Assessment of water-rock interaction processes in the Karst Springs of Makook Anticline (Kurdistan Region, Iraq) using Sr-isotopes, rare earth, and trace elements

  • Omed MustafaEmail author
  • Marion Tichomirowa
  • Nicolai-Alexeji Kummer
  • Broder Merkel
Original Paper


This work characterizes the karst springs of the Makook karst system (Kurdistan Region, Iraq) in terms of geochemistry of Sr-isotopes, rare earth, and trace elements. The aim of the work is to better understand water-rock interaction by geochemical means. Sources of elements, correlation of flow rate and the geochemistry of carbonate aquifers, and effects of organic matter on the rare earth elements were investigated. Furthermore, the degree of karstification and the length of flow path were assessed. The 87Sr/86Sr ratio of two spring waters was similar to the ratio of rocks forming the aquifer, indicating that these rocks are their main and dominant Sr source. In the remaining six spring waters, the 87Sr/86Sr ratios were significantly higher than their corresponding aquifer rocks at the spring outlet and thus pointed to additional Sr sources. A temporal variation of 87Sr/86Sr in the Sarwchawa spring corresponds to flow rate changes. The chemical composition of the spring water reflects some important features of the chemical composition of their aquifers. Springs that stem from the Kometan aquifer (mainly limestone) are characterized by higher mineralization compared to springs that drained from dolomites of the Bekhme aquifer. Low to medium V2+, Rb+, P3+, and Si4+ contents in waters correspond to springs fed by limestone and dolomite aquifers, whereas higher concentrations of these elements reflect water from a marly limestone aquifer (Shkarta spring). The release of these elements is related to the clay fraction of this aquifer. In contrast, the highest concentrations of Ni2+, Se4+, Mo6+, SO4 2−, Sr2+, F¯, and Ba2+ were found in the spring fed by pure limestone but having the highest flow rate and the longest flow path. Therefore, these elements were enriched in the water due to longer interaction of the water with the rock. The temporal variation of REE concentrations in karst waters are controlled by flow, dissolved organic carbon (DOC), temperature, and redox reactions.


Karst 87Sr/86Sr isotope Kurdistan Region Trace elements Sarwchawa Carbonate rocks 



The present study was carried out as a part of a HCDP scholarship offered by the Ministry of Higher Education and Scientific Research/Kurdistan Regional Government. Cordial thanks go to the staff of the isotope laboratory in Institute of Mineralogy, TU Bergakademie Freiberg for their support with lab work and to Katharina Strecker (Institute of Analytical Chemistry, TU Bergakademie Freiberg) for digesting of the rock samples.


