Environmental Science and Pollution Research

, Volume 26, Issue 30, pp 31354–31367 | Cite as

Contaminant sources and processes affecting spring water quality in a typical karst basin (Hongjiadu Basin, SW China): insights provided by hydrochemical and isotopic data

  • Kun Ren
  • Xiaodong PanEmail author
  • Jie Zeng
  • Daoxian Yuan
Research Article


Springs are an important source of drinking water supply in mountainous karst areas of SW China. However, the quality of many spring waters has deteriorated greatly in recent years, which leads to a significant problem of drinking water scarcity. In this study, hydrochemistry and stable sulfur and oxygen isotopic compositions of SO42−34S and δ18OSO4) of 38 representative samples of waters (incl. spring water, surface water, rainwater, and sewage) from the Hongjiadu Basin, Guizhou province, SW China, were investigated in order to identify the sources of contaminates in spring waters and trace the processes affecting the karst groundwater quality. Approximately 28% of the total investigated springs has been suffered from serious contamination and the concentrations of NO3, SO42−, and total iron (TFe) in many spring waters have exceeded the standards for drinking water. The springs that have NO3 concentrations of > 30 mg/L are concentrated in residential and agricultural areas, suggesting that NO3 in spring water are mainly derived from chemical fertilizers, manure, and sewage. δ34S and δ18OSO4 data indicate that SO42− in spring water mainly originates from sulfide oxidation, acid rain, and sewage. Furthermore, the high δ34S and δ18OSO4 values of SO42− in some spring waters may be related to the occurrence of bacterial sulfate reduction. Some springs that are discharged from abandoned coal mines have SO42− concentrations of > 250 mg/L, demonstrating that mining activities have accelerated the deterioration of spring water quality. Also, springs with TFe concentrations of > 0.3 mg/L are discharged from coal-bearing strata, revealing that iron in spring waters is mainly derived from the oxidation of pyrite. Our results show that the karst spring waters are highly vulnerable to anthropogenic contaminations and human activities, such as agricultural fertilizing and sewage and waste disposal as well as mining activities, which exert a great impact on the quality of groundwater in karst areas.


Spring Water quality Hydrochemistry Sulfur and oxygen isotopes Karst groundwater Hongjiadu 



We are grateful to anonymous reviewers and the editor for their constructive comments. We acknowledge Zhijun Wang and Amelia Huang for polishing the article.

