Journal of Hazardous Materials 417 (2021) 126073

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Journal of Hazardous Materials

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Research Paper

Mn-incorporated ferrihydrite for Cr(VI) immobilization: Adsorption

behavior and the fate of Cr(VI) during aging
Chenwei Liang , Fenglian Fu *, Bing Tang
School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China

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

Editor: Dr. Haizhou Liu Chromium(VI) (Cr(VI)) is an environmental priority pollutant, and its mobility in natural environment is strongly
controlled by ferrihydrite. Ferrihydrite always contains various ions, which may change the properties of fer­
Keywords: rihydrite, thereby affecting the behavior of pollutants. This study aims to investigate the adsorption of Cr(VI) by
Chromium(VI) Mn-incorporated ferrihydrite and the mobility behavior of Cr(VI) during aging. Results showed that the incor­
Ferrihydrite
poration of Mn enhanced the adsorption of Cr(VI) on ferrihydrite, and the adsorption performance increased with
Manganese
the increase of Mn content. The maximum adsorption capacity for Cr(VI) reached to 48.5 mg/g with molar ratio
Transformation
Mobilization of Mn/Fe 5%, while it was 36.1 mg/g for pure ferrihydrite. After aging for 7 days, ferrihydrite transformed into
goethite and hematite. The adsorbed Cr(VI) on the surface of ferrihydrite was released into the solution during
aging. The incorporation of Mn retarded the transformation of ferrihydrite, which inhibited the migration of
adsorbed Cr(VI). Nevertheless, the incorporation of Mn resulted in the transformation of adsorbed Cr(VI) to non-
desorbed Cr(VI), thereby enhancing the retention of Cr(VI). Our results suggest that the incorporation of Mn into
ferrihydrite has an important role on the mobility of Cr(VI), which enhances our understanding of the behavior of
Cr(VI) in the environment.

1. Introduction 2019). However, ferrihydrite is metastable in environment and easily

Chromium(VI) (Cr(VI)), as one of the heavy metals widely existing in
the environment, usually derives from metal finishing, electroplating,
and manufacturing dyes (Stoller et al., 2018; Vilardi et al., 2019; Yang
et al., 2019; Yu et al., 2020). Due to its strong carcinogenicity and high
migration, Cr(VI) receives widespread attention (Di Palma et al., 2018;
Brasili et al., 2020; Jiang et al., 2020; Yu et al., 2020; Zeng et al., 2020).
Moreover, the fate and mobilization of Cr(VI) in the natural environ­
ment is tightly associated with the iron oxides (Vilardi et al., 2019; Yang
et al., 2019; Jiang et al., 2020).
Iron oxides are widely present in soil, sediments, lakes, and rocks
(Liu et al., 2016). Because of their good affinity, they are widely used to
remove heavy metals in the environment (Pedersen et al., 2006; Hua
et al., 2012; Jiang et al., 2020). Common iron oxides in the environment
are ferrihydrite, goethite, hematite, and magnetite with different char­
acteristics, such as stability, specific surface area, and reactivity, among
which ferrihydrite has better adsorption capacity for Cr(VI) owing to its
higher specific surface area and abundance of reactive functional groups
(Pedersen et al., 2006; Das et al., 2011a; Karimian et al., 2019; Xue et al.,
transforms into relatively stable lepidocrocite, goethite, and hematite
(Das et al., 2011b; Wang et al., 2015b; Liu et al., 2016; Karimian et al.,
2019; Zhang et al., 2019), which may greatly influence the behaviors of
environmental geochemistry of contaminants associated with ferrihy­
drite in the environment due to the different adsorption capacity of
transformation products (Das et al., 2011b; Karimian et al., 2019; Zhang
et al., 2019). Moreover, the conversion behavior of ferrihydrite was
influenced by various factors such as pH, temperature, oxygen concen­
tration, and ions (Pedersen et al., 2006; Das et al., 2011b; Wang et al.,
2015b; Liu et al., 2016; Karimian et al., 2019). Previous studies have
found that Fe(II) was beneficial to the transformation of ferrihydrite,
and the transformation products of ferrihydrite depended tightly on the
aqueous conditions such as the concentration of aqueous Fe(II), pH, and
temperature (Pedersen et al., 2006; Das et al., 2011a; Hansel et al., 2011;
Zhang et al., 2019).
In addition, in natural systems, Fe(III) (hydr)oxides seldom exist as a
pure phase and usually contain a significant amount foreign ions, such as
Mn2+, Al3+, and Cu2+ (Hansel et al., 2011; Masue-Slowey et al., 2011;
Liu et al., 2016; Dai et al., 2018). These ions are usually sequestered in

