Skip to main content

Advertisement

Log in

Nitrate sources and their influence on hydrogeochemistry in karst caves of Southwest China

  • Original Paper
  • Published:
International Journal of Earth Sciences Aims and scope Submit manuscript

Abstract

Nitrate (NO3) pollution in karst areas has been widely discussed, which affects human health and the ecological environment. To investigate nitrate sources and their perturbations on cave hydrogeochemistry in karst cave systems, this study was conducted in Mahuang Cave, a karst cave in Southwest China, to assess the impact of human activities on the karst carbon cycle and the environment. The results show that (1) the variations of the water-soluble ions in Mahuang Cave are mainly controlled by carbonate weathering, and the cave water chemistry is characterized as the HCO3–Ca–Mg and HCO3–SO4–Ca–Mg types. (2) The dual isotopes and stable isotope Bayesian mixing model (SIAR) show that chemical fertilizers (41.5%) and soil nitrogen (33.75%) are the main nitrate sources in the cave water bodies, followed by manure and sewage (17.25%) and atmospheric precipitation (7.5%). (3) The significant enrichment of dissolved inorganic carbon isotope (δ13CDIC) in Mahuang Cave reveals that nitric acid produced by nitrification accelerates carbonate weathering in Mahuang Cave, and the carbon source effect of the carbon cycle in the cave is enhanced. Consequently, the response of cave drips and sediments to external environments is disturbed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

References

  • Aharon P (1988) A stable-isotope study of magnesites from the Rum Jungle Uranium Field, Australia: implications for the origin of strata-bound massive magnesites. Chem Geol 69:127–145

    Article  Google Scholar 

  • Ali HN, Atekwana EA (2011) The effect of sulfuric acid neutralization on carbonate and stable carbon isotope evolution of shallow groundwater. Chem Geol 284:217–228

    Article  Google Scholar 

  • Amberger A, Schmidt HL (1987) Natürliche isotopengehalte von Nitrat als Indikatoren für dessen Herkunft. Geochim Cosmochim Ac 51:2699–2705

    Article  Google Scholar 

  • Buckerfield SJ, Waldron S, Quilliam RS, Naylor LA, Li SL, Oliver DM (2019) How can we improve understanding of faecal indicator dynamics in karst systems under changing climatic, population, and land use stressors? Research opportunities in SW China. Sci Total Environ 646:438–447

    Article  Google Scholar 

  • Chen B, Yang R, Liu ZH, Sun HL, Yan H, Zeng QR, Zeng SB, Zeng C, Zhao M (2017) Coupled control of land uses and aquatic biological processes on the diurnal hydrochemical variations in the five ponds at the Shawan Karst Test Site, China: implications for the carbonate weathering-related carbon sink. Chem Geol 456:58–71

    Article  Google Scholar 

  • Clark I (2015) Groundwater geochemistry and isotopes. Crc Press, Boca Raton

    Book  Google Scholar 

  • Clark I, Fritz P (1997) Environmental isotopes in hydrogeology: Boca. Lewis Publishers, New York

    Google Scholar 

  • Cui RY, Fu B, Mao K, Chen AQ, Zhang D (2020) Identification of the sources and fate of NO3– N in shallow groundwater around a plateau lake in southwest China using NO3 isotopes (δ15N and δ18O) and a Bayesian model. J Environ Manag 270:110897

    Article  Google Scholar 

  • Desimone LA, Howes BL (1998) Nitrogen transport and transformations in a shallow aquifer receiving wastewater discharge: a mass balance approach. Water Resour Res 34:271–285

    Article  Google Scholar 

  • Dorale JA, Liu ZH (2009) Limitations of Hendy test criteria in judging the paleoclimatic suitability of speleothems and the need for replication. J Cave Karst Stud 71:73–80

