农药残留物浓度的光纤荧光测量系统的研究
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摘要
据不完全统计，目前所使用的农药种类大约有5457种。随着农业科技的发展，农药带来的有机污染物已经普遍存在于各国的农牧生产中，对人、畜、环境生物和水、大气、土壤等环境要素产生了严重的危害和污染，即使农药残留物是痕量的，对人们的生命和健康也会造成极大的危害。目前已经发现了由农药引起的多种疾病，农药的残留物对人类健康的潜在危害已引起广泛的国际关注，因此，对农药残留物及其代谢物的高灵敏度检测就变得异常重要。
荧光分析方法具有灵敏度高、选择性强、方法简便等优点，适用于在线环境监测领域。随着电子学和光纤检测技术的发展，荧光分析技术越来越显示出它在工、农、医等实际应用领域的优越性，尤其在农药残留物检测方面，国内外已成功地探测到几十种农药的荧光光谱，并与光纤传感技术相结合开发了多种分析仪。
本文在理论分析的基础上，通过实验获得几种典型农药的荧光光谱，以此为依据，结合光纤传感技术和微弱信号检测技术，开发了一种用于监测农药残留物浓度的新型光纤荧光测量系统。主要进行的研究工作有：
利用现有实验设备获得几种典型农药(氨基甲酸酯类农药、苯甲酰脲类杀虫剂、吡虫啉杀虫剂)的最佳激发光波长和荧光光谱。同时研究了激发时间，溶液PH值和荧光猝灭剂对荧光信号的影响。
根据农药的荧光特性，设计了荧光激发、收集和传输的光学系统。采用氙灯作为激发光源，配备不同的干涉滤光片组实现对于不同农药的激发波长和发射波长的选择。针对农药本身的化学性质，设计了两种光纤探测方案。光学系统采用双光路来消除光源不稳定带来的影响。另外，光学各部分均采用高效的耦合方式，使损耗降为最低。
微弱信号检测部分采用高性能光电探测器(光电倍增管和硅光二极管)将光信号转换为电信号，通过放大和滤波电路降低噪声的干扰，信号的采集、存储和处理部分由单片机系统实现。
用本系统测定了几种典型农药的标准曲线，进行了回收率、准确度、精密度等实验，并与其它标准方法测得的结果进行了比较。
According to incomplete statistic, species of pesticides in use is about 5,457 at present. With development of agriculture science and technology, organic pollutants which pesticides bring have existed in Agro-Animal manufacture of many countries and brought serious harm and pollution. Though pesticide residua is trace, they also can do harm to mankind’s life and health. Presently, many diseases which are brought by pesticides have been discovered and potential harm to health of pesticide residua has catched international extensive. So it becomes exceptional important to detect pesticide residua and their metabolites.
Fluorescence analysis method has an advantage of high sensitivity, strong selectivity and simpleness and is fit for online monitoring field. With the rapid development of electronics and optical-fiber technology, fluorescence analysis technology shows more and more superiority in industry, agriculture and medicine. Especially in pesticide residua detection, fluorescence spectrums of tens of dozens kind of pesticides have been detected and analysis instruments have been developed by means of combining optical-fiber sensor technology.
Based on the theory analysis, we achieved several typical pesticides’ fluorescence spectrums. Based on this, we develop a new optical-fiber fluorescence measurement system which is used in monitoring concentration of pesticide residua combined with optical-fiber sensor and weak signals measurement technology. The main research work includes:
The best exciting wavelength and fluorescence spectrums of several typical species of pesticides (Carbamate, benzoylurea and imidacloprid) have been obtained by making use of existing experimental equipments. At the same time, we study influence of irradiation time, PH and fluorescence quencher on fluorescence intensity.
Weak signals are measured by high-performance photodetectors (PMT and PIN) transiting optical signal into electrical signal. Noise can be reduced by amplifying and filter circuit. MCS-51 completes signals’ sampling，memory and processing.
Pesticides’ work curve, recovery, veracity, precision and repeatability are determined. Measurement results are compared with other method in the same condition.
