coatings

Article
A Technical Study of Chinese Buddhist Sculptures: First Insights
into a Complex History of Transformation through Analysis of
the Polychrome Decoration
Chiara Ricci 1, * , Paola Buscaglia 1,2 , Debora Angelici 1 , Anna Piccirillo 1 , Enrica Matteucci 1 ,
Daniele Demonte 1 , Valentina Tasso 1 , Noemi Sanna 1,3 , Francesca Zenucchini 1 , Sara Croci 2 , Federico Di Iorio 2 ,
Laura Vigo 4 , Davide Quadrio 5 and Federica Pozzi 1

1 Centro per la Conservazione ed il Restauro dei Beni Culturali “La Venaria Reale”,
10078 Venaria Reale (Turin), Italy; [email protected] (P.B.); [email protected] (A.P.);
[email protected] (E.M.); [email protected] (D.D.);
[email protected] (V.T.); [email protected] (F.Z.);
[email protected] (F.P.)
2 Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, 10129 Turin, Italy;
[email protected] (P.B.); [email protected] (S.C.); [email protected] (F.D.I.)
3 Dipartimento di Scienze dell’Antichità, Università degli Studi di Roma “La Sapienza”, 00185 Rome, Italy;
[email protected]
4 Montreal Museum of Fine Arts, Montreal, QC H3G 1J5, Canada; [email protected]
5 Museo d’Arte Orientale (MAO), 10122 Turin, Italy; [email protected]
* Correspondence: [email protected]; Tel.: +39-011-4993021

Abstract: Artifacts pertaining to Buddhist culture are often studied in relation to their circulation from
India throughout the rest of Asia; however, many traveled to Europe during the last few centuries
as trade commodities and pieces for the art market, losing any devotional purpose in favor of a
specific aesthetic sensitivity that was typically adapted to Western taste to appeal to collectors. This
Citation: Ricci, C.; Buscaglia, P.; article presents a technical study of seven polychrome wooden sculptures from the Museo d’Arte
Angelici, D.; Piccirillo, A.; Matteucci, Orientale (MAO) in Turin, Italy. Originally from China, these objects are generally attributed to the
E.; Demonte, D.; Tasso, V.; Sanna, N.; late Ming–early Qing dynasties (16th–18th centuries) based merely on stylistic and iconographic
Zenucchini, F.; Croci, S.; et al. A considerations. Scientific analysis sought to expand the available knowledge on their constituting
Technical Study of Chinese Buddhist materials and fabrication techniques, to address questions on their authenticity, to assess their state
Sculptures: First Insights into a of preservation, and to trace the history of transformations they have undergone while transitioning
Complex History of Transformation
from devotional objects to private collection and museum artwork. By delving into the sculptures’
through Analysis of the Polychrome
intricate paint stratigraphy, the results were also key to guiding treatment choices. The outcomes
Decoration. Coatings 2024, 14, 344.
of this study were featured in the MAO exhibition “Buddha10. A Fragmented Display on Buddhist
https://doi.org/10.3390/
coatings14030344
Visual Evolution” (October 2022–September 2023).

Academic Editor: Marko Petric Keywords: Chinese artifacts; Buddha; devotional objects; wooden sculptures; polychromy; paint
Received: 2 February 2024 layers; repainting; Museo d’Arte Orientale (MAO); technical study
Revised: 8 March 2024
Accepted: 12 March 2024
Published: 13 March 2024
1. Introduction
Objects pertaining to Buddhist visual and material culture are often studied in relation
to their circulation from India throughout the rest of Asia, while, to date, little attention has
Copyright: © 2024 by the authors.
been paid to understanding their westward migration even though numerous examples
Licensee MDPI, Basel, Switzerland.
This article is an open access article
are currently preserved in both public and private collections in Europe and the United
distributed under the terms and
States. Originating from different geographical areas and cultural contexts within the Asian
conditions of the Creative Commons continent, many of these artifacts traveled to Europe during the last few centuries to be
Attribution (CC BY) license (https:// sold as trade commodities and pieces for the art market. As a result of this transition, they
creativecommons.org/licenses/by/ lost any devotional value or purpose in favor of a specific aesthetic sensitivity that was
4.0/). typically adapted to Western taste to appeal to collectors.

Coatings 2024, 14, 344. https://doi.org/10.3390/coatings14030344 https://www.mdpi.com/journal/coatings

Coatings 2024, 14, 344 2 of 17

This contribution focuses on a selection of seven polychrome wooden sculptures from

the Museo d’Arte Orientale (MAO) in Turin, Italy, which have recently undergone an
in-depth technical study and conservation treatment at the Centro per la Conservazione ed
il Restauro dei Beni Culturali (CCR) “La Venaria Reale” (Figure 1). These objects, never
exhibited until recent times, are generally described in the museum entries as being of
Chinese origin, specifically from the late Ming–early Qing dynasties (16th–18th centuries),
based merely on stylistic and iconographic considerations.

Figure 1. Object of this study. Selection of seven Buddhist polychrome wooden sculptures from the
Museo d’Arte Orientale (MAO) in Turin, Italy, analyzed in this technical study.

While Japanese Buddhist sculpture has been the subject of more extensive art historical
and scientific studies [1–6], Chinese production related specifically to the type of artifacts in
this article constitutes, to date, an understudied field in need of further dedicated research.
Previous investigations of Chinese Buddhist sculpture have focused, for instance, on the
polychromy of stone and clay figures from various temple locations [7–11], as well as
on a relevant body of copper-alloy statues in the collection of the Freer Gallery of Art
(Washington, DC, USA) [12]. In terms of polychrome wooden artifacts, the literature
reports technical studies of 11th to 12th century Guanyin sculptures from the Isabella
Stewart Gardner Museum (Boston, US) [13] and the Nelson-Atkins Museum of Art (Kansas
City, MO, USA) [14], whose surfaces show a similar combination of partial losses and
non-contemporary paints that attest to a complex history of repair and redecoration in
accordance with evolving tastes in statuary. In addition, the Royal Ontario Museum
(Toronto, ON, Canada) carried out a scientific study regarding the Chinese polychrome
sculptures in their holdings as part of a broader survey on Asian sculptural arts [15], and
further work on the examination and treatment of such objects was conducted at the
Victoria and Albert Museum (London, UK) [16,17], the Rijksmuseum (Amsterdam, The
Netherlands) [18], and The Metropolitan Museum of Art (New York, NY, USA) [19].
In this context, the present work sought primarily to fill in the gaps regarding the
sculptures’ materials and fabrication techniques, ultimately aiming to discriminate any
extant paint layers belonging to the original decoration from the later repainting applied as
the objects were transferred to Europe. Data from the technical investigations were used to
verify the current theories related to their authenticity and time of production. A thorough
evaluation of the artifacts’ state of preservation was also performed based on materials
analysis. Not only did the results contribute to an improved understanding of this type of
Chinese sculpture, but they also played a crucial role in guiding CCR conservators in their
treatment choices. Overall, the wealth of information unveiled by this interdisciplinary
endeavor was key to tracing the complex history of transformation that the present selection
of MAO sculptures have undergone while transitioning from devotional objects to private
collection artworks and museum holdings. The methodological approach adopted relied on
Coatings 2024, 14, 344 3 of 17

