跳到主要內容

簡易檢索 / 詳目顯示

回結果列表
研究生： 徐珮瑄
Pei-Hsuan Hsu
論文名稱： 以被動式採樣技術分析空氣中有害揮發性有機化合物
指導教授： 王家麟
Jia-Lin Wang
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
論文出版年： 2023
畢業學年度： 111
語文別： 中文
論文頁數： 182
中文關鍵詞： 有害空氣污染物 、揮發性有機化合物 、自動化熱脫附儀 、吸取速率 、複合式材料
相關次數： 點閱：13  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • 有害空氣污染物 (Hazardous Air Pollutants, HAPs) 隨著工業發展被大量排放，其中包括若干具毒性之揮發性有機化合物 (Toxic VOCs)。為求取空氣中 Toxic VOCs 平均濃度以評估長時間暴露下之健康風險，美國環保署已公告一標準方法 U.S. EPA Method 325A/B，利用化學吸附劑以氣體擴散原理吸附空氣中 VOCs，再利用不同吸附材料對於不同化合物之吸取速率 (Uptake Rate) 求出在採樣時期間各目標物的平均濃度。在樣品分析上採用自動化熱脫附儀 (Automated Thermal Desorption, ATD) 搭配氣相層析質譜儀 (Gas Chromatography- Mass Spectrometer, GC-MS) 作為分析系統以更簡易的採樣方法長時間監測周界 HAPs 濃度。
    首先，本研究之目的是擬將可分析的HAPs物質數目增加，故合併數種不同化學吸附材料之優勢複合成單一採樣管，以達到廣泛應用之目的。研究重點之一是進行複合式材料之條件優化、測試及採樣的應用，其中包含檢量線之相關係數 (R2)、方法偵測極限 (MDL)、精密度 (Accuracy)、準確度 (Precision) 之儲存穩定性(Storage stability)，以達到嚴格的品保品管 (Quality Assurance/Quality Control, QA/QC) 要求，排除未通過 QA/QC 的物種。研究重點之二是利用自製暴露腔在不同溫度、濕度條件下求取個別目標物之專屬吸取速率用於計算周界HAPs濃度。
    本研究考量吸附材料的選擇性，在最佳的複合方式下，結果顯示共可針對69項 HAPs 進行被動式採樣，比起單一吸附材料 Carbopack X 與 Carboxen 569 僅可針對50項及37項 HAPs 高出近30項目標物種。複合式材料檢量線相關係數介於0.990~1.000，方法偵測極限濃度介於0.04 ppbv~0.99 ppbv，精密度相對標準偏差介於0.32%~10.43%，準確度之樣品保存回收率介於74.28%~121.61%，而被動式採樣後之採樣管樣品須保存於4℃環境中，並於14天內分析完畢，以確保樣品品質。
    在實驗室內進行實驗評估完成後，分別於各化學實驗室(有機、分析、生化實驗室)、台北中研院、桃園觀音工業區及大園工業區、彰化和美國中及埔心高中、雲林崙背國中、高雄仁大工業區等地進行實場採樣。以上採樣方式包含主動式採樣及被動式採樣，而於本研究當中，利用採樣管採樣有以下四種應用，第一：進行被動式採樣用於長時間的環境評估；第二：被動式採樣與線上熱脫附氣相層析質譜法 (Online TD-GC-MS) 或線上熱脫附氣相層析火焰離子偵測器 (Online TD-GC-FID) 進行比較；第三：利用被動式採樣以佈點的方式追朔排放源；第四：平行比對驗證，將被動式採樣與上述之線上GC分析方法置於同一地點平行採樣分析以驗證彼此可靠性。實場測試結果顯示被動式採樣與 online TD-GC-MS 分析方法的平均值接近，獲得極佳之驗證效果。日後監測目的是為了獲取各 Toxic VOCs 的平均濃度，而非瞬間濃度變化，則可以利用實施簡易之被動式採樣法評估相對較長時間之目標物的平均濃度，擴大對於這類有害物質的環境調查能力。

    Hazardous Air Pollutants (HAPs) are emitted in large quantities with industrial development, and the threat to public health has been an issue of great concern in recent years. In the past, the passive sampling technique, similar to the U.S. EPA Method 325A/B, was developed, including the determination of uptake rates for different adsorbent materials for a variety of volatile organic compounds (VOCs) under different climatic conditions.
    Firstly, to broaden the range of target compounds, dual commercial adsorbent materials were combined into a tandom adsorbent tube for the complementary benefits and easier deployement and logistics. After excluding the species not passing the QA/QC criteria, the specific experimental uptake rates of the remaining target species were experimentally obtained for calculating concentrations of target compounds after passive sampling. Therefore, another important aspect of this study is to determine the uptake rates with a self-designed exposure chamber under different temperature and humidity conditions. An Automated Thermal Desorption (ATD) with Gas Chromatography-Mass Spectrometer (GC-MS) was used to analze the sorption tubes of passive sampling collected from the field.
