環保專案成果報告查詢系統

專案計畫編號	EPA154110003
經費年度	110
計畫經費	2,830 千元
預算科目	固定污染源管制
專案開始日期	2021/01/29
專案結束日期	2021/12/31
專案主持人	王介亨
主辦單位	環檢所
承辦人	陳孟宜
執行單位	錦雲技術開發有限公司
專案分類	大氣空氣
中文關鍵字	現地質譜、擴散式採樣、有害空氣污染物
英文關鍵字	Diffusive Sampling, Online-GCMS, Hazardous Air Pollutants
協同主持人
共同主持人
計畫聯絡人	楊雅宜
計畫聯絡電話	886-0919192855#
計畫聯絡信箱	yeyi19970927@gmail.com

中文摘要	計畫目標是針對周界環境中若干有機性有害空氣污染物 (Hazardous air pollutants, HAPs) 開發兩種監測技術，分別為:1. 現地質譜技術，2. 擴散式採樣技術。在現地質譜技術部分主要針對空氣中揮發性有機物四氯甲烷等物質和前一計畫之物種，執行方式主要是以NIEA A715.16B標準方法為基礎，藉由線上熱脫附氣相層析質譜技術 (on-line thermal desorption Online TD-GC/MS，簡稱on-line TD-GC/MS) 連續監測空氣中31種有機有害空氣污染物 (Hazardous air pollutants, HAPs)。監測周界環境中HAPs，進行現地質譜監測調查技術的開發精進，目標完成兩場次各45天連續監測。將空氣中揮發性有機物丙酮等現地質譜監測調查技術開發計畫 (前一期計畫) 所建立完成之優化品保/品管條件，進行兩場污染物現地定點監測調查工作，並將實場連續監測數據與採樣罐離線式方式 (NIEA A715.16B)、PTR-MS數據進行比對，以三種方法交互驗證，確立Online TD-GC/MS方法的可靠性及正確性。在兩場次各45天連續監測期間，監測到物種高值稱之為特殊事件，例如氯乙烯伴隨著1,2-二氯乙烷同時出現高值的特殊事件；其他如1,3-丁二烯、丙烯腈和苯乙烯雖然出現濃度沒有氯乙烯高，但仍在同樣時段均出現濃度高值，這些事件推測與附近的塑化工業區有相當大的關聯。在計畫執行過程中，我們更在延長GC/MS離子源壽命上取得巨大的成就，所有的努力都圍繞在減少水氣的干擾。這些努力包含樣品和內標的進樣體積測試、離子源類型及drawout pate孔徑的選擇、分流比例及調機方式等。最終我們連續監測時間可長達兩週以上。在擴散式採樣技術開發部分，參考多種國外方法及文獻，如U.S. EPA Method 325A/B、ASTM、ISO等標準方法及載於Atmospheric Environment、Science of the Total Environment等文獻之採樣技術，並在本計畫中進行驗證與總結。本計畫使用全離子掃描 (Total Ion Chromatogram, TIC) 經由TD-GC/MS分析擴散式採集樣品，採用Carbopack X、Carboxen 569和Tenax GR三種吸附材以覆蓋計畫要求的目標HAPs物種。本研究的核心技術是建立一套暴露系統以進行個別HAPs目標分析物吸取速率 (Uptake rate) 之測定，並可調控溫濕度與標氣濃度，以求取在不同溫濕度條件下之吸取速率變化。檢量線相關係數R2值介於0.990至0.999；方法偵測極限部分，Carbopack X採樣管針對12項目標物種介於0.20至0.45 ppb間；Carboxen 569採樣管針對9項目標物種則介於0.06至1.01 ppb之間；Tenax GR採樣管針對5項目標物種的方法偵測極限介於0.16至0.57 ppb之間。樣品保存之結果顯示Carbopack X採樣管針對12目標物種介於81-125%之間；Carboxen 569採樣管針對9目標物種介於74-101%之間，擴散式採樣後之採樣管樣品須保存於6℃環境中，並於7天內分析完畢。本計畫開發的現地質譜及擴散式採樣兩種技術可精準測得有機HAPs物種即時濃度及長期暴露濃度，透過即時特殊事件搭配氣象條件可追查排放源、透過擴散式採樣可獲得長時間暴露濃度提供健康風險評估之基本數據。這兩種技術在過去三年中已成功執行並多次驗證，並已被認可準備好成為環保署環檢所後續政策擬定參考。
中文關鍵字	現地質譜、擴散式採樣、有害空氣污染物

