Journal of Cleaner Production 261 (2020) 121257

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Properties and microstructure of concrete blocks incorporating

drinking water treatment sludge exposed to early-age carbonation
curing
Yue Liu a, Yan Zhuge a, *, Christopher W.K. Chow a, b, Alexandra Keegan c, Danda Li a,
Phuong Ngoc Pham a, d, Jianyin Huang a, b, Rafat Siddique e
a
Natural and Built Environments Research Centre, School of Natural and Built Environment, University of South Australia, Adelaide, Australia
b
Future Industries Institute, University of South Australia, Adelaide, Australia
c
Australian Water Quality Centre, South Australian Water Corporation, Adelaide, Australia
d
Faculty of Bridge and Road Engineering, The University of Danang-University of Science and Technology, 54 Nguyen Luong Bang Str. Danang, Viet Nam
e
Civil Engineering Department, Thapar Institute of Engineering and Technology, Patiala, India

a r t i c l e i n f o a b s t r a c t

Article history: In recent decades, industrial by-products have gained significant attention for their potential as com-
Received 3 October 2019 ponents of more environmentally friendly construction materials. In this context, this paper presents the
Received in revised form manufacture of concrete blocks (CB), in which sand was replaced with oven-dried drinking water
19 March 2020
treatment sludge (DWTS). In addition, CB with DWTS contents ranging from 0% to 30% by weight were
Accepted 19 March 2020
exposed to early-age carbonation curing. Experiments were conducted to determine the compressive
Available online 26 March 2020
strength, splitting tensile strength, and water capillary absorption of CB subjected to normal or early-age
Handling editor: M.T. Moreira carbonation curing. The results indicated that DWTS degraded durability and mechanical properties of
CB because of the high-water absorption and high organic content of DWTS. However, early-age
Keywords: carbonation curing was found to improve the overall performance of CB with DWTS, such that the
Drinking water treatment sludge carbonated CB mixtures satisfied the strength requirement of load-bearing blocks. The pH values of CB
Early-age carbonation curing after carbonation curing increased with increasing content of DWTS. Microstructural analyses showed
Environmentally friendly concrete blocks that the addition of DWTS into CB caused the formation of ettringites because of the presence of alum
Resource conservation
and gypsum in DWTS, and early-age carbonation curing decomposed these ettringite into calcium car-
bonates. The results also showed that the production of crystalline CaCO3 under carbonation had a filling
effect that refined the pore sizes. Thus, the findings of this study indicate that utilisation of DWTS in CB
offers significant environmental and health benefits via increased greenhouse gas absorption, as well as
reduced DWTS disposal in landfills and unsustainable sand extraction.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction and declining public acceptance of landfilling.

Drinking water treatment sludge (DWTS) is the solid waste
generated from the production of drinkable water. It is composed of
impurities removed and precipitated from raw water, together with
the residuals of the coagulants used. Most DWTS is finally disposed
of in landfill (Ahmad et al., 2016). However, more environmentally
friendly and sustainable approaches to managing DWTS are ur-
gently needed because of the increasing disposal cost, diminishing
number of landfill sites, more stringent environmental regulations,
* Corresponding author.
E-mail address: Yan.Zhuge@unisa.edu.au (Y. Zhuge).
Extensive studies have been conducted on recycling the DWTS
into construction materials, such as ceramic products and supple-
mentary cementitious materials (De Carvalho Gomes et al., 2019;
Nowasell and Kevern, 2015; Wang et al., 2018a; Wolff et al., 2015).
Although DWTS has been highly recommended to replace clay in
ceramic products because of their similar mineralogical composi-
tion (Ling et al., 2017), DWTS has shown significant adverse effects
on the performance of ceramic products. For instance, the
compressive strength decreased from 17 to 7 MPa with an increase
in sludge contents from 5 to 30% (Benlalla et al., 2015), because of
the high water absorption and porous structure of DWTS. As a
supplementary cementitious material, DWTS has also been found

