Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation

Gianluca Pastorelli; Annette S.Ortiz Miranda; Ermanno Avranovich Clerici; Paolo d'Imporzano; Birgit Vinther Hansen; Koen Janssens; Gareth R. Davies; Niels Borring

doi:10.1016/j.microc.2024.109912

Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation

Gianluca Pastorelli^*, Annette S.Ortiz Miranda, Ermanno Avranovich Clerici, Paolo d'Imporzano, Birgit Vinther Hansen, Koen Janssens, Gareth R. Davies, Niels Borring

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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Abstract

Old master drawings and historic prints often feature white highlights, which are typically painted using lead white, one of the most widely used historical white pigments. However, it has been observed that many of these highlights discolour over time, becoming dark brown or black due to unclear degradation processes. This phenomenon not only misrepresents the original artefacts, threatening their suitability for public display, but also diminishes their longevity. To ensure their preservation, it is essential to determine why some lead white highlights in these museum objects retain their light tones while others are prone to darkening. The objective of this study was to identify the relationships between the composition, provenance, and production methods of lead white pigments, and their role in the discolouration observed on drawings, lithographs and early photographs. Selected samples and artefacts were examined using a range of analytical techniques, namely X-ray fluorescence spectroscopy (XRF), X-ray powder diffraction (XRPD), and lead isotope analysis. While XRF analyses confirmed the presence of lead as the primary element in the majority of the highlights, XRPD measurements identified a variety of lead compounds such as the carbonates cerussite and hydrocerussite alongside galena—a black crystalline sulfide—and lead sulfates. Additionally, isotope analyses classified the lead raw materials into five main groups. Through these measurements, the examined lead white pigments were categorised based on their compositional properties in relation to the raw materials used, as well as their geographical and temporal origin. A significant finding is that lead white pigments from different production periods, spanning from older to more modern, may be characterised by varying proneness to discolouration irrespective of their provenance.

Original language	English
Article number	109912
Pages (from-to)	1-10
Number of pages	10
Journal	Microchemical Journal
Volume	199
Early online date	3 Jan 2024
DOIs	https://doi.org/10.1016/j.microc.2024.109912
Publication status	Published - Apr 2024

Bibliographical note

Funding Information:
The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union's Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights.

Funding Information:
The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights.

Publisher Copyright:
© 2024 Elsevier B.V.

Funding

The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union's Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights. The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights.

Funders	Funder number
Danish Agency for Culture and Palaces
Danish Ministry of Culture's Research Committee
Lektor Peer Rander Amundsens Legat – Fond
SLKS
Villum Fonden
Horizon 2020 Framework Programme
Interreg
King Faisal University
European Synchrotron Radiation Facility	HG-172
European Synchrotron Radiation Facility
Horizon 2020	G054719N, 870313
Horizon 2020
European Regional Development Fund

Keywords

Historic prints
Lead isotope analysis
Lead white discoloration
Old master drawings
X-ray fluorescence spectroscopy
X-ray powder diffraction

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10.1016/j.microc.2024.109912

Darkening of lead white in old master drawings and historic printsFinal published version, 11.2 MBLicence: Article 25fa Dutch Copyright Act

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Cite this

@article{8c6a2d94486a4a64a9c413b221d96afa,

title = "Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation",

abstract = "Old master drawings and historic prints often feature white highlights, which are typically painted using lead white, one of the most widely used historical white pigments. However, it has been observed that many of these highlights discolour over time, becoming dark brown or black due to unclear degradation processes. This phenomenon not only misrepresents the original artefacts, threatening their suitability for public display, but also diminishes their longevity. To ensure their preservation, it is essential to determine why some lead white highlights in these museum objects retain their light tones while others are prone to darkening. The objective of this study was to identify the relationships between the composition, provenance, and production methods of lead white pigments, and their role in the discolouration observed on drawings, lithographs and early photographs. Selected samples and artefacts were examined using a range of analytical techniques, namely X-ray fluorescence spectroscopy (XRF), X-ray powder diffraction (XRPD), and lead isotope analysis. While XRF analyses confirmed the presence of lead as the primary element in the majority of the highlights, XRPD measurements identified a variety of lead compounds such as the carbonates cerussite and hydrocerussite alongside galena—a black crystalline sulfide—and lead sulfates. Additionally, isotope analyses classified the lead raw materials into five main groups. Through these measurements, the examined lead white pigments were categorised based on their compositional properties in relation to the raw materials used, as well as their geographical and temporal origin. A significant finding is that lead white pigments from different production periods, spanning from older to more modern, may be characterised by varying proneness to discolouration irrespective of their provenance.",

keywords = "Historic prints, Lead isotope analysis, Lead white discoloration, Old master drawings, X-ray fluorescence spectroscopy, X-ray powder diffraction",

author = "Gianluca Pastorelli and Miranda, \{Annette S.Ortiz\} and Clerici, \{Ermanno Avranovich\} and Paolo d'Imporzano and Hansen, \{Birgit Vinther\} and Koen Janssens and Davies, \{Gareth R.\} and Niels Borring",

note = "Funding Information: The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union's Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkels{\o} Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and J{\o}rgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights. Funding Information: The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union{\textquoteright}s Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkels{\o} Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and J{\o}rgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights. Publisher Copyright: {\textcopyright} 2024 Elsevier B.V.",

year = "2024",

month = apr,

doi = "10.1016/j.microc.2024.109912",

language = "English",

volume = "199",

pages = "1--10",

journal = "Microchemical Journal",

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T1 - Darkening of lead white in old master drawings and historic prints

