Cement and Concrete Composites 104 (2019) 103358

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Cement and Concrete Composites

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Coupled effects of carbonation and bio-deposition in concrete surface T

treatment
Jing Xua,b,*, Xianzhi Wangb, Wu Yaob
a
State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology), 122 Luoshi Road, Wuhan, 430070, PR China
b
Key Laboratory of Advanced Civil Engineering Materials (Tongji University), Ministry of Education, 4800 Caoan Road, Shanghai, 201804, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: This paper reports the coupled effects of carbonation and microbially induced carbonate precipitation (MICP) on
Bio-deposition behaviors in relation to the durability of concrete. Liquid immersion and semi-solid immobilization methods
Surface treatment were compared for their effectiveness in bio-deposition treatment. After bio-deposition, the reduction ratio of
Carbonation water sorptivity coefficient for carbonated concrete was higher than that for untreated concrete; In contrast, the
Transport properties
reduction ratio of water permeability coefficient for carbonated concrete was lower than that for untreated one.
Bacteria
An analysis based on a simple model helps to explain this phenomenon. It shows that the water absorption was
related to both the pore structure and the wettability of concrete surface, while the water permeability depended
solely on the pore structure of concrete. Similar effectiveness of bio-treatment were obtained from liquid im-
mersion and semi-solid immobilization methods, whereas the latter appears more promising in field application.

1. Introduction
Concrete is the most used construction material owing to its wide
range of raw material sources, flexibility in casting, and durability. If
correctly designed and carefully produced with strict quality control,
concrete is capable of serving for decades without any maintenance and
protection. However, it could still be eroded in harsh environments,
such as marine and saline-alkali areas. Highly corrosive species will
react with the surface layer of concrete, increase the porosity, and result
in spalling [1]. Ingress of these substances will further lead to an ad-
verse performance of the major components including aggregate, paste,
or reinforcement by either physical or chemical attack [2]. Unless
certain precautions are taken, degradation or even disintegration of
concrete may occur eventually.
Therefore, it is necessary to protect the concrete on surface and
improve the permeation resistance of the material under harsh condi-
tions. Surface treatment has been utilized as an effective method for
protection and consolidation on concrete surface. It plays an important
role in limiting the uptake of water, and consequently diminishing the
penetration of corrosive species. Up to now, various types of products
such as water repellents, protective coatings, and pore blockers are
available on the market [3]. These products are usually supplied in
organic forms. Besides the health and environmental risks, organic
compounds are intrinsically incompatible with the underlying concrete
layer due to the difference in thermal expansion coefficient [4–6]. They
may need constant maintenance because of delamination and de-
gradation over time.
Recently, some alternative methods have been proposed to offset
the disadvantages of conventional treatments. Among these methods,
microbially induced carbonate precipitation (MICP) has become one of
the most attractive strategies owing to its ecological friendliness and
sustainable aspects [5–9]. Under suitable conditions, a large number of
bacteria can form mineral crystals through microbial metabolic path-
ways, and it is also referred to as bio-mineralization. Calcite, which is
highly compatible with concrete compositions, is produced in most
cases [10–13]. In general, the occurrence of MICP involves various
microorganisms, pathways and environments [14–16]. Considerable
works have been conducted on studying carbonate precipitation via
enzymatic hydrolysis of urea by using ureolytic bacteria [17–21]. Urea
is decomposed into ammonium and carbonate by urease as produced by
bacteria, resulting in a significant increase of pH and carbonate con-
centration. The reaction rate of biological urea hydrolysis is approxi-
mately 1014 times faster than the un-catalyzed rate. In the presence of
Ca2+, precipitation of CaCO3 occurs if the system is oversaturated,
while bacterial cells could serve as nucleation sites [22–24].
The ureolysis-based MICP has already been used for bio-cementa-
tion of soil, ground improvement, rehabilitation of ancient monuments,
remediation or self-healing of concrete structures, etc. [25–34]. As for

*
Corresponding author. State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology), 122 Luoshi Road, Wuhan, 430070, PR
China.
E-mail address: 09105@tongji.edu.cn (J. Xu).

