環保專案成果報告查詢系統

專案計畫編號
經費年度	108
計畫經費	2,800 千元
專案開始日期	2019/03/29
專案結束日期	2019/12/31
專案主持人	許逸群
主辦單位	環檢所
承辦人	方建翔
執行單位	崑山科技大學
專案分類	環境監測及檢測
中文關鍵字	有害空氣污染物，串聯質譜儀，聯苯胺
英文關鍵字	Hazardous Air Pollutants, the tandem mass spectrometer, Benzidine
協同主持人	鄭景智
共同主持人
計畫聯絡人	蘇珮甄
計畫聯絡電話	06-2055952#
計畫聯絡信箱	kksn5488@gmail.com

中文摘要	環保署於民國108年預告「固定污染源有害空氣污染物排放標準」(草案)，其中針對72項重要有害空氣污染物，擬依三階段期程制定其固定污染源排放標準，故本計畫乃參考採樣方法NIEA A807、method 10及分析方法method 8270E，針對硝苯、鄰苯二甲酸二(2-乙基己基)酯、六氯乙烷、聯苯胺、4,4'-亞甲雙(2-氯苯胺)、六氯苯、多氯聯苯等空氣污染物進行調查技術之研究開發。本計畫規劃探討前述污染物相關採集效率、層析儀器最佳化分析條件、適用濃度範圍、保存條件等，建立合宜之調查技術作業程序。並依循環保署環境檢驗所所訂之「環境檢測標準方法驗證程序準則」針對所建立的調查技術進行評估，包括檢量線建立、方法偵測極限測定、品保品管規範（如準確度及精密度）建立及真實樣品採樣、樣品前處理及分析測定等。最後根據計畫執行調查技術建立成效，於期末報告須提出符合環保署環境檢驗所方法格式規範之排放管道中前述污染物調查技術草案。計畫初期，各待測物於先行參考NIEA M731方法採用GC/MS進行測試，在檢量線部分，經以內標準品進行校正 (感應因子校正法)所得結果，各待測物相對標準偏差RSD(%)結果皆能符合方法技術上可接受之規定(< 30%)。由目前GC/MS偵測極限結果比對本計畫預估之排放管道管制標準，顯示多氯聯苯、4,4'-亞甲雙(2-氯苯胺)與六氯苯測試結果尚無法滿足所定(周界距離1公尺計算後之條件)管制標準的需求。為使本計畫能夠達到更佳的成果，因此本計畫乃參考Method 8270E建議方式，以串聯質譜儀（GC / MS / MS）進行分析條件的測試。在GC/MS/MS測試成果部分，各待測物之檢量線建立結果顯示，除聯苯胺(Benzidine)外，其餘待測物之相對標準偏差RSD(%)結果皆能符合方法技術上可接受之規定(<30%)，而聯苯胺部分，參考NIEA M731方法中亦有提及，聯苯胺容易因溶劑濃縮時氧化而使濃度減少，造成其圖譜不佳之情形發生。GC/MS/MS測試同時亦探討及測試待測物與萃取溶劑(二氯甲烷及甲苯)及採樣吸附介質(XAD2)之間相互影響與萃取效益之關聯性，試驗結果顯示二氯甲烷相對甲苯溶劑有相對較佳之萃取回收率，且多數之標準品可達到預期的回收率，目前僅Benzidine及MOCA在使用二氯甲烷萃取後經GC/MS/MS分析結果回收率仍較差，而參考文獻中亦指出Benzidine及MOCA採用NIEA M731方法前處理過程，會有圖譜無再現性、貯存時會氧化及低感應等情形，因此後續嘗試參考行政院勞工委員會CLA 2101方法進行測試。 Benzidine及MOCA經參考委會CLA 2101方法採用甲醇(含0.17%二乙胺)為脫附劑，並以HPLC/UV進行分析下，二種化合物聯苯胺(80.0%~97.1%)及4,4'-亞甲雙(2-氯苯胺) (97.8%~110.2%)皆有良好的回收率，然而4,4'-亞甲雙(2-氯苯胺)MDL值仍無法滿足所定(周界距離5公尺計算後之條件)管制標準的需求，因此本計畫建議可運用HPLC/MS/MS進一步測定之，以獲得較低之MDL。另外，本計畫亦運用上述調查技術開發之採樣及分析條件，完成國內工廠4場次排放管道之硝苯等7種空氣污染物實廠調查，雖部分樣品因實場廢氣較為複雜而影響到定量外，多數的待測物經由實廠驗證可知本計畫調查技術開發之可行性。此外，計畫執行期間(108年6月、10月)分別視方法開發進度成果完成兩場次調查技術擴散課程，並提出2項排放管道空氣有機污染物方法調查技術草案，提供日後環保署檢測技術援引之參考。
中文關鍵字	有害空氣污染物，串聯質譜儀，聯苯胺

