Chemical Geology 487 (2018) 54–62

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Chemical Geology
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Dissolution and phase transformation processes of hausmannite in acidic T

aqueous systems under anoxic conditions
⁎
Yao Luoa, Wenfeng Tana, Steven L. Suibb, Guohong Qiua, , Fan Liua
a
Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture, Hubei Key Laboratory of Soil Environment and
Pollution Remediation, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, Hubei Province, China
b
Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, CT 06269-3060, United States

A R T I C LE I N FO A B S T R A C T

Editor: K. Johannesson Hausmannite is the most widely distributed spinel-structured manganese oxide in soils and sediments. The
Keywords: transformation of this metastable manganese oxide to Mn(IV) oxides with higher adsorption capacity has at-
Hausmannite tracted much research interest, while the transformation mechanisms and influencing factors still remain largely
Disproportionation unknown, especially under acidic condition. In this work, the transformation processes of hausmannite at dif-
Transformation ferent pH values and the influence of cations were studied. Results indicated that hausmannite was transformed
Birnessite into manganite at pH 5.0–9.0. The dissolution of hausmannite was initiated and promoted by protons (≤ 7.0),
Nsutite and the decrease of pH accelerated its conversion to Mn(IV) oxides. The tunnel-structured Mn(IV) oxide was
Cryptomelane
generated via two steps during the dissolution process of hausmannite at pH ≤ 3.0. Hausmannite was dis-
proportionated to δ-MnO2 at first, which was then transformed to nsutite in the presence of Na+ and H+ through
the transfer of electrons from adsorbed Mn(II) to structural Mn(IV). The disproportionation of hausmannite to δ-
MnO2 was not affected by other cations, while the presence of K+ promoted the further transformation of δ-
MnO2 to cryptomelane. The structural rearrangement process of δ-MnO2 was the rate-determining step for the
formation of final products. This work expands the understanding of the formation, transformation and geo-
chemical processes of manganese oxides in supergene environments.

1. Introduction topics of research in soil science, environmental chemistry and miner-

Manganese oxides are widely distributed in soils and sediments.
Their specific physicochemical properties influence the migration,
transformation, and fate of organic pollutants and toxic metalloids/
metals such as As(III,V), Cr(III,VI), and Se(IV,VI) (Katsoyiannis et al.,
2004; Saputra et al., 2013; Scott and Morgan, 1996; Weaver and
Hochella, 2003). The interaction processes are responsible for the bio-
geochemical cycling of corresponding active elements. Crystal structure
plays an important role in the adsorption and oxidation reactivity of
manganese oxides (Landrot et al., 2012; Luo et al., 2017; Post, 1999;
Qiu et al., 2011; Weaver and Hochella, 2003). Compared with todor-
okite, manganite and cryptomelane, layered birnessite exhibits the
highest reactivity for sulfide oxidation (Luo et al., 2017; Qiu et al.,
2011). Although δ-MnO2 and acid birnessite both show hexagonal layer
symmetry, the Cr(III) oxidation capacity of acid birnessite is higher
than that of δ-MnO2 (Landrot et al., 2012). The reactions between seven
manganese oxides and Cr(III) indicated that hausmannite and birnessite
have the highest Cr(III) oxidation ability (Weaver and Hochella, 2003).
Hence, the formation and conversion of manganese oxides are hot
alogy.
Hausmannite, the fifth most common manganese oxide minerals in
soil profiles (McKenzie, 1972), is a mixed-valent spinel manganese
oxide with Mn(III) in the distorted octahedral coordination and Mn(II)
in the tetrahedral coordination (Giovanoli et al., 1976; Jarosch, 1987).
Metastable hausmannite can be generated from the abiotic oxidation of
Mn(II) or reduction of manganese oxides (Murray et al., 1985;
Lefkowitz et al., 2013). In oxygen-containing natural waters, Mn(II) is
easily oxidized to Mn3O4 and β-MnOOH (Murray et al., 1985). Reaction
with Mn(II) causes the reduction of birnessite to β-MnOOH, and the
subsequent transformation into hausmannite would occur at pH 8.0–8.5
(Lefkowitz et al., 2013). Thus, hausmannite is easily generated and is
ubiquitous in supergene environments.
Due to the presence of Mn(III) in the structure, hausmannite can act
as an oxidizing and reducing agent (Madison et al., 2013). The reaction
of hausmannite with As, Cr, and Pu can affect their mobility and toxi-
city (Cantu et al., 2014; Feng et al., 2006; Garcia et al., 2014;
Shaughnessy et al., 2003; Weaver and Hochella, 2003). Hausmannite,
which comprises both Mn(II) and Mn(III), has a higher Cr(III) oxidation

⁎
Corresponding author.
E-mail address: qiugh@mail.hzau.edu.cn (G. Qiu).

