Estimation of velocity function parameters in unconsolidated sands using semblance velocity analysis

To properly understand seismic wave propagation in unconsolidated sand layers, it is important to estimate the parameters of their continuous velocity–depth functions. This study proposes a procedure to estimate the V ₀ and k parameters of a specific velocity function, where V ₀ is the direct P-wave velocity at the ground surface and k is the velocity gradient. The V ₀ and k parameters are generally independent of each other. However, it is possible to relate them numerically because both depend strongly on the porosity (?) and water saturation (S _w). The proposed procedure starts by tabulating V ₀ and k for 0.05?≤???≤?0.5 sampled at Δ??=?0.05 and S _w?=?0.6, so that only V ₀ is needed for fitting. Then, time–distance (T-X) type curves of the direct arrival are calculated for the corresponding values of V ₀ and k parameters values. The type curves are fitted then to the observed shot gather through a modification of the classic semblance velocity analysis method. Once the best-fit V ₀ value is found, the corresponding k, ?, and S _w values are picked from a V ₀–k–? lookup table. The procedure is applied on synthetic shot gathers with various amounts of additive Gaussian random noise. Results show that the method is robust and tolerant to low to moderate amounts of noise.     

The reactivity of iron oxides towards reductive dissolution with ascorbic acid in a shallow sandy aquifer (Rømø, Denmark)

The pool of iron oxides, available in sediments for reductive dissolution, is usually estimated by wet chemical extraction methods. Such methods are basically empirically defined and calibrated against various synthetic iron oxides. However, in natural sediments, iron oxides are present as part of a complex mixture of iron oxides with variable crystallinity, clays and organics etc. Such a mixture is more accurately described by a reactive continuum covering a range from highly reactive iron oxides to non-reactive iron oxide. The reactivity of the pool of iron oxides in sediment can be determined by reductive dissolution in 10 mM ascorbic acid at pH 3. Parallel dissolution experiments in HCl at pH 3 reveal the release of Fe(II) by proton assisted dissolution. The difference in Fe(II)-release between the two experiments is attributed to reductive dissolution of iron oxides and can be quantified using the rate equation J/m₀ = k′(m/m₀)^γ, where J is the overall rate of dissolution (mol s⁻¹), m₀ the initial amount of iron oxide, k′ a rate constant (s⁻¹), m/m₀ the proportion of undissolved mineral and γ a parameter describing the change in reaction rate over time. In the Rømø aquifer, Denmark, the reduction of iron oxides is an important electron accepting process for organic matter degradation and is reflected by the steep increase in aqueous Fe²⁺ over depth. Sediment from the Rømø aquifer was used for reductive dissolution experiments with ascorbic acid. The rate parameters describing the reactivity of iron oxides in the sediment are in the range k′ = 7·10⁻⁶ to 1·10⁻³ s⁻¹ and γ = 1 to 2.4. These values are intermediate between a synthetic 2-line ferrihydrite and a goethite. The rate constant increases by two orders of magnitude over depth suggesting an increase in iron oxide reactivity with depth. This increase was not captured by traditional oxalate and dithionite extractions.     

Vorticity and non-coaxiality in progressive deformations

A measure of the non-coaxiality involved in progressive deformation histories is proposed in the form of the kinematical vorticity number, W_k. This number is a measure of the relative effects of rotation of material lines (relative to the instantaneous stretching axes) and of stretching of these material lines. As such, W_k, is a measure of the instantaneous degree of non-coaxiality. A detailed example is first presented in the form of a progressive simple shearing in which the shear plane rotates relative to an external coodinate system. This is followed by examples of more complicated deformation histories. Three specific types of progressive, isochoric (constant volume) deformation histories are recognized. Those for which 0 ≤ W_k < 1 correspond to deformation histories where no line that has been extended is shortened in future increments; W_k > 0 is a special case of these corresponding to a coaxial history. Histories with W_k > 0 are non-coaxial. Those histories with W_k = 1 correspond to progressive simple shearing. Those histories with 1 < W_k < ∞ are pulsating and lines that have been extended may be shortened in future increments.     

