ARTICLE IN PRESS

Atmospheric Environment 38 (2004) 44574466

Investigation of the effects of acid rain on the deterioration

of cement concrete using accelerated tests established
in laboratory
Shaodong Xiea,*, Li Qia, Ding Zhoub
a
Department of Environmental Science, State Key Joint Laboratory of Environmental Simulation and Pollution Control,
Peking University, Beijing 100871, China
b
Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, China
Received 8 January 2004; accepted 26 May 2004

Abstract

Deterioration of cement concrete specimens caused by simulated acid rain was investigated by laboratory tests.
Before and after cement concrete specimens were exposed to simulated acid rain, the neutralized depth, the compressive
strength and the chemical compositions in the hardened cement paste were measured. The mineralogical composition of
the concrete specimens was analyzed with XRD. The results lead to the following conclusions: the neutralized depth of
the concrete specimens of all experiments can be described as a power function of exposure duration, CaO loss and the
reduction rate of strength increased with H+ and decreased with SO2
4 concentration in simulated acid rain. The
original mineral compounds such as [Na K]AlSi3O8 and [Ca Na][SiAl]4O8 in the hardened cement paste are converted
to CaSO4  2H2O, CaAl2Si2O8 and Ca3Al6O12  CaSO4. And these are larger in volume so that the reaction with SO2
4
ions result in volume expansion and strength decrease. The reduction rate of strength has a binary linear relation to the
CaO loss rate and the ratio of SO3 content to CaO content in the hardened cement paste. So the deterioration of acid
rain on the concrete specimen is caused by both H+ dissolution and SO2
4 expansion.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Acid rain; Cement concrete; Corrosion; Deterioration; Accelerated test

1. Introduction concrete in urban areas may also be damaged due to

The impact of acid deposition on stone monuments
made of marble and limestone and on building materials
containing large amounts of carbonate has been
recognized for over a century and many studies have
addressed the effect of acid wet deposition on stone
material of historic buildings and monuments (Mossotti
et al., 1987; Gauri and Gwinn, 1982/1983; Dolske and
Meakin, 1991; Kucera and Fitz, 1995; Reddy et al.,
1986; Baedecker et al., 1992). High buildings made of
*Corresponding author. Tel.: +86-10-62755852; fax: +86-
10-62751927.
E-mail address: sdxie@pku.edu.cn (S. Xie).
exposure to cloud water with high acidity for a long time
(Okochi et al., 2000). Acid precipitation with a pH level
ranging between 3.0 and 5.0 will affect cement and
concrete (Sersale et al., 1998). The mechanism of
deterioration in cement-based materials and in lime
mortar was studied by Brown and Clifton (1988). The
effect of dry deposition of the single pollution species,
such as SO2, HCl, NO and NO2 on the degradation of
calcareous building stones has been determined by
Haneef et al. (1992), Hutchinson et al. (1992) and
Johnson et al. (1990) through laboratory tests. It has
been found that acid rain causes chemical deterioration
on carbonate stones and formation of soluble Ca2+,
HCO
2

3 , SO4 and that dry deposition of SOx, NOx on

1352-2310/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2004.05.017
 ARTICLE IN PRESS
4458 S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
the surface of stones contributes to salt enrichment on
carbonate stones and plays a major role in the
deposition of acid substances on buildings (Keuken
et al., 1990).
Marble and limestone specimens were also exposed
for one year by Youngdahl and Doe (1986) to ambient
atmospheric conditions in four cities of Eastern USA.
The results show that the specimens were damaged by
calcium loss due to acid deposition. Materials, such as
marble were exposed to simulated acid rain of different
pH values by Neal et al. (1986) to corrosion levels
equivalent to exposure to ambient atmosphere for a 10-
year period and the conclusion was that the dissolution
rate decreased logarithmically with time and was
determined by the transport rate of dissolved ions.
Rands et al. (1986) found that both the acidity and ionic
strength in rainwater played an important role in
limestone deterioration. The impact of local wet and
dry deposition of acid compounds was investigated by
Tsujino et al. (1995) by means of exposing different
materials such as copper, bronze, marble etc. under
indoor and outdoor conditions and the results show that
corrosion depends on the local pollution climate
especially the ratio of SO2/NOx. The incremental effects
of wet and dry deposition on carbonate stone erosion
due to hydrogen ion, sulfur dioxide and nitrogen oxides
were quantied by Baedecker et al. (1992), and the
results suggest that approximately 30% of erosion by
dissolution can be attributed to the wet deposition of
hydrogen ion and the dry deposition of sulfur dioxide
and nitric acid between rain events at the studied
conditions. The relative effect of Cl
, SO2