中文摘要

環保署於民國108年預告「固定污染源有害空氣污染物排放標準」(草案)，其中針對72項重要有害空氣污染物，擬依三階段期程制定其固定污染源排放標準，故本計畫乃參考採樣方法NIEA A807、method 10及分析方法method 8270E，針對硝苯、鄰苯二甲酸二(2-乙基己基)酯、六氯乙烷、聯苯胺、4,4'-亞甲雙(2-氯苯胺)、六氯苯、多氯聯苯等空氣污染物進行調查技術之研究開發。本計畫規劃探討前述污染物相關採集效率、層析儀器最佳化分析條件、適用濃度範圍、保存條件等，建立合宜之調查技術作業程序。並依循環保署環境檢驗所所訂之「環境檢測標準方法驗證程序準則」針對所建立的調查技術進行評估，包括檢量線建立、方法偵測極限測定、品保品管規範（如準確度及精密度）建立及真實樣品採樣、樣品前處理及分析測定等。最後根據計畫執行調查技術建立成效，於期末報告須提出符合環保署環境檢驗所方法格式規範之排放管道中前述污染物調查技術草案。計畫初期，各待測物於先行參考NIEA M731方法採用GC/MS進行測試，在檢量線部分，經以內標準品進行校正 (感應因子校正法)所得結果，各待測物相對標準偏差RSD(%)結果皆能符合方法技術上可接受之規定(< 30%)。由目前GC/MS偵測極限結果比對本計畫預估之排放管道管制標準，顯示多氯聯苯、4,4'-亞甲雙(2-氯苯胺)與六氯苯測試結果尚無法滿足所定(周界距離1公尺計算後之條件)管制標準的需求。為使本計畫能夠達到更佳的成果，因此本計畫乃參考Method 8270E建議方式，以串聯質譜儀（GC / MS / MS）進行分析條件的測試。在GC/MS/MS測試成果部分，各待測物之檢量線建立結果顯示，除聯苯胺(Benzidine)外，其餘待測物之相對標準偏差RSD(%)結果皆能符合方法技術上可接受之規定(<30%)，而聯苯胺部分，參考NIEA M731方法中亦有提及，聯苯胺容易因溶劑濃縮時氧化而使濃度減少，造成其圖譜不佳之情形發生。GC/MS/MS測試同時亦探討及測試待測物與萃取溶劑(二氯甲烷及甲苯)及採樣吸附介質(XAD2)之間相互影響與萃取效益之關聯性，試驗結果顯示二氯甲烷相對甲苯溶劑有相對較佳之萃取回收率，且多數之標準品可達到預期的回收率，目前僅Benzidine及MOCA在使用二氯甲烷萃取後經GC/MS/MS分析結果回收率仍較差，而參考文獻中亦指出Benzidine及MOCA採用NIEA M731方法前處理過程，會有圖譜無再現性、貯存時會氧化及低感應等情形，因此後續嘗試參考行政院勞工委員會CLA 2101方法進行測試。 Benzidine及MOCA經參考委會CLA 2101方法採用甲醇(含0.17%二乙胺)為脫附劑，並以HPLC/UV進行分析下，二種化合物聯苯胺(80.0%~97.1%)及4,4'-亞甲雙(2-氯苯胺) (97.8%~110.2%)皆有良好的回收率，然而4,4'-亞甲雙(2-氯苯胺)MDL值仍無法滿足所定(周界距離5公尺計算後之條件)管制標準的需求，因此本計畫建議可運用HPLC/MS/MS進一步測定之，以獲得較低之MDL。另外，本計畫亦運用上述調查技術開發之採樣及分析條件，完成國內工廠4場次排放管道之硝苯等7種空氣污染物實廠調查，雖部分樣品因實場廢氣較為複雜而影響到定量外，多數的待測物經由實廠驗證可知本計畫調查技術開發之可行性。此外，計畫執行期間(108年6月、10月)分別視方法開發進度成果完成兩場次調查技術擴散課程，並提出2項排放管道空氣有機污染物方法調查技術草案，提供日後環保署檢測技術援引之參考。

