• Journal of Soil and Groundwater Environment
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• v.26 no.1
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• pp.45-53
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• 2021

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution by coupled electro-oxidation and Fe(II) activated persulfate oxidation process was investigated. The electrochemical oxidation was performed using carbon sheet electrode and persulfate using Fe(II) ion as an activator. The oxidation efficiency was investigated by varying current density (2 - 10 mA/㎠), electrolyte (Na2SO4) concentration (10 - 100 mM), persulfate concentration (5 - 20 mM), and Fe(II) concentration (10 - 20 mM). The 2,4-D removal efficiency was in the order of Fe(II) activated persulfate-assisted electrochemical oxidation (Fe(II)/PS/ECO, 91%) > persulfate-electrochemical oxidation (PS/ECO, 51%) > electro-oxidation (EO, 36%). The persulfate can be activated by electron transfer in PS/ECO system, however, the addition of Fe(II) as an activator enhanced 2,4-D degradation in the Fe(II)/PS/ECO system. The 2,4-D removal efficiency was not affected by the initial pHs (3 - 9). The presence of anions (Cl- and HCO3-) inhibited the 2,4-D removal in Fe(II)/PS/ECO system due to scavenging of sulfate radical. Scavenger experiment using tert-butyl alcohol (TBA) and methanol (MeOH) confirmed that although both sulfate (SO4•-) and hydroxyl (•OH) radicals existed in Fe(II)/PS/ECO system, hydroxyl radical (SO4•-) was the predominant radical.

• Journal of Soil and Groundwater Environment
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• v.22 no.2
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• pp.17-25
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• 2017

The efficiency and mechanism of electrochemical phenol oxidation using persulfate (PS) and nanosized zero-valent iron (NZVI) were investigated. The pseudo-first-order rate constant for phenol removal by the electrochemical/PS/NZVI ($1mA^*cm^{-2}/12$ mM/6 mM) process was $0.81h^{-1}$, which was higher than those of the electrochemical/PS and PS/NZVI processes. The electrochemical/PS/NZVI system removed 1.5 mM phenol while consuming 6.6 mM PS, giving the highest stoichiometric efficiency (0.23) among the tested systems. The enhanced phenol removal rates and efficiencies observed for the electrochemical/PS/NZVI process were attributed to the interactions involving the three components, in which the electric current stimulated PS activation, NZVI depassivation, phenol oxidation, and PS regeneration by anodic or cathodic reactions. The electrochemical/PS/NZVI process effectively removed phenol oxidation products such as hydroquinone and 1,4-benzoquinone. Since the electric current enhances the reactivities of PS and NZVI, process performance can be optimized by effectively manipulating the current.

• Journal of Soil and Groundwater Environment
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• v.22 no.1
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• pp.41-48
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• 2017

Persulfate (PS) activated with nanosized zero-valent iron (NZVI) was tested as a reagent to remove phenol from groundwater. Batch degradation experiments indicated that NZVI/PS molar ratios between 1 : 2 and 1 : 5 were appropriate for complete removal of phenol, and that the time required for complete removal varied with different PS and NZVI dosages. Chloride ions up to 100 mM enhanced the phenol oxidation rate, and nitrate of any concentration up to 100 mM did not significantly affect the oxidation rate. NZVI showed greater performance than ferrous iron did as an activator for PS. A by-product was formed along with phenol degradation but subsequently was completely degraded, which showed the potential to attain mineralization with the NZVI/PS system. Tests with radical quenchers indicated that sulfate radicals were a predominant radical. The results of this study suggest that NZVI is a promising activator of PS for treating contaminated groundwater.

• Journal of Soil and Groundwater Environment
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• v.17 no.6
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• pp.43-51
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• 2012

Rreactivity of persulfate (PS) for oxidation of TCE under various conditions such as heat, $Fe^{2+}$, and UV was investigated. It was found that degradation rate of TCE increased with increasing temperature from 15 to $35^{\circ}C$. At pH 7.0, the rate constants (k) at 15, 25, 30, and $35^{\circ}C$ were 0.07, 0.30, 0.74, and $1.30h^{-1}$, respectively. For activation by $Fe^{2+}$, removal efficiency of TCE increased with increasing $Fe^{2+}$ concentration from 1.9 mM to 11 mM. The maximum removal efficiency of TCE was approximately 85% when pH of the solution dropped from 7.0 to 2.5. Degradation of TCE by UV-activated PS was the most effective, showing that the degradation rate of TCE increased with inreasing PS dosage; the rate constants (k) at 0.5, 2.5, and 10 mM were 34.2, 40.5, and $55.9h^{-1}$, respectively. Our results suggest that PS activation by UV/PS process could be the most effective in activation processes tested for TCE degradation. For oxidation process by PS, however, pH should be observed and adjusted to neutral conditions (i.e., 5.8-8.5) if necessary.

