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SEM-EDX Pigment Analysis and Multi-Analytical Study of the Ground and Paint layers of Francesco Fedrigazzi's painting from Kostanje

Jelena Zagora

Abstracts

Francesco Fedrigazzi, Venetian by birth, was a painter active in Istria and Dalmatia in the late 17th and the early part of the 18th century. In the second decade of the 18th century he painted an altar painting for the church of Saint Michael in Kostanje. This painting was later removed from the church and stored in the attic of the parish house. Unfavourable conditions in which it was stored resulted in extensive damage. As part of her Master's thesis, the author investigated stratigraphy and composition of the painting's ground and paint layers using a number of techniques. UV fluorescence analysis and digital X-ray imaging were conducted at the Conservation-Restoration Department of the Arts Academy of the University in Split. Scanning electron microscopy – energy dispersive X-ray analysis (SEM-EDX) was done by a research centre for materials in Istria, METRIS. The investigation gave insight into Fedrigazzi's painting technique and revealed the pigments that he used in his colours.

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The author would like to thank the following people for their invaluable contributions to this paper:

Tea Zubin Ferri of the METRIS Research Centre for Materials of the Region of Istria in Pula for SEM-EDX cross-section imaging, pigment composition analysis and interpretation of the results on which the discussion in this paper is based, as well as for providing the images and technical data.

MSc Frane Mihanović for the digital radiographic imaging and post-processing of the radiographs, providing the images and technical data and reviewing the chapter on radiographic examination of the Kostanje painting.

PhD Radoslav Tomić, member of the Croatian Academy of Sciences and Arts, credited for dating and attribution of the painting discussed, for providing the data from his research paper, which is in print.

PhD Ivica Ljubenkov for reviewing the text.

PhD Goran Nikšić for the French translation of the summary and for copyediting of the text.

Finally, the author is grateful to Jurica Matijević for the mentorship of her Master's thesis, as well as for his valuable comments and suggestions to improve this paper, and to Sagita Mirjam Sunara for editing the paper and providing helpful advice. She would like to thank them both for the encouragement and support of her work during and after her graduate course.

Francesco Fedrigazzi's painting from Saint Michael's church in Kostanje

  • 1  KOVAČIĆ, S., ''Župe splitske nadbiskupije u poljičko-radobiljskom dekanatu g. 1625.'', in Synthesi (...)
  • 2  VLAŠIĆ, D., Vizitacije poljičkih župa u XVIII. Saint, Crkva u svijetu, Poljica – Godišnjak Poljičk (...)
  • 3  VLAŠIĆ, D., op. cit., 1995, p. 112.  

1The first known reference of the parish church of Saint Michael in Kostanje, a village in the hinterland of Dalmatia, in the part historically known as the Poljica Republic, dates from 1625.1 In the early 18th century a new church was built. It was consecrated in 1711.2 Archbishop Pacifik Bizza was the first person to describe the church altars with paintings. This was during his visitation in 1748.3

2Of all the altar paintings documented in Bizza's report, only the painting representing the Baptism of Christ and Our Lady of Mount Carmel has been preserved. The painting depicts two subjects: Christ's Baptism in the lower half and Our Lady of Mount Carmel above it. The baptism scene is typical for Italian iconography, with the characteristic detail of Saint John the Baptist pouring water from a shell. The Virgin is represented among the clouds, crowned by two of angels, while another two hold her mantle. Winged angel heads are painted in the clouds that surround her. In her arms she holds Child Jesus. The Child is holding a scapular, which is the attribute of Our Lady of Mount Carmel.

  • 4  BOŽANIĆ-BEZIĆ, N., ''Majstori od IX do XIX stoljeća u Dalmaciji II'', in Prilozi povijesti umjetno (...)
  • 5  Academician PhD Radoslav Tomić is credited for both dating and attribution of the painting.
  • 6  TOMIĆ, Radoslav, paper forthcoming. I am grateful to the author for the data and advice regarding (...)

3This painting was commissioned around 1711, on the occasion of the consecration of the church, and it was intended for the altar of Saint John the Baptist. It is attributed to Francesco Fedrigazzi, a painter from Venice4 who was active in Istria and Dalmatia at the end of the 17th and in the early 18th century.5 Between 1691 and 1708 Fedrigazzi lived in Poreč. There he painted his most important work, a copy of the painting The Last Supper by Jacopo Palma the Younger from the Euphrasian Basilica. That painting was intended for the Sinčić Palace. Many of Fedrigazzi's paintings have been identified in the region of Dalmatia, principally in the area of Trogir, where the artist probably lived after 1708.6

  • 7  The description of the church altars in the episcopal visitation from 1748 (see note 3) is essenti (...)

4His painting from Kostanje had a turbulent past, having been removed from the church at some point. It was found in the attic of the parish house in Kostanje in 2011, together with two paintings by Filippo Naldi from Florence, dated with 1761.7 Fedrigazzi's painting was found without a stretcher, repeatedly folded and covered in dirt. The left, right and bottom portions of the canvas had been cut off, while the upper part was torn. The paint layer was flaking. Many flakes had detached from the canvas, especially where the canvas was folded.

5The conservation-restoration treatment and one part of the technical study were carried out at the Conservation-Restoration Department of the Arts Academy of the University of Split. They were the topic of Jelena Zagora's Master's thesis. The second part of the technical study, including SEM-EDX imaging and pigment analysis, was done in collaboration with Tea Zubin Ferri from the METRIS Research Centre for Materials of the Region of Istria in Pula.

Multi-analytical study of painting's stratigraphy coupled with SEM-EDX pigment analysis

6When the painting was found, the painter and its provenance were unknown. Although it shows characteristics of Baroque painting, it was not possible to determine its date of origin with certainty. This was due to unusually vivid colours and overall lightness of tonality, which is uncommon for the period. Numerous analytical and imaging techniques were used to examine it.

7Scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDX) was employed for pigment analysis, which was crucial for the dating of the artwork. The stratigraphy of the ground and paint layers was investigated combining optical and electron microscopy, digital X-ray imaging and UV fluorescence analysis.

Fig. 1 Baptism of Christ and Our Lady of Mount Carmel

Fig. 1 Baptism of Christ and Our Lady of Mount Carmel

Painting by Francesco Fedrigazzi before the treatment and after retouching.

Credits: Mladen Čulić, Jelena Zagora

Experimental abstract

Sampling

8In order to perform optical and electron microscopy, samples of yellow, blue, green, red, brown, white and flesh paint, were taken from the parts where the paint was flaking. Many flakes were already detached from the canvas. All samples contained the ground layer. The samples were embedded in polyester resin Chromoplast A 132 UV. Paint cross-section samples were used both for stratigraphic and pigment composition analyses.

Fig. 2 Sampling scheme

Fig. 2 Sampling scheme

(1) yellow, (2) dark blue, (3) light blue, (4) green, (5) red, (6) brown, (7) white, (8) flesh colour.

Credits: Jelena Zagora

Equipment and methods

9UV fluorescence imaging was done using a UVA lamp. The photos were taken with NIKON D90 digital camera.

  • 8  Data generously provided by MSc Frane Mihanović, credited for organizing and conducting the radiog (...)

10MSc Frane Mihanović conducted digital radiographic imaging using a mobile X-ray unit (Nanomobil model, Siemens) with exposure conditions of 48 KV and 80 mAs and phosphorus plate as the image receptor. Latent images from phosphorus plates were digitalised using FCR1 FUJI device (FUJIFILM Holdings Corporation). DICOM files were evaluated and processed using Osirix software (Pixmeo); X-ray digital images were merged using Photoshop software (Adobe Systems).8

  • 9  Tea Zubin Ferri of the Metris research centre and Marijana Fabečić of the Croatian Conservation In (...)

