污水中不同形态氮稳定同位素预处理方法探究
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摘要
本文提出了有机物中胺基氮消解转化为铵盐后的富集与分离方法,探讨了凯氏氮(KTN)、有机氮(DON)消解转化为铵盐的实验条件,完善了污水中铵盐稳定氮同位素预处理的最佳实验条件.经实验分析,KTN、DON在3 mL5%(W/V)的Cu SO_4、10 mL浓H_2SO_4、6 g K2SO_4条件下消解30 min,可稳定高效地转化为(NH4)HSO_4.研究结果表明,铵盐最佳蒸馏时间为50 min,最适碱投加量为5 mL 40%(W/V)的Na OH溶液,当铵盐浓度在0—80 mg·L~(-1)时,蒸馏过程氮回收率均高于95%;通过对比沸石吸附和酸吸收两种方式,发现酸吸收高效稳定,并优选稀硫酸(0.04 mol·L~(-1))作为吸收液,在pH=3.0±0.3、50℃干燥引起的氮同位素分馏效应最小(<0.04‰).将该方法应用于实际生活污水管网中的氮迁移转化分析,验证了方法的可行性和应用价值.
In this study,a enrichment and separation method of amino nitrogen after conversion to ammonium salt was proposed. The experimental conditions for the conversion of KTN and DON into ammonium salt were investigated,and the optimum pretreatment conditions of stable nitrogen isotope in wastewater were improved. The results showed that KTN and DON were transformed to(NH4) HSO4 in 3 mL 5%(W/V) Cu SO4,10 mL H2SO4 and 6 g K2SO4 for 30 min digestion. The best distillation time was 50 min,and the optimum alkali dosage was 5 mL 40%(W/V) Na OH solution. When the concentration of ammonium salt was in the range of 0 mg·L~(-1)and 80 mg·L~(-1),the recovery of nitrogen was higher than 95% in distillation process. After comparing zeolite adsorption and acid absorption,the result showed that acid absorption was stable and efficient,and dilute sulphuric acid(0. 04 mg·L~(-1)) was optimized as the absorbing liquid. Fractionation efficiency of nitrogen isotope was minimum(< 0.04‰) when drying at 50 ℃ and pH 3.0 ± 0.3. The method was applied to analyze the migration and transformation of nitrogen in sewage pipe network,and the feasibility and application potential of the method were verified.
In this study,a enrichment and separation method of amino nitrogen after conversion to ammonium salt was proposed. The experimental conditions for the conversion of KTN and DON into ammonium salt were investigated,and the optimum pretreatment conditions of stable nitrogen isotope in wastewater were improved. The results showed that KTN and DON were transformed to(NH4) HSO4 in 3 mL 5%(W/V) Cu SO4,10 mL H2SO4 and 6 g K2SO4 for 30 min digestion. The best distillation time was 50 min,and the optimum alkali dosage was 5 mL 40%(W/V) Na OH solution. When the concentration of ammonium salt was in the range of 0 mg·L~(-1)and 80 mg·L~(-1),the recovery of nitrogen was higher than 95% in distillation process. After comparing zeolite adsorption and acid absorption,the result showed that acid absorption was stable and efficient,and dilute sulphuric acid(0. 04 mg·L~(-1)) was optimized as the absorbing liquid. Fractionation efficiency of nitrogen isotope was minimum(< 0.04‰) when drying at 50 ℃ and pH 3.0 ± 0.3. The method was applied to analyze the migration and transformation of nitrogen in sewage pipe network,and the feasibility and application potential of the method were verified.
引文
[1]宁卓,张翠云,张胜.地下水铵污染及其氮同位素研究[J].南水北调与水利科技,2011,9(3):129-132.NING Z,ZHANG C Y,ZHANG S.Study of groundwater contamination of ammonium and its nitrogen isotope[J].South-North Water Diversion and Water Science&Technology,2011,9(3):129-132(in Chinese).
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[9]VELINSKY D J,PENNOCK J R,SHARP J H,et al.Determination of the natural abundance level from estuarine waters[J].Marine Chemistry,1989,26(4):351-361.
[10]刘秀娟,俞志明,宋秀贤,等.海水中溶解态硝酸盐的氮同位素分析的预处理方法[J].分析化学,2009,37(5):643-647.LIU X J,YU Z M,SONG X X,et al.Pretreatment method for nitrogen isotopic analysis of nitrate in seawater[J].Chinese Joumal of Analytical Chemistry,2009,37(5):643-647(in Chinese).
[11]刘丽丽,于海燕,俞志明,等.海水中溶解态铵盐氮同位素分析的预处理方法[J].海洋科学,2013,37(12):28-33.LIU L L,YU H Y,YU Z M,et al.Pretreatment method for nitrogen isotopic composition determination of dissolved ammonium nitrogen in estuarine waters[J].Marine Sciences,2013,37(12):28-33(in Chinese).
