臺灣博碩士論文加值系統

Ⅰ.以固相微萃取/氣相層析儀偵測水中有機氯農藥之研究
傳統水中有機氯農藥的萃取方法，大多是採用液相-液相萃取及固相萃取方法進行，再以氣相層析儀進行分析，液相-液相萃取須經過去水、濃縮、淨化、沖提及再濃縮等步驟；固相萃取則須經過過濾、沖提等步驟。整個分析過程不僅繁複且耗時。本研究之目的為採用固相微萃取(Solid Phase Microextraction)方法，利用30 μm polydimethylsioxane(PDMS)萃取60mL之樣品，並使用氣相層析儀-電子捕捉偵測器(GC-ECD)，偵測水中有機氯農藥的濃度。整個分析過程不需要使用有機溶劑，且操作容易，所需時間只需1~2小時，更具潛力的是可在短時間中分析大量的樣品，易於自動化。
實驗設計以田口式直交表法(L9)找出固相微萃取水中有機氯農藥之最佳操作因子。結果顯示最佳因子為：萃取時間60分鐘，吸附溫度25℃，熱脫附溫度230℃，鹽類濃度5 %，此最佳化因子與相關文獻結果相似。採集淡水地區、台北地區及新竹地區之水源地等三處進行真實水樣偵測，結果發現，各地區水源大部分未受有機氯農藥之污染，少數可偵測之有機氯農藥濃度均在偵測極限附近。
Ⅱ.以連續式微波消化/可見光法偵測廢水中化學需氧量
傳統偵測水中化學需氧量(Chemical Oxygen Demand, COD)的方法，主要是以重鉻酸鉀為氧化劑，和水樣加熱迴流2小時，其過程不僅耗時且會產生大量有毒廢液。本研究室以微波加熱，添加硝酸銀替代硫酸汞抑制氯鹽測定水中化學需氧量，已建立最佳微波條件和溶液添加量。本研究之目的為建立連續式管線微波消化系統偵測水中之化學需氧量。
本研究以4個通道之蠕動幫浦吸取硝酸銀溶液，重鉻酸鉀溶液，硫酸銀溶液，水樣各為1mL，在所設定之微波條件進行。結果顯示，連續式微波消化結合分光光度計測定COD裝置已建立並完成測試，連續微波消化水中COD在重鉻酸鉀為原來濃度(0.0417M)時，從入流、微波、冷卻、偵測，硫酸亞鐵銨(FAS)滴定偵測之線性關係R2可達0.9992(COD範圍為100mg/L~500mg/L)；分光光譜儀偵測之檢量線R2可達0.9806。而在重鉻酸鉀濃度減少為0.0167M時，FAS滴定偵測之線性關係R2可達0.9994(COD範圍為100mg/L~500mg/L)；以分光光譜儀偵測之檢量線R2可達0.9600。COD濃度為50mg/L~200mg/L時，FAS滴定偵測之線性關係R2可達0.9993；分光光譜儀偵測之檢量線R2可達0.9821。以連續式管線微波消化配合FAS滴定偵測水中COD，初步方法偵測極限為11.25 mg/L；配合分光光譜儀偵測水中COD，初步方法偵測極限為19.88 mg/L。不論用FAS滴定或分光光譜儀來偵測，其準確性可達90%以上；精密度亦相當不錯(標準偏差均小於5)。

Ⅰ. A Study for the Determination of Organochlorine Pesticides in Waters by the Solid Phase Microextraction/Gas Chromatography (SPME-GC).
The traditional extraction method (liquid-liquid extraction and solid phase extraction) was used as pretreatment in the determination of the organochlorine pesticides in water. The analytical method consisted of water removal, condensation, clean-up, rinsing, fractional distilltion for liquid-liquid extraction and filtering, elution for solid phase extraction followed by gas chromatography detection. The whole processes were complex and time-consuming. In this study, the solid phase microextraction combined gas chromatography-electron capture detector (ECD) for determination of organochlorine pesticides were presented. This analytical method is solvent free and easy to operate, with the potential that can be used to analyze a large number of samples within a short period of time (usually less than two hours). In this study, we used SPME fiber which coating 30 μm polydimethylsioxane(PDMS), and sample volume was 60 mL.
The SPME experiments were designed to use mix level orthogonal array to find four optimized operation factors. The optimized factors were that adsorption time, 60 min; adsorption temperature, 25℃; desorption temperature, 230℃;and salt concentration, 5%.The fiber of SPME after adsorption were analysed by GC-ECD. The method detection limits of organochlorine pesticides were between 0.01 ng/mL and 0.02 ng/mL, and were similar to those in the reference related.
The real water samples were collected from Tamshui, Taipei and Hsinchu and the results analysed by SPME-GC-ECD showed that the concentrations of organochlorine pesticides were very closed to method detection limits.
Ⅱ. Continuous Monitoring Chemical Oxygen Demand in Wastewaters by Microwave Digestion/ Spectrophotometric Method.
The traditional method for the determination of chemical oxygen demand (COD) in wastewater is mainly to digest the wastewater by open reflux method and the potassium dichromate as oxidant. This process is not only time-consuming but also produces a large amount of toxic waste. Therefore the goal of this study was to develop continuous and rapid determination of the COD by flow injection combined microwave digestion.