11Paint cross-section samples were photographed using Olympus BX 51 optical microscope with an integrated XC50 Olympus camera at the laboratory of the METRIS Research Centre for Materials in the Region of Istria in Pula, and at the Natural Science Laboratory of the Croatian Conservation Institute in Zagreb (using an Olympus BX 51 digital camera as well).9

  • 10  Tea Zubin Ferri is credited for SEM-EDX cross-section imaging, pigment composition analysis and in (...)
  • 11  Data kindly provided by Tea Zubin Ferri. The contrast in BSE images primarily depends on the diffe (...)

12Cross-section samples of yellow, blue, green, red, brown, and flesh colour, together with the ground layer, were imaged and analysed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). Tea Zubin Ferri performed the analysis at the laboratory of the METRIS research centre.10 As FEI Quanta 250 FEG (Field Emission Gun) scanning electron microscope was used, sample preparation (sputtering) was not necessary. SEM-EDX imaging was performed at low vacuum (100-120 Pa), 10-20 kV high voltage, working distance of 10 mm and spot size between 4 and 6. All paint cross-section samples were imaged using BSED (Backscattered Electron Detector), which facilitated their examination.11

Results and discussion

Stratigraphic analysis

Ultraviolet fluorescence analysis

13UV fluorescence analysis reveals that the painting has no protective coating. No fluorescence typical of soft resins such as dammar and mastic, nor fluorescence characteristic of resins of a different origin has been observed. In addition, the surface of the painting does not show traces of later interventions (over-painting, retouching) or a fluorescence that would be characteristic of a particular pigment.

X-ray digital imaging

14Microscopic examination of paint cross-sections taken from the lower half of the painting, which will be discussed later in the text, revealed the presence of a layer of white colour between the paint and the ground layer. In order to determine the distribution of this layer, digital radiographic imaging was carried out.

  • 12  The presence of lead in the white layer was proven subsequently by EDX analysis.

15It was presumed that the layer contained lead, which would have attenuated X-ray radiation and reduced the readability of the respective parts of the digital radiograph.12 However, the digital radiograph shows clearly discernible figuration in almost the entire surface of the painting. The areas with a higher degree of X-ray absorption (shown in white or lightershades of grey) mainly correspond with the light painted parts of the painting (flesh tones), which contain lead white. Nevertheless, it is notable that the contrast of the bottom half of the digital radiograph is lower than would be expected, which may indicate the presence of a layer of high X-ray attenuation. In addition, a difference in the degree of X-ray absorption between the upper and the lower portions of the painting is apparent: darker shades of grey and higher contrast (lower absorption) are observable in the upper half of the radiograph, while the lower half shows much lighter shades and lower contrast (higher absorption).

  • 13  SEM-EDX analysis showed that the landscape was painted using green earth, a pigment consisting of (...)

16This corresponds to the stratigraphy of the paint layer. For example, dark green trees surrounding the images of Christ and Saint John the Baptist appear quite light in the X-ray digital image, indicating a higher degree of X-ray absorption due to the layer of lead white. The contrast of the radiograph is lower in these areas: the treetop in the background of Saint John the Baptist is hardly discernible.13 The presence of a white paint layer was determined by cross-section analysis. On the other hand, the light-painted sky with yellow clouds in the top part of the painting appears surprisingly dark in the X-ray digital image, which may be explained by the absence of high absorbing layer of lead white in this area. This layer is not present in cross-sections of the samples taken from this part of the painting.

17The radiograph has also revealed pentimenti (the position of the head of Saint John the Baptist and the face of Christ).

Fig. 3 Digital X-ray image of the Baptism of Christ and Our Lady of Mount Carmel

Fig. 3 Digital X-ray image of the Baptism of Christ and Our Lady of Mount Carmel

Credits: Frane Mihanović

Optical microscopy

18Microscopic examination of paint layer cross-sections shows that the ground layer is applied in two coats, each having the average thickness of 50 – 200 µm. In the samples taken from the lower half of the painting (light blue, green, red, flesh colour from the chest of Saint John the Baptist) a layer of white or sand-coloured paint was observed above the ground layer. Beneath the brown paint from the Christ's mantle edge, a thin (≈10 µm) grey-coloured layer is present. The paint is applied in multiple coatings; it generally consists of 2 – 4 layers. The white colour of the sky behind the scene of the Baptism is an exception, having been applied in a single layer.

19For ease of reference, photographs of the cross-sections and descriptions of ground and paint layers are presented in the chapter on SEM-EDX pigment analysis.

Scanning electron microscopy – energy dispersive X-ray analysis (SEM-EDX)

20SEM-EDX analysis reveals that the white layer observed above the ground in the cross-sections of samples taken from the lower half of the painting (light blue, green, red, flesh colour from the chest of Saint John the Baptist) contains lead white. BSE images and EDX analysis show that the grey layer on the edge of the Christ's mantle, over which brown paint was applied, also contains lead. This leads to the conclusion that the layer containing lead white was applied on the bottom half of the painting and used as an underpainting. This layer of paint served as a basic colour for the sky, as indicated by a single layer of white paint in that area.

21The painter first applied white background of the sky. On top of this he painted the landscape and the figures of Christ and Saint John the Baptist. In the upper half of the painting no such intermediate layer of lead white was detected: the colours were applied directly to the ground.

Fig. 4 BSE cross-section images of: (a) the green paint, (b) the brown paint, both including the ground layer

Fig. 4 BSE cross-section images of: (a) the green paint, (b) the brown paint, both including the ground layer

Layers containing lead white are shown in white and light shades of grey.

Credits: Tea Zubin Ferri

Pigment analysis

Scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDX)

Ground

  • 14  HELWIG, K., ''Iron Oxide Pigments, Natural and Synthetic'', in Artist's Pigments, A Handbook of Th (...)
  • 15  HELWIG, K., op. cit., 2007, p. 89.

22The reddish-brown preparatory layer is mainly composed of iron oxides with aluminosilicates. In addition to aluminium, silicon, calcium, magnesium, manganese, potassium and sulphur, chemical elements originating from accessory minerals commonly present in natural earth pigments from iron oxide deposits,14 traces of titanium are also present. Iron oxide pigments can contain a significant amount of titanium-containing minerals, which often occur in rocks and soils.15

  • 16  HELWIG, K., op. cit., 2007, p. 51.
  • 17  MERRIFIELD, M. Ph., Original Treatises, Dating from the XIIth to the XVIIIth Centuries, on the Art (...)
  • 18  Cf. HRADIL, D.; GRYGAR, T.; HRADILOVÁ, J.; BEZDIČKA, P., ''Clay and iron oxide pigments in the his (...)
  • 19  Cf. GROEN, K. M., ''Earth Matters, The origin of the material used for the preparation of the Nigh (...)
  • 20  Cf. HELWIG, K., op. cit., 2007, p. 89, Fig. 32. d, an X-ray energy spectrum of a red earth from It (...)

23Coloured grounds (yellow-brown and red-brown), consisting mainly of earth colours with the addition of black and white pigments, were developed in northern Italy in the 16th century.16 During the 17th and the 18th century they were predominant in Europe. For instance, Giovanni Battista Volpato's 17th-century manuscript lists a recipe for preparatory layer made of finely ground argil, red earth and umber.17 Argil is generally of aluminosilicate composition. The most noticeable constituents of Fedrigazzi's ground layer are large, coarse orange grains (in some places yellow), which mostly contain Al, Si and Fe, possibly ground argil. Red earth commonly consists mainly of iron oxide (containing clay and quartz in various ratios, depending on the source). The colour in natural reds comes from hematite; coarse-grained, crystalline violet-red particles are visible by optical microscopy in brownish clayey matrix (large Al and Si peaks) of Fedrigazzi's ground, as well, though natural or artificial hematite could have been added intentionally.18 Large, colourless particles of quartz (relic mineral) are also visible. EDX analysis has confirmed high silicon and oxygen content.19 EDX spectrum of an Italian red earth shows considerable similarities in elemental composition with the spectrum of brownish matrix from the ground layer of Fedrigazzi's painting,20 which is not surprising, as he is of Italian descent. To conclude, a combination of these or similar earth pigments could have been used for the ground layer of the Kostanje painting.

