Micro-and macroscale experiments which document the dynamics of salt damage to porous stone have yielded data which expose weaknesses in earlier interpretations. Previously unexplained differences are found in crystal morphology, crystallization patterns, kinetics and substrate damage when comparing the growth of mirabilite (Na 2 SO 4 . 10H 2 O) and thenardite (Na 2 SO 4 ) versus halite (NaCl). The crystallization pattern of sodium sulphate was strongly affected by relative humidity (RH), while a lesser RH effect was observed for sodium chloride. Macroscale experiments confirmed that mirabilite (crystallizing at RH>50 per cent) and thenardite (crystallizing at RH<50 per cent) tend to form subflorescence in highly localized areas under conditions of constant RH and temperature. This crystallization pattern was more damaging than that of halite, since halite tended to grow as efflorescence or by filling the smallest pores of the stone in a homogeneous fashion, a result which contradicts Wellman and Wilson's theoretical model of salt damage. Low RH promoted rapid evaporation of saline solutions and higher supersaturation levels, resulting in the greatest damage to the stone in the case of both sodium sulphate and sodium chloride crystallization. At any particular crystallization condition, sodium chloride tended to reach lower supersaturation levels (resulting in the crystallization of isometric crystals) and created negligible damage, while sodium sulphate reached higher supersaturation ratios (resulting in non-equilibrium crystal shapes), resulting in significant damage. ESEM showed no damage from sodium sulphate due to hydration. Instead, after water condensation on thenardite crystals, rapid dissolution followed by precipitation of mirabilite took place, resulting in stone damage by means of crystallization pressure generation.It is concluded that salt damage due to crystallization pressure appears to be largely a function of solution supersaturation ratio and location of crystallization. These key factors are related to solution properties and evaporation rates, which are constrained by solution composition, environmental conditions, substrate properties, and salt crystallization growth patterns.When combined with a critical review of salt damage literature, these experiments allow the development of a model which explains variations in damage related to combinations of different salts, substrates and environmental conditions.

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Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO 3 polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone.The study of bacterially induced and mediated mineralization is an emerging interdisciplinary research area (see references 6, 28, and 32 for recent reviews on the topic). Bacterially induced precipitation of calcium carbonate, the so-called "carbonatogenesis" (21, 51), has drawn much attention in recent decades because of its numerous implications. These include (i) atmospheric CO 2 fixation through carbonate sediment formation and lithification (22,29,36,48,49,59,65) and dolomite precipitation (76, 93), (ii) solid-phase capture of inorganic contaminants (95), (iii) the production of pathological concretions such as gallstones and kidney stones in humans (41,44,46), and (iv) understanding possible extraterrestrial biological processes like those of Martian carbonate-producing bacteria (58, 88). There is extensive literature on bacterial involvement in carbonate precipitation both in nature and in the laboratory

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The fundamental behavior of sodium sulfate crystallization and induced decay in concrete and other building materials is still poorly understood, resulting in some misinterpretation and controversy. We experimentally show that under real world conditions, both thenardite (Na 2 SO 4 ) and mirabilite (Na 2 SO 4 Á10H 2 O) precipitate directly from a saturated sodium sulfate solution at room temperature (20°C). With decreasing relative humidity (RH) and increasing evaporation rate, the relative proportion of thenardite increases, with thenardite being the most abundant phase when precipitation occurs at low RH in a porous material. However, thenardite is not expected to crystallize from a solution at T < 32.4°C under equilibrium conditions. Non-equilibrium crystallization of thenardite at temperatures below 32.4°C occurs due to heterogeneous nucleation on a defect-rich support (i.e., most porous materials). Anhydrous sodium sulfate precipitation is promoted in micropores due to water activity reduction. Fast evaporation (due to low RH conditions) and the high degree of solution supersaturation reached in micropores before thenardite precipitation result in high crystallization pressure generation and greater damage to porous materials than mirabilite, which crystallizes at lower supersaturation ratios and generally as efflorescence. Data from the environmental scanning electron microscope (ESEM) show no hydration phenomena following wetting of thenardite; instead, thenardite dissolution occurs, followed by thenardite plus mirabilite crystallization upon drying. These results offer new insight into how damage is caused by sodium sulfate in natural geological, archaeological, construction and engineering contexts. They also help explain some of the controversial results of various commonly used sodium sulfate crystallization tests. D

Alcohol dispersions of Ca(OH)2 nanoparticles, the so-called nanolimes, are emerging as an effective conservation material for the consolidation of stone, mortars, and plasters present in old masonry and/or mural paintings. To better understand how this treatment operates, to optimize its performance and broaden its applications, here we study the nano and microstructural characteristics, carbonation behavior, and consolidation efficacy of colloidal alcohol dispersions of Ca(OH)2 nanoparticles produced by both homogeneous (commercial nanolime) and heterogeneous phase synthesis (aged slaked lime and carbide lime putties). We observe that the alcohol not only provides a high colloidal stability to Ca(OH)2 particles, but also affects the kinetics of carbonation and CaCO3 polymorph selection. This is due to the pseudomorphic replacement of Ca(OH)2 particles by calcium alkoxides upon reaction with ethanol or 2-propanol. The extent of this replacement reaction depends on Ca(OH)2 size and time. Hydrolysis of alkoxides speeds up the carbonation process and increases the CaCO3 yield. The higher degree of transformation into calcium alkoxide of both the commercial nanolime and the carbide lime fosters metastable vaterite formation, while calcite precipitation is promoted upon carbonation of the aged slaked lime due its lower reactivity, which limits calcium alkoxide formation. A higher consolidation efficacy in terms of strength gain of treated porous stone is achieved in the latter case, despite the fact that the carbonation is much faster and reaches a higher yield in the former ones. Formation of alkoxides, which has been neglected in previous studies, needs to be considered when applying nanolime treatments. These results show that the use Ca(OH)2 nanoparticle dispersions prepared with either aged slaked lime or carbide lime putties is an economical and effective conservation alternative to commercial nanolimes produced by homogeneous phase synthesis. Ultimately, this study contributes to show that nanotechnology can help saving the built and sculptural heritage.

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