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研究生:鄭百乘
研究生(外文):Pai-Sheng Cheng
論文名稱:台灣地區周界環境中戴奧辛指紋圖譜和分佈之探討
論文名稱(外文):Study of Environmental PCDD/Fs Fingerprints and Distribution in Taiwan
指導教授:凌永健凌永健引用關係
指導教授(外文):Yong-Chien Ling
學位類別:博士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:英文
論文頁數:386
中文關鍵詞:戴奧辛周界空氣土壤植物主成分分析大氣擴散模式資料庫颱風
外文關鍵詞:dioxinairsoilvegetationPCAISCST3databasetyphoon
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戴奧辛是化學工業製程及燃燒過程中所產生的副產物,具高脂溶性易累積在脂肪組織或富碳的基質,其化學、物理及生物穩定性高,可傳播長距離並存在於各種環境區間中。焚化廠排放戴奧辛一直是全球廣受重視的環境議題,欲瞭解周界環境所受的影響衝擊,研究與建立排放來源-焚化廠與周界空氣、土壤、植物中戴奧辛含量的關係,便是最直接方式。
本論文共分為六章,第一章闡述研究動機與目的,第二章介紹本論文研究方法與架構,包含採樣、分析、大氣擴散模式及主成分分析、階層群集分析兩種統計方法,第三章為「新竹市垃圾焚化廠周界空氣及土壤中戴奧辛分佈與 ISCST3 模式預測差異之研究」,本章研究具有現代化污染防制設備之新竹市垃圾焚化廠,於2001年正式運轉前後,所排放的戴奧辛對於周界環境產生之衝擊與影響,本研究自2000年3月新竹市垃圾焚化廠完工前試燒期間,到2001年8月焚化廠完工後正式運轉時,多次採樣分析新竹地區周界空氣及土壤中戴奧辛,藉由比較周界空氣中戴奧辛之樣品實測濃度與ISCST3模式預測值,驗證此兩種截然不同方法之間的差異及相關性。主成分分析、階層群集分析與ISCST3大氣擴散模式結果顯示,焚化廠並非當地戴奧辛主要排放源,人類活動的綜合影響應為此區域戴奧辛之主要來源;冬季周界空氣中戴奧辛濃度高於夏季;研究也發現新竹地區周界空氣中戴奧辛濃度具有自東北向西南減緩之趨勢,而且此趨勢與當時盛行風向一致,顯示空氣中戴奧辛可能來自於東北方之重工業活動,建議未來應從區域性的觀點,探討國內周界空氣中PCDD/Fs濃度與可能來源之關係。
第四章為「台中市垃圾焚化廠、嘉義市垃圾焚化廠、高雄市某電弧爐廠周界空氣、植物、土壤中戴奧辛之分佈與主要來源」,過去相關研究常先選擇一潛在戴奧辛排放源為目標,再分析周界環境中一種或兩種基質與此排放源之關連性,藉以研究該排放源對於周界環境之影響程度,本章研究包含周界空氣、土壤、樹葉及煙道四種基質樣品,主要目的是以區域分佈之角度,探討台中市垃圾焚化廠、嘉義市垃圾焚化廠、高雄市某電弧爐廠周界空氣、植物、土壤中戴奧辛及其主要來源,而植物中戴奧辛分析方法則是修改自美國環保署方法1613B,應用於本論文中樹葉樣品的分析,並符合品保品管要求。三個地區之周界環境中戴奧辛主要來源不同,台中市垃圾焚化廠周界環境與新竹市類似,主要來自於人為活動;嘉義市垃圾焚化廠東北方某醫療廢棄物焚化爐為該地區環境中戴奧辛之主要來源;高雄市某電弧爐則是當地環境中主要戴奧辛排放源的其中之一;當受到高濃度戴奧辛污染時,土壤中戴奧辛濃度與總有機碳濃度呈現正相關,而且榕樹葉可作為台灣地區大氣中戴奧辛污染指標。