  • 21  WINTER, J.; WEST FITZHUGH, E., ''Pigments Based on Carbon'', in Artist's Pigments, A Handbook of T (...)
  • 22  Cf. SPRING, M.; GROUT, R.; WHITE, R., 'Black Earths' – A Study of Unusual Black and Dark Grey Pigm (...)
  • 23  SPRING, M.; GROUT, R.; WHITE, R., op. cit., 2003, p. 96.

24Black particles visible under the optical microscope exhibit splintery, angular and often elongated form, resembling those of charcoal black prepared from wood or fruit stone char.21 However, these particles have very high sulphur content, as observable in the sulphur EDX map of the brown paint cross-section (Fig. 11 b). Therefore, this is probably a sulphur-rich coal-type black; in some cases, this organic black pigment may cleave in a way that the particle shape is resembling a charcoal black, but no wood cell structure is observed.22 Sulphur-rich coal black falls in the class of black earth pigments, which comprise a number of different black minerals.23

Fig. 5 (a) Cross-section of the yellow paint with ground layer (the clouds above Our Lady) from the Baptism of Christ and Our Lady of Mount Carmel (200x). (b) EDX spectrum of the ground layer brownish matrix

Fig. 5 (a) Cross-section of the yellow paint with ground layer (the clouds above Our Lady) from the Baptism of Christ and Our Lady of Mount Carmel (200x). (b) EDX spectrum of the ground layer brownish matrix

Large, coarse orange grains containing mostly Al, Si and Fe (possibly ground argil), coarse-grained violet-red hematite particles, colourless quartz grains and splintery coal black particles are visible in brownish clayey matrix (large Al and Si peaks) of Fedrigazzi's priming. See also Fig. 11 and Fig. 9.

Credits: Tea Zubin Ferri

White underpainting

25The layer of white paint applied over the preparatory layer, which can be observed in the samples taken from the lower half of the painting (light blue, red, green, brown, flesh colour), is white lead in composition (i.e. basic lead carbonate, PbCO₃). This was determined by detection of lead in the layer (large lead peak in EDX spectrum), with significant carbon and oxygen peaks.

26Under the layer of brown paint, a thin dark-grey layer containing lead is observable in the cross-section. This layer is clearly visible in both BSE image and EDX lead map. Since the layer is greyish in colour, it is safe to conclude that it contains an additional pigment, probably some kind of carbon black.

Yellow (the clouds above Our Lady)

  • 24  THOMPSON, D. V., The Materials and Techniques of Medieval Painting, Dover Publications, Inc., New (...)
  • 25  Today it is assumed that both massicot (or masticot, which is the name found in the manuscripts of (...)

27Composition of the yellow paint in the sample taken from the clouds above St. Mary is nearly identical to that of the white underpainting: EDX spectrum of yellow paint layer shows large lead peak, with significant carbon and oxygen peaks. This might indicate lead white mixed with one of the yellow lead pigments, which were particularly used in medieval Italy.24 Pigments from this group may contain tin or antimony, but EDX analysis has not confirmed their presence. Therefore, it can be assumed that the yellow pigment that Fedrigazzi used is massicot (lead oxide, PbO), a pigment that has been produced by calcination of lead white since the antiquity, as an intermediate product in the preparation of red lead.25 Traces of silicon, aluminium and iron are also present; hence small amounts of some kind of yellow earth or yellow lake are possible as well.

Dark blue (Our Lady's mantle)

28The composition of blue particles found in the dark blue paint layer of the sample taken from Our Lady's mantle could not be determined by EDX spectrometry, which indicates that an organic colorant is in question. This layer contains mostly calcium and some aluminium. The bluish-white layers below and above the dark blue layer mostly contain aluminium with some calcium and lead.

  • 26  See, for example: SCHWEPPE, H., ''Indigo and Woad'', in Artist's Pigments, A Handbook of Their His (...)
  • 27  The earliest recorded examples of indigo in oil medium are 13th century Norwegian panel paintings. (...)
  • 28  Though analytical evidence suggest that painters have continued to use it, indigo apparently drops (...)
  • 29  While indigo was identified in only very few works by 15th and 16th century Northern European pain (...)
  • 30  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 120, 121.
  • 31  In all indigo dye plants, the main precursor of blue colorant indigotin is water-soluble indican. (...)
  • 32  EIKEMA HOMMES, M. H. van, op. cit., 2002, 111, 119, 141.

29Although organic compounds cannot be identified by EDX analysis, the prevalence of use of indigo in historical painting, in comparison to other blue dyestuff sources, makes it the most probable option. The majority of published occurences of indigo in painting date from 13th to 19th century.26 A growing number of analytical reports suggest that indigo was quite commonly used in 15th to 17th-century oil painting, particularly in the 17th century.27 The pigment was less frequently employed in 18th and 19th centuries.28 Notably, indigo has been documented in works by Italian 15th and 16th century painters, most of them being active in Venice, the main port of import for Indian indigo at the time.29 Due to increasing import of tropical indigo during the 17th century, contemporary painting manuals almost exclusively refer to this dyestuff source.30 The main sources of tropical indigo are plants of the genus Indigofera. In Europe, the native woad plant, Isatis tinctoria L., was the most important source for indigo until the 17th century.31 Studies have shown that markedly high amounts of both phosphorous and calcium might imply that the pigment derives from woad indigo.32 However, no traces of phosphorous were detected in the blue paint from Kostanje painting. Considering the date of origin of the painting and Venetian origin of Francesco Fedrigazzi, a few references on the use of imported, tropical indigo in oil painting are following.

  • 33  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 145-155. In her dissertation, van Eikema Hommes lists (...)
  • 34  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 150, 151, 152.
  • 35  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 135, 136.

30Painters principally used indigo pigment to depict folds in drapery; in oil paintings dating from 15th and 16th centuries, the pigment was seldom used in uppermost paint layers. From the second half of the 17th century, due to better quality of imported material and developed methods of pigment preparation (i. e. purification and calcination), indigo was no longer restricted to underpaint. When using the pigment in top layers, contemporary texts recommend mixing it with lead white and/or chalk for modelling blue colour.33 Fedrigazzi’s dark blue paint contains both calcium carbonate and lead white in significant amounts. Siccative properties of lead white could also be the reason for its use – since indigo oil paint dries very slowly, it was often advised to mix it with pre-processed drying oil and siccatives.34 Large relative amount of aluminium suggests the addition of calcified rock alum, which was one of the historically employed methods for purifying indigo and improving its permanence.35

  • 36  SCHWEPPE, H., op. cit., 1997, p. 97.
  • 37  Indigo and turnsole were predominant medieval sources for organic blue colour, hence their names w (...)

31Schweppe states that emission-spectrographic analysis can provide ''negative evidence for indigo''. The presence of iron would indicate Prussian blue, while copper, cobalt or sodium would point to azurite, cobalt blue or ultramarine, respectively.36 Since other historical sources of organic blue dyestuff have been documented in manuscripts and (only exceptionally) detected in easel paintings,37 further analysis is required to prove the presence of indigo or to point to a different blue colorant.

