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Review

The limitations of applying zero-valent iron

technology in contaminants sequestration and the
corresponding countermeasures: The development
in zero-valent iron technology in the last two
decades (1994e2014)

Xiaohong Guan a, Yuankui Sun a, Hejie Qin a, Jinxiang Li a, Irene M.C. Lo b,

Di He c, Haoran Dong d,*
a
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering,
Tongji University, Shanghai 200092, China
b
Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Hong
Kong, China
c
School of Civil and Environmental Engineering, University of New South Wales, Sydney 2052, Australia
d
College of Environmental Science and Engineering, Key Laboratory of Environmental Biology and Pollution Control,
Hunan University, Changsha, Hunan 410082, China

article info abstract

Article history: Over the past 20 years, zero-valent iron (ZVI) has been extensively applied for the
Received 19 November 2014 remediation/treatment of groundwater and wastewater contaminated with various
Received in revised form organic and inorganic pollutants. Based on the intrinsic properties of ZVI and the re-
17 February 2015 actions that occur in the process of contaminants sequestration by ZVI, this review
Accepted 18 February 2015 summarizes the limitations of ZVI technology and the countermeasures developed in the
Available online 28 February 2015 past two decades (1994e2014). The major limitations of ZVI include low reactivity due to
its intrinsic passive layer, narrow working pH, reactivity loss with time due to the pre-
Keywords: cipitation of metal hydroxides and metal carbonates, low selectivity for the target
Mass transfer contaminant especially under oxic conditions, limited efficacy for treatment of some
Passive layer refractory contaminants and passivity of ZVI arising from certain contaminants. The
pH countermeasures can be divided into seven categories: pretreatment of pristine ZVI to
Iron oxides remove passive layer, fabrication of nano-sized ZVI to increase the surface area, syn-
Corrosion products thesis of ZVI-based bimetals taking advantage of the catalytic ability of the noble metal,
employing physical methods to enhance the performance of ZVI, coupling ZVI with other
adsorptive materials and chemically enhanced ZVI technology, as well as methods to
recover the reactivity of aged ZVI. The key to improving the rate of contaminants removal
by ZVI and broadening the applicable pH range is to enhance ZVI corrosion and to

* Corresponding author. Tel.: þ86 0731 88822778.

E-mail address: dongh@hnu.edu.cn (H. Dong).
http://dx.doi.org/10.1016/j.watres.2015.02.034
0043-1354/© 2015 Elsevier Ltd. All rights reserved.
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8 225

enhance the mass transfer of the reactants including oxygen and Hþ to the ZVI surface.
The characteristics of the ideal technology are proposed and the future research needs
for ZVI technology are suggested accordingly.
© 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2. Corrosion chemistry of ZVI and limitations of ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.1. Corrosion chemistry of ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.2. Role of mass transfer in the process of contaminants sequestration by ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
2.3. Limitations of ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3. Countermeasures to overcome the limitations of ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3.1. Pretreatment of pristine ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3.1.1. Acid washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.1.2. H2-pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3.1.3. Ultrasound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3.2. Nano-sized ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3.3. Bimetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3.4. Physically enhanced ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
3.4.1. Ultrasound assisted ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
3.4.2. UVevisible light assisted ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
3.4.3. Microwave assisted ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
3.4.4. Gas-bubbled ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
3.4.5. Weak magnetic field assisted ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.5. Coupling ZVI with other materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.5.1. ZVI/activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.5.2. ZVI/zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.5.3. ZVI/pillared bentonite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.5.4. ZVI/iron oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.6. Chemically enhanced ZVI technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.6.1. Ligand enhanced oxidation processes in ZVI system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.6.2. Dosing of Fe2þ, Co2þ and Mn2þ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.7. Methods to recover the reactivity of aged ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.7.1. Electrochemical method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.7.2. Dosing of Fe2þ or Mg2þ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.7.3. Weak magnetic field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3.7.4. Bacteria-mediated regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4. Conclusions and future challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

halogenated compounds at a reaction rate three to eight or-

1. Introduction
Although there had already been several fairly detailed
studies on the removal of organics (e.g., Senzaki, 1991; Senzaki
and Kumagai, 1988, 1989; Khudenko, 1991) and inorganics
(e.g., Gould, 1982; Khudenko, 1985) by zero-valent metals prior
to 1990, little attention was directed towards the application of
zero-valent iron (ZVI or Fe0) for hazardous waste removal until
the seminal works of Gillham and O'Hannesin (1994) as well as
Matheson and Tratnyek (1994) in 1994. Their laboratory works
indicated that ZVI could degrade a wide range of dissolved
ders of magnitude higher than the naturally abiotic degrada-
tion process, thereby indicating the great potential of using
ZVI for contaminant removal (Gillham and Ohannesin, 1994;
Matheson and Tratnyek, 1994). The first field application of
ZVI in permeable reactive barrier (PRB) technology for in situ
remediation of groundwater contaminated by trichloroethy-
lene (TCE) and pentachloroethylene (PCE) at the Canadian
Forces Base, Borden, Ontario in 1991 showed the removal rates
of about 95% and 91% for TCE and PCE, respectively, across the
Fe0-based PRB (O'Hannesin and Gillham, 1992). Due to the
success of the Fe0-based PRB, ZVI technology gained much
226 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
attention. Hereafter, ZVI has been extensively applied for the
remediation/treatment of groundwater and wastewater
contaminated with halogenated organics (Arnold and Roberts,
2000; Johnson et al., 1996; Roberts et al., 1996), nitroaromatics
(Agrawal and Tratnyek, 1996; Keum and Li, 2004), dyes (Nam
and Tratnyek, 2000; Pereira and Freire, 2006), phenolic com-
pounds (Morales et al., 2002), heavy metals (Rangsivek and
Jekel, 2005; Shokes and Moller, 1999) and various oxyanions
including arsenate (Neumann et al., 2013; Su and Puls,
2001a,b), arsenite (Neumann et al., 2013; Su and Puls,
2001a,b), chromate (Alowitz and Scherer, 2002; Puls et al.,
1999), nitrate (Alowitz and Scherer, 2002; Chi et al., 2004;
Huang et al., 1998), bromate (Xie and Shang, 2007), selenite
(Liang et al., 2013), selenate (Klas and Kirk, 2013; Yoon et al.,
2011), and uranyl (Fiedor et al., 1998; Gu et al., 1998). More-
over, there is an increasing interest on employing ZVI for the
removal of contaminants from groundwater and wastewater,
as reflected by the exponentially increasing number of publi-
cations in the last two decades (Fu et al., 2014).
Over the last two decades, studies on ZVI technologies can
be divided into three categories: (1) Developing various ZVI-
based technologies to overcome the limitations of ZVI so that
the efficiency of contaminants removal can be improved; (2)
Exploring the possibility of employing the developed ZVI-
based technologies to sequester various contaminants of
concern; and (3) Applying the ZVI-based technologies in real
practice and tackling with the consequent problems arising.
The application of nano-sized ZVI (nZVI) in the dechlorination
of TCE and polychlorinated biphenyls (PCBs) (Wang and
Zhang, 1997) triggered research activities on developing
various ZVI-based technologies to enhance the performance of
ZVI for contaminants removal. It is essential to comprehen-
sively summarize the development of ZVI-based technologies
so far, as this is crucial for figuring out the future needs in the
research field of ZVI. Although some review papers on ZVI
technologies have been published in recent years, most of
them focused on nZVI technologies (Li et al., 2006; Zhang, 2003)
because of the increasing utilization of ZVI nanoparticles in
the field of environmental remediation. Very few review pa-
pers focused on micro-sized ZVI (mZVI) or ZVI with larger
particle size (Fu et al., 2014; Noubactep, 2008), moreover, these
papers mainly concentrated on contaminants removal and the
reaction mechanisms, and none of them extensively sum-
marizes the development of ZVI-based technologies in the
past two decades. Therefore, the objectives of this study are to
(1) summarize the limitations of ZVI in sequestering contam-
inants by discussing the corrosion chemistry of ZVI, (2) sum-
marize the ZVI-based technologies developed in the past two
decades and discuss the merits and demerits of these coun-
termeasures, and (3) propose the future research needs to
address the pertinent engineering challenges.
2. Corrosion chemistry of ZVI and
limitations of ZVI technology
2.1. Corrosion chemistry of ZVI
ZVI is unstable under environmental conditions and may
undergo a series of corrosion reactions in Fe0/H2O system.
Aqueous Fe0 corrosion is generally agreed to occur through an
electrochemical mechanism. The anodic process is the Fe0
dissolution while the cathodic process is the liberation of
hydrogen as hydrogen gas under anaerobic conditions and
oxygen reduction under oxic conditions (Noubactep, 2008).
The oxidation of Fe0 by Hþ/O2 yields Fe2þ following Eqs. (1) and
(2) listed in Table 1. In the pH range pertaining to natural
waters, Fe2þ may hydrolyze and form Fe(OH)2 at the Fe0 sur-
face (Eq. (3) in Table 1). Fe2þ is of limited stability and is very
sensitive to molecular oxygen (O2) (Aleksanyan et al., 2007a;
Nesic, 2007). The oxidation of Fe2þ species by O2 is quite
rapid with the reaction rate increasing with elevating pH
(Guan et al., 2011). The resulting Fe3þ readily hydrolyses,
precipitates (Fig. 1) and transforms to oxides ((Fe(H2O)6)3þ
(aq) 0 Fe(OH)3 (aq) 0 Fe(OH)3 (s) 0 oxides). Depending on the
O2 availability, various (hydr)oxides (Fe3O4, Fe(OH)3, FeOOH)
are generated (Eqs. (4)e(6) in Table 1) (Mackenzie et al., 1999;
Mielczarski et al., 2005; Wilkin et al., 2003). Therefore, it was
generally anticipated that oxygen would result in a thicker
layer of iron oxides with higher oxidation states (e.g.,
maghemite or lepidocrocite) and thereby, decreasing the
reactivity of ZVI (Flury et al., 2009). In fact, the impact of ox-
ygen has been largely overlooked and misunderstood. Several
studies reported that the presence of oxygen of certain con-
centration could enhance the contaminants sequestration by
ZVI remarkably while the presence of excessive oxygen defi-
nitely would inhibit the removal of contaminants by ZVI
(Huang and Zhang, 2005; Yoon et al., 2011; Klas and Kirk, 2013;
Tang et al., 2015). Consequently, the influence of oxygen on
the process of contaminants removal by ZVI, which may be
dependent on pH and the mechanisms of contaminants
removal, should be further verified.
Moreover, reactive oxygen substances including H2O2 and
hydroxyl radicals ( OH) can be generated in the Fe0/H2O/O2

system under acidic conditions through the two-electron
oxidation of Fe0 followed by the Fenton reaction (Hug and
Leupin, 2003; Lee et al., 2008), as shown by Eqs. (7)e(8) in
Table 1.
The precipitated amorphous and crystalline iron oxy-
hydroxides (Fe3O4, Fe2O3, FeOOH, Fe(OH)2, Fe(OH)3, etc.) in the
vicinity of the ZVI surface are well known for their adsorptive
properties of organic and inorganic contaminants (Noubactep,
2013; Sun et al., 2014). Iron oxide precipitation is a dynamic
process and thus some contaminants will be adsorbed on to
aged iron oxyhydroxides (adsorption), others will be adsorbed
on to nascent iron oxyhydroxides and will be entrapped in
their structure while aging (co-precipitation) (Noubactep,
2009). Furthermore, local supersaturation of the inflowing
Table 1 e Possible reactions occurring in Fe0/H2O system.
Reactions No.
Fe0 þ 2Hþ /Fe2þ þ H2 [ 1
2Fe0 þ O2 þ 2H2 O/2Fe2þ þ 4OH 2
Fe2þ þ 2H2 O/FeðOHÞ2 Y þ 2Hþ 3
6Fe2þ þ O2 þ 6H2 O/2Fe3 O4 Y þ 12Hþ 4
4Fe2þ þ O2 þ 10H2 O/4FeðOHÞ3 Y þ 8Hþ 5
4Fe2þ þ O2 þ 6H2 O/4FeOOHY þ 8Hþ 6
Fe0 þ O2 þ 2Hþ /Fe2þ þ H2 O2 7
Fe2þ þ H2 O2 /Fe3þ þ OH þ OH 8
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8 227