a close and fruitful exchange between scientists, conservators, and Buddhist art specialists,
aiming to balance treatment goals in consideration of both European and traditional
Asian perspectives. The outcomes of this study were featured in the “Buddha10. A
Fragmented Display on Buddhist Visual Evolution” exhibition, held at the MAO from
October 2022 to September 2023. In this context, the museum requested to have all the
artifacts treated except for Inv. 450, which is iconographically specular to Inv. 451. This
choice aimed to provide the public with a direct comparison between a figure that has
undergone conservation and its untreated twin, whose surface was thoroughly documented
through a 3D multispectral model. Some of the conservation work was carried out in the
exhibition space, providing visitors with a unique opportunity to witness this delicate
process firsthand.

2. Materials and Methods

The seven polychrome wooden sculptures in this study, belonging to the collection
of MAO in Turin, Italy, represent different Buddha manifestations and followers of Gau-
tama. Originally conceived for temple areas with an indoor placement, they served the
devotional purpose of guiding devotees in their meditation process. The selection under
investigation includes the following subjects: three Lohuan or Arhat (Inv. 448, Fujian
region, 16th century; Inv. 449, Sichuan region, likely 18th century; Inv. 454, China, exact
provenance unknown, 16th century), representing the followers of Gautama Buddha who
attained the four progressive stages of enlightenment culminating in full awakening; two
Bodhisattva (Inv. 450 and Inv. 451, Shanxi or Shaanxi region, 16th century), namely in-
dividuals on the path to awakening; one Guanyin (Inv. 453, Shanxi or Shaanxi region,
17th century), representing a Bodhisattva associated with compassion; and one Buddha
(Inv. 452, Shanxi or Shaanxi region, 16th century), i.e., the one who has awakened from
the deep sleep of ignorance and has opened his consciousness to encompass all objects
of knowledge.
The analytical protocol entailed the use of non-invasive imaging and point techniques,
followed by sampling and micro-invasive investigations. Visible diffuse light photography
and multiband imaging sought to gather preliminary information on the distribution of
various materials on the objects’ surface. Fiber optics reflectance spectroscopy (FORS),
X-ray fluorescence (XRF) spectroscopy, and Raman spectroscopy were used jointly to
characterize the color palette non-invasively. Overall, 72 microscopic samples, including
46 loose scrapings and 26 multi-layered specimens, were removed from select areas of
interest and analyzed through transmission Fourier-transform infrared (FTIR) spectroscopy,
optical microscopy, and scanning electron microscopy coupled with energy-dispersive
X-ray spectroscopy (SEM/EDS) to complete materials identification, shed light on the paint
stratigraphy, and evaluate any ongoing degradation phenomena. Further details on the
instrumentation and experimental settings employed are reported below.
Visible diffuse light photography. Lighting was achieved with two Elinchrom RX1200
strobes located to the right and left of the object, at an angle of approximately 45◦ to the
normal to the surface, and with the aid of softboxes to diffuse the light. Photographs were
taken with a Nikon D810 DSLR Full Spectrum camera, modified to extend its spectral
sensitivity in the 350–1000 nm range and providing a resolution of 7360 × 4912 pixels,
equipped with a complementary metal oxide semiconductor (CMOS) silicon sensor as
well as Madatec UV-IR Cut and BG40 filters. Image processing, carried out in Adobe
Photoshop 25.3.1, included a color correction step conducted by inserting a 24-color X-Rite
ColorChecker Classic reference in the field of view.
Infrared reflectography (IRR) and false color processing (IRFC). Lighting was achieved with
two Elinchrom RX1200 strobes located to the right and left of the object, at an angle of
approximately 45◦ to the normal to the surface, and with the aid of softboxes to diffuse the
light. Photographs were taken with a Nikon D810 DSLR Full Spectrum camera, modified
to extend its spectral sensitivity in the 350–1000 nm range and providing a resolution of
7360 × 4912 pixels, equipped with a CMOS silicon sensor as well as a Madatec IR 850 filter.
Coatings 2024, 14, 344 4 of 17

