Pigment Identification of Cultural Heritage Materials

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

Deadline for manuscript submissions: closed (31 January 2024) | Viewed by 14046

Special Issue Editors


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Guest Editor
Laboratorio di Diagnostica per I Beni Culturali, Spoleto, Italy
Interests: non-invasive techniques; biochemical methods for cultural heritage; vibrational spectroscopies; electronic spectroscopies; X-ray diffraction; X-ray fluorescence spectrometer; SEM-EDS analysis; multispectral imaging techniques; hyperspectral imaging techniques
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Guest Editor
CNR-IRET, Porano, Italy
Interests: non-invasive techniques; electronic spectroscopies; vibrational spectroscopies; SEM-EDS analysis; NMR spectroscopy; multispectral imaging techniques
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Guest Editor
Department of Musicology and Cultural Heritage, University of Pavia, Cremona, Italy
Interests: non-invasive techniques; FTIR spectroscopy; X-ray fluorescence; artwork cleaning
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Since ancient times, pigments have fascinated artists of all ages. The need to enrich artistic representations with colorful images led to a specific search for durable materials, such as pigments. Many types of pigments with different compositions, both natural and synthetic, have been selected, produced and used, and many colors have been progressively added to the artists’ palettes. For conservation and restoration purposes, it is also important to distinguish original materials from later additions, to recognize the degradation process of organic and inorganic pigments, and to be able to conduct a preliminary in situ analysis that allows for less invasive interventions on artworks. In recent years, research on art materials has contributed not only to conservation but also to the understanding of the genesis of artworks, providing archaeologists with information equal to documentary sources, particularly for those pigments that have been discontinued over time.

Furthermore, the analysis of the constituent materials of works of art helps to understand the artist's technique and, therefore, helps to identify or exclude the artist’s work in dubious situations.

The aim of this Special Issue is to collect contributions highlighting recent achievements in the field of the identification of organic and inorganic pigments in artworks and their alteration processes, in the form of original papers, mini-reviews, and papers. Case studies will also be evaluated.

Contributions are invited on, but not restricted to, the following topics:

  • Studies on ancient and synthetic inorganic pigments;
  • Studies on ancient and synthetic dyes;
  • Studies on the degradation processes of pigments and dyes;
  • Innovative methodologies for the identification of pigments in artworks;
  • Studies on ancient pigments, painting techniques, and craftsmanship;
  • Non-invasive techniques for the characterization of pigments in artworks;
  • Portable, non-invasive spectroscopic techniques for pigment identification in cultural heritage.

Prof. Dr. Manuela Vagnini
Dr. Chiara Anselmi
Dr. Francesca Volpi
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

  • ancient pigments
  • synthetic pigments and dyes
  • degradation process of organic and inorganic pigments
  • non invasive techniques
  • pigments identification
  • portable spectroscopies
  • XRF, reflectance FTIR, Raman spectroscopies
  • SEM-EDX
  • UV-VIS-NIR reflectance and emission spectroscopies
  • multispectral and hyperspectral imaging techniques

Published Papers (9 papers)

