• 한국지하수토양환경학회지:지하수토양환경
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• 제25권1호
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• pp.62-73
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• 2020

PAHs commonly found in industrial sites such as manufactured gas plants (MGP) are potentially toxic, mutagenic and carcinogenic, and thus require immediate remediation. In-situ chemical oxidation (ISCO) is known as a highly efficient technology for soil and groundwater remediation. Among the several types of oxidants utilized in ISCO, persulfate has gained significant attention in recent years. Peroxydisulfate ion (S₂O₈^2-) is a strong oxidant with very high redox potential (E⁰ = 2.01 V). When mixed with Fe²⁺, it is capable of forming the sulfate radical (SO₄^-·) that has an even higher redox potential (E⁰ = 2.6 V). In this study, the influence of various iron activators on the persulfate oxidation of PAHs in contaminated soils was investigated. Several iron sources such as ferrous sulfate (FeSO₄), ferrous sulfide (FeS) and zero-valent iron (Fe(0)) were tested as a persulfate activator. Acenaphthene (ANE), dibenzofuran (DBF) and fluorene (FLE) were selected as model compounds because they were the dominant PAHs found in the field-contaminated soil collected from a MGP site. Oxidation kinetics of these PAHs in an artificially contaminated soil and the PAH-contaminated field soil were investigated. For all soils, Fe(0) was the most effective iron activator. The maximum PAHs removal rate in Fe(0)-mediated reactions was 92.7% for ANE, 83.0% for FLE, and 59.3% for DBF in the artificially contaminated soil, while the removal rate of total PAHs was 72.7% in the field-contaminated soil. To promote the iron activator effect, the effects of hydroxylamine as a reducing agent on reduction of Fe³⁺ to Fe²⁺, and EDTA and pyrophosphate as chelating agents on iron stabilization in persulfate oxidation were also investigated. As hydroxylamine and chelating agents (EDTA, pyrophosphate) dosage increased, the individual PAH removal rate in the artificially contaminated soil and the total PAHs removal rate in the field-contaminated soil increased.

• 한국지하수토양환경학회지:지하수토양환경
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• 제12권2호
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• pp.27-36
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• 2007

기존의 연구를 통해 Fenton's reagent(FR)를 이용하여 MTBE의 제거가 가능하며, 그러나 중성 pH영역에서는 철이온이 수산화물로 침전되어 반응성이 낮아지므로 FR만을 이용한 처리는 높은 수소이온 농도조건(pH $3{\sim}4$)이라는 제약으로 인해 직접적인 토양 및 지하수의 MTBE 오염처리에 있어 여러 가지 어려움이 있다. 이에 본 연구에서는 효과적인 처리를 위하여 NTA, oxalate, acetate 등의 chelating agent가 철이온과 반응하여 생성된 착화합물을 이용하는 modified Fenton reaction을 도입하여 중성 pH영역에서도 철이온이 안정화되어 높은 분해효율을 나타낼 수 있도록 하였다. MTBE의 분해경향은 chelating agent의 종류와 농도, 철이온 농도 그리고 pH 변화에 따라 크게 영향을 받는 것으로 나타났다. 가장 적합한 착화합물을 선택하기 위하여 총 6개의 chelating agent(citrate, oxalate, succinate, acetate, NTA, EDTA)를 실험한 결과, 처리효율과 chelating agent의 생분해도, 독성 등을 고려하여 최종 3가지 종(oxalate, acetate, NTA)이 선정되어 이후의 실험에서는 위의 3종만을 chelating agent로 이용하였다. 동일한 실험조건($H_2O_2$ : 5%, chelating agent : 6 mM, $Fe^{3+}$ : 2 mM, pH 7)하에서의 적용성 평가한 결과, Fe-NTA가 반응시작 30분만에 99.9%의 가장 높은 제거효율을 나타내었다. Oxalate의 경우, NTA보다는 그 분해효율이 낮으나 다른 chelating agent보다 상대적으로 높은 효율(24시간 후 최대효율 : 91.3%)을 보여주며, acetate를 이용한 경우도 본 실험에서 좋은 결과(24시간 후 최대효율 : 75.8%)를 나타내었다. 또한, 적정 철이온의 농도는 oxalate가 chelating agent로 이용되면 철이온 농도가 3 mM일때 가장 큰 분해효율을 보이며, acetate의 경우는 5 mM까지 농도가 증가함에 따라 그 효율도 조금씩 증가하는 것으로 나타났다. 이와같이 MTBE의 in-situ remediation을 위한 modified Fenton 공정은 철이온을 중성 pH영역에서 안정화시켜 실제 토양에 적용하였을 때, 높은 분해효율을 얻을 수 있으며, 경제적인 자체 생분해도가 높은 저분자 유기산을 이용하였으므로 생물학적 처리와 연계를 가능하게 해주는 장점을 나타낸다. 또한 토양 내 존재하는 철광석을 촉매로 이용할 경우, 주입되는 철이온 없이도 $H_2O_2$에서의 hydroxyl radical 생성을 증가 시킬 수 있으므로 보다 경제적이고 친환경적인 처리기법을 도출해 낼 수 있다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제11권6호
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• pp.69-75
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• 2006

