臺灣博碩士論文加值系統

後勁溪、愛河、前鎮河為高雄市三條主要的河川，且均流經人口稠密的住宅區及工業區，大部分的家庭及工業廢水都排入這三條河川中，而愛河及前鎮河注入高雄港區中。本研究採集後勁溪、愛河、前鎮河及高雄港區的海水及底質進行烷基苯酚化合物的分析，來了解這些地區烷基苯酚化合物污染的情況。
本研究以LC/MS/MS做為偵測儀器，分析時間縮短且不需進行衍生或顯色反應，偵測極限更可達到0.03 ng/ml，回收率也可達83.6~91.6 ﹪。對於烷基苯酚化合物有更高的敏感度及選擇性，可以分析具長鍊（EO）的化合物。
四個採樣區域水體中壬基苯酚化合物（NPs）含量介於7.39
~241.82ng/ml，辛基苯酚化合物(OPs)含量介於0.66~64.2ng/ml，水體NPs及OPs污染最嚴重的地方為愛河主流上治平橋及支流上的寶珠溝截流站及民族橋，其NPs濃度都大於200ng/ml，OPs濃度都大於30ng/ml。我們發現愛河主流上主要的污染來源為龍心橋、自由橋、龍華橋、寶珠溝截流站這一區段，前鎮河的污染來源主要是來自於中安路及鎮川橋，高雄港區裡的前鎮漁港則可能不斷的有新的污染源注入。
上層底質NPs含量介於633.1~2113.8ng/g，OPs含量介於50.3~287.9ng/g，NPs含量最高為愛河主流上的河堤橋，最低為前鎮河中安路，OPs含量最高為前鎮河鎮川橋，最低為支流上的民族橋。下層底質NPs含量介於523.9~1919.5ng/g，OPs含量介於39.9~322.0ng/g，NPs含量最高為愛河支流上的中華橋，最低為前鎮河中安路，OPs含量最高為旗津漁港，最低為支流上的民族橋。
水體中鹽度的高低及底質中總有機碳含量會影響烷基苯酚化合物的分配係數，不同EO鍊長的烷基苯酚化合物，其分配係數介於0.48~2.67之間。
參考其它國外文獻發現，本次採樣區域中水體及底質烷基苯酚化合物含量是在其它國家研究的最高最低值之間，但是和國內文獻比較發現，水體中烷基苯酚化合物含量是高於台灣本島其它的河流，而且高出歐盟對NP風險評估提出之預估無顯著影響濃度值，因此我們推估後勁溪、愛河、前鎮河、高雄港區水體及底質中的烷基苯酚化合物污染是相當嚴重的。

Hou-Chin stream, Love river, and Chien-Chen river, the three main rivers in Kaohsiung city, flow through the populous residential and industrial areas. A large portion of sewage from domestic and industrial sources are discharged into these rivers, then the Love river and Chien-Chen river pour into the harbor area. In order to understand the pollution of alkylphenol polyethoxylates in these areas, water and sediment samples in Hou-Chin stream, Love river, Chien-Chen river and harbor area in Kaohsiung city were collected and the contents of alkylphenol and corresponding polyethoxylates were analyzed in this study.

LC/MS/MS was used as the analytical instrument which is relatively time-saving in comparison with other instruments. It is also more convenient due to the facts that no derivation or colorization are needed in sample pretreatment. The detection limit can reach to 0.03 ng/ml and recovery can be around 83.6~91.6%. It can analyze alkylphenols combinded with long ethoxylate chain with improved sensitivity and selectivity.

In the four sampling areas, the concentration of NPs in water were between 7.4~241.8ng/ml, and OPs were between 0.66~64.2ng/ml. The most contaminated water samples were found at Chih-Ping Bridge on the mainstream of Love river and Pau-Chu-Kou Dam Station and Min-Tsu Bridge on the tributary of Love river where the concentrations of NPs were greater than 200ng/ml, OPs were greater than 30ng/ml. We found that the main pollution sources were from Lung-Hsin Bridge, Tzu-Yu Bridge, Lung -Hua Bridge, and Pau-Chu-Kou Dam Station. The pollution sources of the Chien-Chen river were mainly from Chung-An Bridge and Chen-Chuan Bridge.