https://doi.org/10.1016/j.jclepro.2020.121257
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257
to deteriorate the mechanical and durability performance of con-
crete specimens (Ahmad et al., 2018; Alqam et al., 2011).
In addition, several studies have proposed using oven-dried
DWTS as sand replacement in concrete products, which can save
energy and reduce greenhouse gas emissions from unnecessary
high-temperature treatment. For instance, Wang et al. (2018a) and
Fang et al. (2018) successfully added sludge into controlled low
strength materials with strength requirements of only 0.3e2.1 MPa.
Only one study investigated the use of wet DWTS as sand
replacement in concrete, and the results showed a decrease in the
28-day compressive strength from 28 to 4 MPa with an increase in
DWTS content from 5 to 10% (Ramirez et al., 2017). This may be due
to the high content of organic matter in DWTS, which could hinder
the cement hydration reaction. From the above literature review,
the current understanding of the effects of DWTS as sand
replacement on the microstructure, mechanical and durability
properties of concrete products is limited.
Therefore, one of the objectives of this study is to mitigate the
previously observed adverse effects of DWTS on cement-based
materials by introducing early-age carbonation curing to fabrica-
tion process. Excessive greenhouse gas emissions, especially of CO2,
are widely known to be harmful to the environment. In 2017, the
reported global CO2 emissions reached 36 Gt, an increase of almost
50% compared with CO2 emissions twenty years previously (Araizi
et al., 2016). Therefore, an effective method of recycling the abun-
dant CO2 in the ambient environment is crucial to reducing envi-
ronmental degradation, and in this context, cement-based
materials have been intensively studied as a potentially substantial
CO2 sink. Xi et al. (2016) concluded that between 1930 and 2013,
cement-based construction materials absorbed 4.5 Gt of CO2.
However, this passive carbonation process is slow and detrimental
to mature cement-based materials. In contrast, early-age carbon-
ation curing can sequester CO2 in only a few hours to days, and it
has already been shown to improve strength and durability per-
formance by altering the chemical composition and microstructure
of concrete products (Hilal El-Hassan et al., 2014; Qin and Gao,
2019; Wang et al., 2018c, 2020b; Zhan et al., 2016). Early-age
carbonation curing also favours CB because of the absence of
reinforcing steel (Khan et al., 2018). Rostami et al. (2012b) reported
that CO2 may react with fresh dicalcium silicate (C2S) and trical-
cium silicate (C3S) paste to produce stable mineralized products.
The reactions related to the mechanism of early-age carbonation
curing (within 24 h after demoulding) can be summarised by Eqs.
(1) and (2) (Hilal El-Hassan et al., 2014; Rostami et al., 2012b),
where x and y vary with the reaction extents.
C3 S þ ð3  xÞ , CO2 þ y $ H2 O / CX SHy þ ð3  xÞ,CaCO3
C2 S þ ð2  xÞ , CO2 þ y , H2 O / CX SHy þ ð2  xÞ,CaCO3
In the study presented in this paper, DWTS was incorporated
into concrete blocks (CB), which were the primary building mate-
rials in the construction industry (Meng et al., 2018). In addition, in
contrast to standard concrete casting methods, the CB in this study
were manufactured following a dry-mix method, that allows the
mixture to be demoulded immediately after compacting under a
certain load, and this minimum water use can alleviate the creep
and shrinkage of hardened concrete products (Poon et al., 2002).
Thus, the novelty of the proposed approach is the application of
both dry-mixing method and early-age carbonation curing to the
replacement of sand by DWTS in CB, which could address DWTS
disposal and excessive CO2 emission issues. The reminder of this
paper describes the methods and results of the tests conducted to
assess the compressive strength, splitting tensile strength, water
capillary absorption and microstructure of the proposed CB.
2. Methodology
2.1. Materials
The DWTS was obtained from Happy Valley Water Treatment
Plant, which supplies drinking water to approximately 500,000
residents in Adelaide, South Australia. The selected DWTS spec-
imen had been disposed of in the landfill for three years, and
contained 25.0% water content and 29.5% organic matter based on
the results of loss on ignition (LOI) analysis according to ASTM
D7348 (2013). The chemical composition of the DWTS was iden-
tified by X-ray fluorescence analysis (Table 1). The results showed
that Al2O3, SiO2 and organic matter were the major constituents of
the DWTS, followed by Fe2O3 and CaO; a small amount of sulphur
was also found. The mineral constituents of the DWTS were
kaolinite, quartz, dolomite, calcite and gypsum (Fig. S1, supple-
mentary information), as determined by X-ray diffraction (XRD).
After screening with a 1.68 mm sieve, the DWTS had a particle size
distribution that was similar to that of sand (Fig. 1). Fig. 2 shows
scanning electron microscopy (SEM) images of sand and DWTS, and
the images show that the DWTS is much more irregular and porous
than sand.
The binder used for the CB was general purpose cement in
accordance with AS 3972 (2010). The chemical composition
expressed as oxides of the binder is also shown in Table 1. A high-
range superplasticizer complying with AS1478 (2000) was used as a
water reducing agent. Table 2 details the properties of the
aggregates.
2.2. Manufacture of CB
Concrete mixtures were prepared with a constant mass ratio of
1.0:1.8:1.9 (cement: sand: crushed stone). Sand was replaced by
DWTS at weight percentages of 0%, 10%, 20%, and 30% to obtain
variable mixtures of CB. The water/cement ratio was fixed at 0.3
and the superplasticizer/cement ratio was fixed at 0.01 by weight
for all mixtures. Table 3 details the components of each mix.
All aggregates were oven dried at the temperature of 105 ± 3  C
for 24 h prior to mixing. CB with the size of 11511565 mm3
according to AS 4455.2 (2010) were produced following a dry-mix
method, that required minimal water to achieve the desired con-
sistency. All ingredients (sand, crushed stone, cement and DWTS)
were weighted and mixed together for 1 min, which was sufficient
to achieve homogeneity. Water and superplasticizer were then
added to the mixtures and mixed for an additional 3 min. After
mixing, the concrete mixture was compacted by a block compac-
(1) tion machine (Fig. S2) and then immediately demoulded.
2.3. Early-age carbonation curing
(2)
Before early-age carbonation curing, the demoulded samples
were placed in a 23 ± 2  C drying chamber with 60% humidity for
4 h. This pre-curing treatment is important for effective carbon-
ation, because the treatment can remove excess water content
within the specimens, which can block the diffusion of CO2 to re-
actants in capillary voids and limit the carbonation reaction (Zhang
et al., 2017). The samples were then cured in a 20L-carbonation
cabinet (Fig. S3) with a CO2 concentration of 10%. Carbonation is an
exothermic reaction, and the elevated temperature decreases the
aqueous solubility of CO2 and impairs the stability of reaction
products. Therefore, the temperature for the early-age carbonation
curing process was maintained at room temperature (23 ± 2  C).
The humidity in the carbonation cabinet was fixed at 60% because
humidity in the ambient-range was optimal for CO2 diffusion
(Zhang et al., 2017). Additionally, early-age carbonation should be
 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257 3

