臺灣博碩士論文加值系統

長久以來，臭氧空氣品質模式均假設大氣中揮發性有機化合物（VOCs）在垂直高度是均勻混合的；但近年來，科學家開始懷疑此假設之合理性，陸續有些文獻指出大氣中VOC層化現象的存在及需要被重視。高空中揮發性有機化合物之研究，因受限於採樣困難度高、低背景之乾淨、採樣設備不易取得及研究複雜、花費高等問題，所以國內一直缺乏實際量測數據，以驗證事實真相；因此本研究建立一套大氣水平及垂直剖面之VOC採樣與分析方法，收集相關背景資料，可協助空氣品質模式之模擬，以利科學界更進一步掌握臭氧生成及傳輸之相關資訊。
本研究利用繫留氣球採樣設備進行高雄地區大氣中地面（0 m）及上空（100 m）揮發性有機化合物之採樣，以幫浦連接10 L的採樣袋進行採樣，採完樣之後立即轉入不銹鋼採樣罐，並以氣相層析質譜儀進行分析。本研究所建立之分析方法（TO-15）可針對100種VOC化合物同時進行定量及定性分析，多數化合物之精密度均小於6 %，準確度約為15 %，方法偵測極限範圍在0.1 ~ 0.7 ppbv之間；檢量線之RSD皆在15 %之內。研究結果顯示，由不同季節之濃度變化得知於2007/01/24 ~ 26之TVOC-C2平均濃度為最高，符合秋末與冬季時期，不利於污染物擴散之結果。由日夜變化結果顯示，七個測站有85 %之比例均呈現早上08：00之TVOC-C2平均濃度為最高，是受到上班交通高峰時段影響；下午14：00則是受光化學反應及大氣擴散效果佳之影響，使TVOC-C2平均濃度較早上低。就空間面而言，有高達80 %之比例，陸域測站之TVOC-C2平均濃度大於高雄外海；就垂直面而言，五次密集採樣期均有明顯的層化現象，TVOC-C2之0 m平均濃度＞100 m平均濃度之案例約佔28 %之比例，主要發生於陸域測站；TVOC-C2之100 m平均濃度＞0 m平均濃度之案例約佔55 %之比例。由BTEX濃度探討得知，甲苯為最常出現之物種，BEX則較少檢出，且無明顯之日夜變化；BTEX比値結果顯示，BEX之比値則較符合為汽機車所排放；由（m, p）-X/E比値結果証實陸域氣團較為年輕，海域氣團較為老化。
綜合以上之結果，本研究觀察到高雄地區地面及上空VOC濃度存在有層化現象，懷疑是否與逆溫層化現象相關，但由於缺乏上空之氣象資料，並無法完整解釋其原因，不過本研究之發現對未來空氣品質之研究，仍具極大之參考價值，亦期望後續相關研究者可補充不足之處，以探討更詳細之原因。

For long, it has been hypothesized in the ozone air quality model that volatile organic compounds (VOCs) in the atmosphere are evenly mixed at all heights. However, in recent years, scientists have begun to doubt about the reasonability of this hypothesis, and a number of studies have pointed out the existence of VOC stratification and the need for more academic attention. The research of VOC in the air is usually subject to the difficulty in sampling, low background cleanness, difficulty in acquiring sampling facilities, complicated research procedures, and high research costs. Thus, practical measurements are not domestically available for an empirical validation. This study attempted to establish a method of VOC sampling from horizontal and vertical sections of the atmosphere to collect related background information, facilitate the simulation of the air quality model, and help the scientific arena further dominate the information about ozone generation and transmission.
This study used a tethered balloon to collect the VOC samples from the atmosphere at the ground level (0 m) and the height of 100 m. A pump was connected to a 10 L sampling bag, and the samples were immediately transferred into a stainless canister and analyzed with a Gas Chromatography-Mass Spectrometer. The proposed analysis method (TO-15) could quantitatively and qualitatively analyze 100 VOCs. Most of the compounds had a precision level under 6% and accuracy level at approximately 15%. The extreme range of the detection was between 0.1~0.7ppbv. The Relative Standard Deviation (RSD) of the calibration curve was within 15%. It could be discovered from the concentration variations across different seasons that the average concentration of TVOC-C2 was the highest during 2007/01/24~26. The finding was reasonable because the dispersion of pollutants was less efficient during the end of autumn and winter. In the daytime to night-time variations, the seven monitoring stations showed that 85% of the cases had a peak concentration of TVOC-C2 at 08:00am. Its peak concentration was attributed to the peak traffic flow in the morning. At 14:00pm, due to photochemical reaction and better air dispersion, the average concentration was lower than that detected in the morning. In terms of space, the land monitoring stations detected 80% of cases having an average concentration of TVOC-C2 higher than those detected offshore Kaohsiung. In terms of the vertical space, significant stratification was observed from the five intensive sampling periods. 28% cases, mainly detected by the land monitoring stations, showed that the average concentration of TVOC-C2 at 0m > the average concentration at 100m; 55% of cases had an average concentration of TVOC-C2 at 100 m > the average concentration at 0 m. Through the analysis of BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes), B (benzene) was the most common substance, and BEX were seldom detected, and no significant variation from daytime to night-time was observed. The ratio of BTEX showed that the BEX ratio was more similar to that of vehicle exhaust. The (m,p)-X/E ratio empirically proved that the land air mass is younger, while the ocean air mass is older.
