Skip to main content

Advertisement

SpringerLink
Log in

Role of Major Groundwater Ions on Reductive Cr(VI) Immobilization in Subsurface Systems with Pyrite

  • Published:
Water, Air, & Soil Pollution Aims and scope Submit manuscript

Abstract

Laboratory batch and column experiments were performed to better understand the effects of Ca2+, Mg2+, and HCO3 − on Cr(VI) removal from aqueous systems with pyrite. Batch results show that increasing HCO3 − concentration led to an increase in Cr(VI) removal by pyrite due to pH buffering capacity of HCO3 −. However, while Ca2+ and Mg2+ individually had no effect on Cr(VI) removal at pH 4, the addition of Ca2+ or Mg2+ to systems containing HCO3 − resulted in a significant decrease in Cr(VI) removal at pH 8 relative to the systems containing HCO3 − alone. The XPS data proved that while Ca2+ precipitated as CaCO3(S) onto pyrite surface, Mg2+ sorbed and/or accumulated as Mg(OH)2(S) onto oxidized pyrite surface. The formation of surface precipitates (e.g., CaCO3) inhibited further Cr(VI) reduction by blocking electron transfer between Cr(VI) and pyritic surface sites. While the precipitation of Ca2+ as CaCO3 led to a significant decrease in effluent pH, the decrease in effluent pH was very low in systems containing Mg2+, most probably due to much higher solubility of Mg2+ at pH 8. Zeta potential measurements provided further evidence that while Ca2+ or Mg2+ had no effect on zeta potential of pyrite particles under acidic conditions (e.g., pH < 7), the addition of Ca2+ or Mg2+ to systems containing Cr(VI) reversed the pyrite surface potential from negative to positive under alkaline pH conditions (e.g., pH > 8) relative to system containing only Cr(VI), suggesting the sorption and/or accumulation of surface precipitates on pyrite surface.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  • APHA. (1995). Standard methods for the examinations of water and wastewater (19th ed.). Washington, DC: American Public Health Association.

    Google Scholar 

  • Bennett, T.A. (1997). An in Situ Reactive Barrier for the Treatment of Hexavalent Chromium and Trichloroethylene in Groundwater, (M.Sc. Thesis), University of Waterloo, Ontorio, Canada.

  • Blowes, D. W., Ptacek, C. J., & Jambor, J. L. (1997). In-situ remediation of Cr(VI)-contaminated groundwater using permeable reactive walls: laboratory studies. Environmental Science & Technology, 31(12), 3348–3356.

    Article  CAS  Google Scholar 

  • Boddu, V. M., Abburi, K., Talbott, J. L., & Smith, E. D. (2003). Removal of hexavalent chromium from wastewater using a new composite chitosan biosorbent. Environmental Science & Technology, 37, 4449–4456.

    Article  CAS  Google Scholar 

  • Chon, C.-M., Kim, J. G., & Moon, H.-S. (2006). Kinetics of chromate reduction by pyrite and biotite under acidic conditions. Applied Geochemistry, 21, 1469–1481.

    Article  CAS  Google Scholar 

  • Chon, C.-M., Kim, J. G., & Moon, H.-S. (2007). Evaluating the transport and removal of chromate using pyrite and biotite columns. Hydrological Processes, 21, 1957–1967.

    Article  CAS  Google Scholar 

  • Demoisson, F., Mullet, M., & Humbert, B. (2005). Pyrite oxidation by hexavalent chromium: investigation of the chemical processes by monitoring of aqueous species. Environmental Science & Technology, 39, 8747–8752.

    Article  CAS  Google Scholar 

  • Ding, Q., Ding, F., Qian, T., Zhan, D., & Wang, L. (2015). Reductive immobilization of rhenium in soil and groundwater using pyrite nanoparticles. Water, Air, & Soil Pollution, 226, 409–418.

    Article  Google Scholar 

  • Doyle, C. S., Kendelewicz, T., Bostick, B. C., & Brown, G. E., Jr. (2004). Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions. Geochimica et Cosmochimica Acta, 68(21), 4287–4299.