Table 1
Chemical composition expressed as oxides of DWTS and general purpose cement determined by X-ray fluorescence.

DWTS General Purpose Cement

Chemical Composition (wt%) Chemical Composition (wt%)

Al2O3 28.27 CaO 61.80

SiO2 26.43 SiO2 20.78
Fe2O3 7.66 Al2O3 3.57
CaO 5.36 Fe2O3 3.99
K2O 1.23 MgO 2.65
MgO 1.11 K2O 0.82
CuO 0.71 Na2O 0.06
SO3 0.48 SO3 2.82
LOI 29.5 LOI 3.26

Table 2
Properties of aggregates.

Notation DWTS Sand Crushed Stone

Specific gravity 2.27 2.61 2.72

Maximum size (mm) 1.63 1.18 9.00
Water absorption (%) 28.82 0.50 1.17

Table 3
Mix proportions of CB with different contents of DWTS (kg/m3).

Mix notation

Cement Sand Crushed Stone DWTS Superplasticizer

CB-0-N, CB-0-C 468 846 869 0 5

CB-10-N, CB-10-C 468 761 869 85 5
CB-20-N, CB-20-C 468 677 869 169 5
CB-30-N, CB-30-C 468 592 869 254 5

N: Normal curing; C: Early-age carbonation curing.

Fig. 1. Particle size distribution of concrete sand and DWTS.

applied to CB within 24 h after demoulding (Rostami et al., 2012a;
Zhang et al., 2016). The CB samples of each mix were cured in the
carbonation cabinet for 20 h, at which time one-day compressive
strength was tested (after 4 h of precuring followed by 20 h of
carbonation curing), according to the recommended criteria for
early-age carbonation curing (Rostami et al., 2012a). The samples
were then moved to a normal curing chamber (95% humidity and
23 ± 2  C temperature) for subsequent normal curing of 27 days.
2.4. Experimental methods
2.4.1. Compressive test
Samples subjected to early-age carbonation and normal curing
were tested for compressive strength at ages of 1, 7, and 28 days.
Three blocks were tested for each mixture. Each specimen was
loaded using a universal testing machine at a constant rate of 2 kN/s
based on AS 4456.4 (2003), without any shock, until failure.
2.4.2. Splitting tensile test
The splitting tensile strength was measured based on BS6717
(2001). The CB samples were cored using a coring drill with an
inner diameter of 100 mm. Before the test, the top and bottom faces
of the CB specimens were concentrically packed with steel packing
moulds. The load was applied gradually without shock and
increased continuously at a rate of 9 kN/min. The test was stopped
when the samples were split into two segments, and the splitting
tensile strengths of the CB samples were calculated based on the
recorded failure loads.

Fig. 2. SEM images of sand (left) and DWTS (right).