IRFC images were obtained in the RGB color space of Adobe Photoshop by using two
reflection images acquired in the visible and near-IR (NIR) spectral ranges. In particular,
the green (G) and red (R) components of the visible image are transferred into the blue (B)
and green (G) channels, while the red (R) component is replaced with the NIR image. This
methodology yields false color images of the NIR-R-G (RGB) type.
Ultraviolet-induced visible fluorescence (UVF). Lighting was achieved with two Elinchrom
RX1200 strobes equipped with a B + W 403 filter by moving the lights at different angles
at constant distance. The acquisition involved taking several shots on the same frame by
setting the camera to ‘Multiple Exposure’ to merge illuminations from different positions.
Photographs were taken with a Nikon D810 DSLR Full Spectrum camera, modified to
extend its spectral sensitivity in the 350–1000 nm range and providing a resolution of
7360 × 4912 pixels, equipped with a CMOS silicon sensor as well as Madatec UV-IR Cut
and BG40 filters. Image processing, carried out in Adobe Photoshop 25.3.1, was conducted
by inserting a non-fluorescent reference in the field of view.
Visible-induced infrared luminescence (VIL). Lighting was achieved with a Nikon SB-910
portable speedlight, equipped with 3 Hoya UV-IR Cut filters. The acquisition involved
taking several shots on the same frame by setting the camera to ‘Multiple Exposure’ to
merge illuminations from different positions. Images were acquired in the 850–1000 nm
spectral range with a Nikon D810 DSLR Full Spectrum camera, modified to extend its spec-
tral sensitivity in the 350–1000 nm range and providing a resolution of 7360 × 4912 pixels,
equipped with a CMOS silicon sensor as well as a Madatec IR 830 filter. Image processing
was carried out in Adobe Lightroom 13.2 and Adobe Photoshop 25.3.1. A pure Egyptian
blue tablet was included in the frame to obtain optimal image exposure.
FORS. Analysis was conducted using an Ocean Optics HR2000+ spectrophotometer,
an Ocean Optics HL-2000-FHSA halogen lamp, and a Labsphere Spectralon Wavelength
Calibration Standards white reference. The system includes two fiber optics, one single
and one bifurcated, with a 400 µm diameter, equipped with an Ocean Optics RPH-2
anodized aluminum fiber support, enabling reflection measurements at a 90◦ or 45◦ angle
to the bearing surface. Spectra were acquired in reflectance mode, within a 360–1000 nm
spectral range, with 45◦ /0◦ optical geometry. Spectra were interpreted by comparison with
published literature and spectral libraries available at the CCR scientific laboratories.
XRF. Analysis was performed using a Micro-EDXRF Bruker Artax 200 spectrometer
(Milan, Italy) equipped with a fine focus X-ray source including a molybdenum anode and
a Si(Li) silicon drift detector (SDD) with an 8 µm beryllium window, providing an average
resolution of approximately 144 eV for the full width at half maximum of the manganese
Kα line. The system includes a 4096-channel analog-to-digital converter (ADC), a series
of interchangeable filters, as well as two 0.65 mm and 1.5 mm collimators to adjust spot
analysis size. Maximum voltage and current are 50 kV and 1500 µA, respectively, for a
maximum power of 40 W. In the present case, measurements were carried out using 30-kV
voltage, 1300 µA current, 60 s acquisition time, and a 1.5 mm collimator, with no filter, by
fluxing helium gas onto the measurement area to improve the technique’s detection limits
(corresponding, with a helium flux, to Z = 11, sodium).
Raman. Analysis was carried out with a Bruker Bravo handheld spectrometer (Milan,
Italy) equipped with a charge-coupled device (CCD) detector. Two lasers emitting light at
785 and 852 nm (Duo LASER™) were used as the excitation sources, enabling the acquisition
of data in the 170–3200 cm−1 spectral range and at a spectral resolution of 10–12 cm−1 .
The output laser power was ≈50 mW for both lasers, while the number of scans and
integration time were adjusted within the 2–20 and 300–2000-ms ranges, respectively,
according to the color and Raman response of the different areas examined. With this
system, spectral acquisition exploits a sequentially shifted excitation (SSE) algorithm that
allows for automatic fluorescence removal. Spectra were interpreted by comparison with
the published literature and spectral libraries available at the CCR scientific laboratories.
Micro-Raman. In only one instance, a microscopic sample of blue paint from Inv.
454 was analyzed using a benchtop dispersive Renishaw InVia Qontor system, coupled
Coatings 2024, 14, 344 5 of 17

with a Leica DM2700 microscope, available at the Raman Spectroscopy Laboratory of the
Institute of Heritage Science of Italy’s National Research Council (ISPC-CNR, Milan). This
spectrometer is equipped with a Peltier-cooled NIR-enhanced CCD detector. Measurements
were taken with 20× and 50× objectives, using 785 nm as the excitation wavelength. Spectra
were acquired as a sum of 5–10 scans of 1–10 s in the 100–3200 cm−1 spectral range, with
1–2 cm−1 spectral resolution and 0.5–1 mW laser power at the sample.
FTIR. Analysis was conducted with a Bruker Vertex 70 FTIR spectrometer coupled with
a Bruker Hyperion 3000 infrared microscope (Milan, Italy) and equipped with a mercury
cadmium telluride (MCT) detector. Scrapings were analyzed as a bulk in transmission
mode through a 15× objective, upon compression in a diamond cell. Data were collected in
the 4000–650 cm−1 spectral range, at a spectral resolution of 4 cm−1 , as the sum of 64 scans.
A cross section from Inv. 454 was analyzed in attenuated total reflection (ATR) mode using
a 20× objective featuring a germanium crystal. Data were collected in the 4000–650 cm−1
spectral range, at a spectral resolution of 4 cm−1 , as the sum of 64 scans. Spectra were
interpreted by comparison with the published literature and spectral libraries available at
the CCR scientific laboratories.
Preparation of cross sections. Cross sections were prepared by embedding each multi-
layered sample within a double layer of Struers EpoFix epoxy resin. After removal of
the excess resin, the sample surface was finely polished using Struers abrasive cloths of
progressively finer grits to expose the paint stratigraphy, thus enabling observation at high
magnification and scientific analysis with various instrumental techniques.
Optical microscopy. Multi-layered samples were observed and photographed under
visible light using an Olympus SZX10 stereomicroscope equipped with an Olympus Color
View I digital camera (Segrate, Milan, Italy). After being mounted as cross sections, such
samples were observed and photographed under visible and UV light using an Olympus
BX51 minero-petrographic microscope equipped with an Olympus DP71 digital camera. In
both cases, image acquisition and processing were performed with the analySIS FIVE 5.0
proprietary software.
SEM/EDS. Cross sections were observed and analyzed with a Zeiss EVO60 scanning
electron microscope (Milan, Italy) equipped with a lanthanum hexaboride (LaB6 ) cathode
and an SDD, and coupled with a 40 mm2 Oxford Ultim Max EDS microprobe for semi-
quantitative elemental analysis. Samples were coated with a thin layer of carbon and
analyzed in high vacuum mode using an accelerating voltage of 20 kV.

3. Results
The multi-analytical campaign described herein enabled the research team to collect
an initial, yet relevant body of information regarding the materials and techniques used for
the Chinese wooden sculptures’ polychrome decoration, revealing precious aspects of their
preservation state as well as transformation history from ritual items to collection artwork.
The main observed issues that have hindered a full understanding of the artistic techniques
to date include severe abrasion of some of the surfaces, combined with remarkable het-
erogeneity in terms of detected materials, noticeable discontinuity of the paint layers, and
the lack of literature data from similar artifacts to compare our results with. The main
outcomes gathered from this technical study, summarized in Table 1, are presented and
discussed in detail in the following sections. In addition, a selection of representative data
is shown in the Supplementary Materials file.

