Materials and Structures (2012) 45:337–350
DOI 10.1617/s11527-011-9769-y
ORIGINAL ARTICLE
Identification of acid attack on concrete of a sewage system
I. Fernandes • M. Pericão • P. Hagelia •
F. Noronha • M. A. Ribeiro • J. Maia
Received: 27 September 2010 / Accepted: 27 July 2011 / Published online: 11 August 2011
 RILEM 2011
Abstract A sewage system, 300 km long, showed
superficial deterioration of concrete just 2 years after
construction. In order to re-habilitate the structure, it
was necessary to identify the main mechanism of
deterioration and to understand the heterogeneous
distribution of the damage observed. The study was
performed in a three stepped program: site investi-
gation and sampling, laboratory tests and concrete
petrography. During the site inspection it was recog-
nized that there was dissolution of the concrete in
Paper presented at the 12th EMABM—Euroseminar on
Microscopy Applied to Building Materials, Dortmund, 2009.
I. Fernandes (&)
F. Noronha
M. A. Ribeiro
Centro de Geologia/DGAOT, University of Porto, Porto,
Portugal
e-mail: ifernand@fc.up.pt
F. Noronha
e-mail: fmnoronh@fc.up.pt
M. A. Ribeiro
e-mail: maribeir@fc.up.pt
M. Pericão
J. Maia
Instituto de Soldadura e Qualidade, Porto, Portugal
e-mail: mspericao@isq.pt
P. Hagelia
Technology Department, Norwegian Public Roads
Administration, Oslo, Norway
e-mail: per.hagelia@vegvesen.no
some sectors of the structure, with the aggregate
particles protruding in relation to the undulated
surface. In some places a white to yellowish putty-
like product could be excavated by hand. The main
deterioration was observed above the water level. The
composition of the atmosphere inside the sewer was
assessed and a high content of hydrogen sulfide was
detected. Sampling was performed in different struc-
tural elements which showed diverse exposition to
the aggressive environment. Impregnated thin sec-
tions of concrete with fluorescent yellow dye were
analyzed by optical microscope. Concrete petrogra-
phy showed to be crucial for the diagnoses. The study
showed that the putty-like product was composed by
gypsum with small residual particles of siliceous sand
which resisted to the acid attack. SEM/EDS was used
to evaluate the content of sulfur in different sections
of the concrete cores and also to characterize the
putty-like product at the surface of the concrete. This
study led to the confirmation of the presence of an
extensive sulfuric acid attack with rather minor
sulfate attack within the concrete due to the exposi-
tion to aggressive environment. It also showed that
behind the superficial deteriorated level, the concrete
was sound with no signs of internal deleterious
reactions. Ammonium content in residual water
might have also contributed to the superficial dete-
rioration of the concrete sewer.
Keywords Acid attack
Gypsum
Popcorn calcite
deposition
Concrete petrography
338
1 Introduction
The present work refers to a sewage system covering
11,000 ha, which is located in central Portugal. The
system receives the urban residual wastewater and the
effluents from industry existing in the area. It started
working in 1999 and it was further developed until
2004, finally covering twelve municipalities and one
million inhabitants.
The wastewater system is more than 300 km
long and is composed of 17 collection points, a
number of pipes, vertical wells and manhole, more
than 30 pumping stations, transition and pressure
chambers, treatment plants and a trunk sewer into
the sea.
Just 2 years after the completion of the construc-
tion some damage on the concrete walls was
detected by the system owner. In 2008 a site
inspection of the sewage system covered 40 concrete
elements with sampling, analyses and diagnose
made in 19 elements. A total of 218 tests and
analyses was carried out (in each element, one
sample was collected of residual water and gaseous
effluent). The study developed showed that there are
different degrees of deterioration and that about 50%
of the concrete elements in the structure are
damaged. The most serious deterioration occurred
on the concrete walls of one of the interceptors,
close to the treatment plant.
Concrete was sampled by coring in order to
perform petrographic analyses and to identify the
causes of deterioration. The petrographic analyses
based on meticulously impregnated thin sections
showed to be crucial for the identification of the
mechanisms and the extent of the damage.
