Journal of Hazardous Materials 267 (2014) 194–205

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Review

The use of zero-valent iron for groundwater remediation and

wastewater treatment: A review
Fenglian Fu a,∗ , Dionysios D. Dionysiou b , Hong Liu c
a
School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, PR China
b
Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012, USA
c
Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 401122, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• The recent advances in ZVI are

reviewed.
• A review of contaminants removed
by ZVI from groundwater and
wastewater is made.
• Excellent removal efficiencies of con-
taminants by ZVI are reported.
• Reaction mechanisms of ZVI with
contaminants are discussed.
• The review suggests research needs
for future work.

a r t i c l e i n f o a b s t r a c t

Article history: Recent industrial and urban activities have led to elevated concentrations of a wide range of contaminants
Received 6 September 2013 in groundwater and wastewater, which affect the health of millions of people worldwide. In recent
Received in revised form years, the use of zero-valent iron (ZVI) for the treatment of toxic contaminants in groundwater and
23 December 2013
wastewater has received wide attention and encouraging treatment efficiencies have been documented.
Accepted 27 December 2013
This paper gives an overview of the recent advances of ZVI and progress obtained during the groundwater
Available online 7 January 2014
remediation and wastewater treatment utilizing ZVI (including nanoscale zero-valent iron (nZVI)) for
the removal of: (a) chlorinated organic compounds, (b) nitroaromatic compounds, (c) arsenic, (d) heavy
Keywords:
Zero-valent iron (ZVI)
metals, (e) nitrate, (f) dyes, and (g) phenol. Reaction mechanisms and removal efficiencies were studied
Groundwater and evaluated. It was found that ZVI materials with wide availability have appreciable removal efficiency
Wastewater for several types of contaminants. Concerning ZVI for future research, some suggestions are proposed
Contaminants and conclusions have been drawn.
Remediation/Treatment © 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
1.1. The current water pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
1.2. Zero-valent iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2. Recent advances in ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2.1. Nanoscale zero-valent iron (nZVI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
2.2. Immobilization of nZVI onto supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
2.3. Doping of ZVI with other metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196

∗ Corresponding author. Tel.: +86 20 39322296; fax: +86 20 39322547.

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

0304-3894/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.12.062
 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205 195

2.4. Combination of ZVI with Fenton-based oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197

2.5. ZVI based permeable reactive barriers (PRBs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
2.6. Release of Fe ions during application of ZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3. Removal of hazardous contaminants by ZVI from groundwater and wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.1. COCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.2. NACs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.3. Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.4. Heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.5. Nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.6. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.7. Phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
4. Suggestions/remarks on ZVI based technology for the remediation/treatment of contaminants from groundwater and wastewater . . . . . . . . . . . 201
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

transforms the latter into non-toxic or less toxic species. On the

Nomenclature other hand, ZVI can degrade and oxidize a series of organic com-
pounds in the presence of dissolved oxygen (DO) since ZVI transfers
WHO World Health Organization two electrons to O2 to produce H2 O2 (Eq. (1)). The produced H2 O2
ZVI Zero-valent iron can be reduced to water by another two-electron transfer from
DO Dissolved oxygen ZVI (Eq. (2)). Moreover, the combination of H2 O2 and Fe2+ (known
COCs Chlorinated organic compounds as Fenton reaction) can produce hydroxyl radicals (• OH) which
NACs Nitroaromatic compounds possess strong oxidizing capability towards a variety of organic
TCE Trichloroethylene compounds (Eq. (3)).
NB Nitrobenzene
nZVI Nanoscale zero-valent iron Fe0 + O2 + 2H+ → Fe2+ + H2 O2 (1)
PRBs Permeable reactive barriers
COD Chemical oxygen demand Fe0 + H2 O2 + 2H+ → Fe2+ + 2H2 O (2)
EPA Environmental Protection Agency
GAC Granular activated carbon Fe2+ + H2 O2 → Fe3+ + • OH + OH− (3)
AACs Aromatic amine compounds
ZVI has been successfully applied for the remediation/treatment
TNT 2,4,6-trinitrotoluene
of groundwater and wastewater contaminated with chlori-
HA Humic acid
nated organic compounds (COCs) [1–4], nitroaromatic compounds
MWCNTs Multiwalled carbon nanotubes
(NACs) [5,6], arsenic [7–9], heavy metals [10–12], nitrate [13–15],
dyes [16,17] and phenol [18,19]. There is an increasing interest on
the use of ZVI for the removal of contaminants from groundwater
1. Introduction and wastewater, and this is reflected in the increasing number of
journal articles published recently. The articles on ZVI published
1.1. The current water pollution in the last decade comprise approximately 90% of all publications
according to ISI Web of Knowledge data base. It is also notable that
Environmental pollution in certain areas of the world is becom- the major contaminants treated by ZVI during the last 10 years
ing more and more severe. Water is one of the basic necessities include trichloroethylene (TCE), nitrate, arsenic, Cr(VI), phenol, and
required for sustaining life. With the process of industrialization nitrobenzene (NB).
and urbanization, global water utilization has doubled every 15 In this paper, the recent advances of ZVI and the use of ZVI
years. According to the data of the World Health Organization in the remediation/treatment of hazardous contaminants from
(WHO), the scarcity of water resources has created challenges for groundwater and wastewater are reviewed. The review focuses on
over 40% of the world population, i.e., more than 2 billion peo- experimental procedures, efficiency, and reaction mechanism in
ple have no access to enough or clean water. Meanwhile, industrial the investigation of a range of applications of ZVI, including those
and urban activities have led to increasing concentrations of a wide performed with COCs, NACs, arsenic, heavy metals, nitrate, dyes
range of pollutants in groundwater and wastewater, affecting the and phenol. The review also suggests research needs for future
health of millions of people worldwide. So groundwater remedia- work.
tion and wastewater treatment are of critical importance.
2. Recent advances in ZVI
1.2. Zero-valent iron
2.1. Nanoscale zero-valent iron (nZVI)
Iron is the fourth most abundant element in the earth’s crust.
Over the last decade, a great deal of research has been focused on In the last 10 years, the adaptation of nZVI to remove many kinds
the removal of contaminants by zero-valent iron (ZVI) because ZVI of contaminants has received increasing attention due to its higher
is non-toxic, abundant, cheap, easy to produce, and its reduction surface area and higher reactivity than ZVI. The published papers
process requires little maintenance. ZVI is a reactive metal with on nZVI comprise 15.8% of the total ZVI.
standard redox potential (E0 = −0.44 V). It is thus an effective reduc- As is known, nZVI has a strong tendency to become oxidized.
tant when reacting with oxidized contaminants such as Cr(VI). The Greenlee et al. [20] investigated the oxidation kinetics for stabilized
removal mechanism of contaminants by ZVI concerns the direc- nZVI and iron-nickel nanoparticles with a quartz crystal microbal-
tional transfer of electrons from ZVI to the contaminants which ance and found nZVI oxidized primarily to the iron oxide-hydroxide
196 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205

