Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Kinetic Modelling of the Removal of Seven Common Pollutants in Subsurface Flow Constructed Wetlands

The main removal mechanisms for the degradations of seven pollutants in wastewater treatment wetlands were analysed, and a mathematical model was established to quantify the removal of each pollutant, based on its main removal mechanisms. Subsurface horizontal flow wetlands were treated as a series of continuous stirred - tank reactors (CSTRs). Kinetic models for the removal of biochemical oxygen demand, chemical oxygen demand, ammonia, total nitrogen and faecal coliforms were established by combining Monod or first - order kinetics with CSTR assumptions. These tentative models account for a wide range of factors that affect wetland performance, but the models have not been proven by ex periment data. Depending on the derivation of various coefficients in the models and verification by actual performance data, this study may provide a starting point for an integrated pollutant removal model to be developed, and experimen tally verified, thereby making a step forward from the current greenbox' approach of wetland design.     

Relativistic gravitational collapse of a cool white dwarf with allowance for the neutronization kinetics

We consider and numerically solve the problem of the relativistic gravitational collapse of a spherically symmetric cool nonrotating white dwarf with allowance for the neutronization kinetics. We propose a model equation of state and analyze the neutronization kinetics under simplifying assumptions. A comprehensive mathematical model is constructed for the phenomenon. The system of equations is integrated numerically. The gravitational collapse of a white dwarf that lost its stability is shown to lead to the envelope ejection and to the final state of a hot static neutron star. For comparison, we solve the problem with an equilibrium equation of state. We show that in this case, the entire mass ultimately goes under the gravitational radius to form a black hole.     

Biodegradation and transport of benzene,toluene, and xylenes in a simulated aquifer: comparison of modelled and experimental results

Both laboratory experiments and numerical modelling were conducted to study the biodegradation and transport of benzene–toluene–xylenes (BTX) in a simulated semi‐confined aquifer. The factors incorporated into the numerical model include advection, hydrodynamic dispersion, adsorption, and biodegradation. The various physico‐chemical parameters required by the numerical model were measured experimentally. In the experimental portion of the study, BTX compounds were introduced into the aquifer sand. After the contaminants had been transported through the system, BTX concentrations were measured at 12 equally spaced wells. Subsequently, microorganisms obtained from the activated sludge of a sewage treatment plant and cultured in BTX mixtures were introduced into the aquifer through the 12 sampling wells. The distribution data for BTX adsorption by the aquifer sand form a nonlinear isotherm. The degree of adsorption by the sand varies, depending on the composition of the solute. The degradation time, measured from the time since the bacteria were added to the aquifer until a specific contaminant was no longer detectable, was 35–42 h for BTX. The dissolved oxygen, after degradation by BTX compounds and bacteria, was consumed by about 40–60% in the entire simulated aquifer; thus the aerobic conditions were maintained. This study provides insights for the biodegradation and transport of BTX in aquifers by numerical modelling and laboratory experiments. Experimental and numerical comparisons indicate that the results by Monod degradation kinetics are more accurate than those by the first‐order degradation kinetics. Copyright © 2002 John Wiley & Sons, Ltd.     

Inverse methods and kinetic models of hydrocarbon generation: III. Case histories for autoclave product analysis

From a determination of the transformation matrix for three pyrolysis product experimental data sets, an examination is given of both the applicability of the laboratory experimental data to the modeling of oil cracking in a sedimentary basin, and of the appropriateness of an inverse model. The results of the laboratory experimental data sets, which were done under different thermodynamic conditions and using different sources, show that the transformation matrix varies over each data set and also with time. Therefore, it is necessary to check the data sets before applying them to a basin for hydrocarbon modeling. The laboratory experimental data taken at lower temperature and over longer times appear more pertinent for the construction of an oil-cracking kinetic model suitable for geologic conditions.     

High pressure metamorphism in the nappes of the Valle dell'Orco traverse (Western Alps collisional belt) *

Abstract A detailed field and petrological study of rocks from nappes cut by the Valle dell'Orco (Italian Western Alps), in particular the Sesia–Lanzo composite unit, has revealed geological and metamorphic histories which started in pre-alpine times and lasted up to the alpine subduction-collisional processes. During these processes the nappes sustained an early high P–low T stage and a later low P greenschist facies stage, but followed partly distinctive P–T–time trajectories. This paper discusses the kinematic evolution and the thermal history of the alpine belt from the early subduction/underthrust to the later exhumation stage. The metamorphic crystallization is often governed by incomplete and/or local equilibrium, and the pervasive syn-metamorphic deformation and the composition of the syn-metamorphic fluid phase (if present) have exerted an effective local control on reaction kinetics.     

Kinetics of phosphate adsorption by iron oxyhydroxides in aqueous systems

The rate of uptake of phosphate onto synthetic Fe(III)- and Fe(II)-derived oxyhydroxides has been studied using reaction conditions similar to those encountered in natural waters. Kinetic analyses were carried out on the adsorption profiles and both first-order and second-order conditional rate constants were obtained. The temperature dependence of some of the rate constants was investigated and corresponding apparent activation energies calculated. Similar experiments and analyses were undertaken using Fe from natural sources and in general the conditional rate constants obtained in seawater were in agreement with the synthetic ones. The results of this study are of value when comparing the time scales of adsorption processes in natural waters with the time scales of mixing and advection.