環境基質中溴化戴奧辛及多溴聯苯醚之高解析度氣相層析質譜分析

High-Resolution Gas Chromatography-Mass Spectrometric Analysis for PBDD/PBDF/PBDE in Environmental Matrices

彭瑞華(Jui-Hwa Peng)

指導教授 ： 鄭建業 ； 黃金旺

中原大學/理學院/化學研究所/碩士(2002年)

https://doi.org/10.6840/cycu200200520

摘要

難燃劑廣泛的使用在紡織品、塑膠、建築材料、電子電器產品及家庭用品上以減少燃燒的發生。溴化難燃劑是目前使用最廣範的難燃劑，包含polybrominated diphenylethers (PBDEs)、polybrominated biphenyls (PBBs)、 tetrabromobisphenol及hexabromodiphenyl cyclododecane等。商品化的PBDE難燃劑主要包含 penta-、octa-及decabromo diphenylethers (PeBDEs、OBDEs 及DeBDEs)，而最近研究指出作用在甲狀腺之PBDEs屬內分泌干擾物質，同時也會影響肝功能及神經免疫系統等。溴化難燃劑的使用，產生許多含有溴化難燃劑的廢棄物，這些廢棄物再經焚化後即可能產生溴化戴奧辛(Polybrominated dibenzo-p-dioxins/Polybrominated dibenzofurans，PBDDs/PBDFs)對環境造成污染，本研究最主要目的是尋找適合的淨化過程以完全分離PBDEs及PBDDs/ PBDFs。再以高解析度氣相層析質譜儀進行分析都市型垃圾焚化廠煙道氣樣品、電弧爐煉鋼廠煙道氣樣品、都市型垃圾焚化廠飛灰、底灰及反應灰樣品、農地土壤樣品及河川魚肉樣品等。
淨化測試過程包含多層矽膠管柱淨化、酸性矽膠管柱淨化、硝酸銀矽膠管柱淨化、酸性氧化鋁管柱淨化及活性碳管柱淨化等。分析結果酸性矽膠管柱適合進行PBDEs淨化，但對PBDEs及PBDDs/ PBDFs無任何分離效果。硝酸銀矽膠管柱不適合進行PBDEs及PBDDs/ PBDFs淨化。酸性氧化鋁管柱無法完全分離PBDEs及PBDDs/ PBDFs，活性碳管柱可以完全分離PBDEs及PBDDs/ PBDFs。真實樣品之氣相質譜分析結果顯示PBDEs在所有測試樣品中均可檢測出，其中都市型垃圾焚化廠、電弧爐煉鋼廠煙道氣樣品及河川魚肉樣品濃度較高(ppb level)。 PBDDs/ PBDFs僅在焚化廠及煉鋼廠煙道氣樣品可檢測出，總濃度分佈在0.079ng/m3 至 4.01ng/m3之間，其餘則大部份未檢出。

關鍵字

溴化難燃劑 ； 高解析度氣相層析質譜儀 ； 多溴聯苯醚 ； 環境基質 ； 管柱淨化 ； 溴化戴奧辛

並列摘要

Modern technology has invented many heat resistant chemicals to reduce the probability of ignition of a wide range of textiles, plastics ,building materials, and electronic equipments used in commerce and in residential homes. Brominated organic compounds are the most widely used flame retardants in various products and at high concentrations. Most common are polybrominated diphenylethers (PBDEs), polybrominated biphenyls (PBBs), tetrabromobisphenol and hexabromodiphenyl cyclododecane. Commercialized PBDE flame retardants contain mainly penta-, octa-, and decabromo diphenylethers(PeBDEs, OBDEs and DeBDE). Recently, the toxicological work suggests that PBDEs have endocrine disrupting effects on the thyroid system, and can also affect the liver as well as the nervous and immune systems. Due to large consumption of flame retardants, hazardous wastes containing PBDEs were usually treated by the incinerator. Therefore, polybrominated dioxins and furans are formed from brominated flame retardants via thermal reactions. The primary objectives of this study were the complete separation of PBDDs/PBDFs and PBDEs and the analysis of them in real samples from municipal waste incinerator, electric arc furnace incinerator, fly ash/ bottom ash from municipal waste incinerator, soil samples and fish samples with a high-resolution gas chromatography-mass spectrometer.
Several columns were tested, including multilayer silica column, acid silica column, silver nitrate silica column, acid alumina column and activated carbon column. Several real environmental matrices of PBDEs and PBDDs/PBDFs including municipal waste incinerator, electric arc furnace incinerator, fly ash/ bottom ash from municipal waste incinerator, soil samples and fish samples were identified and quantified with GC/MS. The reaults show that activated carbon column can separate PBDDs/PBDFs and PBDEs completely. The PBDEs concentration of municipal waste incinerator, electric arc furnace incinerator and fish samples are higher at about ppb levels. None of the tested matrices for PBDDs/PBDFs is detected. Small amount of PBDDs/PBDFs from 0.079ng/m3 to 4.01ng/m3 in the municipal waste incinerator and the electric arc furnace incinerator have been detected already.

並列關鍵字

PBDFs ； Environmental matrices ； PBDEs ； Brominated flame retardants ； PBDDs ； column cleaning ； High resolution gas chromatography-mass spectrometry

參考文獻

1. Bromine Science and Environmental Forum (BSEF), An introduction to Brominated Flame Retardant

5. Sjodin, A., Hagmar, L., Klasson-Wehler, E., Kronholm-Diab, K., Jakobsson, E. and Bergman, A. (1999a) Flame retardant exposure –Polybrominated diphenyl ether (PBDEs) in blood from Swedish workers. Environ. Health Persp. 107: 643-648.

8. Sellstrome, U., Soderstrom, A., de Wit, C., Tysklind, M. (1998a) Photolytic debromination od decabromodiphenyl ether (DeBDE). Organohalogen Compounds 35: 477-450.

11. Norris, J.M., Kociba, R.J., Schwetz, B,A., Rose, J.Q., Humiston, C.G.., Jewett, G.L., Gehring, P.J. and Mailhes, J.B. (1975b) Toxicology of octabromodiphenyl and decabromodiphenyloxide . Environ. Health. Perspect. 11: 153-161.

12. El Dareer, S.M., Kalin, J.R., Tillery, K.F. and Hill, D.L.J.(1987). Disposition of decabromobiphenyl ether in rats dosed intravenously or by feeding. Toxicol. Environ. Health 22: 405-415.