4 and NO3 in
an articial acid rain solution on limestone deterioration
was studied by Johnson et al. (1996) and the relative
contribution of anions and hydrogen ions was deter-
mined using spray run-off solution rates of 0.2 ml cm
2
day
1 and pH values of 5.5 and 3.8. The inuence of wet
deposition of simulated acid rain on the degradation of
limestone, sandstone, marble and granite was explored
by Haneef et al. (1993) by observing pH change and
analyzing run-off solution and soluble extracts from the
exposed stones, together with EPMA, SEM/EDX and
X-ray diffraction examination of these stones. The effect
of sulfuric acid on carbonate stones has been investi-
gated by Tecer (1999) by collecting samples from
historic building and analyzing the mineralogical com-
position of the samples with XRD, nding that the
major constituent of these stones is calcite. Webb et al.
(1992) point out by eld exposure that there is a
signicant trend that weight loss increases with the
average sulfur dioxide concentration. The distribution of
common construction materials at risk of damage from
acid deposition has been presented by Lipfert and Daum
(1992). The National Materials Exposure Program
(NMEP) determines the rate of decay of the stone and
metal tablets, exposed in ambient atmosphere by
measuring their weight change at 29 sites located
throughout United Kingdom. The preliminary results
indicate (Butlin et al., 1992) that sulfur dioxide is still a
signicant contributor to the degradation of calcareous
stones in areas of high pollution and wet deposition and
natural dissolution of stone are important, especially in
cleaner areas of UK.
It can be seen from laboratory experiment and eld
investigations mentioned above that acid deposition has
obvious inuence on calcareous building materials and
historic buildings. But the effects are only observed after
long-term exposure to ambient conditions, so an
accelerated laboratory test for damage by acid deposi-
tion is very useful. Furthermore there are only few
studies on the effects of acid rainwater on lime mortar
and concrete (Okochi et al., 2000; Webster and
Kukacka, 1986). In this paper, we present accelerated
corrosion test methods by exposing materials to
increasing acidity and other ion concentrations in
simulated acid rain, respectively, i.e. the periodic
soaking method and spraying test method, in order to
observe each stage of deterioration of cement concrete in
a short period and to provide fundamental experimental
data for anti-corrosion technology.
2. Experiment
2.1. Composition of simulated acid rain and cement
concrete specimens
The acid rain in China is for a large part due to
sulfuric acid (Wang et al., 2000), with SO2

4 accounting
for 7090% of total anions. And various sulfurous
pollutants deposited over the samples can be oxidized
and converted to sulfuric acid with higher acidity and
SO2
4 concentration in some parts of samples surface.
Such a fact is taken into consideration in cement
concrete specimens exposed to simulated acid rain.
Consequently, the effects of different H+ concentration
as well as different SO2

4 concentration at high acidity in
simulated acid rain on deterioration of cement concrete
are investigated in this study. And then two categories
of simulated acid rain solution shown in Table 1 were
prepared from reagent grade chemicals to study the
effects of H+ and SO2
4 in acid rain on cement concrete
specimens. It can be seen from Table 1 that one category
Table 1
The pH level and SO2

4 concentration in the simulated acid rain
pH level with SO2

4 =0 SO2

4 concentration
(mol l
1 ) with pH 1.0
5.6 3.5 2.0 1.0 0.06 0.1 0.2
 ARTICLE IN PRESS
S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
of simulated acid rain is used to explore the corrosion
effects by SO2

