Journal of Cultural Heritage 11 (2010) 228–232

Case study

Characterization and origin of weathering crusts on Kylin carved-stone,

Kylin countryside, Nanjing – A case study
Feigao Xu a,b , Jian Tang a , Shixiang Gao a,∗
a State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, 22, Hankou Road, Nanjing 210093, China
b College of Science, Nanchang University, Nanchang 330047, China

Received 4 November 2008; accepted 29 July 2009

Available online 4 January 2010

Abstract
To evaluate the effects of the environment pollution on weathering of outdoor stone artifacts in Kylin countryside, Nanjing, a Kylin carved-stone
was studied accordingly to the observable decay pattern on its surface. Different samples were collected either from the deteriorated areas or from
the sound stone substrate. The samples were characterized by IR, XRD, XRF, SEM, IC and ICP techniques. Gypsum, kaolinite, calcium oxalate
and phosphate together with an high content of heavy metals and soil particulates are mainly located on sheltered or partially exposed areas, while
an extensive network of parallel fissures is mainly developed on surfaces directly exposed to rainwater. Furthermore, an extensive colonization by
lichen is affecting a wide surface of the carved-stone, which is strongly adherent to the surface. The obtained results show that the deterioration is
mainly due to the atmospheric pollutants and its extent is strongly dependent on the surface exposition to the environment.
© 2009 Elsevier Masson SAS. All rights reserved.

Keywords: Kylin carved-stone; Weathering crusts; Rusty-yellow crusts; Washed-out surface; Black crust

1. Introduction
Air pollution is an important factor affecting the weathering
process of building stones used in historical buildings and mon-
uments [1–3]. Formation of crusts is a common phenomenon
observed on the surface of outdoor carved-stones. In polluted
environment, two kinds of crusts are usually developed on cal-
careous rocks; the so-called “white” and “black” crusts [4].
White crusts are formed through the dissolution of gypsum and
the reprecipitation of calcite on the surfaces exposed to the direct
action of rainwater. On the other hand, black crusts are developed
by gypsum formation on sheltered surfaces due to SO2 -polluted
atmosphere. Various colors of crusts are formed due to the type of
the environmental attack (industrial polluted atmosphere, types
of total suspended particles, etc.) and the lithotypes of the stone
substrate [5].
As a result of increasing population and industrialization in
recent decades, Nanjing, China, has faced some environmental
pollution problems. Outdoor Kylin carved-stones in Kylin coun-
∗ Corresponding author. Tel.: +86 02 58 35 96 48 2; fax: +86 02 58 37 07 30 4.
E-mail address: ecsxg@nju.edu.cn (S. Gao).
tryside, Nanjing, were built in six dynasties (317–589 AD) and
belonged to historic cultural heritage of national importance.
The current state of preservation of these stone artifacts is very
bad as the stone surfaces are severely weathered (Fig. 1). The
stone surface is partially lost due to rainwater erosion, lichen and
small grass grow in some cracks, and many black and yellow
incrustations are found on western flank and belly, respectively.
Different samples, collected from sound and weathered areas,
were subjected to a detailed analytical investigation. The compo-
sitions of the samples were studied, and the relationship between
identified deterioration products and air pollution was analyzed.
The deterioration causes of carved-stone are also explored in
order to safeguard these Kylin carved-stones against further
deterioration.
2. The studied area
Nanjing is a metropolitan city in the east of China. It has a
temperate climate. The yearly average temperature is 15.7 ◦ C
(monthly maximum of 40 ◦ C in July and minimum of −10 ◦ C
in January).
The yearly average rainfall amounts to 1106 mm and the sun
exposure is about 2152 h per year. The average relative humidity