Fig. 6 (a) Cross-section of the dark blue paint with ground layer (Our Lady's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 100x. (b) EDX element maps

Fig. 6 (a) Cross-section of the dark blue paint with ground layer (Our Lady's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 100x. (b) EDX element maps

The bluish-white layers above and below the dark blue layer contain mostly aluminium with some calcium (Al-K and CA-KA maps). Calcium is concentrated in the dark blue middle layer.

Credits: Tea Zubin Ferri

Light blue (the sky above Saint John the Baptist)

32The light blue layer of the sky above the figure of St. John the Baptist shows very fine particles of blue pigment mixed with white paint. The composition of blue pigment could not be determined by EDX analysis, which indicates that it is of organic origin (possibly indigo, as explained above). Again, the presence of calcium might be related to calcium carbonate, most likely chalk; lead white was also added to the paint. Both white pigments were apparently added to it to lighten the colour (lead white probably being employed because of its siccative properties as well). Aluminium can be related to the use of alum for the preparation of the dyestuff.

Fig. 7 EDX spectrum of the light blue paint layer (the edge of Christ's mantle)

Fig. 7 EDX spectrum of the light blue paint layer (the edge of Christ's mantle)

Credits: Tea Zubin Ferri

Green (treetop left of Saint John the Baptist's head)

33In the colour layer of the paint sample taken from the treetop left of St. John the Baptist's head, EDX analysis revealed presence of iron, silicon, aluminium and potassium. This is indicative of green earth, a pigment principally composed of clay minerals celadonite or glauconite (depending on the source). Elements characteristic of other historically used green pigments have not been detected.

  • 38  THOMPSON, D. V., op. cit., 1956, p. 163.

34As noted earlier, green earth is a pigment composed of clay minerals. It has a dull colour that can range from bright, bluish or greenish grey to dark olive green. Because of its transparency and low intensity, green earth was rarely used to paint landscapes in oil paintings.38 It is quite surprising that the colour that Fedrigazzi used to paint the landscape in the Kostanje painting is quite intense, with tones ranging from deep blue-green to warmer ochre-green.

  • 39  GRISSOM, C. A., ''Green Earth'', in Artist's Pigments, A Handbook of Their History and Characteris (...)

35The explanation might lie in his painting technique – in the use of white underpainting, to be more precise. By applying the green earth as a glaze over a white surface, maximum saturation (chroma) is achieved, with a significant increase in excitation purity and lightness. In some parts of the Kostanje painting the green colour has a yellowish tone. This happens when the pigment (green earth) is glazed over or mixed with white.39

  • 40  GRISSOM, C. A., op. cit., 1986, p. 146.

36Undiminished intensity of green colour in Fedrigazzi's painting could be attributed to stability of green earth, which is a permanent pigment, resistant to light and air.40 Darkening occurs only when oil or varnish penetrate the pigment particles. The fact that Fedrigazzi's painting was not varnished supports this assumption.

  • 41  Cf. GRISSOM, C. A., op. cit., 1986, p. 150, 151, Fig. 9, and GETTENS, R. J., STOUT, G. L., Paintin (...)

37Microscopically, the samples of green colour from Fedrigazzi's painting indeed exhibit the characteristics of minerals that constitute green earth. The layer of green colour is a mixture of translucent, rounded particles of different shades of green, in places blue, with traces of yellow or brown earth.41

  • 42  GRISSOM, C. A., op. cit., 1986, p. 148, 149, 143. The most significant use of green earth has been (...)

38Because of their similar chemical composition and microscopic characteristics, SEM-EDX analysis cannot distinguish glauconite (warmer tones, occuring more frequently, often containing impurities) from celadonite (bluish tones, less common, comes in a more pure form, famous historical source in Verona).42

Fig. 8 Cross-section of the green paint with ground layer (treetop left of Saint John the Baptist's head) from the Baptism of Christ and Our Lady of Mount Carmel. (500x)

Fig. 8 Cross-section of the green paint with ground layer (treetop left of Saint John the Baptist's head) from the Baptism of Christ and Our Lady of Mount Carmel. (500x)

Translucent, rounded particles of different shades of green, in places blue, with traces of yellow or brown earth.

Credits: Tea Zubin Ferri

Red (the robe of Saint John the Baptist)

39The reddish-orange pigment visible in the cross-section of the paint sample taken from the robe of St. John the Baptist consists of Pb, which indicates red lead.

  • 43  Historically, the preparation of lake pigments from organic dyestuff was based on the precipitatio (...)

40The colorant in the uppermost pale purplish glaze could not be identified by EDX. This indicates organic dyestuff. The presence of aluminium and calcium points to a lake pigment substrate (hydrated alumina and calcium carbonate).43

  • 44  SCHWEPPE, H.; ROOSEN-RUNGE, H., ''Carmine – Cochineal Carmine and Kermes Carmine'', in Artist's Pi (...)
  • 45  SCHWEPPE, H.; WINTER, J., ''Madder and Alizarin'', in Artist's Pigments, A Handbook of Their Histo (...)
  • 46  SCHWEPPE, H.; ROOSEN-RUNGE, H., ''Carmine – Cochineal Carmine and Kermes Carmine'' in op. cit., 26 (...)

41Red lake pigments, such as carmine from kermes scale insect (Kermes vermilio Planchon) or dyestuff obtained from brazilwood (Caesalpinia spp.), have been prepared by precipitation from aqueous extract using alum since the Middle Ages.44 Colorants obtained from madder (Rubia tinctorum L.) and other plants of the Rubiaceae family have also long been employed as lake pigments, commonly on an aluminium substrate.45 Lake pigments that are produced in this way give translucent films when mixed in oil.  It is for this reason that they were mainly used as glazes.46 Thin homogeneous translucent top layer in the paint sample taken from St. John the Baptist's robe is also applied in the form of glaze.

  • 47  KIRBY, J.; SPRING, M.; HIGGITT, C., ''The Technology of Red Lake Pigment Manufacture: Study of the (...)
  • 48  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 81.

42Although the origin of the red lake dyestuff cannot be determined using EDX spectroscopy, some conclusions may be drawn from the presence and proportion, or the absence of certain elements in the lake substrate. Studies have shown that both plants and scale insects from which the dyestuffs are extracted can contribute a number of elements: S, P, Si, Ca, K, Cl, Mg, Na and Cu, the most important in insects being P, S, K and Cl.47 If a significant amount of phosphorus is present in a lake substrate, the dyestuff is probably derived from insects.48 However, no traces of phosphorus were determined in the layer of red lake from the Kostanje painting.

  • 49  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 71, 75, 76, 80.

43Furthermore, when the dyestuff is extracted directly from raw materials, it is much more likely that the elements present in the raw material will remain in the precipitated pigment (as opposed to the use of coloured textile shearings for the extraction of the dyestuff). A number of historical recipes suggest that lake pigments from lac and brazilwood were often prepared by direct extraction from source materials. Recipes for extraction of dyestuff from brazilwood list calcium carbonate (usually chalk) as a common ingredient, thus large amount of calcium, but also aluminium, can be expected in brazilwood lakes.49 The most significant elements in Fedrigazzi's red lake are, indeed, aluminium and calcium, as observable in the aluminium and calcium EDX maps (Fig. 9 b). This red lake also contains traces of silicon, chlorine and potassium, elements that may indicate the presence of a dyestuff of vegetable origin, extracted directly from the raw material.

  • 50  Using, for example, ninhydrin test. KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 76, 77, (...)

44The red lake from the Kostanje painting contains no traces of sulphur. Comparatively high sulphur content could have indicated a dyestuff obtained from the wool dyed with madder, especially if the presence of proteins was confirmed.50 Since no dull orange fluorescence typical of madder lakes was observed under ultraviolet light, it is safe to conclude that Fedrigazzi did not use madder.