第五章為「台灣地區周界空氣、土壤與植物中戴奧辛濃度之全國性分佈研究」,結合歷年來政府委託針對周界環境之戴奧辛相關計畫結果,以及本實驗室近幾年累積之數據,根據聯合國環境規劃署的格式,建立國內第一個環境中戴奧辛資料庫,台灣是一個小型海島國家,卻有超過兩千兩百萬人口居住於西岸,由於高人口密度而具有與大陸型國家不同之生活型態及工業活動,因此本章首度整合國內19座大型垃圾焚化廠和都市周界空氣、土壤及植物樣品中戴奧辛資料,以全國性分佈之角度,探討環境中戴奧辛分佈與人口密度、工業活動之關係。研究結果顯示,各焚化廠周界空氣、土壤與植物中戴奧辛濃度無明顯相關,因此垃圾焚化廠並不是台灣環境中戴奧辛主要來源,但是藉由木柵垃圾焚化廠污染防治設備改善工程前後,周界空氣中戴奧辛濃度之比較,發現該廠的確對周界空氣中戴奧辛濃度造成顯著的影響。然而目前累積之資料,尚不足以解釋台灣地區環境中戴奧辛濃度分佈與人口密度或工業活動之關係,未來需要更多的數據,以區域性計畫取代僅針對特定垃圾焚化廠之研究,進而於未來擴大為全國性監測系統,以瞭解環境中戴奧辛濃度與人類活動之關係。
第六章為「氣象因子對周界空氣中戴奧辛濃度之影響-以颱風為例」,許多研究證實,正常天候下,溫度、風速、降雨以及氣團移動等氣象因子的變化,可以改變空氣中戴奧辛濃度與同源物分佈,然而對於劇烈變化天候下,大氣中戴奧辛變化的研究仍然付之闕如,本章是第一個針對颱風所帶來的強風豪雨等劇烈氣象因子變化,對周界空氣中戴奧辛濃度與同源物分佈造成之影響,所進行的研究。研究發現高降雨量及高風速皆會減少周界空氣中戴奧辛濃度,高風速立即降低濃度,而降雨後數小時濃度才會下降,尤以高降雨量影響最大,颱風過後降雨強度與周界空氣樣品中之戴奧辛濃度下降量呈現一個指數成長的關係;在氣固相中,PCDDs與PCDFs濃度會一起增減,而且颱風過後同時回升,然而受到雨水沖刷,固相濃度回復速度較氣相為慢;氣象因子對戴奧辛同源物分佈之影響乃全面性而非特定幾個同源物;颱風過後一至兩天內,周界空氣中戴奧辛濃度迅速回復至一般水準,所以台灣地區並不會因為夏秋兩季颱風發生頻繁,而造成空氣中戴奧辛濃度的降低;因此周界空氣中戴奧辛採樣應選擇在穩定的天候下進行,以避免大雨或強風之影響,如果時間和資源條件許可,長期多次監測之平均數據,將可獲得最具可信度、代表性與準確性的結果。
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are unwanted byproducts from various combustion processes and numerous chemical industrial processes. The toxic 2,3,7,8-substituted PCDD/Fs are lipophilic and tend to accumulate in carbon-rich matrices and in fatty tissues. PCDD/Fs have been detected in every environmental compartment owing to their chemical, physical and biological stability and long-range transport. Moreover, PCDD/Fs emissions from municipal solid waste incinerators (MSWIs) have become a globally environmental issue. Investigation of the relationship between PCDD/Fs level in stack emission from MSWIs and in ambient air, soil and vegetation provides the PCDD/Fs impact on environment from MSWI emissions.