Fig. 1 e Illustration of the major reactions occurred in the Fe0/H2O system and the mechanisms of contaminants removal.

water can cause contaminant precipitation (Noubactep, 2008;
Noubactep and Schoner, 2010). Besides the three removal
processes discussed above, reduction of some contaminants
(e.g. chromate, nitrate, dyes) by Fe0, Fe2þ and H2 and oxidation
of contaminants (e.g. As(III), Sb(III), chlorophenols) by the

reactive oxygen species (including OH, O2 ) are possible in the

importantly, oxide film formation is intrinsic to iron corrosion
and its development begins when ZVI first comes in contact
with water. The process of aging of oxyhydroxides is usually
accompanied by dehydration and conversion to a less porous
structure. Therefore, the passive layer on the surface of pris-
tine ZVI particles and the deposition of Fe2þ/Fe3þ (oxy)hy-

0
Fe /H2O/O2 system (Noubactep, 2008, 2009). The mechanisms droxides on ZVI surface in the process of contaminants
of contaminants removal by ZVI are schematically illustrated removal by ZVI, especially under near neutral conditions, can
in Fig. 1. Clearly, the corrosion of ZVI governs the rate of act as a diffusion barrier for Fe2þ, O2, Hþ and the oxidized
contaminants removal by ZVI (Triszcz et al., 2009). Conse- contaminants and thus can result in a drop in the corrosion
quently, the methods, which can accelerate ZVI corrosion, can rate, as illustrated in Fig. 2. Moreover, the structure of the
enhance contaminant sequestration by ZVI. oxide film (e.g. composition, porosity, thickness, surface
groups) and the nature of the contaminant (size, chemical
nature, affinity to oxide film) can influence the resistance of
2.2. Role of mass transfer in the process of contaminants
the iron oxides film on mass transport of the solutes towards
sequestration by ZVI
or away from the ZVI surface.
Before diffusing across the iron oxides film to reach the ZVI
The process of contaminants removal by ZVI involves the
surface, O2, Hþ and the oxidized contaminants in the bulk
transfer of electrons between ZVI and the oxidizing species
solution have to cross the diffusion boundary layer, where
(O2, Hþ, and contaminants that can accept electrons). This
whole process due to the interfacial nature of the electron
transfer reactions typically involves a series of steps,
including the transport of the oxidizing species from the bulk
solution to the ZVI surface, the reaction between ZVI and the
oxidizing species, as well as the transport of products (Fe2þ,
OH) away from the ZVI surface to the bulk solution, as
illustrated in Fig. 2. If the rate constant of the reaction between
ZVI and the oxidizing species is large, any reactant (O2, Hþ,
and contaminants that can accept electrons) close to the ZVI
surface is immediately consumed. Under this circumstance,
the whole process will be controlled both by the continuous
supply of O2, Hþ, the oxidized contaminants, and by the rapid
escape of Fe2þ and OH from the Fe0 surface (Noubactep,
2008). The concentration gradients will lead to molecular
diffusion of the species (across the oxide film) toward or away
from the ZVI surface.
Commercial ZVI is usually covered with a discontinuous
passive layer of iron oxides formed during its production
process (Gheju, 2011). The iron is placed in rotary kilns
(700e1200  C) to burn off other non-metallic materials,
particularly cutting oils, associated with the scrap metal from
which the granular iron is produced (Ritter et al., 2002). After
exposed to these elevated temperatures, the iron becomes Fig. 2 e Illustration of the process of contaminants
oxidized, and a high-temperature film will form. More sequestration by ZVI.
228 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8

diffusion is the major driving force for mass transport. Since

the mass transport in a bulk solution driven by convection is
generally very rapid, the net rate of mass transport of the
solutes to the surface of the iron oxides film is essentially
governed by the rate of diffusion in the diffusion boundary
layer (Lioubashevski et al., 2004). Increasing the mixing speed
leads to a thinning of the laminar liquid film that adheres to
the particles and improvement of the mass transfer (Agrawal
and Tratnyek, 1996; Scherer et al., 2001).
Mass transfer resistance in the diffusion boundary layer
and iron oxides film of a ZVI particle plays a crucial role in the
process of contaminants removal by ZVI and it may often limit
the total reaction rate. Agrawal and Tratnyek (1996) concluded
that the rate of nitrobenzene (ArNO2) reduction by ZVI was
controlled by the mass transport of ArNO2 to the ZVI surface
because (i) a linear relationship was found between the reac-
tion rate coefficient and the square root of the batch mixing
rate (rpm1/2), and (ii) no significant substituent effects were
found on the reduction rates, despite significant differences in
the one-electron reduction potentials. Scherer et al. (2001)
further showed that the reaction kinetics of ArNO2 on a ZVI
rotating disk electrode was influenced by the mass transport, Fig. 3 e Summary of the limitations of ZVI technology.
for electrode rotation rates below 4900 rpm. The reduction of
chlorinated methanes by ZVI in batch model systems was also
reported to be coupled with oxidative dissolution (corrosion)
of ZVI through a largely diffusion-limited surface reaction capacity and selectivity for targeted contaminants,
(Matheson and Tratnyek, 1994). All of these results indicate especially for the organic contaminants;
that contaminants removal by ZVI is strongly influenced by (v) Some toxic intermediates may accumulate in the pro-
the mass transport of the contaminants to the ZVI surface cess of contaminants (especially the lightly chlorinated
across a stagnant boundary layer. It is therefore of particular hydrocarbons) removal by ZVI due to the low reactivity
interest to accelerate the mass transfer in the process of of ZVI (Wang and Zhang, 1997).
contaminants sequestration by ZVI so as to enhance the rate
of contaminants removal.
3. Countermeasures to overcome the
limitations of ZVI technology
2.3. Limitations of ZVI technology
Since the publication of two full papers on the degradation of
Considering the intrinsic properties of ZVI and the reactions halogenated aliphatics by ZVI in 1994 (Gillham and Ohannesin,
that occur in the process of contaminants sequestration by 1994; Matheson and Tratnyek, 1994), various countermeasures
ZVI, employing mZVI for contaminants removal has several have been developed in the past two decades to overcome the
intrinsic limitations, as schematically illustrated in Fig. 3. limitations of ZVI technology mentioned above, which are
summarized in Fig. 4. Moreover, the installation of the first full-
(i) ZVI has low reactivity since it is covered with an scale ZVI-PRB in 1995, the first field demonstration of
intrinsic passive layer generated in its manufacturing groundwater remediation with nZVI in 2000, and the desig-
process and has a relatively low specific surface area; nation of ZVI-PRB as a standard remediation technology by
(ii) The reactivity of ZVI drops over time, due to the surface USEPA in 2002 are included in Fig. 4 with other major events in
passivation caused by the corrosion products (e.g., the the field of ZVI technology in the past two decades. According
precipitation of metal hydroxides, such as Fe(OH)2, to the commonalities and characteristics of these counter-
Fe(OH)3 and metal carbonates, such as FeCO3 on the measures, they can be divided into seven categories: pre-
surface of ZVI). Moreover, some contaminants can treatment of pristine ZVI, nZVI, ZVI-based bimetals, physically
passivate ZVI, leading to a drop in the reactivity of ZVI enhanced ZVI technology, coupling ZVI with other materials,
(Liang et al., 2014b); chemically enhanced ZVI technology, and methods to recover
(iii) Due to the direct involvement of Hþ in the corrosion the reactivity of aged ZVI. The mechanisms and drawbacks of
reactions and the mass transport limitations imposed each countermeasure are briefly summarized in Table 2 and
by the precipitation of a passive film on the metal sur- are discussed in this section.
face, the reactivity of ZVI drops sharply with increasing
pH and thus ZVI technology is generally only efficient 3.1. Pretreatment of pristine ZVI
under acidic conditions;
(iv) ZVI has low reactivity towards some refractory con- Non-pretreated commercial iron is covered with a discontin-
taminants, e.g., Se(VI), and it has low adsorption uous passive layer, formed during the manufacturing process
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
Fig. 4 e The major events in the development of ZVI technology in the past two decades.
(Ritter et al., 2002). Additionally, a mixture of non-
stoichiometric iron oxide and oxyhydroxide species may form
in storage (Ruiz et al., 2000). The iron (hydr)oxides covered on
the surface of pristine ZVI can hinder the mass transport,
resulting in the low reactivity of pristine ZVI in the initial re-
action stage since it takes time to eliminate the oxide layer
(Alowitz and Scherer, 2002; Liang et al., 2014b). Consequently,
pretreatment methods to remove the passive oxide layer
before the initial reaction stage were developed to increase the
number of available reactive sites for accelerating the
sequestration of contaminants by ZVI.
3.1.1. Acid washing
Acid washing was frequently employed to pretreat virgin ZVI in
order to remove the passive layer so as to enhance the reactivity
of ZVI. It was reported in many studies that treating ZVI with
dilute HCl resulted in a faster reduction rate of chlorinated or-
ganics, nitroaromatic compounds, and nitrate than in un-
treated cases (Agrawal and Tratnyek, 1996; Lin and Lo, 2005;
Matheson and Tratnyek, 1994). Agrawal and Tratnyek (1996)
pointed out that the effect of HCl pretreatment may be due to
one or more of the following mechanisms: 1) cleaning of the
surface by dissolution of the metal and breakdown of the
passivating oxide layer, 2) increasing the metal surface area by
etching and pitting through corrosion, 3) increase in the density
of highly reactive sites consisting of steps, edges, and kinks,
following corrosion by the acid, and 4) increased concentrations
of adsorbed Hþ and Cl that persist after pretreatment with HCl.
229
However, Lai and Lo (2008) observed a lower Cr(VI) removal
capacity of the acid washed-ZVI than the unwashed ZVI under
various groundwater geochemistry conditions through col-
umn experiments. There was approximately a 57e77% drop in
the Cr(VI) removal capacity after acid-washing. This phe-
nomenon was contrary to the findings of many batch studies
in which acid-washing was reported to be able to enhance the
kinetics of contaminants removal by ZVI (Agrawal and
Tratnyek, 1996; Matheson and Tratnyek, 1994; Su and Puls,
1999; Weber, 1996; Westerhoff, 2003). A similar phenomenon
was observed from the column studies conducted by Lai et al.
(2006) in which the unwashed palladized-ZVI (PdeFe0) also
showed faster TCE degradation kinetics than the acid-washed
PdeFe0. It is generally accepted that acid-washing can in-
crease the initial ZVI reactivity significantly by breaking down
nearly all the indigenous iron oxides on the ZVI surface and/or
increasing the ZVI surface area (Agrawal and Tratnyek, 1996;
Alowitz and Scherer, 2002). Nearly all the indigenous iron
precipitates such as magnetite (Fe3O4) and goethite (a-
FeOOH)/hematite (a-Fe2O3) on the ZVI surface were erased by
acid-washing (Lai and Lo, 2008). However, this might subse-
quently result in more severe mineral precipitation on the ZVI
surface in comparison to the case of unwashed ZVI, thereby
leading to more severe and rapid loss of the acid-washed ZVI
reactivity afterward and poorer long-term efficiency of the
acid-washed ZVI on contaminant removal (Lai and Lo, 2008).
This hypothesis may be the reason why positive influences
from acid-washing were observed from relative short-term
230 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8

