多量程原位水质总磷总氮一体式在线监测仪
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摘要
针对地表水和城镇污水对于总磷(TP)总氮(TN)联合测定的需求,基于国标法提出了联合测定原理,利用顺序注射技术和微控技术建立水质总磷总氮多量程在线监测系统,完成了TP和TN的测定。总磷的测定量程分为0～1.2,1.2～2.5,2.5～5μg·mL~(-1);总氮测定量程分为0～10,10～20,20～40μg·mL~(-1)。测定范围涵盖地表水环境I～V类水和城镇污水处理厂排放标准中总磷、总氮的标准限值。利用交替最小二乘拟合算法建立了总磷与总氮测定的回归模型。实验结果表明,其校正决定系数≥0.996 4,最低检出限分别为0.01μg·mL~(-1)和0.05μg·mL~(-1),重复性相对标准偏差(RSD)分别为1.36%～3.84%、0.78%～3.69%,贵州七大水库实际水样数据比对中,总磷相对误差≤±3.7838%,总氮相对误差≤±3.69%。系统运行稳定,可以精准、高效地分析不同地表水样的总磷总氮,为环境保护和污水排放提供了技术支持,尤其适用于实验室、站房式、便携式在线水质监测。
Aiming at the demand for joint determination of total phosphorus and total nitrogen in surface water and urban sewage, the principle of joint determination is proposed based on the national standard method. The sequential monitoring system and micro-control technology were used to establish a multi-range online monitoring system for total phosphorus and total nitrogen in water, and the determination of total phosphorus and total nitrogen index was completed. The total phosphorus index is measured in the range of 0-1.2, 1.2-2.5, 2.5-5 μg·mL~(-1). The total nitrogen index is measured in the range of 0-10, 10-20, 20-40 μg·mL~(-1). The measurement range covers the standard limits of total phosphorus and total nitrogen in the surface water environment I-V water and urban sewage treatment plant discharge standards. A regression model for determination of total phosphorus and total nitrogen was established by alternating least squares fitting algorithm. The experimental results show that the correction coefficient of the model is more than 0.996 4. The relative standard deviations of TP and TN repeatability were 1.36%-3.84% and 0.78%-3.69% respectively. Comparison of actual water samples in seven reservoirs in Guizhou, the relative error of total phosphorus is below ±3.7838%, the relative error of total nitrogen is below ±3.69%. The system runs steadily, and can accurately and efficiently analyze the total phosphorus total nitrogen index of different surface water samples, and provide technical support for environmental protection and sewage discharge, especially for laboratory, station type and portable on-line water quality monitoring.
Aiming at the demand for joint determination of total phosphorus and total nitrogen in surface water and urban sewage, the principle of joint determination is proposed based on the national standard method. The sequential monitoring system and micro-control technology were used to establish a multi-range online monitoring system for total phosphorus and total nitrogen in water, and the determination of total phosphorus and total nitrogen index was completed. The total phosphorus index is measured in the range of 0-1.2, 1.2-2.5, 2.5-5 μg·mL~(-1). The total nitrogen index is measured in the range of 0-10, 10-20, 20-40 μg·mL~(-1). The measurement range covers the standard limits of total phosphorus and total nitrogen in the surface water environment I-V water and urban sewage treatment plant discharge standards. A regression model for determination of total phosphorus and total nitrogen was established by alternating least squares fitting algorithm. The experimental results show that the correction coefficient of the model is more than 0.996 4. The relative standard deviations of TP and TN repeatability were 1.36%-3.84% and 0.78%-3.69% respectively. Comparison of actual water samples in seven reservoirs in Guizhou, the relative error of total phosphorus is below ±3.7838%, the relative error of total nitrogen is below ±3.69%. The system runs steadily, and can accurately and efficiently analyze the total phosphorus total nitrogen index of different surface water samples, and provide technical support for environmental protection and sewage discharge, especially for laboratory, station type and portable on-line water quality monitoring.
