添加在汽油中的含氧物質種類繁多，其目的為代替鉛以提高辛烷值，避免空氣污染。甲基第三丁基醚(MTBE, methyl tert-butyl ether)是目前含氧添加劑中應用最為廣泛的一種化合物。由於MTBE具備低分配係數、生物難分解性和高水溶性等特性。因此，常成為地下儲油槽洩漏時，土壤及地下水污染整治困難之原因。目前美國環保署已將MTBE列為可能致癌物質，其飲用水建議管制限值為5 µg/L。我國環保署亦將其列管為第四類毒性化學物質，可見其毒性對人體健康有相當程度之影響。本研究主要目的為探討MTBE好氧生物分解性及以生物復育之方式整治受MTBE污染地下水之可行性。
本研究內容是以微生物批次實驗(microcosm study)，探討MTBE分別在好氧及共代謝(cometabolism)之條件下，其生物降解之可行性。在共代謝的批次實驗中，包括丙烷(propane)、乙醇(ethanol)及苯、甲苯、乙苯、二甲苯(BTEX)，分別被利用為替代碳源。微生物之來源為採自某油污染場址之含水層土壤。水樣中的MTBE濃度係利用吹氣捕捉裝置(purge＆trap)及氣相層析儀(GC)檢測。根據研究結果顯示，MTBE在好氧狀態且為唯一碳源之條件下可以被現地微生物分解。此外，若加入替代碳源以共代謝之方式亦可促進其降解。在共代謝實驗中，若另加入現地地下水取代實驗室合成之地下水，則MTBE之降解效果較佳，顯示污染場址之地下水可能存在較易利用之碳源或存在有微生物生長所必需之微量元素。
實驗結果顯示，在本油污染場址中，MTBE可在好氧及共代謝之條件下被現地微生物分解，顯示污染場區中已存在可降解MTBE之菌種，因此，自然衰減在此場址應是可行的整治方式之一。未來亦可自場區篩選出優勢菌種，以有效加強MTBE之整治效率。

Contamination of groundwater supplies by gasoline and other petroleum-derived hydrocarbons released from underground or aboveground storage tanks is a serious and widespread environmental problem. Corrosion, ground movement, and poor sealing can cause leaks in tanks and associated piping. Petroleum hydrocarbons contain methyl tertiary-butyl ether (MTBE) (a fuel oxygenate), benzene, toluene, ethylbenzene, and xylene isomers (BTEX), the major components of gasoline, which are hazardous substances regulated by many nations. MTBE possesses all the characteristics of a persistent compound in the subsurface: high solubility, low volatility, low sediment sorption, and resistance to biodegradation. The objectives of this study were to (1) evaluate the biodegradibility of MTBE under aerobic conditions, and (2) assess the potential of using the aerobic bioremediation technique to clean up aquifers contaminated by MTBE.

In this study, microcosms were constructed to determine the feasibility of biodegrading MTBE by intrinsic microbial consortia (aquifer sediments) under aerobic and aerobic cometabolic conditions. In the cometabolic microcosms, propane, ethanol, and BTEX were applied as the primary substracts to enhance the biodegradation of MTBE. The inocula used in this microcosm study were aquifer sediments collected from the contaminated-zones of a petroleum-hydrocarbon (including MTBE) contaminated site. Microcosms were constructed with nutrient medium (or site groundwater), sediments, and MTBE solution in 70-mL serum bottles sealed with Teflon-lined rubber septa. MTBE was analyzed using purge-and-trap instrument following gas chromatography (GC)/flame ionization detector (FID).
Results show that the indigenous microorganisms were able to biodegrade MTBE under aerobic conditions using MTBE as the sole primary substrate. Microcosms with site groundwater as the medium solution show higher MTBE biodegradation rate. This indicates that site groundwater might contain some trace minerals or organics, which could enhance the MTBE biodegradation rate. Results show that the addition of BTEX would also enhance the MTBE removal. However, no significant MTBE biodegradation was observed in microcosms with propane and ethanol as the primary substrates. This reveals that the supplement of the second carbon source might inhibit the degradation of MTBE due to the preferential removal of some organics over MTBE. Results from the microcosm study suggest that aerobic biodegradation plays an important role on the MTBE removal. Intrinsic bioremediation is a feasible technology to remediate the studied MTBE-contaminated site.

