臺灣博碩士論文加值系統

中文摘要
游離態二氧化氯( free ClO2)的釋放速率主要由亞氯酸鹽的純度與濃度及不同酸之酸度強弱、反應時間及溫度而不同，以乳酸活化，在pH 2.0時釋放free ClO2之速率最快；pH 2.5在5小時可達到較高的活化度。而檸檬酸在pH 2.5下需要36小時才能達到和乳酸一樣之最高的活化度。偏磷酸鈉則從第3小時至48小時之變化都呈現平緩上升的趨勢。可知不同初始的pH值，free ClO2產生之速率就不同，pH值愈低，free ClO2釋解速度愈快。
溫度亦影響free ClO2之釋放速率，以乳酸活化在60℃經24小時作用，幾乎已無Free ClO2；以檸檬酸活化也有相似的情形；而偏磷酸鈉受到溫度的影響較少，顯示以偏磷酸鈉活化可延長ClO2的活性及增加ClO2對溫度的穩定性，而使ClO2同時具殺菌及抑菌作用。
三種酸劑活化ClO2後，再以碳酸鈉中和pH值至6.5~7.0，在碳酸鈉添加後其Free ClO2濃度平均都降低21~25%，而隨著放置時間的增加，Free ClO2濃度愈低。顯示中和後的ClO2活化液只適用於初始狀態的殺菌，不可作為長效之抑菌劑使用。
以各種不同濃度ClO2處理鱸魚與海鱺肉片之殺菌及保鮮的效果，結果顯示ClO2處理對魚片確實有殺菌效果，且ClO2不管有無酸化對魚片皆具有殺菌能力，隨著濃度的提高，可顯著的提高殺菌力。而酸化ClO2較穩定ClO2殺菌效果佳，因此如果使用穩定ClO2濃度必須比酸化ClO2高。
經不同ClO2處理過之魚片在6℃貯存，所有處理組在3天內的貯存期間，總生菌數(TPC)都明顯較對照組低，貯存到第7天，以100 ppm酸化ClO2處理組抑菌效果佳；而以20 ppm酸化ClO2處理，或是100 ppm穩定ClO2單獨處理時，殺菌效果較不明顯，但兩者的搭配使用卻能有效增強殺菌及抑菌效果，尤其在貯存期間之抑菌效果更為明顯，因此酸化及穩定型ClO2的搭配使用，提供了新的ClO2使用方法，可改善ClO2使用在貯存上的時效性缺點。而大腸桿菌群(coliforms)在經7天的貯藏中，只有200 ppm穩定ClO2、100 ppm酸化ClO2及20 ppm酸化ClO2搭配100 ppm穩定ClO2等三組仍符合生食用之衛生標準。然而不管水產品新鮮與否，以適當的ClO2濃度處理，均能有效而顯著的降低大腸桿菌群數，進而大幅減少食物中毒的發生機會。
因此ClO2可使用於各類型的水產品來有效提升其安全性，而以正確的方式使用ClO2可大幅增加ClO2的殺菌活性，經ClO2處理過之水產品的品質可以確保、貯存期限可以延長，不但提高經濟效益，同時也可增加水產品的安全性，達到衛生安全的品質要求。

