臺灣博碩士論文加值系統

傳統上土壤中的游離氧化鐵，包括無定形與結晶性鐵氧化物，皆採用次亞硫酸鈉-檸檬酸鈉-碳酸氫鈉法（Sodium Dithionite-Citrate- Bicarbonate，簡稱 DCB法）來移除及定量。但以 DCB 法溶出之含鐵溶液，由於其中含有大量的鈉鹽，在以原子吸光法來測定鐵時，常造成原子吸光儀之燃燒器阻塞或試樣溶液互相干擾的困擾，影響測定的精密度與準確度，測定時間亦會延長數倍之久。
本研究針對 DCB 法萃取游離氧化鐵在定量上的困擾，提出修正法，以銨鹽取代 DCB 試劑中大部分的鈉鹽，並以飽和氯化銨或聚丙烯醯 ( Polyacrylamide, PAM ) 取代飽和氯化鈉，探討其可行性。以原子吸光法，分光光度計法，感應耦合電漿原子發射光譜法測定溶液中鐵含量，藉以討論不同萃取法與測定方法之差異。共選擇十種台灣代表性土壤進行試驗，分別為初鹿土系 ( Cl )、台南土系 ( Tn )、老埤土系 ( Lo )、五魁寮土系 ( Wkl )、淡水土系 ( TTs )、蘆竹土系 ( Lc )、二林土系 ( Eh )、瑞穗土系 ( Js )、太康土系 ( Tk )、平鎮土系 ( Pc )。傳統之 DCB 法以 TS表示；僅以聚丙烯醯胺取代飽和氯化鈉之方法，以 TA表示。以檸檬酸銨取代檸檬酸鈉，碳酸氫銨取代碳酸氫鈉，飽和氯化銨或聚丙烯醯胺取代飽和氯化鈉之方法，則分別以 MS、MA 表示。
研究結果顯示，改良之 DCB 法的確可有效降低傳統 DCB 法測定上，鈉鹽含量過高之干擾。而在原子吸光法、分光光度計法及感應耦合電漿原子發射光譜法測定的結果中，改良之 DCB 法的測值與傳統之 DCB 法之值接近，並可降低萃取溶液中的鹽類濃度，進而改善鹽類含量過高所造成之干擾現象。

The citrate-bicarbonate-dithionite (CBD) method is the most commonly used procedure to extract the total free iron oxides in soils. However, the high sodium salt content in the CBD extracts not only causes severe carry-over effect and tends to clog the burner head during atomic absorption spectrophotometric (AAS) analysis. Aspiration of deionized water or dilute acids for a longer period between samples is thus needed for accurate analysis. The objectives of this study were (i) to evaluate the effect of using ammonium salts and/or polyacrylamide (PAM) instead of sodium salts in the CBD reagent on the extraction of total free iron oxides in soils, (ii) to compare the results of using AAS, the colorimetric method of Fe2+-1,10-phenanthroline procedure, and the inductively coupled plasma atomic emission spectroscopy (ICP-AES) for the determination of iron in the CBD extracts of soils. Ten representative agricultural soils in Taiwan were used in this study. The result showed that the amounts of total free iron oxides in soils extracted by the ammonium salts of citrate and bicarbonate in the CBD reagent was similar to those by the sodium salts after correcting the matrix interference by using any of the three methods for iron determination. The use of ammonium salts of CBD reagent for the extraction of total free iron oxides in soils and the use of PAM as the flocculating agent could effectively reduce the carry-over effect and avoid the clogging of the burner head during AAS analysis. The matrix interference in the determination of iron in the CBD extracts was most severe by the ICP-AES method, followed by the AAS and the colorimetric method of Fe2+-1,10-phenanthroline procedure was among the least interfered.