3.1. Identification of Paint Materials

3.1.1. Pigments and Dyes
Multiband imaging and non-invasive point analysis provided preliminary information
on the presence, distribution, and identification of pigments and dyes on the objects’
surface, either applied as part of the original decoration or within later interventions. As
the outcomes of FORS, XRF, and Raman investigations were often not sufficient to deliver a
detailed characterization of the polychromy in relation to the overall stratigraphy, multi-
Coatings 2024, 14, 344 6 of 17

layered samples were removed from select areas of interest, mounted as cross sections,
and analyzed with optical microscopy and SEM/EDS. The main results obtained from this
integrated approach are reported below.

Table 1. Summary of materials identified with scientific analysis. Summary of the main results
obtained from scientific analysis of the seven polychrome wooden sculptures from MAO. For each
sculpture, the number of samples removed is indicated, along with information on the ground
layers, pigments and dyes found in the paint layers, binding media, and any other relevant materials
detected. The [?] symbol indicates materials whose identification was uncertain, while the asterisk
marks compounds ascribable to previous conservation treatments, including localized inpainting.

Pigments and Dyes Other Relevant

Sculptures Samples Removed Ground Layers Binding Media
in Paint Layers Materials
Red Fe-containing pigments
Minium
Lithopone-based, Ultramarine blue
Natural resin [?]
Arhat 2 multi-layered additional presence * Prussian blue [traces]
[?] * Acrylic resin
Inv. 448 5 scrapings of Si in innermost Green earth
* Alkyd resin
layer * Chrome green [traces]
* Phthalocyanine green
[traces]
Red Fe-containing pigments
Red lake (calcium carbonate
Lithopone-based, substrate)
innermost layer with Red lake (Al-silicate
Arhat 4 multi-layered Oil [?]
a calcium carbonate substrate) * PVAc
Inv. 449 8 scrapings (Al and Zn stearates)
matrix and minor Minium
silicate inclusions Ultramarine blue
Carbon-based black pigment
* Phthalocyanine green
Fe-containing earths
Minium
Red lake (calcium
carbonate substrate)
Red lake (Al- and
Bodhisattva 4 multi-layered Fe-silicate substrate) Rice starch
Lithopone-based Oil
Inv. 450 4 scrapings Carbon-based black pigment Natural resin [?]
Ultramarine blue
Mn- and Fe-containing
blue pigment
* Cd-, Cr-, Co-containing
pigments [traces]
Fe-containing earths
Minium
Red lake (Al- and
Fe-silicate substrate) Rice starch
Bodhisattva 4 multi-layered Carbon-based black pigment Natural resin [?]
Lithopone-based Oil
Inv. 451 6 scrapings Ultramarine blue * PVAc
Mn- and Fe-containing * Alkyd resin [traces]
blue pigment
* Cd-, Cr-, Co-containing
pigments [traces]
Minium
Fe-containing earths
Buddha 3 multi-layered Ultramarine blue
Lithopone-based [?] * PVAc
Inv. 452 6 scrapings Mn- and Fe-containing
blue pigment
* Phthalocyanine blue
Coatings 2024, 14, 344 7 of 17

Table 1. Cont.

Pigments and Dyes Other Relevant

Sculptures Samples Removed Ground Layers Binding Media
in Paint Layers Materials
Fe-containing earths
Rice starch
Ultramarine blue
Guanyin 3 multi-layered Oil [?] * Beeswax
Lithopone-based Carbon-based black pigment
Inv. 453 9 scrapings (Al and Zn stearates) * PVAc
Minium
* Alkyd resin [traces]
* Organic brown glaze
Titanium white
Carbon-based black pigment
Rice starch
Arhat 6 multi-layered Minium
Lithopone-based Alkyd resin * Acryl resin
Inv. 454 8 scrapings Phthalocyanine blue
* PVAc [?]
Red organic
synthetic pigment

• Arhat—Inv. 448; Inv. 449

The figure in Inv. 448 wears a green garment covered with a red tunic that wraps
around his entire body. Both clothing items show areas that are partly overpainted with
different colors: for instance, green on certain regions of the tunic, especially on the legs’
outer areas and lower drapery, which also displays local applications of blue paint, and
blue over red on the garment edges. The bare skin, visible on the face and hands, has a
dark red tone, while the hair is blue and appears shaved. The same color scheme, as well
as various phases of locally applied repainting, are detected on Inv. 449, altogether similar
to Inv. 448 except for the lack of hair and a whitish flesh tone.
Cross sections from both sculptures show two to three light-colored paint applications
above the wooden surface, possibly used as ground preparation, which in most cases are
interposed with layers of color. These paints are based on lithopone, a white pigment first
produced in the second half of the 19th century through co-precipitation of barium sulfate
and zinc sulfide. In the samples examined, this material was sometimes mixed in with
sparse grains of iron-containing earth pigments to convey a slight pink tone. For Inv. 448,
elemental analysis revealed the additional presence of silicon in the innermost of these
layers (Figure 2, left). The very first layer applied onto the wooden support of Inv. 449,
on the other hand, displayed a different composition, consisting of a calcium carbonate
matrix with minor silicate inclusions; this layer is followed, in the observed stratigraphy, by
an intermediate iron-containing red paint and another lithopone ground layer (Figure S1,
Supplementary Materials).
As far as red pigments are concerned, the flesh tones of Inv. 448 are based on iron-
containing earths; furthermore, minium was identified on details of the drapery, showing
an orange–yellowish tone in IRFC. In Inv. 449, samples removed from the figure’s face, right
sleeve, and lower portion of the garment contain thin layers of organic red lakes within
the stratigraphy, which are no longer visible on the surface due to numerous repainting
campaigns (Figure 2, right). The presence of red lakes in the cross sections was detected
through their distinctive UV-induced autofluorescence and by the absence of elements,
in the EDS spectra, that could be deemed responsible for the layer coloration observed.
SEM/EDS revealed the presence of calcium within these layers, suggesting that the dye
might have been precipitated onto a calcium carbonate substrate to produce the lake
pigment. In certain cases, this red lake was found in combination with either minium or
an iron-containing red. Only in one sample, removed from an area of the Arhat below the
right leg, the red colorant was precipitated onto an aluminum silicate type of substrate.
Ultramarine blue, which appears purple–red in IRFC, was the only blue pigment de-
tected in Inv. 448 on the Arhat‘s hair and garment edges, also identified in one cross section
from Inv. 449. Inner green layers are likely made of green earth, while the detection of
copper with XRF and the typical dull dark blue color in IRFC suggest that the overpainting
might be based on phthalocyanine green.
Coatings 2024, 14, 344 8 of 17

Figure 2. Paint stratigraphy, cross sections from Inv. 448 and 449. Polarized light (top left)
and BSE (bottom left) images of a cross section from Inv. 448; the sequence of paint layers in-
cludes (1) lithopone with presence of silicon, (2) lithopone, (3) green earth with traces of chrome
green, (4) lithopone with earth pigments, (5) ultramarine blue, and (6) organic layer. Polarized
light (top right) and UV (bottom right) images of a cross section from Inv. 449; the sequence of paint
layers includes (1) wooden support, (2) calcium carbonate with minor silicate inclusions, (3) earth
pigments, (4) lithopone, (5) carbon-based black, (6) lithopone, (7) red lake with aluminum silicate
substrate, (8) lithopone with traces of silicates, and (9) organic layer.