    Google Scholar 

  • Drever JI (1988) The geochemistry of natural waters. Prentice Hall, New York

    Google Scholar 

  • Fathmawati FJ, Gravitiani E, Sarto HAH (2017) Nitrate in drinking water and risk of colorectal cancer in Yogyakarta, Indonesia. J Toxicol Environ Health 80:120–128

    Article  Google Scholar 

  • Ford D, Williams PW (2007) Karst hydrogeology and geomorphology. Wiley

    Book  Google Scholar 

  • Goldscheider N, Drew D (2007) Methods in karst hydrogeology. International contributions to hydrogeology. CRC Press, Boca Raton, p 26

    Google Scholar 

  • Heaton THE, Stuart ME, Sapiano M, Sultana MM (2012) An isotope study of the sources of nitrate in Malta’s groundwater. J Hydrol 414:244–254

    Article  Google Scholar 

  • Hu MM, Wang YC, Du PC, Shui Y, Cai AM, Lv C, Bao YF, Li YH, Li SZ, Zhang PW (2019) Tracing the sources of nitrate in the rivers and lakes of the southern areas of the Tibetan Plateau using dual nitrate isotopes. Sci Total Environ 658:132–140

    Article  Google Scholar 

  • Jin ZF, Qin X, Chen LX, Jin MT, Li FL (2015) Using dual isotopes to evaluate sources and transformations of nitrate in the West Lake watershed, eastern China. J Contam Hydrol 177:64–75

    Article  Google Scholar 

  • Kendall C, Elliott EM, Wankel SD (2007) Tracing anthropogenic inputs of nitrogen to ecosystems. In: Michener RH, Lajtha K (eds) Stable isotopes in ecology and environmental science, 3rd edn. Blackwell, New Jersey, pp 375–450

    Chapter  Google Scholar 

  • Kohl DH, Shearer GB, Commoner B (1971) Fertilizer nitrogen: contribution to nitrate in surface water in a corn belt watershed. Science 74:1331–1334

    Article  Google Scholar 

  • Krawczyk WE, Ford DC (2006) Correlating specific conductivity with total hardness in limestone and dolomite karst waters. Earth Surf Proc Land 31:221–234

    Article  Google Scholar 

  • Kuzyakov Y (2006) Sources of CO2 efflux from soil and review of partitioning methods. Soil Biol Biochem 38:425–448

    Article  Google Scholar 

  • Lambert WJ, Aharon P (2011) Controls on dissolved inorganic carbon and δ13C in cave waters from DeSoto Caverns: implications for speleothem δ13C assessments. Geochim Cosmochim Acta 75:753–768

    Article  Google Scholar 

  • Li TY, Li HC, Xiang XJ, Kou TS, Li JY, Zhou FL, Chen HL, Peng LL (2012) Transportation characteristics of δ13C in the plants-soil-bedrock-cave system in Chongqing karst area. Sci China Earth Sci 55:685–694

    Article  Google Scholar 

  • Li C, Li SL, Yue FJ, Liu J, Zhong J, Yan ZF, Zhang CR, Wang ZJ, Xu S (2019) Identification of sources and transformations of nitrate in the Xijiang River using nitrate isotopes and Bayesian model. Sci Total Environ 646:801–810

    Article  Google Scholar 

  • Li Y, Cao MD, Jin MG, Zhang J, Huang X (2020) Hydrochemical characteristics and tracing of nitrate sources in Quanshui River Catchment, Hubei Province, China. Earth Sci 45:1061–1070

    Google Scholar 

  • Liu Z (2012) New progress and prospect in study of rock-weathering-related carbon sinks. China Sci Bull 57:95–102

    Article  Google Scholar 

  • Liu CQ, Li SL, Lang YC, Xiao HY (2006) Using δ15N-and δ18O-values to identify nitrate sources in karst ground water, Guiyang, Southwest China. Environ Sci Technol 40:6928–6933

    Article  Google Scholar 

  • Liu ZH, Li Q, Sun HL, Wang SJ (2007) Seasonal, diurnal and storm-scale hydrochemical variations of typical epikarst springs in subtropical karst areas of SW China: soil CO2 and dilution effects. J Hydrol 337:207–223