目 錄

中文摘要-------------------------------------------------------------------------- Ⅰ
英文摘要-------------------------------------------------------------------------- Ⅲ
目錄-------------------------------------------------------------------------------- Ⅳ
圖目錄----------------------------------------------------------------------------- Ⅴ
表目錄----------------------------------------------------------------------------- Ⅶ
壹、前言-------------------------------------------------------------------------- 1
一、土壤中的鐵----------------------------------------------------------- 1
二、鐵的分析方法-------------------------------------------------------- 2
三、總游離氧化鐵-------------------------------------------------------- 5
四、鐵的定量方法-------------------------------------------------------- 7
五、研究目的 -------------------------------------------------------- 9
貳、材料與方法 -------------------------------------------------------------- 10
一、供試土壤 ----------------------------------------------------------- 10
二、土壤基本理化性質-------------------------------------------------- 11
三、飽和氯化鈉，飽和氯化銨，與聚丙烯醯胺之比較----------- 14
四、傳統與改良之DCB法混合液比較------------------------------ 17
五、傳統與改良之DCB法萃取土壤游離氧化鐵之比較--------- 19
六、試劑-------------------------------------------------------------------- 24
叁、結果與討論----------------------------------------------------------------- 26
一、飽和氯化鈉，飽和氯化銨，與聚丙烯醯胺之比較----------- 26
二、傳統與改良之DCB法混合液比較------------------------------ 31
1. 混合液之酸鹼滴定曲線------------------------------------------ 31
2. 混合液反應前後pH值之變化---------------------------------- 33
3. 混合液pH隨時間之變化---------------------------------------- 37
4. 混合液之初始 pH 值對游離氧化鐵萃取量的影響-------- 39
三、傳統與改良之DCB法萃取土壤游離氧化鐵之比較--------- 42
1. 四種萃取法之比較------------------------------------------------ 42
2. 三種測定法之比較------------------------------------------------ 51
3. 三種測定法之回收率--------------------------------------------- 57
4. 以不同回收率校正後，四種萃取法之比較------------------ 68
5. 以不同回收率校正後，三種測定法之比較------------------ 77
6. 總結------------------------------------------------------------------ 85
肆、結論------------------------------------------------------------------------- 87
伍、參考文獻------------------------------------------------------------------- 88
陸、附錄------------------------------------------------------------------------- 93

圖 目 錄

圖一、飽和氯化鈉，飽和氯化銨與聚丙烯醯胺絮聚實驗之步驟----- 16
圖二、兩種土系絮聚實驗之比較，一分鐘-------------------------------- 27
圖三、兩種土系絮聚實驗之比較，三分鐘-------------------------------- 28
圖四、兩種土系絮聚實驗之比較，十五分鐘----------------------------- 29
圖五、兩種土系絮聚實驗之比較，三十分鐘----------------------------- 30
圖六、酸鹼滴定曲線----------------------------------------------------------- 32
圖七、以原子吸光法測定四種不同之 DCB萃取法之
土壤游離氧化鐵含量-------------------------------------------------- 43
圖八、以比色法測定四種不同之 DCB萃取法之
土壤游離氧化鐵含量-------------------------------------------------- 45
圖九、以感應耦合電漿原子發射光譜法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量------------------------------ 46
圖十、以原子吸光法測定四種不同之 DCB萃取法之
土壤游離氧化鐵含量-------------------------------------------------- 47
圖十一、以比色法測定四種不同之 DCB萃取法之
土壤游離氧化鐵含量-------------------------------------------------- 49
圖十二、以感應耦合電漿原子發射光譜法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量----------------------------- 50
圖十三 ( a )、利用三種測定法測定四種DCB法萃取之游離氧化鐵
含量---------------------------------------------------------------------- 52
圖十三 ( b )、利用三種測定法測定四種DCB法萃取之游離氧化鐵
含量---------------------------------------------------------------------- 53
圖十三（c）、利用三種測定法測定四種DCB法萃取之游離氧化鐵
含量---------------------------------------------------------------------- 54
圖十三（d）、利用三種測定法測定四種DCB法萃取之游離氧化鐵
含量---------------------------------------------------------------------- 55
圖十三（e）、利用三種測定法測定四種DCB法萃取之游離氧化鐵
含量---------------------------------------------------------------------- 56
圖十四、以原子吸光法測定四種DCB萃取法之檢量曲線
，未稀釋------------------------------------------------------------------ 58
圖十五、以原子吸光法測定四種DCB萃取法之標準曲線
，稀釋五倍--------------------------------------------------------------- 59
圖十六、以原子吸光法測定四種DCB萃取法之標準曲線
，稀釋十倍--------------------------------------------------------------- 60


