• Journal of Soil and Groundwater Environment
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• v.11 no.6
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• pp.76-82
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• 2006

Fenton's reaction are difficult to apply in the field due to the low pH requirements for the reaction and the loss of reactivity caused by the precipitation of iron (II) at neutral pH. Moreover, Fenton-like reactions using iron mineral instead of injection of iron ion as a catalyst are operated to get high removal result at low pH. Because hydroxyl radical can generate at the surface of iron mineral, there are competition with a lot of hydroxide at around neutral pH. On the other side, to operate Fenton's reaction series at neutral pH, modified Fenton reaction is suggested. The complexes, composed by iron ions (ferrous ion or ferric ion)-chelating agent, could be acted as a catalyst and presented in the solution at neutral pH. However, modified Fenton reaction requires a lot of hydrogen peroxide. Accordingly, the purpose of this experiment was to effectively combine Fenton-like reaction and modified Fenton reaction for extending application of Fenton's reaction. i.e., injecting chelating agents in Fenton-like reaction at around neutral pH is increasing the concentration of dissolved iron ion and highly promoting the oxidation effect. 2,4,6-trinitrotoluene (TNT) was used as a probe compound for comparing reaction efficiencies in this study. If the concentration of dissolved iron ion in combined Fenton process were existed more than 0.1 mM, the total TNT removal were increased. Magnetite-NTA system showed the best TNT removal (76%) and Magnetite-EDTA system indicated about 56% of TNT removal. The results of these experiments proved more promoted 40-60% of TNT removal than Fenton-like reaction's.

• 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.

• Journal of Soil and Groundwater Environment
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• v.10 no.2
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• pp.35-43
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• 2005

Bioslurping combines the three remedial approaches of bioventing, vacuum-enhanced free-product recovery, and soil vapor extraction. Bioslurping is less effective in tight (low-permeability) soils. The greatest limitation to air permeability is excessive soil moisture. Optimum soil moisture is very soil-specific. Too much moisture can reduce air permeability of the soil and decrease its oxygen transfer capability. Too little moisture will inhibit microbial activity. So Modified Fenton reaction as chemical treatment which can overcome the weakness of Bioslurping was experimented for simultaneous treatment. Although the diesel removal efficiency of SVE process increased in proportion to applied vacuum pressure, SVE process was difficulty to remediation quickly semi- or non-volatile compounds absorbed soil strongly. And SVE process had variation of efficiency with distance from the extraction well and depth a air flow form of hemisphere centering around the well. Below 0.1 % hydrogen peroxide shows the potential of using hydrogen peroxide as oxygen source but the co-oxidation of chemical and biological treatment was impossible because of the low efficiency of Modified Fenton reaction at 0.1 % (wt) hydrogen peroxide. NTA was more efficiency than EDTA as chelating agent and diesel removal efficiency of Modified Fenton reaction increased in proportion to hydrogen peroxide concentration. Hexadecane as typical aliphatic compound was removed less than Toluene as aromatic compound because of its structural stability in Modified Fenton reaction. What minimum 10% hydrogen peroxide concentration has good remediation efficiency of diesel contaminated groundwater may show the potential use of Modified Fenton reaction after bioslurping treatment.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.31 no.4B
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• pp.377-382
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• 2011

In this study, hydrogen peroxide is stabilized in modified Fenton reaction to improve the soil remediation. Phenanthrene, which is the typical compound in PAHs, was spiked into soil samples to copy the original contaminated site. Anionic surfactant, SDS (Sodium dodecyl sulfate) was used for hydrogen peroxide stabilizer. 4 mM of Fe(II), 5~50 mM of SDS and 102.897 mM of $H_2O_2$ was injected into soil samples which is contaminated by 125 mg/kg of phenanthrene to analyze decomposition rate of phenanthrene in modified Fenton reaction. In condition which SDS was injected 30 mM, decomposition rate of phenanthrene has best efficiency as 95% and in condition which SDS was injected over 30 mM, decomposition rate is lower than SDS 30 mM because SDS enacted as scavenger in the system. Results which assess the change of hydrogen peroxide concentration after injecting hydrogen peroxide stabilizer showed that hydrogen peroxide concentration was 14.6995 mM so that is stabilized at Fe(II) 2 mM condition in 48 hours. On the other hand, hydrogen peroxide is not stable in Fe(III) condition. SDS concentration was fixed and iron concentration was changed 2~8 mM to find out optimize proportion between iron concentration and SDS concentration in modified Fenton reaction. Consequentially, in condition of which Fe(II) 4 mM and SDS 30 mM, reaction has the highest removal rate as 95%.