Table 1
Representative studies dealing with contaminants removal by supported nZVI.

Supported material Contaminants Initial conc. (mg/L) Supported nZVI dose Optimum pH Removal efficiency or Ref.
added adsorption capacity

Ordered mesoporous silica NB 20 1 g/L NA 83.9–94.0% [27]

Ordered mesoporous carbon NB 80 0.5 and 1 g/L 5.8 92%, 94% [28]
Activated carbon Arsenic 2.0 1 g/L 6.5 As(III) 18.2 mg/g [29]
As(V) 12.0 mg/g
Resin Arsenic 5 0.50 and 1.04 g/L 6.5 As(III) 121 mg/g, As(V) [30]
125 mg/g
Chitosan Cr(VI) 20 2.0 g/L 3.0 >90% [31]
Bentonite Cr(VI) 20 3 g/L 4.0 Nearly 100% in 20 min [32]
Kaolinite Pb2+ 500 10 g/L 5.1 More than 96% in [11]
30 min
Multiwalled carbon nanotubes Cr(VI) 20 Mass ratio of nZVI to 7.0 98% in 120 min [33]
(MWCNTs) MWCNTs = 1:2
Zeolite Pb2+ 100 1 g/L 4 >96% in 140 min [34]
Enhanced chitosan beads Total Cr, Cu(II), 62.6, 55.8, 32.4, 22.8 In PRBs 4.56 89.4%, 98.9%, 94.9% and [35]
Cd(II), Pb(II) 99.4%, respectively
Polystyrene resins Nitrate 50 mg N/L 2.4 g/L 5 97.2% [14]
Pillared clays Nitrate 50 0.5 g/L 7.0 Nearly 100% in 120 min [36]
Resin Acid Blue 113 dye 100 20 g/L 5.6 Almost 100% after [37]
30 min
Bentonite Methyl orange dye 100 0.5 g/L 6.5 Nearly 100% after [38]
30 min
Palygorskite Methylene blue 94 1 g/L 5.9 89.36% in 30–60 min [39]
dye

NA: not available.

lepidocrocite in oxygenated water. At least six review papers on
nZVI remediation technology have been published in the last 5
years. They summarized different aspects of science and technology
in this field. One review on nZVI specifically for the synthesis, prop-
erties and application was reported by Kharisov et al. [21]. A work
focused on nZVI aqueous corrosion, manufacture, and methods to
enhance particle reactivity, stability and subsurface mobility was
summarized by Crane and Scott from the University of Bristol [22].
Two reviews were focused on the nZVI application for groundwa-
ter remediation in Europe [23] and nZVI/bimetallic nanometals for
remediation of sites contaminated by heavy metals and chlorinated
solvents [24], respectively. The other two reviews contributed to
the benefits and risks of nZVI for in situ remediation [25,26].
electroplating wastewater. Recently, enhanced chitosan beads
were introduced as a support material in PRBs to remove heavy
metals from electroplating wastewater [35]. The removal rate
of total Cr, Cu(II), Cd(II) and Pb(II) from actual electroplating
wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively.
Immobilizing nZVI particles onto supporting materials have also
been investigated to remove dyes from wastewater. Shu et al. stud-
ied a synthesized cation exchange resin supported nZVI for the
decoloration of Acid Blue 113 and found that complete decoloriza-
tion of the dye with the initial dye concentration of 100 mg/L [37].
In addition, more than 99.75% methyl orange can be removed from
actual wastewater by bentonite-supported nZVI [38].