지하 저장 탱크로부터의 유류 유출로 인하여 전세계적으로 넓은 지역의 토양 및 지하수가 오염되고 있다. Methyl tert-butyl ether(MTBE)는 대기 오염 감소를 위하여 널리 사용되고 있는 유류 첨가제이지만 토양 및 지하수로 유입되어 섭취 되었을 때 발암 가능성이 있는 유독 물질이다. 본 연구는 고도 산화 처리 기법 중 유기 오염물의 분해에 높은 효율을 나타내는 고전적 Fenton reaction의 최대 단점인 강한 산성(pH 2.5-3) 의존성을 극복한 새로운 산화 처리 기법을 개발하여 고농도의 MTBE를 효과적으로 분해 하는 것을 그 목적으로 하여 자연 친화적인 chelating agents를 사용하여 중성 영역에서 Fenton reaction을 가능하게 하는 기법인 Modified Fenton reaction과 Ultra Violet light(UV)를 이용하여 분해효율을 극대화 하는 Photo-assisted Fenton reaction을 응용한 Modified Photo-Fenton reaction system을 개발하여 최적 반응 조건 및 반응 차수, 반응 메커니즘을 밝혀내었다. 낮은 독성과 높은 생분해성을 나타낸 Citrate ion을 chelating agents로 선정하였으며 최적 반응 조건은 [$Fe^{3+}$] : [Citrate] = 1 mM : 4 mM, 3% $H_2O_2$, 17.4 kWh/L UV dose, 초기 pH 6.0이며 이 조건에서 1000 ppm MTBE를 분해한 결과 6시간 후 86.75%, 16시간 후 99.99%의 높은 분해율을 나타냈으며 최종 pH는 6.02로 안정적이었다. 또한 Modified Photo-Fenton reaction을 이용한 MTBE 분해 반응은 유사 1차 반응을 나타내었으며 methoxy group이 ${\cdot}OH$ radical과 주로 반응하여 tert-butyl formate(TBF)가 주요 분해 산물이 되는 분해 경로를 따른 다는 것이 밝혀졌다. 본 연구로 개발된 Modified Photo-Fenton reaction에서 발생되는 산화제인 ${\cdot}OH$ radical의 비선택적 반응성을 고려할 때 본 system은 다른 종류의 유기 오염물 분해에도 효과적일 것으로 판단된다.

