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  1. NTU Theses and Dissertations Repository
  2. 公共衛生學院
  3. 環境衛生研究所
請用此 Handle URI 來引用此文件: http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48368
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dc.contributor.advisor蔡詩偉
dc.contributor.authorYen-Hui Liuen
dc.contributor.author劉彥輝zh_TW
dc.date.accessioned2021-06-15T06:54:09Z-
dc.date.available2016-10-03
dc.date.copyright2011-10-03
dc.date.issued2011
dc.date.submitted2011-02-11
dc.identifier.citationReferences
A Bernard, S Carbonnelle, et al. (2003). 'Lung hyperpermeability and asthma prevalence in schoolchildren: unexpected associations with the attendance at indoor chlorinated swimming pools.' Occup. Environ. Med. 60;385-394.
A. Khaled and J. Pawliszyn (2000). 'Time-weighted average sampling of volatile and semi-volatile airborne organic compounds by the solid-phase microextraction device.' J. Chromatogr. A. 892(1-2): 455-467.
Alfred Bernard, Sylviane Carbonnelle, et al. (2006). 'Chlorinated Pool Attendance, Atopy, and the Risk of Asthma during Childhood.' Environ. Health. Persp. 14.
Barbee, S. J., Thackara, J.W. and Rinehart, W.E., (1983). 'Acute inhalation toxicology of nitrogen trichloride.' Am. Ind. Hyg. Assoc. J. 44(2): 145-146.
Basden, K. (2006). 'Swimming pool and spa pool atmospheres.' Clean Air and Environmental Quality Volume 40 No.2. May 2006.
C.J.O. Childress, William T. Foreman, et al. (1999). 'New Reporting Procedures Based on Long-Term Method Detection Levels and Some Considerations for Interpretations of Water-Quality Data Provided by the U.S. .' Geological Survey National Water Quality Laboratory Virginia: Reston.
Christianzwiener, Susand. Richardson, et al. (2007). 'Drowning in Disinfection Byproducts? Assessing Swimming Pool Water.' Environ. Sci. Technol. VOL. 41, NO. 2,.
Clifford White, G. (1972). 'Handbook of chlorination.' Van Nostrand Reinhold.
Daubert, T. E., R.P. Danner (1989). 'Physical and Thermodynamic properties of Pure Chemicals Data Compilation.' Washington, D.C. Taylor and Francis.
EPA method 4500-Cl F (1999). 'Standard methods for the examination of water and waste water 20th edition.'.
Frank E. Scully, Jr. John P. Yang, et al. (1984). 'Derivatization of organic and inorganic N-chloramines for high-performance liquid chromatography analysis of chlorinated water.' Environ. Sci. Technol. 18(10): 787-792.
Gagnaire, F., Azim, S., Bonnet, P., Hecht, G. and Hery, M., (1994). 'Comparison of the sensory irritation response in mice to chlorine and nitrogen trichloride. .' J. Appl. Toxicol. 14(6): 405-409.
Ge, H., G. G. Wallace, et al. (1990). 'Determination of trace amounts of chloramines by liquid chromatographic separation and amperometric detection.' Analytica. Chimica. Acta. 237: 149-153.
H.C. Brown and N. R. D. Lue (1988). 'Organoboranes for synthesis. 12. The reaction of organoboranes with nitrogen trichloride. A convenient procedure for the conversion of alkenes into alkyl chlorides via hydroboration.' Tetrahydron 44, No. 10: 2785-2792.
Heather Lord and J. Pawliszyn (2000). 'Evolution of solid-phase microextraction technology.' J. Chromatogr. A. 885(2000): 153–193.
Hery, M., J. M. Gerber, et al. (1998). 'Exposure to chloraminies in a green salad processing plant.' Ann. Occup. Hyg. 42(7): 437-451.
Hery, M., G. Hecht, et al. (1995). 'Exposure to chloramines in the atmosphere of indoor swimming pools.' Ann. Occup. Hyg. 39: 427-439.
Holzwarth, G., Balmer, R. G. and Sony, L (1984). 'The fate of chlorine and chloramines in cooling towers Henry's law constants for flashoff. .' Water. Res. 18: 1421-1427.
Hui Tao, Zhong-Lin Chen, et al. (2008). 'Salicylate-spectrophotometric determination of inorganic monochloramine ' Anal. Chim. Acta. 615: 184-190.
J. Pawliszyn (1997). 'Solid-Phase Microextraction - Theory and practice. .' New York: Wiley-VCH.
J.A. Koziel and J. Pawliszyn (2001). 'Air sampling and analysis of volatile organic compounds with solid phase microextraction.' J. Air. Waste. Manage. 51(2): 173-184.
