本研究以有機磷農藥之福瑞松 (Phorate)及托福松(Terbufos)為目標物，研究目的為（1）探討Fenton混凝去除福瑞松與托福松、及（2）比較鐵鹽混凝、Fenton及Fenton-like混凝去除福瑞松與托福松。所有實驗採瓶杯試驗，人工原水含有機磷農藥濃度為100 μg/L，操作參數為pH、鐵鹽種類、過氧化氫(H2O2)加藥量及腐植酸有機物共存，鐵鹽加藥量以Fe2+或Fe3+計之。
    研究結果顯示鐵鹽(Fe2+/Fe3+)混凝去除福瑞松及托福松之最適pH為 4.0，主要去除機制為吸附與絆除沉澱，Fe3+混凝去除福瑞松及托福松效果優於Fe2+混凝。此外，Fe2+、Fe3+混凝或H2O2氧化對福瑞松及托福松去除率皆低於55%。Fenton及Fenton-like混凝氧化福瑞松及托福松之最適pH值為4.0，福瑞松及托福松殘留率皆低於5%以下。比較五種程序於pH=4.0時，福瑞松及托福松去除率大小依序為Fenton＞Fenton-like＞Fe3+＞Fe2+＞H2O2。
    原水中含天然有機物腐植酸共存，濃度在1.0~5.0 mg/L as NPDOC，因腐植酸與福瑞松及托福松競爭混凝劑吸附，使Fe2+/Fe3+混凝去除福瑞松之殘留率增加且達到90%，故腐植酸共存會影響Fe2+/Fe3+混凝去除福瑞松及托福松。相對地，腐植酸共存時，Fenton及Fenton-like混凝對福瑞松及托福松之去除率僅減少2~10%，顯示腐植酸共存對Fenton及Fenton-like混凝去除福瑞松及托福松無顯著影響，故H2O2可提高Fe2+/Fe3+混凝去除福瑞松及托福松，且不受腐植酸共存影響。

Phorate and terbufos are organophosphorus pesticides. Using the synthetic raw waters containing 100 μg/L of phorate or terbufos, the purposes of this study are (1) to investigate the removals of phorate and terbufos by the Fenton coagulation process, and (2) to compare the removals of phorate and terbufos among iron salts (Fe2+/Fe3+) coagulation, the Fenton((Fe2+/H2O2) coagulation and the Fenton-like (Fe3+/H2O2)  coagulation processes. The operational variables studied include pH, type of iron salts, hydrogen peroxide (H2O2) dosage and coexisting organics of humic acid. All experiments are conducted by the Jar test.
The results show that the optimum pH for the removal of phorate and terbufos was at 4.0. The mechanism for the removal of phorate and terbufos was mainly by adsorption and precipitation. The removal of phorate and terbufos by ferric coagulation was better than that by ferrous coagulation. Furthermore, the removals of both phorate and terbufos by peroxidation and iron salts coagulation were less than 55%.  The optimum pH for the removal of phorate and terbufos by the Fenton coagulation and Fenton-like coagulation was at 4.0 and the residuals of phorate and terbufos were less than 5%. The removal of phorate and terbufos was mainly by hydroxyl radical oxidation.  Comparing the removals of phorate and terbufos among different processes at pH 4, the sequence of the removals of phorate and terbufos were Fenton coagulation＞Fenton-like coagulation＞ferric coagulation＞Ferrous coagulation＞peroxidation. The increase of phorate removal was not affected significantly by increasing H2O2 dosage.
As the synthetic raw water contained coexisting organics of humic acid of 1.0~5.0 mg/L as NPDOC, the residuals of phorate and terbufos increased and reached to 90% for ferric coagulation and ferrous coagulation processes.  This was due to the competition of adsorption sites on coagulants between humic acid and organophosphorus pesticides. Therefore, coexisting of organics of humic acid affected the removals of phorate and terbufos by iron salts coagulation. In contract, in the presence of humic acid, the removals of phorate and terbufos decreased slightly 2-10%.It implied that the effect of the removals of phorate and terbufos on coexisting humic acid was not significant for the Fenton coagulation and Fenton-like coagulation. It is concluded that H2O2 could enhance the phorate removal by iron salts coagulation and was less affected by coexisting of humic acid.