Table 1 Concrete mix used
for pumping stations
construction (D = 25 mm, Natural sand 4.76–0.149
values in kg/m3 of dry
materials) Crushed sand 4.76–0.149
Coarse aggregate 12.7–4.76
Coarse aggregate 25.4–12.7
CEM II/A-L 42.5R
Fly ash
Plasticizers
Fluidifiers
Materials and Structures (2012) 45:337–350
2 Materials and methods
Strength class of C35/45 was used in the construction
of the concrete elements in contact with residual
water. The mixes are defined on Table 1, based on
data from the supplier, which include the information
about the exposure conditions considered in the
design of the structure according to Portuguese
standards at the time of construction [5, 6]—EQ2
for moderate aggressive chemical environment.
Because the exposure classes for concrete envi-
ronment defined on [5] were different from those
defined on LNEC E378:1993, a new addendum was
published—E378:1996—referring to the equivalence
between both. EQ2 is, according to the NP EN
206:2007, almost the same as XA2 (except in what
concerns the aggressive CO2 content, which range
was 91–200 and now is 40–100 mg/l).
The minimum values admitted in the design for
class C35/45 were of 51/55 MPa compressive
strength and the w/b ratio should be lower than
0.40–0.44.
According to the cement standards at the date of
construction, the CEM II/A-L used in the mixes had a
medium filler limestone content of 16%, which is
equivalent to a dosage of CEM I of 84% of the dosage
showed on Table 1 for CEM II/A-L. Using this
amount of CEM I with the content of fly ash (FA)
incorporated it can be concluded the cement used in
the mixes was equivalent to CEM IV, i.e., a pozzo-
lanic cement. Table 2 shows one annual average
chemical composition of the cement applied in the
structure for which values of 8.13 and 8.85% for C3A
and C4AF, respectively, were provided by the sup-
plier. Despite the structure was constructed for several
C35/45.S2.EQ2 C35/45.S3.EQ2 C35/45.S4.EQ2
360 420 455
330 290 255
380 420 470
670 590 530
315 325 335
110 110 110
– – –
4.9 5.0 6.1
Materials and Structures (2012) 45:337–350 339

Table 2 Average chemical composition of the cement (%) The tests performed in situ included:
Content (%) • Visual examination to identify surface defects.
SiO2 18.40 • Use of a small hammer in order to detect the
Al2O3 4.97 depth of deterioration related to spalling or
Fe2O3 2.98
dissolution of the concrete components.
CaO 60.45
• Evaluation of the Schmidt hardness of concrete in
MgO 2.31
depth, after removal of the deteriorated superficial
materials.
SO3 3.25
• Determination of the atmosphere composition
Others 0.01
mainly related to the safety of the team perform-
Loss on ignition 5.71
ing the inspections, namely, evaluation of H2S,
Insoluble residue 2.40
O2, CH4 and NH4?.
Samples were taken from the putty-like material
Table 3 Specifications of concrete regarding exposure con-
present at the surface of the concrete. They were
ditions according to Portuguese standards [6]
preserved in closed plastic bags for determination of
Aggressive chemical the composition and pH. A total of 21 concrete samples
environment
were cored with a drilling machine chilled by water
Exposure classes EQ2 circulation in order to perform a number of laboratory
Minimum binder content (kg/m3) (a) 360 tests. They were 94 mm in diameter and between 75
Maximum w/b 0.45 and 150 mm in length. The laboratory tests included:
Minimum strength class C35/45
• Evaluation of the chloride content to identify
Minimum cover to reinforcement (mm) –
chloride corrosion.
a
Defined for maximum size aggregate of 31.5 mm • Evaluation of the depth of carbonation by the
phenolphthalein test.
years and by different contractors, the concrete
• Chemical analyses of the gaseous and liquid
should be specified in accordance with Table 3
effluents (one sample from each element
characteristics.
diagnosed).
Aggregates were composed of crushed limestone
• Petrographic analyses of thin sections of concrete
for the coarse particles and siliceous natural sand.
from the different elements.
