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Raman spectroscopic study of “The Malatesta”: A Renaissance painting?
Accepted Manuscript Raman Spectroscopic Study of “The Malatesta” : A Renaissance Painting ? Howell G.M. Edwards, Peter Vandenabeele, Timothy J. Benoy PII: DOI: Reference:
S1386-1425(14)01128-7 http://dx.doi.org/10.1016/j.saa.2014.07.047 SAA 12467
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received Date: Revised Date: Accepted Date:
24 April 2014 2 July 2014 18 July 2014
Please cite this article as: H.G.M. Edwards, P. Vandenabeele, T.J. Benoy, Raman Spectroscopic Study of “The Malatesta” : A Renaissance Painting ?, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.07.047
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Raman Spectroscopic Study of “The Malatesta” : A Renaissance Painting ?
Howell G.M. Edwards 1* , Peter Vandenabeele 2 and Timothy J. Benoy 3
1
Chemical and Forensic Sciences , School of Life Sciences, University of Bradford,
Bradford, West Yorkshire BD7 1DP , UK .
2
Laboratory for Archaeometry ,Department of Archaeology , Faculty of Arts and Philosophy,
University of Ghent , Sint-Pietersnieuwstraat 35, B-9000 Ghent , Belgium.
3
The de Brecy Trust , de Brecy House , Lower Withington , Macclesfield , Cheshire SK11
9DF , UK .
*Author for correspondence : Professor Howell G.M. Edwards [email protected]
1
Abstract Raman spectroscopic analysis of the pigments on an Italian painting described as a "Full Length Portrait of a Gentleman " , known also as the "Malatesta" , and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier . Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet , Prince of Denmark . The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research .
Keywords : Renaissance painting , pigments , chrome yellow addition , Malatesta, art analysis, archaeometry.
2
Highlights - Pigment analysis of an oil painting was performed by using Raman spectroscopy - The majority of the pigments were consistent with assignment to the renaissance period, excepted the presence of chrome yellow. - The presence of chrome yellow is consistent historically with a 19th century retouching. - This work shows that a combination of pigment analysis with historical research is needed for full provenancing of works of art.
3
Introduction
An unsigned oil painting on canvas described as a "Full Length Portrait of a Gentleman", acquired by collector the late George Lester Winward at an auction sale of paintings in Knutsford, Cheshire, UK, in 1982 and measuring some 41" x 29", is shown in Figure 1. It was initially believed to be a copy of a celebrated work of 1801 being a portrait by Sir Thomas Lawrence of the Shakespearean actor J. P. Kemble in the role of Hamlet, Prince of Denmark, now in the Tate Britain Gallery. In that portrait, which later became part of the Royal Collection under King George IV and King William IV and was eventually acquired by the National Gallery in 1836, Hamlet is holding Yorick's skull in his left hand and a pickaxe and grave are evident in the foreground. However, closer inspection reveals that the subject under study here is not in fact holding a skull but a flask or purse and that the graveyard symbols of pickaxe and grave are both absent. Moreover, Lawrence's depiction of Kemble as Hamlet shows that Kemble had dark hair and eyes and a dimpled chin, whereas the figure in the painting under investigation here has fair hair, blue eyes and no dimple. It is therefore considered that it is not in fact a representation of John Kemble as Hamlet but is an actual portrait of a medieval lord. Lawrence's Hamlet has a chest medallion depicting an elephant, apparently just as shown in the Figure 1 painting, the medallion being correlated with the principal ensign of the Royal House of Denmark which is the Order of the Elephant. Significantly however, this Danish Order depicts both an elephant and a castle, whereas close inspection of the medallion in the subject painting reveals that it is a relief of an elephant carrying a howdah, not a castle. Detailed historical research revealed that an elephant, such as that depicted on the medal on the subject's chest, was the symbol of the House of Malatesta, Lords of Rimini, who ruled an area of central Italy from ca. 1300-1500. The most famous scion was Sigismondo Pandolfo Malatesta (1417-1468), who was the archetypal Italian Renaissance prince. A profiled head of Sigismondo in the style of the Emperor Augustus by the Florentine sculptor di Duccio is comparable with the subject of this painting and it is recorded that
4
the Malatestas were fond of their personification and representation as Caesar Augustus (63 BC- 14 AD), the founder of Rimini [1].
In 2004, the de Brecy Trust commissioned an X-ray study of this painting, which indicated that the subject is wearing Ottoman Turkish slippers, an example of luxurious attire and Turkish costumes which have been recorded in an inventory of Sigismondo's effects after his death in Castel Sigismondo and for which he and his wife Isotta da Rimini had particular affection [2].
Historical research has therefore led to the proposition that the subject painting is a portrait of the medieval lord Sigismondo Pandolfo Malatesta standing outside the fortified walls of Rimini. The court painter of Sigismondo at this time was Piero della Francesca (ca. 1415-1492), who for many years has not been recognised for his ability but who is now celebrated as a truly great Renaissance artist. Piero had a preference for direct frontal images and his use of structural colour in a strictly limited palette, often using similar colours to engage with different areas of the canvas [3,4]. A favourite colour was reddish-plum as exemplified here in the Malatesta lord's fur-lined coat. Piero was noted for his use of very few coloured pigments and the expression of the subject figure in the Malatesta painting under investigation here is very similar to that employed in a detail from Piero's famous Madonna della Misericordia painted in 1460-1462.
