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u-Raman, such as plumbonacrite, indicate the need to stabilize chemically these soaps since they are responsible for a continuum of chemical degradation phenomena [5].These chemical reactions also contribute to the physical degradation of the paintings, since the increase of volume of lead carboxylates causes instability in the ground and painting layers, being probably one of the causes contributing to the detachment of these layers from the support. Figure 2. a) Micro-Fourier transform infrared (u-FTIR) spectrum from the green shadow of the grass, in P2, displaying azurite, kaolinite, oil and metallic carboxylates; b) u-FTIR spectrum from the light green of the grass, in P4, displaying azurite, hydrocerussite, oil and lead carboxylates. These results prove the evidence of the poor state of conservation of the studied groups, with no exception. Big areas of lacunae were detected in many parts of the paintings, some of them already restored (P1—P2, P5). These lacunae are more evident in the lower part of each painting as confirmed by IRR and IRP results. This fact suggests that a higher amount of humidity was accumulated in this area. Ascensional absorption of the wood canals in the lower part of each painting was the main cause for this degradation, probably being in contact with floor humidity. Also, the high humidity in the air was verified. Relative humidity was controlled in P1 and P2 in summer and winter. In other paintings (P3—P5) climate verification was not possible for this study, since it takes at least one year to analyze climate changes according to seasoning. P3 and P4 were brought from a church to the museum climate during the last year and P5 remained for several years in a museum climate. Results on P1—-P2 climate verification showed that the change in the relative humidity environment varies between 63% and 70% in the dry season (summer). This means a variation of 7% in relative humidity between morning and afternoon, and the relative humidity should not fluctuate more than 10% in 24 hours. It has to be considered that this maximum value of 70% of relative humidity is the value from which it is agreed that the various objects of organic structure, especially painting, begin to change their dimensions, lose their original rigidity, becoming plastic and more vulnerable to the formation of fungus [6,7]. However, in the wet season (winter) an approximate relative humidity of 78%-83% was detected.

Figure 2 u-Raman, such as plumbonacrite, indicate the need to stabilize chemically these soaps since they are responsible for a continuum of chemical degradation phenomena [5].These chemical reactions also contribute to the physical degradation of the paintings, since the increase of volume of lead carboxylates causes instability in the ground and painting layers, being probably one of the causes contributing to the detachment of these layers from the support. Figure 2. a) Micro-Fourier transform infrared (u-FTIR) spectrum from the green shadow of the grass, in P2, displaying azurite, kaolinite, oil and metallic carboxylates; b) u-FTIR spectrum from the light green of the grass, in P4, displaying azurite, hydrocerussite, oil and lead carboxylates. These results prove the evidence of the poor state of conservation of the studied groups, with no exception. Big areas of lacunae were detected in many parts of the paintings, some of them already restored (P1—P2, P5). These lacunae are more evident in the lower part of each painting as confirmed by IRR and IRP results. This fact suggests that a higher amount of humidity was accumulated in this area. Ascensional absorption of the wood canals in the lower part of each painting was the main cause for this degradation, probably being in contact with floor humidity. Also, the high humidity in the air was verified. Relative humidity was controlled in P1 and P2 in summer and winter. In other paintings (P3—P5) climate verification was not possible for this study, since it takes at least one year to analyze climate changes according to seasoning. P3 and P4 were brought from a church to the museum climate during the last year and P5 remained for several years in a museum climate. Results on P1—-P2 climate verification showed that the change in the relative humidity environment varies between 63% and 70% in the dry season (summer). This means a variation of 7% in relative humidity between morning and afternoon, and the relative humidity should not fluctuate more than 10% in 24 hours. It has to be considered that this maximum value of 70% of relative humidity is the value from which it is agreed that the various objects of organic structure, especially painting, begin to change their dimensions, lose their original rigidity, becoming plastic and more vulnerable to the formation of fungus [6,7]. However, in the wet season (winter) an approximate relative humidity of 78%-83% was detected.

Related Figures (15)

Figure 1. a) “Sao Jodo Baptista no Deserto” (P1); b) “Sao Joao Evangelista em Patmos” (P2); c) “S. Tiago” (P3); d) “Sto.Anténio” (P4); e) “S.Jeroénimo” (P5).
Figure 1. a) “Sao Jodo Baptista no Deserto” (P1); b) “Sao Joao Evangelista em Patmos” (P2); c) “S. Tiago” (P3); d) “Sto.Anténio” (P4); e) “S.Jeroénimo” (P5).
Table 1. Analysis summary of risk factors: natural and derived of human activity in the room (adapted from [7]). 13 °C were detected. Several risk factors were detected in the room exhibiting P1 and P2.Natural factors (Meteorological, Hydrological, Seismic and Building Ruin Conditions) and Disaster derived from human activity (River protection failure and riverbank drainage, Building protection failure -easy to theft and vandalism, failure of poor electrification -over the wooden ceiling, failure of roof and ceiling maintenance (Table1).
