Abstract
Accurate identification of nitrate (NO3−) sources is the premise of non-point source pollution control in watersheds. The multiple isotope techniques (δ15N-NO3−, δ18O-NO3−, δ2H-H2O, δ18O-H2O), combined with hydrochemistry characteristics, land use information, and Bayesian stable isotope mixing model (MixSIAR), were used to identify the sources and contributions of NO3− in the agricultural watershed of the upper Zihe River, China. A total of 43 groundwater (GW) and 7 surface water (SFW) samples were collected. The results showed that NO3− concentrations of 30.23% GW samples exceeded the WHO maximum permissible limit level, whereas SFW samples did not exceed the standard. The NO3− content of GW varied significantly among different land uses. The averaged GW NO3− content in livestock farms (LF) was the highest, followed by vegetable plots (VP), kiwifruit orchards (KF), croplands (CL), and woodlands (WL). Nitrification was the main transformation process of nitrogen, while denitrification was not significant. Hydrochemical analysis results combined with NO isotopes biplot showed that manure and sewage (M&S), NH4+ fertilizers (NHF), and soil organic nitrogen (SON) were the mixed sources of NO3−. The MixSIAR model summarized that M&S was the main NO3− contributor for the entire watershed, SFW, and GW. For contribution rates of sources in GW of different land use patterns, the main contributor in KF was M&S (contributing 59.00% on average), while M&S (46.70%) and SON (33.50%) contributed significantly to NO3− in CL. Combined with the traceability results and the situation that land use patterns are changing from CL to KF in this area, improving fertilization patterns and increasing manure use efficiency are necessary to reduce NO3− input. These research results will serve as a theoretical foundation for controlling NO3− pollution in the watershed and adjusting agricultural planting structures.
Graphical abstract
Similar content being viewed by others
Data availability
All data is provided in full in the supplementary material.
References
Adimalla N, Qian H, Nandan MJ (2020) Groundwater chemistry integrating the pollution index of groundwater and evaluation of potential human health risk: a case study from hard rock terrain of south India. Ecotox Environ Safe 206:111217
Andersson KK, Hooper AB (1983) O2 and H2O are each the source of one O in NO2- produced from NH3 by nitrosomonas: 15N-NMR evidence. Febs Lett 164(2):236–240
Aquilina L, Poszwa A, Walter C, Vergnaud V, Pierson-Wickmann A, Ruiz L (2012) Long-term effects of high nitrogen loads on cation and carbon riverine export in agricultural catchments. Environ Sci Technol 46(17):9447–9455
Barzegar R, Moghaddam AA, Tziritis E, Fakhri MS, Soltani S (2017) Identification of hydrogeochemical processes and pollution sources of groundwater resources in the Marand plain, northwest of Iran. Environ Earth Sci 76(7):296
Biddau R, Cidu R, Da Pelo S, Carletti A, Ghiglieri G, Pittalis D (2019) Source and fate of nitrate in contaminated groundwater systems: assessing spatial and temporal variations by hydrogeochemistry and multiple stable isotope tools. Sci Total Environ 647:1121–1136
Burow KR, Nolan BT, Rupert MG, Dubrovsky NM (2010) Nitrate in groundwater of the United States, 1991–2003. Environ Sci Technol 44(13):4988–4997
Degnan JR, Böhlke JK, Pelham K, Langlais DM, Walsh GJ (2016) Identification of groundwater nitrate contamination from explosives used in road construction: isotopic, chemical, and hydrologic evidence. Environ Sci Technol 50(2):593–603
Diaz RJ, Rosenberg R (2008) Spreading dead zones and consequences for marine ecosystems. Science 321(5891):926–929
Fang Y, Koba K, Makabe A, Zhu F, Fan S, Liu X, Yoh M (2012) Low δ18O values of nitrate produced from nitrification in temperate forest soils. Environ Sci Technol 46(16):8723–8730
Gao J, Lu Y, Chen Z, Wang L, Zhou J (2019) Land-use change from cropland to orchard leads to high nitrate accumulation in the soils of a small catchment. Land Degrad Dev 30(17):2150–2161