[12]LEE K S,LEE D S,LIM S S,et al.Nitrogen isotope ratios of dissolved organic nitrogen in wet precipitation in a metropolis surrounded byagricultural areas in southern Korea[J].Agriculture,Ecosystems and Environment,2012,159(18):161-169.
[13]曾海鳌,吴敬禄.淡水氨氮和硝态氮氮同位素分析方法[J].海洋地质与第四纪地质,2013,33(6):173-177.ZENG H A,WU J L.A method of extract ammonium and nitrate from freshwater for nitrogen isotope analysis[J].Marine Geology&Quaternary Geology,2013,33(6):173-177(in Chinese).
[14]杨志,陈敏,曹建平,等.天然海水硝酸盐氮同位素组成的蒸馏法测定[J].海洋学报,2012,34(3):72-79.YANG Z,CHEN M,CAO J P,et al.Ammonia distillation method for nitrogen isotope analysis of nitrate in seawater[J].Acta Oceanologica Sinica,2012,34(3):72-79(in Chinese).
[15]胡婧,刘卫国.离子交换色层法测定低浓度铵态氮水样的氮同位素研究[J].盐矿测试,2013,32(3):495-501.HU J,LIU W G.Determination of nitrogen isotope of water samples with low ammonium nitrogen by ion exchange method[J].Rock and Mineral Aalysis,2013,32(3):495-501(in Chinese).
[16]孙锦宜.含氮废水处理技术与应用[M].北京:化学工业出版社,2003.SUN J Y.Nitrogen wastewater treatment technology and application[M].Beijing:Chemical Industry Press,2003(in Chinese).
[17]金鹏康,焦丁,任武昂.污水管网中无机氮类营养盐迁变规律[J].环境科学,2015,36(10):3730-3737.JIN P K,JIAO D,REN W A.Transformation of nitrogen nutrients in the urban sewage pipe network[J].Enviromental Science,2015,36(10):3730-3737(in Chinese).
[18]LINDAU C W,DELAUNE R D,ALFORD D P.Monitoring nitrogen pollution from sugarcane runoff using15N analysis[J].Water,Air,and Soil Pollution,1997,98:389-399.
[19]于海燕,俞志明,宋秀贤,等.国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用[J].海洋科学,2013,37(3):6-10.YU H Y,YU Z M,SONG X X,et al.The modification of Chinese natural zeolites and their application in nitrogen isotope analysis of nitrate in seawater[J].Marine Sciences,2013,37(3):6-10(in Chinese).
[20]张曦,吴为忠,温东辉,等.氨氮在天然沸石上的吸附于解吸[J].环境化学,2003,22(2):166-171.ZHANG X,WU W Z,WEN D H,et al.Adsorption and desorption of ammonia-nitrogen onto natural zeolite[J].Enviromental Chemistry,2003,22(2):166-171(in Chinese).
[21]DIACONU C,BRION N,ELSKENS M,et al.Validation of a dynamic ammonium extraction technique for the determination of15N at enriched abundances[J].Analytica Chimica Acta,2005,554:113-122.
[22]JIN P K,WANG B,JIAO D,et al.Characterization of microflora and transformation of organic matters in urban sewer system[J].Water Research,2015,84:112-119.
[2]KOHL D H,SHEARER G B,COMMONER B.Fertilizer nitrogen:Contribution to nitrate in surface water in a corn belt watershed[J].Science,1971,174:1331-1334.
[3]CURT M D,A GUADO P,SANCHEZ G,et al.Nitrogen isotope ratios of synthetic and organic sources of nitrate water contamination in Spain[J].Water,Air,and Soil Pollution,2004,151:135-142.
[4]LI X D,MASUDA H,KOBA K,et al.Nitrogen isotope study on nitrate-contaminated groundwater in the Sichuan Basin,China[J].Water,Air,and Soil Pollution,2007,178:145-156.
[5]SOVIK A K,MORKVED P T.Use of stable nitrogen isotope fractionation to estimate denitrification in small constructed wetlands treating agricultural runoff[J].Science of Total Environment,2008,392:157-165.
[6]张翠云,郭秀红.氮同位素技术的应用:土壤有机氮作为地下水硝酸盐污染源的条件分析[J].地球化学,2005,34(5):533-540.ZHANG C Y,GUO X H.The application of the nitrogen isotope technology:Soil organic nitrogen as the analysis of the condition of groundwater nitrate pollution sources[J].Geochimica,2005,34(5):533-540(in Chinese).