    The results showed that the composite materials could be used for passive sampling of 69 HAPs, nearly 30 more than the single adsorbent material, e.g., Carbopack X and Carboxen 569, which can only target 50 and 37 HAPs, respectively. The correlation coefficients of the composite materials were between 0.990~1.000, the detection limits were between 0.04 ppbv~0.99 ppbv, the relative standard deviations representing precision were between 0.32%~17.57%, and the recoveries representing accuracy were between 74.28%~121.61%. The samples were stored at 4°C and analyzed within 14 days to ensure the sample and thus data quality.
    After thorough preparation, the composite materials were tested in various environments, such as nearby laboratories (organic, analytical, and biochemical laboratories), Academia Sinica, Taoyuan Guanyin Industrial Park. Tayuan Industrial Park, Changhua, and U.S. High School, Puxin High School, Yunlin Lunbei National High School, and Kaohsiung Renda Industrial Park. At some of these sites, both active sampling and passive sampling methods were used. In this study, there are four applications of passive sampling. Firstly, for long-term environmental exposure assessment; secondly, passive sampling with online thermal desorption (TD)-GC-MS or TD-GC with flame ionization detection (FID); thirdly, for emission source investigation; and fourthly, mutual validation with the online TD-GC-MS measurements. Comparing with the online GC method, passive sampling can avoid the complications in operation and maintenance of an instrument in the field. The field tests also revealed comparable results between the two methods when the mean concentrations were compared. As a result, passive sampling can effectively evaluate average concentrations of the target species over a prolonged period at minimal cost and effort, thus adding another useful tool to enhance environmental monitoring capability.

    目次 摘要 i Abstract iii 謝誌 v 目次 vii 圖目次 ix 表目次 xii 第一章 前言 1 1.1 研究背景 1 1.2 研究目的 5 第二章 文獻回顧與整理 7 2.1 有害空氣污染物 7 2.1.1 各國對於HAPs的重視 8 2.1.2 國內對於HAPs的重視 11 2.2 光化學評估監測站 14 2.3 揮發性有機化合物 (VOCs) 的監測 20 2.3.1 離線式採樣分析方法 (Off Line) 23 2.3.2 線上連續式自動監測方法 (On Line) 30 2.4 被動式採樣技術介紹 34 2.4.1 採樣管的介紹 36 2.4.2 擴散吸取速率 (Uptake rate, U) 的介紹 40 2.4.3 採樣管的建置及保存 43 2.4.4 實驗吸取速率之系統裝置 45 2.5 作業健康環境風險 50 第三章 實驗設備與流程介紹 53 3.1 實驗儀器介紹 53 3.1.1 適化設備 (Condition Oven) 53 3.1.2 自動熱脫附系統 54 3.2.3 分析儀器 58 3.2 實驗流程 63 3.3 內標準品 (Internal Standard, IS) 65 3.4 標準氣體 (Standard gas) 67 3.5 暴露腔系統 (Exposure Chamber System) 70 3.5.1 溫控設備 70 3.5.2 稀釋系統 71 3.5.3 暴露腔系統 73 第四章 實驗方法及條件優化 75 4.1 單一吸附材料 76 4.1.1 Carbopack X 及 Carboxen 569 質量控制標準 76 4.1.2 Carbopack X 及 Carboxen 569 之氣候條件測試 81 4.2 複合式吸附材料配置 85 4.2.1 吸附材料的配方 85 4.2.2 