Simulation of acid weathering on natural and artificial building stones according to the current atmospheric SO2/NO x rate

  • S. Gibeaux
  • C. Thomachot-Schneider
  • S. Eyssautier-Chuine
  • B. Marin
  • P. Vazquez
Thematic Issue
Part of the following topical collections:
  1. Stone in the Architectural Heritage: from quarry to monuments – environment, exploitation, properties and durability


The building stones are affected by pollution. Since 1980s, the actions to reduce the greenhouse gas emissions led to the inversion of the SO2/NO x proportions in the atmosphere. This study aims at estimating the effects of nitrogen and sulfur compounds on stones by assessing the changes of three building limestones and one reconstituted stone submitted to acid attacks. Two of these stones were already contaminated with sulfates, while the two others were fresh quarried. Two different types of accelerated aging tests were used: (1) the exposition to two mixed acid and saturated atmospheres (HNO3 and H2SO3) to simulate the ancient and current pollutants ratio and (2) the immersion in a mixed acid solution (HNO3 and H2SO4) and in rainwater (pH 5 and 5.9), with and without agitation to simulate stagnant water and storm runoff water. Macroscopic, binocular and SEM observations, variations of color, weight, porosity, salt content and dissolved calcium were assessed over time. The sulfur amount influences the esthetic alterations such as color changes due to the salt precipitation and the oxidation of metallic compounds. During the immersion tests, the dissolution in the acid solution was more efficient than in the rainwater, due to the combination of the acidity and the karst effects. In the mixed acid atmospheres, the behavior of the porous network depends on the pore size distribution while in the immersion tests it is the open porosity. The high initial sulfur content of the contaminated stones increases the dissolution rate and limits the crystallization.


SO2/NOx Acid rain Acid deposition Aging laboratory tests Building limestone Reconstituted stone 



The authors want to thank Xavier Drothiere, Alexandra Conreux and Julien Hubert for their technical and analytical support.


This study was funded by “Reims Métropole” with the project IFEPAR and the University of Reims-Champagne Ardenne and the “Ville de Reims” with the Project REMITHERM, and “Grand Est” with the project FLUTE.

Compliance with ethical standards

Conflict of interest

The authors confirm that there is no conflict of interest in this research.

Informed consent

Informed consent was obtained from all individual participants included in the study.