ABSTRACT
The release of free ClO2 by acidification of sodium chlorite (activation of ClO2) depends greatly on the type of GRAS acids employed, the ionic strength of the acid, the reaction time and temperature. The release of free ClO2 using lactic acid reaches a maximal level in 3 hours when pH is 2.0, while it takes 5 hours to reach the same maximal activation at pH 2.5. Citric acid, on the other hand, takes 36 hours to release similar concentration of free ClO2 as lactic acid does at pH 2.5. Acidic meta- polyphosphate salts show increasing level of ClO2 activation within a 48-hour time period. Therefore, the activation of ClO2 is partially determined by the resulting pH value or the amount of acids added. In general, the lower the pH value is, the faster the free ClO2 will be released.
The reaction temperature will change the releasing rate of free ClO2. Activation of ClO2 by lactic acid at 60oC shows no residual free ClO2 in the solution at 24 hours after the addition of acid, while citric acid, at the similar condition, gives only 67% reduction of free ClO2 as compared to the initial level of free ClO2. Acidic metapolyphosphate salts is more inert to the temperature changes where, at 60oC, 14% and 34% reduction are respectively observed at 24 and 48 hours. The unique nature of acidic metapolyphosphate salts will extend the functionality and application of ClO2.
Neutralization of acid-activated ClO2 by sodium bicarbonate to a pH between 6.5 and 7.0 will result in a 21-25% reduction of free ClO2 level as compared to the control without neutralization. Additional reduction in free ClO2 concentration (50-60%) occurs at 12 hours after the neutralization suggesting that neutralization of activated ClO2 will result in a reduction of free ClO2 concentration. Therefore, neutralized ClO2 is not suitable for long-term antimicrobial application.
Application of ClO2 in Japanese seabass and cobia fillets shows that ClO2 is significantly effective in reducing the bacteria counts. Regardless of the addition of acids, the higher concentration of total or free ClO2 will give a better antimicrobial activity. Since the acidified or activated ClO2 is generally more effective than the stabilized ClO2 (no acid added), higher concentration of stabilized ClO2 is needed to reach a similar antimicrobial activity as a lower concentration of activated ClO2.
The ClO2-treated fish fillet shows a significant lower total plate count (TPC) than the non-treated control when stored at 6oC for 3 days, while treatment with 100 ppm acidified ClO2 gives a lowest TPC count among all tested concentrations after a 7-day storage period. The fish fillets treated separately with either 20 ppm acidified ClO2 or 100 ppm of stabilized ClO2 do not show significantly reduced TPC counts. However, the combination of the above two ClO2 concentrations synergistically enhances the antimicrobial activity of ClO2 and its effectiveness in long-term storage. The combination of acidified and stabilized ClO2 provides a new application direction for ClO2 and greatly improves the disadvantage of ClO2 in its duration of antimicrobial activity. The ClO2, at the concentrations including 200 ppm stabilized ClO2, 100 ppm acidified ClO2 and the combination of 100 ppm stabilized and 20 ppm acidified ClO2, will maintain the coliforms counts in fish fillets in compliance with the hygiene standards for seafood sashimi(raw fish) even after 7-day storage at 6oC. Therefore, regardless of the sanitary status of the seafood, processing with optimal concentration of ClO2 will significantly and effectively reduce coliforms counts and greatly reduce the risk of food poisoning.
ClO2 can be applied in almost all types of fishery products to improve the safety of the seafood and comply with the standards in hygiene and quality. The proper use of ClO2 will greatly enhance its antimicrobial activity, appreciate the quality of the treated seafood, extend the shelf-life and increase the economical efficacy.

目 錄
頁次
中文摘要….…………………………………….…………………….. I
英文摘要…………….………………………………….…………….. III
目錄…………………………………………………………………….. Ⅴ
壹、前言………………………………………..…….…..……...……. 1
貳、文獻整理…………………….…….……..…………………....… 4
一、二氧化氯的基本性質……………....…..…………..…….… 4
（一）二氧化氯的歷史.…….……………..……………………….. 4
（二）二氧化氯物化特性……..….….……….....…………………. 5
（三）二氧化氯的製造方法…..….….……….....…………………. 6
（四）二氧化氯在水中的反應.……..….….…....…………………. 7
二、二氧化氯的殺菌機制……….…………...….….....…….….. 9
（一）殺菌劑之殺菌方法及作用過程……...……………….…….. 9
（二）二氧化氯殺菌原理….….….……….....………….…………. 10
三、二氧化氯與其他消毒劑之比較..………..……………....… 10
（一）比較消毒劑優劣的幾項標準…….…….………………….... 10
（二）各種消毒劑效果之比較…………..….….……….............…. 11
四、二氧化氯之應用………..…………………....…………..…… 14
（一）淨水工程……………………...….……………...….….……. 14
（二）食品上的應用….….………...…………….………..…….…. 16
五、二氧化氯之毒性………..………….………….…..……….… 18
（一）毒性調查研究………………...….……………...….….……. 18
（二）毒理學………….….………...…………….………..…….…. 18
參、材料與方法….………………...……….…..……………....…… 20
一、實驗項目與材料….………………..…………………..…..… 20
（一）實驗材料……………………………………..………..…...... 20
（二）實驗儀器……………………………………………...…..…. 21
（三）實驗項目……………………………………….…………..... 21
二、分析方法……………………….……….………..……………… 25
（一）Total ClO2檢測…..……………………….………..………... 25
（二）Free ClO2檢測.….….……………………..……….....……... 25
（三）魚肉pH的測定….…...……………………..…………..…... 26
（四）揮發性鹽基態氮…….…………………..………..…………. 26
（五）總生菌數……...…………………………………...………… 27
（六）大腸桿菌…………...………………………...……………… 27
（七）大腸桿菌群……..……………...………….………………… 27
（八）腸炎弧菌………..……………...………….………………… 28
（九）統計分析………..……………...………….………………… 28
肆、結果與討論.……………………………...…..………………….... 29
一、二氧化氯檢測方法之探討……….….….………….………. 29
二、不同酸劑酸化二氧化氯之活性比較….……….…………. 30
三、溫度對酸化二氧化氯活性之影響…….………….………. 32
四、碳酸鈉中和酸化二氧化氯對其活性之影響…...…..…… 33
五、ClO2處理對魚片之殺菌與保鮮效果…………….………. 34
（一）不同ClO2濃度對魚片之殺菌效果……….………………… 34
（二）ClO2處理魚片在貯存期間品質衛生之變化.………….…… 35
伍、結論………………………………………...……………..….…… 40
陸、參考文獻……………………………..……..………………...…… 41
柒、表……………………………………………..……………...……. 49
捌、圖……………………………………..……………………….…… 59

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