Crushed limestone was also used in sand dimension
• Scanning Electron Microscope (SEM)/Energy
in some of the structural elements. The concrete in
Dispersive Spectrometer (EDS) analyses of the
contact with residual water was coated-protected by a
soft material at the surface of the concrete walls.
bituminous epoxy resin in three layers with a
minimum of 150 lm each. Slices of the concrete were cut and glued with
The first step to assess the conditions of the epoxy resin and hardener to a glass slide to produce
structure was a site inspection to the sectors in which thin sections for petrographic analysis. Thin sections
the occurrence of deterioration was previously were produced with fluorescent yellow dye according
detected. The site inspection focused in the manhole to the instructions in NT Build 361 [19]. The thin
and the pumping wells but also included a subaquatic sections were observed under a polarizing micro-
inspection to the trunk sewer. scope with objectives 59, 109, 209 and 509 in
Due to the aggressive fluids and atmosphere inside order to detect and identify possible evidences of
the wells, special safety measures were adopted deterioration and deleterious internal reactions.
during the inspection. The technicians were protected In order to define the composition of the putty-like
with gloves, masks and special clothes. Pictures and product present at the surfaces of the concrete, two sets
movies were made of the different aspects detected in of samples were prepared for SEM/EDS analysis. One
the inspected sectors of the structure. Samples for set corresponded to the five samples received in plastic
analysis were taken from the liquid and gaseous bags. They were taken out of the plastic bags and left in
effluents. open air to dry. The other set of samples was composed
340
of small fragments scratched from the white powder
on the external facing part of the concrete cores and
also from the material occurring as rims around the
aggregate particles at the exposed surface. Small
pieces of each sample were glued with epoxy resin
and hardener to metallic cylinders 6 mm thick and
sealed in airtight containers. Within 4 days, the
samples were sent to the scanning electron micro-
scope laboratory, submitted to vacuum and coated
with gold, just before the examination. They were
examined under SEM/EDS using secondary electron
(SE) beams. The accelerating voltage used was 10
and 15 kV with a working distance of 15 mm. The
collection time for the microanalyses was 60 s with
a dead time of approximately 30%. The spot size
was around 10 nm to produce qualitative standard-
less analyses.
3 Results
3.1 Site inspection
The visual inspection led to the conclusion that there
were different intensities of deterioration in the
Fig. 1 Deterioration of the concrete observed by site inspection. In the most deteriorated sectors a putty-like product was sampled at
the surface of the concrete walls
Materials and Structures (2012) 45:337–350
structural elements (Fig. 1). The deterioration seemed
to be connected to different conditions of exposure
and oxygen availability.
The metallic pieces (ladder) used to access the
wells showed intense corrosion and there was spall-
ing of the bituminous lining. It was immediately
verified that the ventilation inside the sewer was
insufficient as well as deficient cleaning of the
elements and excessive turbulence in the income
flow. The degree of deterioration of the concrete was
highly variable and it was much more intense in the
walls above the water level in the sectors of the
sewage system showing deficient ventilation. The
superficial damage included:
• Superficial evidences of deterioration with efflo-
rescence, micro-organisms, slight cracking, exu-
dations in the concrete joints and popouts;
• Spalling, disintegration and softening of the
concrete involving both the cement paste and
the aggregate particles;
• A soft, putty-like product was detected which
could be removed by hand to a maximum depth of
38 mm. Behind this superficial material concrete
showed to be sound and compact, when tested
with a hammer.
Materials and Structures (2012) 45:337–350 341

The spalling of concrete led to the exposure of 3.2 Concrete cores

reinforcing steel bars. These showed corrosion and
local loss of cross section. The concrete cover of the A total of 21 samples of concrete were taken from
reinforcement steel bars, originally with 40 mm different areas in the manholes, chambers and wells
thickness, was also reduced in the most deteriorated to perform a number of tests in the laboratory.
locations but constant at the places with air circula- The cores had a ‘‘chemical’’ strong smell, as
tion. The worst damage occurred in the elements expected because they came from a sewage system.
located just after the pressure pipes. A particular The depth of carbonation was evaluated by the
situation was found at the inferior face of a concrete phenolphthalein alcoholic solution test. A maximum
slab with 120 mm of thickness, which reinforcement of 10 mm depth was registered. The chloride content
steel was completely destroyed (Fig. 2). The exterior was evaluated in different depths (0–20, 20–40,
upper face was totally sound, with no signs of 40–60 mm). The maximum was obtained in the layer
deterioration, which constitutes a threat to workers on closer to the exposed face (0–20 mm) and was of
the above level of the slab. 2.66% for the concrete.
