水环境重金属检测微传感器及自动分析仪器的研究
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摘要
近年来,我国社会经济发展迅速,但是随之而来的环境污染问题也不容小视。工业废水的大量排放和矿产资源的过度开发等人为因素加重了水环境的重金属污染。水体中溶解的重金属一般无色无味,通过视觉、嗅觉和味觉无法察觉,但是重金属对人体和动植物的危害却非常大,而且有累积效应,因此发展水环境重金属的快速现场检测技术意义重大。
本文选择电化学溶出伏安法作为水环境重金属现场检测的有效手段,分析了溶出伏安检测的基本原理和定量方法,针对溶出伏安法重金属检测传感器新材料、微型化和集成化三个主要发展方向分别进行了研究,并在此基础上开发了海水重金属元素自动分析仪成功应用于渤海现场检测,最后初步设计研制了应用于太湖水质监测的水环境重金属无线监测仪器。本文研究工作得到了国家高技术研究发展计划(863计划)项目和国家重点基础研究发展计划(973计划)项目的资助。
本文所做的主要工作如下：
1.使用实验室自行研制的重金属分析仪,结合差分脉冲溶出伏安法,采用预镀汞膜法对水环境试样中的锌、镉、铅、铜等4种重金属离子进行了测定,并提出了纯水背景溶液和海水背景溶液不同的测试方法,对纯水背景溶液检测的准确度高,精密度达到5%左右,对海水背景溶液也进行了有效测定,精密度控制在15%以内,检出限达到0.1-0.31μg/L。
2.针对传感器敏感膜新材料的发展方向,对同位镀铋膜法测定重金属离子进行了探索,确定了纯水背景溶液的测定条件,并探索了同位镀铋测定海水的方法,发展了环境友好型的重金属敏感物质。
3.针对传感器微型化的发展方向,研制了带状微电极阵列,电极阵列由100个带状微电极组成,电极间距64μm,每个微电极宽6μm,厚1OOnm,长8mm,并对电极进行了尺寸和伏安特性表征,证明电极特性良好,不镀膜用于铅、铜混合标准溶液的检测效果良好。
4.针对传感器集成化的发展方向,在同一个硅基底上将光寻址电位传感器和微电极阵列集成在一起,制作了光电复合微阵列传感器,在检测时可以根据需要充分发挥光寻址电位传感器和微电极阵列各自的优势,在复合检测时可以建立线性回归模型提高抗干扰能力。
5.在传感器研究的基础上,将自动化技术和化学分析技术有效结合,研制了海水重金属元素自动分析仪,仪器各项指标均通过了第三方检测,并经历了多次现场海试,填补了国内海水重金属现场在线检测仪器的空缺。
6.将传统的重金属检测技术与新兴的无线通讯技术结合,研制了水环境重金属无线监测仪器,应用优化的水路结构,大大提高了仪器的便携性,仪器初步测试功能良好,满足设计要求。
In recent years, the environmental pollution in China has become rather serious with the rapid development of economy. Emission of industrial wastewater and overexploitation of metallic minerals strengthens the heavy metal pollution in aqueous environment. For the dissolved heavy metal ions in water are generally colorless and tasteless, it is difficult to be discovered by senses of vision, smell and taste. Since heavy metals of cumulative effect in the body would do a lot of harm to humans, animals and plants, the technique of quick and in-situ heavy metal detection in aqueous environment is of great significance.
In this thesis, electrochemical stripping voltammetry (SV) was selected as an effective method for the in-situ measurements of heavy metal ions in aqueous environment and its principle and quantitative skills are illustrated. We also did researches on the three main development trends which are creative sensing materials, micromation and integration for the sensors focusing on stripping voltammetric detection of heavy metals. Besides that, an automatic monitor and a wireless analysis instrument were developed respectively for the heavy metal detections in the Bohai Sea and the Taihu Lake. The researches were financed by the National High Technology Research Program (863Program) and the National Key Basic Research Program (973Program).
The major contents of this thesis are as follows:
1) Heavy metals including zinc, cadmium, lead and copper ions in aqueous sample were determined by the mercury-film electrode using differential pulse stripping voltammetry (DPSV) with the analysis instrument fabricated by our lab. Specific detection methods were applied depending on the backgrounds of the solutions. The accuracy of measuring pure water-background samples was good and the precision achieved5%while the precision of measuring seawater-background samples was about15%. The detection limits of all the four elements were in the range of0.1-0.3μg/L.
2) For the trend of creative sensing materials in developing electrochemical sensors, in-situ coated bismuth electrode was tested for heavy metal detection and the method of detecting pure water-background samples was determined. The method of detecting heavy metal ions in seawater by bismuth electrode was also studied. Attractive characteristics of bismuth electrodes are mercury-free and environmentally friendly.
3) For the trend of micromation in developing electrochemical electrodes, a microband electrode array consisted of100microelectrodes was developed. The microband electrodes with inter-electrode spacing of64μm were8mm long,6μm wide and100nm thick. The microband electrode array with excellent dimensional and voltammetric traits did good performance in the detection of mixed samples of lead and copper ions.
4) For the trend of integration in developing electrochemical electrodes, a photoelectric integrated sensor combined light addressable potentiometric sensor (LAPS) and microelectrode array (MEA) on the same silicon chip was designed and fabricated. It was possible to take respective advantages of LAPS and MEA according to different conditions of the measurements. When LAPS and MEA were applied together to the detection, the linear regression model was built to improve the anti-interference ability.
5) Based on the researches on sensors and combining the techniques of automation and chemical analysis, an automatic heavy metal monitor for seawater was developed. All the parameters of the monitor passed the third party test. The automatic heavy metal monitor experienced a number of sea trials and filled the vacancy of in-situ heavy metal monitor for seawater in China.