    Article  CAS  Google Scholar 

  • Evangelou, V. P., Seta, A. K., & Holt, A. (1998). Potential role of bicarbonate during oxidation. Environmental Science & Technology, 32, 2084–2091.

    Article  CAS  Google Scholar 

  • Fruchter, J. (2002). In-situ treatment of chromium-contaminated groundwater. Environmental Science & Technology, 36(23), 464A–472A.

    Article  CAS  Google Scholar 

  • Graham, A. M., & Bouwer, J. B. (2012). Oxidative dissolution of pyrite surfaces by hexavalent chromium: surface site saturation and surface removal. Geochimica et Cosmochimica Acta, 83, 379–396.

    Article  CAS  Google Scholar 

  • Hou, M., Wan, H., Liu, T., Fan, Y., Liu, X., & Wang, X. (2008). The effect of different divalent cations on the reduction of hexavalent chromium by zerovalent iron. Applied Catalysis B: Environmental, 84, 170–175.

    Article  CAS  Google Scholar 

  • Hu, J., Chen, G., & Lo, I. M. C. (2005). Removal and recovery of Cr(VI) from wastewater by maghemite nanoparticles. Water Research, 39, 4528–4536.

    Article  CAS  Google Scholar 

  • Kantar, C., & Bulbul, M. S. (2016). Effect of pH-buffering on Cr(VI) reduction with pyrite in the presence of various organic acids: continuous-flow experiments. Chemical Engineering Journal, 287, 173–180.

    Article  CAS  Google Scholar 

  • Kantar, C., & Honeyman, B. D. (2006). Citric acid enhanced remediation of soils contaminated with uranium by soil flushing and soil washing. Journal of Environmental Engineering, 132(2), 247–255.

    Article  CAS  Google Scholar 

  • Kantar, C., Ari, C., Keskin, S., Dagaroglu, Z. G., Karadeniz, A., & Alten, A. (2015a). Cr(VI) removal from aqueous systems using pyrite as the reducing agent: batch, spectroscopic and column experiments. Journal of Contaminant Hydrology, 174, 28–38.

    Article  CAS  Google Scholar 

  • Kantar, C., Ari, C., & Keskin, S. (2015b). Comparison of different chelating agents to enhance reductive Cr(VI) removal by pyrite treatment procedure. Water Research, 76, 66–75.

    Article  CAS  Google Scholar 

  • Karvonen, A. (2004). Cation effects on chromium removal in permeable reactive walls. Journal of Environmental Engineering, ASCE, 8, 863–866.

    Article  Google Scholar 

  • Kosmulski, M. (2009). pH-dependent surface charging and points of zero charge. IV. Update and new approach. Journal of Colloid and Interface Science, 337, 439–448.

    Article  CAS  Google Scholar 

  • Lai, K. C. K., & Lo, I. M. C. (2008). Removal of chromium (VI) by acid-washed zero-valent iron under various groundwater geochemistry conditions. Environmental Science & Technology, 42, 1238–1244.

    Article  CAS  Google Scholar 

  • Lenhart, J. J., & Honeyman, B. D. (1999). Uranium (VI) sorption to hematite in the presence of humic acid. Geochimica et Cosmochimica Acta, 63, 2891–2901.

    Article  CAS  Google Scholar 

  • Lin, Y.-T., & Huang, C.-P. (2008). Reduction of chromium (VI) by pyrite in dilute aqueous solutions. Separation and Purification Technology, 63, 191–199.

    Article  CAS  Google Scholar 

  • Liu, T., & Lo, I. M. C. (2011). Influences of humic acid on Cr(VI) removal by zero-valent iron from groundwater with various constituents: implication for long-term PRB performance. Water, Air, & Soil Pollution, 216, 473–483.

    Article  CAS  Google Scholar 

  • Liu, T., Rao, P., Shi, J., & Lo, I. M. C. (2009). Influences of humic acid, bicarbonate and calcium on Cr(VI) reductive removal by zero-valent iron. Science of the Total Environment, 407, 3407–3414.

