长江流域资源与环境 >> 2015, Vol. 24 >> Issue (05): 742-749.doi: 10.11870/cjlyzyyhj201505005

• 自然资源 • 上一篇    下一篇

稳定同位素识别水体硝酸盐污染来源的研究进展

张千千1, 缪丽萍2, 孙继朝1, 刘景涛1   

  1. 1. 中国地质科学院水文地质环境地质研究所, 河北 石家庄 050061;
    2. 河北省农业区划办公室, 河北 石家庄 050000
  • 收稿日期:2014-02-26 修回日期:2014-08-16 出版日期:2015-05-20
  • 作者简介:张千千(1983~),男,助理研究员,博士,主要从事水体污染与控制方面研究.E-mail:z_qqian@163.com
  • 基金资助:
    西北地区主要城市地下水污染调查评价(1212011220982);中西部地区地下水污染调查评价综合研究(1212011121167);环保公益性行业科研专项(201409029)

RESEARCH ADVANCES IN IDENTIFYING NITRATE POLLUTION SOURCES OF WATER ENVIRONMENT BY USING STABLE ISOTOPES

ZHANG Qian-qian1, MIAO Li-ping2, SUN Ji-chao1, LIU Jing-tao1   

  1. 1. Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Science, Shijiazhuang 050061, China;
    2. Agriculture Regional Planning Office of Hebei Province, Shijiazhuang 050000, China
  • Received:2014-02-26 Revised:2014-08-16 Online:2015-05-20

摘要: 水体硝酸盐污染已经成为一个世界性的水质问题。为了确保供水安全和有效治理水环境中硝酸盐污染, 准确识别水体中硝酸盐的污染来源显得尤为重要。近年来, 硝酸盐稳定氮(δ15N)和氧(δ18O)同位素示踪技术被广泛用于识别水环境中硝酸盐的污染来源。然而, 水环境中硝酸盐污染来源的复杂性和同位素分馏的影响, 致使该项技术的应用存在一定的局限性。概括了硝酸盐中的δ15N和δ18O的典型值域范围, 阐述了多种同位素技术联合识别水体中硝酸盐污染来源的方法以及应用模型定量解析硝酸盐污染源贡献率, 最后, 对该领域未来的发展方向进行了阐述。

关键词: 硝酸盐, 污染来源, 稳定同位素, 源解析

Abstract: Nitrate (NO3-) contamination of surface water and ground water is an environmental problem in many regions across the world. Nowadays, with rapid industrialization, economic and population growth and intensive human activities (such as the discharge of industrial and domestic sewage, increased use of N-containing organic and inorganic fertilizers, animal manure, leakage of fossil fuels, etc.), the concentration of nitrate has raised increasingly and posed a serious threat to water environment, thereby causing the widespread concern of hydrological ecologists. Increased nitrate concentration in the water body has a serious impact on human health and environments. In order to safeguard drinking water supplies and control contamination effectively, it is of great importance to effectively identify the nitrate pollution sources of water body. Nitrate pollution originates from multiple sources via different pathways as point or diffuse sources: mineral nitrogen fertilizers and animal manure in agriculture, domestic or industrial nitrogen-bearing wastewater, atmospheric deposition, mineralization of soil organic nitrogen and biological nitrogen fixation. The traditional methods to identify the nitrate pollution sources are by investigating land use types of study area and combining the characteristics of local water chemistry, however, the results are relatively rough. In recent years, stable nitrogen (δ15N) and oxygen (δ18O) isotope data of NO3- have been frequently used to identify NO3- sources in water environment, because the isotopic composition of N and O in NO3- is generally different among various NO3- sources such as atmospheric N2, soil, chemical fertilizers, and sewage and manure. Nevertheless, the stable isotope technology also has limitations because of the multiple NO3- sources and isotope fractionation caused by N-transformation processes. This review systematically summarizes the typical δ15N and δ18O-NO3- ranges of known NO3- sources, introduced the multiple isotope technology combined to identify NO3- sources in water environment, and presents mixing models and future development directions to quantify the contributions of different NO3- sources. Based on the previous researches about the application of stable isotope methods, we suggest that in the future it is important to combine multiple isotope technology to identify NO3- sources in water environment. In addition, future research hotspot will be quantification of the contribution of different sources of NO3- by using stable isotopes simultaneously, in combination with mathematical models.

