• Title/Summary/Keyword: PCDF

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The Role of (Chloro-) Phenols in the Formation of Polychlorinated Dibenzofurans in Municipal Waste Incinerators

  • Ryu, Jae-Yong;Jang, Seong-Ho
    • Journal of Environmental Science International
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    • v.16 no.1
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    • pp.9-19
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    • 2007
  • Comparing predicted PCDF isomer patterns with those obtained from a municipal waste incinerator assessed the role of two-phenol condensation pathways in the formation of PCDFs. Complete PCDF homologue and isomer distributions were obtained from a Fluidized Bed Incinerator (FBI). Two-phenol condensation model, dependent only on the distributions of phenols, was developed to predict the PCDF congeners produced from phenol precursors. R-squared values from linear correlations are presented for the dichlorinated through hexa-chlorinated isomer distributions between measured and predicted. They range from 0.00: to 0.1 far the di-chlorinated through hexa-chlorinated isomer sets. Agreement between predicted and measured PCDF isomer distributions was very poor for all homologues. Two-phenol condensation pathways are not likely to be the pre-dominant pathways in the formation of PCDF in a FBI. However, dibenzofuran (DF) is likely to be produced from a condensation of two phenols. This work demonstrates the use of PCDF homologue and isomer patterns for testing PCDF formation mechanism from two-phenol condensation pathways in municipal waste incinerators.

Prediction of Polychlorinated-dibenzofurans (PCDFs) Formation in Municipal Waste Incinerator (도시소각로에서 Polychlorinated-dibenzofurans (PCDFs)의 생성 예측)

  • Ryu, Jae-Yong;Suh, Jeong-Min
    • Journal of Korean Society for Atmospheric Environment
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    • v.22 no.6
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    • pp.842-850
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    • 2006
  • The role of chlorination reactions in the formation of polychlorinated dibenzofurans (PCDFs) in a municipal waste incinerator was assessed using a chlorination model for predicting PCDF isomer distributions. Complete distributions of PCDF congeners were obtained from a stoker-type municipal waste incinerator operated under 13 test conditions. Samples were collected from the flue gas prior to the gas cleaning system. While total PCDF yields varied by a factor of five to six, the distributions of congeners were similar. A chlorination model, dependent only on the observed distribution of monochlorinated isomers, was developed to predict the distributions of poly-chlorinated isomers formed by chlorination of dibenzofuran (DF). Agreement between predicted and measured PCDF isomer distributions was high for all homologues, supporting the hypothesis that DF chlorination can play an important role in the formation of PCDF byproducts.

POLYCHLORINATED NAPHTHALENE (PCN) AND DIBENZOFURAN (PCDF) CONGENER PATTERNS FROM PHENOL PRECURSORS IN THERMAL PROCESS: [I] A PRIORI HYPOTHESIS OF PCN AND PCDF FORMATION PATHWAYS FROM MONOCHLOROPHENOLS

  • Ryu, Jae-Yong;Kim, Do-Hyong;Choi, Kum-Chan;Suh, Jeong-Min
    • Environmental Engineering Research
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    • v.11 no.4
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    • pp.217-231
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    • 2006
  • The gas-phase formation of polychlorinated naphthalenes (PCNs) and dibenzofurans (PCDFs) was experimentally investigated by slow combustion of the three chlorophenols (CPs): 2-chlorophenol (2-CP), 3-chlorophenol (3-CP) and 4-chlorophenol (4-CP), in a laminar flow reactor over the range of 550 to $750^{\circ}C$ under oxidative condition. Contrary to the a priori hypothesis, different distributions of PCN isomers were produced from each CP. To explain the distributions of polychlorinated dibenzofuran (PCDF) and PCN congeners, a pathway is proposed that builds on published mechanisms of PCDF formation from chlorinated phenols and naphthalene formation from dihydrofulvalene. This pathway involves phenoxy radical coupling at unsubstituted ortho-carbon sites followed by CO elimination to produce dichloro-9, 10-dihydrofulvalene intermediates. Naphthalene products are formed by loss of H and/or Cl atoms and rearrangement. The degree of chlorination of naphthalene and dibenzofuran products decreased as temperature increased, and, on average, the naphthalene congeners were less chlorinated than the dibenzofuran congeners. PCDF isomers were found to be weakly dependent to temperature, suggesting that phenoxy radical coupling is a low activation energy process. Different PCN isomers, on the other hand, are formed by alternative fusion routes from the same phenoxy radical coupling intermediate. PCN isomer distributions were found to be more temperature sensitive, with selectivity to particular isomers decreasing with increasing temperature.