4 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257

2.4.3. Measurement of pH durability tests.

The carbonation depth and degree of CB were extrapolated
based on pH measurements. The pH values of different regions
from the surface to the core were measured based on ion extraction 3. Results and discussions
method (Rostami et al., 2012b), in which 100 mL of distilled water
was dropped on chromatography paper (1010 mm) on the cut 3.1. Compressive strength
surfaces of block samples, followed by waiting for 15 min to achieve
ionic equilibrium by diffusion and then measurement with an The compressive strengths of CB samples subjected to normal
Extech PH110 pH meter with a flat 9 mm diameter flat sensor was and early-age carbonation curing with varying DWTS contents are
conducted. The pH values were measured at three points and shown in Fig. 3. In general, the compressive strengths of all samples
averaged. decreased with increasing of DWTS contents from 0% to 30%. At 28
days, the compressive strengths of the normally cured samples, CB-
10-N, CB-20-N and CB-30-N, decreased by 64.6%, 69.1% and 82.4%,
2.4.4. Water capillary absorption test
respectively, compared with that of the reference one (CB-0-N).
This test was conducted according to ASTM C1585 (2013). This
Compared to the normally cured specimens, the compressive
process included sealing the lateral sides of pre-treated specimens
strengths of CB-10-C, CB-20-C and CB-30-C were all significantly
(oven-dry at 50  C until reaching a constant weight) with a thin
improved: one-day compressive strengths of CB-10-C, CB-20-C and
layer of resin to avoid the diffusion of water to the horizontal
CB-30-C were 125%, 204% and 273% higher than those of CB-10-N,
direction. The specimens with open area of 115115 mm2 were
CB-20-N and CB-30-N at the same age, and the 28-day compressive
then placed in water, and the water level was kept constant at
strengths of CB-10-C, CB-20-C and CB-30-C were 11%, 16% and 42%
3 mm above the immersed CB surface throughout the experiment.
higher than those of CB-10-N, CB-20-N and CB-30-N, respectively.
After measuring the initial weights of samples, weight measure-
Although, the carbonation cured CB-0-C demonstrated a higher
ments were conducted after soaking time of 60s, 300s, 600s,
one-day compressive strength than CB-0-N, CB-0-C exhibited lower
1200s, 1800s, 3600s, 7200s, 21600s and subsequently taking daily
compressive strengths at the age of 7 and 28 days. All samples
measurements for the next eight days using a balance with an
showed clear strength gain after 7 or 28 days of curing. The 28-day
accuracy of ±0.01 g. The amount of water that penetrated per unit
compressive strengths of all CB samples satisfied the requirement
area could be calculated by dividing the added weight by open
of 7.5 MPa for non-load-bearing blocks. The CB samples subject to
area of CB, as shown in Eq. (3), where, I is the absorption (mm); mt
20 h of early-age carbonation curing also satisfied the requirement
is the change in specimen mass (g) at the time t (s); a is the
of 12.5 MPa for load-bearing blocks, based on BSEN771 (2011).
exposed area of the specimen (mm2); and d is the density of the
The adverse effect of DWTS on the compressive strength of CB
water (g/mm3).
was significant. This effect was attributed to the high-water ab-
mt sorption and high organic matter content of DWTS. Based on Figs. 1
I¼ (3) and 2, the high-water absorption of DWTS was attributed to the
ad
slightly smaller particle size, more porous structure and higher
angularity of DWTS particles compared with sand. Thus, the in-
crease of DWTS content in CB could contribute to less cohesive
2.4.5. Microstructural characterizations concrete mixtures, because the oven-dried DWTS absorbed a large
The fractured samples close to CB surface after compressive amount of free water. In addition, the homogeneity and integrity of
strength test were used for SEM analysis. The microstructure the concrete during compaction were affected by the reduced
morphology of CB was identified by scanning electron micro- cohesiveness, which was indirectly detrimental to mechanical and
scopy (Carl Zeiss Microscopy Crossbeam 540 with GEMINI II durability properties of the hardened cement matrix. Furthermore,
column) equipped with a field emission gun operating at 2 kV. the surface area of a typical DWTS particle was larger than that of
The secondary electron images were recorded with Everhart- sand and therefore, when sand was replaced by DWTS, a larger
Thornley secondary electron detector. The accelerating voltage amount of cement paste was needed to encompass the DWTS,
was increased to 15 kV when the elemental analysis was per- which could result in more defects in the CB. The high organic
formed by silicon-drifted energy dispersive X-ray spectroscopy
(EDS).
The crystalline phases of crushed CB samples at the age of 28
days were determined by X-ray Diffractometry (XRD). Prior to XRD
test, representative pieces of CB taken from 0 to 4 mm depth of the
surface were ground to pass through the sieve with size of 30 mm.
XRD pattern was obtained using conducting CuKa radiation at
40 kV and 40 mA. The scan angle was ranging from 5  C to 90  C and
the scan speed was 0.2 /min based on previous study (Jang et al.,
2016).
The thermogravimetric analysis (TGA) was conducted at the