Kinetics of iron (II) oxidation determined in the field

This paper presents the results of extensive field trials measuring rates of Fe(II) oxidation at a number of Fe-bearing mine drainage discharges in the UK. Batch experiments were carried out with samples taken at regular intervals and Fe(II) concentration determined spectrophotometrically using 2′2-bipyridyl as the complexing agent. Initial concentrations for Fe(II) were 5.65-76.5 mg/L. Temperature, pH and dissolved O₂ (DO) were logged every 10 s, with pH at the start of the experiments in the range 5.64-6.95 and alkalinity ranging from 73 to 741 mg/L CaCO₃ equivalent. A numerical model based on a fourth order Runge-Kutta method was developed to calculate values for k₁, the rate constant for homogeneous oxidation, from the experimental data. The measured values of pH, temperature, [Fe(II)] and DO were input into the model with resulting values for k₁ found to be in the range 2.7 × 10¹⁴-2.7 × 10¹⁶ M⁻² atm⁻¹ min⁻¹. These values for k₁ are 1-3 orders of magnitude higher than previously reported for laboratory studies at a similar pH. Comparison of the observed Fe(II) oxidation rates to data published by other authors show a good correlation with heterogenous oxidation rates and may indicate the importance of autocatalysis in these systems. These higher than expected rates of Fe oxidation could have a significant impact on the design of treatment schemes for the remediation of mine drainage and other Fe-bearing ground waters in the future.     

A quantitative study of the degradation of whale bone lipids: Implications for the preservation of fatty acids in marine sediments

The degradation and preservation affecting the biomarker record of ancient metazoa are not fully understood. We report on a five month experiment on the fate of fatty acids (FAs) during the degradation of recent whale vertebrae (Phocoena phocoena). Whale bones were analysed for extractable FAs and macromolecularly bound n-acyl compounds. Fresh bone showed extractable FAs dominated by 16:1ω7c, 16:0, 18:1ω9c and 18:0. Calculated degradation rate constant (k) values showed a rapid decrease in FA concentration, with k values higher for unsaturated than for saturated compounds (0.08/day for 18:1ω9c, 0.05/day for 16:0). The appearance or increased abundance of distinctive methyl branched (e.g. i/ai-15:0 and -17:0, 10Me-16:0) and hydroxy FAs (e.g. 10OH-16:0 and 10OH-18:0) were observed, providing clear evidence for the microbial degradation of bone organic matter and an input of lipids from specialised bacteria. Catalytic hydropyrolysis (HyPy) of demineralised extraction residues released up to 0.13% of the total n-C₁₆ and n-C₁₈ moieties in the degraded bones. This revealed that only a small, yet sizeable, portion of bone-derived fatty acyl units was sequestered into (proto)kerogen during the earliest stages of degradation.     

Connections between surface complexation and geometric models of mineral dissolution investigated for rhodochrosite

Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO₃H regulates dissolution for pH < 7 while the surface concentration of >MnOH₂⁺ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ_1/2(k_co + k_ca)[>CO₃H] + χ_1/2(k_mo + k_ma)[>MnOH₂⁺ ], where R is the dissolution rate (mol m⁻² s⁻¹), 2χ_1/2 is the fraction of surface sites located at steps, [>CO₃H] and [>MnOH₂⁺ ] are surface concentrations (mol m⁻²), and k_co, k_ca, k_mo, and k_ma are the respective dissolution rate coefficients (s⁻¹) for the >CO₃H and the >MnOH₂⁺ surface species on obtuse and acute steps. We find k_co = 2.7 s⁻¹, k_ca = 2.1 × 10⁻¹ s⁻¹, k_mo = 4.1 × 10⁻² s⁻¹, k_ma = 3.7 × 10⁻² s⁻¹, and χ_1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface step processes, including double-kink initiation and single-kink propagation. We propose that the SSCM model may have general applicability for dissolution far from equilibrium of flat mineral surfaces of ionic crystals, at least those that dissolve by step retreat.     

Physical properties of calcium aluminates from vibrational spectroscopy

Heat capacity (C_V) and entropy (S) as a function of temperature were calculated for phases in the CaO-Al₂O₃ system from vibrational spectra using a quasi-harmonic model. Calculated values of C_V at 298 K for the calcium aluminates may have uncertainties as small as ±1%, based on comparison with published calorimetric data for CaO, Al₂O₃, and CaAl₂O₄. For hibonite (CaAl₁₂O₁₉), we predict C_P as 519.3 J/mol-K and S as 391.7 J/mol-K, at 298 K. For grossite (CaAl₄O₇), calculated values of C_P as 195.9 J/mol-K and of S as 172.0 J/mol-K are slightly smaller than the available calorimetric data at 298 K, consistent with calorimetric data having been obtained from samples containing ∼10 wt% hibonite impurities. Thermal conductivity at 298 K (k₀) is predicted from peak widths of the vibrational modes using the damped harmonic oscillator model of a phonon gas. Calculations of k₀ for CaO and Al₂O₃ differ from the measurements by 17% and 5%, respectively. The discrepancy for lime is larger due to uncertainties in its peak widths. This comparison suggests that our results for the calcium aluminates should be more accurate than conventional measurements of k₀ which are commonly uncertain by ∼25%.     