2.2. Immobilization of nZVI onto supports 2.3. Doping of ZVI with other metals

Using nZVI in remediation of contaminated groundwater or
wastewater is limited due to its lack of stability, easy aggrega-
tion, and difficulty in separating nZVI from the treated solution. To
address these issues, nZVI supported on solid porous materials such
as carbon, resin, bentonite, kaolinite, and zeolite have attempted
to remove different contaminants. Representative studies dealing
with the removal of different contaminants by supported nZVI are
given in Table 1.
Immobilizing nZVI particles on supporting materials for con-
taminants removal does not only provide an easy operation but
also maintain the excellent reduction ability of nZVI. For example,
nZVI supported on ordered mesoporous carbon (nZVI/OMC) was
synthesized to reduce NB where it indicated the enhanced removal
efficiency compared with OMC and nZVI alone [28]. Bifunctional
resin supported nZVI was developed to remove As(III) and As(V),
and showed high removal efficiency towards both As(III) and As(V)
with the maximum adsorption capacities being 121 and 125 mg/g,
respectively [30].
According to the literature reports, most supported nZVI is
used for the removal of heavy metal. For example, kaolin-nZVI was
used to remove Pb(II), where it suggested that 90.1% of Pb(II) from
aqueous solution containing 500 mg/L of Pb(II) could be removed
within 60 min using 5 g/L of kaolin-nZVI [40]. Furthermore, it was
efficient in removing Pb(II) (98.8%) and total Cr (99.8%) from an
To enhance the reactivity of ZVI, bimetallic particles with iron as
the principal metal and the deposition of a thin layer of transition
metals such as palladium (Pd), copper (Cu), nickel (Ni) or platinum
(Pt) on the surface of iron have been effective in the removal of con-
taminants, especially for the reduction dehalogenation of COCs. The
transition metals doping on ZVI surface is believed to enhance the
reduction rates by serving as hydrogen catalysts or reactive electron
donors. Bimetallic particles have several potential advantages over
ZVI, such as faster reaction kinetics and slower deposition of cor-
rosion products on the particle surface. The representative studies
dealing with contaminants removal by bimetal particles are sum-
marized in Table 2. For example, Xu et al. [45] prepared a novel
Ni-Fe bimetal with high dechlorination activity for 4-chlorophenol
and found that 4-chlorophenol oxidation appeared to be enhanced
due to the mechanism of catalytic hydrogenation.
Among the bimetallic particles, Pd/Fe bimetallic system exhibits
extremely high removal efficiency for tetrabromobisphenol A,
2,4-dichlorophenol, monochlorobenzene, pentachlorophenol, and
polychlorinated biphenyls [43,48–51]. The dechlorination rate of
tetrachlorobisphenol A by Pd/Fe bimetallic particles was more
rapid than that by ZVI, and bisphenol A was the major product
[43]. Besides, metal Pd deposited onto the surface of ZVI was able
to effectively reduce the production of toxic intermediates accu-
mulated on the surface of ZVI [52].
 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205
Table 2
Representative studies dealing with contaminants removal by bimetal particles.
Contaminants Initial conc. Bimetal
p-nitrophenol 500 mg/L Cu/Fe
TCE 50 mg/L Pd/Fe
Tetrachlorobisphenol A 20 ␮M Pd/Fe
Hexachlorobenzene 2.91 mg/L Ag/Fe
4-chlorophenol 20 mg/L Ni/Fe
1,2,4-trichlorobenzene 25 mg/L CMC-stabilized Fe–Cu
Explosive compounds 4.98–50 mg/L Ni/Fe, Cu/Fe
NA: not available.
2.4. Combination of ZVI with Fenton-based oxidation
To improve the contaminants removal, ZVI combined with
Fenton-based oxidation reaction was studied and was often
employed to treat NACs. The combination of ZVI with Fenton
was investigated for pretreatment of 2,4-dinitroanisole produc-
ing wastewater [53]. After pretreatment by the process under the
optimal conditions, aromatic organic compound removal was as
high as 77.2%. Barreto-Rodrigues et al. [54] explored the opti-
mization of combined ZVI and Fenton processes for the treatment
of 2,4,6-trinitrotoluene (TNT) industry wastewater. The treatment
can remove 100% of TNT, 100% of the organic nitrogen and 95.4%
of the chemical oxygen demand (COD). Jiang et al. [55] developed
a novel system integrating a reductive pretreatment via ZVI with
Fenton process to degrade NB in aqueous solution and industrial
wastewater. They found that the integrated system increased the
biodegradability and decreased the acute toxicity of the wastewa-
ter, significantly superior to conventional Fenton process.
Advanced Fenton processes based on ZVI and H2 O2 were also
investigated to remove contaminants. The advanced Fenton pro-
cess is an effective method for the removal of total phenol from
coking wastewater and can significantly increase the biodegrada-
tion of coking wastewater [56]. Fu et al. [57] reported advanced
Fenton process can effectively degrade C.I. Acid Red 73 azo dye. Devi
et al. [58] investigated advanced photo Fenton process to degrade
Alizarin Red S anthraquinone dye.
2.5. ZVI based permeable reactive barriers (PRBs)
PRBs systems in groundwater treatment started in early 1990s
[59,60] and have received increasing attention for in situ remedia-
tion of groundwater. ZVI PRBs have been acknowledged as a viable
and cost-effective technology for in situ remediation of ground-
water. ZVI PRBs have been investigated to remediate groundwater
contaminated by COCs [61,62], nitrate [63], arsenic [7], and heavy
metals [64,65]. There have been more than 200 ZVI PRBs developed
and installed at contaminated sites since the first field demon-
stration of the technology in 1995 [66]. The U.S. Environmental
Protection Agency (EPA) designated the ZVI PRB a standard reme-
diation technology in 2002 [67].
2.6. Release of Fe ions during application of ZVI
Fe2+ can be released during the reaction (Eqs. (1) and (2)). The
released Fe2+ would trigger a rapid contaminant oxidation with
the formation of hydroxyl radicals (Eq. (3)). Reactions (Eqs. (1)–(3))
cause the increase of pH due to the consumption of H+ and genera-
tion of OH− . With the increase of Fe2+ and OH− concentration, the
precipitation Fe(OH)2 or Fe(OH)3 occurs (Eqs. (4) and (5)). So the
release of dissolved iron is slower at higher pH values.
Fe2+ + 2OH− → Fe(OH)2 ↓
197
Metal/Fe (wt%) Bimetal dose (g/L) Optimum pH Removal efficiency Ref.
47.1% 35 6.7 98% in 40 min [41]
1.5% 2.5 NA >99% in about 60 min [42]
0.044% 5 6.0 100% in 60 min [43]
0.09% 48.5 Neutral Nearly 100% [44]
15% 100 2.0 96% in 90 min [45]
0.5% 1 NA 88% for 24 h [46]
