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Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects

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A special issue of Heritage (ISSN 2571-9408).

Deadline for manuscript submissions: 31 December 2024 | Viewed by 13575

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Special Issue Editors

Dr. Georgios P. Mastrotheodoros

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Department of Antiquities and Works of Art Conservation, School of Applied Arts and Culture, West Attica University, Aegaleo, Greece
Interests: panel painting conservation; pigment identification; XRF
Special Issues, Collections and Topics in MDPI journals

Dr. Anastasia Rousaki

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Guest Editor

Department of Chemistry, Ghent University, Ghent, Belgium
Interests: Raman spectroscopy; analysis of works of art; degradation
Special Issues, Collections and Topics in MDPI journals

Dr. Eleni Kouloumpi

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Guest Editor

Laboratory of Physicochemical Research, Conservation Department, National Gallery-Alexandros Soutso Museum, Athens, Greece
Interests: analyses of works of art; binding media analysis; pigment analysis; spectroscopy; separation methods

Special Issue Information

Dear Colleagues,

Analytical investigation of pigments and dyes is considered of utmost importance in the field of cultural heritage (CH) studies. Indeed, through the identification of corresponding materials, scholars are often able to gain new insights into various important, pertinent aspects: the characterization of the materials and the (construction) techniques of the artist, the degradation pathways and the preservation state of the artefact, and the (direct or indirect) dating and the determination of the provenance of CH objects. The research on cultural heritage materials and their degradation contributes considerably towards assessing the state of preservation of CH items and can reveal past restoration interventions. By gaining insights into the deterioration processes that are involved in the decay of various pigments and dyes, it is possible to seek out and establish new conservation strategies, and to assess (and potentially restore) the original appearance of artworks. Moreover, studies on pigments and dyes offer unique opportunities to confront the distribution of counterfeit antiquities and works of art. This Heritage (MDPI) Special Issue entitled “Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects” aims to attract original research covering all aspects of the analytical investigation of pigments and dyes. In this framework, authors are encouraged to submit for publication works dealing with recent analytical/methodological approaches and developments that are in alignment with the topic of the Special Issue, including case studies that provide an in depth analysis of pigments and/or dyes and/or their degradation mechanisms, as well as literature reviews. A special interest has been placed upon the potentials and benefits of non-invasive techniques for the identification of pigments and dyes, and thus work conducted with mobile instrumentation is also welcome.

Dr. Georgios P. Mastrotheodoros
Dr. Anastasia Rousaki
Dr. Eleni Kouloumpi
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Heritage is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

cultural heritage
pigments
dyes
degradation
conservation
analytical techniques

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Published Papers (9 papers)

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Research

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18 pages, 8578 KiB

Open AccessArticle

Ultramarine Blue in Edvard Munch’s Collection: A Multi-Analytical Study of Early 20th Century Commercial Oil Paints

by Beatrice G. Boracchi, Eun-Jin Strand Ferrer, Margherita Gnemmi, Laura Falchi, Francesca Caterina Izzo and Irina Crina Anca Sandu

Heritage 2024, 7(8), 4027-4044; https://doi.org/10.3390/heritage7080190 - 31 Jul 2024

Viewed by 856

Abstract

The recurrence of specific deteriorating phenomena in blue paints used by Edvard Munch, observed more frequently from artworks from 1907 and onwards, calls for an analytical investigation of these paints. Ten commercial Ultramarine blue oil paint tubes from Munch’s studio materials were studied, employing a multi-analytical approach comprising ATR-FTIR, µ-Raman, GC-MS, and SEM-EDS techniques. This study aims to ascertain the composition of these industrially produced blue oil paints and shed more light on the potential implications for darkening and other deterioration phenomena observed in Munch’s artworks. The analyzed samples exhibited complex mixtures, characterized by significant presences of additives such as non-drying or partially drying oils, metal soaps, and preservatives. Moreover, extenders including clay minerals and white and other blue pigments were identified. Some compositions diverged from those indicated on the labels of the tubes. This study presents hypotheses regarding the causes of deterioration mechanisms observed in Ultramarine blue paints and outlines future perspectives and implications of darkening and other surface degradation phenomena in paintings from MUNCH’s collection towards best conservation and display practices. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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14 pages, 15812 KiB