* Corresponding author.
E-mail address: fufenglian2006@163.com (F. Fu).

https://doi.org/10.1016/j.jhazmat.2021.126073
Received 25 January 2021; Received in revised form 15 April 2021; Accepted 5 May 2021
Available online 11 May 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
C. Liang et al.
Fe(III) (hydr)oxides through structural incorporation, surface adsorp­
tion, and surface precipitation (Liu et al., 2016; Dai et al., 2018), which
can change the morphology, crystallinity, surface area, solubility, and
surface chemical properties of Fe(III) (hydr)oxides, thereby further
affecting the removal of contaminants (Rout et al., 2014; Wang et al.,
2015b; Liu et al., 2018; Alvarez-Cruz and Garrido-Hoyos, 2019). Dai
et al. (2018) found that the Al and Mn ions increased the zeta potential
of ferrihydrite, which affected the deposition of ferrihydrite, and the Si
decreased the zero potential of ferrihydrite nanoparticles. Masue-Slo­
wey et al. (2011) found that the Al substitution in ferrihydrite had a
significant impact on their reactivity, as well as their adsorption ca­
pacities for As(III) and As(V). Liu et al. (2018) found that Mn substitu­
tion in goethite enhanced the adsorption of Pb(II). Ni et al. (2016) found
that Al substitution in ferrihydrite can improve the adsorption capacity
of Cr(VI).
Mn, which can be found in many geological environments, such as
sediments and soils, can co-exist with iron (oxyhydr)oxides in many
geological settings (Tan et al., 2005; Lan et al., 2017; Dai et al., 2018).
Moreover, Mn is easily incorporated into iron oxide due to its similar
ionic radius to iron and a higher content in the environment (Dai et al.,
2018; Liu et al., 2018). However, the incorporation of Mn changed the
structure of iron (oxyhydr)oxides (Alvarez-Cruz and Garrido-Hoyos,
2019), which further affected the physicochemical properties of iron
oxides (Dai et al., 2018). Given that Cr(VI) is tightly associated with iron
(oxyhydr)oxides in water and soils environment and the incorporation
of Mn may affect the physical and chemical properties of ferrihydrite,
the incorporation of Mn may affect the geochemical behavior of Cr(VI).
Moreover, there is little information about the effect of incorporation of
Mn on the retention Cr(VI) by ferrihydrite. Therefore, it is of great sig­
nificance to investigate the effect of incorporation of Mn on the
adsorption of Cr(VI) by ferrihydrite and its behavior during aging.
Accordingly, the present study is mainly to: (i) investigate the effect
of Mn on the adsorption behavior of Cr(VI) by ferrihydrite, and (ii)
explore the behavior of Cr(VI) during aging process of Mn-incorporated
ferrihydrite. To this end, various techniques, such as X-ray diffraction
(XRD), scanning electron microscopy (SEM), energy dispersion X-ray
spectrometer (EDS), Fourier transform infrared spectroscopy (FTIR),
and X-ray photoelectron spectroscopy (XPS), were used to characterize
solid products. This study can deepen our understanding of the
adsorption behavior of Mn-incorporated ferrihydrite on Cr(VI), as well
as the mobility of Cr(VI) during its transformation process.
2. Materials and methods
2.1. Synthesis of Mn-incorporated ferrihydrite and ferrihydrite
The method of preparing Mn-incorporated ferrihydrite with different
content of Mn is based on the reported procedure (Liu et al., 2018).
Firstly, 0.2 M iron nitrate and x mL 1 M (the x varies with the set molar
ratio of Mn/Fe 0%, 1%, 3% and 5%) manganese chloride were added to
100 mL deionized water. The mixtures were magnetically stirred (~650
rpm), and then the pH of the mixtures was adjusted to 7.0 using 1.0 M
NaOH or HCl. After that, the obtained suspensions were centrifuged at
10,000 rpm for 10 min and filtered through a 0.45 µm filter membrane.
The residual slurry was washed three times with deionized water in
order to remove dissolved salts on the surface of slurry. The obtained
slurry was freeze-dried for 24 h, ground carefully in an agate mortar, and
stored under refrigeration for characterization and further experiments.
The obtained samples at Mn/Fe mole ratios of 0%, 1%, 3%, and 5% were
labelled as Fh, Fh-Mn-1, Fh-Mn-3, and Fh-Mn-5, respectively.
2.2. Adsorption experiments
The adsorption experiments of Cr(VI) on Mn-incorporated
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Journal of Hazardous Materials 417 (2021) 126073
ferrihydrite (Mn/Fe mole ratios = 0%, 1%, 3%, and 5%) were deter­