https://doi.org/10.1016/j.chemgeo.2018.04.016
Received 7 December 2017; Received in revised form 5 April 2018; Accepted 11 April 2018
Available online 15 April 2018
0009-2541/ © 2018 Elsevier B.V. All rights reserved.
Y. Luo et al.
reactivity than tunnel-structured manganese oxides including crypto-
melane and pyrolusite (Weaver and Hochella, 2003). The highest Cr(III)
and Cr(VI) binding capacities of hausmannite were achieved at pH 4.0
and 3.0, respectively (Cantu et al., 2014). Thermodynamic analysis
indicated an adsorption process, but activation energy analysis in-
dicated a chemisorption process for Cr(III,VI) (Cantu et al., 2014),
however, the final products after an hour of reaction was not identified
for further understanding the reaction mechanism. When the pH was
controlled between 2.0 and 6.0, the maximum binding capacities of
hausmannite for As(III) and As(V) were respectively 13.5 and
7.5 mg g−1 at pH 3.0 (Garcia et al., 2014). Hausmannite can work as an
excellent adsorbent for heavy metals, especially at low pH values, but
the adsorption mechanisms are not fully understood. The adsorption
process may be related to the pH-dependent changes in the structure
and transformation compositions of metastable hausmannite, which
have been largely ignored in previous studies.
Hausmannite is considered as a vital intermediate in the oxidation
process of Mn(II) to Mn(IV) oxides. Mn(III) in the structure of haus-
mannite can be disproportionated to Mn(IV) as indicated by a ther-
modynamic model (Hem and Lind, 1983). A two-step cycle for a final
product of MnO2 includes (Hem, 1978): oxidation of Mn(II) to Mn3O4
(Eq. (1)), and disproportionation of Mn3O4 to MnO2 (Eq. (2)). The total
reaction may be expressed as Eq. (3). These equations are listed as
follows.
6 Mn(II) + O2 + 6 H2 O → 2 Mn3O4 + 12 H+ (1)
Mn3O4 + 4H+ → MnO2 + 2 Mn(II) + 2 H2 O (2)
2 Mn(II) + O2 + 2 H2 O → 2 MnO2 + 4 H+ (3)
The incongruent dissolution processes of hausmannite induced by
hydrolysis and protonation have been extensively studied under oxic
conditions. The dissolution of hausmannite occurs first, and 7-Å phase
birnessite is then precipitated in high-concentration NaOH and KOH
solution, while dilute alkaline solution facilitates the transformation of
hausmannite to manganite (Cornell and Giovanoli, 1988). In acidic
solution, conversion of hausmannite to manganite is also dominant at
pH ≥ 4.0, and Mn(IV) oxide precipitates are the major secondary mi-
neral phases at lower pH (Giovanoli et al., 1976; Hem and Lind, 1983).
Bricker found that γ-MnO2 is produced in intense acidification and δ-
MnO2 is produced in mild acidification (Bricker, 1965), but the trans-
formation mechanism from hausmannite to δ- and γ-MnO2 has not been
clarified yet. In previous studies, the above reaction processes were
mainly monitored by conventional characterization methods such as
Mn average oxidation state (Mn AOS), X-ray diffraction (XRD), and
transmission electron microscopy (TEM) for the long-term reaction
products. Besides the limitation of technology, the features of manga-
nese oxides, including fine particles, poor crystallinity, and indis-
tinguishable crystal phases, make it extremely difficult to identify the
reaction intermediates, resulting in a poor understanding of the trans-
formation mechanisms. Synchrotron radiation XRD (SR-XRD) and Mn
K-edge X-ray absorption near edge structure (XANES) spectroscopy
were also used to analyze the dissolution products of hausmannite
(Peña et al., 2007). Manganite, which was observed by XRD in aged
hausmannite products for several weeks or a year at pH ≥ 6.0, was
identified by SR-XRD but not by XANES in the 1-week dissolution
product at pH 6.0 (Peña et al., 2007). The low content of transformation
products also leads to the poor understanding of reaction process.
Collectively, hausmannite can be transformed to manganese (hydr)
oxides under a wide range of environmental conditions. Although the
final products have been well analyzed, the detailed transformation
mechanism, especially the short-term intermediates and crystal
growing process, still remains unknown.
In the present work, we examined the dissolution and phase trans-
formation processes of hausmannite with various pH values and aqu-
eous cations including H+, Na+, and K+. Our objectives are to
55
Chemical Geology 487 (2018) 54–62
understand the mineralogy in the entire reaction to identify the possible
intermediates and clarify the growth of tunnel-structured Mn(IV)
oxides.
2. Materials and methods
2.1. Synthesis of manganese oxides
Hausmannite was synthesized following the modified procedure of
Mckenzie (Feng et al., 2007; McKenzie, 1971). The Mn(OH)2 precipitate
from MnSO4·H2O and NaOH was oxidized by oxygen in air to obtain the
final product. The XRD pattern and Fourier transform infrared spec-
troscopy (FTIR) spectrum of synthesized product indicated that pure-
phase hausmannite was generated (Fig. S1). The Brunauer-Emmer-
Teller surface area was measured to be 22 m2 g−1. The preparation of
references, including cryptomelane (α-MnO2), nsutite (γ-MnO2), feit-
knechtite (β-MnOOH), manganite (γ-MnOOH), and δ-MnO2, is de-
scribed in Supporting Information, and the results of XRD and Mn K-
edge extended X-ray absorption fine structure (EXAFS) are shown in
Fig. S2.
2.2. Mineral dissolution experiments
Dissolution experiments of hausmannite were performed at a pH
range of 3.0–9.0. The whole experiments were conducted under anoxic
conditions. Distilled deionized water (DDW, 18 MΩ cm resistance) was
boiled for 20 min and cooled to room temperature by bubbling high-
purity nitrogen gas (99.999%, Wuhan Iron and Steel (Group) Corp.,
China) before use. About 0.50 g of hausmannite (4.4 mmol L−1) was
added to 500 mL 0.1 mol L−1 Na2SO4 solution in a five-neck bottle with
one neck for pH monitoring, one capped with a rubber stopper
equipped with a port for pH adjustment and sampling, one for bubbling
of nitrogen and the remaining two were sealed. The reaction solutions
were stirred vigorously with a magnetic stir bar throughout the ex-
periments to ensure thorough mixing. The pH of the reaction systems
was continuously adjusted manually in the first 12 h using NaOH (0.01
and 0.1 mol L−1) and H2SO4 solution (0.1 and 1.0 mol L−1), and was
then adjusted three times a day. After the prescribed time, 3.0 mL
suspension was collected from the port of the bottle by a syringe and
filtered through a 0.22 μm microporous membrane filter. The reaction
system was continuously purged with high-purity nitrogen gas in the
first 12 h, and the nitrogen pressure inside the reactor was maintained
to be slightly higher than the atmospheric pressure to prevent air in-
gress. After 12 h of reaction, the reactor was transferred to an anaerobic
glove box to maintain anoxic conditions. Wet samples were identified
by XRD soon after the reaction. The samples in membrane filter were
washed with deoxygenated DDW for three times, dried in a vacuum
oven at 40 °C for 12 h, and stored in a vacuum bag for further analyses
including FTIR, TEM, X-ray photoelectron spectroscopy (XPS), and X-
ray absorption spectra (XAS).
To examine the influence of cations on the hausmannite transfor-
mation process under acidic conditions, parallel experiments were
conducted in 0.1 mol L−1 K2SO4 solution or without background cation
under the same experimental conditions.
2.3. Characterization of intermediates
Wet samples were directly pasted onto the glass slides for XRD
(Bruker D8 ADVANCE) data collection using Cu Kα (λ = 0.15418 nm)
and an operation voltage of 40 kV and current of 40 mA at a scanning
rate of 2° min−1. Fourier transform infrared spectroscopy (FTIR, Bruker
VERTEX 70) was conducted with a Bruker Equinox 55 model spectro-
photometer by making pellets with KBr powder. The Mn AOS of
hausmannite was measured by the oxalic acid method (Kijima et al.,
2001). About 0.1 g of sample was dissolved into 10 mL H2SO4
(0.5 mol L−1) and an excess of 10 mL H2C2O4 (0.5 mol L−1) to reduce
Y. Luo et al. Chemical Geology 487 (2018) 54–62