0.99%, 12.66% 10 2.8, 3.0 Nearly 100% in 60 min [47]
4Fe(OH)2 + 2H2 O + O2 → 4Fe(OH)3 ↓ (5)
3. Removal of hazardous contaminants by ZVI from
groundwater and wastewater
3.1. COCs
COCs, such as trichloroethylene (TCE), tetrachloroethylene,
polychlorinated biphenyls, and many organochlorine pesticides
such as 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) are
well-known chemicals that are highly toxic to human health and
the environment [68]. A number of groundwater aquifers have been
contaminated with COCs. Gillham and O’Hannesin [59] first showed
the effectiveness of ZVI for the dehalogenation of 1,4-chlorinated
ethane, ethane and methane degradation. In the same year, Math-
eson and Tratnyek [69] reported rapid dehalogenation of TCE and
carbon tetrachloride using ZVI.
ZVI has been shown to successfully degrade a large number
of COCs, including TCE [4,70], trichloroethane [71,72], vinyl chlo-
ride [73], carbon tetrachloride [74] and ␥-hexachlorocyclohexane
(lindane) [75], and gained promising experimental results for the
development of remediation technologies to treat the sites con-
taminated with COCs. In these applications, ZVI serves primarily as
a potent and cost-effective electron donor from the iron surface to
hydrocarbon for reductive dehalogenation of COCs.
The use of nZVI has been studied to enhance the reactivity of
ZVI to remove COCs. Numerous studies have documented supe-
rior contaminants degradation rates by nZVI compared to larger
iron particles [75,76]. To maintain the stability and reactivity
of nZVI, many research studies have been focused on the opti-
mal synthesis conditions of nZVI. Surface modification has been
applied for stabilizing nZVI particles, enhancing the dispersion of
nZVI and efficiently sustaining their reactivity. Surface modifica-
tion with carboxymethylcellulose [77], polyelectrolyte multilayers
[78], smectite [79], and poly(methylmethacrylate) [80] has been
employed to stabilize the nZVI in COCs remediation. These sta-
bilizations are achieved by enhancing the steric or electrostatic
repulsions between the particles to inhibit nZVI aggregation. At the
same time, the degradation efficiency of COCs by surface modified
nZVI can significantly increase compared to conventional nZVI.
nZVI coupled with other techniques always enhance the degra-
dation of COCs. Microwave radiation has been considered as an
alternative technique to enhance the degradation of COCs by
nZVI [81,82]. Microwave irradiation combined with nZVI particles
for enhancing the chlorobenzene decomposition was investigated
[81]. When microwave energy was applied at 250 W for 300 s to
irradiate 100 mg/L of chlorobenzene with 20 g/L nZVI particles,
the chlorobenzene removal efficiency was enhanced by 4.6 times
(82.8% vs. 18.1%). Lee et al. [82] applied microwave energy to
enhance chlorobenzene removal using microscale ZVI and nZVI.
They found that 13.6 times and 3.6 times more chlorobenzene was
removed for microscale ZVI and nZVI, respectively, in the presence
(4) of microwave than without microwave. Besides, Truex et al. [83]
198 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205
reported combining electrical resistance heating with in situ ZVI
treatment can accelerate TCE treatment by a factor of about 4 based
on organic daughter products and a factor about 8 based on chloride
concentrations.
ZVI PRBs were applied to remediate COCs. Most of the studies on
ZVI PRBs were focused on experimental parameters optimization,
such as exploring the more effective ZVI forms and combination
of ZVI with other techniques [84]. The Monkstown ZVI PRBs, one
of the oldest field-scale PRBs in the world, has been treating TCE
contaminated groundwater for about 10 years in Northern Ireland.
Groundwater data from 2001 to 2006 indicated that TCE can still
be remediated to below detection limit [85]. In the past decade,
granular activated carbon (GAC) mixed with ZVI has been widely
applied as a reactive media in PRBs for the degradation of COCs
[84,86–88]. For example, PRBs with the modified GAC and ZVI were
more efficient in 2,4-dichlorophenol dechlorination [86]. Control-
lable ZVI–GAC PRBs were designed and successfully applied to the
dechlorination of 1,4-dichlorobenzene because the design could
improve the longevity of the conventional ZVI PRBs [84].
3.2. NACs
With a global production estimated at 108 tons/year, NACs
including NB, TNT, 2,4-dinitrotoluene, and 2,6-dinitrotoluene are
intensively used in several different industrial segments [54]. Many
NACs are considered toxic and potential carcinogens at relatively
low concentrations. Since the nitro groups inhibit the biodegra-
dation of NACs, conventional biological approaches are ineffective
in treating NACs wastewater. ZVI has shown to be effective in the
reduction of NACs from wastewater [5,6]. In the presence of ZVI,
reduction of the nitro groups to generate aromatic amine com-
pounds is the dominant transformation process for NACs. NB could
be reduced to aniline by ZVI [89].
Some studies reported the degradation of NACs using nZVI. For
example, Zhang et al. [90] investigated the degradation of TNT in
wastewater using nZVI and found that more than 99% TNT was
degraded when the initial TNT concentration was 80 mg/L after
degradation for 3 h by 5 g/L nZVI at pH 4. A novel method for syn-
thesizing subnano-sized ZVI using smectite clay layers as templates
was developed [6] and tested for the removal of NB. It was found
that a reaction efficiency of 83% was achieved at a 1:3 molar ratio of
NB/non-structural Fe, and over 80% of the NB was reduced within
1 min. Highly reactive nZVI immobilized in nylon membrane was
synthesized and evaluated for the removal of NB in groundwater.
It was found that NB was rapidly decreased by 68.9% in the first
20 min [91].
3.3. Arsenic
Hazardous arsenic existing in natural waters mostly in the forms
of arsenite (As(III)) and arsenate (As(V)), often found in groundwa-
ter, is one of the most toxic and carcinogenic chemical elements and
is regarded by WHO as a first priority pollutant. WHO has recom-
mended the arsenic level in drinking water to be less than 10 ␮g/L,
which is the regulated level imposed in 2001 by U.S. EPA. In order
to meet recent stringent drinking water standards, the use of ZVI
for arsenic removal and remediation has been explored in recent
years.
The mechanism of arsenic removal by ZVI is rather complex
since different processes are involved. It is generally accepted that
the main mechanism of arsenic removal by ZVI involves adsorption,