It is believed that Sir Thomas Lawrence saw this painting in the London home of Sir Watkin WilliamsWynn, at 20 St James's Square, when he was commissioned to paint the portrait of the 5th Baronet (1772-1840) there in about 1790 [5] and later used it as a model for his 1801 painting of Kemble as Hamlet. In 1768 the 4th Baronet, father of Sir Watkin Williams-Wynn and of the same name, made an 8-month Grand Tour of Italy during which time he acquired an extensive collection of Italian 5
pictures from art dealers. To display his vast collection of Old Master paintings and contemporary theatrical character studies, Williams-Wynn employed Robert and James Adam to rebuild his home in 20 St James's Square, London, between 1772 and 1774 and it is not surprising that London society regarded this address as having the ambience of a private art academy [6]. Lawrence would have been well-acquainted with Williams-Wynn and his family, also painting portraits of his two children, which were delivered to him in 1830 [7]. Lawrence lived close by 20 St James's Square and would have been a frequent visitor to the Baronet's home for nearly three decades because of the art collection amassed there by his friend and patron, especially the portraits of theatrical characters the subject of which were to become Lawrence's artistic professional mainstay. Towards the middle of the 19th Century, many artworks were rehoused in the country home of the Williams-Wynn Family at Wynnstay, Ruabon, North Wales and a new picture gallery was commissioned there for this purpose. During alterations in 1858 a great fire broke out and in the confusion members of the household, estate workers, neighbouring landowners and helpers all assisted in the emergency removal of many priceless works of art, but Wynnstay and much of its art collection were destroyed [8]. However, it is recorded that certain paintings believed to have been lost in the fire were in fact saved, the circumstances therefore affording an opportunity for paintings which survived the fire to be subsequently dispersed onto the local art market over the succeeding two centuries. In this way it is believed that the "Malatesta" found its way into the Cheshire auction rooms, whence it was purchased by the late collector in 1982.
The connection with Sir Thomas Lawrence is a very relevant one historically and scientifically since Lawrence was the first recorded artist to use the newly-synthesised yellow pigment, chrome yellow, lead (II) chromate, in 1809 in his 'Portrait of a Gentleman'. It is, therefore, of critical importance to determine if this painting predates that of Sir Thomas Lawrence and if it was executed during the
6
lifetime of Sigismondo Pandolfo Malatesta, consistent with its possible placement in the Renaissance period.
The scientific analysis of artworks based upon the identification of pigments has been receiving much attention with the adoption of techniques that are either completely noninvasive or which otherwise require only minimal sampling and physical intervention ; in this respect , Raman spectroscopy has provided a demonstrably important role for the characterisation of mineral and organic pigments and their binders from a molecular standpoint , reinforced by the chemical elemental information derived from other more destructive analytical techniques [9,10]. From such pigment studies , although the correct historical provenancing of a painting is only realistically achievable within a broad timescale because of the common usage of pigments often over hundreds of years , the exposure of fakes through forensic scientific art detection is often realised through the identification of rogue pigments in an artwork that did not exist at its supposed time of creation [11] . Some very important landmark case-studies have appeared in the literature in recent years to verify this approach and to vindicate the use of spectroscopic analysis for the correct attribution of artworks to specific timelines [12,13,14] . However, it is necessary to exercise some caution in the interpretation of scientific data relating to art works since unrecorded , later restoration of older artefacts and paintings could have been undertaken for a variety of reasons and this will be apparent in our current study .
Experimental Specimens , Sampling Areas , Colours and Pigments Identified Samples were taken by scalpel excision from selected regions of the painting , which was in an unrestored condition : 7
MAL1 : Staff handle , yellow-orange ; lead white , barytes , chrome yellow , vermilion. MAL2 : Staff handle , yellow; lead white , chrome yellow . MAL3 : Bag/purse , yellow-brown; carbon , yellow ochre. MAL4 : Green fronds , green-brown; lead white , carbon , terre verte , massicot, MAL5 : Cape lining edge , purple; vermilion , carbon . MAL6 : Gold staff , wrist area ;lead white , chrome yellow. MAL 7 : Shirt cuff , white; lead white , calcite , gypsum. MAL8 : Rising sun , yellow-orange ; chrome yellow , vermilion MAL9 : Flesh tone , neck area , pink ; lead white , vermilion .
The initial discovery of chrome yellow in highlighted yellow areas of the painting necessitated a resampling procedure in which a further series of specimens were excised , comprising MAL1'-MAL4' , from two further positions on the staff handle , the purse and the greenish-yellow vegetation fronds , as previously identified above .
Raman Spectroscopy Raman spectra were obtained with a Bruker Senterra microRaman system operating with 785 and 532 nm laser excitation ; spectra were recorded over a wavenumber range of 1800-100 cm-1 with a spectral resolution of 4 cm -1 and a 20 X microscope objective , giving a footprint of approximately 5 microns at the specimen . As the pigment samples were heterogeneous , several spectra were obtained of different sample regions in the same specimen to record the pigment components ; in addition , to obviate the background emission effects of varnish degradation in this unrestored and uncleaned artwork , sample fragments were examined on both upper and lower surfaces.