Li, J. and E. R. Blatchley (2007). 'Volatile disinfection byproduct formation resulting from chlorination of organic-nitrogen precursors in swimming Pools.' Environ. Sci. Technol. 41: 6732-6739.
N Massin, G Hecht, et al. (2007). 'Respiratory symptoms and bronchial responsiveness in lifeguards exposed to nitrogen trichloride in indoor swimming pools.' Occup. Environ. Med. 2007;64:75–81.
OSHA chemical sampling information (2007). 'Chemical sampling information : Nitrogen Trichloride.'
P.A. Martos and J. Pawliszyn (1999). 'Time-weighted average sampling with solid-phase microextraction device: Implications for enhanced personal exposure monitoring to airborne pollutants. .' Anal, Chem. 71(8): 1513-1520.
R. Batlle, A. Colmsjo, et al. (2001). 'Development of a personal isocyanate sampler based on DBA derivatization on solid-phase microextraction fibers. .' Fresenius Journal of Analytical Chemistry, 371(4): 514-518.
Shang, C. and E. R. B. III (1999). 'Differentiation and Quantification of Free Chlorine and Inorganic Chloramines in Aqueous Solution by MIMS.' Environ. Sci. Technol. 1999, 33, 2218-2223.
United States Environmental Protection Agency (1997).
United States National Library of Medicine 'Toxicology Data Network'
Zenilda de Lourdes Cardeal, Eliana Moreira Guimaraes, et al. (2005). 'Analysis of volatile compounds in some typical Brazilian fruits and juices by SPME-GC method.' 22(6): 508-513.
dc.identifier.urihttp://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48368-
dc.description.abstract三氯氨有可能來自氯與有機氮的反應,例如在游泳池中,游泳者會貢獻不同種類的有機氮,包括:汗水、尿液、或皮膚微粒,並可能進一步與氯反應而成為三氯氨;而過去的研究發現暴露於三氯氨可能會造成孩童或者成人的急性以及慢性健康效應。為了監測空氣中三氯氨濃度,現有的方法使用採樣幫浦;然而需要複雜的樣本前處理與分析流程。另一方面,固相微萃取技術則結合採樣、前濃縮、與直接注入樣本進入基本氣相萃取系統等特性,展現許多優於傳統方法之優點。因此,本研究的目的為開發空氣中三氯氨的固相微萃取被動式採樣方法。
本研究首先以氯化氨(或硫化氨)與次氯酸鈉在酸性緩衝液中反應形成三氯氨之溶液,進而將三氯氨溶液注入空氣採樣袋並將之汽化,以獲得已知濃度之氣狀三氯氨。為了評估擴散式固相微萃取採樣器,本研究經測試不同固相微萃取纖維後發現,Carboxen/DVB最適合本研究之所需。
本研究將環己烯先吸附至所選用的纖維上後,接著將纖維插入空氣採樣袋以進行三氯氨之暴露測試;而所生成之衍生物(一氯環己烷)則使用氣相層析/質譜儀分析。本研究所測試的衍生物於0.01ng至1ng之間具有良好線性,而方法偵測極限為0.003ng。
本研究使用氣袋進行靜態暴露測試,而所得之實驗採樣率為1.75×10-7±5.7×10-8 cm3/se。然而,未來應持續驗證,以確認採集效果是否具有重覆性;此外,亦應探討各種環境因素的可能影響。
zh_TW
dc.description.abstractTrichloramine might possibly be formed when organic nitrogen sources, such as creatinine, arginine, histidine, or urea, react with chlorine. In swimming pools, visitors can contribute various kinds of organic nitrogen, such as sweat, urine, or skin particles, which would further react with chlorine to form trichloramine. Trichloramine has been observed that the exposures might cause acute and chronic health effects in both children and adults. To monitor the concentrations of trichloramine in air, current available method employed sampling pump and required complicated sample preparation and analysis procedures which makes it uneasy to assess the exposures. On the other hand, solid phase microextraciton (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC) system. Therefore, the purpose of this study was to develop a convenient sampling method, i.e., diffusive sampling, for trichloramine by SPME.
Trichloramine in solution was first prepared by mixing ammonium sulphate or ammonium chloride with sodium hypochlorite in acidic phosphate buffer. Known concentrations of gaseous trichloramine were then generated in Tedlar air bags through the injections of trichloramine solutions followed by vaporizations.
To quantify the derivative, a range of derivative between 0.01ng to 1ng defined in this research showed good linearity with method detection limit 0.003ng.