reduction, surface precipitation, and co-precipitation with various
iron corrosion products such as ferrous/ferric (hydr)oxides [92].
However, the operating conditions may have an important role
in controlling the overall effectiveness of arsenic removal. There-
fore, in order to gain a better understanding of the overall removal
mechanism, it is desirable to analyze the effect of key variables,
such as pH, DO, hardness, and humic acid (HA) on arsenic removal.
The removal rates of arsenite under different pH values and in the
presence of various ions were investigated and results indicated
that most of these parameters affected negatively the removal of
arsenite [93]. Suna et al. [94] reported in anoxic conditions both
adsorption and reduction of As(V) were fast when As(V) reacted
with commercial ZVI or acid-treated ZVI; commercial ZVI reduced
As(V) to As(III) at pH < 7 while acid-treated ZVI reduced As(V) to
As(0).
DO plays an important role in arsenic removal by ZVI. The spon-
taneous chemical oxidation of ZVI by DO, which involves a variety
of metastable ferrous–ferric intermediate species, was studied [95].
Tanboonchuy et al. [96] found that low pH and high DO would favor
arsenic removal. Mak et al. [92] found that the removal rate of
arsenic by ZVI increased with increasing concentrations of either
Ca2+ or HCO3 − because CaCO3 can form and acts as a nucleation
seed for the growth of iron (hydr)oxides. In the co-existence of Ca2+ ,
HCO3 − and HA, the presence of HA diminished the positive role
of Ca2+ due to the formation of Fe–humate complexes in solution
and delaying of the formation of CaCO3 . Rao et al. [97] investigated
the effects of HA on As(V) removal by ZVI from groundwater and
observed the removal rate of arsenic was inhibited in the presence
of HA probably because of the formation of soluble Fe–humate in
groundwater which hindered the production of iron precipitates.
When the complexation of HA with dissolved Fe was saturated,
further corrosion of ZVI significantly accelerated the removal of
arsenic from groundwater via adsorption and co-precipitation.
As(III) is more mobile and more toxic than As(V), however, the
removal of As(III) is more difficult than the removal of As(V). Klas
and Kirk [8] recently applied limited aeration and acidic condi-
tions in removal of As(III) by ZVI. Simultaneous high reduction
and removal rates of arsenite were demonstrated under limited
aeration and relatively low pH for the formation of Fe(II)–solid
intermediate on the ZVI surface that provided high surface area and
reducing power. Wan et al. [98] conducted the combined processes
of biological As(III) oxidation and removal of As(III) and As(V) by
ZVI to remove high As(III) concentration of 10 mg/L and obtained
a very high As removal capacity (more than 70 mg As/g Fe). Kat-
soyiannis et al. [99] investigated the kinetics and mechanism of
As(III) oxidation and removal by ZVI at pH 3–11 in aerated water.
They found that As(III) was oxidized by the Fenton reaction and
removed by sorption on newly formed hydrous ferric oxides and
hydroxyl radicals were the main oxidant for As(III) at low pH.
Arsenic often co-exists with heavy metal ions. For example,
chromated-copper-arsenate has been extensively used as a wood
preservative over the past 60 years, and the subsurface contamina-
tion by leaching of chromium and arsenic has been widely noticed.
Cr(VI) removal by ZVI is a reduction-dominated process, whereas
As(V) removal principally involves adsorption or co-precipitation
onto iron corrosion products. Liu et al. [100] studied the interac-
tions of co-present Cr(VI) and As(V), and the influences of HA and
bicarbonate in the process of Cr(VI) and As(V) removal by ZVI. They
found Cr(VI) removal was not affected by the presence of As(V) and
HA, however, As(V) removal appeared to be inhibited by co-present
Cr(VI). Lo and co-workers, who have done extensive research on the
simultaneous removal of Cr(VI) and As(V) from groundwater, have
studied the mechanisms of Cr(VI) and As(V) removal by ZVI in the
presence of fulvic acid or HA [101]. They found that fulvic acid and
HA were not involved in the Cr(VI) reduction. Mak et al. [102] also
combined ZVI and iron oxide-coated sand (IOCS) to remove Cr(VI)
and As(V) from groundwater. Compared to using ZVI or IOCS alone,
the ZVI-IOCS exhibited better performance for the removal of both
Cr(VI) and As(V). Metal extraction studies showed that As(V) was
mainly removed by IOCS and iron corrosion products while Cr(VI)
was mainly removed by ZVI and its corrosion products. Besides,
 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205
Fig. 1. Proposed mechanism of As(III)-nZVI reactions.
Reprinted with permission from Yan et al. [108]. Copyright (2012) American Chem-
ical Society.
Mak et al. [103] conducted a column study using a combination
of ZVI and IOCS for removing Cr(VI) and As(V) from groundwater.
They observed that the use of a ZVI and IOCS mixture in a com-
pletely mixed configuration could achieve the highest removal for
both Cr(VI) and As(V). Ludwig et al. [104] discussed the perfor-
mance of a mixed ZVI-compost PRB to treat both heavy metals and
arsenic associated with acid rock drainage impacted groundwater
at a former phosphate fertilizer production site in Charleston, South
Carolina. They reported that effective treatment of As, Pb, Cd, Zn,
and Ni from concentrations as high as 206, 2.02, 0.324, 1060, and
2.12 mg/L, respectively, entering the PRBs, to average concentra-
tions of <0.03, <0.003, <0.001, <0.23, and <0.003 mg/L, respectively,
within the PRBs. Both As(III) and As(V) were effectively removed
from solution indicating the presence of As(V) in oxygen-bound
form and As(III) in both oxygen- and sulfur-bound forms.
Increasing evidence suggests that nZVI is effective for the
removal of arsenic from contaminated water [9,104,105]. For exam-
ple, a novel process, air and/or CO2 bubbling nZVI, was tested for
removal of high concentration of arsenate (3000 ␮g/L) and demon-
strated outstanding performance [105]. Tanboonchuy et al. [9] also
investigated the influence of background species on the removal of
As(III) and As(V) in groundwater by nZVI process. They found that
PO4 3− and HA play an inhibiting role on arsenic removal, while
Ca2+ plays a promoting role. As for HCO3 − and Cl− , the former
inhibits As(III) removal, whereas the later enhances As(III) removal;
As(V) removal was affected only slightly in the presence of HCO3 −
or Cl− . nZVI combined electrocoagulation was evaluated for the
removal of arsenic from copper mineral wastewater [106]. The
