Effect of oxidant-to-substrate ratios on the degradation of MTBE with Fenton reagent

Prior studies have shown the effectiveness of Fenton reagent (FR) for degrading low concentrations (1.0–2.0 mg/L) of methyl tert-butyl ether (MTBE), similar to those found in contaminated groundwater. The present study investigates the effect of increasing FR doses on the extent of degradation and mineralization of a given initial MTBE concentration. The FR to MTBE molar ratio (FMMR) was the operating variable, and was investigated at values between 0.5:1 and 200:1. This approach provided sequential snapshots of the MTBE degradation process, which may help to improve the understanding of MTBE degradation with FR. The initial MTBE concentration (MTBE0) was approximately 22.7 μM (∼2.0 mg/L), and FR was used in a 1:1 molar ratio of ferrous iron (Fe2+) and hydrogen peroxide (H2O2). The concentrations of MTBE and the following main reaction byproducts: tert-butyl formate (TBF), tert-butyl alcohol (TBA), acetone and methyl acetate were determined from samples collected at specific intervals over a total reaction time of 1 h. Total organic carbon (TOC) was monitored to determine MTBE mineralization, and the total concentration of tert-butyl compounds (tBC) was monitored due to the suspected toxicity associated with this functional group. The results showed that the minimum FMMR necessary for achieving complete MTBE degradation was 20:1, but at that FMMR, TOC and tBC reduction were only 45.6% and 24.9%, respectively. Complete MTBE mineralization was not achieved in any case, even at FMMRs as high as 200:1, where only 63.3% of mineralization was observed (although tBC reduction reached 99.6%, since traces of TBA were still detected). These results confirm the relative inability of FR to achieve complete mineralization of a target substrate, even those that are highly reactive with the hydroxyl radical.