https://doi.org/10.1016/j.cemconcomp.2019.103358
Received 29 March 2019; Received in revised form 25 June 2019; Accepted 26 June 2019
Available online 27 June 2019
0958-9465/ © 2019 Elsevier Ltd. All rights reserved.
J. Xu, et al.
surface treatment of concrete, prior researches have shown that the
resistance to water uptake, air permeation, and chloride migration
could be enhanced by the bio-deposition treatment with MICP, while
the effectiveness was even comparable to conventional treatments
[5,6,8,9,35,36]. Nevertheless, we noticed that the effects of carbonation
have not been taken into account previously. For most concrete struc-
tures in service, carbonation occurs in varying degrees. The pore
structure, chemical composition, and wettability of concrete surface
layer can be altered by carbonation [37–39], which will have a sig-
nificant impact on the bio-deposition by MICP.
In the present study, ureolytic type bacterial surface treatment was
conducted on concrete with or without carbonation. Degradation pro-
cesses of concrete were determined in terms of transport tests. Coupled
effects of carbonation and bio-deposition were investigated.
Additionally, different types of bio-treatment were compared to find
out the one with potential application aspects.
2. Materials and methods
2.1. Preparation of concrete specimens
The concrete mixtures were designed to achieve compressive
strength of 40 MPa at 28 days. The mix proportion of concrete (in mass)
was water (0.48): cement (1.00): fine aggregate (1.39): coarse ag-
gregate (2.24). Ordinary Portland cement (P·O 42.5, Conch Co., Ltd,
China) was used in this study. Local natural sand (0–5 mm) with bulk
specific gravity and fineness modulus of 2.65 respectively 2.88 was
used as fine aggregate. Crushed gravel (5–10 mm) with bulk specific
gravity of 2.7 was used as coarse aggregate.
Cylindrical specimens with a dimension of 100 mm and a height of
50 mm were prepared for capillary water absorption and rapid chloride
penetration (RCP) tests, while cylinders with a dimension of 46 mm and
a height of 100 mm were prepared for water permeability test. The
specimens were cured in saturated Ca(OH)2 solution at 25 ± 2 °C for
28 days prior to the drying in an oven at 70 °C until the mass loss was
less than 0.1%. The side opposite to the troweled face was polished by
sand papers to remove the paste on the surface layer. The remaining
sides were covered with a gas-tight paint. All the specimens were
weighed before treatments. Table 1 shows the experimental arrange-
ment of different treatments.
2.2. Carbonation treatment
For each size of the specimens, one half of the amount were put into
a closet (25 ± 2 °C, R.H. of 70 ± 10%, CO2 concentration of 20%) for
an accelerated carbonation procedure, while the other half were stored
in an airtight desiccator for further use. After three days of carbonation,
three cylinders for each size were randomly chosen, cut normal to the
exposed surface, and sprayed with phenolphthalein solution to de-
termine the carbonation depth. Six measurements were recorded on
each specimen and the average carbonation depth was determined as
1.60 ± 0.48 mm. Weight increase was recorded after carbonation.
Table 1
Summary of arrangement of different treatments.
Group Subgroup Treatment
Reference N/A Untreated
Bio-deposition Liquid Treated by
Semi-solid Treated by
Carbonation N/A Treated by
Bio-deposition after carbonation Liquid Treated by
Semi-solid Treated by
2
Cement and Concrete Composites 104 (2019) 103358
2.3. Bio-deposition treatment
2.3.1. Bacteria and growth conditions
S. pasteurii DSM 33 purchased from the China General
Microbiological Culture Collection Center (CGMCC) was used
throughout. The bacteria were first cultured in liquid media consisted
of 5 g peptone, 3 g beef extract, and 20 g urea per liter of distilled water.
The media were sterilized by autoclaving for 20 min at 121 °C and then
cooled to room temperature (25 ± 2 °C). According to the supplier's
recommendation, urea was separately sterilized by filtration through a
sterile 0.2 μm filter. Final pH of the media was adjusted to 7.0. Cultures
were aerobically incubated at 30 °C on a water-bath shaker operated at
130 rpm for 48 h. Growth was regularly checked quantitatively by an
optical microscopy. At the end of incubation, cells were harvested by
