基于三维荧光光谱法的有机农药废水快速检测实验研究

发布时间：2018-01-25 19:32

本文关键词： 三维荧光光谱农药废水在线监测　出处：《合肥工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：工业排放废水在线监控对减少污染事故发生及保障环境水质安全具有重要的现实意义。传统检测方法以色谱、质谱及色谱-质谱联用等现场采样-实验室分析为主,光谱法具有无需样品预处理、选择性好、灵敏度高等特点,可实现水质的在线、自动与实时检测。因此,针对农药企业排放废水在线监测/监控需求,以多菌灵、麦穗宁和西维因三种农药为研究对象,重点研究了三种农药的三维荧光光谱发射特性,以及三维荧光光谱技术用于废水农药的快速定量分析能力。取得主要研究结果如下:(1)不同环境条件杂环农药三维荧光光谱发射特性研究。研究了三种农药在不同pH值和常见阴、阳离子条件下的三维荧光光谱发射特性,初步分析了Fe3+和Cu2+对三种农药的荧光猝灭机制。结果表明,多菌灵和麦穗宁均具有两个荧光峰,西维因仅有一个荧光区域,三种农药的主要荧光峰分别位于λex/λem=280/300nm、310/340nm、280/335nm;多菌灵与麦穗宁随pH值变化表现为相似的荧光发射特征,在酸性/碱性降低时,荧光强度增大;酸性条件下西维因的荧光发射强度无明显变化,但在碱性条件下,随pH值的减小荧光强度不断增强;三种农药在pH值6.16-7.4范围内均可获得较好的荧光发射特征。Fe3+和Cu2+的存在对三种农药的荧光发射强度均有较大影响,随着离子浓度的增加荧光强度不断降低,因此在实际测量中,需重点考虑Fe3+和Cu2+对测量结果的影响。(2)农药企业排放废水在线监测方法实验研究。研究了基于三维荧光光谱技术的农药企业排放废水在线监测方法,实验测量了三种农药的荧光发射强度随浓度变化关系,计算分析了不同农药的检测限,并对比研究了不同水体中高、低浓度农药的回收率与准确性。结果表明:三种农药荧光发射强度随浓度的增加均呈指数增长,浓度范围覆盖了现有已知农药工业排放限值;多菌灵、麦穗宁和西维因的检测限分别为0.6μg.L-1、0.01μg.L-1和0.06μg.L-1,可满足地表水与地下水痕量农药的检测需求;不同浓度农药在矿泉水与水库水体中的平均回收率均大于96%,平均相对误差小于7%。研究结果为农药企业排放废水的在线监测/监控以及周边地表水/饮用水安全保障提供了方法。(3)高浓度下农药废水三维荧光光谱特征及在线检测分析方法研究。研究了高浓度条件下三种农药的荧光光谱特征以及不同积分宽度下的在线检测定量分析方法。结果表明,多菌灵、麦穗宁的荧光特征区域随浓度的增大发生红移,致使定量分析误差增大;基于不同发射波长范围(10nm、5nm)和固定发射波长点做荧光特征做积分校正曲线,多菌灵和西维因荧光强度随浓度呈指数增长,且相关系数分别为0.9999和0.9997,麦穗宁呈先增大后减小趋势,相关系数分别为0.9995和0.9932。研究结果为高浓度下农药废水的在线检测定量分析提供了依据,为进一步发展农药企业排放废水快速在线监测仪器奠定了基础。
[Abstract]:On-line monitoring of industrial wastewater discharge has important practical significance in reducing pollution accidents and ensuring environmental water quality safety. The traditional detection method is chromatography. Mass spectrometry and chromatography-mass spectrometry are mainly used in the field sampling-laboratory analysis. The spectral method has the advantages of no sample pretreatment, good selectivity and high sensitivity, so it can realize on-line, automatic and real-time detection of water quality. In order to meet the demand of on-line monitoring and monitoring of wastewater discharged from pesticide enterprises, three pesticides, carbendazim, wheisuanning and carbaryl, were selected as the research objects, and the emission characteristics of three kinds of pesticides were mainly studied. And the rapid quantitative analysis of pesticide in wastewater by three dimensional fluorescence spectrometry. The main results are as follows: 1). Three dimensional fluorescence emission characteristics of heterocyclic pesticides under different environmental conditions were studied. The fluorescence quenching mechanism of three pesticides by Fe3 and Cu2 was preliminarily analyzed. The results showed that both carbendazim and maisuanning had two fluorescence peaks. Carbaryl has only one fluorescence region, and the main fluorescence peaks of the three pesticides are located at 位 ex / 位 emn 280 / 300 nm ~ (-1) 310 / 340 nm ~ (-1) ~ 280 / 335nm ~ (-1), respectively. Carbendazim and wheat panicle showed similar fluorescence emission characteristics with the change of pH value, and the fluorescence intensity increased with the decrease of acid / alkalinity. The fluorescence emission intensity of carbaryl did not change obviously under acidic condition, but the fluorescence intensity increased with the decrease of pH value in alkaline condition. The fluorescence emission characteristics of the three pesticides were obtained in the pH range of 6.16-7.4. The existence of Fe _ 3 and Cu2 had a great influence on the fluorescence emission intensity of the three pesticides. The fluorescence intensity decreases with the increase of ion concentration, so it is measured in practice. The influence of Fe3 and Cu2 on the measurement results should be considered. Experimental study on on-line monitoring method of wastewater discharge from pesticide enterprises. The method of on-line monitoring of wastewater discharge from pesticide enterprises based on three-dimensional fluorescence spectroscopy was studied. The relationship between fluorescence emission intensity and concentration of three pesticides was measured and the detection limits of different pesticides were calculated and analyzed. The recovery and accuracy of low concentration pesticides. The results showed that the fluorescence emission intensity of three pesticides increased exponentially with the increase of concentration, and the concentration range covered the known industrial emission limits of pesticides. The detection limits of carbendazim, wheisuanning and carbaryl were 0.6 渭 g 路L ~ (-1) and 0.06 渭 g 路L ~ (-1), respectively. The average recoveries of different concentrations of pesticides in mineral water and reservoir water were all greater than 96%. The average relative error is less than 7. The results provide a method for the on-line monitoring / monitoring of wastewater discharge from pesticide enterprises and the safety guarantee of peripheral surface water / drinking water. The characteristics of three dimensional fluorescence spectrum and on-line detection and analysis method of pesticide wastewater under high concentration were studied. The fluorescence spectrum characteristics of three pesticides under high concentration and the quantitative analysis method of on-line detection under different integral widths were studied. The fruit shows. The fluorescence characteristic region of carbendazim and wheat panning shifted red with the increase of concentration, which resulted in the increase of quantitative analysis error. The fluorescence intensity of carbendazim and carbaryl increased exponentially with the concentration of carbendazim and carbaryl. The correlation coefficients were 0.9999 and 0.9997, respectively. The correlation coefficients were 0.9995 and 0.9932, respectively. The results provided the basis for on-line detection and quantitative analysis of pesticide wastewater with high concentration. It lays a foundation for the further development of a fast on-line monitoring instrument for wastewater discharge from pesticide enterprises.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X839.2

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