Combined Micro- and Macro scale X-ray powder diffraction mapping of degraded Orpiment paint in a 17th century still life painting by Martinus Nellius
The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by...
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| Published in: | Heritage science Vol. 7; no. 1; pp. 1 - 12 |
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| Main Authors: | , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
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Springer International Publishing
01.12.2019
Springer Nature B.V SpringerOpen |
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| ISSN: | 2050-7445, 2050-7445 |
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| Abstract | The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As
2
S
3
) or realgar (α-As
4
S
4
) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (μ-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO
4
), mimetite (Pb
5
(AsO
4
)
3
Cl), palmierite (K
2
Pb(SO
4
)
2
) and syngenite (K
2
Ca(SO
4
)
2
∙H
2
O) have formed. Closer inspection of the cross-sectioned paint layer stack with μ-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting. |
|---|---|
| AbstractList | The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As
2
S
3
) or realgar (α-As
4
S
4
) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (μ-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO
4
), mimetite (Pb
5
(AsO
4
)
3
Cl), palmierite (K
2
Pb(SO
4
)
2
) and syngenite (K
2
Ca(SO
4
)
2
∙H
2
O) have formed. Closer inspection of the cross-sectioned paint layer stack with μ-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting. The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As2S3) or realgar (α-As4S4) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (μ-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO4), mimetite (Pb5(AsO4)3Cl), palmierite (K2Pb(SO4)2) and syngenite (K2Ca(SO4)2∙H2O) have formed. Closer inspection of the cross-sectioned paint layer stack with μ-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting. Abstract The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As2S3) or realgar (α-As4S4) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (μ-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO4), mimetite (Pb5(AsO4)3Cl), palmierite (K2Pb(SO4)2) and syngenite (K2Ca(SO4)2∙H2O) have formed. Closer inspection of the cross-sectioned paint layer stack with μ-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting. |
| ArticleNumber | 83 |
| Author | Simoen, Jonas Van der Snickt, Geert Van Loon, Annelies de Keyser, Nouchka Keune, Katrien De Meyer, Steven Vanmeert, Frederik Janssens, Koen Avranovich, Ermanno |
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| Cites_doi | 10.1039/C4JA00387J 10.1016/j.microc.2016.05.006 10.1039/C4JA00424H 10.2298/JMMB0901059S 10.1002/sia.3125 10.1154/1.1938983 10.1016/j.culher.2011.09.003 10.1179/sic.2002.47.Supplement-1.56 10.1016/j.jas.2014.12.001 10.1107/S1600576714008218 10.2138/am.2005.1785 10.1016/j.jnoncrysol.2006.01.017 10.1002/jrs.4065 10.1016/j.nima.2009.10.094 10.1021/acs.analchem.8b00240 10.1002/jrs.5037 10.2138/am-2003-11-1244 10.1039/c3an00892d 10.1021/ac802518z 10.1002/jrs.4556 10.1186/s40494-017-0151-4 10.2113/gscanmin.41.6.1463 10.1039/C6JA00134C 10.1017/S1431927613009033 10.1016/j.microc.2010.05.013 10.1007/s10064-001-0150-1 10.1016/j.conbuildmat.2015.08.101 10.1127/0935-1221/2004/0016-0609 10.1039/b801358f 10.1021/acs.analchem.8b00241 10.1111/arcm.12087 10.1039/c3ja30341a 10.1039/c0ja00151a 10.1021/ac3015627 10.1186/s40494-017-0125-6 10.1021/acs.analchem.9b00328 |
| ContentType | Journal Article |
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| Snippet | The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are... Abstract The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while... |
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| SubjectTerms | 17th century 5th International Congress on Chemistry for Cultural Heritage Arsenates Arsenic trisulfide Arsenic-based pigments Artists Chemistry and Materials Science Degradation Inspection Light diffraction Mapping Materials Science Minerals Non-invasive imaging Organic chemistry Oxidation Pigments Research Article Still life painting Valence X ray powder diffraction |
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| Title | Combined Micro- and Macro scale X-ray powder diffraction mapping of degraded Orpiment paint in a 17th century still life painting by Martinus Nellius |
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