基于拉曼光谱的海水COD检测方法的研究
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摘要
海水的化学需氧量大小直接决定海水水质的污染程度,传统的紫外-可见光波段检测时荧光干扰较大,近红外光波段检测时,水分子红外吸收峰影响较严重。提出一种基于拉曼光谱的海水化学需氧量检测方法,以不同浓度的模拟海水样本为被测对象,确定特征拉曼位移为981.6cm-1,对拉曼光谱预处理后,通过偏最小二乘法对拉曼光谱的相对强度与碱性高锰酸钾法检测得到的海水化学需氧量进行回归建模。实验结果显示,训练集和预测集相关系数达到0.99,验证集决定系数可达到0.990 9,预测均方根误差为0.79mg/L。
The chemical oxygen demand(COD)of seawater directly determines the degree of pollution of seawater water quality.The fluorescence interference in the traditional ultraviolet(UV)-visible light detection is relatively large,and the infrared absorption peak of water molecules is seriously affected when the chemical oxygen demand of seawater is detected by the near infrared light.A COD detection method for seawater based on Raman spectroscopy was proposed.The simulated seawater samples of different concentrations were used as the subjects to determine the characteristic Raman displacement of 981.6 cm-1.After pre-processing of Raman spectroscopy,by partial least square method,a regression model was established for the relative strength of Raman spectrum and the seawater COD values measured by potassium permanganate method.The experimental results show that the correlation coefficient between the training set and the prediction set reaches 0.99,the determination coefficient of the verification set reaches 0.990 9,and the predicted mean square root error is 0.79 mg/L.
The chemical oxygen demand(COD)of seawater directly determines the degree of pollution of seawater water quality.The fluorescence interference in the traditional ultraviolet(UV)-visible light detection is relatively large,and the infrared absorption peak of water molecules is seriously affected when the chemical oxygen demand of seawater is detected by the near infrared light.A COD detection method for seawater based on Raman spectroscopy was proposed.The simulated seawater samples of different concentrations were used as the subjects to determine the characteristic Raman displacement of 981.6 cm-1.After pre-processing of Raman spectroscopy,by partial least square method,a regression model was established for the relative strength of Raman spectrum and the seawater COD values measured by potassium permanganate method.The experimental results show that the correlation coefficient between the training set and the prediction set reaches 0.99,the determination coefficient of the verification set reaches 0.990 9,and the predicted mean square root error is 0.79 mg/L.
引文
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[16]WU Xiaoli,LI Yanjun,WU Tiejun.Water quality analysis by three-dimensional fluorescence spectra based on selective model combination[J].Spectroscopy and Spectral Analysis,2010,30(04):996-1001.武晓莉,李艳君,吴铁军.基于选择性模型组合的三维荧光光谱水质分析方法[J].光谱学与光谱分析,2010,30(04):996-1001.
[2]WANG Lili.Research on seawater quality detection technology based on ultraviolet-visible spectroscopy[D].Tianjin:Tianjin University,2014.王莉丽.基于紫外-可见光谱法的海水水质检测技术研究[D].天津:天津大学,2014.
[3]HE Wen.Brief discussion on near infrared spectroscopy analysis technology and its application[J].Chemical Industry Management,2018(31):62-63.何文.略论近红外光谱分析技术及其应用[J].化工管理,2018(31):62-63.
[4]WANG Lei,QIAO Xiaoyan,ZHANG Shu,et al.Fluorescence spectrometry for pesticide residues detection based on BP neural network[J].Journal of Applied Optics,2010,31(03):442-446.王雷,乔晓艳,张姝,等.基于BP神经网络的荧光光谱法农药残留检测[J].应用光学,2010,31(03):442-446.
[5]HE Wei,SUN Xianjun.Research on raman spectrum applied technology[J].Standard Science,2018(03):70-75.何蔚,孙贤君.拉曼光谱应用技术研究[J].标准科学,2018(03):70-75.
[6]TAO Jiayou,XU Daisheng,MEI Xiaoan,et al.Laser raman spectroscopic detection of benzene[J].Journal of Applied Optics,2010,31(02):273-276.陶家友,徐代升,梅孝安,等.苯的激光拉曼光谱检测研究[J].应用光学,2010,31(02):273-276.
[7]QIAO Xiya.Application of josiah raman spectral feature extraction method in qualitative analysis[D].Hangzhou:Zhejiang University,2010.乔西娅.拉曼光谱特征提取方法在定性分析中的应用[D].杭州:浙江大学,2010.
[8]RUAN Hua,DAI Liankui.Joint modeling method of support vector machine classification and regression and its application in raman spectrum analysis[J].Journal of Instruments and Instruments,2010,31(11):2440-2446.阮华,戴连奎.支持向量机分类与回归联合建模方法及其在拉曼光谱分析中的应用[J].仪器仪表学报,2010,31(11):2440-2446.
[9]YANG Cheng,HAN Sen,WU Quanying.Interferogram calibration method based on weighted least squares method[J].Journal of Applied Optics,2016,37(03):392-396.杨程,韩森,吴泉英.基于加权最小二乘法的干涉图校准方法[J].应用光学,2016,37(03):392-396.
[10]CHENG Guangxu.Raman brillouin scattering[M].Beijing:Science Press,2008.程光煦.拉曼布里渊散射[M],北京:科学出版社,2008.
[11]CHEN Yueyang,GAO Zhishan,YU Xiaohui,et al.Screening near infrared spectral information based on interval combination moving window method[J].Journal of Applied Optics,2017,38(01):99-105.陈玥洋,高志山,郁晓晖,等.基于区间组合移动窗口法筛选近红外光谱信息[J].应用光学,2017,38(01):99-105.
[12]WANG Jinli,SUN Yongli,SHANG Wei,et al.Rapid determination of chemical oxygen demand in seawater[J].China Water&Wastewater,2014,30(02):95-97.王金丽,孙永利,尚巍,等.海水化学需氧量的快速测定[J].中国给水排水,2014,30(02):95-97.
[13]LI Jianping,GUO Dandan,ZHAO Li.The improvement of chemical oxygen demand(COD)determination method in seawater[J].Environmental Science Survey,2016,35(01):102-104.李俭平,郭丹丹,赵丽.海水化学需氧量测定方法的改进[J].环境科学导刊,2016,35(01):102-104.
[14]WANG Xiaoming,ZHANG Hailiang,LUO Wei,et al.Measurement of water COD based on UV-Vis spectroscopy technology[J].Spectroscopy and Spectral Analysis,2016,36(01):177-180.王晓明,章海亮,罗微,等.基于UV-Vis检测养殖水体中化学需氧量含量研究[J].光谱学与光谱分析,2016,36(01):177-180.
[15]LIU Yan,BAI Qiang,HOU Guangli,et al.Quick analysis of seawater COD by ozone oxidation chemiluminescence[J].Marine Environmental Science,2008,27(02):182-185.刘岩,白强,侯广利,等.臭氧法海水化学需氧量(COD)现场快速分析技术研究[J].海洋环境科学,2008,27(02):182-185.
[16]WU Xiaoli,LI Yanjun,WU Tiejun.Water quality analysis by three-dimensional fluorescence spectra based on selective model combination[J].Spectroscopy and Spectral Analysis,2010,30(04):996-1001.武晓莉,李艳君,吴铁军.基于选择性模型组合的三维荧光光谱水质分析方法[J].光谱学与光谱分析,2010,30(04):996-1001.