Process Safety and Environmental Protection 117 (2018) 684–693

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Process Safety and Environmental Protection

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

Potential solidification/stabilization of clay-waste using green

geopolymer remediation technologies
Jean-Baptiste Mawulé Dassekpo, Jiaqian Ning, Xiaoxiong Zha ∗
Department of Civil and Environmental Engineering, Shenzhen Graduate School, Harbin Institute of Technology, 518055, China

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

Article history: Solidification and stabilization is a remediation technique for hazardous wastes that promotes resource
Received 13 October 2017 recycling and reduces the environmental burdens of waste management. To accomplish this success-
Received in revised form 13 June 2018 fully, different types of wastes or hazardous materials are treated with different binders and techniques.
Accepted 13 June 2018
This study proposed a green remediation approach to treat and recycle clay-waste by using solidifi-
Available online 21 June 2018
cation/stabilisation which is enhanced by the injection of two chemical solutions, sodium hydroxide
(NaOH) and sodium silicate (Na2 SiO3 ) and partial addition of low-calcium class F fly ash. The unconfined
Keywords:
and compressive strength tests were conducted to investigate the mechanical properties of the developed
Solidification/stabilization
Green remediation geopolymer pastes at different time conditions. The change in the microstructures was characterized by
Clay-waste using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Microanalysis (EDX). The effects
Mechanical properties of Si/Al ratio on the compressive strength and the microstructure of the solidified geopolymer product
Si/Al ratio are also summarized in this paper. In addition, the normalized weight variations after 28 days curing in
Leaching deionized water (pH = 7.0) was highlighted and the leaching behavior of heavy metals in the clay-waste
Heavy metals based geopolymer specimens after soaking up to 14 days was examined with atomic absorption spec-
SEM-EDX troscopy. Experimental results demonstrate the potential treatment, solidification and stabilization of the
clay-waste by employing geopolymer remediation technologies and the optimum compressive strength
can be obtained with a ratio of 30% fly ash. The collected clay-waste has strength of up to 5–20 MPa at
28 days curing which meet suitable mechanical properties and compact microstructure characterization.
© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction The solidification/stabilization (S/S) technology is most suitable

During the past decade, the concept of sustainable development
has continued to improve and this has allowed geopolymerization
technology to emerge as a possible solution for the effective solidi-
fication and stabilization of toxic and waste materials. The principle
of solidification/stabilization (S/S) aim to immobilize the toxic con-
stituents of hazardous wastes to prevent their leaching from the
wastes once disposed. It involves both physical and chemical pro-
cess formulations that is accomplished by reducing the solubility
of the waste components, and by physically isolating the waste and
decreasing its surface area. The material used for S/S not only stabi-
lizes the hazardous waste by chemical means but also insolubilizes,
immobilizes by solidifying them, encapsulates, destroys, sorbs, or
otherwise interacts with the selected waste components (Rachana
and Rubina, 2006).
∗ Corresponding author.
E-mail addresses: dassekpo.jb@gmail.com (J.-B.M. Dassekpo),
ningjiaqian@foxmail.com (J. Ning), zhaxx@hit.edu.cn (X. Zha).
for treating inorganic wastes and has received a lot of attention
in recent years. Researchers have investigated a range of wastes
for which proportions of cement wastes, and fillers are used in
solidification/stabilization and they have consistently produced
satisfactory results (Peng et al., 2015; Viguri et al., 2001; Du et al.,
2014; Zhang et al., 2010a; Naamane et al., 2016; Li et al., 2015;
Elzbieta et al., 2014). On the other hand, the cement industry have
been found to be a highly energy intensive industry acting as a
major source for carbon dioxide emission that leads to some serious
environmental hazards such as global warming and large amounts
of carbon dioxide (CO2) production (Imbabi et al., 2012). Extensive
research works were carried out to demonstrate the performance
of industrial waste byproduct materials used as reactive binders
for S/S of contaminated soil with good strength, durability and eco-
nomic properties (Lei et al., 2015; Mijno et al., 2007; Ogundiran
et al., 2013; Arun and Sivashanmugam, 2015; Shi and Fernandez-
Jimenez, 2006; Zhang et al., 2010b; Li and Poon, 2017).
Several materials containing large amounts of silica and alu-
mina that partially dissolve in alkaline solutions have been used
as reagents for geopolymerization reactions. These include blast