4 while pH is kept at 1.0 and the other
category is used to investigate the corrosion effects
by H+ in absence of SO2
4 . The amounts of other
components in simulated acid rain solutions are the
same as the average value of precipitation from 1982 to
1988 in Guiyang, China. The acidity was measured by a
pH meter and adjusted by HNO3.
Portland and Slag cement are widely used in South-
west China where acid rain pollution is quite severe and
these cements are hence chosen. All the cement concrete
specimens used in the study were cast in cubes of
100 mm  100 mm  100 mm using general Portland ce-
ment and slag cement as binders and crushed cobble
stone with maximum diameter of 25 mm as coarse
aggregate, named concrete P and S, respectively. The
mass proportions of raw materials in the preparation of
general Portland cement to sand to stone to water in P is
1:1.992:3.250:0.5 by weight and the ratio of slag cement
to sand to stone to water in S is 1:1.992:3.250:0.5. After
28 days of water-curing, the concrete specimens were
naturally dried in a cool dark place for several days
(Okochi et al., 2000).
2.2. Experiment methods
2.2.1. Periodic soaking experiment
The basis of the periodic soaking experiment is that
the erosion of concrete specimens can be accelerated by
alternating between wetting and drying them. A similar
experiment method was also presented by Sersale et al.
(1998). The concrete specimens subjected to a 6-day
cycle; they are immersed in 20 L simulated acid rain
solution for 5 days and then naturally dried them at
room temperature for 1 day. The specimens were
exposed to simulated acid rain solutions of pH 5.6 and
3.5 for 90 days and to solutions of pH 1.0 for 66 days.
Experiments were carried out at room temperature
(about 1971 C) and humidity (about 60%). It is very
important to keep the pH value constant during the
periodic immersion experiment process. The pH value of
the immersion solution is hourly observed at the
beginning of each experiment and adjusted to initial
values with 6 mol l
1 HNO3 every day by using a pH-
meter. It is found from the observed results for 30 days
that the pH changed greatly even after 1 day in the
solutions of pH 5.6 and 3.5, while for the solution of pH
1.0 the pH value hardly ever altered even after 5 days,
so the experimental conditions are determined that
the simulation acid rain solution is refreshed each day
for pH 5.6 and 3.5 whilst for the pH 1.0 only after
5 days.
2.2.2. Spraying experiment
The spraying method is based on several publications
dealing with this methodology (Sersale et al., 1998;
4459
Johnson et al., 1996 and Mart!nez-Ram!rez et al., 1998).
The simulated acid rain solution is sprayed intermit-
tently as small drops with diameter ranging from 0.2 to
0.5 mm by means of a proper ejector on specimen
surface. The impact of the drops emulates the action of
precipitation. As soon as the specimen is dry, the surface
is sprayed again. The effects of acid rain are accelerated
by means of these wetting and drying cycles. The
concrete specimens were exposed to simulated acid rain
solution at the ow rate of 60 ml h
1 equivalent to the
rainfall intensity of 7.7 mm day
1. In the same way as
described for the soaking procedures, 6 day cycles are
used consisting of 120 h (5day) spraying the acid
solution and 24 h drying up at room temperature (about
1971 C) and humidity (about 60%).The exposure to
the spraying drops is running continuously for 180 days.
The total volume of sprayed solution is nearly equal to
that of the annual rainfall in Guiyang, China (about
1198.9 mm).
2.3. Items to be determined
Three concrete specimens are used for each experi-
ment method and each solution. The reported results are
the average values of these three specimens.
2.3.1. Neutralized depth
There is a possibility that the neutralization of cement
concrete specimen is inuenced by major anions in
rainwater. H+ will react with calcium oxide and calcium
hydrate and secondary products can be formed. The
measurement of the neutralized depth is carried out as
follows: the cement concrete specimen is cut to a smaller
size of 25 mm  25 mm  100 mm. The surfaces are
sealed using heated parafn wax with exception of
opposite side faces of 25 mm  100 mm, and then
parallel lines at 10 mm spacing distance are drawn with
pencil along the length orientation on the unsealed faces
to set the measurement points for neutralization depth.
After exposed for a period of time, one piece of the
segment with thickness about half of the entire width is
cut vertically from one end of the clumps to measure the
neutralized depth. The cross section of the remainder is
sealed and exposed to simulation acid rain solution
again until the next measurement. A 1% Phenolphtha-
lein solution in alcohol containing 20% distilled water is
sprayed on the cross-section surface of that cut segment.
After 30 s, the depth of the red part is measured with
vernier caliper. Half of the difference between the width
and the red part depth is the neutralized depth
corresponding to different measurement points of this
segment. The same experiment and measurement are
carried out as mentioned above to obtain each
neutralized depth of different segments and then the
neutralized depth of the specimen is determined by
averaging all of the measurement values.
 ARTICLE IN PRESS
4460 S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
2.3.2. Compressive strength
The strength of concrete cured in standard curing
room for 28 days is taken as the original strength. By
measuring the original strength of the cement concrete
specimen and that after erosion, the reduction rate of
strength can be obtained. The compressive strength of
the samples is measured by a universal oil pressure
(600,000 tons) compression-testing machine. The reduc-
tion rate of strength of the cement concrete specimen
can be calculated as follows:
RC0
RCe
RC %  100%; 1 compounds (D/max-g BX-ray diffracting meter made in
RC0
where RC stands for the reduction rate of compressive
strength of cement concrete specimen, RC0 is the
compressive strength value after cured in standard
curing room for 28 days, namely initial strength value;
RCe is the compressive strength value after exposure to
simulated acid rain.
2.3.3. Chemical analysis of powder over the sample
surface and corrosion product
Hardened cement paste (ex coarse aggregate) from
cement concrete specimens that has been measured the
compressive strength and corrosion products formed in
the process of exposure on the surface of cement
concrete specimens are collected, and then ground into
powder that can pass through an 80-mesh sieve. The
powder is reduced to about 50 g with quartering method
and ground into ner powder that can pass through a
140-mesh sieve in an agate mortar for stand-by storage.
Afterward the ground powder samples of 1 g, which is
baked for 2 h at 110 C120 C in a baking box and dried
for 4 h in an exsiccator, is accurately weighed and
dissolved with HCl solution. And then Ca2+, Mg2+,
Fe3+, Al3+ in the solution are measured using
complexometric titration method to obtain the chemical
composition percentage of CaO, MgO, Fe2O3 and Al2O3
in the powder. Another powder sample of 1 g is
accurately weighed to measure SO3 amount in the
powder using iodometric method. The loss rate of CaO
Fig. 1. Effect of the acidity and SO2

