Li₂O·2SiO₂ (Li/Si=1), the H_x is indistinguishable from 0. By decreasing the Li/Si to 0.667 (composition LS3) and beyond (e.g., LS4), the disproportionation reaction shifts to the left as the temperature is increased. For a given ratio of M/Si (M=K, Na, Li), there is a positive, near linear correlation between the H_x and the Z/r² of the metal cation. The slope of the H_x vs Z/r² regression lines increases as the system becomes more silica rich (i.e., M/Si is decreased). Activity coefficients for the individual structural units, _i, were calculated from the structural data combined with liquidus phase relations. These coefficients are linear functions of their mol fraction of the form _i=a lnX _i+b, where a is between 0.6 and 0.87, and X _i is the mol fraction of the unit. The value of the intercept, b, is near 0. The relationship between activity coefficients and abundance of individual structural units is not affected by temperature or the electronic properties of the alkali metal. The activity of the structural units, however, depend on their concentration, type of metal cation, and on temperature.     

Compressional behavior of omphacite to 47 GPa

Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si₂O₆ omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V ₀ = 423.9(3) Å³, K _T0 = 116(2) GPa and K _T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO₄ tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.     

Simulation of yielding and stress–stain behavior of shanghai soft clay

In this paper, a simple bounding surface plasticity model is used to reproduce the yielding and stress–strain behavior of the structured soft clay found at Shanghai of China. A series of undrained triaxial tests and drained stress probe tests under isotropic and anisotropic consolidation modes were performed on undisturbed samples of Shanghai soft clay to study the yielding characteristics. The degradation of the clay structure is modeled with an internal variable that allows the size of the bounding surface to decay with accumulated plastic strain. An anisotropic tensor and rotational hardening law are introduced to reflect the initial anisotropy and the evolution of anisotropy. Combined with the isotropic hardening rule, the rotational hardening rule and the degradation law are incorporated into the bounding surface formulation with an associated flow rule. Validity of the model is verified by the undrained isotropic and anisotropic triaxial test and drained stress probe test results for Shanghai soft clay. The effects of stress anisotropy and loss of structure are well captured by the model.     

Application of mass-balance and flow simulation calculations to interpretation of mixing at Äspö, Sweden

The hydrogeology of a vertical fracture zone at 70 m depth at the access tunnel to the Äspö Hard Rock Laboratory was monitored over 3 a for hydrochemical changes that could be effected by construction of a deep repository for high-level nuclear waste. Tunnel construction dramatically disturbed the hydrogeological system, but this provided an opportunity to integrate hydrogeochemical and hydrological evaluation of the zone. The objective of this study was to evaluate hydrogeochemical evolution, groundwater flow and surface water intrusion during the experiment using an integrated approach of geochemical mass-balance calculations and numerical flow simulations.The dilution of major ions was the dominant hydrochemical trend. However, HCO₃ and SO₄ showed significant enrichment. Increasing activity of ¹⁴C suggested that oxidation of organic C was the likely source of HCO₃. Any mineral source dissolving during the experiment seemed insufficient to account for changes in SO₄ and current intrusion of sea water was excluded according to the data. Cation exchange as well as minor calcite reactions in fractures were assumed probable in such temporary chemical conditions. Conservative two end-member mixing models with shallow groundwater in the zone and initial groundwater at tunnel level also assumed remarkable mass transfer (several mmol/l). Therefore a third SO₄-rich end-member, a regional shallow groundwater type which may mix by lateral flow in the system, was tested. This was also expected from hydraulic measurements and preliminary flow simulations assuming homogeneity.Three end-member mixing calculations using Cl and SO₄ as conservative tracers give a constant proportion of lateral water in all boreholes after 300 days, which is consistent with the steady state character of the flow field in the late part of the experiment. To predict reactions on plausible levels needs significant adjustments of initial and final waters, indicating uncertainties in the hydrochemical information of the fracture zone. In the flow simulations the transmissivities were selected so that the chemical mixing proportions would match simulated portions of flow as closely as possible. The simulated total recoveries (drawdowns) differ from the measurements mainly due to overly simple parametrisation of the transmissivity in the fracture zone. However, integrating hydrochemistry in flow modelling is considered encouraging in producing additional information of the heterogeneity of a flow structure.     