https://doi.org/10.1016/j.psep.2018.06.013
0957-5820/© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693 685

furnace slag, coal fly ash, phosphorus slag, steel slag, metakaolin,
CDG, loess, and so one. Also, a combination of two or more of them
can be used as an alternative to Portland cement (Li and Poon,
2017; Dassekpo et al., 2017a; Dassekpo et al., 2017b). Although
geopolymerization is not a new concept, the application of this
technology to remediate various waste materials is relatively little.
Thus, only in the last decade has it been applied to fly ash. A typical
fly ash-based geopolymer mix consists of approximately 60% mass
of dry fly ash, and approximately 15% mass of dry additional Al–Si
source materials, and the rest of the mix is the alkali activators solu-
tion (van Jaarsveld et al., 1998). However, this percentage can vary
greatly depending on the characteristics needed and that includes
the Si and Al contents of the fly ash. Thus, percentages of fly ash
as low as 10% have been employed in some geopolymer reactions
(Bankowski et al., 2004a; Bankowski et al., 2004b).
In addition, the contamination risk of geopolymer to surround-
ing soils and its suitability in immobilizing toxic metals and the
leaching behavior of synthesized geopolymers from different raw
materials was investigated (Aly et al., 2008; Temuujin et al., 2011;
Izquierdo et al., 2009; Alvarez-Ayuso et al., 2008; Arioz et al., 2012;
Fernando and Said, 2010). Álvarez-Ayuso et al. (Alvarez-Ayuso et al.,
2008) studied the leaching behavior of fly ash based geopolymer in
deionized water, and found the leaching ability of metals depended
on the type of chemical elements. Aly et al. (Aly et al., 2008) exam-
ined the leaching ability of Cs, Sr, Na and Al from metakaolin based
geopolymer powder in deionized water, where a small amount
of Cs and Sr were added in the geopolymers. They found that Cs
and Sr were well and partly bound with geopolymers. Izquierdo
et al. (Izquierdo et al., 2009) have investigated the leaching tests
on fly ash-slag based geopolymer in deionized water and found
that geopolymers can provide an efficient encapsulation for heavy
metals once the dosage, synthesis and curing conditions were well
tailored for the synthesis of geopolymers.
In light of all the above, a systematic study was conducted
to treat and recycle clay-waste for its potential utilization by
using green geopolymer remediation stabilization/solidification
approaches. The Unconfined Compressive Strength (UCS) and the
standard compressive strength test were carried out to study the
mechanical performance of the developed S/S products. The Scan-
ning Electron Microscopy (SEM) and EDX microanalysis imaging
were also applied on the developed material to characterize their
microstructure and the effect of Si/Al ratio on their strength per-
formance. In addition, the leaching behavior of the synthesized
geopolymer pastes was also investigated to access the contami-
nation risk.
2. Geopolymerization reaction and formulation
The geopolymerization reaction is essentially based on the syn-
thetic alkali aluminosilicate material produced from the chemical
reaction of a solid aluminosilicate with a highly concentrated
alkaline hydroxide and/or silicate solution. This reaction can be
achieved at either ambient or elevated temperatures (Hansen,
1992). The geopolymerization involves the dissolution of silica and
