含氯有機物如三氯乙烯(Trichloroethylene)等含氯脂肪族碳氫化合物
(Chlorinated Aliphatic Hydrocarbons, CAHs)，為地下水中常見之受關切化學
物質，而含氯脂肪族碳氫化合物因具有低沸點、化學安定性及強溶解等特
性被廣泛使用在各種商業用途。由於儲存槽的破裂、地面油品的意外洩漏
及人為蓄意排放，造成土壤與地下水中污染的主要原因。現地化學氧化法
為目前對於含氯有機污染整治極具潛力的整治方法之ㄧ，可處理地表下污
染區域而不受地面結構物之干擾，而且氧化劑之高氧化性能夠使污染物迅
速破壞縮短復育時程。因此，本研究使用自行合成之微奈米尺寸片錳礦
(δ-MnO2)，其為錳氧化物之ㄧ，也是天然存在於土壤環境中的礦物。模擬
於土壤底層受三氯乙烯污染之地下水，利用先前學者自行設計之氣體吸收
反應瓶，探討在有氧或無氧(通氮氣)狀態下，添加δ-MnO2對三氯乙烯進行
礦化作用和脫氯作用釋放出Cl－，之後再以曝氣反應瓶注入空氣及氮氣比較
兩模組氧化與還原反應之差異性。
研究結果顯示，在有氧與無微生物的活動下，添加δ-MnO2可促進三氯
乙烯進行氧化礦化脫羧作用和脫氯作用釋放出Cl－。然而，在無氧(通氮氣)
的狀態下，添加δ-MnO2對三氯乙烯進行礦化脫羧作用則較有氧狀態下減
少，而脫氯作用釋放出Cl－則成為主要反應。這明確指出添加δ-MnO2可對
三氯乙烯進行非生物性破壞其結構而釋放出CO2及Cl－，且隨著時間增加所
II
測得之CO2及Cl－皆有明顯上升的趨勢，而在未添加污染物的狀態下則無此
趨勢。進而，計算釋放出CO2及Cl－的莫耳比例，來推測不同反應系統下之
反應機制。由實驗室模擬受污染場址處理所獲得之參數與數據，可用於未
來規劃現地受三氯乙烯污染場址之整治過程是非常有用的，特別是可作為
土壤底層之地下水飽和層中對三氯乙烯降解去除作用的指導方針。
關鍵字： 三氯乙烯、δ-MnO2、地下水、化學氧化

Trichloroethylene and other chlorinated organic compounds such as
chlorinated aliphatic hydrocarbons are widely used in a variety of commercial
purposes and are common pollutants in groundwater due to low boiling point,
high solubility and chemical stability. Considerable amount of soil and ground
water have been contaminated as a result of leaks from underground storage
tanks, man-made accidental emissions and improper disposal. Chemical
oxidation of organic chlorine is one of the potential remediation methods
where the process is within the source zone in subsurface environment, and the
oxidant having high oxidation properties could reduce the complex
contaminants to smaller non-pollutant compounds by rapid destruction.
Manganese oxide is a very common mineral component present in the mineral
soil. Hence, in this study, synthesized micro nano-sized particles of δ-MnO2
were used as catalyst, simulations at the bottom of the soil pollution of
groundwater by TCE, usage of formerly designed gas absorption reaction flask,
investigating under aerobic and anaerobic (passing nitrogen) conditions,
adding δ-MnO2 for mineralization, decarboxylation (CO2 evolution) and
dechlorination (release of Cl－) reactions of TCE. After completion of the
experimental process of TCE under aerobic and anerobic conditions in
presence δ-MnO2, the two modules of oxidation and reduction reactions
differences were compared.
The results showed that under aerobic conditions having no microbial
activity, addition of δ-MnO2 promotes oxidation of TCE mineralization,
decarboxylation and dechlorination. However, in the absence of oxygen
(passing nitrogen), addition of δ-MnO2 promoted mineralization of TCE, but
IV
the amount of decarboxylation is less compared to aerobic conditions, while
dechlorination was found to be the major reaction. These experiments
implicates that δ-MnO2 under non-biological activity conditions causes
breakdown of TCE structure and releases CO2 and Cl－, and when the reaction
time period is increased, increase in the release of CO2 and Cl－ is observed,
whereas this trend is not observed in absence of pollutants. The release of CO2
and Cl－molar ratio was calculated under different reaction mechanisms. By the
laboratory simulation of contaminated sites and the data obtained from
different parameters, this process can be extended for further studies on
TCE contaminated soil and water sites and this remediation process is very
useful, especially for the underlying groundwater saturated soil layer of
contaminated TCE.

