Groundwater hydrogeochemical formation and evolution in a karst aquifer system affected by anthropogenic impacts

  • Xiancang Wu
  • Changsuo LiEmail author
  • Bin Sun
  • Fuqiang Geng
  • Shuai Gao
  • Minghui Lv
  • Xueying Ma
  • Hu Li
  • Liting Xing
Original Paper


Karst groundwater, an important water source, is often highly influenced by human impacts, causing environmental damage and threats to human health. However, studies on the anthropogenic influences on the hydrogeochemical evolution of karst groundwater are relatively rare. To assess hydrogeochemical formation and evolution, we focused on a typical karst groundwater system (Jinan, China) which is composed of cold groundwater (av. temperature 13–17 °C), springs and geothermal water (av. temperature > 30 °C) and is significantly affected by human activities. The study was performed by means of water samples collecting and analyzing and isotope analysis (2H, 18O and 14C). The statistical analysis and inverse models were also applied to further understand geochemical processes and anthropogenic influences. The 2H, 18O and 14C results indicate that the cold karst groundwater is easily influenced and contaminated by the local environment, while geothermal water is relatively old with a slow rate of recharge. The hydrochemical types of cold karst groundwater are mainly HCO3–Ca and HCO3·SO4–Ca, while geothermal water hydrochemical types are SO4–Ca·Na and SO4–Ca. Groundwater Ca2+, Mg2+, HCO3 and SO42− are mainly controlled by carbonate equilibrium, gypsum dissolution and dedolomitization. Groundwater Na+, K+ and Cl are mainly derived from halite dissolution, and in geothermal water, they are also affected by incongruent dissolution of albite and K-feldspar. Anthropogenic nitrogen produces ammonium resulting in nitrification and reduction in CO2(g) consumption and HCO3 release from carbonate dissolution. Principal component analysis and inverse models also indicate that nitrification and denitrification have significantly affected water–rock interactions. Our study suggests that karst groundwater quality is dominated by water–rock interactions and elucidates the influence of anthropogenic nitrogen. We believe that this paper will be a good reference point to study anthropogenic influences on the groundwater environment and to protect karst groundwater globally.


Water–rock interaction Dedolomitization Nitrogen Nitrification Inverse model 



The research is funded by major scientific and technological tackling projects of Shandong Geology and Mineral Resources (No. 2012-045), Open Fund of Key Laboratory of Groundwater Resources and Environment (Shandong Provincial Bureau of Geology & Mineral Resources) and National Natural Science Foundation of China (41772257, 41472216). The authors would like to thank the journal editors and the reviewers for their valuable comments, which have improved the paper considerably. The authors would also like to express their gratitude to EditSprings ( for the expert linguistic services provided.


