Geomechanics for Energy and the Environment 25 (2021) 100195

Contents lists available at ScienceDirect

Geomechanics for Energy and the Environment

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

Effect of phosphogypsum on physiochemical and mechanical

behaviour of cement stabilized dredged soil from Fuzhou, China
∗
Ling-Ling Zeng a , Xia Bian b , , Lun Zhao c , Ye-Jiao Wang d , Zhen-Shun Hong e
a
College of Civil Engineering and Architecture, Zhejiang University of Technology, Hanzhou 310014, China
b
Key Laboratory of Ministry of Education for Geomechanics and Embankment Engineering, Hohai University, Nanjing 210098, China
c
Qujing Urban Transportation Research Institute, Qujing 655000, China
d
Department of Civil Engineering, Shanghai University, Shanghai 200444, China
e
Institute of Geotechnical Engineering, School of Transportation, Southeast University, Nanjing 211189, China

article info a b s t r a c t

Article history: Chemical treatment is one of the popular methods dealing with geoenviromental problems related
Received 17 October 2019 to soil, such as waste dredged materials, soil with heavy metal pollutions, among others. This paper
Received in revised form 11 May 2020 performed a series of laboratory tests to investigate the effect of phosphogypsum on water content,
Accepted 12 May 2020
density, pH, unconfined compressive strength and deformation modulus of cement stabilized soil.
Available online 27 May 2020
It is found that the water content and pH value decreased whereas the density increased, as the
Editors-in-Chief: phophogysum content increased. These changes were attributable to the formation of ettringite related
Professor Lyesse Laloui and Professor Tomasz to the chemical reaction between phosphogypsum and cementitious materials (calcium aluminate
Hueckel hydrates). The unconfined compression strengths of the cement stabilized soil with phosphogypsum
content of 1.4% to 8.6% were approximately 1.7 to 9.4 times of those without phosphogypsum.
Keywords:
Particularly, the earlier strength of the stabilized soil with phosphogypsum cured at 3 and 7 days
Phosphogypsum
increased by 1.3 and 2.1 times in comparison with those lacking phosphogypsum. The mineralogical
Cement stabilized soil
Unconfined compression strength changes revealed that when the cementation bonding was sufficiently formed at 28 days of curing,
Deformation modulus the increase in ettringite with phosphogypsum content behaved positive influence on strength
Mineralogical change development of cement stabilized soil. When cementation bonding was relatively low before 7 days of
curing, adequate phosphogypsum content might produce moderate level of ettringite, tended to swell
and make denser fabric, resulting in the strength increase. It should be also noted that over-dosage of
phosphogypsum might cause volume increase and structure disruption, leading to the strength loss.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction Note that the main composition of phosphogypsum is

CaSO4 ·H2 O, which can easily react with cement or lime stabilized
Phosphogypsum is the main by-product during the manufac- soil to formulate pozzolanic products under high pH value, due
ture process of phosphoric acid from phosphate rock.1 Because to high level of hydroxide ions (OH)− released from hydration
phosphoric acid is one of the most important composition in reaction of cement or lime.2,3 Hence, some researchers have
fertilizer industry, the amount of phosphogypsum rapidly in- recommended utilizing phosphogypsum with fly ash and cement
creases at a rate of about 70 million tons per year with a very stabilized soil to produce raw materials as road base.4,5 The
low utilization ratio (less than 15%) in China. The total amount chemical reaction between phosphogypsum and the hydration
of phosphogypsum was about 5 hundred million tons in China, products of cement stabilized soil,2,6 can be expressed as follows:
according to China Phosphate and Compound Fertilizer Industry
Association. Commonly, phosphogypsum was discarded in land- Al2 Si4 O10 (OH)2 ·nH2 O + 2(OH)− + 10H2 O
fills regarding as wastes, which would bring risks on water and →2Al(OH)−
4 + 4H4 SiO4 ·nH2 O (1)
soil pollutions, as well as long-term requisition of land causing 2+ − − −
potential severe social tension. 6Ca + 2Al(OH)4 + 4(OH) + 3(SO4 ) + 26H2 O
→Ca6 [Al(OH)6 ]2 ·(SO4 )3 26H2 O (2)
∗ Correspondence to: Key Laboratory of Ministry of Education for (Formation of ettringite)
Geomechanics and Embankment Engineering, Hohai University, China
E-mail addresses: linglz413@126.com (L.-L. Zeng), xia.bian@hhu.edu.cn Or expressed as
(X. Bian), 220162693@seu.edu.cn (L. Zhao), yejiaowang@shu.edu.cn
(Y.-J. Wang), zshong@seu.edu.cn (Z.-S. Hong). 3CaSO4 + 3CaO·Al2 O3 + 32H2 O

https://doi.org/10.1016/j.gete.2020.100195
2352-3808/© 2020 Elsevier Ltd. All rights reserved.
2 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195

Table 1
Physical properties of untreated Fuzhou soil.
Liquid Plastic Gs Clay Silt (0.005– Sand (0.0075–
limit : % limit : % (<0.005 mm): 0.075 mm): 2 mm):
% % %
Untreated 79.2 35.3 2.56 43 47 10
Fuzhou soil

