• Title/Summary/Keyword: Chlorophenols

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Dechlorination of Individual Congeners in Aroclor 1248 as Enhanced by Chlorobenzoates, Chlorophenols, and Chlorobenzenes

  • Kim, Jong-Seol;Cho, Young-Cheol;Frohnhoefer, Robert C.;Rhee, G-Yull
    • Journal of Microbiology and Biotechnology
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    • v.18 no.10
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    • pp.1701-1708
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    • 2008
  • Previous investigations showed that three classes of haloaromatic compounds (HACs; chlorobenzoates, chlorophenols, and chlorobenzenes) enhanced the reductive dechlorination of Aroclor 1248, judging from the overall extent of reduction in CI atoms on the biphenyl. In the present study, we further investigated the kind of polychlorinated biphenyl (PCB) congeners involved in the enhanced dechlorination by four isomers belonging to each class (2,3-, 2,5-, 2,3,5-, and 2,4,6-chlorobenzoates; 2,3-, 3,4-, 2,5-, and 2,3,6-chlorophenols; and 1,2-, 1,2,3-, 1,2,4-, and penta-chlorobenzenes). Although the PCB congeners involved in the enhanced dechlorination varied with the HACs, the enhancement primarily involved para-dechlorination of the same congeners (2,3,4'-, 2,3,4,2'-plus 2,3,6,4'-, 2,5,3',4'- plus 2,4,5,2',6'-, and 2,3,6,2',4'-chlorobiphenyls), regardless of the HACs. These congeners are known to have low threshold concentrations for dechlorination. To a lesser extent, the enhancement also involved meta dechlorination of certain congeners with high threshold concentrations. There was no or less accumulation of 2,4,4'- and 2,5,4'-chlorobiphenyls as final products under HAC amendment. Although the dechlorination products varied, the accumulation of ortho-substituted congeners, 2-, 2,2'-, and 2,6-chlorobiphenyls, was significantly higher with the HACs, indicating a more complete dechlorination of the highly chlorinated congeners. Therefore, the present results suggest that the enhanced dechlorination under HAC enrichment is carried out through multiple pathways, some of which may be universal, regardless of the kind of HACs, whereas others may be HAC-specific.

Effect of pH on the sorption kinetics of chlorophenols onto HDTMA-montmorillonite (염화페놀류 화합물의 HDTMA-montmorillonite에 대한 수착 동력학에 미치는 ph의 영향)

  • Mun Yong, Gwak;Dong Ik, Song
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.186-191
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    • 2004
  • Sorption kinetics of 2-chlorophenol(2-ChP), 2,4-dichlorophenol(2,4-DChP) and 2,4,5-trichlorophenol (2,4,5-TChP), onto montmorillonite modified with hexadecyltrimethyl ammonium cations(HDTMA-mont) were investigated. One-site mass transfer model(OSMTM) and two compartment first-order kinetic model(TCFOKM) were used to analyze kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption and desorption kinetics of chlorophenols in HDTMA-mont. For all chlorophenols, the results of OSMTM analysis indicate that the predominant deprotonated speciation(at pH 9.15) exhibited higher mass transfer coefficient( $k_{s}$ ) than the protonated speciation(at pH 4.85). This is because the deprotonated speciation has stronger hydrophobic interaction than protonated speciation. Most sorption completes in three hours. The fraction of the fast sorption and the first-order sorption rate constants for the fast and slow compartments in TCFOKM were determined by fitting experimental data to the TCFOKM. The results of kinetics reveal that the fraction of the fast sorption( $f_1$) and the sorption rate constants in the fast compartments( $k_1$) were in the order 2,4,5-TChP > 2,4-DChP > 2-ChP, which agrees with the magnitude of the $K_{ow}$ . The first-order sorption rate constants in the fast compartment(10$^{0.8}$ - 10$^{1.22}$ h $r^{-1}$ ) were much larger than those in the slow compartment(10$^{-1}$.74/ - 10$^{-2}$.622/ h $r^{-1}$ ).> ).).

