臺灣博碩士論文加值系統

台灣地狹人稠，農業土地的使用常緊鄰工業地區而有重金屬汙染之疑慮。鎘在自然界有八個穩定同位素 (106-116amu)，地球化學系統中鎘同位素之分化介於δ114/110Cd=-0.3~0.4‰範圍之間，而工業高溫程序將較輕核種以飛灰形式釋出、較重核種以熔渣殘留而造成明顯之同位素分化(δ114/110Cd=-0.28~0.28‰)，因此可利用其顯著之分化特性釐清並示蹤自然與污染訊號。本研究應用高精度鎘同位素方法量測工業原料、放流水、灌溉用水、地下水、底泥、集塵灰及氣膠質等樣品，系統性定量樣品之重金屬濃度及鎘同位素，以高解析感應耦合電漿質譜儀(Finnigan Element2)定量微量元素濃度，精密度約為3%；利用多接收器感應耦合電漿質譜儀(Neptune)量測鎘同位素，精密度可小於0.1‰。各樣品經消化後使用AG 1-X8及TRU兩階段樹脂進行純化，成功地將鎘與其他干擾元素(鈀、銦、錫)分離以達純化目的。鎘同位素分析前，添加NIST978a銀標準品至樣品中以EEN( Empirical External Normalization)及SSB(Standard Sample Bracketing)方法修正質譜儀之同位素分化與漂移，而SPEX標準品長時間之再現性為δ114/110CdJMC = 0.34±0.08‰ (2S.D., n=18)。岩石基質樣品純化後殘留之元素錫所造成之同重素干擾可利用113Cd成功地做同位素的修正。研究結果顯示農業灌溉用水鎘濃度範圍為10ppt~1ppb，未超過環保署污染標準，鎘同位素比值範圍為δ114/110CdJMC =-0.5‰~0.7‰；沉積物樣品濃度範圍為1~11ppm，鎘同位素比值範圍為δ114/110CdJMC =-0.65‰~0.95‰；但富集因子與地質累積指數同時顯示研究地區有嚴重的重金屬汙染(汞、鉛、鉻、砷……等)。由鎘同位素技術顯示距離工廠越近之汙染來自工業熔渣，較遠區域傳遞途徑主要由大氣沉降而來，受到數據限制尚未能直接指示汙染源，未來將進一步分析工業原料與集塵灰，以釐清工業程序所造成之同位素分化程度，並標定農作物與土壤之鎘同位素，利用鎘濃度與同位素之變化區別不同端源，藉此指示各樣品與污染源之混雜情形，針對研究地區提供系統性之評估，並釐清汙染遷移之特性與潛能，建立汙染傳遞模型。

Taiwan is a densely populated country with lots of crowded and overused land. The rapidly developing economic growths and industrialization resulted serious heavy metal pollution on agriculture land nearby the factories. Cadmium (Cd) has eight stable isotopic at a mass range from 106 to 116 amu, where a natural isotope fractionation of -0.08~0.05‰/amu was found in various terrestrial samples. Significant isotope fractionation of Cd (-0.28~0.28‰/amu) was detected only during industrial processes at very high temperature, resulting in the lighter nuclides enriched in aerosols and ashes, and heavy nuclides remained in slag. The fractionated Cd isotopic ratios driven by the artificial activities have therefore become specific markers for distinguishing the sources from other naturally available Cd. In this study, we present a high precision Cd isotopic determination method using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS, Neptune) with a combined standard-sample bracketing (SSB) procedures and empirical external normalization (EEN) for mass bias correction during the measurement. A two-stage chemical separation using AG 1-X8 and TRU resin was applied to purify Cd from potential interference elements (Pd, In and Sn). The long term reproducibility of replicated standard measurement was δ114/110CdJMC-SPEX = 0.34±0.08‰ (2S.D., n=18). Significant isobaric interference occurred in some rock samples that containing high amounts of Sn, however it can be corrected successfully by monitoring the 113Cd. The industrial wastes, including effluent water, irrigation water, ground water, sediment, and dust, were systematic processed in this study to further quantify the possible pollution sources and the contamination spreading pathways. Our preliminary result reveals that about 10ppt~1ppb of Cd was found in irrigation water, lower than the EPA’s standard, and about 1~11ppm of Cd in sediments was found. The δ114/110CdJMC value of -0.5‰~0.7‰ and -0.65‰~0.95‰ were determined in irrigation water and sediment, respectively. However, the enrichment factor and geo-accumulation index both shows great pollution of other heavy metals of Hg, Pb, Cr and As, etc. The result of Cd isotope reveals that the main polluted reason for the area surrounds the factory is contributed to the industrial sludge but affected by the atmospheric transport away from the factory. Due to the limited isotopic data available, industrial materials and dusts samples are being processed for clarifying the possibility of Cd contamination on crops and soils. The high precision Cd isotopic determination conducted in this study helps to clarify the extent of Cd isotopic fractionation in local high pollution industries, their possible sources and migration of Cd pollution in natural environment.

