Environmental Earth Sciences

, Volume 69, Issue 5, pp 1733–1750 | Cite as

Petrophysical properties, composition and deterioration of the Calatorao biogenic stone: case of the sculptures masonry of the Valley of the Fallen (Madrid, Spain)

  • Javier Garcia-GuineaEmail author
  • Lorena Recio-Vazquez
  • Gonzalo Almendros
  • David Benavente
  • Virgilio Correcher
  • Antonio Perez-Garcia
  • Sergio Sanchez-Moral
  • Angel Fernandez-Cortes
Original Article


The huge sculptures placed outdoors in the Valley of the Fallen Memorial Park (El Escorial, Madrid) made with blocks of Black-Limestone from Calatorao-Zaragoza, Spain (BLCZ) and disposed on a concrete core exhibit weathering traces, flaking, saline efflorescence and falling fragments, currently represent a danger for visitors. Frost action is important in the Valley of the Fallen by the large number of freeze–thaw cycles produced during Sculptures‘live under a temperate Mediterranean climate with severe seasonality. The formation of fissures facilitates the water transport within the rock and the salt- and ice-induced deterioration. Temperate climates with frequent freezing and thawing cycles can be the most effective drivers of the visible physical weathering. In order to propose a suitable weathering model, collected black-limestones from sculptures and Calatorao quarries were analyzed by optical microscopy, environmental scanning electron microscopy with energy dispersive spectrometry (ESEM-EDS), inductively coupled mass spectrometry (ICP-MS) and X-ray diffraction. Mercury intrusion porosimetry (MIP), nitrogen absorption and helium pycnometry techniques were used for pore analyses of the BLCZ micro-blocks (10 × 10 × 10 cm) described in terms of pore size distribution, pore volume and specific surface area. The appreciable amount of organic matter was isolated by solvent extraction, acid treatment, flotation and perborate degradation followed by Gas Chromatography–Mass Spectrometry (GC–MS), Analytical Pyrolysis (Py-GC/MS), Fourier Transformed Infrared Spectroscopy and Raman techniques. Both weathered and fresh BLCZ samples contained more than 90 % calcite shells with circa 10 % of pyrite (fresh samples) or iron hydroxides (weathered samples), quartz grains, claystone and fossil organic matter consisting of a condensed matrix with polyalkyl chains and polycyclic methoxyl-lacking aromatic structures. The petrophysical analyses revealed volumes of pores, sized <0.025 μm obtained by N2 adsorption, of 3.18 × 10−3 cm3 g−1 while the measured porosity by MIP in the pore range from 0.005 to 200 μm was 3.30 × 10−3 cm3 g−1. These data could be explained by the existence of clay minerals and organic matter in the pore system less than 50 nm of diameter. Concerning BLCZ deterioration it was found that the porous framework of BLCZ was filled with sulphates formed from artificial cement observed in the sculptures inside trough a testing hole and from its intrinsic pyrite. The results suggested that although biological processes were not major agents in rock deterioration, there was also weak compatibility between sculptures‘constituents, (limestone, concrete and oxidized iron clamps) which under, continental Mediterranean conditions, were continuously releasing weathering compounds accelerating disruption of the cut-stone sculptures.


Weathering Cultural heritage Black-limestone Organic matter Spectroscopy Petrophysics 



We gratefully acknowledge to projects CGL2008-04296, CGL2010-17108, and CGL2009-09247 of the Spanish National Planning for R&D for financial support. We thank to Capa Sculptors, a company devoted to the restoration and conservation of Historical Sculptures and to the Spanish National Heritage Agency (Patrimonio Nacional de España) for assisting us during the samples collection in the initial restoration works of La Piedad Sculpture.