There are six chapters in this thesis. Chapter 1 describes the research motive and purposes. Chapter 2 introduces the methods of PCDD/Fs sampling, PCDD/Fs analysis, ISCST3 model, PCA and HCA statistics. The title of chapter 3 is “Comparative study of monitored levels of PCDD/Fs in ambient air, soil and ISCST3 model predictions in the vicinity of a municipal solid waste incinerator in Hsinchu”. As a result of the newly construction of Hsinchu city MSWI, this study seized a wonderful opportunity to research how PCDD/Fs emission from a new MSWI equipped with modern APCDs could impact the ambient environment. This chapter presents the PCDD/Fs measured in ambient air and in soil around Hsinchu city MSWI during the trial burns in 2000 and compared to those measured in 2001 when it was fully operational. Concentration discrepancies between instrumental quantification and ISCST3 model prediction of ambient air were examined to test the precision and correlation among these two different types of method. Results of PCA, HCA and ISCST3 prediction reveal that Hsinchu city MSWI is not the major PCDD/Fs emission source to the ambient region. Human activities and unknown PCDD/Fs sources may fill up the gap among the model predictions and the instrument measurements. A systematic decrease of PCDD/Fs concentration in the ambient air from the northeast area to southwest was observed. This decreasing trend along the direction of wind is attributed to the heavy industrial activities on the northeast of Hsinchu city and wind flow towards southwest. Higher PCDD/Fs levels in the ambient air were found during spring and lower concentration was observed in summer. We recommend monitoring MSWI on a regional basis where the industrial and human activities are dense as in Taiwan.
The title of chapter 4 is “Distributions and principal sources of PCDD/Fs in ambient air, soil and vegetation in the vicinity of Taichung city and Chiayi city municipal solid waste incinerators together with an arc furnace in Kaohsiung”. Most related researches generally hypothesize a potential emission source at first, and measure the environmental PCDD/Fs levels in simply one or two kinds of matrices to evaluate the influences from targeted source. In this study, PCDD/Fs in four matrices including stack gas, ambient air, soil and vegetation were collected and analyzed from or in the vicinity of Taichung city MSWI, Chiayi city MSWI and one arc furnace in Kaohsiung city, respectively. The main purpose is to investigate the PCDD/Fs distributions in the three areas on the basis of regional viewpoint, and find out the major PCDD/Fs sources in the area. The determination of PCDD/Fs in leaves was carried out using modified and verified USEPA method 1613B. Different type of PCDD/Fs source in the respective investigation areas were proposed: 1. PCDD/Fs in the vicinity of Taichung city MSWI might because of the human activity like the case of Hsinchu MSWI; 2. medical waste incineration was probably the major PCDD/Fs source in the ambient environment of Chiayi city MSWI; 3. the arc furnace was considered one of the principal PCDD/Fs emission source to the surrounding environment in Kaohsiung Lin Hai industrial district. Furthermore, high PCDD/Fs amount occurred in soil resulting in positive correlation between TOC and PCDD/Fs content. It is suggested that banyan leaf could be selected as an atmospheric PCDD/Fs biomonitor in Taiwan.
The title of chapter 5 is “Nationwide PCDD/Fs levels in ambient air, soil and vegetation in Taiwan”. Reported data/results from the existing survey projects and our lab were collected and integrated into the first “Taiwan Environmental PCDD/Fs Database” based on the UNEP guidance document. Taiwan is a small island populated with twenty-two million people in the west living in an area of 36,179 km2. High population density leads different human lives and activities comparative to the continental countries. For the first time, PCDD/Fs levels in ambient air, vegetation and soil around 19 MSWIs and samples from urban areas in Taiwan are discussed and summarized to bring up a nationwide view of dioxin distributions. Typically, correlation between PCDD/Fs levels in ambient air, soil and vegetation was not observed. The MSWIs are therefore not the only or major dioxin emission source. The Mucha MSWI showed clear influence on ambient PCDD/Fs concentrations, i.e. when comparing the previous and currently improved APCDs. Due to short of data, conclusions can not be made between human activity (population or industrial park) distributions and dioxin level distributions in Taiwan. It is suggested regional (county) basis monitoring instead of the measurements simply surrounding MSWIs, and extended to a nationwide monitoring system in the long run.
