• Journal of Soil and Groundwater Environment
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• v.12 no.5
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• pp.105-114
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• 2007

The most advanced oxidation processes (AOPs) are based on reactivity of strong and non-selective oxidants such as hydroxyl radical (${\cdot}OH$). Decomposition of typical DNAPL chlorinated compounds (TCE, PCE) using various advanced oxidation processes ($UV/Fe^{3+}$-chelating agent/$H_2O_2$ process, $UV/H_2O_2$ process) was approached to develop appropriate methods treating chlorinated compound (TCE, PCE) for further field application. $UV/H_2O_2$ oxidation system was most efficient for degrading TCE and PCE at neutral pH and the system could remove 99.92% of TCE after 150 min reaction time at pH 6($[H_2O_2]$ = 147 mM, UVdose = 17.4 kwh/L) and degrade 99.99% of PCE within 120 min ($[H_2O_2]$ = 29.4 mM, UVdose = 52.2 kwh/L). Whereas, $UV/Fe^{3+}$-chelating agent/$H_2O_2$ system removed TCE and PCE ca. > 90% (UVdose = 34.8 kwh/L, $[Fe^{3+}]$ = 0.1 mM, [Oxalate] = 0.6 mM, $[H_2O_2]$ = 147 mM) and 98% after 6hrs (UVdose = 17.4 kwh/L, $[Fe^{3+}]$ = 0.1 mM, [Oxalate] = 0.6 mM, $[H_2O_2]$ = 29.4 mM), respectively. We improved the reproduction system with addition of UV light to modified Fenton reaction by increasing reduction rate of $Fe^{3+}$ to $Fe^{2+}$. We expect that the system save the treatment time and improve the removal efficiencies. Moreover, we expect the activity of low molecular organic compounds such as acetate or oxalate be effective for maintaining pH condition as neutral. This oxidation system could be an economical, environmental friendly, and practical treatment process since the organic compounds and iron minerals exist in nature soil conditions.

• Journal of Soil and Groundwater Environment
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• v.11 no.6
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• pp.69-75
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• 2006

Improper disposal of petroleum and spills from underground storage tanks have created large areas with highly toxic contamination of the soil and groundwater. Methyl tert-butyl ether (MTBE) is widely used as a fuel additive because of its advantageous properties of increasing the octane value and reducing carbon monoxide and hydrocarbon exhausts. However, MTBE is categorized as a possible human carcinogen. This research investigated the Modified Photo-Fenton system which is based on the Modified Fenton reaction and UV light irradiation. The Modified Fenton reaction is effective for MTBE degradation near a neutral pH, using the ferric ion complex composed of a ferric ion and environmentally friendly organic chelating agents. This research was intended to treat high concentrations of MTBE; thus, 1,000 mg/L MTBE was chosen. The objectives of this research are to find the optimal reaction conditions and to elucidate the kinetic and mechanism of MTBE degradation by the Modified Photo-Fenton reaction. Based on the results of experiments, citrate was chosen among eight chelating agents as the candidate for the Modified Photo-Fenton reaction because it has a relatively higher final pH and MTBE removal efficiency than the others, and it has a relatively low toxicity and is rapidly biodegradable. MTBE degradation was found to follow pseudo-first-order kinetics. Under the optimum conditions, [$Fe^{3+}$] : [Citrate] = 1 mM: 4 mM, 3% $H_2O_2$, 17.4 kWh/L UV dose, and initial pH 6.0, the 1000 ppm MTBE was degraded by 86.75% within 6 hours and 99.99% within 16 hours. The final pH value was 6.02. The degradation mechanism of MTBE by the Modified Photo-Fenton Reaction included two diverse pathways and tert-butyl formate (TBF) was identified to be the major degradation intermediate. Attributed to the high solubility, stability, and reactivity of the ferric-citrate complexes in the near neutral condition, this Modified Photo-Fenton reaction is a promising treatment process for high concentrations of MTBE under or near a neutral pH.