The results are organized according to the support (plasters), pigments, painting procedures, and painting techniques. Mural cycles are compared regarding two principal groups, as suggested by art historians. The first group includes paintings in Marz, St. Johann am Steinfelde and the older pictorical register in Rust, attributed to the Master of St. Johann am Steinfelde. The second group is formed by the younger pictorical layer in Rust, paintings in Kobenz and in Ofenbach, linked to the Master of Kobenz or his workshop.
3.1. Plasters
All plasters are composed of lime as binder and sand as aggregate. However, they differ in the proportion of these materials, their cleanliness, as well as in the color and granulation of the sand. All XRD spectra show the principal presence of calcite and quartz. Calcite indicates lime as the binder; however, it could also be partially interpreted as crushed lime-rock, added to quartz as the main aggregate.
The principal difference between both proposed groups is the predominance of calcite in plasters from Marz, St. Johann, and Rust (
Figure 1a,c,e), while there is a surprisingly low amount of calcite in Ofenbach and Kobenz (
Figure 2a,c). This indicates different plaster preparation by corresponding workshops. In the XRD spectra of the last two locations, quartz presents a very intense peak, while also some impurities were detected, such as albite (found also in Rust), muscovite, chlinochlore, and gypsum; the last two compounds are probably a result of a degradation process caused by salts present in the wall and sulfurization [
5,
6,
7,
16]. Such low presence of calcite added to high amount of poorly washed sand results in weak stability of the plaster, which tends to pulverize. On the other hand, plasters in St. Johann, in Rust (older pictorical register), and Marz are more solid, being rich with lime as binder. XRD analyses are supported by optical microscopy of stratigraphic sections: plasters of the first group are much whiter (
Figure 1b,d,f); the one from Marz presents a high amount of aggregate, probably containing a lot of crushed lime-rock, while those from St. Johann and Rust contains more binder and less aggregate. In Marz, calcium oxalates were also detected, probably related to some consolidant conservation treatments.
On the contrary, in the second group (Ofenbach, Kobenz—
Figure 2b,d) the plaster is darker and saturated with sand, characterized by large angular grains of different colors from light yellow to brown. These two plasters are clearly different from the first group, even taking into consideration that artists generally obtained the sand from a nearby site. However, the important difference in the amount of lime and the selection and cleanliness of the sand indicate a completely different working manner among the murals of both groups. Despite that, the plasters from the first group do not show a lot of homogeneity and their material analysis is not sufficient to link them to the same workshop.
3.2. Pigments
EDX and XRF chemical analyses identified most of the inorganic pigments applied in all five selected locations, while ESEM and OM images often supported this identification regarding the shape of the pigment grains. They were characterized on the basis of their principal chemical elements, but no complementary molecular analysis could have been carried out up to now. In all selected murals a very similar palette was found (
Table 1), composed mostly of traditional natural inorganic pigments that were generally used in mural painting and were suitable in the alkaline and humid environment of
a fresco or lime technique [
5,
6,
7,
8,
9,
17,
18]: lime white (Ca), yellow earths, mainly alumosilicates (Al, Si, Fe), red earths, iron oxides (Fe), green earth (Mg, Al, Si, K), malachite or some other copper based green pigment (Cu), azurite (Cu), while for a black color carbon (C) or bone (P, Ca) blacks were applied.
Only in Kobenz, was a synthetic lead pigment detected (
Figure 3), probably lead white as well as minium. The letter one can be seen as a vivid orange color that still remains partially on one sample (
Figure 3a). In most areas, this lead pigment darkened, as observed already in situ by the naked eye (
Figure 3b). On cross-sections, this color layer looks brownish (
Figure 3a), indicating that the pigment most likely degraded to PbS [
19]. This change is confirmed by the XRF spectra of these samples, revealing the presence of S (
Figure 3f). Although S K-peaks are generally overlapped by Pb M-peaks, in this sample the peak intensity of this area is higher than in the only Pb containing samples where such degradation is not observed. Lead pigments were long known to be unstable and sensitive, among others, to sulfur containing compounds, especially in manuscripts and wall paintings [
5,
9,
17,
19]. Despite that, they were still used by some mural painters, but were generally applied
a secco.
Regarding green pigments, painters used to mix green earth with a copper-based pigment (
Figure 4), generally malachite was the most used one in mural painting. With XRF and ESEM-EDX, in several samples a copper based green pigment was confirmed by high Cu peaks (
Figure 4b,e). At that time several copper-based green pigments were known [
5,
7,
9,
17] and it is not possible to distinguish them only on the basis of elemental analysis. However, in most cases, the characteristic angular form of light green grains on cross-sections can confirm the use of malachite (
Figure 4a,d) [
17,
18]. Two degradation processes were detected: in Rust; the presence of Cl (
Figure 4b) reveals the formation of copper hydroxychlorides (atacamite, paratacamite, or similar) due to Cl
− ions or chloride salts present in the plaster, sand or brick [
19], while in St. Johann the darkening of some malachite grains occur (
Figure 4d). ESEM-EDX spectra reveal high Cu, O, and S presence (
Figure 4e), indicating the possible change to copper oxides (cuprite or tenorite), which can occur because of high temperature, or due to copper oxalates (mooloite) or other carboxylates due to acidic conditions resulting from the deterioration of organic binders [
19]. A similar process of darkening was also observed on blue azurite in Rust. In Kobenz, some black areas can be seen on the surface of several green areas, but no samples were extracted for the analysis. Green earth, mixed with other pigments, could be used for the shades of the uppermost layers, as well (
Figure 4d).