centrifuging the culture (4000 rpm, 25 °C) for 10 min and resuspension
in sterile saline solution (0.15 M NaCl). Before the treatments in liquid
and semi-solid cultures, a layer of bacterial strains (3 × 108 cells/mL)
with volume of 10 mL respectively 2.1 mL was applied on the polished
side of the concrete cylinders with sizes of 100 × 50 mm and
46 × 100 mm.
2.3.2. Treatment in liquid culture
Liquid calcium-containing media, which consisted of 5 g peptone,
3 g beef extract, 20 g urea, and 120 g Ca(NO3)2·4H2O per liter of dis-
tilled water, were used for the bio-deposition. Liquid culture was ob-
tained by inoculating pure bacteria to the sterilized media that the final
cell density achieved 107 cells/mL. Treatment was processed by
ponding the liquid culture of volume 15 mL respectively 3.2 mL on the
polished top side of concrete cylinders with sizes of 100 × 50 mm and
46 × 100 mm. Aluminum foil was attached peripherally to the upper
edge of the specimens with a water-proof adhesive to prevent the media
from leaking. The specimens were cured in an ambient condition
(25 ± 2 °C, R.H. 60 ± 10%) for 7 days to observe the effect of pre-
cipitation. Liquid media of 1 mL were added each day to compensate
liquid uptake by the specimens and water evaporation.
2.3.3. Treatment in semi-solid culture
For the semi-solid culture, 2% agar was added to the sterilized li-
quid calcium-containing media and then bacterial strains were in-
oculated to achieve a final cell density of 107 cells/mL. Treatment was
processed by brushing the cooled molten semi-solid culture on the
polished side. The applied volume was the same as that for the liquid
culture. The specimens were also cured in the same ambient condition
for 7 days and liquid media of 1 mL were supplemented each day during
the period.
At the end of bio-deposition, the liquid or semi-solid cultures were
removed by repeatedly washing in 60 °C distilled water. This process
ensured the removal of fragments or debris while keeping the pre-
cipitates intact. All the specimens, including the ones without any
surface treatment, were again dried in the oven at 70 °C until the mass
loss was less than 0.1%. The specimens were weighed again to de-
termine the mass increase after treatment.
Abbreviation
Ref.
bio-deposition in liquid culture Bio. L
bio-deposition in semi-solid culture Bio. S
accelerated carbonation C
bio-deposition in liquid culture after carbonation C Bio. L
bio-deposition in semi-solid culture after carbonation C Bio. S
J. Xu, et al.
2.4. Contact angle measurement
The sessile drop method coupled with a digital image analysis were
used to determine the contact angle on the top side of concrete cylin-
ders after treatments. A water drop with a volume of 40 μL was placed
on the surface. The image of the drop profile was analyzed by the
software of Image-Pro Plus. Values of contact angle were taken by
average of 5 measurements randomly chosen on each sample surface.
2.5. Transport tests
Transport tests include capillary water absorption, water perme-
ability, and RCP were carried out at 25 ± 2 °C and at R.H. 60 ± 10%.
Before the tests, the gas-tight paint on the troweled face was removed
by sand papers to ensure a free exposure of the two opposite sides. In
each group, triplicate samples were used.
2.5.1. Capillary water absorption
The water uptake capacity after surface treatment was evaluated by
capillary water absorption. Cylindrical specimens with size of
100 × 50 mm were submerged in water, 35 ± 2 mm deep, with the
treated side facing downwards but elevated above with supports at each
corner of the specimens. An unidirectional absorption through the
treated side can be ensured, for the specimens were coated at the four
edges adjacent to the treated side. The water level was kept constant by
an addition of water. The mass change was recorded at regular time
intervals. A wet towel was used to remove the remaining water droplets
on the surface before weighing. Results of the water absorption were
quantitatively evaluated by the sorptivity coefficient k polishing of about 1 h. The section including the surface treatment edge
[g·cm−2·min−0.5] which was calculated as
Q
= k⋅ t
A (1)
where Q is the amount of water absorbed [g], A is the cutting section