Key words: nitrate, pollution source, stable isotope, source apportionment

中图分类号: 

  • X522
[1] NESTLER A, BERGLUND M, ACCOE F, et al.Isotopes for improved management of nitrate pollution in aqueous resources:review of surface water field studies[J].Environmental Science and Pollution Research, 2011, 18:519-533.
[2] XUE D M, BAETS B D, VAN O, et al.Cleemput classification of nitrate polluting activities through clustering of isotope mixing model outputs[J].Journal of Environmental Quality, 2013, 42:1486-1497.
[3] 毛巍, 梁志伟, 李伟, 等.利用氮、氧稳定同位素识别水体硝酸盐污染源研究进展[J].应用生态学报, 2013, 24(4):1146-1152.
[4] FAN A M, STEINBERG G A.Health implications if nitrate and nitrite in drinking water:An update on methemoglobinemia occurrence and reproductive and developmental toxicity[J].Regulatory Toxicology and Pharmacology, 1996, 23:35-43.
[5] 杨琰, 蔡鹤生, 刘存富, 等.NO3-中N和O同位素新技术在岩溶地区地下水氮污染研究中的应用[J].中国岩溶, 2004, 23(3):206-212.
[6] RIORDAN O T, BENTHAM G.The politics of nitrate in the UK[J]//BUT T P, HEATH WAITE A L, TRUDGILL S T.Nitrate—processes, pattersand management.New York:Wiley, 2004:406-416.
[7] LI, S L, LIU C Q, LI J, et al.Assessment of the sources of nitrate in the Changjiang River, China using a nitrogen and oxygen isotopic approach[J].Environmental Science and Technology, 2010, 44(5):1573-1578.
[8] LI, S L, LIU C Q, LI J, et al.Evaluation of nitrate source in surface water of southwestern China based on stable isotopes[J].Environment Earth Science, 2013, 68:219-228.
[9] FUKADA T, HISCOCK K M, DENNIS P F, et al.A dual isotope approach to identify denitrification in groundwater at a river-bank infiltration site[J].Water Research, 2003, 37:3070-3078.
[10] XUE D M, BOTTE B J, De Baets, et al.Present limitations and future prospects of stable isotope methods for nitrate source identification in surface-and groundwater[J].Water Research, 2009, 43:1159-1170.
[11] GRANGER J, SIGMAN D M, ROHDE M M, et al.N and O isotope effects during nitrate assimilation by unicellular prokaryotic and eukaryotic plankton cultures[J].Geochim Cosmochim Acta, 2010, 74:1030-1040.
[12] 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.
[13] KREITLER C W.Determining the source of nitrate in ground water by nitrogen isotope studies[J].Report of Investigations, 1975, 83:1-57.
[14] 张翠云, 张胜, 李政红, 等.利用氮同位素技术识别石家庄市地下水硝酸盐污染源[J].地球科学进展, 2004, 19(2):183-190.
[15] FREYER H.Seasonal variation of 15N/14N ratios in atmospheric nitrate species[J].Tellus B, 1991, 43:30-44.
[16] CAO Y C, SUN G Q, XING G X, et al.Natural abundance of 15N in main N-containing chemical fertilizers of China[J].Pedosphere, 1991, 1:377-382.
[17] LI X D, MASUDA H, KOBA K, et al.Nitrogen isotope study on nitrate-contaminated groundwater in the Sichuan Basin, China[J].Water Air Soil Pollut, 2007, 178:145-156.
[18] ZHANG Y, LIU X J, FANGMEIER A, et al.Nitrogen inputs and isotopes in precipitation in the North China Plain[J].Atmospheric Environment, 2008, 42:1436-1448.
[19] TOWNSEND-SMALL A, MCCARTHY M J, BRANDES J A, et al.Stable isotopic composition of nitrate in Lake Taihu, China, and major inflow rivers[J].Hydrobiologia, 2007, 581:135-140.
[20] ELLIOTT E M, KENDALL C, WANKEL S D, et al.Nitrogen isotopes as indicators of NOx source contributions to atmospheric nitrate deposition across the Midwestern and Northeastern United States[J].Environmental Science and Technology, 2007, 41:7661-7667.
[21] HEATON T H E.Isotopic studies of nitrogen pollution in the hydrosphere and atmosphere:A review[J].Chemical Geology, 1986, 59:87-102.