→3CaO·Al2 O3 ·3CaSO4 32H2 O (Ettringite) (3) Table 2

Mineral composition of Fuzhou soil.
It should be emphasized that the reaction product named as Clay mineral (%) Kaolinite Illite Chlorite Smectite
Ettringite (Aft), which was one of the main sources of strength 48 19 23.8 9.2
of cementitious materials. Hence, phosphogypsum could be used
to increase the strength of cement stabilized soil.5 On the other
hand, the formation of ettringite absorbed large amount of water, Table 3
Oxides composition of ordinary Portland cement and phosphogypsum.
leading to a great swelling potential, and thus strength loss.7 This
Oxide CaO SiO2 Al2 O3 Fe2 O3 SO3 MgO F P2 O5 Loss on
might result in potential heaving failure by using these filling content ignition
materials in road base or other projects.8 (%)
Meanwhile, a large volume of dredged soil with high initial Cement 59.3 22.4 4.3 3.4 4.1 3.5 – – 1.8
water content were generated during dredging of rivers and phospho- 27.8 6.4 0.62 0.3 41.7 0.5 0.8 0.7 20.5
lakes, in the background of the Outline of Yangtze River eco- gypsum
nomic belt development plan in 2016.9–11 These problematic
materials contained complex geological composition and behaved
Table 4
poor engineering properties, resulting in difficulty on treatment Test programme for unconfined compression test and pH value.
with environmental perspective. In general, the cement mixing Initial water Cement Phosphogypsum Curing times (day)
method was recommended to improve the engineering prop- content (%) content (%) content (%)
erties of dredged soil.12–15 It should be addressed that some 3 7 28 90
additives, especially waste materials such as fly ash, metakaolin 7.1 0 11.9 11.9 11.5 10.6
and others were commonly added to consume the water and im- 7.1 1.4 11.8 11.3 11.3 10.4
prove the cementation strength for the economical purpose.16,17 7.1 2.9 11.5 11.2 10.9 10.0
To this end, it is logically to expect that reusing phosphogypsum 10.7 0 12.2 12.4 11.9 11.3
10.7 2.1 12.1 11.6 11.2 11.1
to stabilize dredge soil with high water content can consume
10.7 4.3 11.6 11.4 10.9 10.3
large amount of water and produce ettringite, which may benefit 14.3 0 – – 12.0 11.5
to the strength improvement of cement stabilized soil. This is also 103.0 14.3 1.4 – – 11.8 –
supposed to be environmental friendly and cost efficiently, since 14.3 2.9 – – 11.5 11.1
both phosphogypsum and dredged soil are considered as waste 14.3 5.7 – – 10.9 10.8
21.4 0 12.5 12.7 12.6 12.4
materials.
21.4 1.4 12.5 12.3 12.3 12.0
Typically, to achieve utilization of cement stabilized soil as raw 21.4 2.9 12.5 12.2 12.2 12.0
materials in practice, engineering properties, such as strength, de- 21.4 4.3 12.4 12.2 12.1 11.8
formation modulus, permeability, needed to be thoroughly inves- 21.4 8.6 12.3 11.9 11.7 11.2
tigated correlating with the change in physiochemical
behaviour.18 Recently, some researcher also focused on the effect
of wet and dry cycling, freeze and thaw cycling and other envi- be classified as high plasticity clay (CH). The in-situ water content
ronmental change on the durability of cement stabilized soil in of Fuzhou soil was approximately 95.0–112.8%. Table 2 shows
dealing with the real work condition.19–21 To better understand
that the predominant clay mineral of Fuzhou soil is kaolinite at
the macroscopic engineering behaviour of cement stabilized soil,
48%, and the amounts of illite, chlorite and smectite are 19%,
the change in microstructure as well as mineralogy was of-
23.8% and 9.2%, respectively.
ten studied, evaluating the fundamental mechanism involving
Two additives were used in this study as the cement binder:
the chemical reaction among binders and the improvement of
ordinary Portland cement (32.5R/N) and phosphogypsum. Ce-
engineering properties accordingly.16,22,23
ment used in this study was manufactured by Nanjing Conch
This study carried out an investigation on the potential use and
Cement Co. Lt. Phosphogypsum powder was taken from a landfill
engineering properties of cement and phosphogypsum stabilized
of waste phosphogypsum in Nanjing city, China. Table 3 presents
dredged soil with high water content. The objectives of this
the chemical compositions of cement and phosphogypsum. Note
study are: (1) to investigate the effect of phosphogypsum on the
that the ratio of CaO to SiO2 is 2.64, exceeding 2, and MgO
physiochemical behaviour of the cement stabilized soil; (2) to
content is 3.5% higher than 2.0%, which is compliance with the
study the variation of strength properties with phosphogypsum
guidelines of the European Cement Standard (EN 197-1). The
content; (3) to correlate the changes in physiochemical-strength
behaviour with the mineralogical variations. main composition of phosphogypsum includes 41.7% SO3 and
27.8% CaO. Meanwhile, the hazardous composition content of F
2. Materials and methods and P is at very low level.