Concluding from the above research results, stratification of VOC concentrations was observed across the land and atmosphere of Kaohsiung area. It was speculated that the stratification could be associated with temperature inversion stratification. However, due to the absence of weather data about the high air, the causes could not be completely explained. Nonetheless, the findings of this study would still be valuable to the research of air quality. It was also expected that follow-up studies could complement the insufficiencies of this study and probe into more detailed causes.

摘要 i
Abstract iii
誌謝 vi
目錄 vii
圖目錄 viii
表目錄 x
第一章 前言 1
1.1 研究動機 1
1.2 研究目的 2
1.3 研究流程 2
第二章 文獻回顧 4
2.1 揮發性有機化合物之定義 4
2.2 大氣中揮發性有機化合物之來源 4
2.3 揮發性有機化合物對人體及環境之影響 6
2.4 揮發性有機化合物之光化學反應 7
2.5 氣象條件對空氣污染物之影響 8
2.5.1 混合層高度 8
2.5.2 海陸風環流 9
2.6 國外VOC垂直剖面採樣及分析方法 11
2.6.1 飛機 11
2.6.2 繫留氣球 12
2.6.3 高塔 13
2.7 國內VOC垂直剖面採樣及分析方法 13
第三章 研究方法與設備 18
3.1 採樣位置及採樣頻率之選定 18
3.2 垂直剖面VOC採樣方法與設備 18
3.3 揮發性有機化合物分析方法與設備 20
3.4 品保品管措施 23
3.4.1 採樣幫浦空白測試 23
3.4.2 採樣袋空白測試 23
3.4.3 不銹鋼採樣罐 24
3.4.4 分析方法之品管 26
第四章 結果與討論 41
4.1 數據品質之成果 41
4.1.1 採樣幫浦空白 41
4.1.2 採樣袋空白 42
4.1.3 標準品圖譜 42
4.1.4 精密度、準確度、方法偵測極限、檢量線 43
4.2 地面氣象觀測資料分析 43
4.3 揮發性有機物化合物採樣與分析結果 45
4.3.1 時間面VOC差異之探討 45
4.3.2 空間面VOC差異之探討 54
4.3.3 垂直面VOC差異之比較 57
4.4 BTEX濃度探討 62
4.4.1 BTEX之比値 63
4.4.2 BTEX相關性 64
4.5 （m, p）-X/E之比値 64
第五章 結論與建議 103
5.1 結論 103
5.2 建議 105
參考文獻 107
附錄 114
密集採樣期Ⅰ原始數據 114
密集採樣期Ⅱ原始數據 118
密集採樣期Ⅲ原始數據 122
密集採樣期Ⅳ原始數據 126
密集採樣期Ⅴ原始數據 130
圖目錄
圖1.1.1 各空品區空氣品質不良比例比較圖 3
圖1.3.1 研究流程圖 3
圖2.5.1 混合層高度之日變化 14
圖2.5.2 海風環流之形成機制 14
圖2.5.3 高雄氣象站2004年夏季及冬季風向變化圖 15
圖3.1.1 採樣位置圖 32
圖3.2.1 自動空氣品質監測車 33
圖3.2.2 垂直剖面VOC採樣設備 33
圖3.2.3 不銹鋼採樣罐 34
圖3.4.1 Canister清洗設備 40
圖4.1.1 UAT分析化合物（共59種VOC化合物）之圖譜 68
圖4.1.2 PAMS分析化合物（共54種VOC化合物）之圖譜 69
圖4.1.3 內標準品與BFB標準品之空白分析圖譜 70
圖4.2.1 2006/08/16~18高屏地區各測站風向變化圖 73
圖4.2.2 2006/11/02~04高屏地區各測站風向變化圖 73
圖4.2.3 2007/01/24~26高屏地區各測站風向變化圖 73
圖4.2.4 2007/03/06~08高屏地區各測站風向變化圖 74
圖4.2.5 2007/05/02~04高屏地區各測站風向變化圖 74
圖4.3.1 不同季節之TVOC-C2濃度變化圖 76
圖4.3.2 不同季節VOC物種之變化圖 76
圖4.3.3 2006/08/16~18四個測站之TVOC-C2日夜變化 77
圖4.3.4 2006/08/16~18四個測站日夜VOC物種變化 78