alumina compounds in the alkaline solution and then bonding to
each other to form a polymeric structure. According to the research
work of Duxson et al. (Tavakoli and Soroushian, 1996) and Dimas
et al. (Sagoe-Crentsil et al., 2001), the geopolymerization process
includes the dissolution of solid aluminosilicate materials into a
strong concentration of alkaline solution, the formation of silica-
alumina oligomers, the polycondensation of oligomeric species to
form inorganic polymeric material, and the bonding of undissolved
solid particles in the final geopolymeric structure. The general
geopolymers chemical formula can be written as follow:
Mn [-(Si-O2 -)z -Al-O2 -]n • wH2 O
where M is the cation (sodium or potassium), n is the degree of poly-
merization, z is the quantifying factor for amount of SiO2 monomer
units (typically 1, 2, or 3), and w is the amount of binding water,
which can be up to 7 (Shayan and Xu, 2003). Based on z value, three
types of oligomers can be formed: poly sialate (PS) (-Si-O-Al-O-),
poly sialate-siloxo (PSS) (Si-O-Al-O-Si-O), and poly sialate-disiloxo
(PSDS) (Si-O-Al-O-Si-O-Si-O) which is obtained by packing SiO2 in
the polymeric network of PSS and has the highest density and the
lowest porosity (Tam et al., 2005). Each type of the oligomers has
certain Si/Al ratio that means that, the type of the oligomer can be
identified by the ratio of constituting silica and alumina species.
According to Joseph Davidovits, the hardening mechanism for
geopolymerization is based essentially on the polycondensation
reaction of the geopolymeric precursors, usually alumino-silicate
oxides with alkali polysilicates yielding polymeric Si-O-Al bonds
(Davidovits, 1994) as is described below:
NaOH/KOH (-)
(Si2 O5 ,Al2 O2 )n +3nH2 O−−−−−−→n(OH)3 -Si-O-Al - (OH)3
| |
(-) NaOH/KOH (-)
n(OH)3 -Si-O-Al - (OH)3 −−−−−−→(Na,K)-(-Si-O-Al - O-)n +3nH2 O
| |
O O
| |
Orthosialate (Na,K)-Poly(sialate)
(2)
NaOH/KOH
(Si2 O5 ,Al2 O2 )n +nSiO2 +4nH2 O−−−−−−→n(OH)3 -Si-O- Al -(OH)3
|
(OH)2
(-)
NaOH/KOH
| | |
(-)
n(OH)3 -Si-O-Al-(OH)3 −−−−−−→(Na,K)-(-Si-O-Al - O-Si-O-)n +4nH2 O
| | |
O O O
| | |
Ortho(sialate-siloxoxo) (Na,K)-poly(sialate-siloxo)
(3)
3. Materials and methodology
3.1. Materials
The clay used in this study was collected from Shenzhen Bay
construction site. The low-calcium class F fly ash conforming
to ASTM C-618 specification (ASTM C618-08a, 2008) supplied
from Shenzhen coal power plants in China served as a comple-
ment precursor in the solidification/stabilization process (Fig. 1).
The geopolymerization reaction was produced by mixing clay-
waste and clay-waste-fly ash with sodium hydroxide (NaOH) and
sodium silicate (Na2 SiO3 ). The solutions were prepared by dissolv-
ing sodium hydroxide in pellets form with 98% purity in water to
form 14 M molarity concentration and mixed with sodium silicate
solution.
3.2. Mix design
The mix design adopts in this research is presented in Table 1.
The main materials used are clay-waste with partial addition of fly
ash ratio of 0%, 10%, 20% and 30%.
3.3. Solidified specimens preparation
The solidified specimens were prepared as paste using plastic
molds of 70 mm cubes by mixing until homogenous and compacted
using a vibrating table and hand tamping as and when needed.
(1) Three replicate samples i.e. 9 cubes for each mixture ratio were
686 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693

