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研究生:李宜玲
研究生(外文):Yi-Ling Lee
論文名稱:雷射剝蝕取樣法結合感應偶合電漿質譜儀於泥土及沉積土樣品中微量元素分析之研究
論文名稱(外文):Determination of V,Cr,Cu,Zn,Cd,Tl and Pb in soil and sediment samples by Laser ablation inductively coupled plasma mass spectrometry
指導教授:江旭禎江旭禎引用關係
指導教授(外文):Shiuh-Jen Jiang
學位類別:碩士
校院名稱:國立中山大學
系所名稱:化學系研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:121
中文關鍵詞:沉積土雷射剝蝕DRC泥土感應偶合電漿質譜儀
外文關鍵詞:sedimentsoilinductively coupled plasma mass spectrometryLaser ablation
相關次數:
  • 被引用被引用:4
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  • 下載下載:52
  • 收藏至我的研究室書目清單書目收藏:1
雷射剝蝕感應耦合電漿質譜分析法(LA-ICP-MS)係利用高能量的雷射照射在固體表面後,以ICP-MS分析其氣態產物及微小顆粒,是一種可以對固體樣品做直接分析的分法。自1985年來雷射剝蝕感應耦合電漿質譜分析法(LA-ICP-MS)分析固體樣品的研究報告相當多,樣品種類則涵蓋了合金、地質樣品及生物體樣品。因為是直接分析固體,除可以避免傳統分析固體時,溶解樣品時所帶入的污染,避免分析物於消化過程中的損失等優點,同時具有分析速度快、不受樣品不易溶解之限制、無稀釋效應及導入效率高等優點。
在進行LA-ICP-MS分析時,所遭遇的主要問題為標準樣品的製備,一般而言,環境樣品基質的成分相當複雜,因此很難找到與樣品基質完全相同的標準品。本研究以混合乾燥及壓片的方式做為粉末環境樣品(泥土、沉積土) 的製備程序,定量粉末狀樣品在添加適當Triton X-100當作修飾劑,與標準溶液或濃縮同位素充分混合後,置於100℃烘箱中烘乾。再以壓片器壓成一片狀,片狀樣品可直接置於樣品槽,而以LA-ICP-MS方法直接測定泥土及沉積土中一些微量元素如鉻、釩、銅 、鉛等重金屬元素的含量。研究中探討雷射的操作參數如能量大小、雷射光束在樣品表面的離焦(Defocus)距離,並探討固體樣品製備的變數對分析靈敏度的影響,以尋求此系統的最佳分析條件。
另外,研究中結合動力反應室(Dynamic Reaction Cell,簡稱DRC)的裝置,使用NH3當作反應氣體,藉著反應氣體與分析物、干擾物離子間反應速率的不同以去除多原子離子對分析物的干擾,如Ar40C12+對Cr52+及C137O16+對Cr53+的干擾。最後利用標準添加法與同位素稀釋法來對泥土、沉積土樣品及其標準參考樣品進行定量分析,以避免基質不同所造成的靈敏度差異。
Laser ablation inductively coupled plasma mass spectrometry(LA- ICP-MS)has been applied to the determination of V,Cr,Cu,Zn,Cd,Tl and Pb in soil and sediment samples. The powder were pressed into a pellet for LA-ICP-MS analysis,Triron X-100 was used as the modifier to
enhance the ion signals.The influences of instrument operating conditions (laser ablation and ICP-MS)and pellet preparation on the ion signals were reported. For Cr determination, the ICP-MS was operated under the DRC mode which alleviated the mass overlap interference significantly. Standard addition method and isotope dilution method were used for the quantitation work. The powder sample was spiked with suitable amount of element standard and/or enriched isotope, well mixed, dried, well mixed and then pressed into a pellet for LA-ICP-MS analysis.This method has been applied to the determination of V,Cr,Cu,Zn,Cd,Tl and Pb in NIST SRM 2709 San Joaquin soil reference materials and NIST SRM 2711 Montana soil reference materials. The analysis results were agreed with the certified values. The precision between sample replicates was better than 10% with LA-ICP-MS method. Detection limits estimated from standard addition curves were about 260-620,3-5,0.3-1 and 9-20 ng g-1 for Cr,Cu,Zn,Cd,Tl and Pb, respectively, in different samples.
