Analytical Letters

ISSN: 0003-2719 (Print) 1532-236X (Online) Journal homepage: https://www.tandfonline.com/loi/lanl20

Chromatographic, Microscopic, and Spectroscopic

Characterization of a Wooden Architectural
Painting from the Summer Palace, Beijing, China

Zhenzhen Ma, Liqin Wang, Jing Yan, Wenhui Zhou, Václav Pitthard, Tatjana
Bayerova & Gabriela Krist

To cite this article: Zhenzhen Ma, Liqin Wang, Jing Yan, Wenhui Zhou, Václav Pitthard,
Tatjana Bayerova & Gabriela Krist (2019): Chromatographic, Microscopic, and Spectroscopic
Characterization of a Wooden Architectural Painting from the Summer Palace, Beijing, China,
Analytical Letters

To link to this article: https://doi.org/10.1080/00032719.2018.1561707

Published online: 22 Jan 2019.

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ANALYTICAL LETTERS
https://doi.org/10.1080/00032719.2018.1561707

Chromatographic, Microscopic, and Spectroscopic

Characterization of a Wooden Architectural Painting from
the Summer Palace, Beijing, China
Zhenzhen Maa,b, Liqin Wanga,c, Jing Yana,b, Wenhui Zhoua,d, V
aclav Pittharde,
Tatjana Bayerovaf, and Gabriela Kristf
a
School of Cultural Heritage, Northwest University, Xi’an, China; bConservation and Research
Department, Shaanxi Academy of Archaeology, Xi’an, China; cMinistry of Education, Key Laboratory of
Cultural Heritage Research and Conservation, Northwest University, Xi’an, China; dConservation and
Research Department, Fujian Museum, Fuzhou, China; eConservation Science Department,
Kunsthistorisches Museum Wien, Vienna, Austria; fDepartment for Conservation and Restoration,
University of Applied Arts Vienna, Vienna, Austria

ABSTRACT ARTICLE HISTORY

The wooden construction painting is a type of an ancient decorative Received 23 October 2018
art on Chinese ancient structures. Comprehensive reports concerning Accepted 16 December 2018
the composition of these materials are rather limited. Here multiple
KEYWORDS
analytical methods were applied to systematically explore the
Gas chromatography–mass
morphology and materials. Several paintings were characterized spectrometry; scanning
using a morphological microscope. Scanning electron microscopy–e- electron microscopy–energy
nergy dispersive spectrometry (SEM-EDS), X-ray fluorescence (XRF), dispersive spectroscopy;
and X-ray diffraction (XRD) detected emerald green and ultramarine Summer Palace; X-ray
in the paint layers. Gas chromatography–mass spectrometry (GC-MS) diffraction; X-ray
indicated that the binding medium in the first layer was composed fluorescence
of blood. Our study helps to comprehensively understand the prep-
aration of the wooden construction paintings in the renowned
Summer Palace and provide a scientific basis for its restoration and
related archeology work.

Introduction
As a world-renowned royal garden and temporary imperial palace during the Qing
Dynasty in China, the Summer Palace has generally been recognized as an outstanding
representative of Chinese garden art for its intact grand buildings, delicate gardening
skills, and exquisite painting techniques. In 1998, it was added to the World Heritage
List by UNESCO (Zhao et al. 2016). As for the decoration of the structure, typical
Chinese ancient wooden construction paintings were invariably applied, embellishing
the wooden structure and fulfilling the protecting function. The wooden architectural
painting samples investigated in this paper are of high historical, scientific, and artistic
value. Hence the study of these materials is significant and provides a solid foundation
for later restoration.

CONTACT Liqin Wang wangliqin@nwu.edu.cn School of Cultural Heritage, Northwest University, Beilin District
710069, Xi’an, China.
Color versions of one or more of the figures in this article can be found online on at www.tandfonline.com/lanl.
ß 2019 Taylor & Francis Group, LLC
2 Z. MA ET AL.

Presently, numerous papers have described the application of scanning electron

microscopy–energy dispersive spectroscopy (SEM-EDS), X-ray fluorescence (XRF), and
X-ray diffraction (XRD) for the characterization of inorganic substances in paintings
(Wang et al. 2015; Zhang et al. 2015; Antunes et al. 2018; Cosano et al. 2018; Demir,
Şerifaki, and B€
oke 2018). Gas chromatography–mass spectrometry (GC-MS) is a routine
method for organic analysis (Ma et al. 2017; Gismondi et al. 2018; Sotiropoulou et al.
2018). However, general studies concerning the structure and constituting materials of
the wooden construction paintings in the Summer Palace have been rarely published. A
few papers covered only one aspect, either on pigment analysis (Yan, Wang, and Li
2010) or organic additive analysis in the mortar (Rao et al. 2015). Of particular interest
is the identification of the binder used in the paint layer.
This study was therefore designed to provide the systematic analysis of the morph-
ology of the cross-section, characterization of pigments, and the binding media of the
wooden architectural painting samples obtained from the Summer Palace in Qinglong
Street, Haidian, Beijing, to produce an integrated understanding of the samples and a
basis for future archeology study.