圖十七、以比色法測定四種DCB萃取法之標準曲線
，稀釋十倍--------------------------------------------------------------- 62
圖十八、以比色法測定四種DCB萃取法之標準曲線
，稀釋五十倍------------------------------------------------------------ 63
圖十九、以感應耦合電漿原子發射光譜法測定四種
DCB萃取法之標準曲線，稀釋十倍-------------------------------- 65
圖二十、以回收率校正原子吸光法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量-------------------------------- 69
圖二十一、以回收率校正原子吸光法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量-------------------------------- 70
圖二十二、以回收率校正比色法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量-------------------------------- 72
圖二十三、以回收率校正比色法測定四種不同之
DCB萃取法之土壤游離氧化鐵含量-------------------------------- 74
圖二十四、以回收率校正感應耦合電漿原子發射光譜法
測定四種不同之 DCB萃取法之土壤游離氧化鐵含------------ 75
圖二十五、以回收率校正感應耦合電漿原子發射光譜法
測定四種不同之 DCB萃取法之土壤游離氧化鐵含------------ 76
圖二十六（a）、以回收率校正三種測定法測定四種不同DCB法
萃取之土壤游離氧化鐵含量----------------------------------------- 78
圖二十六（b）、以回收率校正三種測定法測定四種不同DCB法
萃取之土壤游離氧化鐵含量----------------------------------------- 79
圖二十六（c）、以回收率校正三種測定法測定四種不同DCB法
萃取之土壤游離氧化鐵含量----------------------------------------- 80
圖二十六（d）、以回收率校正三種測定法測定四種不同DCB法
萃取之土壤游離氧化鐵含量----------------------------------------- 82
圖二十六（e）、以回收率校正三種測定法測定四種不同DCB法
萃取之土壤游離氧化鐵含量----------------------------------------- 83







表 目 錄

表一、十種供試土壤之基本性質-------------------------------------------- 13
表二、本研究四種DCB萃取法之處理內容------------------------------ 20
表三、兩種混合液，調整/不調整pH值，反應後之pH值變化----- 34
表四、兩種混合液調整/不調整pH值萃取兩土系
反應後之pH值變化--------------------------------------------------- 36
表五、兩種混合液與兩種pH處理下，pH值隨時間之變化---------- 38
表六、兩種處理與兩種pH值之土壤游離氧化鐵萃取量--------------- 40
表七、以三種測定法測定四種DCB萃取法在不同稀釋倍數
下之回收率-------------------------------------------------------------- 67
附錄一、本研究選取之十種土系名稱-------------------------------------- 93
附錄二之一、以原子吸光法測定四種DCB萃取法萃取之
土壤游離氧化鐵含量-------------------------------------------------- 94
附錄二之二、以比色法測定四種DCB萃取法萃取之
土壤游離氧化鐵含量-------------------------------------------------- 95
附錄二之三、以感應耦合電漿發射光譜法測定四種DCB萃取法
萃取之土壤游離氧化鐵含量----------------------------------------- 96
附錄三之一、以回收率校正原子吸光法測定四種DCB萃取法
萃取之土壤游離氧化鐵含量----------------------------------------- 97
附錄三之二、以回收率校正比色法測定四種DCB萃取法
萃取之土壤游離氧化鐵含量----------------------------------------- 98
附錄三之三、以回收率校正感應耦合電漿發射光譜法測定
四種DCB萃取法萃取之土壤游離氧化鐵含量------------------ 99

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