In Kobenz, the use of malachite cannot be determined, although the analysis shows intense Cu peaks; the pigment grains are small and rounded, indicating its synthetic origin. Perhaps verdigris was used, mixed with very low amount of a lead-based pigment, probably lead white (
Figure 5).
On the younger pictorical register in Rust, yellow, red, green, blue, and black colors are observed. Regarding material analysis carried out on other murals of this research and based on general knowledge on pigments in medieval mural painting, the palette of this register should include lime white, yellow and red earths. On the other hand, the presence of green earth or malachite (or both) and the application of azurite or a mixed blue cannot be established without chemical analysis; similarly which black pigment was selected cannot be determined. There are some black areas, which suggest pigment degradation and therefore different original color, as for example a probable green soil under the kneeling Christ in the Gethsemane Garden which looks black today (malachite alteration?).
3.3. Painting Procedure
In all five selected monuments, there are variations regarding preparatory drawings, incisions and pouncing, underpaintings, or modeling, which can be observed in
Table 2. Deep and wide incisions and pouncing for nimbus and medallions, pressed into a fresh plaster, can be well observed in St. Johann am Steinfelde and the older pictorical register in Rust. In Marz and Ofenbach, they were used only for nimbus (
Figure 6). The pouncing is mostly linear, however, in Marz and on the older register in Rust circular forms were also applied (
Figure 6b,d). This could reveal a work of two principal artists in the same workshop, while, at the same time, link the Marz and Rust workshops. On the contrary, in the younger register in Rust and in Kobenz neither incisions nor pouncing can be discerned.
For underdrawing, the preparatory drawing carried out on a fresh
intonaco, only red and yellow colors were used. In Marz, a dark red color was applied with wide brushstrokes using a half-dry brush. This can be observed in situ by the naked eye due to the loss of the overlaid color layers (
Figure 7a), as well as on cross-sections (
Figure 7b). A similar dark red line traced with a half-dry brush was used for the underdrawing in the older pictorical register in Rust (
Figure 7c), which is another link between these two mural cycles. The red line was observed also in the upper younger register in the same location, but a brighter red was used. In addition, a pressed rope, soaked in red color, was applied for straight lines (
Figure 7d), which was also found in Kobenz (
Figure 7g). Here, the underdrawing was also traced in red, although difficult to discern under the color layers (
Figure 7h). On the other hand, in St. Johann and in Ofenbach the underdrawing was carried out with yellow color (
Figure 7e,f). In the first one it seems that on the right side of the wall, depicting the
Salvation of the Souls, a more orange-reddish color was selected, perhaps a sign of two different artists hands. All murals, except of the younger register in Rust, reveal a confident brushstroke.
Regarding underpaintings in the mural cycles of this study, the greyish color of blue backgrounds already observed by the naked eye, shows the general use of
veneda under azurite (
Figure 8a), following the Northern-European tradition [
5,
6,
7,
8]. On the contrary, in Marz (
Figure 7a) and Kobenz (
Figure 8e), the red background with some overlaid blue remains and indicates a possible loss of blue azurite applied on
morello, consistent with the Italian Trecento painting [
5,
6,
7,
9]. Surprisingly, the cross-sections of related samples confirmed the use of the grey underpainting only in St Johann (
Figure 8b) and the older register in Rust, where its color is very light grey, almost white (
Figure 8c). In Marz, a red
morello is clearly seen under the green color, probably malachite (
Figure 8d).
As already observed by art historians [
2,
3,
4], the modeling in Marz, St. Johann and the older pictorical register in Rust is stylistically quite similar (
Figure 6a–e and
Figure 9). The figures are presented with rounded heads, small noses, and small eyes, emphasized with strong dark brown or/and black straight line, semi-circular upper eyelids and high eyebrows. A strong brownish shading under the eyelids, around the nose, and under the cheekbones is characteristic. The mouth is also small, performed with two brushstrokes; a longer straight one for the upper lip, and a rounded short one for the lower lip. The bodies are elongated and elegant, as was common for the time around 1400. The hands are small, with short fingers, separated with a thick brown line and also strongly shaded. The black final contour is wide and strong, but in many places it is lost. Despite a very similar pictorical language, diverse hands, active in these three locations, can be distinguished. There are significant differences in flesh tones: some are lighter and more pinkish, with much softer shading and a smoother color transition, while others are darker, with strong brown shading. This observation does not correspond to the general representation of lighter female and darker male carnations. In the darker ones, the face lines are thicker, superficial, the color transition rougher, and highlights and shades applied with wide brushstrokes, showing lower quality and, thus, revealing the work of assistant(s). On the contrary, the lighter ones manifest much smoother modeling with thinner brushstrokes, indicating the hand of a skillful artist, probably the principal master. This duality can be observed in Marz, St. Johann, and Rust, pointing towards work of the same workshop in all three locations, but by different artists.