all the Mn(III)/Mn(IV) to Mn(II). The excess H2C2O4 in the solution was
determined by titration with a standard solution of KMnO4
(0.02 mol L−1) at 60 °C. Manganese content in the product was de-
termined by atomic absorption spectroscopy (AAS, Varian AAS240FS).
The concentration of Mn(II) in the filtrate was also determined by AAS.
Transmission electron microscopy (TEM, FEI Talos F200C) were used to
characterize the micromorphology of hausmannite and the transfor-
mation intermediates.
The relative contents of Mn(II), Mn(III), and Mn(IV) in the surface of
samples were analyzed by XPS (VG Multilb2000) with Al Kα at
1486.71 eV. The Mn AOS and mineral compositions of reaction pro-
ducts were further characterized by Mn K-edge XAS at the 1W1B
beamline of the Beijing Synchrotron Radiation Facility (BSRF), China.
Mn K-edge XAS data were collected in transmission mode over the
energy range of 6340–7327 eV. The Mn AOS of hausmannite and
transformation products was also analyzed by XANES spectra using
Combo method in the 6521–6653 eV interval (Manceau et al., 2012),
and the fractional contributions of the mineral compositions in the
transformation intermediates were quantitatively calculated by linear Fig. 1. Concentration of released Mn(II) from the transformation of hausman-
combination fitting of the Mn K-edge EXAFS data. Wet solid inter- nite suspension at pH 3.0–9.0 in 0.1 mol L−1 Na2SO4.
mediates were in situ characterized by attenuated total reflectance
Fourier transform infrared (ATR-FTIR) spectroscopy. The detailed de-
decreasing pH, which agrees well with the Mn(II) release tendency
scriptions for XAS and ATR-FTIR analysis are presented in the Sup-
(Fig. 1). When pH was decreased to 3.0, all the diffraction peaks for the
porting Information.
product were indexed to γ-MnO2 (JCPDS card no. 14–0644), indicating
the formation of pure-phase γ-MnO2. Diffraction peaks at 2θ values of
3. Results
22°, 34.5°, 37.1°, 38.8°, 42.6°, and 56.1° correspond to the (120), (031),
(131), (230), (300), and (160) crystal planes of γ-MnO2 (Fig. 2a).
3.1. Dissolution reaction at various pHs
Fig. 2b shows the FTIR spectra of 15-day transformation products
after washing and drying. The absorption bands at 624, 523, and
The transformation reaction of hausmannite (1.0 g L−1) was con-
426 cm−1 are assigned to the stretching and bending vibrations of
ducted at pH 3.0–9.0 in an anoxic environment. After 15 days of reac-
MneO in hausmannite (Kirillov et al., 2009). The bands at 713, 576,
tion, the suspension retained the color of cinnamon brown just like
and 523 cm−1 are attributed to the MneO stretching vibration of MnO6
pristine hausmannite particles when the pH was between 5.0 and 9.0.
octahedra in γ-MnO2 (Potter and Rossman, 1979). The bands at 1094
With the decrease of pH to 3.0, shortly after the beginning of dissolu-
and 1048 cm−1 correspond to the characteristic adsorption peaks of γ-
tion experiments, visible color changes were observed in the solid
MnOOH and β-MnOOH, respectively (Elzinga, 2011; Kirillov et al.,
phase. The solid turned nearly black, indicating the surface oxidation or
2009). γ-MnOOH and β-MnOOH were formed possibly due to the oxi-
transformation of Mn3O4 to a secondary mineral phase under oxic
dation of the sample by air during the washing and drying process (Qiu
conditions as previously reported (Bricker, 1965). In the anoxic reac-
et al., 2011). The band at 1156 cm−1 is assigned to the OeH bending
tion systems, surface oxidation of Mn3O4 did not occur, suggesting the
vibration of γ-MnOOH (Kirillov et al., 2009). Only γ-MnOOH was ob-
formation of a new phase. These results are consistent with the previous
tained during hausmannite hydrolysis at pH 7.0–9.0 (Giovanoli et al.,
report, which showed apparent dissolution of hausmannite at pH ≤ 4.0
1976). The transformation mechanism exhibited significant differences
(Hem and Lind, 1983). However, under oxic conditions, remarkable
at various pHs as indicated by the transformation products.
color changes were observed in Mn3O4 dissolution experiments which
The pH of the experiments was maintained by the addition of H2SO4
used 50 mmol L−1 formic acid to buffer the pH at 5.0 (Peña et al.,
under acidic conditions, suggesting the consumption of protons. The
2007). The different results in this work indicated that oxygen or buffer
dissolution and disproportionation of hausmannite may proceed as Eq.
solution affects the dissolution process of Mn3O4.
(2) at pH ≤ 3.0 in anoxic environment. γ-MnO2 is usually formed as the
The dissolution rate of hausmmanite was further evaluated by
final product in the intense acidification of hausmannite, and will be
comparing the concentration of dissolved Mn(II) at different pHs. The
further transformed to more stable tunnel-structured β-MnO2
concentration of Mn(II) increased and then reached a plateau after
(Giovanoli et al., 1976). After multicycles of the charge-discharge tests,
1 day of reaction (Fig. 1). With the decrease of pH, the release rate of
hausmannite would be electrochemically oxidized to birnessite (Dubal
Mn(II) from the structure of hausmmanite increased, suggesting that
et al., 2010). Our results revealed that hausmannite was dis-
low pH accelerates the dissolution process of hausmmanite. After 2 h of
proportionated in acidic condition and finally transformed to γ-MnO2
reaction, the release ratio of Mn(II) reached about 1%, 8%, and 53%
after equilibration in the Mn(II)-containing solution in the experimental
when pH was respectively controlled at 7.0, 5.0, and 3.0. At pH 3.0, the
period.
concentration of dissolved Mn(II) showed no significant change after
2 h of reaction. The above results confirmed that protons induce and
promote the dissolution of hausmannite, which is consistent with pre- 3.2. Disproportionation processes
vious reports (Peña et al., 2007).
The mineral composition of wet solid products at different pHs after The fast phase change and disproportionation process were con-
15 days of reaction was characterized by XRD (Fig. 2a). When pH was firmed by the changes in the color and Mn(II) concentration, and the
controlled at 5.0–9.0, the diffraction peaks of hausmannite could al- long-term transformation products were fully characterized. However,
ways be observed without the formation of apparent new peaks. The it is still unknown how the disproportionation proceeds and whether
fact that no other phase was observed may be ascribed to the poor other intermediates are preferentially formed directly from the dis-
crystallinity or low abundance of the transformation products. The proportionation. The mineral compositions for different time intervals
diffraction peaks of hausmannite were attenuated with pH decreasing at pH 3.0 were further characterized by XRD to identify the possible
from 9.0 to 5.0, suggesting an increase of dissolution rate with intermediates (Fig. 3). After 30 min of reaction, the diffraction peaks of