Discussion of Analytical Results
8
The Malatesta painting pigments include those which are typically found in use over a long period of art history during the Renaissance ; the white pigment is characterised by several combinations of lead white , barytes , calcite and gypsum , black pigment by vegetable charcoal , yellow ochre ( goethite ) , terre verte , and vermilion . Massicot , lead (II ) oxide , is clearly identified in several regions and indicates a probable early date for this painting as it was superseded in the 17th Century by newer , more vibrant yellow pigments such as Naples yellow and the tin yellows , types I and II . The use of vermilion and lead white in admixture for the flesh tones is quite typical of a quality painting of this period and other , cheaper red pigments have not been identified in these regions. Figure 2 shows the Raman spectrum of vermilion , with characteristic bands at 250 , 285 , 340 cm -1 and a very weak feature characteristic of lead white at 1050 cm -1 . The most intriguing discovery , however, relates to the presence of lead (II) chromate in the golden yellow areas of the staff and sun , in particular . This is an important discovery as , although lead (II) chromate does occur naturally as the mineral crocoite , it first appeared as a synthetic pigment ( chrome yellow ) following its isolation from crocoite by Vauquelin in 1809 . After this date , chrome yellow quickly became adopted as the vibrant golden yellow pigment of choice by early 19th Century artists , until its decline some three or four decades later because of concerns about lead toxicity and its deterioration in tonal quality due to its darkening in air. Close inspection of the specimens taken from the staff reveals the presence of both massicot ( 140 cm-1 ) and lead chromate ( 827 , 374 , 358 , 324 cm -1 ) in different compositions , as evidenced in Figures 3 and 4; Figure 4 indicates the presence of almost pure massicot , with only a very small signal for lead chromate . Hence , it can be concluded that the pigments identified in the Malatesta painting were of a Renaissance origin , with the exclusion of the chrome yellow ; one possibility is the use of the natural mineral crocoite for the source of the lead chromate , otherwise , a possible attribution to the early 19th century could be considered. The omnipresence of lead white is certainly compatible with the Renaissance but the occasional identification of barytes signals is rather unusual in this context .
9
One should be rather careful , however, in making rigid conclusions about dating a painting to the 19th century solely on the discovery of the presence of a synthetic pigment which properly belongs there ; it is reasonable to infer that after several centuries most artworks would have required some restorative attention and perhaps a “re-touching ” of key areas , especially if they have been exhibited in locations which have been heated with coal fires and lit with candles and oil lamps. Another interesting feature is revealed by the analysis of the Raman spectra of the orange pigment colours ; the spectrum of a specimen taken from the region of the staff handle in Figure 5 shows a rather unusual composition of vermilion , realgar and lead chromate along with barytes. it is interesting to speculate as to whether the original orange composition comprised vermilion (red ) and realgar (yellow) which was heightened later by the application of the yellow lead chromate as it would be inconceivable that the artist would have originally used a mixture of two yellow pigments with the red to achieve the desired orange pigment colour. Figure 6 shows the Raman spectrum of a blue-black coloured cratered area , devoid of varnish , on the right hand side of the painting in which the signatures of lapis lazuli at 545 and 254 cm-1 are evident . Finally , a very curious Raman spectrum was obtained for a dark brown area near the fortification situated at the lower middle left of the painting : a complex group of spectral signatures , shown in Figure 7 , can be assigned to vermilion ( bands at 255 and 283 cm -1 ) and a trio at 1520 , 1157 and 1006 cm -1 which are indicative of a the C=C and C-C stretching vibrations in the polyisoprene skeletal chain of a natural carotenoid [15]. The presence of a carotenoid has two possible implications namely , the artist has utilised the natural bright red-brown colouration of the extracted product found widespread in nature in tomatoes , carrots , lichens and the carapaces of shellfish such as lobster , or alternatively that presence of the carotenoid has arisen from localised biological colonisation of this area of the artwork. The latter occurrence has already been described in the literature [16,17,18] and indeed has been proposed as an early warning signal indicative of 10
the onset of degradative biological colonisation of artworks -- in this , the presence of the toxic mercury (II) ions in the associated vermilion pigment has been shown to not be detrimental to the biological invasion because of the combatative extremophilic survival strategies adopted by the lichens or cyanobacteria concerned [19,20,21].
We have already alluded to a very interesting possible association between this painting in its London home and the artist Sir Thomas Lawrence , who is renowned for his recorded groundbreaking artistic use of chrome yellow as a pigment in his “Portrait of a Gentleman” in 1810 ; Gettens and Stout 22 in their seminal and well-respected encyclopaedia of artists’ pigments comment that the evidential brightening of a yellow ochre pigment in the 19th Century by the newly discovered chrome yellow was recorded . Who better to effect this treatment on a friend’s painting during one of his visits in the early decades of the 19th century than the first advocate and renowned exponent of chrome yellow pigment , Sir Thomas Lawrence , perhaps on occasions in connection with the commission to paint Sir Watkin Williams-Wynn’s two children ? during the period 18201826 when he was commissioned to paint the Sir Watkin Williams-Wynn family portraits in St James Square, London [5] ?
Conclusions It is apparent that the Raman spectroscopic analyses of the putative Renaissance painting are consistent with the pigments identified therein , such as cinnabar , massicot, carbon black, terre verte, calcite, gypsum, and lead white . However, the discovery of chrome yellow , which was synthesised in 1809, in limited zones could probably be attributed to a 19th century retouching process. The probable association of the painting at that time with Sir Thomas Lawrence , an early exponent of the use of chrome yellow pigment ,who executed a similar but later version in 1801 of
11
John Kemble in the role of Hamlet , Prince of Denmark, in Shakespeare’s play , manifestly encourages the invoking of compatible historical research to explain satisfactorily anomalies in otherwise consistent analytical data. The major purpose of this work was pigment identification by using Raman spectroscopy, coupled with historical provenancing. Future research activities should clearly include binder analysis and parallel studies on the physical construction of the canvas. Eventually, isotopical analysis could provide further insight into the possible synthetic or natural origin of particular pigments, such as ultramarine. The results from this current Raman study will provide a focus for targeted future research into the areas of destructive sampling, necessary to solve these problems.
Acknowledgement The authors thank the de Brecy Trust for permission to sample the painting for this study .
