【作者】 侯延民；

【导师】 谢吉民；

【作者基本信息】 江苏大学 ， 环境工程， 2009， 博士

【摘要】 四环素类抗生素（Tetracycline Antibiotics,TCs）主要包括土霉素（OTC）、金霉素（CTC）、四环素（TC）等,其它半合成种类主要包括甲烯土霉素、强力霉素、二甲胺基四环素,被广泛应用于畜禽、水产动植物的病害预防、控制和治疗。经各种途径进入环境的残留物质,毒性强,难以生化降解。土壤、植物、食品以及动物排泄物中存在的四环素类抗生素残留最终归趋自然水体,通过水体再向动植物和人体迁移,已经对自然界生态平衡系统和人类健康构成了严重威胁。四环素类抗生素残留分析方法主要有高效液相色谱法（HPLC）、高效液相色谱-质谱联用（HPLC-MS）和生物免疫分析法（BIA）等,这些研究偏重于食品、土壤的残留分析,很少涉及水环境中四环素类抗生素的分离/富集与检测。课题首次提出建立集分离/富集与分析检测于一体的绿色新型综合技术,并研究该技术对水体中四环素类抗生素的分离/富集行为,旨在为控制水体抗生素残留污染奠定理论与实践基础。主要研究结果如下:（1）以传统有机溶剂萃取（TOSE）理论为基础,耦合亲水有机溶剂双水相萃取（HATPE）和气浮溶剂浮选技术（GSF）优势,构建了亲水有机溶剂气浮浮选分离/富集新技术（HOSF）。双水相萃取中使用的水溶性高分子聚合物、小分子有机溶剂和离子液体被称为三大类绿色溶剂,气浮溶剂浮选技术是痕量物质的高效分离/富集方法,建立的新体系由二者融合而成。阐释了工作原理,建立了试验模型,设计并制作了试验设备。课题对选用的小分子亲水有机溶剂、析相无机盐、捕集剂进行了筛选与修饰,通过试验研究对水样中四环素类抗生素残留的分离/富集行为,考察了新体系的实效性。（2）研究了Fe（Ⅲ）、Co（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Mg（Ⅱ）、Ca（Ⅱ）、Al（Ⅲ）与TC、OTC、CTC之间的配位化学反应和Co（Ⅱ）-OTC、Ni-CTC与DAN之间的三元缔合作用,发现新化合物的形成显著改善了TC、OTC、CTC的亲水性能,使其由亲水物质转变为疏水物质,有利于提高亲水有机溶剂气浮浮选体系对水样中痕量四环素类抗生素的测定灵敏度和分离/富集效率。（3）研究了亲水有机溶剂气浮浮选体系对环境水样中痕量土霉素的分离/富集行为。以氯化钙为捕集剂,以正丙醇和无水乙醇（体积比为4/1）为溶剂,对养殖废水中土霉素残留进行了分离/富集与测定。考察了试验参数对分离/富集和检测结果的影响,被测物浓度与吸光度在两个数量级范围内呈良好线性,方法检出限为2.43×10^-7 mol/L,回收率大于97%;以金属离子钴（Ⅱ）和DNA为双向捕集剂,以四氢呋喃为溶剂,对制药废水中土霉素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在三个数量级范围内呈良好线性,方法检出限为3.82×10^-9mol/L,回收率大于99%。（4）研究了亲水有机溶剂气浮浮选体系对环境水样中痕量金霉素的分离/富集行为。以硝酸铁为捕集剂,以四氢呋喃和正丁醇（体积比为4/1）为溶剂,对汝河和湛河水样中金霉素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在两个数量级范围内呈良好线性,方法检出限为3.39×10^-7mol/L,回收率大于96%;以金属离子镍（Ⅱ）和DNA为双向捕集剂,以四氢呋喃为溶剂,对尿液中金霉素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在三个数量级范围内呈良好线性,方法检出限为1.8×10^-9mol/L,回收率大于99%。（5）研究了亲水有机溶剂气浮浮选体系对环境水样中痕量四环素的分离/富集行为。以硫酸铜为捕集剂,以正丙醇为溶剂,对医疗废水中四环素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在两个数量级范围内呈良好线性,方法检出限为9.0×10^-7mol/L,回收率大于97%;以金属离子铝（Ⅲ）为捕集剂,以正丙醇为溶剂,对地下水中四环素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在两个数量级范围内呈良好线性,方法回收率大于95%;以金属离子镁（Ⅱ）为捕集剂,以四氢呋喃为溶剂,对湖水中四环素类抗生素残留进行了分离/富集与测定。考察了试验参数对分离/富集与检测结果的影响,被测物浓度与吸光度在两个数量级范围内呈良好线性,方法回收率大于96%。研究结果表明,亲水有机溶剂气浮浮选体系是水体中四环素类抗生素的有效分离/富集与检测方法,应用过程中不产生二次污染残留。更多还原

