Engineering Geology 303 (2022) 106665

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Engineering Geology
journal homepage: www.elsevier.com/locate/enggeo

Role of free iron oxides in the physicochemical and mechanical properties

of natural clay
Xianwei Zhang a, b, Xinyu Liu a, c, d, *, Lingwei Kong a, Cheng Chen a
a
State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan, China
b
State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu, China
c
University of Chinese Academy of Sciences, Beijing, China
d
Key Laboratory of Environmental Change and Natural Disaster, Ministry of Education, Beijing Normal University, Beijing, China

A R T I C L E I N F O A B S T R A C T

Keywords: While it is widely acknowledged that interparticle bonding due to free iron oxide (FIO) dramatically affects the
Natural clay behavior of natural clay, the exact role of FIO in determining soil physicochemical and mechanical properties
Iron oxides and the underlying mechanism remain unknown. In response, this study removes FIO from natural Zhanjiang
Microstructure
clay, a structured marine clay with cementation, to investigate how FIO affects the physicochemical and me­
Cementation
Mechanical characteristics
chanical behaviors of soil. The immersion method and leaching method (with dithionite-citrate-bicarbonate
Occurrence solution) are used for FIO removal. The test results indicate that the removal of FIO significantly changes the
soil physical indices and degrades the mechanical properties. The effects of FIO removal are explained from the
perspective of microstructural alterations as revealed by scanning electron microscopy (SEM) observations,
mercury intrusion porosimetry (MIP) tests, energy-dispersive X-ray spectroscopy (EDS), and zeta potential
measurements. FIO is distributed at the contacts between soil particles and exists in the bridging form. Due to the
attraction between the positively-charged FIO and the negatively-charged clay mineral surfaces, soil particles are
bounden to form larger soil aggregates with enhanced stability. The removal of FIO leads to the breakdown of
soil aggregates and the generation of large pores, thereby increasing soil compressibility and decreasing the shear
strength. This study provides some new micro-level understandings of how FIO affects the behavior of natural
clay.

1. Introduction
It is widely known that the mechanical responses of natural soil differ
significantly from those of reconstituted soils (Burland, 1990; Leroueil
and Vaughan, 1990) because of the soil structure namely the combina­
tion of the soil fabric and the interparticle forces (Mitchell and Soga,
2005). Natural clay is the result of sedimentation, which involves
geological, physical, mechanical, and chemical processes and these
processes enable the development of soil structure. Specifically,
compared to reconstituted soil, natural soil is characterized by higher
shear resistance, higher stiffness, and lower compressibility (Burland,
1990; Okewale and Coop, 2017, 2018, 2020; Okewale and Grobler,
2021; Okewale, 2020a, 2020b). Interparticle bonding is known to play
an important role in soil structure. Free iron oxide (FIO), which is the
iron oxides and their hydrates [FeO(OH)⋅nH2O] existing independently
in the soil alongside pure silicate minerals, are some of the most com­
mon cementing substances in soil. FIO has been studied in terms of its
effects on soil aggregation and microstructure (Schofield, 1950; Desh­
pande et al., 1964; Greenland et al., 1968). The positive charges at the
edges of FIO attract the negative charges on the surfaces of clay mineral
particles, especially in neutral or acidic chemical environments. The
effects of FIO on soil properties have been widely studied. FIO mainly
exists in lateritic soil (Gidigasu, 1976; Ng et al., 2020), residual soils
from granite (Liu et al., 2021, 2022a), basalt residual soil (Zhang et al.,
2017a), mudstone (Zhang et al., 2020), and marine and terrestrial clays
(Low and Phoon, 2008; Zhang et al., 2014). FIO has been shown to bind
soil particles together (Deshpande et al., 1964) and form porous ag­
gregates (Wilsona et al., 2013). The presence of iron oxides enhances the
stability of soil aggregates (Ng et al., 2020; Liu et al., 2022b), increases
the roughness of the soil surface (Larrahondo et al., 2011), improves

* Corresponding author at: State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of
Sciences, Xiaohongshan, Wuchang, Wuhan 430071, PR China.
E-mail addresses: xwzhang@whrsm.ac.cn (X. Zhang), liuxinyu17@mails.ucas.ac.cn (X. Liu), lwkong@whrsm.ac.cn (L. Kong), cchen@whrsm.ac.cn (C. Chen).