mined as a function of initial pH (5.0–9.0). 0.375 g Mn-incorporated
ferrihydrite was added into the 250 mL Erlenmeyer flask containing
150 mL of 50.0 mg/L Cr(VI) after the adjustment of pH by 1.0 M HCl or
NaOH solutions. After that, the suspension mixtures were shaken for 12
h on a thermostatic shaker (120 ± 5 rpm) at the room temperature of 25
± 1 ◦ C.
The adsorption isotherms of Cr(VI) were performed by adding 0.125
g Mn-incorporated ferrihydrite to 50 mL centrifuge tubes containing
various initial Cr(VI) concentration ranging from 20.0 to 250.0 mg/L.
The initial pH of each reaction solution was adjusted to 3.0 ± 0.1 by
dropwise addition of either 1.0 M HCl or NaOH solutions. The centrifuge
tubes were shaken for 24 h for sufficient contact on a thermostatic
shaker (120 ± 5 rpm) at the room temperature of 25 ± 1 ◦ C. Finally, 3.0
mL of the mixtures were taken, and then passed through a 0.45 µm filter
membrane to determine Cr(VI) concentration in the solution. The
amount of adsorbed Cr(VI) was calculated from the difference between
the initial and final concentrations.
2.3. Transformation experiments
Firstly, 0.375 g Mn-incorporated ferrihydrite was added to 250 mL
Erlenmeyer flask containing 150 mL of 50.0 mg/L Cr(VI) solution after
the pH of the solution was adjusted to 5.0, 7.0, 9.0 with HCl or NaOH
solution. Secondly, the mixtures were shaken on a thermostatic shaker
(120 ± 5 rpm) at the room temperature of 25 ± 1 ◦ C for 24 h to obtain
the Cr(VI)-adsorbed Mn-incorporated ferrihydrite (named as Cr(VI)-
adsorbed Fh, Fh-Mn-1, Fh-Mn-3, and Fh-Mn-5). Finally, they were
sealed with wrap film and transferred to an oven at 70 ◦ C for 7 days.
Since the transformation of ferrihydrite at room temperature is very
slow, a temperature of 70 ◦ C was selected to obtain a reasonable length
of time (Das et al., 2011a; 2011b). Approximate 3.0 mL mixtures were
collected and filtered through a 0.45 µm filter membrane at specific time
intervals to analyze the concentration of Cr(VI) in the solution. The
remaining samples were used for desorption and characterization.
2.4. Determination of Cr(VI) concentrations
Different types of Cr(VI) were tracked during the transformation
experiments. At specific time intervals, the suspension mixtures were
sampled and filtered through a 0.45 µm membrane filter to determine
the Cr(VI) concentration by 1,5-diphenylcarbohydrazide spectrophoto­
metric method with a UV/visible spectrophotometer at 540 nm (Wang
et al., 2015a). Adsorbed Cr(VI) on the surface of Mn-incorporated fer­
rihydrite was obtained by desorption of Cr(VI)-adsorbed Mn-incorpo­
rated ferrihydrite with 1.0 M Na2HPO4 (Hai et al., 2020). Non-desorbed
Cr(VI) was obtained by subtracting the Cr(VI) concentration in the so­
lution and the adsorbed Cr(VI) from the initial Cr(VI).
2.5. Characterization of the solid phase
Mineral phases of the solid samples were characterized by XRD
(Bruker D8 Advance X-ray diffractometer) with a Cu Kα radiation
source. The morphologies and surface element composition of the solid
samples were tested by SEM (SU8010, Hitachi, Japan) equipped with
EDS (550i, IXRF Systems, Inc). The molecular structures of the powders
were analyzed by FTIR (Nicolet IS50, Thermo Fisher, USA). 1.0 mg of
the dried sample was ground and mixed in an agate mortar at a mass
ratio of 1:150 with dry KBr powder, and the measurement was per­
formed at a wavelength of 400–4000 cm− 1. XPS (Shimadzu Co., Japan)
was employed to measure the chemical composition on the surface of
samples, and the obtained data were analyzed using the XPSPEAK 41
software.
C. Liang et al.
Fig. 1. (a) XRD patterns of series of Mn-incorporated ferrihydrite (Mn/Fe mole ratios = 0%, 1%, 3%, and 5%) and (b) magnified XRD patterns in the range of 2θ
with 25–46.5◦ .
3. Results and discussion
3.1. Characterization of Mn-incorporated ferrihydrite and ferrihydrite
3.1.1. XRD analysis
The XRD patterns of Mn-incorporated ferrihydrite and ferrihydrite
displayed two characteristic broad peaks at 2θ of around 35◦ and 61◦ ,
which were indicative of poorly crystallized ferrihydrite-like phase, in
line with the previous results (Mitsunobu et al., 2013). Besides, no
additional peak occurred after the incorporation of Mn in the XRD
patterns, which indicated that ferrihydrite was the predominant phase.
However, compared with pure ferrihydrite, the shifts of the diffraction
peaks were observed for Mn-incorporated ferrihydrite in 2θ of 35◦
