Margarito d’Arezzo: Orpiment

Discover how the pigment orpiment is used in one of the oldest paintings in the National Gallery’s collection and why it can be so difficult to find

The Virgin and Child Enthroned, with Scenes of the Nativity and the Lives of the Saints (probably about 1263-4) by Margarito d'ArezzoThe National Gallery, London

The Gallery's oldest painting

One of the oldest paintings in the National Gallery’s collection is 'The Virgin and Child Enthroned' by Margarito d’Arezzo, dated to about 1263–4.  It was purchased by the Gallery in 1857. 

The painting shows the Christ Child and his mother, the Virgin Mary, in a mandorla (an almond-shaped enclosure) surrounded by scenes of the nativity and from the lives of saints, all set against a gilded (gold leaf) background. 

During a recent conservation treatment, overpaint was removed from the wide red border of the inner edge of the frame to reveal an original red border with a foliate (leaflike) decoration.

This decoration was painted in a strongly-coloured yellow.

Photomicrograph of NG564 and image of sample cross-section, acquired using a microscopeThe National Gallery, London

Microscopic examination of the paint surface and analysis of a tiny sample obtained from this yellow design, revealed that the yellow pigment, orpiment, had been used. 

Photomicrograph of NG564 (detail of design uncovered on frame)The National Gallery, London

Orpiment

Orpiment is a yellow arsenic-containing pigment. It has a long history of use and has been identified in early European panel paintings, manuscript illumination and polychrome sculpture. It continued to be used by later artists, particularly in 16th-century Venetian paintings.  

Orpiment can degrade over time, decomposing to the white substance, arsenic trioxide.​​ However, in the foliate design, it has not degraded because it was protected by various layers above it, including a yellow glaze and the red overpaint.  

Detail of NG564 with corresponding arsenic map, acquired using the scanning X-ray fluorescence (sXRF) instrumentThe National Gallery, London

Scanning X-ray fluorescence

To identify where orpiment had been used in other areas of the painting, analysis using a non-destructive technique (scanning X-ray fluorescence) was performed. This technique can map where a specific chemical element is present. 

Here, arsenic-containing areas in this detail are shown in white on the map on the right. 

Detail of the arsenic map for NG564, acquired using the scanning X-ray fluorescence (sXRF) instrumentThe National Gallery, London

Since both orpiment and its alteration product contain arsenic, we can use this technical image to identify where orpiment was used, even if the pigment has degraded and no longer appears yellow in colour. 

The border design, painted using orpiment, is clearly visible at the top of the image. ​ 

Detail of NG564 (showing the mandorla) and the corresponding area indicated on the arsenic mapThe National Gallery, London

Orpiment was also used in other areas of the painting, such as in the design on the mandorla around the Virgin. ​ These areas are clearly visible in the arsenic map, but the orpiment here has degraded and is therefore now scarcely visible to the naked eye (see painting detail on the left).

Detail of NG564 and the corresponding area on the combined arsenic (yellow) and lead (blue) map, acquired using the scanning X-ray fluorescence (sXRF) instrumentThe National Gallery, London

Perhaps most spectacularly, an intricate repeat pattern on the Virgin’s dress, originally painted using bright yellow orpiment and now barely visible when looking at the painting with the human eye, is revealed in incredible detail through XRF scanning.

The Virgin and Child Enthroned, with Scenes of the Nativity and the Lives of the Saints (probably about 1263-4) by Margarito d'ArezzoThe National Gallery, London

This modern scientific analysis is providing new insights into both the materials and techniques which would have been used to create our oldest painting, Margarito d’Arezzo’s, 'The Virgin and Child Enthroned'. 

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