4 in acid rain on the neutralized depth of the cement concrete specimen after 30, 74, 105 and 135
days exposed by periodic soaking experiment.
content on the cement concrete specimen surface CaOL
is calculated as following:
CaOO
CaOe
CaOL %  100%; 2
CaOO
where CaOo is the original CaO content, CaOe is CaO
content after exposure, and CaOL is the loss ratio of
CaO content in hardened cement paste.
2.3.4. X-ray diffraction analysis of surface powders
X-ray diffraction analysis is used to identify specic
Tokyo, Japan).
3. Results and discussion
3.1. Neutralized depth
The neutralization depth gives a measure of the
penetration depth of H+ in acid rain in the concrete
specimens. It reects the degree of corrosion due to acid
rain on the material and it can be used to evaluate the
resistance to corrosion of the material.
The found neutralization depths in Fig. 1 show an
increase with the decrease in pH of simulated acid rain
solutions and decrease at increasing of SO2
4 concentra-
tions. The variation tendency is also observed through
spraying experiment. It can be also seen from Fig. 1 that
the neutralized depth of S is a little greater than that of P
under the condition of different acid rain solutions
throughout experiment. It can be deduced from those
phenomena that high H+ concentration in acid rain
promotes its penetration into the inner part of concrete
specimen, whereas the presence of SO2
4 suppresses H
+
to penetrate.
The neutralized depths of concrete are also shown in
Fig. 1 after exposure for 30, 74, 105 and 135 days.
Regression analysis results in Table 2 show signicant
correlation between neutralized depth and exposure
time, which can be expressed as y atb ; where y is the
 ARTICLE IN PRESS
S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
Table 2
Regression analysis results on relationship between neutralization depth Y(mm) and exposure time t(day)
The condition of simulation acid rain

1
pH 1.0 and SO2

4 =0(mol l )
pH 1.0 and SO2

4 =0.06(mol l
1)

1
pH 1.0 and SO2

4 =0.1(mol l )