Funding information

This study is financially supported by the National Natural Science Foundation of China (grant no. 41702278) and the China Geological Survey Project (grant no. DD20160285).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Barnes RT, Raymond PA (2009) The contribution of agricultural and urban activities to inorganic carbon fluxes within temperate watersheds. Chem Geol 266:318–327. CrossRefGoogle Scholar
  2. Bartlett R, Bottrell SH, Sinclair K, Thornton S, Fielding ID, Hatfield D (2010) Lithological controls on biological activity and groundwater chemistry in quaternary sediments. Hydrol Process 24:726–735. CrossRefGoogle Scholar
  3. Bottrell S, Tellam J, Bartlett R, Hughes A (2008) Isotopic composition of sulfate as a tracer of natural and anthropogenic influences on groundwater geochemistry in an urban sandstone aquifer, Birmingham, UK. Appl Geochem 23:2382–2394. CrossRefGoogle Scholar
  4. Cravotta CA (1994) Secondary iron-sulfate minerals as sources of sulfate and acidity: the geochemical volution of acidic ground water at a reclaimed surface coal mine in Pennsylvania. In: Alpers CN, Blowes DW (eds) Environmental geochemistry of sulfide oxidation, American Chemical Society Symposium Series, vol 550, pp 345–364CrossRefGoogle Scholar
  5. Dugin K, Dongchan K, Bernhard M et al (2009) Identification of nitrate and sulfate sources in groundwater using dual stable isotope approaches for an agricultural area with different land use (Chuncheon, mid-eastern Korea). Agric Ecosyst Environ 132(3–4):223–231. CrossRefGoogle Scholar
  6. Edmond JM, Palmer MR, Measures CI, Grant B, Stallard RF (1995) The fluvial geochemistry and denudation rate of the Guayana shield in Venezuela, Colombia, and Brazil. Geochim Cosmochim Acta 59(16):3301–3325. CrossRefGoogle Scholar
  7. Ford D, Williams P (2007) Karst hydrogeology and geomorphology. John Wiley & Sons, New YorkCrossRefGoogle Scholar
  8. Galloway JN, Zhao DW, Xiong JL et al (1987) Acid rain: China, United States, and a remote area. Science 236:1559–1562. CrossRefGoogle Scholar
  9. Han G, Liu CQ (2004) Water geochemistry controlled by carbonate dissolution: a study of the river waters draining karst-dominated terrain, Guizhou Province, China. Chem Geol 204:1–21. CrossRefGoogle Scholar
  10. Han G, Tang Y, Xu Z (2010) Fluvial geochemistry of rivers draining karst terrain in Southwest China. J Asian Earth Sci 38:65–75. CrossRefGoogle Scholar
  11. Hosono T, Siringan F, Yamanaka T, Umezawa Y, Onodera SI, Nakano T, Taniguchi M (2010) Application of multi-isotope ratios to study the source and quality of urban groundwater in Metro Manila, Philippines. Appl Geochem 25:900–909. CrossRefGoogle Scholar
  12. Hou MY, Zhang L, Wang ZW et al (2017) Estimation of fertilizer usage from main crops in China. J Agric Resour Environ 34(4):360–367 (in Chinese). CrossRefGoogle Scholar
  13. Jakóbczyk-Karpierz S, Sitek S, Jakobsen R, Kowalczyk A (2016) 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. CrossRefGoogle Scholar
  14. Jiang Y (2012) Sources of sulfur in the Nandong underground river system, southwest China: a chemical and isotopic reconnaissance. Appl Geochem 27:1463–1470. CrossRefGoogle Scholar
  15. Jiang Y, Liu C, Tao F (2006) The role of sulfur cycling in carbonate weathering: isotope geochemistry of sulfur in the Wujiang River catchment, Southwest China. Chin J Geochem 25(1):278. CrossRefGoogle Scholar
  16. Jiang Y, Wu Y, Groves C, Yuan D, Kambesis P (2009) Natural and anthropogenic factors affecting the groundwater quality in the Nandong karst underground river system in Yunan, China. J Contam Hydrol 109:49–61. CrossRefGoogle Scholar
  17. Kroopnick P, Craig H (1972) Atmospheric oxygen: isotopic composition and solubility fractionation. Science 175:54–55. CrossRefGoogle Scholar