Open AccessArticle

The Application of Cathodoluminescence (CL) for the Characterization of Blue Pigments

by Eleni Palamara, Stelios Kesidis, Laura Tormo Cifuentes, Partha Pratim Das, Stavros Nicolopoulos and Nikolaos Zacharias

Heritage 2024, 7(6), 3048-3061; https://doi.org/10.3390/heritage7060143 - 5 Jun 2024

Viewed by 1238

Abstract

The combined application of Cathodoluminescence (CL) with Scanning Electron Microscopy (SEM) on paintings and painted surfaces has the potential to identify both organic and inorganic pigments on a micrometre or even nanometre scale. Additionally, the combination with Energy-Dispersive Spectrometry (EDS) allows for a more holistic, elemental, and mineralogical characterization of pigments. In addressing the need for the creation of a robust, open access database of characteristic CL spectra of pigments, a large project has been undertaken, focusing primarily on common organic and inorganic pigments. The present paper focuses on the CL characterization of 10 significant blue pigments in pure powder form: cerulean blue, Egyptian blue, Han blue, indigo, lapis lazuli, Maya blue, phthalo blue, vivianite, ultramarine blue, and zirconium blue. The CL spectra present characteristic bands for most of the pigments, allowing their secure identification, especially when combining the results with the EDS analyses. The effect of binding media and of the mixture of different pigments was also studied, via the analysis of mixtures of pigments with oil painted over canvas. Overall, both the binding medium and the mixture of pigments do not appear to create significant differences in the occurring spectra, thus allowing the identification of individual pigments. EDS and RAMAN spectra are included in order to facilitate comparison with other databases. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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23 pages, 9542 KiB

Open AccessArticle

A Characterisation of the Protrusions on Liu Kang’s Boat scene (1974) from the National Gallery Singapore

by Damian Lizun and Teresa Kurkiewicz

Heritage 2024, 7(6), 2811-2833; https://doi.org/10.3390/heritage7060133 - 29 May 2024

Viewed by 651

Abstract

This paper investigates the oil on canvas painting Boat scene (1974) by Liu Kang (1911–2004), belonging to the National Gallery Singapore (NGS). The focus is on disfiguring paint protrusions in a specific area and colour in the composition. Moreover, in search of the possible factors responsible for the creation of the protrusions, the structure and composition of the paint layers were determined. Three possible reasons were put forward to explain this phenomenon: deliberate textural effects, the expansion of metal soaps and unintentional paint contamination during the artistic process. Investigative techniques such as technical photography, digital microscopy, optical microscopy (OM), polarised light microscopy (PLM), field emission scanning electron microscope (FE-SEM-EDS) and attenuated total reflectance micro-Fourier transform infrared spectroscopy (ATR μ-FTIR) were employed to analyse paint layers, including protrusion samples. The analyses revealed that the protrusions resulted from an unintentional contamination of the oil paint during the artistic process by dry fragments of different pigment mixtures bound in drying oil. Zinc soaps were found in significant concentrations within the protrusions and other parts of the painted scene. Nevertheless, the metal soaps do not pose a direct risk to the integrity of the paint layers at the time of this research. The analyses highlight the potential challenges caused by the protrusions that conservators may face while caring for the painting. The research contributes to our ongoing comprehension of the artist’s working process. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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21 pages, 49374 KiB

Open AccessArticle

Archaeological and Archaeometric Insights into a Roman Wall Painting Assemblage from the Blanes Dump (Mérida)

by Gonzalo Castillo Alcántara, Daniel Cosano Hidalgo, Alicia Fernández Díaz and José Rafael Ruiz Arrebola