2.1. Materials 2.2. Sample preparation

The soil used in this study was taken from river bed of Pudong The soil-cement samples were prepared from the slurry soil
River in Fuzhou city, Fujian province, China. The basic physical with initial water content of 103% to simulate the nature state of
properties of the Fuzhou soil are summarized in Table 1. Accord- Fuzhou river bed soil. Afterwards, cement (7.1%, 10.7%, 14.3% and
ing to the Unified Soil Classification System,24 the Fuzhou soil can 21.4%, by weight of dry soil) and phosphogypsum powder (1.4
 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
Fig. 1. Variation of after-curing water content (28 days of curing).
Fig. 2. After-curing water content versus curing time (cement content = 21.4%).
to 8.6%, by weight of dry soil) were poured into the slurry and
mixed for 5 to 10 min to achieve uniformity. Then, the mixed
soil–cement–phosphogypsum paste was transferred into plastic
mould (50 mm in diameter, 100 mm in height). Two detachable
plastic lids were used to seal both ends. After 1–2 days of curing,
the stabilized soil samples were removed from the mould and
wrapped in plastic bags, cured in a controlled environment (20 ±
2 ◦ C and 95% relative humidity).
2.3. Experimental methods
Unconfined compression tests (UCT) were performed on sam-
ples after 3, 7, 28 and 90 days of curing, following.25 The rate
of vertical displacement in UCT was 1 mm/min. Test programme
for UCT is listed in Table 4. The after-curing water content was
3
Fig. 3. Variation of density (28 days of curing).
Fig. 4. Density versus curing time (cement content = 21.4%).
determined by oven-drying the specimens at 105 ◦ C for 24 h, us-
ing the soil immediately after UCT. Triplicate measurements were
conducted for the after-curing water content and unconfined
compressive strength qu , and the average values were reported.
The density was determined based on the soil volume for the
specimen immediately after UCT, using the fluid displacement
technique by wax coating the soil sample before immersed into
distilled water.
The pH measurement for the stabilized soil was using HORIBA
D-54 pH meter based on.26 The soil samples from UCT specimens
were firstly air-dried, and then crushed to pass through a 2 mm
sieve. Then, 10 g of the sieved soil was mixed with 50 mL of
distilled water within a glass container. After 3 min of vibra-
tion mixing and a 1 h delay period the pH measurement was
performed. The fluid temperature was also measured along with
the pH readings, which ranged from 19.6 to 23.8 ◦ C. For each
4 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
Fig. 5. Measured pH of stabilized soil (28 days of curing).
Fig. 6. Measured pH versus curing time (cement content = 21.4%).
specimen, triplicate measurements were conducted to minimize
the error, and the average value of pH was reported.
The X-ray diffraction analysis was also conducted on the soil
samples from UCT specimens by using a Rigaku D/Max-2500.
The sample was first freeze-dried using liquid nitrogen, vacuum
cooled to approximately −210 ◦ C.27,28 Then, the lyophilized sam-
ples were scanned for a two-theta (2θ ) value ranging between 5◦
to 60◦ with a step length of 0.02◦ and a scanning rate of 2◦ /min.
The results were semi-qualitatively analysed using JADE 5.0.
3. Results and discussions
3.1. Physical properties
Fig. 1 shows the variation of water content for cement and
phosphogypsum stabilized soil after 28 days of curing. The graph
showed a remarkable reduction in water content for stabilized
soil in comparison with the initial soil slurry without cement and
Fig. 7. Typical stress–strain curves of cement and phosphogypsum stabilized
soil.
phosphogypsum binders. This was attributable to the hydration
and pozzolanic reactions in the mixture of cement, phosphogyp-
sum, soil and water, which consumed large amount of water.18,22
For a given phosphogypsum content, it is evident that the wa-
ter content significantly decreased with the increase in cement
content, which attributed to the larger extent of hydration and
pozzolanic reactions due to higher amount of cement clinkers in
the soil slurry system with high initial water content. Further-
more, a significant decrease in water content with phosphogyp-
sum content can also be observed at a given cement content.
It can be deduced from Eqs. (2) or (3) that with an increase
in phosphogypsum content (more CaSO4 ), the chemical reaction
consumed significant amount of water, leading to the drastically
decrease in water content.
Fig. 2 depicts the variation of after-curing water content over
curing time. As expected, the after-curing water content de-
creased with curing time. It is also evident that large proportion
of water reduction occurred in the first 7 days, while the de-
crease in water content became moderate afterwards. Similar
observations have also been reported by Chew et al. 18 . In ad-
dition, at all curing times, the after-curing water content for
higher phosphogypsum content lied below that of lower ones.
This indicated a long term pozzolanic reaction led to the in-
crease in solid composition and the decrease in water content
over time.18,29 Meanwhile, it suggests that the chemical reaction
between phosphogypsum and hydration products (i.e. calcium
aluminate hydrate) consumed larger quantity of water in the
stabilized soil with higher phosphogypsum content.
The change of density with phosphogypsum content and cur-
ing time are plotted in Figs. 3 and 4, respectively. For a given
curing time, the density of stabilized soil increased with cement
content and phosphogypsum content. This behaviour could be
attributed to more solids part in soil as more cementing products
generated in the case of higher cement content. Similar trend
appeared in the case of higher phosphogypsum content according
to the chemical reaction as proposed in Eqs. (2) or (3). At the
same time, the remarkable reduction in water content as shown
in Fig. 1 could be also attributable to the subsequent decrease of
water volume in the stabilized soil.
 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195 5

Fig. 8. Relationship between qu and phosphogypsum content.