  18. Krouse HR, Crinenko VA (eds) (1991) Stable isotopes: natural and anthropogenic sulphur in the environment. Wiley, New YorkGoogle Scholar
  19. Krouse HR, Mayer B (2000) Sulphur and oxygen isotopes in sulphate. In: Cook PG, Herczeg AL (eds) Environmental tracers in subsurface hydrology. Kluwer Academic Press, BostonGoogle Scholar
  20. Lang YC, Liu CQ, Zhao ZQ, Li SL, Han GL (2006) Geochemistry of surface and ground water in Guiyang, China: water/rock interaction and pollution in a karst hydrological system. Appl Geochem 21:887–903. CrossRefGoogle Scholar
  21. Ledoux STM, Szynkiewicz A, Faiia AM et al (2016) Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin, Eastern United States. Appl Geochem 71:73–85. CrossRefGoogle Scholar
  22. Li XD, Liu CQ, Harue M, Li SL, Liu XL (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. Appl Geochem 25:1924–1936. CrossRefGoogle Scholar
  23. Li XD, Liu CQ, Liu XL, Bao LR (2011) Identification of dissolved sulfate sources and the role of sulfuric acid in carbonate weathering using dual-isotopic data from the Jialing River, Southwest China. J. Asian Earth Sci 42:370–380. CrossRefGoogle Scholar
  24. Li X, Gan Y, Zhou A, Liu Y, Wang D (2013) Hydrological controls on the sources of dissolved sulfate in the Heihe River, a large inland river in the arid northwestern China, inferred from S and O isotopes. Appl Geochem 35:99–109. CrossRefGoogle Scholar
  25. Li J, Qi Y, Zhong Y, Yang L, Xu Y, Lin P, Wang S, He J (2016) Karst aquifer characterization using storm event analysis for black dragon springshed, Beijing, China. Catena 145:30–38. CrossRefGoogle Scholar
  26. Liu CQ, Lang YC, Satake H, Wu J, Li SL (2008) Identification of anthropogenic and natural inputs of sulfate and chloride into the karstic ground water of Guiyang, SW China: combined δ37Cl and δ34S approach. Environ Sci Technol 42:5421–5427. CrossRefGoogle Scholar
  27. Marques JM, Graça H, Eggenkamp HGM, Neves O, Carreira PM, Matias MJ, Mayer B, Nunes D, Trancoso VN (2013) Isotopic and hydrochemical data as indicators of recharge areas, flow paths and water–rock interaction in the Caldas da Rainha–Quinta das Janelas thermomineral carbonate rock aquifer (Central Portugal). J Hydrol 476(18):302–313. CrossRefGoogle Scholar
  28. McMahon PB, Carney CP, Poeter EP et al (2010) Use of geochemical, isotopic, and age tracer data to develop models of groundwater flow for the purpose of water management, northern High Plains aquifer, USA. Appl Geochem 25:910–922. CrossRefGoogle Scholar
  29. Merchán D, Otero N, Soler A, Causapé J (2014) Main sources and processes affecting dissolved sulphates and nitrates in a small irrigated basin (Lerma Basin, Zaragoza, Spain): isotopic characterization. Agric Ecosyst Environ 195:127–138. CrossRefGoogle Scholar
  30. Négrel P, Pauwels H (2004) Interaction between different groundwaters in Brittany catchments (France): characterizing multiple sources through strontium- and sulphur isotope tracing. Water Air Soil Pollut 151:261–285. CrossRefGoogle Scholar
  31. Otero N, Canals À, Soler A (2007) Using dual-isotope data to trace the origin and processes of dissolved sulphate: a case study in Calders stream (Llobregat basin, Spain). Aquat Geochem 13:109–126. CrossRefGoogle Scholar
  32. Otero N, Sole A, Canals À (2008) Controls of δ34S and δ18O in dissolved sulphate: learning from a detailed survey in the Llobregat River (Spain). Appl Geochem 23:1166–1185. CrossRefGoogle Scholar
  33. Pu T, He Y, Zhang T, Wu J, Zhu G, Chang L (2013) Isotopic and geochemical evolution of ground and river waters in a karst dominated geological setting: a case study from Lijiang basin, South-Asia monsoon region. Appl Geochem 33:199–212. CrossRefGoogle Scholar