  1. Ansted DT (1860) On the decay and preservation of building materials. J Franklin Inst 70:155–163. CrossRefGoogle Scholar
  2. Baedecker PA, Reddy MM (1993) The erosion of carbonate stone by acid rain: laboratory and field investigations. J Chem Educ 70:104–108CrossRefGoogle Scholar
  3. Bai Y, Thompson GE, Martinez-Ramirez S, Brüeggerhoff S (2003) Mineralogical study of salt crusts formed on historic building stones. Sci Total Environ 302:247–251CrossRefGoogle Scholar
  4. Bai Y, Thompson GE, Martinez-Ramirez S (2006) Effects of NO2 on oxidation mechanisms of atmospheric pollutant SO2 over Baumberger sandstone. Build Environ 41:486–491. CrossRefGoogle Scholar
  5. Bionda D (2005) RUNSALT—a graphical user interface to the ECOS thermodynamic model for the prediction of the behaviour of salt mixtures under changing climate conditions.
  6. Bonazza A, Messina P, Sabbioni C et al (2009) Mapping the impact of climate change on surface recession of carbonate buildings in Europe. Sci Total Environ 407:2039–2050. CrossRefGoogle Scholar
  7. Camaiti M, Bugani S, Bernardi E et al (2007) Effects of atmospheric NOx on biocalcarenite coated with different conservation products. Appl Geochem 22:1248–1254. CrossRefGoogle Scholar
  8. Camuffo D (1995) Physical weathering of stones. Sci Total Environ 167:1–14CrossRefGoogle Scholar
  9. Cardell-Fernández C, Vleugels G, Torfs K, Van Grieken R (2002) The processes dominating Ca dissolution of limestone when exposed to ambient atmospheric conditions as determined by comparing dissolution models. Environ Geol 43:160–171. CrossRefGoogle Scholar
  10. CEN (Comité Européen de Normalisation) (2002) EN 13919: natural stone test methods: determination of resistance to ageing by SO2 action in the presence of humidity. BrusselsGoogle Scholar
  11. Charola AE, Pühringer J, Steiger M (2007) Gypsum: a review of its role in the deterioration of building materials. Environ Geol 52:339–352. CrossRefGoogle Scholar
  12. CITEPA (2015) Inventaire des émissions de polluants atmosphériques et de gaz à effet de serre en France, Ministère de l’Écologie, du Développement durable et de l’Énergie.
  13. Dewanckele J (2013) Spatial reorganization processes at a (sub)micron scale due to natural and artificial alteration inside natural stones. Ghent University, GhentGoogle Scholar
  14. Dewanckele J, De Kock T, Fronteau G et al (2014) Neutron radiography and X-ray computed tomography for quantifying weathering and water uptake processes inside porous limestone used as building material. Mater Charact 88:86–99. CrossRefGoogle Scholar
  15. Dolske DA (1995) Deposition of atmospheric pollutants to monuments, statues, and buildings. Sci Total Environ 167:15–31CrossRefGoogle Scholar
  16. Eyssautier-Chuine S, Marin B, Thomachot-Schneider C et al (2016) Simulation of acid rain weathering effect on natural and artificial carbonate stones. Environ Earth Sci 75:1–19. CrossRefGoogle Scholar
  17. Franzoni E, Sassoni E (2011) Correlation between microstructural characteristics and weight loss of natural stones exposed to simulated acid rain. Sci Total Environ 412:278–285. CrossRefGoogle Scholar
  18. Fronteau G (2000) Comportements télogénétiques des principaux calcaires de champagne-ardenne, en relation avec leur faciès de dépôt et leur séquençage diagénétique. Université d’OrléansGoogle Scholar
  19. Fronteau G, Moreau C, Thomachot-Schneider C, Barbin V (2010) Variability of some Lutetian building stones from the Paris Basin, from characterisation to conservation. Eng Geol 115:158–166. CrossRefGoogle Scholar
  20. Gardner ES (2006) Exponential smoothing: the state of the art—Part II. Int J Forecast 22:637–666. CrossRefGoogle Scholar
  21. Graue B, Siegesmund S, Oyhantcabal P et al (2013) The effect of air pollution on stone decay: the decay of the Drachenfels trachyte in industrial, urban, and rural environments—a case study of the Cologne, Altenberg and Xanten cathedrals. Environ Earth Sci 69:1095–1124. CrossRefGoogle Scholar
  22. Grossi CM, Murray M, Butlin RN (1995) Response of porous building stones to acid deposition. Water Air Soil Pollut 85:2713–2718. CrossRefGoogle Scholar
  23. Grossi CM, Brimblecombe P, Esbert RM, Alonso FJ (2007) Color changes in architectural limestones from pollution and cleaning. Color Res Appl 32:320–331. CrossRefGoogle Scholar
  24. Haneef SJ, Johnson JB, Dickinson C et al (1992) Effect of dry deposition of NOx and SO2 gaseous pollutants on the degradation of calcareous building stones. Atmos Environ 26A:2963–2974CrossRefGoogle Scholar
  25. Haneef SJ, Johnson JB, Thompson GE, Wood GC (1993) The degradation of coupled stones by wet deposition processes. Corros Sci 34:497–510. CrossRefGoogle Scholar
  26. Huber FC, Reid EE (1926) Influence of rate of stirring on reaction velocity. Ind Eng Chem 18:535–538. CrossRefGoogle Scholar
  27. Kuhlman F (1863) New researches upon the preservation of building materials. J Franklin Inst 76:383–389. CrossRefGoogle Scholar