Moreover, the density of stabilized soil increased with curing
time as shown in Fig. 4. Similar to the variation of water content,
most of increase in density took place within the first 7 days.
Hence, the mechanism of increasing density over time was due
to the consumption of water and the generation of cementitious
products in the chemical reaction among cement, soil, water and
phosphogypsum, resulting in a decrease in water volume and an
increase in solid volume during curing.
3.2. pH value
The measured pH values of stabilized soil at various cement
and phosphogypsum contents and curing times are summarized
in Table 4. The high pH value of stabilized soil (pH > 10 for all
samples) was mainly attributable to the increasing of hydroxyl
ions (OH− ) in the pore water due to the hydration reactions of
cement at early stage. Fig. 5 presents the variation of pH value
with cement and phosphogypsum content at 28 days of curing.
For a given phosphogypsum content, the measured pH value
increased with the increase in cement content. For a given cement
content, the measured pH value was remarkably lower with high
phosphogypsum content. For example, when phosphogypsum
content increased from 0% to 2.8% at cement content = 7%, the
pH value decreased from 12.0 to 10.9. It should be emphasized
that phosphogypsum was the by-product in the production of
phosphoric acid, with a low pH value of about 3.2 in this study.
As shown in Eq. (2), with an increase in phosphogypsum content,
more hydroxyl ions (OH− ) would be consumed to form the ce-
mentitious products (i.e. ettringite). Therefore, the concentration
of hydroxyl ions (OH− ) in the pore water decreased with the
increase in phosphogypsum content, leading to the decrease in
pH value of stabilized soil.
6 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
Fig. 9. Relationship between strength increase ratio and phosphogypsum
content.
Fig. 10. Effect of phosphogypsum replacing cement on qu .
Furthermore, the change of measured pH value with curing
time is plotted in Fig. 6. It can be observed that the measured pH
value decreased with curing time (with the exception of highest
pH value at 7 days for 0% phosphogypsum content). This be-
haviour is consistent with previous findings of cement stabilized
soil, which resulted from the time-dependent pozzolanic reaction
accompanied with the consummation of portlandite and water,
consequently leading to the decrease in pH.18,22 Moreover, the
large change in pH value within the first 7 days can be observed in
Fig. 6, which coincided with the trend of water content reduction
and density increase.
For the case of 0% phosphogypsum, the increase in pH value
from 3 days to 7 days could be attributed to the relationship
between the consummation of Ca2+ and OH− by the pozzolanic
reaction and Ca(OH)2 generated by cement hydration.30 At early
Fig. 11. Effect of phosphogypsum content on the deformation modulus E50 .
stage, the generation of Ca(OH)2 seemed higher than the con-
summation of those due to pozzolanic reaction for high cement
content. Similar observation can also be found in Kawamura
et al. 30
3.3. Stress–strain behaviour
Fig. 7 shows the typical stress–strain curves of cement and
phosphogypsum stabilized soil. It can be observed that when
phosphogypsum content was lower than 2.9%, the stabilized soil
possessed a ductile behaviour, with the post-peak stress decreas-
ing gradually with strain. With an increasing phosphogypsum
content (≥2.9%), the stabilized specimen exhibited a brittle char-
acteristic, with abrupt drops in post-peak stress with strain. The
 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
Fig. 12. Relationship between deformation modulus (E50 ) and unconfined
compressive strength (qu ).
transition from ductile to brittle behaviour of stabilized soil also
demonstrated the increase in modulus with phosphogypsum con-
tent. As shown in Fig. 7, the stabilized soil containing 1.4% to 8.6%
phosphogypsum possessed much higher strength, approximately
2 to 7 times higher than those lacking phosphogypsum. These
behaviours suggested that phosphogypsum make a great contri-
bution to the soil strength and modulus. This point will be further
discussed in latter sections.
3.4. Unconfined compressive strength and deformation modulus
Fig. 8 depicts the effect of phosphogypsum content on uncon-
fined compressive strength (qu ) of the cement stabilized soil at 3,
7, 28 and 90 days of curing. The graphs showed that the relation-
ship between qu and phosphogypsum content at 3 and 7 days of
curing was very different from that at 28 and 90 days of curing.
It can be observed that qu almost proportionately increased with
phosphogypsum content in the whole variation range of cement
content, as investigated at 28 and 90 days of curing. Whereas, qu
at 3 and 7 days of curing showed a complex trend. For example,
at 3 days of curing, qu rapidly increased up to 1.6–2.9% phos-
phogypsum content. As the phosphogypsum content exceeded
2.9%, qu showed a decrease trend with phosphogypsum content.
Hence, an optimal phosphogypsum content with the maximum
qu occurred at 3 and 7 days of curing, as the dashed line shown in
Fig. 8(a) and (b). At 3 days of curing, the phosphogypsum content
for the maximum qu increased from 1.6 to 2.9%, when the cement
content increased from 7.1 to 21.6%. Similar trend can also be
observed at 7 days of curing. Furthermore, the maximum qu line
at 7 days of curing was shifted to the right of that at 3 days.
This indicated that the phosphogypsum content for the maximum
qu increased with the curing time at a given cement content.
This means, the phosphogypsum content for the maximum qu
increased with both cement content and curing time. It should
be emphasized that when curing time exceed 28 days, qu almost
linearly increased with phosphogypsum content for the range
from 0 to 8.6% used in this study. Therefore, it can be deduced that
the effect of phosphogypsum on the strength gain in stabilized
soil was largely related to the cementation bonding due to higher
7
cement content or more pozzolanic reaction at longer curing
times.
To illustrate the strength gain due to phosphogypsum, a
strength increase ratio was plotted with phosphogypsum content
as shown in Fig. 9. Strength increase ratio was defined as:
qup − qu0
SIR = (4)
qu0
where qu0 and qup were the unconfined compressive strength for
stabilized soil without and with phosphogypsum, respectively.
