Biodeterioration of Historic Buildings and Monuments

Growth of microorganisms on buildings of cultural heritage and historic monuments has aroused a great concern within last two decades. Microbial growth and various biochemical activities taking place on the surfaces of these buildings cause the damages such as discoloration and degradation .This may result less strong and aesthetically damaged buildings and monuments which almost losing their archeological importance as well. Microorganisms involving bacteria, Archea, fungi, actinomycetes and cyanobacteria, algae are mainly participating in these biodeterioration phenomena as they are forming biofilms on stones, painted buildings, archeological monuments, the major reason and the first step of the biodeterioration. It has been discovered that protozoa and other small animals are also participating in this process in lesser amounts. The interactions among these organisms within an association (since biofilms is a symbiotic association), can either enhance or retard the rate of biodeterioration. This article is an attempt to bring forward various situations and their respective locations that biodeterioration has been reported. Along with each and every location/construction, its causative agent (responsible microorganism/s), the damage which they have caused and preventive measures are included as much as possible.

Introduction
Taj Mahal is threatened by air pollution, Da Vincis Mona Lisa is cracking and Michel Anjalos David recently has to be cleaned. We have to understand that historic monuments buildings of archeological value, historic manuscripts are in danger for certain extent due to microbial activities which are caused by the biofilms grown on them. In the most simple form, this deterioration process caused by biological agents is basically called by Biodeterioration. Prior paying attention to the locations where Biodeterioration has taken place, lets see what is defined by biodeterioration?.... Biodeterioration can be defined as the harmful effect caused by the colonizing of microorganisms on a surface .this surface can be a surface of a building, monument or a stone. Microorganisms form biofilms on these surfaces after colonizing. Microorganisms within the biofilms structure known as endoliths are causing the damage. These may grow in cracks and pores within the material and may bore into rocks such as limestone. True endoliths, present within the rock itself rather than voids in the rock, are found in material such as soapstone are predominantly bacteria. Both historic and modern buildings are subjected to the deteriorative and degradative action of environment and living organisms which are generally reffered to as weathering. Biological and abiotic processes can occur concurrently, each contribute to the overall deleterious effect, and it can be difficult to determine the contribution of each.

However there is no doubt that biological processes (growth) have considerable impact on the soundness of structural materials.

General Mechanism of Biodeterioration

Microorganisms that colonize on building, monument or stone surfaces form biofilms. Biofilms are collections of bacterial cells on surfaces that are maintained by electrostatic forces and adhering exopolymers. Formation of biofilms begins with the initial adhesion of microorganisms to a surface. Division of attached cells produces micro colonies containing large amount of exopolymers separated by sparse areas relatively devoid of growth. Production of exopolymers and other exudates are stimulated in response to cellular density by cell- cell signaling. The exopolymers matrix is composed mainly of polysaccharides and serves a variety of functions such as providing protection from desiccation, radiation, erosion and disinfection as well as storage of organic carbon and nutrients. Additionally, the exopolymers matrix limits the rate of diffusion within the micro colonies, resulting the formation of microenvironments due to gradients in pH, O2, nutrients and organic carbon.

Deterioration of Stones of Archeological Value and Archeological Monuments made out of stones
In a general view point. Cyanaobacterial species and their role in biodegradation
Under this subtopic, group cyanobacteria would be discussed including their various genera and species and how they are participating in Biodeterioration process in a microbiological view point. Cyanobacteria colonize a wide variety of terrestrial habitats, including rocks, hot and cold desert crusts as well as modern buildings. The microbial community of both deteriorated and undeteriorated locations was dominated by Cyanobacteria. In undeteriorated locations the dominant organism was Anabaena cylindrica. A. cylindrica is a filamentous nitrogen-fixing cyanobacterium commonly found in freshwater. In deteriorated locations, the dominant organism was Chroococcidiopsis sp. Choococcidiopsis is a unicellular cyanobacterium that is also tolerant of harsh environments (e.g., both hot and cold deserts). Differences between the communities suggest that microbial indicators could provide a simple and rapid means for early detection of stone biodeterioration. The microbial community from deteriorated locations was more diverse than that from undeteriorated locations. In a research preformed on this fact, nine different microbial taxa were found . Phormidium murrayi was observed to make up approximately the same percentage of the community (16.4%) as on undeteriorated stone. P. murrayi is a filamentous Cyanobacterium that is tolerant of extreme temperatures and radiation. Chroococcidiopsis sp. was the most

common organism found on the deteriorated stone (61.8% of clones). A. cylindrica was not detected on deteriorated stone. The differences observed between the microbial communities on deteriorated and undeteriorated stone present several possibilities for the development of a microbial indicator of deterioration. Dominance of the community by A. cylindrica or Choococcidiopsis sp. could indicate, respectively, either non-deteriorating or deteriorating communities. Another potential indicator is the difference in diversity between the two communities. Presumably, the more porous and rough surface of the deteriorated stone provides numerous microhabitats or niches in which the additional taxa can survive. The presence of consistently higher levels of microbial diversity on deteriorated stone could be an indicator of deterioration. A third possibility is that one of the less abundant taxa found on deteriorated stone (e.g., Xylophilus ampelinus or Symploca atlantica) is a good indicator of deterioration.