• Journal of Soil and Groundwater Environment
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• v.28 no.1
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• pp.15-24
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• 2023

A persulfate(PS)/sulfidated microscale zero-valent iron(S-mZVI) system was tested for treating a soil contaminated with phenol. Sulfidation of bare mZVI was conducted using a mechanochemical process utilizing a ball mill in order to improve persulfate activation capacity and stability of unmodified mZVI. The synthesized S-mZVI performed markedly better than the bare mZVI in activating PS. The optimum molar ratio of sulfur to mZVI was around 0.12. In the soil slurry experiments, a very rapid and complete removal of phenol was observed at the optimum molar ratios of PS to S-mZVI of 2:1 and PS to phenol of 16:1. The phenol removal efficiencies decreased as the water content of the slurries decreased. This was believed to be due to increased soil oxidant demand as the amount of soil was increased as relative to the water content. To evaluate the field applicability of the process, slurry experiments adopting high soil contents were carried out that simulated in-situ soil mixing conditions. These experiments resulted in substantially compromised degradation efficiencies of 54.3% and 43.8% within 4 hours. The current study generally shows that the PS/S-mZVI process has a potential to be developed into a remediation technology for soils contaminated with organics.

• Environmental Engineering Research
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• v.25 no.2
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• pp.178-185
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• 2020

The aim of this study is to investigate the degradation of ciprofloxacin (CIP) from its aqueous solutions via different advanced oxidation processes (AOP). The effects of persulfate (PS) concentration, pH, zinc oxide nanoparticles (ZnO-NPs) dose, initial CIP concentration, and reaction time on the degradation of CIP were studied. It was found that the sonochemical (US) degradation is a less efficient process (with removal efficiency of 36%) compared to the sono-nano-chemical (US/ZnO) process which resulted in removal efficiency of 70%. Maximum removal of 99% was obtained using the sono-nano-chemical/PS (US/ZnO/PS) process at a frequency of 60 kHz, time of 10 min, pH of 7, initial CIP concentration of 25 mg/L, and PS concentration of 476.06 mg/L. The addition of PS and ZnO-NPs to the process enhanced the rate of US degradation of CIP. In addition, the kinetic parameters for the US/ZnO/PS process were obtained by fitting the kinetic data into the pseudo-first-order and pseudo-second-order kinetic models. The kinetic data was found to fit into the pseudo-first-order kinetic model than the pseudo-second-order model. The results showed that the AOP using US/ZnO/PS is a promising technique for the treatment of ciprofloxacin containing solutions.

• Journal of Industrial and Engineering Chemistry
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• v.67
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• pp.301-311
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• 2018

In this study, the ion-gelation method was applied to fabricate novel Fe-carbon-bentonite-alginate beads ($Fe^0$/C-BABs). $Fe^0$/C-BABs could effectively control Fe release during persulfate (PS) activation in N-acetyl-p-aminophenol (APAP) oxidation. A novel two-stage approach that combined $Fe^0$/C-BABs and an oyster-shell-filled bed (OSFB) column was developed to address the low pH and high Fe concentration of the effluent of the traditional PS process. The application of the $Fe^0$/C-BABs and OSFB column regulated pH levels and Fe release during the advanced oxidation of APAP. The characteristics of $Fe^0$/C-BABs were also investigated through scanning electron microscopy, energy dispersive spectrometry, and Fourier transform infrared spectroscopy. The long-term operation performance of $Fe^0$/C-BABs in a continuous fixed-bed reactor under simultaneous PS and APAP feeding was also evaluated. The effects of initial PS concentration, pH, fixed-bed weight, in-flow rate, and dissolved oxygen (DO) were investigated. Under selected conditions, 86.3% efficiency was achieved during the first stage of APAP degradation (effluent pH of 3.05, Fe contents: $106.25mgL^{-1}$). Water quality improved after the effluent was passed through the OSFB column (effluent pH of 6.32, Fe contents: $21.43mgL^{-1}$). Moreover, this study analyzed the free radicals and intermediates produced during APAP degradation to identify the possible routes of APAP degradation.