results demonstrated that after a preliminary Ca(OH)2 addition to
remove sulphate and increase pH to 2, arsenic could be removed
completely by the combined process.
nZVI is effective for the removal of arsenic from contaminated
water, but transformations and translocation of arsenic at and
within the nanoparticles are not clearly understood. Ramos et al.
[107] reported that reduction As(III) or As(V) species to elemental
arsenic by nZVI was an important mechanism for arsenic immo-
bilization. Yan et al. [108] observed that As(III) species undergo
two stages of transformation upon adsorption at the nZVI surface.
The first stage corresponds to breaking of As–O bonds at nZVI sur-
face, and the second stage involves further reduction and diffusion
of arsenic across the thin oxide layer enclosing the nanoparticles
(Fig. 1).
3.4. Heavy metals
Unlike organic contaminants, heavy metals are not biodegrad-
able and tend to accumulate in living organisms. Many heavy metal
ions are known to be toxic or carcinogenic. Toxic heavy metals of
199
particular concern in treatment of wastewater include chromium,
copper, nickel, mercury, cadmium and lead. During the last few
years, ZVI has been reported to demonstrate effective removal of
different types for metallic ions, including Cr(VI) [32,109], Ni2+
[110], Pb2+ [111], Cu2+ [112], and Zn2+ [113]. Most studies on the
removal of heavy metals by ZVI were focused on the removal of
Cr(VI). In this aspect, Gheju [114] provided updated information
regarding the developments and innovative approaches in the use
of ZVI for the treatment of Cr(VI)-polluted waters.
Cr(VI) is a commonly identified contaminant from the metal-
lurgy, leather tanning, and electroplating industries. Cr(VI) is toxic,
carcinogenic, and its high subsurface mobility does great harm to
the environment [115]. In China, it is considered as one of the envi-
ronmental priority control pollutants. The reaction mechanisms of
Cr(VI) with ZVI are believed to involve instantaneous adsorption of
Cr(VI) on the surface of ZVI where electron transfer takes place and
Cr(VI) is reduced to Cr3+ with the oxidation of ZVI to Fe3+ , followed
by the subsequent precipitation of mixed Cr and Fe hydroxides (Eqs.
(6) and (7)).
Cr2 O7 2− + 2Fe + 14H+ → 2Cr3+ + 2Fe3+ + 7H2 O (6)
Cr3+ + Fe3+ + 6OH− → Cr(OH)3 ↓ + Fe(OH)3 ↓ (7)
Cr(VI) reduction using ZVI was successfully applied in ground-
water remediation. It has been acknowledged that groundwater
chemistry plays a significant role in the ZVI PRBs. The influences
of various geochemical constituents, such as HA, HCO3 − and Ca2+ ,
on Cr(VI) removal by ZVI were investigated by Liu et al. [116]. They
found that the sole presence of Ca2+ or HA did not show a signifi-
cant impact to Cr(VI) reduction, whereas HCO3 − greatly enhanced
Cr(VI) removal. Researchers have investigated Cr(VI) removal by
ZVI in a 9-month-long continuous flow column studies in the pres-
ence of HA [117]. They found that co-present Ca2+ and bicarbonate
significantly decreased Cr(VI) removal by ZVI.
Long-term behavior is a major issue related to the use of ZVI
in PRBs for groundwater remediation. To solve this problem, the
use of granular mixtures of ZVI and natural pumice in column
tests has been proposed to treat various concentrations of nickel
and copper [118]. Iron–pumice granular mixtures performed well
both in contaminant removal and in maintaining the long-term
hydraulic conductivity. A novel combination of pillared bentonite
(OH–Al–bent) with ZVI was studied in column experiments to
enhance Cr(VI) removal efficiency and improve the longevity of
ZVI PRBs [119]. The enhanced removal was attributed to the syn-
ergistic effect between adsorption by OH–Al–bent and reduction
by ZVI. The conventional ZVI has shown a lower activity at neutral
pH, however, ZVI activity can be improved by electrodeposition
preparation method. Liu et al. [120] investigated the effect of co-
existing organic matters on Cr(VI) reduction by electrodeposited
ZVI at neutral pH and found the added organic matters benefited
the subsequent Cr(VI) reduction. Besides, Wang et al. [121] inves-
tigated the role of HA in Cr(VI) removal by ZVI and the reduction
mechanism.
nZVI possessed higher Cr(VI) removal efficiency than ZVI
powder [115]. nZVI was also employed to treat other heavy metal
ions. Efecan et al. [122] investigated the removal of Ni2+ ions by
nZVI and observed a high potential towards uptake of Ni2+ ions
through complexation and surface precipitation. For other heavy
metal cations such as Cu2+ , Cd2+ and Zn2+ , the studies revealed high
uptake capacities, fast uptake kinetics, and very limited desorption
of metal ions from nZVI. Üzüm et al. [123] investigated fresh and
2-month aged nZVI for the removal of Co2+ ions. They found both
fresh and 2-month aged nZVI were effective for the removal of Co2+
ions and the uptake of Co2+ was related to the speciation of surface
oxohydroxyl groups on the nZVI surface. Yan et al. [124] examined
aspects of the core-shell model of nZVI to remove Hg(II), Zn(II) and
200 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205
hydrogen sulfide and found that Hg(II) was sequestrated via chemi-
cal reduction to elemental Hg, while Zn(II) was removed by sorption
to the iron oxide shell followed by zinc hydroxide precipitation.
3.5. Nitrate
Nitrate pollution in groundwater and surface water has become
an increasingly serious problem in both developed and develop-
ing countries. The sources of NO3 − include chemical fertilizers,
pesticides, animal-feeding operations, petroleum products and
waste contamination through storm and urban runoff. Health
problems on nitrate contamination are methemoglobinemia, car-
cinoma, malformation and mutation defects [125]. Because of its
toxic effects, the WHO and U.S. EPA have set a maximum concen-
tration of nitrate–nitrogen (NO3 − –N) 10 mg/L in drinking water
[126,127]. In China, the drinking water standard for NO3 − –N was
also changed from 20 to 10 mg/L in 2000 [128]. Numerous treat-
ment processes, including electrochemical method, adsorption,
and chemical reduction, have been developed for removing nitrate
from contaminated water [129–131]. However, these treatment
processes have the disadvantages of being relatively expensive,
difficult to maintain, or generate concentrated wastes [132].
Although chemical reduction of nitrate by ZVI was reported as
early as 1964, it has not gained popularity until the last decade
[128]. In recent years, ZVI has been intensively studied for its
ability to reduce NO3 − in water and groundwater. Nitrate can be