Table 1. Analysis summary of risk factors: natural and derived of human activity in the room (adapted from [7]). 13 °C were detected. Several risk factors were detected in the room exhibiting P1 and P2.Natural factors (Meteorological, Hydrological, Seismic and Building Ruin Conditions) and Disaster derived from human activity (River protection failure and riverbank drainage, Building protection failure -easy to theft and vandalism, failure of poor electrification -over the wooden ceiling, failure of roof and ceiling maintenance (Table1).
Table 2. Main pigments by the color of the paintings P1-P4 assigned to Master of Lourinha, Santa Casa da Misericordia da Lourinha (SCM Lourinha) with results by X-ray fluorescence spectroscopy (XRF) and p-Raman.
Table 2. Main pigments by the color of the paintings P1-P4 assigned to Master of Lourinha, Santa Casa da Misericordia da Lourinha (SCM Lourinha) with results by X-ray fluorescence spectroscopy (XRF) and p-Raman.
Table 3. Micro-FTIR and u-Raman wavenumbers of compounds found in P1—P5 and database comparing source
Table 3. Micro-FTIR and u-Raman wavenumbers of compounds found in P1—P5 and database comparing source
- Underdrawing has a first phase of a geometrical point made by incision and by dry charcoal, as is evident in the face of “Sao Joao Baptista no Deserto” (P1) where a geometrical trace marks the nose position (Figure 3). Figure 3. a) “Sao Joao Baptista no Deserto” (P1); b) underdrawing in geometrical trace marking the nose position u; c) corrections to the form of the hand of the saint (infrared reflectography (IRR)).
- Underdrawing has a first phase of a geometrical point made by incision and by dry charcoal, as is evident in the face of “Sao Joao Baptista no Deserto” (P1) where a geometrical trace marks the nose position (Figure 3). Figure 3. a) “Sao Joao Baptista no Deserto” (P1); b) underdrawing in geometrical trace marking the nose position u; c) corrections to the form of the hand of the saint (infrared reflectography (IRR)).
Figure 4. a) “Sao Joao Evangelista em Patmos” (P2); b) griffon wings, changed in the final painting (IRR).
Figure 4. a) “Sao Joao Evangelista em Patmos” (P2); b) griffon wings, changed in the final painting (IRR).
Figure 5. a) Micro-Raman spectrum displaying in P1, in the region of the pre-gilding layer, under the golden halo, the presence of minium (226, 315, 390, 551cm *); b) Micro-Raman spectrum displaying in P2, in the region of the black book, the presence of carbon black (1333, 1583 cm“).
Figure 5. a) Micro-Raman spectrum displaying in P1, in the region of the pre-gilding layer, under the golden halo, the presence of minium (226, 315, 390, 551cm *); b) Micro-Raman spectrum displaying in P2, in the region of the black book, the presence of carbon black (1333, 1583 cm“).
Saint John the Baptist, made in Bruges, Netherlands, circa 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout (South Netherlandish, active ca. 1485-1530) [18,26] (Figure 6). Figure 6. a) and c) Minuteness figures in brown contour in the painting “Sado Jodo Evangelista em Patmos” (P2);b) and d) Minuteness figures in brown contour in the manuscript Ilumination with Scenes from the Life of Saint John the Baptist, Made in Bruges, Netherlands, ca. 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout, Metropolitan Museum of Art.
Saint John the Baptist, made in Bruges, Netherlands, circa 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout (South Netherlandish, active ca. 1485-1530) [18,26] (Figure 6). Figure 6. a) and c) Minuteness figures in brown contour in the painting “Sado Jodo Evangelista em Patmos” (P2);b) and d) Minuteness figures in brown contour in the manuscript Ilumination with Scenes from the Life of Saint John the Baptist, Made in Bruges, Netherlands, ca. 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout, Metropolitan Museum of Art.
The infrared photography of this pair of paintings shows that a carbon-based ink was used to perform the underdrawing. The first planned eyes direction of the saints, looking down, was changed in the final painting of the two panels, looking ahead, probably to coincide with the previous models, as it is possible to deduce from Figures 7,8. Models of illuminated books by Horenbout workshop seem to have been used, as it is the case of St James in the Book of Hours of James IV and Margaret Tudor, 1503, or of the illuminated image of Saint Anthony of Padua, belonging to the group manuscript of the Spinola Hours, made ca. 1510-1520.
The infrared photography of this pair of paintings shows that a carbon-based ink was used to perform the underdrawing. The first planned eyes direction of the saints, looking down, was changed in the final painting of the two panels, looking ahead, probably to coincide with the previous models, as it is possible to deduce from Figures 7,8. Models of illuminated books by Horenbout workshop seem to have been used, as it is the case of St James in the Book of Hours of James IV and Margaret Tudor, 1503, or of the illuminated image of Saint Anthony of Padua, belonging to the group manuscript of the Spinola Hours, made ca. 1510-1520.
Figure 8. a) and c) “Sto. Antonio” (P4); b) and d) Saint Anthony of Padua, Spinola Hours, ca. 1510-1520, Master of James IV of Scotland, Getty Museum. Figure 7. a) “S. Tiago” (P3); b) detail from the Book of Hours of James IV and Margaret Table 1503. Osterreichische Nationalbibliothek, Vienna; c) IRR detail, the first planned eye direction of the saints was changed in the final (P3).