area of the specimen that was in contact with water [cm2], t is the time
[min]. After the last measurement a full saturation was established by a
vacuum injection. The specimens were first kept in a vacuum chamber
(~0.8 kPa for 3 h) and then submerged in water for 18 h. The surface-
dry weight of the specimens was recorded after saturation. The incre-
ment of water by vacuum saturation is regarded as the porosity of the
concrete. Following this vacuum saturation, specimens were used for
RCP test.
2.5.2. Water permeability
The water permeability test was conducted on the specimens with
size of 46 × 100 mm. The cylinders were first fixed into the perme-
ability test rigs, which were installed in a concrete permeability device
for testing. Water head equivalent to 1 MPa was applied on the treated
side of the cylinders. The pressure was released after 24 h. All the
specimens were taken out from the rigs and axially split into two halves
to measure the water penetration depth. The mean value was calculated
by six equidistant spots along each section of the split specimens. The
relative permeability coefficient kr [mm/h] was determined by
εD 2
kr =
2tH (2)
where ε is the concrete porosity which is determined as 0.03 by the
vacuum saturation as mentioned above, D is the water penetration
Table 2
Mass increase and surface contact angle after surface treatments.
Group Ref. Bio. L Bio. S
Mass increase (g) N/A 0.60 ± 0.07 0.44 ± 0.06
Contact angle (°) 86.0 ± 1.7 90.8 ± 7.2 79.5 ± 3.1
3
Cement and Concrete Composites 104 (2019) 103358
depth [mm], and H is the water head [mm] holding for a period of time
t [h].
2.5.3. RCP
The resistance towards chloride migration was measured by means
of the RCP test according to the ASTM C1202-17. The cylinders with
size of 100 × 50 mm after a full saturation were inserted into a test cell
accompanied by two copper meshes and sealed tightly. The reservoir of
the cell connected to cathode and anode terminals were filled with 3%
NaCl solution respectively 0.3 N NaOH solution. Conductivity of the
specimens was measured by a power supply with a potential of 60 V d.c.
applied. Current and temperature were recorded every 10 min over 6 h
test period. The total charge passed Qc [coulomb] was calculated by
Qc = 900(I0 + 2 ∑ It ) (3)
where I0 is the initial current reading [ampere]. and It is the current at t
minutes after the voltage is applied [ampere].
2.6. Visual inspection
After transport tests, specimens were broken up. Pieces containing
the portion with carbonation or bio-deposition treatments were then
collected. For bio-deposition, the composition at a certain depth is the
main interest. Thus, the cutting section of the pieces was first embedded
in epoxy resin and then ground on SiC papers of 360, 800, 1200, and
3000 fineness. Ethanol was used as the cooling and lubricating medium.
For each grade, approximate grinding time was 5 min. After grinding,
0.25 mm oil-based diamond particle suspension was used for the final
was observed by a metallographic microscope (Hirox rh-2000).
2.7. XRD/SEM/EDS analysis
Precipitates were scraped from the treated surface and ground into
powder. X-ray diffraction (XRD, Rigaku D/MAX 2550VB3) analysis was
performed on the powder with a Cu anode (40 kV and 100 mA) and
scanning from 5° to 75° 2θ. Precipitates were analyzed by scanning
electron microscopy (SEM, FEI Nova NanoSEM 450) coupled with en-
ergy dispersion spectrum (EDS) on both top and section sides. For EDS
analysis on the section side, five test points were selected in a straight
line from top to interior of the specimens. The spacing between each
point was 5 μm.
3. Results
3.1. Mass increase
When compared with the untreated specimens, a mass increase was
found after treatment by bio-deposition or carbonation. However, the
difference of mass increase was not significant among the groups
treated by bio-deposition and carbonation. An additional mass increase
of 0.2–0.4 g was observed by bio-deposition performed after carbona-
tion (Table 2).
3.2. Contact angle
The bio-deposition in liquid culture and semi-solid culture resulted
in a slight increase respectively a decrease of contact angle on the
C C Bio. L C Bio. S
0.52 ± 0.08 0.84 ± 0.14 0.76 ± 0.10
58.0 ± 5.0 84.2 ± 2.6 70.2 ± 5.3
J. Xu, et al. Cement and Concrete Composites 104 (2019) 103358

