Item talk:Q234267
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{
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The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2\u00a0outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law \u2212d[Fe(II)]/dt\u00a0=\u00a0k1\u00b7[O2]\u00b7[H+]\u22122\u00b7[Fe(II)] that indicates an increase in pH by 1 unit at pH 5\u20138 and at constant dissolved O2\u00a0(DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1\u2032) of 0.5\u20131.7 times the reference value of\u00a0k1\u00a0=\u00a03\u00a0\u00d7\u00a010\u221212\u00a0mol/L/min (for pH 5\u20138 and 20\u00a0\u00b0C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2\u00a0outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2\u00a0mass transfer rate constant (kL,CO2a). The value of\u00a0kL,CO2a estimated for the stream (0.010\u00a0min\u22121) was within the range for the batch aeration experiments (0\u20130.033\u00a0min\u22121). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2\u00a0outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).", "description": "12 p.", "publisher": { "@type": "Organization", "name": "Pergamon" }, "author": [ { "@type": "Person", "name": "Cravotta, Charles A. 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