6) By integrating techniques of traditional heavy metal detection and wireless communication, a wireless heavy metal analysis instrument was developed. The optimized water path greatly improved the portability. Preliminary test showed that the instrument functioned well and satisfied the requests of the design.
本文选择电化学溶出伏安法作为水环境重金属现场检测的有效手段,分析了溶出伏安检测的基本原理和定量方法,针对溶出伏安法重金属检测传感器新材料、微型化和集成化三个主要发展方向分别进行了研究,并在此基础上开发了海水重金属元素自动分析仪成功应用于渤海现场检测,最后初步设计研制了应用于太湖水质监测的水环境重金属无线监测仪器。本文研究工作得到了国家高技术研究发展计划(863计划)项目和国家重点基础研究发展计划(973计划)项目的资助。
本文所做的主要工作如下：
1.使用实验室自行研制的重金属分析仪,结合差分脉冲溶出伏安法,采用预镀汞膜法对水环境试样中的锌、镉、铅、铜等4种重金属离子进行了测定,并提出了纯水背景溶液和海水背景溶液不同的测试方法,对纯水背景溶液检测的准确度高,精密度达到5%左右,对海水背景溶液也进行了有效测定,精密度控制在15%以内,检出限达到0.1-0.31μg/L。
2.针对传感器敏感膜新材料的发展方向,对同位镀铋膜法测定重金属离子进行了探索,确定了纯水背景溶液的测定条件,并探索了同位镀铋测定海水的方法,发展了环境友好型的重金属敏感物质。
3.针对传感器微型化的发展方向,研制了带状微电极阵列,电极阵列由100个带状微电极组成,电极间距64μm,每个微电极宽6μm,厚1OOnm,长8mm,并对电极进行了尺寸和伏安特性表征,证明电极特性良好,不镀膜用于铅、铜混合标准溶液的检测效果良好。
4.针对传感器集成化的发展方向,在同一个硅基底上将光寻址电位传感器和微电极阵列集成在一起,制作了光电复合微阵列传感器,在检测时可以根据需要充分发挥光寻址电位传感器和微电极阵列各自的优势,在复合检测时可以建立线性回归模型提高抗干扰能力。
5.在传感器研究的基础上,将自动化技术和化学分析技术有效结合,研制了海水重金属元素自动分析仪,仪器各项指标均通过了第三方检测,并经历了多次现场海试,填补了国内海水重金属现场在线检测仪器的空缺。
6.将传统的重金属检测技术与新兴的无线通讯技术结合,研制了水环境重金属无线监测仪器,应用优化的水路结构,大大提高了仪器的便携性,仪器初步测试功能良好,满足设计要求。
In recent years, the environmental pollution in China has become rather serious with the rapid development of economy. Emission of industrial wastewater and overexploitation of metallic minerals strengthens the heavy metal pollution in aqueous environment. For the dissolved heavy metal ions in water are generally colorless and tasteless, it is difficult to be discovered by senses of vision, smell and taste. Since heavy metals of cumulative effect in the body would do a lot of harm to humans, animals and plants, the technique of quick and in-situ heavy metal detection in aqueous environment is of great significance.
In this thesis, electrochemical stripping voltammetry (SV) was selected as an effective method for the in-situ measurements of heavy metal ions in aqueous environment and its principle and quantitative skills are illustrated. We also did researches on the three main development trends which are creative sensing materials, micromation and integration for the sensors focusing on stripping voltammetric detection of heavy metals. Besides that, an automatic monitor and a wireless analysis instrument were developed respectively for the heavy metal detections in the Bohai Sea and the Taihu Lake. The researches were financed by the National High Technology Research Program (863Program) and the National Key Basic Research Program (973Program).
The major contents of this thesis are as follows:
1) Heavy metals including zinc, cadmium, lead and copper ions in aqueous sample were determined by the mercury-film electrode using differential pulse stripping voltammetry (DPSV) with the analysis instrument fabricated by our lab. Specific detection methods were applied depending on the backgrounds of the solutions. The accuracy of measuring pure water-background samples was good and the precision achieved5%while the precision of measuring seawater-background samples was about15%. The detection limits of all the four elements were in the range of0.1-0.3μg/L.
2) For the trend of creative sensing materials in developing electrochemical sensors, in-situ coated bismuth electrode was tested for heavy metal detection and the method of detecting pure water-background samples was determined. The method of detecting heavy metal ions in seawater by bismuth electrode was also studied. Attractive characteristics of bismuth electrodes are mercury-free and environmentally friendly.
3) For the trend of micromation in developing electrochemical electrodes, a microband electrode array consisted of100microelectrodes was developed. The microband electrodes with inter-electrode spacing of64μm were8mm long,6μm wide and100nm thick. The microband electrode array with excellent dimensional and voltammetric traits did good performance in the detection of mixed samples of lead and copper ions.
4) For the trend of integration in developing electrochemical electrodes, a photoelectric integrated sensor combined light addressable potentiometric sensor (LAPS) and microelectrode array (MEA) on the same silicon chip was designed and fabricated. It was possible to take respective advantages of LAPS and MEA according to different conditions of the measurements. When LAPS and MEA were applied together to the detection, the linear regression model was built to improve the anti-interference ability.
5) Based on the researches on sensors and combining the techniques of automation and chemical analysis, an automatic heavy metal monitor for seawater was developed. All the parameters of the monitor passed the third party test. The automatic heavy metal monitor experienced a number of sea trials and filled the vacancy of in-situ heavy metal monitor for seawater in China.
6) By integrating techniques of traditional heavy metal detection and wireless communication, a wireless heavy metal analysis instrument was developed. The optimized water path greatly improved the portability. Preliminary test showed that the instrument functioned well and satisfied the requests of the design.
引文
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