The submerged concrete showed better preserva- The observation of the cores by naked eye showed
tion conditions. There was just slight deterioration of a concrete dominantly sound and compact but with
the walls in the sectors where ventilation occurred.
The use of the Schmidt hammer on the concrete
behind the soft material on the surfaces was influ-
enced by the irregularities of the surfaces (with Table 4 Minimum and maximum contents of the main com-
ondulations and aggregate particles protruding). ponents in gaseous effluents in 19 different locations of the
sewage system (one sample collected at each location)
Therefore, the results found varied from 9 to
25 MPa. However, when used on the surface of Gaseous effluent
healthy concrete, the average value obtained was of
Cl- (ppm) \0.025
51 MPa.
CO2 (%) N.D.–0.9
Chemical analyses were performed in the gaseous
CH4 (%) \0.046
effluent and also on residual water. The results
O2 (%) 17.4–20.9
obtained are presented in Tables 4 and 5.
CO (ppm) \3.3
The values of H2S in the gaseous effluent were
N2 (%) 81–85
obtained by two different methods and the maximum
N2O (ppm) N.D.–7.2
was of 204 ppm, showing a variable content along
H2S (ppm) 0–204a
the day. The maximum content of NH4? was of
0–159b
200 ppm in the residual water. The content of SO42-
Volatile organic compounds (ppm) Usually \9.4 Max 300
in the residual water was variable (14–290 ppm)
a
depending on the timing of the sampling. Values of Portable Analyser Gas Data GFM 430
b
pH in the residual water varied from 5.9 to 7.4. GC/FPD—Gas Chromatography/Flame Photometric Detector

Fig. 2 Deterioration of a concrete slab showing destruction of the reinforcement steel

342
Table 5 Minimum and maximum contents of the main com-
ponents in residual water in 19 different locations of the
sewage system (one sample collected at each location)
Residual water
Cl- (ppm) 68–2,400
SO42- (ppm) 14–290
Mg2? (ppm) 4.4–150
?
NH4 (ppm) 5.3–200
CO2 (ppm of CaCO3) 34–362
pH (20C) 5.9–7.4
different features on the exposed surface. Some of the
cores showed that the superficial bituminous lining
was intact but in ten of the cores the surface was
irregular, with cavities in the cement paste and the
aggregate particles protruding from the surrounding
cement paste. This irregular surface was lined by a
white putty-like product with a dusty appearance
when dry at ambient temperature (Fig. 3). Around the
aggregate particles there were halos a few millimeters
in thickness, being white in contact with the cement
paste and slightly orange closer to the particles.
The cores were cut lengthwise in order to allow the
observation of the concrete in the interior. The
concrete was sound and compact in all the cores,
without macrocracks.
Fig. 3 Concrete cores showing irregular exposed surface with dissolution of the cement paste and in some places with a white putty-
like product
Materials and Structures (2012) 45:337–350
3.3 Concrete petrography
The analysis of thin sections permitted the charac-
terization of aggregates. Coarse aggregates were
composed of oolitic and micritic limestones with
sparitic portions (Fig. 4). Fine aggregates included
sand from a natural deposit and are composed of
grains of quartz, grains of strained quartz with
subgrains, feldspar, shell fragments, mica, tourma-
line, epidote, opaque minerals and amphibole and
also some crushed particles of limestone. This sand
included microcrystalline quartz and subgrains in
siliceous rock fragments (Fig. 4).
In the impregnated thin sections with yellow dye it
was confirmed that crystals of gypsum occurred at the
surface of the more intensely deteriorated cores. There
was dissolution of the cement paste which was
partially replaced by gypsum. In some of the calcar-
eous aggregate particles dissolution was more intense
on the sparitic portions giving rise to empty spaces
(Fig. 5). In about half of the cores, halos around both
calcareous and siliceous aggregate particles were
observed, composed of gypsum in rims detached from
the particles. The thin sections showed that the attack
to the cement paste occurred in levels developing
parallel to the external face of the concrete, with some
spalling and parallel microcracks.
