Efficacy of Chitosan-Carboxylic Acid Hydrogels in Reducing and Chelating Iron for the Removal of Rust from Stone Surface.

In the field of stone conservation, the removal of iron stains is one of the most challenging issues due to the stability and low solubility of the ferrous species. In the present paper, three different chitosan-based hydrogels added with acetic, oxalic or citric acids are applied on different lithotypes, i.e., granite, travertine and marble, widely diffused in monumental heritages, and artificially stained by deposition of a rust dispersion. The reducing power of carboxylic acids is combined with the good chelating properties of chitosan to effectively remove rust from stone surfaces. As evidenced by colorimetry on three samples of each lithotype and confirmed by 1H-NMR relaxometry and SEM/EDS analyses, the chitosan-oxalic acid hydrogel shows the best performance and a single application of 24 h is enough to get a good restoration of the stone original features. Lastly, the chitosan-oxalic acid hydrogel performs well when a rusted iron grid is placed directly on the lithic surfaces to simulate a more realistic pollution. Current work in progress is devoted to finding better formulations for marble, which is the most challenging to clean or, with a different approach, to developing protective agents to prevent rust deposition.

Natural Deep Eutectic Solvents as Rust Removal Agents from Lithic and Cellulosic Substrates.

The peculiar physicochemical features of deep eutectic solvents (DESs), in particular their tunability, make them ideal media for various applications. Despite their ability to solubilize metal oxides, their use as rust removers from valuable substrates has not yet been thoroughly investigated. In this study, we chose three known DESs, consisting of choline chloride and acetic, oxalic or citric acid for evaluating their ability to remove corrosion products from a cellulose-based material as linen fabric and two different lithotypes, as travertine and granite. The artificial staining was achieved by placing a rusty iron grid on their surfaces. The DESs were applied by means of cellulose poultice on the linen fabrics, while on the rusted stone surfaces with a cotton swab. Macro- and microscopic observations, colorimetry and SEM/EDS analysis were employed to ascertain the cleaning effectiveness and the absence of side effects on the samples after treatment. Oxalic acid-based DES was capable of removing rust stains from both stone and cellulose-based samples, while choline chloride/citric acid DES was effective only on stone specimens. The results suggest a new practical application of DESs for the elimination of rust from lithic and cellulosic substrates of precious and artistic value.

Biodeterioration of stone monuments: Studies on the influence of bioreceptivity on cyanobacterial biofilm growth and on the biocidal efficacy of essential oils in natural hydrogel.

An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is crucial to consider the features of substrates on which biocides must be applied, to define the so-called bioreceptivity of the lithic faces. In this research five different lithotypes, namely Lecce stone, Travertine, Peperino, Serena stone, and Granite, have been used as substrates for the growth of cyanobacterial biofilms. Open porosity, hygroscopic properties, and roughness parameters have been investigated for each lithotype and correlated to the photosynthetic yields of the biofilms colonizing the different stones to propose an easy method to estimate stone bioreceptivity. Different levels of coverage of the stone surfaces have been accomplished in relation to the typology of lithotypes. To develop innovative restoration methodologies against biodeterioration of stone monuments, a hydrogel-biocide system has been optimized by using a polysaccharide dispersion as a matrix where to embed T. vulgaris essential oil (at 0.25 % or 0.1 %) or its main component thymol (at 0.18 % or 0.07 %). The efficacy and the effect of the innovative biocide have been evaluated combining microscopy, photosynthetic measurements, and colorimetric analyses and both the biocides (with T. vulgaris EO or thymol) showed to be highly effective against the cyanobacterial biofilms for at least six months from the treatment without inducing any significant alteration to the lithic surfaces. The efficacy of thymol alone allows to treat colonized surfaces with a single active ingredient, or at least a mixture thereof, much cheaper and reproducible. The results obtained in this work pave the way to develop a sustainable cleaning protocol to counteract the biodeterioration of stone monuments or historic buildings induced by the presence of phototrophic biofilms that endangered their conservation.

Noninvasive monitoring of moisture uptake in Ca(NO3)2 -polluted calcareous stones by 1H-NMR relaxometry.

NMR transverse relaxation time (T(2)) distribution of (1)H nuclei of water has been used to monitor the moisture condensation kinetics in Ca(NO(3))(2) · (4)H(2)O-polluted Lecce stone, a calcareous stone with highly regular porous structure often utilized as basic material in Baroque buildings. Polluted samples have been exposed to water vapor adsorption at controlled relative humidity to mimic environmental conditions. In presence of pollutants, the T(2) distributions of water in stone exhibit a range of relaxation time values and amplitudes not observed in the unpolluted case. These characteristics could be exploited for in situ noninvasive detection of salt pollution in Lecce stone or as damage precursors in architectural buildings of cultural heritage interest.

Nuclear magnetic resonance for cultural heritage.

Nuclear magnetic resonance (NMR) portable devices are now being used for nondestructive in situ analysis of water content, pore space structure and protective treatment performance in porous media in the field of cultural heritage. It is a standard procedure to invert T(1) and T(2) relaxation data of fully water-saturated samples to get "pore size" distributions, but the use of T(2) requires great caution. It is well known that dephasing effects due to water molecule diffusion in a magnetic field gradient can affect transverse relaxation data, even if the smallest experimentally available half echo time tau is used in Carr-Purcell-Meiboom-Gill experiments. When a portable single-sided NMR apparatus is used, large field gradients due to the instrument, at the scale of the sample, are thought to be the dominant dephasing cause. In this paper, T(1) and T(2) (at different tau values) distributions were measured in natural (Lecce stone) and artificial (brick samples coming from the Greek-Roman Theatre of Taormina) porous media of interest for cultural heritage by a standard laboratory instrument and a portable device. While T(1) distributions do not show any appreciable effect from inhomogeneous fields, T(2) distributions can show strong effects, and a procedure is presented based on the dependence of 1/T(2) on tau to separate pore-scale gradient effects from sample-scale gradient effects. Unexpectedly, the gradient at the pore scale can be, in some cases, strong enough to make negligible the effects of gradients at the sample scale of the single-sided device.

Large surface mapping by a unilateral NMR scanner.

The nuclear magnetic resonance (NMR) surface scanner, which provides images of sample surfaces larger than the probe dimension, has been realized using a single-sided device. Although conditioned by distortion effects originated by convolution between the sensitive volume of the probe and the space structures to be imaged, the scanner is able to provide images with good spatial resolution. The images obtained by the surface scanner can be made sensitive to relaxation parameters, magnetization or molecular self-diffusion; also, the dimension perpendicular to the sample surface can be scanned by varying the depth from which the probe detects the sample signal. It may scan surfaces arbitrarily large and with some degree of curvature. This aspect, together with the noninvasive characteristic of the apparatus, indicates that the surface scanner could be used profitably in the field of cultural heritage, where it could provide NMR maps of frescos, paintings on wood, marble artifacts, books and others.

Bayesian analysis of in vivo dynamic 13C-edited 1H images.

We propose an application of a Bayesian methodology to dynamic MR images of protons J-coupled to 13C nuclei for monitoring the in vivo 13C-glucose uptake of mouse brain. The very low population of these protons and the random noise make the analysis of these images extremely difficult. The proposed method restores the images and provides an "activation" map of the mouse brain by means of a hypothesis testing procedure. The restoration step is performed in the Bayesian framework so that among the other advantages of a stochastic approach, it is possible to model spatial and temporal information about neighboring pixels. This leads to a restoration procedure able to reduce the noise level while preserving the information about the edges of signal areas. Based on the restored images, the testing procedure provides us with a reliable map of pixels characterized by the 13C-glucose uptake.