中文關鍵字

有害空氣污染物，串聯質譜儀，聯苯胺

類型	檔名	檔案大小	說明	最新版公開日期
期末報告	專案成果上傳(期末定稿版).pdf	4MB		2020/1/1 上午 12:00:00

摘要	The Environmental Protection Administration Executive Yuan announced the “Emission Standards for Hazardous Air Pollutants from Stationary Pollution Sources” (draft) in 2019. There are 72 important hazardous air pollutants planned to develop the emission standards according to a three-stage schedule. The research method is based on NIEA A807, Method 10, and Method 8270E for sampling and analytical development of Nitrobenzene, Bis(2-ethylhexyl)phthalate, Hexachloroethane, Benzidine, 4,4'-Methylenebis(2-chloroaniline), Hexachlorobenzene, and Polychlorinated biphenyl. The project aims to establish appropriate survey technology of the aforementioned pollutants, and the factors of collection efficiency, chromatography instrument optimization analysis conditions, applicable concentration range, storage conditions, and possible interference and removal methods caused by moisture, etc. should be considered. And then the research must be evaluated according to the "Environmental Testing Standard Method Verification Procedures Guidelines" set by the Environmental Analysis Laboratory, EPA. In the final report, the draft of development of sampling and analytical methods for semi-volatile organic compounds in stacks must be proposed, and that meets the specifications of the method format. In the beginning, each analyte was tested by GC/MS with reference to the NIEA M731 method. The calibration curve was verified by internal standard, and the results show that the standard deviation (RSD %) complies with the technically acceptable requirements of the method (<30%). Nevertheless, the results of detection limit compared with the project's estimated emission standards, showing that PCBs, 4,4'-Methylenebis(2-chloroaniline) and Hexachlorobenzene didn't meet the requirements of the regulatory standards (after calculation of the perimeter distance of 1 meter). To achieve better results, this research is based on the recommended method of Method 8270E, and the tandem mass spectrometer (GC/MS/MS) is used to test the analytical conditions. The tandem mass spectrometer (GC/MS/MS) test results of the calibration curve show that the relative standard deviation (RSD %) complies with the technically acceptable requirements of the method (<30%), except for Benzidine. Referred to NIEA M731 method, the concentration of Benzidine is prone to reduce due to oxidation when the solvent is concentrated, resulting in its poor spectrum. The GC/MS/MS test results show that Dichloromethane has a better extraction recovery rate than Toluene. Currently, only Benzidine and MOCA are still poor in GC/MS/MS analysis after extraction with Dichloromethane. It also pointed out that the pretreatment process of Benzidine and MOCA may have non-repeatable spectrum, oxidation and low sensitivity during storage, therefore, CLA 2101 method of the Labor Commission of the Executive Yuan is referred to test. Referring to CLA 2101 method, Benzidine and MOCA used Methanol (containing 0.17% Diethylamine) as the desorbent and then were analyzed by HPLC/UV. There are great recovery rate that Benzidine and 4,4'-Methylenebis(2-chloroaniline) reach 80.0 ~ 97.1% and 97.8 ~ 110.2% respectively. However, the MDL of 4,4'-Methylenebis(2-chloroaniline) cannot meet the requirements of regulatory standards (the distance is 5 meters). Thus, a further suggestion is to use HPLC/MS/MS to obtaining a lower MDL. There are 4 samplings of stacks in the domestic factory completed. Although some samples are affected by the complexity of the exhaust gas affecting quantitative and DEHP needs to further confirm the storage conditions, the outcomes indicate the viable development of investigative techniques. Besides, two sessions of technological diffusion were held in June and October 2019 respectively. In conclusion, the draft program of sampling and analytical methods for semi-volatile organic compounds in stacks is proposed to provide future reference of the detection technology.
英文關鍵字	Hazardous Air Pollutants, the tandem mass spectrometer, Benzidine

