• Journal of Soil and Groundwater Environment
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• v.26 no.1
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• pp.54-64
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• 2021

The chemical warfare agents (CWAs) have been developed for offensive or defensive purposes and used as chemical weapons in war and terrorism. The CWAs are exposed to the natural environment, transported through the water system and then eventually contaminate soil and groundwater. Therefore, effective decontamination technology to remediate CWAs are needed. The CWAs are extremely dangerous and prodution is strictly prohibited, therefore, it is difficult to use CWAs even in experimental purpose. In this study, 2,4-dichlorophenoxyacetic acid (2,4-D) was chosen as a model representative CWA because it is a simulant of anti-plant CWAs and one of the major component of agent orange. The optimum degradation conditions such as oxidant:activator ratio were determined. The effects of hydroxylamine and chelating agents such as citric acid (CA), oxalic acid (OA), malic acid (MA), and EDTA addition to increase Fe2+ activation were also investigated. Scavenger experiments using tert-butyl alcohol (TBA) and ethanol confirmed that although both sulfate (SO4•-) and hydroxyl radical (•OH) existed in Fe2+-persulfate system, sulfate radical was the predominant radical. To promote the Fe2+ activator effect, the effect of hydroxylamine as a reducing agent was investigated. In chelating agents assisted Fe2+-persulfate oxidation, the addition of 2 mM of CA and MA enhanced 2,4-D degradation. In contrast, EDTA and OA inhibited the 2,4-D removal due to steric hindrance effect.

• 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.

• 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.

• Membrane and Water Treatment
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• v.9 no.6
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• pp.405-419
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• 2018

Persulfates (i.e., peroxymonosulfate and peroxydisulfate) are capable of oxidizing a wide range of organic compounds via direct reactions, as well as by indirect reactions by the radical intermediates. In aqueous solution, persulfates undergo self-decomposition, which is accelerated by thermal, photochemical and metal-catalyzed methods, which usually involve the generation of various radical species. The chemistry of persulfates has been studied since the early twentieth century. However, its environmental application has recently gained attention, as persulfates show promise in in situ chemical oxidation (ISCO) for soil and groundwater remediation. Persulfates are known to have both reactivity and persistence in the subsurface, which can provide advantages over other oxidants inclined toward either of the two properties. Besides the ISCO applications, recent studies have shown that the persulfate oxidation also has the potential for wastewater treatment and disinfection. This article reviews the chemistry regarding the hydrolysis, photolysis and catalysis of persulfates and the reactions of persulfates with organic compounds in aqueous solution. This article is intended to provide insight into interpreting the behaviors of the contaminant oxidation by persulfates, as well as developing new persulfate-based oxidation technologies.

• Journal of the Korean Wood Science and Technology
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• v.48 no.2
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• pp.231-244
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• 2020

As a way of finding value-added materials from waste medium density fiberboard (MDF), this study characterized cellulose nanocrystals (CNCs) isolated by ammonium persulfate (APS) oxidation using recycled MDF fibers. Chemical composition of the recycled MDF fibers was done to quantify α-cellulose, hemicellulose, lignin, nitrogen, ash and extractives. The APS oxidation was performed at 60 ℃ for 16 h, followed by ultrasonication, which resulted in a CNC yield of 11%. Transmission electron microscope images showed that rod-like CNCs had an average length and diameter of 167±47 nm and 8.24±2.28 nm, respectively, which gave an aspect ratio of about 20. The conductometric titration of aqueous CNCs suspension resulted in a carboxyl content of 0.24 mmol/g and the degree of oxidation was 0.04. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy clearly showed the presence of carboxyl group on the CNCs prepared by the APS oxidation. The change of pH of the aqueous CNC suspension from 4 to 7 converted the carboxyl group to sodium carboxylate group. These results showed that the APS oxidation was facile and CNCs had a one-step preparation method, and thus suggested an optimization of the oxidation condition in future.

• 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.

• Macromolecular Research
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• v.12 no.1
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• pp.107-111
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• 2004

We have studied the polymerization kinetics of acrylamide in aqueous solution with potassium persulfate as an initiator by using quantitative real-time in situ IR spectroscopy and monitoring the profiles of peaks in the range 1900-850 cm$\^$-1/. The conversion of acrylamide was calculated from the disappearance of the peak at 988 cm$\^$-1/, which is the out-of-plane bending mode of the=C-H unit, normalized to the C=O stretching peak at 1675 cm$\^$-1/, as an internal standard. For reaction temperatures in the range 40-65$^{\circ}C$ and initiator and monomer concentrations of 0.9-2.6 mmol/L and 0.5-1.1 mol/L, respectively, we deduced that the rate of monomer consumption follows the relation R$\_$p/=k［K$_2$S$_2$O$\_$8/］$\^$0.5/ [Μ］$\^$1.35${\pm}$0.10/. In addition, we obtained activation parameters from an evaluation of the kinetic data.

• Journal of the Korean Wood Science and Technology
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• v.47 no.5
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• pp.597-606
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• 2019

Cellulose nanocrystals (CNCs) were successfully isolated from oil palm fronds (OPFs) using different concentrations of ammonium persulfate (APS), and their characteristics were analyzed by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, and thermogravimetric analysis (TGA). APS oxidation effectively isolated CNCs with rod-like morphology in nanometer scale. The dimensions of the CNCs decreased with increasing APS concentration. FTIR and XRD analyses revealed that all the CNCs showed crystals in the form of cellulose I without crystal transformation occurring during APS treatment. The relative crystallinity of the CNCs increased with increasing APS concentration, whereas their thermal stability decreased. An APS concentration of 2 M was found to be optimal for isolating the CNCs.

• Journal of Environmental Science International
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• v.29 no.12
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• pp.1205-1211
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• 2020

In this study, the applicability of reduction-oxidation-linked treatment was evaluated for nitrobenzene and a by-product by analyzing the reaction kinetics. Nitrobenzene showed very low reactivity to persulfate that was activated using various methods. Nitrobenzene effectively reacted through the reduction process using Zero-Valent Iron (ZVI). However, aniline, a toxic substance, was produced as a by-product. Reduction-oxidation-linked treatment is a method that can allow the oxidative degradation of aniline after reducing nitrobenzene to aniline. The experimental results show improved reactivity and complete decomposition of the by-product. Improved reactivity and decomposition of the by-product were observed even under conditions in which the reduction-oxidation reaction was induced simultaneously. No activator was injected for persulfate activation in the process of reducing oxidant linkage, and the activation reaction was induced by ferrous iron eluted from the ZVI. This indicates that this method can be implemented relatively simply.

• Clean Technology
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• v.4 no.2
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• pp.11-22
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• 1998

The photo-sensitized oxidation of benzene in water was investigated under various reaction conditions using persulfate, sulfate, nitrate, nitrite and chloride ions as sensitizers. Persulfate ion was proved to be the most effective sensitizer, while sulfate and nitrite could not play any sensitizing role on the benzene photooxidation. When exited together with other ions, the nitrite ion inhibited the photooxidation of benzene by quenching the produced hydroxyl radicals.