The title of chapter 6 is “Investigation of meteorological factors influences on PCDD/Fs levels in ambient air using evidences from typhoons”. PCDD/Fs congener concentrations and profile in ambient air under stable weather condition have been proven readily altered by meteorological factors including temperature, wind, rain and air mass origin. However, little has been reported for the atmospheric PCDD/Fs condition right after severe weather variations. This is the first study aiming at the influences of meteorological factors on dioxin congener levels and distributions in ambient air exactly after typhoons. High rainfall and wind speed are both verified to reduce the PCDD/Fs level in ambient air, whereas rainfall influences the most. Relation between rain rate and reduced PCDD/Fs concentration in ambient air samples after typhoons was successfully correlated with an exponential growth curve. High wind speed eliminates the PCDD/Fs concentration in air immediately, but the affect of rain is usually reflected several hours later. PCDD/Fs levels in gaseous phase or particulate phase showed the same trend of variations. It is consequently suggested that both PCDDs and PCDFs in gaseous phase and in particular phase were persistently rose back to their original levels after the typhoon, but rainfall slow down the recovering speed in particulate phase. Severe meteorology factors altered the PCDDs to PCDFs ratio in ambient air, but not the profiles. Moreover, PCDD/Fs level in ambient air would revive in one or two days after the strict weather. These phenomena reveal that atmospheric PCDD/Fs level in Taiwan is not likely to become lower in summer or in autumn due to the prevalence of typhoon in these seasons. A long-term steady weather without heavy rain or high average wind speed is important during atmospheric PCDD/Fs measurement. If time and resources are permitted, chronic ambient air monitoring should be the best strategy to acquire faithful, representative and accurate data.
CHAPTER 1 EXORDIUM
1.1 preface…………………………………………………………….…….…... 1-1
1.2 Research motive and purposes……………………………………..……….. 1-3
References………...………………………………………………..…................. 1-5
CHAPTER 2 METHODS OF PCDD/FS SAMPLING, PCDD/FS ANALYSIS, INDUSTRIAL SOURCE COMPLEX — SHORT TERM MODEL, PRINCIPAL COMPONENT ANALYSIS, AND HIERARCHICAL CLUSTER ANALYSIS
2.1 PCDD/Fs sampling methods………………………………………………… 2-1
2.1.1 Ambient air………………………………………………………….… 2-1
2.1.1.1 Summary of method………………………...………………… 2-2
2.1.1.2 Apparatus and materials……………………………………….. 2-3
2.1.2 Stack gas…………………………………..………………….………... 2-3
2.1.2.1 Summary of method……………………………………….…... 2-3
2.1.2.2 Apparatus and materials………..………………………….…... 2-4
2.1.3 Soil……………………………….………..………………….………... 2-5
2.1.3.1 Summary of method……………………………………….…... 2-5
2.1.3.2 Apparatus…………......………..…………………………..…... 2-5
2.1.4 Vegetation…………………………………………………….………... 2-6
2.1.4.1 Summary of method……………………………………….…... 2-6
2.1.4.2 Apparatus and materials………..………………………….…... 2-6
2.2 PCDD/Fs analysis methods………………………………………………….. 2-7
2.2.1 Ambient air…………………………………………………………….. 2-7
2.2.1.1 Summary of method…………………………………………… 2-7
2.2.2 Stack gas……………………………………………………………….. 2-8
2.2.2.1 Summary of method…………………………………………… 2-8
2.2.3 Soil and vegetation……………………………………………………. 2-9
2.2.3.1 Summary of method…………………………………………… 2-10
2.2.4 Apparatus, equipment and reagents………………………...……….…. 2-12