引文
[1] 张景飞,牛晓君,马宏瑞,等.流动注射分光光度法测定水体总磷 [J].分析化学,2002,30(7):839-842.ZHANG J F,NIU X J,MA H R,et al..Determination of total phosphorus in waters using flow injection analysis [J].Chin.J.Anal.Chem.,2002,30(7):839-842.(in Chinese)
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[5] 魏康林,王飞,陈明,等.超声辅助Fenton试剂消解-光谱分析法快速测定水质总磷 [J].光谱学与光谱分析,2014,34(1):180-184.WEI K L,WANG F,CHEN M,et al..Rapid determination of total phosphorus by ultrasonic assisted sample digestion-spectrum analysis [J].Spectrosc.Spec.Anal.,2014,34(1):180-184.(in Chinese)
[6] 刘建利,张沛,宋蓓,等.连续流动分析法测定水中总磷、总氮比对研究 [J].化学研究与应用,2016,28(7):936-941.LIU J L,ZANG P,SONG B,et al..Comparison study of determination of total phosphorus and total nitrogen in water by continuous flow analysis [J].Chem.Res.Appl.China,2016,28(7):936-941.(in Chinese)
[7] 王中荣,魏福祥,王盼盼,等.微顺序注射-镉柱还原分光光度法测定海水中总氮 [J].分析化学,2016,44(9):1328-1334.WANG Z R,WEI F X,WANG P P,et al..Determination of total nitrogen in seawater by microsequential injection-cadmium column reduction spectrophotometry [J].Chin.J.Anal.Chem.,2016,44(9):1328-1334.(in Chinese)
[8] 吕伟仙,葛滢,吴建之,等.植物中硝态氮、氨态氮、总氮测定方法的比较研究 [J].光谱学与光谱分析,2004,24(2):204-206.LV W X,GE Y,WU J Z,et al..Study on the method for the determination of nitric nitrogen,ammoniacal nitrogen and total nitrogen in plant [J].Spectrosc.Spec.Anal.,2004,24(2):204-206.(in Chinese)
[9] 章海亮,何勇.便携式短波近红外光谱仪器检测土壤总氮含量研究 [J].光谱学与光谱分析,2016,36(1):91-95.ZHANG H L,HE Y.Measurement of soil total n based on portable short wave NIR spectroscopy technology [J].Spectrosc.Spec.Anal.,2016,36(1):91-95.(in Chinese)
[10] 国家环境保护总局.GB11893-1989水质总磷的测定钼酸铵分光光度法 [S].北京:中国标准出版社,1990.State Environmental Protection Administration.GB 11893-1989 Water Quality-determination of Total Phosphorus—Ammonium Molybdate Spectrophotometric Method [S].Beijing:China Standard Press,1990.(in Chinese)
[11] 丁明军,杨慧中.水中总磷和总氮含量的离子色谱测定法 [J].分析化学,2012,40(3):381-385.DING M J,YANG H Z.Determination of total phosphorus and nitrogen in water by ion chromatography [J].Chin.J.Anal.Chem.,2012,40(3):381-385.(in Chinese)
[12] 陈艳玲,黎艳葵.氯化亚锡还原光度法测定总磷的方法改进 [J].环境科学与技术,2004,27(S1):43-44.CHEN Y L,LI Y K.Improvement of TP measurement by reduction photometry of tin chloride [J].Environ.Sci.Technol.,2004,27(S1):43-44.(in Chinese)
[13] 国家环境保护局.GB11894-1989水质总氮的测定碱性过硫酸钾消解紫外分光光度法 [S].北京:中国标准出版社,1990.State Environmental Protection Administration.GB 11894-1989 Water Quality-determination of Total Nitrogen UV Spectrophotometric Method—Alkaline Potassium Persulfate Digestion Method [S].Beijing:China Standard Press,1990.(in Chinese)
[14] 王中瑗,张宏康,方宏达,等.总磷和总氮的海水与淡水分析方法比较 [J].海洋环境科学,2016,35(3):428-433.WANG Z Y,ZHANG H K,FANG H D,et al..Comparison of the determination of TP and TN using national seawater method and surface water method [J].Mar.Environ.Sci.,2016,35(3):428-433.(in Chinese)
[15] DE BORBAB M,JACKR F,ROHRER J S,et al..Simultaneous determination of total nitrogen and total phosphorus in environmental waters using alkaline persulfate digestion and ion chromatography [J].J.Chromatogr.A,2014,1369:131-137.