1
pH 1.0 and SO2

4 =0.2(mol l )
Fig. 2. Effects of H+ and SO2

4 concentration in acid rain on the compressive strength of the concrete specimens after 90 days for pH
3.5, and 5.6 and 66 days for pH 1.0 in periodic soaking experiment and 180 days in spraying experiment.
neutralized depth, t is exposure duration. Both a and b
are constants, at values of bo1 the neutralized depth
increases quickly at the beginning then slows down,
and increases slowly at the beginning then rapidly when
b > 1:
3.2. Variation of the compressive strength in the concrete
specimens caused by simulated acid rain
The compressive strength of the concrete specimens
was measured after the soaking and spraying experi-
ments. By comparing with the initial strengths, the
reduction rate of compressive strength was calculated
using Eq. (1) and the results were shown in Fig. 2.
Fig. 2 illustrates that the reduction rate of the
compressive strength of the concrete specimens after
exposure changes with H+ and SO2
4 concentration in
acid rain. It can be seen that the compressive strength of
the concrete specimens decreased after exposure to
different simulated acid rain solutions except S exposure
to pH 3.5 in periodic soaking experiment and increased
except P exposure to pH 1.0 in spraying experiments.
Whats more, the reduction rate of compressive strength
of S made from slag cement is lower than that of P made
from general Portland cement except under the condi-

1
tion of pH 1.0 and SO2
4 0.2 mol l in periodic soaking
experiment. The compressive strength of S originally
increased with the reduction of pH after exposure to
simulated acid rain, and when the pH of the acid rain
solution was reduced to a certain value between 3.5 and
4461
P S
Y
3 1:33
6:88  10 t r 0:997 Y 0:124t0:74 r 0:99
Y 0:222t0:55 r 0:986 Y 0:617t0:37 r 0:954
Y 0:119t0:68 r 0:987 Y 0:023t1:04 r 0:987
Y 2:66  10
2 t0:92 r 0:984 Y 0:4129t0:36 r 0:87
1.0, the strength decreased rapidly with the reduction of
pH and the increase of SO2
4 . The compressive strength
of P decreased slowly with the reduction of pH and
increased slowly with the increase of SO2
4 , and then
decreased rapidly when SO2
4 concentration increased to
a certain value between 0.1 and 0.2 mol l
1. It is deduced
from these results that the attack of H+ and SO2
4 in
acid rain on the concrete specimen will cause the
strength to decrease.
3.3. Chemical components change and CaO loss in the
hardened cement paste of the concrete specimens
The chemical compositions in the hardened cement
paste of the original concrete specimens and the concrete
specimens after exposure to simulated acid rain were
measured by means of chemical analysis method. The
CaO percentage composition in the hardened cement
paste of P exposed by periodic soaking experiment at pH
1.0, pH 3.5, and pH 5.6 for 90 days is 15.44%, 15.94%,
and 16.33%, respectively. That of S is 14.19%, 15.33%,
and 15.80%, respectively. By comparing them with the
original values of 18.01% and 18.18% for P and S,
respectively, the CaO amount clearly decreased with
increase in the acidity of simulated acid rain solution for
both types. It may be concluded that H+ in acid rain
dissolves Ca(OH)2 and other calcium hydrates in the
hardened cement paste, leading to a decrease of CaO.
The variation tendency was observed through spraying
experiment. And the CaO percentage composition in the
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4462 S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
Fig. 3. The variation in the CaO loss rate in the cement concrete specimen after exposure 90 days for pH 3.5, and 5.6 and 66 days for
pH 1.0 in periodic soaking experiment and 180 days in spraying experiment.
hardened cement paste of P was 17.80% and 17.31% at
pH 1.0 and pH 5.6, respectively when the total amount
of solution volume equal to 1198 mm annual rainfall in
China was sprayed on the surface. That of S was 14.81%
and 16.48% at pH 1.0 and 5.6, respectively. It is clear
that there is remarkable CaO loss in the hardened
cement paste by calculating the loss amount using
Eq. (2). Fig. 3 illustrates the relationship between CaO
loss and H+ concentration in simulated acid rain. It can
be seen that CaO loss in the concrete specimens
decreased greatly with increase of H+ concentration in
simulated acid rain.
The CaO percentage composition in the hardened
cement paste of P through periodic soaking experiment
for 90 days is 5.56%, 15.74%, 21.88%, and 15.44%,
respectively under the condition of SO2
4 concentrations
of 0, 0.06, 0.1, and 0.2 mol l
1 while the acidity
maintained at pH 1.0. And that of S is 4.86%,
10.99%, 16.02% and 14.19%, respectively, under those
conditions as above. It is found by comparing them with
the original values of 18.01% and 18.18% for P and S,
respectively, that both of the CaO percentage composi-
tions decreased signicantly, especially under the condi-
tion of SO2