Table 2 e Countermeasures to improve the performance of ZVI technology and their respective mechanisms and
drawbacks.
Countermeasures Mechanisms Drawbacks Ref.
Pretreatment of Acid-washing ✧ Breakdown of the ✧ Production of strongly (Agrawal and Tratnyek,
pristine ZVI passivating oxide layer acidic wastewater or 1996; Lin and Lo, 2005;
✧ Increasing the metal sludge with a high Matheson and Tratnyek,
surface area by etching concentration of 1994; Su and Puls, 1999)
and pitting through iron ions
corrosion ✧ Loss of Fe0 mass
✧ Increase in the density ✧ Acceleration of corrosion
of highly reactive sites by sorbed Hþ and Cl
H2-reduction ✧ Reduction of iron oxide ✧ High temperature (Lin and Lo, 2005; Liou et al.,
layer (e.g., 400  C) for reaction 2005)
✧ Carbonization of carbon-
containing subjects on
the iron's surface
✧ Increase in active site
concentration
✧ Increase in the sorption
capacity per unit iron
surface area
Ultrasound ✧ Clearance of the iron ✧ Large amount of energy (Geiger et al., 1996, 2002;
surface debris and input Gotpagar et al., 1999; Hung
increase in the surface and Hoffmann, 1998)
area
✧ Cause pitting and
cracking of metal
surfaces, increasing the
percentage of active sites
✧ Enhance rates of mass
transport resulting from
cavitation
nZVI nZVI (in situ/ex situ) ✧ Large specific surface ✧ Short service life due to (Comba et al., 2011; Kanel
area high reactivity et al., 2007; Saleh et al., 2008)
✧ High reactivity ✧ Aggregation and poor
mobility
✧ Possible ecotoxicity
✧ High material costs
ZVI-based bimetals Bimetals (in situ/ex situ) ✧ Enhanced corrosion ✧ Short lifetimes due to (Lien and Zhang, 2002; Lin
rate of Fe0 through the surface passivation et al., 2004; Schrick et al.,
formation of infinite ✧ Structural changes 2002; Zhu and Lim, 2007)
galvanic cells during reaction, leading
✧ Facilitate the generation to decreased reactivity
of surface-bond atomic ✧ Possible ecotoxicity
hydrogen for reducing
contaminants
Physical methods Ultrasound assisted ZVI ✧ Continuous cleaning and ✧ Large amount of energy (Hung and Hoffmann, 1998;
to enhance the technology (in situ/ex situ) chemical activation of input Liu et al., 2007; Zhang et al.,
reactivity of the Fe0 surfaces by 2005)
pristine ZVI acoustic cavitation
✧ Accelerated mass
transport rates of
reactants, intermediates,
and products between
the solution phase and
the Fe0 surface
UVeVisible light assisted ✧ Formation of Reactive ✧ Improvement was not (Morgada et al., 2009; Son
ZVI technology (ex situ) Oxygen Species significant under UV-A or et al., 2009)
✧ Formation of multiple visible light illumination
active species
Microwave assisted ZVI ✧ Enhance rates of mass ✧ Large amount of energy (Remya and Lin, 2011;
technology (ex situ) transport input Venkatesh and Raghavan,
✧ Increase in active site 2004)
concentration
✧ Accelerated ZVI
corrosion
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8 231

Table 2 e (continued )
Countermeasures
Weak magnetic field
assisted ZVI technology
(ex situ)
Gas-bubbled ZVI process
(ex situ)
Coupling ZVI with ZVI/activated carbon
other materials (in situ/ex situ)
ZVI/zeolite (in situ/ex situ)
ZVI/pillared bentonite
(in situ/ex situ)
ZVI/iron oxide
(in situ/ex situ)
Chemically enhanced Addition of organic
ZVI technology ligands (e.g., EDTA,
oxalate)
(in situ/ex situ)
Addition of ions
(e.g., Fe2þ, Co2þ
and Mn2þ)
(in situ/ex situ)
Mechanisms
✧ Enhanced mass
transport
✧ Forming passive film
with greater morphology
✧ Supplying Hþ to create
a favorable acidic
environment for iron
corrosion
✧ Formation of numerous
microscopic galvanic
couples
✧ Enhanced adsorption of
organic pollutants
✧ Synergistic effect of
sorption and reduction
✧ Promoted mass transfer
✧ Synergistic effect of
sorption and reduction
✧ Promoted mass transfer
✧ Buffering effect of
bentonite
✧ Provide additional
adsorption sites
✧ Catalyze contaminant
reduction by Fe2þ
✧ Increased oxidant

(e.g., OH) production
under aerobic conditions
✧ Formation of strong
complexes between
ligands with Fe(II)/Fe(III)
and thus elimination of
iron (hydr)oxides
precipitates on ZVI
surface
✧ Enhanced electron
transfer
✧ Formation of a bimetallic
(e.g., Co0eFe0) catalytic
system
Drawbacks Ref.
✧ Difficulty in generating a (Jiang et al., 2008; Kim et al.,
WMF around a large scale 2011; Liang et al., 2014b; Sun
ZVI-based filter or PRB et al., 2014)
✧ The electricity (Hsu et al., 2004;
consumption necessary Ruangchainikom et al.,
for pumping CO2 and 2006a,b)
chemical cost of CO2
✧ Time-consuming (Dou et al., 2010; Ghauch,
synthetic processes 2008; Keum and Li, 2004;
✧ High production cost of Ruan et al., 2010)
activated carbon
✧ Limited longevity (Curkovic et al., 1997;
✧ High material costs Hedstro€ m, 2001; Mier et al.,
2001; Park et al., 2002)
✧ The synergistic effect (Cho et al., 2005; Lo, 2001;
was observed only when Zhu et al., 1997)
the pillared bentonite
was uniformly mixed
with ZVI
✧ A completely mixed (Gu et al., 1994; Mak et al.,
configuration is 2011; Saito et al., 2004)
required
✧ High concentrations of (Fu et al., 2013; Keenan and
ligands (e.g., oxalate) Sedlak, 2008; Noradoun and
were usually required Cheng, 2005; Zhang et al.,
✧ Concerns over the 2011a)
possibility of ligand
degradation and the
ability of ligands to
mobilize toxic metals
✧ Potential ecotoxicity
(e.g. EDTA)
✧ Generation of extra (Costa et al., 2006; Huang
sludge and introduction et al., 2012, 2013; Liu et al.,
of unexpected anions 2013a; Tang et al., 2014a,b;
(i.e., SO2
4 ) in the treated Xu et al., 2012)
solution
✧ Secondary pollution
arising from the added
alien ions