Heritage 2024, 7(6), 2709-2729; https://doi.org/10.3390/heritage7060129 - 27 May 2024

Viewed by 748

Abstract

In this paper we describe the archaeological and archaeometric analysis of a Third Pompeian Style assemblage from the Blanes dump in Mérida (Spain). Based on the pottery context, the material would have been part of the decoration of a public or private space remodelled towards the end of the 1st century AD. Several samples from to the middle area of the assemblage, including panels, inter-panels and a frieze, were selected and studied using X-ray diffraction (XRD), X-ray fluorescence (XRF), Raman, gas chromatography and petrographic analysis. The results revealed the use of hematite, cinnabar, minium and goethite in different panels, as well as goethite, Egyptian blue, calcite, glauconite and carbon for the decorative motifs. They allowed us to define the painting techniques used and how they have affected the degradation of the pigments. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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20 pages, 5060 KiB

Open AccessArticle

X-ray Synchrotron Radiation to Look at Pigments in Antiquities: Overview and Examples

by Alessandra Gianoncelli, Sebastian Schöder, Jasper R. Plaisier, Maura Fugazzotto, Germana Barone, Alfonsina Russo, Paolo Mazzoleni and Simona Raneri

Heritage 2024, 7(4), 2118-2137; https://doi.org/10.3390/heritage7040100 - 5 Apr 2024

Cited by 1 | Viewed by 1725

Abstract

The recent upgrading of synchrotron radiation (SR) sources has favored, in the last few years, the construction and design of beamlines optimized for the study of cultural heritage materials, which may require ad hoc setups, specific spatial resolutions, and detection limits. In the field of cultural heritage, integrated approaches combining different techniques are often required, even at large facilities, where some beamlines offer the possibility of performing different types of measurements at the same point of analysis, complementing preliminary information usually obtained by conventional laboratory and/or portable in situ methods. An overview of the last ten years of synchrotron applications for the study of pigments is given, with discussion of upstream and downstream challenges to methods and techniques. The possibilities offered by the synchrotron techniques are illustrated by a case study of a particular class of painted ceramics, as an example of different research questions that are solved by a combination of SR-based methods. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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12 pages, 1455 KiB

Open AccessArticle

Identification of Degradation Products and Components in Shellfish Purple by Ultrahigh Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry

by Athina Vasileiadou, Ioannis Sampsonidis, Georgios Theodoridis, Anastasia Zotou, Ioannis Karapanagiotis and Stavros Kalogiannis

Heritage 2024, 7(4), 1935-1946; https://doi.org/10.3390/heritage7040092 - 26 Mar 2024

Viewed by 1336

Abstract

Ultrahigh performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was used to analyze a colorant and silk, which were prepared and dyed using shellfish (Hexaplex trunculus L.) purple. Solutions of colorant and silk extracts were analyzed immediately after preparation (fresh samples) and after storing them in the dark for thirty days (aged sample I). Moreover, a silk sample was subjected to artificially accelerated ageing under UV radiation (aged sample II). The application of the UHPLC-MS/MS method leads to the detection of (i) the major coloring components of shellfish purple, which are indigotin, indirubin, 6-bromoindigotin, 6′-bromoindirubin, 6-bromoindirubin, 6,6′-dibromoindigotin, 6,6′-dibromoindirubin; (ii) four minor indigoid components in shellfish purple (compounds A, B, C and D), which belong to the same structural class as indirubin, and whose identification has been reported only once in the past; and (iii) eight degradation products (isatin, degradation products DP3, DP4, DP5, DP6, DP7, DP9 and DP10). The latter were also detected in stored indigotin solution, except for DP 6, which was used as reference sample. The method development was assisted by a new solution preparation approach for investigating compound fragmentation, using a solvent system compatible with direct infusion ESI. This system replaceddimethyl sulfoxide, which inhibits detection through electrospray ionization. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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15 pages, 4158 KiB