(Fig. 1(b)), indicating the changes in ferrihydrite structure after the
incorporation of Mn.
3.1.2. SEM-EDS analysis
Fig. S1 showed the SEM images of pure ferrihydrite and Mn-
incorporated ferrihydrite. The morphologies of freshly prepared ferri­
hydrite and Mn-incorporated ferrihydrite were irregular aggregates that
composed of many spherical particles. It was found that the size of the
spherical particles between pure ferrihydrite and Mn-incorporated fer­
rihydrite was different. Compared with pure ferrihydrite, the size of
spherical particles in Mn-incorporated ferrihydrite was larger. The dif­
ference of particles size of ferrihydrite and Mn-incorporated ferrihydrite
indicated that the incorporation of Mn changed the morphology of fer­
rihydrite. Additionally, the study of EDS of Fh-Mn-3 confirmed that Fe,
O, and Mn existed on the surface of Fh-Mn-3.
3.1.3. FTIR spectra
FTIR spectra of pure ferrihydrite and Mn-incorporated ferrihydrite
were shown in Fig. S2. The types of functional group of all Mn-
incorporated ferrihydrite were similar to the types of functional group
of pure ferrihydrite. For example, the bands at 3200–3600 cm− 1 corre­
sponded to O-H stretching vibration of stoichiometric or non-
stoichiometric hydroxyl unites, while the band at 1636 cm− 1 was
ascribed to H2O bending bands vibrations. A sharp peak at 1384 cm− 1
was regarded as N-O anti-symmetric stretching in nitrate (Salama et al.,
2015). The types and locations of these functional groups on mineral
surface were consistent with previous studies (Liu et al., 2018; Zhang
et al., 2019). In addition, the bands at 3200–3600 cm− 1, that
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Journal of Hazardous Materials 417 (2021) 126073
corresponded to the hydroxyl functional group shifted to lower wave­
numbers after the incorporation of Mn. This can be explained as a
change in internal structure of ferrihydrite. The incorporation of Mn
distorted the internal structure of ferrihydrite (Ruan et al., 2002; Liu
et al., 2018), which made the dilation of hydrogen bonds (Ruan et al.,
2002). This caused elongation and weakening of hydrogen bonds. Thus,
the position of surface hydroxyl groups was shifted.
3.1.4. XPS analysis
To further explore the effects of Mn on the surface properties of
ferrihydrite, valence states of surface elements of synthetic samples were
investigated by XPS analysis. As shown in Fig. 2, the peaks of 711.0 and
710.7 eV corresponded to the Fe 2p3/2 characteristic peak, while the
peaks at 724.5 and 724.3 eV were characteristic peaks of Fe 2p1/2 (Liu
et al., 2017; Jiang et al., 2020). The binding energy of Fe 2p slightly
shifted to lower binding energy in the presence of Mn. This can be
explained by the difference in electronegativity between Mn and Fe
(Radha et al., 2019; Jiang et al., 2020). The incorporation of Mn resulted
in the appearance of Fe-O-Mn pairs. Compared with Fe-O-Fe pairs, the
electron density around Fe in Fe-O-Mn pairs increased, which was
attributed to the fact that the electronegativity of Mn (1.55) is lower
than that of Fe (1.83). This leaded the Mn-O pair having more ionic bond
characteristics, while the Fe-O pair has more covalent bond character­
istics. Thus, this resulted in the reduce of Fe 2p binding energy. Besides,
no obvious changes in the Fe 2p spectra were found (Fig. 2(a) and (b)),
implying that there was no change of valence state of Fe. The O 1s
spectra of minerals presented in Fig. 2(c) and (d) could be divided into
three peaks that assigned to the oxygen in the crystal (Fe-O), oxygen on
the surfaces (-OH), and oxygen in the adsorbed water of ferrihydrite
(H-O-H), respectively. The peaks located at 529.7 and 529.6 eV were
assigned to Fe-O of ferrihydrite, while the peaks at 531.1 and 530.9 eV
were attributed to the -OH (Liu et al., 2018; Xue et al., 2019; Huang
et al., 2020). The peaks at 532.2 and 532.1 eV were attributed to H-O-H
(Xue et al., 2019). It was found that the proportion of -OH was 32.9% in
Fh, while it was 34.1% in Fh-Mn-3. This revealed that the incorporation
of Mn enhanced the proportion of surface hydroxyl groups. In case of Mn
2p spectra, the Mn 2p3/2 spectrum was fitted by two peaks corre­
sponding to Mn(II) (640.6 eV) and Mn(III) (641.8 eV) (He et al., 2019;
Wan et al., 2020; Yang et al., 2020), indicating that part of Mn(II) was
oxidized.
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Fig. 2. XPS spectra of prepared Fh ((a) and (c)) and Fh-Mn-3 ((b), (d) and (e)).