  1. Adriano D (1986) Trace elements in the terrestrial environment. Springer, New YorkCrossRefGoogle Scholar
  2. Al Manmi D (2008) Water resources management in Rania area, Sulaimaniyah NE-Iraq. Unpublished PhD dissertation, University of BaghdadGoogle Scholar
  3. Al-Khatony F, Al-Sabha T, Aldabbagh S (2013) The chemistry of rain water in relation to dust fall over Mosul City and Ba’aj Town/Northern Iraq. JES, XI, pp. 63–69Google Scholar
  4. Andersson K, Dahlqvist R, Turner D, Stolpe B, Larsson T, Ingri J, Andersson P (2006) Colloidal rare earth elements in a boreal river: changing sources and distributions during the spring flood. Geochim Cosmochim Acta 70:3261–3274CrossRefGoogle Scholar
  5. APHA (1998) Standard methods for the examination of water and wastewater, 20th edn. American Public Health Association, WashingtonGoogle Scholar
  6. Barbieri M, Boschetti T, Petitta M, Tallini M (2005) Stable isotope (2H, 18O and 87Sr/86Sr) and hydrochemistry monitoring for groundwater hydrodynamics analysis in a karst aquifer (Gran Sasso, Central Italy). Appl Geochem 20(11):2063–2081CrossRefGoogle Scholar
  7. Basu R, Haque S, Tang J, Ji J, Johannesson K (2007) Evolution of selenium concentrations and speciation in groundwater flow systems: Upper Floridan (Florida) and Carrizo Sand (Texas) aquifers. Chem Geol 246:147–169CrossRefGoogle Scholar
  8. Bellen R, Dunnington H, Wetzel R, Morton D, Dubertret L (2005) Stratigraphic lexicon of Iraq. Gulf PetroLink, Manama, BahrainGoogle Scholar
  9. Chadha DA (1999) proposed new diagram for geochemical classification of natural waters and interpretation of chemical data. Hydrogeol J 7:431–439CrossRefGoogle Scholar
  10. Chiarenzelli J, Shrady C, Cady C, General K, Snyder J, Benedict-Debo A, David T (2007) Multi-element analyses of private wells on the St. Regis Mohawk Nation (Akwesasne). Northeastern Geol. Environ Sci 29:167–175Google Scholar
  11. Christian L, Banner J, Mack L (2011) Sr isotopes as tracers of anthropogenic influences on stream water in the Austin, Texas, area. Chem Geol 282(3/4):84–97CrossRefGoogle Scholar
  12. Church M (1979) Marine barite. In: Burns G (ed) Marine minerals. Min Soc Am. Rev Mineralog 6:175–209Google Scholar
  13. Currell M, Cartwright I (2011) Major-ion chemistry, δ13C and 87Sr/86Sr as indicators of hydrochemical evolution and sources of salinity in groundwater in the Yuncheng Basin. China Hydrol J 19:835–850Google Scholar
  14. Delbart C, Barbecot F, Valdes D, Tognelli A, Fourre E, Purtschert R, Couchoux L, Jean-Baptiste P (2014) Investigation of young water inflow in karst aquifers using SF6–CFC–3 H/He–85Kr–39Ar and stable isotope components. Appl Geochem 50:164–176CrossRefGoogle Scholar
  15. Dia A, Gruau G, Olivié-Lauquet G, Riou C, Molénat J, Curmi P (2000) The distribution of rare earth elements in groundwaters: assessing the role of source-rock composition, redox changes and colloidal particles. Geochim Cosmochim Acta 64(24):4131–4151CrossRefGoogle Scholar
  16. Edmunds M, Guendouz A, Mamou A, Moulla A, Shand P, Zouari K (2003) Groundwater evolution in the Continental Intercalaire aquifer of southern Algeria and Tunisia: trace element and isotopic indicators. Appl Geochem 18:805–822CrossRefGoogle Scholar
  17. Faure G, Mensing T (2005) Isotopes. Principles and applications, 3rd edn. Wiley, Hoboken, NJGoogle Scholar
  18. Frost C, Toner R (2004) Strontium isotopic identification of water-rock interaction and ground water mixing. Ground Water 42:418–432CrossRefGoogle Scholar
  19. Gillon M, Barbecot F, Gibert E, Corcho Alvarado J, Marlin C, Massault M (2009) Open to closed system transition traced through the TDIC isotopic signature at the aquifer recharge stage, implications for groundwater 14C dating. Geochim Cosmochim Acta 73:6488–6501CrossRefGoogle Scholar
  20. Guo H, Zhang B, Wang G, Shen Z (2010) Geochemical controls on arsenic and rare earth elements approximately along a groundwater flow path in the shallow aquifer of the Hetao Basin, Inner Mongolia. Chem Geol 270:117–125CrossRefGoogle Scholar