Concentration of NPs in upper sediments were between 633.1~2113.8ng/g, OPs were between 50.3~287.9ng/g. The highest concentration of NPs was at Ho-Ti Bridge on the mainstream of Love river, and the lowest concentration of NPs was at Chung-An Bridge on Chien-Chen river. The highest concentration of OPs was at Chen-Chuan Bridge in Chien-Chen river, and the lowest concentration of OPs was Min-Tsu Bridge on the tributary of Love river. The concentration of NPs in deeper sediments were between 523.9~1919.5ng/g, OPs were between 39.9~322.0ng/g. The highest concentration of NPs was at Chung-Hua Bridge on the tributary of Lover river, and the lowest concentration of NPs was at Chung-An Bridge on Chien-Chen river. The highest concentration of OPs was at Chi-Chin Fishing Port, and the lowest concentration of OPs was at Min-Tsu Bridge on the tributary of Love river.

The salinity of water samples and the total organic carbon in sediment sample will influence the distribution coefficient of alkylphenol polyethoxylates with different length of ethoxylate chains, their distribution coefficients were between 0.48~2.67.

In comparison with foreign studies, the concentrations of alkylphenol polyethoxylates of water and sediments amples in this study were between the highest and lowest values reported. However, the observed concentrations of alkylphenols in these study areas were higher then other rivers in Taiwan. These values were higher than the Probable No Effect Concentrations ( PNEC) of NP risk assessed by European Union. It can be concluded that the pollution of alkylphenol polyethoxylates of water and sediment is getting more serious in Hou-Chin stream, Love river, Chien-Chen river and harbor area in Kaohsiung city.

目錄
謝誌 .............................................................I
中文摘要 .........................................................II
英文摘要 .........................................................IV
目錄 .............................................................VI
表目錄 ..........................................................VIII
圖目錄 ...........................................................IX
壹 前言
1-1 烷基苯酚化合物之用途..........................................1
1-2 各國對烷基苯酚之相關規定及使用限制............................4
1-3 環境荷爾蒙....................................................7
1-4 水體環境中的烷基苯酚化合物 ...................................8
1-4-1 在水體環境的命運.........................................8
1-4-2 在水體環境的濃度........................................12
1-4-3 毒性作用................................................16
1-5 研究目標.....................................................19

貳 材料與方法
2-1 藥品及試劑配製...............................................22
2-1-1 藥品及試劑水............................................22
2-1-2 試劑配製................................................23
2-2 儀器及器材...................................................24
2-3 採樣方法.....................................................25
2-3-1 水體採樣................................................25
2-3-2 底質採樣................................................25
2-4 分析方法......................................................31
2-4-1 沉積物中總有機碳之分析..................................31
2-4-2 水體及底質中烷基苯酚化合物之分析方法....................32

參 結果與討論
3-1 品保及品管....................................................37
3-2 儀器最佳化條件................................................43
3-2-1 離子條件.................................................43
3-2-2 移動相液體及比例的選擇...................................43
3-3 水文資料......................................................51
3-3-1 鹽度....................................................51
3-3-2 pH值....................................................52
3-4 沈積物中總有機碳之比例.......................................52
3-5 水體及底質中烷基苯酚化合物的濃度.............................58
3-5-1 水體中壬基苯酚（NP）及壬基苯酚聚乙氧基醇化合物
含量分析...............................................58
3-5-2 底質中壬基苯酚（NP）及壬基苯酚聚乙氧基醇化合物
含量分析...............................................64
3-5-3 水體中辛基苯酚（OP）及辛基苯酚聚乙氧基醇化合物
含量分析...............................................77
3-5-4 底質中辛基苯酚（OP）及辛基苯酚聚乙氧基醇化合物
含量分析...............................................83
3-6 不同EO數烷基苯酚化合物的分布比例.............................93
3-6-1 水體中不同EO數烷基苯酚化合物的分布比例.................93
3-6-2 底質中不同EO數烷基苯酚化合物的分布比例.................98
3-7 烷基苯酚化合物在水體及底質中的分配係數.......................104
肆 結論
4-1 分析方法及偵測極限之比較.....................................106
4-2 不同區域水體及底質中烷基苯酚化合物的含量.....................108
4-3 不同區域水體中烷基苯酚化合物的含量比例.......................110
4-4 總有機碳和烷基苯酚化合物分配係數的相關性.....................116
4-5 不同因素對烷基苯酚化合物含量之影響...........................118
4-5-1 鹽度的影響..............................................113
4-5-2 總有機碳含量的影響......................................121
4-6 和其它文獻比較...............................................123