It is evident that qu increased by 0.7 to 8.4 times that just
using cement as the binder, strength increase ratio varying mainly
between 1 and 4 in the phosphogypsum content range (up to
8.6%) and curing time (up to 90 days) investigated in this study.
This suggested that phosphogypsum can progressively improve
the strength of cement stabilized soil. In addition, at 3 and 7 days
of curing, the average qu increased by 1.3 and 2.1, respectively.
A rapid strength increase of stabilized soil with phosphogypsum
at early stage made the early transportation of stabilized soil
being possible. This can shorten the storage time of dredged soil,
thus reducing the project cost. Also, the early transportation of
stabilized soil can reduce the risk of contamination from leachate
of stabilized soil on natural environment.
Furthermore, due to the significant strength gain from phos-
phogypsum abovementioned, it is logical to use phosphogypsum
partially replacing cement to reduce the overall cost. Fig. 10
presents the effect of phosphogypsum replacing cement on qu at
the same binder content. As expected, using phosphogypsum to
replace 10% and 20% of cement at the same binder content, qu
dramatically increased by 1.6 and 2.2 times that without phos-
phogypsum, respectively, at 28 days of curing. This behaviour
suggested that phosphogypsum can partially replace cement to
achieve the required performance in engineering practice from
the perspective of environment and economy.
The deformation modulus (E50 ), obtained from stress–strain
relationship of UCT, was an important parameter in any analy-
sis of deformation behaviour of cement stabilized soil, since it
potentially used as the filling material in land reclaim projects
or road engineering. The definition of E50 was expressed as the
slope of the stress–strain curve at 50% of peak axial stress.31
Fig. 11 shows the typical variation of E50 with phosphogypsum
content at 7 and 28 days of curing. The graphs showed that at 7
days, E50 increased with phosphogypsum content till to reach the
peak value, followed by a decrease in E50 with further increase in
phosphogypsum content at a given cement content. The phospho-
gypsum content for the maximum E50 increased with the increase
in cement content. While E50 showed an increase tendency with
phosphogypsum content after 28 days of curing. The variation
of E50 was consistent with the change in qu at different curing
periods. It should also be mentioned that the internal erosion of
filling materials may be the main risk in the earth structure.32–34
Hence, some further studies should be focused on the effect of
erosion on engineering properties of cement and phosphogypsum
stabilized soils.
It has been widely reported that E50 correlated well with qu
for cement stabilized soil with various binder or contaminated
by heavy metal.17,22,29,35 Fig. 12 depicts the relationship between
deformation modulus and unconfined compression strength of
cement and phosphogypsum stabilized soil. It can be observed
that the ratios of E50 to qu ranged from 50 to 140. The aver-
age value of this linear relationship (E50 /qu ) was 111, with the
squares of the correlation coefficient (R2 ) of 0.91 for the presented
study. These findings are consistent with the previous studies of
cement stabilized dredged marine sediments (E50 = 100–200
qu )35 and Dunkirk sediments stabilized with cement, lime and fly
ash (E50 = 60–170 qu ).36
8 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
Fig. 13. X-ray diffraction patterns of untreated and cement and phosphogypsum stabilized soil.
3.5. Discussions
It has been widely accepted that the improvement of engi-
neering properties of cement stabilized soil was attributable to
the soil–cement–water reaction, which produced primary and
secondary cementitious materials in soil.3,37,38 Hence, the analysis
on the mineralogical composition of cement and phosphogypsum
stabilized soil can provide a better understanding on the effect
of phosphogypsum on engineering properties improvement. The
X-ray diffraction patterns of the untreated soil and cement sta-
bilized soil with various phosphogypsum contents at 28 days of
curing are presented in Fig. 13. It is clear that when cement
and phosphogypsum were added into the Fuzhou soil, some new
reflections were detected as hydration products, such as calcium
silicate hydrate (CSH), calcium aluminate hydrate (CAH), and et-
tringite, in comparison with that of untreated Fuzhou soil. These
cementitious materials have been commonly identified in cement
stabilized soil generated by the pozzolanic reaction.39
By comparing the XRD results at different phosphogypsum
contents, it can be observed that the intensity of the cementitious
materials (i.e., CSH, CAH, and ettringite) changed remarkably,
with an increase in ettringite and a decrease in CAH with the
increase in phosphogypsum content. While the intensity of CSH
remained almost unchanged. As reported by Tremblay et al. 40
and Shen et al. 5 , the presence of ettringite in cement stabilized
soil may enhance its early strength, which corresponded to the
needlelike ettringite crystals bridging the conjunctures of solid
particles in soil-cement matrix. Meanwhile, the swelling nature
of ettringite would compress the pore space in soil matrix es-
pecially for the soil with high water content (high initial void
ratio), leading to the increase in density (as shown in Fig. 3). The
relationship between intensity of ettringite and qu is shown in
Fig. 14 for 14.3% and 21.4% cement content at 28 days of curing.
It is evident that the intensity of ettringite (all three main peaks)
increased with phosphogypsum content. At the same time, qu
also showed the increase tendency with phosphogypsum content.
Hence, the strength gain with the increase of phosphogypsum
was mainly attributable to the increase in ettringite, resulted
from the chemical reaction listed in Eq. (2) or (3). Meanwhile,
phosphogypsum will react with CAH to form ettringite as shown
in Eq. (3). Hence, the amount of CAH decreased with phospho-
gypsum content as shown in Fig. 15. Moreover, with the reaction
between phosphogypsum and CAH, the pH value decreased with
phosphogypsum content as shown in Fig. 5. However, lowest pH
value recorded in this study was 10.9 at 28 days of curing, which
could provide adequate alkaline environment for the pozzolanic
 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195 9