  1. Ahnert F, Arnold E (1998) Introduction to geomorphology. Wiley, London, p 352Google Scholar
  2. Almendros G, Sanz J (1992) A structural study of alkyl polymers in soil after perborate degradation of humin. Geoderma 53:79–95CrossRefGoogle Scholar
  3. Almendros G, Martin F, González-Vila FJ (1987) Depolymerization and degradation of humic acids with sodium perborate. Geoderma 39:235–247CrossRefGoogle Scholar
  4. Almendros G, Martín F, González-Vila FJ (1988) Effects of fire on humic and lipid fractions in a Dystric Xerochrept in Spain. Geoderma 42:115–127CrossRefGoogle Scholar
  5. Almendros G, Dorado J, Sanz J, Alvarez-Ramis C, Fernández Marrón MT, Archangelsky S (1999) Compounds released by sequential chemolysis from cuticular remains of Cretacic gymnosperm Squamastrobus tigrensis Patagonia. The Argentine. Org Geochem 30:623–634CrossRefGoogle Scholar
  6. Aoyama T, Shioiri T (1990) Trimethylsilyldiazomethane a convenient reagent for the O-methylation of alcohols. Tetrahedr Lett 31:5507–5508CrossRefGoogle Scholar
  7. Atkinson BK, Meredith PG (1987) Experimental fracture mechanics data for rocks and minerals. In: Atkinson BK (ed) Fracture mechanics of rock. Academic Press, London, pp 477–526Google Scholar
  8. Attanasio D, Armiento G, Brilli M, Emanuele MC, Platania R, Turi B (2000) Multi-method marble provenance determinations, the Carrara marbles as a case study for the combined use of isotopic, electron spin resonance and petrographic data. Archaeometry 42:3–14CrossRefGoogle Scholar
  9. Attanasio D, Conti L, Platania R, Turi B (2002) Multimethod provenance determinations: isotopic, ESR and petrographic discrimination of fine-grained white marbles. In: Lazzarini L (ed) ASMOSIA VI, Interdisciplinary studies in ancient stone. Padova. pp 141–147Google Scholar
  10. Benavente D, Lock P, García del Cura MA, Ordóñez S (2002) Predicting the capillary imbibition of porous rocks from microstructure. Transp Porous Med 49:59–76CrossRefGoogle Scholar
  11. Benavente D, Cueto N, Martinez–Martinez J, Garcia-del-Cura MA, Cañaveras JC (2007) The influence of petrophysical properties on the salt weathering of porous building rocks. Environ Geol 52:197–206CrossRefGoogle Scholar
  12. Benavente D, Cultrone G, Gomez-Heras M (2008) The combined influence of mineralogical, hygric and thermal properties on the durability of porous building stones. Eur J Miner 20:673–685CrossRefGoogle Scholar
  13. Berner RA (1984) Sedimentary pyrite formation an update. Geochim Cosmochim Acta 48:605–615CrossRefGoogle Scholar
  14. Brilli M (2010) Black limestones used in antiquity: the petrographic, isotopic and EPR database for provenance determination. J Archaeol Sci 37:994–1005CrossRefGoogle Scholar
  15. Clark M, Small J (1982) Slopes and weathering. Cambridge University Press, CambridgeGoogle Scholar
  16. Cueto N, Benavente D, Martinez–Martinez J, Garcia-del-Cura MA (2009) Rock fabric, pore geometry and mineralogy effects on water transport in fractured dolostones. Eng Geol 107:1–15CrossRefGoogle Scholar
  17. D’Heur M (1984) Porosity and hydrocarbon distribution in the North Sea chalk reservoirs marine and petroleum. Geology 1:211–238Google Scholar
  18. Dullien FAL, El-Sayed MS, Batra VK (1977) Rate of capillary rise in porous media with nonuniform pores. J Colloid Interf Sci 60:497–506CrossRefGoogle Scholar
  19. Durand B (1980) Kerogen insoluble organic matter from sedimentary rocks. Technip, ParisGoogle Scholar
  20. Farmer VC, Morrison RI (1964) Lignin in Sphagnum and Phragmites and in peats derived from these plants. Geochim Cosmochim Acta 82:1537–1546CrossRefGoogle Scholar
  21. Fein JB (1991) Experimental-study of aluminum-oxalate complexing at 80 °C—implications for the formation of secondary porosity within sedimentary reservoirs. Geology 19:1037–1040CrossRefGoogle Scholar
  22. Fengel D, Wegener G (1984) Wood chemistry, ultrastructure and reactions. Walter de Gruyter, BerlinGoogle Scholar
  23. Gibson DL (1985) Pyrite-organic matter relationships currant bush limestone, Georgina basin, Australia. Geochim Cosmochim Acta 49:989–992CrossRefGoogle Scholar
  24. Gomez-Heras M, Smith BJ, Fort R (2006) Surface temperature differences between minerals in crystalline rocks implications for granular disaggregation of granites through thermal fatigue. Geomorphology 78:236–249CrossRefGoogle Scholar
  25. Guardiola F, Boatella J, Codony R (2002) Determination of cholesterol oxidation products by gas chromatography. In: Guardiola F, Dutta PC, Codony R, Savage GP (eds) Cholesterol and phytosterol oxidation products analysis, occurrence and biological effects. AOCS Press, ChampaignGoogle Scholar
  26. Hall K, Lindgren BS, Jackson P (2005) Rock albedo and monitoring of thermal conditions in respect of weathering some expected and some unexpected results. Earth Surf Process Land 30:801–811CrossRefGoogle Scholar