https://doi.org/10.1016/j.enggeo.2022.106665
Received 4 December 2021; Received in revised form 3 March 2022; Accepted 7 April 2022
Available online 12 April 2022
0013-7952/© 2022 Elsevier B.V. All rights reserved.
X. Zhang et al.
Fig. 1. Devices used to remove FIO: (a) modified rigid-wall permeameter; and (b) modified flexible-wall permeameter.
mechanical properties such as stiffness and strength (Zhang et al.,
2017a; Ng et al., 2020; Liu et al., 2021), and decreases compressibility
(Okewale, 2020b).
The above studies have significantly improved the understanding of
how FIO affects soil properties However, existing investigations of FIO
could be improved based on the following considerations. (i) Currently,
iron oxides are commonly mixed with clay minerals or coated on the
surfaces of sand particles to study the effect of cementation. However,
the samples produced in this way do not accurately represent naturally
cemented soils. For example, while goethite in natural soil occurs as
flaky plates (Liu et al., 1994), synthetic goethite has a needle-shaped
micromorphology (Schwertmann and Taylor, 1989). Thus, these artifi­
cial samples cannot entirely reflect the occurrence mechanism of FIO.
(ii) FIO appears in the soil in the forms of crystalline, amorphous, and
quasicrystalline iron oxides (Cornell and Schwertmann, 1999; Zhang
et al., 2016). To date, most research has focused on FIO in residual soils
(Gidigasu, 1976; Ng et al., 2020), in which FIO appears in a ferric
crystalline form due to the long-term weathering process. However, this
is not the case in marine clay, which is the focus of this paper. The FIO in
marine clay mainly occurs in ferrous free form. This form is sensitive to
environmental agents such as weathering and oxidation, which can
affect the physicochemical and mechanical properties of the soil (Yong
et al., 1979; Zhang et al., 2014). (iii) Existing studies largely focus on
how FIO binds to soil particles or aggregates (Larrahondo et al., 2011).
However, the relationship between the cementing effect of FIO and the
macro-level mechanical behavior of soil is yet to be established.
This paper focuses on Zhanjiang clay from China, a typical marine
structured clay with cementation. The FIO in natural Zhanjiang clay was
removed, thereby enabling the investigation of how FIO affects the
physical, mechanical, chemical, mineral, and microstructural features of
natural Zhanjiang clay. This paper is organized as follows. First, the
properties of natural Zhanjiang clay are briefly introduced. Next, the
principles of FIO removal using the leaching method through modified
rigid-wall and flexible wall permeameters are detailed. The effects of
FIO on the behavior of Zhanjiang clay are then evaluated by comparing
the soil samples before and after the FIO removal. Reconstituted soil
samples with the same physical state as the natural soil are also studied
for comparison. Finally, the occurrence of FIO and how it affects soil
behavior are discussed. This study reveals the cementation mechanism
2
Engineering Geology 303 (2022) 106665
and helps to enhance the overall understanding of the mechanical
behavior of natural clay.
2. Materials and methods
2.1. Tested soil
The studied natural clay is from Zhanjiang City (110◦ 22′ 55′′ N,
21◦ 09′ 02′′ E), Guangdong Province, China. In this region, an interactive
marine and terrestrial deposit formed during the Lower Pleistocene of
the Quaternary period. For convenience, many previous studies (Zhang
et al., 2014, 2017b) have termed this soil stratum “Zhanjiang clay.” The
soil samples in this study were collected from depths of 14.0–16.0 m
using thin-walled tube samplers.
2.2. Removal of FIO
In this study, three types of Zhanjiang clay samples, namely the
natural soil sample, the reconstituted soil sample, and the FIO-removed
soil sample, are investigated. To study the effect of FIO on soil behavior,
immersion and leaching methods were used to remove FIO, and soil
treated in these ways is referred to as “FIO-removed soil”. Both methods
use dithionite-citrate-bicarbonate (DCB) solution, which has been
shown to remove 85% or more of the FIO (Mehra and Jackson, 1960;
Zhang et al., 2016). Immersion is used to obtain FIO-removed soil for
physical, chemical, and mineralogical tests, whereas leaching can pre­
pare samples suitable for mechanical and microstructural investigations.
For the immersion method, the uncrushed dried soil (~500 g) was
immersed in DCB solution for 90 d while keeping the soil and solution
fully sealed in a container to avoid the oxidation of ferrous iron oxides.
The soil was then washed repeatedly in distilled water and dried at
105 ◦ C.
For the leaching method, modified rigid-wall and flexible wall per­
meameters (Fig. 1b) were used to prepare undisturbed FIO-removed
specimens with different sizes. The modified rigid-wall permeameter
was used to prepare samples for one-dimensional compression tests,
SEM observations, and MIP tests. An undisturbed soil specimen with a
diameter of 61.8 mm and a height of 20 mm (referred to as the cutting-
ring sample) was firstly prepared using a cutting ring. After placing the
X. Zhang et al. Engineering Geology 303 (2022) 106665

Table 1
Test schemes for Zhanjiang clay.
Test type Test Sample* Critical test
parameters
N FIR R LDW