Fig. 14. Relationship between intensity of ettringite or qu and phosphogypsum

content.

reactions to develop the cementitious products.3 It should be

emphasized that CAH had strong influence on the early hydration
and rheology of cement.6 By 28 days of curing, the pozzolanic
reaction was almost completed, to form a strong cementation
bonding with large amount of cementitious compounds (i.e. CSH,
CAH). Hence, the increase in ettringite with phosphogypsum had
positive influence on qu at 28 and 90 days of curing as shown in
Fig. 8(c) and (d), with respect to the pore structure refinement
abovementioned.
However, at short curing period (3 and 7days), the bonding
was not yet to be strongly formed due to less quantity of cementi-
tious products. Under such circumstance, the amount of ettringite
may significantly affect the microstructure of soil matrix, thus
resulting in different effects on strength characteristic. With ad-
equate amount of phosphogypsum, the formation of ettringite
tended to squeeze the large pore volume (especially for dredged
soil with high water content), leading to denser soil structure (in-
creasing density as show in Fig. 3). This behaviour resulted in the
increase in strength. With the increase in phosphogypsum con-
tent, the consummation of CAH (similar to Fig. 15) would reduce
the bonding between soil particles. Meanwhile, large amount of
ettringite showed expansive potential, which would enlarge the
soil volume and disrupt the weak cementation bonding, leading
Fig. 15. Relationship between intensity of CAH and phosphogypsum content.
to the strength loss.7 This agrees well with the observation of
strength development with phosphogypsum content at 3 and
7days of curing as shown in Fig. 8(a) and (b). Therefore, moderate
phosphogypsum content is recommended to be utilized as addi-
tional or replacement binder for cement stabilized soil, which can
improve the strength characteristic of stabilized soil, and avoid
the overuse of phosphogypsum causing ettringite-induced heav-
ing problem.8 It should be emphasized that the micro-mechanism
regarding the strength gain with various phosphogypsum content
range were based on the experimental findings of XRD tests and
physicomechanical behaviour abovementioned. Further investi-
gations should be focused on the evolution of microstructure with
different phosphogypsum content, cement content and curing
times, via SEM, EDX and MIP test.
10 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
As previously mentioned, the engineering properties of sta-
bilized soil with cement and phosphogypsum improved signif-
icantly, with qu at 28 days of curing up to 600 kPa, and E50
at 28 days of curing up to 80 MPa. Hence, these man-made
materials are suitable to be used as the backfill for earth dams
or retaining structure, as well as the raw materials for roadbed
or embankment. This can be considered as part of metabolism of
soil in city, which is environmental friendly and sustainable for
the rapidly urbanization in China. Meanwhile, it is still need to be
cautious with the amount of phosphogypsum used to avoid the
swelling potential of ettringite products, which may result in the
ettringite-induced heaving problem during the field application.
4. Conclusions
This paper proposed a study to use phosphogypsum as ad-
ditional binder improving the engineering properties of cement
stabilized dredged soil with high water content. The effect of
phosphogypsum on physiochemical properties, unconfined com-
pressive strength and deformation modulus of stabilized soil were
investigated. The changes in strength characteristic with respect
to the modification of mineralogical composition were discussed.
The following conclusions can be drawn from this study:
(1) With the increase in phosphogypsum content, the water
content decreased sharply whereas the density increased.
The main changes in water content and density took place
within the first 7 days. In addition, the increases in cement
content and curing time also resulted in a considerable
decrease in water content and an increase in density. The
measured pH value decreased remarkably with an increase
in phosphogypsum content.
(2) Phosphogypsum can effectively improve the strength of