The role of cyanobacteria in biodegradation of the surfaces of historic buildings has been subjected to several studies recently. They are generally adapted to resist adverse conditions because of their thick outer envelope and the presence of protective pigments. It was suggested that chasmoendolithic cyanobacteria, (those who colonize and grow within fissures) contribute to the decay of calcareous stones by exerting pressure from within the stone as a result of water uptake, expansion of cell mass and the precipitation of carbonates and oxalates around the cell. The resulting opening of the fissure allows the entry of dust, pollen grains, small animals such as mites, and the increasing pressure of the internal superficial layer of the structure leads to its detachment. (spalling).

The precipitation of calcium salts on cyanobacterial cells growing on limestone suggests the migration of calcium from neighboring sites and is an important mechanism of stone degradation by these organisms. Photosynthetic organisms deposit CaCO3 in the presence of light and solubilize it at night due to a change in carbonate concentrations. The cyanobacterium SynechococcusGL24 for an example pocesses an external S-layer that binds calcium ions. These complexes with carbonate ions at pH > 8.3 , which are readily produced, when bicarbonate ions are absorbed by the cells are acted upon by carbonic anhydrase and converted into CO2 and OH-. The OH- ions are released and concentrated around the cells producing a localized microenvironment of high pH. It has been shown that Synechococcus cells have become encrusted with calcite within 8 h under the correct conditions and must continually shed patches of mineralized S-layer to remain viable. In order to remain alive, they must slough off this mineralized S-layer, allowing the whole process to be repeated. This mobilization of calcium ions and the trapping of released particles of calcite in the gelatinous sheaths of cyanobacterial cells lead to degradation of calcareous stone. The increase in local pH levels in phototrophic biolms throws some doubts on the acid degradation suggested to be produced by algae and cyanobacteria, eventhough it has been shown that Cyanothece carries out mixed acid fermentation and could, therefore, induce acid degradation of stone. However, there is little evidence that cyanobacteria produce acids in-situ, and suggested that it is the associated heterotrophic bacteria that lead to acid decay of calcareous materials in the presence of cyanobacteria, as also shown by Fungal components of biolms may act in a similar manner. On chemically polluted or painted buildings, however, nutrients for non-phototrophs are already present and heterotrophic bacteria could, indeed, be the primary colonizers. The role of cyanobacteria in the degradation of cultural heritage cannot be neglected. Since they are phototrophs and require no more than light, water, and mineral ions to grow, these microorganisms, along with algae, readily colonize the external surfaces of historic monuments and develop a biolm, which, in turn, alters the appearance of the building and serves as a substrate for the growth of other deteriogens. Both these and the cyanobacteria themselves can cause aesthetic, chemical, and physical decay. The detection and identication of this group of organisms is extremely important for the future study of the deteriogenic process and the development of control methods.

Control Measures
It has been suggested that heterotrophic bacteria, rather than phototrophs, may be primary colonizers of stone buildings. They demonstrated that fungal and bacterial growth was inhibited by the treatment of external walls with an algicidal substance (a copper-containing compound), even though the concentration of copper used was to alow for bacteriostatic and fungi static activity. This indicated that the inhibition of algal colonization reduced the growth of fungi and heterotrophic bacteria, and supports the accepted colonization sequence.

A research was performed to study the behavior of cyanobacteria that cause deterioration of Stone cultural heritage (outdoor monuments and stone works of art) in European countries of the Mediterranean Basin. A wide range of stone monuments in the Mediterranean Basin support considerable colonization of cyanobacteria and chlorophyta, showing notable biodiversity. About172 taxa have been described by different authors, including 37 genera of cyanobacteria and 48 genera of chlorophyta. The most wide spread and commonly reported taxa on the stone cultural heritage in the Mediterranean Basinare, among cyanobacteria, Gloeocapsa, Phormidium and Chroococcus and, among chlorophyta, Chlorella, Stichococcus and Chlorococcum. The results suggest that cyanobacteria and chlorophyta colonize a wide variety of substrata and that this is related primarily to the physical characteristics of the stone surface, micro climate and environmental conditions and secondarily to the lithotype.

