• 한국환경과학회지
• /
• 제26권11호
• /
• pp.1201-1208
• /
• 2017

Oxidative degradation of chlorinated ethenes was carried out using heat-activated persulfate. The activation rate of persulfate was dependent on the temperature and the activation reaction rate could be explained based on the Arrhenius equation. The activation energy of persulfate was 19.3 kcal/mol under the assumption that the reaction between the sulfate radical and tricholoroethene (TCE) is very fast. Activation could be achieved at a moderate temperature, so that the adverse effects due to high temperature in the soil environment were mitigated. The reaction rate of TCE was directly proportional to the concentration of persulfate, indicating that the remediation rate can be controlled by the concentration of the injected persulfate. The solution was acidized after the oxidation, and this was dependent on the oxidation temperature. The consumption rate of persulfate was high in the presence of the target organic, but the self-decomposition rate became very low as the target was completely removed.

• 한국지하수토양환경학회지:지하수토양환경
• /
• 제25권4호
• /
• pp.77-86
• /
• 2020

Persulfate-based advanced oxidation processes (AOPs) can oxidize various organic pollutants. In this study, persulfate/Fe(II) system was utilized in phenol removal, and the effect of various organic and inorganic chelators on Fe(II)-medicated persulfate activation was investigated. The feasibility of persulfate/Fe(II)/chelator in cleanup of phenol-contaminated sediment was confirmed through toxicity assessment. In persulfate/Fe(II) conditions, the rate and extent of phenol removal increased in proportion to persulfate concentration. In chelator injection condition, the rate of phenol removal was inversely proportional to chelator concentration when it was injected above optimum ratio. Thiosulfate showed greater chelation tendency with persulfate than citrate and interfered with persulfate access to Fe(II), making the latter a more suitable chelator for enhancing persulfate activation. In contaminated clay sediment condition, 100% phenol removal was obtained within an hour without chelator, with the removal rate increased up to four times as compared to the rate with chelator addition. A clay sediment toxicity assessment at persulfate:Fe(II):phenol 20:10:1 ratio indicated 71.3% toxicity reduction with 100% phenol removal efficiency. Therefore, persulfate/Fe(II) system demonstrated its potential utility in toxicity reduction and cleanup of organic contaminants in sediments.

• 한국환경과학회지
• /
• 제32권1호
• /
• pp.57-65
• /
• 2023

The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

• 대한환경공학회지
• /
• 제33권10호
• /
• pp.723-730
• /
• 2011

본 연구는 토양이나 지하수 원위치 화학적 산화법(In-Situ Chemical Oxidation, ISCO)에서 사용할 수 있는 산화제 Persulfate를 상온에서 활용할 수 있도록 RDX를 처리대상물질로 연구하였다. Persulfate로 RDX를 처리한 결과, 반응은 유사1차반응으로 나타났으며 온도가 증가함에 따라 분해속도도 증가하였고, 이 때 활성화에너지(Activation energy)는 $1.14{\times}10^2kJ/mol$으로 산정되었다. Persulfate에 의한 RDX의 분해반응속도는 pH에 비례하여 증가하였으며, pH값이 4, 6, 8일 때 반응속도의 변화가 크지 않았다. 그러나 pH 10에서는 13배 이상 증가하였는데, persulfate에 의한 산화가 아니라 alkaline hydrolysis로 나타났다. Persulfate에 의한 RDX의 분해반응속도는 persulfate/RDX의 몰 비율에 따라 선형적으로 증가하였으며, $70^{\circ}C$에서 측정한 비례상수는 $4{\times}10^{-4}$ ($min^{-1}$/몰 비율)이었다. 용액 내 천연유기물(NOM) 농도가 증가함에 따라 persulfate에 의한 RDX 분해속도 선형 감소하였으며 $70^{\circ}C$, persulfate/RDX 몰비 10/1에서 측정한 비례상수는 $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$)이었다. 반응속도의 감소는 NOM 첨가량에 선형적으로 비례하였다. NOM 20 mg/L을 첨가한 반응의 Ea값은, 무첨가 반응에서 산정된 Ea값과 3.3% 오차에 불과하였는데, 이는 NOM의 첨가가 본래의 산화반응을 변화시키지는 않음을 의미한다.