Gradation √ √ √ √ –
Density √ √ √ – –
Specific gravity √ √ √ – –
Physical Water content √ √ √ – –
Atterberg limits √ √ √ – –
Hydraulic
√ √ √ – –
conductivity
dεa/dt = 0.5%/
UCS √ √ √ –
min
σv = 12.5–3200
kPa; Incremental
One-dimension load ratio = 2;
√ √ √ –
compression Duration for
each σv level = Fig. 2. Particle compositions of natural Zhanjiang clay, reconstituted clay, and
24 h the soil with FIO removed.
Mechanical BP = 500 kPa; B
> 0.98; dεa/dt =
0.05%/min; increased to 85 kPa, allowing the dissolution and discharge of FIO under
CIU √ √ √ – p'0 = 100–1000 the infiltration pressure of 15 kPa. The leaching using DCB solution
kPa (N) or lasted for 30 d, while leaching with distilled water lasted for 10 d. A total
100–400 kPa
of six specimens were prepared in this way and used in unconfined
(FIR and R)
Swelling-
compressive strength (UCS), consolidated undrained triaxial (CIU), and
shrinkage
√ √ √ – – gradation tests. To examine the disturbance of the soil specimen during
Cu Ka radiation the leaching process, an additional natural soil specimen was prepared
at 40 kV and 40 using an identical procedure except that this specimen was leached with
X-ray
Mineralogical mA;
distilled water for 40 d. During the leaching process, the permeability of
√ √ – –
diffraction
Steps = 0.02; 2θ
= 0–70◦ the soil specimen was measured according to ASTM D5084-16 (2016).
X-ray Numerous trials using the above methods showed that the immersion
√ √ – – –
fluorescence and leaching methods removed at least 92% and 85% of FIO, respec­
Specific surface tively (Zhang et al., 2016). As shown in Fig. 1, the methods adopted for
√ √ √ – –
area
Cation
FIO removal have the following merits: (i) by adopting the proper hy­
exchange √ √ √ – – draulic gradient, the FIO can be rapidly and effectively removed; (ii) the
capacity leachate is discharged easily, thereby preventing the interruption of the
Free iron oxides √ √ √ – – test and disturbance of the soil sample; and (iii) the formed specimens
pH
can be directly used in laboratory tests without further preparation
√ – √ – –
Chemical
Total soluble
salt √ √ √ – – procedures.
concentration The reconstituted samples were also prepared to evaluate the effect
Carbonate
√ √ √ – – of the FIO removal process on soil structure. The natural Zhanjiang clay
content was dried and broken apart. The soil that passed through a 1-mm sieve
Samples are
Organic matter
√ – √ – heated at over
was mixed with distilled water according to the water content and void
content ratio of natural soil. The prepared reconstituted specimens were used for
1000 ◦ C for 2 h
Zeta potential pH = 2–13 mechanical tests.
SEM √ √ – – –
Microstructural EDS √ √ – – –
MIP √ √ √ – – 2.3. Test procedures
*
N = natural sample; FIR = FIO-removed soil; R = reconstitute soil; LWD =
natural sample leached with distilled water (see Subsection 2.2). 2.3.1. Physical and mechanical tests
The physical and mechanical properties of natural Zhanjiang clay
soil specimen and cutting ring in an infiltration cell, the soil sample was and the FIO-removed soil were studied following ASTM standards. The
subjected to leaching under a 3-m-water-head hydraulic gradient pro­ detailed test conditions are provided in Table 1. The reconstituted soil
vided by air pressure. The holder (Fig. 1a) prohibited variations in the and the sample leached with distilled water were also tested. The me­
sample volume through mechanical constraints, and the leachate was chanical tests performed included one-dimensional compression, UCS,
discharged through the effluent hole at the bottom of the device. The and CIU tests. The one-dimensional compression tests were performed
leaching process with DCB lasted for 90 d, while leaching with distilled using the cutting-ring samples, while the other mechanical tests were
water was conducted for 30 d. A total of two specimens were prepared in conducted using the standard triaxial specimens. The specimens for
this way. compression and UCS tests were saturated under vacuum, while those
Fig. 1b shows how the FIO-removed specimen with a diameter of 50 used in CIU tests were saturated through a backpressure of 500 kPa. For
mm and a height of 100 mm was prepared using the modified flexible all tests, the pore water pressure coefficient was greater than 0.98. The
wall permeameter. The apparatus applied a hydraulic gradient along the test details are summarized in Table 1.
specimen, thereby enabling rapid leaching. The standard triaxial spec­
imen was saturated under a backpressure of 75 kPa and a cell pressure of 2.3.2. Mineralogical and chemical tests
100 kPa (approaching in-situ overburden stress σ 'v) for 3 d. Note that the The mineral compositions of natural soil and FIO-removed soil were
cell pressure was applied through distilled water, while the backpressure determined by X-ray diffraction (XRD) using a Bruker D8 ADVANCE
was applied through DCB solution. Subsequently, the backpressure was powder diffractometer. The effect of FIO removal on the chemical
composition was evaluated by X-ray fluorescence spectrometry (XRF).