Experimental
Sampling
The fragments (Figure 1) were obtained from a building which is now the Summer
Palace Primary School on the side of the main entrance of the Summer Palace, on
Qinglong Street, Haidian, Beijing. The sample was collected due to the natural flaking
with a visible priming layer underneath and blue pigment on the surface. The material

Figure 1. Polychromic fragments from the building which is now the Summer Palace Primary School
at the side of the main entrance of the Summer Palace.
 ANALYTICAL LETTERS 3

had an irregular shape with a maximum length of 5 cm and minimum length of

approximate 1 cm.

Cross-section observation
A stereoscopic microscope (Stemi 2000-c, Zeiss, Germany) was used for the cross-sec-
tion observation of the sample.

Pigment and priming layer analysis

Scanning electron microscopy (SEM; JSM-6390A, Jeol, Japan)-EDS (JED2300, Jeol,
Japan) was employed to quantitatively analyze the pigments. The acceleration voltage
was 0.5 to 30 kV with a resolution ratio of 5 nm and a maximum magnification
of 300,000.
X-ray fluorescence (XRF; RIX2100, Rigaku, Japan) was used for the quantitative ana-
lysis of pigment elements using a rhodium target under vacuum with a maximum
power of 3 kW.
X-ray diffraction (XRD; D/max2400, Rigaku, Japan) was utilized for identification of
the phase of the pigment and priming layer, which were analyzed using a copper target
with a 40 kV tube voltage, 100 mA tube current, 1.5418 Å characteristic wavelength, 0.02
scanning step, and 5 to 70 scanning angle range.

Characterization of the binding medium

GC-MS analyses were performed on a 6890 N gas chromatograph connected to a quad-
rupole mass spectrometer (Model 5973 N, Agilent Technologies, USA). The separations
of lipids and proteins were all performed on a DB-5MS [poly(5% phenyl-95% methylsi-
loxane), J & W, USA] capillary column (30 m  0.25 mm  0.25 lm) . The temperature
of the oven program for lipids, resins and waxes was 50  C (1 min) to 320  C (12 min)
at 10  C
min 1. A temperature program of 80  C (1 min) to 280  C (1 min) at a rate of
6  C
min 1 was used for proteins.
For the polysaccharides, the separations were performed on a DB-WAX [J & W,
USA] capillary column (30 m  0.25 mm  0.25 lm). The temperature of the oven was
programed from 155  C (1 min) to 235  C (5 min) at 3  C min 1. Analytical pretreat-
ment for lipids, resins, waxes, proteins, and polysaccharides followed the procedure
described in the literature (Pitthard et al. 2006; Sefců et al. 2017) .

Results and discussion

Cross-section observation and study of the priming layer
Six layers, including three painting layers and three priming layers, were character-
ized using cross-section analysis (Figure 2). The sample had obviously been repainted
and was exquisitely made since all the repainting layers were accomplished with
their corresponding priming layers. The details of each layer are illustrated in Table
1. Quartz (SiO2), anorthite (CaAl2Si2O8), illite (Al2O3-2SiO2-2H2O), and calcite
4 Z. MA ET AL.

Figure 2. Cross-section observation of the sample.

Table 1. Information of each layer acquired by the stereoscopic microscope observation of the
cross-section.
Layer Thickness (mm) Material Function
1 0.2 Blue pigment Painting layer
2 0.3–0.5 Grey brick ash Priming layer
3 0.1 Green pigment Painting layer
4 2.0–2.8 Red brick ash Priming layer
5 0.1–0.3 Green pigment Painting layer
6 0.9 Red brick ash Priming layer

(CaCO3) were identified by XRD in the priming layers. The composition was similar
to brick. Records concerning the conventional preparation of wooden architectural
paintings on Chinese ancient buildings indicate that it was common practice to util-
ize brick ash as the priming layer (Du 1983). Thus, the inorganic padding in layer
2 was determined to be gray brick ash while layers 4 and 6 were red brick ash
based on their colors. More specifically, layers 2 and 6 were composed of fine ash
while the particles of red brick ash in layer 4 were larger with a maximum diameter
of 0.7 mm.