吸附材料的比例 86 4.2.3 重複測試採樣管 88 4.3 自動熱脫附系統參數優化 89 4.3.1 Dry Purge 89 4.3.2 熱脫附 91 4.4 品保品管 (Quality Assurance/Quality Control, QA/QC) 97 4.4.1 質譜儀調整 97 4.4.2 檢量線 (Calibration curve) 98 4.4.3 方法偵測極限 (Method Detection Limit, MDL) 102 4.4.4 精密度 (Accuracy) 105 4.4.5 準確度 (Precision) / 樣品保存 108 4.5 實驗吸取速率 111 4.5.1 計算方法 112 4.5.2 溫度及濕度調整 114 4.6 採樣管之適用性 117 第五章 實場採樣及結果討論 119 5.1 實場監測準備 119 5.1.1 主動式採樣 119 5.1.2被動式採樣 120 5.2 監測結果 122 5.2.1 實驗室採樣 122 5.2.2 高雄仁武採樣 125 5.2.3 桃園大園觀音採樣 130 5.2.4 台北中研院採樣 133 5.2.5 彰化和美高中採樣 134 5.2.6 雲林崙背採樣 139 5.2.7 濾紙分析 142 第六章 結論 147 參考文獻 151 圖目次 圖1 二次污染物的產生 2 圖2 大氣中主要反應性排放來源 3 圖3 對流層臭氧的生成機制 4 圖4 全臺灣石化及科學工業區分佈 14 圖5 光化學評估監測網設置原則 16 圖6 臺灣光化學評估監測站地理位置 17 圖7 VOCs監測的流程圖 23 圖8 不鏽鋼採樣筒示意圖 25 圖9 NIEA A715.16B標準方法系統圖 26 圖10 TO-15標準方法系統圖 26 圖11 TO-14標準方法系統圖 27 圖12 採樣袋示意圖 27 圖13 TO-18標準方法設備組裝示意圖 28 圖14 不鏽鋼採樣管示意圖 29 圖15 TO-17標準方法系統圖 29 圖16 NIEA A505.12B標準方法系統圖 31 圖17 GC-MS分析系統流路 33 圖18 採樣管剖面示意圖 36 圖19 U.S. EPA Method 325A採樣據點建議設置方法 43 圖20 被動式採樣廠區配置圖 44 圖21 採樣管之黃銅蓋、鐵氟龍蓋與擴散蓋 44 圖22 T.D.Ramos暴露腔體裝置圖 46 圖23 W.A.McClenny暴露腔體裝置圖 46 圖24 PerkinElmer TurboMatrix TC 220 Condition Oven 230 V 54 圖25 PerkinElmer Turbo Matrix 650 Automated Thermal Desorption 55 圖26 PerkinElmer之Air Monitoring Trap 56 圖27 PerkinElmer Clarus 690 GC 59 圖28 升溫梯度 59 圖29 PerkinElmer Clarus SQ 8T 60 圖30 實驗流程 64 圖31 內標準品層析圖譜 66 圖32 標準品圖譜 69 圖33 暴露腔系統示意圖 70 圖34 溫控設備實際圖 (a)上層 (b)下層 71 圖35 (a)MFC控制設備 (b)加濕設備 (c)標準氣體鋼瓶 71 圖36 (a)止逆閥 (b)浮子流量計及針閥 (c)Arduino模組 73 圖37 (a)進氣口 (b)出氣口 (c)Arduino模偵測器 (d)採樣管架 74 圖38 (a) Carbopack X BD 柱狀圖 (b) Carboxen 569 BD 柱狀圖 80 圖39 (a)分層配置 (b)混層配置示意圖 85 圖40 調整複合式材料配置含量之層析圖 86 圖41 調整複合式材料比例之層析圖 87 圖42 調整複合式材料比例之二次脫附層析圖 87 圖43 不同支複合式材料之濃度差 88 圖44 ATD Dry Purge步驟示意圖 89 圖45 Dry Purge流速優化 90 圖46 Dry Purge時間優化 91 圖47 ATD熱脫附步驟示意圖 92 圖48 脫附溫度優化 93 圖49 複合式材料分層殘留比 93 圖50 複合式材料混層殘留比 93 圖51 脫附時間優化層析圖 94 圖52 脫附時間優化柱狀圖 94 圖53 Air Monitoring Trap材料崩解 95 圖54 更換Trap管前後層析圖譜比較 95 圖55 更換Trap管前內標層析疊圖 96 圖56 全氟三丁胺 (PFTBA) 實際圖 97 圖57 吸取速率計算流程 113 圖58 溫度及濕度影響之實驗設計 114 圖59 Markes MTS-32 (multiple-tube sampler) 120 圖60 PerkinElmer STS-25 (sequential tube sampler) 120 圖61 採樣遮罩實際架設圖 121 圖62 本研究採樣地點 (藍色：主動式；紅色：被動式) 122 圖63 火災後有機化學實驗室 123 圖64 事件日與平常日之層析圖譜疊圖 123 圖65 (a)有機實驗室 (b)氣體分析實驗室 (c)液體分析實驗室 (d)生化實驗室 124 圖66 實驗室被動式採樣疊圖 125 圖67 (a) 高雄測站外觀 (b)採樣遮罩架設 (c)現地質譜採樣口 126 圖68 2021年被動式採樣與現地質譜之氯乙烯濃度結果 127 圖69 2021年被動式採樣與現地質譜之四氯化碳濃度結果 127 圖70 2021年被動式採樣與現地質譜之氯仿濃度結果 128 圖71 2022年被動式採樣與現地質譜之氯乙烯濃度結果 128 圖72 2022年被動式採樣與現地質譜之四氯化碳濃度結果 129 圖73 2022年被動式採樣與現地質譜之氯仿濃度結果 129 圖74 Canister與現地質譜之氯仿濃度結果 130 圖75 氯仿數據後推軌跡 130 圖76 大園工業區採樣佈點圖 131 圖77 Chloroform離子碎片層析圖 132 圖78 含氯化物之全圖譜 132 圖79 83, 62, 117離子碎片層析圖 132 圖80 (a)環境變遷研究中心 (b)地球科學研究所 (c)STS-25架設 133 圖81 中研院主要出現物種濃度 134 圖82 彰化和美高中及光化測站相對位置 134 圖83 (a) PM2.5及VOCs採樣設備 (b)MTS-32內部 