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X. Zhang et al. Engineering Geology 303 (2022) 106665

Table 2
Geotechnical characterizations of the studied soils.
Index Sample

N FIR R

Physical indices
Dry density ρd (g/cm3) 1.092 1.063
Specific gravity Gs 2.682 2.646
Void ratio e 1.428 1.489
The same as natural
Liquid limit wL (%) 64.26 55.60
sample
Plastic limit wp (%) 32.25 26.30
Plasticity index Ip 32.01 29.3
Activity Ad a 0.82 0.52
8
Permeability coefficient K (10−
7.33 49.03 12.36
cm/s)

Swelling-shrinkage indices
Free swell index FSI (%) 47 58 –
Linear shrinkage Ls (%) 14.47 15.77 15.36 w
Shrinkage limit SL (%) 15.5 15.12 15.15
Gradation Fig. 3. Positions of the natural soil and FIO-removed soil in the plasticity chart.
Clay (%) 70.9 78.3
Silt (%) 28.3 21.1
The same as natural
Sand (%) 0.8 0.6
sample
d50 (μm) 3.4 0.8
USCS CH CH

Mechanical parameters
Unconfined compressive strength
175 61.3 24.3
qu (kPa)
Effective cohesion c'cu 75.60 37.2 28.45
Effective internal friction angle φ'cu 12.86 16.48 14.1
Yield stress σ'vy (kPa) 500 350 –
Yield stress ratio YSR 4.4 3.1 –
Chemical properties
Specific surface area SSA (m2/g) 138 95.2
Cation exchange capacity CEC
20.44 24.98
(meq/100 g)
The same as natural
Free iron oxides FIO (%) 4.96 0.4–0.7
sample
pH 6.5 –
Total soluble salt concentration (%) 0.48 0.25
Carbonate content in soil (%) 0.07 Undetected
Fig. 4. Variations in the permeability coefficients of soil samples leached with
Mineralogy DCB solution and distilled water.
Quartz 41.91 52.3
Illite 18.06 15.65
Montmorillonite 8.17 7.36
Kaolinite 15.3 12.03
Chlorite–Serpentine Mixed-Layer The same as natural
5.1 3.91
Mineral sample
Potash Feldspar 4.04 5.57
Manganocalcite 0.77 1.89
Pyrite 3.62 0.32
Hematite 3.02 0.96
a
Activity = Ip/clay fraction (by weight).

The specific surface area (SSA) of Zhanjiang clay was measured using
ethylene glycol monoethyl ether absorption following Carter et al.
(1965). The FIO content was quantified using the method proposed by
Mehra and Jackson (1960); briefly, FIO was extracted by DCB solution,
and the iron content was measured by atomic absorption at 882 nm. The
soil pH was determined using an FG2–FiveGo pH meter (Toledo Inter­
national, Toledo, OH).
Fig. 5. Compression curves of natural Zhanjiang clay, reconstituted clay, and
To evaluate the stability of soil aggregates, the zeta potentials of the soil with FIO removed. The ICL and SCL are determined according to
natural soil and FIO-removed soil were measured using a NanoBrook Burland (1990).
90Plus PALS zeta potential analyzer. Zeta potential indicates the relative
strength of the repulsive and attractive forces among particles; a lower
NaOH. For each sample, the measurement was performed five times, and
absolute value of zeta potential indicates stronger inter-attraction
the average value was taken.
among soil particles and thus higher aggregate stability (Mitchell and
Soga, 2005). The natural or FIO-removed soil was added to distilled
2.3.3. Microstructure tests
water to form a suspension with a concentration of 100 mg/L, and 50 mL
Micro-level observations were performed by SEM using an FEI
of the suspension was used for each test. Before measurement, the pH of
Quanta 250 scanning electron microscope with an EDS system, which
the sample was adjusted in the range of 2–13 using 0.5 M HCL or 0.5 M

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X. Zhang et al. Engineering Geology 303 (2022) 106665

Fig. 6. UCS test results: (a) stress–strain curves; (b) photograph of the failed natural sample; (c) photograph of the failed FIO-removed sample; (d) photograph of the
failed reconstituted sample.

Fig. 7. CIU test results obtained under various effective confining pressures: (a) q–εa curves; (b) effective stress paths. N = natural soil; FIR = FIO-removed soil; R =
reconstituted soil.

allows the analysis of elemental distributions. The pore size distribution
(PSD) of soil was determined by MIP tests following BS-7951 (British
Standard Institution, 1992) using a Quantachrome Pore Master 33
mercury injection apparatus. For all these tests, the vacuum freeze-
drying technique (Mitchell and Soga, 2005) was used for specimen
preparation to avoid any alteration to the soil microstructure because of
shrinkage. The procedures are as follows. The natural soil block is firstly
broken into several pieces (sub-block) by hand and the sub-blocks with
newly-exposed (fresh) surfaces are adopted for SEM observation. The
sub-blocks are then moved to a Polymethyl methacrylate (PMMA) tube.
Subsequently, the liquid nitrogen is poured into the PMMA tube thus the
sub-blocks are cooled down rapidly to − 196 ◦ C and the water in the soil
is transformed to amorphous ice. The isopentane placed in advance in
the tube prevents uneven frost during the cooling. Following this, the ice
in sub-blocks sublimates under the vacuum condition and a temperature
of − 50 ◦ C. Finally, the SEM specimens are obtained without disturbing
the initial structure of soil.