Pigment analysis
According to the XRF results (Table 2), high contents of Na, Al, Si and S in layer 1
were detected, matching the constituting element of ultramarine with a molecular for-
mula of Na6Al4Si6S4O20. In layer 5, large concentrations of Cu and As were found,
which are the main components of emerald green, with formula
Cu(C2H3O2)2
3Cu(AsO2)2. The XRD results of layer 1 shown in Figure 3 indicate that
there were peaks at 2h values of 23.92 , 27.76 , 29.78 , and 34.16 , respectively, coincid-
ing with the diffraction peaks of standard ultramarine (He et al. 2010). The absorption
peak at 2h equal to 26.56 is a characteristic peak of SiO2, probably originating from
dust. These results show that ultramarine was the coloring pigment.
 ANALYTICAL LETTERS 5

Table 2. Elemental contents of layer 1 and layer 5 by X-ray fluorescence using

a rhodium target under vacuum and maximum power of 3 kW.
Content (%)
Component Layer 1 Layer 5
Na2O 7.85 ± 0.06 1.33 ± 0.05
MgO 2.94 ± 0.05 —
Al2O3 13.50 ± 0.08 3.99 ± 0.06
SiO2 42.8 ± 0.10 17.90 ± 0.06
P2O5 0.31 ± 0.08 0.39 ± 0.05
SO3 13.30 ± 0.10 4.39 ± 0.09
Cl 1.14 ± 0.10 3.70 ± 0.10
K2O 2.27 ± 0.08 0.85 ± 0.07
CaO 9.32 ± 0.09 9.58 ± 0.08
TiO2 0.53 ± 0.05 —
Fe2O3 2.62 ± 0.09 1.86 ± 0.07
NiO 0.07 ± 0.05 0.23 ± 0.05
CuO 0.71 ± 0.09 19.30 ± 0.09
ZnO 1.85 ± 0.06 6.39 ± 0.07
As2O3 0.60 ± 0.06 29.90 ± 0.06

Figure 3. X-ray diffraction spectrum of the blue paint layer 1 using a 5 to 70 spectral domain setting
at the copper target with 40 kV tube voltage, 100 mA tube current, 1.5418 Å characteristic wavelength,
and 0.02 scanning step.

Moreover, a strong diffraction peak at a 2h value of 8.80 was detected in the XRD
measurements of layer 5 (Figure 4), suggesting that emerald green was present (Wang
et al. 2010). Compared with other ancient green mineral pigments, the artificially syn-
thesized emerald green was not used in Chinese watercolor painting and scroll painting
until the 1850 s ( Mazzeo et al. 2004) .Consequently, the painting of the green pigment
in layer 5 was performed later than the middle of the nineteenth century.
Lastly, C, O, Si, Ca and Pb were identified to be present in layer 3 by SEM-EDS
(Table 3). The carbon content was extremely high, which indicates the presence of
organic dyes since there were no blue mineral pigments detected.
6 Z. MA ET AL.

Figure 4. X-ray diffraction spectrum of the green paint layer 5 using a 5 to 70 spectral domain set-
ting at the copper target with a 40 kV tube voltage, 100 mA tube current, 1.5418 Å characteristic
wavelength, and 0.02 scanning step.

Table 3. Elemental contents of the green paint layer 3 by scanning electron

microscopy–energy dispersive spectrometry with 0.5 to 30 kV acceleration volt-
age, 5 nm resolution ratio, and maximum magnification of 300,000.
Element Mass (%) Atom (%)
C 28.40 ± 0.09 54.53 ± 0.09
O 9.99 ± 0.07 14.41 ± 0.08
Si 0.69 ± 0.04 0.56 ± 0.04
Ca 51.11 ± 0.06 29.41 ± 0.06
Pb 9.81 ± 0.06 1.09 ± 0.06

Characterization of the binding medium

No organic material was found in the two procedures for lipids and polysaccharides,
but the protein protocol provided positive results. As shown in Figures 5 and 6,
both samples were composed of proteinaceous binding media. Based on the literature
(Colombini et al. 2010; Yang et al. 2010; Serefidou et al. 2016), the traditional
binder collagen is characterized by hydroxyprolin and high content of glycine. Egg
owns average distribution of 10 amino acids. Casein was identified with a high con-
centration of glutamic acid. Figures 5 and 6 did not show these characteristics, thus
preliminarily excluding collagen, eggs, and casein. Interestingly, the chromatograms
matched a standard chromatogram of blood profile as shown in Figure 7, indicating
its presence in the samples.
The profile of the blue paint layer 1 exactly resembled the profile of the reference
standard with its dominant concentration of the amino acid leucine. In the green
paint sample of layer 5, the profile of the first five amino acids also corresponded
to the blood reference standard. However, the remaining amino acids were missing,
 ANALYTICAL LETTERS 7

