Damaging and protective interactions of lichens and biofilms on ceramic dolia and sculptures of the International Museum of Ceramics, Faenza, Italy.

Although ceramic objects are an important part of the worldwide cultural heritage, few investigations on the effects of lithobiontic growth on their outdoor conservation are available in the literature. Many aspects of the interaction between lithobionts and stones are still unknown or strongly debated, as in the case of equilibria between biodeterioration and bioprotection. This paper describes research on the colonization by lithobionts on outdoor ceramic Roman dolia and contemporary sculptures of the International Museum of Ceramics, Faenza (Italy). Accordingly, the study i) characterized the mineralogical composition and petrographic structure of the artworks, ii) performed porosimetric measurements, iii) identified lichen and microbial diversity, iv) elucidated the interaction of the lithobionts with the substrates. Moreover, v) the measurements of variability in stone surface hardness and in water absorption of colonized and uncolonized areas were collected to assess damaging and/or protective effects by the lithobionts. The investigation showed how the biological colonization depends on physical properties of the substrates as well on climatic conditions of environments in which the ceramic artworks are located. The results indicated that lichens Protoparmeliopsis muralis and Lecanora campestris may have a bioprotective effect on ceramics with high total porosity and pores with very small diameters, as they poorly penetrate the substrate, do not negatively affect surface hardness and are able to reduce the amount of absorbed water limiting the water ingress. By contrast, Verrucaria nigrescens, here widely found in association with rock-dwelling fungi, deeply penetrate terracotta causing substrate disaggregation, with negative consequences on surface hardness and water absorption. Accordingly, a careful evaluation of the negative and positive effects of lichens must be carried out before deciding their removal. Regarding biofilms, their barrier efficacy is related to their thickness and composition. Even if thin, they can impact negatively on substrates enhancing the water absorption in comparison to uncolonized parts.

Deterioration and discoloration of historical protective treatments on marble.

This study integrates the complex research conducted on the sources of brown discolorations that occur on marble statues (fifteenth century) of the Church of Orsanmichele in Florence (Italy). They underwent conservative interventions in the past and the brownish discolorations on their surfaces strongly altered the clear tone of the marble. In this study, Carrara marble model specimens were treated with organic and inorganic substances (non-pasteurised milk; linseed oil; walnut oil; ammonium oxalate; microcrystalline wax; beeswax; milk + linseed oil; and milk + ammonium oxalate + linseed oil) to simulate their effects on the stone. Some of the substances were commonly used in the past (as on the Orsanmichele statues) but most of them are still used in many countries. The treated specimens were exposed to natural and artificial ageing. The main results of the research were (i) the specimens treated with linseed oil, milk + linseed oil, and milk + linseed oil + ammonium oxalate showed a severe change of colour after either artificial or natural ageing; (ii) an extensive polymerisation of the organic substances occurred; (iii) calcium oxalate and several oxidised diacylglycerols (DAGs) and triacylglycerols (TAGs) were the last chemical products of the oxidation processes induced by ageing; (iv) Maillard reaction, producing brownish coloration, likely occurred in specimens containing milk as a result of the interaction between sugars and proteins.

A follow-up on the analytical study of discolouration of the marble statues of Orsanmichele in Florence.

The research complements the complex study carried out to understand the source of brown discolourations of ten marble statues in the Church of Orsanmichele in Florence, Italy. Originally located in exterior niches, the statues were restored to reverse the extensive alterations they had undergone throughout the centuries. One of the major alterations was the application of a dark brown patina that dated just after 1789. After the statues were placed indoors, brownish discolourations started to appear on their surfaces. Cross sections were examined using FTIR mapping and immunological methods. In parallel, the pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) data already obtained from the statues' scrapings were compared with data from aged casein films applied to microscope glass slides and aged milk-treated marble. All the statues had been treated with milk-based substances before the time the bronze patina was applied. The values of temperature and illumination of the room were important factors in the ageing of organic substances and in the formation of calcium oxalates. It is likely that products of thermo-oxidation and photo-oxidation of the oils together with the oxalates caused the darkening. The marble samples corresponded to a Lunense provenance.

Performance evaluation of two protective treatments on salt-laden limestones and marble after natural and artificial weathering.

Salt crystallization is a major damage factor in stone weathering, and the application of inappropriate protective products may amplify its effects. This research focuses on the evaluation of two protective products' performance (organic polydimethylsiloxane and inorganic ammonium oxalate (NH4)2(COO)2·H2O) in the case of a salt load from behind. Experimental laboratory simulations based on salt crystallization cycles and natural weathering in an urban area were carried out. The effects were monitored over time, applying different methods: weight loss evaluation, colorimetric and water absorption by capillarity measurements, stereomicroscope observations, FTIR and SEM-EDS analyses. The results showed minor impact exerted on the short term on stones, particularly those treated with the water repellent, by atmospheric agents compared to salt crystallization. Lithotypes with low salt load (Gioia marble) underwent minor changes than the heavily salt-laden limestones (Lecce and Ançã stones), which were dramatically damaged when treated with polysiloxane. The results suggest that the ammonium oxalate treatment should be preferred to polysiloxane in the presence of soluble salts, even after desalination procedures which might not completely remove them. In addition, the neo-formed calcium oxalate seemed to effectively protect the stone, improving its resistance against salt crystallization without occluding the pores and limiting the superficial erosion caused by atmospheric agents.

Monitoring the performance of innovative and traditional biocides mixed with consolidants and water-repellents for the prevention of biological growth on stone.

In this study, some mixtures of consolidants or water-repellent products and biocides developed to prevent biological growth, were tested over time on three stone substrates with different bioreceptivity. The performance of both traditional (tetraethylorthosilicate, methylethoxy polysiloxane, Paraloid B72, tributyltin oxide, dibutyltin dilaurate) and innovative compounds (copper nanoparticles) was assessed using colour measurements, the water absorption by contact sponge method, and observation under stereo and optical microscopes. The application of the mixtures had also the purpose of controlling re-colonization on stone after a conservation treatment. The study site was the archaeological Area of Fiesole; the mixtures were applied in situ to sandstone, marble and plaster which had been cleaned beforehand. An innovative aspect of the study is that, by using non-invasive methods, it also permitted monitoring the mixtures' effectiveness in preventing biological growth. The monitoring results made it possible to assess the bioreceptivity of the treated stones (sandstone, marble, plaster) over a period of almost three years. The results showed that the mixtures of consolidants or water-repellent products with biocides were effective in preventing biological growth on both a substrate with low bioreceptivity like plaster and a substrate with high bioreceptivity such as marble. The innovative mixture of nano-Cu particles with a water-repellent yielded good results in terms of preventing biological colonization. Moreover, they apparently did not affect the substrates' colour. Mixtures of nano-Cu particles with a consolidant and a water-repellent hold great promise for preventing re-colonization of stone after conservation treatment.