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Degradation Kinetic and Mechanism of Methyl Tert-butyl Ether (MTBE) by the Modified Photo-Fenton Reaction (Modified Photo-Fenton Reaction을 이용한 Methyl Tert-butyl Ether (MTBE)의 분해 Kinetic 및 메커니즘 규명에 관한 연구)

  • Kim, Min-Kyoung;Kong, Sung-Ho
    • 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.

Influence of Toxic Heavy Metals on Germination of Rice Seeds and Growth of Rice Seedling (수도생육(水稻生育)에 대한 유해(有害) 중금속(重金屬)의 영향(影響) - 발아 및 묘대기(苗垈期) 생육(生育)에 대하여 -)

  • Kim, B.J.;Ha, Y.L.;Kim, J.O.;Han, K.H.
    • Korean Journal of Soil Science and Fertilizer
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    • v.11 no.2
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    • pp.119-126
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    • 1979
  • Rice seeds, suweon 264, were germinated under 5 levels of toxic heavy metals, Cd(0, 0.05, 0.5, 5, 20ppm), Cu(0, 0.05, 0.5, 5, 20, ppm), Cr(0, 0.5, 1, 5, 10ppm), Ni(0, 0.5, 1, 5, 10ppm), Co(0, 0.5, 1, 5, 10ppm), Zn(0, 0.5, 5, 20, 40, ppm), Pb(0, 0.5, 5, 20, 40ppm) and Mn(0, 1, 10, 25, 50, ppm) in culture solution, and then grown with supplying culture solution contained respective concentrations. Germination and growth response to the toxic heavy metals were studied. Results obtained are as follows : 1) The germination injury of rice seeds by excess concentration of toxic heave metal in culture solution occured in Cd and Cu; below 0.05 ppm, Ni; below 0.5 ppm, Mn; below 1.0 ppm, Co and Cr; 0.5-1.0 ppm, and 0.5-5 ppm, Zn and Pb. Thereby, in the order of degrees of the elements toxicity to germination, they were arranged as follows : Cd>Cu>Ni>Co>Cr>Mn>Zn$$\geq_-$$Pb. 2) Toxic heavy metal concentrations in culture solution, which result in decreasing dry weight due to the injury of excess concentration of treated elements, were Cd: below 0.05 ppm, Ni, Cr and Co; below 0.5 ppm, Cu and Zn; 0.5-5 ppm, Pb; 5-20 ppm and Mn; 10-25 ppm. The order was Ni>Cd>Cr>Co>Cu$$\geq_-$$Zn>Pb>Mn. 3) The critical contents of Cd, Ni, Pb, Cu, Zn, Mn, and Co in dry matter, Which result in decreasing dry weight, were considered to be 0.05-15.5, 1.50-25.0, 24.0-28.0, 26.5-62.5, 470-645.0, 231.0-500.0 and below 15.0 ppm, respectively. 4) The contents of Cr, Co, Cd, Pb, Ni, Cu and Zn in dry matter by 0.5 ppm treatment concentration of each heavy metals was trace, 15.0, 17.5, 24.0, 25.0, 84.5 and 470.0 ppm, respectively. Thereby, in the order of each element to uptaked by rice seedlings, they were arranged as follow; Zn>Cu>Ni>Pb>Cd>Co>Cr. 5) The hazardous concentrations of root activity by toxic heavy metals in culture solution were Cd; below 0.05, Cu; 0.05-0.5, Cr; below 0.5, Ni; 0.5-1.0, Co; 0.5-1.0, Zn; above 0.5, Pb; 0.5-5.0 and Mn; 1.0-10.0 ppm. The hazardous degree of root activity by toxic heave metals was in the order of Cd>Cu>Cr>Zn>Ni>Co>Pb>Mn.