Shear behavior of sensitive marine clay–steel interfaces

Many soil–structure interaction problems require the knowledge of the shear resistance and behavior between the soil and construction materials. Although sensitive marine clay deposits are widely found in Canada (Leda clay) and many regions in the world (e.g., Scandinavia), and steel is a common construction material for many civil engineering structures, our understanding of the interface shear behavior between sensitive marine clay and steel is still limited. This paper presents the results of an experimental study on the interface shear behavior between Leda clay and steel. In this research, direct shear tests (DSTs) are conducted to investigate the interface shear strength parameters and behavior between Leda clay and steel, and the effect of several factors (e.g., steel surface roughness, properties of the Leda clay) on the interface shear behavior and parameters. All tests have been carried out with a standard DST apparatus at normal loads which range from 250 to 450 kPa. The results show that the Leda clay interface shear behavior can be significantly affected by the steel surface roughness, the Leda clay’s OCR, dry density, and salt content. The results presented in this paper will contribute to a more cost-effective design of geotechnical structures in Leda clay.     

Consolidation behavior of soil–cement column improved ground

Columnar inclusion is one of the effective and widely used methods for improving the engineering properties of soft clay ground. This article investigates the consolidation behavior of composite soft clay ground using both physical model tests under an axial-symmetry condition and finite element simulations using the PLAXIS 2D program. It was determined that the final settlement and the rate of consolidation of the composite ground depended on the stress state. For an applied stress that is much lower than the failure stress, the final settlement of the composite ground was lower, and the consolidation was rapid. When the soil–cement column failed, the stress on the column suddenly decreased (due to strain-softening); meanwhile, the stress on the soil increased to maintain the force equilibrium. Consequently, the excess pore pressure in the surrounding clay increased immediately. The cracked soil–cement column acted as a drain, which accelerated the dissipation of the excess pore pressure. The consolidation of the composite ground was mainly observed in the vertical direction and was controlled by the area ratio, which is the ratio of the diameter of the soil–cement column to the diameter of the composite ground, a. The stress on the column was shown to be low for a composite ground with a high value of a, which resulted in less settlement and fast consolidation. For a long soil–cement column, the excess pore pressures in the surrounding clay and the column were essentially the same at a given consolidation time throughout the improvement depth. It is proposed that the soil–cement column and surrounding clay form a compressible ground, and the consolidation occurs in the vertical direction. The composite coefficient of consolidation (c_v(com₎) that was obtained from the physical model test on the composite ground can be used to approximate the rate of consolidation. This approximation was validated via a finite element simulation. The proposed method is highly useful to geotechnical engineers because of its simplicity and reliable prediction.     

Nonconservative behavior of Br−/Cl− ratios during alteration of volcaniclastic sediments

Other than halite diagenesis and organic matter degradation, Cl⁻ and Br⁻ are considered to be conservative in marine pore fluids. Consequently, Br⁻/Cl⁻ ratios should remain constant during most diagenetic reactions. Nonetheless, Br⁻/Cl⁻ molar ratios decrease to 1.27 × 10⁻³ (≈18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl⁻ and Br⁻. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br⁻/Cl⁻ ratio. Some Cl⁻ may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br⁻/Cl⁻ ratio. The limited source of Cl⁻ suggests that proportionately more Br⁻ than Cl⁻ is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl⁻ and Br⁻ may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.     