0.14 Ref. 0.0020

Bio. L
0.12 Bio. S
C
Water absorption (g/cm2)

C Bio. L 0.0015
0.10
C Bio. S

k (g·cm-2·min-0.5)
0.08

0.0010
0.06

0.04
0.0005
0.02

0.00
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0.0000
Ref. Bio. L Bio. S C C Bio. L C BIo. S
Time (min)
Fig. 2. Results of capillary water absorption as indicated by sorptivity coeffi-
Fig. 1. Effect of carbonation and biodeposition on the capillary water absorp-
cient.
tion of concrete.

3.0x10-6
concrete surface. In contrast, the carbonation resulted in a sharp de-
crease of contact angle. Further bio-deposition on the carbonated con-
crete seemed to increase the contact angle, especially in liquid culture 2.5x10-6
(Table 2). Since a higher contact angle indicates lower wettability, the
results showed that bio-deposition is likely to reduce the wettability of 2.0x10-6
carbonated concrete.
kr (mm/h)

1.5x10-6
3.3. Transport properties

3.3.1. Capillary water absorption 1.0x10-6

Concrete treated by bio-deposition resulted in a decrease of water

absorption rate. Accelerated carbonation group showed slightly higher 5.0x10-7
water absorption rate as compared with bio-deposition. When the bio-
deposition was conducted after carbonation, a further reduction of
0.0
water absorption was observed (Fig. 1). Ref. Bio. L Bio. S C C Bio. L C BIo. S
The value of the sorptivity coefficient k decreased by 25.6% after
Fig. 3. Results of water permeability as indicated by relative permeability
carbonation process. This is lower than the percentage of reduction by
coefficient.
bio-treatment in liquid and semi-solid cultures, which were 45.8% re-
spectively 34.5%. If the carbonated specimens were taken as control,
reduction of k values by 55.7% respectively 46.5% were obtained for 4000
further bio-treatment in liquid and semi-solid cultures (Table 3).

3.3.2. Water permeability 3500

Water permeability test was carried out by applying a constant
Qc (Coulomb)

water pressure on the specimens and holding for 24 h. The lower the
water permeability coefficient, the higher the resistance to the water
permeation. It revealed that both bio-deposition and carbonation im- 3000
prove the resistance towards water permeation significantly (Fig. 3).
The relative permeability coefficient kr decreased by 46.6% after car-
bonation. In contrast, the values of kr decreased by 63.1% respectively
81.5% for bio-deposition in liquid and semi-solid cultures. If the car- 2500
bonated specimens were regarded as control, a reduction of kr was
obtained by 45.1% and 57.5% after liquid treatment respectively semi-

2000
Table 3 Ref. Bio. L Bio. S C C Bio. L C BIo. S
Reduction percentage of sorptivity coefficient, relative permeability coefficient,
and total charge passed by bio-deposition on untreated concrete and carbonated Fig. 4. Results of rapid chloride permeability as indicated by total charge
concrete, respectively, as control groups (%). passed.

Parameter Untreated concrete as control Carbonated concrete as control

solid bio-treatment (Table 3).
Carbonation Liquid Semi-solid Liquid Semi-solid

k 25.6 45.8 34.5 55.7 46.5

3.3.3. RCP
kr 46.6 63.1 81.5 45.1 57.5
Qc 10.6 6.2 10.5 8.7 8.8 Carbonation and bio-deposition resulted in an increase of the re-
sistance to chloride migration (Fig. 4). The resistance of concrete

4
J. Xu, et al. Cement and Concrete Composites 104 (2019) 103358

Fig. 5. Cutting section of concrete after carbonation and biodeposition, (a) Ref.; (b) Bio. L; (c) Bio. S; (d) C.; (e) C Bio. L; (f) C Bio. S.

toward chloride penetration was improved by 10.6% after carbonation. 8000

Q - Quartz
Bio-deposition enhanced the resistance to chloride penetration by 6.2% C - Calcite
and 10.5% in liquid culture respectively semi-solid culture. An addi- 7000 Q
C V - Vaterite
tional enhancement by approximately 9% was observed after bio-de- E - Ettringite
position on carbonated specimens (Table 3). 6000
C Bio. S
Intensity (cps)

