<strong>Stone</strong> Decay 23have appeared determined to see bacteria and nothing else. A troublingnumber <strong>of</strong> authors have noted high numbers <strong>of</strong> bacteria in decayingstone, in comparison to low numbers in sound stone, and have concludedthat the bacteria cause the decay. However, an alternative explanationcould be that decayed stone presents a preferred habitat for the bacteria.Bacteria that attack stone chemically fall into two groups: autotrophicbacteria derive their carbon from carbon dioxide (CO 2 ), and mayderive their energy from light (photolithotrophs) or from chemical redoxreactions (chemolithotrophs). Heterotrophic bacteria, by contrast, utilizeorganic compounds on the stone to derive their carbon. Autotrophic bacteriainclude those that are capable <strong>of</strong> oxidizing sulfur and nitrogen compoundsto produce sulfuric acid and nitric acid, respectively. They are onemore means, therefore, by which air pollutants such as sulfur dioxideand nitrogen oxide are turned into sulfates and nitrates. This underlinesthe difficulty <strong>of</strong> separating out the individual causes <strong>of</strong> stone decay; severaldifferent factors may play integral roles in the overall decay process.The question remains <strong>of</strong> whether bacteria or catalyzing metal compounds,for example, are the main routes <strong>of</strong> sulfate production. However,if oxidation by both bacteria and metal compounds is rapid bycomparison with the rate at which sulfur dioxide arrives at the stonesurface, then the arrival rate will be the rate-determining step, not theroute taken. The synergistic effects <strong>of</strong> air pollution and bi<strong>of</strong>ilm formationhave been researched, with the finding that there is strong evidencethat bi<strong>of</strong>ilms enhance the absorption <strong>of</strong> air pollutants (Young 1996;Mansch and Bock 1998).Heterotrophic bacteria produce chelating agents and organicacids that are weaker than the inorganic acids produced by the sulfuroxidizingand nitrifying bacteria. They have received comparatively littleattention, but their role in deterioration is well established nonetheless(Lewis, May, and Bravery 1988; Saarela et al. 2004; Gorbushina 2007;Maruthamuthu et al. 2008).Recent work on bacteria has helped to quantify the effect theyhave on the dissolution <strong>of</strong> limestone, with one example showing a tw<strong>of</strong>oldincrease in the laboratory dissolution rate compared to control limestonesamples (McNamara et al. 2005). Bacteria typically produce slimeor extracellular polymeric substances (EPS) as part <strong>of</strong> a complex bi<strong>of</strong>ilmmade up <strong>of</strong> polysaccharides, water, and proteins that has been shown tochange the dissolution rate and dissolution pit morphology on samples <strong>of</strong>limestone (Perry et al. 2004). Damage from bacteria in the field has beendescribed by McNamara and others (2006) and Mansch and Bock (1998).Biodeterioration studies <strong>of</strong> important cave painting sites such asAltamira have resulted in recent advances in understanding. <strong>Research</strong>ershave found that cyanobacteria and algae (phototrophs) and networks <strong>of</strong>heterotrophic bacteria increase stone deterioration through their metabolicproducts, biomediated dissolution, and mechanical alteration, suchas scaling (Cañaveras et al. 2001). As expected, the control <strong>of</strong> moisture,food, and light levels appears to be the most effective prevention method(Dornieden, Gorbushina, and Krumbein 2000; Zammit et al. 2008).Environmental control <strong>of</strong> cave environments has proven to becomplex and controversial, as in the cave at Lascaux, where efforts to
24 Chapter 1limit the introduction <strong>of</strong> fungal strains through the use <strong>of</strong> a formalde -hyde foot-wash treatment for visitors resulted in the growth <strong>of</strong> aformaldehyde-resistant strain <strong>of</strong> white Fusarium solani fungus (Bastianet al. 2007; Dupont et al. 2007; Jurado et al. 2009; Bastian andAlabouvette 2009; Bastian et al. 2009; Bastian, Alabouvette, and Saiz-Jimenez 2009). This condition may have been exacerbated by the installation<strong>of</strong> a new ventilation system (Brunet, Malaurent, and Lastennet 2006;Lacanette et al. 2009). Computer modeling <strong>of</strong> the airflow at the Lascauxcave suggests that reducing the airflow may help avoid future damage(Malaurent et al. 2007).The role <strong>of</strong> halophilic microbes (mostly archaea, with some bacteria)is important in stone decay (Laiz et al. 2000; Saiz-Jimenez and Laiz2000). A significant and open question is if hydroscopic salts