Materials and Structures (2012) 45:337–350
Fig. 4 Example of aggregate particles: oolitic limestone of coarse aggregate (left) (N//) and microcrystalline quartz in a fine
aggregate particle (right) (NX)
The interior of the concrete cores was also
observed. Carbonation of the cement paste was
identified, mainly in the cores showing intense
deterioration. A pattern of popcorn calcite deposition
(PCD) (Fig. 6) and some large calcite crystals were
also identified. These areas correspond to the brown-
ish cement paste in plane polarised light, probably due
to depletion of calcium hydroxide and the destruction
Fig. 5 Dissolution of the cement paste and of the calcareous
aggregate particles leaving empty spaces and residual siliceous
particles. In the left bottom image, particles of limestone were
343
of the components of the cement paste. The cement
paste was not homogeneous, showing in plane polar-
ised light different density and lighter colour close to
and between the aggregate particles. There were thin,
discontinuous microcracks along the interfaces
between the cement paste and the calcareous particles.
In other places, there was a rim of reaction with
diffuse interfaces with the limestone particles and a
partially replaced by gypsum. Thin section impregnated with
fluorescent yellow dye (N//)
344 Materials and Structures (2012) 45:337–350

darker brownish colour. However, microcracks in the
cement paste were scarce (Fig. 7) and they rarely cut
the aggregate particles. Abundant FA particles could
be identified. The air voids were not filled, except by
rare needle like crystals of ettringite.
To confirm the possible sulphate attack, EDS
qualitative point analyses were performed on thin
sections from different depths of the cores. It was
concluded that the content of sulphur was much
higher in the first millimeters of the cement paste,
when compared to the cement in the interior of the
cores. The transition between the affected surface
concrete and the sound inner concrete was abrupt and
ettringite crystals were scarce. No alkali-silica reac-
tion signs were identified.
3.4 Powdered and putty-like products
Two sets of samples of the putty-like products were
prepared for observation by SEM/EDS. The first set
was composed by both the white reaction product at
the surface of the cores and the material present in the
halos around aggregate particles. It was confirmed
that these products consist of gypsum and some
compounds with Si and Al, in different proportions
(Fig. 8). The characteristics of this Si–Al product
were variable in the samples examined. In one of
them there was a smooth surface with shrinkage
cracks resembling alkali-silica gel.
The second set of samples was composed by the
material of the five samples of the putty-like product
sampled in the site inspection from the surface of
the concrete and received in the laboratory. The
samples had an unpleasant smell of rotten eggs.
They showed a plastic behaviour when handled and
there were fine particles of sand among the muddy
material. Colour varied from white to yellowish.
Measurements of pH were performed with a Hanna
Hi255 Combineda Meter. The values obtained
varied from 1.5 to 2.9 in four of the samples. The
fifth sample, orange to brownish in colour, had a pH
of 7.5.

Fig. 6 Carbonation of the cement paste (left) and PCD (right image) (NX)

Fig. 7 Cracks in the interior of the concrete mainly in the interfaces cement paste-aggregate. There were just a few cracks crossing
the cement paste and some particles of aggregate. These thin sections were not impregnated with fluorescent dye (N//)
Materials and Structures (2012) 45:337–350
Fig. 8 Composition of the white product at the surface of
concrete and forming the halos of aggregate particles. Crystals
of gypsum are the most abundant compound and there is also
In order to identify the composition of this
material, small pieces were taken from the samples,
after having dried at ambient temperature (&20C)
for 5 days, and prepared for SEM/EDS analyses. It
was verified that this product was mainly composed
by gypsum crystals. A material composed of silicium
and some aluminum was also present, with no defined
habit or with vacuolar habit resembling silica gel
(Fig. 9).
4 Discussion
Although at the time of the design and construction of
the structure Portuguese recommendations were fol-
lowed to define the concrete characteristics, the data
present in Tables 1 and 3 show that the concrete to be
used in this aggressive chemical environment (with
the designation EQ2) is in conformity with the
limiting values in what concerns the minimum binder
content, the w/b ratio and the strength class. Never-
theless, the chemical results showed on Table 5 lead
to actual classification of an aggressive environment
345
some Al and Si remaining from the previous cement paste
(SE—Secondary Electrons SEM images and EDS spectra)
exposure not less than XA3, according NP EN
206-1:2007 [18].