Fig. 1. Source materials used in this study.

Table 1
Specimens mix proportion.

Specimen Clay-waste Fly ash (%) Clay-waste Fly ash (g) Alkaline Solution (g) Water (g)
Label (%) (g)
NaOH Na2 SiO3 H2 O

CW-00 100 0 3900 0 300 1060 150

CW-10 90 10 3510 390 300 1060 150
CW-20 80 20 3120 780 300 1060 150
CW-30 70 30 2730 1170 300 1060 150

7, 14 and 28 days, which is the time assigned for the compressive

test.

3.4. Leaching tests

The leaching behavior of clay-waste based geopolymer speci-

mens was studied following the Toxicity Characteristic Leaching
Procedure: Method 1311 (E.P. Agency, 2003). One type of clay-
waste based geopolymer samples were used for the leaching tests,
i.e. small cylindrical samples (25.4 mm x 63.5 mm). The sam-
ples were soaked at room temperature (23 ◦ C) in the deionized
water (pH = 7.0) for 4 h, 8 h, 12 h, 16 h, 24 h, 3 days, 7 days, and
14 days, respectively. The leachate was collected and pressure fil-
tered through a 0.45 ␮m filter paper, and then the concentration
of Al and As in the collected leachate was measured with atomic
absorption spectroscopy (AA) test.

4. Experimental results and discussion

4.1. Effectiveness of solidification/stabilization

The methods used to study the effectiveness of S/S process are

Fig. 2. Solidified specimens in curing conditions.
prepared and cured for 7, 14 and 28 days respectively. After four
hours rest period, fresh specimens were cured at a constant tem-
perature of 75 ◦ C and 50% Relative Humidity (RH) for 24 h (Fig. 2).
This temperature value was chosen because researchers found that
the curing temperature, the time and the sequential addition of the
synthesized parameters have a great impact on the strength devel-
opment of geopolymer materials (Palomo et al., 1999; Swanepoel
and Strydom, 2002; Dassekpo et al., 2017c). After 24 h curing, all the
specimens were exposed to ambient temperature respectively for
essentially physical, chemical and microstructural. Hills and Pollard
(Hills and Pollard, 1997) used settings and strength parameters as
indicators of solidification and studied the interference effect on
the mechanical, microstructural and fixation characteristics of the
solidified hazardous cement waste forms. Researchers have inves-
tigated a range of wastes which can be used as simple mixtures or
added to OPC and other stabilizing agents such as ashes of different
origin, lime, clay, silicates, and so on to stabilize the contaminant of
concern. Emphasis is given on the mix design effect on Unconfined
Compressive Strength (UCS) and the chemical and physical qual-
ity criteria for solidified/stabilized waste (Skalny and Daugherty,
1972; Glasser, 1993).
4.2. Unconfined compressive strength (UCS)
The unconfined compression test is the most frequent method
of soil shear testing because it is one of the fastest and cheapest
 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693 687

Fig. 3. Unconfined specimen failure pattern.

experimental methods to evaluate the shear strength. The strength

test data are always used to provide a baseline comparison between
unstabilized and stabilized wastes. On the other hand, unstabilized
waste materials generally do not present good shear strength, but
if the waste is stabilized into a cement like form, the strength char-
acteristics can be expected to increase significantly (Barth et al.,
1989; EPA/625/6-89/022, 1989). The minimum required UCS for a
stabilized/solidified material should be evaluated on the basis of
the design loads.
According to the ASTM D2166-standard (ASTM D, 2018), the
unconfined compressive strength (qu ) is defined as the compressive
stress at which an unconfined cylindrical specimen of soil will fail
in a simple compression test. In addition, in this test method, the
unconfined compressive strength is taken as the maximum load
attained per unit area, or the load per unit area at 15% axial strain,
whichever occurs first during the performance of a test.
The unconfined compressive strength (qu ) value at 7, 14 and
28 days in this study are respectively 0.44 MPa, 0.56 MPa and
0.81 MPa, which is widely acceptable according to the minimum
guideline of 0.35 MPa for S/S materials suggested by Environmen-
tal Protection Agency (EPA) (U.S. EPA SW872, 1982) to provide a
stable foundation for materials. Based on the research work of Hills
and Pollard (Hills and Pollard, 1997), the acceptable 28 day strength
is 0.7 MPa but as low as 0.35 MPa is also considered depending
on the test specimen. Stegemann et al. (Stegmann et al., 1988;
Stegemann and Cote, 1990) also reported the unconfined compres-
sive strength values for 69 stabilized/solidified wastes ranging from
0.06 to 19.99 MPa. In their study, the UCS test was performed at dif-
ferent time frames of 1, 3, 7, 14, 28, 90, etc. days to investigate the
effect of the changes in the mineralogical composition of waste,
with increasing time, and environmental exposure. Fig. 3 shows
the failure pattern of the specimen after being subjected to com-
pression. It can be seen that there are small cracks in the soil sample
under the confining pressure with no obvious failure appearing on
the surface. Three cracks with symmetrical distribution and differ-
ent thicknesses appear in the high deformation zone.