References [1] N. Pozza (ed.), Città di Rimini, Sigismondo Pandolfo Malatesta E il suo tempo, 1970, pp. 9495. [2] M.G.Pernis and L.S. Adams, Federico da Montefeltro & Sigismondo Malatesta: The Eagle and the Elephant, Peter Lang, 1996, pp. 66-67 .
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[3] C. Gregory, The Great Artists : Their Lives, Works and Inspiration – Piero della Francesca No. 40, Volume II, 1985, p.1282 and ff., Marshall Cavendish Collection.
[4] K. Clark, Piero della Francesca, Phaidon, London, p.14, 1969.
[5] K. Garlick, Sir Thomas Lawrence, Phaidon, London, 1989, p.200.
[6] S. Houfe, A Wealth of Taste, Country Life, 19th September, 1991, pp.108-109.
[7] K. Garlick, Sir Thomas Lawrence, Phaidon, London, 1989, p.200 .
[8] T. Pritchard, The Wynns of Wynnstay, Old Court Press, Caerwys, 1982, p.27.
[9] P. Vandenabeele , H.G.M. Edwards and L.Moens , Chemical Reviews , 107 , pp.675-686 ( 2007).
[10] H.G.M. Edwards and J.M. Chalmers ( eds.) , Raman Spectroscopy in Archaeology and Art History, RSC Analytical Chemistry Spectroscopy Monographs Series , Royal Society of Chemistry Publishing , Cambridge , UK , 476 pp. (2005) ; ISBN : 0-85404-522-8.
[11] H.G.M. Edwards , Raman Spectroscopy of Inorganic Materials in Art & Archaeology : Spectroscopic Analysis of Historical Mysteries , , Specialist Periodical Reports , Spectroscopic Properties of Inorganic and Organometallic Compounds : Materials and Applications , Volume 40 , eds. J. Yarwood , R. Douthwaite and S.B. Duckett , Royal
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Society of Chemistry Publishing , Cambridge , pp. 16-48 (2009). (ISBN : 978-1-84755- 9180). [12] L. Burgio, R.J.H. Clark, L. Sheldon and G.D. Smith, Analytical Chemistry, 77, pp.1261-1267 (2005). [13] H.G.M. Edwards and T.J. Benoy , Analytical and Bioanalytical Chemistry , 387 , pp.837-846 (2007). [14] P. Vandenabeele, M. Vandekerckhove, B. Vandekerckhove and L. Moens, Comment peut la spectroscopic Raman aider à l'etude de l'oeuvre du René Magritte? In: Actes du colloque Magritte en perspective cavalière, Brussels 5-7 may 2003 (2003). [15 ] C.G. de Almeida , B.S. Ferreira , M. le Hyaric , V.E. de Oliveira , H.G.M. Edwards and L.F.C. de Oliveira, Spectroscopy Letters , 46 , pp.122-127 ( 2013 ).
[16] H.G.M. Edwards , Raman Spectroscopy in Art and Archaeology : A New Light on Historical Mysteries , In “Frontiers of Molecular Spectroscopy”, ed. J. Laane , Elsevier Press , Amsterdam , pp. 133-173 (2009) ISBN 13: 978-0-444-53175-9.
[17] F.Rull Perez and H.G.M. Edwards ,FT-Raman Spectroscopy of Frescoes and Ancient WallPaintings : Their Pigment Application , Adulteration , Biodeterioration and Restoration , In “ Selected Topics in Raman Spectroscopic Applications : Geology , Biomaterials and Art” , eds. F.Rull Perez , H.G.M. Edwards , D.C. Smith and P. Vandenabeele , University of Valladolid Press Publidisia , Valladolid , Spain , pp.161-192 ( 2007) ( ISBN : 978-84-690-9239-2 ). [18] H.G.M. Edwards and P. Vandenabeele, Analytical Archaeometry : Selected Topics , Eds., Royal Society of Chemistry , Cambridge , 604 pp. ( 2012 ). ISBN : 978-1-84973162-1. [19] H.G.M. Edwards, Spectrochimica Acta Part A , 68 , pp. 1531-1539 (2007 ).
[20] H.G.M. Edwards, Analyst , 129 , pp.870-879 (2004 ). 14
[21] D.D.Wynn-Willams and H.G.M.Edwards, Icarus, 144, pp. 486-503 (2000).
[22] R.J. .Gettens and G.L. Stout , Painting Materials : A Short Encyclopedia , D. van Nostrand , New York ,1962.
Figure Captions Figure 1. " Full Length Portrait of a Gentleman" , known as the Malatesta painting , analysed in the present work. Figure 2. The Raman spectrum of a flesh tone specimen ( MAL 9) with characteristic bands of vermilion at 250 , 280 and 340 cm -1 , and a very weak feature of basic lead (II) carbonate ( lead white ) at 1050 cm-1 . Figure 3. Raman spectrum of the yellow staff handle ( MAL4P) indicative of a mixture of chrome yellow ( major component ) and massicot ( minor component ) . Figure 4 . Raman spectrum of the yellow staff handle ( MAL4G) indicative of almost pure massicot with a very minor chrome yellow component . Figure 5. Raman spectrum of orange pigment (MAL1D) with characteristic bands of vermilion , realgar and lead chromate along with barytes and lead white. Figure 6. Raman spectrum of blue-black cratered area ( M1J ) with characteristic bands of lapis lazuli. Figure 7 . Raman spectrum of dark brown area near fortification (M7K) with complex spectrum indicative of vermilion and a carotenoid .
15
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Highlights - Pigment analysis of an oil painting was performed by using Raman spectroscopy - The majority of the pigments were consistent with assignment to the renaissance period, excepted the presence of chrome yellow. - The presence of chrome yellow is consistent historically with a 19th century retouching. - This work shows that a combination of pigment analysis with historical research is needed for full provenancing of works of art.