  34. Puig R, Folch A, Menció A, Soler A, Mas-Pla J (2013) Multi-isotopic study (15N, 34S, 18O, 13C) to identify processes affecting nitrate and sulfate in response to local and regional groundwater mixing in a large-scale flow system. Appl Geochem 32:129–141. CrossRefGoogle Scholar
  35. Ren K, Pan X, Zeng J, Jiao Y (2017) Distribution and source identification of dissolved sulfate by dual isotopes in waters of the Babu subterranean river basin, SW China. J Radioanal Nucl Chem 312:317–328. CrossRefGoogle Scholar
  36. Samborska K, Halas S, Bottrell SH (2013) Sources and impact of sulphate on groundwaters of Triassic carbonate aquifers, Upper Silesia, Poland. J Hydrol 486:136–150. CrossRefGoogle Scholar
  37. Sharma S, Sack A, Adams JP, Vesper DJ, Capo RC, Hartsock A, Edenborn HM (2013) Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA. Appl Geochem 29:32–42. CrossRefGoogle Scholar
  38. Singh KP, Gupta S, Mohan D (2014) Evaluating influences of seasonal variations and anthropogenic activities on alluvial groundwater hydrochemistry using ensemble learning approaches. J Hydrol 511:254–266. CrossRefGoogle Scholar
  39. Strebel O, Bottcher J, Fritz P (1990) Use of isotope fractionation of sulfate-sulfur and sulfate-oxygen to assess bacterial desulfurication in a sandy aquifer. J Hydrol 121:155–172. CrossRefGoogle Scholar
  40. Sun J, Tang C, Wu P, Strosnider WHJ, Han Z (2013) Hydrogeochemical characteristics of streams with and without acid mine drainage impacts: a paired catchment study in karst geology, SW China. J Hydrol 504:115–124. CrossRefGoogle Scholar
  41. Tostevin R, Craw D, Hale V et al (2016) Sources of environmental sulfur in the groundwater system, southern New Zealand. Appl Geochem 70:1–16. CrossRefGoogle Scholar
  42. Tuttle MLW, Breit GN, Cozzarelli IM (2009) Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA. Chem Geol 265:455–467. CrossRefGoogle Scholar
  43. Vesper DJ, White WB (2004) Spring and conduit sediments as storage reservoirs for heavy metals in karst aquifers. Environ Geol 45(4):481–493. CrossRefGoogle Scholar
  44. Vitòria L, Otero N, Soler A et al (2004) Fertilizer characterization: isotopic data (N, S, O, C, and Sr). Environ Sci Technol 38(12):3254–3262. CrossRefGoogle Scholar
  45. Watanabe Y, Farquhar J, Ohmoto H (2009) Anomalous fractionations of sulfur isotopes during thermochemical sulfate reduction. Science 324:370–373. CrossRefGoogle Scholar
  46. Worden RH, Smalley PC (1996) H2S-producing reactions in deep carbonate gas reservoirs: Khuff Formation, Abu Dhabi. Chem Geol 133:157–171. CrossRefGoogle Scholar
  47. Wu Y, Luo ZH, Luo W, Ma T, Wang Y (2018) Multiple isotope geochemistry and hydrochemical monitoring of karst water in a rapidly urbanized region. J Contam Hydrol 218:44–58. CrossRefGoogle Scholar
  48. Xiao HY, Liu CQ (2002) Sources of nitrogen and sulfur in wet deposition at Guiyang, southwest China. Atmos Environ 36(33):5121–5130. CrossRefGoogle Scholar
  49. Yang PH, Li Y, Groves C, Hong A (2019) Coupled hydrogeochemical evaluation of a vulnerable karst aquifer impacted by septic effluent in a protected natural area. Sci Total Environ 658:1475–1484. CrossRefGoogle Scholar
  50. Zhang D, Li XD, Zhao ZQ, Liu CQ (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. CrossRefGoogle Scholar
  51. Zhou J, Zhang Y, Zhou A, Liu C, Cai H, Liu Y (2016) Application of hydrochemistry and stable isotopes (δ34S, δ18O and δ37Cl) to trace natural and anthropogenic influences on the quality of groundwater in the piedmont region, Shijiazhuang, China. Appl Geochem 71:63–72. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Kun Ren
    • 1
    • 2
  • Xiaodong Pan
    • 1
    • 2
    Email author
  • Jie Zeng
    • 1
    • 2
  • Daoxian Yuan
    • 1
    • 2
  1. 1.Institute of Karst Geology, Chinese Academy of Geological SciencesGuilinChina
  2. 2.Karst Dynamics Laboratory, Ministry of Natural Resources & GuangxiGuilinChina

Personalised recommendations