Organic maturity of Late Cretaceous and Tertiary coal measures,Canadian Arctic Archipelago

Maastrichtian and Lower Tertiary strata of the Eureka Sound Formation are widespread in the Canadian Arctic Archipelago and include major resources of lignite, subbituminous and high-volatile bituminous coal. The level of organic maturity of the strata for the most part reflects pre-orogenic (pre-Late Eocene-Miocene) depths of burial and thus helps define Early Tertiary depositional patterns. In the Remus Basin, in the eastern Canadian Archipelago, over 90 seams of coal occur ranging in rank from lignite (0.15% R_{0 max}) to high-volatile bituminous (0.70% R_{0 max}). The maturity values at the base of the Eureka Sound Formation, in conjunction with measured maturation gradients, indicate a maximum paleothickness of 4500 m and outline a basin with well defined eastern, western and southern margins. On the bases of numerical modeling, the maturation gradients are interpreted to reflect paleogeothermal gradients up to 55°C/km in the eastern part of the basin and of about 20°C/km in the western part.Elsewhere in the Canadian Arctic Archipelago the level of organic maturity of the Eureka Sound Formation varies from 0.15% R_{0 max} to 0.70% R_{0 max}. Maturation gradients measured from Meighen Island in the Strand Fiord Basin and from Melville Island in the southern part of the West Sverdrup Basin are about 0.10 log R_{0 max/km}, and when compared to numerical models suggest paleogeothermal gradients on the order of 15°C/km. At Meighen Island the paleodepth of burial of the Eureka Sound Formation may have been up to 6000 m. As a first approximation, the Melville Island gradient is considered representative of West Sverdrup and Banks Basin. Using this gradients, a paleodepth of burial of 3000 m is calculated for central West Sverdrup Basin and 4000 m for the southern part. In Banks Basin the paleodepth of burial is estimated to be on the order of 4000 m. Maturity values obtained from the Lake Hazen and Judge Dally Basins, Eclipse Trough and Somerset, Devon and Cornwallis Islands and at Bache Peninsula on eastern Ellesmere Island cannot be readily interpreted in terms of paleodepth of burial. No measured sections are thick or complete enough to establish maturation gradients, and the Tertiary history of these areas is only poorly known.The low paleogeothernal gradients calculated from Meighen Island, Melville Island and from the western part of the Remus Basin (15–20°C/km) are considered to reflect low heat flow or rapid Tertiary sedimentation and uplift such that an equilibrium geothermal gradient may never have existed. The higher maturation gradients and interpreted paleogeothermal gradients in the eastern Remus Basin are considered to be the product of higher heat flow on eastern Ellesmere Island.Anomalously high levels of maturity obtained along the Stolz Fault and adjacent Strand Fiord on Axel Heiberg Island are attributed to the thermal effects of evaporite diapirs.     

Laboratory Investigation on High Values of Restitution Coefficients

Restitution coefficients are used to quantify the energy dissipation upon impact when predicting rock fall events. These coefficients can be determined in situ or in the laboratory. In any case, the usual values for the normal restitution coefficient k _n are below unity. Values greater than one are quite rare, seen as unusual and barely explained. Previous experimental research conducted in Australia has shown consistent and systematic values of the normal restitution coefficient greater than one. This was tentatively explained by a combination of parameters such as low impacting angle, rotational energy and block angularity. The study presented in this paper aims at (1) identifying the critical parameters conducting to high k _n values and (2) at explaining the associated motion mechanisms. The objective was reached with values of k _n up to almost 2. In addition, the study has confirmed the significance of low impacting angle, rotational energy and block shape in this context.     

Exploring Cd,Cu, Pb,and Zn dynamic speciation in mining and smelting-contaminated soils with stable isotopic exchange kinetics

The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E₁) with a kinetic rate constant k₁ having values around 1 min⁻¹ and a much slower exchangeable pool (E₂) with k₂ ranging from 0.0001 min⁻¹ to 0.001 min⁻¹. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k₁ values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k₂ values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

Time-Variant Reliability Analysis of Unsaturated Soil Slopes Under Rainfall

Time-variant reliability analysis for a typical unsaturated soil slope is performed. Eight rainfall conditions are considered, and three slope models are set up for studying the influence of shear strength parameters, hydraulic conductivity parameters, rainfall intensity and duration on the reliability of the soil slope. Sensitivity analysis shows that when the saturated hydraulic conductivity (k _s) is very small, the variation of hydraulic conductivity has little effect on the reliability index (β). For saving the computation effort, only the shear strength parameters are needed in performing the reliability analysis in this condition. With the increase of k _s, the importance of hydraulic conductivity becomes large. The reliability index of the soil slope is changing with time (t), and the shape of β–t curves for different slope model is quite different for they depend on the value of k _s. When k _s is very small, β keeps decreasing for all the 18 simulation days. With the increase of k _s, β decreases to its minimum value at about the cessation day of rainfall events, and it then increases gradually due to the redistribution of suction in the soil slope.     