圖4.3.5 2006/11/02~04四個測站之TVOC-C2日夜變化 79
圖4.3.6 2006/11/02~04四個測站日夜VOC物種變化 80
圖4.3.7 2007/01/24~26四個測站之TVOC-C2日夜變化 81
圖4.3.8 2007/01/24~26四個測站日夜VOC物種變化 82
圖4.3.9 2007/03/06~08四個測站之TVOC-C2日夜變化 83
圖4.3.10 2007/03/06~08四個測站日夜VOC物種變化 84
圖4.3.11 2007/05/02~04四個測站之TVOC-C2日夜變化 85
圖4.3.12 2007/05/02~04四個測站日夜VOC物種變化 86
圖4.3.13 2006/08/16~18四個測站之TVOC-C2空間變化 87
圖4.3.14 2006/08/16~18四個測站之空間VOC物種變化 87
圖4.3.15 2006/11/02~04四個測站之TVOC-C2空間變化 88
圖4.3.16 2006/11/02~04四個測站之空間VOC物種變化 88
圖4.3.17 2007/01/24~26四個測站之TVOC-C2空間變化 89
圖4.3.18 2007/01/24~26四個測站之空間VOC物種變化 89
圖4.3.19 2007/03/06~08四個測站之TVOC-C2空間變化 90
圖4.3.20 2007/03/06~08四個測站之空間VOC物種變化 90
圖4.3.21 2007/05/02~04四個測站之TVOC-C2空間變化 91
圖4.3.22 2007/05/02~04四個測站之空間VOC物種變化 91
圖4.3.23 2006/08/16~18四個測站之TVOC-C2垂直面變化 92
圖4.3.24 2006/08/16~18四個測站之垂直面（100m）VOC物種變化 92
圖4.3.25 2006/08/16~18四個測站之垂直面（0m）VOC物種變化 92
圖4.3.26 2006/11/02~04四個測站之TVOC-C2垂直面變化 93
圖4.3.27 2006/11/02~04四個測站之垂直面（100m）VOC物種變化 93
圖4.3.28 2006/11/02~04四個測站之垂直面（0m）VOC物種變化 93
圖4.3.29 2007/01/24~26四個測站之TVOC-C2垂直面變化 94
圖4.3.30 2007/01/24~26三個測站之垂直面（100m）VOC物種變化 94
圖4.3.31 2007/01/24~26四個測站之垂直面（0m）VOC物種變化 94
圖4.3.32 2007/03/06~08四個測站之TVOC-C2垂直面變化 95
圖4.3.33 2007/03/06~08三個測站之垂直面（100m）VOC物種變化 95
圖4.3.34 2007/03/06~08四個測站之垂直面（0m）VOC物種變化 95
圖4.3.35 2007/05/02~04四個測站之TVOC-C2垂直面變化 96
圖4.3.36 2007/05/02~04四個測站之垂直面（100m）VOC物種變化 96
圖4.3.37 2007/05/02~04四個測站之垂直面（0m）VOC物種變化 96
圖4.4.1 2006/08/16~18四個測站之BTEX濃度變化 97
圖4.4.2 2006/11/02~04四個測站之BTEX濃度變化 98
圖4.4.3 2007/01/24~26四個測站之BTEX濃度變化 99
圖4.4.4 2007/03/06~08四個測站之BTEX濃度變化 100
圖4.4.5 2007/05/02~04四個測站之BTEX濃度變化 101
表目錄
表2.6.1 繫留氣球採樣設備之發展 16
表2.6.2 國內在VOC垂直剖面之研究 17
表3.3.1 TO-15所能檢測之有害空氣化合物（UAT） 35
表3.3.2 TO-15所能檢測之臭氧前驅污染物（PAMS） 36
表3.3.3 標準氣體之來源與規格 37
表3.3.4 冷凝濃縮裝置之參數設定 38
表3.3.5 空氣壓縮機之規格 38
表3.3.6 氣相層析儀（GC）升溫之參數設定 39
表3.3.7 質譜儀（MSD）之參數設定 39
表4.1.1 SKC採樣幫浦空白測試結果 66
表4.1.2 採樣袋清洗前後之空白測試結果 67
表4.1.3 UAT標準品之精密度、MDL及檢量線結果 71
表4.1.4 PAMS標準品之精密度、MDL及檢量線結果 72
表4.3.1 樣品採集之成功率 75
表4.3.2 不同季節之TVOC-C2變化 76
表4.4.1 五次採樣均有檢測出BTEX濃度比値 102
表4.4.2 五次採樣均有檢測出BTEX濃度之相關性分析 104
表4.5.1 陸域與海域之X/E比値結果 104

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