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Analytical Determination of Alkylphenols, Chlorophenols and Bisphenol A in Biota Samples using Gas Chromatography/Mass Spectrometry (기체 크로마토그래피/질량분석기를 이용한 생물시료 중 알킬 페놀류, 클로로페놀류 및 비스페놀 A의 분석법)

  • Hong, Jongki;Kim, Hyup;Baek, In-Girl;Kim, Do-Gyun;Seo, Jung-Joo;Seo, Jong-Bok;Chung, Bong-Chul;Pyo, Hee-Soo;Kim, Kyung-Rae;Kim, Yong-Hwa
    • Analytical Science and Technology
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    • v.13 no.4
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    • pp.484-493
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    • 2000
  • The simultaneous analysis of alkylphenols, chlorophenols and bisphenol A in biota samples was performed by gas chromatography-mass spectrometry-selected ion monitoring mode. The phenols were extracted from sample with organic solvent and Forisil and Silica columns for clean-up procedure were compared. Recovery studies were performed at 1-ppm level of phenols added to each biota sample. Their recoveries ranged between 83 and 116% with coefficient of variations of 2.4-11.9%. To improve the detection limits of phenols, trimethylsilyl (TMS) derivatization was applied. The gas chromatographic properties of free phenols and TMS derivatized phenols were also investigated.

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Formation Characteristics of Chlorobenzenes and Chlorophenols from TCE (TCE (trichloroethylene)으로부터 클로로벤젠과 클로로페놀의 생성특성)

  • 김은미;심영숙;이우근
    • Journal of Korean Society for Atmospheric Environment
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    • v.18 no.2
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    • pp.149-159
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    • 2002
  • The objective of this study was to evaluate the formation characteristics of CBs and CPs from TCE, aliphatic compound. The experiment was carried out in a fixed reactor during 30 min under the oxidation condition at the range of temperature, 300~$700^{\circ}C$. MSWI fly ash was used as catalyst in this study. Total amount of CBs formed greater magnitude than that of CPs overall range of reaction temperature. It is proposed that the formation of CPs was caused from hydroxylation of CBs. According to increasing temperature to $600^{\circ}C$, the yield of CBs and CPs increased but significantly decreased at $700^{\circ}C$. It is suggested that decomposition rate was faster than formation rate at the high temperature. In the homologue distribution of CBs, DCBs were major products at 30$0^{\circ}C$ and the amount of higher chlorinated compound increased to $600^{\circ}C$. Because they were formed by chlorination of lower chlorinated compounds. In case of CPs, the amount of DCPs was 90% of total amounts in both thermal formation and catalytic reaction. On the other hand it was clearly observed that the chlorination rate in catalytic reaction was higher than in thermal formation with TCE only.

Sensitive Determination of Alkylphenols, Chlorophenols, and Bisphenol A using GC/MS-SIM in Paper Materials (기체 크로마토그래피/질량분석기를 이용한 종이류 중 알킬페놀류, 클로로페놀류 및 비스페놀 A 정량)

  • Kim, Hyub;Kim, Jin-Ho
    • Environmental Analysis Health and Toxicology
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    • v.18 no.1
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    • pp.45-55
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    • 2003
  • The alkylphenols, chlorophenols and bisphenol A were determined by gas chromatography/mass spectrom-etry-selected ion monitoring (GC/MS-SIM) mode followed by two work-up methods for comparison; isoBOC derivatization method and TBDMS derivatization method. Eleven phenols in paper samples were extracted with acetonitrile. Also, solid -phase extraction (SPE) with XAD -4 and subsequent conversion to isobutoxycarbonyl derivatives or tert.-butyldimethylsilyl derivatives for sensitive analysis with the selected ion-monitoring (SIM) mode. The SIM responses were linear with the correlation coefficient varying 0.9717 ∼ 0.9995 (isoBOC derivatization), and 0.9842 ∼ 0.9980 (TBDMS derivatization). The recoveries were 82.4 ∼ 108.8%) by area ratio of phenanthrene -d$\_$10/ vs bisphenol A-d$\^$l6/. (isoBOC derivatization and TBDMS derivatization) The range of concentrations was respectively, 0.95 ∼ 1.44 ng/g in 2,4-dichlorophenol, 1.01 ∼ 1.17 ng/g in t-butylphenol,2.17 ∼ 5.84 ng/g in pentachlorophenol, 12.68 ∼ 14.88 ng/g in nonylphenol and 30.84 ∼ 153.72 ng/g in bisphenol A.