It has been referred in literature that 20% of the
total damage in sewer systems is caused by sulphuric
acid or sulphate attack [12]. The surface of concrete
in sewer concrete elements is frequently deteriorated
when the atmosphere contains a high quantity of
hydrogen sulfide [25] in consequence of a process
designated as biogenic sulphuric acid attack (BSA)
[23, 28]. The bacterial and chemical activity in this
type of environment leads to a sulphur cycle resulting
in the ultimate formation of sulphuric acid. The first
phase of the process occurs under anaerobic condi-
tions below the flow line, especially when there is a
long residence time or slow flow in the sewage.
Under these conditions, bacteria that exist in the
wastewater, the mud at the bottom of the sewer
elements and in the slime layer formed on the wall
and situated below the water level reduce organic
bound sulphur compounds to H2S [28]. In the case of
turbulence, H2S escapes as gas into the headspace,
above the water level. This process is followed by an
aerobic process in which the H2S reacts with the
346
Fig. 9 Texture and composition of the putty-like reaction product sampled by hand during site inspection and which was sent in
plastic bags for analysis (SE—Secondary Electrons SEM images and EDS spectra)
oxygen and sulphur is deposited on the walls. Sulphur
is oxidised by bacteria such as Acidithiobacillus
thiooxidans [14] (previously referred to as Thioba-
cillus concretivorus by Parker [21]), to produce
sulphuric acid. The colonisation of such bacteria is
mainly sustained by low pH values and elevated
ammonium concentrations, and it is more aggressive
for lower pH environment such as that observed in
the present environment. The sulphuric acid formed
quickly corrodes the concrete at a rate dependent on
its concentration, the location within the sewage
system and the time over which the concrete is
exposed to the acid [13], resulting in a depth of
corrosion nearly proportional to the time of exposure.
In this process a dissolution of the cement paste
occurs and, in the case of the presence of limestone
aggregates, also dissolution of the aggregate particles.
In consequence a soft putty-like mass is formed,
leaving the less acid-soluble residual sand particles
embedded. In the biologically produced sulphuric
acid the soft layer creates excellent conditions for the
growth of the bacteria. Due to increased porosity, the
bacteria penetrates into the un-attacked concrete [16]
and the gypsum layer preserves the humidity,
protecting the bacteria from drying. In periods of
high loading, the velocity of the flow may disturb the
Materials and Structures (2012) 45:337–350
corroded area, drain out the decomposition products
and contribute to the development of the attack [32].
Regarding the considerations above and the
results published by other authors, it may be
concluded that the manifestations of deterioration
found during the site investigation in this sewage
system are compatible with the occurrence of acid
attack to concrete resultant from microbiological
activity. In fact, the tests performed in situ detected a
high content of H2S in the gaseous effluents, and the
conditions of low pH and high humidity found were
appropriate to the development of biological oxida-
tion to produce sulphuric acid. The deterioration
evidences were not the same in all the elements of
the sewage system but were concentrated in the
places were ventilation was not sufficient to keep a
‘‘clean’’ atmosphere. Also the content in ammonium
was very high. The deterioration was mainly
observed above the water level, as found by Assaad
Abdelmseeh et al. [1] in samples above the solution
level in laboratory experiments, and is more intense
just above the daily high water level, as referred by
Mori et al. [17]. The removal of the weakened
surface of the concrete leads to a higher rate of
corrosion in the sectors of the structure showing
higher turbulence.
Materials and Structures (2012) 45:337–350
The white to yellowish putty-like product found in
the most damaged places is similar to that referred by
other authors [4, 11, 13, 24, 26–28, 31, 32] and also
showed very low values of pH. This product is the
result of the reaction of the cement compounds with
the acid, with the dissolution of portlandite for a pH
of 12.5 and the precipitation of gypsum for pH
between 11.6 and 10.6 [22], using the Ca from the
cement paste and leaving other elements free to
produce silica gel (pH 8.8). In some places this gel
contains aluminum, as has been shown from the
results of SEM/EDS and also referred by Bertron
et al. [3]. The process of decalcification of the cement
paste under aggressive environment was proved by
Bertron et al. [3] in experiments with organic acids,
in which the authors describe the zones formed close
to the exposed surface.