age of 28 days for all CB samples and it could be used for the
quantification of the hydration product changes of CB induced by
addition of DWTS and early-age carbonation curing. In the TGA
test, the samples were selected from the similar position with
XRD analysis. The crushed samples were then placed in 150 mL
crucible and heated from 30 to 1000  C at a rate of 10  C/min. The
atmosphere was air and N2 was selected as purging gas. In this
paper, the microstructure analysis will focus on CB with 0% and Fig. 3. Compressive strengths of CB samples subjected to normal and early-age
30% content of DWTS based on the results of mechanical and carbonation curing with different DWTS proportions.
 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257
content in DWTS (29.5%) hindered the formation of portlandite or
calcium silicate hydrate (CeSeH) because of the complexity of the
reaction with calcium cations in the pore solution. Thus, the high
organic content impeded cement hydration, which severely dete-
riorated the mechanical and durability properties of the CB. Wang
et al. (2018c) and Liu et al. (2020) also reported similar detri-
mental effect of organic matter in concrete products.
The SEM analysis in Section 3.5.1, below, demonstrated that
incorporating DWTS to replace up to 30% of the sand content could
contribute to the formation of excessive ettringite ((CaO)3(A-
l2O3)(CaSO4)3$32H2O) due to available source of CaSO4 and Al-
contained compounds in DWTS. The excessive production of
ettringites could be related to the partial decomposition of CeSeH,
Ca2þ ions from portlandite or gypsum dissolved in solution would
react with C3A and sulfate ions to form ettringite. Furthermore, the
sulfates would react with the monosulfate and Ca2þ ions, where
Ca2þ was provided by portlandite or CeSeH after depletion of CH,
following Eqs. (4) and (5) (Mene
ndez et al., 2013).
3CaO , Al2 O3 þ 3ðCaSO4 , 2H2 OÞ þ 26H2 O / 6Cao , Al2 O3 , 3SO3 ,32H2 O
2SO2
4 þ Ca4 Al2 ðOHÞ12 :SO4 :6H2 O
þ 2Ca2þ /Ca6 Al2 ðOHÞ12 ðSO4 Þ3 ,26H2 O
The increase in the compressive strengths of carbonated CB
containing DWTS could be explained as follows. Early-age
carbonation is different from the carbonation of mature concrete
because of the consumption of portlandite and partial CeSeH to
produce CaCO3. The high concentration of CO2 in curing cabinet
make the pore solution saturate with CO2
3 and a large number of
other ions from the cement dissolved in pore solution at the same
time. Thus, Ca2þ in the pore solution could react with OH  or CO2
3 ,
and simultaneously involved in the production of CeSeH (Jang and
Lee, 2016). This reduction of Ca2þ by carbonation may speed up the
hydration process to balance the concertation of Ca2þ. In addition,
previous research has indicated that early-age carbonation of C2S is
more rapid than that of C3S (Jang and Lee, 2016), whereas, the
hydration rate of C2S is much slower than that of C3S in the normal
curing condition. Thus, carbonation curing may facilitate the
overall reaction rate at early-age and thereby mitigate the adverse
effect on compressive strength of the CB caused by DWTS.
The SEM image of CB-30-C (in Section 3.5.1) showed less
ettringite compared with CB-30-N. This was explained by the fact
that ettringite was prone to react with CO2, following Eq. (6), and
could decompose to calcium carbonate, which would benefit the
strength development and durability performance (Grounds et al.,
1988). The generation of calcium carbonate could also inhibit the
conversion of residual ettringites into monosulfoaluminate. This
could benefit the mechanical performance of CB by increasing the
volume of hydrates (Matschei et al., 2007).
ðCaOÞðCaOÞ3 , ðAl2 O3 Þ,ðCaSO4 Þ3 ,32H2 O
þ 3CO2 /3CaSO4 ,2H2 O þ 3CaCO3 þ 2AlðOHÞ3 þ 23H2 O
In addition, early-age carbonation is a diffusion-controlled re-
action (Zhang et al., 2017), and the diffusivity of CO2 in the gaseous
state is much greater than in the aqueous state. Thus, the porous
5
structure of DWTS could allow the CO2 to diffuse more quickly.
These mechanisms could explain the significant strength increase
of CB-30-C induced by early-age carbonation curing.
The slightly decrease in strength of CB-0-C compared to CB-0-N
at the ages of seven and 28 days could be attributed to lack of water
for subsequent hydration reaction due to the exothermic carbon-
ation reaction and pre-curing process. Even curing in a 95%
humidity-controlled chamber, moisture could not penetrate
through the entire concrete specimen (Balapour et al., 2020) and
the extra demand for water of carbonation curing made the sam-
ples were not completed cured compared with those without
carbonation curing in subsequent seven and 28 days. On the con-
trary, for CB containing DWTS, the DWTS initially absorbed a large
amount of water and later partly released some water into cement
matrix, which advanced the hydration process. This is well-known
as the benefit of internal curing, in which DWTS acts like internal
curing agent (Nowasell and John, 2014).
(4)
3.2. Splitting tensile strength
The splitting tensile strengths of CB samples subjected to
normal and early-age carbonation curing with different DWTS
(5) proportions are shown in Fig. 4. The splitting tensile strengths of
the mixtures decreased with increasing DWTS contents from 0 to