  1. Anthonisen, A. C., Loehr, R. C., Prakasam, T. B. S., et al. (1976). Inhibition of nitrification by ammonia and nitrous acid. Journal (Water Pollution Control Federation), 48, 835–852.Google Scholar
  2. Antonellini, M., Nannoni, A., Vigna, B., et al. (2019). Structural control on karst water circulation and speleogenesis in a lithological contact zone: The Bossea cave system (Western Alps, Italy). Geomorphology, 345, 106832.CrossRefGoogle Scholar
  3. Appelo, C. A. J., & Postma, D. (2004). Geochemistry, groundwater and pollution. Boca Raton: CRC Press.CrossRefGoogle Scholar
  4. Capaccioni, B., Didero, M., Paletta, C., et al. (2001). Hydrogeochemistry of groundwaters from carbonate formations with basal gypsiferous layers: an example from the Mt Catria–Mt Nerone ridge (Northern Appennines, Italy). Journal of Hydrology, 253(1–4), 14–26.CrossRefGoogle Scholar
  5. Clark, I. (2015). Groundwater geochemistry and isotopes. Boca Raton: CRC Press.CrossRefGoogle Scholar
  6. Craig, H. (1961). Isotopic variation in meteoric waters. Science, 133, 1833–1834.CrossRefGoogle Scholar
  7. Dvory, N. Z., Livshitz, Y., Kuznetsov, M., et al. (2018). Caffeine vs. carbamazepine as indicators of wastewater pollution in a karst aquifer. Hydrology and Earth System Sciences, 22(12), 6371–6381.CrossRefGoogle Scholar
  8. Fleury, T. L. (1999). A geochemical modeling study of the effects of urea-degrading bacteria on groundwater contaminated with acid mine drainage. National Library of Canada Bibliothèque nationale du Canada.Google Scholar
  9. Ford, D., & Williams, P. D. (2013). Karst hydrogeology and geomorphology. Hoboken: Wiley.Google Scholar
  10. Han, Y., Wang, G., Cravotta, C. A., III, et al. (2013). Hydrogeochemical evolution of Ordovician limestone groundwater in Yanzhou, North China. Hydrological Processes, 27(16), 2247–2257.CrossRefGoogle Scholar
  11. Hartmann, A., Goldscheider, N., Wagener, T., et al. (2014). Karst water resources in a changing world: Review of hydrological modeling approaches. Reviews of Geophysics, 52(3), 218–242.CrossRefGoogle Scholar
  12. Hem, J. D. (1989). Study and interpretation of the chemical characteristics of natural water (p. 2254). Washington: US Geological Survey, Water Supply Paper.Google Scholar
  13. Jeannin, P. Y., Hessenauer, M., Malard, A., et al. (2016). Impact of global change on karst groundwater mineralization in the Jura Mountains. Science of the Total Environment, 541, 1208–1221.CrossRefGoogle Scholar
  14. Kang, F., Jin, M., & Qin, P. (2011). Sustainable yield of a karst aquifer system: a case study of Jinan springs in northern China. Hydrogeology Journal, 19(4), 851–863.CrossRefGoogle Scholar
  15. Kaufmann, G., & Romanov, D. (2019). The initial phase of cave formation: Aquifer-scale three-dimensional models with strong exchange flow. Journal of Hydrology, 572, 528–542.CrossRefGoogle Scholar
  16. Kohfahl, C., Sprenger, C., Herrera, J. B., et al. (2008). Recharge sources and hydrogeochemical evolution of groundwater in semiarid and karstic environments: A field study in the Granada Basin (Southern Spain). Applied Geochemistry, 23(4), 846–862.CrossRefGoogle Scholar
  17. Lan, J. C., He, Q. F., Hu, N., et al. (2013). Effects of anthropogenic on karst groundwater geohydrochemistry in an urbanized area. Advanced Materials Research, 726, 2418–2423.CrossRefGoogle Scholar
  18. Ledesma-Ruiz, R., Pastén-Zapata, E., Parra, R., et al. (2015). Investigation of the geochemical evolution of groundwater under agricultural land: a case study in northeastern Mexico. Journal of Hydrology, 521, 410–423.CrossRefGoogle Scholar
  19. Li, C. S., Wu, X. C., Sun, B., et al. (2018). Hydrochemical characteristics and formation mechanism of geothermal water in northern Ji’nan. Earth-Science (in Chinese with English abstract).
  20. Li, X. D., Liu, C. Q., Harue, M., et al. (2010). The use of environmental isotopic (C, Sr, S) and hydrochemical tracers to characterize anthropogenic effects on karst groundwater quality: a case study of the Shuicheng Basin, SW China. Applied Geochemistry, 25(12), 1924–1936.CrossRefGoogle Scholar
  21. Liu, J. R., Song, X. F., Yuan, G. F., et al. (2010). Characteristics of δ 18O in precipitation over Eastern Monsoon China and the water vapor sources. Chinese Science Bulletin, 55(2), 200–211.CrossRefGoogle Scholar
  22. Ma, Z. M., Luo, Y. Y., Fang, Y. Z., et al. (2013). Hydrogeochemical mechanism of the petroleum hydrocarbon pollution in Karst Fissure groundwater system. Applied Mechanics and Materials, 295, 159–163.CrossRefGoogle Scholar
  23. Ma, R., Wang, Y., Sun, Z., et al. (2011). Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China. Applied Geochemistry, 26(5), 884–897.CrossRefGoogle Scholar
  24. Nikolaidis, N. P., Bouraoui, F., & Bidoglio, G. (2013). Hydrologic and geochemical modeling of a karstic Mediterranean watershed. Journal of Hydrology, 477, 129–138.CrossRefGoogle Scholar
  25. Parkhurst, D., & Appelo, C. (1999). User’s guide to PHREEQC (Version 2)—A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. US Geol. Surv. Water Resour. Invest. Rep. No. 99-4259.Google Scholar
