• Journal of Korean Society on Water Environment
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• v.21 no.6
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• pp.549-563
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• 2005

The study was carried out to develop and standardize the analytical method of 1,4-dioxane in water. The National Institute of Environmental Research in Korea has monitored for 1,4-dioxane in water since 1998 and it has been detected in environmental water occasionally. But the environmental pollution and analytical method in water is not well known over the world. The trace analytical method at low-${\mu}/L$ level is prerequisite in order to evaluate the residue of 1,4-dioxane in water. Evaluation of the method was demonstrated by comparing and analyzing with liquid-liquid extraction, solid-phase extraction and purge & trap technique. As a result of experiment by standard solutions and raw samples, the precision and accuracy for three methods were obtained within error rate of about 10%. Therefore, three methods were standardized as official monitoring method in Korea. Also, a convenient and simple liquid-liquid extraction method for the analysis of 1,4-dioxane in water was developed by combined with gas chromatography/mass spectrometry and applied to the water samples in Korea

• Journal of the Korean Wood Science and Technology
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• v.12 no.4
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• pp.19-30
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• 1984

This experiment was carried out to investigate the effects of autohydrolysis and extraction conditions on the separation of the chemical substances, the extractability of lignin by dioxane, and the yield of reducing sugars from cellulosic substrates by using a commercial cellulase derived from Trichoderma viride. Air-dried wood meals through 0.42mm (40 mesh) screen and retained on 0.25 mm (60 mesh) of Populus alba-glandulosa and Pinus koraiensis were autohydrolyzed with water at $180^{\circ}C$ for 30 and/or 60 minutes in a 6 liter stainless-steel digester with or without 2% 2-naphthol. The hydrothermally-treated wood meals were extracted the lignin with 100%, 90%, 75% and 50% dioxane solutions at $70^{\circ}C$ for 4 hours, respectively. The results obtained were as follows; 1) After autohydrolysis of Populus alba-glandulosa, the yield of wood meals decreased with lengthening the auto hydrolysis time from 30 minutes to 60 minutes and with 2% 2-naphthol addition. In case of Pinus koraiensis, the yield was not affected by 2%, 2-naphthol addition at the autohydrolysis in the digester. 2) After autohydrolysis and lignin extraction of Populus alba-glandulosa, the yield of wood meals decreased with lengthening the autohydrolysis time from 30 minutes to 60 minutes and with 2% 2-naphthol addition. Extraction of 50% dioxane solution was the best solvent for the yield among the solutions of 100%, 90%. 75% and 50% dioxane. In case of Pinus koraiensis, the yield was not affected by 2% 2-naphthol addition and the solution of 90% dioxane was the poorest solvent for the yield. 3) After autohydrolysis and lignin extraction of Populus alba-glandulosa, the Klason lignin content in cellulosic substrates for enzymatic hydrolysis decreased with lengthening the autohydrolysis time from 30 minutes to 60 minutes and with 2% 2-naphthol addition. Klason lignin content was the lowest after extraction by 90% or 75% dioxane solution. The content was also affected by interaction of the three factors-autohydrolysis time, 2% 2-naphthol addition and concentration of dioxane. In case of Pinus koraiensis, the Klason lignin content increased with 2% 2-naphthol addition but was not affected by the concentration of dioxane solution. 4) After autohydrolysis and lignin extraction of Populus alba-glandulosa, the extractable Klason lignin content by extraction increased with lengthening the auto hydrolysis time from 30 minutes to 60 minutes and with 2% 2-naphthol addition. The extractable lignin content was the highest after extraction by 90% or 75% dioxane solution. In case of Pinus koraiensis, the extractable lignin content increased with 2% 2-naphthol addition. Extractions by 100%, 90% and 50% dioxane solutions were more effective for the extraction of Klason lignin than by 75% dioxane solution. 5) After autohydrolysis and lignin extraction of Populus alba-glandulosa, the yield of reducing sugars increased with lengthening the autohydrolysis time from 30 minutes to 60 minutes but was not affected by 2% 2-naphthol addition and the concentration of dioxane. The yield of reducing sugars after enzymatic hydrolysis was slightly higher by extractions with 90%, 75% and 50% dioxane solutions than with 100% dioxane. In case of Pinus koraiensis, the yield of reducing sugars was not affected by 2% 2-naphthol addition but affected by the concentration of dioxane. The yield of reducing sugars was the highest in cellulosic substrates extracted by 100% dioxane solution.

• Environmental Analysis Health and Toxicology
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• v.18 no.3
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• pp.219-224
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• 2003

1,4-Dioxane is used as a solvent for lacquers, paints, varnish removers, dye baths and printing compositions. And it is also used for detergent preparations, cosmetics, deodorants and fumigants. A method is described for the determination of 1,4-dioxane in water samples by GC/MS. The extraction recoveries were studied for some solvents and solvent volume ratio were investigated using r-butyl methyl ether (MTBE). Optimum condition was obtained by the liquid-liquid extraction using the 10 mL of MTBE for 10 mL of water. Method detection limit of 1,4-dioxane in the 20 mL of water samples was 0.05 ng/mL. It could be determined in the range of 0.24∼240 ng/mL in treated water, and in the range of 0.69∼81.9 ng/mL in raw water, respectively. Risk assessments with 1,4-dioxane exposure by drinking water ingestion were carried out. Based on the results of analysis, chronic daily intake of 1,4-dioxane was 2.22${\times}$10$\^$-4/ mg/kg/day and excess cancer risk was calcu-lated to be 2.44${\times}$10$\^$-6/.