30% for all samples. This result was attributed to the fact that the
DWTS absorbed a large amount of water during the mixing and
curing procedures, resulting in insufficient water availability for the
cement hydration reaction and an increase in the ratio of water to
cement in areas close to the DWTS. These local areas are also called
the Interfacial Transition Zone (ITZ), which has been reported to be
the main factor affecting the splitting tensile strength of CB (Poon
et al., 2009). The splitting tensile strengths of carbonated CB sam-
ples with DWTS were higher than those of normally cured samples.
For instance, CB-30-C was even slightly higher than CB-10-N, a
result that was not exhibited in compressive strength analysis. This
result was attributed to the production of small crystalline CaCO3
that may have filled spaces around the DWTS and thereby refined
the ITZ by filling effect. The tensile splitting strength of CB-0-C was
lower than that of CB-0-N, which was a similar result to that of the
compressive strength test and was due to similar reasons as dis-
cussed for compressive strength. Thus, the results indicated that
the early-age carbonation curing enhanced both the splitting ten-
sile strength and the compressive strength of the CB specimens that
replaced 10%e30% of the sand constituent with DWTS.
3.3. Changes in pH of carbonated samples
The pH distribution of CB samples after early-age carbonation
curing is shown in Fig. 5. The pH values of all samples were
significantly lower, compared with those of uncarbonated concrete
samples, which were approximately 12.9. The pH results indicated
that the overall carbonation degrees of all samples subjected to
early-age carbonation curing were high. The exterior surfaces of
(6)
different mixtures generated the lowest pH values, ranging from 7.1
to 7.8. This result indicated that the interiors of CB were less
carbonated than their outside surfaces. The distribution of the pH
values of individual sample was consistent with the theory that CO2
6 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257
Fig. 4. Splitting tensile strength of CB samples subjected to normal and early-age carbonation curing with different DWTS proportions.
Fig. 5. Distribution of pH values of carbonated CB with varying DWTS contents.
ingresses into the concrete by diffusion from the outer surface to
the internal part.
The pH values of the CB generally increased with increasing of
DWTS contents. The pH values of CB-0-C ranged from 7.1 to 7.6
across the different thicknesses, whereas the pH values of CB-30-C
ranged from 7.8 to 8.1. In this case, the increase in pH of CB with the
increasing of DWTS contents could be attributed to the fact that
DWTS buffers the pH change from the carbonation reaction. This
explanation is further corroborated by carbonation degrees of CB
samples, determined using the thermogravimetric analyses present
in Section 3.5.3. The CO2 uptake percentages of CB-0-C, CB-10-C,
CB-20-C and CB-30-C were 27.3%, 27.2%, 27.5% and 28.3%, respec-
tively, indicating no significant difference of carbonation degrees,
and thus the increase in pH with increasing DWTS content was
more effected by the DWTS content.
3.4. Water capillary absorption
The durability of concrete in aggressive environments greatly
depends on transport properties, which are driven by three main
mechanisms in the cement matrix: capillary absorption, perme-
ability and diffusion (Castro et al., 2011). Therefore, considering that
capillary absorption is an important indicator of quantifying the
durability of concrete products. The time-dependent water ab-
sorption for different CB specimens is presented in Fig. 6. In general,
the water absorption increased with increasing of DTWS, and the
CB-30-N sample absorbed the most water. This result could be
Fig. 6. Water capillary absorption versus quare root of time.
attributed to the high-water absorption of DWTS compared with
sand, and the porous structure of cement matrix resulting from the
addition of DWTS (shown in SEM images in Section 3.5.1).
In addition, in all samples, after a certain duration of high-speed
water ingress, the rate of water capillary absorption slowed for the
reminder of the eight-day test period. These results were attributed
to the easily penetration of water into open pores at the beginning
of test, relative to the more difficult infiltration of water through the
closed pores as the test progressed (Pham et al., 2018).
Compared with normally cured CB, water capillary absorption of
carbonated samples was lower, regardless of the amount of DTWS
contents. Moreover, the curves of the initial period of water ab-
sorption for CB-0-N, CB-10-N, CB-20-N, and CB-30-N were steeper
than those for CB-0-C, CB-10-C, CB-20-C and CB-30-C, respectively,
which may have resulted from more open pores in the normally
cured CB samples. Thus, the improvement in the carbonated sam-
ples could be attributed to pore refinement caused by early-age
carbonation curing. The production of CaCO3 may have filled
open pores and convert them to gel pores or closed pores and
reduce pores connectivity. Therefore, early-age carbonation curing
could improve the durability of all CB mixtures, including CB-0-C,
despite its inferior mechanical performance.
 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257 7