1296-2074/$ – see front matter © 2009 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.culher.2009.11.006
 F. Xu et al. / Journal of Cultural Heritage 11 (2010) 228–232
Fig. 1. The weathering Kylin: (a) whole, (b) part.
is 72% in winter and 81% in summer. The daily average value of
SO2 and NOx concentrations in the atmosphere is 0.05–0.06 and
0.13 mg m−3 , respectively [6]. Kylin carved-stone is situated on
the Eastern countryside of Nanjing city near a high traffic road.
A major industrial area is located 20 km north of Nanjing.
3. Materials and methods
3.1. Sample collection and sample preparation
Samples of original rock and crusts were collected from dif-
ferent parts of Kylin carved-stone (Table 1), according to:
• the decay pattern and the damage levels, assessed through
macroscopic observation;
• the orientation of the Kylin carved-stone;
• the degree of sheltering from rainwater.
3.2. Analytical methods
Mineralogy of original rock and crusts were determined with
X-ray diffraction (XRD) (X’TRA, ARL, Switzerland) using Cu
Ka radiation with a scanning rate of 1◦ min−1 from 10 to 80◦
(2␪). The wavelength is selected as 1.54056 A (Cu).
X-ray fluorescence (XRF) results were finished on ARL-9800
(ARL, Switzerland). This spectrometer is equipped with a Rh-
X-ray tube working at 60 kV, and also has the following different
analyzing crystals: LiF 220, LiF 200, Ge, PET and LTAP. For
pellet preparation, a sample intake of 0.4 g was weighed in a filter
paper support and pressed. The X-ray spectra were accumulated
during 3000 s and analysed using the QuantAS software.
Infrared spectra were recorded employing a Nicolet Nexus
870 FTIR spectrometer. A small amount of original rock or crust
samples were mixed with KBr and pressed into pellets, then
scanned from 4000 to 400 cm−1 .
Table 1
Description of the samples.
Sample no. Type Location
A1 Original rock Base
A2 Rusty-yellow crust Abdomen
A3 Washed-out surface Eastern flank exposed to northern winds
A4 Black crust Western flank exposed to eastern winds
A5 Light-red crust Fractured sample in gap
229
Thin cross-sections from the fragments of crusts col-
lected were prepared for observation using scanning electron
microscope (SEM) (Hitachi model S-3400N II), operated at
accelerating voltage of 25 kV.
To qualitatively and quantitatively evaluate the contents of
the ions coming from water-soluble salts, 100 mg of crushed
samples were solubilized with 100 ml of deionized water. After
filtering on a Millipore filter (0.45 ␮m pore size), the solutions
were analyzed using a Dionex 1000 ion chromatograph (IC)
and an J-A1100 inductively coupled plasma (ICP) spectrom-
eter (Jarrell-Ash Corporation, America), for the anions and the
cations, respectively.
The bulk densities of the crusts were determined using an
immersion method based on Christian [7]. After weighing the
air-dried crusts samples, they were allowed to saturate with a
low-viscosity kerosene. Excess kerosene was removed with fil-
ter paper and the crusts were then suspended in a measuring
cylinder of water placed on a balance to obtain the volume by
displacement of water. The bulk density was calculated from the
weight of the air-dried sample and the volume of the sample.
4. Results and discussion
4.1. Chemical analysis of the weathering crusts
FTIR spectra of sample A2 and sample A3 are shown in
Figs. 2 and 3. Fig. 2 shows that the characteristic absorption
peaks of CaCO3 is at 1798, 1424, 874, 711 cm−1 , the character-
istic absorption peaks of, CO3 -apatite [(Ca5 (PO4 )3 )2 CO3 ] is at
565, 604, 1040 cm−1 and the characteristic absorption peaks of
gypsum is at 672, 1623, 3408 cm−1 [8–10]. FTIR spectra of sam-
ple A3 (Fig. 3) shows that the characteristic absorption peaks of
quartz is at 469, 1081 cm−1 , the characteristic absorption peaks
of calcium oxalate is at 778, 1648 cm−1 , and the characteris-
tic absorption peaks of kaolinite [Al2 (Si2 O5 )(OH)4 ] is at 1032,
3619, 3694 cm−1 [9–11]. Infrared spectroscopy of sample A4
shows that it has a similar composition to sample A3 .
The results of infrared spectroscopy are also confirmed by
XRD analysis (Table 2) which provides information on the
crystalline components. The original rock (A1 ) contains calcite
and quartz, while gypsum has been identified in rusty-yellow
material (A2 ). According to Juan Luis and Miguel [12] and in
consideration of the high average relative humidity and rainwater
in the Nanjing area, the most probable process of crust forma-
230 F. Xu et al. / Journal of Cultural Heritage 11 (2010) 228–232