• Membrane and Water Treatment
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• 제9권3호
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• pp.137-146
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• 2018

Soil washing is one of the most frequently used remediation technologies for heavy metal-contaminated soils. Inorganic and organic acids and chelating agents that can enhance the removal of heavy metals from contaminated soils have been employed as soil washing agents. However, the toxicity, low removal efficiency and high cost of these chemicals limit their use. Given that humic substance (HS) can effectively chelate heavy metals, the development of an eco-friendly, performance-efficient and cost-effective soil washing agent using a nano-scale chelator composed of HS was examined in this study. Copper (Cu) and lead (Pb) were selected as target heavy metals. In soil washing experiments, HS concentration, pH, soil:washing solution ratio and extraction time were evaluated with regard to washing efficiency and the chelation effect. The highest removal rates by soil washing (69% for Cu and 56% for Pb) were achieved at an HS concentration of 1,000 mg/L and soil:washing solution ratio of 1:25. Washing with HS was found to be effective when the pH value was higher than 8, which can be attributed to the increased chelation effect between HS and heavy metals at the high pH range. In contrast, the washing efficiency decreased markedly in the low pH range due to HS precipitation. The chelation capacities for Cu and Pb in the aqueous phase were determined to be 0.547mmol-Cu/g-HS and 0.192mmol-Pb/g-HS, respectively.

• Journal of Ecology and Environment
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• 제30권3호
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• pp.271-276
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• 2007

A simple and efficient protocol was developed for culturing Cu-tolerant and Cu-accumulating plants via pre-adaptation to Cu during plant tissue culture. We induced multiple shoots from begonia (Begonia evansiana Andr.) leaf explants on MS medium supplemented with naphtaieneacetic acid and benzyladenine. After 3 months, small plantlets were transferred to MS medium supplemented with $100{\mu}M\;CuCl_2$ for pre-adaptation to Cu and cultured for 5 months. Then, these plantlets were individually planted in pots containing artificial soil. An additional 500 mg of Cu dissolved in 1/4 strength MS solution was applied to each pot during irrigation over the course of 2 months. We planted pre-adapted and control begonias in soil from the II-Kwang Mine, an abandoned Cu mine in Pusan, Korea, to examine their ability to tolerate and accumulate Cu for phytore-mediation. Pre-adapted begonias accumulated $1,200{\mu}g$ Cu/g dry root tissue over the course of 45 days. On the other hand, non-Cu-adapted controls accumulated only $85{\mu}g$ Cu/g dry root tissue. To enhance Cu extraction, chelating agents, ethylenediamine tetraacetic acid (EDTA)-dipotassiun and pyridine-2,6-dicarboxylic acid (PDA), were applied. While the chelating agents did not enhance accumulation of Cu in the roots of control begonias, EDTA application increased the level of Cu in the roots of pre-adapted begonias twofold (to $2,500{\mu}g$ Cu/g dry root tissue). Because pre-adapted begonias accumulated a large amount of Cu, mainly in their roots, they could be used for phytostabilization of Cu-contaminated soils. In addition, as a flowering plant, begonias can be used to create aesthetically pleasing remediation sites.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2004년도 총회 및 춘계학술발표회
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• pp.307-310
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• 2004

Micellar enhanced ultrafiltration (MEUF) is a surfactant-based separation process and it can remove heavy metal ions from aqueous stream effectively. However, it is necessary to recover and reuse surfactants for economic feasibility because surfactant is expensive. Foam fractionation was investigated for both anionic and cationic surfactant recovery. Chelating agent such as ethylenediaminetetraacetic acid (EDTA) was studied for the separation of heavy metals from surfactant solution. Anionic surfactants bound with heavy metals can be recovered by lowering pH (acidification). In this study, citric acid and imminodiacetic acid (IDA) were applied to release copper from sodium dodecyl sulfate (SDS) micellar solution and compared with EDTA. Precipitation of copper by ferricynide and sodium sulfide were also investigated. As a result, ca. 100 % of copper was released from SDS micellar solution by 5 mM of EDTA and citric acid. And 3.3 mM of ferricyanide formed precipitate with 82.7 % of copper. 5 mM of IDA and sodium sulfide released or formed precipitate 82.5 % and 58.9 % of copper, respectively. Citric acid is harmless to environments and ferricyanide precipitates with Cu easily. Therefore, it is considered that citric acid and ferricyanide have competiveness over a famous chelating agent, EDTA, for the separation of Cu from SDS solution.

