Int. J. Environ. Sci. Technol.
(2018) 15:1243–1248
https://doi.org/10.1007/s13762-017-1468-y
REVIEW
A review on the synthesis and applications of green rust
for environmental pollutant remediation
C. Bhave1 • S. Shejwalkar1
Received: 4 October 2016 / Revised: 5 March 2017 / Accepted: 16 July 2017 / Published online: 2 August 2017
Ó Islamic Azad University (IAU) 2017
Abstract This paper discusses the various approaches to
the synthesis of green rust. Green rusts are synthesized by
changing the average oxidation state of iron compounds so
that the ratio of ferric/ferrous ions is between 0.25 and
0.33. This can be achieved by mixing ferrous and ferric
hydroxides, oxidation of ferrous compounds or reduction
of ferric compounds. Characterization of the samples with
analytical methods such as Mossbauer spectroscopy, X-ray
diffraction spectroscopy, scanning electron microscopy,
transmission electron microscopy and atomic-force
microscopy is discussed. Green rusts have a layered double
hydroxide structure, with an interchangeable anion layer
and a mixed ferrous–ferric cation layer. This structure can
adsorb ions by intercalation or exchange anions with its
environment. The cation layer can oxidize, which gives a
reducing nature to green rusts. These properties make them
excellent candidates for the reduction and immobilization
of several inorganic pollutants. Green rusts also have
applications in dechlorination of organic compounds and in
the synthesis of nanohybrid materials. These environmental
and nanochemistry applications are also covered in this
paper.
Keywords Green rust chemistry  Environmental
remediation  Nanohybrids  Heavy metal  Reduction 
Hydrocarbon dechlorination
Editorial responsibility: Hari Pant.
& C. Bhave
chaitanya.bhave@siesgst.ac.in
1
SIES Graduate School of Technology, Nerul 400706, India
Introduction
Green rusts are characterized by a variable oxidation ratio,
with the Fe(III)–Fe(II) ratio of 0.5:0.66 in mineral green
rust and 0.25–0.33 in laboratory-synthesized green rust
(Ruby 2015). These compounds consist of alternating
layers of cationic Fe(II)–Fe(III)–hydroxide and inter-
changeable anions, majorly OH-, Cl- and SO42- (Ruby
2016). It has been found that sodium ions (Na?) are a
necessary part of the green rust LDH structure. The iron
hydroxide layer forms the base (cationic layer), while Na?,
SO42- and H2O form the overlying anionic layer (Chris-
tiansen et al. 2009). Some of the iron ions in the cationic
layer can be replaced by other cations such as Mg2?, Al3?
and Zn2?. This has been found to lend stability to the green
rust crystal structure.
They are formed naturally in hydromorphic soils under
reducing conditions due to the slow oxidation of iron. The
naturally occurring mineral form of green rust is called
fougerite. The presence of these impurities lends stability
to the crystalline structure of green rusts. Green rusts were
first synthesized by Keller in 1948. These compounds are
extremely unstable and oxidized in the presence of air to
form various oxides depending on the environment. How-
ever, this oxidation is reversible and green rusts can be
reformed by reduction of the oxide compounds.
All research was conducted at SIES Graduate School of
Technology, Nerul (India), in 2016.
Synthesis
Green rusts have an oxidation state that lies between fer-
rous compounds (?2) and magnetite (?2.67). Thus, we
have two major routes to green rust synthesis. If the
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precursor iron compound has an oxidation state lower than
that of green rust, synthesis is performed by oxidation of
the precursor or by addition of ferric ions. If the precursor
has a high oxidation state, the synthesis proceeds by
reduction of iron or addition of ferrous ions. This can be
diagrammatically represented using Fig. 1.
Co-precipitation
Co-precipitation method mixes stoichiometric quantities of
ferrous and ferric salts to generate the proper oxidation
state of green rust. It is one of the most widely used
methods for synthesis of green rust. As the ratio of fer-
rous/ferric ions can be controlled by concentration of the
precursor salts, co-precipitation can produce green rusts
with controlled ferrous/ferric ratios. Cuttler et al. and
Gehin et al. have performed considerable work on this
synthesis procedure.
In co-precipitation synthesis, a mixture of ferrous and
ferric salt solutions is stirred continuously in an inert gas.
The pH of the solution is raised to 7 using sodium
hydroxide or potassium hydroxide. The solution is then
stirred under the inert atmosphere resulting in the forma-
tion of a green rust precipitate.
Cuttler (1990) used ferrous sulphate and ferric nitrate or
ferric chloride as the ferrous and ferric precursors,
respectively. Mossbauer spectra indicate the formation of
well-ordered crystalline structure characteristic of green
rust.
Géhin et al. (2002) used ferric sulphate as the ferric
precursor salt. They have confirmed that GR was the only
solid product formed during the reaction using Mossbauer
spectroscopy and X-ray spectroscopy.
