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The comprehensive evaluation of nitrate origin and transformation pathways in the oxic alluvial aquifer in Serbia

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Abstract

Accurate pollution source identification is essential for establishing adequate water management strategies, particularly in groundwater with slow flow and prolonged recharge process allowing long-term pollution retention. An integrated study based on hydrogeochemical, dual isotopic (δ15NNO3 and δ18ONO3), and microbiological approaches (DN, IRB, and SRB BART tests) along with the statistical data processing was conducted to determine nitrate origin and fate in oxic alluvial groundwater source Ključ in Serbia. The findings from a comprehensive investigation, encompassing 20 groundwater sampling locations during the period 2010–2019, delineated three distinct zones — the hinterland (anthropogenic impact area-untreated sewage inflow), the middle zone (area of mixed influence from fertilizer application, accompanied by a mitigated anthropogenic impact), and the zone of riparian denitrification. Significant linear relationship between anthropogenic impact parameters (Na, Cl, B, NO3, NH4+, and electrical conductivity) along with the isotopic signatures (δ15N-NO3 ranking from + 10.01 to + 11.18‰ and δ18O-NO3 ranking from + 1.15 to + 6.24‰) and grouped sampling objects by cluster analysis indicated that hinterland is burdened by the nitrates originating from anthropogenic impact. The cross-section of groundwater flow data, concurrent increase of NH4+, and pH levels, along with the highest values of δ15N-NO3 (+ 12.90‰) and δ18O-NO3 (+ 9.70‰), indicated area of fertilizers (urea) impact. BART test results, pH increase, and low oxygen concentration, along with the groundwater flow data in riparian zone, indicated the unfolding of denitrification process. Presented research emphasizes the importance, necessities, and advantages of simultaneous and complementary use of hydrogeochemical, microbiological, and isotopic data.

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References

  • Abascal E, Gómez-Coma L, Ortiz I, Ortiz A (2022) Global diagnosis of nitrate pollution in groundwater and review of removal technologies. Sci Total Environ 810:152233. https://doi.org/10.1016/j.scitotenv.2021.152233. (ISSN 0048-9697)

    Article  CAS  Google Scholar 

  • American Public Health Association; American Water Works Association; Water Environment Federation (2005) In: Greenberg A (ed) Standard methods for the examination of water and wastewater, 21st edn. American Public Health Association, Washington, D.C

    Google Scholar 

  • Baily A, Rock L, Watson CJ, Fenton O (2011) Spatial and temporal variations in groundwater nitrate at an intensive dairy farm in south-east Ireland: insights from stable isotope data. Agric Ecosysts Environ 144:308–318

    Article  CAS  Google Scholar 

  • Barth S (1998) Application of boron isotopes for tracing sources of anthropogenic contamination in groundwater. Water Resour 32:685–690

    CAS  Google Scholar 

  • Bateman AS, Kelly SD (2007) Fertilizer nitrogen isotope signatures. Isotopes Environ Health Stud 43(3):237–427

    Article  CAS  Google Scholar 

  • Bhatnagar, Sillanpää (2011) A review of emerging adsorbents for nitrate removal from water. Chem Eng J 168:493–504. https://doi.org/10.1016/j.cej.2011.01.103

    Article  CAS  Google Scholar 

  • Burgin AJ, Hamilton SK (2007) Have we overemphasized the role of denitrification in aquatic ecosystems? A review of nitrate removal pathways. Front Ecol Environ 5(2):89–96

    Article  Google Scholar 

  • Cao G, Scanlon BR, Han D, Zheng C (2016) Impacts of thickening unsaturated zone on groundwater recharge in the North China Plain. J Hydrol 537:260–270. https://doi.org/10.1016/j.jhydrol.2016.03.049

    Article  Google Scholar 

  • Choi WJ, Han GH, Lee SM, Lee GT, Yoon KS, Choi SM, Ro HM (2007) Impact of land-use types on nitrate concentration and δ15N in unconfined groundwater in rural areas of Korea. Agric Ecosyst Environ 120(2):259–268

    Article  CAS  Google Scholar 

  • Clark I (2015) Groundwater geochemistry and isotopes, 1st edn. CRC Press. https://doi.org/10.1201/b18347