4
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Fig. 3. Adsorption experiments of Cr(VI) by Mn-incorporated ferrihydrite (Mn/Fe mole ratios = 0%, 1%, 3%, and 5%) at initial pH 5.0, 7.0, and 9.0.
3.2. Adsorption experiments
The adsorption behaviors of Cr(VI) on Fh, Fh-Mn-1, Fh-Mn-3, and Fh-
Mn-5 were investigated under different initial pH conditions. It was
noted that the incorporation of Mn enhanced the adsorption of Cr(VI) by
ferrihydrite (Fig. 3). For example, at initial pH 5.0, the concentration of
Cr(VI) decreased from 50.0 mg/L to 7.8 mg/L for Fh after reaction for
12 h, while it was 5.6 mg/L for Fh-Mn-1. Moreover, the promotion effect
enhanced with the increase of Mn content. For Fh-Mn-5, the Cr(VI)
concentration decreased from 50.0 mg/L to 3.6 mg/L. These could be
explained by the following two reasons. On the one hand, the incorpo­
ration of Mn changed the surface structure of ferrihydrite. It was
observed that the hydroxyl groups on the surface of ferrihydrite
increased, which was certified by the results of O (1 s) XPS spectra
(Fig. 2(c) and (d)). On the other hand, a small amount of Mn was present
on the surface of ferrihydrite (Fig. 2(e)), which increased the positive
charge on the surface of ferrihydrite (Ren et al., 2012), thereby
enhancing the adsorption of Cr(VI).
Besides, the sorption behavior of ferrihydrite for Cr(VI) was strongly
dependent on the initial pH values. Compared with neutral and alkaline
conditions, acidic conditions were more conducive to the adsorption of
Cr(VI) by ferrihydrite. This might be attributed to the Cr(VI) speciation
and the abundance of positively charged adsorption sites on ferrihydrite.
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Journal of Hazardous Materials 417 (2021) 126073
Firstly, under acidic conditions, the Cr(VI) in the solution mainly existed
in the form of HCrO-4, while in alkaline conditions, Cr(VI) mainly existed
as CrO2-4 (Fig. S3) (Ni et al., 2016; Yu et al., 2020; Mpouras et al., 2021).
Since HCrO-4 had a smaller free energy of adsorption than CrO2- 4
(Chowdhury et al., 2012), it was easier to be adsorbed to the surface of
ferrihydrite. Secondly, it has been reported that the pH of zero-charge of
the ferrihydrite was about 7.5 (Kosmulski, 2009; Ni et al., 2016), which
meant that at initial pH of 5.0, the surface of ferrihydrite was positively
charged, which attracted negatively charged Cr(VI) species. Moreover,
the pH of the solution during adsorption in acidic conditions was lower
than that in neutral and alkaline conditions (Fig. S4). Thus, more Cr(VI)
was adsorbed under acidic conditions.
Additionally, in order to further study the adsorption behavior of
ferrihydrite and Mn-incorporated ferrihydrite on Cr(VI), the isotherm
adsorption experiments were conducted. The Langmuir and Freundlich
isotherm adsorption models were employed to fit the adsorption data.
The related fitting results were shown in Fig. S5, and fitting parameters
were shown in Table S1. It was found that the values of correlation
coefficient (R2) of Langmuir model were greater than 0.99, which was
higher than all the R2 of Freundlich model, indicating that Cr(VI)
adsorption process was well fitted using the Langmuir equation. The
adsorption was regarded as a monolayer adsorption. The maximum
adsorption capacities of Cr(VI) by Fh, Fh-Mn-1, Fh-Mn-3, and Fh-Mn-5
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Fig. 4. XRD patterns of transformation products of Cr(VI)-adsorbed Fh and Fh-Mn-3 at different time (0, 4, and 7 d) at initial pH 5.0, 7.0, and 9.0 (H: hematite).

