核電廠放射性廢棄物中Tc-99、I-129核種分析技術之精進

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研究生：	簡立維 Jian, Li-Wei
論文名稱：	核電廠放射性廢棄物中Tc-99、I-129核種分析技術之精進 The enhancement of analytical technology for Tc-99、I-129 in the nuclear power plant radwastes
指導教授：	王竹方 Wang, Chu-Fang
口試委員:	黃素珍李振弘王竹方
學位類別：	碩士 Master
系所名稱：	原子科學院 - 生醫工程與環境科學系 Department of Biomedical Engineering and Environmental Sciences
論文出版年：	2011
畢業學年度：	99
語文別：	英文
論文頁數：	71
中文關鍵詞：	比例因數
相關次數：	點閱：2 下載：0
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為了針對放射性廢料工程障壁的設計，放射性強度的測量是非常重要的。長半衰期元素例如Tc-99(半衰期為21.3萬年)其具有非常液溶於水的特性及I-129(半衰期為1600萬年)其具有非常易揮發的特性，上述兩者對於環境及人體均扮演著非常重要的角色。一般而言再測量放性活度的方法有：測量核種衰變所釋放出來的能量或者是經由美國電力研究所所開發出來的比例因數的方法來進行量測。然而，上述的兩種方法均不適用於長半衰期核種的量測當中。在本研究當中，鹼消化法被選用為針對碘的樣品前處理步驟，而TEVA管柱則被選用為針對鎝的樣品前處理步驟，並將上述的兩種樣品前處理步驟搭配ICP-MS的偵測來克服這些問題。
整體的流程來說，碘及鎝的樣品前處理步驟均擁有良好的精密度及準確度，且ICP-MS的方法偵測極限(碘的為3 ng/L、鎝的為0.02 ng/L)均優於傳統的液態閃爍偵檢器(碘的為700 ng/L、鎝的為10 ng/L)。在本研究當中實際樣品所偵測到的放射性強度值也均小於利用比例因數所得到的值，也證明了本方法可以有效改善利用傳統方法測量所產生的問題。

For the design of radwaste disposal repository, the measurement of radioactivity in it is very important. Long half-life nuclides such as Tc-99 (t1/2=2.13x105y) which is very soluble and I-129 (t1/2=1.6x107y) which is easy to volatile play important roles for the environment and human. In general, the radioactivity is obtained from the energy of radiation emitted from the nuclides or from the “Scaling factor” method developed by Electric Power Research Institute (EPRI) of America. However, both of the methods are difficult to measure the radioactivity for long half-life nuclides. In this study, alkaline digestion used as the method of sample pretreatment for iodine and the TEVA extraction chromatographic resin for technetium are combined with ICP-MS to overcome these difficulties. The overall sample pre-treatment steps of both iodine and technetium have good precision and accuracy and the method detection limits of iodine and technetium by ICP-MS are 3 ng/L and 0.02 ng/L that are extremely lower than that by the traditional liquid scintillation counter (10 ng/L for 99Tc and 700 ng/L for 129I). The radioactivity of the real samples obtained by this method are all greatly lower than that obtained by the scaling factor. It proves that this method can improve the disadvantages of traditional methods.

Contents

摘要...II
ABSTRACT...III
謝誌...IV
CONTENTS...V
TABLE INDEX...VIII
FIGURE INDEX...X

CHAPTER 1  INTRODUCTION...1
1.1    General overview...1
1.2    Purpose of this study...3

CHAPTER 2  LITERATURE REVIEW...4
2.1    Characterization and regulations of radioactive elements...4
2.1.1    I-129...4
2.1.2    Tc-99...5
2.2    Pretreatment of iodine from samples...7
2.2.1    Pyrohydrolysis...7
2.2.2    Alkaline digestion...9
2.3    Pretreatment of technetium from samples...13
2.3.1    Introduction of TEVA...14
2.3.2    Application...16
2.4    Applications of ICP-MS...19
2.5    Scaling factor...21

CHAPTER 3  EXPERIMENTAL AND METHODS...23
3.1    Apparatus and conditions...23
3.1.1    Inductively coupled plasma...24
3.1.2    Quadrupole Mass Spectrometer...25
3.2    Reagents and materials...26
3.2.1    Iodine...26
3.2.2    Technetium...27
3.3    Experimental procedure...28
3.3.1    Iodine...28
3.3.2    Technetium...35
3.3.3    Real sample...37