Open AccessArticle

Components of Mid-Nineteenth- and Mid-Twentieth-Century Cudbears

by Laura Maccarelli, Terry T. Schaeffer, Gregory D. Smith and Victor J. Chen

Heritage 2024, 7(3), 1357-1371; https://doi.org/10.3390/heritage7030065 - 9 Mar 2024

Viewed by 1489

Abstract

Analysis of purple dyestuff from a tin labeled “1 oz. Cudbear, No. 1 N. F. Powdered”, marketed by the American business S. B. Penick & Company, “Manufacturers of fine drugs and chemicals”, confirmed that the material was indeed a lichen dyestuff. It contains the same major orcein components identified in several other lichen dyes and dyed samples dating from the mid-19th century to today. These dyestuffs were analyzed using several analytical techniques. Fluorescence and fiber optic reflectance spectroscopic data for all the samples were similar. High performance liquid chromatography with diode array detection coupled to mass spectrometry confirmed that this commercial American cudbear was very similar to the samples from the United Kingdom but rather different from the archil-dyed reference yarns from Europe. The significance of the observations is discussed, and chemical structures are proposed for several of the unknown dye components detected in this study. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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16 pages, 2689 KiB

Open AccessArticle

Dye Analysis of a 17th-Century Mattens Workshop Tapestry Based on Raphael’s Drawing, The Miraculous Draught of Fishes

by Victor J. Chen, Gregory D. Smith, Amanda Holden and Sadie Arft

Heritage 2024, 7(3), 1221-1236; https://doi.org/10.3390/heritage7030059 - 27 Feb 2024

Cited by 1 | Viewed by 1593

Abstract

This paper describes the identification of dyes on fifty yarn samples from a tapestry created by the well-known 17th-century Flemish workshop of the Mattens family. The design of the tapestry is based on the first of ten drawings known as the Acts of the Apostles by the famed 16th-century Italian painter Raphael. The drawings were commissioned by Pope Leo X and translated into tapestries by Pieter van Aelst; these original tapestries are still in the collection of the Vatican Museums. The present work was reproduced over a century later from the original drawing and is one in a possible set of nearly fifty known copies of the original tapestry cycle. Most of the Mattens yarn samples were found to be dyed by weld, indigo, and madder, as well as a few using brazilwood and lichen, but no insect dyes were detected. A significant finding in the present study was the detection of the dye component pseudoindirubin 1, alongside indigotin and indirubin, as well as yarns that only yielded the latter two dyes. The implication of using this new marker as objective evidence of the use of both woad and most likely Asian indigo is explored. The historical and conservation significance of the dyestuffs identified is also discussed. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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32 pages, 1470 KiB

Open AccessReview

The Study of Pigments in Cultural Heritage: A Review Using Machine Learning

by Astrid Harth

Heritage 2024, 7(7), 3664-3695; https://doi.org/10.3390/heritage7070174 - 11 Jul 2024

Viewed by 1804

Abstract

In this review, topic modeling—an unsupervised machine learning tool—is employed to analyze research on pigments in cultural heritage published from 1999–2023. The review answers the following question: What are topics and time trends in the past three decades in the analytical study of pigments within cultural heritage (CH) assets? In total, 932 articles are reviewed, ten topics are identified and time trends in the share of these topics are revealed. Each topic is discussed in-depth to elucidate the community, purpose and tools involved in the topic. The time trend analysis shows that dominant topics over time include T1 (the spectroscopic and microscopic study of the stratigraphy of painted CH assets) and T5 (X-ray based techniques for CH, conservation science and archaeometry). However, both topics have experienced a decrease in attention in favor of other topics that more than doubled their topic share, enabled by new technologies and methods for imaging spectroscopy and imaging processing. These topics include T6 (spectral imaging techniques for chemical mapping of painting surfaces) and T10 (the technical study of the pigments and painting methods of historical and contemporary artists). Implications for the field are discussed in conclusion. Full article

(This article belongs to the Special Issue Latest Trends and Challenges in the Study of Pigments and Dyes and Their Degradation in Cultural Heritage Objects)

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