batch studies, whereas long-term column study results
showed deterioration of the ZVI efficiency on contaminants
removal by acid-washing. The Auger electron spectra of the
acid-washed PdeFe0 and unwashed PdeFe0 reported by Lai
et al. (2006) further support this hypothesis. The palladium
on the acid washed PdeFe0 was found to be buried under iron
oxide layers, whereas the palladium on the unwashed PdeFe0
was still located on the ZVI surface, without being buried, after
3000 PVs of the column experiment.
Moreover, employing acid washing to pretreat ZVI has
several other drawbacks: 1) the production of strongly acidic
wastewater with a high concentration of iron ions, 2) the loss
of about 15% mass of the initial ZVI (Matheson and Tratnyek,
1994), 3) the acceleration of corrosion by sorbed Hþ and Cl
(Agrawal and Tratnyek, 1996) and 4) a complicated operation
since acid-washing is generally performed under N2-purging
conditions to avoid further surface oxidation to metal oxides.
All of the above factors may cause high variability in the
observed rate constant (kobs) for different acid-washing pro-
cesses and place serious restrictions on its application to in
situ remediation.
3.1.2. H2-pretreatment
Liou et al. (2005) employed hydrogen gas at 400  C to activate
the ZVI surface to improve nitrate removal by ZVI. Compared
with the non-pretreated ZVI, the lag period of nitrate removal
by H2-pretreated ZVI disappeared and the first-order reaction
rate constant (kobs) was increased by 4.7 times. Scanning
electron microscopy (SEM) and temperature-programmed
reduction (TPR) showed a visibly cleaner surface without
pitting and cracking and less oxygen fractions on the pre-
treated iron relative to the non-pretreated iron. The results
indicated that the enhancement in nitrate reduction by H2-
pretreated ZVI could mainly be attributed to the increase in
232 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
surface active sites. Lin and Lo (2005) employed H2-pretreat-
ment (H2/Ar, 20 vol%) at 400  C to reduce the oxide layer and to
carbonize the carbon containing subjects on the surface of ZVI
so as to improve the destruction of TCE by cast iron. Both the
number of reactive sites and the sorption capacity per unit
iron surface area were increased due to the H2-reducing pre-
treatment. Hence, the H2-pretreatment of cast iron promoted
the removal of TCE from contaminated water by the concur-
rent sorption and reduction.
This method offered several advantages over the acid-
washing method for pretreating cast iron, e.g., it produced
no wastewater or sludge. However, the application of H2-
pretreatment may be limited by the high temperature neces-
sary for the reaction to occur.
3.1.3. Ultrasound
Ultrasound has been demonstrated to remove corrosion
products, precipitates and other debris from iron surfaces
(Geiger et al., 1996; Hung and Hoffmann, 1998). This method
serves to increase the active iron surface, improve reaction
rates and, increase the concentration of terminal by-products.
The application of ultrasonic energy is a direct approach that
cleans the iron surface and restores reactivity. Geiger et al.
(2002) showed the kinetic improvement caused by ultra-
sound pretreatment and illustrated the physical and chemical
changes that take place at the iron surface. Their results
showed that ultrasound could clear the iron surfaces of debris
and thus increase the surface area up to 169%. In addition,
exposure to ultrasound altered the ratios of surface species
(such as adventitious carbon to carbonyl carbon and iron to
oxygen) and removed hydroxides thus making the iron more
reactive to reductive dehalogenation. Hung and Hoffmann
(1998) found that the cleaning and activation of ZVI surface
by ultrasound waves resulted in increased rate constant for
the degradation of carbon tetrachloride. Ultrasound causes
pitting and cracking of many metal surfaces thus increasing
the degradation reaction rates (Heuter and Bolt, 1955) and can
remove corrosion products down to a thin layer of oxide. A
thin oxide layer is capable of acting as a semiconductor for
electron transfer or as a coordination site for electron transfer
through Fe2þ/Fe3þ species (Scherer et al., 1999). However,
Moore et al. (2003) indicated that there was no significant
difference between the reaction rate of sonicated aged iron
and that of unsonicated aged iron. It was suggested that the
sonication procedure did not successfully remove superficial
oxides in recovering the reactivity of the iron. The contrasting
findings may have resulted from the varying nature of the
oxides and other mineral phases on the surface of the iron
filings and the input of sonication energy. Generally, a large
amount of energy was input for sonication pretreatment (Ruiz
et al., 2000), which was not environmentally friendly for
conveniently overcoming the disadvantages of iron.
3.2. Nano-sized ZVI
Since the conventional mZVI has a low reactivity towards
lightly chlorinated hydrocarbons, Wang and Zhang (1997)
pioneered the application of nZVI in environmental remedi-
ation. nZVI can remove contaminants through reduction,
oxidation, adsorption, precipitation or co-precipitation
(O'Carroll et al., 2013) and the chemistry behind nZVI is
much the same as with mZVI. The advantages of nZVI over
mZVI for aqueous contaminants removal are as follows
(Comba et al., 2011): (1) some aqueous contaminant species
that have been proven unsuccessful for remediation using
mZVI can be effectively removed using nZVI because of its
large reactive surface area, (2) nZVI can be used for more rapid
degradation of contaminants, (3) the formation of some un-
desirable by-products during remediation using mZVI can be
avoided by using the more reactive nZVI, resulting from a
more complete degradation of pollutants, and (4) injecting
nZVI to the source of contamination is believed to be faster
and more effective for groundwater treatment than either the
pump-and-treat or PRB methods (EPA, 2008).
Even though the USA and some European countries are
already pioneering the use of nZVI for the remediation of
contaminated soils and groundwater (Grieger et al., 2010),
there are still some major issues (e.g., long-term reactivity,
mobility and possible ecotoxicity) to be resolved by re-
searchers, environmental consultants, and also by govern-
ments. In practice, nZVI particles are subject to two processes
which reduce their effectiveness: agglomeration and passiv-
ation. nZVI particles are attracted to each other and aggregate
into larger, microscale particles, which in almost all cases
reduces their mobility in water and their effective surface area
(Kanel et al., 2007; Saleh et al., 2008). The formed microscale
particles are then thought to behave in the same way as mZVI.
Moreover, nZVI particles are intended to react with water,
groundwater constituents such as nitrate and dissolved
organic matter and the subsurface matrix, leading to the
passivation of nZVI before reaching the contaminants.
To enhance their reactivity and mobility, nZVI particles
have been modified in several ways: (1) Bimetallic nano-
particles (BNPs) are particles of nZVI that have been coated
with a catalyst, such as platinum, gold, nickel, or palladium, to
enhance the reduction reactions (Keane, 2009), (2) Emulsified
nZVI particles are nZVI particles that have been coated with a
membrane made from biodegradable oil and water to facili-
tate the treatment of chlorinated hydrocarbons by making the
particles more hydrophobic. This allows the particles to mix
directly with dense non-aqueous phase liquids (DNAPL), such
as TCE, to increase mass transfer between DNAPL and nZVI
through the emulsion membrane (Keane, 2009), and (3)
Surface-modified nZVI particles are nZVI particles that have
been coated with surface stabilizers (e.g., polyelectrolyte,
surfactant and biopolymer) in order to increase the suspen-
sion stability and therefore particle mobility.
The use of nanoparticles in environmental applications
will invariably raise concerns on the adverse effects of nano-
particles on the environment. Assessing their potential risks
in the environment requires a fundamental understanding of
their mobility, potential bioavailability/bioaccumulation and
impacts on a wide variety of organisms. Currently the envi-
ronmental fate, ecotoxicity of nZVI and its oxidation products
are not well understood for the variety of environmental
conditions that may actually occur. In general, the high ten-
dency of bare nZVI to agglomerate indicates that migration in
the groundwater should not be an issue for groundwater
drinking wells, streams and other bodies of water. The bare
nZVI particles used for remediation are rapidly filtered out
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
through agglomeration and passivation processes, limiting
the risk of human and environmental exposure to nZVI (Kanel
et al., 2007; Saleh et al., 2008). Besides, nZVI particles that have
reacted in the treatment zone will end up as inert iron oxides.
The general consensus in published studies is that passivated
metallic nanoparticles have no significant cellular toxicity
(Lee et al., 2008; Phenrat et al., 2009). Issues, however, may
exist for organisms in the environment that are directly
exposed to the nZVI before much oxidation of the particles
takes place. Moreover, depending on their modification, the
modified nZVI particles may have increased persistence,
enhanced subsurface migration and improved catalytic
properties (or any combinations of these). Concerns also exist
with the offsite mobilization of contaminants that bind to the
nZVI (e.g., arsenic-loaded nZVI) (Dong et al., 2012). It is pre-
sumed that the transport of contaminant-loaded nZVI,
together with the potential remobilization of contaminants,
could cause widespread contamination.
Due to all of the unanswered questions regarding the
effectiveness of nZVI applications and the impacts of nZVI on
the environment, there is currently a significant amount of
research being undertaken. In summary, the following
research needs are highlighted as having the highest priorities
in the development of nZVI technology: (1) Research on the
fate and transport of pristine nZVI, modified nZVI and
contaminants-loaded nZVI, (2) Research on the toxicity of
nZVI particles and derivatives formed after their release to the
environment, and (3) Research to design nZVI particles with
appropriate reactivity and mobility for different contaminants
and site conditions.
In regard to real field applications, the cost of material is
obviously another key consideration. At present, nZVI parti-
cles costs are typically of the order of 30e40 USD lb1 while
conventional ZVI is on the order of 1e5 USD lb1 and granular
iron is generally in the range of 0.25e0.75 USD lb1 (Bardos
et al., 2011). Even though the cost of iron has decreased in
the past year due to the decrease in the cost of raw materials,
increased manufacturing capacity, and increasing numbers of
suppliers and vendors, nZVI particles do tend to be expensive
compared to their larger scale counterparts, on a per unit
basis. However, there is very little information in the peer
reviewed literature with respect to cost analyses for nZVI
remediation projects.
3.3. Bimetals
ZVI is oxidized more rapidly when it is attached to a less active
(noble) metal (e.g., Pd) and hence the transformation of envi-
ronmental contaminants can be enhanced by coupling ZVI to
a noble metal (Harendra and Vipulanandan, 2008). Many
bimetal materials (Lien and Lee, 2005; Lien and Zhang, 1999,
2001) have been shown to possess enhanced reactivity to-
wards chlorinated organic compounds compared to ZVI.
These bimetallic particles are composed of a corrosive metal
(i.e., Fe0) along with a noble metal such as Pd, Pt, Ni, Ag, Co or
Cu (O'Carroll et al., 2013). In such electrochemical couples, Fe0
with a negative redox potential (i.e., E(Mnþ/M) < E(Hþ/H2)) is
considered to behave as an anode, becoming sacrificially
oxidized to galvanically protect the noble metal. The noble
233
metal with a positive redox potential (i.e., E(Mnþ/M) > E(Hþ/H2))
acts as a catalyst and increases the rate of reduction.
Previous studies suggest that the noble metal can enhance
the catalytic reactivity of ZVI towards recalcitrant organic
contaminants (e.g. aromatics and PCBs) (Tee et al., 2005), as
these noble metals have different reactivity enhancements for
the prepared bimetallic reductants. Lin et al. (2004) found that
the catalytic activity of the noble metal followed the order of
Pd > Ru > Pt > Au. Cwiertny et al. (2006) also found the
following reactivity trend of the prepared bimetallic re-
ductants towards 1,1,1-TAC: NieFe0 z PdeFe0 >
CueFe0 > CoeFe0 > AueFe0 z Fe0. The mechanisms for the
increased reactivity of bimetallic particles have been widely
debated among researchers, and two types of catalytic
mechanisms of the bimetallic reductants have been proposed
by the previous researchers: (1) direct reduction on the cata-
lytic activity site by accepting electrons from ZVI, and the
surface additives (i.e., noble metal) can increase the oxidation
of ZVI through the formation of infinite galvanic cells, wherein
iron serves as the anode and becomes preferably oxidized.
Meanwhile, the noble metal (cathode) is protected and re-
mains unchanged (Lien and Zhang, 2002; Ma et al., 2004; Xu
and Gao, 2007), and (2) indirect reduction by the atomic
hydrogen absorbed on the surface of bimetallic reductants,
and the noble metal additives can facilitate the generation of
surface-bond atomic hydrogen (Bransfield et al., 2007; Lin
et al., 2004). Hydrogen is likely present as a dissolved gas,
some of which is adsorbed at the particle surfaces, with an
undetermined fraction possibly present as an active metal
hydride having undergone diatomic dissociation and reaction
with the exposed noble metal (Zhang et al., 1998). For the
clean-up of chlorinated organic contaminants such as TCE or
pentachlorophenol (PCP), hydrogen is observed to be the
predominant driver for degradation, by breaking the CeCl
bonds and swapping itself for chlorine, which is liberated as a
gas (Barnes et al., 2010; Liu et al., 2005; Schrick et al., 2002; Xiu
et al., 2010).
Even though it was reported in most studies that the
combination of ZVI with noble metals increased the dechlo-
rination rates, some studies have reported that bimetals pre-
pared by coating a catalytic metal on ZVI were worse for PCP
dechlorination compared to the unmodified ZVI (Kim and
Carraway, 2000). Similarly, Gunawardana et al. (2012)
observed contradictory effects of deposited Ni on the dechlo-
rination of PCP by two types of ZVI powder (with different
types of iron oxide layer). It was proposed that the effective-
ness of dechlorination is largely dependent on the composi-
tion of the iron oxides on the particle surface formed during
reaction (Su and Puls, 1999). Oxides such as lepidocrocite,
hematite, wustite and ferrihydrite have low conductivity at
room temperature (Cornell and Schwertmann, 2003). Forma-
tion of these oxides can decrease the number of reactive sites
on the ZVI surface and the electron transfer process, thus
hindering dechlorination. However, the reactivity of ZVI sur-
face can be sustained in the presence of oxides such as
magnetite (Fe3O4) and green rust (Fe(II)/Fe(III) hydroxide)
(Aleksanyan et al., 2007b; Farrell et al., 2000; Huang et al., 2003;
Satapanajaru et al., 2003). Moreover, the contradictory find-
ings from different studies may result from the difference in
the methods of producing the bimetallic metals
234 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
(Gunawardana et al., 2012). A previous study reported an
enhanced PCP dechlorination rate with physically mixed
NieFe0 particles (Cheng et al., 2010). Similarly, a higher
dechlorination rate of PCP was observed in bimetallic systems
prepared by physically mixing Ni with ZVI compared with the
Ni coated ZVI (Gunawardana et al., 2012). However, in another
study, Pd coated on ZVI had better performance in TCE
dechlorination compared to ZVI and physically mixed PdeFe0
(Zhang et al., 1998). Therefore, the catalytic reactivity of bi-
metals and the dechlorination rate may depend on the prop-
erties and surface characteristics of ZVI used as well as the
methods of bimetallic preparation. Further studies are needed
to address these discrepancies.
One disadvantage of using bimetallic particles is their
potentially short lifetimes due to the loss of activity of the
bimetals over time, resulting from a build up of the metal
(hydr)oxide film or the chemisorption of compounds to
active sites or a loss of the loosely bound second metal par-
ticles (Lin et al., 2004). The bimetallic particles may also show
structural changes during the reaction, leading to decreased
reactivity (Yan et al., 2010; Zhu and Lim, 2007). Hu et al. (2010)
reported that higher Cu loading of the bimetallic particles is
needed for Cr(VI) removal than for other oxidant organic
pollutants, due to the greater oxidation potential of Cr(VI).
Otherwise, the copper on the bimetallic particle surface
would be completely oxidized to Cu(II) during the reaction
and lose its catalytic ability. Zhu and Lim (2007) recom-
mended that PdeFe0 particles be prepared at the time of use,
rather than preparing the PdeFe0 particles a priori and
storing them in order to achieve the highest reactivity.
However, Barnes et al. (2010) reported that no oxidized spe-
cies of Pd were observed, suggesting that the catalyst remain
unchanged during the reaction. Schrick et al. (2002) also
noticed that Ni was cathodically protected by the iron, but no
long term study was performed to examine whether Ni
would be oxidized once all the ZVI was depleted. Besides,
leaching of these noble metals (e.g., Ni or Cu) when the ZVI
has been exhausted would also be of environmental concern
(Lin et al., 2004). Therefore, the frequency of replacement and
the high cost of noble metals result in little practical appli-
cation without effective methods of regeneration. There is a
resultant need for fundamental characterization and quan-
tification of the reactivity, toxicity and fate of different
bimetallic ZVI materials.
3.4. Physically enhanced ZVI technology
3.4.1. Ultrasound assisted ZVI technology
In heterogenous reactions, the primary mode of action by
sonication is erosion involving the removal of oxide layers and
impurities together with pitting of metal surfaces (Hung et al.,
2000). It is thought that sonication serves to sweep reactive
intermediates or products from metal surfaces thereby reac-
tivating and cleaning the surfaces for subsequent reactions
(Liu et al., 2007). Since the reaction rates of contaminants with
ZVI are generally controlled by mass transfer of the substrates
to the ZVI surface, Huang and his colleagues proposed
employing ultrasound to enhance carbon tetrachloride (Hung
and Hoffmann, 1998) and nitrobenzene (Hung et al., 2000)
degradation by ZVI. Their results showed that the rate of CCl4
degradation was enhanced by a factor of 40 compared to the
same reaction system in the absence of ultrasound (Hung and
Hoffmann, 1998). The rates of nitrobenzene reduction by ZVI
were also substantially enhanced in the presence of ultra-
sound (Hung et al., 2000). The observed rate enhancements for
the degradation of CCl4 and nitrobenzene can be attributed
primarily to the continuous cleaning and chemical activation
of the ZVI surfaces by acoustic cavitation and to accelerated
mass transport rates of reactants, intermediates, and prod-
ucts between the solution phase and the ZVI surface (Hung
and Hoffmann, 1998; Hung et al., 2000).
Zhang et al. (2005) reported that the decolorization effi-
ciency reached 91% in a coupled ultrasound/Fe0 system under
anaerobic conditions after 30 min of treatment, while only
63% of decolorization efficiency was achieved with ZVI alone.
The application of ultrasound was reported to induce a 3.5-
fold increase in the degradation rate of Acid Orange 7 (AO7)
by Fe0/GAC and the degradation efficiency of AO7 by ultra-
soundeFe0/GAC was much higher than the sum of the indi-
vidual effects of Fe0/GAC and ultrasound, due to a synergistic
effect (Liu et al., 2007). Tsai et al. (2009) reported that the
reduction rate of nitrate by ZVI rose from 45% to 99% at pH 2.0
when ultrasound was used.
Liu et al. (2007) proposed that in the presence of ultra-
sound, acoustic cavitation led to the cleaning of iron chip-
pings, and accordingly more reactant surface areas were
formed for further surface reactions. Therefore, the ultra-
sound/Fe0 system utilized the actions of the physical effects
associated with the continuous ultrasonic cleaning and acti-
vation of the ZVI surface. Most of the sediments were sepa-
rated and transferred into the bulk solution, the contaminant
molecules continued to transfer to the vicinity of ZVI surface
and the subsequent degradation remained. Moreover, the
enhancement of the mass transfer resulting from the turbu-
lent effects of cavitations may also contribute to the enhanced
contaminants removal in the presence of ultrasound irradia-
tion (Yang et al., 2014).
Although the application of ultrasound did improve con-
taminants removal by ZVI, most of the studies on ultrasound
were carried out in the lab. The report on in situ application of
ultrasound-assisted ZVI technology is absence, which may be
ascribed to the noise, extensive energy consumption as well
as cavitational erosion arising from ultrasound application
(Ince et al., 2001).
3.4.2. UVevisible light assisted ZVI technology
The combined reaction of Fe0 with UV can produce Fe2þ by the
oxidation of Fe0 and H2O2 from the HO2 radical resulting from

