【作者】 张丽丽；

【导师】 谭培功；

【作者基本信息】 青岛理工大学 ， 环境科学与工程， 2018， 硕士

【摘要】 联苯胺和4-氟苯胺均是合成染料的重要中间体原料,具有较强的“三致作用”。我国地表水环境质量标准中制定联苯胺的环境限制,环境监测部门已对地表水中联苯胺列为日常监测项目。为此,准确的监测水中联苯胺和4-氟苯胺的污染状况,对于保护人民的身体健康具有重要的意义。本论文以环境水体中联苯胺和4-氟苯胺为目标化合物,对水质中联苯胺的4-氟苯胺的分析方法进行了系统的研究,建立了水质中联苯胺和4-氟苯胺的固相萃取-液相色谱荧光检测的分析方法。研究的主要内容包括以下四个部分:第一部分:联苯胺和4-氟苯胺的环境特性以及分析方法的综述,主要包括联苯胺和4-氟苯胺的结构、物理化学性质、毒性、污染处理技术以及国内外有关联苯胺和4-氟苯胺的分析方法研究进展。对国内外有关水中联苯胺和4-氟苯胺各种检测分析方法标准的优缺点进行了比较。第二部分:以联苯胺和4-氟苯胺为研究对象,确定最佳前处理条件。采用固相萃取法,考察了不同类型的固相萃取柱对联苯胺和4-氟苯胺的萃取效果,发现PCX混合型阳离子交换固相萃取柱能同时富集联苯胺和4-氟苯胺。优化了上样体积、上样速度、淋洗和洗脱条件,最后确定上样体积为150m L,以2?3m L/min的速度通过固相萃取柱,用3%乙酸锁定目标化合物,加8m L甲醇淋洗杂质后用7mL5%氨水甲醇洗脱;比较了不同pH值条件下的水样对联苯胺和4-氟苯胺的影响,确定水样pH值在6?10范围内回收率最好;水样中的悬浮物对联苯胺和4-氟苯胺测定有干扰,研究了调节水样pH值来降低悬浮物的干扰的方法。第三部分:建立了水中联苯胺和4-氟苯胺的液相色谱-编程荧光法分析方法。通过优化最佳检测波长、流动相组成和柱温,确定了色谱最佳分离条件,线性范围和方法检出限。联苯胺和4-氟苯胺在1.0~100μg/L和2.0~200μg/L范围内,线性关系良好,相关系数分别为0.9999和0.9998,方法检出限分别为0.0094μg/L和0.014μg/L,6次测定结果的相对标准偏差在2.1%~7.6%之间,实际样品加标回收率在75.2%~105%之间。研究了联苯胺和4-氟苯胺在三种不同水质中的稳定性。结果表明,在0℃~4℃冷藏密封避光条件下,水样中联苯胺和4-氟苯胺的可保存5d。第四部分:对青岛市饮用水源地水质、自来水水质、污水处理厂出口水质和印染及染整废水处理厂进出口水质等四种水质进行检测分析。结果表明,青岛市自来水水质、饮用水源地水质和污水处理厂出口水质中均未检出联苯胺和4-氟苯胺,符合我国《地表水环境质量标准》(GB 3838-2002)水质标准;部分印染厂的废水出水水质满足我国强制性标准《国家纺织产品基本安全技术规范》(GB18401-2003)中的规定;个别染料制造厂出水水质中联苯胺浓度超出标准限制。更多还原

【Abstract】 Benzidine and 4-fluoroaniline are important intermediates of synthetic dyes.They have potential carcinogenic effects.Benzidine and 4-fluoroaniline mainly presents in the industrial dye production wastewater.It is significant to precise scientific monitor the emission of benzidine and 4-fluoroaniline in the dye wastewater in order to control the dye pollution and maintain the ecological balance.This paper have systematically studied on extraction and determination techniques for benzidine and 4-fluoroaniline in water.The analysis method of Solid phase extraction and liquid chromatography with fluorescence detection were developed for determining benzidine and 4-fluoroaniline in water.The primary coverage contain the following four aspects:Part 1:Review of environmental characteristics of benzidine and 4-fluoroaniline as well as the analysis method,mainly including structure,physical and chemical properties,toxicity,pollution treatment technology and the domestic and foreign currently benzidine and 4-fluoroaniline detection methods reported in the literature.The advantages and disadvantages of the existing standards of benzidine and 4-fluoro aniline at home and abroad are compared.Part 2:The best pre-treatment conditions of benzidine and 4-fluoroaniline were optimized.Solid phase extraction(SPE)was used to investigate the extraction effect of different types of solid phase extraction columns on benzidine and 4-fluoroaniline.It was found that PCX mixed cation exchange solid-phase extraction column can simultaneously enrich benzidine and 4-fluoroaniline.The volume of sample,sample speed,leaching and elution conditions were optimized to determine the sample size for 150 m L,at a speed of 2?3mL/min through the SPE columns,target compounds with 3% acetic acid water,add 8mL of methanol eluting impurity and elution with 7mL5% ammonia methanol.Influence of different pH to benzidine and 4-fluoroaniline was compared,and it was determined that recoveries were best when pH is 6?10.The suspended substance has adsorption effect on benzidine and 4-fluoroaniline,and the adsorption of suspended substance is reduced by adjusting the pH.Part 3:The liquid-chromatography with fluorescence detection wavelength programming for determination of benzidine and 4-fluoroaniline in environmental water was developed.The optimum chromatographic separation conditions were determined by optimizing the best detection wavelength,elution mode and column temperature.The linear range and detection limit of benzidine and 4-fluoroaniline were studied by external standard quantitative determination.The results indicated that benzidine and 4-fluoroaniline had a good linear relationship at 1.0~100 μg/L and 2.0~200 μg/L with a correlation coefficient of 0.9999 and 0.9998,and the method detection limits(MDL)were 0.0094 μg/L and 0.014 μg/L,respectively.The RSD of precisions were 2.1%~7.6%,the recoveries of practical samples were within 75.2%~105%.The stability of benzidine and 4-fluoroaniline in three different water was studied.The results showed that the water samples containing benzidine and 4-fluoroaniline could be stabilized 5 days at 0℃?4℃ under the refrigeration in dark.Part 4: The samples from tap water,drinking water sources,sewage treatment plants and dyeing as well as finishing wastewater treatment plants were analyzed.The results showed that 4-fluoroaniline and benzidine in tap water,drinking water sources and sewage treatment plants were not detected,and the quality could achieve the water quality standard《Standards for Surface Water Quality》(GB 3838-2002).And the water quality of some printing and dyeing factories could meet the requirements of China’s mandatory standard《Basic Safety Technical Specification for National Textile Products》(GB18401-2003).The concentration of benzidine in the individual dye manufacturer exceeds the standard limit.更多还原