• Journal of Soil and Groundwater Environment
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• v.12 no.2
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• pp.27-36
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• 2007

A recent study showed that MTBE can be degraded by Fenton's Reagent (FR). The treatment of MTBE with FR, however, has a definite limitation of extremely low pH requirement (optimum pH $3{\sim}4$) that makes the process impracticable under neutral pH condition on which the ferrous ion precipitate forming salt with hydroxyl anion, which result in the diminishment of the Fenton reaction and incompatible with biological treatment. Consequently, this process using only FR is not suitable for in-situ remediation of MTBE. In order to overcome this limitation, modified Fenton process using NTA, oxalate, and acetate as chelating reagents was introduced into this study. Modified Fenton reaction, available at near neutral pH, has been researched for the purpose of obtaining high performance of oxidation efficiency with stabilized ferrous or ferric ion by chelating agent. In the MTBE degradation experiment with modified Fenton reaction, it was observed that this reaction was influenced by some factors such as concentrations of ferric ion, hydrogen peroxide, and each chelating agent and pH. Six potential chelators including oxalate, succinate, acetate, citrate, NTA, and EDTA were tested to identify an appropriate chelator. Among them, oxalate, acetate, and NTA were selected based on their remediation efficiency and biodegradability of each chelator. Using NTA, the best result was obtained, showing more than 99.9% of MTBE degradation after 30 min at pH 7; the initial concentration of hydrogen peroxide, NTA, and ferric ion were 1470 mM, 6 mM, and 2 mM, respectively. Under the same experimental condition, the removal of MTBE using oxalate and acetate were 91.3% and 75.8%, respectively. Optimum concentration of iron ion were 3 mM using oxalate which showed the greatest removal efficiency. In case of acetate, $[MTBE]_0$ decreased gradually when concentration of iron ion increased above 5 mM. In this research, it was showed that modified Fenton reaction is proper for in-situ remediation of MTBE with great efficiency and the application of chelatimg agents, such as NTA, was able to make the ferric ion stable even at near neutral pH. In consequence, the outcomes of this study clearly showed that the modified Fenton process successfully coped with the limitation of the low pH requirement. Furthermore, the introduction of low molecular weight organic acids makes the process more available since these compounds have distinguishable biodegradability and it may be able to use natural iron mineral as catalyst for in situ remediation, so as to produce hydroxyl radical without the additional injection of ferric ion.

• Clean Technology
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• v.5 no.1
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• pp.49-61
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• 1999

Fenton's oxidation can improve the biodegradability of refractory organic wastewater by generating $OH{\cdot}$ which is one of the most reactive species. Fenton's reagent is used to treat a variety of industrial waste containing a range of toxic organic compounds. But this process cannot be economical because of high chemical cost of $H_2O_2$, ferrous ion solution and high sludge disposal cost. In this study, we proposed a modified Fenton's oxidation process which can reduce the reagent cost and obtain better removal efficiencies with less Fenton's reagents, and have a good potential of sludge recycling. In modified Fenton reaction, ferrous ion solution is adjusted to optimal pH with NaOH. Then it added to the sample and reacted to $H_2O_2$. For the experiment, synthetic wastewater made of phenol, which is one of the typical water pollutants, was used and the ionic strength of this wastewater was controlled by adding $NaHCO_3$. The effects of DO, ionic strength, and $H_2O_2$ dosing methods were investigated. As a result, modified Fenton's treatment efficiencies are better than conventional Fenton's reaction treating leachate and dyeing wastewater. And modified Fenton's treatment efficiencies combined to the sludge recycling for a half of Iron dosage are as good as the conventional Fenton's for a normal Iron dosage.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.153-160
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• 2005