  26. People’s Government of Jinan. (2019). Statistical Bulletin of National Economic and Social Development of Jinan in 2018.
  27. Petit, J. R., Jouzel, J., Raynaud, D., et al. (1999). Climate and atmospheric history of the past 420,000 years from the Vostok ice core, Antarctica. Nature, 399(6735), 429–436.CrossRefGoogle Scholar
  28. Qian, J., Zhan, H., Wu, Y., et al. (2006). Fractured-karst spring-flow protections: A case study in Jinan, China. Hydrogeology Journal, 14(7), 1192.CrossRefGoogle Scholar
  29. Rajmohan, N., & Elango, L. (2004). Identification and evolution of hydrogeochemical processes in the groundwater environment in an area of the Palar and Cheyyar River Basins, Southern India. Environmental Geology, 46(1), 47–61.Google Scholar
  30. Sarrazin, F., Hartmann, A., Pianosi, F., et al. (2018). V2Karst V1. 1: a parsimonious large-scale integrated vegetation-recharge model to simulate the impact of climate and land cover change in karst regions. Geoscientific Model Development, 11(12), 4933–4964.CrossRefGoogle Scholar
  31. Sharif, M. U., Davis, R. K., Steele, K. F., et al. (2008). Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA). Journal of Hydrology, 350(1–2), 41–55.CrossRefGoogle Scholar
  32. Sui, H., Kang, F., Li, C., et al. (2017). Relationship between north Ji’nan geothermal water and Ji’nan spring water revealed by hydrogeochemical characteristics. Carsologica Sinica, 36(1), 49–58. (in Chinese with English abstract).Google Scholar
  33. Sullivan, P. L., Macpherson, G. L., Martin, J. B., et al. (2019). Evolution of carbonate and karst critical zones. Chemical Geology. Scholar
  34. Sun, S., Li, L., Wang, J., et al. (2018). Karst development mechanism and characteristics based on comprehensive exploration along Jinan Metro, China. Sustainability, 10(10), 3383.CrossRefGoogle Scholar
  35. Sung, K. Y., Yun, S. T., Park, M. E., et al. (2012). Reaction path modeling of hydrogeochemical evolution of groundwater in granitic bedrocks, South Korea. Journal of Geochemical Exploration, 118, 90–97.CrossRefGoogle Scholar
  36. van Geldern, R., Schulte, P., Mader, M., et al. (2018). Insights into agricultural influences and weathering processes from major ion patterns. Hydrological Processes, 32(7), 891–903.CrossRefGoogle Scholar
  37. Wan, L. (2008). Trace study on karst groundwater in Jinan spring area. China University of Geosciences (Beijing) (Chinese doctoral dissertation with English abstract).Google Scholar
  38. Wang, J., Jin, M., Jia, B., et al. (2015). Hydrochemical characteristics and geothermometry applications of thermal groundwater in northern Jinan, Shandong, China. Geothermics, 57, 185–195.CrossRefGoogle Scholar
  39. Wang, J., Jin, M., Lu, G., et al. (2016). Investigation of discharge-area groundwaters for recharge source characterization on different scales: The case of Jinan in northern China. Hydrogeology Journal, 24(7), 1723–1737.CrossRefGoogle Scholar
  40. Wen, C., Dong, W., Meng, Y., et al. (2019). Application of a loose coupling model for assessing the impact of land-cover changes on groundwater recharge in the Jinan spring area, China. Environmental Earth Sciences, 78(13), 382.CrossRefGoogle Scholar
  41. World Health Organization. (2011). Guidelines for drinking-water quality, 4th edn.Google Scholar
  42. Xu, H., Duan, X., Gao, Z., et al. (2007). Characteristics of groundwater regimes and affecting factors near Jinan. Hydrogeology & Engineering Geology, 34(2), 87–89. (in Chinese with English abstract).Google Scholar
  43. Zhang, B. (2011). Hydrogeochemical characteristics and formation conditions of the geothermal water in Northwestern Shandong Province. China University of Geosciences (Beijing) (Chinese doctoral dissertation with English abstract).Google Scholar
  44. Zhang, Y., Kelly, W. R., Panno, S. V., et al. (2014). Tracing fecal pollution sources in karst groundwater by Bacteroidales genetic biomarkers, bacterial indicators, and environmental variables. Science of the Total Environment, 490, 1082–1090.CrossRefGoogle Scholar
  45. Zhang, Z., Wang, W., Qu, S., et al. (2018). A new perspective to explore the hydraulic connectivity of karst aquifer system in Jinan spring catchment, China. Water, 10(10), 1368.CrossRefGoogle Scholar
  46. Zhao, H. L., Deng, J. F., & He, H. Y. (1998). Petrological record of orogenic belt crust thickening: A discussion on Jinan gabbro and its xenolith. Earth Science Frontiers, 5(4), 251–256. (in Chinese with English abstract).Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Xiancang Wu
    • 1
    • 2
  • Changsuo Li
    • 1
    • 2
    Email author
  • Bin Sun
    • 1
    • 2
  • Fuqiang Geng
    • 1
    • 2
  • Shuai Gao
    • 1
    • 2
  • Minghui Lv
    • 1
    • 2
  • Xueying Ma
    • 1
    • 2
  • Hu Li
    • 3
  • Liting Xing
    • 4
  1. 1.801 Institute of Hydrogeology and Engineering GeologyShandong Provincial Bureau of Geology and Mineral ResourcesJinanChina
  2. 2.Key Laboratory of Groundwater Resources and EnvironmentShandong Provincial Bureau of Geology and Mineral ResourcesJinanChina
  3. 3.Jinan Rail Transit Group Co., LtdJinanChina
  4. 4.School of Resources and EnvironmentUniversity of JinanJinanChina

Personalised recommendations