reduced to NH3 , N2 and NH4 + , and the iron may be oxidized to
Fe2+ , Fe3+ , Fe2 O3 , or Fe3 O4 depending on the reaction conditions.
Several researchers have carried out numerous studies on nitrate
reduction mechanism by ZVI [13,133]. Suzuki et al. [133] reported
that NO3 − directly received electrons from ZVI through an iron cor-
rosion product layer, rather than via H2 produced from Fe0 and
an acid. As understood, nitrate reduction by ZVI is a rapid process
under acidic conditions. For example, 95% of nitrate was rapidly
removed by ZVI under strong acidic conditions (pH < 2–3), while
lower than 50% of nitrate was removed at pH > 5 [134]. The reduc-
tive efficiency of nitrate by ZVI at initial neutral pH was increased
through addition of Fe2+ , accompanied by generating Fe3 O4 , which
favored the electron transfer on iron surface and accelerated the
reductive denitrification rate of nitrate [134].
Recently, considerable research has been conducted on nitrate
reduction by nZVI [15,135,136]. nZVI has great ability to reduce
nitrate and fast and highly effective denitrification can be achieved.
Zhang et al. [135] showed that more than 85% of the nitrate
was transformed into ammonia. However, the question of what
end-product results from nitrate reduction by nZVI has sparked
controversy. Hwang et al. [13] investigated the fate of nitrogen
species during nitrate reduction by nZVI and related reaction mech-
anisms. They reported that ammonia was the major product of
nitrate reduction by nZVI, and the nitrate would be absorbed onto
the nZVI surface, and then reduction and desorption followed in
consecutive steps.
Compared to ZVI, nitrate reduction by nZVI could improve
the denitrification and generate large amounts of ammonium,
which might lead to further treatment requirements. In evaluating
the potential use of nZVI in nitrate reduction, investigations on
controlling ammonium amounts are important. nZVI combined
with Alcaligenes eutrophus, a kind of hydrogenotrophic denitrifying
bacteria, was conducted to remove nitrate and decrease the gener-
ation of ammonium [137]. The combined treatment process could
remove all nitrate without ammonium release. On the other hand,
some studies have concentrated on seeking a solution to convert
nitrate to N2 . Pan et al. [138] investigated nitrate removal from
solution by single (TiO2 and nZVI), and composite (Nano-TiO2 –Fe0
composite) system under UV illumination and found only the
composite system could satisfactorily transform nitrate to N2 for
the maintenance of high level of ferrous ions in the system.
Previous works typically focused on nitrate remediation were
mostly limited to levels less than 100 mg/L. Highly concentrated
nitrate reduction for industrial wastewater treatment using freshly
synthesized nZVI, dried nZVI and dried-sonicated nZVI has been
investigated by Ryu et al. [15]. They found that different types of
nZVI could effectively reduce highly concentrated nitrate without
pH control. Many efforts have been carried out to prepare sta-
ble suspensions of nZVI by modifying particle surface to enhance
the mobility of nZVI in porous media. A modified surface nZVI as
bimetallic Fe/Cu particles to remove high concentration of NO3 − –N
through packed sand column has been investigated [139]. It was
found that coating metal can assist the electron transfer from core
(ZVI) to reduce the NO3 − .
3.6. Dyes
Dyes are of great concern because of their widespread use, biore-
calcitrance for conventional aerobic wastewater treatment, and
toxic aromatic intermediates [140]. ZVI reduction in anoxic con-
dition has received wide attention for the decolorization of the
most used azo and anthraquinone dyes and representative studies
dealing with heavy metal removal are given in Table 3. However,
reduction of dyes by ZVI under anoxic condition often achieves
low COD removal ability. Several studies have reported that ZVI
under oxic condition can generate strong oxidants and degrade
dyes. For example, the degradation of Remazol Brilliant Blue R
and Acid Black 1 dye by Fenton oxidation and ZVI/air process was
studied in comparison [145]. It was found that the ZVI/air pro-
cess can decolorize dyes more rapidly and significantly higher COD
removals for both dyes were achieved than those obtained by Fen-
ton oxidation. Similarly, the ZVI/air process demonstrated a higher
decolorization rate compared to the ZVI/N2 process in the degra-
dation of anthraquinone Reactive Blue 4 and azo Reactive Black 5
[146]. Shirin and Balakrishnan [17] investigated the reduction of
Acid Blue 129 by ZVI under oxic conditions and identified novel
reaction intermediates and products, including a genotoxic end-
product, 2,4,6-trimethylaniline. Wang et al. [141] investigated the
effect of DO concentration on the removal of three types of dyes
by ZVI. They observed that increase the DO concentrations and gas
flow rates enhanced decolorization and COD removal.
ZVI combined with ultrasound radiation was used for the decol-
orization of dyes. The degradation of azo dye direct sky blue 5B
by ZVI combined with ultrasound was investigated and an evi-
dent synergistic effect was observed [147]. Ultrasound radiation
could enhance the degradation reaction rates due to the pitting
and cracking formed on the ZVI surface by cavitational bubbles.
The degradation of Acid Orange 7 using ZVI/GAC in the absence and
presence of ultrasound was studied in comparison and a significant
synergistic effect was observed between ultrasound and ZVI/GAC
[148]. GAC was added as cathode to increase the unit of internal bat-
teries and enhance the current efficiency of the internal electrolysis.
Besides, the combination of ultrasound and the advanced Fenton
process for the degradation of Reactive Black 5, direct blue 15, and
Acid Orange 7 were respectively investigated [143,144,149].
Several studies reported that dye decolorization could be
enhanced by a combined use of ZVI and anaerobic microbes. Addi-
tion of ZVI may provide an efficient and long-term effective strategy
to enhance anaerobic environment that might improve the per-
formance of anaerobic treatment. Zhang et al. [150] developed a
ZVI packed upflow anaerobic sludge blanket (ZVI–UASB) reactor
to treat azo dye Reactive Brilliant Red X-3B wastewater, which
showed greater removal of COD and color. Li et al. [151] combined
ZVI and anaerobic sludge to decolorize reactive blue 13. Addition
of 1.0 g/L ZVI into sludge accelerated the decolorization, with the
 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205 201