中文摘要............................................................................................................I
Abstract .......................................................................................................... III
誌 謝................................................................................................................ V
目錄................................................................................................................. VI
表目錄.............................................................................................................. X
圖目錄............................................................................................................XII
第一章 前言..................................................................................................... 1
1.1 研究緣起.............................................................................................. 1
1.2 研究目的............................................................................................... 2
第二章 前人研究.............................................................................................. 3
2.1.1 地下水中常見的污染物.................................................................... 3
2.1.2 地下水中含氯有機物之來源及分佈................................................ 4
2.2.1 三氯乙烯起源................................................................................... 6
2.2.2 三氯乙烯特性.................................................................................... 6
2.2.3 三氯乙烯之危害............................................................................... 7
2.3 含氯有機污染土壤及地水之整治現況................................................ 8
2.4 化學氧化法......................................................................................... 12
2.5 高錳酸鉀運用在受三氯乙烯污染之地下水...................................... 14
VII
2.6 二氧化錳介紹..................................................................................... 17
2.7 高錳酸鉀生成二氧化錳之型態及特性.............................................. 19
2.8 合成二氧化錳之織型態及生成途徑.................................................. 20
2.9 合成二氧化錳之特性......................................................................... 21
2.10 二氧化錳應用於環境污染整治........................................................ 22
第三章 材料與方法........................................................................................ 26
3.1 試驗材料............................................................................................. 26
3.1.1 藥品........................................................................................... 26
3.1.2 試驗設備................................................................................... 27
3.1.3 供試水樣.................................................................................. 28
3.1.4 δ-MnO2 製備............................................................................ 28
3.1.5 微奈米級尺寸δ-MnO2 特性分析............................................. 30
3.1.6 回收率試驗.............................................................................. 31
3.2 試驗方法............................................................................................. 31
3.2.1 有氧曝氣在不同反應時間下對有、無添加δ-MnO2 之脫離子
水與三氯乙烯污染水之氧化礦化反應及還原脫氯之反應.............. 33
3.2.2 無氧曝氣在不同反應時間下對有、無添加δ-MnO2 之脫離子
水與三氯乙烯污染水之氧化礦化反應及還原脫氯之反應.............. 33
3.2.3 有氧震盪在不同反應時間下對有、無添加δ-MnO2 之脫離子
VIII
水與三氯乙烯污染水之氧化礦化反應及還原脫氯之影響.............. 34
3.2.4 無氧震盪是否對有、無添加δ-MnO2 之脫離子水與三氯乙烯
污染水在不同時間下進行氧化礦化及還原脫氯反應之影響.......... 34
3.3 儀器分析............................................................................................ 36
3.3.1 自動滴定儀.............................................................................. 36
3.3.2 離子層析儀.............................................................................. 37
3.3.3 pH meter .................................................................................... 39
3.3.4 水中揮發性有機化合物檢測方法—吹氣捕捉/氣相層析質譜
儀........................................................................................................ 39
第四章 結果與討論........................................................................................ 43
4.1 δ-MnO2 尺寸鑑定................................................................................ 43
4.2 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯振盪後之礦化效率........................................................................... 46
4.3 無氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯振盪後之礦化效率........................................................................... 49
4.4 比較有氧及無氧在有、無添加δ-MnO2 對於不同時間反應時間脫離
子水與三氯乙烯振盪後之礦化效率........................................................ 52
4.6 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯曝氣後之礦化及還原效率................................................................ 57
IX
4.7 無氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯曝氣後之礦化效率........................................................................... 61
4.8 比較有氧及無氧在添加δ-MnO2 對於不同反應時間下三氯乙烯曝氣
後之礦化效率及還原效率....................................................................... 64
4.9 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯震盪後在石英砂之礦化效率............................................................ 66