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Research

17 pages, 4969 KiB  
Article
Correlation of Visible Reflectance Spectrometry and Portable Raman Data for Red Pigment Identification
by Anna M. Gueli, Rosaria Galvagno, Adriana Incardona, Eleonora Pappalardo, Giuseppe Politi, Giuseppe Paladini and Giuseppe Stella
Heritage 2024, 7(4), 2161-2175; https://doi.org/10.3390/heritage7040102 - 06 Apr 2024
Viewed by 600
Abstract
The accurate identification of pigments is of principal relevance in the field of cultural heritage conservation and restoration practices. In this preliminary study, a first attempt to set up a procedure for accurate red pigment identification, based on the assessment of the correlations [...] Read more.
The accurate identification of pigments is of principal relevance in the field of cultural heritage conservation and restoration practices. In this preliminary study, a first attempt to set up a procedure for accurate red pigment identification, based on the assessment of the correlations existing between visible reflectance spectrometry (vis-RS) and Raman data, is presented. The proposed approach involved the realization of a library consisting of data acquired on a set of 35 pure red historical pigments supplied by ©Kremer Pigmente. In particular, vis-RS data, collected through a Konica Minolta CM-2600d spectrophotometer, were registered, together with the position of the Extrema Points (E.P.s) encompassing both the maximum and minimum points of the first derivative of the % spectral reflectance factor (SRF%) curves. Portable Raman spectroscopy measurements were collected by a B&W Tek Inc. portable Raman spectrometer equipped with a 785 nm laser. For each tested pigment, the positions and relative intensities of the characteristic Raman peaks were considered. The library was then tested for the characterization of the red/reddish painted areas of the medieval wall painting located within The Norman Castle of Aci Castello (Catania, Italy), and was shown to be essential for the unambiguous identification of the pigment used. It is worth noting that this study represents the first novel attempt to establish a reliable and efficient methodology for pigment identification, offering promising prospects in reducing uncertainties and ambiguities arising from the application of a single stand-alone approach. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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26 pages, 13898 KiB  
Article
pXRF and Polychromy: Identifying Pigments on Limestone Statuary from the Roman Limes, Preliminary Results
by Louisa Campbell and Charleen Hack
Heritage 2024, 7(3), 1701-1726; https://doi.org/10.3390/heritage7030080 - 18 Mar 2024
Viewed by 1010
Abstract
This paper presents the preliminary results of an investigation on the unexplored topic of polychromy on provincial stone sculptures from the Roman provinces in Germania through the innovative application of heritage materials science techniques. A group of three life-sized statues dating to the [...] Read more.
This paper presents the preliminary results of an investigation on the unexplored topic of polychromy on provincial stone sculptures from the Roman provinces in Germania through the innovative application of heritage materials science techniques. A group of three life-sized statues dating to the 1st Century CE recovered from Ingelheim, near Mainz, retains remarkably well-preserved traces of pigments. These are ripe for emerging non-invasive technologies supplemented by micro-sampling to validate results and provide information relating to mixing and layering not available to the naked eye. The most strikingly visible areas of extant polychromy were retained on the sculpture of a young woman, reported on here as the first phase of this programme of research. The results suggest that the statue was originally covered in a gypsum layer before the application of complex and diverse recipes of pigment applied as mixtures and in layers to create required hues and shadowing on sculpted features. The palette includes ochres and green earth mixed with small amounts of minium (red lead), realgar and lapis lazuli (ultramarine blue) added to create skin tones, and a vibrant blue-green tunic created from Egyptian blue, bone black, ochres, cinnabar and green earth; the palla and peplos contained ochres, bone black, and orpiment, and mixes of these created the detail of coloured jewellery. Of great interest was the detection of bone black on many features, particularly as a shading agent to enhance sculpted features, such as folds in cloth, providing a more realistic and flowing articulation. This is a revolutionary observation that provides previously unexplored insights into artistic polychromic practice in Antiquity. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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14 pages, 5020 KiB  
Article
Advances in Lead-Barium-Zinc-Silicate-Type Glazed Warming Bowl Related to the Chinese Xuande Reign (1426–1435)
by Maria Letizia Amadori, Serse Cardellini and Valeria Mengacci
Heritage 2024, 7(3), 1496-1509; https://doi.org/10.3390/heritage7030072 - 12 Mar 2024