[22] FOGG G E, ROLSTON D E, DECKER D L, et al.Spatial variation in nitrogen isotope values beneath nitrate contamination sources[J].Ground Water, 1998, 36:418-426.
[23] IQBAL M Z, KROTHE N C, SPALDING R F.Nitrogen isotope indicators of seasonal source variability to ground water[J].Environmental Geology, 1997, 32:210-218.
[24] CHOI W J, HAN G H, LEE S M, et al.Impact of land-use types on nitrate concentration and δ15N in unconfined ground water in rural areas of Korea[J].Agriculture Ecosystems & Environment, 2007, 120:259-268.
[25] CHOI W J, LEE S M, RO H M, et al.Natural 15N abundances of maize and soil amended with urea and composted pig manure[J].Plant Soil, 2002, 245:223-232.
[26] CHOI W J, RO H M, LEE S M.Natural 15N abundances of inorganic nitrogen in soil treated with fertilizer and compost under changing soil moisture regimes[J].Soil Biology & Biochemistry, 2003, 35:1289-1298.
[27] CURT M D, AGUADO P, SA'NCHEZ G, et al.Nitrogen isotope ratios of synthetic and organic sources of nitrate water contamination in Spain[J].Water Air Soil Pollut, 2004, 151:135-142.
[28] WIDORY D, KLOPPMANN W, CHERY L, et al.Nitrate in groundwater, an isotope multi-tracer approach[J].Journal of Contaminant Hydrology, 2004, 72:165-188.
[29] BATEMAN A S, KELLY S D.Fertilizer nitrogen isotope signatures[J].Isotopes in Environmental and Health Studies, 2007, 43:237-247.
[30] 邢光熹, 曹亚澄, 施书莲, 等.太湖地区水体氮的污染源和反硝化[J].中国科学(B辑), 2001, 31(2):130-137.
[31] ROADCAP G S, HACKLEY K C, HWANG H H, et al.Application of nitrogen and oxygen isotopes to identify sources of nitrate[C].Illinois Groundwater Consortium Conference on 9 April 2001.
[32] KARR J D, SHOWERS W J, WENDELL G J, et al.Tracing nitrate transport and environmental impact from intensive swine farming using delta nitrogen-15[J].Journal of Environmental Quality, 2001, 30:1163-1175.
[33] MARIOTTI A, LANDREAU A, SIMON B.15N isotope biogeochemistry and natural denitrification process in ground water:Application to the chalk aquifer in northern France[J].Geochim Cosmochim Acta, 1988, 52:1869-1878.
[34] MCCLELLAND J W, VALIELA I.Linking nitrogen in estuarine producers to land-derived sources[J].Limnology and Oceanography, 1998, 43:577-585.
[35] BEDARD-HAUGHN A, VAN GROENIGEN J W, VAN KESSEL C.Tracing 15N through landscapes:Potential uses and precautions[J].Jourbal of Hydrology, 2003, 272:175-190.
[36] 李思亮, 刘丛强.贵阳地下水硝酸盐氧同位素特征及应用[J].中国岩溶, 2006, 25(2):108-111.
[37] WASSENAAR L I.Evaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of 15N and 18O in NO3-[J].Applied Geochemistry, 1995, 10:391-405.
[38] ROCK L, MAYER B.Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and ground water of Luxembourg[J].Isotopes in Environmental and Health Studies, 2002, 38:191-206.
[39] MAYER B, BOLLWERK S M, MANSFELDT T, et al.The oxygen isotope composition of nitrate generated by nitrification in acid forest floors[J].Geochim Cosmochim Acta, 2001, 65:2743-2756.
[40] DEUTSCH B, MEWES M, LISKOW I, et al.Quantification of diffuse nitrate inputs into a small river system using stable isotopes of oxygen and nitrogen in nitrate[J].Organic Geochemistry, 2006, 37:1333-1342.
[41] SPOELSTRA J, SCHIFF S L, HAZLETT P W, et al.The isotopic composition of nitrate produced from nitrification in a hardwood forest floor[J].Geochim Cosmochim Acta, 2007, 71:3757-3771.
[42] KENDALL C.Tracing sources and cycling of nitrate in catchments[M]//KENDALL C, MCDONNELL J J.Isotope tracers in catchment hydrology.Elsevier, Amsterdam, 1998:519-576.