目  錄
目    錄	Ⅰ
表 目 錄	Ⅴ
圖 目 錄	Ⅵ

第一章   前 言	1
1-1 研究緣起	1
1-2 研究目的	3
第二章   文獻回顧	4
2-1 淨水程序去除有機磷農藥	4
2-1-1 福瑞松與托福松有機磷農藥之特性	4
2-1-2 飲用水水質標準福瑞松與托福松之管制值	9
2-1-3 淨水程序去除福瑞松與托福松	10
2-2 Fenton 程序原理	11
2-2-1 鐵鹽混凝原理	11
2-2-2 混凝機制	12
2-2-3 Fenton 程序前氧化原理	18
2-2-4 Fenton 程序前氧化影響因素	22
2-3 Fenton 與相關高級氧化程序於淨水處理之應用	25
2-3-1 Fenton 程序去除農藥與有機物	25
2-3-2相關高級氧化程序去除農藥與有機物	26
第三章    實驗方法與材料	30
3-1 實驗方法	30
3-1-1含有機磷農藥人工原水	30
3-1-2鐵鹽混凝瓶杯實驗	31
3-1-3 Fenton 混凝瓶杯實驗	31
3-2 實驗設備及藥品	33
3-2-1實驗設備	33
3-2-2實驗藥品	34
3-3 水質分析	36
3-3-1 福瑞松與托福松有機磷農藥分析	36
3-3-2 非氣提溶解性有機碳（NPDOC）分析	42
3-3-3 鐵鹽之分析	44
3-3-4 品質管制（QAQC）	47
第四章    結果與討論	48
4-1 Fenton或Fenton-like程序去除有機磷農藥效率探討	48
4-1-1 鐵鹽混凝或過氧化氫氧化去除農藥效率	48
4-1-2 Fenton程序去除農藥之效率	53
4-1-3 Fenton-like程序去除農藥之效率	56
4-1-4 綜整不同組合程序對農藥之影響	58
4-2 H2O2加藥量對Fenton及Fenton-like去除有機磷農藥之效率
探討	63
4-2-1 H2O2加藥量對Fenton程序去除農藥之影響	63
4-2-2 H2O2加藥量對Fenton-like程序去除農藥之影響	70
4-2-3 比較H2O2加藥量對Fenton及Fenton-like去除農藥之
             影響	76
4-3 天然有機物-腐植酸對去除有機磷農藥之影響	82
4-3-1腐植酸對Fenton程序去除農藥之影響	82
4-3-2 腐植酸對Fenton-like程序去除農藥之影響	89
第五章    結論與建議	96
參考文獻	97
 
表 目 錄
表2-1  福瑞松及托福松基本性質	8
表2-2  各國飲用水水質標準	9
表2-3  常用之無機金屬鹽混凝劑	11
表2-4  膠體穩定性和界達電位平均值之相關性	13
表2-5  氧化劑及其衍生自由基之氧化還原電位	21
表2-6  常用去除農藥的高級氧化法（AOPs）	28
表3-1  氣相層析儀（GC）之操作參數	40
表3-2  脈衝式火焰光度偵測器（PFPD）之操作參數	40
表4-1  福瑞松及托福松於各程序間之去除效率比較	60
表4-2  福瑞松及托福松於各程序之操作條件與殘留率之比較	60
表4-3  福瑞松及托福松最適參數（pH=4.0）	76
 