56
Y. Luo et al.
Fig. 2. XRD patterns (a) and FTIR spectra (b) of solid products from the transformation of hausmannite suspension for 15 days at pH 3.0–9.0 in 0.1 mol L−1 Na2SO4.
Fig. 3. XRD patterns of wet intermediate products from hausmannite suspen-
sion in 0.1 mol L−1 Na2SO4 at pH 3.0. The intermediate changes are highlighted
by dashed lines.
hausmannite were attenuated, and only the diffraction peaks at 2θ
values of ~18 and 36° were observed, indicating a remarkable dis-
solution process. Two weak peaks were formed at ~37 and 66° after 2 h
of reaction. The newly formed peaks correspond to the MneO spacing
in the octahedral arrangement. The initial disproportionation product
of hausmannite was MnOx octahedral units with a highly disordered
network. γ-MnO2 was formed as the major product and its diffraction
peaks increased over time. The release rate of Mn(II) indicated that the
dissolution of Mn3O4 occurred rapidly, but the formation process of γ-
MnO2 was quite slow as indicated by XRD results (Figs. 1 and 3).
Mn AOS is commonly used as an indicator for the oxidation degree
of manganese oxides. The relative contents of Mn(II,III,IV) and Mn AOS
in the transformation products at pH 3.0 were quantitatively calculated
by the Combo method (Fig. 4a). The Mn AOS of pristine hausmannite
was determined to be 2.85 by the Combo method (Table S1), which is
slightly higher than that obtained by titration (2.69). The precision of
the Combo method decreases with increasing content of structural Mn
(III) due to the strong Jahn-Teller distortion effect caused by Mn(III),
which affects the plot of the XANES spectra (Manceau et al., 2012). The
Mn AOS value increased to 3.63 after 2 h of reaction, and then reached
3.90 after 7 days of reaction (Fig. 4b, Table S1). The relative content of
Mn(IV) increased along with the decrease of Mn(II) and Mn(III) in the
transformation products with the extension of reaction time, indicating
57
Chemical Geology 487 (2018) 54–62
the disproportionation of Mn(III) in hausmannite. The relative content
of Mn(IV) changed from 8% to 67% after 2 h of reaction, and then
approached to 90% after 7 days. The relative content of Mn(II) de-
creased to below 10% within 1 h, indicating that Mn(II) in the structure
was quickly released from the spinel structure under the induction by
protons. The AOS data further confirmed the formation of Mn(IV) in a
short reaction time, which is in agreement with the color change.
The fractional contributions of the compositions in the dissolution
products at pH 3.0 were further quantitatively calculated by linear
combination fitting of the Mn K-edge EXAFS data. The raw χ spectra
could be well fitted by the linear combinations of the χ spectra of
Mn3O4, β-MnOOH, γ-MnOOH, δ-MnO2, and γ-MnO2. The k3-weighted χ
functions of the transformation products exhibited significant changes
with time (Fig. 5a). In consistence with the XRD results, the fitting
results indicated a progressive increase in the amount of γ-MnO2 gen-
erated from the consumption of hausmannite, and hausmannite almost
completely disappeared after 2 h of reaction (Table S2, Fig. 5b). The
relative contents of β-MnOOH, γ-MnOOH, and δ-MnO2 all increased at
first and then decreased with time. The content of δ-MnO2 accumulated
at the expense of hausmannite and showed a decreasing trend in the
absence of hausmannite after 2 h of reaction. β-MnOOH and γ-MnOOH
were formed as the minor products and exhibited a changing trend si-
milar to that of δ-MnO2.
Before the determination by XAS, products were exposed to air and
could be potentially oxidized during the washing and tablet preparation
process, which might lead to changes in the mineral composition. β-
MnOOH and γ-MnOOH can be easily formed from Mn(II) oxidation by
air (Murray et al., 1985). When interacting with Mn(II), birnessite is
reduced to β-MnOOH and γ-MnOOH (Lefkowitz et al., 2013). To further
investigate the real-time transformation of hausmannite, the inter-
mediate products obtained from the reaction were measured by in-situ
ATR-FTIR (Fig. 6). Among the bands between 700 and 1200 cm−1, a
broad vibration band at 1056 cm−1 appeared after 30 min of reaction.
This band corresponds to β-MnOOH, suggesting that γ-MnOOH is not a
direct transformation product in the dissolution process of hausman-
nite. The formation of β-MnOOH may be ascribed to the presence of δ-
MnO2, and SR-XRD and in-situ XAS can be used to analyze the forma-
tion of β-MnOOH in future work.
Fig. 7 shows the TEM images of dissolution products of hausmannite
at pH 3.0. The as-synthesized hausmannite is uniform flaky particles
with diameters of about 50–100 nm. Porous products with irregular
particle edges were observed after 1 day of reaction. Small particles
were aggregated to form some spindle-shaped structure as the reaction
proceeded. The spindle-shaped particles were observed to increase and
were the major products after 15 days of reaction. The lattice fringe
distance was measured to be 0.40 nm, which corresponds to the (120)
planes of γ-MnO2 (Fig. 7d).
Y. Luo et al. Chemical Geology 487 (2018) 54–62