4 concentration 0 in simulated acid rain of
pH 1.0. These change trends of the CaO percentage
composition in the hardened cement paste were ob-
served through spraying experiment under the same
conditions mentioned above. The CaO percentage
composition in the hardened cement paste of P is
17.01%, 14.65%, 19.59% and 17.80%, respectively, at

1
SO2

4 concentrations of 0, 0.06, 0.1, and 0.2 mol l in
simulated acid rain of pH 1.0, at a total amount of
solution sprayed on the surface equal to 1198 mm
annual rainfall. And that of S is 14.32%, 14.17%,
17.17% and 16.48%, respectively. It is obvious that the
CaO percentage composition is also decreased when
exposed to different SO2
4 concentration solutions and
the decrease level is related to SO2
4 concentration in
simulated acid rain. Fig. 3 illustrated the relationship
between the CaO content loss calculated with Eq. (2)
and SO2
4 concentration in simulated acid rain. It can be
seen that the CaO percentage composition decreased
greatly at pH 1.0 in acid rain solution, especially at pH
1.0 and SO2
4 concentration of 0 in the periodic soaking
experiments in which the reduction rate of CaO
composition in the hardened cement paste of P and S
amounted to 69.13% and 73.27%, respectively. The
amount of CaO loss decreased observably with increase
in SO2
4 concentration in acid rain, which indicates that
SO2
4 ion can inhibit CaO loss in the concrete specimen
due to the formation of CaSO4 through SO2
4 reacting
with Ca(OH)2 in the hardened cement paste.
The SO3 content in the hardened cement paste of the
concrete specimens before and after exposure experi-
ment was also measured by means of chemical analysis.
The change of SO3 content in the concrete specimens
after exposure to different simulated acid rain is
illustrated in Fig. 4. It can be seen by comparing them
with the SO3 content in the original concrete specimens
which are 1.43% for P and 1.15% for S that the SO3
content in the concrete specimens after exposure
increased obviously with increase of SO2
4 concentration
in simulated acid rain but decreased under the condition

1
of pH 1.0 and SO2
4 0 mol l .
Corrosion products formed on the surface of speci-
mens were collected for chemical analysis after exposure
to pH 1.0 and different SO2
4 concentrations through
periodic soaking experiment for 30 days. The results
shown in Table 3 were obtained from which it can be
seen that the percentage composition of Fe2O3, Al2O3,
MgO in the corrosion product is quite low, while the
CaO and SO3 content increase with increase in SO2
4
concentration in exposed acid rain. The ratio of SO3/
CaO in corrosion product of the concrete specimens
exposure to pH 1.0 and the SO2
4 concentration of 0.06,
0.1, and 0.2 mol l
1 is approximate to or even larger than
the theoretical value 1.4 in CaSO4, indicating that the
major component in the corrosion product is CaSO4 and
that other sulfate compounds are formed at high sulfate
concentrations.
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S. Xie et al. / Atmospheric Environment 38 (2004) 44574466 4463

Fig. 4. The SO3 percentage composition in the hardened cement paste after exposure 90 days for pH 3.5, and 5.6 and 66 days for pH
1.0 in periodic soaking experiment and 180 days in spraying experiment.

Table 3
Chemical analysis of corrosion product formed on the surface after exposure for 30 days by using periodic soaking experiment

Measured item (%) Concrete P Concrete S

1
1
SO2

4 concentration(mol l ) (pH=1.0) SO2

4 concentration(mol l ) (pH=1.0)

0 0.06 0.1 0.2 0 0.06 0.1 0.2

Fe2O3 1.13 0.56 0.43 0.45 1.37 0.58 0.65 0.62

Al2O3 0.75 0.81 0.49 0.39 0.79 0.65 0.43 0.50
CaO 0.46 12.33 22.46 13.40 0.82 11.62 18.88 15.24
MgO 0.77 0.34 0.35 0.37 0.28 0.30 0.32 0.40
SO3 0.33 19.48 22.64 23.73 0.39 18.86 24.00 21.56
SO3/CaO 0.72 1.58 1.01 1.77 0.48 1.62 1.27 1.42