Fig. 7. SEM images and EDS analysis of carbonation or normally cured CB samples with 0% and 30% content of DWTS, (aeb) CB-30-C, (c) CB-30-N, (d) CB-0-C, and (e) CB-0-N.
8 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257

3.5. Microstructural analyses addition to calcite, the ettringite proportion was significantly
decreased in CB-30-C compared to CB-30-N. This result was
3.5.1. SEM-EDS consistent with the SEM images and the ettringite may have been
Fig. 7 shows the SEM images and EDS analysis of carbonation decomposed by reacting with CO2 to form CaCO3. Crystalline C3S
cured and normally cured CB with 30% and 0% DWTS contents at and C2S were found in both CB-30-C and CB-30-N, indicating that
the age of 28 days. SEM images and EDS analysis of carbonation and the hydration reactions were conducted inefficiently. Furthermore,
normally cured samples at the age of one day are presented under the reduction of the overlapping peaks of C3S and C2S in CB-30-C
supplementary information (Fig. S4). Fig. 7(aeb) show the compared to CB-30-N could be associated with the partial
carbonated CB with 30% sand replaced by DTWS, for which the EDS carbonation of cement. In contrast, the peaks of C3S and C2S were
analysis showed strong peaks of Ca, C, O, Al and S. These results noticeably reduced in the samples of CB-0-C and CB-0-N. These
indicated that the fractured surface of CB-30-C was mainly covered results confirmed the adverse effect of DWTS on cement hydration.
by CaCO3. In addition, ettringites and portlandite were also visible. The portlandite peak was higher in CB-0-N, whereas the peak was
The appearance of portlandite could be attributed to cement hy- significantly reduced in CB-0-C, owing to the reaction of portlandite
dration reactions that occurred during the period of the normal with abundant CO2.
curing after carbonation or to the isolation of the portlandite
crystals by CaCO3 formation on their surface, which was also 3.5.3. Thermogravimetric analysis (TGA)
observed by Rostami et al. (2012b). Fig. 7(c) presents an image of Fig. 9 shows the TGA curves of CB with 0% and 30% of DWTS
normally cured CB-30-N. Combined with EDS results together, it contents, where mass loss after 540  C can be predominantly
indicated that ettringites were distributed over the surface of CB- attributed to decarbonation (Qin and Gao, 2019). The CB-30-C curve
30-N, and large voids were interspersed. Compared with CB-30-N, became steeper than that of CB-30-N after 540  C, clearly indicating
the carbonated CB-30-C showed less ettringites induced by the a higher rate of mass loss related to bonded CO2, associated with
addition of DWTS, which made the cement paste denser by pro- the early-age carbonation curing of CB-30-C. However, the TGA
ducing more crystalline CaCO3.3.
Fig. 7(dee) present SEM images and EDS analyses of CB-0-C and
CB-0-N. Fig. 7(d) shows that crystalline CaCO3 was stockpiled on
the fractured section of CB-0-C. The CeSeH gel was also visible. The
peaks of C, O, Si and Ca in the EDS result confirmed the presence of
CeSeH and CaCO3. However, the dominant compound in the CB-0-
N image in Fig. 7(e) was the cotton-shaped CeSeH gel, which was
the main product of the cement hydration reaction, although the
cubic-shaped crystalline CaCO3 was also observed. Furthermore,
the CeSeH gel in CB-0-N was distributed more evenly around the
observed surface area, in comparison with CB-0-C. These results
further corroborated the supposition that the reduced strength of
CB-0-C relative to CB-0-N was due to lack of water for subsequent
hydration reactions.

3.5.2. XRD
Fig. 8 illustrates XRD patterns of carbonation cured and nor-
mally cured CB samples with 0% and 30% DWTS contents at 28 days.
The carbonated CB samples exhibited higher calcite peaks
compared to the normally cured samples. This result could be
Fig. 9. Thermogravimetric results from normally cured and carbonation cured CB with
related to the formation of CaCO3 in the carbonated zone. In 0% and 30% DWTS contents.