Fig. 1 Green rust synthesis
summary
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Int. J. Environ. Sci. Technol. (2018) 15:1243–1248
Oxidation of ferrous salts
This synthesis proceeds by the controlled oxidation of a
ferrous salt. The salt solution is mixed with sodium
hydroxide leading to ferrous hydroxide precipitation. Then,
the solution is stirred in air inside a beaker to oxidize the
ferrous hydroxide. Once the white ferrous hydroxide turns
greenish blue, the beaker is covered to stop oxidation. The
partial oxidation of the ferrous ions to ferric results in the
formation of a green rust. Genin et al. have performed a
significant work on this process. Melanterite (FeSO47H2-
O) can be used as the ferrous salt to produce a sulphate
green rust (GR2(SO42-)). Alternatively, FeCl24H2O can
be used as the precursor salt (Génin et al. 1996).
This process occurs according to the following reaction
(Génin et al. 1996):
6 FeC12 + 10 NaOH ! 5 FeðOHÞ2
+ Feþþ + l0 Naþ + 12 Cl
5 FeðOHÞ2 þFeþþ þ SO 4 þ ð =2ÞO2 þ ðn + 1ÞH2 O
1
 þþ
þ FeðIIÞ4 FeðIIIÞ2 ðOHÞ12 ½SO4  nH2 O
Sodium sulphate (Na2SO4) can then be added to the
ferrous hydroxide to incorporate sulphate ions into the
green rust structure. The aerial oxidation of ferrous
chloride-derived ferrous hydroxide without addition of
sodium sulphate results in the formation of chloride green
rust (GR(Cl-)) (Génin et al. 1998).
It is not necessary, however, to perform the oxidation
using oxygen. The oxidation of ferrous ions to synthesize
green rusts has been performed using sodium nitrite
(Hansen et al. 1994) and sodium nitrate (Miot et al.
2014).
Int. J. Environ. Sci. Technol. (2018) 15:1243–1248
Remineralization of ferric oxides
Like co-precipitation, remineralization synthesis mixes
ferrous and ferric hydroxides to precipitate a green rust. It
is not necessary, however, for the ferric hydroxide to be
synthesized in situ. Ferric oxides such as ferrihydrite
((Fe3?)2O30.5H2O), goethite (a-FeOOH) and haematite
(a-Fe2O3) have been converted to green rusts (Hansen
1989, Usman et al. 2012).
FeSO47H2O is added to the ferric oxide at a concen-
tration of 47.6 mM. Then, 1 M NaOH is added so that the
ratio of (OH-)/Fe3? becomes 3. This results in the
immediate formation of a green bluish-coloured suspension
(Usman et al. 2012).
Reduction of iron oxide nanoparticles
Jones et al. (2015) have synthesized a novel sulphide green
rust. This synthesis uses iron oxide nanoparticles sus-
pended in an organic solvent as the iron precursor material.
These nanoparticles are then treated with cysteamine-HCl.
This results in the reduction of iron and the formation of
green aqueous solution of sulphide green rust nanoparti-
cles. These nanoparticles retain some of the previous iron
oxide content, existing as a hybrid of sulphide green rust
and iron oxide material.
Electrochemistry
Moreno et al. (2007) synthesized green rust by the elec-
trolytic oxidation of an iron anode. The presence of chlo-
ride anions in the electrolyte was found to be essential to
the formation of green rust containing divalent anions.
Addition of divalent anions such as sulphate and carbonate
to the chloride (KCl or NaCl) electrolyte results in the
formation of sulphate and carbonate rust. This method also
resulted in the synthesis of phosphate green rust.
Bacterial reduction
Etique et al. (2015) have synthesized a green rust by the
reduction of magnetite (Fe3O4) using Shewanella putrefa-
ciens. During incubation, the bacteria convert magnetite
into green rust and siderite (Fe(II)CO3) using dihydrogen
(H2) as the electron donor. c-FeOOH was found to reduce
to hydroxysulphate green rust when reduced by Shewanella
putrefaciens if sulphate was added to the growth medium
(Zegeye et al. 2005).
1245
Characterization
Green rusts can be identified using Mossbauer spec-
troscopy and X-ray diffraction (XRD). Other techniques
such as scanning electron microscopy (SEM), transmission
electron microscopy (TEM) and atomic-force microscopy
(AFM) are used to study the topological and morphological
characteristics of green rust.
Mossbauer
Mossbauer spectroscopy can detect changes in oxidation
state, ligands and magnetic environment of the sample.
Mossbauer can be used to detect the presence of green rust
in a sample. It is used to study the ratio of ferric to ferrous
ions in green rust. A ratio of 0.25:0.33 usually indicates
unoxidized, fresh green rust. As the green rust oxidizes
over time, this ratio increases till it finally becomes 1.0,
indicating complete oxidation of the green rust.
X-ray diffraction
X-ray diffraction (XRD) yields the cell parameters and
oxidation state of the sample material. The peaks observed
by XRD are used to identify green rust and the oxidation
state of the same. The oxidation state data from XRD are
the same as those from Mossbauer spectroscopy and are
used to cross-check the Mossbauer results. XRD is used to
calculate cell parameters, which provide vital information
about the green rust, such as the anion and the presence of
sodium or potassium ions in the cationic layer.