16
S1386-1425(14)01128-7 http://dx.doi.org/10.1016/j.saa.2014.07.047 SAA 12467
To appear in:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Received Date: Revised Date: Accepted Date:
24 April 2014 2 July 2014 18 July 2014
Please cite this article as: H.G.M. Edwards, P. Vandenabeele, T.J. Benoy, Raman Spectroscopic Study of “The Malatesta” : A Renaissance Painting ?, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.07.047
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Raman Spectroscopic Study of “The Malatesta” : A Renaissance Painting ?
Howell G.M. Edwards 1* , Peter Vandenabeele 2 and Timothy J. Benoy 3
1
Chemical and Forensic Sciences , School of Life Sciences, University of Bradford,
Bradford, West Yorkshire BD7 1DP , UK .
2
Laboratory for Archaeometry ,Department of Archaeology , Faculty of Arts and Philosophy,
University of Ghent , Sint-Pietersnieuwstraat 35, B-9000 Ghent , Belgium.
3
The de Brecy Trust , de Brecy House , Lower Withington , Macclesfield , Cheshire SK11
9DF , UK .
*Author for correspondence : Professor Howell G.M. Edwards [email protected]
1
Abstract Raman spectroscopic analysis of the pigments on an Italian painting described as a "Full Length Portrait of a Gentleman " , known also as the "Malatesta" , and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier . Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet , Prince of Denmark . The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research .
Keywords : Renaissance painting , pigments , chrome yellow addition , Malatesta, art analysis, archaeometry.
2
Highlights - Pigment analysis of an oil painting was performed by using Raman spectroscopy - The majority of the pigments were consistent with assignment to the renaissance period, excepted the presence of chrome yellow. - The presence of chrome yellow is consistent historically with a 19th century retouching. - This work shows that a combination of pigment analysis with historical research is needed for full provenancing of works of art.
3
Introduction
An unsigned oil painting on canvas described as a "Full Length Portrait of a Gentleman", acquired by collector the late George Lester Winward at an auction sale of paintings in Knutsford, Cheshire, UK, in 1982 and measuring some 41" x 29", is shown in Figure 1. It was initially believed to be a copy of a celebrated work of 1801 being a portrait by Sir Thomas Lawrence of the Shakespearean actor J. P. Kemble in the role of Hamlet, Prince of Denmark, now in the Tate Britain Gallery. In that portrait, which later became part of the Royal Collection under King George IV and King William IV and was eventually acquired by the National Gallery in 1836, Hamlet is holding Yorick's skull in his left hand and a pickaxe and grave are evident in the foreground. However, closer inspection reveals that the subject under study here is not in fact holding a skull but a flask or purse and that the graveyard symbols of pickaxe and grave are both absent. Moreover, Lawrence's depiction of Kemble as Hamlet shows that Kemble had dark hair and eyes and a dimpled chin, whereas the figure in the painting under investigation here has fair hair, blue eyes and no dimple. It is therefore considered that it is not in fact a representation of John Kemble as Hamlet but is an actual portrait of a medieval lord. Lawrence's Hamlet has a chest medallion depicting an elephant, apparently just as shown in the Figure 1 painting, the medallion being correlated with the principal ensign of the Royal House of Denmark which is the Order of the Elephant. Significantly however, this Danish Order depicts both an elephant and a castle, whereas close inspection of the medallion in the subject painting reveals that it is a relief of an elephant carrying a howdah, not a castle. Detailed historical research revealed that an elephant, such as that depicted on the medal on the subject's chest, was the symbol of the House of Malatesta, Lords of Rimini, who ruled an area of central Italy from ca. 1300-1500. The most famous scion was Sigismondo Pandolfo Malatesta (1417-1468), who was the archetypal Italian Renaissance prince. A profiled head of Sigismondo in the style of the Emperor Augustus by the Florentine sculptor di Duccio is comparable with the subject of this painting and it is recorded that
4
the Malatestas were fond of their personification and representation as Caesar Augustus (63 BC- 14 AD), the founder of Rimini [1].
In 2004, the de Brecy Trust commissioned an X-ray study of this painting, which indicated that the subject is wearing Ottoman Turkish slippers, an example of luxurious attire and Turkish costumes which have been recorded in an inventory of Sigismondo's effects after his death in Castel Sigismondo and for which he and his wife Isotta da Rimini had particular affection [2].
Historical research has therefore led to the proposition that the subject painting is a portrait of the medieval lord Sigismondo Pandolfo Malatesta standing outside the fortified walls of Rimini. The court painter of Sigismondo at this time was Piero della Francesca (ca. 1415-1492), who for many years has not been recognised for his ability but who is now celebrated as a truly great Renaissance artist. Piero had a preference for direct frontal images and his use of structural colour in a strictly limited palette, often using similar colours to engage with different areas of the canvas [3,4]. A favourite colour was reddish-plum as exemplified here in the Malatesta lord's fur-lined coat. Piero was noted for his use of very few coloured pigments and the expression of the subject figure in the Malatesta painting under investigation here is very similar to that employed in a detail from Piero's famous Madonna della Misericordia painted in 1460-1462.
