Oxidation kinetics and effect of pH on the degradation of MTBE with Fenton reagent

Abstract

The fundamentals of the Fenton reagent-based degradation of low concentrations of methyl tert-butyl ether (MTBE) in batch reactors under initially anaerobic conditions are discussed in this work. The objective of the study was to quantitatively verify the feasibility of MTBE degradation with Fenton reagent under such conditions. The conclusions may be potentially helpful to further develop an effective in situ treatment of MTBE-contaminated groundwater. Initial MTBE concentrations ([MTBE](0)) of 11.4 and 22.7 microM (approximately 1.0 and 2.0 mg/L, respectively) were treated with Fenton reagent (FR) using a [FR](0):[MTBE](0) molar ratio of 10:1. FR was used in equimolar mixture of Fe(2+)and H(2)O(2) (i.e., [Fe(2+)](0):[H(2)O(2)](0)=1:1). This analysis considers the hydroxyl radicals (OH(*)) produced by FR as the main species responsible for the degradation processes. The effects of [MTBE](0) and pH on the oxidation kinetics were investigated. Under these conditions it was observed that: (i) MTBE was degraded at high extent (90-99%) after 1h of reaction time, (ii) MTBE mineralization was low in all cases and reached only 31.7% at the best conditions, and (iii) In all cases, most of MTBE degradation occurred during the initial 3-5 min of reaction. During this brief initial phase, MTBE transformation followed pseudo-first order kinetics, while the subsequent phase exhibited a sharp drop in degradation rate and had almost negligible contribution to the overall degradation. Experiments performed at acidic pH exhibited the best degradation results, while at neutral pH the degradation rates dropped significantly. Other parameters included in this analysis were: TOC reduction and total concentration of compounds containing the tert-butyl group in their structure (tBC). These compounds were analyzed because of the concerns related to their potential toxicity. Tert-butyl formate (TBF), Tert-butyl alcohol (TBA), acetone and methyl acetate were identified and quantified as major reaction intermediates.