[43] DURKA W, SCHULZE E D, GEBAUER G, et al.Effects of forest decline on uptake and leaching of deposited nitrate determined from 15N and 18O measurements[J].Nature, 1994, 372:765-767.
[44] PIATEK K B, MITCHELL M J, SILVA S R, et al.Sources of nitrate in snowmelt discharge:Evidence from water chemistry and stable isotopes of nitrate[J].Water Air Soil Pollut, 2005, 165:13-35.
[45] HALES H C, ROSS D S, LINI A.Isotopic signature of nitrate in two contrasting watersheds of Brush Brook, Vermont, USA[J].Biogeochemistry, 2007, 84:51-66.
[46] LEE K S, BONG Y S, LEE D, et al.Tracing the sources of nitrate in the Han River watersheds in Korea, using δ15N-NO3- and δ18O- NO3- values[J].Science of the Total Environment, 2008, 395:117-124.
[47] PARDO L H, KENDALL C, PETT-RIDGE J, et al.Evaluating the source of stream water nitrate using 15N and 18O in nitrate in two watersheds in New Hampshire, USA[J].Hydrological Processes, 2004, 18:2699-2712.
[48] FINLAY J C, STERNER R W, KUMAR S.Isotopic evidence for in-lake production of accumulating nitrate in Lake Superior[J].Ecological Application, 2007, 17:2323-2332.
[49] HVBNER H.Isotope effects of nitrogen in the soil and biosphere.[M]//FRITZ P, FONTES J C.Handbook of Environmental Isotope Geochemistry.Amsterdam:Elsevier, 1986:361-425.
[50] RIVERS C N, BARRETT M H, HISCOCK K M, et al.Use of nitrogen isotopes to identify nitrogen contamination of the Sherwood sandstone aquifer beneath the city of Nottingham, United Kingdom[J].Hydrogeology Journal, 1996, 4(1):90-102.
[51] MARIOTTI A, LETOLLE R.Application de l'etude isotopique de l'azote en hydrologie et en hydrogeology-analyse des resultats obtenus sur un exemple precis:Le Bassin de Melarchez (Seine-et-Marne, France)[J].Journal of Hydrology, 1977, 33:157-172.
[52] FLIPSE W J, BONNER F T.Nitrogen-isotope ratios of nitrate in ground water under fertilized fields, Long Island, New York[J].Ground Water, 1985, 23:59-67.
[53] KENDALL C, CAMPBELL D H, BURNS D A, et al.Tracing sources of nitrate in snowmelt runoff using the oxygen and nitrogen isotopic compositions of nitrate[J].Biogeochemistry of Seasonally Snow-Covered catchments, Proceedings of a Boulder Symposium, 1995, 228:339-347.
[54] ARAVENA R M L, CHERRY E J A.Stable isotopes of oxygen and nitrogen in source identification of nitrate from septic systems[J].Ground Water, 1993, 31:180-186.
[55] WILLIARD K W J, DE WALLE D R, EDWARDS P J, et al.18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds[J].Journal of Hydrology, 2001, 252:174-188.
[56] KENDALL C, ELLIOTT E M, WANKEL S D.Tracing anthropogenic inputs of nitrogen to ecosystems[M]//MICHENER R, LAJTHA K.Stable isotopes in ecology and environmental science.2nd ed.Blackwell publishing, 2007:375-449.
[57] AMBERGER A, SCHMIDT H L.Natural isotope contents of nitrate as indicators for its origin[J].Geochim Cosmochim Acta, 1987, 51:2699-2705.
[58] FUKADA T, HISCOCK K M, DENNIS P F.A dual isotope approach to the nitrogen hydrochemistry of an urban aquifer[J].Applied Geochemistry, 2004, 19:709-719.
[59] KENDALL C.Tracing nitrogen sources and cycling in catchments[J].Isotope Tracers in Catchment Hydrology, 1998, 1:519-576.
[60] HOLLOCHER T C.Source of the oxygen atoms of nitrate in the oxidation of nitrate by nitrocacter agilis and evidence against a P-O-N anhydride mechanism in oxidative phosphorylation[J].Archives of Biochemistry and Biophysics, 1984, 233:721-727.