For the validations of the SPME diffusive sampler, Carboxen/DVB fiber was chosen, and cyclohexene was first loaded onto the fiber. After the exposure of trichloramine, the derivative formed o-fiber, i.e., chlorocyclohexane, was quantified by GC/MS.
By using the airbags as the static exposure system, the sampling rate of the SPME diffusive sampler for trichloramine was estimated to be 1.75×10-7±5.7×10-8 cm3/sec.
However, further experiments are still needed to confirm the repeatability of the findings, and also to validate the effects of environmental factors on the performance of the sampler.
en
dc.description.provenanceMade available in DSpace on 2021-06-15T06:54:09Z (GMT). No. of bitstreams: 1
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Previous issue date: 2011
en
dc.description.tableofcontents致謝 II
中文摘要 IV
ABSTRACT V
TABLE OF CONTENTS VII
LIST OF FIGURES X
LIST OF TABLES XII
CHAPTER1: INTRODUCTION 1
MECHANISM OF TRICHLORAMINE FORMATION 2
PHYSICAL/CHEMICAL PROPERTIES 4
TOXICITY OF TRICHLORAMINE 5
HUMAN EPIDEMIOLOGY STUDY 5
SAMPLING AND ANALYSIS METHODS FOR TRICHLORAMINE 8
PURPOSE 9
CHAPTER 2: MATERIALS AND METHODS 10
RESEARCH FLOW CHART 10
INSTRUMENTS AND REAGENTS 11
TRICHLORAMINE SYNTHESIS 12
STANDARD METHOD DPD FERROUS TITRIMETRIC METHOD (DPD/FAS) 12
TRICHLORAMINE GAS STATIC EXPOSURE SYSTEM 14
SOLID PHASE MICROEXTRACTION, SPME 14
ON-FIBER DERIVATIZATION 15
DERIVATIZING AGENT STOCK SOLUTION 16
LOADING DERIVATIZING AGENT 16
SPME FIBERS 17
SPME DIFFUSIVE SAMPLER 17
GAS CHROMATOGRAPHY/MASS SPECTROMETRY 18
LINEAR RANGE AND PRECISION 19
METHOD DETECTION LIMIT (MDL) 19
CHAPTER3: RESULT AND DISCUSSION 21
TRICHLORAMINE SYNTHESIS 21
I. CL/N MOLAR RATIO 21
II. TRICHLORAMINE SYNTHESIS 22
STABILITY OF TRICHLORAMINE SOLUTION 23
PREPARATION OF DERIVATIZING AGENT 24
I. DERIVATIZING AGENT CALIBRATION CURVE 24
II. ADSORBING DERIVATIZING AGENTS 24
FIBER SELECTION 25
DESORPTION EFFICIENCY 26
LINEARITY OF THE DERIVATIVE 26
DETECTION LIMIT 26
STORAGE OF DERIVATIVE 27
ON-FIBER DERIVATIZATION 27
I. IDENTIFICATION OF DERIVATIZATION REACTION 27
II. DERIVATIZATION REACTION IN STATIC EXPOSURE SYSTEM 28
VALIDATION OF SAMPLING RATE 30
COMPARISON WITH PAST RESEARCH 30
LIMITATIONS OF THIS RESEARCH 31
CHAPTER4: CONCLUSION 35
REFERENCES 37
TABLE 1 DPD/FAS TITRATION 52
TABLE 2 FIBER CHARACTER(J. PAWLISZYN 1997) 53
TABLE 3 TRICHLORAMINE SYNTHESIS UNDER DIFFERENT CL/N RATIO 54
TABLE 4 TRICHLORAMINE SYNTHESIS BY MIXING SODIUM HYPOCHLORITE WITH AMMONIUM SULPHATE 55
TABLE 6 TRICHLORAMINE SOLUTION STABILITY 57
TABLE 7 100MG/L AND 200MG/L CYCLOHEXENE STABILITY 58
TABLE 8 50MG/L CYCLOHEXENE STABILITY 58
TABLE 9 FIBER SELECTION 58
TABLE 10 THERMO DESORPTION EFFICIENCY 59
TABLE 12 COMPARISON WITH PAST STUDIES 60


List of Figures
FIGURE 1 THE MECHANISM TO FORM TRICHLORAMINE BY CHLORINATION OF CREATININE AND UREA,(LI AND BLATCHLEY 2007) 39