• Bodhisattva—Inv. 450; Inv. 451

Both figures, each dressed in a red garment covered with a red tunic with blue
edges, sit on what looks like a green and brownish lotus flower; in both cases, losses
in the superficial paint layer reveal an underlying blue color for the tunic, as well as red
and blue tones for the lotus flower. Both figures show a cavity on their back of about
7–7.5 cm width × 14–15 cm height, perhaps used to collect offerings from devotees.
These two Bodhisattvas, which differ from one another only by a mirror gesture of
their hands, present evident similarities also in terms of paint materials used for their
polychrome decoration. Both sculptures contain one or two lithopone-based ground layers,
often including scattered grains of earth pigments and minium. In all cases, the upper-
most of these layers is applied onto an underlying layer of variable thickness, mostly
consisting of minium. Visual examination of the microsamples with more complete stratig-
raphy shows that the minium paint is applied onto a lowermost layer based on lithopone
with calcium carbonate inclusions. The complete layer structure would, therefore, in-
clude a minium layer sandwiched between two lithopone layers (Figure 3 and Figure S1,
Supplementary Materials).
Flesh tones are obtained as mixtures of lithopone, iron-containing earths, and minium.
XRF data highlight the use of earth pigments also in the two figures’ garments. Red lakes
were identified either on the objects’ surface or within the stratigraphy, making them
no longer visible in the latter instance. SEM/EDS analysis of an inner layer in a single
sample from Inv. 450 indicated that the organic red dye was likely precipitated onto a
calcium carbonate substrate; in all other cases, the inorganic substrate used for the lake
preparation is based on aluminum and iron-rich silicates. When these lakes were found on
the sculptures’ surface, as in the present case, their nature could be further investigated by
FORS: the results suggested the use of a dye of animal origin, likely obtained from scale
insects of the Coccidae family (Figure 3).
The colorful paint stratigraphy of the two Bodhisattvas was found to also include
carbon-based black and ultramarine blue layers. While the latter is typically associated
with a purple–red color in IRFC, another blue pigment with a dark blue tone in IRFC was
extensively detected for later repainting both in Inv. 450 and Inv. 451, mainly located on
the figures’ hair and blue details of their garments. XRF analysis revealed the presence
Coatings 2024, 14, 344 9 of 17

of manganese and iron, although the exact pigment currently remains unidentified. The
chemical composition of the green pigments also eluded non-invasive point analysis. The
surface of both sculptures showed limited retouching, where cadmium-, cobalt-, and
chromium-rich pigments of industrial production were found.

Figure 3. Paint stratigraphy, cross section from Inv. 450. Polarized light (left) and UV (right)
images of a cross section from Inv. 450; the sequence of paint layers includes (1) lithopone with
sparse calcium carbonate inclusions and earth pigments, (2) minium, (3) lithopone with sparse earth
pigments, (4) ultramarine blue, (5) red lake with calcium carbonate substrate, (6) lithopone with
sparse earth pigments, and (7) red lake with aluminum and iron silicate substrate.

Finally, a close inspection of the polychrome decoration highlighted the presence, in

some areas, of canvas underneath the paint layers, possibly added in both sculptures to
join different wooden blocks or to repair existing fractures.
• Buddha—Inv. 452
Inv. 452 is a Buddha sitting in meditation posture, with crossed legs and clasped
hands, corresponding to the so-called lotus position. The figure is wearing a green garment
covered with draperies: two are used for the body, one red and one blue, and one for
the legs, of a dark blue tone. His hair is shaped into regular rows of curls, painted blue
according to the Chinese iconographic tradition. A smooth ovoid-shaped protuberance is
located halfway between the forehead and the top of the head. The center of the forehead
currently displays a hole, where perhaps a semi-precious stone or glass ornament was
originally placed to mark the figure’s “third eye”, now missing. As in the case of Inv.
450 and 451, a cavity of about 10.5 cm width × 25 cm height is located on the Buddha’s
back, likely intended for devotees to place offerings.
The multi-analytical protocol adopted in this study proved particularly useful to shed
light on the peculiar technique used to create this Buddha’s hairstyle: the volume appears to
have been obtained by modeling clay mixtures, which were then painted with ultramarine
blue; the presence of an intermediate ground containing lithopone was revealed by optical
microscopy and SEM/EDS analysis of the cross sections.
Compared to the other sculptures under study, the variety of pigments and number of
overlapping paint layers found in Inv. 452 are limited. In samples removed from both the
flesh tones and garment, a lowermost grayish lithopone-based ground layer is followed by
a thin layer of minium and one or two additional layers containing primarily lithopone
with scattered grains of earth pigments or ultramarine blue. Flesh tones, indeed, were
obtained by mixing lithopone with minium. The Buddha’s red garment is made of a
thick single layer of minium mixed in with iron-containing pigments, jointly yielding an
overall orange–greenish color in IRFC. Similarly to Bodhisattvas Inv. 450 and Inv. 451, the
drapery’s blue pigment, appearing dark blue in IRFC and containing both manganese and
iron, could not be identified conclusively. Multiband imaging suggested the presence of
extensive retouching on the figure’s back: based on the XRF identification of copper and
IRFC data, it is possible to hypothesize the use of phthalocyanine blue.
Coatings 2024, 14, 344 10 of 17

As in the case of Inv. 450 and 451, careful observation of the surface revealed the
presence of at least two types of canvas underneath the polychrome decoration in some
areas of this sculpture.
• Guanyin—Inv. 453
Inv. 453 is limply lying on a support shaped in the form of a perforated rock, with
the body slightly twisted to the right and the face oriented frontally. The figure is dressed
in a brownish-colored robe covered with a blue drapery, which leaves parts of the pink
torso and arms exposed. The hair is styled conventionally, with large locks extending to
the shoulders. The hair bun at the top of the head is adorned frontally by a tripartite tiara,
while the chest and arms are embellished with jewels.
Among the seven pieces examined in this study, this sculpture shows the most complex
paint stratigraphy, with each layer obtained as a mixture of various pigments. At least four
ground layers are present, with lithopone mixed in with very fine grains of ultramarine
blue, as well as yellow and red iron-containing pigments. In the cross sections, these layers
are located in between other colored layers, namely a red layer made of an iron-based
pigment, an organic black, and ultramarine blue (Figure 4).