5000
3.4. Visual inspection C Bio. L
4000
From the images of the cutting section, no obvious precipitated C VV V
layer was observed on concrete surfaces except for the specimens 3000
treated by bio-deposition in semi-solid culture (Fig. 5). The thickness of Bio. S
the deposited layer was around 10 μm. 2000
Bio. L
1000
Q Q
3.5. XRD/SEM/EDS analysis Ref. E C C C CC
C E Q QQ Q Q C Q Q
0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
Crystalline phases of the deposits after carbonation and bio-de-
position were analyzed by XRD (Fig. 6). Hydration products such as 2Theta (deg.)
ettringite was found on the surface of the untreated specimens. Mean- Fig. 6. X-ray diffraction (XRD) patterns of the deposited layer on the surface of
while, calcite instead of portlandite was identified, possibly due to the concrete.
slight carbonation occurred on the surface during the sample prepara-
tion and testing. Small amount of vaterite appeared for the group
calcite, which derived from carbonation on the surface. Treatment on
processed by accelerated carbonation, while abundant calcite was
concrete by bacteria resulted in the deposition of a layer of larger
found for all the specimens treated by bio-deposition.
rhombohedral crystals (up to 5 μm) at the outer surface. It seemed that
Typical morphology of hydration products from Ordinary Portland
the type of bio-treatment has negligible impact on the morphology of
cement could be observed for untreated specimens (Fig. 7a). A few
precipitates (Fig. 7b and c). Both XRD and EDS results confirmed that
rhombohedral crystals smaller than 1 μm revealed the presence of

5
J. Xu, et al. Cement and Concrete Composites 104 (2019) 103358

Fig. 7. Scanning electron microscopy (SEM) and energy dispersion spectrum (EDS) analyses on the surface of concrete by carbonation and biodeposition, (a) Ref.; (b)
Bio. L; (c) Bio. S; (d) C.; (e) C Bio. L; (f) C Bio. S.

the crystals are calcite. Relatively denser morphology of concrete sur- 100
Concrete surface Ref.
face was noticed after accelerated carbonation treatment (Fig. 7d). Si-
milar pattern of rhombohedral crystals were clearly identified on car-
Bio. L
bonated specimens after bio-treatment, indicating the presence of 80
Bio. S
bacterial mediated calcite precipitation (Fig. 7e and f). C
A sharp decrease of Ca/Si ratio was found about 10 μm away from C Bio. L
the outer surface for the groups treated in semi-solid culture, which 60
C Bio. S
indicated the existence of a CaCO3 layer (Fig. 8). The EDS analysis on
Ca/Si

cutting ccsections is highly in line with visual inspection results.

40

4. Discussion

20
4.1. Comparison between carbonation and bio-deposition

In this work, accelerated carbonation and bacterial surface treat-

ment were applied to concrete. Generally, natural carbonation is a slow 0
0 5 10 15 20
process. Atmospheric carbon dioxide diffuses through the pores and Distance (m)
dissolves in the pore water since concrete pores are partly filled with
water in normal conditions. Carbonation occurs upon the chemical Fig. 8. Variation of Ca/Si ratio from superficial to subsurface layer of concrete
reaction between dissolution of CO2 and hydration products of cement, by carbonation and biodeposition. Content of elements were obtained by EDS
mainly Ca(OH)2 and C-S-H gel, according to the reactions [37,39,40]. analysis.

Ca(OH)2(s) + CO2(g) → CaCO3(s) + H2O (4)

C-S-H + 3CO2 → (3CaCO3·2SiO2·3H2O)
For the MICP, carbonate ions result from the microbial hydrolysis of
urea reacting with calcium ions in concrete. This process is much faster
than natural carbonation, which may last for months or even years due
to the fact that the diffusion of CO2 is the rate controlling step in most
(5) cases.
Both the bio-deposition and carbonation resulted in a mass increase
(Table 2). For accelerated carbonation, the mass increase was about
0.5 g. This weight gain was attributed to the absorption of CO2. For bio-