中文摘要

計畫目標是針對周界環境中若干有機性有害空氣污染物 (Hazardous air pollutants, HAPs) 開發兩種監測技術，分別為:1. 現地質譜技術，2. 擴散式採樣技術。在現地質譜技術部分主要針對空氣中揮發性有機物四氯甲烷等物質和前一計畫之物種，執行方式主要是以NIEA A715.16B標準方法為基礎，藉由線上熱脫附氣相層析質譜技術 (on-line thermal desorption Online TD-GC/MS，簡稱on-line TD-GC/MS) 連續監測空氣中31種有機有害空氣污染物 (Hazardous air pollutants, HAPs)。監測周界環境中HAPs，進行現地質譜監測調查技術的開發精進，目標完成兩場次各45天連續監測。將空氣中揮發性有機物丙酮等現地質譜監測調查技術開發計畫 (前一期計畫) 所建立完成之優化品保/品管條件，進行兩場污染物現地定點監測調查工作，並將實場連續監測數據與採樣罐離線式方式 (NIEA A715.16B)、PTR-MS數據進行比對，以三種方法交互驗證，確立Online TD-GC/MS方法的可靠性及正確性。在兩場次各45天連續監測期間，監測到物種高值稱之為特殊事件，例如氯乙烯伴隨著1,2-二氯乙烷同時出現高值的特殊事件；其他如1,3-丁二烯、丙烯腈和苯乙烯雖然出現濃度沒有氯乙烯高，但仍在同樣時段均出現濃度高值，這些事件推測與附近的塑化工業區有相當大的關聯。在計畫執行過程中，我們更在延長GC/MS離子源壽命上取得巨大的成就，所有的努力都圍繞在減少水氣的干擾。這些努力包含樣品和內標的進樣體積測試、離子源類型及drawout pate孔徑的選擇、分流比例及調機方式等。最終我們連續監測時間可長達兩週以上。在擴散式採樣技術開發部分，參考多種國外方法及文獻，如U.S. EPA Method 325A/B、ASTM、ISO等標準方法及載於Atmospheric Environment、Science of the Total Environment等文獻之採樣技術，並在本計畫中進行驗證與總結。本計畫使用全離子掃描 (Total Ion Chromatogram, TIC) 經由TD-GC/MS分析擴散式採集樣品，採用Carbopack X、Carboxen 569和Tenax GR三種吸附材以覆蓋計畫要求的目標HAPs物種。本研究的核心技術是建立一套暴露系統以進行個別HAPs目標分析物吸取速率 (Uptake rate) 之測定，並可調控溫濕度與標氣濃度，以求取在不同溫濕度條件下之吸取速率變化。檢量線相關係數R2值介於0.990至0.999；方法偵測極限部分，Carbopack X採樣管針對12項目標物種介於0.20至0.45 ppb間；Carboxen 569採樣管針對9項目標物種則介於0.06至1.01 ppb之間；Tenax GR採樣管針對5項目標物種的方法偵測極限介於0.16至0.57 ppb之間。樣品保存之結果顯示Carbopack X採樣管針對12目標物種介於81-125%之間；Carboxen 569採樣管針對9目標物種介於74-101%之間，擴散式採樣後之採樣管樣品須保存於6℃環境中，並於7天內分析完畢。本計畫開發的現地質譜及擴散式採樣兩種技術可精準測得有機HAPs物種即時濃度及長期暴露濃度，透過即時特殊事件搭配氣象條件可追查排放源、透過擴散式採樣可獲得長時間暴露濃度提供健康風險評估之基本數據。這兩種技術在過去三年中已成功執行並多次驗證，並已被認可準備好成為環保署環檢所後續政策擬定參考。

中文關鍵字

現地質譜、擴散式採樣、有害空氣污染物

類型	檔名	檔案大小	說明	最新版公開日期
期末報告	期末報告(上傳).pdf	11MB		2022/1/1 上午 12:00:00

摘要	This project is purposed to develop monitoring techniques for ambient organic Hazardous Air Pollutants (HAPs), i.e., 1. on-line in-field gas chromatography mass spectrometry (GC/MS), 2. diffusive sampling. The on-line GC/MS technique is aimed to analyze a large variety of ambient organic HAPs including carbon tetrachloride. The method is derived from NIEA A715.16B employing thermal desorption (TD) coupled with GC/MS to form an on-line technique, denoted as TD-GC/MS which is capable of measuring 31 target organic HAPs along with other numerous hazardous compounds. This technique had been deployed in the field for over 45 days of continuous monitoring with hourly resolution. For method validation multiple existing techniques, such as NIEA A715.16B and PTR-MS, were employed in the project to demonstrate the robustness of the TD-GC/MS method. The comparison showed extremely high agreement between the three techniques. During the 45 days of continuous monitoring elevated concentrations called episodes or spikes for selected target HAPs were frequently observed. For instance, vinyl chloride and 1,2-dichloroethane were found to exhibit similar variability. Other target HAPs such as 1,3-butadiene, acrylonitrile, and styrene also showed frequent concentration spikes, though not as high as vinyl chloride. These spikes are thought to have strong linkage to the plastic related factories in the neighboring industrial parks. Our past efforts in extending the lifetime of the ion source in the GC/MS have resulted in great success. These efforts include the test of optimal sampling volume, the quality control based on internal standards, the selection of ion source type, MS tuning recipes, the aperture of the draw out plate, etc. We found that reducing water vapor plays a critical role in extending the lifetime of the ion source and thus allows continuous monitoring for at least two weeks. With regard to the development of diffusive sampling technique, it is based on multiple international methods, such as U.S. EPA Method 325A/B, ASTM and ISO, as well as renowned journal papers from Atmospheric Environment and Science of the Total Environment. These research papers have been reviewed and summarized in this report. The diffusive samples are analyzed by TD-GC/MS using the mode of Total Ion Chromatogram (TIC). The selection of the sorption tubes was successfully assessed by this project to include the use of Carbopack X, Carboxen 569 and Tenax GR to cover a wide range of target HAPs as required by NIEA. The core technique of the diffusive sampling lies in the test of an exposure chamber to evaluate the uptake rates for individual target HAPs at different temperatures and humidities. The correlation coefficients for the target HAPs ranged from 0.990 to 0.999. In terms of the method detection limits, the Carbopack X sampling ranged from 0.20 to 0.45 ppb for 12 target species. The Carboxen 569 ranged from 0.06 to 1.01 ppb for 9 target species, and Tenax GR added another five target species between 0.16 to 0.57 ppb. The test of sample storage suggests that Carpack X for the 12 target species showed recoveries between 81- 125%, Carboxen showed 74 - 101% for 9 target species. The samples should be stored at 6℃ and analyzed within a week. These two techniques, i.e., on-line TD-GC/MS and diffusive sampling, developed in this project allow precise capture of the concentration spikes of organic HAPs, as well as their long-term exposure in a given environment, based on which more accurate and realistic risk assessment can be performed. By coupling spikes and chemical composition with local wind data, emission source investigation becomes much more straightforward. These two techniques have been successfully executed and validated over the past three years and are deemed ready to serve as compendium methods of NIEA.
英文關鍵字	Diffusive Sampling, Online-GCMS, Hazardous Air Pollutants

