The society has become increasingly interested in using natural products over chemicals for cleaning activities. In this study, the cleaning potential of formulations embedded in a hydrogel matrix and composed respectively of essential oils (EOs) of Origanum vulgare, Thymus vulgaris, and Calamintha nepeta, and their respective main active components (EO-ACs), viz., Carvacrol, Thymol, and Pulegone, on a phototropic biofilm growing on granite was investigated. In addition, and for comparative purposes, analysis with the combination of the three EOs, the combination of the three EO-ACs, and Preventol RI-80^® (one of the most effective commercial cleaning agents based on quaternary ammonium salts) in all three cases embedded in a hydrogel matrix, as well as only the hydrogel matrix, distilled water, and Preventol RI-80^®, in both latter cases applied with brush, were also studied. The cleaning effect of the treatments was assessed immediately after the treatment and after one and two weeks by color spectrophotometry, a reliable tool to evaluate the presence and vitality of the phototrophs and the cleaning effectiveness in granite. C. nepeta and its active component Pulegone proved to be the most effective and yielded similar results, comparable to those of uncolonized granite, and better than those obtained with Preventol RI-80^® applied with brush (most common way), especially at the end of the experiment. These promising first results support the suitable use of the phytochemical compounds used on phototrophs field where there are still few published studies and encourage further investigation toward the evaluation of their exhibited biocidal activity.

In this work, we investigated the potential of PVA-borax hydrogel for cleaning limestones and the dependence of the cleaning on the porosity of the rock and on the action time of the hydrogel treatment. Towards this goal, we used a nuclear magnetic resonance (NMR) spectrometer, developed for non-invasive and non-destructive applications on cultural heritage. T₂-NMR parameters were quantified on different samples of Lecce stone and Travertine cut perpendicular (Pe) and parallel (Pa) to the bedding planes under different experimental conditions: untreated samples, treated with Paraloid B72 and cleaned with PVA-PEO-borax hydrogel applied for 4 min and 2 h. The T₂ results suggest that the effectiveness of the cleaning strongly depended on the porosity of the stones. In Lecce stone, the hydrogel seemed to eliminate both the paramagnetic impurities (in equal measure with 4 min and 2 h treatment) and Paraloid B72. In Travertine Pe, characterized by a smaller pore size compared to Lecce stone, no significant effects were found regarding both the cleaning and the treatment with Paraloid B72. In Travertine Pa, characterized by a larger pore size than the other two samples, the hydrogel seemed to clean the paramagnetic agents (it worked better if applied for a longer time) but it did not appear to have any effect on Paraloid B72 removal.

Currently, one of the most important challenges for the conservation of stone artworks is the removal of metal corrosion products on their surfaces. Traditional cleaning methods, which typically involve the application of aqueous solutions containing chelating agents capable of complexing these metal ions, have shown some weaknesses. These weaknesses become apparent when such methods are applied to statues and other vertical surfaces or when aiming to limit the cleaning process to a specific area with controlled application times. Furthermore, the porosity of the stone surface plays a role concerning the cleaning efficiency. To address these issues, chelating agents can be incorporated into gel-like materials. This study is a proof of concept to evaluate the cleaning efficacy of various gel formulations composed of polyvinyl alcohol (PVA), borax (B), and agarose (AG), loaded with two chelators: ethylenediaminetetraacetic acid (EDTA) and potassium sodium tartrate (PST or Rochelle salt). Three types of carbonate stones (travertine, Lecce stone, and Carrara marble) characterized by different porosities were artificially stained with copper sulphates and treated with the different PVA-B-AG formulations. The effectiveness of the treatment was directly monitored on the stones using a multi-technique approach that included scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and non-invasive portable nuclear magnetic resonance (NMR). Additionally, the rheological properties of the gels were investigated, and the Fourier transform infrared attenuated total reflection spectroscopy (FTIR ATR) was used to analyse the chemical structure of the gel before and after treatment, aiming to understand the changes induced by the cleaning process.

Natural derivatives, such as essential oils, are presented as an alternative to classical biocides to the treatment of biocolonization. Thus, in this work, the cleaning and biocidal potential of some natural derivatives towards two natural biofilms’ growth on the same granite wall, with different microbial composition, was evaluated. For this purpose, three essential oils (EOs) (from Origanum vulgare, Thymus vulgaris and Calamintha nepeta) and their main active principles (APs) (carvacrol, thymol and R-(+)-pulegone, respectively) were embedded in a hydrogel matrix, with different combinations of EOs and APs, in order to evaluate the synergistic action of different actives. For comparative purposes, pure hydrogel and a mechanical method (brushing) were also used. Colorimetric measurements and chlorophyll a fluorescence analyses were performed to evaluate the cleaning action of the treatments on the biofilms. Overall, the EOs and APs present in the hydrogel proved to be reliable treatments to limit natural biocolonization, with O. vulgare being one of the most effective treatments in combination with other compounds, due to the majority presence of carvacrol. Moreover, the effect of the different treatments strictly depended on the biofilm in question, as well as its ability to adhere to the substrate.