The major components in the hardened cement paste
are hydrate calcium salts such as hydrate silicate,
hydrate calcium aluminosilicate and Ca(OH)2. The H+
and SO2

4 will react with the hardened cement paste of
the concrete specimen as follows:
CaOH2 2H Ca2 2H2 O; 3 the surface of the concrete specimens but also possibly in
1=55CaO  6SiO  5:5H2 Os 2H aq
2:1H2 Oaq Ca2 aq 6=5SiO2 s; 4 produced and gradually cumulate on the surface and in

the inner part of the pores, and thus Ca2+ loss caused by
CaOH2 SO2

4 CaSO4 2OH ; 5
Ca2 SO2

4 CaSO4 ; 6
CaSO4 2H2 O CaSO4  2H2 O; 7
4CaO  Al2 O3  19H2 O 3CaSO4  2H2 O 16H2 O
3CaO  Al2 O3  3CaSO4  31H2 O CaOH2 :
8
It is clear that the calcareous material on the surface
of the concrete specimens will react with H+ in acid rain
by means of reaction equation (3) and (4), forming free
calcium ions in aqueous solution so as to promote H+
penetration, causing the porosity to increase so that it is
more propitious to H+ and SO2
4 penetration and
accelerates reactions described in (5) and (6) to form
CaSO4. Nevertheless, the CaO loss can be suppressed by
means of the reactions in (5), (6) and (7). CaSO4 and/or
salt or water crystallization will be formed not only on
the inner part, which results in blocking the pore way
and suppressing H+ and SO2
4 to penetrate into the
inner pores of the concrete specimen. So CaSO4 will be
reaction in (3) and (4) is suppressed and sulfur content in
the concrete specimens are enhanced. The reaction of
Eq. (8) will result in more release of Ca(OH)2.
3.4. X-ray diffraction phase analysis in the hardened
cement paste of the concrete specimens
The hardened cement paste of P after being exposed
to different simulated acid rain solutions was analyzed
using X-ray diffraction in order to study the structure
changes and the results are shown in Table 4. It can be
seen from Table 4 that [Ca Na][SiAl]4O8 and [Na
K]AlSi3O8 present in the hardened cement paste of P
before exposure are converted to CaSO4  2H2O and
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4464 S. Xie et al. / Atmospheric Environment 38 (2004) 44574466

Table 4
The result of X-ray diffraction phase analysis in the hardened cement paste of the concrete P

1
Method Mineral construct Original specimen pH SO2

4 concentration(mol l ) (pH=1.0)

5.6 3.5 0 0.06 0.1 0.2

SiO2 S S S S S S S
[Ca Na][SiAl]4O8 S W W W M M W
Periodic soaking method Ca1.5SiO3.5  XH2O M M M M S S M
CaAl2Si2O8 S S S S
CaSO4  2H2O W S S S
Mg3O[CO3]2 M
Fe2Al4Si5O18 M
[Na K] AlSi3O8 S S S A W W W

SiO2 S S S S S S S
[Ca Na][Si Al]4O8 S S S M
[Na K]AlSi3O8 S W
Ca1.5SiO3.5  XH2O M M M M M M
Spraying method KASi3O8 S M S W
CaAl2Si2O8  4H2O
CaSO4  2H2O S S S
NaAlSi3O8 S W S
CaAl2Si2O8 M
[Ca Na]4[Si Al]6O12SO4 M

Note: S, M, and W indicate the peak value of X-ray diffraction is strong, middle strong and weak.