135 圖84 苯每小時濃度比較及柱狀圖 136 圖85 甲苯每小時濃度比較 136 圖86 物種之同源性 137 圖87 和美高中與光化測站物種出現頻率之濃度 137 圖88 光化測站物種出現頻率之濃度 138 圖89 和美高中每天平均濃度高值物種呈現 138 圖90 (a)崙背測站地點 (b)測站鄰近工廠相對距離 139 圖91 光化測站高值圖譜 140 圖92 (a)崙背測站外觀 (b)STS-25架設位置 (c)光化ATD-GC-FID 140 圖93 光化測站圖譜 141 圖94 崙背層析圖譜 141 圖95 甲苯比對 142 圖96 採樣空管實際圖 143 圖97 濾紙填充示意圖 143 圖98 濾紙脫附溫度層析圖 145 圖99 (a)濾紙空白 (b)濾紙樣品 145 圖100 濾紙樣品層析圖 146   表目次 表1 VOCs的定義 7 表2 各國HAPs管制相關法規 10 表3 臺灣及美國HAPs排放管制及相關標準方法檢測物種清單 12 表4 特殊性工業區管制之特殊性工業 15 表5 特殊性工業區依區內容納工業需個別監測之其他空氣污染物 17 表6 特殊性工業區應監測之有機光化前驅物 18 表7 特殊性工業區應監測之有害空氣污染物 19 表8 周界VOCs國內外監測方法比較 22 表9 採樣分析方法優缺點比較 24 表10 離線式採樣分析方法統計 24 表11 NIEA A715.16B標準方法及文獻的比較 32 表12 U.S. EPA Method 325B中提及物種之吸取速率 35 表13 吸附劑的種類及性質比較 39 表14 物種之溫度、濕度與反擴散的差異a 48 表15 採樣管之適化參數 54 表16 常見系統彙整 56 表17 常用之吸附劑種類 57 表18 除水方式之比較 58 表19 目標物種相關資訊 61 表20 內標準品基本資料 65 表21 目標物種對照表 67 表22 多重床吸附材料的配置 75 表23 Carbopack X 之 R2、MDL、樣品儲存回收率、BD 76 表24 Carboxen 569 之 R2、MDL、樣品儲存回收率、BD 78 表25 Carbopack X 實驗吸取速率之溫度及相對濕度變化影響 81 表26 Carboxen 569 實驗吸取速率之溫度及相對濕度變化影響 83 表27 複合式材料配置含量 86 表28 複合式材料配置比例 87 表29 分層配置比例 88 表30 混層配置比例 88 表31 自動化熱脫附儀條件 95 表32 更換Trap之相對標準偏差比較 96 表33 檢量線相關係數 100 表34 採樣管之方法偵測極限 (ppbv) 104 表35 採樣管之精密度 106 表36 採樣管之準確度 109 表37 與文獻實驗吸取速率 112 表38 採樣管之實驗吸取速率 115 表39 採樣管之適合採集目標物種 117 表40 實驗室內之物種 124 表41 濾紙Condition最適溫度 144 表42 濾紙脫附最適溫度 144

    參考文獻
    1. 行政院環境保護署. 空氣污染防制法. 2018.
    2. 陳王琨. 台灣與美國實施空氣品質管理計畫的歷史經驗回顧. 2001.
    3. EPA US. The original list of hazardous air pollutants. 2016.
    4. 蔡俊鴻，溫麗琪，李楟貽，葉惠芬，姚永真，張立鵬. 都會區有害性空氣污染物之管制策略及效益評估子計畫：工業都會區有機性有害空氣污染物影響暨管制有效性評估研究. 2003.
    5. Burnett R, Chen H, Szyszkowicz M, Fann N, Hubbell B, Pope CA, Apte JS, Brauer M, Cohen A, Weichenthal S, Coggins J, Di Q, Brunekreef B, Frostad J, Lim SS, Kan HD, Walker KD, Thurston GD, Hayes RB, Lim CC, Turner MC, Jerrett M, Krewski D, Gapstur SM, Diver WR, Ostro B, Goldberg D, Crouse DL, Martin RV, Peters P, Pinault L, Tjepkema M, Donkelaar A, Villeneuve PJ, Miller AB, Yin P, Zhou MG, Wang LJ, Janssen NAH, Marra M, Atkinson RW, Tsang H, Thach Q, Cannon JB, Allen RT, Hart JE, Laden F, Cesaroni G, Forastiere F, Weinmayr G, Jaensch A, Nagel G, Concin H, Spadaro JV. Global estimates of mortality associated with long-term exposure to outdoor fine particulate matter. Proceedings of the National Academy of Sciences of the United States of America. 2018;115:9592-7.
    6. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change. Intergovernmental Panel on Climate Change, Climate Change 2013. 2013.
    7. Heald CL, Kroll JH. The fuel of atmospheric chemistry: Toward a complete description of reactive organic carbon. Science Advances. 2020;6.
    8. Anderson JG. Free radicals in the Earth’s atmosphere: Their measurement and interpretation. Annu Rev Phys Chem. 1987;38:489-520.