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X. Zhang et al. Engineering Geology 303 (2022) 106665

particle composition. Compared to the natural soil, the FIO-removed soil

had a lower silt content (21.1%), lower mean diameter, and a larger clay
content (78.3%). The removal of FIO also resulted in a dramatic increase
in the content of colloidal particles (diameter < 0.002 mm) from 28.1%
to 62.3% (Fig. 2). These phenomena indicate that the FIO in natural
Zhanjiang clay serves as a cementing agent that binds clay-sized soil
particles or colloidal particles together, forming silt-sized aggregates
with enhanced stability and water resistance. The grading curves in
Fig. 2 diverge at the diameter of 0.009 mm, indicating that the stability-
enhancing effect of FIO on soil particles was strongest for small aggre­
gates (diameter < 0.009 mm). The affected soil particles are perhaps
conditioned to the occurrence feature of FIO and particle morphology.
For example, Zhang et al. (2017b) reported that larger soil particles were
affected in basalt residual soil. However, for some tropical laterites, the
iron oxides in the soil appear in the form of discrete crystals and thus
barely interact or bind with soil particles (Schwertmann and Latham,
1986). In this case, although the soils contain large amounts of iron
Fig. 8. XRD patterns of the studied soils. oxides, the stability of macroaggregates with diameters of 1–2 mm is
almost unaffected by the iron oxides (Deshpande et al., 1964).
Table 2 shows the changes in the physical properties of the soil after
Table 3 the removal of FIO. In general, Table 2 reveals that Zhanjiang clay is
Chemical composition of natural Zhanjiang clay and FIO-removed clay. typical structured clay with poor physical properties, including high
Chemical composition Natural sample Sample with FIO removed water content and high void ratio. Compared to the natural soil, the FIO-
removed soil was characterized by a reduced dry density, reduced spe­
SiO2 60.13 64.5
TFe 6.22 1.52 cific gravity, and a higher void ratio, possibly reflecting the breakdown
Al2O3 18.36 16.88 of soil aggregates. In addition, the FIO-removed soil had lower liquid,
TiO2 0.85 1.25 plastic, and shrinkage limits and lower activity compared to the natural
MnO 0.09 0.2 soil. These changes demonstrate the contribution of FIO to the soil
CaO 0.52 0.4
MgO 1.43 1.17
Atterberg limits; a similar conclusion was reached by Deng et al. (2017)
Na2O 0.56 3.71 for tropical granitic soil. The plasticity index decreased slightly upon the
K2O 2.59 2.93 removal of FIO because both the liquid and plastic limits were reduced.
P2O5 Trace Trace Accordingly, the removal of FIO led to descending trends along the A-
Loss on ignition (%) 9.22 7.63
line and approaching the B-line (Fig. 3). Both the natural and FIO-
removed soil are classified as CH according to USCS. The removal of
FIO also increased the free swell index and linear shrinkage, reflecting
the development of swelling and shrinkage due to the lack of cemen­
tation in the absence of FIO.
Fig. 4 presents the variations in the permeability coefficient (K) of
the soil samples during leaching with DCB solution and distilled water.
During the initial stage of leaching with DCB solution (< 6 d), the
removal of FIO led to a consistent increase in K. Subsequently, soil
particle rearrangement occurred as cementation decreased, and the PSD
also changed in response to seepage within the soil. Hence, Fig. 4 shows
fluctuation in K value during the first 16 d of leaching. In contrast, such
complex hydraulic properties were not observed in the soil leached with
distilled water; in this soil, K remained almost constant during leaching,
confirming the effectiveness of the adopted leaching method.

3.2. Effect of FIO on soil compression behavior

The compression behaviors of the natural and FIO-removed soils are

Fig. 9. Effect of FIO on the zeta potential of Zhanjiang clay.
3. Test results and analysis
3.1. Influence of FIO on soil physical properties
Fig. 2 and Table 2 compare the particle compositions of the natural
and FIO-removed samples. To assess the effect of the leaching process on
natural soil, the results for the sample leached with distilled water are
also presented. The primary components of the natural Zhanjiang clay
were clay (70.0%) and silt (28.3%). Leaching with distilled water had a
negligible effect on the gradation of soil, confirming that seepage
erosion did not affect soil aggregation under the adopted hydraulic
gradients. However, the removal of FIO significantly changed the
shown in Fig. 5, which plots the void index Iv (Burland, 1990) against σ 'v.
Fig. 5 also shows the intrinsic compression line (ICL) and sedimentation
compression line (SCL) to interpret the effect of structure on compres­
sion. According to the previous studies (Cotecchia and Chandler, 2000;
Amorosi and Rampello, 2007; Gasparre et al., 2007), the further to the
right that the yield stress σ'vy is located on the ICL, the more dominantly
the natural microstructure of the soil affects its mechanical behavior. For
the natural soil, the yield states are away from the ICL and located on the
right of SCL, and the difference between this soil and the reconstituted
soil reflects soil fabric and interparticle bonding. A yield state located to
the right of the SCL indicates that the soil is highly sensitive with a brittle
and cemented microstructure. Upon the onset of yielding, the
compression curve of the soil gradually approaches the ICL.
Fig. 5 indicates that the natural Zhanjiang clay had a relatively high
degree of cementation with σ 'vy = 500 kPa, and the yield state was