    Article  Google Scholar 

  • Liu T, Wang F, Michalski G, Xia XH, Liu SD (2013) Using 15N, 17O, and 18O to determine nitrate sources in the Yellow River, China. Environ Sci Technol 47:13412–13421

    Article  Google Scholar 

  • Lu L, Cheng HG, Pu X, Liu XL, Cheng QD (2015) Nitrate behaviors and source apportionment in an aquatic system from a watershed with intensive agricultural activities. Environ Sci-Process Impacts 17:131–144

    Article  Google Scholar 

  • Mayer B, Boyer EW, Goodale C, Jaworski NA, Breemen V, Howarth RW, Seitzinger S, Billen G, Lajtha K, Nadelhoffer K, Dam DV, Hetling LJ, Nosal M, Paustian K (2002) Sources of nitrate in rivers draining sixteen watersheds in the northeastern US: isotopic constraints. Biogeochemistry 57:171–197

    Article  Google Scholar 

  • Paredes I, Otero N, Soler A, Green AJ, Soto DX (2020) Agricultural and urban delivered nitrate pollution input to Mediterranean temporary freshwaters. Agr Ecosyst Environ 294:106859

    Article  Google Scholar 

  • Parkhurst DL, Appelo CAJ (1999) User’s guide to PHREEQC version 2: computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. Water-Resour Investig Rep 99(4259):312

    Google Scholar 

  • Parnell AC, Inger R, Bearhop S, Jackson AL (2010) Source partitioning using stable isotopes: coping with too much variation. PLoS ONE 5:e9672

    Article  Google Scholar 

  • Petitta M, Fracchiolla D, Aravena R, Barbieri M (2009) Application of isotopic and geochemical tools for the evaluation of nitrogen cycling in an agricultural basin, the Fucino Plain, Central Italy. J Hydrol 372:124–135

    Article  Google Scholar 

  • Pracný P, Faimon J, Všianský D, Přichystal A (2019) Evolution of Mg/Ca and Sr/Ca ratios during the experimental dissolution of limestone. Chem Geol 523:107–120

    Article  Google Scholar 

  • Sabina JK, Slawomir S, Rasmus J, Andrzej K (2017) Geochemical and isotopic study to determine sources and processes affecting nitrate and sulphate in groundwater influenced by intensive human activity-carbonate aquifer Gliwice (southern Poland). Appl Geochem 76:168–181

    Article  Google Scholar 

  • Schulte P, Van Geldern R, Freitag H, Karim A, Négrel P, Giraud EP, Probst A, Probst JL, Telmer K, Veizer J (2011) Applications of stable water and carbon isotopes in watershed research: weathering, carbon cycling, and water balances. Earth-Sci Rev 109:20–31

    Article  Google Scholar 

  • Shi LX, Zhou ZF, Zhang H, An D, Ding SJ, Huang J, Dong H (2022) Sources of SO42 and NO3 and their disturbances to water rock processesin karst cave systems. Earth Sci 47:607–621 (in Chinese with English abstract)

    Google Scholar 

  • Tayefeh M, Sadeghi SM, Noorhosseini SA, Bacenetti J, Damalas CA (2018) Environmental impact of rice production based on nitrogen fertilizer use. Environ Sci Pollut Res 25:15885–15895

    Article  Google Scholar 

  • Tooth AF, Fairchild IJ (2013) Soil and karst aquifer hydrological controls on the geochemical evolution of speleothem-forming drip waters, Crag Cave, southwest Ireland. J Hydrol 273:51–68

    Article  Google Scholar 

  • Touhari F, Meddi M, Madjid M, Razack M (2015) Hydrogeochemical assessment of the upper cheliff groundwater (North West Algeria). Environ Earth Sci 73:3043–3061