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Determination of Sulfur Requirement to Adjust pH of Alkaline Soil by Buffer Curve Method (알칼리성 토양 pH 교정시 완충곡선법을 이용한 황 시용량 결정)

  • Lee, In-Bog;Lim, Jae-Hyun;Yiem, Myoung-Soon
    • Korean Journal of Soil Science and Fertilizer
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    • v.33 no.6
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    • pp.405-415
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    • 2000
  • To determine application rate of elemental sulfur to adjust pH of alkaline soil, buffer curve method was investigated. The elemental sulfur required to control pH 8.3 to pH 6.3 by buffer curve calculation was treated in two soils of silty loam and sandy loam, and the sulfur-mixed soils were moistened with 50% of water holding capacity during incubation of 6 weeks at $30^{\circ}C$. Soil pH was lowered with incubation and reached to target point after 4 weeks of incubation, and elemental sulfur was oxidised entirely to sulfate. This means that buffer curve has the accuracy to determine sulfur application rate in alkaline soil. However it is estimated that application rate of sulfur should be carefully determined in the field scale. Excess application of elemental sulfur resulted in extremely low soil pH and caused the hinderance of lettuce growth by nutritional imbalance and ion toxicity. To simplify the determination procedure of sulfur requirement, buffer curve method by addition of 0.1N-HCl solution as unit of mL was developed, it was compared with theroutine methods which diluted $H_2SO_4$ solution and $Ca(OH)_2$ are added as cmolc per kg soil to adjust each pH step. Buffer capacities, cmolc kg $soil^{-1}$ $pH^{-1}$, calculated from two buffer curves were not significantly different. The result indicates that buffer curve method by 0.1N-HCl can be used to adjust high pH of alkaline soil.

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Long-term Results of Radiotherapy for Subfoveal Choroidal Neovascularization (CNV) in Age-related Macular Degeneration (ARMD) (연령관련 황반하 맥락막 신생혈관증에서 방사선의 장기적 치료 결과)

  • Kim, Bo-Kyong;Kim, Il-Han
    • Radiation Oncology Journal
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    • v.25 no.2
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    • pp.63-69
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    • 2007
  • [ $\underline{Purpose}$ ]: We performed this prospective randomized study to evaluate the efficacy and the complications of radiotherapy for Subfoveal CNV in ARMD and to compare the treatment results at two dosages (14.4 Gy and 19.8 Gy). $\underline{Materials\;and\;Methods}$: 60 eyes of 55 patients were enrolled, and randomized into 14.4 Gy (31 eyes) or 19.8 Gy (29 eyes) groups. CT was used to plan the radiotherapy. All patients received radiotherapy with a 1.8 Gy daily dose using 4 MV photon. We categorized treatment results as improved, stable, or deteriorated based on visual acuity changes of more than 2 lines on the ETDRS chart. $\underline{Results}$: Median follow-up period was 33.5 months. At 12 months, visual acuity improved in 9 (16.7%), stable in 41 (75.9%), and aggravated in 4 (7.4%) of 54 evaluated eyes. At 24 months, 49 eyes (81.7%) were evaluated. Visual acuity improved in 6 (12.2%), was stable in 33 (67.4%), and deteriorated in 10 (20.4%). At 36 months, 37 eyes were evaluated. Six (16.2%) eyes were improved, 21 (56.8%) stable, and 10 (27.0%) deteriorated. No significant difference in response was observed between the 14.4 Gy and 19.8 Gy groups (Mantel-Haenszel $x^2=0.4756$). The proportion of eyes with a vision of $20/100{\leq}increased$ from 28.3% initially to 32.7% after 24 months of radiotherapy. There were no severe acute or chronic complications. $\underline{Conclusion}$: External beam radiotherapy with doses of 14.4 or 19.8 Gy may be an effective treatment for subfoveal CNV in ARMD. No dose-response relationships with respect to treatment response or toxicity were observed between the 14.4 Gy and 19.8 Gy groups.