It is believed that Sir Thomas Lawrence saw this painting in the London home of Sir Watkin WilliamsWynn, at 20 St James's Square, when he was commissioned to paint the portrait of the 5th Baronet (1772-1840) there in about 1790 [5] and later used it as a model for his 1801 painting of Kemble as Hamlet. In 1768 the 4th Baronet, father of Sir Watkin Williams-Wynn and of the same name, made an 8-month Grand Tour of Italy during which time he acquired an extensive collection of Italian 5
pictures from art dealers. To display his vast collection of Old Master paintings and contemporary theatrical character studies, Williams-Wynn employed Robert and James Adam to rebuild his home in 20 St James's Square, London, between 1772 and 1774 and it is not surprising that London society regarded this address as having the ambience of a private art academy [6]. Lawrence would have been well-acquainted with Williams-Wynn and his family, also painting portraits of his two children, which were delivered to him in 1830 [7]. Lawrence lived close by 20 St James's Square and would have been a frequent visitor to the Baronet's home for nearly three decades because of the art collection amassed there by his friend and patron, especially the portraits of theatrical characters the subject of which were to become Lawrence's artistic professional mainstay. Towards the middle of the 19th Century, many artworks were rehoused in the country home of the Williams-Wynn Family at Wynnstay, Ruabon, North Wales and a new picture gallery was commissioned there for this purpose. During alterations in 1858 a great fire broke out and in the confusion members of the household, estate workers, neighbouring landowners and helpers all assisted in the emergency removal of many priceless works of art, but Wynnstay and much of its art collection were destroyed [8]. However, it is recorded that certain paintings believed to have been lost in the fire were in fact saved, the circumstances therefore affording an opportunity for paintings which survived the fire to be subsequently dispersed onto the local art market over the succeeding two centuries. In this way it is believed that the "Malatesta" found its way into the Cheshire auction rooms, whence it was purchased by the late collector in 1982.
The connection with Sir Thomas Lawrence is a very relevant one historically and scientifically since Lawrence was the first recorded artist to use the newly-synthesised yellow pigment, chrome yellow, lead (II) chromate, in 1809 in his 'Portrait of a Gentleman'. It is, therefore, of critical importance to determine if this painting predates that of Sir Thomas Lawrence and if it was executed during the
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lifetime of Sigismondo Pandolfo Malatesta, consistent with its possible placement in the Renaissance period.
The scientific analysis of artworks based upon the identification of pigments has been receiving much attention with the adoption of techniques that are either completely noninvasive or which otherwise require only minimal sampling and physical intervention ; in this respect , Raman spectroscopy has provided a demonstrably important role for the characterisation of mineral and organic pigments and their binders from a molecular standpoint , reinforced by the chemical elemental information derived from other more destructive analytical techniques [9,10]. From such pigment studies , although the correct historical provenancing of a painting is only realistically achievable within a broad timescale because of the common usage of pigments often over hundreds of years , the exposure of fakes through forensic scientific art detection is often realised through the identification of rogue pigments in an artwork that did not exist at its supposed time of creation [11] . Some very important landmark case-studies have appeared in the literature in recent years to verify this approach and to vindicate the use of spectroscopic analysis for the correct attribution of artworks to specific timelines [12,13,14] . However, it is necessary to exercise some caution in the interpretation of scientific data relating to art works since unrecorded , later restoration of older artefacts and paintings could have been undertaken for a variety of reasons and this will be apparent in our current study .
Experimental Specimens , Sampling Areas , Colours and Pigments Identified Samples were taken by scalpel excision from selected regions of the painting , which was in an unrestored condition : 7
MAL1 : Staff handle , yellow-orange ; lead white , barytes , chrome yellow , vermilion. MAL2 : Staff handle , yellow; lead white , chrome yellow . MAL3 : Bag/purse , yellow-brown; carbon , yellow ochre. MAL4 : Green fronds , green-brown; lead white , carbon , terre verte , massicot, MAL5 : Cape lining edge , purple; vermilion , carbon . MAL6 : Gold staff , wrist area ;lead white , chrome yellow. MAL 7 : Shirt cuff , white; lead white , calcite , gypsum. MAL8 : Rising sun , yellow-orange ; chrome yellow , vermilion MAL9 : Flesh tone , neck area , pink ; lead white , vermilion .
The initial discovery of chrome yellow in highlighted yellow areas of the painting necessitated a resampling procedure in which a further series of specimens were excised , comprising MAL1'-MAL4' , from two further positions on the staff handle , the purse and the greenish-yellow vegetation fronds , as previously identified above .
Raman Spectroscopy Raman spectra were obtained with a Bruker Senterra microRaman system operating with 785 and 532 nm laser excitation ; spectra were recorded over a wavenumber range of 1800-100 cm-1 with a spectral resolution of 4 cm -1 and a 20 X microscope objective , giving a footprint of approximately 5 microns at the specimen . As the pigment samples were heterogeneous , several spectra were obtained of different sample regions in the same specimen to record the pigment components ; in addition , to obviate the background emission effects of varnish degradation in this unrestored and uncleaned artwork , sample fragments were examined on both upper and lower surfaces.