  28. Laycock EA, Spence K, Jefferson DP et al (2008) Testing the durability of limestone for cathedral façade restoration. Environ Geol 56:521–528. CrossRefGoogle Scholar
  29. Lipfert F (1989) Atmospheric damage to calcareous stones: comparison and reconciliation of recent experimental findings. Atmos Environ (1967) 23:415–429CrossRefGoogle Scholar
  30. Livingston RA (1992) Graphic methods for examining the effect of sulphur dioxide on carbonate stones. In: Proceedings of 7th international congress deterioration and conservation of stone, Laboratorio Nacional de Engenheria Civil, Lisbon, pp 375–386Google Scholar
  31. Massey SW (1999) The effects of ozone and NOx on the deterioration of calcareous stone. Sci Total Environ 227:109–121CrossRefGoogle Scholar
  32. Monna F, Puertas A, Lévêque F et al (2008) Geochemical records of limestone façades exposed to urban atmospheric contamination as monitoring tools? Atmos Environ 42:999–1011. CrossRefGoogle Scholar
  33. Price CA (2000) An expert chemical model for determining the environmental conditions needed to prevent salt damage in porous materials. European Commission Research Report No 11, (Protection and Conservation of European Cultural Heritage) Archetype Publications, LondonGoogle Scholar
  34. Reddy MM (1988) Acid rain damage to carbonate stone: a quantitative assessment based on the aqueous geochemistry of rainfall runoff from stone. Earth Surf Process Landforms 13:335–354. CrossRefGoogle Scholar
  35. Reeder RJ (ed) (1983) Carbonates: mineralogy and chemistry. Rev Mineral Mineralog Soc Am 11Google Scholar
  36. Rodriguez-Navarro C, Sebastian E (1996) Role of particulate matter from vehicle exhaust on porous building stones (limestone) sulfation. Sci Total Environ 187:79–91CrossRefGoogle Scholar
  37. Ross M, McGee ES, Ross DR (1989) Chemical and mineralogical effects of acid deposition on Shelburne Marble and Salem Limestone test samples placed at four NAPAP weather-monitoring sites. Am Miner 74:367Google Scholar
  38. Sabbioni C, Zappia G (1992) Decay of sandstone in urban areas correlated with atmospheric aerosol. Water Air Soil Pollut 63:305–316. CrossRefGoogle Scholar
  39. Shah SIA, Kostiuk LW, Kresta SM (2012) The effects of mixing, reaction rates, and stoichiometry on yield for mixing sensitive reactions 2014; Part I: model development. Int J Chem Eng 2012:16Google Scholar
  40. Simao J, Ruiz-Agudo E, Rodriguez-Navarro C (2006) Effects of particulate matter from gasoline and diesel vehicle exhaust emissions on silicate stones sulfation. Atmos Environ 40:6905–6917. CrossRefGoogle Scholar
  41. Tecer L (1999) Laboratory experiments on the investigation of the effects of sulphuric acid on the deterioration of carbonate stones and surface corrosion. Water Air Soil Pollut 114:1–12. CrossRefGoogle Scholar
  42. Thomachot-Schneider C, Gommeaux M, Fronteau G et al (2011) A comparison of the properties and salt weathering susceptibility of natural and reconstituted stones of the Orval Abbey (Belgium). Environ Earth Sci 63:1447–1461. CrossRefGoogle Scholar
  43. Thomachot-Schneider C, Gommeaux M, Lelarge N et al (2016) Relationship between Na2SO4 concentration and thermal response of reconstituted stone in the laboratory and on site. Environ Earth Sci. Google Scholar
  44. Török Á, Rozgonyi N (2004) Morphology and mineralogy of weathering crusts on highly porous oolitic limestones, a case study from Budapest. Environ Geol. Google Scholar
  45. Török Á, Licha T, Simon K, Siegesmund S (2011) Urban and rural limestone weathering; the contribution of dust to black crust formation. Environ Earth Sci 63:675–693. CrossRefGoogle Scholar
  46. Vazquez P, Alonso FJ (2015) Colour and roughness measurements as NDT to evaluate ornamental granite decay. Proc Earth Planet Sci 15:213–218CrossRefGoogle Scholar
  47. Vazquez P, Luque A, Alonso FJ, Grossi CM (2013) Surface changes on crystalline stones due to salt crystallisation. Environ Earth Sci 69:1237–1248. CrossRefGoogle Scholar
  48. Vazquez P, Carrizo L, Thomachot-Schneider C et al (2016) Influence of surface finish and composition on the deterioration of building stones exposed to acid atmospheres. Constr Build Mater 106:392–403. CrossRefGoogle Scholar
  49. Völz HG, Kischkewitz J, Woditsch P et al (2000) Pigments, inorganic. In: Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH Verlag GmbH & Co., KGaAGoogle Scholar
  50. Webb AH, Bawden RJ, Busby AK, Hopkins JN (1992) Studies on the effects of air pollution on limestone degradation in Great Britain. Atmos Environ Part B Urban Atmos 26:165–181CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Groupe d’Etudes sur les Géomatériaux et les Environnements Naturels, Anthropiques et Archéologiques (GEGENAA, EA 3795Université de Reims Champagne-ArdenneReimsFrance

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