The Levels of PCDFs and PCDDs in the four kinds of Fish in Korea (우리 나라에서 많이 소비되고 있는 몇가지 생선류 중의 PCDFs와 PCDDs 함유도 조사)

  • Kim, Yunje;Lee, SunYoung;Lee, Hyomin;Yoon, Eunkyung;Yang, KyuHwan;Kim, EunKyung;Kim, Myungsoo
    • Analytical Science and Technology
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    • v.15 no.2
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    • pp.142-148
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    • 2002
  • They were analyzed that the levels of PCDDs/PCDFs in mackerel, walleye pollack, croaken and cuttlefish, which were mainly consumed in Korea, by high resolution gas chromatography/high resolution mass spectrometr (HRGC/HRMS). The samples measured in this study had been bought 3 sets of each fish from different 5 cities, Seoul, Chunchon, Daejon, Kwangju and Pusan. The TEQ level of PCDDs in mackerel (0.032 pgTEQ/g) was the highest. The TEQ level of PCDFs in walleye pollack (0.010 pgTEQ/g) was the lowest. The level of PCDDs was higher than PCDFs in fish.

POLYCHLORINATED NAPHTHALENE (PCN) AND DIBENZOFURAN (PCDF) CONGENER PATTERNS FROM PHENOL PRECURSORS IN THERMAL PROCESS: [II] EXPERIMENTAL RESULTS FROM DICHLOROPHENOLS (DCPs)

  • Ryu, Jae-Yong;Kim, Do-Hyong;Choi, Kum-Chan;Suh, Jeong-Min
    • Environmental Engineering Research
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    • v.11 no.4
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    • pp.232-240
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    • 2006
  • Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at $600^{\circ}C$ were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same interemediate. Tautomerization of the intermediate and $H_2O$ elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.

Analysis of 2,3,7,8-substituted PCDDs, PCDFs, and DL-PCBs in muscle of crucian carp (Carassius auratus and Carassius cuvieri) from major rivers and lakes (주요 하천 및 호수에 서식하는 붕어 (Carassius auratus and Carassius cuvieri) 근육에 축적된 2,3,7,8-치환 PCDDs, PCDFs 및 DL-PCBs 분석)

  • Jeong, Gi-Ho;Moon, Ji-Yong;Moon, Dong-Ho
    • Analytical Science and Technology
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    • v.24 no.6
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    • pp.484-492
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    • 2011
  • Bioaccumulation status and distribution characteristics of PCDDs, PCDFs and DL-PCBs in cruian carp collected from the four representative sites of major river systems in Korea were investigated. The recovery rates of PCDDs and PCDFs ranged from 50.6% to 88.3%, and those of DL-PCBs ranged from 52.3% to 93.2%. The mean, median and concentration range of ${\sum}$dioxins, which represents the total concentratons of PCDDs, PCDFs and DL-PCBs accumulated in the muscle of crucian carp, were 0.39, 0.14 and 0.047-1.0 pg TEQ/g wet wt., respectively. DL-PCBs were detected above the detection limit from all the samples, whereas PCDDs and PCDFs were detected from limited crucian samples. The relative contribution of DL-PCBs to ${\sum}$dioxins was remarkably larger than those for PCDDs and PCDFs. The percent contribution was 83.6% for DL-PCBs, and followed by 12.7% and 3.7% for PCDFs and PCDDs, respectively.