[16] 韩双来,项光宏,唐小燕,等.基于顺序注射分析技术的总氮在线分析仪 [J].中国环境监测,2013,29(3):94-98.HAN S L,XIANG G H,TANG X Y,et al..A novel on-line total nitrogen analyzer based on sequential injection analysis technology [J].Environ.Monit.China,2013,29(3):94-98.(in Chinese)
[17] 李军,陈程.总氮总磷在线自动监测仪的现状与问题 [J].环境科学与管理,2012,37(1):161-164.LI J,CHEN C.Present situation and problems of automatic online TN and TP monitor [J].Environ.Sci.Manag.,2012,37(1):161-164.(in Chinese)
[18] 国家环境保护总局,国家质量监督检验检疫总局.GB3838-2002地表水环境质量标准 [S].北京:中国标准出版社,2002.State Environmental Protection Administration,State Administration of Quality Supervision,Inspection and Quarantine.GB 3838-2002 Environmental Quality Standards for Surface Water [S].Beijing:China Standards Press,2002.(in Chinese)
[19] 国家环境保护总局.GB18918-2002城镇污水处理厂污染物排放标准 [S].北京:中国标准出版社,2002.State Environmental Protection Administration.GB18918-2002 Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant [S].Beijing:China Standards Press,2002.(in Chinese)
[20] 李军会,秦西云,张文娟,等.局部偏最小二乘回归建模参数对近红外检测结果的影响研究 [J].光谱学与光谱分析,2007,27(2):262-264.LI J H,QIN X Y,ZHANG W J,et al..Influence of LPLS algorithm parameters on NIR veracity [J].Spectrosc.Spec.Anal.,2007,27(2):262-264.(in Chinese)
[21] 陈鹏飞,刘良云,王纪华,等.近红外光谱技术实时测定土壤中总氮及磷含量的初步研究 [J].光谱学与光谱分析,2008,28(2):295-298.CHEN P F,LIU L Y,WANG J H,et al..Real-time analysis of soil n and p with near infrared diffuse reflectance spectroscopy [J].Spectrosc.Spec.Anal.,2008,28(2):295-298.(in Chinese)
[22] 张雪莲,李晓娜,武菊英,等.不同类型土壤总氮的近红外光谱技术测定研究 [J].光谱学与光谱分析,2010,30(4):906-910.ZHANG X L,LI X N,WU J Y,et al..Study on the determination of total nitrogen (TN) in different types of soil by near-infrared spectroscopy (NIS) [J].Spectrosc.Spec.Anal.,2010,30(4):906-910.(in Chinese)
[23] LEE E,HAN S,KIM H.Development of software sensors for determining total phosphorus and total nitrogen in waters [J].Int.J.Environ.Res.Public Health,2013,10(1):219-236.
[24] DAFNER E V,SZMANT A M.A modified segmented continuous flow analysis method for simultaneous determination of total dissolved nitrogen and phosphorus in marine environments [J].Limnol.Oceanogr.Methods,2014,12(8):577-591.
[25] LIU Z P,SHAO M A,WANG Y Q.Spatial patterns of soil total nitrogen and soil total phosphorus across the entire Loess Plateau region of China [J].Geoderma,2013,197-198:67-78.
[26] YOSHIOKA K,KAMIYA H,KANO Y,et al..The relationship between seasonal variations of total-nitrogen and total-phosphorus in rainfall and air mass advection paths in Matsue,Japan [J].Atmos.Environ.,2009,43(22-23):3496-3501.