• Analytical Science and Technology
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• v.18 no.2
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• pp.154-162
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• 2005

Recently, 1,4-Dioxane is known as the contaminant in water plants in Korea. Owing to its toxicity and potential health effect, 1,4-Dioxane must be determined at very low levels in drinking water. Studies on the removal of 1,4-Dioxane in drinking water were performed by using multi filtration system with activated carbons and membrane filter. For extraction of 1,4-Dioxane, methyl-t-butyl ether (MTBE) was used and then analyzed using gas chromatography-mass selective detection (GC/MSD). Removal experiment was proceeded for 300 L with a sample volume of 30 L. At first. The removal was 70%, 95% and 100% after using activated carbon, membrane and second activated carbon respectively. At larger accumulated water fluxes, the removal rate decreased at each filter. After the flow volume was 300 L, the removal rate was 30%, 88% and 99% through the first activated carbon, membrane and second activated carbon respectively.

• Analytical Science and Technology
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• v.27 no.1
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• pp.22-26
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• 2014

1,4-Dioxane was classified as a Group 2B carcinogen by the International Agency for Research on Cancer. The compound was measured in surface water with a headspace gas chromatographic mass spectrometric detection. A 5 mL water sample was placed in a 10 mL headspace vial and saturated with NaCl, and the solution was spiked with 1,4-dioxane-d8 as an internal standard and sealed with a cap. Water samples were collected from twenty-two basins of Gum-River on June and September 2012, respectively. As a result, 1,4-dioxane was detected in the concentration range of $0.49-43.0{\mu}g/L$ (mean $2.0{\mu}g/L$) in the frequency of about 30% in surface water samples.

• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.42 no.4
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• pp.64-70
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• 2010

In this study, hemicelluloses were pre-extracted from mixed hardwood chips using sodium hydroxide solution and then they were isolated from pre-extractives by using various solvents. Isolation was conducted by precipitating hemicelluloses with isopropanol, ethanol, 1,4-dioxane, dimethylsulfoxide (DMSO) and potassium hydroxide (KOH), respectively. The precipitate yield on alkali pre-extractives was the highest when hemicelluloses were isolated by DMSO and then precipitated with ethanol. Most precipitates were yellow colored. The efficiency of isolation was evaluated by analysing the characteristics of isolated hemicelluloses. Isolation using DMSO, KOH and 1,4-dioxane ($80^{\circ}C$) showed rather high efficiency. The highest total separation efficiency was about 77% when alkali pre-extractives were reacted with KOH and precipitated with ethanol. The quantity and purity of isolated hemicelluloses were affected by the solvent type.

• Analytical Science and Technology
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• v.8 no.4
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• pp.511-517
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• 1995

A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

• Analytical Science and Technology
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• v.25 no.4
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• pp.236-241
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• 2012

There are many industrial factories in the central Nakdong river basin and have been occurred water pollution accidents by hazardous chemicals such as phenol, 1,4-dioxane and perchlorate. In this study, ten compounds of semi-volatile organic compounds (SVOCs) (dichlorvos, toluene-2,4-diisocyanate, 4,4'-methylenedianiline, 4,4'-methylenebis (2-chloroaniline), diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthaltate, bis (2-ethylhexyl) adipate, benzophenone, 4,4'-bisphenol A) of hazardous chemicals which may be potentially discharged into the Nakdong river, were determined by gas chromatography-mass spectrometry (GC-MS) with disk-type solid-phase extraction. Accuracy and precision were in the range of 75.6~110.5%, and 4.6~12.7%, respectively and recovery was in the range of 72.4~127.9%. Three compounds (bis (2-ethylhexyl)adipate, benzophenone, 4,4'-bisphenol A) were detected in industrial wastewater such as wastewater treatment plants (WWTPs) and wastewater discharge facilities in the Nakdong River basin.

• Journal of the Korean Society of Food Science and Nutrition
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• v.32 no.7
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• pp.965-970
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• 2003

This study has been performed to develope a method for the simultaneous determination of 1,4-dioxane (DOX), epichlorohydrin (EPC), propylene chlorohydrin (PCH), ethylene chlorohydrin (ECH) and 1,3-dichloro-2-pro-panol (DCP) in polysorbates, chloline chloride, choline bitartrate, modified starch and spices by purge and trapgas chromatography. Experimental design was used to select a suitable trap by measuring the limit of detection (LOD) and to investigate the effect of temperature and salt of extraction, and the percentage of recovery in various matrix. The LOD of DOX, EPC, PCH, ECH and DCP were 1.38$\mu\textrm{g}$, 0.23$\mu\textrm{g}$, 3.30$\mu\textrm{g}$, 3.97$\mu\textrm{g}$, 20.43$\mu\textrm{g}$ respectively, by means of using Vorcarb 3000 trap with 5$0^{\circ}C$ sample sparger. Excluding EPC, the recoveries of target compounds were above 90% in all matrix. Target compounds in polysorbates (17), choline chloride (5), choline bitartrate (5), modified starch (8) and spices (25) were not detected. But 2.5 ppm of DOX was detected in Tween 80.

• Journal of Korea Foresty Energy
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• v.17 no.1
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• pp.56-70
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• 1998

This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.