4.3. Compressive strength measurements

Following ASTM C39/C39M-16a (ASTM C39/C39M-16a, 2016)

standard test method, the compressive strength test was carried
out on the solidified specimens after 7, 14 and 28 days curing. The
Fig. 4. Compressive load-deformation curves of the specimens.
compressive strengths values were calculated after the compres-
sive test using Eq. (4) and the results are summarized in Table 2.

␴c = P/A (4) of 4.445–17.203 MPa compressive strengths can be observed,

where, P = Load applied (kN), and A the specimen pressed area, in
(mm2 ).
It can be observed that the average compressive strengths of the
solidified paste specimens are in the range of 3.890–15.926 MPa
for a curing period of 7 days. At 14 days curing time, the range
while at 28 days curing, the strength values varies between
5.266–20.849 MPa. It was noticed that in all cases, the solidified
paste which contains 70% clay-waste and 30% fly ash presents
the highest average compressive with 15.926 MPa, 17.203 MPa
and 20.849 MPa respectively at 7, 14 and 28 days curing period.
Similarly, at 7, 14 and 28 days curing period, the solidified paste
688 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693

Table 2
Solidified paste specimens compressive strength values.

Specimen 7 days curing 14 days curing 28 days curing

Label
Comp. Load (kN) Comp. Str. (MPa) Comp. Load (kN) Comp. Str. (MPa) Comp. Load (kN) Comp. Str. (MPa)

CW-00 19.061 3.890 21.785 4.445 25.805 5.266

CW-10 44.489 9.079 48.346 9.866 59.196 12.080
CW-20 76.766 15.666 80.579 16.444 101.734 20.762
CW-30 78.039 15.926 84.299 17.203 102.164 20.849

Fig. 5. Curve describing the time variation on the loading conditions.