Fig. 8. XRD patterns of CB with varying DWTS contents (CH: Portlandite; E: Ettringite; C: Calcite; C2S: Dicalcium Silicate; C3S: Tricalcium silicate).
 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257
Fig. 10. Differential TGA results from normally cured or carbonated cured CB with 0%
and 30% DWTS contents: (a) CB with 30% DWTS and (b) CB with 0% DWTS.
curve of CB-0-C was only slightly steeper than that of CB-0-N after
heating above 540  C. This could be attributed to the high hydration
rate of CB-0-N in the absence of the adverse effect from DWTS and
the production of a large amount of portlandites, which could react
with CO2 in the atmosphere to precipitate CaCO3 during the 28-day
period of normal curing.
The differential TGA curves in Fig. 10 show the mass loss in the
temperature range from 105 to 540  C, which corresponds to the
decomposition of cement hydration products (Qin and Gao, 2019).
For instance, mass loss in the range from 105 to 200  C can be
attributed to the dehydration of CeSeH, ettringite (at 120  C) and
gypsum (Rostami et al., 2012b; Tang et al., 2015), and mass loss
between 200 and 400  C corresponds to the decomposition of C3A
and C4AF. Mass loss between 420 and 540  C is associated with the
9
Fig. 11. Weight loss of CB within the temperature of 105  Ce540 C and
540  Ce950  C.
decomposition of calcium hydroxide (Rostami et al., 2012b).
Decarbonation of calcium carbonate occurs between 540 and
950  C (Goto et al., 1995).
From Fig. 10(a), the peak intensity of CB-30-N at approximately
120  C was greater than that of CB-30-C, which could be related to
the decomposition of ettringite (Tang et al., 2015). Thus, this result
further confirmed the formation of ettringite induced by DWTS,
and that the ettringite can be decomposed by reaction with CO2.
The highest peak intensities for CB-30-N and CB-30-C occurred at
approximately 704  C and 720  C, respectively. These peaks were
likely related to the decarbonation of poorly-crystallized CaCO3
(Borges et al., 2010): a large proportion of the CaCO3 was derived
from the carbonation reaction, and a small amount was from the
original content of DTWS. The decarbonation of CB-30-C was more
intensive than in CB-30-N because of the higher amount of CaCO3
produced by early-age carbonation curing.
Fig. 10(b) shows the deferential TGA curves of CB-0-N and CB-
0-C, it demonstrated that one distinctive difference in the curves
of CB with 0% and 30% DWTS contents was the higher peak in-
tensity rate at approximately 450  C, which was related to the
decomposition of portlandite. This result could be explained by
the well-developed hydration product of portlandite in CB-0-N
and CB-0-C. The results also indicated that the organic matter
could hinder portlandite formation and impede further cement
hydration. The peak intensity of CB-0-N at 450  C was higher
than that of CB-0-C, because the carbonation reaction consumed
portlandite, and these results were consistent with the XRD re-
sults. In addition, some residual CO2 in the pore solution after
carbonation curing was not fully reacted because of the
extremely low diffusion coefficient of CO2 in the aqueous con-
dition, which was only one ten-thousandth of the coefficient in
gas (Wang et al., 2018c). Therefore, CO2 could continually react
with the newly formed portlandite produced by the subsequent
27-day cement hydration. The most intense peaks of CB-0-C and
CB-0-N were observed at the temperatures of 747  C and 718  C,
respectively. Thus, the decarbonation of CB-0-N was less inten-
sive than that of CB-0-C, although the difference was not as
obvious as the CB samples with 30% DWTS. This further
confirmed the significant atmospheric carbonation of CB-0-N.
The weight losses associated with all endothermic peaks from
105 to 540  C, and 540 to 950  C are summarised in Fig. 11. The
weight losses of the carbonated samples, CB-0-C and CB-30-C, from
105 to 540  C were lower than those of the corresponding normally
cured samples, CB-0-N and CB-30-N. This was attributed to the
10 Y. Liu et al. / Journal of Cleaner Production 261 (2020) 121257
consumption of hydration products of portlandite, as well as
ettringite induced by carbonation. The weight loss of CB-30-N in
the temperature range from 105 to 540  C was the highest value
due to the formation of ettringite and the organic matter. CB-0-C
showed the highest weight loss related to decarbonation, in the
range from 540 to 950  C.
The CO2 uptake percentages of different mixtures were calcu-
lated by Eq. (7), where Dw was the weight loss of carbonated CB
samples in the temperature range from 540 to 950  C. The CO2
uptake percentages of CB-0-C, CB-10-C, CB-20-C and CB-30-C were
27.3%, 27.2%, 27.5% and 28.3%, respectively. Thus, there was no
significant difference in the CO2 uptake percentages for each
mixture. However, the CO2 uptake of up to 28.3% by weight of the
initial CB mixture indicates that CO2 captured by early-age
carbonation curing could greatly contribute to the reduction of
greenhouse gas emission.
Dw
CO2 Uptake ¼
Weight at 105 C
4. Conclusions
This paper explored the potential offered by adding DWTS into
CB as a substitute for sand. In addition, the effects of early-age
carbonation curing on CB incorporating DWTS was investigated.
This combined approach presents an efficient reuse of DWTS, that
can be leveraged to recycle excessive CO2 in an environmentally
friendly construction material. Based on the experimental results,
the following conclusions could be drawn.
1. DWTS in CB was detrimental to the compressive and splitting
tensile strengths of the composites. Early-age carbonation
curing helped to improve the strengths significantly, especially
for CB incorporating 30% of DWTS by weight, and made the CB
suitable for load-bearing applications.
2. The higher water capillary absorption of normally cured CB with
DWTS was attributed to their porous structure, which had been
reduced as the CB were exposed to early-age carbonation curing
because of the reduction of pore size and pore connectivity. It
signalized an enhanced durability performance of carbonated
CB, a subject of on-going laboratory works.
3. CO2 appeared to react with ettringite formed in CB with high
DWTS content. Hence, CB with 30% content of DWTS exposed to
carbonation curing showed less ettringite than that of in the
normally cured samples.
4. TGA showed a reduction of portlandite and higher amount of
CaCO3 in carbonated samples. XRD further confirmed the
decrease of ettringite and the increase of CaCO3 in CB subjected
to early-age carbonation curing.
Author contributions
Yue Liu: Conceived and designed the analysis, Collected the
data, Contributed data or analysis tools, Performed the analysis,
Wrote the paper. Yan Zhuge: Conceived and designed the analysis,
Contributed data or analysis tools, Performed the analysis, Wrote
the paper. Christopher W.K. Chow: Contributed data or analysis
tools, Wrote the paper. Alexandra Keegan: Wrote the paper. Danda
Li: Contributed data or analysis tools, Wrote the paper. Phuong
Ngoc Pham: Contributed data or analysis tools, Wrote the paper,
Formal analysis, Methodology. Jianyin Huang: Performed the
analysis, Wrote the paper. Rafat Siddique: Wrote the paper.
Acknowledgements
The authors would like to acknowledge UniSA and SA Water for
the research scholarship and financial support for this project. The
authors also would like to thank Boral Australia for the supply of
aggregates.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2020.121257.
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