摘要

This project is purposed to develop monitoring techniques for ambient organic Hazardous Air Pollutants (HAPs), i.e., 1. on-line in-field gas chromatography mass spectrometry (GC/MS), 2. diffusive sampling. The on-line GC/MS technique is aimed to analyze a large variety of ambient organic HAPs including carbon tetrachloride. The method is derived from NIEA A715.16B employing thermal desorption (TD) coupled with GC/MS to form an on-line technique, denoted as TD-GC/MS which is capable of measuring 31 target organic HAPs along with other numerous hazardous compounds. This technique had been deployed in the field for over 45 days of continuous monitoring with hourly resolution. For method validation multiple existing techniques, such as NIEA A715.16B and PTR-MS, were employed in the project to demonstrate the robustness of the TD-GC/MS method. The comparison showed extremely high agreement between the three techniques. During the 45 days of continuous monitoring elevated concentrations called episodes or spikes for selected target HAPs were frequently observed. For instance, vinyl chloride and 1,2-dichloroethane were found to exhibit similar variability. Other target HAPs such as 1,3-butadiene, acrylonitrile, and styrene also showed frequent concentration spikes, though not as high as vinyl chloride. These spikes are thought to have strong linkage to the plastic related factories in the neighboring industrial parks. Our past efforts in extending the lifetime of the ion source in the GC/MS have resulted in great success. These efforts include the test of optimal sampling volume, the quality control based on internal standards, the selection of ion source type, MS tuning recipes, the aperture of the draw out plate, etc. We found that reducing water vapor plays a critical role in extending the lifetime of the ion source and thus allows continuous monitoring for at least two weeks. With regard to the development of diffusive sampling technique, it is based on multiple international methods, such as U.S. EPA Method 325A/B, ASTM and ISO, as well as renowned journal papers from Atmospheric Environment and Science of the Total Environment. These research papers have been reviewed and summarized in this report. The diffusive samples are analyzed by TD-GC/MS using the mode of Total Ion Chromatogram (TIC). The selection of the sorption tubes was successfully assessed by this project to include the use of Carbopack X, Carboxen 569 and Tenax GR to cover a wide range of target HAPs as required by NIEA. The core technique of the diffusive sampling lies in the test of an exposure chamber to evaluate the uptake rates for individual target HAPs at different temperatures and humidities. The correlation coefficients for the target HAPs ranged from 0.990 to 0.999. In terms of the method detection limits, the Carbopack X sampling ranged from 0.20 to 0.45 ppb for 12 target species. The Carboxen 569 ranged from 0.06 to 1.01 ppb for 9 target species, and Tenax GR added another five target species between 0.16 to 0.57 ppb. The test of sample storage suggests that Carpack X for the 12 target species showed recoveries between 81- 125%, Carboxen showed 74 - 101% for 9 target species. The samples should be stored at 6℃ and analyzed within a week. These two techniques, i.e., on-line TD-GC/MS and diffusive sampling, developed in this project allow precise capture of the concentration spikes of organic HAPs, as well as their long-term exposure in a given environment, based on which more accurate and realistic risk assessment can be performed. By coupling spikes and chemical composition with local wind data, emission source investigation becomes much more straightforward. These two techniques have been successfully executed and validated over the past three years and are deemed ready to serve as compendium methods of NIEA.

英文關鍵字

Diffusive Sampling, Online-GCMS, Hazardous Air Pollutants