Skip to main content

Concentration of Iron(II) in Fresh Groundwater Controlled by Siderite, Field Evidence


Iron(II) concentrations in fresh groundwater in Dutch aquifers range from absent up to 50 mg/l. Evaluation of extensive chemical data sets learned that the maximum logarithmic concentration of iron(II) in aquifers, between ± 6.5 < pH <  ± 8, is a linear function of pH, governed by Siderite. It is a broad relation due to oversaturation with respect to Siderite and to variation in alkalinity. Iron(II) is continuously supplied to groundwater by reduction of hydrous ferric oxides (HFO), until becoming saturated with respect to Siderite, and from then on, HFO reduction and Siderite precipitation occur simultaneously. In Dutch aquifers, the electron supply rate (equivalent to the organic matter oxidation rate) apparently exceeds the HFO electron uptake rate (equivalent to the HFO reduction rate) and the excess supply is taken up by sulfate (equivalent to the sulfate reduction rate): HFO reduction, sulfate reduction and FeS precipitation occurring simultaneously, where the presence of Siderite prevents a dip in the iron(II) concentration. After sulfate becomes exhausted, the excess electron supply is transferred to methane production: HFO reduction and methane production occurring simultaneously. This evaluation also demonstrated that the organic matter oxidation rate and the HFO reduction rate decrease over time. The results of this study are also relevant for the behavior of As and of Co, Ni and Zn in groundwater, as HFO, Pyrite and Siderite may contain variable contents of these elements.

This is a preview of subscription content, access via your institution.

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


  • Appelo CAJ, Postma D (2007) Geochemistry, groundwater and pollution. Third corrected reprint. Balkema, Rotterdam

    Google Scholar 

  • Breeuwsma A (1990) Mineral composition of sand and clay soils in the Netherlands. In: Locher WP, de Bakker H (eds) Soil science of the Netherlands, part 1: general soil science, chapter 7, 2nd edn. Malmberg, Den Bosch, pp 103–108 (in Dutch)

    Google Scholar 

  • Cirkel DG, van Beek CGEM, Witte JPM, van der Zee SEATM (2014) Sulfate reduction and calcite precipitation in relation to internal eutrophication of groundwater fed alkaline fens. Biogeochemistry 117:375–393.

    Article  Google Scholar 

  • Drever JI (1988) The geochemistry of natural waters, 2nd edn. Prentice Hall, Englewood Cliffs, NJ

    Google Scholar 

  • Geelhoed JS, Hiemstra T, van Riemsdijk WH (1997) Phosphate and sulfate adsorption on goethite: single anion and competitive adsorption. GCA 61(12):2389–2396

    Google Scholar 

  • Hartog N, Griffioen J, van Bergen PF (2005) Depositional and paleohydrogeological controls on the distribution of organic matter and other reductants in aquifer sediments. Chem Geol 216:113–131

    Article  Google Scholar 

  • Hem JD (1967) Equilibrium chemistry of iron in ground water. In: Faust SD, Hunter JV (eds) Principles and applications of water chemistry. Wiley, New York, pp 625–643

    Google Scholar 

  • Huisman DJ (1998) Geochemical characterization of subsurface sediments in the Netherlands. Ph.D. Thesis Agricultural Un. Wageningen, The Netherlands, ISBN 90–54858613.

  • Jakobsen R, Postma D (1999) Redox zoning, rates of sulfate reduction and interactions with Fe-reduction and methanogenesis in a shallow sandy aquifer, Rømø, Denmark. GCA 63(1):137–151

    Google Scholar 

  • Jessen S, Postma D, Thorling L, Műller S, Leskelä J, Engesgaard P (2016) Decadal variations in groundwater quality: a legacy from nitrate leaching and denitrification by pyrite in a sandy aquifer. Water Res Res 53:184–198.

    Article  Google Scholar 

  • Langmuir D (1997) Aqueous environmental geochemistry. Prentice-Hall, Upper Saddle River, NJ

    Google Scholar 

  • Postma D, Boesen C, Kristiansen H, Larsen F (1991) Nitrate reduction in an unconfined sandy aquifer: water chemistry, reduction processes, and geochemical modeling. Water Res Res 27(8):2027–2045

    Article  Google Scholar 

  • Postma D, Larsen F, Hue NTM, Duc MT, Viet PH, Nhan PQ, Jessen S (2007) Arsenic in groundwater of the Red River floodplain, Vietnam: Controlling geochemical processes and reactive transport modeling. GCA 71:5054–5071.

    Article  Google Scholar 

  • Postma D, Trang PTK, Sø HU, Van Hoan H, Lan VM, Thai NT, Larsen F, Viet PH, Jakobsen R (2016) A model for the evolution in water chemistry of an arsenic contaminated aquifer over the last 6000 years, Red River floodplain, Vietnam. GCA 195:277–292.

    Article  Google Scholar 

  • Rickard D, Luther GW III (2007) Chemistry of iron sulfides. Chem Rev 107:514–562

    Article  Google Scholar 

  • Strebel O, Böttcher J, Kölle W (1985) Stoffbilanzen im Grundwasser eines Einzugsgebiets als Hilfsmittel bei Klärung und Prognose von Grundwasserqualitätsproblemen (Beispiel Fuhrberger Feld) (Mass balances in groundwater of a recharge area as help in the explanation and prognosis of groundwater quality problems (Example Fuhrberger Field)). Ztschr dt geol Ges 136:533–541 (in German)

    Google Scholar 

  • Stumm W, Morgan JJ (1996) Aquatic chemistry, chemical equilibria and rates in natural waters, 3rd edn. Wiley-Interscience, New York

    Google Scholar 

  • Todd DK, Mays LW (2005) Groundwater Hydrology, 3rd edn. Wiley-Interscience, New York

    Google Scholar 

  • van Beek CGEM, van der Jagt H (1996) Mobilization and speciation of trace elements in groundwater. In: IWSA international workshop: natural origin inorganic micropollutants: arsenic and other constituents, Vienna, May 6–8, 1996

  • van Beek CGEM, Hettinga FAM, Straatman R (1989) The effects of manure spreading and acid deposition upon groundwater quality at Vierlingsbeek, the Netherlands. Proc Third IAHS Sci Assem Baltim IAHS Publ 185:155–162

    Google Scholar 

  • Zhang Y (2012) Coupled biogeochemical dynamics of nitrogen and sulfur in a sandy aquifer and implications for groundwater quality. Ph.D. Thesis Utrecht University

Download references


The authors are very grateful to G.J. Zweere (Water Utility Vitens) for making available the drinking water database, to C.A.J. Appelo for his support and discussions, confirming the importance of Siderite, and to T. Olsthoorn for discussions about groundwater flow toward well fields. The authors appreciate very much the constructive remarks by the reviewers.

Author information

Authors and Affiliations


Corresponding author

Correspondence to C. G. E. M. van Beek.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 656 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

van Beek, C.G.E.M., Cirkel, D.G., de Jonge, M.J. et al. Concentration of Iron(II) in Fresh Groundwater Controlled by Siderite, Field Evidence. Aquat Geochem 27, 49–61 (2021).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:


  • Iron(II) concentration in fresh groundwater
  • Redox zoning
  • Hydrous ferric oxides
  • Siderite