    Book  Google Scholar 

  • Coban O, Kuschk P, Wells NS et al (2015) Microbial nitrogen transformation in constructed wetlands treating contaminated groundwater. Environ Sci Pollut Res 22:12829–12839. https://doi.org/10.1007/s11356-014-3575-3

    Article  CAS  Google Scholar 

  • Cullimore DR (2007) Practical manual of groundwater microbiology. CRC Press. https://doi.org/10.1201/9781420008166

  • Cullimore DR (2010) Standard methods for the application of BART testers in environmental investigations of microbiological activities, 3rd edn. Droycon Bioconcepts Inc., Regina, Saskatchewan, Canada

  • Danielescu S, MacQuarrie KT (2013) Nitrogen and oxygen isotopes in nitrate in the groundwater and surface water discharge from two rural catchments: implications for nitrogen loading to coastal waters. Biogeochemistry 115(1–3):111–127

    Article  CAS  Google Scholar 

  • Di Lorenzo T, Brilli M, Del Tosto D, Galassi DMP, Petitta M (2012) Nitrate source and fate at the catchment scale of the Vibrata River and aquifer (central Italy): an analysis by integrating component approaches and nitrogen isotopes. Environ Earth Sci 67:2383–2398

    Article  CAS  Google Scholar 

  • Dimkić M, Pušić M (2014) Correlation between entrance velocities, increase in local hydraulic resistances and redox potential of alluvial groundwater sources. Water Res Manag 4(1):3–23

    Google Scholar 

  • Dimkić MA, Brauch HJ, Kavanaugh M (2008) Groundwater management in large river basins. https://doi.org/10.2166/9781780401843

    Book  Google Scholar 

  • Feaga JB, Selker JS, Dick RP, Hemphill D (2010) Long-term nitrate leaching under vegetable production with cover crops in the Pacific Northwest. Soil Sci Soc Am J 74:186–195. https://doi.org/10.2136/sssaj2008.0178

    Article  CAS  Google Scholar 

  • Grant WD, Long PE (1981) Environmental microbiology. In: Tertiary level biology. Springer Science & Business Media

  • Green CT, Liao L, Nolan BT, Juckem PF, Shope CL, Tesoriero AJ, Jurgens BC (2018) Regional variability of nitrate fluxes in the unsaturated zone and groundwater, Wisconsin, USA. Water Resour Res 54:301–322. https://doi.org/10.1002/2017WR022012

    Article  Google Scholar 

  • Griebler C, Lueders T (2009) Microbial biodiversity in groundwater ecosystems. Freshw Biol 54:649–677

    Article  Google Scholar 

  • Hernández-del Amo E, Menció A, Gich F, Mas-Pla J, Bañeras L (2018) Isotope and microbiome data provide complementary information to identify natural nitrate attenuation processes in groundwater. Sci Total Environ 613–614:579–591. https://doi.org/10.1016/j.scitotenv.2017.09.018. (ISSN 0048-9697)

    Article  CAS  Google Scholar 

  • Hinkle SR, Böhlke JK, Duff JH, Morgan DS, Weick RJ (2007) Aquifer-scale controls on the distribution of nitrate and ammoniumin groundwater near La Pine, Oregon, USA. J Hydrol 333:486–503

    Article  Google Scholar 

  • Izbicki JA (2014) Fate of nutrients in shallow groundwater receiving treated septage, Malibu, CA, Groundwater 52 Focus Issue: 218–233. https://doi.org/10.1111/gwat.12194

  • Kadlec RH, Wallace S (2008) Nitrogen. In: Treatment wetlands, 2nd edn. CRC Press

    Chapter  Google Scholar 

  • Kelso B, Smith RV, Laughlin RJ, Lennox SD (1997) Dissimilatory nitrate reduction in anaerobic sediments leading to river nitrite accumulation. Appl Environ Microbiol 63(12):4679–4685

    Article  CAS  Google Scholar 

  • Kendall C (1998) Chapter 16 - tracing nitrogen sources and cycling in catchments. In: Kendall C, McDonnell JJ (eds) Isotope tracers in catchment hydrology, pp 519–576. https://doi.org/10.1016/B978-0-444-81546-0.50023-9

