臺灣博碩士論文加值系統

環境中砷的濃度和移動主要是藉由吸附到金屬氧化物的表面，特別是鐵、鋁、錳來控制。腐植酸亦可以影響此種吸附之行為，進而增加砷之遷移率。這種形成之複合物的相互作用將影響每一個局部濃度及確定它們在天然含水層中的可用性。本研究利用各種光譜來闡明腐植酸、鐵、砷之結合性質，進而證明複合物之鍵結，以及在不同的氧化還原電位和酸鹼性條件下之鍵結變化。研究結果將可以在地下環境中的鐵、砷及腐植酸得到更好的理解，以對砷移動之動力學有更進一步的瞭解。
本研究即要探討腐植酸與砷之鍵結程度，利用X光吸收光譜EXAFS方法分析複合物鍵結之鍵長及配位數，用紅外線光譜分析鍵結之官能基變化，XPS則分析複合物之表面鍵結情形。另外，本研究也討論腐植酸-鐵-砷複合物於不同條件下之酸鹼性或氧化還原電位是否會造成鍵結上之變化。
本研究結果顯示，腐植酸與毒化物砷於鐵離子存在下形成雙齒之複合物砷酸鐵，而其鐵-砷之鍵長約為3.27~3.29 Å，配位數為2，腐植酸則憑藉著羧基與鐵離子形成鐵-氧之鍵結，鍵長約為1.98 Å，配位數為4;腐植酸中的碳亦能與鐵形成鍵結，其鍵長約3.05 Å，配位數為1;砷酸中之砷-氧鍵結其配位數為4，鍵長為1.70 Å。而腐植酸-鐵-砷複合物在極酸性環境下(pH=2)其鐵-砷之鍵結會遭受破壞，不易存在。當還原電位增加時，鐵-砷之鍵長及砷-氧之鍵長隨而減少，鐵-氧之德拜瓦勒因子(Debye-Waller factor)隨還原電位的增加而增加。然而腐植酸-鐵-砷的鍵結之氧化還原電位由+25 mV降至 -120 mV都沒有明顯的變化。
本研究成果能提供鐵、砷、腐植酸之間相互作用的重要參考基礎。此外，其也會影響到毒化物砷在土壤或水體中之移動過程，然而，腐植酸、鐵、砷的鍵結之形成將影響到毒化物砷的去除率及傳輸與生物利用等問題。由實驗室合成的腐植酸、鐵、砷複合物之鍵結，可瞭解其在自然環境中形成及分離的條件及控制因子(如酸鹼度、氧化還原電位)。

Summary
Arsenic is a widespread toxicant in the soil or aquifer in the global environment. Humic acid contains multiple functional groups capable of chelating with heavy metals. In this study, Fourier transform infrared (FTIR), X-ray photon spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) were used to study the bonding between the groups. The degree of bonding between humic acid and arsenic was investigated in this study. The bond distance and coordination number were analyzed by XAS, the binding energy of the humic acid-iron-arsenic complex was determined by XPS, and the functional groups of humic acid were analyzed by FTIR. The results of this study provide the binding properties of iron, arsenic, humic acid interactions. In the cationic state, iron may bind with humic acid and arsenic more easily between the bonds. This information could be valuable to understand the arsenic pollution in the soil or water due to its release or mobilization. The results proved that humic acid in the presence of iron ions can form a bidentate ternary complex. The bond distance and coordination number of Fe-As are 3.27~3.29 Å and 2, respectively. The Fe-As bonds of HA-Fe-As complex were subjected to break under strongly acidic conditions (pH=2), but not significantly affected by changing oxidation-reduction potentials (25, 0, -25, -50, -120 mV)

摘要 Ⅰ
ABSTRACT Ⅱ
致謝 Ⅷ
目錄 IX
表目錄 XI
圖目錄 XII
第一章 緒論 1
1.1 背景介紹 1
1.2 研究動機 2
1.3 文獻回顧 2
1.4 研究目的 4
1.5 研究重要性及環境衝擊 4
第二章 研究方法 5
2.1 複合物合成 5
2.1.1 酸鹼性影響 5
2.1.2 氧化還原作用影響 5
2.2 傅立葉紅外線分析複合物鍵結及腐植酸官能基 6
2.3 X射線光電子分析複合物表面之元素成份及鍵結 6
2.4 X光吸收能譜分析砷、鐵氧化態及複合物之鍵結 7
2.5 複合物表面形貌觀察及化學成分分析 8
第三章 結果 9
3.1 複合物之傅立葉轉換紅外線光譜分析 9
3.2 複合物之X射線光電子能譜儀分析 12
3.2.1 碳1s 軌域光電子能譜 12
3.2.2 氧1s軌域光電子能譜分析 16
3.2.3 鐵2p 軌域及砷 3d 軌域光電子能譜分析 24
3.3 複合物之X光吸收光譜分析 25
3.3.1 鐵吸收邊緣 25
3.3.2砷吸收邊緣 35
3.4 複合物表面形態觀察及化學成份分析 43
第四章 討論 48
4.1 腐植酸-鐵-砷複合物間的鍵結情形 48
4.1.1 複合物官能基變化 48
4.1.2 碳、氧、鐵及砷軌域上之鍵結變化 49
4.1.3 複合物鍵長及配位數之變化 50
4.2 酸鹼性對腐植酸複合物鍵結影響 52
4.3 氧化還原電位對腐植酸複合物之影響 54
第五章 結論 56
參考文獻 57
附錄 60
附錄一 鐵吸收邊緣擬合參數 61
附錄二 砷吸收邊緣擬合參數 66

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