摘要

The Environmental Protection Administration Executive Yuan announced the “Emission Standards for Hazardous Air Pollutants from Stationary Pollution Sources” (draft) in 2019. There are 72 important hazardous air pollutants planned to develop the emission standards according to a three-stage schedule. The research method is based on NIEA A807, Method 10, and Method 8270E for sampling and analytical development of Nitrobenzene, Bis(2-ethylhexyl)phthalate, Hexachloroethane, Benzidine, 4,4'-Methylenebis(2-chloroaniline), Hexachlorobenzene, and Polychlorinated biphenyl. The project aims to establish appropriate survey technology of the aforementioned pollutants, and the factors of collection efficiency, chromatography instrument optimization analysis conditions, applicable concentration range, storage conditions, and possible interference and removal methods caused by moisture, etc. should be considered. And then the research must be evaluated according to the "Environmental Testing Standard Method Verification Procedures Guidelines" set by the Environmental Analysis Laboratory, EPA. In the final report, the draft of development of sampling and analytical methods for semi-volatile organic compounds in stacks must be proposed, and that meets the specifications of the method format. In the beginning, each analyte was tested by GC/MS with reference to the NIEA M731 method. The calibration curve was verified by internal standard, and the results show that the standard deviation (RSD %) complies with the technically acceptable requirements of the method (<30%). Nevertheless, the results of detection limit compared with the project's estimated emission standards, showing that PCBs, 4,4'-Methylenebis(2-chloroaniline) and Hexachlorobenzene didn't meet the requirements of the regulatory standards (after calculation of the perimeter distance of 1 meter). To achieve better results, this research is based on the recommended method of Method 8270E, and the tandem mass spectrometer (GC/MS/MS) is used to test the analytical conditions. The tandem mass spectrometer (GC/MS/MS) test results of the calibration curve show that the relative standard deviation (RSD %) complies with the technically acceptable requirements of the method (<30%), except for Benzidine. Referred to NIEA M731 method, the concentration of Benzidine is prone to reduce due to oxidation when the solvent is concentrated, resulting in its poor spectrum. The GC/MS/MS test results show that Dichloromethane has a better extraction recovery rate than Toluene. Currently, only Benzidine and MOCA are still poor in GC/MS/MS analysis after extraction with Dichloromethane. It also pointed out that the pretreatment process of Benzidine and MOCA may have non-repeatable spectrum, oxidation and low sensitivity during storage, therefore, CLA 2101 method of the Labor Commission of the Executive Yuan is referred to test. Referring to CLA 2101 method, Benzidine and MOCA used Methanol (containing 0.17% Diethylamine) as the desorbent and then were analyzed by HPLC/UV. There are great recovery rate that Benzidine and 4,4'-Methylenebis(2-chloroaniline) reach 80.0 ~ 97.1% and 97.8 ~ 110.2% respectively. However, the MDL of 4,4'-Methylenebis(2-chloroaniline) cannot meet the requirements of regulatory standards (the distance is 5 meters). Thus, a further suggestion is to use HPLC/MS/MS to obtaining a lower MDL. There are 4 samplings of stacks in the domestic factory completed. Although some samples are affected by the complexity of the exhaust gas affecting quantitative and DEHP needs to further confirm the storage conditions, the outcomes indicate the viable development of investigative techniques. Besides, two sessions of technological diffusion were held in June and October 2019 respectively. In conclusion, the draft program of sampling and analytical methods for semi-volatile organic compounds in stacks is proposed to provide future reference of the detection technology.

英文關鍵字

Hazardous Air Pollutants, the tandem mass spectrometer, Benzidine