A Study of Polychlorinated dibenzo-p-dioxins(PCDDs) and Polychlorinated dibenzofurans(PCDFs) Formation from Phenols in Thermal Process[I] (열공정에서 페놀류로부터 Polychlorinated dibenzo-p-dioxins(PCDDs)과 Polychlorinated dibenzofurans(PCDFs)의 생성에 관한 연구[I])

  • Ryu, Jae-Yong;Suh, Jeong-Min;Park, Jeong-Ho
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.5
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    • pp.511-521
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    • 2006
  • Homologue and isomer patterns of polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans(PCDFs) congeners formed from phenols in the gas-phase at $600{\sim}700^{\circ}C$ and via particle-mediated reactions at $400^{\circ}C$ were studied in an isothermal flow reactor. A mixture of 20 phenols in relative concentrations found in a municipal waste incinerator(MWI) stack gas was used for this study. PCDDs and PCDFs homologue and isomer patterns obtained from the phenol. From the phenol experiments, gas-phase formation at $600{\sim}700^{\circ}C$ favors PCDFs formation whereas particle-mediated formation at $400^{\circ}C$ favors PCDDs formation. DD and DF were most abundant homologue groups, PCDDs and PCDFs homologue fraction decreased with increasing number of chlorine substituents. PCDDs and PCDFs homologue and isomer fractions were almost constant from gas-phase formation and particle-mediated formation. Unsubstituted phenol, which was present in high concentration, played a significant role in the formation of PCDD/Fs congeners under both sets of experimental conditions.

The Concentrations and TEQ Levels of PCDFs and PCDDs in Human Adipose Tissue and First Breast Milk of Korean (체지방 조직 및 초유중에 잔류되어 있는 다이옥신 함유도에 관한 연구)

  • Kim, Yunje;Lee, Sun Young;Han, Soon Young;Park, Kui Lea;Kil, Kwang Sup;Yang, Kyu Hwan;Kim, Eun Kyung;Kim, Myungsoo
    • Analytical Science and Technology
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    • v.14 no.6
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    • pp.504-509
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    • 2001
  • The concentrations and TEQ levels of PCDFs/PCDDs in human aipose tissue and first breast milk were analyzed by high resolution gas chromatography/high resolution mass spectrometry. The human adipose tissue samples measured in this study have been collected at hospital in Seoul. The total concentration and TEQ level of PCDFs were showed 5.812 pg/g and 1.485 pgTEQ/g. The total concentration and TEQ level of PCDDs were showed 26.648 pg/g and 1.176 pgTEQ/g, respectively. This paper also reported dioxin levels in 20 breast milks of Korean mothers from hospital in Seoul National University. Total concentration and TEQ levels of PCDFs were showed 7.019 pg/mL and 0.177 pgTEQ/mL, respectively. Total concentrations and TEQ levels of PCDDs were showed 14.224 pg/mL and 0.693 pgTEQ/mL, respectively. According to the contribution of dioxin congeners in samples, PCDDs was higher than PCDFs. And OCDD had the highest concentration.

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Dioxin Distributions from Combustion: Incinerator Data, Thermodynamic Data, and Kinetic Hypotheses

  • James A. Mulholland;Ryu, Jae-Yong
    • Proceedings of the Korea Air Pollution Research Association Conference
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    • 1999.10a
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    • pp.225-228
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    • 1999
  • The formation of dioxin (term used here to refer to both polychlorinated dibenzo-p-dioxins, PCDDS, and dibenzofurans, PCBFs) in combustion processes is of concern because of the extreme toxicities of some of these compounds and because of their resistance to degradation in the environment. The number and location of chlorine substituents differentiate dioxin homologues and isomers, respectively. There are a total of 75 PCDD congeners and 135 PCDF congeners.(omitted)

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