45To summarize, the red dye in the sample contains a significant amount of calcium and aluminium, with traces of Si, Cl and K. That could indicate a colorant of vegetable origin, extracted directly from the raw material and precipitated on hydrated alumina with addition of calcium carbonate. It is, hence, possible that the red lake from Fedrigazzi's painting is derived from brazilwood.

  • 51  THOMPSON, D. V., op. cit., 1956, p. 120, 121.
  • 52  THOMPSON, D. V., op. cit., 1956, p. 120, 121. See also KIRBY, J.; WHITE, R., ''The Identification (...)
  • 53  BERRIE, B. H., ''Rethinking the History of Artists' Pigments Through Chemical Analysis'', in Annua (...)
  • 54  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 83. Brazilwood lake has been confirmed in t (...)

46Yet, a few remarks have to be made. According to some authors, brazilwood colour was vastly used for painting and for dyeing in the Middle Ages due to its cheapness and ease of use.51 Following the Spanish conquest of Mexico in 1512, carmine derived from the New World cochineal (Dactylopius coccus Costa) gradually replaced kermes carmine and brazilwood in textile dyeing and painting, becoming widespread during the 17th century.52 Although the use of brazilwood lake has often been noted in manuscripts, the pigment seems to have scarcely been detected by chemical analyses.53 Furthermore, examples of paintings with brazilwood lake used as an underlayer have been documented, the reason for both probably being the well known impermanence of the dyestuff.54

  • 55  See KIRBY, J., WHITE, R., op. cit., 1996, p. 70, 71 and KIRBY, J.; SPRING, M.; HIGGITT, C., op. ci (...)

47Bearing in mind that Francesco Fedrigazzi was an Italian painter, it should be noted that the New World cochineal dyestuff has been reported in red lakes from the majority of examined 17th and 18th-century Italian paintings.55 However, different analytical techniques should be employed to confirm brazilin or substances that would indicate other dyestuff sources.

Fig. 9 (a) Cross-section of the red paint with ground layer (the robe of Saint John the Baptist) from the Baptism of Christ and Our Lady of Mount Carmel. 200x. (b) EDX element maps

Fig. 9 (a) Cross-section of the red paint with ground layer (the robe of Saint John the Baptist) from the Baptism of Christ and Our Lady of Mount Carmel. 200x. (b) EDX element maps

As observable in Al-K and CA-KA maps, aluminium and calcium are concentrated in the uppermost layer of pale purplish glaze, indicating a lake pigment substrate.

Credits: Tea Zubin Ferri

Fig. 10 EDX spectrum of a purplish glaze (red lake) depicted in Fig. 9

Fig. 10 EDX spectrum of a purplish glaze (red lake) depicted in Fig. 9

Credits: Tea Zubin Ferri

Brown (the edge of Christ's mantle)

48The brown pigment that Fedrigazzi used to paint Christ's mantle is mainly composed of iron, silicon, oxygen, potassium and sulphur. It also contains a small amount of manganese, which suggests that some sort of natural sienna and/or umber is in question.

Fig. 11 (a) Cross-section of the brown paint with ground layer (the edge of Christ's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 500x. (b) EDX maps

Fig. 11 (a) Cross-section of the brown paint with ground layer (the edge of Christ's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 500x. (b) EDX maps

In Pb-LA map, a layer of lead white is visible above the ground layer. Sulphur-rich particles, probably of a coal black, are observable in S-KA map.

Credits: Tea Zubin Ferri

Flesh colour (the chest of Saint John the Baptist)

49The flesh colour consists mostly of white lead. Coloured particles resembling those of red lead, red lake, green earth etc. can be seen in the paint cross-section, but EDX analysis did not provide clear answers regarding their chemical composition.

Fig. 12 Cross-section of the flesh colour (the chest of Saint John the Baptist) fromthe Baptism of Christ and Our Lady of Mount Carmel. (500x)

Fig. 12 Cross-section of the flesh colour (the chest of Saint John the Baptist) fromthe Baptism of Christ and Our Lady of Mount Carmel. (500x)

Credits: Tea Zubin Ferri

Conclusion

50This research provided valuable insight into Francesco Fedrigazzi's painting technique and supported the dating of his painting from the church of Saint Michael in Kostanje. Various imaging and analytical techniques were employed to study this artwork: X-ray imaging, UV fluorescence analysis, optical microscopy, SEM-EDX imaging and spectroscopy.

51The detailed technical examination showed that Fedrigazzi first applied two layers of reddish-brown preparation to canvas. The ground was coloured with earth pigments, probably ground argil and red earth with addition of coal black, which was a common practice in 17th and 18th century. Before applying the paint, he coated the lower half of the painting with lead white. This was rather unusual for the period, but added to the lightness of tonality of the scene depicting the Christ and Saint John the Baptist in the landscape. Fedrigazzi's palette consisted of traditional pigments, common for his period: lead white, massicot, possibly indigo, red lead in combination with red lake, and natural earth pigments, such as green earth, sienna and/or umber. The pigments were bound in an oil medium. He did not varnish the Kostanje painting, which is why his colours have retained their freshness and intensity to date.

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Bibliography

AMADORI, M. L.; BARALDI, P.; BARCELLI, S.; POLDI, G., ''New Studies on Lorenzo Lotto's Pigments: Non-Invasive and Micro-Invasive Analyses'', in Atti del VII Congresso Nazionale di Archeometria (Modena), edited by Giovanna Vezzalini and Paolo Zannini, Pàtron Editore, Bologna, 2012, p. 793-815.

BERRIE, B. H., ''Rethinking the History of Artists' Pigments Through Chemical Analysis'', in Annual Review of Analytical Chemistry, 2012, n°5, p. 441-459. Retrieved on 10/26/12 from Annual Reviews: http://www.annualreviews.org/doi/abs/10.1146/annurev-anchem-062011-143039?journalCode=anchem

BOŽANIĆ-BEZIĆ, N., ''Majstori od IX do XIX stoljeća u Dalmaciji II'', in Prilozi povijesti umjetnosti u Dalmaciji, 1966, n°16, p. 297-345, Konzervatorski zavod Dalmacije, Split.

EDWARDS, H. G. M.; BENOY, T. J., ''The de Brécy Madonna and Child tondo painting: a Raman spectroscopic analysis'', Analytical and Bioanalytical Chemistry, 2007, n°387, p. 837-846.

EIKEMA HOMMES, M. H. van, Discoloration in Renaissance and Baroque Oil Paintings. Instructions for Painters, theoretical Concepts, and Scientific Data (dissertation), Faculty of Humanities, University of Amsterdam, Amsterdam, 2002.

GETTENS, R. J., STOUT, G. L., Painting Materials, A Short Encyclopaedia, Dover Publications, Inc., New York, 1966.

GRISSOM, C. A., ''Green Earth'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Robert L. Feller, National Gallery of Art, Washington, 1986, p. 141-167.

GROEN, K. M., ''Earth Matters, The origin of the material used for the preparation of the Night Watch and many other canvases in Rembrandt's workshop after 1640'', in Art Matters – Netherlands Technical Studies in Art, 2005, n°3, p. 128-154.

HELWIG, K., ''Iron Oxide Pigments, Natural and Synthetic'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Barbara H. Berrie, National Gallery of Art, Washington, 2007, p. 39-95.

HRADIL, D.; GRYGAR, T.; HRADILOVÁ, J.; BEZDIČKA, P., ''Clay and iron oxide pigments in the history of painting'', in Applied Clay Science, 2003, n°22, p. 223-236.