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Fig. 5. SEM images of transformation products of Cr(VI)-adsorbed Fh (a) and Fh-Mn-3 (b), and (c) EDS image of Cr(VI)-adsorbed Fh-Mn-3 after aged for 7 days at
initial pH 7.0 (F: ferrihydrite, G: goethite, and H: hematite).
were 36.1, 42.6, 43.5, and 48.5 mg/g, respectively. The adsorption ca­
pacities increased with the increase of Mn content, which was consist the
results of batch experiments. The increase in the adsorption capacity of
Cr(VI) with increasing Mn content might be due to the increase in the
content of surface hydroxyl groups and positive charge on the surface of
ferrihydrite (Ren et al., 2012), which increased availability of
exchangeable sites and/or sites for surface complexation.
3.3. Transformation experiments
3.3.1. XRD results
The XRD diffraction phases of transformation products at different
aging time were presented in Fig. 4. The Cr(VI)-adsorbed Fh and Fh-Mn-
3 showed two broad peaks at around 35◦ and 61◦ , suggesting that their
main phase after the adsorption of Cr(VI) was ferrihydrite. As the aging
processed, the two broad peaks began to disappear. Some peaks iden­
tified as hematite gradually developed along with the parallel disap­
pearance of the ferrihydrite peaks, and gradually became sharper with
aging. At initial pH 7.0 and 9.0, Cr(VI)-adsorbed Fh transformed to
hematite after aging for 4 days, while no transformation product
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Journal of Hazardous Materials 417 (2021) 126073
generated at initial pH 5.0, indicating that neutral and alkaline condi­
tions were conducive to mineral transformation in comparison with
acidic conditions. After aging for 7 days, the intensity of peaks belonging
to the transformation product of Fh became stronger and sharper,
indicating that the transformation products were better crystallized.
However, the transformation product of Fh-Mn-3 displayed a lower
degree of crystallinity. This indicated that the transformation of ferri­
hydrite was inhibited after the incorporation of Mn.
Ferrihydrite can transform to more stable forms mainly through
dissolution, recrystallization, dehydration, and rearrangement process
(Wang et al., 2015b; Chen et al., 2020). Hematite is favorable to pre­
cipitate via dehydration and rearrangement, while goethite forms due to
the dissolution-recrystallization process. These processes compete each
other during the transformation of ferrihydrite (Wang et al., 2015b). It
was seen that due to the incorporation of Mn, the transformation of
ferrihydrite was inhibited, which was similar to previous studies re­
ported by Wang et al. (Wang et al., 2015b). However, no goethite was
formed during the entire reaction process, which may be related to the
form of Mn and the pH in the solution. Since no Mn was detected in the
solution (Fig. S6), the incorporated Mn was more present in the structure
C. Liang et al. Journal of Hazardous Materials 417 (2021) 126073