Figure 4. Paint stratigraphy, cross section from Inv. 453. Polarized light (left) and BSE (right) images
of a cross section from Inv. 453; the sequence of paint layers includes (1) lithopone with sparse earth
pigments and ultramarine blue, (2) earth pigments, (3) lithopone with sparse earth pigments and
ultramarine blue, (4) carbon-based black, (5) lithopone with sparse calcium carbonate inclusions and
earth pigments, (6) ultramarine blue, (7) lithopone with sparse earth pigments, and (8) minium.

Based on FORS data, the use of a mixture of earth pigments and red lake in the flesh
tones may not be ruled out (Figure S2, Supplementary Materials). Only in one sample
removed from the red drapery and examined by SEM/EDS, minium was applied to the
surface as an extremely thin layer.
Close inspection of the artifact, along with the outcomes of laser cleaning testing
carried out in a second phase of this project, suggested the presence of a thin brown layer,
presumably of organic nature, used as a superficial glaze. As for Inv. 450, 451, and 452, a
canvas layer is visible underneath the paint layers in some areas of the Guanyin.
• Arhat—Inv. 454
Inv. 454 represents a monk with white skin, wearing a greenish garment covered with
a red tunic while sitting on a wooden trunk with crossed legs. Close inspection of this
sculpture reveals a complex layering of materials, generally of the same color, especially for
the tunic and skin, the latter heavily retouched in a recent intervention. No overpainting
appears to be present for the green garment upon visual examination.
Since the onset of this research, Inv. 454 has raised the most questions: from an
iconographic point of view, some features appear unusual, such as the garment’s cut,
revealing the figure’s breast, and the proportions of the light blue–greenish drapery in
the lower part of the sculpture, which looks stiff and overly elongated. The presence of a
square-shaped cavity of about 6 cm width × 6.5 cm height on the figure’s back posed an
additional challenge: indeed, the current interpretation of these cavities as places originally
Coatings 2024, 14, 344 11 of 17

used to collect devotees’ offerings applies to sculptures depicting Buddha or Bodhisattvas,

but would be unusual for a monk.
At least two lithopone-based white layers are present within the stratigraphy in the
cross sections examined, separated by two very thin adjacent layers, one appearing as
a black organic layer and the other as a discontinuous layer of minium. In two out of
four samples analyzed by optical microscopy and SEM/EDS, an additional innermost thin
minium layer was applied directly onto the wooden support. A sample removed from the
light blue–greenish drapery stands out due to the absence of minium (Figure 5, right). In
all cases, a titanium-rich white thin layer is present on top of the outer preparation, which
also matches the composition of the white flesh tone. Phthalocyanine blue, along with
anatase and barite, was identified in a sample from the drapery with micro-Raman analysis
(Figure S3a, Supplementary Materials). The red pigment used for the garment could not
be unambiguously characterized, although FTIR measurements suggested the presence of
an organic synthetic pigment. Portable Raman analysis of a paint loss on the figure’s red
garment, revealing another red color underneath, detected the presence of an underlayer
based on minium and gypsum. Measurements conducted on other color fields, including
various shades of blue on the garment, the green hue of the waistband, and a red tone on
the elbow’s outer part, only yielded the typical signals of anatase and barite (Figure S3b,
Supplementary Materials).

Figure 5. Paint stratigraphy, cross sections from Inv. 454. Polarized light images of cross sections
from Inv. 454; the sequence of paint layers includes at (left) (1) minium, (2) lithopone, (3) carbon-based
black, (4) minium, (5) lithopone, (6) carbon-based black, (7) lithopone and titanium white, and
(8) organic layer; at (right) (1) lithopone, (2) lithopone with sparse earth pigments, (3) carbon-based
black, (4) lithopone, (5) titanium white, and (6) titanium white and phthalocyanine blue.

3.1.2. Binding Media and Other Organic Materials

FTIR analysis of the microscopic scrapings provided hints as to the identification
of binding media and synthetic organic materials in the sculptures’ current polychrome
decoration. A selection of spectra showing the presence of different classes of binders and
other organic substances detected is shown in Figure S4, Supplementary Materials.
The presence of oil was detected in Bodhisattvas Inv. 450 and 451. The same material
was found in Arhat Inv. 449 and Guanyin Inv. 453, where zinc and aluminum stearates were
also identified as possible additives from industrial paint tube colors. A limited presence
of natural resin or oleoresin cannot be ruled out in these three artifacts based on the data
collected. Moreover, beeswax was detected as a final coating in a scraping removed from
the left knee of Guanyin Inv. 453, interpreted as a brownish finish applied in the past to
minimize a particularly fragmentary aspect of the surface while mimicking the appearance
of a monochrome object.
Polyvinyl acetate was found in samples from Inv. 449, 451, 452, and 453, and its
presence was also hypothesized for Inv. 454; this material, which appears to have penetrated
the paint layers, was likely applied within later interventions. The presence of acrylic and
alkyd resins, used individually or together, was identified in samples from Inv. 448; alkyd
resins may have been used in Inv. 451 and 453 as well.
Coatings 2024, 14, 344 12 of 17

As regards Arhat Inv. 454, the main binding medium detected in the polychrome
decoration was alkyd resin, although acrylic resin and polyvinyl acetate were also found,
possibly used as conservation materials.