2.3 Industrial Source Complex — Short Term model…………………………….. 2-14
2.3.1 Basic input data requirements…………………………………………. 2-14
2.3.2 Overview of available modeling options………………………………. 2-14
2.3.2.1 Dispersion option……………………..………………………... 2-15
2.3.2.2 Source option..…………………………………………………. 2-15
2.3.2.3 Receptor option………………………………………………... 2-16
2.3.2.4 Meteorology option.…………………………………………… 2-17
2.3.2.5 Output option..……………………………………..……….….. 2-17
2.4 Multivariate analysis methods………………………….……………………. 2-19
2.4.1 Factor analysis (principal component)………………………………… 2-19
2.4.2 Hierarchical cluster analysis…………………………………………… 2-21
References……………………………………………………………………….. 2-24
CHAPTER 3 COMPARATIVE STUDY OF MONITORED LEVELS OF PCDD/FS IN AMBIENT AIR, SOIL AND ISCST3 MODEL PREDICTIONS IN THE VICINITY OF A MUNICIPAL SOLID WASTE INCINERATOR IN HSINCHU
3.1 Introduction………………………………………………………………….. 3-1
3.2 Experimental………………………………………………………………… 3-4
3.2.1 Sampling sites and time……………………………………………….. 3-4
3.2.2 Sample preparation and analysis………………………………………. 3-4
3.2.3 PCA and HCA methods………………………………………………... 3-5
3.2.4 ISCST3 Model..………………………………………………………... 3-5
3.3 Results and discussion….……………………………………………………. 3-7
3.3.1 Ambient air samples…………………………………………………… 3-7
3.3.2 Soil samples…………………………………………………………… 3-10
3.3.3 Comparison of TEQ profiles and concentration profiles……………… 3-11
3.3.4 PCA and HCA…………………………………………………………. 3-11
3.3.5 ISCST3 model predictions…………………………………………….. 3-13
3.4 Conclusions………………...………………………………………………... 3-18
References…...…………………………………………………………………… 3-19
CHAPTER 4 DISTRIBUTIONS AND PRINCIPAL SOURCES OF PCDD/FS IN AMBIENT AIR, SOIL AND VEGETATION IN THE VICINITY OF TAICHUNG CITY AND CHIAYI CITY MUNICIPAL SOLID WASTE INCINERATORS TOGETHER WITH AN ARC FURNACE IN KAOHSIUNG
4.1 Introduction…………………………………………………….……………. 4-1
4.1.1 Survey of PCDD/Fs levels in ambient air from literature..……………. 4-2
4.1.2 Survey of PCDD/Fs levels in soil in from literature.………………….. 4-5
4.1.3 Survey of PCDD/Fs levels in vegetation from literature..……………... 4-8
4.1.4 Selection of vegetation species as a biomonitor of PCDD/Fs pollution in this study…………………………………………………………………... 4-12
4.1.5 Background of the incinerators in the present study…………………... 4-14
4.2 Experimental………………………………………………………………… 4-16
4.2.1 Sampling sites and time……………………………………………….. 4-16
4.2.2 Sample preparation and analysis………………………………………. 4-17
4.2.3 PCA method..………………………………………………………….. 4-17
4.2.4 ISCST3 Model...……………………………………………………….. 4-17
4.3 Results and discussion……………………………………………………….. 4-19
4.3.1 Taichung……………………………………………………………….. 4-19
4.3.1.1 PCDD/Fs levels in ambient air, soil and vegetation…………… 4-19
4.3.1.2 Comparison of concentration profiles and TEQ profiles……… 4-20
4.3.1.3 Correlations between the different matrices…………………… 4-21
4.3.1.4 Predictions using ISCST3 model……………...……………….. 4-22
4.3.2 Chiayi………………………………………………………………….. 4-23
4.3.2.1 PCDD/Fs levels in ambient air, soil and vegetation…………… 4-23
4.3.2.2 Comparison of concentration profiles and TEQ profiles……… 4-25
4.3.2.3 Correlations between the different matrices…………………… 4-26
4.3.2.4 Predictions using ISCST3 model...…………………………….. 4-27
4.3.3 Kaohsiung……………………………………………………………… 4-28
4.3.3.1 PCDD/Fs levels in ambient air, soil and vegetation…………… 4-28
4.3.3.2 Comparison of concentration profiles and TEQ profiles……… 4-29
4.3.3.3 Correlations between the different matrices…………………… 4-30
