Advanced oxidation of five contaminants in water by UV/TiO2: Reaction kinetics and byproducts identification.

The extent and kinetics of degradation of 1,4 dioxane, n-nitrosodimethylamine (NDMA), tris-2-chloroethyl phosphate (TCEP), gemfibrozil, and 17ß estradiol in a prepared aqueous matrix by means of UV/TiO2 (ultraviolet light/titanium dioxide) oxidation was evaluated. Degussa P25 TiO2 was employed as a photocatalyst excited by UV light in a 1 L water-jacketed batch photoreactor. The rate of degradation was modeled using a pseudo-first order rate model and the Langmuir-Hinshelwood rate model with a high correlation. Degradation rate constants were found to be maximum at pH 5.0 and 1.5 g L(-)(1) TiO2 dose. For these conditions first order rate constants, values were as follows: 0.29 min(-1) for 1,4 dioxane, 0.50 min(-1) for NDMA, 0.12 min(-1) for TCEP, 0.61 min(-1) for gemfibrozil, and 0.53 min(-1) for 17ß estradiol. While for the Langmuir-Hinshelwood rate model, the following constants were found: 0.11 Lmg(-1) and 2.81 mgL(-1) min(-1) for 1,4 dioxane, 0.12 Lmg(-1) and 4.35 mgL(-1) min(-1) for NDMA, 0.06 Lmg(-1) and 1.79 mgL(-1) min(-1) for TCEP, 0.21 Lmg(-1) and 3.27 mgL(-1) min(-1) for gemfibrozil, and 0.15 Lmg(-1) and 3.43 mgL(-1) min(-1) for 17ß estradiol. In addition, specific byproducts of degradation were identified using GC/MS analysis. The results obtained from the kinetics analysis showed that UV/TiO2 oxidation is a promising process for treating trace organic contaminants in water, but further research is needed to better understand how to incorporate these findings into pilot and full-scale designs. The toxicity of oxidation byproducts, and their potential for interacting with other compounds should be considered in the treatment of contaminated waters using the UV/TiO2 oxidation process.

Adsorption of methyl tertiary butyl ether on granular zeolites: Batch and column studies.

Methyl tertiary butyl ether (MTBE) has been shown to be readily removed from water with powdered zeolites, but the passage of water through fixed-beds of very small powdered zeolites produces high friction losses not encountered in flow through larger sized granular materials. In this study, equilibrium and kinetic adsorption of MTBE onto granular zeolites, a coconut shell granular activated carbon (CS-1240), and a commercial carbon adsorbent (CCA) sample was evaluated. In addition, the effect of natural organic matter (NOM) on MTBE adsorption was evaluated. Batch adsorption experiments determined that ZSM-5 was the most effective granular zeolite for MTBE adsorption. Further equilibrium and kinetic experiments verified that granular ZSM-5 is superior to CS-1240 and CCA in removing MTBE from water. No competitive adsorption effects between NOM and MTBE were observed for adsorption to granular ZSM-5 or CS-1240, however there was competition between NOM and MTBE for adsorption onto the CCA granules. Fixed-bed adsorption experiments for longer run times were performed using granular ZSM-5. The bed depth service time model (BDST) was used to analyze the breakthrough data.

Observations on solid phase micro-extraction for MTBE analysis.

In a recent study of aqueous phase methyl tertiary butyl ether (MTBE) adsorption onto hydrophobic molecular sieves, the solid phase micro-extraction gas chromatography analytical technique was used to measure MTBE concentrations in water. The method was especially beneficial in measuring MTBE concentrations in the microg/l range, but anomalies were observed that investigators should be aware of before employing this technique. Specifically, it was observed that the calibration of the extraction fiber with known MTBE concentrations was non-linear over all concentration ranges. The technique was not suited to higher concentrations, and dilutions were necessary to increase the working range of the technique. Lastly, the fiber was observed to extract increasingly less MTBE from known standard solutions over time, requiring repeated calibrations to obtain reliable concentrations of unknown samples.

Fenton's oxidation of MTBE with zero-valent iron.

Methyl tert-butyl ether (MTBE) has become a contaminant of increasing concern in the U.S. Traditional remediation technologies are successful in removing MTBE from contaminated water, but usually transfer the contaminant from the aqueous to another phase. Fenton's oxidation of MTBE provides a promising alternative to traditional remediation techniques in that it may mineralize the contaminant rather than just phase transfer. This bench-scale study investigated the feasibility of Fenton's oxidation of MTBE using zero-valent iron as the source of catalytic ferrous iron. The oxidation reactions were able to degrade over 99% of the MTBE within 10 min, and showed significant generation, and subsequent degradation, of the MTBE oxidation byproduct acetone. Second-order rate constants for MTBE degradation were 1.9 x 10(8) M(-1) s(-1) at pH 7.0 and 4.4 x 10(8) M(-1) s(-1) at pH 4.0. The total organic carbon was reduced by over 86% when a H2O2:MTBE ratio of 220:1 or greater was used.

Mechanistic basis for particle detachment from granular media.

Colloids may become detached from surfaces in environmental systems as a result of chemical and physical conditions. Many researchers reporting on colloidal detachment in natural and model systems have stopped short of mechanistically and quantitatively describing their observations. In this work, a mathematical construct is presented that quantitatively determines the effect of thermodynamics and hydrodynamics on particle detachment from surfaces in granular media. Using the Buckingham pi theorem, a mathematical model is structured based on governing dimensionless groupings. Determining dimensionless numbers elucidates conditions conducive for detachment in engineered and natural porous media. Published detachment data are compared to the mathematical model developed herein and provide support for its utility. Extensions of this technique have utility in many applications where fluid interaction with particulate-laden porous media is encountered.

Pilot-scale Fenton's oxidation of organic contaminants in groundwater using autochthonous iron.

A pilot-scale study was conducted to evaluate Fenton's oxidation with autochthonous iron for treating extracted groundwater contaminated with organic solvents. Based on a previous bench-scale treatability study, a batch reactor pilot-plant system was designed and operated to evaluate the effects of various parameters including pH, iron concentration, hydrogen peroxide dose, and reaction time. Effective system conditions were found to be pH of 3.5, hydrogen peroxide to iron molar ratio of 75/1, and autochthonous iron at an average concentration of 10mg/l. The data collected demonstrate the effectiveness of Fenton's oxidation using autochthonous iron for treating this contaminated water, with reductions to below method detection limits for many contaminants. This pilot-scale study provided kinetic rate constants for predicting contaminant disappearance, information necessary for designing a full-scale Fenton's oxidation system.