Fig. 6. FTIR spectra of C(VI)-adsorbed Mn-incorporated ferrihydrite (Mn/Fe mole ratios = 0% and 3%) before and after aging for 7 days at initial pH 7.0.

Fig. 7. XPS spectra of Cr(VI)-adsorbed Fh ((a) and (c)) and Fh-Mn-3 ((b) and (d)) after aging for 7 days at initial pH 7.0.

8
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Fig. 8. Variation of Cr(VI) in the solution during the aging process of Cr(VI)-adsorbed Mn-incorporated ferrihydrite at different initial pH of (a) 5.0,(b) 7.0, and
(c) 9.0.
or surface, and the change of the structure may affect the dehydration
and rearrangement of ferrihydrite, thereby inhibiting the transformation
of ferrihydrite. According to the EDS and XPS results (Fig. S1(c) and
Fig. 2(e)), it was seen that Mn existed on the surface of the ferrihydrite,
which limited the accessibility of the surface sites of ferrihydrite,
impeding its transformation via dissolution-recrystallization (Cudennec
and Lecerf, 2006; Das et al., 2011a; Hansel et al., 2011; Chen et al.,
2020). Besides, after aging for 7 days under different initial pH (5.0, 7.0,
and 9.0), the pH of the final solution was between 6 and 7.5 (Fig. S7),
which was more conducive to the formation of hematite (Cudennec and
Lecerf, 2006; Das et al., 2011a). Therefore, no goethite was found, and
the incorporation of Mn inhibited the transformation of ferrihydrite.
3.3.2. SEM results
The morphologies of the transformation products of Cr(VI)-adsorbed
Fh and Fh-Mn-3 were shown in Fig. 5. For Cr(VI)-adsorbed Fh, it was
found that the rhomb-shaped hematite was the main transformation
product, and a minor amount of rod-shaped goethite was also found
after aging for 7 days. These indicated that ferrihydrite transformed to
hematite and goethite, which was similar to the previous results (Das
et al., 2011b; Wang et al., 2015b). Compared with Fh, the main
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Journal of Hazardous Materials 417 (2021) 126073
transformation products of Cr(VI)-adsorbed Fh-Mn-3 were spherical
ferrihydrite aggregates and small amount of rhomb-shaped hematite,
implying that the incorporation of Mn inhibited the conversion of fer­
rihydrite to relatively stable minerals. Besides, the elemental composi­
tion on the surface of Cr(VI)-adsorbed Fh-Mn-3 after aging for 7 days
was measured by EDS. It could be noted that after conversion, the
content of O on the surface of ferrihydrite decreased from 55.6% to
52.8% (Fig. S1(c) and Fig. 5(c)), which was attributed to the dehydra­
tion process of ferrihydrite and the ligand exchange mechanism between
hydroxyl groups and oxyanions. The content of Cr was 0.8%, suggesting
the existent of Cr on the surface of transformation products of
Mn-incorporated ferrihydrite.
3.3.3. FTIR results
FTIR was used to analyze the changes of Fh and Fh-Mn-3 surface
functional groups before and after aging (Fig. 6). It could be found that
after aging for 7 days, the intensity of some peaks was weakened, and
new peaks occurred. For example, the band at 1384 cm− 1 corresponding
to N-O anti-symmetric stretching has been significantly weakened. Be­
sides, the bands at 467 and 564 cm− 1 occurred in Fh, which was
attributed to Fe-O vibration of goethite or hematite (Salama et al.,
C. Liang et al.
Fig. 9. Proportions of Cr(VI) in aqueous, adsorbed, and non-desorbed state at initial pH 5.0, 7.0, and 9.0 during the aging process of Cr(VI)-adsorbed Fh, Fh-Mn-1,
Fh-Mn-3, and Fh-Mn-5.
2015). Nevertheless, the peaks assigned to Fe-O were not obvious in
Fh-Mn-3, indicating that only a small amount of conversion products
occurred. These results suggested that Mn impeded the transformation
process of ferrihydrite, consistent with the results of XRD and SEM.
3.3.4. XPS results
In order to fully understand the changes of chemical composition and
valence of elements on the surface of minerals after aging, XPS analysis
was employed (Fig. 7). For O 1s spectra, the spectra could be fit up to
three bands with the binding energies of 529.6, 531.0, and 532.0 eV.
The band at 529.6 eV was attributed to the Fe-O, while the bands at
531.0 and 532.0 eV were due to -OH and H-O-H, respectively. From the
proportion of oxygen-containing functional groups in Fh, it was found
that no fitting peak belonging to H-O-H occurred after aging for 7 days
(Fig. 2(c) and Fig. 7(a)). Moreover, the proportion of H-O-H for Fh-Mn-3
decreased from 21.9% to 12.5% after aging for 7 days (Fig. 2(d) and
Fig. 7(b)). It was reported that hematite was nucleated by dehydration
and rearrangement within ferrihydrite (Cudennec and Lecerf, 2006;
Chen et al., 2020). The reduce of surface H-O-H indicated that the fer­
rihydrite has undergone dehydration process. Compared with pure fer­
rihydrite, the reduce of proportion of H-O-H was smaller in Fh-Mn-3
after aging. Thus, the above results indicated that the incorporation of
Mn inhibited the transformation of ferrihydrite.
The presence of the Cr 2p peak indicated that Cr was adsorbed on the
surface of ferrihydrite. In addition, the existence form of Cr on ferrihy­
drite surface was Cr(VI). The Cr 2p spectra located at 577.4 and
10
Journal of Hazardous Materials 417 (2021) 126073
587.4 eV corresponded to Cr 2p3/2 and Cr 2p1/2, respectively (Sarkar
et al., 2013). Moreover, the relative intensity of the Cr 2p peak of
Fh-Mn-3 was slightly higher than that of Fh, suggesting that more Cr(VI)
was present on Fh-Mn-3 than Fh.
3.4. Distribution of Cr(VI) during aging