6
X. Zhang et al.
Fig. 10. SEM images of the soil samples: (a) natural soil (800× magnification); (b) natural soil (2000×); (c) natural soil (5000×); (d) natural soil containing pyrite
crystals (2000×); (e) FIO-removed soil (800×); (f) FIO-removed soil (2000×); (g) FIO-removed soil (5000×); (h) reconstituted soil (800×).
Fig. 11. Results of EDS analyses: (a) EDS patterns of the different soils; and (b)
effect of FIO on the soil elemental contents. Note that Area I–II and Point I–II
correspond to Figs. 10(b) and 10(f), respectively. The numbers in subfigure (b)
stand for the Fe content (unit: %).
7
Engineering Geology 303 (2022) 106665
after reconstitution
located to the right of the SCL. After the removal of FIO, the compression
curve shifted to the left (approaching the SCL) compared to that of
natural soil, σ 'vy decreased to 350 kPa, and the yield stress ratio (YSR, =
σ 'vy/σ 'v) (Cotecchia and Chandler, 1997) decreased to 3.1. However, the
compression curve in this case does not coincide with the ICL, indicating
that even the elimination of cementation did not cause the soil to behave
in the same way as reconstituted soil. Under higher vertical stress of
3200 kPa, the compression curves for both the natural soil and FIO-
removed soil converged to the ICL.
3.3. Influence of FIO on shear strength
The effect of FIO on soil shear response was assessed by conducting
UCS and CIU tests on natural soil, FIO-removed soil, and reconstituted
soil samples (Figs. 6 and 7). For the UCS test, the strain-softening and
well-defined peaks for deviator stress at axial strain εa < 5.0% were
observed for natural soil and FIO-removed soil (Fig. 6a). These two types
of soil also developed shear bands while the reconstituted soil showed
slightly bugling (Figs. 6b–6d). Similar conclusions can also be made
according to the soil behavior in CIU tests. As can be seen from Fig. 7a,
the natural soil showed well-defined peaks for q–εa curves when σ '3 <
σ 'vy. The strain-softening behavior results from degraded cementation
(Leroueil and Vaughan, 1990; Zhang et al., 2017a). Subsequently, as the
strain increased, the shear strength decreased considerably. In addition,
the increase in confining pressure led to more ductile stress–strain
behavior in the soil (Fig. 7a). When σ'3 > σ'vy, the soil exhibited a strain-
hardening response, with the effective stress path turning left with shear
strain, similar to the reconstituted soil (Fig. 7b). The FIO-removed soil
exhibited a strain-hardening response in CIU tests without any peak
value for deviator stress (Fig. 7a). In addition, the FIO-removed soil had
a higher shear strength than the reconstituted soil (Figs. 6a and 7a),
indicating that damaging the cementation of natural soil does not make
soil behavior in shear identical to that of reconstituted soil. The results
also indicate that FIO has different effects on shear strength parameters
(Table 2). The removal of FIO significantly decreased c'cu from 75.6 to
37.2 kPa and caused a slight increase in φ'cu, indicating that the decline
in soil shear strength was primarily reflected by reduced soil cohesion.
X. Zhang et al.
Fig. 12. MIP results for the studied soils: (a) cumulative pore volume curves; (b) PSD curves; and (c) pore volume as a function of particle diameter. The numerical
labels in (c) indicate the relative pore contents.
3.4. Interactions between FIO and clay minerals
The FIO–mineral interactions were evaluated by XRD (Fig. 8 and
Table 2). The natural Zhanjiang clay consisted mostly of clay minerals
including illite, kaolinite, and montmorillonite. Some iron-bearing
minerals such as pyrite and hematite were also detected. The removal
of FIO led to apparent changes in mineral content, including reductions
in iron-bearing and clay minerals and increases in original minerals
(quartz and feldspar). In contrast, the removal of FIO did not change the
mineral type or crystallographic orientation in the soil. Such a phe­
nomenon perhaps indicated compared to soil microstructure, soil
mineralogy was less affected by FIO. FIO acts as a cementing agent to
connect the clay and original minerals, resulting in the formation of soil
aggregates. The quartz in these aggregates is partially masked by the
flaky clay minerals. After the removal of FIO, this masking effect was
largely eliminated, causing the contents of original minerals to increase,
which is consistent with the increase in φ'cu.
3.5. Effects of FIO on the soil chemical composition and aggregate
stability
Table 3 compares the elemental contents between the natural
Zhanjiang clay and the FIO-removed soil. Although the results for Na,
Ca, and Mg may be unrealistic due to the treatment with DCB solution,
the results in Table 3 still reliably reflect the changes in oxide content
due to FIO removal because the contents of Na, Ca, and Mg in the studied
soil were very low (Table 3). It should also be noted that this study did
not focus on organic matter, soluble salts, or carbonates because of their
relatively low contents in the studied soil (see Table 2).
The removal of FIO led to a significant reduction in Fe content and an
increase in the SiO2 content, which is consistent with the XRD results.
Table 3 also indicates that DCB solution removed some aluminum oxides.
As shown in Fig. 2, the removal of FIO caused the clay fraction to increase.
8
Engineering Geology 303 (2022) 106665
It is thus natural to expect a higher SSA for FIO-removed soil than natural
soil; however, Table 2 indicates the opposite trend. This counterintuitive
result might suggest that FIO occurs in a bridging form rather than a
cladding form. FIO distributes among clay minerals and serves as a
cementation agent. A previous study found that free iron oxides have SSA
values higher than 300 m2/g (Borggaard, 1983). Consequently, the
removal of these high-SSA oxides would lead to a decrease in the soil SSA
that cannot be compensated by the increase in clay particle size.
The presence of FIO also affects the adsorption of positive charge by
the soil particle surface and thus also affects the soil stability. This is
reflected in the CEC results (Table 2) and the measured zeta potentials
(Fig. 9). The zeta potential of natural Zhanjiang clay was negative and its
absolute value increased with increasing pH, confirming the negative
charges on the clay mineral surfaces. The removal of FIO reduced the
positive charge and caused the zeta potential to become more negative
(namely increased absolute value). This variation in zeta potential in­
dicates decreased soil stability after the removal of FIO, which is
consistent with the mechanical test results discussed in Section 3.2.
3.6. Effect of FIO removal on soil microstructure
The microstructural properties of natural Zhanjiang clay, recon­
stituted soil, and FIO-removed soil are shown in Fig. 10. The natural soil
exhibited an open flocculated structure with interconnected domains
and granular detrital minerals with edge-to-face or edge-to-edge con­
tacts (Fig. 10a and b). Here, the term domain refers to aggregated clay
plates (Aylmore and Quirk, 1960). Fig. 10c shows that the domains in
natural clay were clusters of parallel clay plates with diameters of 1–10
μm. These microstructural features are responsible for the high porosity
and sensitivity of natural Zhanjiang clay. Interestingly, Fig. 10d shows
the presence of some discrete pyrite crystals in the natural sample.
Although this iron-bearing mineral is also associated with soil cemen­
tation, it barely interacts with clay minerals and thus has a limited effect
X. Zhang et al. Engineering Geology 303 (2022) 106665