the UV irradiation of H2O, allowing a Fenton-like reaction
without the requirement for adding H2O2. In light of this, Son
et al. (2009) investigated the degradation kinetics of 1,4-
dioxane using ZVI and UV light and explored the involved
mechanisms. Their results revealed that the degradation rate
constant (19  104 min1) in the combined reaction with UV-
C (4.2 mW cm2) and Fe0 (5 mg L1) was significantly enhanced
compared to Fe0-only (4.8  104 min1) and photolytic re-
actions (2.25  104 min1), respectively. UV light at the UV-C
region was very effective in improving the 1,4-dioxane
removal by Fe0, indicating that the 1,4-dioxane was

degraded mostly by OH in the combined reaction. The UV
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
irradiation enhanced the transformation rate of Fe0 to Fe2þ/
Fe3þ and the reduction of Fe3þ to Fe2þ was facilitated by an
increase in UV energy. The authors concluded that the
enhancement of 1,4-dioxane removal rate occurred via an

increased supply of OH from the Fenton-like reaction induced
by the photolysis of Fe0 and H2O (Son et al., 2009). However,
the efficiency of 1,4-dioxane removal by ZVI, even in the
presence of UV-A irradiation, was low.
Morgada et al. (2009) determined the influence of UV light
on arsenate removal by ZVI with or without humic acid
addition. The application of UV illumination increased the
removal efficiency of arsenate by ZVI in 4 h from ~78% to ~87%
and the removal efficiency of arsenate was further increased
to ~95% in the presence of HA. Adsorption on the iron corro-
sion phases was found to be the main mechanism of As(V)
removal, promoted by the formation of reactive oxygen spe-
cies and enhanced under UV irradiation by the formation of
multiple active species. In treating a real groundwater sample
containing 173 mg L1 arsenic by ZVI, the arsenic concentra-
tions in the treated water with and without UV light illumi-
nation were ~41 mg L1 and 10 mg L1, respectively. Montesinos
et al. (2014) reported that Cr(VI) removal using nZVI was
enhanced from 60% to 77% under visible light with wave-
lengths above 555 nm in comparison with the dark process.
The proposed mechanism involved a heterogenous photo-
catalytic process promoted by the iron oxides present in the
form of external layer of the nanoparticles acting as semi-
conductors after excitation with light, overcoming the
passivation of the material taking place in the dark. However,
the results presented in these two studies revealed that the
improvement induced by UV illumination on As(V) and Cr(VI)
removal by ZVI was not significant.
3.4.3. Microwave assisted ZVI technology
Microwave (MW) radiation is a form of electromagnetic radi-
ation with frequency ranging from 100 MHz to 300 GHz (Tai
and Jou, 1999). MW heating has several advantages over
traditional heating such as lower energy consumption,
shorter treatment time (Venkatesh and Raghavan, 2004), more
efficient heating, no direct contact between the heat source
and the material being heated, selective heating, smaller
heating equipment, and less wastes generated (Acierno et al.,
2004; Clark et al., 2000; Hsieh et al., 2008). Therefore, Jou et al.
(2010) combined nZVI particles of high reactivity and micro-
wave as a new method for treating aqueous chlorobenzene
(CB) solution. When the MW energy was applied at 250 W for
300 s to irradiate 100 mg L1 of CB solution containing 1.0 g ZVI
particles, the chlorobenzene activation energy was decreased
from 21.9 to 13.3 kJ mol1 so that the chlorobenzene removal
efficiency was enhanced by 3.6 times. Their group further
investigated the influence of MW irradiation on chloroben-
zene removal by mZVI and nZVI freshly prepared in their lab
and showed that the MW could induce a 13.6 fold increase and
a 2.6 fold increase in the removal of chlorobenzene by mZVI
and nZVI, respectively (Lee and Jou, 2012). The MW radiation
facilitated the diffusion of chlorobenzene from the solution to
the surface of the suspended ZVI particles, accelerated the
iron oxidization, increased the surface active sites and thus
enhanced the chlorobenzene decomposition rate. Although
MW was effective in enhancing chlorobenzene by ZVI, the
235
power consumption of MW is always a concern in practical
applications (Remya and Lin, 2011).
3.4.4. Gas-bubbled ZVI technology
It is well known that lowering the pH accelerates the con-
taminants removal by ZVI. Therefore, various acids,
including H2SO4 and HCl and acetic acid, have often been
employed to enhance the reaction of ZVI with contaminants.
Though these species are effective in lowering the solution
pH, they may result in an adverse impact on the treated
water quality, due to the presence of such alien species as
sulfate, chloride, and acetate (Ruangchainikom et al., 2006a).
Liao and his colleagues (Hsu et al., 2004) proposed to combine
ZVI with CO2 bubbling, which could effectively create an
acidic environment favorable to ZVI corrosion and the
consequent nitrate removal. Their results showed that ni-
trate removal by ZVI was negligible under neutral conditions
without CO2 bubbling while CO2 bubbling significantly
improved nitrate transformation by ZVI to ammonia since it
could reduce pH from neutral to 3.5 in less than 5 min. The
CO2 bubbling rate of 200 mL min1 was sufficient for sup-
plying Hþ to create a favorable acidic environment for the
nitrate reduction, as reported by Ruangchainikom et al.
(2006a). Ruangchainikom et al. (2006b) further investigated
the influence of co-existing ions on nitrate reduction by the
Fe0/CO2 process and showed that nitrate removal was
inhibited significantly by the presence of humic acid, which
may arise from the strong competition of humic acid with
nitrate for the available reactive surface sites of ZVI. Calcium
ions strongly retarded nitrate removal, whereas chloride ions
significantly promoted the reduction of nitrate in the Fe0/CO2
process (Ruangchainikom et al., 2006b).
To reduce the consumption of CO2 and induce potentially
faster pH equalization and faster nitrate reduction rate, a flu-
idized ZVI reactor pressurized by CO2 gas for controlling pH
was employed for nitrate reduction (Li et al., 2007). The authors
declared that at reaction time of 30 min, the CO2-bubbled
system proposed by Ruangchainikom et al. (2006a) performed
equally well as did the CO2-pressurized system, with the CO2-
bubbled system consuming much more CO2 gas compared to
the proposed CO2-pressurized system. The disadvantage of
both the pressurized CO2/ZVI and bubbled CO2/ZVI systems for
nitrate removal was that ammonium was the only by-product
of nitrate reduction which required post treatment.
In the process of arsenate removal by ZVI, CO2 bubbling
could create a favorable acidic environment for arsenate
removal without sacrificing the treated water quality and air
bubbling could facilitate the generation of iron corrosion
products in the process of arsenic removal which provide
reactive sites for arsenic adsorption. Therefore, a pretreat-
ment step, CO2 bubbling at 300 mL min1 for 5 min, was taken
to adjust the solution pH to an acidic environment, followed
by air bubbling at 300 mL min1 for 10 min to increase DO in
the solution to enhance arsenate removal by ZVI
(Tanboonchuy et al., 2011). Furthermore, in groundwater ap-
plications, the arsenate removal rate for the proposed process
was 5 times faster than the rate measured when the system
was pretreated by acidic chemical species only.
Although it was declared that using CO2 to supply
hydrogen ions for contaminants removal by ZVI did not
236 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
introduce alien species other than Hþ and thus had little
negative effect on treated water quality, the electricity con-
sumption necessary for pumping CO2 and chemical cost of
CO2 need to be considered.
3.4.5. Weak magnetic field assisted ZVI technology
Interest in the interactions of magnetic fields with electro-
chemical systems stems from the possibilities of controlling
the morphology of products that are electrodeposited on the
electrodes (Coey et al., 1999) and to control the mass transport
of reactive components at the electrode surface (Hinds et al.,
2001), thus controlling the reaction rate at the electrode/
electrolyte interface. Magnetic forces give rise to convection in
the solution which narrows the diffusion layer, resulting in
higher currents (Hinds et al., 2001; Lioubashevski et al., 2004;
Tacken and Janssen, 1995). The most significant magnetic
forces are the Lorentz force, FL, which arises from the inter-
action between the magnetic field and the motion of charged
species, and the field gradient force, FB, which tends to move
paramagnetic ions along the field gradient (Hinds et al., 2002;
Waskaas and Kharkats, 2001).
Although the study of magnetic field effects on electro-
chemical systems dates back more than 100 years with the
research efforts of Faraday, very few studies have employed
magnetic fields to enhance contaminants removal by ZVI.
Jiang et al. (2008) reported that there was a 30e50% improve-
ment in SO2 absorption by cast iron scraps due to the appli-
cation of a DC (direct current) magnetic field (10e20 mT),
which may be associated with the increased ZVI corrosion
rate facilitated by the looser corrosion products. Kim et al.
(2011) reported that the application of a magnetic field
(40 mT) on a ZVI slurry markedly enhanced 4-chlorophenol
removal from 26% to 54% under air equilibrated conditions.
They ascribed this phenomenon to the production of more