cement stabilized soil with high water content. The un-
confined compressive strength of cement stabilized soil
containing 1.4% to 8.6% phosphogypsum were approxi-
mately 1.7–9.4 times that of soil lacking phosphogypsum.
In addition, the strength increased by 1.3 and 2.1 times in
comparison with those without phosphogypsum at 3 and
7 days, respectively. This finding indicated phosphogypsum
induced sufficient early strength of cement stabilized soil.
(3) Deformation modulus E50 for cement and phosphogyp-
sum stabilized soil correlated well with unconfined com-
pressive strength qu , which was consistent with the stud-
ies of cement-stabilized dredged soil without phosphogyp-
sum. For the presented study, a first-order relationship of
deformation modulus can be expressed as E50 = 111 qu .
(4) At the same binder content, using phosphogypsum to re-
place 10% and 20% of cement, qu were approximately 2.6
and 3.2 times that without phosphogypsum at 28 days of
curing. This finding suggested that phosphogypsum can be
partially used to replace cement, achieving the required
strength in engineering practice.
(5) The significant increase in ettringite due to the presence
of phosphogypsum was the main reason for the strength
improvement of stabilized soil. The increase in ettringite
tended to refine the microstructure of cement stabilized
soil with strong cementation bonding, which positively
contributed to the strength gain. Otherwise, when bond-
ing was limited, the increase in ettringite resulted in the
structure disruption, which led to the strength loss.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This study is supported by the National Natural Science Foun-
dation of China (Grant Nos. 51678157; 41977243), and the China
Postdoctoral Science Foundation (Grant Nos. 2016M600396 and
2017T100355). Partial financial support from the Fundamental
Research Funds for the Central Universities (Grant No.
B200204001) is also acknowledged.
References
1. Tayibi H, Choura M, López FA, Alguacil FJ, López-Delgado A. Environ-
mental impact and management of phosphogypsum. J Environ Manag.
2009;90(8):2377–2386.
2. Hunter D. Lime-induced heave in sulfate-bearing clay soils. J Geotech Eng.
1988;114(2):150–167.
3. Chrysochoou M, Grubb DG, Drengler KL, Malasavage NE. Stabilized
dredged material. III: Mineralogical perspective. J Geotech Geoenviron Eng.
2009;136(8):1037–1050.
4. Degirmenci N, Okucu A, Turabi A. Application of phosphogypsum in soil
stabilization. Build Environ. 2007;42(9):3393–3398.
5. Shen W, Zhou M, Zhao Q. Study on lime–fly ash–phosphogypsum binder.
Constr Build Mater. 2007;21(7):1480–1485.
6. Gartner EM, Young JF, Damidot DA, Jawed I. Hydration of Portland cement.
Struct Perform Cements. 2002;2:57–113.
7. Pollard SJT, Montgomery DM, Sollars CJ, Perry R. Organic compounds
in the cement-based stabilisation/ solidification of hazardous mixed
wastes—Mechanistic and process considerations. J Hazardous Mater.
1991;28(3):313–327.
8. Puppala AJ, Intharasombat N, Vempati RK. Experimental studies
on ettringite-induced heaving in soils. J Geotech Geoenviron Eng.
2005;131(3):325–337.
9. Zeng LL, Hong ZS, Cui YJ. On the volumetric strain–time curve pat-
terns of dredged clays during primary consolidation. Géotechnique.
2015;65(12):1023–1028.
10. Bian X, Wang ZF, Ding GQ, Cao YP. Compressibility of cemented dredged
clay at high water content with super-absorbent polymer. Eng Geol.
2016;208:198–205.
11. Bian X, Ding GQ, Wang ZF, Cao YP, Ding JW. Compression and strength
behavior of cement-lime-polymer solidified dredged material at high water
content. Mar Georesour Geotechnol. 2017;35(6):840–846.
12. Tang YX, Miyazaki Y, Tsuchida T. Practices of reused dredgings by cement
treatment. Soils Found. 2001;41(5):129–143.
13. Federico A, Vitone C, Murianni A. On the mechanical behaviour of dredged
submarine clayey sediments stabilized with lime or cement. Can Geotech J.
2015;52(12):2030–2040.
14. Rosone M, Ferrari A, Celauro C. On the hydro-mechanical behaviour of
a lime-treated embankment during wetting and drying cycles. Geomech
Energy Environ. 2018;14:48–60.
15. Gajo A, Cecinato F, Hueckel T. Chemo-mechanical modeling of artificially