on the mechanical behaviors of soil. the FIO-removed soil were similar at the particle surface and particle
The removal of FIO led to the deflocculation of the soil microstructure. contacts, suggesting that the residual Fe, which had a higher level of
As shown in Fig. 10, the FIO-removed soil showed an aggregated structure crystallization than the initial Fe, was not involved in cementation.
with large pores and residual framboidal pyrite (Fig. 10e) resulting from
the leaching with DCB solution. The higher-magnification SEM images
3.7. Influence of FIO on the pore characteristics
indicate that the aggregates consisted of irregular flaky plates that were
more dispersed and finer (diameter < 5 μm) than the original clay particles
The PSDs of the studied soils were determined through MIP tests
in natural Zhanjiang clay (Fig. 10f and g). The aggregation of these plates
(Fig. 12). The pores were classified according to their diameters as
formed an unstable soil structure containing domains with point-to-face
nanopores (< 0.1 μm), micropores (0.1–1 μm), mesopores (1.0–10 μm),
and point-to-edge contacts. The reconstituted soil showed a similar
and macropores (> 10 μm). Nanopores and micropores were dominant
microstructure with large pores and fine particles (Fig. 10h), suggesting
in the natural Zhanjiang clay, accounting for ~85% of the total pore
that the reconstituted soil had lower shear strength and higher
volume, and the PSD curve showed a single peak (Fig. 12). The removal
compressibility compared to natural Zhanjiang clay.
of FIO decreased the micropore volume but increased the volume of
To examine the distribution of Fe in the soil microstructure, EDS tests
macropores (Fig. 12c). The PSD curve of the FIO-removed soil showed
were performed simultaneously with the SEM observations. The selected
two peaks corresponding to pore diameters of 0.15 and 135 μm
areas (or points) for EDS detection covered the aggregate surfaces and
(Fig. 12b). Interestingly, the reconstituted soil and FIO-removed soil
the contacts among soil particles. In total, ten SEM images including 10
exhibited similar pore features, suggesting that the removal of FIO and
points and 10 areas are used for natural soil. This is also the case for FIO-
reconstitution had similar effects on the pore distribution. This finding is
removed soil. Typical EDS patterns are shown in Fig. 11a and the rela­
consistent with the SEM observations. Consequently, due to their higher
tive content of each element is given in Fig. 11b. It should be clarified
contents of macropores, it is reasonable to expect the reconstituted soil
that Au and Pd were not originally present in the soil; they resulted from
and FIO-removed soil to be more compressive than natural clay.
sample preparation. The Fe content at the particle contacts was much
higher than that at the particle surface. Hence, the distribution of Fe
4. Discussion
within the soil microstructure was not uniform, implying that FIO acts as
a cementing agent to bind soil particles and aggregates together (in
Laboratory characterization has revealed significant effects of FIO on
contrast to the cladding form of FIO, in which FIO wraps soil aggre­
the physical, mechanical, chemical, and microstructural features of the
gates). The soil failure during mechanical tests is thus a result of the
soil. How the FIO controls soil behavior is related not only to the
degradation of Fe cementation. Fig. 11a confirms that the removal of
intrinsic properties of FIO but also its occurrence characteristics. Ac­
FIO barely affected the EDS patterns except for the dramatic decrease in
cording to our previous investigation (Zhang et al., 2016), FIO occurs in
the intensity of the Fe peak. Consistent with this finding, the relative
the soil in three forms (Fig. 13): a bridging form, a cladding form, and
contents of Fe at both the aggregate surface and particle contacts were
individual crystalline particles. The bridge-type FIO is common in ma­
reduced upon FIO removal (Fig. 11b). Furthermore, the Fe contents in
rine clays (Cotecchia and Chandler, 1997; Zhang et al., 2014). In these