The effects of selenium on fetal growth and development in CD-1 mice exposed with mercury for the gestation period (임신 중 수은을 섭취한 CD-1 마우스 태아의 성장발육과 기형발생에 미친 셀레늄의 효과)

  • Kim, Jin-suk;Lee, Sang-mok;Choi, Seok-wha;Lee, Won-chang
    • Korean Journal of Veterinary Research
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    • v.34 no.2
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    • pp.361-368
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    • 1994
  • Teratogenic and embryotoxic effects of mercury have been reported, however, there is little information about possible antidotes against mercury exposure during gestation. In order to evaluate therapeutic effects of selenium as an antidote against mercury poisoning, pregnant CD-1 mice were exposed to methylmercury chloride(20ppm) through the drinking water with treatment of sodium selenite (1.0mg, 2.0mg or 3.0mg/kg b.w., subcutaneously) or BAL(5.0mg/kg b.w., subcutaneously) under the single or combination base as the therapeutic agents from day 6 to 15 of gestation. Fetal growth parameters such as body weight and crown-rump length in the mice exposed to mercury, were reduced as was placental weight compared to those in the control. Treatment of selenium(alone, combination with BAL) reduced the harmful effects induced by mercury on the fetal growth parameters even though no specific relationship between dose and therapeutic effect. The incidence of dead fetuses/resorptions and malformed fetuses(especially cleft palate) was also increased in the mercury only treated group. Selenium treatment demonostrated reduced the incidence of abnormal fetuses under the exposure of mercury. Relative maternal organ weights(liver, kidney, spleen) were increased significantly but relative brain weight was decreased as evidenced by decreased in the mercury treated mice compared to that in the control. A subtle indication of maternal mercury toxicity evidenced by changes of relative maternal organ weights, decreased water and feed consumption were also prevented efficiently by selenium treatment. The present study suggests that methylmercuric chloride is embrytoxic and teratogenic in CD-1 mice when exposured during organogenesis and that selenium administration may have therapeutic application for the treatment of mercury poisoning although more applicable study in human should be performed with caution in the future.

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Determination of Target Clean-up Level and Risk-Based Remediation Strategy (위해성에 근거한 정화목표 산정 및 복원전략 수립)

  • Ryu, Hye-Rim;Han, Joon-Kyoung;Nam, Kyoung-Phile
    • Journal of Soil and Groundwater Environment
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    • v.12 no.1
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    • pp.73-86
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    • 2007
  • Risk-based remediation strategy (RBRS) is a consistent decision-making process for the assessment and response to chemical release based on protecting human health and the environment. The decision-making process described integrates exposure and risk assessment practices with site assessment activities and remedial action selection to ensure that the chosen actions are protective of human health and the environment. The general sequences of events in Tier 1 is as follows: initial site assessment, development of conceptual site model with all exposure pathways, data collection on pollutants and receptors, and identification of risk-based screening level (RBSL). If site conditions do not meet RBSL, it needs further site-specific tier evaluation, Tier 2. In most cases, only limited number of exposure pathways, exposure scenarios, and chemicals of concern are considered the Tier 2 evaluation since many are eliminated from consideration during the Tier 1 evaluation. In spite of uncertainties due to the conservatism applied to risk calculations, limitation in site-specific data collections, and variables affecting the selection of target risk levels and exposure factors, RBRS provides us time- and cost-effectiveness of the remedial action. To ensure reliance of the results, the development team should consider land and resource use, cumulative risks, and additive effects. In addition, it is necessary to develop appropriate site assessment guideline and reliable toxicity assessment method, and to study on site-specific parameters and exposure parameters in Korea.