Discussion of Analytical Results
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The Malatesta painting pigments include those which are typically found in use over a long period of art history during the Renaissance ; the white pigment is characterised by several combinations of lead white , barytes , calcite and gypsum , black pigment by vegetable charcoal , yellow ochre ( goethite ) , terre verte , and vermilion . Massicot , lead (II ) oxide , is clearly identified in several regions and indicates a probable early date for this painting as it was superseded in the 17th Century by newer , more vibrant yellow pigments such as Naples yellow and the tin yellows , types I and II . The use of vermilion and lead white in admixture for the flesh tones is quite typical of a quality painting of this period and other , cheaper red pigments have not been identified in these regions. Figure 2 shows the Raman spectrum of vermilion , with characteristic bands at 250 , 285 , 340 cm -1 and a very weak feature characteristic of lead white at 1050 cm -1 . The most intriguing discovery , however, relates to the presence of lead (II) chromate in the golden yellow areas of the staff and sun , in particular . This is an important discovery as , although lead (II) chromate does occur naturally as the mineral crocoite , it first appeared as a synthetic pigment ( chrome yellow ) following its isolation from crocoite by Vauquelin in 1809 . After this date , chrome yellow quickly became adopted as the vibrant golden yellow pigment of choice by early 19th Century artists , until its decline some three or four decades later because of concerns about lead toxicity and its deterioration in tonal quality due to its darkening in air. Close inspection of the specimens taken from the staff reveals the presence of both massicot ( 140 cm-1 ) and lead chromate ( 827 , 374 , 358 , 324 cm -1 ) in different compositions , as evidenced in Figures 3 and 4; Figure 4 indicates the presence of almost pure massicot , with only a very small signal for lead chromate . Hence , it can be concluded that the pigments identified in the Malatesta painting were of a Renaissance origin , with the exclusion of the chrome yellow ; one possibility is the use of the natural mineral crocoite for the source of the lead chromate , otherwise , a possible attribution to the early 19th century could be considered. The omnipresence of lead white is certainly compatible with the Renaissance but the occasional identification of barytes signals is rather unusual in this context .
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One should be rather careful , however, in making rigid conclusions about dating a painting to the 19th century solely on the discovery of the presence of a synthetic pigment which properly belongs there ; it is reasonable to infer that after several centuries most artworks would have required some restorative attention and perhaps a “re-touching ” of key areas , especially if they have been exhibited in locations which have been heated with coal fires and lit with candles and oil lamps. Another interesting feature is revealed by the analysis of the Raman spectra of the orange pigment colours ; the spectrum of a specimen taken from the region of the staff handle in Figure 5 shows a rather unusual composition of vermilion , realgar and lead chromate along with barytes. it is interesting to speculate as to whether the original orange composition comprised vermilion (red ) and realgar (yellow) which was heightened later by the application of the yellow lead chromate as it would be inconceivable that the artist would have originally used a mixture of two yellow pigments with the red to achieve the desired orange pigment colour. Figure 6 shows the Raman spectrum of a blue-black coloured cratered area , devoid of varnish , on the right hand side of the painting in which the signatures of lapis lazuli at 545 and 254 cm-1 are evident . Finally , a very curious Raman spectrum was obtained for a dark brown area near the fortification situated at the lower middle left of the painting : a complex group of spectral signatures , shown in Figure 7 , can be assigned to vermilion ( bands at 255 and 283 cm -1 ) and a trio at 1520 , 1157 and 1006 cm -1 which are indicative of a the C=C and C-C stretching vibrations in the polyisoprene skeletal chain of a natural carotenoid [15]. The presence of a carotenoid has two possible implications namely , the artist has utilised the natural bright red-brown colouration of the extracted product found widespread in nature in tomatoes , carrots , lichens and the carapaces of shellfish such as lobster , or alternatively that presence of the carotenoid has arisen from localised biological colonisation of this area of the artwork. The latter occurrence has already been described in the literature [16,17,18] and indeed has been proposed as an early warning signal indicative of 10
the onset of degradative biological colonisation of artworks -- in this , the presence of the toxic mercury (II) ions in the associated vermilion pigment has been shown to not be detrimental to the biological invasion because of the combatative extremophilic survival strategies adopted by the lichens or cyanobacteria concerned [19,20,21].
We have already alluded to a very interesting possible association between this painting in its London home and the artist Sir Thomas Lawrence , who is renowned for his recorded groundbreaking artistic use of chrome yellow as a pigment in his “Portrait of a Gentleman” in 1810 ; Gettens and Stout 22 in their seminal and well-respected encyclopaedia of artists’ pigments comment that the evidential brightening of a yellow ochre pigment in the 19th Century by the newly discovered chrome yellow was recorded . Who better to effect this treatment on a friend’s painting during one of his visits in the early decades of the 19th century than the first advocate and renowned exponent of chrome yellow pigment , Sir Thomas Lawrence , perhaps on occasions in connection with the commission to paint Sir Watkin Williams-Wynn’s two children ? during the period 18201826 when he was commissioned to paint the Sir Watkin Williams-Wynn family portraits in St James Square, London [5] ?
Conclusions It is apparent that the Raman spectroscopic analyses of the putative Renaissance painting are consistent with the pigments identified therein , such as cinnabar , massicot, carbon black, terre verte, calcite, gypsum, and lead white . However, the discovery of chrome yellow , which was synthesised in 1809, in limited zones could probably be attributed to a 19th century retouching process. The probable association of the painting at that time with Sir Thomas Lawrence , an early exponent of the use of chrome yellow pigment ,who executed a similar but later version in 1801 of
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John Kemble in the role of Hamlet , Prince of Denmark, in Shakespeare’s play , manifestly encourages the invoking of compatible historical research to explain satisfactorily anomalies in otherwise consistent analytical data. The major purpose of this work was pigment identification by using Raman spectroscopy, coupled with historical provenancing. Future research activities should clearly include binder analysis and parallel studies on the physical construction of the canvas. Eventually, isotopical analysis could provide further insight into the possible synthetic or natural origin of particular pigments, such as ultramarine. The results from this current Raman study will provide a focus for targeted future research into the areas of destructive sampling, necessary to solve these problems.
Acknowledgement The authors thank the de Brecy Trust for permission to sample the painting for this study .
References [1] N. Pozza (ed.), Città di Rimini, Sigismondo Pandolfo Malatesta E il suo tempo, 1970, pp. 9495. [2] M.G.Pernis and L.S. Adams, Federico da Montefeltro & Sigismondo Malatesta: The Eagle and the Elephant, Peter Lang, 1996, pp. 66-67 .