Comparison of rates of ureolysis between Sporosarcina pasteurii and an indigenous groundwater community under conditions required to precipitate large volumes of calcite

Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L⁻¹). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, k_urea, ranged between 0.06 and 3.29 d⁻¹ and were only affected by inoculum density. Higher Ca²⁺ concentration (50-500 mM Ca²⁺) as well as differences in fO₂ did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact k_urea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl₂. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, k_urea, ranged between 0.03 and 0.05 d⁻¹ and were similar to k_urea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to begin is almost instantaneous if an inoculum of S. pasteurii is included, while it may take several weeks for ureolytic groundwater communities to grow and become ureolytically active.     

Re-evaluating the US Geological Survey’s pumping tests (1967) in the Punjab region of Pakistan for use in groundwater studies

In 1967, the US Geological Survey (USGS) published the results of 141 pumping tests carried out throughout the Pakistani Punjab to establish representative hydraulic parameters of its large aquifer. Many authors have since concluded that the USGS had over-estimated the horizontal hydraulic conductivity (k _r) by 25–100 %, leaving vertical anisotropy and aquifer depth unresolved. No test wells have ever been drilled below 450 m to reach the base of the aquifer, although petroleum explorations mention depths between 1,500 and 4,500 m. After comparison and re-evaluation of all related papers, this study concludes that the USGS interpretation was correct, that its hydraulic values still stand without change, and that the USGS’s applied distance drawdown interpretation is valid to prevent influence of partial penetration on the results. This study also uniquely resolved vertical anisotropy and aquifer thickness by using early- and late-time drawdowns separately and proper scaling of the coordinates, which has often been omitted. With appropriate scaling, all interpretations match the data. The representative hydraulic aquifer values are: k _r?=?65 m/d, vertical anisotropy k _r/k _z?=?25 and aquifer depth 500–1,500 m. The conclusion is that these values can be used, at least as first estimates, for groundwater studies in the Pakistani Punjab.     

The effect of ionic interactions on the oxidation of metals in natural waters

The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation

$\text{-d in [Fe(II)]/dt = k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{] + k}{}_2\text{β}{}_2\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{]}{}^2$

where k₁ and k₂ are the pseudo first order rate constants, β₁ and β₂ are the hydrolysis constants for Fe(OH)⁺ and Fe(OH)⁰. The value of α_FE is the fraction of free Fe²⁺. The value of k₁ (2.0 ±0.5 min^?1) in water and seawater are similar within experimental error. The value of k₂ (1.2 × 10⁵ min^?1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model.For the oxidation of Cu(I) a rate equation of the form

$\text{?d ln [Cu(I)]/dt = k}{}_0\text{α}{}_{\mathrm{Cu}}\text{+ k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Cu}}\text{[Cl]}$

was found where k₀ (14.1 sec^?1) and k₁ (3.9 sec^?1) are the pseudo first order rate constants for the oxidation of Cu⁺ and CuCl⁰, β₁ is the formation constant for CuCl⁰ and α_Cu is the fraction of free Cu⁺. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.     

The effect of organic compounds in the oxidation kinetics of Cr(III) by H2O2

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant (k₁) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min⁻¹) for the pseudo first order rate constant k_1CrAha²⁺ and values approaching zero for and k_1CrAha3. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H₂O₂ by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100.The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H₂O₂. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H₂O₂ appear to be lowered probably because of steric hindrance of the chelated Cr(III).     

Estimation of critical state-related formula in advanced constitutive modeling of granular material

Different critical state-related formulas, for the critical state line and the critical state-dependent interlocking effect, have been proposed in constitutive modeling of granular material during last decades, which rises up a confusion on how to select an appropriate model in the geotechnical applications. This paper aims to discuss the selection of these critical state-related formulas and parameters identification. Three formulas of critical state line together with two formulas of critical state-dependent interlocking effect are combined to propose six elasto-plastic models. Drained and undrained triaxial tests on four different granular materials are selected for simulations. In order to eliminate artificial errors, a new hybrid genetic algorithm-based intelligent method is proposed and used to identify parameters and estimate simulations with minimum errors for each granular material and each model. Then, the performance of each CSL and each state parameter is evaluated using two information criteria. Furthermore, the performance was evaluated by simulating three footing tests using finite-element analysis in which the models are implemented. All comparisons demonstrate the incorporation of nonlinear critical state line combined with the state parameter e/e _c in constitutive modeling can result in relatively more satisfied simulated results.     