[27] RATTAN K J,CORRIVEAU J C,BRUA R B,et al..Quantifying seasonal variation in total phosphorus and nitrogen from prairie streams in the Red River Basin,Manitoba Canada [J].Sci.Total Environ.,2017,575:649-659.李文(1975-),男,山东泰安人,博士,副教授,硕士生导师,2011年于北京航空航天大学获得博士学位,主要从事机器人辅助加工、电极式和光学智能传感器的研究。E-mail:buaa_liwen@126.com吕赫(1993-),男,甘肃庆阳人,硕士研究生,2016年于北方工业大学获得学士学位,主要从事光学水质传感器的研究。E-mail:503496670@qq.com
[2] 蔡秀萍.分光光度法测定水中总磷的若干影响因素 [J].江苏农业科学,2011,39(4):436-438.CAI X P.Spectrophotometric determination of total phosphorus in water [J].Jiangsu Agric.Sci.,2011,39(4):436-438.(in Chinese)
[3] 张丰如,汤兵,苑星海.总磷测定中温度浓度时间对显色的影响 [J].环境科学与技术,2005,28(6):40-41.ZHANG F R,TANG B,YUAN X H.Effects of temperature,concentration and time on determination of total phosphorus [J].Environ.Sci.Technol.,2005,28(6):40-41.(in Chinese)
[4] 邓金花,吴清平,廖富迎,等.环境水质总磷的快速检测 [J].农业环境科学学报,2006,25(S2):763-765.DENG J H,WU Q P,LIAO F Y,et al..Rapid determination of total phosphorus in environmental water [J].J.Agro-Environ.Sci.,2006,25(S2):763-765.(in Chinese)
[5] 魏康林,王飞,陈明,等.超声辅助Fenton试剂消解-光谱分析法快速测定水质总磷 [J].光谱学与光谱分析,2014,34(1):180-184.WEI K L,WANG F,CHEN M,et al..Rapid determination of total phosphorus by ultrasonic assisted sample digestion-spectrum analysis [J].Spectrosc.Spec.Anal.,2014,34(1):180-184.(in Chinese)
[6] 刘建利,张沛,宋蓓,等.连续流动分析法测定水中总磷、总氮比对研究 [J].化学研究与应用,2016,28(7):936-941.LIU J L,ZANG P,SONG B,et al..Comparison study of determination of total phosphorus and total nitrogen in water by continuous flow analysis [J].Chem.Res.Appl.China,2016,28(7):936-941.(in Chinese)
[7] 王中荣,魏福祥,王盼盼,等.微顺序注射-镉柱还原分光光度法测定海水中总氮 [J].分析化学,2016,44(9):1328-1334.WANG Z R,WEI F X,WANG P P,et al..Determination of total nitrogen in seawater by microsequential injection-cadmium column reduction spectrophotometry [J].Chin.J.Anal.Chem.,2016,44(9):1328-1334.(in Chinese)
[8] 吕伟仙,葛滢,吴建之,等.植物中硝态氮、氨态氮、总氮测定方法的比较研究 [J].光谱学与光谱分析,2004,24(2):204-206.LV W X,GE Y,WU J Z,et al..Study on the method for the determination of nitric nitrogen,ammoniacal nitrogen and total nitrogen in plant [J].Spectrosc.Spec.Anal.,2004,24(2):204-206.(in Chinese)
[9] 章海亮,何勇.便携式短波近红外光谱仪器检测土壤总氮含量研究 [J].光谱学与光谱分析,2016,36(1):91-95.ZHANG H L,HE Y.Measurement of soil total n based on portable short wave NIR spectroscopy technology [J].Spectrosc.Spec.Anal.,2016,36(1):91-95.(in Chinese)
[10] 国家环境保护总局.GB11893-1989水质总磷的测定钼酸铵分光光度法 [S].北京:中国标准出版社,1990.State Environmental Protection Administration.GB 11893-1989 Water Quality-determination of Total Phosphorus—Ammonium Molybdate Spectrophotometric Method [S].Beijing:China Standard Press,1990.(in Chinese)
[11] 丁明军,杨慧中.水中总磷和总氮含量的离子色谱测定法 [J].分析化学,2012,40(3):381-385.DING M J,YANG H Z.Determination of total phosphorus and nitrogen in water by ion chromatography [J].Chin.J.Anal.Chem.,2012,40(3):381-385.(in Chinese)
[12] 陈艳玲,黎艳葵.氯化亚锡还原光度法测定总磷的方法改进 [J].环境科学与技术,2004,27(S1):43-44.CHEN Y L,LI Y K.Improvement of TP measurement by reduction photometry of tin chloride [J].Environ.Sci.Technol.,2004,27(S1):43-44.(in Chinese)
[13] 国家环境保护局.GB11894-1989水质总氮的测定碱性过硫酸钾消解紫外分光光度法 [S].北京:中国标准出版社,1990.State Environmental Protection Administration.GB 11894-1989 Water Quality-determination of Total Nitrogen UV Spectrophotometric Method—Alkaline Potassium Persulfate Digestion Method [S].Beijing:China Standard Press,1990.(in Chinese)
[14] 王中瑗,张宏康,方宏达,等.总磷和总氮的海水与淡水分析方法比较 [J].海洋环境科学,2016,35(3):428-433.WANG Z Y,ZHANG H K,FANG H D,et al..Comparison of the determination of TP and TN using national seawater method and surface water method [J].Mar.Environ.Sci.,2016,35(3):428-433.(in Chinese)
[15] DE BORBAB M,JACKR F,ROHRER J S,et al..Simultaneous determination of total nitrogen and total phosphorus in environmental waters using alkaline persulfate digestion and ion chromatography [J].J.Chromatogr.A,2014,1369:131-137.