4.3.3.4 Predictions using ISCST3 model……………...………….……. 4-31
4.3.4 Correlations between all samples……………………………………… 4-32
4.3.5 Correlations between TOC and concentration or TEQ in soil………… 4-36
4.3.6 Suspected PCDD/Fs emission sources in Chiayi……………………… 4-37
4.4 Conclusions………………………………………………………………….. 4-39
References………………………..………………………………………………. 4-41
CHAPTER 5 NATIONWIDE PCDD/FS LEVELS IN AMBIENT AIR, SOIL AND VEGETATION IN TAIWAN
5.1 Introduction…………………………………………………………………. 5-1
5.2 Experimental………………………………………………………………… 5-3
5.2.1 Data sources…………………………………………………………… 5-3
5.2.2 Sampling sites and time…………………………..……………………. 5-3
5.2.2.1 Mucha…………………………………….……………………. 5-3
5.2.2.2 Hsinchu………………………………………………………… 5-3
5.2.2.3 Taichung, Chiayi and Kaohsiung………………………………. 5-4
5.2.2.4 Nankan………………………………………………………… 5-4
5.2.2.5 Yanshuei………………………………………………………... 5-4
5.2.3 Sample preparation and analysis………………………………….…… 5-4
5.3 Preview of existing projects……...………………………………………….. 5-6
5.3.1 Commissioned research program for assessing the hazardous factors around Mucha MSWI……………………………………………………….. 5-6
5.3.2 The establishment program of PCDD/Fs level information in ambient air, vegetation and soil in the vicinity of Sulin MSWI……………………… 5-6
5.3.3 The establishment program of PCDD/Fs level information in ambient air and soil in the vicinity of Hsinchu City MSWI…………………………. 5-7
5.3.4 The establishment program of PCDD/Fs level information in ambient air, vegetation and soil in the vicinity of 8 MSWIs…………………………. 5-7
5.3.5 2001’s Survey of Dioxin/Furan compounds in atmosphere and environment in Tainan County district……………………………………… 5-8
5.3.6 Survey program of PCDD/Fs levels in ambient air, vegetation and soil in the vicinity of one arc furnace and four MSWIs…………………………. 5-8
5.3.7 Survey and analysis program of PCDD/Fs levels in ambient air, vegetation and soil in the vicinity of Taitung City MSWI…………………... 5-9
5.4 Results and discussion………………………………………………………. 5-10
5.4.1 Taiwan Environmental PCDD/Fs Database…………………………… 5-10
5.4.2 PCDD/Fs levels in the environment in the vicinity of MSWIs and some urban/suburban areas in Taiwan………………………………………. 5-11
5.4.3 Comparison between Nationwide PCDD/Fs levels distributions and human activities……………………………………………………………… 5-14
5.5 Conclusions………………...………………………………………………... 5-16
References……………………………………………………………………….. 5-17
CHAPTER 6 INVESTIGATION OF METEOROLOGICAL FACTORS INFLUENCES ON PCDD/FS LEVELS IN AMBIENT AIR USING EVIDENCES FROM TYPHOONS
6.1 Introduction………………………………………………………………….. 6-1
6.2 Background of typhoons Toraji, Nari and Sinlaku…………..…………….… 6-4
6.3 Experimental……………………………………………………….………… 6-5
6.3.1 Sampling sites and time……………………………………….……….. 6-5
6.3.2 Meteorology data collection…………………………………………… 6-6
6.3.3 Sample preparation and analysis………………………………………. 6-7
6.3.4 PCA and correlation methods………………………………………….. 6-7
6.4 Results and discussion………………………………………………………. 6-8
6.4.1 General information of ambient air samples…………………………... 6-8
6.4.2 Comparison of concentration profiles and TEQ profiles……………… 6-10
6.4.3 Influences of rain and wind speed to PCDD/Fs in ambient air……….. 6-11
6.4.4 Washed away PCDD/Fs distributions in gaseous phase and particulate phase after the typhoon……………………………………………………… 6-14
6.4.5 PCA……………………………………………………………………. 6-15
6.5 Conclusions………………………………………………………………….. 6-18
References…………………………………………………………..……………. 6-20
APPENDIX 1
APPENDIX 2
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