    Chapter  Google Scholar 

  • Kendall C, Aravena R (2000) Nitrate isotopes in groundwater systems. In: Cook PG, Herczeg AL (eds) Environmental tracers in subsurface hydrology. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-4557-6_9

    Chapter  Google Scholar 

  • Kloppmann W, Chikurel H, Picot G, Guttman J, Pettenati M, Aharoni A, Guerrot C, Millot R, Gaus I, Wintgens T (2009) B and li isotopes as intrinsic tracers for injection tests in aquifer storage and recovery systems. Appl Geochem 24(7):1214–1223

    Article  CAS  Google Scholar 

  • Kovačević S (2017) Analysis of self-purifying potential of groundwater for removal of pharmaceuticals using the riverbank filtration method. Doctoral dissertation, University of Novi Sad, Faculty of Technical Sciences

  • Kurtzman D, Shapira RH, Bar-Tal A, Fine P, Russo D (2013) Nitrate fluxes to groundwater under citrus orchards in a Mediterranean climate: observations, calibrated models, simulations and agro-hydrological conclusions. J Contam Hydrol 151:93–104. https://doi.org/10.1016/j.jconhyd.2013.05.004

    Article  CAS  Google Scholar 

  • Levy Y, Shapira RH, Chefetz B, Kurtzman D (2017) Modeling nitrate from land surface to wells’ perforations under agricultural land: success, failure, and future scenarios in a Mediterranean case study. Hydrol Earth Syst Sci 21:3811–3825. https://doi.org/10.5194/hess-21-3811-2017

    Article  CAS  Google Scholar 

  • Li Q, Zhang H, Guo S et al (2020) Groundwater pollution source apportionment using principal component analysis in a multiple land-use area in southwestern China. Environ Sci Pollut Res 27:9000–9011. https://doi.org/10.1007/s11356-019-06126-6

    Article  CAS  Google Scholar 

  • Lindebaum J (2012) Identification of sources of ammonium in groundwater using stable nitrogen and boron isotopes in Nam Du, Hanoi. Dissertations in Geology at Lund University, No 300, 38 p 45

    Google Scholar 

  • Martinelli G, Dadomo A, De Luca DA, Mazzolad M, Lasagnac M, Pennisie M, Pillaf G, Sacchi E, Saccon P (2018) Nitrate sources, accumulation and reduction in groundwater from Northern Italy: insights provided by a nitrate and boron isotopic database. Appl Geochem 91:21–35

    Article  Google Scholar 

  • Meckenstock RU, Elsner M, Griebler C et al (2015) Biodegradation: updating the concepts of control for microbial cleanup in contaminated aquifers. Environ Sci Technol 49(12):7073–7081. https://doi.org/10.1021/acs.est.5b00715

    Article  CAS  Google Scholar 

  • Miljević N, Boreli-Zdravković Đ, Obradović V, Golobočanin D, Mayer B (2012) Evaluation of the origin of nitrate influencing the Kljuc groundwater source, Serbia. Water Sci Technol 66(3):472–478. https://doi.org/10.2166/wst.2012.179

    Article  CAS  Google Scholar 

  • Nikolenko O, Jurado A, Borges AV, Knӧller K, Brouyre S (2018) Isotopic composition of nitrogen species in groundwater under agricultural areas: a review. Sci Total Environ 621:1415–1432

    Article  CAS  Google Scholar 

  • Pastén-Zapata E, Ledesma R, Ramírez AI, Harter T, Mahlknecht J (2014) Assessment of sources and fate of nitrate in shallow groundwater of an agricultural area by using a multi-tracer approach. Sci Total Environ 470–471:855–864

    Article  Google Scholar 

  • Paul EA, Clark FE (1996) Soil microbiology and biochemistry. Academic Press

  • Perović M (2019) Assessment of the influence and regional specificity of hydrogeochemical conditions on the transformation of nitrogen compounds in groundwater. Doctoral dissertation, Faculty of Technical Sciences, Novi Sad

    Google Scholar 

  • Perović M, Šenk I, Tarjan L et al (2021) Machine learning models for predicting the ammonium concentration in alluvial groundwaters. Environ Model Assess 26:187–203. https://doi.org/10.1007/s10666-020-09731-9

