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Physical Chemistry in Cultural Heritage

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (15 November 2021) | Viewed by 26350

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Prof. Dr. Maria Luisa Saladino

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STEBICEF Department, University of Palermo, Palermo, Italy
Interests: luminescent nanoparticles; mesoporous silica materials; controlled release systems; polymeric nanocomposites; innovative materials for conservation of cultural heritage; non invasive methods and multi
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Dr. Francesco Armetta

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STEBICEF Department, Università degli Studi diPalermo, Palermo, Italy
Interests: neutron techniques; statistical approaches; X-ray fluorescence; nanomaterials synthesis and characterization; archaeometallurgy

Special Issue Information

Dear Colleagues,

Recently, the application of chemistry to the knowledge of works of art and archaeological objects has played an important role in the conservation and restoration of the developed world's cultural heritage. From this point of view, the investigation of physico-chemical processes involving both natural and voluntary surface modification of artifacts need to be considered, especially the study of degradation processes and the application of new materials for restoration.

It is, thus, important for Molecules to dedicate a Special Issue to this field of research, since it is one of the interesting subjects of applied physical chemistry. This Special Issue will contain contributions discussing all the aspects that are broadly indicated by the keywords. Reviews articles by experts in the field of materials characterization and diagnostic and surface chemistry are welcome.

Prof. Dr. Maria Luisa Saladino
Dr. Francesco Armetta
Guest Editors

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Keywords

Physical chemistry methodologies
Non-invasive approaches
Smart materials for preventive conservation
In situ characterization
Interface phenomena
Degradation processes

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Published Papers (10 papers)

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13 pages, 3840 KiB

Open AccessArticle

Chemometric Tools to Point Out Benchmarks and Chromophores in Pigments through Spectroscopic Data Analyses

by Giulia Festa, Claudia Scatigno, Francesco Armetta, Maria Luisa Saladino, Veronica Ciaramitaro, Viviana Mollica Nardo and Rosina Celeste Ponterio

Molecules 2022, 27(1), 163; https://doi.org/10.3390/molecules27010163 - 28 Dec 2021

Cited by 17 | Viewed by 2628

Abstract

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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20 pages, 4149 KiB

Open AccessArticle

Attribution Markers and Data Mining in Art Authentication

by Barbara I. Łydżba-Kopczyńska and Janusz Szwabiński

Molecules 2022, 27(1), 70; https://doi.org/10.3390/molecules27010070 - 23 Dec 2021

Cited by 5 | Viewed by 2994

Abstract

Today’s global art market is a billion-dollar business, attracting not only investors but also forgers. The high number of forged works requires reliable authentication procedures to mitigate the risk of investments. However, with the developments in the methodology, continuous time pressure and the threat of litigation, authenticating artwork is becoming increasingly complex. In this paper, we examined whether the decision process involved in the authenticity examination may be supported by machine learning algorithms. The idea is motivated by existing clinical decision support systems. We used a set of 55 artworks (including 12 forged ones) with determined attribution markers to train a decision tree model. From our preliminary results, it follows that it is a very promising technique able to support art experts. Decision trees are able to summarize the existing knowledge about all investigations and may also be used as a classifier for new paintings with known markers. However, larger datasets with artworks of known provenance are needed to build robust classification models. The method can also utilize the most important markers and, consequently, reduce the costs of investigations. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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12 pages, 17504 KiB

Open AccessArticle

Sicilian Byzantine Icons through the Use of Non-Invasive Imaging Techniques and Optical Spectroscopy: The Case of the Madonna dell’Elemosina

by Francesco Armetta, Gabriella Chirco, Fabrizio Lo Celso, Veronica Ciaramitaro, Eugenio Caponetti, Massimo Midiri, Giuseppe Lo Re, Vladimir Gaishun, Dmitry Kovalenko, Alina Semchenko, Dariusz Hreniak and Maria Luisa Saladino

Molecules 2021, 26(24), 7595; https://doi.org/10.3390/molecules26247595 - 15 Dec 2021

Cited by 3 | Viewed by 2658

Abstract

The iconographic heritage is one of the treasures of Byzantine art that have enriched the south of Italy, and Sicily in particular, since the early 16th century. In this work, the investigations of a Sicilian Icon of Greek-Byzantine origin, the Madonna dell’Elemosina, is reported for the first time. The study was carried out using mainly non-invasive imaging techniques (photography in reflectance and grazing visible light, UV fluorescence, infrared reflectography, radiography, and computed tomography) and spectroscopic techniques (X-ray fluorescence and infrared spectroscopy). The identification of the constituent materials provides a decisive contribution to the correct historical and artistic placement of the Icon, a treasure of the Eastern European historical community in Sicily. Some hidden details have also been highlighted. Most importantly, the information obtained enables us to define its conservation state, the presence of foreign materials, and to direct its protection and restoration. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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15 pages, 4334 KiB