CHAPTER 4  RESULT AND DISCUSSION...38
4.1    The establishment of Iodine analysis technique...38
4.1.1    External calibration curve, Correlation coefficient(R2), Detection limit(DL)...38
4.1.2    Optimization of Pyrohydrolysis analysis technique...40
4.1.3    Optimization of Alkline digestion analysis technique...43
4.1.4    Xe+ interference...45
4.1.5    Spike test, Precision and Accuracy...46
4.2    The establishment of Technetium analysis technique...48
4.2.1    External calibration curve, correlation coefficient, detection limit...48
4.2.2    Optimization Analysis conditions with TEVA...50
4.2.3    Vacuum pressure...52
4.2.4    Precision and accuracy...54
4.3    Real sample analysis...55
4.3.1    Iodine...56
4.3.2    Technetium...58
4.3.3    Comparison with scaling factor method and liquid scintillation counter...60

CHAPTER 5  CONCLUSIONS AND FUTURE WORK...63
5.1    Conclusions...63
5.2    Future work...64
Reference...65



Table Index

Table 1   Basic information of 99Tc and 129I...2

Table 2   Three different methods of sample pretreatment with TEVA in Jose Luis Mas et al. 2004...18

Table 4.1  The recovery of SRM2711 with V2O5 and without V2O5 (n=3)...41
Table 4.2  The recovery of SRM2711 with different heating time (n=3), SRM2711 reference value of iodine is 3 ug/g...42
Table 4.3  Recovery of SRM2709 and SRM2711 for different formula (n=3), reference value of SRM2709 and SRM2711 are 5 ug/g and 3 ug/g...44
Table 4.4  Na127I-spiked and Na129I-spiked cement standard recovery test (n=3)...47
Table 4.5  99Tc-spiked cement standard recovery (n=3). (A) part prior wash the column with 50ml of 1M HNO3 solution and then elute the column with 5ml of 14.4M HNO3 solution. (B) part directly elute the column with 5ml of 14.4M HNO3 solution...51
Table 4.6  99Tc-spiked cement standard recovery in different vacuum pressure (n=3)...53
Table 4.7  99Tc-spiked cement standard recovery (n=3)...54
Table 4.8  The data of iodine in the real samples. Gray words mean that the concentration of iodine is ＜LOD and we use the detection limit to represent it (n=3)...57
Table 4.9  The data of technetium in the real samples. Gray words mean that the concentration of technetium is ＜LOD and we use the detection limit to represent it (n=3)...59
Table 4.10  The radioactivity data of scaling factor and ICP-MS in the real samples. Gray words mean that the value is ＜LOD and we use the detection limit to represent it...62
Table 4.11  The detection limit between different apparatus...62



Figure Index

Figure 2.1  The decay scheme of 99Tc...6
Figure 2.2  Combustion apparatus for halogen separation from solid samples. (Bernhard Schnetger et al. 1996)...8
Figure 2.3  Evaporation of iodine from soil sample at different temperatures. (Yasuyuki Muramatsu et al. 2008)...9
Figure 2.4  UV–vis absorbance spectra of potassium iodide solution after oxidation (a) with H2O2 at pH 1, (b) with H2O2 at pH 2.2 (Helen et al. 2008)...11
Figure 2.5  Quaternary ammonium salt (Horwitz et al. 1995)...15
Figure 2.6  TEVA resin elution profiles in HNO3 and HCl solutions. (TRISKEN,TEVA resin product sheet)...16

Figure 3.1  A photograph of Agilent 7500a ICP-MS...23
Figure 3.2  Ion source and interface in ICP MS...25
Figure 3.3  Schema of the ICP-MS...26
Figure 3.4  High-temperature pyrolysis with air-extracting filtration bottle...30
Figure 3.5  The flow chart of high-temperature pyrolysis procedure...31
Figure 3.6  The flow chart of alkaline digestion for SRM standard and the processes of simulated real samples analysis are marked with thick lines...32
Figure 3.7  The appearance of high pressure digestion system...34
Figure 3.8  The flow chart of Technetium analysis...36
Figure 3.9  Increase the flow rate via vacuum pump...37

Figure 4.1  External calibration curve of 127I and 129I, the detection limit of iodine is around 3ppt...39
Figure 4.2  External calibration curve of 99Ru and 99Tc and the detection limit of 99Ru and 99Tc are around 0.3 and 0.02 ppt...49

                                

邱鍠盛助理研究員, 低放射性廢棄物分類之核種與活度量測及認證制度之研究,行政院原子能委員會放射性物料管理局委託研究計畫研究報告,2008

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