    9. Seinfeld JH. Progress and Problems in Atmospheric Chemistry. Advanced Series in Physical Chemistry. 1995;3:956.
    10. Zhang Q, Jimenez JL, Canagaratna MR, Allan JD, Coe H, Ulbrich I, Alfarra MR, Takami A, Middlebrook AM, Sun YL, Dzepina K, Dunlea E, Docherty K, DeCarlo PF, Salcedo D, Onasch T, Jayne JT, Miyoshi T, Shimono A, Hatakeyama S, Takegawa N, Kondo Y, Schneider J, Drewnick F, Borrmann S, Weimer S, Demerjian K, Williams P, Bower K, Bahreini R, Cottrell L, Griffin RJ, Rautiainen J, Sun JY, Zhang YM, Worsnop DR. Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes. Geophysical Research Letters. 2007;34.
    11. Kroll JH, Ng NL, Murphy SM, Flagan RC, Seinfeld JH. Secondary organic aerosol formation from isoprene photooxidation under high-NOx conditions. Geophysical Research Letters. 2005;32.
    12. Volkamer R, Ziemann PJ, Molina MJ. Secondary Organic Aerosol Formation from Acetylene (C2H2): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase. Atmospheric Chemistry and Physics. 2009;9:1907-28.
    13. Chan AWH, Kautzman KE, Chhabra PS, Surratt JD, Chan MN, Crounse JD, Kurten A, Wennberg PO, Flagan RC, Seinfeld JH. Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs). Atmospheric Chemistry and Physics. 2009;9:3049-60.
    14. Carlton AG, Turpin BJ, Altieri KE, Seitzinger S, Reff A, Lim HJ, Ervens B. Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments. Atmospheric Environment. 2007;41:7588-602.
    15. Yee LD, Kautzman KE, Loza CL, Schilling KA, Coggon MM, Chhabra PS, Chan MN, Chan AWH, Hersey SP, Crounse JD, Wennberg PO, Flagan RC, Seinfeld JH. Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols. Atmospheric Chemistry and Physics. 2013;13:8019-43.
    16. Lim YB, Ziemann PJ. Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx. Environmental Science & Technology. 2005;39:9229-36.
    17. A. L. Robinson NMD, M. K. Shrivastava, E. A. Weitkamp, A. M. Sage, A. P. Grieshop, T. E. Lane, J. R. Pierce, S. N. Pandis. Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging. Science. 2007;315:1259-62.
    18. Donahue NM, Robinson AL, Stanier CO, Pandis SN. Coupled partitioning, dilution, and chemical aging of semivolatile organics. Environmental Science & Technology. 2006;40:2635-43.
    19. Tolocka MP, Jang M, Ginter JM, Cox FJ, Kamens RM, Johnston MV. Formation of oligomers in secondary organic aerosol. Environmental Science & Technology. 2004;38:1428-34.
    20. Kalberer M, Paulsen D, Sax M, Steinbacher M, Dommen J, Prevot ASH, Fisseha R, Weingartner E, Frankevich V, Zenobi R, Baltensperger U. Identification of polymers as major components of atmospheric organic aerosols. Science. 2004;303:1659-62.
    21. Jimenez JL, Canagaratna MR, Donahue NM, Prevot ASH, Zhang Q, Kroll JH, DeCarlo PF, Allan JD, Coe H, Ng NL, Aiken AC, Docherty KS, Ulbrich IM, Grieshop AP, Robinson AL, Duplissy J, Smith JD, Wilson KR, Lanz VA, Hueglin C, Sun YL, Tian J, Laaksonen A, Raatikainen T, Rautiainen J, Vaattovaara P, Ehn M, Kulmala M, Tomlinson JM, Collins DR, Cubison MJ, Dunlea EJ, Huffman JA, Onasch TB, Alfarra MR, Williams PI, Bower K, Kondo Y, Schneider J, Drewnick F, Borrmann S, Weimer S, Demerjian K, Salcedo D, Cottrell L, Griffin R, Takami A, Miyoshi T, Hatakeyama S, Shimono A, Sun JY, Zhang YM, Dzepina K, Kimmel JR, Sueper D, Jayne JT, Herndon SC, Trimborn AM, Williams LR, Wood EC, Middlebrook AM, Kolb CE, Baltensperger U, Worsnop DR. Evolution of Organic Aerosols in the Atmosphere. Science. 2009;326:1525-9.
    22. Kroll JH, Lim CY, Kessler SH, Wilson KR. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon. Journal of Physical Chemistry A. 2015;119:10767-83.
    23. Molina MJ, Ivanov AV, Trakhtenberg S, Molina LT. Atmospheric evolution of organic aerosol. Geophysical Research Letters. 2004;31.
    24. Kwan AJ, Crounse JD, Clarke AD, Shinozuka Y, Anderson BE, Crawford JH, Avery MA, McNaughton CS, Brune WH, Singh HB, Wennberg PO. On the flux of oxygenated volatile organic compounds from organic aerosol oxidation. Geophysical Research Letters. 2006;33.
    25. Baird CaC, M. Environmental Chemistry. New York : WH 608. 2005.
    26. Wang L, Atkinson R, Arey J. Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C-1- and C-2-alkylnaphthalenes. Environmental Science & Technology. 2007;41:2803-10.