6
J. Xu, et al.
deposition, the mass increase was within the range of 0.4–0.6 g, which
is very close to that of carbonation. One could attribute this weight gain
to the formation of CaCO3 crystals. If we assume that the density of
CaCO3 was 2.71 g·cm−3 and the deposition occurred on the top side of
the 100 × 50 mm cylinder only, the calculated thickness of precipitated
CaCO3 layer is within the range of 19–28 μm. However, when con-
sidering the initial concentration of calcium ions present in the media,
the theoretical maximum weight of deposited CaCO3 should be 0.76 g,
which corresponds to a thickness of CaCO3 layer of 36 μm. Both values
are much higher than the thickness measured by the visual inspection
and EDS analysis on the cutting sections (about 10 μm as shown in
Figs. 5 and 8). It implied that there must be some other factors con-
tributing to the mass increase after bio-deposition. One possible reason
for the mass increase is the absorption of bacteria and nutrients.
Muynck et al. [6] reported that bacterial cells not only retained in large
capillary pores when the pore size is about 1–4 times the cell size, but
formed a biofilm on the surface of concrete. The amount of cells applied
in this work was 3 × 109 cells on the specimen. As the dry weight of one
cell was estimated to be 10−12 g [41], the applied bacterial cells only
accounts for less than 1% of the total mass increase. Therefore, the
other part of the mass increase could be attributed to the absorption of
nutrients in the media.
Concrete cylinders treated by carbonation resulted in a reduction on
water absorption rate, water permeability, and chloride migration
(Table 3). This is in agreement with other findings which reported that
carbonation reduced the permeability, especially for the low quality
concrete [39]. Large capillary pores were blocked by CaCO3 and the
pore size distribution shifted from large pores to small ones [38]. It was
confirmed by our SEM images that the surface becomes densified after
carbonation (Fig. 7d). Higher values of reduction were obtained after
bio-deposition in terms of transport properties when compared with
carbonation (Table 3). According to prior researches, the decrease in
the rate of transport processes by bio-deposition was attributed to the
biomass on the one hand, and to the precipitated CaCO3 on the other
hand [6]. Both the biomass and the CaCO3 crystals filled or plugged the
pores and acted as a blocking film on the concrete surface.
4.2. Coupled effects of carbonation and bio-deposition
In order to study the coupled effects of carbonation and bio-de-
position, bacterial surface treatment was conducted on concrete with or
without accelerated carbonation. After bio-treatment, the reduction
percentage for carbonated concrete was higher than that for untreated
one in terms of the water absorption coefficient. In contrast, the re-
duction percentage for carbonated concrete was lower than that for
untreated one regarding the water permeability coefficient (Table 3). It
implied that the impact of carbonation on water absorption and water
permeation of concrete after bio-treatment is different. Factors con-
tributing to the absorption and permeation behaviors are not the same.
An analysis based on a simple model would be helpful for explaining
this phenomenon.
Assuming that a cylindrical specimen contained a large number of
uniformly distributed cylindrical capillary tubes parallel to the axis of
the specimen. The tubes were derived from connected capillary pores.
An equivalent radius req was assigned to the capillary tube, while the
length of the tube was equal to the height of the specimen. According to
the Washburn dynamic method [42], the level of water absorbed h [cm]
along with time t [min] was given by
γreq cosθ
h= ⋅t
2η (6)
where γ is the surface tension of water [cm−2], η is the viscosity of
water [Pa·s], θ is the contact angle [°]. Then the amount of water ab-
sorbed Q [g] was expressed as
7
Cement and Concrete Composites 104 (2019) 103358
2
Q = nρπreq h (7)
−3
where ρ is the density of water [g·cm ], n is the number of the ca-
pillary tubes, which was obtained by
εR2
n= 2
req (8)
where ε is the total porosity of capillary pores, R is the radius of the
cylindrical specimen [cm]. Substituting Eqs. (6) and (8) into Eq. (7) and
we noted that the cutting section area of the specimen A = πR2, the
following equation was obtained
Q γreq cos θ
= ερ ⋅t
A 2η (9)
Comparing Eq. (9) and Eq. (1), we found out that the sorptivity
coefficient k [g·cm−2·min−0.5] could be rewritten as
γreq cos θ
k = ερ
2η (10)
Therefore, the water absorption was related to both the pore
structure and the wettability of concrete surface. As shown in Table 2,
the contact angle decreased remarkably after carbonation, suggesting
that carbonation improves the hydrophilicity of concrete surface and
results in a higher rate of water absorption. Further bio-deposition on
carbonated concrete resulted in an increase of the contact angle, which
in turn reduced the water absorption rate. Thus, the reduction of water
absorption coefficient by bio-treatment for carbonated concrete was not
only attributed to the blocking effect of bio-deposition, but also attri-
butable to the reduced hydrophilicity by bio-deposition. For untreated