目 錄
論 文 摘 要--------------------------------------------------------------------Ⅰ
謝 誌-----------------------------------------------------------------------------Ⅲ
目 錄-----------------------------------------------------------------------------IV
圖 表 目 錄--------------------------------------------------------------------VII
第一章 感應偶合電漿質譜儀簡介------------------------------------------1
壹、前 言------------------------------------------------------------------------1
貳、基 本 原 理---------------------------------------------------------------2
參、功 能 與 限 制---------------------------------------------------------- 7
1、光譜性干擾---------------------------------------------------------------- 8
2、非光譜性干擾-------------------------------------------------------------8
肆、應 用---------------------------------------------------------------------- 11
1、同位素測量-------------------------------------------------------------- 11
2、元素分析----------------------------------------------------------------- 13
伍、參 考 資 料--------------------------------------------------------------14
第二章 雷射剝蝕取樣法結合感應偶合電漿質譜儀於土壤樣品中鉻、銅、鋅、鎘、鉈及鉛等元素之分析應用----------------------16
壹、前 言-----------------------------------------------------------------------16
貳、LA-ICP-MS的文 獻 回 顧---------------------- ----------------------- 29
叁、實 驗 部 份-----------------------------------------------------------------34
一、實驗設備------------------------------------------------------------------34
二、試劑藥品------------------------------------------------------------------34
三、實驗過程------------------------------------------------------------------38
肆、儀 器 原 理---------------------------------------------------------------- 41
一、雷射剝蝕系統------------------------------------------------------------45
二、雷射操作模式之探討---------------------------------------------------48
三、Dynamic Reaction Cell原理-------------------------------------------49
伍、結 果 與 討 論------------------------------------------------------------56
一、LA-ICP-MS儀器最適化條件之探討--------------------------------- 56
二、雷射離焦距離之探討----------------------------------------------------56
三、雷射能量之探討----------------------------------------------------------57
四、雷射Repetition rate之探討---------------------------------------------57
五、雷射Spot sise之探討----------------------------------------------------58
六、雷射Scan rate之探討----------------------------------------------------58
七、載流氣體流速之探討-----------------------------------------------------62
八、載流氣體組成成份之探討----------------------------------------------62
九、電漿輸出功率之探討---- -----------------------------------------------65
十、修飾劑的選擇---- --------------------------------------------------------65
十一、DRC系統的最佳化----------------------------------------------------71
十二、定量結果----------------------------------------------------------------76
陸、結 論-------------------------------------------------------------------------84
柒、參 考 資 料----------------------------------------------------------------85
第三章 雷射剝蝕取樣法結合感應偶合電漿質譜儀於沉積土樣品中釩及鉻等元素之分析應用--------------------------------------------91
壹、前 言------------------------------------------------------------------------91
貳、實 驗 部 份---------------------------------------------------------------94
一、實驗設備------------------------------------------------------------------94
二、試劑藥品------------------------------------------------------------------94
參、實 驗 過 程--------------------------------------------------------------- 96