Viewed by 692
Abstract
Diagnostic investigations were carried out on a rare Chinese polychrome glazed ceramic dating back to the reign of the Xuande Emperor (1426–1435). The double-walled warming bowl was investigated using several non-invasive methods such as portable optical microscopy, endoscopy, portable X-ray fluorescence spectrometry, X-radiography, [...] Read more.
Diagnostic investigations were carried out on a rare Chinese polychrome glazed ceramic dating back to the reign of the Xuande Emperor (1426–1435). The double-walled warming bowl was investigated using several non-invasive methods such as portable optical microscopy, endoscopy, portable X-ray fluorescence spectrometry, X-radiography, and computed tomography. One microsample was collected and analyzed by scanning electron microscopy with an energy dispersive X-ray detector. According to the results, the chemical composition of the paste suggested a porcelain typology, while the glaze belongs to the lead–barium–silicate (PbO-BaO-ZnO-SiO2) system. These unexpected data contrast with common knowledge, which attests that the addition of barium in glass and ceramics manufacturing disappeared soon after the Han dynasty (206 BCE-220 CE). Moreover, the combination of PbO-BaO-ZnO-SiO2 seems to be quite rare both in ancient pre-Han times and during the Ming and Qing dynasties. This paper aims to demonstrate that (a) the use of barium for glaze and glass composition, which seems to have its roots in Taoist alchemy, was not totally halted in later periods compared to the Han dynasty; (b) lead–barium–zinc–silicate glaze was used during the Xuande Emperor’s reign. Through a review of ancient Chinese literary sources, we found a lot of unpublished information on the use of barium, lead, and zinc in the production of glazed ceramics during this period. The polychrome glazed warming bowl suggests a particular production that flourished during the brief reign of the Xuande Emperor. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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22 pages, 8204 KiB  
Article
Unveiling Polychrome Printing Methods on Textiles: Preliminary Results from the Mariano Fortuny y Madrazo Collection in Venice
by Virginia Farinelli, Laura Falchi, Cristina da Roit, Margherita Gnemmi and Francesca Caterina Izzo
Heritage 2024, 7(3), 1298-1319; https://doi.org/10.3390/heritage7030062 - 01 Mar 2024
Viewed by 1946
Abstract
At the beginning of the 20th century, the eclectic artist Mariano Fortuny y Madrazo patented two innovative methods for polychrome printing on fabrics and textiles, giving life to Fortuny fabric production in Venice. The first patent was related to colour application, while the [...] Read more.
At the beginning of the 20th century, the eclectic artist Mariano Fortuny y Madrazo patented two innovative methods for polychrome printing on fabrics and textiles, giving life to Fortuny fabric production in Venice. The first patent was related to colour application, while the second to a special machine that allows continuous printing using cylindrical rollers. Despite the descriptions, the methodology and materials used remain a secret. In collaboration with the Fortuny Museum in Venice, this research aimed at studying and identifying the different steps of Fortuny printing methodologies. Printing matrices, fabrics and raw materials found in the artist’s studio were analysed in a multi-analytical campaign through digital microscopy, X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy in attenuated total reflectance (FTIR-ATR), μ-Raman spectroscopy and gas chromatography–mass spectrometry (GC–MS). Three main pigments were identified in paper samples: ivory black, a copper-based pigment, and a carbon black pigment with ultramarine for blues. The pigments were bound with linseed oil and colophony in varying proportions. Polychrome silk fabrics were dyed with a base colour, and then the coloured patterns were superimposed by continuous printing. Prussian blue was identified as one of the textile inks. Results provided a better understanding of printing methodology. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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19 pages, 4168 KiB  
Article
Integrated Investigations of Painting Materials in the Sasanian City of Ardaxšīr Khwarrah, near Firuzabad (Southern Iran)
by Maria Letizia Amadori, Valeria Mengacci, Pierfrancesco Callieri, Alireza Askari Chaverdi, Matteo Bartolucci, Negar Eftekhari, Alessia Andreotti and Parviz Holakooei
Heritage 2024, 7(3), 1202-1220; https://doi.org/10.3390/heritage7030058 - 26 Feb 2024
Viewed by 1032
Abstract
Ancient Ardaxšīr Khwarrah, today known as Shahr-e Gur, situated near the modern town of Firuzabad in Fars, Iran, holds historical significance as the inaugural capital city of the Sasanian Empire. During archaeological excavations conducted in 2005 by an Iranian–German team directed by Mas‘oud [...] Read more.