KIRBY, J.; SPRING, M.; HIGGITT, C., ''The Technology of Red Lake Pigment Manufacture: Study of the Dyestuff Substrate'', in National Gallery Technical Bulletin, 2005, n°26, p. 71-80, National Gallery, London.

KIRBY, J.; WHITE, R., ''The Identification of Red Lake Dyestuffs and a Discussion of Their Use'', in National Gallery Technical Bulletin, 1996, n°17, p. 56-80, National Gallery, London.

KOVAČIĆ, S., ''Župe splitske nadbiskupije u poljičko-radobiljskom dekanatu g. 1625.'', in Synthesis Theologica, Zbornik u čast p. Rudolfa Brajčića SJ prilikom 75. obljetnice života, edited by Marijan Steiner, 1994, Filozofsko teološki institut Družbe Isusove, Zagreb, p. 637-648.  

KÜHN, H., ''Lead-Tin Yellow'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Ashok Roy, National Gallery of Art, Washington, 1993, p. 83-111.

MERRIFIELD, M. Ph., Original Treatises, Dating from the XIIth to the XVIIIth Centuries, on the Arts of Painting, London: John Murray, Albemarle Street, London, 1849.

NEVIN, A. et. al., ''Advances in the Analysis of Red Lake Pigments from 15th and 16th c. Using Fluorescence and Raman Spectroscopy'', Dipartimento di Fisica, Politecnico di Milano, Milano, 2011. Retrieved on 10/1/2012 from The Open Access NDT Database: http://www.ndt.net/article/art2011/papers/NEVIN%20-%20NDT%2038.pdf

PENNY, N.; SPRING, M.,''Veronese's Paintings in the National Gallery. Technique and Materials: Part I'', in National Gallery Technical Bulletin, 1995, n°16, National Gallery, London, p. 4-29.

SCHWEPPE, H., ''Indigo and Woad'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Elizabeth West Fitzhugh, National Gallery of Art, Washington, 1997, p. 81-98.

SCHWEPPE, H.; ROOSEN-RUNGE, H., ''Carmine – Cochineal Carmine and Kermes Carmine'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Robert L. Feller, National Gallery of Art, Washington, 1986, p. 255-283.

SCHWEPPE, H.; WINTER, J., ''Madder and Alizarin'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Elizabeth West Fitzhugh, National Gallery of Art, Washington, 1997, p. 109-134.

SERRANO, A., ''The Red Road of the Iberian Expansion: Cochineal and the global dye trade'', ARCHLAB Access report, 2001 (lead researcher: Jessica Hallett, project: Textiles, Trade and Taste: Portugal and the World). Retrieved on 1/20/2013 from Charisma Project: http://www.charismaproject.eu/media/80196/icn,%20ng,%20bm_hallet.pdf

SPRING, M.; GROUT, R.; WHITE, R., '''Black Earths' – A Study of Unusual Black and Dark Grey Pigments Used by Artists in the Sixteenth Century'', in National Gallery Technical Bulletin, 2003, n°24, p. 96-114, National Gallery, London.

THOMPSON, D. V., The Materials and Techniques of Medieval Painting, Dover Publications, Inc., New York, 1956.

VLAŠIĆ, D., Vizitacije poljičkih župa u XVIII. Saint, Crkva u svijetu, Poljica – Godišnjak Poljičkog dekanata, Split, 1995.  

WINTER, J.; WEST FITZHUGH, E., ''Pigments Based on Carbon'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Barbara H. Berrie, National Gallery of Art, Washington, 2007, p. 1-37.

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Notes

1  KOVAČIĆ, S., ''Župe splitske nadbiskupije u poljičko-radobiljskom dekanatu g. 1625.'', in Synthesis Theologica, Zbornik u čast p. Rudolfa Brajčića SJ prilikom 75. obljetnice života, edited by Marijan Steiner, 1994, Filozofsko teološki institut Družbe Isusove, Zagreb, p. 642-644.  

2  VLAŠIĆ, D., Vizitacije poljičkih župa u XVIII. Saint, Crkva u svijetu, Poljica – Godišnjak Poljičkog dekanata, Split, 1995, p. 32, 33.  

3  VLAŠIĆ, D., op. cit., 1995, p. 112.  

4  BOŽANIĆ-BEZIĆ, N., ''Majstori od IX do XIX stoljeća u Dalmaciji II'', in Prilozi povijesti umjetnosti u Dalmaciji, 1966, n°16, Konzervatorski zavod Dalmacije, Split, p. 323.

5  Academician PhD Radoslav Tomić is credited for both dating and attribution of the painting.

6  TOMIĆ, Radoslav, paper forthcoming. I am grateful to the author for the data and advice regarding the history and iconography of the painting. I am thankful to Mr. Tomić for the data about Francesco Fedrigazzi's oeuvre and his advice regarding the history of the Kostanje painting. Fedrigazzi's paintings were first recognised in Poreč by PhD Višnja Bralić, who attributed the painting from the Euphrasian Basilica to Fedrigazzi. BRALIĆ, V., ''I dipinti ritrovati della cattedrale parentina'', Saggi e Memorie di storia dell'arte, 2006, n°30, Venezia, p. 163-179. Mr. Tomić is credited for the identification of a number of Fedrigazzi's paintings in the region of Dalmatia.

7  The description of the church altars in the episcopal visitation from 1748 (see note 3) is essential for the history of the paintings found. According to the visitation, the painting from the altar devoted to Saint John the Baptist represented the Baptism of Christ and Our Lady of Mount Carmel. One of the two found paintings by Naldi represents the same iconography. Since it is dated with 1761, it is clear that the painting documented in the visitation from 1748 is the one painted by Francesco Fedrigazzi in the early 18th century.  Naldi's second painting, which depicts Our Lady of Rosary, Saint Jerome and Saint Roche, adorned Saint Jerome's altar.

8  Data generously provided by MSc Frane Mihanović, credited for organizing and conducting the radiographic imaging and post-processing at the Arts Academy of the University of Split.

9  Tea Zubin Ferri of the Metris research centre and Marijana Fabečić of the Croatian Conservation Institute provided the cross-section photos.

10  Tea Zubin Ferri is credited for SEM-EDX cross-section imaging, pigment composition analysis and initial interpretation of the results on which the discussion in this paper is based.

11  Data kindly provided by Tea Zubin Ferri. The contrast in BSE images primarily depends on the differences in the average atomic number of the specimen, thus the images provide information on distribution of different elements in the cross-sections.

12  The presence of lead in the white layer was proven subsequently by EDX analysis.

13  SEM-EDX analysis showed that the landscape was painted using green earth, a pigment consisting of elements with comparatively low atomic number (Fe, Mg, Al, K), which, therefore, absorb X-rays less than lead.

14  HELWIG, K., ''Iron Oxide Pigments, Natural and Synthetic'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Barbara H. Berrie, National Gallery of Art, Washington, 2007, p. 60, 61, 88.

15  HELWIG, K., op. cit., 2007, p. 89.

16  HELWIG, K., op. cit., 2007, p. 51.

17  MERRIFIELD, M. Ph., Original Treatises, Dating from the XIIth to the XVIIIth Centuries, on the Arts of Painting, John Murray, Albemarle Street, London, 1849, p.731.

18  Cf. HRADIL, D.; GRYGAR, T.; HRADILOVÁ, J.; BEZDIČKA, P., ''Clay and iron oxide pigments in the history of painting'', in Applied Clay Science, 2003, n°22, p. 230, 231.

19  Cf. GROEN, K. M., ''Earth Matters, The origin of the material used for the preparation of the Night Watch and many other canvases in Rembrandt's workshop after 1640'', in Art Matters – Netherlands Technical Studies in Art, 2005, n°3, p. 145, 146, Fig. 9-11. and HRADIL, D.; GRYGAR, T.; HRADILOVÁ, J.; BEZDIČKA, P., op. cit., p. 230, Fig. 3.