Gao J, Li Z, Chen Z, Zhou Y, Liu W, Wang L, Zhou J (2021) Deterioration of groundwater quality along an increasing intensive land use pattern in a small catchment. Agr Water Manage 253:106953
He S, Li P, Su F, Wang D, Ren X (2022) Identification and apportionment of shallow groundwater nitrate pollution in Weining Plain, northwest China, using hydrochemical indices, nitrate stable isotopes, and the new Bayesian stable isotope mixing model (MixSIAR). Environ Pollut 298:118852
Huang X, Jin M, Ma B, Liang X, Cao M, Zhang J, Zhang Z, Su J (2022) Identifying nitrate sources and transformation in groundwater in a large subtropical basin under a framework of groundwater flow systems. J Hydrol 610:127943
Ji X, Xie R, Hao Y, Lu J (2017) Quantitative identification of nitrate pollution sources and uncertainty analysis based on dual isotope approach in an agricultural watershed. Environ Pollut 229:586–594
Kang P, Li S, Wang F, Zhao H, Lv S (2021) Use of multiple isotopes to evaluate nitrate dynamics in groundwater under the barrier effect of underground cutoff walls. Environ Sci Pollut R 28(6):7076–7089
Kaushal SS (2016) Increased salinization decreases safe drinking water. Environ Sci Technol 50(6):2765–2766
Kendall C, Elliott EM, Wankel SD (2007) Tracing anthropogenic inputs of nitrogen to ecosystems. Blackwell Publishing Ltd, Oxford, UK, pp 375–449
Kloppmann W, Girard J, Négrel P (2002) Exotic stable isotope compositions of saline waters and brines from the crystalline basement. Chem Geol 184(1):49–70
Kohl DH, Shearer GB, Commoner B (1971) Fertilizer nitrogen: contribution to nitrate in surface water in a corn belt watershed source. Science 174(4016):1331–1334
Kou X, Ding J, Li Y, Li Q, Mao L, Xu C, Zheng Q, Zhuang S (2021) Tracing nitrate sources in the groundwater of an intensive agricultural region. Agr Water Manage 250:106826
Li J, Zhu D, Zhang S, Yang G, Zhao Y, Zhou C, Lin Y, Zou S (2022) Application of the hydrochemistry, stable isotopes and MixSIAR model to identify nitrate sources and transformations in surface water and groundwater of an intensive agricultural karst wetland in Guilin. China Ecotox Environ Safe 231:113205
Li M, Zheng L, Sun Y (2012) Effects of climate conditions on organic agriculture in Boshan District of Shandong and Countermeasures. Meteorol Environ Res 6(3):61–63
Li Q, Zhou J, Zhou Y, Bai C, Tao H, Jia R, Ji Y, Yang G (2014a) Variation of groundwater hydrochemical characteristics in the plain area of the Tarim Basin, Xinjiang Region, China. Environ Earth Sci 72(11):4249–4263
Li X, Liu C, Liu X, Yu J, Liu X (2014b) Sources and processes affecting nitrate in a dam-controlled subtropical river, Southwest China. Aquat Geochem 20(5):483–500
Liu C, Li S, Lang Y, Xiao H (2006) Using δ15N- and δ18O-values to identify nitrate sources in karst ground water, Guiyang, southwest China. Environ Sci Technol 40(22):6928–6933
Liu J, Song X, Yuan G, Sun X, Liu X, Wang S (2010) Characteristics of δ18O in precipitation over Eastern Monsoon China and the water vapor sources. Chin Sci Bull 55:200–211
Mahlknecht J, Daessle L, Esteller M, Torres-Martinez J, Mora A (2018) Groundwater flow processes and human impact along the arid US-Mexican border, evidenced by environmental tracers: the case of Tecate, Baja California. Int J Env Res Pub He 15(5):887
Mayer B, Bollwerk SM, Mansfeldt T, Huetter B, Veizer J (2001) The oxygen isotope composition of nitrate generated by nitrification in acid forest floors. Geochim Cosmochim Acta 65(16):2743–2756
Mayer B, Boyer EW, Goodale C, Jaworski NA, Breemen VN, Howarth RW, Seitzinger S, Billen G, Lajtha K, Nadelhoffer K, Dam VD, Hetling LJ, Nosal M, Paustian K (2002) Sources of nitrate in rivers draining sixteen watersheds in the northeastern U.S.: isotopic constraints. Biogeochemistry 57(1):171–197