[16] 韩双来,项光宏,唐小燕,等.基于顺序注射分析技术的总氮在线分析仪 [J].中国环境监测,2013,29(3):94-98.HAN S L,XIANG G H,TANG X Y,et al..A novel on-line total nitrogen analyzer based on sequential injection analysis technology [J].Environ.Monit.China,2013,29(3):94-98.(in Chinese)
[17] 李军,陈程.总氮总磷在线自动监测仪的现状与问题 [J].环境科学与管理,2012,37(1):161-164.LI J,CHEN C.Present situation and problems of automatic online TN and TP monitor [J].Environ.Sci.Manag.,2012,37(1):161-164.(in Chinese)
[18] 国家环境保护总局,国家质量监督检验检疫总局.GB3838-2002地表水环境质量标准 [S].北京:中国标准出版社,2002.State Environmental Protection Administration,State Administration of Quality Supervision,Inspection and Quarantine.GB 3838-2002 Environmental Quality Standards for Surface Water [S].Beijing:China Standards Press,2002.(in Chinese)
[19] 国家环境保护总局.GB18918-2002城镇污水处理厂污染物排放标准 [S].北京:中国标准出版社,2002.State Environmental Protection Administration.GB18918-2002 Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant [S].Beijing:China Standards Press,2002.(in Chinese)
[20] 李军会,秦西云,张文娟,等.局部偏最小二乘回归建模参数对近红外检测结果的影响研究 [J].光谱学与光谱分析,2007,27(2):262-264.LI J H,QIN X Y,ZHANG W J,et al..Influence of LPLS algorithm parameters on NIR veracity [J].Spectrosc.Spec.Anal.,2007,27(2):262-264.(in Chinese)
[21] 陈鹏飞,刘良云,王纪华,等.近红外光谱技术实时测定土壤中总氮及磷含量的初步研究 [J].光谱学与光谱分析,2008,28(2):295-298.CHEN P F,LIU L Y,WANG J H,et al..Real-time analysis of soil n and p with near infrared diffuse reflectance spectroscopy [J].Spectrosc.Spec.Anal.,2008,28(2):295-298.(in Chinese)
[22] 张雪莲,李晓娜,武菊英,等.不同类型土壤总氮的近红外光谱技术测定研究 [J].光谱学与光谱分析,2010,30(4):906-910.ZHANG X L,LI X N,WU J Y,et al..Study on the determination of total nitrogen (TN) in different types of soil by near-infrared spectroscopy (NIS) [J].Spectrosc.Spec.Anal.,2010,30(4):906-910.(in Chinese)
[23] LEE E,HAN S,KIM H.Development of software sensors for determining total phosphorus and total nitrogen in waters [J].Int.J.Environ.Res.Public Health,2013,10(1):219-236.
[24] DAFNER E V,SZMANT A M.A modified segmented continuous flow analysis method for simultaneous determination of total dissolved nitrogen and phosphorus in marine environments [J].Limnol.Oceanogr.Methods,2014,12(8):577-591.
[25] LIU Z P,SHAO M A,WANG Y Q.Spatial patterns of soil total nitrogen and soil total phosphorus across the entire Loess Plateau region of China [J].Geoderma,2013,197-198:67-78.
[26] YOSHIOKA K,KAMIYA H,KANO Y,et al..The relationship between seasonal variations of total-nitrogen and total-phosphorus in rainfall and air mass advection paths in Matsue,Japan [J].Atmos.Environ.,2009,43(22-23):3496-3501.
[27] RATTAN K J,CORRIVEAU J C,BRUA R B,et al..Quantifying seasonal variation in total phosphorus and nitrogen from prairie streams in the Red River Basin,Manitoba Canada [J].Sci.Total Environ.,2017,575:649-659.李文(1975-),男,山东泰安人,博士,副教授,硕士生导师,2011年于北京航空航天大学获得博士学位,主要从事机器人辅助加工、电极式和光学智能传感器的研究。E-mail:buaa_liwen@126.com吕赫(1993-),男,甘肃庆阳人,硕士研究生,2016年于北方工业大学获得学士学位,主要从事光学水质传感器的研究。E-mail:503496670@qq.com