In this sewage system, coarse aggregate particles
were composed by limestone, also soluble by acids.
Due to their composition, the limestone aggregates
might have also created a buffering environment
protecting the cement paste [30]. Although they were
attacked at a lower rate than the cement paste and are
now protruding in the exposed concrete surfaces, they
show a rim of reaction composed by gypsum and
some of the particles close to the exposed surface are
broken and partially replaced by gypsum. The
development of the crystals of gypsum along the
interfaces between the cement paste and the aggre-
gate particles led to the debonding and the reduction
of concrete strength, as already referred in Tulliani
et al. [27]. The existence of thin microcracks partially
surrounding the aggregate particles, as observed in
the concrete from the interior of the cores, far from
the corroded surface, might have promoted the easier
inflow of the fluids and the acid, due to local
increased permeability.
The reaction between the gypsum and the calcium
aluminate in the cement paste forms ettringite [16]
and, under certain circumstances, thaumasite [27]
which can also contribute to deterioration of the
concrete mix. This might be the consequence of a
combined action of acid and sulphate attack (cf. [9].
However, the petrographic analysis did not confirm
this in the present case as just a few secondary
ettringite crystals were identified in voids. Apparently
the externally derived sulphate did not penetrate
deeply into the more sound domains of this concrete,
which upon reaction with CSH and limestone
347
carbonate should have caused extensive thaumasite
formation and even thaumasite sulphate attack.
Nevertheless the thin section showed levels of
intense ordinary carbonation of the cement paste.
This carbonation occurs behind the deteriorated
surface. Coarser calcium carbonate was also identi-
fied in some areas of the thin sections, showing a
distribution similar to PCD [10]. This, together with
the elevated micro porosity of the outer cement paste
and the brownish colour observed in plane polarised
colour light indicates that there is a depletion of
calcium hydroxide [24], just behind the acid deteri-
orated surface. It may be concluded that the very
strong acid attack at pH B 2 did not facilitate the
formation of thaumasite sulphate attack deeper inside
the concrete. This was likely due to the extremely
steep pH gradient, which led to complete destruction
of the outer cement paste matrix upon sulphuric acid
dissolution and formation of an extensive gypsum
mush which likely trapped most of the available
sulphate. This coating of gypsum may have slowed
down the corrosion. In fact, according to some
authors, the formation of gypsum leads to a protective
layer which slows down the process of deterioration
[7, 15].
Taking into account the composition of the
concrete, it must be referred that the use of FA has
been studied by a number of authors. Kawai et al.
[13] performed a number of experiments and con-
cluded that specimens containing FA showed a
smaller depth of deterioration when exposed to acids
than those containing no mineral mixtures, due to the
lower permeability and lower content of calcium
hydroxide [2, 32]. The use of supplementary cemen-
titious materials such as silica fume and FA was
referred by Mehta [15] to improve the resistance of
concrete to acid attack because of reduced presence
of calcium hydroxide. However, [20] refer that the
strong leaching of samples in laboratory experiments
containing FA shows the bad performance of these
samples in acetic acid solution. These authors found
that metakaolin samples and those containing blast
furnace slag present a better resistance to the acid
attack. The concrete applied in the investigated
structure was made with FA, which should therefore
to some extent counteract the acid attack. However,
calcium aluminate cement based concretes would be
the most appropriate to resist the biogenic corrosion
[8, 23] as a high aluminium ions concentration
348
impairs the bacteria multiplication and keeps the pH
stabilised around 3–4. This pH leads to a slower
growth of the bacteria, with lower production of
sulphuric acid. Also, the calcium aluminate cement
presents a degree of toxicity towards bacteria.
Fourie and Alexander [8] concluded that the use of
silica fume and the size of the aggregate particles
influence the resistance of the siliceous aggregate
concrete, concluding that the addition of silica fume
to the mixture improved the binding of the aggregate
particles.
Concerning the w/b ratio, [7, 16] found that in
order to obtain a concrete mix relatively resistant to
different degradation mechanisms a low cement
content and w/b ratio below 0.4 should be used. [1]
also developed work with different concrete mixes.
The authors state that lowering the w/b ratio implies
the increase in cement content thereby increasing the
tricalcium aluminate and decreasing resistance of the
concrete. The use of supplementary cementitious
materials contributes to the properties of concrete
through hydraulic or pozzolanic activity.
