Environmental effects on surface lead–calcium apatite formation on Roman wall paintings

Abstract The formation of lead apatites in heritage objects is increasingly recognized as a recurrent phenomenon, however their origins and formation mechanisms remain poorly understood. This study explores the process behind the darkening and surface clouding in Roman fresco paintings, providing no...

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Main Authors: Francesc Albert-Tortosa, Núria Jiménez, Trinitat Pradell, Salvador Butí, Victoria Beltran, Lídia Font, Nati Salvadó
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Scientific Reports
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Online Access:https://doi.org/10.1038/s41598-025-03620-5
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author Francesc Albert-Tortosa
Núria Jiménez
Trinitat Pradell
Salvador Butí
Victoria Beltran
Lídia Font
Nati Salvadó
author_facet Francesc Albert-Tortosa
Núria Jiménez
Trinitat Pradell
Salvador Butí
Victoria Beltran
Lídia Font
Nati Salvadó
author_sort Francesc Albert-Tortosa
collection DOAJ
description Abstract The formation of lead apatites in heritage objects is increasingly recognized as a recurrent phenomenon, however their origins and formation mechanisms remain poorly understood. This study explores the process behind the darkening and surface clouding in Roman fresco paintings, providing novel insights into the formation of lead-calcium phosphates, PbxCa(5−x)(PO4)3Cly(OH)(1−y), and plattnerite, β-PbO2, from the pigment minium, Pb3O4, linked to interactions with environmental factors and dust deposition. A combination of microanalytical techniques was used, including optical microscopy, scanning electron microscopy and elemental analysis, synchrotron-based X-ray diffraction and Raman and FTIR spectroscopy. The results show that slightly acidic rainwater or atmospheric moisture reacts with the minium and the calcium carbonate present in the wall painting’s binder, resulting in the formation of plattnerite and the release of Pb2+ and Ca2+ ions, while the environment supplies chloride and phosphate ions, present in the infiltrating water. This process culminates in the precipitation of the lead-calcium apatite, due to its high stability. This apatite acts as a cement that incorporates dust and organic residues, forming a layer several tens of micrometres thick that tends to expand outwards. These findings contribute to a better understanding of pigment degradation mechanisms and will help inform conservation strategies.
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spelling doaj-art-3fec36292bbf44beb1828dd5d7f5193a2025-08-20T03:16:51ZengNature PortfolioScientific Reports2045-23222025-05-0115111310.1038/s41598-025-03620-5Environmental effects on surface lead–calcium apatite formation on Roman wall paintingsFrancesc Albert-Tortosa0Núria Jiménez1Trinitat Pradell2Salvador Butí3Victoria Beltran4Lídia Font5Nati Salvadó6Departament d’Enginyeria Química, Universitat Politècnica de Catalunya·BarcelonaTech (UPC). EPSEVGDepartament d’Enginyeria Química, Universitat Politècnica de Catalunya·BarcelonaTech (UPC). EPSEVGDepartament de Física, Centre de Recerca en Ciència i Enginyeria Multiescala de Barcelona, Universitat Politècnica de Catalunya·BarcelonaTech (UPC)Departament d’Enginyeria Química, Universitat Politècnica de Catalunya·BarcelonaTech (UPC). EPSEVGA-sense lab, University of AntwerpMuseu d’Història de Barcelona MUHBA, Institut de Cultura, Ajuntament de BarcelonaDepartament d’Enginyeria Química, Universitat Politècnica de Catalunya·BarcelonaTech (UPC). EPSEVGAbstract The formation of lead apatites in heritage objects is increasingly recognized as a recurrent phenomenon, however their origins and formation mechanisms remain poorly understood. This study explores the process behind the darkening and surface clouding in Roman fresco paintings, providing novel insights into the formation of lead-calcium phosphates, PbxCa(5−x)(PO4)3Cly(OH)(1−y), and plattnerite, β-PbO2, from the pigment minium, Pb3O4, linked to interactions with environmental factors and dust deposition. A combination of microanalytical techniques was used, including optical microscopy, scanning electron microscopy and elemental analysis, synchrotron-based X-ray diffraction and Raman and FTIR spectroscopy. The results show that slightly acidic rainwater or atmospheric moisture reacts with the minium and the calcium carbonate present in the wall painting’s binder, resulting in the formation of plattnerite and the release of Pb2+ and Ca2+ ions, while the environment supplies chloride and phosphate ions, present in the infiltrating water. This process culminates in the precipitation of the lead-calcium apatite, due to its high stability. This apatite acts as a cement that incorporates dust and organic residues, forming a layer several tens of micrometres thick that tends to expand outwards. These findings contribute to a better understanding of pigment degradation mechanisms and will help inform conservation strategies.https://doi.org/10.1038/s41598-025-03620-5Lead calcium apatitePlattneriteWall paintingLead pigmentsSynchrotron-based X-ray diffractionScanning electron microscopy
spellingShingle Francesc Albert-Tortosa
Núria Jiménez
Trinitat Pradell
Salvador Butí
Victoria Beltran
Lídia Font
Nati Salvadó
Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
Scientific Reports
Lead calcium apatite
Plattnerite
Wall painting
Lead pigments
Synchrotron-based X-ray diffraction
Scanning electron microscopy
title Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
title_full Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
title_fullStr Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
title_full_unstemmed Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
title_short Environmental effects on surface lead–calcium apatite formation on Roman wall paintings
title_sort environmental effects on surface lead calcium apatite formation on roman wall paintings
topic Lead calcium apatite
Plattnerite
Wall painting
Lead pigments
Synchrotron-based X-ray diffraction
Scanning electron microscopy
url https://doi.org/10.1038/s41598-025-03620-5
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