臺灣博碩士論文加值系統

四環黴素(TC)，為一種常用的抗生素，長期以來一直被添加在動物飼料中用來治療病菌感染或是促進動物的生長，但大部分的抗生素不能在動物體內代謝掉，因此約有30-90%會經由動物的排泄物排出體外，可能導致其散佈在土壤及自然水體中。過去的研究指出，土壤中存在的無機膠體(如礦物)由於具粒徑小及比表面積大的優點，因此對抗生素等環境污染物具有一定的吸附能力，其中又以膨潤土(Bentonite)較常為學者所利用，此礦物為一種主要由蒙特石組成的黏土礦物，由於蒙特石親水性的表面卻不利於非極性分子的吸附，故常會加入陽離子界面活性劑，如烷胺類化合物使其成為有機膨潤土(organo-bentonite)來促進蒙特石類礦物對非極性分子的吸附能力。但陽離子型界面活性劑通常對生物的毒性較高，若作為抗生素的載體施用於動物飼料中將可能造成動物本身的毒害，因此，本研究以非離子型界面活性劑來改質黏土礦物膨潤土，瞭解此改質後的有機黏土與TC間的交互作用。結果顯示，改質前後之膨潤土對TC之吸附皆較符合Langmuir吸附模式，且膨潤土插層之非離子型界面活性劑在pH 5-8的條件下均無促進TC吸附的效果，反而會因佔據TC的吸附位置而抑制TC的吸附，因此對TC的吸附量皆有下降的現象。pH 3的條件下，因TC與帶負電的膨潤土表面會以靜電作用力吸引，故不論是否有經過Brij30改質，均有最高的TC吸附量；由pH及離子強度影響實驗發現，與pH 5的結果相較，在pH 8條件下有助於改質膨潤土對TC的吸附，XRD分析結果也顯示TC吸附後最大的層間距出現在pH 8，此可能是由於TC間疏水性作用的結合，使得進入層間的分子較大並與非離子型界面活性劑的疏水端作用，因而促進改質膨潤土對TC的吸附。而FTIR的分析結果則顯示，TC結構上A環、C環的C=O鍵與O=C-NH2鍵在膨潤土吸附上扮演著重要的角色。

Tetracyclines (TCs) are commonly used as feed supplements to enhance animal growth or to treat diseases derived from microbial infections. Because TC cannot be completely metabolized in vivo, about 30-90 % TCs are excreted via the feces and urine as integral. As a result, TC has been found in many soils and natural waters, particularly in those areas near the farmlands. Inorganic colloids, such as clay minerals, distribute widely in the environments which may perform as a good adsorbent for TC or other pollutants because these minerals exhibit unique properties of small particle size and large surface area. Bentonite, one of the soil minerals consisting mainly of montmorillonite, can be a scavenger for environmental pollutants; however, the hydrophilic surfaces of bentonite may limit its application for removing less or non-polar organic molecules. Therefore, a cationic surfactant, such as alkyl amines, had been used to convert the bentonite surfaces becoming more hydrophobic to promote its adsorption capacity of non-polar molecules. Cationic surfactant exhibits a higher bio-toxicity, and this kind of surfactant may lead to a poison while being used as an antibiotic carrier. In this study, a non-ionic surfactant, i.e., Brij30, was used to modify bentonite, and its interaction with TC over a pH range of 3-8 was investigated. Results showed that TC adsorption on bentonite/or Brij30 modified bentonite could be described by the Langmuir model. However, Brij30 would inhibit TC adsorption on bentonite due probably to the blockage of the adsorptive sites of bentonite by Brij30. At pH 3, each bentonite sample exhibited a better adsorption ability of TC, attributing to the electrostatic attractions between TC and bentonite. The results of pH and ionic strengthen effects indicated that TC adsorption on Brij30-modified bentonite was more favorable at pH 8 than that at pH 5. This may be attributed to the hydrophobic interactions of TC molecules with Brij30. Besides, XRD diagram indicated that the d-spacing of TC-loading bentonite exhibited the highest at pH 8 which suggested that TC molecules may associate each other, probably through hydrophobic forces, prior to entering the interlayer of bentonite. FTIR spectra showed that the C=O from A ring and O=C-NH2 group may play an important role in TC adsorption.

目錄
謝誌 i
摘要 ii
Abstract iii
圖目錄 viii
表目錄 x
第一章、前言 1
第二章、前人研究 4
2.1抗生素的歷史 4
2.2抗生素的種類與抑菌機制 5
2.3細菌抗藥性的產生 7
2.4環境中抗生素的主要來源 9
2.5世界各國及台灣對農用抗生素的管制情形 12
2.6 四環素 13
2.6.1四環類抗生素簡介 13
2.6.2環境中的四環素殘留濃度 17
2.6.3四環素在環境中的吸附 18
2.7黏土礦物-膨潤土(Bentonite) 19
2.7.1膨潤土簡介 19
2.7.2有機黏土礦物的改質 19
2.8黏土礦物作為飼料添加劑 21
第三章、材料與方法 22
3.1藥品 22
3.2儀器設備 23
3.3 膨潤土樣品來源 24
3.4非離子型界面活性劑改質之膨潤土製備 24
3.5 膨潤土樣品的X光繞射分析 25
3.6 膨潤土樣品的紅外線光譜分析 26
3.7 膨潤土樣品的總有機碳分析 26
3.8 膨潤土樣品對於TC的吸附 26
3.8.1不同pH下 TC標準曲線製作 26
3.8.2 膨潤土樣品在不同pH下對TC的動力吸附實驗 27
3.8.3 膨潤土樣品在不同pH下對TC的等溫吸附實驗 27
3.8.4不同pH影響膨潤土樣品吸附TC 28
3.8.5離子強度影響膨潤土樣品吸附TC 28
3.9吸附於膨潤土樣品上TC之多次脫附實驗 29
3.10動力吸附模式 29
3.10.1擬一階動力吸附模式 (Pseudo-first-order kinetic model) 29
3.10.2擬二階動力吸附模式 (Pseudo-second-order kinetic model) 30
3.11等溫吸附模式 30
3.11.1 Freundlich吸附理論 30
3.11.2 Langmuir吸附理論 31
第四章、結果與討論 33
4.1非離子型界面活性劑改質膨潤土 33
4.1.1改質膨潤土的總有機碳含量 33
4.1.2 膨潤土樣品的層間間距分析 34
4.1.3 膨潤土樣品的紅外線光譜分析 35
4.2 膨潤土對TC的動力吸附實驗 37
4.3不同pH對膨潤土樣品吸附TC的影響 40
4.3.1 pH影響膨潤土樣品吸附TC實驗 40
4.3.2 不同pH下膨潤土樣品對TC的等溫吸附實驗 43
4.3.3陽離子交換 49
4.4離子強度對膨潤土樣品吸附TC的影響 50
4.5 不同pH影響TC從吸附劑上的脫附 53
4.5.1 膨潤土對TC的動力脫附實驗 53
4.5.2 不同pH下脫附次數對TC脫附的影響 54
4.6 膨潤土樣品吸附TC前後的層間間距分析 56
4.7 膨潤土樣品吸附TC前後的紅外線光譜分析 61
第五章、結論 66
參考文獻 67

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