containing 100% clay-waste presents the lowest and considerable
average strength of 3.890 MPa, 4.445 MPa and 5.266 MPa respec-
tively.
4.4. Load deformation curves analysis
The average compressive load versus displacement curves at 7,
14 and 28 days curing period of all the geopolymer specimens by
varying the FA ratio including the geopolymer specimen with 100%
clay-waste are shown in Fig. 4(a-b-c). It can be observed that the
specimens present different trend shapes and the specimen with
30% FA presented the most resistance in compression, followed by
the specimens with 20% and 10% FA and 100% clay-waste.
The solidified specimens with 100% clay-waste can reach an
average peak load of up to 19.061 kn, 21.785 kn and 25.805 kn
with average displacement of 1.992 mm, 1.779 mm and 2.182 mm
respectively at 7, 14 and 28 days curing time. This indicates that the
collected residual clay can react in the presence of sodium hydrox-
ide and sodium silicate to form a geopolymer material. The peak
load average under compressive loading at 7, 14 and 28 days curing
time for the specimen with ratio of 10% FA is 44.489 kn, 48.346 kn
and 59.196 kn with a failure displacement of 2.101 mm, 1.829 mm
and 2.062 mm, respectively. For the specimen with ratio of 20%
FA, the average peak load is 76.766 kn, 80.579 kn and 101.734 kn
with a failure displacement of 2.599 mm, 1.779 mm and 2.271 mm,
respectively. The ratio of 30% has an average peak load of 78.039 kn,
84.299 kn and 102.164 kn with a failure displacement of 2.118 mm,
1.742 mm and 2.335 mm, respectively.
This high rate of compressive loading confirms the potential
synthesis of the clay-waste mixed with sodium hydroxide (NaOH),
sodium silicate (Na2 SiO3 ) and a partial volume of fly ash to achieve
the solidification and stabilization remediation by using green and
sustainable geopolymer approaches.
 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693
Fig. 6. Average compressive strengths of the solidified specimens.
4.5. Compression time variation on the loading conditions
The influence of the variation of clay-waste/fly ash ratio on the
loading conditions is presented in (Fig. 5). The trend line is drawn
for each specimen ratio to aid in describing the progression of the
data point throughout the compression duration. It can be observed
that the trend line presents a linear shape and the ratio between
compressive strength of geopolymer pastes is not constant for the
tested paste specimens. This indicates that the loading condition
becomes more influential when increasing fly ash ratio at some
proportions. At 7 days curing period, the ratios of clay-waste/fly ash
of 20% and 30% present the highest load with compression duration
of 260.1 s and 212 s respectively. For the same ratio, the duration
values at 14 days curing period are 178.1 s and 174.4 s respectively,
while at 28 days curing the compression duration are 227.3 s and
235.7 s respectively.
Fig. 7. EDX spectra of the stabilized geopolymer specimens.
689
From the results at 7 and 14 days curing, one can conclude that
as the compressive strength increases, the compression duration
decreases, which have direct correlation with the specimens curing
time. But this hypothesis is not verified with the specimens with
30% ratio cured at 28 days, which presents a duration which far
exceeds the specimens of 7 and 14 days.
4.6. Effect of curing time on the compressive strength
It is evident that the curing duration greatly influenced the
compressive strengths of the solidified geopolymer pastes. Fig. 6
shows the column chart describing the effect of curing time on
the specimen’s compressive strengths. An analysis of the results
demonstrated that, the longer the curing period, the higher the
value of the strength, which means that longer curing time,
improves the polymerization process resulting in higher compres-
sive strength. This indicated that the solidification/stabilization was
a success and a high volume of clay-waste can be combined into
low volume of FA to form a high strength solidified product within
a specified time.
In conclusion, the compressive strength results of the solidi-
fied geopolymer pastes obtained in this study is largely acceptable
compared to the research works of (Qian et al., 2006; Mangialardi
et al., 1999), and agrees with the specified strengths limit of Chi-
nese standard CJJ/T80-98 (CJJ/T80-98, 1998) for waste chemical
stabilization.
4.7. Effect of Si/Al ratio on the compressive strength
Research was performed to investigate the role of the Si/Al
ratio, and how it relates to the mechanical property performance
of geopolymer materials. There is a strong correlation between
the Si/Al ratio and the strength of a geopolymer. It has been
shown that strength is related to composition and nanostructure
of geopolymers. Theoretically, there should be a direct correlation
with mechanical strength and silica content because increasing the
amount of silica increases the amount of Si-O-Si bonds, which are
stronger than Si-O-Al and Al-O-Al bonds (Davidovits, 1991). It was
also found that the reduction in strength for high Si/Al ratio mixes
690 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693
Fig. 8. Collected clay-waste SEM micrograph.
was the result of unreacted material, which was soft and acted as
a defect in the binder phase (ASTM Standard, 2003).
The Energy Dispersive X-Ray Microanalysis (EDX) on the sta-