We used peristaltic pump (4 channels) to sucked silver nitrate solution 1mL, potassium dichromate solution 1mL, silver sulfate solution 1 mL, sample volume 1 mL. First, a simple method for the continuous and rapid determination of the COD by flow injection with combined microwave digestion was setup. The results showed that the linearity relation R-squared for determination of the COD (concentration between 100mg/L and 500mg/L, potassium dichromate solution concentration is 0.0417M) with ferrous ammonium sulfate (FAS) titration and spectrophotometric detection were 0.9992 and 0.9806 respcetively. The detection limits for COD with FAS titration and spectrophotometric detection were 11.25 mg/L and 19.88 mg/L respectively.

Ⅰ.以固相微萃取/氣相層析儀偵測水中有機氯農藥之研究
第一章 緒論…………………………………………………… 1
1.1 前言…………………………………………………… 1
1.2 研究緣起……………………………………………… 2
1.3 研究目的及內容……………………………………… 3
第二章 文獻回顧……………………………………………… 4
2.1 農藥的定義…………………………………………… 4
2.2 農藥的分類…………………………………………… 4
2.3 農藥的毒性與中毒…………………………………… 7
2.3.1 毒性…………………………………………………… 7
2.3.2 農藥中毒……………………………………………… 7
2.4 有機氯農藥…………………………………………… 8
2.4.1 氯系殺蟲劑…………………………………………… 9
2.4.1.1 DDT…………………………………………………… 10
2.4.1.2 DDD…………………………………………………… 11
2.4.1.3 DDE…………………………………………………… 12
2.4.1.4 BHC…………………………………………………… 12
2.4.2 特靈類殺蟲劑………………………………………… 15
2.4.2.1 飛佈達………………………………………………… 15
2.4.2.2 阿特靈………………………………………………… 17
2.4.2.3 地特靈………………………………………………… 18
2.4.2.4 安特靈………………………………………………… 19
2.4.2.5 安殺番………………………………………………… 20
2.5 農藥在土壤中的宿命………………………………… 21
2.6 農藥多重殘留分析技術……………………………… 25
2.7 固相微萃取(SPME) ………………………………… 27
2.7.1 固相微萃取法之原理………………………………… 27
2.7.2 固相微萃取法之萃取方式…………………………… 28
2.7.3 固相微萃取法在有機物種分析上的應用…………… 29
2.7.3.1 固定靜相的種類及體積大小………………………… 31
2.7.3.2 樣品體積大小………………………………………… 31
2.7.3.3 吸附時間及脫附時間的長短………………………… 31
2.7.3.4 樣品攪拌程度的快慢………………………………… 32
2.7.3.5 萃取溫度及脫附溫度的高低………………………… 32
2.8 氣相層析儀…………………………………………… 33
第三章 實驗材料、設備及方法……………………………… 36
3.1 實驗藥品與試劑……………………………………… 36
3.1.1 有機氯農藥(OCPS)標準品…………………………… 36
3.1.2 有機溶劑……………………………………………… 36
3.1.3 一般藥品……………………………………………… 36
3.2 實驗設備……………………………………………… 36
3.2.1 一般實驗設備………………………………………… 36
3.2.2 氣相層析儀( Gas Chromatography, GC ) …………… 37
3.2.3 氣體…………………………………………………… 37
3.2.4 氣體純化裝置………………………………………… 37
3.2.5 層析管柱……………………………………………… 38
3.2.6 數據處理系統………………………………………… 38
3.2.7 線性流速……………………………………………… 38
3.3 儀器操作條件………………………………………… 38
3.4 固相微萃取裝置……………………………………… 39
3.4.1 固相微萃取裝置……………………………………… 39
3.4.2 SPME 纖維之清理…………………………………… 40
3.5 實驗方法與步驟……………………………………… 41
3.5.1 容器之清洗…………………………………………… 41
3.5.2 有機氯農藥標準溶液的配置………………………… 41
3.5.2.1 有機氯農藥標準品儲備溶液，100 ng/mL…………… 41
3.5.2.2 10 ng/mL有機氯農藥標準品………………………… 41
3.5.2.3 SPME最佳實驗條件操作之樣品溶液配製………… 42
3.5.2.4 標準品初步檢量線溶液之配製……………………… 42
3.5.2.5 標準品檢量線溶液之配製…………………………… 42
3.5.3 氯化鈉試劑水之配製………………………………… 42
3.5.4 SPME萃取步驟……………………………………… 43
3.5.5 SPME最佳實驗條件之探討………………………… 45
第四章 結果與討論…………………………………………… 46
4.1 標準品的鑑定………………………………………… 46
4.2 固相微萃取法最佳吸附條件結合GC-ECD分析…… 46
4.3 影響固相微萃取水中有機氯農藥之因子探討……… 61
4.3.1 吸附溫度之影響……………………………………… 61