3.1.3. The Finding of Starch Lumps

SEM investigation of the cross sections removed from Inv. 454 highlighted the presence
of organic lumps with rounded to irregular shapes within the stratigraphy, most of which
are embedded in the lithopone-based ground layers. These lumps, showing variable sizes
(30–120 µm width × 10–50 µm height), consist of aggregates of polyhedral granules of
about 3 µm diameter. Micro-ATR-FTIR analysis identified this material as starch; according
to the literature [20–22], the observed granule size is most compatible with rice starch,
normally falling into the 2–7 µm range (Figure 6). The abundance and distribution of these
starch lumps suggest that they might have been added intentionally, although different
hypotheses on their purpose may be entertained. Finally, examining the SEM images
collected from the cross sections of all seven sculptures, the presence of rice starch lumps
was also hypothesized for Bodhisattvas Inv. 450 and 451, and for Guanyin Inv. 453, based
on morphological data. However, in these three sculptures, the aggregates typically have
smaller sizes than in Inv. 454.

Figure 6. Starch lumps. BSE and SE images of a starch lump as found in a cross section from
Inv. 454 (top); micro-ATR-FTIR spectrum of the starch lump (bottom).
Coatings 2024, 14, 344 13 of 17

3.2. Conservation Issues

Aside from widespread dust deposits, all seven sculptures displayed an untidy ap-
pearance before treatment due to the sequential application of multiple materials over
time and to a fragmented condition that particularly concerned the uppermost paint layer.
Moreover, significant embrittlement of the wooden structure and the entire decoration
was observed in combination with frequent paint cracking (Figure 7). Scientific analysis,
especially optical and electron microscopy, was key to highlighting issues related to the
presence of biodeteriogenic microorganisms and structural degradation of the paint.

Figure 7. Surface condition. Microphotographs of the surface condition in Inv. 450 (left) and
Inv. 449 (right), showing multiple layers of polychromy and severe paint cracking.

In particular, examination of the cross sections from Arhat Inv. 449 via optical micro-
scope revealed a former growth of micro-colonial fungi, which penetrated the lithopone-
based ground layers (Figure 8, left). Moreover, the joint presence of hyphae from different
fungal species was detected within the same layers by means of SEM: the hyphae were
identified in the backscattered electron (BSE) images by their rounded transversal sections,
showing 10–15 µm diameter (Figure 8, middle). Similar hyphae transversal sections, al-
though less numerous and dense, were also observed in Bodhisattvas Inv. 450 and 451,
Buddha Inv. 452, and Guanyin Inv. 453.

Figure 8. Microbiological colonization. Polarized light (left) and BSE (middle and right) images of
cross sections from Inv. 449 (left and middle) and 448 (right), showing a growth of micro-colonial
fungi (left) and the transversal sections of hyphae from different fungal species (middle and right).

SEM analysis of the available cross sections shed light on another distinctive feature
of the paint stratigraphy that appears to be common to all the sculptures investigated,
except for Buddha Inv. 452: all the lithopone-based grounds found in the samples from
Arhats Inv. 449 and Inv. 454, as well as Guanyin Inv. 453, display widespread black
rounded dots with an average size of 2–5 µm in BSE mode. Careful inspection in BSE
and secondary electron (SE) modes did not clarify whether this pattern might be due to a
dense distribution of pores that are now filled with epoxy resin as a result of cross section
Coatings 2024, 14, 344 14 of 17

preparation or with an organic substance from the paint formulation. The observed dotted
pattern does not appear to be consistent with a distribution of single rice starch granules,
which would display a polyhedral shape instead (Figure 6). The same feature is observed
in other cases as well, including Arhat Inv. 448 and Bodhisattvas Inv. 450 and 451, for
which the dot density seems to decrease from the inner to the outer portion of the layer. It
is worth noting that the innermost lithopone layers with the additional presence of silicon
(Inv. 448) or calcium carbonate inclusions (Inv. 450 and 451) do not show such a pattern.
The considerations above suggest that this feature is likely due to a deterioration process,
possibly of a biological nature, which might have determined a considerable depletion
in binder. This might justify the extremely fragile condition of the paint layers, observed
for all the sculptures and particularly evident in the cross sections from Inv. 453. The
sequential application of many superimposed layers of paint, presumably occurring over a
few decades, might be related to an attempt to remedy the ongoing deterioration process.
This may also explain the decreasing porosity of the outer lithopone layers in Inv. 448, 450,
and 451, which, after repainting, underwent deterioration again (Figure 8, right). In this
context, the presence of polyvinyl acetate and acrylic resins, detected by FTIR down to the
inner layers of the sculptures’ decoration, might be related to the use of consolidants and
adhesives as a treatment for the observed porosity.

4. Discussion
The presence of lithopone-based ground layers in all the sculptures analyzed is in
contrast with dating hypotheses initially formulated by experts based on stylistic consid-
erations and a comparison of the carving techniques, which placed the objects before the
19th century. A careful review of the results of this study, and particularly the widespread
identification of lithopone in the lowermost layers of the cross sections, suggests that, while
the sculptures appear to retain an original wooden body, a complete refurbishment of
their polychrome decoration may have occurred sometime after they were first created.
This interpretation is further corroborated by an in-depth examination of their fabrication
techniques based on data from computed tomography, which will be the subject of a forth-
coming publication. The repainting and refurbishment of sculptures are documented as
common practices in ancient China and during the Qing dynasty [9–11,14,19].
While lithopone-based ground layers were likely applied as part of the sculptures’
repainting campaigns, the detection of trace remnants of a calcium carbonate layer in a
cross section from Inv. 449 may provide clues as to the presence of a more ancient, possibly
original decoration. This finding is consistent with data from previous studies in the
literature [23], in which calcite, along with lead white, is reported to be one of the materials
most commonly used for white grounds, especially on Buddhist clay sculptures and wall
paintings. However, the almost complete lack of material in the cross sections examined
suggests that this former, possibly original decoration was completely stripped at some
point in time prior to the repainting campaigns.
The use of iron-based and lead-based red pigments such as red earth and minium,
ubiquitous in the samples examined, is well documented in Chinese painted productions.
As revealed by historical records and ancient Chinese building construction manuals [24,25],
the sculptures’ polychrome decoration shows interesting similarities with the architectural
painting practice of the Qing dynasty. Among these, it is worth mentioning the detection
of red pigments, such as iron oxides, as underlayers in some of the architectural elements
of the Fushan Temple’s Bell and Drum Towers in China’s Shaanxi Province [24]. Further
information about the layering of colors as a typical technical feature of Chinese painting
in the Shaanxi region is provided elsewhere [25]. The use of minium as an underlayer in
painted clay sculptures from Northern China was reported in a previous work [10]: in
that case, two overlapping layers, blue and red, respectively, were found in a cross section,
each composed of a paper ground layer with pigments applied onto it. The practice of
repainting sculptures with several layers of painted paper to cover the previous damaged
decoration is reported for both the Ming and Qing dynasties [9]. As for the blue pigments,
Coatings 2024, 14, 344 15 of 17