Figure 8. a) and c) “Sto. Antonio” (P4); b) and d) Saint Anthony of Padua, Spinola Hours, ca. 1510-1520, Master of James IV of Scotland, Getty Museum. Figure 7. a) “S. Tiago” (P3); b) detail from the Book of Hours of James IV and Margaret Table 1503. Osterreichische Nationalbibliothek, Vienna; c) IRR detail, the first planned eye direction of the saints was changed in the final (P3).
Lighter tones were achieved in certain areas by hatching parallel white brushstrokes, to finalize the highlighting of the figures, as occurs in illuminated books [18] (Figure 9). Figure 9. detail first planned eyes direction of the saint changed in the final (P4); b) and c) detail of hatching parallel white brushstrokes to achieve lighter areas.
Lighter tones were achieved in certain areas by hatching parallel white brushstrokes, to finalize the highlighting of the figures, as occurs in illuminated books [18] (Figure 9). Figure 9. detail first planned eyes direction of the saint changed in the final (P4); b) and c) detail of hatching parallel white brushstrokes to achieve lighter areas.
Under the flesh tones was applied a brownish-grayish modelling layer to contrast in the final composition. This technique is also visible in the illuminated minuteness figures in the Scenes from the Life of Saint John the Baptist, made in Bruges, Netherlands, ca. 1515 (Figure 10). Figure 10. a) IRR detail contour drawing in the nose and first planned eye direction of the saint, changed in the final (P3); b) brownish-grayish layer under the flesh tone of the figure (P3); c) brownish-grayish layer under the flesh tone of the figure in the manuscript IIlumination with Scenes from the Life of Saint John the Baptist, Made in Bruges, Netherlands, ca. 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout, Metropolitan Museum of Art.
Under the flesh tones was applied a brownish-grayish modelling layer to contrast in the final composition. This technique is also visible in the illuminated minuteness figures in the Scenes from the Life of Saint John the Baptist, made in Bruges, Netherlands, ca. 1515 (Figure 10). Figure 10. a) IRR detail contour drawing in the nose and first planned eye direction of the saint, changed in the final (P3); b) brownish-grayish layer under the flesh tone of the figure (P3); c) brownish-grayish layer under the flesh tone of the figure in the manuscript IIlumination with Scenes from the Life of Saint John the Baptist, Made in Bruges, Netherlands, ca. 1515, assigned to Master of James IV of Scotland, probably Gerard Horenbout, Metropolitan Museum of Art.
Figure 11. Optical microsocpy (OM) of sample of the rock grey in P5; b) elementary analysis by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) of the same sample showing the thickness of the calcium sulfate ground layer, in blue, as well as the thin layer of calcium carbonate that overlaps it, in green; c) diffractogram of the chemical analysis of the lower layer of sample, highlighting the increased intensity of the anhydrite peaks (A) (3.50A), orthorhombic structure, followed by those of gypsum dehydrate (G) (3.06A), monoclinic structure, majority compounds of the calcium sulfate preparation.
Figure 11. Optical microsocpy (OM) of sample of the rock grey in P5; b) elementary analysis by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) of the same sample showing the thickness of the calcium sulfate ground layer, in blue, as well as the thin layer of calcium carbonate that overlaps it, in green; c) diffractogram of the chemical analysis of the lower layer of sample, highlighting the increased intensity of the anhydrite peaks (A) (3.50A), orthorhombic structure, followed by those of gypsum dehydrate (G) (3.06A), monoclinic structure, majority compounds of the calcium sulfate preparation.
It is also to highlight the fact that in this painting, when performing the IRR analysis, abandoned drawing of a male bust and some faces were found [12]. The experimentation that characterizes this panel is, therefore, noticeable, given that the abandoned drawing, located in the sky area, on the upper left side, does not have correspondence to the painted theme. Figure 12. a) “S.Jerdnimo” (P5); b) IRR characters found in the sky area or the cross of Christ, left to be painted in a lower position; c) changing of the lion position, previously painted facing the trees; d) illuminated “SJer6nimo”, belonging to the Book of Hours of D. Fernando, ca. 1530 - 1534, by Gant-Brugee School (Simon Bening/Horenbout), Museu Nacional de Arte Antiga, Lisboa, Portugal.
It is also to highlight the fact that in this painting, when performing the IRR analysis, abandoned drawing of a male bust and some faces were found [12]. The experimentation that characterizes this panel is, therefore, noticeable, given that the abandoned drawing, located in the sky area, on the upper left side, does not have correspondence to the painted theme. Figure 12. a) “S.Jerdnimo” (P5); b) IRR characters found in the sky area or the cross of Christ, left to be painted in a lower position; c) changing of the lion position, previously painted facing the trees; d) illuminated “SJer6nimo”, belonging to the Book of Hours of D. Fernando, ca. 1530 - 1534, by Gant-Brugee School (Simon Bening/Horenbout), Museu Nacional de Arte Antiga, Lisboa, Portugal.
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PaintingConservation of Cultural HeritageGround layer
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