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博碩士論文 etd-0924113-164041 詳細資訊
Title page for etd-0924113-164041
論文名稱
Title
海水中防曬劑分析方法之研究
Studies of the analytical method for suntan agents in sea water
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
75
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2013-11-22
繳交日期
Date of Submission
2013-12-05
關鍵字
Keywords
Oxybenzone、液相層析串聯式質譜儀、液液萃取法、Benzophenone、恆春半島、4-Methylbenzylidene camphor
, 4-Methylbenzylidene camphor, Oxybenzone, Benzophenone, Liquid-liquid phase extraction, Hengchun peninsula, LC-MS/MS
統計
Statistics
本論文已被瀏覽 5684 次,被下載 1414
The thesis/dissertation has been browsed 5684 times, has been downloaded 1414 times.
中文摘要
本研究中建立了海水中防曬劑快速、可靠的分析方法。使用液液萃取法 (Liquid-liquid phase extraction)進行水樣前處理,取水樣450 mL以1 mL的正辛醇與異辛烷 (2:8, v/v)混合溶液為萃取液,震盪5分鐘後靜置30分鐘,取出有機層後置入樣品瓶,利用液相層析串聯式質譜儀 (LC-MS/MS)分析水體中五種防曬劑成分含量,分別為Benzophenone (BP)、2,4-Dihydroxybenzophenone (BP-1)、 Oxybenzone (BP-3)、2,2'-Dihydroxy-4-methoxybenzophenone (BP-8)及4-Methyl- benzylidene camphor (4-MBC)。移動相使用甲醇與去離子水做梯度沖堤,各防曬劑化合物回收率介於53.3-115.0 %,偵測極限為1.0-1.7 ng/L,定量極限為3.2-5.7 ng/L。
針對恆春半島沿岸水體在2013年10月3日和10月12日採集5個測站進行環境水體中防曬劑成分含量分析,各測站均檢出防曬劑。BP濃度範圍在1.2-6.7 ng/L;BP-3濃度範圍在5.2-156.2 ng/L;4-MBC濃度範圍在N.D.-2.1 ng/L;BP-1與BP-8各個採樣點皆為未檢出,各測站總含量為9.9-160.3 ng/L。
Abstract
A quick and reliable analytical method for the determination of suntan agents in sea water was developed. Liquid-liquid phase extraction was used for sample pretreatment. To 450 mL of sea water sample, 1 mL of extraction solvent mixture composed of 1-octanol and iso-octane (2:8, v/v) was added. The sample was shaken for five minutes and then stood for thirty minutes. The organic layer was transfered into a sample vial. Five suntan agents including Benzophenone (BP), 2,4-Dihydroxy- benzophenone (BP-1), Oxybenzone (BP-3), 2,2'-Dihydroxy-4-methoxybenzophe- none (BP-8) and 4-Methylbenzylidene camphor (4-MBC) were analyzed by LC-MS/MS equipped with a mobile phase composed of deionized water and methanol. The recovery rates were 53.3-115.0 %, limit of detection were 1.0-1.7 ng/L and limit of quantitative were 3.2-5.7 ng/L.
In October 3rd and 12th 2013, environmental water samples were collected from five sampling sites along the coast of Hengchun peninsula to investigate the contents of suntan agents. Contents of BP, BP-3, 4-MBC, BP-1 and BP-8 were 1.2-6.7 ng/L, 5.2-156.2 ng/L, N.D.-2.1 ng/L, N.D. and N.D., respectively. The total concentration of suntan agents ranged between 9.9 and 160.3 ng/L.