may raisemoisture levels to the point where halophilic microbes increase in abundance,setting the stage for further microbial development <strong>of</strong> adjacentareas <strong>of</strong> stone.Differential StressWhile air pollution, salts, and biodeterioration capture the lion’s share<strong>of</strong> attention, there are advances in our understanding <strong>of</strong> other, <strong>of</strong>tenrelated decay mechanisms that are worth some consideration. Reviewingthe recent literature on stone conservation, it is clear that there is animportant trend in decay mechanism research that is focusing on whatis called here (for want <strong>of</strong> a better term) “differential stress.” This decaymechanism includes the effects <strong>of</strong> wet/dry cycling, clay swelling, differentialhygric stress, differential thermal stress, and stress from differentialexpan sion rates <strong>of</strong> material in pores (such as salts or organic material)versus in the stone. The general idea is that treatments, salts, water films,or bi<strong>of</strong>ilms—anything that causes the stone surface to react differentlythan the interior—can result in a shear stress, crack propagation, and,eventually, surface parallel detachment (e.g., flaking). For example, significantshear stress is generated when, during a brief afternoon rain, thesurface <strong>of</strong> a clay-containing stone swells, while the interior <strong>of</strong> the stoneremains dry (Doehne et al. 2005). This would be considered an example<strong>of</strong> differential hygric stress and is typically found on the corners <strong>of</strong> stonessuch as Sydney sandstone and Portland brownstone. As mentioned earlier,sodium chloride expands at approximately five times the rate <strong>of</strong> calcite atsurface temperatures, so decay in limestone from this mechanism wouldbe an example <strong>of</strong> stress induced by differential thermal expansion (Nocita1987; Holmer 1998; Smith et al. 2005). Note that salts naturally tend toaccumulate near the stone surface, setting up differences in how the twoparts <strong>of</strong> the stone (surface and interior) react to environmental changes.Modeling has shown that there may be a particular depth beneath thestone surface where moisture is present and salts may accumulate(Snethlage and Wendler 1997). This depth is <strong>of</strong>ten the same as the thickness<strong>of</strong> stone flakes or scales. Differential thermal expansion stresses mayalso be induced at the interface between minerals having different colors,for instance in granites exposed to direct sunlight (Casta 1988). Fieldmeasurements <strong>of</strong> stone surfaces show that rapid thermal variations aremore common than previously thought (Molaro and McKay <strong>2010</strong>).
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References 83ed. D. Decrouez, J. Ch
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References 85Balboni, E., R. M. Esp
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References 87Bläuer, C., and A. Ku
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References 89carried out on Lecce s
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References 91Charola, A. E. 1995. W
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References 93Davis, K. J., and A. L
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References 95Doehne, E., and S. Pin
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References 97Facaoaru, I., and C. L
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References 99Buildings and Monument
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References 101Historia. http://www.
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References 103Poland, ed. J. W. Luk
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References 119Paradise, T. R. 2002.
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References 121of porous stones: A u
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References 123Rodríguez-Navarro, C
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References 125Sawdy, A., A. Heritag
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References 127Siedel, H. 2008. Salt
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References 137Whitley, D. S. 2005.
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References 139Zezza, F. 1990. Compu
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Index 153calcium hydroxide (slaked
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Index 155hexafluoropropene-vinylide
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Index 157research needed on, 55-56w
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About the AuthorsEric Doehne holds