CaAl2Si2O8 after exposure. Comparing Table 4 and
Fig. 2 learns that the strength of the concrete specimen
decreases clearly with changing crystal structure. The
concrete specimen was exposed to pH 1.0 and SO2
4 Ca(OH)2 loss and CaSO4 content respectively. Next a
concentration of 0.06, 0.1 and 0.2 mol l
1 solutions. The
substance structure in the hardened cement paste
changed greatly and CaSO4  2H2O was newly formed.
The compressive strength after periodic soaking experi-

1
ments at SO2
4 concentration of 0.06, 0.1 and 0.2 mol l
in simulated acid rain with pH 1.0 exposure decreased to
59.17%, 32.19% and 36.6%, respectively, and 26.03%,
6.24% and 21.76% for spraying experiment, respec-
tively. [Ca Na][SiAl]4O8 is converted to Ca3A-
l6O12  CaSO4 and CaSO4  2H2O which are larger in
volume. Internal stress within inner part of the concrete
specimen is the result of this volume expansion resulting
in signicant decrease of the compressive strength.
property and the formation of CaSO4, in volume larger
than Ca(OH)2.
CaO loss and the ratio of SO3/CaO are represented as
binary linear regression analysis on the complete data
set was made with the reduction rate of strength R as the
dependent variable and CaO loss and the ratio of SO3/
CaO as the independent variables, and the results were
shown in Table 5, where YP and YS represent the
reduction rate of compressive strength of P and S,
respectively, X1 is the ratio of SO3/CaO in the hardened
cement paste, X2 is CaO loss rate (%).
The high correlation coefcients indicate that the
main reason for the decrease of strength of the concrete
specimens is the CaO loss and increase of sulfur content
in the hardened cement paste of the concrete specimens.

3.5. The relationship among strength decrease, CaO loss
and the ratio of SO3/CaO
As mentioned above, the hardened cement paste
consists of hydrated calcium salt, silicate, calcium
aluminosilicate and Ca(OH)2 and the strength is created
by adhesion between those compounds. So, any change
of structure, due to CaO loss and uptake of sulfur
compounds in the hardened cement paste of the concrete
specimens must affect the strength. The decrease in
strength is mainly caused by Ca(OH)2 loss with caking
4. Conclusions
The experimental results show that the trends in
results obtained by soaking and spraying methods are
consistent with each other, which indicate that the
methods are comparable and the results are reliable for
application to simulation of corrosion in building
materials by acid rain. However, corrosion rate is higher
in the soaking method compared to the spraying
method, resulting in the difference in data obtained by
these two methods, i.e. the corrosion process observed
by periodic soaking method is developing more rapidly
 ARTICLE IN PRESS
S. Xie et al. / Atmospheric Environment 38 (2004) 44574466
Table 5
The binary linear regression function between Rd and CaOd and the SO3 to CaO ratio
Periodic soaking method
Binary linear regression function Correlation coefcient F(2,3) Binary linear regression function Correlation coefcient F(2,3)
YP 3:14 44:82X1 0:77X2 0.991 77.85 YP
6:92 81:64X1 0:85X2 0.802
YS
18:93 33:74X1 0:91X2 0.950 13.90 YS
52:0 107:7X1 1:45X2 0.888
Note: Y: Rd %, X1: SO3/CaO, X2: CaOd%.
than that by spraying method. So the soaking method is
suitable to perform a fast test on corrosion of cement
concrete by acid rain while the spray method takes more
time but is much more similar to the natural process and
hence more suitable to investigate the effect of acid rain
on concrete more realistically.
Based on the experiment results it is concluded that
H+ in acid rain dissolves Ca(OH)2 in the hardened
cement paste and that SO2
4 also corrodes it. The
dissolution effect of H+ will lead to the reduction of
Ca(OH)2 concentration in the concrete specimens. The
change of neutralized depth of the concrete specimen
caused by H+ in acid rain can be expressed as a power
function of exposure time.
The corrosion of SO2

4 produces the substances which
are larger than Ca(OH)2 in volume such as Ca3A-
l6O12  CaSO4 and CaSO4  2H2O, leading to a large
reduction in strength. Yan et al. (1997) has reported
expansion of Portland cement mortar due to internal
sulfate attack too. The relationship between the reduc-
tion rate of strength, and CaO loss rate and the ratio of
SO3/CaO can be described as a binary linear correlation.
If only compressive strength is concerned, slag cement is
more resistant than Portland cement as can be seen in
Fig. 2. So if considering the harm to concrete by acid
rain, it is more suitable to produce nonmetal building
materials with slag cement for construction in those area
of China which are exposed to severe acid rain.
Acknowledgements
We would like to express our sincere thanks to Mr.
Sjaak Slanina for his kind suggestions on the language
construction and valuable remarks.
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