concrete, the reduction of water absorption coefficient by bio-treatment
was primarily derived from the blocking effect since the variation of
contact angle before and after bio-deposition was not evident (Table 2).
The mass measurement results showed that bio-treatment performed on
carbonated concrete resulted in an additional mass increase of
0.2–0.4 g, which was lower than that performed on untreated one
(Table 2). If the degree of blocking effect contributing to the reduction
of water absorption was proportional to the mass increase by bio-de-
position, then the reduction of water absorption for carbonated con-
crete was primarily ascribed to the reduced hydrophilicity by bio-de-
position, due to the fact that the percentage of reduction for carbonated
concrete was higher than that for untreated one.
As for the water permeability performance, it usually follows the
Darcy's law
H
ν=κ
x (11)
where ν is the velocity of water flow [m/s], H is the water head [m/s], x
is the thickness of the specimen [m], and κ is the permeability coeffi-
cient [m/s]. According to Song et al. [38], the permeability coefficient κ
[m/s] was expressed by the equation
ε 2 ρg
κ = C⎛ ⎞ ⋅
⎝ Bn ⎠ η (12)
where C is a constant, B is a parameter derived from micro pore
structure, n is the torturity factor (= π2/4), g is the acceleration due to
gravity [m2/s]. Thus, the water permeability only depended on the pore
structure of concrete, which could be altered by blocking effect from
bio-deposition. Once again, if we assume that the degree of blocking
effect was proportional to the mass increase by bio-deposition, the
lower percentage of reduction of water permeability coefficient by bio-
deposition for carbonated concrete compared to that for untreated one
was mainly ascribed to the lower mass increase of bio-deposition for
carbonated concrete. Results from the charge pass of RCP were similar
to water permeability, for the chloride migration resembled the water
permeation process.
J. Xu, et al.
4.3. Influence of bio-treatment type
Two types of bio-treatment including liquid immersion and semi-
solid agar immobilization were compared in this work. In order to
ensure the compatibility, the amount of inoculated bacteria and nu-
trients was the same for the two methods during processing. Difference
in the crystalline phases and the morphology of precipitates was not
evident that large calcite crystals in rhombohedral shape were observed
by the two methods. Although the mass increase after bio-deposition in
liquid culture was slightly higher than that in semi-solid culture
(Table 2), a remarkably high Ca/Si ratio was noted for the surface layer
of about 10 μm thickness by bio-deposition from semi-solid culture
(Fig. 8). This implied that the precipitated CaCO3 by semi-solid im-
mobilization method was limited to the outer surface of concrete,
whereas it could occur in the sub-surface layer for liquid immersion
method. The water sorptivity coefficient of concrete treated by liquid
immersion was lower than that by semi-solid immobilization, but it was
reversed when it comes to the water permeability coefficient (Figs. 2
and 3). The phenomenon could also be reasoned by the wettability
since a higher contact angle was observed for liquid immersion method
compared to semi-solid immobilization method. However, semi-solid
immobilization is more potentially applicable in practice since it can be
easily brushed or sprayed on a desired part of concrete structures. In
addition, a mild microenvironment can be provided for bacteria by agar
immobilization.
5. Conclusions
Both carbonation and bio-deposition resulted in a weight gain and
in turn improved the resistance to transportation. The increase of mass
by bio-deposition was not only ascribed to the precipitation of CaCO3
and biomass on the surface, but also due to the uptake of nutrients in
the media.
The effects of a combined performance of carbonation and bio-de-
position on the behavior of capillary water absorption and water per-
meability were different. The reduction percentage of water sorptivity
coefficient for carbonated concrete was higher than that for untreated
one; however, the reduction percentage of water permeability coeffi-
cient for carbonated concrete was lower than that for untreated one.
This phenomenon is due to the fact that water absorption was related to
both the pore structure and the wettability of concrete surface, while
water permeability depended solely on the pore structure of concrete.
Similar amount of mass increase was obtained by using the liquid
immersion and semi-solid immobilization methods, provided that the
dosage of precipitation precursors are the same. Precipitation of CaCO3
was limited to the outer surface of concrete by semi-solid agar im-
mobilization. Although the wettability was slightly increased with
semi-solid immobilizing method, it is still very promising owing to its
ease of handling and potentially high adaptability in field application.
Acknowledgements
This work was supported by State Key Laboratory of Silicate
Materials for Architectures (Wuhan University of Technology)
Foundation (SYSJJ2019-04) and the Shanghai Natural Science
Foundation (17ZR1441900).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cemconcomp.2019.103358.
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