• Journal of the Korea Organic Resources Recycling Association
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• v.32 no.3
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• pp.5-18
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• 2024

Chemical oxygen demand (COD), an organic material measurement index, has a limit to the management of the total amount of all organic materials including non-degradable organic materials due to low oxidation rate. So total organic carbon (TOC) that can measure organic materials more accurately is introduced and used as a measurement index. Several environmental companies including company A in Gyeonggi-do dilute raw wastewater first and then treats it with chemicals. And an activated carbon is used at the rear stage to treat total organic carbon even though various treatment processes can be applied to reduce TOC in wastewater. There are some problems such as use of a lot of diluting water and generation of an excessive amount of sludge, so it is urgent to come up with an alternative plan. Therefore, in this study, an application experiment was conducted on two different methods for improving the TOC reduction efficiency of waste water from Company A. The first method is the evaluation of the substitution potential of powered activated carbon(PAC), an adsorbent currently used, by manufacturing cellulose-based graphene like carbon (CGLC). This first study showed that CGLC had about 10% higher TOC adsorption efficiency than commercial PAC, showing the possibility of being applied as an alternative adsorbent for PAC in water treatment sites. The second method relates to the removal of TOC by sulfate radials produced by persulfate (PS) activation. Two activation methods were applied: using CGLC and PAC as carbon-based catalyst and using the high temperature of wastewater for PS activation. As a result of using PAC and CGLC as PS activation materials, the TOC removal rate was lower than the adsorption amount of TOC by CGLC and PAC due to excessive chlorine ions present in the real wastewater. However, as a result of using the high water temperature (55~60℃) of the field wastewater for PS activation, it showed a much greater TOC removal efficiency than PAC alone, CGLC alone, and using a carbon-based catalyst for PS activation. When PS was injected more than 0.5%, it showed a TOC removal efficiency of 95% or more within 24 hr. In addition, when PS was injected more than 0.3%, the TOC concentration could be lowered to less than 75 ppm, which is the wastewater discharge standard applied to company A. When these results were summarized, raw wastewater of high temperature can be treated with a simple process of only adding of PS and discharged by treating TOC below the wastewater discharge standard applied to company A.

• Korea-Australia Rheology Journal
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• v.21 no.3
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• pp.185-191
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• 2009

Polystyrene/multi-walled carbon nanotube (PS/MWCNT) composites were prepared by the use of latex technology. The monodisperse PS latex was synthesized by an emulsifier-free emulsion polymerization from styrene/potassium persulfate/water system in the presence of ethanol. The MWCNTs were first treated with acid mixture to eliminate impurities, dispersed in deionized water driven by ultrasonicator, and then mixed with the PS latex. From these mixtures, PS/MWCNT composites were prepared by freeze-drying and subsequent compression molding. In the small-amplitude oscillatory shear experiments, both complex viscosity and storage modulus increased with increasing MWCNT content. A pronounced effect of MWCNT content was observed, resulting in larger storage modulus and stronger yield behavior at low frequencies when compared to unmodified PS. It showed a transition from viscous to elastic behavior with increasing MWCNT content. Over the MWCNT content of 3 wt%, the storage modulus was higher than the loss modulus across all frequencies.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2966-2970
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• 2012

Fullerene/polystyrene ($C_{60}$/PS) nano particle was prepared by using emulsion polymerization. Styrene and fullerene were emulsified in aqueous media in the presence of poly(N-vinyl pyridine) as an emulsion stabilizer, and polymerization was initiated by water soluble radical initiator, potassium persulfate. The obtained nano particles have an average diameter in the range of 400-500 nm. The fullerene contents in the nano particle can be controlled up to 15 wt % by varying the feed ratio, which was confirmed by themogravimetric analysis (TGA) and elemental analysis (EA). The structure and morphologies of the $C_{60}$/PS nano particles were examined by various analytical techniques such as dynamic light scattering (DLS), scanning electron microscope (SEM), transmission electron microscope (TEM), electron diffraction (ED) pattern, X-ray powder diffraction (XRD), and UV spectroscopy. Unlike conventional $C_{60}$/PS particles initiated by organic free radical initiators, in which the fullerene is copolymerized forming a covalent bond with styrene monomer, the prepared $C_{60}$/PS nano particles contain pristine fullerene as secondary particles homogeneously distributed in the polystyrene matrix.