  21. Hannigan R (2005) Rare earth, major, and trace element geochemistry of surface and geothermal waters from the Taupo Volcanic Zone, North Island New Zealand. In: Johannesson K (ed) Rare earth elements in groundwater flow systems. Springer-Verlag, Berlin/Heidelberg, pp. 67–88CrossRefGoogle Scholar
  22. Jassim S, Goff J (2006) Geology of Iraq, 1st edn. Moravian Museum, Prague, Brno, DolinGoogle Scholar
  23. Johannesson K, Lyons W, Yelken M, Gaudette H, Stetzenbach K (1996) Geochemistry of the rare-earth elements in hypersaline and dilute acidic natural terrestrial waters: complexation behavior and middle rare-earth element enrichments. Chem Geol 133:125–144CrossRefGoogle Scholar
  24. Johannesson K, Stetzenbach K, Hodge V, Kreamer D, Zhou X (1997) Delineation of ground-water flow systems in the Southern Great Basin using aqueous rare earth element distributions. Ground Water 35:807–819CrossRefGoogle Scholar
  25. Karim K, Al Hamadani R, Ahmad S (2012) Relations between deep and shallow stratigraphic units of Northern Iraq during Cretaceous. Iranian J Earth Sci 4:95–103Google Scholar
  26. Karimi H, Raeisi E, Bakalowicz M (2005) Characterising the main karst aquifers of the Alvand basin, northwest of Zagros, Iran, by a hydrogeochemical approach. Hydrol J 13(5–6):787–799Google Scholar
  27. Kilchmann S, Waber H, Parriaux A, Bensimon M (2004) Natural tracers in recent groundwaters from different Alpine aquifers. Hydrol J 12:643–661Google Scholar
  28. Klimas A, Mališauskas A (2008) Boron, fluoride, strontium and lithium anomalies in fresh groundwater of Lithuania. Geologija 50:114–124CrossRefGoogle Scholar
  29. Ladouche B, Luc A, Nathalie D (2009) Chemical and isotopic investigation of rainwater in Southern France (1996–2002): potential use as input signal for karst functioning investigation. J Hydrol 367:150–164CrossRefGoogle Scholar
  30. Landau S, Everitt B (2004) A handbook of statistical analyses using SPSS. Chapman & Hall/CRC, Boca RatonGoogle Scholar
  31. Leybourne M, Cousens B (2005) Rare earth elements (REE) and Nd and Sr isotopes in groundwater and suspended sediments from the Bathurst Mining Camp, New Brunswick: water–rock reactions and elemental fractionation. In: Johannesson K (ed) Rare Earth Elements in Groundwater Flow Systems. Springer-Verlag, Berlin/Heidelberg, pp. 253–293CrossRefGoogle Scholar
  32. Liu L, Shu L, Chen X, Oromo T (2010) The hydrologic function and behavior of the Houzhai underground river basin, Guizhou Province, southwestern China. Hydrol. J. 18(2):509–518Google Scholar
  33. Ludwig K (2003) User’s Manual for Isoplot 3.00. A geochronological toolkit for Microsoft Excel, Berkeley Geochronology Center Special Publication No. 4Google Scholar
  34. Möller P, Rosenthal E, Dulski P, Geyer S (2009) Characterization of recharge areas by rare earth elements and stable isotopes of H2O. In: Hötzl H, Möller P, Rosenthal E (eds) The water of the Jordan Valley. Springer, Scarcity and deterioration of groundwater and its impact on the regional development. Berlin, pp. 123–147CrossRefGoogle Scholar
  35. Musgrove M, Stern L, Banner J (2010) Spring water geochemistry at Honey Creek State Natural Area, central Texas: implications for surface water and groundwater interaction in a karst aquifer. J Hydrol 388:144–156CrossRefGoogle Scholar
  36. Mustafa O, Merkel B (2015a) Classification of karst springs based on discharge and water chemistry in Makook karst system, Kurdistan Region, Iraq. Freiberg Online Geoscience 39:1–24Google Scholar
  37. Mustafa, O, Merkel, B, 2015b. Geochemical Evolution and Water–Rock interactions in Makook Karst Aquifers, Kurdistan Region, Iraq. Topical issues of rational use of natural resources, April 22–24, 2015, St. Petersburg, Russia, National Mineral Resources University, P. 12–14Google Scholar
  38. Mustafa O, Merkel B, Weise S (2015) Assessment of hydrogeochemistry and environmental isotopes in karst springs of Makook Anticline, Kurdistan Region. Iraq Hydrol 2:48–68CrossRefGoogle Scholar
  39. Nijenhuis I, Bosch H, Sinninghe Damsté J, Brumsack H, Lange G (1999) Organic matter and trace element rich sapropels and black shales: a geochemical comparison. Earth Planet Sci Lett 169(3–4):277–290CrossRefGoogle Scholar