Table 3
Samples components detected with XRFS (%).
Elements A1 A2 A3 A4 A5

CaO 47.2 34.9 41.1 9.14 28.6

SiO2 1.79 20.9 13.2 20.3 23.5
Al2 O3 0.819 4.38 5.30 7.68 11.7
K2 O 0.200 0.581 1.26 1.27 2.86
Fe2 O3 0.155 1.44 0.959 2.07 5.58
MgO 0.481 1.22 0.642 1.10 0.957
F 0.323 0.433 — — 0.251
SO3 0.0720 2.89 0.364 0.961 0.614
TiO2 0.0240 0.168 0.239 0.362 0.655
P2 O5 0.0320 11.7 0.114 0.384 0.305
SrO 0.0910 0.0390 0.0590 0.0069 0.153
MnO 0.00920 0.219 0.0220 0.0840 0.0310
Cl 0.0100 0.141 0.0180 0.0120 —
ZnO 0.00310 0.0600 0.00710 0.0420 0.0150
Fig. 2. FTIR spectra of sample A2 . C, calcite (1798, 1424, 874, 711 cm−1 ); V2 O5 — — 0.00410 0.0100 0.0140
G, gypsum (672, 1623, 3408 cm−1 ); A, CO3 -apatite (565, 604, 1040 cm−1 ); Q, Cr2 O3 — — — 0.0100 0.0110
quartz (469 cm−1 ). CuO 0.00230 0.0120 — 0.0098 —
LOI 48.8 20.7 36.7 56.3 24.8
Total 100 100 100 100 100

—, not detected; LOI, loss on ignition.