伍 結論.........................................................127

陸 參考文獻.....................................................128

柒 附錄.........................................................133







表目錄
表1-1 壬基苯酚、辛基苯酚之理化特性及用途...........................3
表1-2 各國河川壬基酚類化合物的檢出濃度值..........................13
表1-3 台灣河川壬基酚類化合物的檢出濃度值..........................15
表1-4 烷基酚類化合物的相對雌性激素作用強度........................17
表2-1 母離子、子離子及電壓值......................................36
表3-1 烷基苯酚化合物的檢量線 R平方值..............................38
表3-2 烷基苯酚化合物的偵測極限....................................41
表3-3 烷基苯酚化合物之添加回收率..................................42　
表3-4 烷基苯酚化合物各個的子離子、母離子、電壓及滯留時間..........45
續表3-4 烷基苯酚化合物各個的子離子、母離子、電壓及滯留時間.......45
表3-5 各區域採樣點水文資料........................................53
表3-6 各採樣點水體中NPEOs及OPEOs總量............................63
表3-7 各採樣點底質上層中NPEOs及OPEOs總量........................69
表3-8 各採樣點底質下層中NPEOs及OPEOs總量........................76
表3-9 壬基苯酚及辛基苯酚化合物在水體及底質中
的分配係數（log Kd）.......................................105
表4-1 LC-MSMS和其它方法之比較....................................107
表4-2 愛河水體ANOVA檢定結果......................................111
表4-3 前鎮河水體ANOVA檢定結果....................................112
表4-4 愛河水體之DUNCAN’S檢定表..................................113
表4-5 前鎮河水體之DUNCAN’S檢定表................................115
表4-6 表層底質TOC與壬基苯酚化合物Kd值（底質上層含量/水體中含量）
之相關性...................................................117
表4-7 表層底質TOC與辛基苯酚化合物Kd值（底質上層含量/水體中含量）
之相關性...................................................117
表4-8 不同鹽度對Kd的影響.........................................119
表4-9 水體中鹽度高低和壬基苯酚化合物及辛基苯酚化合物含量之
相關性.....................................................120

表4-10 水體濃度及鹽度、底質中總有機碳量和底質中壬基苯酚化合物及
辛基苯酚化合物含量之相關性................................122
表4-11 水體中烷基苯酚含量含其它國家之比較........................124
表4-12 底質中烷基苯酚含量含其它國家之比較........................125