and naturally bonded soils. Geomech Energy Environ. 2019;18:13–29.
16. Horpibulsuk S, Rachan R, Raksachon Y. Role of fly ash on strength and
microstructure development in blended cement stabilized silty clay. Soils
Found. 2009;49(1):85–98.
17. Zhang T, Yue X, Deng Y, Zhang D, Liu S. Mechanical behaviour and micro-
structure of cement-stabilised marine clay with a metakaolin agent. Constr
Build Mater. 2014;73:51–57.
18. Chew SH, Kamruzzaman AHM, Lee FH. Physicochemical and engi-
neering behavior of cement treated clays. J Geotech Geoenviron Eng.
2004;130(7):696–706.
19. Khattab SA, Al-Mukhtar M, Fleureau JM. Long-term stability characteristics
of a lime-treated plastic soil. J Mater Civil Eng. 2007;19(4):358–366.
20. Kampala A, Horpibulsuk S, Prongmanee N, Chinkulkijniwat A. Influence of
wet-dry cycles on compressive strength of calcium carbide residue–fly ash
stabilized clay. J Mater Civ Eng. 2014;26(4):633–643.
21. Horpibulsuk S, Suksiripattanapong C, Samingthong W, Rachan R, Arul-
rajah A. Durability against wetting–drying cycles of water treatment
sludge–fly ash geopolymer and water treatment sludge–cement and silty
clay–cement systems. J Mater Civ Eng. 2016;28(1). 04015078.
22. Du YJ, Jiang NJ, Liu SY, Jin F, Singh DN, Puppala AJ. Engineering properties
and microstructural characteristics of cement-stabilized zinc-contaminated
kaolin. Can Geotech J. 2014;51(3):289–302.
23. Wang Y, Cui YJ, Tang AM, Tang CS, Benahmed N. Changes in thermal
conductivity, suction and microstructure of a compacted lime-treated silty
soil during curing. Eng Geol. 2016;202:114–121.
24. ASTM D2487. Standard Practice for Classification of Soils for Engineering
Purposes (Unified Soil Classification System). West Conshohocken, PA: ASTM
International; 2011.
 L.-L. Zeng, X. Bian, L. Zhao et al. / Geomechanics for Energy and the Environment 25 (2021) 100195
25. ASTM D4219. Standard Test Method for Unconfined Compressive Strength In-
dex of Chemical-Grouted Soils. West Conshohocken, PA: ASTM International;
2011.
26. ASTM D4972. Standard Test Method for pH of Soils. West Conshohocken, PA:
ASTM International; 2011.
27. Bian X, Cui YJ, Li XZ. Voids effect on the swelling behaviour of compacted
bentonite. Géotechnique. 2019;69(7):593–605.
28. Bian X, Cui YJ, Zeng LL, Li XZ. State of compacted bentonite inside a
fractured granite cylinder after infiltration. Appl Clay Sci. 2020;186:105438.
29. Lorenzo GA, Bergado DT. Fundamental parameters of cement-admixed
clay—New approach. J Geotech Geoenviron Eng. 2004;130(10):1042–1050.
30. Kawamura M, Hasaba S, Sugiura S. A fuction of free lime and characteristics
of cement hydration in compacted clay-cement mixtures. Proc Japan Soc
Civil Eng. 1971;191:117–131.
31. Yin JH. Stress–strain strength characteristics of a marine soil with different
clay contents. Geotech Test J. 2002;25(4):459–462.
32. Yang J, Yin ZY, Laouafa F, Hicher PY. Internal erosion in dike-on-foundation
modeled by a coupled hydromechanical approach. Int J Numer Anal Methods
Geomech. 2019;43(3):663–683.
11
33. Yang J, Yin ZY, Laouafa F, Hicher PY. Modeling coupled erosion and filtration
of fine particles in granular media. Acta Geotech. 2019;14(6):1615–1627.
34. Zhao J, Shi XS. Practical estimation of compression behavior of clayey/silty
sands using equivalent void-ratio concept. J Geotech Geoenviron Eng.
2020;146(6). 04020046.
35. Tang YX, Liu HL, Zhu W. Study on engineering properties of cement-
stabilized soil. Chin J Geotech Eng. 2000;22(5):549–554 [in Chinese].
36. Wang D, Abriak NE, Zentar R. Strength and deformation properties of
Dunkirk marine sediments solidified with cement, lime and fly ash. Eng
Geol. 2013;166:90–99.
37. Mitchell JK. Soil improvement state of the art report. In: Proc., 10th Int. Conf.
on Soil Mechanics and Foundation Engineering. Vol. 4. 1981;509–565.
38. Bell FG. Lime stabilization of clay minerals and soils. Eng Geol.
1996;42(4):223–237.
39. Wang Y, Duc M, Cui YJ, et al. Aggregate size effect on the development of
cementitious compounds in a lime-treated soil during curing. Appl Clay Sci.
2017;136:58–66.
40. Tremblay H, Duchesne J, Locat J, Leroueil S. Influence of the nature of
organic compounds on fine soil stabilization with cement. Can Geotech J.
2002;39(3):535–546.