  27. Hatcher PG, Lerch HE, Kotra RK, Verheyen TV (1988) Pyrolysis GC–MS of a series of degraded woods and coalified logs that increase in rank from peat to subbituminous coal. Fuel 67:1069–1075CrossRefGoogle Scholar
  28. Jimenez-Gonzalez I, Scherer GW (2004) Effect of swelling inhibitors on the swelling and stress relaxation of clay bearing stones. Environ Geol 46:364–377CrossRefGoogle Scholar
  29. Klemm W, Siedel H (2002). Evaluation of the origin of sulphate compounds in building stone by sulphur isotope ratio. In: Siegesmund S, Weiss T, Vollbrecht A (eds) Natural stone, weathering phenomena. Conservation strategies and case studies. Geol Soc London Spec Publ 205 pp 419–430Google Scholar
  30. Low MJD, Glass AS (1989) The assignment of the 1600 cm−1 band of carbons. Spectrosc Lett 22:417–429CrossRefGoogle Scholar
  31. Moens L, Roos P, Derudder J, Hoste J, Depaepe P, Vanhende J, Marechal R, Waelkens M (1988) White marble from Italy and Turkey—an archaeometric study based on minor-element and trace-element analysis and petrography. J Radioanal Nucl Chem 123:333–348CrossRefGoogle Scholar
  32. Munsell, A.H. (1975) Soil Color Charts. Macbeth a Division of Kollmorgen Corporation. Baltimore, MarylandGoogle Scholar
  33. Pye K, Schiavon N (1989) Cause of sulphate attack on concrete, render and stone indicated by sulphur isotope ratios. Nature 342(6250):663–664CrossRefGoogle Scholar
  34. Quirico E, Rouzaud JN, Bonal L, Montagnac G (1995) Maturation grade of coals as revealed by Raman spectroscopy. Progress and problems. Spectrochim Acta Part A-Mol Biomol Spectrosc 10(61):2368–2377Google Scholar
  35. Rosenfeld A, Kak AC (1982) Digital picture processing. Academic Press, New YorkGoogle Scholar
  36. Sanchez-Moral S, Fernandez-Cortes A, Cañaveras JC, Elez J, Saiz-Jimenez C (2011) Salt damage and microclimate in the Postumius Tomb, Roman Necropolis of Carmona, Spain. Environ Earth Sci 63:1529–1543CrossRefGoogle Scholar
  37. Scherer GW (1999) Crystallization in pores. Cement Concr Res 29:1347–1358CrossRefGoogle Scholar
  38. Schiavon N (2002) Biodeterioration of calcareous and granitic building stones in urban environments. In: Siegesmund S, Weiss T, Vollbrecht VA (eds) Natural stone, weathering phenomena, conservation strategies and case studies. Geol Soc London Spec Publ 205, pp 195–206Google Scholar
  39. Schnitzer M, Griffith SM (1975) Novel method for estimating hydrogen bonded CO2H groups in humic substances. Can J Soil Sci 55:491–493CrossRefGoogle Scholar
  40. Siegesmund S, Weis T, Ullemeyer K, Tschegg EK (2000) Physical weathering of marbles caused by anisotropic thermal expansion. Int J Earth Sci 89:170–182CrossRefGoogle Scholar
  41. Siegesmund S, Török A, Hüpers A, Chr Müller, Klemm D (2007) Mineralogical, geochemical and microfabric evidences of gypsum crusts: a case study from Budapest. Environ Geol 52:385–397CrossRefGoogle Scholar
  42. Simoneit BRT, Mazurek MA (1982) Organic matter of the troposphere-II natural background of biogenic lipid matter in aerosols over the rural western United States. Atmos Environ 16:2139–2159CrossRefGoogle Scholar
  43. Stránský K, Streibl M, Herout V (1967) On natural waxes VI distribution of wax hydrocarbons in plants at different evolutionary levels. Collect Czech Chem C 32:3213–3220CrossRefGoogle Scholar
  44. Surdam RC, Crossey LJ (1985) Organic inorganic reactions during progressive burial—key to porosity and permeability enhancement and preservation. Philos Trans R Soc Lond A 315:135–156CrossRefGoogle Scholar
  45. Thierry J, Wilde S (1990) Bathonian-Callovian middle jurassic ammonite faunas of the Northwest Iberian ranges biostratigraphy and palaeobiogeography. Cuad Geol Iberica 14:143–156Google Scholar
  46. Van Krevelen DW (1950) Graphical-statistical method for the study of structure and reaction processes of coal. Fuel 29:269–284Google Scholar
  47. Weiss T, Siegesmund S, Kirchner D, Sippel J (2004) Insolation weathering and hygric dilatation two competitive factors in stone degradation. Environ Geol 46:402–413CrossRefGoogle Scholar
  48. Wiley J (1986) 130 K mass spectra database, John Wiley licensed to Hewlett-Packard companyGoogle Scholar
  49. Zhang Y, Zeng J, Yu B (2009) Experimental study on interaction between simulated sandstone and acidic fluid. J Petrol Sci 6:8–16CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Javier Garcia-Guinea
    • 1
    Email author
  • Lorena Recio-Vazquez
    • 1
  • Gonzalo Almendros
    • 1
  • David Benavente
    • 2
  • Virgilio Correcher
    • 3
  • Antonio Perez-Garcia
    • 4
  • Sergio Sanchez-Moral
    • 1
  • Angel Fernandez-Cortes
    • 1
  1. 1.Museo Nacional de Ciencias NaturalesCSICMadridSpain
  2. 2.Unidad Asociada UA-CSIC. Dpto. Ciencias de la Tierra y del Medio AmbienteUniversidad de AlicanteAlicanteSpain
  3. 3.Dpto Dosimetría de RadiacionesCIEMATMadridSpain
  4. 4.Dpto. Ciencias de la TierraUniversidad de ZaragozaZaragozaSpain

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