    27. Atkinson R. Atmospheric chemistry of VOCs and NOx. Atmospheric Environment. 2000;34:2063-101.
    28. 行政院環境保護署. 固定污染源有害空氣污染物排放標準. 2017.
    29. 陳光彥，陳藹然. 揮發與揮發性有機化合物. 科學Online. 2009.
    30. Culp TA. A reevaluation of the National Emission Standards for Hazardous Air Pollutants (NESHAP - 40 CFR 61, Subpart H) program at Sandia National Laboratories, New Mexico. 1997.
    31. EPA US. National Emission Standards for Hazardous Air Pollutants: Solvent Extraction for Vegetable Oil Production. 2001:19005-26.
    32. EPA US. Toxic Organics-1 (TO-1) Method For The Determination Of Volatile Organic Compounds In Ambient Air Using Tenax® Adsorption And Gas Chromatography/Mass Spectrometry (GC/MS). 1984.
    33. EPA US. Toxic Organics-2 (TO-2) Method For The Determination Of Volatile Organic Compounds In Ambient Air By Carbon Molecular Sieve Adsorption And Gas Chromatography/Mass Spectrometry (GC/MS). 1984.
    34. EPA US. Toxic Organics-15 (TO-15) Determination Of Volatile Organic Compounds (VOCs) In Air Collected In Specially-Prepared Canisters And Analyzed By Gas Chromatography/ Mass Spectrometry (GC/MS). 1999.
    35. EPA US. Toxic Organics-14A (TO-14A) Determination Of Volatile Organic Compounds (VOCs) In Ambient Air Using Specially Prepared Canisters With Subsequent Analysis By Gas Chromatography. 1999.
    36. EPA US. Toxic Organics-11A (TO-11A) Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC). 1999.
    37. EPA US. Toxic Organics-17 (TO-17) Compendium Method TO-17 Determination of Volatile Organic Compounds in Ambient Air Using Active Sampling Onto Sorbent Tubes. 1999.
    38. 歐盟成員國執行工業排放指令的情形. 2010.
    39. 經濟部國際貿易局. 英國政府近期制定新工業污染排放監管系統，以減少排放造成的污染. 2022.
    40. Technische Anleitung zur Reinhaltung der Luft – TA Luft. 2002;24.
    41. 蔡俊鴻，元曉琴，姚永真. 各國有害空氣污染物管制比較. 1998.
    42. 日本環境省中央環境審議会大氣環境部會. 有害大気汚染物質に該当する可能性がある物質リスト及び優先取組物質の見直し並びに有害大気汚染物質のリスクの程度に応じた対策のあり方について.
    43. 日本環境省. 大気汚染防止法. 1996.
    44. 香港環境保護署. Toxic Air Pollutant Emissions Inventory from Stationary Sources in Hong Kong. 1997.
    45. 行政院環境保護署. 廢棄物焚化爐空氣污染物排放標準. 2006.
    46. 行政院環境保護署. 揮發性有機物空氣污染管制及排放標準. 2013.
    47. 行政院環境保護署. 空氣中揮發性有機化合物檢測方法－不銹鋼採樣筒／氣相層析質譜儀法. 2014.
    48. 行政院環境保護署. 空氣中氣態有機溶劑檢驗方法－以活性碳吸附之氣相層析⁄火焰離子化偵測法. 1992.
    49. 行政院環境保護署. 空氣中氣態芳香烴化合物檢驗方法－以活性碳吸附之氣相層析／火焰離子化偵測法. 1992.
    50. 行政院環境保護署. 空氣中總揮發性有機化合物檢測方法－不銹鋼採樣筒／火焰離子化偵測法. 2006.
    51. 行政院環境保護署. 空氣中有機光化前驅物檢測方法－氣相層析／火焰離子化偵測法. 2014.
    52. 行政院環境保護署. 空氣中環氧氯丙烷、乙酸丁酯、丙烯酸乙酯及丙烯酸丁酯等揮發性有機物檢測方法－不銹鋼採樣筒／氣相層析質譜儀法. 2022.
    53. 行政院環境保護署. 特殊性工業區緩衝地帶及空氣品質監測設施設置標準. 2014.
    54. 行政院環境保護署. 氯乙烯及聚氯乙烯製造業空氣污染物管制及排放標準. 2017.
    55. 行政院環境保護署. 空氣中揮發性有機化合物檢測方法－不銹鋼採樣筒／氣相層析質譜儀. 2021.
    56. 行政院環境保護署. 固定污染源有害空氣污染物排放標準. 2021.
    57. 行政院環境保護署. 空氣品質監測網-光化背景介紹. 2022.
    58. 國立科學工藝博物館. 文物史料-產業簡史-石化業. 2009.
    59. 行政院環境保護署. 開發特殊性工業區應監測之有機光化前驅物. 2014.
    60. 行政院環境保護署. 開發特殊性工業區應監測之有害空氣污染物. 2014.
    61. 行政院環境保護署. 特殊性工業區監測. 2023.