  40. O’Connor M, Zabik M, Cady C, Cousens B, Chiarenzelli J (2010) Multi-element analysis and geochemical spatial trends of groundwater in rural Northern New York. Water 2(2):217–238CrossRefGoogle Scholar
  41. Parkhurst D, Appelo C (2013) Description of input and examples for PHREEQC (Version 3)—a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. Chapter 43 of section A, Groundwater Books, Modeling Techniques, United States Geological Survey, Washington DC.
  42. Parsons C (2006) Mini master plan for the public water supplies for the Governorate of Sulaymaniyah Iraq. Public Works/Water Sector, Contract No. W914NS-04-C-0003Google Scholar
  43. Pavlovskiy I, Selle B (2014) Integrating hydrogeochemical, hydrogeological, and environmental tracer data to understand groundwater flow for a karstified aquifer system. Ground Water. doi: 10.1111/gwat.12262 Google Scholar
  44. Petrini R, Italiano F, Ponton M, Slejko F, Aviani U, Zini L (2013) Geochemistry and isotope geochemistry of the Monfalcone thermal waters (northern Italy): inference on the deep geothermal reservoir. Hydrol J 21:1275–1287Google Scholar
  45. Pin C, Bassin C (1992) Evaluation of a strontium-specific extraction chromatographic method for isotopic analysis in geological materials. Anal Chim Acta 269(2):249–255CrossRefGoogle Scholar
  46. Pitikakis E, Katsanou K, Lambrakis N (2011) The behaviour of REE in Agios Nikolaos karstic aquifer, NE Crete, Greece. In: Lambrakis N, Stournaras G, Katsanou K (Eds.) Advances in the research of aquatic environment. Springer Berlin Heidelberg (Environmental Earth Sciences), pp 161–168Google Scholar
  47. Scholle P, Stemmerik L, Harpoth O (1990) Origin of major karst-associated celestite mineralization in Karstryggen, Central East Greenland. SEPM JSR 60. J Sediment Petrol 60:397–410Google Scholar
  48. Semhi K, Abdalla O, Al Khirbash S, Khan T, Asaidi S, Farooq S (2009) Mobility of rare earth elements in the system soils–plants–groundwaters: a case study of an arid area (Oman). Arab J Geosci 2(2):143–150CrossRefGoogle Scholar
  49. Shouyang H, Lijun Z, Ruidong Y, Zheng S, Xiaohong Y (2011) The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City. China Chinese J Geochem 30(1):114–124CrossRefGoogle Scholar
  50. Simon G, Kesler S, Essene E (1997) Phase relations among selenides, tellurides, and oxides; II. Applications to selenide-bearing ore deposits Econ Geol 92:468–484Google Scholar
  51. Stevanović Z, Iurkiewicz A (2004) Geologic-tectonic factors controlling groundwater flow patterns and discharge of karst aquifers in Western Zagros (Northern Iraq), Proceedings of 33rd IAH Congress & 7th ALHSUD (CD) ZacatecasGoogle Scholar
  52. Stevanović Z, Marcovic M (2004) Hydrogeology of Northern Iraq. General Hydrogeology and Aquifer System, vol 2, 1st edn, FAOGoogle Scholar
  53. Stevanović Z, Iurkiewicz A, Maran A (2009) New insights into karst and caves of Northwestern Zagros (Northern Iraq). Acta Carsologica 38:83–96Google Scholar
  54. Tang J, Johannesson K (2006) Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer, Texas. USA Chem Geol 225:156–171CrossRefGoogle Scholar
  55. Tesmer M, Möller P, Wieland S, Jahnke C, Voigt H, Pekdeger A (2007) Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation. Hydrol. J. 15(7):1291–1306Google Scholar
  56. Wedepohl K (1978) Handbook of Geochemistry. Springer, Heidelberg, Berlin, New YorkGoogle Scholar
  57. Yuan J, Mao X, Wang Y, Deng Z, Huang L (2014) Geochemistry of rare-earth elements in shallow groundwater, northeastern Guangdong Province. China Chinese J Geochem 33(1):53–64CrossRefGoogle Scholar

Copyright information

© Saudi Society for Geosciences 2016

Authors and Affiliations

  • Omed Mustafa
    • 1
    • 3
    Email author
  • Marion Tichomirowa
    • 2
  • Nicolai-Alexeji Kummer
    • 1
  • Broder Merkel
    • 1
  1. 1.Institute of GeologyTU Bergakademie FreibergFreibergGermany
  2. 2.Institute of MineralogyTU Bergakademie FreibergFreibergGermany
  3. 3.Department of General Sciences, College of Basic EducationCharmo UniversityKurdistan RegionIraq

Personalised recommendations