    Article  Google Scholar 

  • Treble PC, Fairchild IJ, Griffiths A (2015) Impacts of cave air ventilation and in-cave prior calcite precipitation on Golgotha Cave dripwater chemistry, southwest Australia. Quat Sci Rev 127:61–72

    Article  Google Scholar 

  • Viswanathan VC, Jiang YJ, Berg M, Hunkeler D, Schirmer M (2016) An integrated spatial snap-shot monitoring method for identifying seasonal changes and spatial changes in surface water quality. J Hydrol 539:567–576

    Article  Google Scholar 

  • Wei YL, Luo SW, Chen WH, Ouyang ZH, Luo QK, Li CZ (2018) Characteristics and formation and evolution analysis of the dolomite karst landscape of Suiyang Geopark, Guizhou Province. Acta Geosci Sin 39:365–383 (in Chinese with English abstract)

    Google Scholar 

  • Widory D, Petelet-Giraud E, Négrel P, Ladouche B (2005) Tracking the source of nitrate in groundwater using coupled nitrogen and boron isotopes: a synthesis. Environ Sci Technol 39:539–548

    Article  Google Scholar 

  • Williard KWJ, Dewalleb DR, Edwardsc PJ, Sharpeb WE (2001) 18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds. J Hydrol 252:174–188

    Article  Google Scholar 

  • Xu S, Li SL, Su J, Yue FJ, Zhong J, Chen S (2021) Oxidation of pyrite and reducing nitrogen fertilizer enhanced the carbon cycle by driving terrestrial chemical weathering. Sci Total Environ 768:144

    Article  Google Scholar 

  • Xue DM, Botte J, Baets BD, Accoe F, Nestler A, Taylor P, Cleemput OV, Berglund M, Boeckx P (2009) Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater. Water Res 43:1159–2117

    Article  Google Scholar 

  • Xue DM, Baets BD, Cleemput OV, Hennessy C, Berglund M, Boeckx P (2012) Use of a Bayesian isotope mixing model to estimate proportional contributions of multiple nitrate sources in surface water. Environ Pollut 161:43–49

    Article  Google Scholar 

  • Yue FJ, Li SL, Zhong J, Liu J (2018) Evaluation of factors driving seasonal nitrate variations in surface and underground systems of a karst catchment. Vadose Zone J 17(170):071

    Google Scholar 

  • Zhang H, Xu Y, Cheng SQ, Li QL, Yu HR (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 717:13713

    Article  Google Scholar 

Download references

Funding

This research was jointly supported by the National Natural Science Foundation of China (42161048), the Science and Technology Program of Guizhou Province (Qiankehe Support [2023] General 218 and Qiankehezhongyindi [2023] 005) and the Academic New Seedling Fund Project of Guizhou Normal University (Qian Shi Xinmiao [2022] 23). We sincerely thank all the staff of Shuanghe Cave National Geopark and Mr Jie Zhang for their help in sampling campaigns conducted in the Mahuang Cave. We are grateful for the constructive comments and suggestions from the reviewers and editor.

Author information

Authors and Affiliations

Authors

Contributions

ZZ: investigation, methodology, writing—review and editing, funding acquisition. SD: conceptualization, methodology, formal analysis, data curation, writing—original draft. YX: writing—review and editing, investigation, data curation, and contributed to manuscript writing and revision. LS: conceptualization, writing—original draft, writing—review and editing. DS: investigation, data curation. XG: investigation, visualization. DH: methodology and image editing. LY: funding acquisition and contributed to manuscript writing and revision.

Corresponding author

Correspondence to Zhongfa Zhou.

Ethics declarations

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhou, Z., Ding, S., Xiong, Y. et al. Nitrate sources and their influence on hydrogeochemistry in karst caves of Southwest China. Int J Earth Sci (Geol Rundsch) 112, 2325–2338 (2023). https://doi.org/10.1007/s00531-023-02343-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00531-023-02343-0

Keywords

Navigation