The younger register in Rust is very much retouched, with very strong black contours which predominate in the composition (
Figure 10a). The original color is largely lost, therefore, not much can be specified about the modeling. Nevertheless, it is clear that these paintings were executed by a different artist compared to the older pictorical register. The heads are oval with a large upper scull part. The eyes are elongated and often almond-shaped, the eyebrows are high, straight, or semi-circular, large lips are separated with a strong black middle line and a short line under the lower lip. The hands are big with thick fingers, defined with a strong black final contour, while the bodies are long, trying to be elegant following the general taste of the time, but are rather clumsy and not proportional. It seems that the artist used cartoons, as was already stated by art historians [
2,
4]. Due to the color loss and overall retouching, the original color modeling cannot be evaluated. In Kobenz (
Figure 10b), the figures are very elegant, with thin waists, dressed in contemporary clothes. Their hands are long, narrow, with thin fingers. The heads are elongated, with a high forehead, a long straight nose, and fleshy lips. The eyes are big, almond-shaped, and emphasized with strong half-circles for the upper and lower eyelid. Thin and half-circled eyebrows crown them. The modeling results are very different as in Rust, but this could be due to the heavy retouching already mentioned. Although the color modeling is mostly lost today, on some areas, the combination of thick and thin brushes that create soft color transitions can still be discerned.
A great part of the color layers is lost also in Ofenbach (
Figure 6f and
Figure 10c), mostly due to the outdoor location of these paintings. Some basic color layers are still conserved, but on many areas, especially in the lower part of the wall, the paintings have faded almost entirely. On the upper part, being the most protected against weather changes, some faces on the
Crucifixion can still be perceived. The heads are rounder with small, pointed chins. Almond-shaped eyes are marked with upper and lower eyelids, which are much softer and less arched as in Kobenz. In addition, the eyebrows are long, straight, and rounded only at the exterior end. The nose is straight and sometimes too long, while fleshy lips are characterized by a rounded lower lip. The basic flesh tone is pinkish, similar to Kobenz, but it differs from it by some strong shading in brownish tones conserved in some areas. The hands are small, with thick fingers, separated with a strong brown final contour that frames the entire figures. The bodies are long, slim, but not as sophisticated as in Kobenz. Regarding these parameters, different artists must have worked on the younger pictorical register in Rust, in Kobenz, and in Ofenbach.
3.4. Painting Techniques
Already by the naked eye it can be discerned, that
a fresco was the principal painting technique in all five mural cycles. The basic color layers are generally well preserved; the application of plasters was carried out by the system of
giornatas (portions of fresh plaster to be painted in one day) [
5,
6,
7,
9]. Nevertheless, all paintings were finished
a secco for the modeling and final contours. The proportion between
a fresco and
a secco varies from mural to mural, which resulted in a better or worse conservation state of the color layers. The paintings in Ofenbach are in the worst conservation state, principally due to their exterior location, being exposed to extreme atmospheric changes such as temperature and humidity [
5,
7]. It seems, that the paintings in Marz, St. Johann and the older register in Rust were largely carried out
a fresco with only a smaller portion painted on already dry mortar. XRD spectra show high calcite peaks (
Figure 1a,c,d), which indicate plasters prepared with a high amount of lime to serve as a binder for uplaid pigments. The exceptions are azurite and malachite, which were painted
a secco and in many cases fell off. Such is the case of the donor’s vestments in Marz (
Figure 7a) and was also confirmed in other localities on the basis of several sample cross-sections (
Figure 4a,b,
Figure 7b, and
Figure 8c). On the other hand, the younger register in Rust, the paintings in Kobenz, and those in Ofenbach must have been carried out largly
a secco. This can already be estimated from the XRD spectra that show very low calcite peaks, indicating a low amount of this inorganic binder (
Figure 2a,c). Additionally,
intonaco seems to have been applied in quite thin layers, as already observed in situ, and therefore, started to dry quickly. This caused the loss of almost the entire modeling of the faces, the application of shades and highlights, as well as the final contours. On some areas, remains of the upper color layers, glued to the lower
a fresco painted surface, can still be observed. They indicate the use of an organic binder that must have degraded, causing color-layer loss. Unfortunately, the organic binders have not been studied so far. The combination of both principal painting techniques is supported also by cross-sections (
Figure 2a,d, and
Figure 5a). In Rust, a thick underlayer applied with wide brushstrokes over the entire surface can be observed under the color layers of this pictorical register. It indicates a possible application of lime wash; in this case, lime technique was used. While lacking samples, only a visual inspection was made, therefore this is only a hypothesis. The comparison of painting techniques among the mural cycles is presented in
Table 2.