Cyanobacteria on monuments Most of the works of art considered in this study were built in limestone(32%) and marble(30%). Travertine(7%) and dolomite(2%) were less represented lithotypes.The data on cyanobacteria occurring on stone monuments and works of art is rather wide. A total of 96 taxa of cyanobacteria were found.The genus Gloeocapsa was the most wide spread, occurring on 20 of the 45 monuments reported, on all substrata and represented by eight species. Cyanobacterial species from the genera Phormidium and Chroococcus were able to colonize five of the six stone substrata considered and they were represented by high species diversity: eight species of Phormidium and four species of Chroococcus were reported. Chroococcus species were detected colonizing 13 different monuments while Phormidium was found on 15 monuments. Pleurocapsa occurred on 13 monuments but only one species was identified, while the genus Scytonema occurred with five specie sand colonizing eight different monuments . Therefore, we can consider that Gloeocapsa, Phormidium and Chroococcus are the most common cyanobacterial genera on the monuments of the Mediterranean Basin. This is in accordance with Ortega Calvo etal. (1995), who stated that the most common species found on monuments located in Europe, America and Asia belong to the genera Gloeocapsa, Phormidium, Chroococcus and Microcoleus. These genera are ubiquitous and therefore their presence is not strictly related to a specific lithic substratum or climate. Tomaselli etal.(2000b) also found that the data reported in the literature did not establish a clear relationship between organisms and the nature of the substratum. Nevertheless, these authors contend that Phormidiumtenue, Phormidium autumnale and Microcoleus vaginatus prefer siliceous substrata.

Biodeterioration by Algae
Green algae on monuments A considerable number of green algae (chlorophyta) have adapted to life on land. The chlorophyta constitute the most common group of algae colonizing stone cultural heritage(Ortega-Calvo etal.,1993b).Most of these genera are soil algae. This is predictable, since the main source of biological colonization of stone is the surrounding soil, containing large numbers of many different types of bacteria, algae and fungi, which can contaminate the stone shortly after quarrying. Wind blown detritus or rising ground water in filtration may also be a source of stone inoculation (Koestler,2000). The genus Chlorella was the most widespread, occurring on 20 of the monuments reported, represented by four species and occurring on four different substrata. Stichococcus was found on 17 monuments and was also present on four substrata. Members of the chlorophyte genus Chlorococcum were detected on all the stone substrata considered, with the exception of dolomite, and this genus occurred on 15 distinct monuments. Therefore,we can consider that Chlorella, Stichococcus and Chlorococcum are the green algal genera most abundant on the monuments of the Mediterranean Basin. This is in fair agreement with Ortega-Calvo etal. (1995), who stated that Chlorella, Chlorococcum Klebsormidium and Trentepohlia can be readily observed in monuments located in Europe, America and Asia. However, it was not possible to establish a correlation between these genera and a specific substratum or climate. Klebsormidium, Trebouxia and Trentepohlia also showed a significant representation among the chlorophyte genera colonizing stone substrata in the Mediterranean Basin. The occurrence of Trebouxia and Trentepohlia indicates that these microalgae could be involved in the lichenization process leading to colonization by lichens. In fact, the genus Trebouxia occurs in approximately 20% of all lichens and has rarely been found freeliving. Regarding endolithic growth of green algae, Trentepohlia, Chorella and Klebsormidium were found growing under a black patina, probably a cryptoendolithic niche,in the OrdemdeSa oFranciscoChurch,Portugal(Pe reirade Oliveira, 2008;Pereira de Oliveira etal.,2008). Crypto endolithic growth of Stichococcus bacillaris was also observed in granite from the Cathedral of Toledo, Spain (Ortega-Calvo etal.,1995). Limestone was colonized by the highest number of taxa(34), followed by marble. Travertine and granite were colonized by about the same number of taxa although the number of monuments built of travertine(7%) was considerably lower than the number made of granite(18%). Nevertheless, the majority of the results suggest that green algae can colonize a wide variety of substrata and this is primarily related to the physical characteristics of the stone surface (porosity, roughness and permeability) and secondarily to the nature of the substratum.This is in accordance withTiano etal. (1995).

Damage
The presence of cyanobacterial and algal biofilms on stone surfaces can be considered bio deteriogenic, simply because of the aesthetic damage they cause, producing variously coloured patinas(Ortega-Calvo etal.,1995).These micro-organisms have an important role in the disfigurement of monuments and stone works of art Bio geophysical deterioration can be defined as the mechanical damage caused by exerted pressure during biological growth, resulting in surface detachment, superficial losses, or penetration and increased porosity This kind of deterioration also occurs due to the presence of cyanobacterial and algal biofilms that undergo large volume changes and exert considerable force through cycles of drying and moistening, loosening rock grains(Saiz-Jimenez,1999) .This can lead to the alteration of the stone spore-size distribution and result in changes of moisture circulation patterns and temperature response(Saiz-Jimenez,1999;Warscheid & Braams,2000). Furthermore, the formation of crusts induced by cyanobacterial and algal growth also results in longer moisture retention at the stone surface, increasing the stone colonization potential