Advertisement

Kinetics of Dissolution of Monument Building Materials

  • Dimitra G. Kanellopoulou
  • Petros G. Koutsoukos
Chapter

Abstract

Built heritage consists to a large part of calcitic minerals (marble, limestone) which are prone to dissolution over a wide pH range. Indeed, chemical is solution is among the most significant factors contributing to the deterioration and damage of the built cultural heritage. Carbon dioxide dissolved in atmospheric water contributes to the development of acid conditions on the surface of the calcitic materials which accelerate dissolution of calcite crystals. These effects are enhanced in the case of polluted atmosphere which contributes to more aggressive environment for the dissolution process. The measurement of parameters that determine the kinetics of dissolution is very important for the understanding of dissolution mechanism and hence the design of efficient strategy for the prevention of it. As a result, precise and reproducible methods are necessary for drawing reliable mechanistic information. In the present work, the dissolution kinetics were investigated at conditions of constant driving force for the dissolution process. The methodology used to measure the rates of dissolution of calcitic marbles (>98% calcite) and sandstone was both accurate and highly reproducible. The rates of crystal dissolution measured were correlated with the corresponding solution undersaturation. The dissolution kinetics measurements showed that calcitic limestone at pH 8.25 had a lower dissolution rate constant in comparison with the respective value for Pentelic marble, a calcitic material (ca. 98% calcite). The mechanism was the same, i.e., surface diffusion controlled at alkaline pH values. The prevention of dissolution strategy therefore shall depend either on the alteration of fluid dynamics at the acid pH values or on the modification of the surfaces at the alkaline domain. The latter can be achieved by the addition of substances with functional groups, which may interact with the surface of the calcite crystals. Several inorganic ions (fluoride and sulfate) and one organic environmentally friendly compound, polycarboxymethyl inulin (CMI) (MW 15000), have been tested, and their effect on the rates of dissolution was discussed.

Keywords

Dissolution kinetics Constant undersaturation Calcitic marble Sandstone Inhibitors 

Notes

Acknowledgment

The authors wish to acknowledge support of the work from KRHPIS program – POLITEIA.

References

  1. 1.
    Baedecker PA, Reddy MM (1993) The Erosion of carbonate stone by acid rain. Laboratory and field investigations. J Chem Ed 70(2):104–108.  https://doi.org/10.1021/ed070p104 CrossRefGoogle Scholar
  2. 2.
    Graede TE (2000) Mechanisms for the atmospheric corrosion of carbonate stone. J Electrochem Soc 147(3):1006–1009.  https://doi.org/10.1149/1.1393304. http://jes.ecsdl.org/content/147/3/1006.full.pdf+html CrossRefGoogle Scholar
  3. 3.
    Carrels RM, Christ CL (1966) Solutions, minerals and equilibrium. Harper and Row, New York, p 450Google Scholar
  4. 4.
    Krauskopf KB (1961) Introduction to geochemistry. McGraw-Hill, New York, p 721Google Scholar
  5. 5.
    Stumm W, Morgan J (1981) Aquatic chemistry, 2nd edn. Wiley, New York, p 780Google Scholar
  6. 6.
    Wang L, Nancollas GH (2008) Calcium orthophosphates: crystallization and dissolution. Chem Rev 108(11):4628–4669.  https://doi.org/10.1021/cr0782574 CrossRefGoogle Scholar
  7. 7.
    Kanellopoulou DG, Koutsoukos PG (2003) The calcite marble/water Interface: kinetics of dissolution and inhibition with potential implications in stone conservation. Langmuir 19(14):5691–5699.  https://doi.org/10.1021/la034015x CrossRefGoogle Scholar
  8. 8.
    Xyla AG, Mikroyannidis J, Koutsoukos PG (1992) The inhibition of calcium carbonate precipitation in aqueous solutions by organophosphorus compounds. J Colloid Interface Sci 153(2):537–551.  https://doi.org/10.1016/0021-9797(92)90344-L CrossRefGoogle Scholar
  9. 9.
    Knepper TP (2003) Synthetic chelating agents and compounds exhibiting complexing properties in the aquatic environment. Trends Anal Chem 22(10):708–724.  https://doi.org/10.1016/S0165-9936(03)01008-2 CrossRefGoogle Scholar
  10. 10.
    Guo J, Severtson SJ (2004) Inhibition of calcium carbonate nucleation with Aminophosphonates at high temperature, pH and ionic strength. Ind Eng Chem Res 43(17):5411–5417.  https://doi.org/10.1021/ie049787i CrossRefGoogle Scholar
  11. 11.
    Spanos N, Kanellopoulou DG, Koutsoukos PG (2006) The interaction of diphosphonates with calcitic surfaces: understanding the inhibition activity in marble dissolution. Langmuir 22(5):2074–2081.  https://doi.org/10.1021/la052062e CrossRefGoogle Scholar
  12. 12.
    Boels L, Witkamp GJ (2011) Carboxymethyl inulin biopolymers: a green alternative for phosphonate calcium carbonate growth inhibitors. Cryst Growth Des 11(9):4155–4165.  https://doi.org/10.1021/cg2007183 CrossRefGoogle Scholar
  13. 13.
    Demadis KD, Preari M (2013) Green scale inhibitors in water treatment processes: the case of silica scale inhibition. In: Proceedings of the 13th international conference on environmental science and technology, Athens, 5–7 Sept 2013, CEST2013_0280Google Scholar
  14. 14.
    Parkhurst DL, Appelo CAJ (2013) Description of input and examples for PHREEQC version 3 – a computer program for speciation, batch- reaction, one-dimensional transport, and inverse geochemical calculations: U.S. Geological Survey Techniques and Methods, Book 6, Chap. A43, 497 p. Available only at http://pubs.usgs.gov/tm/06/a43
  15. 15.
    Cailleau P, Jaquin C, Dragone D, Girou A, Roques H, Humbert L (1979) Influence of foreign ions and of organic matter on the crystallization of calcium carbonates. Oil Gas Sci Technol Rev IFP 34(1):83–112.  https://doi.org/10.2516/ogst:1979003. https://ogst.ifpenergiesnouvelles.fr/articles/ogst/abs/1979/01/vol34n1p83/vol34n1p83.html CrossRefGoogle Scholar
  16. 16.
    Tlili MM, Ben AM, Gabrielli C, Joiret S, Maurin G (2006) On the initial stages of calcium carbonate precipitation. Eur J Water Qual 37(1):89–108. https://www.scopus.com/inward/record.uri?eid=2-s2.0-33745142866&partnerID=40&md5=6905d0b52da80490b3dc22a88f7d0433 Google Scholar
  17. 17.
    Paquette J, Vali H, Mucci A (1996) TEM study of Pt-C replicas of calcite overgrowths precipitated from electrolyte solutions. Geochim Cosmochim Acta 60(23):4689–4701. https://www.sciencedirect.com/science/journal/00167037/60/23 CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  • Dimitra G. Kanellopoulou
    • 1
    • 2
  • Petros G. Koutsoukos
    • 1
  1. 1.Department of Chemical EngineeringUniversity of Patras and FORTH-ICEHTPatraGreece
  2. 2.Department of Environment TechnologistsT.E.I of Ionian Islands, School of Technological Applications, PanagoulaZakynthosGreece

Personalised recommendations