• 셀메드
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• 제5권2호
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• pp.14.1-14.6
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• 2015

Antioxidative and free radical scavenging properties of different stem extracts of Euphorbia trigona were evaluated and correlated with its total phenolic content. Aqueous, acetone and methanolic extracts of shade dried stem were obtained and were concentrated in vacuo. The antioxidant and free radical scavenging activities of stem extracts was determined by 2,2-Diphenyl-1-picrylhydrazyl (DPPH) scavenging assay, reducing power assay, deoxyribose degradation assay and $Fe^{2+}$ chelating assay. Total phenolic contents (TPC) were evaluated using Folin-Ciocalteu reagent. The results confirmed that the plant is a rich source of polyphenolic compounds which are invariably higher compared to other herbs. All extracts showed TPC in the range of 146.6 - 168.6 mg/g gallic acid equivalents at $300{\mu}g/ml$ of extract. Among the three extracts ME showed highest scavenging activity as evidenced by maximum scavenging of DPPH (83.2%), $OH{\bullet}$ radicals (94.81%), $Fe^{2+}$ chelating activity (88.59%) and a high reducing power 0.623 at $300{\mu}g/ml$. Our results demonstrate that Euphorbia trigona, an unexplored xerophytic plant could be potential source of natural antioxidants and phytotherapeutic agents. The plant possess invariably high amount of polyphenolic compounds with a broad spectrum of antioxidant properties and could be further used for food, feed and pharmaceutical applications.

• 한국식품과학회지
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• 제19권4호
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• pp.295-299
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• 1987

유안염석과 column chromatography 및 gel여과등으로 비활성이 23.4U/mg이 되는 정제된 mungbean lipoxygenase를 12%의 수율로 얻었다. 정제효소의 작용최적 pH는 8.4이었으며 linoleic acid를 기질로 사용하였을 때 Km값은 0.25mM이었다. 정제효소는 pH $5.0{\sim}7.0$범위와 $50^{\circ}C$이하의 온도에서 비교적 안정하였다. 효소의 활성은 항산화제인 NDGA에 의해 현저히 저해되었고 chelating agents에 의해 저해되었다.

• Nuclear Engineering and Technology
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• 제15권2호
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• pp.117-122
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• 1983

$\beta$-diketo의 관능기를 가진 1-phenyl-3-methyl-4-acyl-pyrazolone-5-one (acyl pyrazolone)이라고 이름지어진 킬레이팅 화합물은 오랫동안 동위원소 분리 및 추출에 이용되어 왔다. 새로운 acylating 물질을 사용해서 만들어진 succinyl, malenyl 그리고 phthalyl pyrazolone이 우라늄이온(VI)과 고가의 산화상태를 지니는 다른 중금속의 추출에 이용되었다. Succinyl pyrazolone이 우라늄(VI) 추출에서 매우 뛰어나다는 것이 밝혀졌으며, 대체로 카르복실 관능기를 가진 킬레이팅 화합물이 우라늄(VI) 혹은 악티나이드 계열의 중금속 추출에 매우 효과적인 것으로 나타났다.

• 대한임상독성학회지
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• 제19권1호
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• pp.59-63
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• 2021

Copper sulfate is widely used as a fungicide and pesticide. Acute copper sulfate poisoning is rare but potentially lethal in severe cases. Copper sulfate can lead to cellular damage of red blood cells, hepatocytes, and myocytes. Toxic effects include intravascular hemolysis, acute tubular necrosis and, rhabdomyolysis. A 76-year-old man presented with vomiting and epigastric pain. He had ingested a copper-containing fungicide (about 13.5 g of copper sulfate) while attempting suicide 2 hours prior to presentation. From day 3 at the hospital, laboratory findings suggesting intravascular hemolysis were noted with increased serum creatinine level. He was treated with a chelating agent, dimercaptosuccinic acid (succimer). His anemia and acute kidney injury gradually resolved with a 19-day regimen of succimer. Our case suggests that succimer can be used for copper sulfate poisoning when other chelating agents are not available.