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研究生: 黃柏菁
Huang, Po-Chin
論文名稱: 都市垃圾焚化爐周界空氣中多氯戴奧辛與 多氯呋喃之粒徑分布研究
Size Distribution of Particle Phase Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans of Atmospheric Particles Near the Incineration of Municipal Wastes.
指導教授: 廖寶琦
Liao, Pc-Chi
李俊璋
Lee, Ching-Chang
學位類別: 碩士
Master
系所名稱: 醫學院 - 環境醫學研究所
Department of Environmental and Occupational Health
論文出版年: 2002
畢業學年度: 90
語文別: 中文
論文頁數: 145
中文關鍵詞: 都市垃圾焚化爐粒徑分布多氯戴奧辛與呋喃
外文關鍵詞: MWIs, PCDD/Fs, size distribution
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  • 多氯戴奧辛(Polychlorinated Dibenzo-p-Dioxins,以下簡稱戴奧辛)及多氯呋喃(Polychlorinated Dibenzo-Furans,以下簡稱呋喃)為半揮發性有毒物質,而都市垃圾焚化爐為目前已知重要的戴奧辛來源之一。戴奧辛自焚化爐排放後,可經由大氣擴散進行長距離之傳輸,對於環境影響的程度可由地區性到全球性。戴奧辛在環境中的流布,依其吸附於粒徑不同微粒的能力不同,將影響戴奧辛在環境中的傳輸及沉降行為。為了能夠瞭解戴奧辛在大氣中的傳輸和沈降,以及人體經由呼吸道所接觸到戴奧辛的濃度,因此有必要對戴奧辛在大氣不同微粒中的分布作進一步的調查。
    本研究以台南市垃圾焚化爐為對象,以工業污染源複合模式(ISCST3)進行戴奧辛大氣擴散模擬後,依擴散濃度之高低,選擇焚化爐附近濃度區域較高之土城國小分校、安佃國小、顯宮國小,以及建功國小為背景點。在戴奧辛粒徑分布採樣方面,使用高量採樣器配合五階階梯式採樣器(7.2、3.0、1.5、0.95、0.49μm),以石英纖維濾紙進行大氣中固相PCDD/Fs粒徑分布採樣,採樣過程中同時進行氣象條件之量測與記錄。採集之樣品遵循本國環檢所公告之NIEA810.10B方法進行萃取、濃縮、酸洗、酸性矽膠、氧化鋁、活性碳等淨化後,使用高解析氣相層析/高解析質譜儀進行分析,以獲得固相PCDD/Fs之粒徑分布資料。
    研究結果顯示,都市垃圾焚化爐周界空氣中懸浮微粒之粒徑分布為一雙峰分布(Bimodal distribution),最高濃度值皆出現在粒徑<0.49μm之微粒,dC/dlog Dp平均值為15.6 μg/m3(10.1~21.9 μg/m3);次高濃度出現在7.2~3μm之粒徑,dC/dlog Dp平均值為10.0 μg/m3(7.5~12.3 μg/m3)。該結果顯示台南市垃圾焚化爐周界空氣之氣膠微粒的分布包括細微粒分布模式與粗微粒分布模式均存在。
    都市垃圾焚化爐周界空氣中戴奧辛之粒徑分布呈現偏左之單峰分布,最大濃度值出現在粒徑小於0.49 μm之微粒,三次採集所分析之戴奧辛平均濃度為0.603 pg/Nm3 (0.906~0.389 pg/Nm3) ,以累積模式(accumulative mode)來計算時,則有83%以上的戴奧辛存在粒徑小於1.5 μm以下之微粒。在毒性當量方面,三次採集所分析之戴奧辛平均濃度為0.016 pg I-TEQ/Nm3 (0.011~0.024 pg I-TEQ/Nm3) ,粒徑小於1.5 μm之微粒在總毒性當量的貢獻度達78%以上。同時也發現,平均而言PCDFs的濃度約為PCDDs的1.4倍,但PCDFs毒性當量貢獻量卻平均為PCDDs的2.9倍。戴奧辛同族物(homologue)分布方面,三次採樣各點皆以六氯、七氯和八氯戴奧辛與呋喃為主。單位質量微粒的戴奧辛含量分布方面,各採樣點之戴奧辛含量分布皆有隨粒徑減小而遞增之趨勢,在最小粒徑範圍(<0.49μm)之微粒有最大戴奧辛含量,此應為較小之懸浮微粒具有較大的比表面積,經大氣冷凝等作用可以吸附較多戴奧辛之故。同時在與溫度的比較時發現,隨著溫度下降,粒徑小於0.49 μm之微粒所含戴奧辛的比例有逐漸下降的趨勢,而在粒徑1.5~0.95μm、0.95~0.49μm所含有戴奧辛的濃度比例有逐漸上升的趨勢可能是由於凝結所引起的微粒成長。戴奧辛主要同源物(congener)方面,戴奧辛粒徑分布之pattern主要為OCDD/F,1,2,3,4,6,7,8-HpCDD/F及1,2,3,4,7,8HxCDF,此分布與氣固相所觀察到的分布近似,但是在戴奧辛氣固相之固相的八氯分布卻與本研究不同。整體而言,戴奧辛粒徑分布之pattern與氣固相之固相pattern是相當一致的。

    Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are well known persistence organic pollutants (POPs). They are characterized as persistent, semivolatile and toxicologically significant trace organic contaminants. Municipal wastes incinerators (MWIs) is one of the important sources of dioxin as we known. PCDD/Fs emitted from incinerators can be transported over long distances from local to global scale and are distributed into various environmental components. Several studies indicated that most of PCDD/Fs are strongly adsorbed to particulate. The distribution of particle-bound PCDD/Fs in the atmosphere are influenced by the properties of atmospheric particles, especially for size distribution. The size distribution patterns of particles in the atmosphere is important to determine the transport and removal mechanism of PCDD/Fs and contribution of human exposure to PCDD/Fs through inhalation. Therefore, the size distribution of particle-bound PCDD/Fs in the atmosphere is the main issue to explore.
    Industrial source Complex short-term model (ISCST3) is applied to estimate the annual averaged ambient PCDD/Fs concentrations emission by measured PCDD/Fs data from Cheng-xi municipal wastes incinerator in Tainan and meteorological data from 1996-1999. According to the emitted from stack of distribution of estimated ambient PCDD/Fs concentration, four elementary schools, Tu-Cheng, An-Dian, Xian-Gong and Jian- Gong, near Cheng-xi MWI were selected as sampling site during Oct to Dec in 2001. The size distribution of airborne particles at four sites were measured using quartz fiber filter (QFF) and high volume air sampler equipped with cascade impactor. The cutoff size of cascade impactor is 7.2、3.0、1.5、0.95、0.49μm. Samples were extracted by a Soxhlet for 24h with toluene and a cocktail of isotope labelled standards was added. The cleanup of the extraction was accomplished with an acid-base silica column, an alumina column and a carbon column. The quantification of PCDD/Fs was performed with high-resolution gas chromatography/ high-resolution mass spectrometry.
    The size distribution of total suspend particles is bimodal distribution. First peak presented in the <0.49μm and secondary maxima presented in the 3-7.2μm. The size distribution of particle-bound PCDD/Fs is unimodal distribution, which maximum size range in the <0.49μm. The large amounts of particle-bound PCDD/Fs were found on small particles with dae less than 1.5μm that accounted for over 83% of the total PCDD/Fs, contributing mostly to the toxicity and providing over 78% of the total TEQs. Observation of particle-bound PCDD/Fs on large particles were different from the small particles and the concentrations of PCDD/Fs decreased with increasing particle size.

    中英文摘要 Ⅰ 目錄 Ⅴ 圖目錄 Ⅷ 表目錄 Ⅹ 第一章 序論 1-1研究背景 1 1-2研究目的 3 1-3研究意義、重要性 3 第二章 文獻回顧 4 2-1 背景資料 4 2-1-1戴奧辛特性與發生源 4 2-1-2戴奧辛的毒理作用 5 2-3戴奧辛的氣固相研究 8 2-4戴奧辛的粒徑分布 9 2-5戴奧辛的粒徑分布對人體暴露途徑的影響 13 2-6戴奧辛的粒徑分布對環境流布的影響 13 第三章 方法與材料 16 3-1研究架構 16 3-2研究對象選取 16 3-3採樣策略及方法 17 3-3-1採樣時間 17 3-3-2採樣點選擇 17 3-3-3採樣頻率 18 3-3-4採樣方法 18 3-3-4-1採樣設備 18 3-3-4-2採樣材料及前處理 18 3-3-4-3採樣設備流量校正 19 3-3-4-4樣品數 19 3-4戴奧辛粒徑分布樣品分析方法 20 3-4-1樣品前處理方法 20 3-4-2樣品分析方法 22 3-4-3分析儀器及條件設定 23 3-5樣品之品保品管 24 3-5-1建立滯留時間 24 3-5-2管柱解析度 24 3-5-3儀器靈敏度 25 3-5-4起始檢量校正 25 3-5-5檢量線 25 3-5-6同位素標準品添加與回收率 26 3-5-7品管樣品 26 3-5-8基質添加樣品驗證 27 3-5-9實驗空白樣品驗證 27 3-6數據結果解析 27 第四章 結果與討論 28 4-1氣象資料整理 28 4-2品保品管資料(QA/QC) 29 4-2-1建立滯留時間 29 4-2-2建立起始檢量線 29 4-2-3起始檢量校正 30 4-2-4管柱解析度 30 4-2-5儀器靈敏度 30 4-2-6實驗空白和基質樣品添加 30 4-3大氣中懸浮微粒之粒徑分布 31 4-4大氣中戴奧辛之粒徑分布 32 4-5大氣中不同粒徑單位質量微粒中之戴奧辛粒徑分布 36 4-6大氣中戴奧辛之粒徑分布與國外研究結果之比較 38 4-7大氣中戴奧辛之粒徑分布與溫度之比較 39 4-8大氣中戴奧辛之粒徑分布與氣固相研究結果之比較 40 第五章 結論與建議 42 5-1 結論 42 5-2 建議 44 參考文獻 45 附圖 49 附表 86 附件 141

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