In this concrete the w/b ratio was bellow the
recommended 0.45 value at the time of construction.
This fact is, however not consensual, as higher w/b
ratio indicates the existence of more voids and, there-
fore, should better accommodate the expansion due to
the growth of gypsum [13] and the lower w/b concrete
would erode earlier. But lower w/b contributes to the
decrease in permeability and reduces porosity. In fact, it
seems that there is no satisfactory type of cement and
concrete mix offering a long-term resistance to acid
attack [32]. As referred by Saucier and Lamberet [23],
even in a well designed sewer network there is probably
5–10% of the length that will be exposed to biogenic
corrosion. Probably more emphasis should be given
on the protective coating material, as studied by
Vipulanandan and Liu [29].
5 Conclusions
A case history of acid attack on a long sewage system
was reported. This study suggests that the deteriora-
tion of the concrete was due to acid attack related
with microbiological processes and the presence of
aggressive compounds in the residual water and in the
gaseous effluent. The aggressive exposure conditions
were possibly underestimated and difficult to preview
Materials and Structures (2012) 45:337–350
during the design of the structure. Although the
distribution of deterioration is random when a map of
the all structure is considered, from the 19 elements
in which samples have been collected and analyses
performed, the eight elements showing strongest
deterioration evidences were those in which aeration
was deficient. In the worst cases, both the epoxy
coating and the concrete were damaged.
The speed and extent of reaction indicates that
bacteria might have been involved promoting the
formation of H2SO4. To define the cause of deteri-
oration, the tests performed in situ and the petro-
graphic analyses were essential. It was confirmed
both by optical microscopy and SEM/EDS that the
putty-like product on the surfaces showing the most
severe deterioration was composed of gypsum with
portions of silica gel and residual siliceous particles
of aggregate. The acid not only dissolved the cement
paste but also attacked the limestone aggregate
directly. The gypsum crystals developed perpendic-
ularly to the border of the particles and attacked
preferentially the portions with sparitic calcite, as was
shown by the microphotographs. The siliceous
aggregate particles were not attacked but also showed
a rim of gypsum surrounding the particles. Most of
the cement paste was dissolved on the first few
millimeters of the concrete cores, leaving empty
spaces between the gypsum crystals. Ettringite was
locally detected within the sounder concrete behind.
In the cement paste there were areas depleted in
calcium hydroxide and textures of PCD were iden-
tified, compatible with deterioration by sulphate
attack or leaching in presence of a carbonate source.
Although there was not a large quantity of ettringite
the features referred are compatible with the simul-
taneous action of acid and sulphate attack to the
concrete. In the present case sulphuric acid attack was
greatly predominating although the concrete compo-
sition included FA, supposed to retard the effect of
the acid attack and the w/b ratio was lower than that
recommended to resist deterioration.
As rehabilitation measures it was recommended
that the deteriorated concrete surfaces and the lining
were washed out by the use of water jet, the
deteriorated concrete removed and replaced by new
concrete. Also the reinforcement steel should be
repaired and concrete cover rebuilt. It was decided
that a periodic cleaning would be mandatory, as well
as a guarantee of circulation of the air. The team
Materials and Structures (2012) 45:337–350
recommended that measures were taken to decrease the
velocity and turbulence of the inflow of wastewater in
order to avoid mechanical corrosion of the concrete
walls and that a chemical product was applied to
decrease the content in H2S. Also, in order to limit the
activity of bacteria, a calcium aluminate lining or a
lining resistant to acid attack should be used.
Acknowledgements Authors are particularly indebted to the
companies involved in the study for the permission to publish
these results. The research was developed in the scope of the
GeoREMAT Project, of the Centro de Geologia da
Universidade do Porto, funded by FCT, Fundação para a
Ciência e Tecnologia. The analyses by SEM/EDS were
performed at CEMUP which equipment was funded by the
projects REEQ/1062/CTM/2005 and REDE/1512/RME/2005
of FCT, Fundação para a Ciência e Tecnologia. Authors are
also grateful to Professors Josée Duchesne, Özge Andiç-Çakir
and Armando Camelo for the revision of this paper and for the
very constructive comments.
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