Open AccessArticle

Multi-Analytical Characterization and Radiocarbon Dating of a Roman Egyptian Mummy Portrait

by Alice Dal Fovo, Mariaelena Fedi, Gaia Federico, Lucia Liccioli, Serena Barone and Raffaella Fontana

Molecules 2021, 26(17), 5268; https://doi.org/10.3390/molecules26175268 - 30 Aug 2021

Cited by 4 | Viewed by 3127 | Correction

Abstract

Fayum mummy portraits, painted around 2000 years ago, represent a fascinating fusion of Egyptian and Graeco-Roman funerary and artistic traditions. Examination of these artworks may provide insight into the Roman Empire’s trade and economic and social structure during one of its most crucial yet still hazy times of transition. The lack of proper archaeological documentation of the numerous excavated portraits currently prevents their chronological dating, be it absolute or relative. So far, their production period has been defined essentially on the basis of the relevant differences in their pictorial style. Our study introduces the use of Accelerator Mass Spectrometry (AMS) to assess the age of a fragment of an encaustic painting belonging to the corpus of the Fayum portraits. The unexpected age resulting from ¹⁴C analysis suggests the need to reconsider previous assumptions regarding the period of production of the Fayum corpus. Furthermore, our multi-analytical, non-invasive approach yields further details regarding the fragment’s pictorial technique and constituting materials, based on spectral and morphological analysis and cross-sectional examination. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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20 pages, 3015 KiB

Open AccessArticle

Water-Based Aerosol for Book Deacidification: Experimental Apparatus and Theoretical Interpretation of Results

by Giuseppe Chidichimo, Alessandra Crispini, Antonio Tursi, Maria Rita Basile, Ilaria Lania, Giovanni De Filpo, Cesare Oliviero Rossi and Francesca Scarpelli

Molecules 2021, 26(14), 4249; https://doi.org/10.3390/molecules26144249 - 13 Jul 2021

Cited by 1 | Viewed by 2001

Abstract

One of the major problems in book conservation is the long-term deconstructive effect of acidity introduced into the paper by several additives, which, in the presence of humidity, generates a hydrogen cation with a strong catalytic role in cellulose depolymerization. Many types of treatment have been used in the past, but up to now, research for less-invasive, fast and cheap methods is still vividly ongoing. In this study, an approach to book deacidification is presented, where alkaline water solutions are administered to bound books in the form of micrometer-sized aerosol droplets, without using vacuum apparatus accessories. Alkaline clouds treatments were alternated with gentle air fluxes of drying steps. Few cycles are required to achieve uniform deacidification of books. The treatment could be conducted with proper apparatus on large volumes, resulting in rapid treatment time and low cost. The titration curve reporting the variation of book pH, with respect to the amount of absorbed alkaline aerosol, was built and interpreted in terms of a chemical model for the neutralization process. FTIR, PXRD and XRF spectroscopies were used to characterize the book chemistry. The effects of the treatment on the book were evaluated by measuring the degree of polymerization (DP) of the paper and the colorimetric coordinates of the paper and ink. Artificial aging tests revealed a general increase in the aging stability of the deacidified paper samples with respect to the untreated samples. Finally, the alkaline reserve data are discussed. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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17 pages, 3967 KiB

Open AccessArticle

Single-Sided Portable NMR Investigation to Assess and Monitor Cleaning Action of PVA-Borax Hydrogel in Travertine and Lecce Stone

by Valeria Stagno, Chiara Genova, Nicole Zoratto, Gabriele Favero and Silvia Capuani

Molecules 2021, 26(12), 3697; https://doi.org/10.3390/molecules26123697 - 17 Jun 2021

Cited by 9 | Viewed by 2933

Abstract

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. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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19 pages, 3680 KiB

Open AccessArticle

Soluble Salts Quantitative Characterization and Thermodynamic Modeling on Roman Bricks to Assess the Origin of Their Formation

by Claudia Scatigno, Nagore Prieto-Taboada, Giulia Festa and Juan Manuel Madariaga

Molecules 2021, 26(10), 2866; https://doi.org/10.3390/molecules26102866 - 12 May 2021

Cited by 5 | Viewed by 2579

Abstract

The environmental weathering and the formation of efflorescences on the brick walls are studied at the “Casa di Diana” Mithraeum at Ostia Antica archaeological site. Previous studies on subsoil, bedrock, hydrological systems and environmental conditions, and new ion chromatography analysis combined with ECOS-RUNSALT and Medusa-Hydra thermodynamic modelling software, had allowed us to identify the subsoil contamination related to soluble salts. The atmospheric acidic gases, CO₂ and SO₂, are determined as the main salt weathering species. A dry deposition after a subsequent hydration action from the shallow freshwater aquifer that reaches up to 1 m on the walls is identified as the mechanism of salt formation. An evaluation of potential sources such as the nearby Fiumicino airport, CO₂-rich gases inputs from fumaroles and CO₂ inputs was also debated. The risk level of contamination the surfaces of the materials should be considered mildly/very polluted with a medium/high risk of hygroscopic moisture due to the high concentration of sulphates. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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13 pages, 3617 KiB