Fig. 4. Normalized Mn K-edge XANES spectra of pristine hausmannite and transformation products in 0.1 mol L−1 Na2SO4 at pH 3.0 (Open circles and lines re-
spectively present experimental and best-fit lines, and difference plots are revealed at bottom) (a), and the relative content of Mn(II,III,IV) and Mn AOS determined by
Combo method (b).

3.3. Effect of cations on the disproportionation processes

Cation plays an important role in the crystal structure of manganese

oxides. Manganese oxides with either α-, β-, or γ-structure types or the
mixtures of these structure types are produced from the reaction of
acidic MnSO4 with H+, Li+, Na+, K+, or NH4+ solution (Hill et al.,
2003). The background electrolyte may influence the transformation of
hausmannite. Therefore, K+ or H+ was used instead of Na+ to in-
vestigate the dissolution process of hausmannite.
Fig. 8a shows the XRD pattern of the 15-day reaction product at
pH 3.0 with the addition of K+ under anoxic conditions. The diffraction
peaks of the final products were well indexed to cryptomelane (JCPDS
card no. 72-1982). In the absence of background cation, γ-MnO2 was
formed as the major product (a similar figure to that in the presence of
Na+ is not shown here). Cryptomelane is easily generated during the
preparation of manganese oxides in high K+ solution. Well-crystallized
cryptomelane could also be obtained by holding K-birnessite in a mixed
solution of 0.1 mol L−1 HNO3 and 1 mol L−1 KNO3 at 70 °C (Cornell and
Giovanoli, 1988). How metastable hausmannite is transformed to
cryptomelane in K+ solution still remains elusive. The relative contents Fig. 6. ATR-FTIR spectra of hausmannite dissolution for different time intervals
of compositions in the transformation products after 1 day and 15 days in 0.1 mol L−1 Na2SO4 at pH 3.0.
of reaction were quantitatively calculated by linear combination fitting
of the Mn K-edge EXAFS data (Fig. 8b, Table S3). The fitting results
decreased from 34% to 18%, while that of cryptomelane increased from
indicated that the relative content of δ-MnO2 and γ-MnOOH decreased
42% to 76% when the reaction proceeded for 1 day and 15 days, re-
together with that of hausmannite. The relative content of δ-MnO2
spectively. This changing trend of mineral composition is similar to that