Inhibitory effect of Hypericum ascyron on pro-inflammatory responses in lipopolysaccharide-induced Raw 264.7 Cells (Lipopolysaccharide로 유도된 Raw 264.7 cell에서 물레나물(Hypericum asctron)의 Pro-inflammatory 억제 효과)

  • Hong, Eun-Jin;Park, Hye-Jin;Kim, Na-Hyun;Jo, Jae-Bum;Lee, Jae-Eun;Lim, Su-Bin;Ahn, Dong-Hyun;Jung, Hee-Young;Cho, Young-Je
    • Journal of Applied Biological Chemistry
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    • v.60 no.4
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    • pp.363-372
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    • 2017
  • Hypericum ascyron has long been used as medicinal plant and recent studies reported that H. ascyron has anti-diabetic, anti-oxidant, and anti-bacterial effects. In this study, inhibitory effect from H. ascyron on pro-inflammatory responses has been investigated. H. ascyron was extracted at optimal extraction condition. Total phenolic contents in water and 90% ethanol were 29.75 and 31.82 mg/g, respectively. Hyaluronidase inhibitory activity of H. ascyron extracts ($50-200{\mu}g/mL$ phenolics) was 0.00-14.81% and 15.33-47.49%, respectively. In cell viability, cell toxicity was shown at concentration of $100{\mu}g/mL$ and $30{\mu}g/mL$ of water and 90% ethanol extract. Therefore, $10-50{\mu}g/mL$ in water extracts and $5-20{\mu}g/mL$ in ethanol extracts was selected each for further study. Inducible nitric oxide synthase (iNOS) derived nitric oxide (NO) and cyclooxygenase (COX)-2-derived prostaglandin $E_2$ ($PGE_2$) protein expression inhibitory effect of extracts were inhibited in a dose dependent manner, significantly. Also, the pro-inflammatory cytokines inhibitory effect such as tumor necrosis $factor-{\alpha}$, nterleukin (IL)-6 and $IL-1{\beta}$ were decreased in the dose dependent manner. The results indicate that H. ascyron extracts reduced inflammatory responses in lipopolysaccharide-induced 264.7 cells via the regulation of the iNOS, COX-2, NO, $PGE_2$, and pro-inflammatory cytokines. Therefore, H. ascyron extracts have significant anti-inflammatory effect and a source as therapeutic materials.

Antibacterial and Antimutagenic Effects of Sweetpotato Tips Extract (고구마 끝순 추출물의 항균 및 항돌연변이 효과)

  • Lee, Joon-Seol;Shin, Mee-Jin;Park, Yang-Kyun;Ahn, Young-Sup;Chung, Mi-Nam;Kim, Hag-Sin;Kim, Jeong-Mok
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.52 no.3
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    • pp.303-310
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    • 2007
  • Sweetpotato shoot tops (leaves, tips and petioles) are known to be very useful parts as vegetables because of their high nutritive values and great biomass yield. In this study, the phenolic compound contents, antibacterial activity, mutagenic activity, and antimutagenic activity were investigated in sweetpotato tips that were 10-15cm of shoot top including stems, petioles and tender leaves after sprout of storage roots. The study was done by extracting sweetpotato tips with 80% ethanol and the ethanol fraction was re-extracted with hexane, chloroform, ethyl acetate, butanol and water. In ethyl acetate and butanol fractions, total phenolic compounds contained 95. 6mg/g extract and 69.3 mg/g extract, respectively, The antibacterial activity was measured using the paper disk method with concentrations of 1, 2, 5 and 10 mg/disk of butanol and ethyl acetate fractions against L. monocytogenes and S. Typhimurium strains. Higher doses of solvent extracts showed the higher antibacterial activities. In addition, 5, 10 and 20 mg/mL of the extracts were tested to determine the antibacterial activity in liquid culture. The sweetpotato leaf extract by ethyl acetate showed 1 log reduction compared to control after 24 hrs on Listeria monocytogenes, but 20 mg/ml of butanol extract completely inhibited the growth of the pathogen after 12 hrs. The extracts from ethyl acetate or butanol on Salmonella Typhimurium did less than 1 log reduction during cultivation compared to control. The numbers of S. Typhimirium TA98 and TA100 revertant colonies were 29-33 and 159-188 CFU/plate, respectively, indicating that solvent extracts were no mutagenic activity. The antimutagenic test was performed by adding direct mutagen 2-NF and MMS, and butanol and ethyl acetate showed antimutagenic effect. Thus, this study showed that sweetpotato tips had high phenolic contents and both antimicrobiol and antimutagenic properties. Sweetpotato tips would be good nutritive source because of their high nutrient content without any toxicity in consuming.