• 한국환경과학회지
• /
• 제29권1호
• /
• pp.69-77
• /
• 2020

Oxidative degradation of phenol, three monochlorophenols (2-chlorophenol, 2-CP; 3-chlorophenol, 3-CP; 4-chlorophenol, 4-CP), four dichlorophenols (2,3-dichlorophenol, 2,3-DCP; 2,4-dichlorophenol, 2,4-DCP; 2,5-dichlorophenol, 2,5-DCP; 2,6-dichlorophenol, 2,6-DCP), and two trichlorophenols (2,4,5-trichlorophenol, 2,4,5-TCP; 2,4,6-trichlorophenol, 2,4,6-TCP) was conducted with heat activated persulfate. As the number of chlorinations increased, the reaction rate also increased. The reaction rate was relatively well fitted to the zero-order kinetic model, rather than the pseudo-first order kinetic model for the reactions at 60 ℃, which can be explained by insufficient activation of the persulfate at 60 ℃, and the oxidation reaction of 2,4,6-TCP at 70 ℃ was relatively well fitted to the pseudo-first order kinetic model. The oxidation reaction rate generally increased with increase of persulfate concentration in the solution. 2,6-dichloro-2,5-cyclohexadiene-1,4-dione was found as a degradation product in a GC/MS analysis. This compound is a non-aromatic compound, and one chlorine was removed. This result is similar to the result of previous studies. The current study proved that heat activated persulfate activation could be an alternative remediation technology for phenol and chlorophenols in soil and groundwater.

• 한국지하수토양환경학회지:지하수토양환경
• /
• 제27권1호
• /
• pp.31-38
• /
• 2022

The common algae and industrial waste, chlorella and red mud, were co-pyrolyzed in carbon dioxide condition to fabricate iron-biochar composite. In order to investigate the direct effect of chlorella and red mud in the syngas generation and the property of biochar, experiments were performed using mixture samples of chlorella and red mud. The evolution of flammable gasses (H₂, CH₄, CO) was monitored during pyrolysis. The produced biochar composite was employed as a catalyst for persulfate activation for methylene blue removal. BET analysis indicated that the iron-biochar composite mainly possessed meso- and macropores. The XRD analysis revealed that hematite (Fe₂O₃) contained in red mud was transformed to Fe₃O₄ during co-pyrolysis. The composite effectively activated persulfate and removed methylene blue. Among the composite samples, the composite fabricated from the mixture composed of 1:2 chlorella:red mud showed the best performance in syngas generation and methylene blue removal.

• 한국지하수토양환경학회지:지하수토양환경
• /
• 제17권6호
• /
• pp.43-51
• /
• 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.

• 한국환경과학회지
• /
• 제29권12호
• /
• pp.1205-1211
• /
• 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.

• Advances in environmental research
• /
• 제3권3호
• /
• pp.185-197
• /
• 2014

Efficient defluorination of perfluorooctanoic acid (PFOA) was achieved by integrating UV irradiation and $Fe^{2+}$ activation of persulfate ($S_2O{_8}^{2-}$). It was found that the UV-$Fe^{2+}$, $Fe^{2+}-S_2O{_8}^{2-}$, and UV-$S_2O{_8}^{2-}$ processes caused defluorination efficiency of 6.4%, 1.6% and 23.2% for PFOA at pH 5.0 within 5 h, respectively, but a combined system of UV-$Fe^{2+}-S_2O{_8}^{2-}$ dramatically promoted the defluorination efficiency up to 63.3%. The beneficial synergistic behavior between $Fe^{2+}-S_2O{_8}^{2-}$ and UV-$S_2O{_8}^{2-}$ was demonstrated to be dependent on $Fe^{2+}$ dosage, initial $S_2O{_8}^{2-}$ concentration, and solution pH. The decomposition of PFOA resulted in generation of shorter-chain perfluorinated carboxylic acids (PFCAs), formic acid and fluoride ions. The generated PFCAs intermediates could be further defluorinated by adding supplementary $Fe^{2+}$ and, $S_2O{_8}^{2-}$ and re-adjusting solution pH in later reaction stage. The much enhanced PFOA defluorination in the UV-$Fe^{2+}-S_2O{_8}^{2-}$ system was attributed to the fact that the simultaneous employment of UV light and $Fe^{2+}$ not only greatly enhanced the activation of $S_2O{_8}^{2-}$ to form strong oxidizing sulfate radicals ($SO{_4}^{\cdot-}$), but also provided an additional decarboxylation pathway caused by electron transfer from PFOA to in situ generated $Fe^{3+}$.

• 한국지하수토양환경학회지:지하수토양환경
• /
• 제22권2호
• /
• pp.17-25
• /
• 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.