SENSITIVE DETERMINATION OF ELEVEN PHENOLIC ENDOCRINE-DISRUPTING CHEMICALS IN HUMAN URINE USING GAS CHROMATOGRAPHY/MASS SPECTROMETRY -SELECTED ION MONITORING

  • Kim, Hyub;Jang, Cheol-Hyeon
    • Environmental Engineering Research
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    • v.12 no.3
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    • pp.93-100
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    • 2007
  • I improved an analytical method for determining trace amounts of eleven phenolic endocrine-disrupting chemicals (11 phenolic EOCs) in human urine. The 11 phenolic EOCs were subjected to hydrolysis and then to solid phase extraction with a XAD-4 column. Alkylphenols, chlorophenols, and bisphenol A in XAD-4 column were eluted with acetonitrile, and the eluate was concentrated under a nitrogen stream, and then tert-butyldimethylsilylation. Separation and determination were done by gas chromatography, using mass spectrometry operating in the selective ion monitoring mode for quantitation. For tert-butyldimethylsily (TBDMS) derivatization the recoveries were $91.2{\sim}125.9%$, the limits of quantitation (LOQ) for the 11 phenolic EOCs in the nanogram-per-milliliter range ($0.025{\sim}1.000\;ng/mL$) were thus achieved by using 1 mL of urine, and the SIM responses were linear with the correlation coefficient varying by $0.9300{\sim}0.9943$. Based on the results for urine samples from unexposed individuals, 4-tert-octylphenol and pentachlorophenol were detected in hydrolysed urine sample. Other alkylphenols, chlorophenols and bisphenol A were not detected.

Combined Isobutoxycarbonylation and tert-Butyldimethylsilylation for the GC/MS-SIM Detection of Alkylphenols, Chlorophenols and Bisphenol A in Mackerel Samples

  • Kim, Hyub;Hong, Jong-Ki;Kim, Yong-Hwa;Kim, Kyoung-Rae
    • Archives of Pharmacal Research
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    • v.26 no.9
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    • pp.697-705
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    • 2003
  • The alkylphenols, chlorophenols, and bisphenol A were determined by gas chromatography/mass spectrometry-selected ion monitoring (GC/MS-SIM) followed by two work-up methods for comparison: isobutoxycarbonyl (isoBOC) derivatization and tert-butyldimethylsilyl (TBDMS) derivatization. Eleven endocrine disrupting chemicals (EDCs) of phenols in biological samples were extracted with acetonitrile and then the acetonitrile layer underwent freezing filtration 6$0^{\circ}C$ for 2 hours. Solid-phase extraction (SPE) was used with XAD-4 and subsequent conversion to isoBOC or TBDMS derivatives for sensitivity analysis with the GC/MS-SIM mode. For isoBOC derivatization and TBDMS derivatization the recoveries were 92.3∼150.6% and 93.8∼108.3%, the method detection limits (MDLs) of bisphenol A for SIM were 0.062 $\mu$ g/kg and 0.010 $\mu$ g/kg, and the SIM responses were linear with the correlation coefficient varying by 0.9755∼0.9981 and 0.9908∼0.9996, respectively. When these methods were applied to mackerel samples, the concentrations of the 11 phenol EDCs were below the MDL.

Application of Freezing Filtration Method to the Analysis of Alkylphenols, Chlorophenols and Bisphenol a in Korean Aquatic Biological Samples Using GC/MS-SIM (GC/MS-SIM을 이용한 우리나라 수중 생물시료 중 알킬페놀, 클로로페놀과 비스페놀 A의 분석을 위한 냉동필터법의 응용)

  • Kim, Hyub;Jang, Cheol-Hyeon
    • Journal of Korean Society of Environmental Engineers
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    • v.29 no.6
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    • pp.689-698
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    • 2007
  • A new technique was proposed for the determination of alkylphenols, chlorophenols and bisphenol A in korean aquatic biological samples. The alkylphenols, chlorophenols and bisphenol A in korean aquatic biological samples were extracted with acetonitrile and then acetonitrile layer was refrigerated at $-60^{\circ}C$ for 2 hours(freezing filtration method). Also, solid-phase extraction(SPE) was used to XAD-4 and subsequent conversion to isobutoxycarbonyl(isoBOC) or tert-butyldimethylsilyl(TBDMS) derivatives for sensitive analysis with gas chromatography/mass spectrometry-selected ion monitoring(GC/MS-SIM) mode. For isoBOC derivatization and TBDMS derivatization the recoveries were $70.1\sim150.6%$ and $93.8\sim108.3%$, the method detection limit(MDLs) of bisphenol A for SIM were $0.062{\mu}g/kg$ and $0.010{\mu}g/kg$, and the SIM respectively. When these methods were applied to korean aquatic biological samples, the concentrations of the 11 phenolic EDCs were $0.675\sim1.970{\mu}g/kg$.