Figure 5. Chromatogram of the binding media of the blue paint layer 1. Separations were performed
on a DB-5MS capillary column and the temperature was programed from 80  C for 1 min to 280  C
for 1 min at a rate of 6  C
min 1. Peak identification: (1) alanine, (2) glycine, (3) valine, (4) leucine,
(5) isoleucine, (6) proline, (7) serine, (8) phenyalanine, (9) aspartic acid, and (10) glutamic acid.

possibly due to the degradation since the layer 5 was painted during the earliest
period. However, this is initial speculation according the chromatographic profiles.
Hence, principal component analysis (PCA) was used to provide more accur-
ate results.
The amino acids contents of the blue paint layer 1 (Table 4) were subjected to multi-
variate statistical analysis (Colombini and Modugno 2009) using a data set of 96 refer-
ence samples. The first two principal components accounted for 88% of the total
variance, which was sufficient to characterize the relationship between the 10 amino
acids and reference and the samples. The resulting principal component analysis dia-
gram in Figure 8 shows that the sample was located in the blood cluster, confirming
that the binding medium in the layer 1 was composed of blood. The literature has
reported that blood was applied both in Indian paintings (Schilling, Derrick, and
Khanjian 1996) and ancient Chinese rock paintings (Wei 2014).
The use of blood was adopted from our ancestors 2000 years ago. Ancient Egyptians,
Greeks, and Romans used blood, lipids and proteins in building materials (White 1984).
The ancient Chinese also realized the functionality of blood with the earliest applica-
tions in the Qing Dynasty (221 B.C–206 B.C) when blood, lime, and stone were mixed
to build the floor of the Xian Yang Palace (Xing 1995). A related paper (Zhang, Zhang,
and Fang 2013) explained that blood was widely used because of advantages that
include excellent adhesive properties; good waterproofing; aerating properties, as the
foaming of the proteins may induce bubbles to more evenly disperse the mortar par-
ticles and enhance the workability, and its ability to resist crazing.
8 Z. MA ET AL.

Figure 6. Chromatogram of the binding media of the green paint layer 5. Separations were per-
formed on a DB-5MS capillary column and the temperature was programed from 80  C for 1 min to
280  C for 1 min at a rate of 6  C
min 1. Peak identification: (1) alanine, (2) glycine, (3) valine, (4) leu-
cine, and (5) isoleucine.

Figure 7. Chromatogram of the blood standard. Separations were performed on a DB-5MS capillary
column and the temperature was programed from 80  C at 1 min to 280  C for 1 min at a rate of 6  C
min 1. Peak identification: (1) alanine, (2) glycine, (3) valine, (4) leucine, (5) isoleucine, (6) proline, (7)
serine, (8) phenyalanine, (9) aspartic acid, and (10) glutamic acid.
 ANALYTICAL LETTERS 9

Table 4. Amino acid content of the blue paint layer 1

determined by gas chromatography–mass spectrometry.
Amino acid Content (%)
Alanine 17.48 ± 0.04
Glycine 13.03 ± 0.03
Valine 16.89 ± 0.05
Leucine 20.70 ± 0.05
Isoleucine 2.53 ± 0.06
Proline 4.69 ± 0.13
Serine 8.74 ± 0.14
Phenyalanine 3.43 ± 0.07
Aspartic acid 10.78 ± 0.06
Glutamic acid 1.53 ± 0.10

Figure 8. Principal component analysis diagram of the sample.

Conclusions
Comprehensive scientific analysis indicated that the wooden architectural paintings in
the Summer Palace experienced different periods of repair. The pigments were com-
posed of emerald green and ultramarine while traditional binder blood was identified
in the layer 1. In layer 5, the binder could not be characterized due to degradation.
The results have enriched the knowledge of the wooden architectural painting mate-
rials of the Summer Palace, laying a scientific foundation for the proper choice of
conservation materials, while providing evidence for materials’ history and related
archeology study.
10 Z. MA ET AL.

Disclosure statement
No potential conflict of interest was reported by the authors.

Funding
This work was supported by the National Natural Science Foundation of China (No.21175104)
and the China Scholarship Council (No.201506970013).

ORCID
Gabriela Krist http://orcid.org/0000-0002-4782-6438

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