T2 - A multi-analytical investigation

AU - Pastorelli, Gianluca

AU - Miranda, Annette S.Ortiz

AU - Clerici, Ermanno Avranovich

AU - d'Imporzano, Paolo

AU - Hansen, Birgit Vinther

AU - Janssens, Koen

AU - Davies, Gareth R.

AU - Borring, Niels

N1 - Funding Information: The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union's Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights. Funding Information: The authors gratefully acknowledge funding from The Villum Foundation, Tauck Ritzau Innovative Philanthropy, The Danish Ministry of Culture's Research Committee (KFU), Lektor Peer Rander Amundsens Legat – Fond, and The Danish Agency for Culture and Palaces (SLKS). The authors also express sincere gratitude to the European Synchrotron Radiation Facility (ESRF) for providing access to their synchrotron radiation resources, and are grateful to Marine Cotte, Manfred Burghammer, Alexey Melnikov, Jiliang Liu and Ida Fazlic for assistance in using beamline ID13 (proposal HG-172, pilot of a BAG project supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline). FWO (Brussels) is acknowledged for financial support under grant G054719N and Smart*Light (funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund ERDF). Finally, the authors thank Sofie Wikkelsø Jensen (National Gallery of Denmark) for technical assistance in the collection and preparation of the samples used in this research, and Jørgen Wadum (WATS – Wadum Art Technological Studies, Denmark) for his valuable insights. Publisher Copyright: © 2024 Elsevier B.V.

PY - 2024/4

Y1 - 2024/4

N2 - Old master drawings and historic prints often feature white highlights, which are typically painted using lead white, one of the most widely used historical white pigments. However, it has been observed that many of these highlights discolour over time, becoming dark brown or black due to unclear degradation processes. This phenomenon not only misrepresents the original artefacts, threatening their suitability for public display, but also diminishes their longevity. To ensure their preservation, it is essential to determine why some lead white highlights in these museum objects retain their light tones while others are prone to darkening. The objective of this study was to identify the relationships between the composition, provenance, and production methods of lead white pigments, and their role in the discolouration observed on drawings, lithographs and early photographs. Selected samples and artefacts were examined using a range of analytical techniques, namely X-ray fluorescence spectroscopy (XRF), X-ray powder diffraction (XRPD), and lead isotope analysis. While XRF analyses confirmed the presence of lead as the primary element in the majority of the highlights, XRPD measurements identified a variety of lead compounds such as the carbonates cerussite and hydrocerussite alongside galena—a black crystalline sulfide—and lead sulfates. Additionally, isotope analyses classified the lead raw materials into five main groups. Through these measurements, the examined lead white pigments were categorised based on their compositional properties in relation to the raw materials used, as well as their geographical and temporal origin. A significant finding is that lead white pigments from different production periods, spanning from older to more modern, may be characterised by varying proneness to discolouration irrespective of their provenance.

AB - Old master drawings and historic prints often feature white highlights, which are typically painted using lead white, one of the most widely used historical white pigments. However, it has been observed that many of these highlights discolour over time, becoming dark brown or black due to unclear degradation processes. This phenomenon not only misrepresents the original artefacts, threatening their suitability for public display, but also diminishes their longevity. To ensure their preservation, it is essential to determine why some lead white highlights in these museum objects retain their light tones while others are prone to darkening. The objective of this study was to identify the relationships between the composition, provenance, and production methods of lead white pigments, and their role in the discolouration observed on drawings, lithographs and early photographs. Selected samples and artefacts were examined using a range of analytical techniques, namely X-ray fluorescence spectroscopy (XRF), X-ray powder diffraction (XRPD), and lead isotope analysis. While XRF analyses confirmed the presence of lead as the primary element in the majority of the highlights, XRPD measurements identified a variety of lead compounds such as the carbonates cerussite and hydrocerussite alongside galena—a black crystalline sulfide—and lead sulfates. Additionally, isotope analyses classified the lead raw materials into five main groups. Through these measurements, the examined lead white pigments were categorised based on their compositional properties in relation to the raw materials used, as well as their geographical and temporal origin. A significant finding is that lead white pigments from different production periods, spanning from older to more modern, may be characterised by varying proneness to discolouration irrespective of their provenance.

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KW - Lead isotope analysis

KW - Lead white discoloration

KW - Old master drawings

KW - X-ray fluorescence spectroscopy

KW - X-ray powder diffraction

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M3 - Article

AN - SCOPUS:85182625095

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VL - 199

SP - 1

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JF - Microchemical Journal

M1 - 109912

ER -

Darkening of lead white in old master drawings and historic prints: A multi-analytical investigation

Abstract

Bibliographical note

Funding

Keywords

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