荧光分析方法具有灵敏度高、选择性强、方法简便等优点，适用于在线环境监测领域。随着电子学和光纤检测技术的发展，荧光分析技术越来越显示出它在工、农、医等实际应用领域的优越性，尤其在农药残留物检测方面，国内外已成功地探测到几十种农药的荧光光谱，并与光纤传感技术相结合开发了多种分析仪。
本文在理论分析的基础上，通过实验获得几种典型农药的荧光光谱，以此为依据，结合光纤传感技术和微弱信号检测技术，开发了一种用于监测农药残留物浓度的新型光纤荧光测量系统。主要进行的研究工作有：
利用现有实验设备获得几种典型农药(氨基甲酸酯类农药、苯甲酰脲类杀虫剂、吡虫啉杀虫剂)的最佳激发光波长和荧光光谱。同时研究了激发时间，溶液PH值和荧光猝灭剂对荧光信号的影响。
根据农药的荧光特性，设计了荧光激发、收集和传输的光学系统。采用氙灯作为激发光源，配备不同的干涉滤光片组实现对于不同农药的激发波长和发射波长的选择。针对农药本身的化学性质，设计了两种光纤探测方案。光学系统采用双光路来消除光源不稳定带来的影响。另外，光学各部分均采用高效的耦合方式，使损耗降为最低。
微弱信号检测部分采用高性能光电探测器(光电倍增管和硅光二极管)将光信号转换为电信号，通过放大和滤波电路降低噪声的干扰，信号的采集、存储和处理部分由单片机系统实现。
用本系统测定了几种典型农药的标准曲线，进行了回收率、准确度、精密度等实验，并与其它标准方法测得的结果进行了比较。
According to incomplete statistic, species of pesticides in use is about 5,457 at present. With development of agriculture science and technology, organic pollutants which pesticides bring have existed in Agro-Animal manufacture of many countries and brought serious harm and pollution. Though pesticide residua is trace, they also can do harm to mankind’s life and health. Presently, many diseases which are brought by pesticides have been discovered and potential harm to health of pesticide residua has catched international extensive. So it becomes exceptional important to detect pesticide residua and their metabolites.
Fluorescence analysis method has an advantage of high sensitivity, strong selectivity and simpleness and is fit for online monitoring field. With the rapid development of electronics and optical-fiber technology, fluorescence analysis technology shows more and more superiority in industry, agriculture and medicine. Especially in pesticide residua detection, fluorescence spectrums of tens of dozens kind of pesticides have been detected and analysis instruments have been developed by means of combining optical-fiber sensor technology.
Based on the theory analysis, we achieved several typical pesticides’ fluorescence spectrums. Based on this, we develop a new optical-fiber fluorescence measurement system which is used in monitoring concentration of pesticide residua combined with optical-fiber sensor and weak signals measurement technology. The main research work includes:
The best exciting wavelength and fluorescence spectrums of several typical species of pesticides (Carbamate, benzoylurea and imidacloprid) have been obtained by making use of existing experimental equipments. At the same time, we study influence of irradiation time, PH and fluorescence quencher on fluorescence intensity.
Weak signals are measured by high-performance photodetectors (PMT and PIN) transiting optical signal into electrical signal. Noise can be reduced by amplifying and filter circuit. MCS-51 completes signals’ sampling，memory and processing.
Pesticides’ work curve, recovery, veracity, precision and repeatability are determined. Measurement results are compared with other method in the same condition.
引文
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A. Garrido Frenich. Resolution (and Quantitation) of Mixtures with Overlapped Spectra by Orthogonal Projection Approach and Alternating Least Squares. Analytic Chimica Acta,2001,449:143-155
李亮亮,于维军,刘文娥.荧光法快速测定有机磷农药.辽宁农业科学,2001(5):44-45
黄德智,岳永德,汤锋.农药残留分析的研究进展.安徽农业学,2002,30(4):523-526
曲红云,张军民.当前国际上先进的农药残留分析技术.黑龙江农业科学,2000,(5):37-39
刘曙照,钱传范.90年代农药残留分析技术.农药,1998,37(6):11-13
Lehotay S, Aharonson N, Pfeil E, et al. Ibrahim Development of a Sample Preparation Technique for Supercritical Fluid Extraction for Multiresidue Analysis of Pesticides in Produce. AOAC Int,1995,78(3):831-840
付颖.食品中农药残留分析.农药,2001,40(6):5-7
Kamiansky D. Online Isotachophoretic Sample Pretreatment in Ultratrace Determination of Paraquat and Diquat in Water by Capillary Ione Eletrophoresis[J]. Anal Chem,1994,678(66):1917-1824
Benz J, Garrison D. Optimization of Separations of Alkyl-sub Stituted Phenolate Anions by Capillary. Ione Electrophoresis,1995,18(3):175-178
Dineui C. Comparison of Eapiuary Electrophoresis, HPLC, and Enzyme Zmmunoassay for Terbuthylazine Detetion in Water. Agric Food Chem, 1993,(41):742-746
郭立,张清敏.氨基甲酸酯类农药残留分析方法的研究进展.天津农学院学报,2001,8(4):15-20
Ngeh Newainbi J, Foley D H, Kuan S. Parathion Antibodies on Piezoelectric
Crystals. Am Chem Soc,1995,108(5):5444-5447
黄卫平.食品中有机氯农药残留分析方法.中国卫生检验杂志,2001,11(6):739-740
黄薇,肖上甲,熊建娟.微量化学法快速测定蔬菜酱中有机氯农药残留量.中国卫生检验杂志,1998,16(6):封3
赵晓联,赵春城,蔡建荣.有机磷农药检测方法综述.江苏食品与发酵,2001,(1):28-30
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