代理参数法检测有机干扰中硝酸盐氮的研究
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摘要
为解决双波长法在硝酸盐氮检测过程中由于有机干扰吸光度叠加造成预测精度下降的问题,提出了代理参数法。把混合谱中的6个积分面积值作为代理参数,基于4阶导数谱的分割算法来寻找代理参数的分界点;通过面积积分法获得分界点前后各代理参数的值;根据有机干扰代理参数的比例,得到分界点前有机干扰对混合谱的贡献程度。基于处理后的数据,采用最小二乘法建立硝酸盐氮水样浓度与其积分面积的预测模型。并将该模型应用于实际水样检测,结果表明,对比传统双波长法,模型的决定系数达到了0.999 8,平均标准偏差小于3%,并且拥有更低的检出限(≥0.009 mg/L)、更好的回收率(95%～104%)和更宽的线性区间,能够为水样中硝酸盐氮的检测提供可靠的技术支持。
When the double-wavelength method is applied to detect nitrate nitrogen, its prediction accuracy is affected by the superposition of absorbance of organic pollutants. To solve this problem, one kind of method based on agent parameters is proposed. The six integral area values contained in the hybrid spectrum are used as the agent parameters. The demarcation point of the agent parameters is determined by the dynamic segmentation algorithm of the fourth derivative spectrum. Each agent parameter at the demarcation point is obtained by the area integral method. According to the ratio of organic pollutants agent parameters, their contribution degree for the hybrid absorption spectrum before the demarcation point is obtained. By using the pre-processed data, the least square method is used to formulate the prediction model for nitrate concentration and its integral area. This model is applied to the practical water sample detection. Compared with the traditional dual-wavelength method, experimental results show that the determination coefficient of the model is 0.9998 and the average standard deviation is less than 3%. It can also realize lower detection limit(≥0.009 mg/L), better recovery(95%～104%) and wider linear range, which provides reliable technical support for the accurate detection of nitrate nitrogen in water samples.
When the double-wavelength method is applied to detect nitrate nitrogen, its prediction accuracy is affected by the superposition of absorbance of organic pollutants. To solve this problem, one kind of method based on agent parameters is proposed. The six integral area values contained in the hybrid spectrum are used as the agent parameters. The demarcation point of the agent parameters is determined by the dynamic segmentation algorithm of the fourth derivative spectrum. Each agent parameter at the demarcation point is obtained by the area integral method. According to the ratio of organic pollutants agent parameters, their contribution degree for the hybrid absorption spectrum before the demarcation point is obtained. By using the pre-processed data, the least square method is used to formulate the prediction model for nitrate concentration and its integral area. This model is applied to the practical water sample detection. Compared with the traditional dual-wavelength method, experimental results show that the determination coefficient of the model is 0.9998 and the average standard deviation is less than 3%. It can also realize lower detection limit(≥0.009 mg/L), better recovery(95%～104%) and wider linear range, which provides reliable technical support for the accurate detection of nitrate nitrogen in water samples.
引文
[1] ZHOU B,BIAN C,TONG J,et al.Fabrication of a miniature multi-parameter sensor chip for water quality assessment[J].Sensors,2017,17(1):157-170.
[2] 刘思乡,范卫华,郭慧,等.机器学习在紫外法测定硝酸盐氮浓度中的应用[J].光谱学与光谱分析,2017,37(4):1179-1182.LIU S X,FAN W H,GUO H,et al.Application of machine learning in determination of nitrate nitrogen based on ultraviolet spectrophometry[J].Spectroscopy and Spectral Analysis,2017,37(4):1179-1182.
[3] FUKUSHI K,ISHIO N,URAYAMA H,et al.Simultaneous determination of bromide,nitrite and nitrate ions in seawater by capillary zone electrophoresis using artificial seawater as the carrier solution[J].Journal of Chromatogr- aphy A,2015,21(2):303-311.
[4] RASOOL R,TAYEBEH S,ALI M,et al.Indirectultratr ace determination of nitrate and nitrite in food samples by insyringe liquid microextraction and electrothermal atomic absorption spectrometry[J].Microchemical Journal,2018 (142):135-139.
[5] DAVIES A R,ANDERSSEN R S,HOOG F R D,et al.Derivative spectroscopy and the continuous relaxation spectrum[J].Journal of Non-Newtonian Fluid Mechanics,2016(233):107-118.
[6] CAUSSE J,THOMAS O,JUNG A V,et al.Direct DOC and nitrate determination in water using dual pathlength and second derivative UV spectrophotometry[J].Water Research,2016(108):312-319.
[7] 柳玲,高晓庆,苗振华,等.离子色谱法与分光光度法测定水中亚硝酸盐含量的对比[J].中国给水排水,2016,32(2):93-96.LIU L,GAO X Q,MIAO ZH H,et al.Comparison between ion-chromatography and spectrophotometry for determin ing nitrite in water[J].China Water & Wastewater,2016,32(2):93-96.
[8] 赵彦涛,单泽宇,常跃进,等.基于MI-LSSVM的水泥生料细度软测量建模[J].仪器仪表学报,2017,38(2):487- 496.ZHAO Y T,SHAN Z Y,CHANG Y J,et al.Soft sensor modeling for cement fineness based on least squares support vector machine and mutual information[J].Chinese Journal of Scientific Instrument,2017,38(2):487- 496.
[9] 王智宏,陈琛,千承辉,等.基于粒子群寻优的光谱仪波长误差修正方法[J].仪器仪表学报,2017,38(10):82- 88.WANG ZH H,CHEN CH,QIAO CH H,et al.Spectrometer wavelength error correction method based on particle swarm optimization[J].Chinese Journal of Scientific Instrument,2017,38(10):82- 88.