    62. EPA US. Method for the Determination of Aldehydes and Ketones in Ambient Air Using High Performance Liquid Chromatography (HPLC). 1984.
    63. S. Inomata HT, S. Kato, J. Suthawaree, Y. Kanaya, P. Pochanart, Y. Liu, and Z. Wang. PTR-MS measurements of non-methane volatile organic compounds during an intensive field campaign at the summit of Mount Tai, China, in June 2006. 2010;10:7085-99.
    64. EPA US. Method 325A-Volatile Organic Compounds from Fugitive and Area Sources: Sampler Deployment and VOC Sample Collection. 2019.
    65. EPA US. Method 325B-Volatile Organic Compounds from Fugitive and Area Sources: Sampler Preparation and Analysis. 2019.
    66. 行政院環境保護署. 排放管道中氣態有機化合物檢測方法－採樣袋採樣/氣相層析火焰離子化偵測法. 2019.
    67. 行政院環境保護署. 排放管道中C5-C10非極性氣態有機物檢測方法－採樣袋採樣／氣相層析質譜分析法. 2007.
    68. 行政院環境保護署. 排放管道中環氧氯丙烷等氣態有機化合物檢測方法－採樣袋採樣／氣相層析火焰離子化偵測法. 2019.
    69. 行政院環境保護署. 空氣中揮發性含鹵素碳氫化合物檢驗方法－以Tenax-TA吸附劑採樣之氣相層析法. 2011.
    70. 行政院環境保護署. 周界空氣中N-甲基吡咯酮、乙二醇及異丁醇等揮發性有機物檢測方法－吸附管採樣／氣相層析質譜儀法. 2015.
    71. McGlenny WA, Pleil JD, Evans GF, Oliver KD, Holdren MW, Winberry WT. Canister-based method for monitoring toxic VOCs in ambient air. Journal of the Air & Waste Management Association. 1991;41:1308-18.
    72. Wang D, Austin C. Determination of complex mixtures of volatile organic compounds in ambient air: canister methodology. Analytical and bioanalytical chemistry. 2006;386:1099-120.
    73. EPA US. Method-18 Volatile Organic Compounds by Gas Chromatography. 2019.
    74. Wang Y, Raihala TS, Jackman AP, StJohn R. Use of Tedlar bags in VOC testing and storage: Evidence of significant VOC losses. Environmental Science & Technology. 1996;30:3115-7.
    75. McClenny WA, Oliver KD, Jacumin HH, Daughtrey EH, Whitaker DA. 24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis - laboratory studies. Journal of Environmental Monitoring. 2005;7:248-56.
    76. Martin NA, Duckworth P, Henderson MH, Swann NRW, Granshaw ST, Lipscombe RP, Goody BA. Measurements of environmental 1,3-butadiene with pumped and diffusive samplers using the sorbent Carbopack X. Atmospheric Environment. 2005;39:1069-77.
    77. Walgraeve C, Demeestere K, Dewulf J, Van Huffel K, Van Langenhove H. Diffusive sampling of 25 volatile organic compounds in indoor air: Uptake rate determination and application in Flemish homes for the elderly. Atmospheric Environment. 2011;45:5828-36.
    78. Oliver KD, Adams JR, Daughtrey EH, McClenny WA, Yoong MJ, Pardee MA, Almasi EB, Kirshen NA. Technique for monitoring toxic VOCs in air: Sorbent preconcentration, closed-cycle cooler cryofocusing and GC/MS analysis. Environmental Science & Technology. 1996;30:1939-45.
    79. Ramos TD, de la Guardia M, Pastor A, Esteve-Turrillas FA. Assessment of air passive sampling uptakes for volatile organic compounds using VERAM devices. Science of the Total Environment. 2018;619:1014-21.
    80. ASTM. Standard Practice for Choosing Sorbents, Sampling Parameters and Thermal Desorption Analytical Conditions for Monitoring Volatile Organic Chemicals in Air. 2018.
    81. Mukerjee S, Smith LA, Thoma ED, Oliver KD, Whitaker DA, Wu T, Colon M, Alston L, Cousett TA, Stallings C. Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers. Journal of the Air & Waste Management Association. 2016;66:492-8.
    82. Mukerjee S, Smith LA, Thoma ED, Whitaker DA, Oliver KD, Duvall R, Cousett TA. Spatial analysis of volatile organic compounds using passive samplers in the Rubbertown industrial area of Louisville, Kentucky, USA. Atmospheric Pollution Research. 2020;11:81-6.
    83. Kume K, Ohura T, Amagai T, Fusaya M. Field monitoring of volatile organic compounds using passive air samplers in an industrial city in Japan. Environmental Pollution. 2008;153:649-57.
    84. R.H. Brown JC, and K.J. Saunders. The development of an improved diffusive sampler. American Industrial Hygiene Association. 1981;42:865-9.
    85. Hafkenscheid TL, Mowrer J. Intercomparison of tube-type diffusive sampling for the determination of volatile hydrocarbons in ambient air. Analyst. 1996;121:1249-52.