[61] KENDALL C, ARAVENA R.Nitrate isotopes in groundwater systems[M].Environmental tracers in subsurface hydrology.Springer US, 2000:261-297.
[62] LEENHOUTS J M, BASSETT R L, MADDOCK III T.Utilization of intrinsic boron isotopes as co-migrating tracers for identifying potential nitrate contamination sources[J].Ground Water, 1998, 36:240-250.
[63] WIDORY D, PETELET-GIRAUD E, NE'GREL P, et al.Tracking the sources of nitrate in groundwater using coupled nitrogen and boron isotopes:A synthesis[J].Environmental Science and Technolegy, 2005, 39:539-548.
[64] SEILER R L.Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater[J].Applied Geochemistry, 2005, 20:1626-1636.
[65] MICHALSKI G, SCOTT Z, KABILING M, et al.First measurements and modeling of Δ17O in atmospheric nitrate[J].Geophysical Research Letters, 2003, 30:1870.
[66] TSUNOGAI U, KOMATSU D D, Daita S, et al.Tracing the fate of atmospheric nitrate deposited onto a forest ecosystem in eastern Asia using Δ17O[J].Atmos Chem Phys Discuss, 2009, 9:23073-23101.
[67] SACCON P, LEIS A, MARCA A, et al.Multi-isotope approach for the identification and characterization of nitrate pollution sources in the Marano lagoon (Italy) and parts of its catchment area[J].Applied Geochemistry, 2013, 34:75-89.
[68] HEATON T H E, STUART M E, SAPIANO M, et al.An isotope study of the sources of nitrate in Malta's groundwater[J].Journal of Hydrology, 2012, 414-415:244-254.
[69] PHILLIPS D L, KOCH P L.Incorporating concentration dependence in stable isotope mixing models[J].Oecologia, 2002, 130:114-125.
[70] MOORE J W, SEMMENS B X.Incorporating uncertainty and prior information into stable isotope mixing models[J].Ecology Letters, 2008, 11:470-480.
[71] PARNELL A C, INGER R, BEARHOP S, et al.Source partitioning using stable isotopes:Coping with too much variation[J].PLOS ONE, 2010, 5(3):e9672.
[72] XUE D M, DE BAETS B, VAN CLEEMPUT O, et al.Use of a Bayesian isotope mixing model to estimate proportional contributions of multiple nitrate sources in surface water[J].Environmental Pollution, 2012, 161:43-49.
[73] 邵益生, 纪杉.应用氮同位素方法研究污灌对地下水氮污染的影响[J].工程勘察, 1992(4):37-41.
[74] 金赞芳, 王飞儿, 陈英旭, 等.城市地下水硝酸盐污染及其成因分析[J].土壤学报, 2004, 41(2):252-258.
[75] 刘君, 陈宗宇.利用稳定同位素追踪石家庄市地下水中的硝酸盐来源[J].环境科学, 2009, 30(6):42-48.
[76] 陈惟财, 陈伟琪, 张珞平, 等.九龙江流域地表水中硝酸盐来源辨析[J].环境科学, 2008, 29(6):1484-1487.
[1] 周毅, 吴华武, 贺斌, 李静, 段伟利, 王建锋, 童世贤. 长江水δ18O和δD时空变化特征及其影响因素分析[J]. 长江流域资源与环境, 2017, 26(05): 678-686.
[2] 葛成军, 俞花美. 南京市典型工业区耕地中多环芳烃源解析[J]. 长江流域资源与环境, 2009, 18(9): 843-.
[3] 章新平, 孙维贞,刘晶淼. 西南水汽通道上昆明站降水中的稳定同位素[J]. 长江流域资源与环境, 2005, 14(5): 665-669.
[4] 刘英华,张世熔, 张素兰, 魏 甦, 肖鹏飞. 成都平原地下水硝酸盐含量空间变异研究[J]. 长江流域资源与环境, 2005, 14(1): 114-118.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
[1] 陈 勇,陈国阶,杨定国. 岷江上游聚落分布规律及其生态特征——以四川理县为例[J]. 长江流域资源与环境, 2004, 13(1): 72 -77 .
[2] 陈正洪,万素琴,毛以伟. 三峡库区复杂地形下的降雨时空分布特点分析[J]. 长江流域资源与环境, 2005, 14(5): 623 -627 .
[3] 张磊,董立新,吴炳方,周万村. 三峡水库建设前后库区10年土地覆盖变化[J]. 长江流域资源与环境, 2007, 16(1): 107 -112 .
[4] 李 娜,许有鹏, 陈 爽. 苏州城市化进程对降雨特征影响分析[J]. 长江流域资源与环境, 2006, 15(3): 335 -339 .
[5] 禹 娜,陈立侨,赵泉鸿. 太湖介形类动物丰度与生物量[J]. 长江流域资源与环境, 2008, 17(4): 546 .
[6] 孔令强. 水电工程农村移民入股安置模式初探[J]. 长江流域资源与环境, 2008, 17(2): 185 .
[7] 孙维侠, 赵永存, 黄 标, 廖菁菁, 王志刚, 王洪杰. 长三角典型地区土壤环境中Se的空间变异特征及其与人类健康的关系[J]. 长江流域资源与环境, 2008, 17(1): 113 .
[8] 于苏俊,张 继,夏永秋. 基于遗传算法的可持续土地利用动态规划[J]. 长江流域资源与环境, 2006, 15(2): 180 -184 .
[9] 时连强,李九发,应 铭,左书华,徐海根. 长江口没冒沙演变过程及其对水库工程的响应[J]. 长江流域资源与环境, 2006, 15(4): 458 -464 .
[10] 杨丽霞,杨桂山,苑韶峰. 数学模型在人口预测中的应用——以江苏省为例[J]. 长江流域资源与环境, 2006, 15(3): 287 -291 .