【Abstract】 Tetracycline antibiotics（TCs） include primarily oxytetracycline（OTC）, chlortetracycline（CTC） and tetracycline（TC）,other types include semi-synthetic methylene oxytetracycline,doxycycline and tetracycline dimethylamino,which are widely used in disease prevention,control and treatment of livestock and poultry,aquatic animal and plant.The residual substances of TCs which enter into the environment via various channels are toxic and difficult to biodegradation.TCs in the soil,plants,food and animal waste would eventually enter the natural water body,and that,the residue of TCs would be transfered to flora,fauna and human body from water.This is a serious threat for the natural ecological balance system and human health.The analysis methods of TCs residue have HPLC,HPLC-MS,ELISA and so on.These studies focus on the residual analysis in food and soil and very few related to the separation and enrichment of TCs in water.In this thesis,we would first set up a green and new integrated technique,which combines separation and collection with analysis.Furthermore,the behaviour of separation and preconcentration of the technology to the TCs residues in water was investigated.The aim of the research is to build a foundation of theory and practice for controlling the pollution of TCs residues,the main research contents are as follows:（1） The new separation and preconcentration technology of hydrophilic organic solvent floatation（HOSF） has been set up on the basis of traditional organic-solvent extraction,which coupled the advantage of hydrophilic organic solvent eatraction and solvent floatation.The water-soluble polymer,small molecule organic solvent and ionic liquid used in aqueous two-phase extraction are koown as the three main types of green solvents,the technology of solvent floatation is a efficient method of separation and enrichment,the new system is built by a combination of both.The basic work principle of the technology was illustrated,test model was created,test equipment was designed and producted.Moreover,the hydrophilic organic solvent,trapping agent and phase-separating salt were screened and modified,effectiveness of the methodology were studied.（2） Studied the coordination chemical reaction of Fe（Ⅲ）、Co（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Mg（Ⅱ）、Ca（Ⅱ）、Al（Ⅲ） with TC,OTC,CTC and the ternary association of Co（Ⅱ）-OTC、Ni-CTC with DAN,we found that the formation of new compounds improved significantly the hydrophilic properties of TCs,the TCs are transformed into hydrophobe from hydrophilic matter.The achievement improved the sensitivity and efficiency of separation and preconcentration of trace TCs in water by HOSE（3） The behavior of separation and preconcentration on the trace OTC in environmental water samples was studied by HOSE Calcium chloride as the trapping agent,the mixture of n-propanol and n-butyl alcohol（volume ratio 4/1） as solvent,the OTC residue in aquaculture wastewater has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated, concentration and the absorbance measured in the range of two orders of magnitude showed good linearity.The detection limit is 2.43×10^-7 mol/L,recovery is more than 97%:Cobalt（Ⅱ） and DNA as the two-way trapping agent,tetrahydrofuran as solvent,the OTC residue in pharmaceutical wastewater has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated,concentration and the absorbance measured in the range of there orders of magnitude showed good linearity.The detection limit is 3.82×10^-9 mol/L,recovery is more than 99%.（4） The behavior of separation and preconcentration on the trace CTC in environmental water samples was studied by HOSE Iron nitrate as the trapping agent,the mixture of tetrahydrofuran and ethanol（volume ratio 4/1） as solvent,the CTC residue in Ruhe water and Zhanhe water has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated, concentration and the absorbance measured in the range of two orders of magnitude showed good linearity.The detection limit is 3.39×10^-7 mol/L,recovery is more than 96%;Nickel（Ⅱ） and DNA as the two-way trapping agent,tetrahydrofuran as solvent,the CTC residue in urine has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated, concentration and the absorbance measured in the range of there orders of magnitude showed good linearity.The detection limit is 1.8×10^-9 mol/L,recovery is more than 99%.（5） The behavior of separation and preconcentration on the trace TC in environmental water samples was studied by HOSE Copper sulfate as the trapping agent,n-propanol as solvent,the TC residue in medical wastewater has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated, concentration and the absorbance measured in the range of two orders of magnitude showed good linearity.The detection limit is 9.0×10^-7 mol/L,recovery is more than 97%;Aluminium（Ⅲ） chloride as trapping agent,n-propanol as solvent,the TC residue in groundwater has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated, concentration and the absorbance measured in the range of two orders of magnitude showed good linearity.The recovery is more than 99%; Magnesium（Ⅲ） chloride as trapping agent,tetrahydrofuran as solvent,the TCs residue in lake water has been separated,preconcentraed and determinated.The potential effects of test parameters on separation and preconcentration were investigated,concentration and the absorbance measured in the range of two orders of magnitude showed good linearity. The recovery is more than 96%.The results of the study showed that the technique of hydrophilic organic-solvent floatation is an efficient method of separation, preconcentration and detection of TCs residues in water,the application process does not produce secondary pollution.更多还原