    Article  Google Scholar 

  • Perović M, Dimkić M (2021) Chapter 8: transformation of nitrogen compounds in groundwater. IWA Publishing, Alluvial Aquifer Proscesses. https://doi.org/10.2166/9781789060904

    Book  Google Scholar 

  • Perovic M, Obradović V, Kovačević S, Mitrinović D, Živančev N, Nenin T (2017) Indicators of groundwater potential for nitrate transformation in a reductive environment. Water Environ Res 89(1):4–16. https://doi.org/10.2175/106143016X14733681696121

  • Rivett MO, Buss SR, Morgan P, Smith JWN, Bemment CD (2008) Nitrate attenuation in groundwater: a review of biogeochemical controlling processes. Water Res 42:4215–4232

    Article  CAS  Google Scholar 

  • Scheible O, Mulbarger M, Sutton P, Simpkin T, Daigger G, Heidman J, Yoder M, Schwinn D, Storrier D (1993) Process design manual: nitrogen control. EPA/625/R-93/010 (NTIS PB94159142)

    Google Scholar 

  • Sharp Z (2007) Principles of stable isotope geochemistry: nitrogen. Pearson Prentice Hal, Upper Saddle River, NJ, 206–219

  • Soldatova E, Guseva N, Sun Z, Bychinsky V, Boeckx P, Gao B (2017) Sources and behaviour of nitrogen compounds in the shallow groundwater of agricultural areas (Poyang Lake basin, China). J Contam Hydrol 202:59–69. https://doi.org/10.1016/j.jconhyd.2017.05.002. (ISSN 0169-7722)

    Article  CAS  Google Scholar 

  • Vitòria L, Soler A, Canals À, Otero N (2008) Environmental isotopes (N, S, C, O, D) to determine natural attenuation process in nitrate contaminated waters: example of Osona (NE Spain). Appl Geochem 23(12):3597–3611

    Article  Google Scholar 

  • Vymazal J (2007) Removal of nutrients in various types of constructed wetlands. Sci Total Environ 380:48–65

    Article  CAS  Google Scholar 

  • Wells NS, Hakoun V, Brouyère S, Knöller K (2016) Multi-species measurements of nitrogen isotopic composition reveal the spatial constraints and biological drivers of ammonium attenuation. Water Res 98:363–375

    Article  CAS  Google Scholar 

  • Widory D, Kloppmann W, Chery L, Bonnin J, Rochdi H, Guinamant JL (2004) Nitrate in groundwater: an isotopic multi-tracer approach. J Contam Hydrol 72:165–188

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Zhang YC, Prommer H, Broers H, Slomp CP, Greskowiak J, van der Grift B, Van Cappellen P (2013) Model-based integration and analysis of biogeochemical and isotopic dynamics in a nitrate-polluted pyritic aquifer. Environ Sci Technol 47(18):10415–10422

    CAS  Google Scholar 

  • Zhang L, Liang X, Xiao C et al (2023) Hydrochemical characteristics and the impact of human activities on groundwater in a semi-arid plain: a case study of western Jilin Province, Northeast China. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-023-29603-5

    Article  Google Scholar 

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Acknowledgements

We would like to express our special gratitude to the Helmholtz Centre for Environmental Research, UFZ, Department Catchment Hydrology, Halle/Saale, Germany, for their expertise and assistance in conducting the isotopic analyses.

Funding

The research was supported by the Ministry of Education, Science and Technology Development of the Republic of Serbia under the Project “Methodology for the Assessment, Design and Maintenance of Groundwater Sources in Alluvial Environments Depending on the Aerobic State,” No. TR37014.

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All authors contributed to the study conception and design. Data collection and analysis were performed by Marija Perović, Vesna Obradović, and Kay Knoeller. The first draft of the manuscript was written by Marija Perović and Vesna Obradović, and all authors commented on previous versions of the manuscript. Data processing was performed by Vesna Zuber -Radenković. Review was done by David Mitrinović and Zoran Čepić. All authors read and approved the final manuscript.

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Correspondence to Marija Perović.

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Perović, M., Obradović, V., Zuber-Radenković, V. et al. The comprehensive evaluation of nitrate origin and transformation pathways in the oxic alluvial aquifer in Serbia. Environ Sci Pollut Res (2024). https://doi.org/10.1007/s11356-024-33403-w

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