目次 Table of Contents
目錄
論文審定書 ................................................................................................................... i
誌謝 ..............................................................................................................................ii
摘要 ............................................................................................................................ iii
Abstract ........................................................................................................................ iv
目錄 .............................................................................................................................. v
表目錄 ........................................................................................................................vii
圖目錄 ...................................................................................................................... viii
壹、前言 ...................................................................................................................... 1
一、研究緣起 ...................................................................................................... 1
(一)新興汙染物 ........................................................................................... 1
(二)防曬劑介紹 ........................................................................................... 2
(三)防曬劑分析方法相關研究 ................................................................... 5
1.水樣前處理 ....................................................................................... 5
(1)固相萃取法 ............................................................................. 5
(2)液液萃取法 ............................................................................. 5
2.分析儀器 ........................................................................................... 7
二、研究目標 .................................................................................................... 10
貳、材料與方法 ........................................................................................................ 14
一、實驗藥品與材料 ........................................................................................ 14
(一)藥品與器材 ......................................................................................... 14
(二)防曬劑溶液製備 ................................................................................. 15
(三)人工海水製備 ..................................................................................... 15
二、儀器設備 .................................................................................................... 16
三、分析方法 .................................................................................................... 17
(一)液相層析串聯式質譜儀參數條件 ..................................................... 17
(二)水樣中防曬劑液液萃取步驟 ............................................................. 17
(三)海水採樣地點 ..................................................................................... 17
参、結果與討論 ........................................................................................................ 19
一、層析條件設定與質譜儀參數最佳化 ........................................................ 19
(一)質譜分析參數的選擇 ......................................................................... 19
(二)層析條件選擇與設定 ......................................................................... 19
二、液液萃取方法最佳化 ................................................................................ 23
(一)萃取溶劑選擇 ..................................................................................... 23
(二)正辛醇與異辛烷混合萃取溶劑對回收率之影響 ............................. 26
(三)水體樣品液液萃取法流程 ................................................................. 26
(四)液液萃取法與固相萃取法比較 ......................................................... 31
三、品保與品管 ................................................................................................ 33
(一)校正曲線 ............................................................................................. 33
(二)最低偵測極限與最低定量極限 ......................................................... 33
四、恆春半島沿岸水體防曬劑含量分析 ........................................................ 38
(一)水文資料 ............................................................................................. 38
(二)水體中防曬劑含量分析 ..................................................................... 38
肆、結論 .................................................................................................................... 46
參考文獻 .................................................................................................................... 47
附錄一、恆春半島各採樣點水樣中防曬劑層析圖 ................................................ 51
附錄二、恆春半島各採樣點照片 ............................................................................ 61
表目錄
表1-1、防曬劑成分限量表 ........................................................................................ 4
表1-2、防曬劑成分的分析方法 ................................................................................ 6
表1-3、防曬劑相關資料 .......................................................................................... 10
表3-1、防曬劑化合物之母離子定性與定量離子質量與質譜儀電壓參數(volt) . 20
表3-2、移動相梯度沖提設定 .................................................................................. 21
表3-3、防曬劑化合物沖提時間 (min) ................................................................... 21
表3-4、以不同有機溶劑萃取防曬劑成分之回收率 R(%) ................................... 25
表3-5、正辛醇與異辛烷不同混合比例的萃取回收率 R(%) ............................... 29
表3-6、水體樣品中防曬劑分析方法與回收率比較 .............................................. 32
表3-7、以混合標準品配製出校正曲線之R值 ..................................................... 34
表3-8、分析防曬劑化合物之LOD與LOQ .......................................................... 34
表3-9、水體樣品分析方法與LOD比較 ................................................................ 37
表3-10、恆春半島沿岸測站水文資料(2013/10/3) ................................................. 39
表3-11、恆春半島沿岸測站水文資料(2013/10/12) ............................................... 39
表3-12、各採樣點中防曬劑成分含量(2013/10/3) ................................................. 42
表3-13、各採樣點中防曬劑成分含量(2013/10/12) ............................................... 42
表3-14、不同地區水體防曬劑成分含量比較 ........................................................ 45
圖目錄
圖1-1、串聯式質譜儀示意圖 .................................................................................... 8
圖1-2、電灑式離子化器(ESI)示意圖 ....................................................................... 9
圖1-3、防曬劑成分結構 .......................................................................................... 11
圖1-4、防曬劑成分進入環境的途徑 ...................................................................... 13
圖2-1、採樣地點 ...................................................................................................... 18
圖3-1、不同移動相層析圖譜 .................................................................................. 22
圖3-2、各萃取溶劑層析圖譜(水樣體積450 mL),(a)乙酸乙酯(50 mL,以1 mL甲醇回溶)、(b)異辛烷(1 mL)、(c)正辛醇(1 mL) ..................................... 24
圖3-3、以不同有機溶劑萃取防曬劑成分之回收率折線圖 .................................. 25
圖3-4、不同混合比例萃取溶劑層析圖譜,正辛醇:異辛烷比例分別為 (a)1:9、(b)2:8、(c)3:7、(d)4:6 ............................................................................... 27
圖3-5、正辛醇與異辛烷不同混合比例的萃取回收率折線圖 .............................. 29
圖3-6、水體樣品液液萃取法流程 .......................................................................... 30
圖3-7、混合標準品校正曲線,(a)BP、(b)BP-1、(c)BP-3、(d)BP-8、(e)4-MBC、(f)BP-d10 ....................................................................................................... 35
圖3-8、各採樣點防曬劑成分含量長條圖 .............................................................. 43
圖3-9、各採樣點防曬劑成分總含量長條圖 .......................................................... 44
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