The concentration of Cr(VI) in the solution during the conversion
was traced. As was shown in Fig. 8, the content of aqueous Cr(VI) in Fh,
Fh-Mn-1, Fh-Mn-3, and Fh-Mn-5 systems gradually increased from 9.0,
8.6, 6.5, and 4.4 mg/L to 16.6, 13.5, 8.3, and 7.2 mg/L, respectively,
after aging for 7 days at initial pH 5.0, which indicated that part of the
originally adsorbed Cr(VI) was gradually released into the solution
during aging. Similar trend was also found under neutral and alkaline
conditions. This was due the transformation of ferrihydrite. Ferrihydrite
is metastable in environment and easily transforms into relatively stable
lepidocrocite, goethite, and hematite (Mitsunobu et al., 2013; Liu et al.,
2016; Karimian et al., 2019). Compared with ferrihydrite, the conver­
sion products of ferrihydrite had smaller specific surface area and weak
adsorption capacity for pollutants (Das et al., 2011b), which resulted in
the release of adsorbed Cr(VI) with aging. However, it was found that
compared with acidic conditions, more Cr(VI) was released under
neutral and alkaline conditions. This was attributed to the fact that
ferrihydrite was easier to transform under neutral and alkaline condi­
tions than acidic conditions (Das et al., 2011b; Zhang et al., 2017;
Sakakibara et al., 2019), which could be found in the results of XRD
C. Liang et al.
Fig. 10. Schematic diagram of the formation and transformation of Mn-incorporated ferrihydrite and the mobilization behavior of Cr(VI) during aging.
(Fig. 4). In addition, it was seen that the amount of released Cr(VI) was
less in Fh-Mn-1, Fh-Mn-3, and Fh-Mn-5 systems in comparison to Fh
system. This was because the incorporation of Mn inhibited the trans­
formation of ferrihydrite, which resulted in the less release of adsorbed
Cr(VI).
Besides, in order to fully understand the distribution behavior of Cr
(VI) in the conversion process and the effects of Mn on the mobilization
behavior of Cr(VI), in addition to monitoring the change of aqueous Cr
(VI), the adsorbed Cr(VI) and non-desorbed Cr(VI) were also monitored
(Fig. 9). At 0 day, only two types of Cr(VI) (adsorbed and aqueous Cr
(VI)) existed in all systems. As the aging progressed, the proportion of
aqueous Cr(VI) gradually increased due to the release of adsorbed Cr
(VI). Additionally, for Mn-incorporated ferrihydrite systems, non-
desorbed Cr(VI) was found during the aging process, while it was not
found in Mn-free system. Moreover, the proportion of non-desorbed Cr
(VI) increased with the increase of Mn content, which indicated that the
incorporation of Mn enhanced the immobilization of Cr(VI) during the
transformation of ferrihydrite.
3.5. Cr(VI) sequestration mechanism on the Mn-incorporated ferrihydrite
Based on the above analysis, the effects of incorporation of Mn on the
sequestration of Cr(VI) by ferrihydrite and its redistribution during the
aging were proposed in Fig. 10. The incorporation of Mn changed the
surface properties of ferrihydrite, thereby improving its adsorption ca­
pacity for Cr(VI). During the aging process of ferrihydrite, ferrihydrite
transformed into hematite or goethite with a smaller surface area, which
caused the adsorbed Cr(VI) to be released into the solution. The incor­
poration of Mn impeded the transformation process of ferrihydrite,
thereby inhibiting the migration behavior of adsorbed Cr(VI). Moreover,
the incorporation of Mn resulted in the conversion of adsorbed Cr(VI) to
non-desorbed Cr(VI) during the aging process, so as to achieve further
immobilization of Cr(VI).
4. Conclusions
This study showed that the incorporation of Mn enhanced the
adsorption of Cr(VI) on ferrihydrite due to the change of surface prop­
erties. The Cr(VI) sorption process for Mn-incorporated ferrihydrite and
ferrihydrite followed the Langmuir model. The maximum adsorption
capacity of Fh-Mn-5 for Cr(VI) could reach 48.5 mg/g, while it was
36.1 mg/g for Fh. Besides, the adsorbed Cr(VI) on the surface of ferri­
hydrite released into solution during aging process. The transformation
11
Journal of Hazardous Materials 417 (2021) 126073
products of Cr(VI)-adsorbed Fh was mainly hematite. The incorporation
of Mn hindered the mineralogical transformation of ferrihydrite, which
inhibited the mobilization of adsorbed Cr(VI). Meanwhile, the adsorbed
Cr(VI) on the surface of ferrihydrite transformed into non-desorbed Cr
(VI) during the aging process for Mn-incorporated ferrihydrite, thereby
achieving further immobilization of Cr(VI). The incorporation of foreign
metals into iron oxides is common in the environment. Our findings
clarify the important role of the Mn incorporation into ferrihydrite on
the immobilization of Cr(VI) and its behavior during aging, which will
help us understand the fate of Cr(VI) in the environment.
CRediT authorship contribution statement
Chenwei Liang: Methodology, Investigation, Data curation and
analysis, Writing - original draft. Fenglian Fu: Conceptualization, Su­
pervision, Writing - review & editing, Funding acquisition. Bing Tang:
Writing - review & editing.
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.
Acknowledgements
This research was supported by National Natural Science Foundation
of China (No. 51978174), and Natural Science Foundation of Guang­
dong Province (No. 2018A030313099).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2021.126073.
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