FIGURE 2 RELATIONSHIP BETWEEN SWIMMING FREQUENCY AND SP-A(SURFACTANT PROTEIN A), SP-B(SURFACTANT PROTEIN B)(A BERNARD, S CARBONNELLE ET AL. 2003) 40
FIGURE 3 THE RELATIONSHIP BETWEEN CPA AND ENO IN HIGH IGE AND LOW IGE CONCENTRATION CHILDREN GROUP. (CPA: CUMULATED POOL ATTENDANCE; ENO: EXHALED NO) 41
FIGURE 4 SOLID PHASE MICROEXTRACTION(SPME) STRUCTURE (HEATHER LORD AND PAWLISZYN 2000) 42
FIGURE 5 SPME ON-FIBER DERIVATIZATION(HEATHER LORD AND PAWLISZYN 2000) 43
FIGURE 6 TO LOAD DERIVATIZING AGENT ONTO THE SPME FIBER, THERE ARE THREE APPROACHES, WHICH ARE A) DIRECT EXTRACTION, B) HEADSPACE EXTRACTION, AND C) MEMBRANE-PROTECTED METHOD. (HEATHER LORD AND PAWLISZYN 2000) 44
FIGURE 7 PTFE TUBE PROTECTED TWA SPME PASSIVE SAMPLER. 45
FIGURE 8 DERIVATIZING AGENT (CYCLOHEXENE) LINEARITY 46
FIGURE 9 DERIVATIVE CHLOROCYCLOHEXANE LINEAR RANGE 46
FIGURE 10 THE RESULT OF 8 HOURS DERIVATIZATION. THE SPECTRUM IN THE LEFT IS SPME WITH DERIVATIZING AGENTS, AND THE RIGHT SPECTRUM IS THE BLANK SPME WITHOUT DERIVATIZING AGENT. 47
FIGURE 11 DERIVATIZATION IN THE AIRBAG FOR 4 HOURS 48
FIGURE 12 DERIVATIZATION IN THE AIRBAG FOR 9 HOURS 48
FIGURE 13 MASS COLLECTED VERSUS EXPOSURE OF TRICHLORAMINE GAS AFTER 11.5 HOURS 49
FIGURE 14 DYNAMIC SYSTEM WITH TRICHLORMAINE SYNTHESIS (HERY, GERBER ET AL. 1998) 50
FIGURE 15 51


LIST OF TABLES
TABLE 1 DPD/FAS TITRATION 52
TABLE 2 FIBER CHARACTER(J. PAWLISZYN 1997) 53
TABLE 3 TRICHLORAMINE SYNTHESIS UNDER DIFFERENT CL/N RATIO 54
TABLE 4 TRICHLORAMINE SYNTHESIS BY MIXING SODIUM HYPOCHLORITE WITH AMMONIUM SULPHATE 55
TABLE 5 TRICHLORAMINE SYNTHESIS BY MIXING SODIUM HYPOCHLORITE WITH AMMONIUM CHLORIDE 56
TABLE 6 TRICHLORAMINE SOLUTION STABILITY 57
TABLE 7 100MG/L AND 200MG/L CYCLOHEXENE STABILITY 58
TABLE 8 50MG/L CYCLOHEXENE STABILITY 58
TABLE 9 FIBER SELECTION 58
TABLE 10 THERMO DESORPTION EFFICIENCY 59
TABLE 11 STABILITY OF CHLOROCYCLOHEXANE ON SPME FIBER 59
TABLE 12 COMPARISON WITH PAST STUDIES 60
dc.language.isoen
dc.subjectCyclohexenezh_TW
dc.subjectChlorocyclohexanezh_TW
dc.subject三氯氨zh_TW
dc.subject固相微萃取zh_TW
dc.subject被動式採樣zh_TW
dc.subjectchlorocyclohexaneen
dc.subjectpassive samplingen
dc.subjectsolid phase microextractionen
dc.subjectcychlohexeneen
dc.subjecttrichloramineen
dc.title使用固相微萃取技術進行空氣中三氯氨被動式採樣之方法開發zh_TW
dc.titlePassive Air Sampling for Trichloramine by Solid-Phase Microextractionen
dc.typeThesis
dc.date.schoolyear99-1
dc.description.degree碩士
dc.contributor.oralexamcommittee林嘉明,陳美蓮
dc.subject.keyword三氯氨,Cyclohexene,Chlorocyclohexane,固相微萃取,被動式採樣,zh_TW
dc.subject.keywordtrichloramine,cychlohexene,chlorocyclohexane,solid phase microextraction,passive sampling,en
dc.relation.page60
dc.rights.note有償授權
dc.date.accepted2011-02-11
dc.contributor.author-college公共衛生學院zh_TW
dc.contributor.author-dept環境衛生研究所zh_TW
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