bilized geopolymer pastes (Fig. 7) revealed that it composed
essentially of silica and alumina. The elemental composition of Si
varies from 16.82% to 27.11% and for Al in the range of 06.58% to
18.36%. The specimen with 30% fly ash and 70% clay-waste presents
the higher Si/Al ratio of 2.565, followed by the specimen with
20% fly ash and 80% clay-waste with Si/Al ratio of 2.409, and the
specimen with 10% fly ash and 90% clay-waste with Si/Al ratio of
2.117. Note that, the specimen with 0% fly ash and 100% clay-waste
presents the lower Si/Al ratio of 1.260.
The stabilized geopolymer pastes with Si/Al ratios of 2.409 and
2.565 contained less Si and Al than geopolymer pastes with Si/Al
ratios of 1.260 and 2.117 based on the EDX elemental analyses. It
can be seen that, the higher the Si/Al ratio, the higher the compres-
sive strength. This explains the reason for higher compressive rates
of the specimens CW-20 and CW-30 which contain respectively
Fig. 9. SEM imaging of the solidified geopolymer paste.
2.409 and 2.565 Si/Al ratios. The higher mechanical properties of
these stabilized geopolymer pastes was due to the increased Si-O-
Si bonds which have been formed during the geopolymerization
process.
4.8. Microstructure characterization
The SEM imaging was performed to study the effect of the
alkaline solution and the partial replacement of fly ash on the
microstructure of the solidified geopolymer paste. The SEM image
shown in Fig. 8 represents the micromorphology of the collected
clay-waste. It can be seen that, it composed of several residual
wastes, especially solid and organic wastes. The visual inspection
on the dried clay-waste also showed that the residues are embed-
ded solidly in the material.
In view of the microstructure analysis of the synthesized
geopolymer paste (Fig. 9), it can be seen that all the solidified
specimens showed agglomerated fine particles, which implies the
effects of geopolymerization activated by the presence of sodium
hydroxide (NaOH) and sodium silicate (Na2 SiO3 ) in the mixture.
The stabilized clay-waste specimen with 100% clay-waste
presents an acceptable appearance, with compacted lamellae struc-
ture, but with compressive strengths largely inferior to those
specimens with addition of fly ash. The ratio of 10% fly ash also
presents good results but with compressive strengths inferior to the
ratios of 20% and 30% fly ash. This indicated that the remediation of
the presented clay-waste require a significant quantity of fly ash to
acquire good resistance. The ratio of 20% fly ash in the mixture, pre-
sented more satisfactory results in comparison to the ratios of 90%
and 100% clay-waste, but had a very unique microstructure with
the presence of micro pore or alveoli. This phenomenon can be due
to the unreacted fly ash particle quantities in the mixture during
the geopolymerization process. Regarding the specimen cured with
30% fly ash, the microstructure is very satisfactory, with high degree
of compaction. It can be observed that the geopolymer stabilized
clay-waste at this ratio is of a much denser microstructure com-
pared to the other samples. This higher degree of binding and more
 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693
Fig. 10. Normalized weight of the clay-waste based geopolymer specimens during
the soaking period of 28 days in deionized water (pH = 7.0).
compact microstructure agrees well with the increasing of strength
values, which testify to the improvement of waste stabilization
with this ratio of fly ash, and can also be explained further by the
high compressive strength values obtained during the mechanical
analysis. The increasing of fly ash ratio in the mixture also greatly
impacted the compactness of the microstructure.
From the mechanical and microstructural analysis, this research
suggested that, to further improve the mechanical properties of the
stabilized/solidified waste, efforts are required to ensure a good mix
design proportion of the source materials and their full dissolution
during the synthesis process of the geopolymer production.
5. Leaching behavior of heavy metals in deionized water
5.1. Normalized weight variations
To study the weight variation, the clay-waste based geopolymer
specimens were soaked in deionized water for 1, 3, 7, 10, 14, 21
and 28 days. The initial weights (Mo) for all of the specimens were
recorded. The weight measurement (Mt) of each specimen was
taken periodically using a precision scale. The normalized weight
(Mt/Mo) is plotted as a function of the soaking time, as shown
in Fig. 10. It can be seen that the weight of the clay-waste based
geopolymer specimens increased considerably after the first day of
soaking, due to a large amount of deionized water absorbed by the
pores in the specimens.
During the soaking period of 3–14 days, the weight started
to decrease due to the partial dissolution of geopolymers. After
14 days, the weight of the clay-waste based geopolymer specimens
stayed nearly constant throughout the rest of the soaking period
up to 28 days, implying that no further dissolution of geopolymers
happened. Thus the final normalized weight of the specimens varies
depending on the amount and density of the mixture components
and the entrained air which has a close relationship with the voids
formed in the geopolymer specimens. It can also be seen that from
14 to 28 days, the specimens with ratio of 10 and 20% FA present