OH resulting from the easier transport of oxygen to the ZVI
surface in the presence of magnetic field. However, these
authors did not consider the role of Lorentz force and field
gradient force in contaminants sequestration by ZVI in the
presence of magnetic field.
In our lab it was found that replacing the magnetic stirrer
with a mechanical stirrer considerably decreased Se(IV)
removal by ZVI. Careful examination of the literature implied
that this phenomenon should be ascribed to the weak mag-
netic field (WMF) (<70 mT) supplied by the magnetic stirrer
and the magnetic rotor. Consequently, we employed WMF to
enhance contaminants removal by ZVI. It was found that the
presence of WMF significantly accelerated Se(IV) removal and
extended the working pH range of pristine mZVI from 4.0e6.0
to 4.0e7.2 and the WMF induced greater enhancement in
Se(IV) removal at lower initial Se(IV) concentrations (Liang
et al., 2014b). The influence of WMF on Se(IV) removal by
pristine ZVI was associated with a more dramatic drop in ORP
and a more rapid release of Fe2þ compared to the case without
WMF.
Applying a WMF can also substantially enhance the
removal rates and efficiencies of As(V)/As(III) removal by ZVI
at pHini 3.0e9.0 (Sun et al., 2014). The application of WMF
accelerated the transformation of As(III) to As(V) in both
aqueous and solid phases at pHini 5.0e9.0 and enhanced the
oxidation of As(III) to As(V) in solution at pHini 3.0.
Experiments with real arsenic-bearing groundwater revealed
that WMF could greatly improve arsenic removal by ZVI even
in the presence of various cations and anions. The WMF-
induced improvement in As(V)/As(III) removal by ZVI is pri-
marily associated with the accelerated ZVI corrosion, evi-
denced by the pH variation, Fe2þ release and the formation of
corrosion products characterized with X-ray absorption
spectroscopy.
WMF was also applied to enhance Cu(II) and Cr(VI) removal
by ZVI (Feng et al., in press; Jiang et al., 2015). It was found that
the rate constants of paramagnetic Cu(II) removal by ZVI with
WMF at pH 3.0e6.0 were 10.8- to 383.7-fold greater than those
without WMF (Jiang et al., 2015). X-ray diffraction (XRD) and X-
ray photoelectron spectroscopy (XPS) analyses revealed that
applying a WMF enhanced both the Cu(II) adsorption to the
ZVI surface and the transformation of Cu(II) to Cu(0) by ZVI.
The removal rate of Cr(VI) by ZVI was elevated by 1.12e5.89
times due to the application of a WMF, and there was a posi-
tive correlation between the WMF-induced promotion factor
of Cr(VI) removal rate and that of Fe2þ release rate in the
absence of Cr(VI) at pH 4.0e5.5 (Feng et al., in press). None-
theless, the superimposed WMF had negligible influence on
the apparent activation energy of Cr(VI) removal by ZVI,
indicating that WMF accelerated Cr(VI) removal by ZVI but did
not change the mechanisms. Jiang et al. (2015) further showed
that the accelerated ZVI corrosion in the presence of WMF was
ascribed to the enhanced mass transfer by performing elec-
trochemical analysis.
To evaluate the flux density distribution near the ZVI
sphere surface, numerical simulations were performed,
assuming a 10 mm diameter spherical particle of pure ZVI in an
externally-applied magnetic field with homogenous flux
density (Bappl) of 10 mT. It was found that the magnetic field
around the ZVI particle surface was stronger than the external
imposed one and the magnetic field gradient at 1.0 mm away
from the ZVI surface was as large as 7154 T m1. At the point of
peak field gradient, the calculated magnetic forces acting on
Fe2þ are FMHD ¼ 0.17 N m3 and FDB ¼ 64.4 N m3 (with a molar
magnetic susceptibility of 14,750  109 L mol1 and assuming
a Fe2þ concentration of 0.01 M) (Liang et al., 2014a). The Lor-
entz force can give rise to convection in the solution which
narrows the diffusion layer and enhances mass transport
(Lioubashevski et al., 2004). The field gradient force tends to
move paramagnetic ions (Fe2þ) along the higher field gradient
at the ZVI particle surface, which creates localized galvanic
couples and electromagnetic forces that stimulate the
migration of ions, breakdown of the passive film and even-
tually localized corrosion (Sueptitz et al., 2011).
Although employing WMF to enhance Se(IV), As(V), As(III),
Cr(VI), and Cu(II) removal by ZVI is a promising and
environmental-friendly method since it does not need extra
energy and costly reagents, generating a WMF around a large
scale ZVI-based filter or PRB is costly. Therefore, further study
is necessary to optimize this technology so that it can be
applied in real practice.
3.5. Coupling ZVI with other materials
In investigating the reactions of chlorinated solvents with ZVI,
it was found that ZVI had a limited sorption capacity for PCE
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
and TCE, resulting in slower reduction rates with half-lives of
the order of days, or more (Zhang et al., 2002). Moreover, as
mentioned by Cheng et al. (1997), the main disadvantages of
nitrate reduction using ZVI are ammonium production and
the pH control requirement (by initial pH reduction or using a
buffer). In this sense, the use of ZVI alone is not an appropriate
and sufficiently reactive material for treating chlorinated
solvents and nitrate. Therefore, many reactive materials have
been proposed to improve the performance of contaminants
removal by ZVI.
3.5.1. ZVI/activated carbon
ZVI/activated carbon (ZVI/AC) micro-electrolysis was devel-
oped as a wastewater treatment technology during the 1970s.
In such a reaction system, numerous microscopic galvanic
couples are naturally formed between ZVI and carbon, and
Fe2þ, OH and nascent hydrogen are then released from the

galvanic corrosion reaction, which are highly active in
decomposing organic pollutants (Zhou et al., 2013). Since then,
this technology has been widely used in pesticide, pharma-
ceutical and dye wastewaters treatment because of the ad-
vantages of easy operation, low running cost and high
treatment efficiency (Dou et al., 2010; Ghauch, 2008; Keum and
Li, 2004; Ruan et al., 2010).
In the past decade, granular AC mixed with granular ZVI
has been widely applied as a reactive media in PRB for
removing common groundwater contaminants such as chlo-
rinated hydrocarbons (Yang et al., 2010). When the ZVI/AC
composites are used to treat TCE, AC adsorption attracts TCE
which accumulates around ZVI imbedded in the pores of the
AC. The TCE is then dechlorinated by ZVI, which degrades
both the sorbed and dissolved TCE (Sunkara et al., 2010, 2011;
Tseng et al., 2011). The ZVI/AC composite combines the
physical adsorption capacity of AC with the dechlorination
destructive reactivity of ZVI and can be used as a reactive AC,
which is not subject to the limitations of using AC and ZVI
separately (Tseng et al., 2011).
It is generally believed that the reactivity and effectiveness
of ZVI/AC could be further improved by increasing the particle
surface area of AC and ZVI. Therefore, the supported nZVI on
AC has been synthesized (Zhu et al., 2009). The high surface
area of nZVI/AC may allow for better adsorption of contami-
nants and more efficient reduction of chlorinated organic
compounds, but a decrease in reactivity is still expected with
the build-up of iron oxides on the surface, especially under
high pH. Another way to improve the effectiveness of ZVI/AC
is to introduce proper selectivity to AC and ZVI, thus
improving the pollutants adsorption. Yang et al. (2010) re-
ported that granular AC could be modified with dimethyl
dichlorosilane to improve its surface hydrophobicity, and
therefore to improve the performance of ZVI/AC. XPS analysis
shows that the surface silicon concentration of the modified
granular AC is higher than that of the original one, leading to
an increased surface hydrophobicity. Messele et al. (2014)
employed AC with different amounts of surface oxygenated
groups as adsorbents or supports for ZVI and tested their
performances in phenol adsorption and catalytic wet peroxide
oxidation, respectively. The results revealed that the surface
chemistry of the support played an important role in phenol
adsorption and in the catalytic performance of the respective
237
iron-supported catalysts. ZVI was active when the carbon
support had only a limited number of oxygenated groups on
the surface. Coughlin and Ezra (1968) suggested that the
phenol adsorption is governed by pep dispersive interactions
between electrons in the basal plane of carbon and electrons
of the aromatic ring of phenol. The lower surface oxygen
content favors the interaction between the peelectron system
of the basal planes of AC and the phenolic aromatic rings, and
thus increasing the adsorption capacity of phenol on the
surface. Additionally, Zhou et al. (2013) reported that ZVI/AC
micro-electrolysis could also be assisted by ultrasonic irradi-
ation for the degradation of ionic liquid residues in water.
The preparation of ZVI/AC is generally carried out via
several tedious consecutive steps including incipient wet
impregnation of commercial AC, chemical reduction of iron
salt and heat treatment (Chang et al., 2011; Choi et al., 2008;
Hoch et al., 2008; Pereira et al., 2010; Tseng et al., 2011; Zhu
et al., 2009). The time-consuming synthesis processes
together with the high production cost of AC has, so far,
limited the practical, large-scale application of ZVI/AC tech-
nology. Recently, carbonaceous material synthesized from
waste biomass has attracted much attention due to the
increased environmental concerns of waste disposal and
recycling. A ZVI/AC composite has been synthesized using
pinewood sawdust and ferric chloride as the starting mate-
rials (Liu and Zhang, 2010). Su et al. (2013) synthesized ZVI/AC
using coir pith (a waste byproduct from the coconut process-
ing industries) and ferrous sulfate as starting materials
through a simple one-step pyrolysis process. It is expected
that decreasing the cost of ZVI/AC preparation will advance its
application on a larger scale.
3.5.2. ZVI/zeolite
Both natural and synthesized zeolites have been applied in
industry as sorbents, soil amendments, ion exchangers, and
molecular sieves (Haggerty and Bowman, 1994). Particularly,
natural zeolites have exhibited a high sorption capacity for
inorganic cations including heavy metals (Curkovic et al.,
1997; Mier et al., 2001) and ammonium (Hedstro € m, 2001;
Park et al., 2002). Moreover, natural zeolites were proven to
be available in PRBs for controlling the spread of cation-
contaminated groundwater (Fuhrmann et al., 1995; Lee,
2000; Park et al., 2002). However, zeolites have little or no af-
finity for anionic species such as Cr(VI), as they possess a net
negative structural charge. To sorb Cr(VI) as well as cationic
heavy metals in water, cationic surfactant-modified zeolite
(SMZ) has been developed and employed as an innovative
sorbent (Haggerty and Bowman, 1994; Li and Bowman, 1997).
SMZ is capable of sorbing nonpolar organic contaminants
such as chlorinated ethylenes (Bowman et al., 1995; Li and
Bowman, 1998), ionizable organics such as phenol and ani-
line (Li et al., 2000), and inorganic anions such as nitrate and
chromate (Haggerty and Bowman, 1994; Li et al., 1998). Thus,
in the past decades, combining SMZ with ZVI in a pelletized
form has been widely investigated to enhance the seques-
tration of contaminants by the synergistic effect of sorption
and reduction. Batch studies using granular SMZ/ZVI pellets
showed that the reduction rates for PCE and chromate
increased by factors of 3e9 as compared to raw ZVI or zeolite/
ZVI pellets (Li et al., 1999). It was speculated that the sorption
238 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
of PCE or chromate by SMZ increased the local concentration
in the vicinity of the ZVI surface, thereby enhancing the
reduction (Li et al., 1999). The increased local PCE concentra-
tion in the vicinity of the iron surface may promote mass
transfer and sorption of PCE onto the surface of ZVI, since the
diffusive mass flux of a contaminant is proportional to the
concentration gradient across the thin mass transfer layer
surrounding the solid particle (Fogler, 1999). The enhanced
mass transfer may lead to an increased surface reaction rate,
especially in systems where mass transfer is the rate-limiting
step. Zhang et al. (2002) also observed an enhancement of PCE
reduction by SMZ/ZVI pellets.
Li et al. (1999) and Zhang et al. (2002) physically combined
ZVI and SMZ to enhance the reduction rate of a chlorinated
compound. However, the physical methods employed in their
studies, such as homogenizing and pelletizing, may limit the
large-scale production of materials for field application. Lee
et al. (2007) developed a new material, referred to as ZanF,
by combining ZVI and zeolite chemically. ZanF was produced
from zeolite modified by FeCl2 followed by reduction with
sodium borohydride. The results showed that ZanF was effi-
cient for reducing nitrate. Although both ZVI and ZanF pro-
duced ammonium as the reaction product (which should be
regarded as another groundwater contaminant), ZanF
removed ammonium to below the detection limit via
adsorption to zeolite, whereas ZVI released it into the solu-
tion. In addition, ZanF showed high reactivity for nitrate at an
initial pH of 6.2, which falls within the typical aquifer pH range
of 6e8. These results indicate that ZanF has the potential as an
alternative to ZVI for remediating nitrate contaminated
groundwater in PRBs. However, when applied in PRBs, ZanF is
said to have some shortcomings over ZVI, such as the limited
longevity and relatively high material costs.
3.5.3. ZVI/pillared bentonite
Bentonite, having a larger surface area than silica or zeolite, is
a kind of expandable clay mineral consisting primarily of
montmorillonite (Li et al., 2009; Zhu et al., 1997). Moreover,
bentonite can be easily modified by intercalating inorganic/
organic cations and the resulting products are more efficient
adsorbents than the original one, due to the increased surface
area and more functional groups. Cho et al. (2005) reported
that the reduction of TCE was significantly accelerated when
the organo-bentonite was mixed with ZVI. Organo-bentonite,
bentonite modified with a cationic surfactant (e.g., HDTMA) by
ion exchange, can effectively sorb organic contaminants due
to its organic sorption capacity (Lo, 2001; Xu and Boyd, 1995).
The organo-bentonite is believed to contribute to the increase
in TCE concentration on the iron surface so that more TCE can
be available for reduction. Li et al. (2010) indicated that the
removal of nitrate by ZVI was enhanced with pillared
bentonite. The pillared bentonite played multiple roles in the
mixture including: (1) adsorption to nitrate ions, which facil-
itated the mass transfer of nitrate from the solution onto the
solid surface, (2) acid catalyst for the nitrate reduction due to
its surface acidity, and (3) the sustained release of hydrogen
protons through cation exchange with iron cations (by-prod-
ucts in nitrate reduction), which could explain the high effi-
ciency on nitrate removal even when the solution was fed at
nearly neutral pH. Zhang et al. (2012) employed a novel
combination of pillared bentonite (OHeAl-bent) with ZVI in
column experiments so as to enhance Cr(VI) removal effi-
ciency and improve the longevity of Fe0-based PRBs. The
enhanced removal was attributed to the synergistic effect
between the adsorption by OHeAl-bent and the reduction by
ZVI. The adsorption facilitated the mass transfer of Cr(VI)
from aqueous to iron surface, and thus accelerated the
reduction of Cr(VI) by ZVI. However, because direct contact of
Cr(VI) with ZVI is necessary for electron transfer to occur,
close contact of the pillared bentonite with ZVI is very
important for accelerating the surface reaction. Therefore, the
synergistic effect was observed only when the pillared
bentonite was uniformly mixed with ZVI. Furthermore, the
higher removal efficiency was observed under lower pH, and
the complete Cr(VI) removal could last longer due to the
buffering effect of OHeAl-bent. XPS analysis indicated that
Cr(VI) was reduced to Cr(III), and then precipitated in the
forms of Cr(III) and Fe(III) hydroxides or Cr(III)eFe(III) hy-
droxides. However, fewer precipitates on the iron surface
were detected when OHeAl-bent was combined with ZVI,
which might also contribute to the extended longevity of the
reaction medium. The pillared bentonite may exhibit surface
acidity (Kurian and Sugunan, 2005; Zhang et al., 2011b), which
can act as the scavenger to reduce reactive precipitations and
iron deactivation.
Moreover, bentonite has also been employed as a support
media for nZVI for contaminants removal. Lin et al. (2014)
prepared a bentonite (Bent)-supported nZVI to remove acid
violet red B from an aqueous solution. The results indicated
that the presence of bentonite decreased the aggregation of
nZVI and increased its reactivity. Sheng et al. (2014) found that
the reductive removal of U(VI) by nZVI was enhanced by using
Naþ-saturated bentonite (Na-bent) as the support. Further
research also indicated that the removal of anionic Cr(VI) and
NO 3 by nZVI was enhanced by using hydroxy-aluminum pil-
lared bentonite (Al-bent) as the support, so was the removal of
organic contaminants by organo-bentonite-supported nZVI
(Li et al., 2011, 2012; Zhang et al., 2011b).
3.5.4. ZVI/iron oxide
Although ZVI has been proven to be capable of simultaneously
removing multiple heavy metals (e.g., Cr(VI) and As(V)) from
groundwater (Blowes et al., 1997; Manning et al., 2002),
numerous problems were encountered during the process.
Firstly, inhibitory effects between different contaminants
were observed. For instance, in the co-removal of Cr(VI) and
As(V), Cr(VI) would compete with As(V) for the adsorption
sites of the iron corrosion products (Liu et al., 2009). Another
problem is that some geochemical constituents, such as nat-
ural organic matter (NOM), can impact the performance of a
ZVI system. A column study was reported when using ZVI to
treat Cr(VI) with the presence of humic acid (HA), one of the
major components of NOM, HA was aggregated and deposited
on ZVI surfaces, and as a result, the reactivity of ZVI was
reduced (Liu and Lo, 2011). Coupling the iron oxides with ZVI
could provide solutions for the problems of using ZVI alone.
The iron oxides can provide additional adsorption sites for
As(V), thus reducing the inhibitory effects of As(V) removal by
ZVI (Mak et al., 2011). Besides, iron oxides can adsorb NOM by
forming inner sphere complexes (Gu et al., 1994; Saito et al.,
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
2004), which can reduce the impacts of NOM on the ZVI sys-
tem. Furthermore, Fe2þ, which is produced from ZVI corro-
sion, can be catalyzed by iron oxides for contaminant
reduction, such as Cr(VI), U(VI) and NO 3 (Buerge and Hug,
1999; Jang et al., 2008; Tai and Dempsey, 2009). Among
numerous types of iron oxides, iron oxide-coated sand (IOCS)
was found to be suitable for enhancing the co-removal of
Cr(VI) and As(V). Since IOCS is commonly in granular form, it
is suitable for packing in columns or PRBs. USEPA has pro-
posed the use of IOCS in fixed-bed filtration for As removal
(Mohan et al., 2007). Khaodhiar et al. (2000) reported the use of
IOCS in removing CCA in groundwater. The feasibility of using
ZVI and IOCS as a combination of reactive media in PRBs for
removing Cr(VI) and As(V) from groundwater with various
geochemical constituents such as hardness, alkalinity and
NOM was investigated (Mak et al., 2011). The results showed
that the ZVI and IOCS mixture performed better in the
removal of both Cr(VI) and As(V), compared to using ZVI or
IOCS alone. A synergistic effect in these reactive materials
occurred as Fe2þ was adsorbed onto the IOCS so that the iron
oxides were transformed to magnetite, providing more reac-
tive surface areas for Cr(VI) reduction and in reducing the
passivation on the ZVI. HA was adsorbed onto the IOCS so that
the impacts of the deposition of HA aggregates on the ZVI
surface were reduced, thus enhancing the ZVI corrosion. The
findings of these studies suggested that the use of a combi-
nation of ZVI and IOCS can have a higher removal efficiency in
Cr(VI) and As(V), and could be considered in the design of a
more environmental sustainable PRB. Smaller amount of the
iron corrosion products would be deposited in the ZVI-IOCS
packed PRB, thereby decreasing the rate of porosity loss of
the PRB and correspondingly prolonging its life span.
3.6. Chemically enhanced ZVI technology
3.6.1. Ligand enhanced oxidation processes in ZVI system
It has been reported that the reaction of mZVI or nZVI and
oxygen can produce reactive oxidants capable of oxidizing
As(III), pesticides, aromatic compounds, and chelating agents
(Englehardt et al., 2007; Joo et al., 2004; Leupin and Hug, 2005;
Noradoun et al., 2003). The rapid oxidation of recalcitrant
compounds during iron oxidation provides a new approach
for remediating contaminated soil and groundwater.
The mechanisms of oxidation in the ZVI/O2 system have
been investigated and were found pH dependent. Oxidation
under acidic conditions is attributable to the generation of
H2O2 during ZVI oxidation, which then reacts with Fe2þ via the