McMahon PB, Böhlke JK (2006) Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, high plains, U.S.A. Environ Sci Technol 40(9):2965–2970
Narany TS, Aris AZ, Sefie A, Keesstra S (2017) Detecting and predicting the impact of land use changes on groundwater quality, a case study in Northern Kelantan, Malaysia. Sci Total Environ 599:844–853
Nejatijahromi Z, Nassery HR, Hosono T, Nakhaei M, Alijani F, Okumura A (2019) Groundwater nitrate contamination in an area using urban wastewaters for agricultural irrigation under arid climate condition, southeast of Tehran, Iran. Agr Water Manage 221:397–414
Ogrinc N, Tamše S, Zavadlav S, Vrzel J, Jin L (2019) Evaluation of geochemical processes and nitrate pollution sources at the Ljubljansko polje aquifer (Slovenia): a stable isotope perspective. Sci Total Environ 646:1588–1600
Phillips DL, Koch PL (2002) Incorporating concentration dependence in stable isotope mixing models. Oecologia 130(1):114–125
Singh S, Anil AG, Kumar V, Kapoor D, Subramanian S, Singh J, Ramamurthy PC (2022) Nitrates in the environment: a critical review of their distribution, sensing techniques, ecological effects and remediation. Chemosphere 287:131996
Song H, Meng Y, Jiang F, Li L, Li Y, Du C (2021) Isotope characteristic of surface water and groundwater in the middle reaches of Yarlung Zangbo river and their indicators. J Arid Land Resour Environ 35(7):122–128
Song X, Zhao C, Wang X, Li J (2009) Study of nitrate leaching and nitrogen fate under intensive vegetable production pattern in northern China. Cr Biol 332(4):385–392
Stock BC, Jackson AL, Ward EJ, Parnell AC, Phillips DL, Semmens BX (2018) Analyzing mixing systems using a new generation of Bayesian tracer mixing models. PeerJ 6:e5096
Taufiq A, Effendi AJ, Iskandar I, Hosono T, Hutasoit LM (2019) Controlling factors and driving mechanisms of nitrate contamination in groundwater system of Bandung Basin, Indonesia, deduced by combined use of stable isotope ratios, CFC age dating, and socioeconomic parameters. Water Res 148:292–305
Tian D, Niu S (2015) A global analysis of soil acidification caused by nitrogen addition. Environ Res Lett 10(2):1714–1721
Torres-Martínez JA, Mora A, Mahlknecht J, Daesslé LW, Cervantes-Avilés PA, Ledesma-Ruiz R (2021) Estimation of nitrate pollution sources and transformations in groundwater of an intensive livestock-agricultural area (Comarca Lagunera), combining major ions, stable isotopes and MixSIAR model. Environ Pollut 269:115445
Utom AU, Werban U, Leven C, Müller C, Knöller K, Vogt C, Dietrich P (2020) Groundwater nitrification and denitrification are not always strictly aerobic and anaerobic processes, respectively: an assessment of dual-nitrate isotopic and chemical evidence in a stratified alluvial aquifer. Biogeochemistry 147(2):211–223
Vavilin VA, Rytov SV (2015) Nitrate denitrification with nitrite or nitrous oxide as intermediate products: stoichiometry, kinetics and dynamics of stable isotope signatures. Chemosphere 134:417–426
Wang K, Guo F, Jiang G, Bian H (2014) Application of 15N and 18O to nitrogen pollution source in karst water in Eastern Guilin. China Environ Sci 34(9):2223–2230
WHO (2011) Guidelines for drinking-water quality. World Health Organization. WHO, Geneva
Xue D, Botte J, De Baets B, Accoe F, Nestler A, Taylor P, Van Cleemput O, Berglund M, Boeckx P (2009) Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater. Water Res 43(5):1159–1170
You J (2019) Research on and controlling factors of shallow groundwater in the source region of the Zihe River. Dissertation, China University of Mining and Technology (in Chinese)
You J, Qi Y, Shao G, Ma C, Yang Y, Pei Y (2020) Hydrochemical characteristic and main ion sources of shallow groundwater in Zihe River source region, Shandong, China. J Guangxi Normal Univ (Nat Sci Ed) 38(04):132–139 (in Chinese)
Yu L, Zheng T, Zheng X, Hao Y, Yuan R (2020) Nitrate source apportionment in groundwater using Bayesian isotope mixing model based on nitrogen isotope fractionation. Sci Total Environ 718:137242