[10] HU Y,WEN Y,WANG X.Novel method of turbidity compensation for chemical oxygen demand measurements by using UV-vis spectrometry[J].Sensors & Actuators B Chemical,2016(227):393-398.
[11] 张朕,姜劲,傅嘉豪,等.基于功能近红外光谱的多生理脑力疲劳检测[J].仪器仪表学报,2017,38(6):1345-1352.ZHANG ZH,JIANG J,FU J H,et al.Multi-physiological mental-fatigue detection based on the functional near infrared spectroscopy[J].Chinese Journal of Scientific Instrument,2017,38(6):1345-1352.
[12] UUSHEIMO S,TULONEN T,ARVOLA L,et al.Organic carbon causes interference with nitrate and nitrite measur- ements by UV/Vis spectrometers:the importance of local calibration[J].Environmental Monitoring & Assessment,2017,189(7):357-366.
[13] CHAUDHARY A,SINGH A,VERMA P K.Method development and validation of potent pyrimidine derivative by UV-VIS spectrophotometer[J].Organic and Medicinal Chemistry Letters,2014,4(1):15- 20.
[14] TUDORACHE A,IONI?? D E,MARIN N M,et al.In- house validation of a UV spectrometric method for measur- ement of nitrate concentration in natural groundwater sampl es[J].Accreditation & Quality Assurance,2017,22(1):29-35.
[15] KOVACS Z,OSHIMA M.Water spectral pattern as holi- stic marker for water quality monitoring[J].Talanta,2016(147):598- 608.
[2] 刘思乡,范卫华,郭慧,等.机器学习在紫外法测定硝酸盐氮浓度中的应用[J].光谱学与光谱分析,2017,37(4):1179-1182.LIU S X,FAN W H,GUO H,et al.Application of machine learning in determination of nitrate nitrogen based on ultraviolet spectrophometry[J].Spectroscopy and Spectral Analysis,2017,37(4):1179-1182.
[3] FUKUSHI K,ISHIO N,URAYAMA H,et al.Simultaneous determination of bromide,nitrite and nitrate ions in seawater by capillary zone electrophoresis using artificial seawater as the carrier solution[J].Journal of Chromatogr- aphy A,2015,21(2):303-311.
[4] RASOOL R,TAYEBEH S,ALI M,et al.Indirectultratr ace determination of nitrate and nitrite in food samples by insyringe liquid microextraction and electrothermal atomic absorption spectrometry[J].Microchemical Journal,2018 (142):135-139.
[5] DAVIES A R,ANDERSSEN R S,HOOG F R D,et al.Derivative spectroscopy and the continuous relaxation spectrum[J].Journal of Non-Newtonian Fluid Mechanics,2016(233):107-118.
[6] CAUSSE J,THOMAS O,JUNG A V,et al.Direct DOC and nitrate determination in water using dual pathlength and second derivative UV spectrophotometry[J].Water Research,2016(108):312-319.
[7] 柳玲,高晓庆,苗振华,等.离子色谱法与分光光度法测定水中亚硝酸盐含量的对比[J].中国给水排水,2016,32(2):93-96.LIU L,GAO X Q,MIAO ZH H,et al.Comparison between ion-chromatography and spectrophotometry for determin ing nitrite in water[J].China Water & Wastewater,2016,32(2):93-96.
[8] 赵彦涛,单泽宇,常跃进,等.基于MI-LSSVM的水泥生料细度软测量建模[J].仪器仪表学报,2017,38(2):487- 496.ZHAO Y T,SHAN Z Y,CHANG Y J,et al.Soft sensor modeling for cement fineness based on least squares support vector machine and mutual information[J].Chinese Journal of Scientific Instrument,2017,38(2):487- 496.
[9] 王智宏,陈琛,千承辉,等.基于粒子群寻优的光谱仪波长误差修正方法[J].仪器仪表学报,2017,38(10):82- 88.WANG ZH H,CHEN CH,QIAO CH H,et al.Spectrometer wavelength error correction method based on particle swarm optimization[J].Chinese Journal of Scientific Instrument,2017,38(10):82- 88.
[10] HU Y,WEN Y,WANG X.Novel method of turbidity compensation for chemical oxygen demand measurements by using UV-vis spectrometry[J].Sensors & Actuators B Chemical,2016(227):393-398.
[11] 张朕,姜劲,傅嘉豪,等.基于功能近红外光谱的多生理脑力疲劳检测[J].仪器仪表学报,2017,38(6):1345-1352.ZHANG ZH,JIANG J,FU J H,et al.Multi-physiological mental-fatigue detection based on the functional near infrared spectroscopy[J].Chinese Journal of Scientific Instrument,2017,38(6):1345-1352.
[12] UUSHEIMO S,TULONEN T,ARVOLA L,et al.Organic carbon causes interference with nitrate and nitrite measur- ements by UV/Vis spectrometers:the importance of local calibration[J].Environmental Monitoring & Assessment,2017,189(7):357-366.
[13] CHAUDHARY A,SINGH A,VERMA P K.Method development and validation of potent pyrimidine derivative by UV-VIS spectrophotometer[J].Organic and Medicinal Chemistry Letters,2014,4(1):15- 20.
[14] TUDORACHE A,IONI?? D E,MARIN N M,et al.In- house validation of a UV spectrometric method for measur- ement of nitrate concentration in natural groundwater sampl es[J].Accreditation & Quality Assurance,2017,22(1):29-35.
[15] KOVACS Z,OSHIMA M.Water spectral pattern as holi- stic marker for water quality monitoring[J].Talanta,2016(147):598- 608.