    86. Mowrer J, Svanberg PA, Potter A, Lindskog A. Diffusive monitoring of C-6-C-9 hydrocarbons in urban air in Sweden. Analyst. 1996;121:1295-300.
    87. Gelencser A, Kiss G, Hlavay J, Hafkenscheid TL, Peters RJB, Deleer EWB. The Evalution of a Tenax GR Diffusive Sampler for the Determination of Benzene and Other Volatile Aromatics in Outdor air. Talanta. 1994;41:1095-100.
    88. Cao XL, Hewitt CN. Evaluation of Tenax-GR Adsorbent for the Passive Sampling of Volatile Organic-Compounds at Low Concentrations. Atmospheric Environment Part a-General Topics. 1993;27:1865-72.
    89. Gallego E, Roca FJ, Perales JF, Gadea E. Outdoor air 1,3-butadiene monitoring near a petrochemical industry (Tarragona region) and in several Catalan urban areas using active multi-sorbent bed tubes and analysis through TD-GC/MS. Science of the Total Environment. 2018;618:1440-8.
    90. Thoma ED, Miller MC, Chung KC, Parsons NL, Shine BC. Facility Fence-Line Monitoring Using Passive Samplers. Journal of the Air & Waste Management Association. 2011;61:834-42.
    91. Eisele AP, Mukerjee S, Smith LA, Thoma ED, Whitaker DA, Oliver KD, Wu T, Colon M, Alston L, Cousett TA, Miller MC, Smith DM, Stallings C. Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers. Journal of the Air & Waste Management Association. 2016;66:412-9.
    92. Mukerjee S, Smith LA, Caudill MP, Oliver KD, Whipple W, Whitaker DA, Cousett TA. Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting, Indiana. Journal of the Air & Waste Management Association. 2018;68:170-5.
    93. Vallecillos L, Maceira A, Marce RM, Borrull F. Evaluation of active sampling strategies for the determination of 1,3-butadiene in air. Atmospheric Environment. 2018;176:21-9.
    94. Oliver KD, Cousett TA, Whitaker DA, Smith LA, Mukerjee S, Stallings C, Thoma ED, Alston L, Colon M, Wu T, Henkle S. Sample integrity evaluation and EPA method 325B interlaboratory comparison for select volatile organic compounds collected diffusively on Carbopack X sorbent tubes. Atmospheric Environment. 2017;163:99-106.
    95. Woolfenden E. Sorbent-based sampling methods for volatile and semi-volatile organic compounds in air Part 1: Sorbent-based air monitoring options. Journal of Chromatography A. 2010;1217:2674-84.
    96. Woolfenden E. Sorbent-based sampling methods for volatile and semi-volatile organic compounds in air. Part 2. Sorbent selection and other aspects of optimizing air monitoring methods. Journal of Chromatography A. 2010;1217:2685-94.
    97. Helmig D. Air analysis by gas chromatography. Journal of Chromatography A. 1999;843:129-46.
    98. Sakurai K, Miyake Y, Amagai T. Reliable passive-sampling method for determining outdoor 1,3-butadiene concentrations in air. Atmospheric Environment. 2013;80:198-203.
    99. Brown VM, Crump DR, Gardiner D, Yu CWF. LONG-TERM DIFFUSIVE SAMPLING OF VOLATILE ORGANIC-COMPOUNDS IN INDOOR AIR. Environmental Technology. 1993;14:771-7.
    100. Martin NA, Marlow DJ, Henderson MH, Goody BA, Quincey PG. Studies using the sorbent Carbopack X for measuring environmental benzene with Perkin-Elmer-type pumped and diffusive samplers. Atmospheric Environment. 2003;37:871-9.
    101. ISO. Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography-Part2: Diffusive sampling. 16017-2. 2003.
    102. 行政院環境保護署. 固定污染源有害空氣污染物健康風險評估作業方式. 2019.
    103. 行政院環境保護署. 固定污染源有害空氣污染物健康風險評估作業方式總說明. 2018.
    104. Gallego E, Teixidor P, Roca FJ, Perales JF, Gadea E. Outdoor air 1,3-butadiene monitoring: Comparison of performance of Radiello (R) passive samplers and active multi-sorbent bed tubes. Atmospheric Environment. 2018;182:9-16.
    105. Lee YH. A wide range of toxic VOCs measured by dual-sorbent passive sampling with validation by field online measurements. Environmental Pollution. 2022;314.
    106. 行政院環境保護署. 環境檢驗檢量線製備及查核指引(NIEA-PA103). 2018.
    107. 行政院環境保護署. 環境檢驗方法偵測極限測定指引(NIEA-PA107). 2018.
    108. 自由時報. 仁大工業區空污 四區致癌風險高. 2016.
    109. Chu CH. On-line thermal desorption (TD)-GC/MS analysis of hazardous air pollutants (HAPs). 2020.
    110. Tseng MH. Effect of Aperture Size of the Drawout Plate in GC-MS on the Measurement Stability of Hazardous Air Pollutants. 2021.

    QR CODE
    :::