圖目錄
圖1-1. 烷基苯酚類持久性有機污染物結構.............................2
圖1-2. 壬基苯酚(NP)及雌二醇(Estradiol)化合物結構.....................6
圖1-3 .APnEO好氧與厭氧微生物分解途徑..............................9
圖1-4 烷基酚類化合物生物降解作用示意圖...........................11
圖2-1. 後勁溪流域採樣圖...........................................27
圖2-2. 愛河流域採樣圖.............................................28
圖2-3. 前鎮河流域採樣圖...........................................29
圖2-4. 高雄港區採樣圖.............................................30
圖2-5a 水體樣品萃取方法...........................................33
圖2-5b 底質樣品萃取步驟...........................................34
圖3-1 NP及OP檢量線圖............................................39
圖3-2 烷基苯酚化合物之LC/MS/MS之圖譜，移動相為醋酸銨
及甲醇混合溶液.............................................46
圖3-3 烷基苯酚化合物之LC/MS/MS之圖譜，移動相為醋酸銨
及氫甲烷混合液.............................................47
圖3-4 烷基苯酚化合物之LC/MS/MS之圖譜，移動相為
醋酸銨︰甲烷=20：80........................................48
續圖3-4 烷基苯酚化合物之LC/MS/MS之圖譜，移動相為
醋酸銨︰氰甲烷=30：70....................................49
續圖3-4 烷基苯酚化合物之LC/MS/MS之圖譜，移動相為
醋酸銨︰氰甲烷=40：60....................................50
圖3-5a 後勁溪各採樣點底質總有機碳含量............................54
圖3-5b 愛河各採樣點底質總有機碳含量..............................56
圖3-5c 前鎮河各採樣點底質總有機碳含量............................56
圖3-5d 高雄港區各採樣點底質總有機碳含量.........................57
圖3-6a 後勁溪水體壬基苯酚化合物含量.............................59
圖3-6b 愛河水體壬基苯酚化合物含量...............................60
圖3-6c 前鎮河水體壬基苯酚化合物含量.............................61 圖3-6d 高雄港區水體壬基苯酚化合物含量...........................62圖3-7a 後勁溪底質上層壬基苯酚化合物含量.........................65
圖3-7b 愛河底質上層壬基苯酚化合物含量...........................66
圖3-7c 前鎮河底質上層壬基苯酚化合物含量.........................67
圖3-7d 高雄港區底質上層壬基苯酚化合物含量.......................68
圖3-8a 後勁溪底質下層壬基苯酚化合物含量.........................72
圖3-8b 愛河底質下層壬基苯酚化合物含量...........................73
圖3-8c 前鎮河底質下層壬基苯酚化合物含量.........................74
圖3-8d 高雄港區底質下層壬基苯酚化合物含量.......................75
圖3-9a 後勁溪水體辛基苯酚化合物含量.............................79
圖3-9b 愛河水體辛基苯酚化合物含量...............................80
圖3-9c 前鎮河水體辛基苯酚化合物含量.............................81
圖3-9d 高雄港水體辛基苯酚化合物含量.............................82
圖3-10a 後勁溪底質上層辛基苯酚化合物含量........................84
圖3-10b 愛河底質上層辛基苯酚化合物含量..........................85
圖3-10c 前鎮河底質上層辛基苯酚化合物含量........................86
圖3-10d 高雄港區底質上層辛基苯酚化合物含量......................87
圖3-11a 後勁溪底質下層辛基苯酚化合物含量........................89
圖3-11b 愛河底質下層辛基苯酚化合物含量..........................90
圖3-11c 前鎮河底質下層辛基苯酚化合物含量........................91
圖3-11d 高雄港區底質下層辛基苯酚化合物含量......................92
圖3-12 後勁溪水體烷基苯酚化合物含量比例分布.....................94
圖3-13 愛河水體烷基苯酚化合物含量比例分布.......................95
圖3-14 前鎮河水體烷基苯酚化合物含量比例分布.....................96
圖3-15 高雄港區水體烷基苯酚化合物含量比例分布...................97
圖3-16 後勁溪底質上下層烷基苯酚化合物含量比例分布...............99
圖3-17 愛河底質上下層壬基苯酚化合物含量比例分布................100
圖3-18 愛河底質上下層辛基苯酚化合物含量比例分布................101
圖3-19 前鎮河底質上下層烷基苯酚化合物含量比例分布..............102
圖3-20 高雄港區底質上下層烷基苯酚化合物含量比例分布............103
圖 4-1a 不同區域水體中烷基苯酚化合物含量.......................109
圖 4-1b 不同區域底質中烷基苯酚化合物含量.......................109

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