4.3.2 吸附時間之影響……………………………………… 62
4.3.3 熱脫附溫度之影響…………………………………… 62
4.3.4 氯化鈉濃度之影響…………………………………… 63
4.3.5 固相微萃取水中有機氯農藥的最佳化因子………… 63
4.4 有機氯農藥初步檢量線的建立……………………… 63
4.5 有機氯農藥檢量線的建立…………………………… 67
4.6 初步方法偵測極限…………………………………… 72
4.7 方法空白實驗………………………………………… 75
4.8 真實原水樣品的測定………………………………… 77
4.8.1 原水樣品的採集及保存……………………………… 77
4.8.2 真實原水樣品的檢測結果…………………………… 78
第五章 結論與建議…………………………………………… 82
5.1 結論…………………………………………………… 82
5.2 建議…………………………………………………… 83
第六章 參考文獻……………………………………………… 84
附錄 ………………………………………………………… 91
Ⅱ.以連續式微波消化/可見光法偵測廢水中化學需氧量
第一章 緒論………………………………………………………106
1.1 前言………………………………………………………106
1.2 研究緣起…………………………………………………106
1.3 研究目的及內容…………………………………………107
第二章 文獻回顧…………………………………………………108
2.1 化學需氧量………………………………………………108
2.1.1 化學需氧量概述…………………………………………108
2.1.2 COD檢測方法之進展…………………………………… 108
2.1.3 COD廢液之性質………………………………………… 109
2.1.4 COD廢液之危害性……………………………………… 109
2.1.5 化學需氧量測定物質之限制……………………………110
2.2 化學需氧量之干擾………………………………………111
2.3 化學需氧量之測定方法…………………………………112
2.3.1 重鉻酸鉀迴流法…………………………………………112
2.3.2 密閉式迴流法……………………………………………113
2.3.3 密閉式比色法……………………………………………114
2.3.4 高錳酸鉀法………………………………………………114
2.4 微波加熱法………………………………………………115
2.4.1 微波原理…………………………………………………115
2.4.2 微波應用於測定COD之相關文獻……………………… 116
2.5 流動注入分析法(Flow Injection Analysis) ………118
2.5.1 流動注入法之原理………………………………………118
2.5.2 分散度……………………………………………………119
2.5.3 樣品和試劑之輸送系統…………………………………121
2.5.4 樣品注射器和偵測器……………………………………121
2.5.5 流動注入法相關文獻……………………………………122
第三章 實驗材料、設備及方法…………………………………124
3.1 實驗藥品與試劑…………………………………………124
3.1.1 一般藥品…………………………………………………124
3.1.2 化學需氧量測定試劑……………………………………124
3.2 實驗設備…………………………………………………126
3.2.1 一般實驗設備……………………………………………126
3.2.2 微波消化設備……………………………………………126
3.3 實驗方法與步驟…………………………………………127
3.3.1 微波爐功率測定程序……………………………………127
3.3.2 中壓微波瓶微波消化實驗步驟…………………………128
3.3.3 連續式管線微波消化實驗步驟…………………………129
第四章 結果與討論………………………………………………130
4.1 微波功率測試結果………………………………………130
4.2 連續式管線微波消化測試………………………………131
4.3 微波消化法配合FAS滴定測定之線性關係(中壓微波瓶)133
4.4 微波消化法配合分光光譜儀測定之檢量線(中壓微波瓶)134
4.5 連續式管線微波法配合FAS滴定測定之線性關係…… 135
4.6 連續式管線微波法配合分光光譜儀測定之檢量線……136
4.7 改變重鉻酸鉀濃度微波消化法配合FAS滴定測定之線性關係(中
壓微波瓶) ………………………………………………137
4.8 改變重鉻酸鉀濃度微波消化法配合分光光譜儀測定之檢量線
(中壓微波瓶) ……………………………………………138
4.9 改變重鉻酸鉀濃度連續式管線微波法配合FAS滴定測定之線性
關係…………………………………………………………139
4.10 改變重鉻酸鉀濃度連續式管線微波法配合分光光譜儀測定之檢
量線…………………………………………………………140
4.11 連續式管線微波法配合FAS滴定偵測廢水中低濃度COD之線性關
係(50mg/L~200mg/L) ……………………………………141
4.12 連續式管線微波法配合分光光譜儀偵測廢水中低濃度COD之檢
量線(50mg/L~200mg/L) …………………………………142
4.13 初步方法偵測極限………………………………………143
4.13.1 連續式管線微波法配合FAS滴定初步方法偵測極限… 143
4.13.2 連續式管線微波法配合分光光譜儀初步方法偵測極限144
4.14 連續式管線微波法再現性測試…………………………145
4.14.1 連續式管線微波法配合FAS滴定之再現性…………… 145
4.14.2 連續式管線微波法配合分光光譜儀之再現性…………145
4.15 連續式管線微波消化配合FAS滴定與分光光譜儀偵測廢水中COD
之討論……………………………………………………146
第五章 結論與建議………………………………………………147
5.1 結論………………………………………………………147
5.2 建議………………………………………………………149
第六章 參考文獻…………………………………………………150

Ⅰ.以固相微萃取/氣相層析儀偵測水中有機氯農藥之研究
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Ⅱ.以連續式微波消化/可見光法偵測廢水中化學需氧量
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