Fig. 5. Mn K-edge k3-weighted EXAFS spectra (The lines and dash dots are the experimental and best-fit curves) (a), and the linear combination fitting results of the
k3-weighted χ spectra (b) of the transformation products in 0.1 mol L−1 Na2SO4 at pH 3.0. The changes of spectra are highlighted by shaded areas.

58
Y. Luo et al. Chemical Geology 487 (2018) 54–62

a 0.25 nm b
0.25 nm

2 nm

100 nm 100 nm
c d
0.40 nm

5 nm

100 nm 100 nm
Fig. 7. TEM images of synthesized hausmannite (a) and the transformation intermediate products of hausmannite suspension in 0.1 mol L−1 Na2SO4 at pH 3.0 for
1 day (b), 5 days (c), and 15 days (d).

in the presence of Na+. That is to say, poorly crystalline δ-MnO2 is the
initial transformation product of hausmannite, which is further slowly
transformed to cryptomelane.
Fig. 9 shows the TEM images of intermediates after 1 day and
15 days of reaction in the presence of K+. The products were a mixture
of aggregated amorphous and rod-like structures after 1 day of reaction.
The lattice fringes at 0.72, 0.54, and 0.32 nm correspond to the (110),
(200), and (310) planes of cryptomelane. As shown in Fig. 9b, the rod-
like structures were composed of thin sheets for 1-day reaction product.
The characteristic morphology of hausmannite disappeared after
15 days. Rod-like particles and irregular plates were respectively
formed as the major and minor products. The lattice spacings of the
irregular plates at 0.25 nm may correspond to the (110) planes of δ-
MnO2 (Fig. 9d).
4. Discussion
4.1. Disproportionation pathway
In the reaction system, dissolved Mn(II) was detectable at pH ≤ 7.0
and obvious transformation products of hausmannite were only ob-
served at pH 3.0. These results indicated that the dissolution and dis-
proportionation of hausmannite are initiated by protons. The transfor-
mation rate and products varied at different pHs, and mild acidification
only induced the transformation of a small portion of hausmannite.
When the pH was kept at 3.0 with different cations in the reaction
solution systems, the early formed black precipitate was of poor crys-
tallinity as indicated by XRD analysis. Broad peaks were only observed
at 37° and 66°, which were related to the octahedral structure of

Fig. 8. XRD pattern of transformation product after 15 days of reaction (a) and Mn K-edge k3-weighted EXAFS spectra of intermediate products (b) from the
transformation of hausmannite suspension in 0.1 mol L−1 K2SO4 at pH 3.0. The changes of spectra are highlighted by shaded areas.