ultramarine blue was identified in all the samples examined in this work, its use being
documented in China since antiquity [7,8].
Another interesting outcome of the present study is the identification of red lakes
produced by precipitating an organic colorant of animal origin onto two different inorganic
substrates: calcium carbonate or aluminum- and iron-rich silicates. Both lakes were iden-
tified in cross sections from Inv. 449 and 451, suggesting that these repainting may have
occurred at different times or within distinct campaigns. Only the second type of red lake,
with an aluminum and iron silicate substrate, was found in Inv. 451.
Among the materials identified, a brown paint layer observed in historical pho-
tographs for Inv. 450, 451, 452, and 453 appears to have been summarily removed during
previous treatments. This layer may be interpreted as an attempt to adapt the decoration’s
tone to the taste of 20th-century European collectors. This common element suggests that
these four sculptures likely underwent similar processes upon their arrival in Europe.
In addition, a brownish organic layer found on Inv. 453, which is neither original nor
a Western pseudo-lacquer, was probably applied as a superficial glaze upon removal of
the monochrome brown paint to soften the perceived visual contrast resulting from the
presence of numerous paint losses in the polychrome decoration. This glaze is indicative of
a specific European taste that, in line with the dictates of the Italian conservation discipline,
is constantly seeking an overall chromatic balance.
Overall, scientific analysis revealed a similar color palette for all the sculptures an-
alyzed, except for Arhat Inv. 454. This was the only artifact to include titanium white,
phthalocyanine blue, and a red organic synthetic pigment, all dispersed in alkyd resin,
which indicates that the painted decoration was applied no earlier than the 1930s. These
elements point to a different history compared to the other artifacts, either traceable to the
sculpture’s transfer from China to Europe or, at least, related to a heavier paint makeover.
Buddha Inv. 452 displays a series of distinctive features compared to the rest of the
group: on the one hand, it has a significantly simpler polychrome decoration, with fewer
overlapping paint layers; on the other, it is the only artifact whose lithopone-based ground
layers are not affected by porosity-related deterioration, which may be ascribable to a
different conservation history prior to its acquisition by the MAO.
The presence of starch lumps within the lithopone-based ground layers, as well as the
interpretation of their intended purpose, prompted careful thinking: as a first consideration,
the abundance of these lumps within the layers suggests that they may have been added
intentionally to the paint formulation. The use of starch is documented, for instance, in an
ancient Chinese building construction manual, entitled “Gongcheng Zuofa Zeli” [26], when
referring to the current practices of the Qing dynasty (1636–1912 C.E.). According to this
manual, starch, in the form of flour, was commonly mixed with other ingredients within the
ground layer of architectural paintings [24]. Moreover, starch-based yellow pigments have
been detected in mixtures for red, white, blue, green, and yellow colors from the Tibetan
Buddhist Monastery of Puren, China [27]. As for Inv. 454, the larger size and more regular
shape of the starch lumps more evidently indicate a deliberate addition, perhaps aiming to
prompt cracking of the paint layers in an attempt to simulate an ancient appearance for this
sculpture through induced degradation of its surface decoration. This property of starch,
enabled by its hygroscopic behavior, is mentioned in the literature with regard to forgery
techniques [28,29].
In summary, the seven sculptures examined showed multiple layers of polychromy,
indicating extensive repainting and changes in design over time, which may have been
carried out to repair particularly degraded paint conditions at various points in their history
for ritual use, or to facilitate their sale on the European art market. The overall homogeneity
of the current paint layers suggests that the original decoration was likely removed prior
to the repainting campaigns. Based on the paint materials identified, it is not possible to
ascertain whether the repainting might have been completed in China or if some of it may
have occurred after the sculptures were transferred to Europe as well.
Coatings 2024, 14, 344 16 of 17

5. Conclusions
The technical study presented herein aims to fill in the gaps regarding the materials and
techniques of ancient Chinese painting, especially in relation to the production of Buddhist
polychrome wooden sculptures. As the objects examined have different provenance and
dating, striking similarities were detected, for instance, in terms of deterioration and
microbiological colonization that appear to indicate a common conservation history at least
from a specific point in time onward.
Scientific analysis of the polychrome decoration, combined with a thorough examina-
tion of numerous paint cross sections with optical and electron microscopy, suggest that
the sculptures were completely repainted upon removal of the former, possibly original
decoration. Possible reasons for these repainting campaigns include an intention to rem-
edy ongoing paint degradation phenomena and an attempt to adapt their appearance to
Western taste, thus facilitating their sale on the European art market. Further details on the
sculptures’ fabrication techniques and assembly from multiple wooden elements will be
shared as part of a forthcoming publication, along with a discussion of the most relevant
implications in terms of dating and authenticity.

Supplementary Materials: The following supporting information can be downloaded at https:

//www.mdpi.com/article/10.3390/coatings14030344/s1, Figure S1: Representative EDS spectra;
Figure S2: Representative FORS spectra; Figure S3: Representative Raman spectra; Figure S4: Repre-
sentative FTIR spectra.
Author Contributions: Conceptualization, C.R., P.B. and F.P.; methodology, C.R. and F.P.; scientific
analysis, C.R., A.P., D.A., F.P., D.D. and F.D.I.; data interpretation, C.R., P.B., F.P., D.A., A.P., E.M., V.T.,
N.S., F.Z., S.C., L.V. and D.Q.; writing—original draft preparation, C.R., P.B. and F.P.; writing—review
and editing, C.R., P.B. and F.P.; supervision, F.P.; funding acquisition, D.Q. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by the Museo d’Arte Orientale (MAO).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data generated during this study are either included in this
published article or available from the corresponding author upon reasonable request.
Acknowledgments: We would like to dedicate this article to our dear friend and colleague Debora
Angelici, who passed away prematurely in June 2023. We are grateful to the Raman Spectroscopy
Laboratory, Institute of Heritage Science of Italy’s National Research Council (ISPC-CNR, Milan) for
analyzing one sample with micro-Raman spectroscopy. We would also like to acknowledge Paola
Manchinu and Michela Cardinali, CCR “La Venaria Reale”, for supporting this research.
Conflicts of Interest: The authors declare no conflicts of interest.

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