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Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions

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Abstract

Dissolved arsenic (As) concentrations detected in groundwater bodies of the Emilia-Romagna Region (Italy) exhibit values which are above the regulation limit and could be related to the natural composition of the host porous matrix. To support this hypothesis, we present the results of a geochemical modeling study reproducing the main trends of the dynamics of As, Fe, and Mn concentrations as well as redox potential and pH observed during batch tests performed under alternating redox conditions. The tests were performed on a natural matrix extracted from a deep aquifer located in the Emilia-Romagna Region (Italy). The solid phases implemented in the model were selected from the results of selective sequential extractions performed on the tested matrix. The calibrated model showed that large As concentrations have to be expected in the solution for low crystallinity phases subject to dissolution. The role of Mn oxides on As concentration dynamics appears significant in strongly reducing environments, particularly for large water–solid matrix interaction times. Modeled data evidenced that As is released firstly from the outer surface of Fe oxihydroxides minerals exhibiting large concentrations in water when persistent reducing conditions trigger the dissolution of the crystalline structure of the binding minerals. The presence of organic matter was found to strongly affect pH and redox conditions, thus influencing As mobility.

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Acknowledgments

The research has been performed in the framework of a research agreement between the Politecnico di Milano and ARPA—Regional Agency for Environmental Protection. Funding from ARPA and the Emilia-Romagna Region is gratefully acknowledged. X. S. acknowledges support from ICREA Academia program.

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Authors and Affiliations

  1. Politecnico di Milano, Dipartimento di Ingegneria Civile e Ambientale, Piazza L. Da Vinci 32, 20133, Milan, Italy

    A. Molinari, L. Guadagnini & A. Guadagnini

  2. Institute of Environmental Assessment and Water Research, CSIC, Jordi Girona 18, 08034, Barcelona, Spain

    C. Ayora

  3. Arpa Emilia-Romagna, Largo Caduti del Lavoro 6, 40122, Bologna, Italy

    M. Marcaccio

  4. Universitat Politècnica de Catalunya-BarcelonaTech, Jordi Girona 1-3, 08034, Barcelona, Spain

    X. Sanchez-Vila

  5. Department of Hydrology and Water Resources, University of Arizona, 85721, Tucson, AZ, USA

    A. Guadagnini

Authors
  1. A. Molinari
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  2. C. Ayora
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  3. M. Marcaccio
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  4. L. Guadagnini
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  5. X. Sanchez-Vila
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  6. A. Guadagnini
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Corresponding author

Correspondence to A. Molinari.

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Responsible editor: Céline Guéguen

Highlights

As displays a rapid release rate under rapidly varying redox conditions

Organic matter strongly affects Eh and pH conditions and dynamics of As release

Large As release occurs when low crystallinity phases are subject to dissolution

Mn oxides dissolution could be crucial on As release after long solid–water contact

Our geochemical model reproduces key experimental trends of As, Fe, Mn, Eh, and pH

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Molinari, A., Ayora, C., Marcaccio, M. et al. Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions. Environ Sci Pollut Res 21, 1628–1637 (2014). https://doi.org/10.1007/s11356-013-2054-6

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  • DOI: https://doi.org/10.1007/s11356-013-2054-6

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