20  Cf. HELWIG, K., op. cit., 2007, p. 89, Fig. 32. d, an X-ray energy spectrum of a red earth from Italy (M. Dolci e Figli Snc.). Matching elements are Si, Al, K, Ca, Ti and Fe.

21  WINTER, J.; WEST FITZHUGH, E., ''Pigments Based on Carbon'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Barbara H. Berrie, National Gallery of Art, Washington, 2007, p. 23, 29.

22  Cf. SPRING, M.; GROUT, R.; WHITE, R., 'Black Earths' – A Study of Unusual Black and Dark Grey Pigments Used by Artists in the Sixteenth Century, in National Gallery Technical Bulletin, 2003, n°24, National Gallery, London, p. 97, Table 1. A number of Italian paintings containing S-rich black in the priming (predominantly) and paint layers is listed in the aforementioned study (see p. 113).

23  SPRING, M.; GROUT, R.; WHITE, R., op. cit., 2003, p. 96.

24  THOMPSON, D. V., The Materials and Techniques of Medieval Painting, Dover Publications, Inc., New York, 1956, p. 179.

25  Today it is assumed that both massicot (or masticot, which is the name found in the manuscripts of the northern countries) and giallorino (or giallolino, in the Italian painting handbooks) in the past probably denoted lead-tin yellow. KÜHN, H., ''Lead-Tin Yellow'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Ashok Roy, National Gallery of Art, Washington, 1993, p. 83-89. Among other, as an argument for such clarification of terminology, the author of the above mentioned paper lists the fact that the yellow lead oxide (PbO) has rarely been detected among the paintings made between the 13th and 20th century, as opposed to lead-tin yellow which has been found in many paintings throughout Europe. The earliest examples of the use of lead antimoniate (Naples yellow) as pigment, however, date from the 17th century.

26  See, for example: SCHWEPPE, H., ''Indigo and Woad'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Elizabeth West Fitzhugh, National Gallery of Art, Washington, 1997, p. 99-101.

27  The earliest recorded examples of indigo in oil medium are 13th century Norwegian panel paintings. EIKEMA HOMMES, M. H. van, Discoloration in Renaissance and Baroque Oil Paintings. Instructions for Painters, theoretical Concepts, and Scientific Data (dissertation), Faculty of Humanities, University of Amsterdam, 2002, p. 109-114.

28  Though analytical evidence suggest that painters have continued to use it, indigo apparently drops from use in oil painting after the 17th century, the reason for this probably being the invention of Prussian blue (1704), a pigment of better quality. Yet, many 18th century manuals recommend the use of indigo in oil and list recipes for its preparation and advice for improoving its permanence. EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 124, 128, 134.

29  While indigo was identified in only very few works by 15th and 16th century Northern European painters, it has been detected in a number of Italian paintings of the period, including works by Antonio Vivarini, Giorgio Schiavone, Francesco del Cossa and Jacopo Tintoretto. Influenced by the Italian painters during his stay in Italy from 1600 to 1608, Peter Paul Rubens was the first painter north of the Alps known to have used indigo extensively. EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 121. Other reports of indigo in 16th century paintings from Venice and surrounding areas include works by Paolo Veronese, Titian and Lorenzo Lotto. PENNY, N.; SPRING, M., ''Veronese's Paintings in the National Gallery. Technique and Materials: Part I'', in National Gallery Technical Bulletin, 1995, n°16, National Gallery, London, p. 7, 8; AMADORI, M. L.; BARALDI, P.; BARCELLI, S.; POLDI, G., ''New Studies on Lorenzo Lotto's Pigments: Non-Invasive and Micro-Invasive Analyses'', in Atti del VII Congresso Nazionale di Archeometria (Modena), edited by Giovanna Vezzalini and Paolo Zannini, Pàtron Editore, Bologna, 2012, p. 809-811.

30  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 120, 121.

31  In all indigo dye plants, the main precursor of blue colorant indigotin is water-soluble indican. There are different methods for the indigo dyestuff extraction, but all involve the fermentation of plant material in order to break indican, causing the formation of indoxyl and glucose. In contact with air, indoxyl is oxidised to water-soluble leuco-indigo ('indigo white') and subsequently to insoluble indigotin ('indigo blue'). See EIKEMA HOMMES, M. H. van, op. cit., 2002, 112.

32  EIKEMA HOMMES, M. H. van, op. cit., 2002, 111, 119, 141.

33  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 145-155. In her dissertation, van Eikema Hommes lists Frans Hals as the first painter known to have used indigo abundantly in the top paint layers of important commissions – the portraits of the St. George and St. Adrian civic guards from 1627 (p. 122).

34  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 150, 151, 152.

35  EIKEMA HOMMES, M. H. van, op. cit., 2002, p. 135, 136.

36  SCHWEPPE, H., op. cit., 1997, p. 97.

37  Indigo and turnsole were predominant medieval sources for organic blue colour, hence their names were often applied to blue colours made from other vegetable sources. THOMPSON, D. V., op. cit., 1956, p. 140, 141. As previously explained, indigo has been quite frequently identified in historical oil painting (see notes 26-29). Though widely used in medieval book painting, blue made from turnsole (Crozophora tinctoria), known as folium, has been detected only in a painting by Raphael. EDWARDS, H. G. M.; BENOY, T. J., ''The de Brécy Madonna and Child tondo painting: a Raman spectroscopic analysis'', Analytical and Bioanalytical Chemistry, 2007, n°387, p. 837-846.  Archil, a purplish-blue dye made from Roccella tinctoria lichen, was sometimes used to make a pigment as well. THOMPSON, D. V., op. cit., 1956, p. 158, 159.

38  THOMPSON, D. V., op. cit., 1956, p. 163.

39  GRISSOM, C. A., ''Green Earth'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Robert L. Feller, National Gallery of Art, Washington, 1986, p. 145, 146. Grissom has reached these conclusions through research. She refers to an 18th-century manual (Bardwell, 1756, p. 38) as at least one in which the use of green earth as glaze in oil painting is advised. Interestingly, Grissom also notes that green earth ground into an oil medium is usually dark; the colour becomes much lighter when the concentration of the pigment in relation to the binding medium is increased. In regard of the Kostanje painting, this should be further inspected.

40  GRISSOM, C. A., op. cit., 1986, p. 146.

41  Cf. GRISSOM, C. A., op. cit., 1986, p. 150, 151, Fig. 9, and GETTENS, R. J., STOUT, G. L., Painting Materials, A Short Encyclopaedia, Dover Publications, Inc., New York, 1966, p. 117.

42  GRISSOM, C. A., op. cit., 1986, p. 148, 149, 143. The most significant use of green earth has been the underpainting of flesh in medieval painting.

43  Historically, the preparation of lake pigments from organic dyestuff was based on the precipitation of hydrated alumina, Al(OH)₃, from the mixture of solutions of alum, generally potassium aluminium sulfate (KAl(SO₄)₂ ∙ 12H₂O) and potassium carbonate (K2CO3). When a solution of alum is mixed with a solution of lye containing potassium carbonate, a transparent, colourless precipitate of hydrated alumina is deposited. If the solution contains an organic dyestuff, it will precipitate together with hydrated alumina and form a transparent, coloured mixture. THOMPSON, D. V., op. cit., 1956, p. 79. See also KIRBY, J.; SPRING, M.; HIGGITT, C., ''The Technology of Red Lake Pigment Manufacture: Study of the Dyestuff Substrate'', in National Gallery Technical Bulletin, 2005, n°26, National Gallery, London, p. 71.