肆、結 果 與 討 論---------------------------------------------------------- 99
一、最適化條件之探討----------------------------------------------------- 99
二、以超音波霧化器進樣方式探討DRC變數之影響---------------111
三、定量結果-----------------------------------------------------------------118
伍、結 論---------------------------------------------------------------------- 120
陸、參 考 資 料------------------------------------------------------------- 121
圖 表 目 錄
第一章
圖1-1 典型ICP-MS的構造圖-----------------------------------------------3
圖1-2 ICP中元素的游離程度-----------------------------------------------5
圖1-3 ICP及取樣界面--------------------------------------------------------6
表1-1 無機酸在ICP-MS中,可能形成的背景干擾------------------10
第二章
圖2-1 樣品製備流程圖----------------------------------------------------- 40
圖2-2 LA-ICP-MS裝置圖-------------------------------------------------- 42
圖2-3 LSX-200雷射系統--------------------- ----------------------------- 44
圖2-4 雷射樣品式的構造圖------------------------------------------------46
圖2-5 雷射與樣品的作用圖---------------------------------------------- 47
圖2-6 F模式與Q模式雷射脈衝時間比較----------------------------- 51
圖2-7 F模式與Q模式作用於樣品表面坑洞形狀比較-------------- 52
圖2-8 ICP-DRC-MS的構造------------------------------------------------ 53
圖2-9 碰撞反應槽ICP-MS作用是意圖--------------------------------- 54
圖2-10 不同雷射離焦距離對分析物訊號的影響---------------------- 59
圖2-11 不同雷射能量對分析物訊號的影響-----------------------------605
圖2-12 不同Repetition rate對分析物訊號的影響--------------------- 61
圖2-13 不同Spot size對分析物訊號的影響---------------------------- 63
圖2-14 不同Scan rate對分析物訊號的影響---------------------------- 64
圖2-15 載送氣流流速之探討對分析物訊號的影響-------------66
圖2-16 Ar 及 He的剝蝕情形-------------------------------------------- 67
圖2-17 Ar與He載送氣流流速之探討---------------------------------- 68
圖2-18 電漿輸出功率之探討---------------------------------------------- 69
圖2-19 不同修飾劑的結構式---------------------------------------------- 73
圖2-20 不同修飾劑對分析物訊號的影響------------------------------ -74
圖2-21 不同濃度之修飾劑對分析物訊號的影響---------------------- 75
圖2-22 Cr訊號及其ratio隨NH3氣體流速變化的情形---------------- -78
圖2-23 背景訊號隨NH3流速變化的情形------------------------------- 79
圖2-24 soil中添加基質Cr訊號及ratio隨氣體流速變化的情形-- -80
表2-1 LA-ICP-MS與ICP-MS之比較----------------------------------- 28
表2-2 Cr、Cu、Zn、Cd、Tl及Pb的同位素含量比------------------ 37
表2-3 ICP-MS與Laser ablation系統的操作條件----------------------43
表2-4 泥土參考樣品2709標準添加法分析之結果-------------------- 81
表2-5 泥土參考樣品2711標準添加法分析之結果-------------------- 82
表2-6 泥土參考樣品同位素稀釋法分析之結果----------------------- 83
第三章
圖3-1 樣品製備流程圖------------------------------------------------------97
圖3-2 不同雷射離焦距離對分析物訊號的影響------------------------ 99
圖3-3 不同雷射能量對分析物訊號的影響-- --------------------------102
圖3-4 不同Scan rate對分析物訊號的影響------------- ---------------103
圖3-5 不同Repetition rate對分析物訊號的影響---------------------104
圖3-6 不同Spot size對分析物訊號的影響----------------------------105
圖3-7 電漿輸出功率之探討-----------------------------------------------107
圖3-8 載送氣流流速之探討對分析物訊號的影響--------------------108
圖3-9 不同修飾劑對分析物訊號的影響------------------------------- 109
圖3-10 不同濃度之修飾劑對分析物訊號的影響-----------------------110
圖3-11 超音波霧化器結構圖---------------------------------------------- 113
圖3-12 q=0.5下V及Cr訊號隨NH3氣體流速變化的情形------- 114
圖3-13 q=0.6下V及Cr訊號隨NH3氣體流速變化的情形-------- 115
圖3-14 q=0.7下V及Cr訊號隨NH3氣體流速變化的情形------- 116
圖3-15 sediment中添加基質訊號及ratio隨氣體流速變化情形-- 117
表3-1 ICP-MS與Laser ablation系統的操作條件--------------------- 98
表3-2 沉積土參考樣品標準添加法分析之結果---------------------- 119
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