Fig. 13. Occurrence characteristics of FIO (modified from Zhang et al., 2016): (a) the bridging form of FIO, which is distributed at the contacts between domains; (b)
the cladding form of FIO, which wraps the domains or aggregates of domains; and (c) individual crystalline particles of FIO, which do not participate in cementation.
9
X. Zhang et al.
soils, FIO is distributed at the contacts of domains and serves as bridges
to flocculate these domains, which have edge-to-face or edge-to-edge
contacts. In this case, the domains are formed by the aggregation of
clay mineral plates under the action of molecular attraction, electro­
static attraction, and adsorption (Fig. 13a). The cladding form of FIO is
commonly found in laterite and residual soils (Gidigasu, 1976). In this
case, the domains or aggregates of domains are wrapped by FIO in the
form of cladding (Fig. 13b). The formed aggregates are similar to indi­
vidual soil particles but have superior resistance to external loads, which
enhances the soil strength. In some tropical oxisols, FIO frequently oc­
curs in the form of individual crystalline particles that fill the pores
(Schwertmann and Latham, 1986), as seen in Fig. 13c. Deshpande et al.
(1964) reported the limited cementing effect of this form of FIO.
The results of the present study suggest that in natural Zhanjiang
clay, FIO occurs mainly in the bridging form, although a small number of
individual pyrite crystals were also observed. DCB leaching or immer­
sion destroyed the soil cementation, leading to (i) the release of
exchangeable cations that were previously absorbed by the clay mineral
plates; (ii) the deflocculation of the soil microstructure, which involved
the breaking of domains into smaller-sized plates; (iii) an increase in the
clay fraction along with enhanced swelling and shrinkage potential; (iv)
the rearrangement of soil particles and pores, which increased the
macropore volume and the susceptibility to deformation; and (v)
decreased stiffness and strength.
5. Conclusions
The effects of FIO on the physical, mechanical, chemical, and
microstructural properties of Zhanjiang clay are experimentally inves­
tigated by removing FIO from natural soil. Modified rigid-wall and
flexible wall permeameters were adopted to remove FIO with the help of
DCB solution. Leaching with DCB using these modified apparatuses
effectively removed FIO from the natural soil. The removal of FIO
significantly changed the physical properties of Zhanjiang clay and led
to the degradation of the soil mechanical properties. These changes were
demonstrated to be related to the breakdown of cementation and the
structural degradation of the soil. FIO in the Zhanjiang clay occurs in a
bridging form, as revealed by XRD, SEM, and EDS analyses. The FIO in
the studied soil was mainly distributed at the contacts between soil
particles or aggregates. The attraction between the positive charges
within FIO and the negative charges at the surfaces of clay mineral
particles results in the formation of soil aggregates, thereby enhancing
the soil stability. FIO can also bind soil aggregates to form larger ag­
gregates. Thus, the removal of FIO led to soil de-aggregation and the
generation of large pores, as indicated by the MIP results. Consequently,
the FIO-removed soil was more compressible and had lower shear
resistance compared to the natural soil.
Data availability statement
Some or all data, models, or code that support the findings of this
study are available from the corresponding author upon reasonable
request. Supplementary materials are available.
CRediT authorship contribution statement
Xianwei Zhang: Visualization, Investigation, Writing – review &
editing. Xinyu Liu: Conceptualization, Methodology, Software, Data
curation, Writing – original draft. Lingwei Kong: Supervision. Cheng
Chen: Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
10
Engineering Geology 303 (2022) 106665
Acknowledgments
The authors are grateful for financial support from the National
Natural Science Foundation of China (Nos. 42177148, 41972285,
41972293, 52178372), the Youth Innovation Promotion Association
CAS (Grant No. 2018363), the opening fund of State Key Laboratory of
Geohazard Prevention and Geoenvironment Protection (Grant No.
SKLGP2020K024), Science Fund for Distinguished Young Scholars of
Hubei Province (2020CFA103) and the opening fund of Key Laboratory
of Environmental Change and Natural Disaster, Ministry of Education of
the People's Republic of China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.enggeo.2022.106665.
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