謝誌 Ⅰ
摘要 Ⅱ
Abstract Ⅳ
目錄 Ⅵ
表目錄 Ⅷ
圖目錄 Ⅸ
第一章 前言 1
1.1研究緣起 1
1.1.1地下水污染 1
1.1.2地下儲油槽之洩漏 2
1.2研究內容 4
1.3研究目的 4
第二章 文獻回顧 5
2.1污染源起 5
2.2MTBE物理化學性質 8
2.3MTBE對健康之影響 11
2.4整治技術 13
2.4.1土壤整治技術 13
2.4.2地下水整治技術 16
2.5 MTBE文獻整理 30
第三章 實驗設備與方法 39
3.1實驗材料 39
3.1.1實驗用水 39
3.1.2碳源 39
3.1.3菌種來源 40
3.1.4無機營養鹽 40
3.1.5其它實驗材料 41
3.2污染場址背景描述 42
3.2.1污染廠區概述 42
3.2.2地下水採樣分析 46
3.2.3土壤採樣分析 48
3.3實驗設備 50
3.4實驗方法與步驟 52
3.4.1好氧批次實驗流程 52
3.4.2實驗條件 57
3.4.3 檢量線之配製 59
3.4.4吹氣捕捉裝置原理 60
第四章 實驗結果與討論 61
4.1好氧及好氧共代謝 61
4.1.1好氧分解組 61
4.1.2好氧共代謝組 63
4.2化學需氧量(COD)檢測結果 72
第五章 結論與建議 77
5.1結論 77
5.2建議 79
第六章 參考文獻 80
附錄 88

表目錄

表2.1 MTBE物化性質表 9
表2.2 MTBE和苯化學性質之比較表 10
表2.3 MTBE好氧及厭氧分解之相關文獻 30
表3.1營養基質成分表 40
表3.2總生菌數土壤分析結果 48
表3.3 Micorcosm 分類表 54
表4.1各組MTBE檢測值 71

圖目錄

圖2.1 SVE處理系統圖 14
圖2.2 LTTD處理系統 15
圖2.3 Landfarming處理系統圖 16
圖2.4 空氣氣提法示意圖 17
圖2.5現地反應牆系統 19
圖2.6生物洗滌排氣處理系統 21
圖2.7 BioRemedy biobarrier system 22
圖2.8 Bioventing處理系統 23
圖2.9氮、碳、硫之好氧循環圖 24
圖2.10厭氧性的氮、碳和硫循環圖 25
圖2.11共代謝反應圖 27
圖2.12在好氧下MTBE降解之途徑 29
圖3.1廠區各監測井及土壤取樣點位置圖 45
圖3.2監測井位置及污染濃度示意圖 46
圖3.3 Varian 3800氣相層析儀 50
圖3.4 Tekmar 3000吹氣捕捉器 51
圖3.5 STMN-Y222高壓蒸氣滅菌器 51
圖3.6 A組之好氧分解流程圖 55
圖3.7 B組之好氧共代謝流程圖 56
圖3.8 MTBE及TBA層析圖 58
圖3.9 MTBE檢量線圖 59
圖3.10 TBA檢量線圖 59
圖4.1 A1組之MTBE降解情形圖 66
圖4.2 A2組之MTBE降解情形圖 66
圖4.3 A2-2組之MTBE降解情形圖 67
圖4.4 A3組之MTBE降解情形圖 67
圖4.5 B1組之MTBE降解情形圖 68
圖4.6 B2組之MTBE降解情形圖 68
圖4.7 B3組之MTBE降解情形圖 69
圖4.8 B3組之BTEX降解情形圖 69
圖4.9各組MTBE降解情形圖 70
圖4.10 A1組COD變化情形圖 74
圖4.11 A2組COD變化情形圖 74
圖4.12 A3組COD變化情形圖 75
圖4.13 B1組COD變化情形圖 75
圖4.14 B2組COD變化情形圖 76
圖4.15 B3組COD變化情形圖 76

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