水体毒害有机化学污染物三维荧光混叠光谱解混方法研究

Toxic & organic chemical pollutants in water may induced carcinogenesis, teratogenic and gene mutation, and threaten human's health by food chain. Three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) technique is a flexible tool for element determination in comparison with conventional field sampling and laboratory assay, and it provide a rapid and in real time analysis method for toxic & organic chemical pollutants in water. However, 3DEEM technique is still faced with various factors influences in real application at present time, such as accurate determination the number of unknown components pollutants and serious spectra aliasing of coexisting species, which may cause the difficulty of spectrum separation and quantitative analysis for different components. This project will focus on the key technique issues of 3DEEM concerning the above problems. The research work will start with the study of 3DEEM fluorescence characteristics of toxic & organic chemical pollutants in water, and will be more focus on the fluorescent features and time emission characteristics of polycyclic aromatic hydrocarbons(PAHs), such as phenanthrene, anthracene, pyrene, fluoranthene and benzo[a]pyrene. The method of accurate determining the number of unknown components pollutants in water will be studied with frequency localization for solving the automatic recognition of the number of unknown components pollutants, and the method using comprehensive similarity index will be studied for accurate determination pollutants composition and separation serious overlapping spectra. An algorithm model will be established for precise unmixing the spectrum and exact identification the composition of unknown toxic & organic chemical pollutants in water based on 3DEEM fluorescence characteristics. The coming out project will provide a novel method for rapid accurate detection of the toxic & organic chemical pollutants in water.

水体毒害有机化学污染物具有致癌、致畸、致基因突变作用，通过食物链威胁人体健康。与传统现场采样、实验室检测方法相比，三维荧光光谱（3DEEM）技术提供了一种快速、实时分析的新方法，但目前该技术尚面临未知组份污染物组份数准确确定以及由于共存组份光谱严重混叠而引起的光谱精确定量化分离困难。本项目针对3DEEM所面临的问题提出解决方案并开展研究。 项目将从水体毒害有机化学污染物的3DEEM光谱特征入手，重点研究水体多环芳烃类（菲、蒽、芘、萤蒽、苯并[a]芘等）污染物的荧光特征与时间发射特性；研究采用频谱局域度准确确定未知组份水体污染物组份数的方法，解决未知组份水体污染物组份数自动识别的难题；研究采用综合相似度指数准确确定污染物成份与精确分离严重混叠光谱的方法，建立未知组份水体毒害有机化学污染物3DEEM光谱的准确识别与光谱精确解混算法模型，为发展水体毒害有机化学污染物的快速、精确测量提供方法基础。

针对三维荧光光谱技术用于水体毒害有机化学污染物分析面临的混叠光谱组分数准确确定、识别以及共存组分干扰精确定量难题，研究了水体多环芳烃、农药和酚类等污染物的荧光光谱特征与发射特性，重点研究了多环芳烃类污染物的组分数确定、识别及光谱分离方法，建立了三维荧光光谱定量分析算法模型并进行了验证。取得主要研究成果如下：.（1）研究了水体多环芳烃（菲、芘、蒽、芴、苊和荧蒽）、农药（多菌灵、麦穗宁、西维因和百克威）及酚类（苯酚、间甲酚和百里酚）等的三维荧光光谱特征及不同环境因素（溶剂、DOM、阴阳离子等）下的发射特性，为光谱定性定量解析提供了特征数据。.（2）研究了基于频谱分析、形态学理论及综合相似度指数的组分数确定及光谱判定方法，基于非负矩阵分解、右因子稀疏非负矩阵分解以及小波域盲分解的三维荧光混叠光谱组分识别方法，实现了水体污染物组分数的准确识别与判定。结果表明，实际水体随机初始值下右因子稀疏非负矩阵分解得到计算光谱相似性因子大于0.80。.（3）研究了基于平行因子分析、交替三线性分解、多维偏最小二乘结合残差双线性分解及部分展开偏最小二乘结合残差双线性分解算法的去离子水、水库水与河水菲、芘、蒽、芴、苊及荧蒽的定量分析方法，基于四维平行因子分析及三维平行因子算法修正模型的复杂环境水体多环芳烃定量测量方法，建立了水体毒害有机化学污染物三维荧光光谱准确识别与精确定量分析算法模型。结果表明，部分展开偏最小二乘结合残差双线性分解算法对不同环境水体分析结果均为最优，菲、芘、蒽、芴相对误差小于6%，三维平行因子算法修正模型分析河水菲、芘、蒽和芴的回收率为82.0-102.0%。.（4）基于项目研究方法探索了三维荧光光谱技术用于农药企业排放废水和饮用水体消毒副产物的在线监测可行性，并进行了水体有机物在线监测设备的研发与测试。项目研究成果为发展水体毒害有机化学污染物的快速精确测量提供了方法，为进一步开展三维荧光光谱技术的应用研究奠定了基础。