    Article  CAS  Google Scholar 

  • Lo, I. M. C., Lam, C. S. C., & Lai, K. C. K. (2006). Hardness and carbonate effects on the reactivity of zero-valent iron for Cr(VI) removal. Water Research, 40, 595–605.

    Article  CAS  Google Scholar 

  • Mohan, D., & Pittman, C. U. (2006). Activated carbons and low cost adsrobents for remediation of tri- and hexavalent chromium from water. Journal of Hazardous Materials, B137, 762–811.

    Article  Google Scholar 

  • Mullet, M., Demoisson, F., Humbert, B., Michot, L. J., & Vantelon, D. (2007). Aqueous Cr(VI) reduction by pyrite: speciation and characterization of the solid phases by X-ray photoelectron, Raman and X-ray absorption spectroscopies. Geochimica et Cosmochimica Acta, 71, 3257–3271.

    Article  CAS  Google Scholar 

  • Nesbitt, H. W., Bancroft, G. M., Pratt, A. R., & Scaini, M. J. (1998). Sulfur and iron surface states on fractured pyrite surfaces. American Mineralogist, 83, 1067–1076.

    Article  CAS  Google Scholar 

  • Song, M.-R., Chen, M., & Zhang, Z.-J. (2008). Preparation and characterization of Mg nanoparticles. Materials Characterization, 59, 514–518.

    Article  CAS  Google Scholar 

  • Tayfur, G., Kirer, T., & Baba, A. (2008). Groundwater quality and hydrogeochemical properties of Torbalı Region, Izmir, Turkey. Environmental Monitoring and Assessment, 146, 157–169.

    Article  CAS  Google Scholar 

  • Van der Heide, P. A. W. (2006). Photoelectron binding energy shifts observed during oxidation of group IIA, IIIA and IVA elemental surfaces. Journal of Electron Spectroscopy and Related Phenomena, 151, 79–91.

    Article  Google Scholar 

  • Wang, Q., Cissoko, N., Zhou, M., & Xu, X. (2011). Effects and mechansims of humic acid on chromium (VI) removal by zero-valent iron (Feo) nanoparticles. Physics and Chemistry of the Earth, 36, 442–446.

    Article  Google Scholar 

  • Zouboulis, A. I., Kydros, K. A., & Matis, K. A. (1995). Removal of hexavalent chromium anions from solutions by pyrite fines. Water Research, 29(7), 1755–1760.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We would like to thank the Scientific and Technological Research Council of Turkey (Project No: 114Y024) for the financial support.

Author information

Authors and Affiliations

  1. Department of Environmental Engineering, Faculty of Engineering, Canakkale Onsekiz Mart University, 17100, Canakkale, Turkey

    Muhammet Samet Bulbul & Cetin Kantar

  2. NanoMagnetics Instruments Ltd, Hacettepe - İvedik OSB Teknokent, 1368. Cad., No: 61/33, 06370, Ankara, Turkey

    Selda Keskin

Authors
  1. Muhammet Samet Bulbul
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Cetin Kantar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Selda Keskin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Cetin Kantar.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

ESM 1

Experimental details on spectroscopic analysis, pyrite and column properties; column tracer experiments; the effects of major groundwater on Cr(VI) removal capacity of pyrite; the effects of bicarbonate concentration on solution pH, the variations in effluent Fe concentrations, the Cr 2p spectra of pyrite surface exposed to Cr(VI) at pH 8 in systems containing 103 mg/L HCO3 − as CaCO3 and 500 mg/L as CaCO3 Ca2+ and Mg2+, scanning electron microscope image (SEM) of pyrite surface exposed to Cr(VI) in the presence of Ca2+, Cr(VI) removal by pyrite as a function of solution pH. Supplementary data associated with this article can be found in the online version at. (DOC 375 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bulbul, M.S., Kantar, C. & Keskin, S. Role of Major Groundwater Ions on Reductive Cr(VI) Immobilization in Subsurface Systems with Pyrite. Water Air Soil Pollut 227, 72 (2016). https://doi.org/10.1007/s11270-016-2777-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11270-016-2777-3

Keywords

Search

Navigation