Yu L, Zheng T, Yuan R, Zheng X (2022) APCS-MLR model: a convenient and fast method for quantitative identification of nitrate pollution sources in groundwater. J Environ Manage 314:115101
Yue F, Li S, Liu C, Zhao Z, Hu J (2013) Using dual isotopes to evaluate sources and transformation of nitrogen in the Liao River, northeast China. Appl Geochem 36:1–9
Zaryab A, Nassery HR, Knoeller K, Alijani F, Minet E (2022) Determining nitrate pollution sources in the Kabul Plain aquifer (Afghanistan) using stable isotopes and Bayesian stable isotope mixing model. Sci Total Environ 823:153749
Zhang D, Li X, Zhao Z, Liu C (2015) Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain. Appl Geochem 52:43–56
Zhang H, Xu Y, Cheng S, Li Q, Yu H (2020) Application of the dual-isotope approach and Bayesian isotope mixing model to identify nitrate in groundwater of a multiple land-use area in Chengdu Plain, China. Sci Total Environ 717:137134
Zhang Q, Li P, Lyu Q, Ren X, He S (2022) Groundwater contamination risk assessment using a modified DRATICL model and pollution loading: a case study in the Guanzhong Basin of China. Chemosphere 291:132695
Zhang Y, Shi P, Li F, Wei A, Song J, Ma J (2018) Quantification of nitrate sources and fates in rivers in an irrigated agricultural area using environmental isotopes and a Bayesian isotope mixing model. Chemosphere 208:493–501
Zhu A, Chen J, Gao L, Shimizu Y, Liang D, Yi M, Cao L (2019) Combined microbial and isotopic signature approach to identify nitrate sources and transformation processes in groundwater. Chemosphere 228:721–734
Zhu X, Fu W, Kong X, Chen C, Liu Z, Chen Z, Zhou J (2021) Nitrate accumulation in the soil profile is the main fate of surplus nitrogen after land-use change from cereal cultivation to apple orchards on the Loess Plateau. Agr Ecosyst Environ 319:107574
Funding
This work was supported by the Groundwater Nitrate Traceability Project in Boshan District (Grant number 1460021014); the National Natural Science Foundation of China (Grant number 41977144); and the Agricultural Major Technology Collaborative Promotion Plan of Shandong province (Grant number SDNYXTTG-2022–22).
Author information
Authors and Affiliations
Contributions
Wanning Zhao: Conceptualization, Methodology, Software, Formal analysis, Investigation, Writing-original draft, Writing-review and editing.
Deqing Yang: Conceptualization, Methodology, Writing-review and editing.
Qiang Sun: Methodology, Writing-review and editing.
Yandong Gan: Methodology, Writing-review and editing.
Liyong Bai: Methodology, Investigation, Writing-review and editing.
Shuangshuang Li: Methodology, Investigation.
Dongmei Liu: Methodology, Investigation.
Jiulan Dai: Conceptualization, Methodology, Formal analysis, Investigation, Writing-original draft, Writing-review and editing.
Corresponding author
Ethics declarations
Ethical approval
Not applicable.
Consent to participate
Not applicable.
Consent to publish
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Xianliang Yi
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Highlights
• Soil organic nitrogen, manure, and sewage are the main sources of nitrate in the upstream area of Zihe River.
• Hydrochemical information combined with multi-isotope technology and Bayesian isotope mixing model is a practical method for joint traceability.
• The results will provide basic data for regional water resource protection and a reference for effective water resource management in multi-land use areas.
Supplementary information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhao, W., Yang, D., Sun, Q. et al. Combining multi-isotope technology, hydrochemical information, and MixSIAR model to identify and quantify nitrate sources of groundwater and surface water in a multi-land use region. Environ Sci Pollut Res 30, 80070–80084 (2023). https://doi.org/10.1007/s11356-023-27720-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-023-27720-9