Evaluation of the hydraulic conductivity of aquifers with piles

Distributed piles are often installed in the foundation pit in sandy soil before dewatering. Hydraulic conductivity should be estimated considering the block effect of piles on groundwater seepage. Research shows that the effective medium theory (EMT) could be used to calculate the equivalent hydraulic conductivity (k _eq) of a heterogeneous medium with other material inclusions. In order to verify the applicability of EMT in an aquifer with piles, an experimental investigation is conducted. In this experiment, a sandy soil is considered as an aquifer and polyvinylchloride pipes are adopted as piles. Piles are distributed in rectangular and triangular layouts. The relationship between k _eq of the aquifer and the volume replacement ratio is plotted for these two layouts. The results indicate that EMT could well predict k _eq for the cases with the rectangular layout; however, for triangular layouts, the prediction becomes poor. To provide a better prediction of k _eq of the aquifer with piles distributed in a triangular layout, a modified EMT (MEMT) is proposed, in which a correction factor is adopted considering different layouts of piles. The MEMT can provide better k _eq predictions for an aquifer with piles in the triangular layout pattern than those obtained using the EMT.     

Optimisation of operating variables of fine coal flotation using a combination of modified flotation parameters and statistical techniques

Optimisation of flotation parameters using rate models is not a new concept. The kinetic model based on time recovery data, which uses the extra dimension of rate, has been in vogue since time immemorial for scaling up of lab data. Often, interpretation on the performance of a flotation circuit, based only on R_∞ (the ultimate recovery) and k_s (the first-order rate constant of the component) may lead to wrong conclusions. In such cases, a modified flotation rate constant k_mod defined as the product of R_∞ and k_s, i.e., k_mod=R_∞k_s and selectivity index (SI), defined as the ratio of the modified rate constant of valuables to the modified rate constant of gangue, can be used. An attempt has been made in this paper to optimize the batch laboratory froth flotation parameters of fine coal using the above two concepts, i.e., k_mod and SI and statistical techniques.A flotation bank containing four Outukumpu cells was optimized using the results obtained from the lab study. The airflow number and the froth number were used as a basis for scale up. To gauge the performance of the froth flotation circuit, an efficiency parameter called the coefficient of separation or the CS was used. The yield from the flotation circuit improved, the froth ash reduced and the rejects ash went up.     

Using the Maximum Effective Moment Criterion to Interpret Quartz <c>‐Fabric Patterns

The Maximum Effective Moment (MEM) criterion predicts that the initial orientation of ductile shear zones and shear bands is ~55° relative to the maximum principal stress axis (σ1) and that the kinematic vorticity number (Wk) is ~0.94. These preferred orientations should be reflected in the pattern of quartz -fabrics in shear zones and shear bands. Common quartz -fabrics in plane strain can be divided into low-temperature (L) and high-temperature (H) fabrics, with each group showing three patterns. A steady flow with a constant value of Wk≈0.94 gives rise to L-1 and H-1 patterns, which are commonly characterized by a single axis girdle normal to the shear zone and a single -point maximum parallel to the shear zone.Once the conjugate set develops, L-1 and H-1 have opening angles of ~70° and ~110°, respectively. L-2 and H-2 are asymmetric patterns associated with variable deformation partitioning and vorticity values of 0< Wk<0.94. In contrast, L-3 and H-3 are symmetric patterns associated with 100% deformation partitioning and Wk=0. The opening angle in quartz -fabrics is implicitly linked to the temperature during deformation. The opening angle is ~70° at low temperature and ~110° at high temperature. However, a linear correction between the opening angle and the temperature cannot be established. During deformation partitioning, synthetic shear bands form earlier than antithetic bands and are more easily developed. This may result in opening angles of <70° for low-temperature fabrics and of >110° for high-temperature fabrics. The following criteria can be used to recognize reworked shear zones that have experienced multiple orogenic phases and changes in the stress state: 1) the initial Wk is larger or smaller than ~0.94; 2) the change in Wk is abrupt, rather than progressive; 3) inconsistent shear senses are inferred for the different phases of deformation; and 4) a negative value of Wk is found in reworked shear zones.