圖 目 錄
圖2-1  有機磷農藥依鍵結之官能基分類	5
圖2-2  DLVO理論之位能曲線圖	14
圖2-3  電解質濃度對電雙層壓縮效應	14
圖2-4  懸浮液中帶負電之固體顆粒的界達電位	15
圖3-1  實驗流程圖	32
圖3-2  PFPD訊號脈衝循環過程	37
圖3-3  GC/PFPD層析圖(a)福瑞松(b)托福松（25μg/L）	39
圖4-1  鐵鹽在各pH值條件混凝去除福瑞松及殘留溶解性鐵鹽。（Phorate = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L）	50
圖4-2  鐵鹽在各pH值條件混凝去除托福松及殘留溶解性鐵鹽。（Terbufos = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L）	50
圖4-3  H2O2加藥量在兩種pH值條件對福瑞松之去除效率。（Phorate = 100 μg/L）	52
圖4-4  H2O2加藥量在兩種pH值條件對托福松之去除效率。（Terbufos = 100 μg/L）	52
圖4-5  Fenton程序在各pH條件去除福瑞松之去除及殘留溶解性鐵鹽。（Phorate = 100 μg/L, Fe2+ = 2 mg/L, H2O2= 2 mg/L）	55
圖4-6  Fenton程序在各pH條件去除托福松之去除及殘留溶解性鐵鹽。（Terbufos = 100 μg/L, Fe2+ = 2 mg/L, H2O2= 2 mg/L）	55
圖4-7  Fenton-like程序在各pH條件去除福瑞松之去除及殘留溶解性鐵鹽。（Phorate = 100 μg/L, Fe3+ = 2 mg/L, H2O2= 2 mg/L）	57
圖4-8  Fenton-like程序在各pH條件去除托福松之去除及殘留溶解性鐵鹽。（Terbufos = 100 μg/L, Fe3+ = 2 mg/L, H2O2= 2 mg/L）	57
圖4-9  五種試程去除福瑞松之比較。（Phorate = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, H2O2= 2 mg/L；ND：Not Detected：Not Analyzed）	61
圖4-10  五種試程去除托福松之比較。（Terbufos = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, H2O2= 2 mg/L；ND：Not Detected, NA：Not Analyzed）	62
圖4-11  H2O2加藥量對Fenton程序去除福瑞松之影響。（Phorate = 100 μg/L, Fe2+ = 2 mg/L）	65
圖4-12  H2O2加藥量對Fenton程序去除福瑞松之殘留溶解性鐵鹽。（Phorate = 100 μg/L, Fe2+ = 2 mg/L）	65
圖4-13  H2O2加藥量對Fenton程序去除托福松之影響。（Terbufos = 100 μg/L, Fe2+ = 2 mg/L）	68
圖4-14  H2O2加藥量對Fenton程序去除托福松之殘留溶解性鐵鹽。（Terbufos = 100 μg/L, Fe2+ = 2 mg/L）	68
圖4-15  H2O2加藥量對Fenton-like程序去除福瑞松之影響。（Phorate = 100 μg/L, Fe3+ = 2 mg/L）	71
圖4-16  H2O2加藥量對Fenton-like程序去除福瑞松之殘留溶解性鐵鹽。（Phorate = 100 μg/L, Fe3+ = 2 mg/L）	71
圖4-17  H2O2加藥量對Fenton-like程序去除托福松之影響。（Terbufos = 100 μg/L, Fe3+ = 2 mg/L）	74
圖4-18  H2O2加藥量對Fenton-like程序托福松之殘留溶解性鐵鹽。（Terbufos = 100 μg/L, Fe3+ = 2 mg/L）	74
圖4-19  H2O2加藥量對Fenton及Fenton-like去除福瑞松之比較。（Phorate = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, pH 4）	78
圖4-20  福瑞松於Fenton及Fenton-like對H2O2加藥量所提升氧化效率之比較。（Phorate = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, pH 4）	78
圖4-21  H2O2加藥量對Fenton及Fenton-like去除托福松之比較。（Terbufos = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, pH 4）	80
圖4-22  托福松於Fenton及Fenton-like對H2O2加藥量所提升氧化效率之比較。（Terbufos = 100 μg/L, Fe2+ or Fe3+ = 2 mg/L, pH 4）	80
圖4-23  背景有機物（HA）對Fenton程序去除福瑞松之影響。（Phorate = 100 μg/L, pH 4）	84
圖4-24  背景有機物（HA）對Fenton程序去除福瑞松殘留溶解性鐵鹽之影響。（Phorate = 100 μg/L, pH 4）	84
圖4-25  背景有機物（HA）對Fenton程序去除托福松之影響。（Terbufos = 100 μg/L, pH 4）	87
圖4-26  背景有機物（HA）對Fenton程序去除托福松殘留溶解性鐵鹽之影響。（Terbufos = 100 μg/L, pH 4）	87
圖4-27  背景有機物（HA）對Fenton-like程序去除福瑞松之影響。（Phorate = 100 μg/L, pH 4）	91
圖4-28  背景有機物（HA）對Fenton-like程序去除福瑞松殘留溶解性鐵鹽之影響。（Phorate = 100 μg/L, pH 4）	91
圖4-29  背景有機物（HA）對Fenton-like程序去除托福松之影響。（Terbufos = 100 μg/L, pH 4）	94
圖4-30  背景有機物（HA）對Fenton-like程序去除托福松殘留溶解性鐵鹽之影響。（Terbufos = 100 μg/L, pH 4）	94

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