[7]卢安根,莫建光,陈秋红.EA-IRMS技术在牛磺酸碳、氮同位定素测定中的应用[J].湖北农业科学,2015,54(8):1971-1973.LU A G,MO J G,CHEN Q H.Application of EA-IRMS technology on the analysis on isotopes ratio of carbon and nitrogen in taurine[J].Hubei Agricultural Sciences,2015,54(8):1971-1973(in Chinese).
[8]肖化云,刘丛强.水样氮同位素分析预处理方法的研究现状与进展[J.]盐矿测试,2001,20(2):125-130.XIAO H Y,LIU C Q.Present situation and development of water sample preparation methods for15N analysis[J].Rock and Mineral Analysis,2001,20(2):125-130(in Chinese).
[9]VELINSKY D J,PENNOCK J R,SHARP J H,et al.Determination of the natural abundance level from estuarine waters[J].Marine Chemistry,1989,26(4):351-361.
[10]刘秀娟,俞志明,宋秀贤,等.海水中溶解态硝酸盐的氮同位素分析的预处理方法[J].分析化学,2009,37(5):643-647.LIU X J,YU Z M,SONG X X,et al.Pretreatment method for nitrogen isotopic analysis of nitrate in seawater[J].Chinese Joumal of Analytical Chemistry,2009,37(5):643-647(in Chinese).
[11]刘丽丽,于海燕,俞志明,等.海水中溶解态铵盐氮同位素分析的预处理方法[J].海洋科学,2013,37(12):28-33.LIU L L,YU H Y,YU Z M,et al.Pretreatment method for nitrogen isotopic composition determination of dissolved ammonium nitrogen in estuarine waters[J].Marine Sciences,2013,37(12):28-33(in Chinese).
[12]LEE K S,LEE D S,LIM S S,et al.Nitrogen isotope ratios of dissolved organic nitrogen in wet precipitation in a metropolis surrounded byagricultural areas in southern Korea[J].Agriculture,Ecosystems and Environment,2012,159(18):161-169.
[13]曾海鳌,吴敬禄.淡水氨氮和硝态氮氮同位素分析方法[J].海洋地质与第四纪地质,2013,33(6):173-177.ZENG H A,WU J L.A method of extract ammonium and nitrate from freshwater for nitrogen isotope analysis[J].Marine Geology&Quaternary Geology,2013,33(6):173-177(in Chinese).
[14]杨志,陈敏,曹建平,等.天然海水硝酸盐氮同位素组成的蒸馏法测定[J].海洋学报,2012,34(3):72-79.YANG Z,CHEN M,CAO J P,et al.Ammonia distillation method for nitrogen isotope analysis of nitrate in seawater[J].Acta Oceanologica Sinica,2012,34(3):72-79(in Chinese).
[15]胡婧,刘卫国.离子交换色层法测定低浓度铵态氮水样的氮同位素研究[J].盐矿测试,2013,32(3):495-501.HU J,LIU W G.Determination of nitrogen isotope of water samples with low ammonium nitrogen by ion exchange method[J].Rock and Mineral Aalysis,2013,32(3):495-501(in Chinese).
[16]孙锦宜.含氮废水处理技术与应用[M].北京:化学工业出版社,2003.SUN J Y.Nitrogen wastewater treatment technology and application[M].Beijing:Chemical Industry Press,2003(in Chinese).
[17]金鹏康,焦丁,任武昂.污水管网中无机氮类营养盐迁变规律[J].环境科学,2015,36(10):3730-3737.JIN P K,JIAO D,REN W A.Transformation of nitrogen nutrients in the urban sewage pipe network[J].Enviromental Science,2015,36(10):3730-3737(in Chinese).
[18]LINDAU C W,DELAUNE R D,ALFORD D P.Monitoring nitrogen pollution from sugarcane runoff using15N analysis[J].Water,Air,and Soil Pollution,1997,98:389-399.
[19]于海燕,俞志明,宋秀贤,等.国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用[J].海洋科学,2013,37(3):6-10.YU H Y,YU Z M,SONG X X,et al.The modification of Chinese natural zeolites and their application in nitrogen isotope analysis of nitrate in seawater[J].Marine Sciences,2013,37(3):6-10(in Chinese).
[20]张曦,吴为忠,温东辉,等.氨氮在天然沸石上的吸附于解吸[J].环境化学,2003,22(2):166-171.ZHANG X,WU W Z,WEN D H,et al.Adsorption and desorption of ammonia-nitrogen onto natural zeolite[J].Enviromental Chemistry,2003,22(2):166-171(in Chinese).
[21]DIACONU C,BRION N,ELSKENS M,et al.Validation of a dynamic ammonium extraction technique for the determination of15N at enriched abundances[J].Analytica Chimica Acta,2005,554:113-122.
[22]JIN P K,WANG B,JIAO D,et al.Characterization of microflora and transformation of organic matters in urban sewer system[J].Water Research,2015,84:112-119.
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