59
Y. Luo et al.
a b
100 nm
c d
100 nm
Fig. 9. HRTEM images of the transformation intermediates of hausmannite suspension for 1 day (a, b) and 15 days (c, d) in 0.1 mol L−1 K2SO4 at pH 3.0.
birnessite, indicating a slight ordering of the product. In fact, only the
reflection peak of (00l) planes of birnessite was not observed, which
was due to the disordered stacking of octahedral sheets. The release of
Mn(II) together with the disproportionation of Mn(III) in the structure
of hausmannite led to the formation of poor crystalline δ-MnO2.
MnO4−/Mn2+ was used to synthesize α-MnO2, γ-MnO2, β-MnO2,
and birnessite by controlling the reaction conditions such as pH and
cations, and poorly ordered MnO2 was formed as the precursor for the
well-crystallized manganese oxides (Portehault et al., 2009). During the
preparation of manganese oxides from different Mn sources, δ-MnO2 is
responsible for the initial formation of tunnel-structured Mn oxides
(Wang and Li, 2003). Flower-like birnessite was formed from the ro-
tating, orienting and attaching of poorly crystalline δ-MnO2 nano-
particles, and these nanopetals grew mainly along the a–b planes via the
oriented attachment mechanism (Liang et al., 2017). δ-MnO2 is com-
monly formed as the initial product in the growth of manganese oxide,
and works as an important precursor for birnessite and tunnel-struc-
tured Mn(IV) oxides. Bricker proposed that birnessite can be formed
from the disproportionation of hausmannite via Eq. (2). δ-MnO2
showed an electron micromorpology of poorly organized crystals with a
plat-like appearance (Bricker, 1965). Poorly ordered δ-MnO2 was also
observed as a metastable intermediate in this work.
In the disproportionation process of hausmannite, the early pre-
cipitate was constituted of MnO6 octahedral layers randomly stacked
with each other, and was considered as δ-MnO2 that was disordered
along the c axis. The EXAFS fitting data further confirmed that δ-MnO2
was one of the compositions in the product, which increased at first and
then decreased. The above results indicated that hausmannite was
broken down to tiny thin plate-like δ-MnO2, which was then trans-
formed to tunnel-structured manganese oxides. Although cations were
needed to compensate for the charge balance of layer-structured bir-
nessite, δ-MnO2 was always formed in different cation (H+, Na+, and
K+) systems, indicating that the presence of other cations is not es-
sential to the formation of δ-MnO2.
60
Chemical Geology 487 (2018) 54–62
0.54 nm
0.72 nm
0.32 nm
10 nm
1 nm
4.2. Formation mechanism of tunnel-structured Mn oxides
Under anoxic conditions, the cinnamon brown color of hausmannite
rapidly turned to black at pH 3.0. In background electrolyte with H+,
Na+, or K+, the black particles subsequently aggregated to form an
inhomogeneous suspension. These phenomena suggested that the
physiochemical properties of the δ-MnO2 newly formed from the dis-
solution process underwent changes during the aging process.
Layer structures were compressed and simultaneously closed up to
form tunnel structures by hydrothermal treatment of birnessite in 1 M
HNO3, and the formation of MnO2 nanorods/nanowires was attributed
to a rolling mechanism (Shen et al., 2006). In this work, the rolling of
plate was not observed in the transformation of spinel structure to layer
and tunnel structures. Xiao et al. speculated that nanofibrous crypto-
melane is developed from an agglomerated mass of nanoparticles (Xiao
et al., 1998). Orthogonal birnessite probably grows through an oriented
aggregation mechanism from hexagonal birnessite (including δ-MnO2
and acid birnessite), and the smaller size of δ-MnO2 may favor the
growth of orthogonal birnessite (Landrot et al., 2012; Zhao et al.,
2016). In this work, the XRD and EXAFS results demonstrated that a
large amount of δ-MnO2 disordered along the c axis was generated in
the early stage of dissolution. The micromorphology was porous for the
initial intermediate (Figs. 7b and 9a), which might be composed of δ-
MnO2. The oriented aggregation of δ-MnO2 facilitated the further
generation of one-dimensional γ-MnO2 and α-MnO2.
After complete disproportionation of hausmannite, the theoretical
Mn(II) concentration was calculated to be 8.7 mmol L−1. The con-
centration of dissolved Mn(II) reached about 7.0 mmol L−1 after 2 h of
reaction at pH 3.0 (Fig. 1). Hence, most of the Mn(II) in the structure
and disproportionation products of Mn(III) was released to the aqueous
solution. Birnessite has a high affinity for Mn(II), which permits the
reaction of birnessite with adsorbed Mn(II). MnOOH and Mn3O4 are
formed through the transfer of electrons from adsorbed Mn(II) to
structural Mn(IV), which causes the rearrangement of the crystal
Y. Luo et al.
structure of birnessite (Elzinga, 2011). The transformation from hex-
agonal birnessite to orthogonal birnessite follows a similar mechanism
(Zhao et al., 2016). δ-MnO2 owns a larger specific surface than acid
birnessite (Zhao et al., 2016), which favors the surface adsorption of Mn
(II). The structural rearrangement of δ-MnO2 may also contribute to the
formation of γ-MnO2 and α-MnO2 in this work.
In order to investigate the adsorption process of Mn(II), relative
contents of manganese with different valence states in the surface of
intermediates were investigated by XPS (Figs. 10 and S3). The Mn AOS
of pristine hausmannite was calculated to be 2.65 by XPS analysis,
which is close to the value measured by titration. The major peak at
~641.4 eV shifted to ~642.2 eV after 10 min of reaction, and then
shifted towards the low energy value (Fig. 10b). Mn AOS of the inter-
mediates increased at first and then decreased. The relative contents of
surface Mn(II), Mn(III), and Mn(IV) were obtained from XPS Mn 2p3/2
spectra fitting of intermediates at different times, and the relative
content of Mn(II) increased to 31.9% and 51.6% after 10 min and 12 h
of reaction, respectively (Fig. S3, Table S4). The relative content of Mn
(II) obtained by XPS had a trend opposite to that obtained by XANES,
and the value of the former was apparently lower than that of the latter,
because XPS methods only detect a surface depth of ~2 nm in minerals
and the XAS results are bulk measurements. The Mn(II) in the crystal
structure and disproportionation products of Mn(III) was released to