There have been large areas of soil contaminated with high levels of explosives. For this experimental work, 2,4,6-trinitrotoluene (TNT) was tested as a representative explosive contaminant of concern in both aqueous and soil samples and its removal was evaluated using three different chemical treatment methods: 1) the classical Fenton reaction which utilizes hydrogen peroxide ($H_2O_2$) and soluble iron at pH less than 3; 2) a modified Fenton reaction which utilizes chelating agents, $H_2O_2$, and soluble iron at pH 7; and 3) a Fenton-like process which utilizes iron minerals instead of soluble iron and $H_2O_2$, generating a hydroxyl radical. Using classic Fenton reaction, 93% of TNT was removed in 20 h at pH 3 (soil spiked with 300 mg/L of TNT, 3% $H_2O_2$ and 1mM Fe(III)), whereas 21% removed at pH 7. The modified Fenton reaction, using nitrilotriacetic acid (NTA), oxalate, ethylenediaminetetraacetic acid (EDTA), acetate and citrate as representative chelating agents, was tested with 3% $H_2O_2$ at pH 7 for 24 h. Results showed the TNT removal in the order of NTA, EDTA, oxalate, citrate and acetate, with the removal efficiency of 87%, 71%, 64%, 46%, and 37%, respectively, suggesting NTA as the most effective chelating agent. The Fenton-like reaction was performed with water contaminated with 100 mg/L TNT and soil contaminated with 300 mg/L TNT, respectively, using 3% $H_2O_2$ and such iron minerals as goethite, magnetite, and hematite. In the goethite-water system, 33% of TNT was removed at pH 3 whereas 28% removed at pH 7. In the magnetite-water system, 40% of TNT was removed at pH 3 whereas 36% removed at pH 7. In the hematite-water system, 40% of TNT was removed at pH 3 whereas 34% removed at pH 7. For further experiments combining the modified Fenton reaction with the Fenton-like reaction, NTA, EDTA, and oxalate were selected with the natural iron minerals, magnetite and hematite at pH 7, based on the results from the modified Fenton reaction. As results, in case magnetite was used, 79%, 59%, and 14% of TNT was removed when NTA, oxalate, and EDTA used, respectively, whereas 73%, 25%, and 19% removed in case of hematite, when NTA, oxalate, and EDTA used, respectively.

• Journal of Soil and Groundwater Environment
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• v.17 no.2
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• pp.15-21
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• 2012

MTBE (Methyl tertiary-butyl ether) has been commonly used as an octane enhancer to replace tetraethyl lead in gasoline, because MTBE increases the efficiency of combustion and decreases the emission of carbon monoxide. However, MTBE has been found in groundwater from the fuel spills and leaks in the UST (Underground Storage Tank). Fenton's oxidation, an advanced oxidation catalyzed with ferrous iron, is successful in removing MTBE in groundwater. However, Fenton's oxidation requires the continuous addition of dissolved $Fe^{2+}$. Zero-valent iron is available as a source of catalytic ferrous iron of MFO (Modified Fenton's Oxidation) and has been studied for use in PRBs (Permeable Reactive Barriers) as a reactive material. Therefore, this study investigated the condition of optimization in MFO-PRBs using waste zero-valent iron (ZVI) with the waste steel scrap to treat MTBE contaminated groundwater. Batch tests were examined to find optimal molar ratio of MTBE : $H_2O_2$ on extent to degradation of MTBE in groundwater at pH 7 with 10% waste ZVI. As the results, the ratio of optimization of MTBE to hydrogen peroxide for MFO was determined to be 1:300[mM]. The column experiment was conducted to know applicability of MFO-PRBs for MTBE remediation in groundwater. As the results of column test, MTBE was removed 87% of the initial concentration during 120days of operational period. Interestingly, MTBE was degraded not only within waste ZVI column but also within sand column. It means the aquifer may affect continuously the MTBE contaminated groundwater after throughout the waste ZVI barrier. The residual products showed acetone, TBF (Tert-butyl formate) and TBA (Tert-butyl acetate) during this test. The results of the present study showed that the recycled materials can be effectively used for not only a source of catalytic ferrous iron but also a reactive material of the MFO-PRBs to remove MTBE in groundwater.

• 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.

• The Journal of the Korea Contents Association
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• v.6 no.4
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• pp.146-157
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• 2006

Causal relationship means what relations the result occurred have with a fact as a reason. In general, a formular that no result exists without reasons is used for the method to confirm existence and inexistence of causal relationship. Problematic causal relationships in Private Law are reparations (Article No. 393 of Private Law) due to debt nonfulfillment and reparation due to tort (Application of Article No. 393 by Article No. 750, and No. 763 of Private Law). The purpose pursued by reparation system in private law is to promote equal burden of damages, and the range of reparation at this time is decided by the range of damage and the range of damage is decided by the principle of causal relationship. That the causal relationship theory fairly causes confusion by treating one problem and the other problem as the same thing, instead of dividing them according to the purpose of protection presented by the law is a reason of the criticism from different views.