Saturation states of carbonate minerals in a freshwater-seawater mixing zone of small tropical island’s aquifer

Groundwater is a crucial resource on the Manukan Island as it is the only source of freshwater available on the island. The aquifer has deteriorated to a high degree, during the last decade. Nine domestic wells were sam-pled from March 2006 to January 2007 to probe the hydrochemical components that influence the water quality. Geochemical data on dissolved major constituents in groundwater samples from the Manukan Island revealed the main processes responsible for their geochemical evolution. The results using statistical analyses, graphical method and numerical model output (PHREEQC) showed that the groundwater was chemically highly enriched in Na and Cl, indicative of seawater intrusion into the aquifer as also supported from the Na-Cl signature on the Piper diagram. From the PHREEQC simulation model, calcite, dolomite and aragonite solubility showed positive values of the saturation indices (SI), indicating supersaturation which led to mineral precipitation condition of water by these min-erals.     

Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

Laboratory investigation and constitutive modeling of the mechanical behavior of sand–GRP interfaces

Acta Geotechnica - The frictional behavior of soil–pipe interfaces plays a paramount role in the design and construction of underground pipes, particularly applying trenchless technologies...     

Three-dimensional elastic–viscoplastic consolidation behavior of transversely isotropic saturated soils

Acta Geotechnica - This paper investigates three-dimensional elastic–viscoplastic consolidation behaviors of transversely isotropic saturated soils. The Drucker–Prager yield criterion...     

Stress–strain behavior of cement-improved clays: testing and modeling

The results of a series of laboratory tests on unimproved and cement-improved specimens of two clays are presented, and the ability of a bounding surface elastoplastic constitutive model to predict the observed behavior is investigated. The results of the oedometer, triaxial compression, extension, and cyclic shear tests demonstrated that the unimproved soil behavior is similar to that of soft clays. Cement-improved specimens exhibited peak/residual behavior and dilation, as well as higher strength and stiffness over unimproved samples in triaxial compression. Two methods of accounting for the artificial overconsolidation effect created by cement improvement are detailed. The apparent preconsolidation pressure method is considerably easier to use, but the fitted OCR method gave better results over varied levels of confining stresses. While the bounding surface model predicted the monotonic behavior of unimproved soil very well, the predictions made for cyclic behavior and for improved soils were only of limited success.     

Comparison of antimony behavior with arsenic under various soil redox conditions

Antimony （Sb） is a toxic element and belongs to group 15 of the periodic table, under arsenic （As）. The geochemical behavior of Sb in the environment is still largely unknown. Since the behavior of Sb in the environment depends on its oxidation state, Sb analysis in environmental samples requires quantitative measurement of Sb （Ⅲ） and Sb （Ⅴ）. The aim of this study is the speciation of Sb in both solid and water phases to understand the reaction and dynamics of Sb in soil-water system. Accordingly, we employed X-ray absorption fine structure （XAFS） analysis to determine the Sb and As species in soil in laboratory and natural systems, while we also determined the oxidation states in soil water by the conventional HPLC-ICP-MS method. Natural soil and soil water samples containing Sb and As were collected around the Ichinokawa mine pithead, Ehime, Japan. To observe the species under various redox conditions, the soil and soil water samples were collected at four depths. Soil containing Sb and As were incubated for 7 days at 25℃ to observe their oxidation states under various redox condition by changing the total amount of water in the soil. Antimony K-edge XAFS spectra were measured at the beamline BL01B 1 at SPring-8 （Hyogo, Japan） and K-edge XAFS spectra of As, Fe, and Mn at the beamline BL12C in Photon Factory, KEK （Thukuba, Japan）. In the natural soil-water system, Sb was present exclusively as Sb （Ⅴ） over a wide redox range （from Eh=-140 to 360 mV; pH 8）, while As was present as a mixture of As （Ⅲ） and As （Ⅴ）. This trend was confirmed in the laboratory experiments. These results suggest that Sb （Ⅴ） is a very stable form in the environment and that Sb is oxidized under more oxic condition than As. Combining the results of Fe and Mn XAFS analyses and a positive correlation among Sb, As, and Fe abundances in the soil, the host phases of Sb and As in soil were Fe （Ⅲ） hydroxide. EXAFS analyses of Sb and As are also consistent with this fact. Under reducing conditions, the concentrations of As in the soil water increased whereas those of Sb decreased in both the natural and laboratory systems.     