In the black crust collected from the Western side of the statue
(A4 ), it has been identified an high content of quartz in compar-
ison to calcite, the main component of the stone substrate (A1 ),
together with calcium oxalate. This indicates that the deterio-
ration process can be related to the growth of microorganisms
such as lichen on the surface of the stone, whose secretion of
oxalic acid is responsible for the enhanced calcite dissolution
and subsequent calcium oxalate formation [9,13].
The X-ray fluorescence analysis of compositions (Table 3)
Fig. 3. FTIR spectra of sample A3 . C, calcite (1798, 1424, 874, 711 cm−1 ); showed significant difference among samples from different
Q, quartz (469, 1081 cm−1 ); O, oxalate calcium (778, 1648 cm−1 ); K, kaolinite parts of the carved-stone. Ratio of MCaO to MMgO greater than
(1032, 3619, 3694 cm−1 ). 50.1 shows that the original rock belongs to limestone [14].
The sample (A2 ) collected from a sheltered position in the
tion on stone substrate is the absorption of sulphur dioxide in abdomen, has the following characteristics compared with orig-
rainwater, liquid atmospheric aerosols or moist film supported inal rock:
on a stone surface, where it is oxidized to form a sulphuric
acid solution that dissolves the calcium carbonate by gypsum
• the amount of SiO2 , Al2 O3 and Fe2 O3 (20.9, 4.38 and 1.44%,
formation.
respectively) are much higher than that in the original rock
Kaolinite has been identified on a stone flake collected from
(1.79, 0.819 and 0.155%). The relative enrichment of Si, Al
a washed-out surface (A3 ). Its presence can be related to cal-
and Fe might be derived from the deposition of wind-borne
cite dissolution, which is strongly enhanced by its exposition to
particles [9,15] since the Kylin carved-stone is near a road
rainwater and Northern winds in comparison to other side of the
with much traffic (the average value of TSP concentration in
artifact. The deposition of wind-born soil dust on the surface
the atmosphere is 2.1 mg m−3 near the Kylin carved-stone)
may also be a source of kaolinite.
[16];
• the amount of SO3 is 2.89% which is higher than that in
Table 2 the original rock (0.0720%). Rich-S is originated from SO2
Relative abundance of salts from analysis of XRD.
emitted by anthropogenic sources like combustion of fossil
Sample Calcite Quartz Gypsum Kaolinite Calcium oxalate fuels, automobile emissions, foundries and smelters;
A1 +++ + — — — • the amount of P2 O5 is 11.7% which is higher than that
A2 +++ ++ + — — measured either in the original rock (0.032%) or in other dete-
A3 +++ ++ — + — riorated areas. The yellow material was characterized by the
A4 ++ +++ — — + presence of apatite, mostly as carbonate-apatite. High content
A5 +++ ++ — — —
of phosphate salts are often originated by natural conversion
+++, very abundant; ++, abundant; +, present; —, not detected. of biogenic aerosols [17,18], although it cannot be excluded
 F. Xu et al. / Journal of Cultural Heritage 11 (2010) 228–232
Table 4
Ion content of soluble salts in samples (data in mg/100 mg).
Specimen Na+ K+
A1 0.01900 0.008200
A2 0.04600 0.09100
A3 0.1770 0.01800
A4 0.06230 0.07500
—, not detected.
that in polluted region, they can be ascribed to the reaction
of stone with phosphorus-bearing pollutants due to phospho-
rus industry, one of the most rapidly growing industrializing
economies in China [19];
• the amount of TiO2 and MnO are 0.168 and 0.219%, respec-
tively. Rich-Ti-Mn is associated with industrial and urban
emissions [2,20]. The fly-ash particles play an active role in
the damage processes affecting stone, since the content of
transition metal oxides contribute to the catalytic oxidation
of atmospheric gaseous SO2 and to the sulphation of calcium
carbonate.
XRF measurements performed on sample A4 (Western flank)
show SiO2 and CaO contents of 20.3 and 9.14%, respectively,
and LOI is 56.3%. These data clearly indicate that sample A4
has a high content of organic material, which is ascribable to
macroscopically observable lichen colonization.
The high content of Fe, identified on sample A5 , and respon-
sible of the light red color of the incrustation, may be attributed
to the dissolution and oxidation of constituent Fe-bearing com-
pounds enhanced by rainwater.
As regarding the amounts of soluble salts measured by IC
(Table 4), sulphates are the most abundant ions in comparison
to chlorides and nitrates, although they all have been identified,
together with K+ , Na+ , Mg2+ on samples collected from deteri-
orated surfaces. On sound stone, no anionic species have been
identified, thus clearly indicating that the soluble salts belong
to atmospheric pollutants rather than to solubilized constituent
materials.
Samples of crusts show a very porous surface by SEM obser-
vation. The bulk densities of the crusts roughly estimated are in
the range of 1.2 to 1.6 g cm−3 , much lower than the bulk den-
sity of calcite (2.7 g cm−3 ). The high porosity of the crusts can
enhance the deterioration of underneath stone due to its high
permeability either to water or to atmospheric pollutants.
4.2. Mechanisms responsible for the formation of crusts
The mineralogical, textural and physicochemical differences
of the examined crusts suggest that it is unlikely that they have
the same origin or the same pattern of development. In Nanjing,
high relative humidity, frequent fogs, sulphur, phosphorus, nitro-
gen pollutants, carbonaceous and heavy metal particles favor
the development of gypsum and calcium phosphate and nitrate
and deposition of airborne particles either on exposed or shel-
tered areas of the Kylin carved-stone. In consequence of these
processes, these deterioration products grow on sheltered areas
231
Mg2+ Ca2+ NO3 − SO4 2− Cl−
0.009800 0.9390 — — —
0.02400 2.430 0.1409 1.205 0.1532
0.03500 1.200 0.07788 0.1601 0.09978
0.01490 1.081 0.07164 0.1793 0.08187
leading to thick encrustations, which are washed-out on surfaces
exposed to rainwater. Furthermore, the dissolution and oxidation
of constituent Fe-containing constituent materials bring to the
deposition of yellowish iron oxide, which stains either the stone
or the crusts.
On the unsheltered surfaces, newly formed soluble salts,
washed-out by water and percolated through the bedding planes
of the stone substrate, create a network of parallel and deep
fissures, which increase the stone susceptibility to further dete-
rioration.
Black crusts, mainly composed of quartz, calcite and organic
materials have been identified on areas where microorganisms
such as lichens can grow in rainseason and die in dry season,
and pollutants from atmospheric dust is deposited on the surface.
Lichens colonization can enhance or decrease the cohesion of the
surface. On the one hand, the dense network of hyphae and thalli
forms a protective structure against the removal of stone surface.
On the other hand, lichens favor the rock surface weathering
through the secretion of oxalic acid, which react with CaCO3
of the stone and also their hyphae growth decreases the stone
cohesion.
5. Concluding remarks
The influence of heavily polluted atmosphere in the urban
environment results in different weathering patterns, mainly in
the form of crusts. It might be assumed that the analytical results
of IR, XRD, XRF, SEM, IC and ICP alone are not sufficient to
clarify and interpret the growth mechanisms of crusts. However,
they do provide valuable information about changes in compo-
sitions of crusts and original rock, and the relationship between
crusts composition and air pollution.
The compositions of the crusts collected from areas on the
carved-stone with different decay patterns show that the dete-
rioration is mainly due to the atmospheric pollutants and its
extent is strongly dependent on the surface exposition to the
environment. Gypsum, kaolinite, calcium oxalate and phosphate
together with a high content of heavy metals and soil particu-
lates are mainly located on sheltered or partially exposed areas,
while an extensive network of parallel fissures is mainly devel-
oped on surfaces directly exposed to rainwater. Furthermore,
an extensive colonization by lichen is affecting a wide surface
of the carved-stone, which is strongly adherent to the surface.
According to the obtained results, an appropriate conservation
plan will be developed, that includes the steps of cleaning and
consolidation, in order to identify the most suitable materials
and methodologies to remove the lichens and the deterioration
232 F. Xu et al. / Journal of Cultural Heritage 11 (2010) 228–232
crusts avoiding the loss of original substrate and ensuring an
increased cohesion to deteriorated stone.
Acknowledgement
This work has been supported by the Social Development
Program of Jiangsu province (BS2006050).
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