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[3] C. Gregory, The Great Artists : Their Lives, Works and Inspiration – Piero della Francesca No. 40, Volume II, 1985, p.1282 and ff., Marshall Cavendish Collection.
[4] K. Clark, Piero della Francesca, Phaidon, London, p.14, 1969.
[5] K. Garlick, Sir Thomas Lawrence, Phaidon, London, 1989, p.200.
[6] S. Houfe, A Wealth of Taste, Country Life, 19th September, 1991, pp.108-109.
[7] K. Garlick, Sir Thomas Lawrence, Phaidon, London, 1989, p.200 .
[8] T. Pritchard, The Wynns of Wynnstay, Old Court Press, Caerwys, 1982, p.27.
[9] P. Vandenabeele , H.G.M. Edwards and L.Moens , Chemical Reviews , 107 , pp.675-686 ( 2007).
[10] H.G.M. Edwards and J.M. Chalmers ( eds.) , Raman Spectroscopy in Archaeology and Art History, RSC Analytical Chemistry Spectroscopy Monographs Series , Royal Society of Chemistry Publishing , Cambridge , UK , 476 pp. (2005) ; ISBN : 0-85404-522-8.
[11] H.G.M. Edwards , Raman Spectroscopy of Inorganic Materials in Art & Archaeology : Spectroscopic Analysis of Historical Mysteries , , Specialist Periodical Reports , Spectroscopic Properties of Inorganic and Organometallic Compounds : Materials and Applications , Volume 40 , eds. J. Yarwood , R. Douthwaite and S.B. Duckett , Royal
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Society of Chemistry Publishing , Cambridge , pp. 16-48 (2009). (ISBN : 978-1-84755- 9180). [12] L. Burgio, R.J.H. Clark, L. Sheldon and G.D. Smith, Analytical Chemistry, 77, pp.1261-1267 (2005). [13] H.G.M. Edwards and T.J. Benoy , Analytical and Bioanalytical Chemistry , 387 , pp.837-846 (2007). [14] P. Vandenabeele, M. Vandekerckhove, B. Vandekerckhove and L. Moens, Comment peut la spectroscopic Raman aider à l'etude de l'oeuvre du René Magritte? In: Actes du colloque Magritte en perspective cavalière, Brussels 5-7 may 2003 (2003). [15 ] C.G. de Almeida , B.S. Ferreira , M. le Hyaric , V.E. de Oliveira , H.G.M. Edwards and L.F.C. de Oliveira, Spectroscopy Letters , 46 , pp.122-127 ( 2013 ).
[16] H.G.M. Edwards , Raman Spectroscopy in Art and Archaeology : A New Light on Historical Mysteries , In “Frontiers of Molecular Spectroscopy”, ed. J. Laane , Elsevier Press , Amsterdam , pp. 133-173 (2009) ISBN 13: 978-0-444-53175-9.
[17] F.Rull Perez and H.G.M. Edwards ,FT-Raman Spectroscopy of Frescoes and Ancient WallPaintings : Their Pigment Application , Adulteration , Biodeterioration and Restoration , In “ Selected Topics in Raman Spectroscopic Applications : Geology , Biomaterials and Art” , eds. F.Rull Perez , H.G.M. Edwards , D.C. Smith and P. Vandenabeele , University of Valladolid Press Publidisia , Valladolid , Spain , pp.161-192 ( 2007) ( ISBN : 978-84-690-9239-2 ). [18] H.G.M. Edwards and P. Vandenabeele, Analytical Archaeometry : Selected Topics , Eds., Royal Society of Chemistry , Cambridge , 604 pp. ( 2012 ). ISBN : 978-1-84973162-1. [19] H.G.M. Edwards, Spectrochimica Acta Part A , 68 , pp. 1531-1539 (2007 ).
[20] H.G.M. Edwards, Analyst , 129 , pp.870-879 (2004 ). 14
[21] D.D.Wynn-Willams and H.G.M.Edwards, Icarus, 144, pp. 486-503 (2000).
[22] R.J. .Gettens and G.L. Stout , Painting Materials : A Short Encyclopedia , D. van Nostrand , New York ,1962.
Figure Captions Figure 1. " Full Length Portrait of a Gentleman" , known as the Malatesta painting , analysed in the present work. Figure 2. The Raman spectrum of a flesh tone specimen ( MAL 9) with characteristic bands of vermilion at 250 , 280 and 340 cm -1 , and a very weak feature of basic lead (II) carbonate ( lead white ) at 1050 cm-1 . Figure 3. Raman spectrum of the yellow staff handle ( MAL4P) indicative of a mixture of chrome yellow ( major component ) and massicot ( minor component ) . Figure 4 . Raman spectrum of the yellow staff handle ( MAL4G) indicative of almost pure massicot with a very minor chrome yellow component . Figure 5. Raman spectrum of orange pigment (MAL1D) with characteristic bands of vermilion , realgar and lead chromate along with barytes and lead white. Figure 6. Raman spectrum of blue-black cratered area ( M1J ) with characteristic bands of lapis lazuli. Figure 7 . Raman spectrum of dark brown area near fortification (M7K) with complex spectrum indicative of vermilion and a carotenoid .
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Highlights - Pigment analysis of an oil painting was performed by using Raman spectroscopy - The majority of the pigments were consistent with assignment to the renaissance period, excepted the presence of chrome yellow. - The presence of chrome yellow is consistent historically with a 19th century retouching. - This work shows that a combination of pigment analysis with historical research is needed for full provenancing of works of art.
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