Fenton reaction to produce OH (Keenan and Sedlak, 2008). At
neutral pH values, Fe2þ oxidation by O2 produces a different
oxidant, most likely the ferryl ion (Fe(IV)) (Hug and Leupin,
2003; Keenan and Sedlak, 2008). As demonstrated in Fig. 5,
Reaction 1 is responsible for H2O2 production under acidic
conditions and Reactions 3e4 become the dominant H2O2
source at pH values above 5.0.
However, the yields of species capable of oxidizing organic
compounds in the ZVI/O2 system are too low to be useful for
remediation applications (e.g., approximately 7% of the ZVI is
converted to Fe (IV) at pH 7.0 under optimal conditions

(Keenan and Sedlak, 2008)). Furthermore, OH production re-
quires acidification, which is often impractical in treatment
239
Fig. 5 e Scheme of Fe0 oxidation in the ZVI/O2 system.
Adopted from Keenan and Sedlak, 2008.
systems. Several researchers reported that dosing of ligands
to the ZVI/O2 system substantially increased the reaction rates
(Noradoun et al., 2003; Sun and Pignatello, 1992). The addition
of ligands may alter the oxidant production in several ways.
Firstly, as demonstrated in Fig. 5, H2O2 reacts with either Fe0(s)
or Fe2þ (reactions 2, 5). Complexation between ligands and
Fe2þ may accelerate the Fenton reaction (reaction 5),
increasing the branching ratio between reactions 2 and 5 and
allowing a larger fraction of H2O2 to produce oxidants. Sec-
ondly, following reactions 3, 4, or 5, Fe3þ may precipitate to
form a ferric oxide or hydroxide (reaction 6), which may lead
to the precipitation of Fe2þ or passivation of the ZVI surface,
decreasing the product yields. Organic ligands may form
strong complexes with Fe3þ and thus could inhibit the pre-
cipitation of iron (hydr)oxides on ZVI surface. Thirdly, Fe2þ
oxidation by oxygen is strongly pH dependent and is negligible
at pH level below 5 in the absence of ligands over 1 h duration
of these experiments (reaction 3 in Fig. 5) (Keenan and Sedlak,
2008; Singer and Stumm, 1970). Accelerating reaction 3 by
complexation may increase the yield of H2O2. Finally, coordi-
nation of the metal may alter the nature of the reactive
oxidant produced in reaction 5 (Goldstein et al., 1993).
It has been revealed that addition of ligands such as eth-
ylenediaminetetraacetic acid (EDTA) to the ZVI/O2 system can