4.10 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三
氯乙烯震盪後在沖積土之礦化效率........................................................ 68
4.11 有氧條件下未添加土壤、添加石英砂及添加沖積土在不同反應時
間下添加δ-MnO2 對於DIW 與TCE 經震盪後礦化效率之影響........... 69
4.12 震盪及曝氣在有、無氧下TCE 添加δ-MnO2 二氧化碳釋放量與氯
離子量在不同反應時間下趨勢之比........................................................ 70
4.13 震盪及曝氣在有、無氧下TCE 添加δ-MnO2 二氧化碳釋放量與氯
離子量在不同反應時間下之化學劑量.................................................... 73
第五章 結論與建議........................................................................................ 75
參考文獻......................................................................................................... 77
附錄................................................................................................................. 82
X
表目錄
表2-1 台灣常見之含氯有機物及相關管制標準............................................. 4
表2-2 TCE 物理化學特性................................................................................ 7
表2-3 三氯乙烯中毒之症狀............................................................................. 8
表2-4 適用於不同污染物強度之整治技術................................................... 11
表3-1 試驗材料與藥品................................................................................... 26
表3-2 試驗設備與儀器................................................................................... 27
表3-3 IC 分析條件......................................................................................... 38
表4-1 有氧在不同時間反應下對於有、無添加δ-MnO2 之脫離子水與三氯
乙烯經震盪後之礦化效率.............................................................................. 48
表4-2 無氧在不同時間反應下對於有、無添加δ-MnO2 之脫離子水與三氯
乙烯經震盪後之礦化效率.............................................................................. 51
表4-3 有氧及無氧在不同時間反應下對於添加δ-MnO2 之三氯乙烯經震盪
後之還原氯離子釋放率.................................................................................. 56
表4-4 有氧在不同時間反應下對於有、無添加δ-MnO2 之脫離子水與三氯
乙烯經曝氣後之礦化效率.............................................................................. 59
表4-5 有氧在不同時間反應對於有添加δ-MnO2 之三氯乙烯經曝氣後還原
氯離子之釋放及降解率.................................................................................. 59
表4-6 有氧在不同時間反應對於有添加δ-MnO2 之三氯乙烯經曝氣後反應
XI
瓶內三氯乙烯之殘留率。.............................................................................. 60
表4-7 無氧在不同時間反應下對於有、無添加δ-MnO2 之脫離子水與三氯
乙烯經曝氣後之礦化效率.............................................................................. 62
表4-8 無氧在不同時間反應對於有添加δ-MnO2 之三氯乙烯經曝氣後還原
氯離子之釋放及降解率.................................................................................. 62
表4-9 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯震盪後在石英砂之礦化效率.................................................................. 67
表4-10 有氧在有、無添加δ-MnO2 對於不同時間反應時間脫離子水與三氯
乙烯震盪後在沖積土之礦化效率.................................................................. 68
XII
圖目錄
圖2-1 DNAPL 洩漏於土壤之流動與分佈情形............................................... 5
圖2-2 三氯乙烯氧化作用之路徑.................................................................. 15
圖2-3 二氧化錳表面構造及其反應途徑....................................................... 20
圖2-4 不同合成的二氧化錳氧化物之間的關系圖21
圖3-1 δ-MnO2 製備流程................................................................................. 29
圖3-3 氣體吸收釋放反應瓶........................................................................... 35
圖3-4 碳酸鹽系統在不同pH 條件下的分佈圖............................................. 37
圖3-5 IC 層析效能圖譜.................................................................................. 38
圖4-1 場發射掃描式電子顯微鏡(FE-SEM)，分析鑑定δ-MnO2 尺寸........ 44
圖4-2 場發射掃描式電子顯微鏡(FE-SEM)，分析鑑定δ-MnO2 尺寸........ 44
圖4-3 高效能粒徑分析儀(HPPS)，分析鑑定δ-MnO2 粒徑........................ 45
圖4-4 有氧及無氧在震盪下DIW 有、無添加δ-MnO2 在不同時間下CO2
之釋放............................................................................................................. 54
圖4-5 有氧及無氧在震盪下TCE 添加δ-MnO2 在不同時間下CO2 之釋放54
圖4-6 有氧及無氧在不同時間反應下對於添加δ-MnO2 之三氯乙烯經震盪
後還原氯離子換算之降解率.......................................................................... 56
圖4-7 有氧在不同時間反應下對於添加δ-MnO2 之三氯乙烯經曝氣後之二
氧化碳釋放量.................................................................................................. 60
XIII
圖4-8 有氧在不同時間反應下對於添加δ-MnO2 之三氯乙烯經曝氣後之二
氧化碳釋放量.................................................................................................. 63
圖4-9 有氧及無氧在曝氣下TCE 添加δ-MnO2 在不同時間下CO2 之釋放65
圖4-10 有氧及無氧在不同時間反應下對於添加δ-MnO2 之三氯乙烯曝氣後
還原氯離子之降解率...................................................................................... 65
圖4-11 有氧未添加土壤、石英砂、沖積土在不同反應時間下DIW 添加
δ-MnO2 所測得CO2 釋放................................................................................ 70
圖4-12 有氧未添加土壤、石英砂、沖積土在不同反應時間下TCE 添加
δ-MnO2 所測得CO2 釋放................................................................................ 70
圖4-13 震盪及曝氣在有、無氧下TCE 添加δ-MnO2 二氧化碳釋放量之趨
勢..................................................................................................................... 72
圖4-13 震盪及曝氣在有、無氧下TCE 添加δ-MnO2 氯離子釋放量之趨勢72
圖4-14 震盪及曝氣在有、無氧下TCE 添加δ-MnO2 二氧化碳釋放量與氯
離子量在不同反應時間下之化學劑量關係................................................... 74

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