Directionally dependent strength and dilatancy behavior of soil–structure interfaces

Acta Geotechnica - Soil–structure interfaces typically exhibit a shear behavior that is independent of the direction of relative displacement due to symmetry in the solid material's...     

What drives low-carbon consumption behavior of Chinese college students? The regulation of situational factors

Carbon dioxide contributes about 90% of global warming, which is mainly generated by residents’ daily consumption activities. This article explores the factors of low-carbon consumer behavior among college students and situational factors which contribute to explain intention–behavior gap. Combined with the existing research literature and the Model of Responsible Environmental Behavior, a model of the factors of Chinese college students’ low-carbon consumption behavior was constructed through a sample survey of college students in Jiangsu Province. Analysis results show that (1) College students’ low-carbon behavior intention has a significant positive effect on low-carbon consumption behaviors; (2) Attitudes, emotions, and habits indirectly affect low-carbon consumer behaviors through low-carbon behavior intention; (3) Low-carbon behavior ability and habits can also affect low-carbon consumption behaviors in a direct way; (4) The study of situational factors found that policies and regulations, economic costs, goals and feedback, and social norms have a significant regulating effect in the process of low-carbon behavior intention which has an impact on low-carbon consumption behaviors; (5) In terms of demographic factors, gender and education have a significant effect on low-carbon consumption behavior. Finally, this article discusses the policy measures to guide college students’ low-carbon consumption behavior from the government and the school level, respectively, and place a high hope on college students who can positively influence the entire social group to carry out low-carbon consumption and achieve the realization of China’s low-carbon goals.

     

Crystallization behavior of Na2SO4–MgSO4 salt mixtures in sandstone and comparison to single salt behavior

We report on the crystallization behavior and the salt weathering potential of Na₂SO₄, MgSO₄ and an equimolar mixture of these salts in natural rock and porous stone. Geochemical modeling of the phase diagram of the ternary Na₂SO₄–MgSO₄–H₂O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Model calculations include stable and metastable solubilities of the various hydrated states of the single salts and the double salts Na₂Mg(SO₄)₂·4H₂O (bloedite), Na₂Mg(SO₄)₂·5H₂O (konyaite), Na₁₂Mg₇(SO₄)₁₃·15H₂O (loeweite) and Na₆Mg(SO₄)₄ (vanthoffite). In situ Raman spectroscopy was used to study the phase transformations during wetting of pure MgSO₄·H₂O (kieserite) and of the incongruently soluble salts bloedite and konyaite. Dissolution of kieserite leads to high supersaturation resulting in crystallization of higher hydrated phases, i.e. MgSO₄·7H₂O (epsomite) and MgSO₄·6H₂O (hexahydrite). This confirms the high damage potential of magnesium sulfate in salt damage of building materials. The dissolution of the incongruently soluble double salts leads to supersaturation with respect to Na₂SO₄·10H₂O (mirabilite). However, the supersaturation was insufficient for mirabilite nucleation. The damage potential of the two single salts and an equimolar salt mixture was tested in wetting–drying experiments with porous sandstone. While the high damage potential of the single salts is confirmed, it appears that the supersaturation achieved during wetting of the double salts at room temperature is not sufficient to generate high crystallization pressures. In contrast, very high damage potentials of the double salts were found in experiments at low temperature under high salt load.1     

Modeling of the swelling–shrinkage behavior of expansive clays during wetting–drying cycles

Acta Geotechnica - This paper presents a constitutive model for simulating the swelling–shrinkage volume change of expansive soils during wetting–drying cycles. Based on the concept of...     

Geochemical modeling of leaching behavior of heavy metals in municipal solid waste incinerator fly ashes

Municipal solid waste incinerator (MSWI) fly ash is world-widely defined as hazardous waste because of its high concentration of heavy metals and high toxic equivalents of dioxin-like compounds. Therefore, if not properly disposed, it would pose a risk of…