enhance reaction rates and OH yields (Keenan and Sedlak,
2008; Zhang et al., 2011a). Zhang et al. (2011a) demonstrated
that the addition of organic ligands (EDTA, citric acid, tartaric
acid, malic acid and oxalic acid) significantly enhanced the
rates and the extent of carbon tetrachloride (CT) removal, as
indicated by the rate constant increases of 39, 31, 32, 28 and 18
times in the presence of EDTA, citric acid, tartaric acid, malic
acid and oxalic acid, respectively. The enhanced CT degrada-
tion in the presence of organic ligands was primarily attrib-
uted to the elimination of a surface passivation layer of Fe(III)
(hydr)oxides on the ZVI through chelating of organic ligands
with Fe3þ, which maintained the exposure of active sites on
the ZVI surface to CT.
The ligand-assisted contaminants degradation by ZVI was
a new approach that could treat recalcitrant compounds in
the environment more efficiently and at a much lower cost.
However, relatively high concentrations of ligands (e.g., oxa-
late) were usually required (Keenan and Sedlak, 2008) and it
may not be practical to discharge high concentrations of these
ligands to the aquatic environment. Although only a small
concentration of EDTA was needed to improve the oxidant
yield, the toxicity of EDTA, the possibility of EDTA degrada-
tion, and the ability of EDTA to mobilize toxic metals suggest
240 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
that it may not be an ideal additive to the ZVI system unless
EDTA is the target contaminant (Englehardt et al., 2007;
Noradoun and Cheng, 2005). Thus, further research should
be carried out to find environmentally benign ligands that
could be applied in the ZVI/O2 systems.
3.6.2. Dosing of Fe2þ, Co2þ and Mn2þ
Previous studies showed that addition of a certain amount of
Fe2þ could significantly accelerate nitrate reduction by ZVI (Xu
et al., 2012). Huang et al. (2012) demonstrated that the addition
of a small amount of Fe2þ (e.g., 0.1 mM) significantly increased
molybdate and the selenate removal by ZVI. Fe2þ served as
partial electron donor for selenate and molybdate reduction
(e.g., Fe2þ was consumed with a Fe2þ:Se stoichiometry of ~1:1),
and facilitated the transformation of a passive ferric coating
on the iron surface to Fe3O4, and thus enhanced electron
transfer and selenate reduction. Fe3O4 was the main corrosion
product in anaerobic conditions and played an important role
in selenate and molybdate reduction by ZVI (Huang et al.,
2012, 2013; Tang et al., 2014a). This process can be described
using the equations as below (Cornell and Schwertmann,
2003):
Fe2 O3 þ H2 O42FeOOH ðHydrationÞ
Fe0 þ 2H2 O/FeðOHÞ2 þ H2 [ðAnaerobic corrosionÞ
FeðOHÞ2 þ OxðOxidantÞ/FeðOHÞ3 þ ReðReductantÞ
2FeðOHÞ3 þ Fe2þ /Fe3 O4 þ 2H2 O þ 2Hþ
2FeOOH þ Fe2þ /Fe3 O4 þ 2Hþ
2þ 2þ
Mn and Co have similar chemical properties as Fe .
Slight amounts of manganese and cobalt usually are incor-
porated into iron materials during smelting. They will dissolve
simultaneously during iron corrosion in the ZVI system. Due
to the similar chemical properties to Fe2þ and co-existence in
ZVI material as impurities, Mn2þ and Co2þ have been evalu-
ated as alternatives in contaminant removal by ZVI.
Tang et al. (2014b) also investigated the effect of Co2þ and
Mn2þ on selenate removal by ZVI. The results showed that
Co2þ and Mn2þ, especially the former, significantly enhanced
selenate removal by ZVI. Co2þ promoted Fe2þ release and the
formation of a bimetallic (Co0eFe0) catalytic system by redox
reaction. Co2þ and Mn2þ provided around 69% and 30% of the
electrons for selenate reduction, respectively. Reduction of
selenate and subsequent adsorption of selenite was the main
mechanism for selenate removal in the presence of Co2þ, but
simultaneous reduction of selenate and selenite occurred in
the presence of Mn2þ.
3.7. Methods to recover the reactivity of aged ZVI
During the process of contaminants removal by ZVI, the for-
mation of Fe(III) oxides (such as goethite (a-FeOOH), maghe-
mite (g-Fe2O3), and hematite (a-Fe2O3)), carbonate minerals
(such as calcite (CaCO3) and siderite (FeCO3)), and other solid
phases may adhere to the ZVI surfaces (Phillips et al., 2000;
Roh et al., 2000). In most cases, the generation of the oxide
film that takes place over a time frame of hours to days or
weeks, results in transformations that are collectively referred
to as “aging” (Liang et al., 2014a). Although thicker passive
films (and the formation of secondary authigenic phases) in-
crease the surface area for contaminant removal by non-
reductive processes, breakdown of the passive film on ZVI
generally favors contaminant reduction by exposing more
strongly reducing surface area (Turcio-Ortega et al., 2012; Xie
and Cwiertny, 2010). Depending upon the thickness and
composition of the precipitates, which mask the redox active
sites, electrical resistance increases and ZVI reactivity is
decreased to varying extent (Lu et al., 2012). Flury et al. (2009)
found that thick layers of Fe-hydroxides resulted in dimin-
ished ZVI reductive capacity, which impacted on the long-
term effectiveness of a full-scale PRB, while pore space
reduction was a minor factor. Therefore, the negative effect of
iron corrosion products on the reactivity of ZVI has become a
major concern in further development of the ZVI technology
and several methods have been developed to increase the
reactivity of aged ZVI.
3.7.1. Electrochemical method
Lu et al. (2012) and Chen et al. (2012) proposed to recover the
(1)
reactivity of passivated ZVI using the electrochemical
method. Lu et al. (2012) showed that the Cr(VI) removal rates
(2) and observed kinetic constants were initially high and then
showed a continuous decrease with time, due to the variable
(3) reactivity of Fe0 caused by mineral fouling. After Fe0 was
passivated, electrochemical depassivation was introduced for
(4) different electrolysis times to recover the reactivity of Fe0. It
was found that the initial rate was almost completely recov-
(5) ered, due to the electrochemical breakdown of precipitates on
the Fe0 surfaces.
2þ
Chen et al. (2012) further investigated the possibility of
restoring the reductive capacity of passivated ZVI with low
electrical direct current (DC). Variable voltage settings (0e12 V)
were applied through two stainless steel electrodes placed at
the ends of the reactor. While only partial restoration of the
reductive capacity of the passivated ZVI was observed, higher
rates of TCE removal were always obtained when current was
applied, and the rates of TCE removal were roughly propor-
tional to the voltage level. However, the results in this study
revealed that complete “depassivation” of ZVI could not be
achieved by applying DC.
3.7.2. Dosing of Fe2þ or Mg2þ
Liu et al. (2013a,b) reported that the dosing of 10 mM Mg2þ or
Fe2þ could significantly improve the degradation of TCE by
ZVI (~70 mesh) aged in air for about three months. The aged
ZVI was inactive with regard to TCE degradation in Milli-Q
water but Mg2þ or Fe2þ could depassivate the aged ZVI by
forming the surface complex > FeOMgþ, which could induce
the protonation of surface sites, reductive dissolution of the
passivating Fe(III) oxyhydroxide layer coating the underlying
Fe0 and enhancement in TCE reduction. In these two studies,
the authors did not show the reaction rate constants of TCE
removal by the virgin aged ZVI and thus it is unknown
whether the aged ZVI could be completely depassivated or
not. Moreover, applying excessive Mg2þ or Fe2þ salts to
recover the reactivity of ZVI will generate much sludge and
 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8 241

introduce unexpected anions (i.e., SO2

4 ) in the treated
solution.

3.7.3. Weak magnetic field

WMF was proposed to recover the reactivity of ZVI aged at pH
6.0 with MES as the buffer for different durations (0e96 h) in
our lab for the first time (Liang et al., 2014a). It was found that
(i) unaged ZVI gave the fastest Se(IV) removal rates, with little
increase due to WMF; (ii) aging 80 or more hours gave the
slowest Se(IV) rates, with little enhancement by WMF; and (iii)
aging between 6 and 60 h gave nearly constant rates of Se(IV)
removal, but with rate constants that were 10- to 100-fold
greater with WMF than without. With WMF, sequestration of
Se(IV) generally was accompanied by an almost linear in-
crease in Fe2þ, and without WMF, there was sequestration of
Se(IV) but with little increase in Fe2þ, which was consistent
with the X-ray Absorption Near Edge Structure (XANES) re-
sults. The XANES analysis revealed that without WMF the
degree of Se(IV) reduction to Se(0) decreased with aging of the
ZVI while the effect of aging on the Se(IV) sequestration
Fig. 6 e The characteristics of an ideal ZVI technology.
mechanism was less. Se(IV) was directly reduced to Se(0) by
pristine ZVI, independent on the presence of WMF. The
application of WMF changed the mechanism of Se(IV) removal bacteria and sulfate reducing bacteria (SRB). The P element in
by ZVI aged for 6e60 h from adsorption followed by reduction the Fe3(PO4)2 and FePO4 crystals can be released into aqueous
to direct reduction to Se(0) and it also greatly enhanced the solution in the form of PO3
4 ions. Furthermore, the FeS and

reduction of Se(IV) by ZVI aged for 80 h. After 96 h of aging,
negligible reduction of Se(IV) to Se(0) was observed over 24 h
with and without WMF, due to the nearly complete exhaus-
tion of Fe0.
3.7.4. Bacteria-mediated regeneration
Several iron reducing bacteria using Fe(III) oxyhydroxide and
iron oxides as terminal electron acceptors have been identi-
fied (Lovley, 1997). These dissimilatory iron reducing bacteria
(DIRB) are widely distributed in both pristine and contami-
nated terrestrial, aquatic, and subsurface environments. DIRB
may play an important role in the long-term performance of
Fe0-based PRBs, i.e., respiration by DIRB can convert oxidized
Fe3þ to Fe2þ, thus, prolonging the reduction of chlorinated
organic contaminants (Gerlach et al., 2000). Shin et al. (2007)
investigated the regeneration of ZVI for TCE reduction by a
strain of iron reducing bacteria of the group Shewanella alga
BrY (S. alga BrY) and observed the reduction of Fe(II, III) oxide
and Fe(III) oxide in both aqueous and solid phases. The results
suggested that iron-reducing bacteria in the oxidized ZVI
barriers could enhance the removal rate of chlorinated
organic compounds and influence their longevity by reducing
the oxidized iron particles to Fe2þ, which become available for
reduction of additional contaminants, such as TCE. However,
several practical problems, such as the potential decrease in
hydraulic conductivity by biomass accumulation and the
means for delivering electron donors to the DIRB, need to be
addressed for successful application of this technology in the
field.
Lai et al. (2012) investigated the removal of FePO4 and
Fe3(PO4)2 crystals on the surface of passive fillings in an Fe0/
GAC reactor using the acclimated bacteria. According to their
results, the Fe3(PO4)2 and FePO4 crystals with high density in
the passive film could be decomposed or removed by the joint
action between the typical propionic acid type fermentation
sulfur (S) in the passive film also can be decomposed or
removed easily due to their oxidation by the sulfur-oxidizing
bacteria. This study provides some theoretical references for
the further study of a cost-effective bio-regeneration tech-
nology to solve the passive problems of the fillings in the ZVI
or Fe0/GAC reactor.
4. Conclusions and future challenges
In our opinion, an ideal ZVI technology should be inexpensive,
easy to use, sustainable, highly efficient and selective for the
target contaminants. The characteristics of an ideal ZVI
technology are summarized in Fig. 6. It should be emphasized
that the longevity of ZVI should be carefully considered when
it is applied in groundwater remediation, and when it comes
to wastewater or drinking water treatment the reaction rates
become crucial. Despite the increased use and development in
the last 20 years, ZVI technology still has several important
limitations. Research and development in this area are
necessary to overcome or mitigate these limitations and to
expand the use of ZVI technology. Based on this review, the
key areas for future research are proposed as follows:
1) Reduction in the fraction of ZVI consumed by water, O2,
or other background matrix so as to improve the
selectivity of ZVI towards to contaminants, especially
when the contaminants are removed by reduction;
2) Tailored reaction pathway of contaminants (e.g., ni-
trate, chlorinated organic contaminants) reduction by
ZVI to avoid the generation of toxic byproducts;
3) Development of practical and efficient methods to
decelerate the passivation of ZVI and to recover the
reactivity of the passivated ZVI;
242 w a t e r r e s e a r c h 7 5 ( 2 0 1 5 ) 2 2 4 e2 4 8
4) Better understanding of the influence of oxygen on
sequestering contaminants of different properties by
ZVI so as to take advantage of oxygen to improve the
reactivity and selectivity of ZVI technology;
5) More detailed work on simultaneous removal of multi-
ple contaminants by ZVI-based technologies to simu-
late the actual complicated situation;
6) Further design of 2-D or 3-D testing systems for
groundwater remediation by ZVI-based technologies to
simulate the real situation in PRB (e.g., clogging, hy-
draulic characterizations);
7) Many of the ZVI-based technologies developed are still
at an experimental or pilot stage. However, there is a
need to demonstrate their application in large-scale,
rather than laboratory, practicability, i.e. to show that
they are capable of safe, effective and low-cost scale-up;
8) Design, classification and cost-benefit analysis of
various ZVI-based technologies for different application
fields and appropriate conditions and explore the pos-
sibility of combined use of ZVI-based technologies with
other technologies to expand the scope of application;
9) Fundamental characterization and quantification of the
reactivity, toxicity and fate of different bimetallic ZVI
materials;
10) Safe disposal or potential utilization of the iron-
containing sludge generated from the process of con-
taminants sequestration by ZVI.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (21277095, 51478329, 51409100) and the
Research Fund for the Doctoral Program of Higher Education
(20130072110026). The authors thank Prof. Paul Tratnyek for
his constructive suggestions on the characteristics of an ideal
ZVI technology. Yuankui Sun wishes to thank Shanghai Tongji
Gao Tingyao Environmental Science & Technology Develop-
ment Foundation (STGEF).
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