44  SCHWEPPE, H.; ROOSEN-RUNGE, H., ''Carmine – Cochineal Carmine and Kermes Carmine'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Robert L. Feller, National Gallery of Art, Washington, 1986, p. 255.

THOMPSON, D. V., op. cit., 1956, p. 115-120.

45  SCHWEPPE, H.; WINTER, J., ''Madder and Alizarin'', in Artist's Pigments, A Handbook of Their History and Characteristics, edited by Elizabeth West Fitzhugh, National Gallery of Art, Washington, 1997, p. 109, 111, 131.

46  SCHWEPPE, H.; ROOSEN-RUNGE, H., ''Carmine – Cochineal Carmine and Kermes Carmine'' in op. cit., 264.

47  KIRBY, J.; SPRING, M.; HIGGITT, C., ''The Technology of Red Lake Pigment Manufacture: Study of the Dyestuff Substrate'', in National Gallery Technical Bulletin, 2005, n°26, National Gallery, London, p. 72.

See also NEVIN, A. et. al., ''Advances in the Analysis of Red Lake Pigments from 15th and 16th c. Using Fluorescence and Raman Spectroscopy'', Dipartimento di Fisica, Politecnico di Milano, Milano, 2011, p. 4.

48  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 81.

49  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 71, 75, 76, 80.

50  Using, for example, ninhydrin test. KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 76, 77, 82, 86, 87.

51  THOMPSON, D. V., op. cit., 1956, p. 120, 121.

52  THOMPSON, D. V., op. cit., 1956, p. 120, 121. See also KIRBY, J.; WHITE, R., ''The Identification of Red Lake Dyestuffs and a Discussion of Their Use'', in National Gallery Technical Bulletin, 1996, n°17, National Gallery, London, p. 64.

53  BERRIE, B. H., ''Rethinking the History of Artists' Pigments Through Chemical Analysis'', in Annual Review of Analytical Chemistry 2012, n°5, p. 5. KIRBY, J.; WHITE, R., op. cit., 1996, p. 64.

54  KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 83. Brazilwood lake has been confirmed in two paintings belonging to the National Gallery in London: Pietro da Cortona's Saint Cecilia, 1620-5, oil on canvas, and Raphael's The Ansidei Madonna, 1505, oil on wood (brazilwood as an underpaint). KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 87. Other reports include: Portrait of Frederick Rihel on Horseback by the follower of Rembrandt, probably 1663, where cochineal and seemingly brazilwood were detected, and Pope Innocent X by Velazquez, Apsley House (English Heritage, formerly V&A), where both cochineal and brazilwood were identified. SERRANO, A., The Red Road of the Iberian Expansion: Cochineal and the global dye trade, ARCHLAB Access report, 2001 (lead researcher: Jessica Hallett, project: Textiles, Trade and Taste: Portugal and the World), p. 24, 26.

55  See KIRBY, J., WHITE, R., op. cit., 1996, p. 70, 71 and KIRBY, J.; SPRING, M.; HIGGITT, C., op. cit., 2005, p. 86, 87.

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List of illustrations

Title Fig. 1 Baptism of Christ and Our Lady of Mount Carmel
Caption Painting by Francesco Fedrigazzi before the treatment and after retouching.
Credits Credits: Mladen Čulić, Jelena Zagora
URL http://ceroart.revues.org/docannexe/image/3248/img-1.jpg
File image/jpeg, 1.0M
Title Fig. 2 Sampling scheme
Caption (1) yellow, (2) dark blue, (3) light blue, (4) green, (5) red, (6) brown, (7) white, (8) flesh colour.
Credits Credits: Jelena Zagora
URL http://ceroart.revues.org/docannexe/image/3248/img-2.jpg
File image/jpeg, 1.0M
Title Fig. 3 Digital X-ray image of the Baptism of Christ and Our Lady of Mount Carmel
Credits Credits: Frane Mihanović
URL http://ceroart.revues.org/docannexe/image/3248/img-3.jpg
File image/jpeg, 1020k
Title Fig. 4 BSE cross-section images of: (a) the green paint, (b) the brown paint, both including the ground layer
Caption Layers containing lead white are shown in white and light shades of grey.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-4.jpg
File image/jpeg, 552k
Title Fig. 5 (a) Cross-section of the yellow paint with ground layer (the clouds above Our Lady) from the Baptism of Christ and Our Lady of Mount Carmel (200x). (b) EDX spectrum of the ground layer brownish matrix
Caption Large, coarse orange grains containing mostly Al, Si and Fe (possibly ground argil), coarse-grained violet-red hematite particles, colourless quartz grains and splintery coal black particles are visible in brownish clayey matrix (large Al and Si peaks) of Fedrigazzi's priming. See also Fig. 11 and Fig. 9.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-5.jpg
File image/jpeg, 408k
Title Fig. 6 (a) Cross-section of the dark blue paint with ground layer (Our Lady's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 100x. (b) EDX element maps
Caption The bluish-white layers above and below the dark blue layer contain mostly aluminium with some calcium (Al-K and CA-KA maps). Calcium is concentrated in the dark blue middle layer.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-6.jpg
File image/jpeg, 576k
Title Fig. 7 EDX spectrum of the light blue paint layer (the edge of Christ's mantle)
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-7.jpg
File image/jpeg, 468k
Title Fig. 8 Cross-section of the green paint with ground layer (treetop left of Saint John the Baptist's head) from the Baptism of Christ and Our Lady of Mount Carmel. (500x)
Caption Translucent, rounded particles of different shades of green, in places blue, with traces of yellow or brown earth.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-8.jpg
File image/jpeg, 884k
Title Fig. 9 (a) Cross-section of the red paint with ground layer (the robe of Saint John the Baptist) from the Baptism of Christ and Our Lady of Mount Carmel. 200x. (b) EDX element maps
Caption As observable in Al-K and CA-KA maps, aluminium and calcium are concentrated in the uppermost layer of pale purplish glaze, indicating a lake pigment substrate.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-9.jpg
File image/jpeg, 892k
Title Fig. 10 EDX spectrum of a purplish glaze (red lake) depicted in Fig. 9
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-10.jpg
File image/jpeg, 332k
Title Fig. 11 (a) Cross-section of the brown paint with ground layer (the edge of Christ's mantle) from the Baptism of Christ and Our Lady of Mount Carmel. 500x. (b) EDX maps
Caption In Pb-LA map, a layer of lead white is visible above the ground layer. Sulphur-rich particles, probably of a coal black, are observable in S-KA map.
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-11.jpg
File image/jpeg, 696k
Title Fig. 12 Cross-section of the flesh colour (the chest of Saint John the Baptist) fromthe Baptism of Christ and Our Lady of Mount Carmel. (500x)
Credits Credits: Tea Zubin Ferri
URL http://ceroart.revues.org/docannexe/image/3248/img-12.jpg
File image/jpeg, 896k
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References

Electronic reference

Jelena Zagora, « SEM-EDX Pigment Analysis and Multi-Analytical Study of the Ground and Paint layers of Francesco Fedrigazzi's painting from Kostanje », CeROArt [Online], EGG 3 | 2013, Online since 20 May 2013, connection on 18 August 2017. URL : http://ceroart.revues.org/3248

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About the author

Jelena Zagora

Jelena Zagora graduated with MA in Conservation and Restoration at the Arts Academy of the University in Split, specializing in Easel Paintings and Polychrome Wood Conservation. Her research interests include art history and historical painting techniques and materials. She is currently pursuing an internship at the Croatian Conservation Institute in Split.

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Copyright

Licence Creative Commons
CeROArt – Conservation, exposition, restauration d'objets d'arts est mis à disposition selon les termes de la licence Creative Commons Attribution - Pas d'Utilisation Commerciale - Pas de Modification 4.0 International.

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