Ancient Ardaxšīr Khwarrah, today known as Shahr-e Gur, situated near the modern town of Firuzabad in Fars, Iran, holds historical significance as the inaugural capital city of the Sasanian Empire. During archaeological excavations conducted in 2005 by an Iranian–German team directed by Mas‘oud Azarnoush and Dietrich Huff, a mud-brick complex was uncovered, revealing a remarkably well-preserved stretch of wall painting and a polychrome painted floor. The discovery prompted the hypothesis of a potential funerary context dating back to the Sasanian period. Both the wall painting and painted floor have suffered extensive deterioration attributed to the environmental conditions of the archaeological site, which was inscribed on the UNESCO World Heritage List in 2020. To address the urgent need for preservation and further understanding of the site’s artistic and structural elements, an emergency diagnostic project was initiated. Non-invasive investigations were carried out on the wall and floor by optical digital microscopy and portable energy-dispersive X-ray fluorescence. Additionally, representative minute samples underwent analysis through various techniques, including micro-X-ray fluorescence, polarised light microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, micro-Raman spectroscopy, micro-Fourier Transform Infrared Spectroscopy, gas chromatography-mass spectrometry and pyrolysis coupled with gas chromatography-mass spectrometry. The palette of the floor and mural paintings were identified to contain red and yellow ochres, lead-based pigments, carbon black and bone white. The unexpected presence of Egyptian blue mixed with green earth was recognised in the green hues of the wall painting. The detection of protein material in both the wall painting and polychrome floor indicates the use of “a secco” technique, thereby shedding light on the artistic practices employed in Ardaxšīr Khwarrah. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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17 pages, 1981 KiB  
Article
Archeometrical Characterization of Rock Art Pigments from Puerto Roque Open-Air Rock Art Shelter (Valencia De Alcantara, Extremadura, Spain)
by Hugo Gomes, Hipólito Collado, Sara Garcês, Virginia Lattao, Maria Nicoli, Negar Eftekhari, Elena Marrocchino and Pierluigi Rosina
Heritage 2024, 7(3), 1123-1139; https://doi.org/10.3390/heritage7030053 - 21 Feb 2024
Viewed by 1769
Abstract
The study seeks to unravel the intricate operational sequence involved in preparing prehistoric pigments for rock art within the Puerto Roque rock art shelter. Sixteen pigment samples were meticulously collected from specific figurative representations. Additionally, three ochre samples were sourced from the shelter’s [...] Read more.
The study seeks to unravel the intricate operational sequence involved in preparing prehistoric pigments for rock art within the Puerto Roque rock art shelter. Sixteen pigment samples were meticulously collected from specific figurative representations. Additionally, three ochre samples were sourced from the shelter’s soil. Employing a comprehensive multi-analytical approach, including Raman microspectroscopy, X-ray microfluorescence (EDxrf), Fourier-transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy (SEM-EDS), all nineteen samples underwent thorough analysis. Notably, darker pigments revealed a composition of hematite with the added presence of carbon. Meanwhile, one sample exhibited an orange hue primarily composed of goethite and bright red pigments predominantly characterised by hematite, as confirmed by Raman analysis. EDxrf analysis demonstrated an elemental composition akin to the three ochre pieces examined. Furthermore, ATR-FTIR spectroscopy suggested the potential influence of a heating process in enhancing red coloration, corroborated by spectral results from specific samples. This finding aligns with prior research, underscoring the technological sophistication embedded in early artistic endeavours. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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16 pages, 6981 KiB  
Article
Yellow Dyes of Historical Importance: A Handful of Weld Yellows from the 18th-Century Recipe Books of French Master Dyers Antoine Janot and Paul Gout
by Mara Santo, Dominique Cardon, Natércia Teixeira and Paula Nabais
Heritage 2023, 6(12), 7466-7481; https://doi.org/10.3390/heritage6120391 - 29 Nov 2023
Cited by 1 | Viewed by 1421
Abstract
Antoine Janot and Paul Gout were 18th-century master dyers who specialised in the piece-dyeing of fine wool broadcloths manufactured in Languedoc (southern France) for exportation to the Levant. They wrote treatises, similarly entitled Mémoires de Teinture (Memoirs on Dyeing), illustrated with dozens of [...] Read more.