aqueous solution or adsorbed on the surface of the reaction product.
The release of Mn(II) was initially rapid and the amount of released Mn
(II) was much larger than that of adsorbed Mn(II) in the early stage of
reaction (within 10 min), leading to the decrease of Mn(II) on the sur-
face of the reaction product. Then, more Mn(II) was adsorbed on the
surface of the products with the increased content of δ-MnO2 due to the
high affinity of δ-MnO2 for Mn(II) (within 2 h). After 2 h of reaction,
there was still a small amount of Mn(II) adsorbed by the products as the
reaction proceeded.
Birnessite exhibits a high stability in the absence of Mn(II) at
pH ≤ 3.0, and a certain concentration of Mn(II) induces the transfor-
mation of birnessite to γ-MnO2 (Tu et al., 1994). Tu et al. speculated
that Mn(IV) in the crystal structure of birnessite works as the electron
acceptor and is reduced to Mn(II) by adsorbed Mn(II) in an auto-
catalysis process (Tu et al., 1994). Some adsorbed Mn(II) was in-
corporated into the birnessite structure, causing changes in the length
of MneO bonds and the imbalanced charge. The structure of birnessite
became unstable and was rearranged to a new stable phase due to the
incorporation of a large amount of Mn(II) (Feitknecht et al., 1960; Tu
et al., 1994). Hence, the initial transformation product δ-MnO2 ad-
sorbed Mn(II), and then electrons were transferred from surface Mn(II)
to structural Mn(IV) in δ-MnO2, followed by the crystal structure
Fig. 10. Mn 2p3/2 spectra of pristine hausmannite (The open circles are experimental curves and the lines are the best-fit linear combination) (a) and Mn 2p3/2
spectra of intermediates after transformation in 0.1 mol L−1 Na2SO4 at pH 3.0 for different times (b).
61
Chemical Geology 487 (2018) 54–62
rearrangement with the generation of tunnel-structured γ-MnO2. The
total transformation process can be summarized as the following
equations.
Mn(II)Mn(III)2 O4 + 4 H+ → δ‐Mn(IV)O2 + 2 Mn(II) + 2 H2 O (4)
δ‐Mn(IV)O2 (layer) + Mn(II) → γ‐Mn(IV)O2 (tunnel) (5)
In particular, inorganic cation templates play critical roles in the
formation of different tunnel structures, as the tunnels of different Mn
(IV) oxide crystals have different sizes and need different amounts of
cations to be stabilized (Hill et al., 2003). In the rearrangement of solid
phase, γ-MnO2 was formed in the presence of H+ and Na+; however,
cryptomelane was formed when K+ was added instead. The ionic radius
of H+ (0.29 Å) and Na+ (0.95 Å) is far smaller than that of K+ (1.33 Å).
K+ ions can serve as a template for the formation of the [2 × 2] tunnel
structure of α-MnO2. In the early stage of self-assembly process of thin
plates, K+ ions play an important role in supporting the tunnel of α-
MnO2.
This study demonstrates that disproportionation of hausmannite is
accompanied by the release of Mn(II) in the intense acidification, and
hausmannite is be transformed into MnO2 (γ-, α-MnO2) with δ-MnO2 as
an intermediate in the presence of Mn(II). Solution pH determines the
transformation rate and products, significantly affecting the reactivity
of manganese oxides with nutrients and trace toxic elements as well as
the geochemical cycling of related elements in the environment. δ-
MnO2 can be formed through biological and abiotic pathways, and is
widely distributed in soils, suboxic marine, fresh water sediments, and
riparian zones. High reactivity of δ-MnO2 influences the migration and
toxicity of organic compounds and heavy metals such as Se(IV), Cr(III),
and As(III). Hausmannite is easily formed in natural environment from
the oxidation of Mn(II) and reduction of Mn(IV) oxides and more easily
found in alkaline medium. Although ocean and most surficial en-
vironments have pH above 7.0, the decomposition of organics, acid
mine drainage, and acid rain may cause very low pH values in local
areas. In recent years, the pH of acid rain is below 4.5 in large areas of
southern China (Du et al., 2012; Zhang et al., 2007), and can be even as
low as 2.7 in Pennsylvania and 1.5 in west Virginia (LaBastille, 1981).
Mn(II) release and structure alteration of hausmannite may occur in
these environments. The above transformation processes can com-
pletely alter the adsorption and redox reactivity of hausmannite. The
disproportionation and dissolution of hausmannite, which may affect
the migration and fates of trace elements and pollutants, should be fully
considered in these spots.
Y. Luo et al.
5. Conclusion
The transformation process and intermediate products of haus-
mannite are influenced by pH and cations. Hausmannite is transformed
into manganite at pH 5.0–9.0. The decrease of pH promotes the trans-
formation of hausmannite to Mn(IV) oxides, and hausmmanite is
completely consumed within 2 h of reaction at pH 3.0. The structural
Mn(II) and disproportionated Mn(III) are released from hausmannite to
aqueous solution in the form of Mn(II) ions. When the pH is controlled
at 3.0, hausmannite is disproportionated to δ-MnO2 at first, which is
then transformed to tunnel-structured Mn(IV) oxide through the
structural rearrangement of δ-MnO2. Nsutite is formed in the presence
of H+ and Na+ in the reaction systems, and the presence of K+ ac-
celerates the transformation of δ-MnO2 to cryptomelane. The structural
rearrangement process of δ-MnO2 is the rate-determining step for the
transformation of hausmannite to tunnel-structured Mn(IV) oxide.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 41571228 and 41425006), the
National Key Research and Development Program of China (Grant No.
2017YFD0801000), the Fok Ying-Tong Education Foundation (Grant
No. 141024) and the Fundamental Research Funds for the Central
Universities (Program No. 2662015JQ002). S. L. S. thanks the support
of the US Department of Energy, Office of Basic Energy Sciences,
Division of Chemical, Biological and Geological Sciences under grant
DE-FG02-86ER13622.A000. We greatly acknowledge Dr. Lirong Zheng
at beamline 1W1B of Beijing Synchrotron Radiation Facility (BSRF) for
the technical assistance with data collection and analysis. The authors
also thank Dr. Jianbo Cao at the Public Laboratory of Electron
Microscope in Huazhong Agricultural University for the help of TEM
characterization.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.chemgeo.2018.04.016.
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