Scanning electron microscopy
Scanning electron microscopy (SEM) is used to study the
size, shape and morphology of the green rust crystals.
Green rust occurs as hexagonal platelets with a diameter of
a few nanometres to 2 lm. The particle size and mor-
phology of a material play a very important role in the
kinetics of its reactions. The high reactivity of green rusts
is attributed, in part, to their small particle size.
Transmission electron microscopy
Transmission electron microscopy is used to study the
morphology and thickness of green rust crystals. As in the
case of scanning electron microscopy, the shape of green
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rust crystals provides key information regarding its reac-
tivity and adsorption properties.
Atomic-force microscopy
Atomic-force microscopy (AFM) is a technique used to
study the surface topography of the sample. Surface
properties of a material affect its reactivity. The compar-
atively lower reactivity of green rust with biochemical
origins as compared to chemically synthesized green rust
may be attributed to the presence of bacterial biopolymers
in biochemical green rust (Zegeye et al. 2005). Biochem-
ical green rust has also been demonstrated to have a lower
surface-to-volume ratio than chemical green rust.
Applications of green rust
The applications of green rust can be briefly described by
Fig. 2.
Heavy metal reduction and immobilization
Green rusts have been shown to reduce chromium (VI).
These reductions result in the formation of low-mobility
compounds of the heavy metals that do not disperse easily
into the environment. In addition, there is evidence that
green rusts act as substrates for reduction of hexavalent
chromium by supernatant Fe(II) ions. Green rust is most
effective at immobilizing hexavalent chromium when it is
in excess in comparison with the Cr(VI) concentration.
When the Cr(VI) is in excess, however, a poorly crystalline
Fig. 2 Synthesis and
applications of Green Rust
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Int. J. Environ. Sci. Technol. (2018) 15:1243–1248
but stable Cr(III)–Fe(III) compound forms (Skovbjerg et al.
2006).
Green rusts are also effective at reducing and immobi-
lizing selenates (SeO24-) (Myneni 1997), uranium (VI)
(O’Loughlin et al. 2003a, b) and copper (II), Ag(I), Au(III)
and Hg(II). However, reduction of Hg(II) to Hg(0) actually
increases the mobility of Hg, due to its high vapour pres-
sure. Thus, green rusts should not be used for pollutant
remediation in systems with Hg ions in solution
(O’Loughlin et al. 2003a, b). They also adsorb arsenic
reducing its toxicity in the environment (Randall et al.
2001).
Nitrate reduction
Green rusts can reduce nitrates to ammonium (Hansen and
Koch 1998). Etique et al. (2014) have suggested that green
rust can be used in passive water denitrification. The
presence of phosphates in the solution chemically stabilizes
the green rust, hindering effective nitrate reduction. While
the reduction of nitrates using green rust is desired, for-
mation of ammonium ions is problematic. To solve these
problems, a phosphate adsorbtion system before green rust
reduction and an ammonium adsorption system post-re-
duction have been suggested for effective denitrification of
water (Etique et al. 2014).
Organic pollutants
Sulphide green rusts have been found to be highly effective
at the degradation of an orange II, a potentially mutagenic
azo dye. The maximum remediation capacity was found to
Int. J. Environ. Sci. Technol. (2018) 15:1243–1248
be 150 mmol of azo dye per gram of green rust (Jones et al.
2015).
Green rust has been shown to dechlorinate chlorinated
methanes and ethenes. This reaction occurs 4–7 times
faster in the presence of copper(II). Addition of copper ions
also results in complete dechlorination of CCl4, as opposed
to formation of chloroform (CCl3) when Cu(II) was not
used. This reaction is suggested to proceed via the for-
mation of zero-valent metal nanoparticles (Maithreepala
and Doong 2005).
Metal/exGR-Fe(III) nanohybrids
Individual green rust particles can be used as microreactors
for the reduction of silver and gold, leading to the forma-
tion of nanoparticles that are firmly attached to the exGR
particles. The nanoparticles can be easily separated from
the exGR particles by acidic or reducing treatments. These
nanohybrids are biocompatible and functionalizable and
are expected to have a wide range of potential applications
(Ayadi et al. 2013). As discussed in the previous section,
the formation of zero-valent metal nanoparticles greatly
enhances organic pollutant remediation.
Conclusion
Green rusts have been shown to be effective at the reme-
diation of a variety of heavy metal and organic pollutants.
The biocompatible nature of iron oxides and the high
reactivity and ease of synthesis of green rusts make them
very attractive for environmental remediation. Their newly
found applications in nanochemistry and catalysis indicate
new areas for research in the field. Despite this, however,
use of green rusts for environmental remediation remains
difficult due to the instability of green rusts in oxygenated
environments. Further research is required in the field of
green rust stabilization in order to make use of green rusts a
practical solution to remediating pollutants. Alternatively,
in situ methods for green rust synthesis in polluted envi-
ronments may be utilized.
Acknowledgements The authors wish to thank all who assisted in
performing this study.
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