Antoine Janot and Paul Gout were 18th-century master dyers who specialised in the piece-dyeing of fine wool broadcloths manufactured in Languedoc (southern France) for exportation to the Levant. They wrote treatises, similarly entitled Mémoires de Teinture (Memoirs on Dyeing), illustrated with dozens of dyed textile samples. Janot’s is dated 1744, and Gout’s is dated 1763. These books are full of extremely valuable information, which is unique to its time: the books are composed of carefully described recipes for every colour, each originally preceded by a sample swatch. The yellows of both master dyers made from weld (Reseda luteola L.), belonging to recipes described as Jaune (yellow), were reproduced. The influence of the ingredients, in both the mordanting and dyeing baths, was assessed, and the timings for both baths, which in many recipes are not clear, were tested. This provided key knowledge on the technological processes for dyeing with weld from these 18th c. French masters. The resulting reference samples were preliminarily analysed by a multi-analytical approach. Their chromatic specifications, expressed in the CIEL*a*b*, were compared with those in the Mémoires. Moreover, the influence of the recipe on the percentages of the chromophores was assessed by HPLC-DAD. It was found that the bran and tartar in the mordanting bath influence the final obtained colour and that lime is essential to obtain a bright yellow. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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21 pages, 30447 KiB  
Article
Paul Delvaux: The Study of Nine Paintings by Non-Invasive Methods
by Edène Derzelle, David Strivay, Antoine Defeyt, Sarah-Jane Klein, Francisca Vandepitte and Catherine Defeyt
Heritage 2023, 6(11), 7181-7201; https://doi.org/10.3390/heritage6110376 - 17 Nov 2023
Viewed by 1935
Abstract
Paul Delvaux (1897–1994) was a Belgian Surrealist painter known for his dreamlike and enigmatic compositions. His works often featured nude or semi-nude women and deserted urban landscapes, evoking a sense of mystery and intrigue. Delvaux’s meticulous attention to detail and masterful use of [...] Read more.
Paul Delvaux (1897–1994) was a Belgian Surrealist painter known for his dreamlike and enigmatic compositions. His works often featured nude or semi-nude women and deserted urban landscapes, evoking a sense of mystery and intrigue. Delvaux’s meticulous attention to detail and masterful use of light and shadow added depth and realism to his surrealistic style, making him one of the leading figures of the Belgian Surrealist movement. Although writings about Paul Delvaux’s work are not lacking, the literature mainly deals with the stylistic and iconographic aspects of his work. Taking an interest in painting materials and the painter’s technique allows us to understand his personality and to apprehend his work in a different way. In order to collect such information, the early painted production of Delvaux was studied in situ with imaging methods (high-resolution photography, infrared reflectography and X-ray radiography) and non-invasive analytical techniques (MA-XRF and Raman spectroscopy). The results obtained for nine oil paintings produced from 1928 to 1958 are discussed in terms of the support, the preparatory layer, the preparatory drawing, the changes in composition and reuse of paintings, the pictorial layer and the dripping phenomenon. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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19 pages, 11811 KiB  
Article
On Devotional Artworks: A Non-Invasive Characterization of Pigments of the Madonna della Croce Wall Painting in Triggiano (Bari, Southern Italy)
by Giovanna Fioretti, Cinzia Campobasso, Giacomo Eramo, Alessandro Monno and Gioacchino Tempesta
Heritage 2023, 6(5), 4263-4281; https://doi.org/10.3390/heritage6050225 - 11 May 2023
Cited by 1 | Viewed by 1546
Abstract
Devotional artworks represent a valuable form of art, as they are evidence of religious worship and the demo-ethno-anthropological, as well as historical-artistic, heritage of a community, which is why they definitely belong to the cultural identity of a geographic area. The Madonna della [...] Read more.
Devotional artworks represent a valuable form of art, as they are evidence of religious worship and the demo-ethno-anthropological, as well as historical-artistic, heritage of a community, which is why they definitely belong to the cultural identity of a geographic area. The Madonna della Croce wall painting is an example of devotional art preserved today in the homonymous church in Triggiano (Bari, Italy). The presented study concerns the characterization of pigments used in the painting. The identification of pictorial materials had the aim of providing a contribution to knowledge about the painting, the history of restorations, and other historical events, and to increase the information about the Apulian painting to better reconstruct the social, cultural, and economic contexts of the region. Through a non-invasive and fast methodological approach, including portable digital microscopy, colorimetry, fibre optic reflectance spectroscopy (FORS), and X-ray fluorescence spectroscopy (XRF); 42 points considered on coloured areas were analysed in situ, and results on pigment identification were achieved. According to the local wall painting tradition, red and yellow ochres, green earth, vine black, massicot, and lead-tin yellow were found. Furthermore, both indigo-woad dye and a mixture of vine black and yellow ochre to obtain a blueish colour on the Virgin’s mantle were highlighted. Full article
(This article belongs to the Special Issue Pigment Identification of Cultural Heritage Materials)
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