approximatively the same normalized weight.
In addition, it can be observed that as the ratio of FA increases,
the normalized weight increases, which means that the quantity of
FA greatly influenced the weight of the specimens and prove the fly
ash used in the experimental test has better solubility than the clay-
waste. The specimen with ratio of 100% clay-waste presents the
lowest normalized weight with decreased ratio of 3.693% compared
to the others specimens. The specimens with 10, 20 and 30% FA
691
Fig. 11. Concentration of Al leached from clay-waste based geopolymer specimens
cured at room temperature soaked in deionized water for 4–336 h (14 days).
addition present the decreased ratio of 2.833, 3.535 and 2.872%
respectively.
5.2. Leaching behavior of Al
The leaching behavior of Al in clay-waste based geopolymer
specimens was also investigated to shed light on the dissolution
of geopolymer gels in the deionized water. The concentrations of
Al in the collected leachates were obtained with AA tests, as shown
in Fig. 11. More Al was leached out at a faster rate from the ratio
of 100% clay-waste than the ratio of 90%, 80% and 70%. It can be
observed that by increasing the volume of FA in the clay-waste
based geopolymer, the leaching concentration of Al decreases. This
is because the increasing of FA proportion resulted in a decrease in
the content of Al in the geopolymer stabilized paste. This behavior
has a close relationship with the results obtained from EDX spec-
tra of the stabilized geopolymer specimens as shown in Fig. 7. It is
important to emphasize that the Al concentration in all specimens
might have not reached the theoretical maximum level, even with
the increasing trend of the leaching curve observed with the ratio
of full clay-waste.
5.3. Leaching behavior of As
The concentration of leached As (Arsenic) was also detected with
AA tests as well. The leached concentration of As from the clay-
waste based geopolymer cylindrical specimens soaked in deionized
water increased with the leaching time, as illustrated in Fig. 12. At
the beginning, the leaching of As is less than the leaching of Al,
until about 72 h. After this period, an increase of leaching amount
was observed. At around 168 h, the specimen with ratio of 100%,
90%, 80% and 70% reached an average leaching concentration of
0.611 ppm, 1.182 ppm, 1.668 ppm and 1.972 ppm respectively. It
should be noticed that as the leaching time increases, the leaching
concentration of As also gradually increases and the peak amount of
leaching was observed around the soaking period of 225 h. After this
period, the concentration decreased gradually to 1.182-1.246 ppm,
1.668-1.641 ppm and 1.972-1.838 ppm respectively for the ratio of
10%, 20% and 30% FA; and increased from 0.611-0.766 ppm with
the ratio of 0% FA during the rest of the soaking period. Contrary
to the leaching behavior of Al, as the FA proportion in the mixture
increases, the leaching concentration of As also increases.
692 J.-B.M. Dassekpo et al. / Process Safety and Environmental Protection 117 (2018) 684–693
Fig. 12. Concentration of As leached from clay-waste based geopolymer specimens
cured at room temperature soaked in deionized water for 4–336 h (14 days).
6. Conclusion
This paper examines the potential treatment and recycling of
residual clay by solidification/stabilization (S/S) technique using
green geopolymer remediation approach. Among the performed
tests, an unconfined and compressive strength investigation was
conducted to study the mechanical properties, followed by the
leaching of Al and As in the clay-waste based geopolymer speci-
mens. All the tests are included in the relevant specifications for
the treatment and recycling of residual waste, and all the tested
specimens meet the requirements for waste acceptance criteria,
including suitable compressive strengths, binding and compact
microstructure characterization.
The results demonstrated that there is a strong correlation
between the Si/Al ratio and the strength of a geopolymer. It was
also found that the reduction in strength for high Si/Al ratio mixes
was the result of unreacted material. The experimental analysis
also suggested that, to further improve the mechanical properties
of the S/S waste, efforts are required to ensure a good mix design
proportion of the source materials and a good and full dissolution
of the mix components during the synthesis process.
The results in this study also demonstrates that, the use of waste
materials to stabilize hazardous wastes by using green remedia-
tion methods could make waste materials a useful resource and
also offer an economical and efficient technique of reducing the
environmental impact of hazardous wastes.
From all the foregoing results, it can be concluded that the use
of green remediation approach in S/S technology proved to be suc-
cessful. However, to ensure the requirements in terms of security in
reclamation or the building industry, numerous deep investigations
are still necessary.
Acknowledgements
This paper has been worked out under the project No. 51578181,
supported by the National Nature Science Foundation of China,
and under project No. JCYJ20150327155221857, Shenzhen Science
and Technology Plan. Acknowledgement is also given to Shenzhen
Carbon Storage Cement-based Materials Engineering Laboratory.
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