Open AccessArticle

Role of pH on Nanostructured SERS Active Substrates for Detection of Organic Dyes

by Viviana Mollica Nardo, Vincenzo Renda, Sebastiano Trusso and Rosina Celeste Ponterio

Molecules 2021, 26(8), 2360; https://doi.org/10.3390/molecules26082360 - 19 Apr 2021

Cited by 6 | Viewed by 2340

Abstract

Surface Enhanced Raman Spectroscopy is commonly used as analytical improvement to conventional Raman spectroscopy, able to respond to qualitative diagnostic enquiries, which involve low-concentrated molecular species in complex matrix. In this paper, we described fabrication, characterization and testing of a type of SERS-active substrates realized specifically to detect pigments in work of art. In particular, we detailed the SERS activity of nanostructured noble metal films deposited by pulsed laser ablation onto glass and polishing sheets substrates. The SERS response of the substrates was tested against the presence of some organic dyes in aqueous solutions. Measurements were performed at different pH values, in acidic or basic range, in order to investigate its role in the adsorption mechanism, thus fostering the SERS amplification. In addition, we checked the possible deterioration of the structural properties of the substrates that could occur in presence of alkaline or acidic environment. SERS activity of the substrates was tested against a commonly dye used as a SERS standard (Blue Methylene). Thereafter, substrates have been tested on two organic dyes (Alizarine red-S and Brazilwood), which had proven to be Raman active but present also either a weak Raman scattering cross section and/or a high fluorescence emission. The substrates have proven effective in amplifying Raman scattering of all dyes, quenching troubling fluorescence effects. Furthermore, they have proven to be stable in the pH range between 3 and 11. Furthermore, we carry out of vibrational DFT-calculation of dyes that provide a complete description of the observed SERS spectra. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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16 pages, 9749 KiB

Open AccessArticle

Vibrational Spectroscopic Analyses and Imaging of the Early Middle Ages Hemp Bast Fibres Recovered from Lake Sediments

by Grzegorz Kalisz, Barbara Gieroba, Olga Chrobak, Magdalena Suchora, Agata L. Starosta and Anna Sroka-Bartnicka

Molecules 2021, 26(5), 1314; https://doi.org/10.3390/molecules26051314 - 1 Mar 2021

Cited by 17 | Viewed by 2790

Abstract

Fourier Transform Infrared (FT-IR) spectroscopy and imaging combined with hierarchical cluster analysis (HCA) was applied to analyse biochemical properties of Early Middle Ages hemp (Cannabis sativa L.) bast fibres collected from lake bottom sediment of lake Słone. The examined plant macrofossil material constitutes residues of the hemp retting process that took place in the 7th–8th century. By comparison of three samples: untreated isolated bast fibres, and fibres incubated overnight at 4 and 37 °C, we were able to mimic the retting conditions. Using FT-IR qualitative and semi-quantitative assessment of the primary polysaccharides content, total protein content, and their spatial distribution was performed within the hemp fibres. The concentration of cellulose remained vastly unchanged, while the concentration of lignin and pectin was the highest in the untreated sample. The spatial distributions of compounds were heterogeneous in the untreated and 4 °C-incubated samples, and homogenous in the specimen processed at 37 °C. Interestingly, a higher amide content was detected in the latter sample indicating the highest degree of enzymatic degradation. In this study, we show that the spectroscopic methods allow for a non-destructive evaluation of biochemical composition of plant fibres without preparation, which can be an appropriate approach for studying ancient plant remains. Full article

(This article belongs to the Special Issue Physical Chemistry in Cultural Heritage)

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1 pages, 160 KiB

Open AccessCorrection

Correction: Dal Fovo et al. Multi-Analytical Characterization and Radiocarbon Dating of a Roman Egyptian Mummy Portrait. Molecules 2021, 26, 5268

by Alice Dal Fovo, Mariaelena Fedi, Gaia Federico, Lucia Liccioli, Serena Barone and Raffaella Fontana

Molecules 2022, 27(12), 3822; https://doi.org/10.3390/molecules27123822 - 14 Jun 2022

Viewed by 995

Abstract

Due to the fact that the policy regarding the publication of images from the collection of the Papyrological Institute, the owner of the object under study, changed when the article was already in publication, the authors would like to make the following corrections [...] Read more.

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