摘要 (Abstract in Mandarin)…………2
Abstract…4
Acknowledgment……………6
Table of Content……………7
List of Tables……8
List of Figures……8

Chapter1: Introduction………9
Chapter2: Methodology………13
2.1 Materials and chemistry………13
2.1.1 Introduction………13
2.1.2 Study area and sampling………15
2.1.3 Chemical digestion………21
2.2 Instrumentation………23
2.2.1 Introduction………23
2.2.2 Instrumental Mass Fractionation Laws………26
2.2.3 Instrumental Mass Fractionation Correction………27
2.2.4 Empirical External Normalization (EEN)………32
2.3 Matrix separation………33
2.3.1 Matrix Effect………33
2.3.2 Chemical Separation………35
2.4 Analytical procedure………39
2.5 Accuracy and precision………41
Chapter3: Results and Discussion………43
3.1 Correction for Sn interference………43
3.2 Enrichment factor and geo-accumulation index……47
3.2.1 Introduction……47
3.2.2 Enrichment factor……47
3.2.3 Geo-accumulation index……50
3.3 Cd isotope values of natural samples……52
3.3.1 Introduction……52
3.3.2 Cd isotopic composition in natural samples……54
3.3.3 Comparison with previous data……56
3.3.4 Comparison with distance from the factory……59
3.3.5 Results and discussions……61
Chapter4: Conclusion……62
References……64

List of Tables
Table 2.1 | Experimental flow chart…………22
Table 2.2 | Potential interferences on Cd isotopes………………………24
Table 2.3 | Instrumental operating conditions and measurement parameters………25
Table 2.4 | Cd purification standard operation procedures………….37
Table 3.1 | Summary of enrichment factors for average of all heavy metal elements……49
Table 3.2 | Summary of geo-accumulation index for average of all heavy metal
elements………51
Table 3.3 | Isotope and concentration of natural samples……53

List of Figures
Figure 1.1 | Cd stable isotope data for various terrestrial sediments and rocks
and selected meteorites………11
Figure 1.2 | Cd isotope data for samples from Zn-Pb smelting/refining plants
…12
Figure 2.1 | The evaluation of chemical reagent background…………14
Figure 2.2 | Sampling location of irrigation ditch at TCHL…16
Figure 2.3 | Sampling location of water samples at Fung-Xiang steel factory, TCHL………17
Figure 2.4 | Sampling location of irrigation ditch at YLHW…18
Figure 2.5 | Sampling location of sediments at TCHL………………19
Figure 2.6 | Sampling location of sediments at YLHW………………20
Figure 2.7 | High-pressure bomb for sediment digestion……22
Figure 2.8 | Schematic of Thermo Scientific Neptune………24
Figure 2.9 | Schematic of cup configuration…………25
Figure 2.10 | Cd versus silver instrumental mass fractionation (Previous study)……………28
Figure 2.11 | Cd versus silver instrumental mass fractionation (This study)……29
Figure 2.12 | Mass independent fractionation…………30
Figure 2.13 | Flow chart for EEN Cd isotope combined with SSB analytic protocol…………31
Figure 2.14 | Deviation of instrumental mass fractionation factor……32
Figure 2.15 | Matrix effect on Cd isotope measurements…34
Figure 2.16 | Elution curves of the two-stage separation technique………38
Figure 2.17 | Schematic of standard-sample bracketing method………40
Figure 2.18 | Accuracy of NIST RM3108 normalized to BAM I012……41
Figure 2.19 | Long-term reproducibility of Cd isotope analysis………42
Figure 3.1 | Evaluation of Sn interference correction on Cd IC analysis……………44

Figure 3.2 | Mass dependent fractionation line between 112Cd, 113Cd and 114Cd, 113Cd
….45
Figure 3.3 | Evaluation of Sn interference and correction……46
Figure 3.4 | Evaluation of Cd isotope value from different corrections…46
Figure 3.5 | Cd isotopic composition versus the inverse Cd concentration (ppm)54
Figure 3.6 | Cd isotopic composition versus the inverse Cd concentration (ppm) in
TCHL……………55
Figure 3.7 | Cd isotopic composition versus the inverse Cd concentration (ppm) in
YLHW……………55
Figure 3.8 | Comparison of this study data and previous Cd isotope data……57
Figure 3.9 | Cd isotopic composition versus the inverse Cd concentration (ppm) with
water value plotted……………58
Figure 3.10 | Cd isotopic composition of polluted topsoils and refinery
materials versus the sampling distance from the refinery (meters) in
previous study…………59
Figure 3.11 | Cd isotopic composition of polluted topsoils and refinery materials versus the sampling distance from the factory (meters) in this study………10

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