Monitoring of Seasonal Water Quality Variations and Environmental Contamination in the Sambo Mine Creek, Korea (삼보광산 하류 수계의 계절별 수질변화와 오염도 평가)

  • Jung, Goo-Bok;Lee, Jong-Sik;Kim, Won-Il;Ryu, Jong-Su;Yun, Sun-Gang
    • Korean Journal of Environmental Agriculture
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    • v.27 no.4
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    • pp.328-336
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    • 2008
  • Metal mining district drainage is a well recognized source of environmental contamination. Oxidation of metal sulfides produces acidic and metal-rich waters that contaminate local surface water and ground water in mines, mine dumps, and tailing impoundments. This monitoring study was carried out to investigate the stream water quality and pollution as affected by the Sambo mine drainage in relation to the relative distance from the mine. It obvious that pH values of the mine drainage ranged from 5.8 to 6.9, while the average concentrations of the dissolved chemical constituents for EC, $SO_4^{2-}$, $K^+$, $Ca^{2+}$, and $Mg^{2+}$ were $1.77\;dS\;m^{-1}$, 929, 14.6, 263.3, and 46.9 mg/L in mine drainage discharged from the main waste rock dumps (WRD), respectively. Furthermore, EC values and sulfate concentrations exceeded the critical toxicity levels in agricultural water for rice plant ($1.0\;dS\;m^{-1}$ for EC and 54.0 mg/L for $SO_4^{2-}$). Also, the average of dissolved cadmium concentrations ($0.016{\sim}0.021\;mg/L$) was higher than water quality standard (0.01 mg/L) for agricultural water in Korea, in addition to Zn, Fe and Mn were higher than trace metals maximum concentrations which recommended by FAO for irrigation water. The results indicate that mine drainage discharged from the Sambo mine affected stream water at least to distance of 1 km downstream of the mine water discharge point. EC values, $SO_4^{2-}$ and $Ca^{2+}$ concentrations in discharged water positively correlated with dissolved Cd, Zn, Al and Mn concentrations, while the pH values negatively correlated. In addition, EC values, $SO_4^{2-}$ and $Ca^{2+}$ concentrations were negatively correlated with pH values.

Toxic effects of phenanthrene on fertilization and normal embryogenesis rates of Mesocentrotus nudus and Hemicentrotus pulcherrimus (둥근성게(Mesocentrotus nudus)와 말똥성게(Hemicentrotus pulcherrimus)의 수정 및 정상 배아발생률을 이용한 Phenanthrene의 독성영향)

  • Choi, Hoon;Lee, Ju-Wook;Park, Yun-Ho;Lee, Seung-Min;Choi, Yoon-Seok;Heo, Seung;Hwang, Un-Ki
    • Korean Journal of Environmental Biology
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    • v.38 no.3
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    • pp.333-342
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    • 2020
  • The aim of this study was to define the toxic effects of phenanthrene (PAHs) on the fertilization and normal embryogenesis rates in the two species of sea urchin (Hemicentrotus pulcherrimus and Mesocentrotus nudus). The sperm and fertilized eggs of both sea urchin species were exposed to serial dilutions of phenanthrene for 10 min and 48 hours, respectively. The fertilization rate and normal embryogenesis rate of H. pulcherrimus and M. nudus were decreased in a concentration-dependent manner. The EC50 for the fertilization rate of H. pulcherrimus and M. nudus was 17.48 mg L-1 and 16.21 mg L-1, and the EC50 for the normal embryogenesis rate was 2.99 mg L-1 and 0.36 mg L-1, respectively. Between the two species, H. pulcherrimus was more sensitive to phenanthrene exposure, and 48 h normal embryogenesis was the more sensitive endpoint. Therefore, the results of this study demonstrated that the exposure of both sea urchin species to phenanthrene caused alterations in egg fertilization and the early developmental stages.