Table 3
Representative studies dealing with dyes removal by ZVI.

ZVI type Dye Initial dye conc. Operational conditions Removal Ref.
efficiency

Microscale ZVI Acid Orange 7, Reactive Red 100 mg/L ZVI 30 g/L, pH 3 >99% [141]
120, Acid Blue 9
Resin-nZVI Acid Blue 113 100 mg/L nZVI/resin 50 mg/g, 20 g/L resin, pH 5.6 100% [37]
Polyvinylpyrrolidone stabilized ZVI Brilliant Red K-2G, Reactive 300–700 mg/L ZVI 2 g/L, pH 2.0, 4.2 and 7.0, 95.7–99.2% [142]
Brilliant Blue KN-R, respectively
triphenylmethane
Bentonite supported nZVI Methyl orange 100 mg/L B-nZVI 1.0 g/L, pH 3–6 99% [38]
Rectorite supported nZVI Orange II 70 mg/L Rectorite-nZVI 2.0 g/L, natural pH 100% [16]
Advanced Fenton/Ultrasound Reactive Black 5 5.0 × 10−4 M ZVI 1 g/L, pH 3.0, H2 O2 1.03 × 10−2 M, 99% [143]
ultrasound power 120 W/L at 60 kHz
Advanced Fenton/Ultrasound Direct blue 15 4.7 × 10−5 M ZVI 1 g/L, pH 3.0, H2 O2 5.15 × 10−3 M, 99% [144]
ultrasound power 120 W/L at 60 kHz

decoloration ratio after 1-h treatment increased by 29.4% com- (2) There exists a large variety of contaminants and their removal
pared with the sum of the individual systems, indicating a synergy by ZVI is based on various factors which include type of con-
between the sludge and ZVI. Besides, azo dye wastewater treatment taminants, ZVI-contaminant interactions, size of ZVI, initial pH,
was enhanced in an acidogenic reactor by ZVI dosing [152]. batch or column conditions, temperature, hardness, DO, and
the presence of natural organic compounds. So a more detailed
work on these interactions is needed to obtain further insights.
3.7. Phenol
Besides, how to use the DO more effectively in ZVI system is
still a question.
Phenol and its derivatives are common pollutants discharged by
(3) Studies on ZVI process are mostly carried out at the lab scale.
petrochemical, chemical, coking plants, oil refineries and pharma-
Most laboratory studies have evaluated the performance of ZVI
ceutical industries. Carcinogenic compounds such as chlorophenol
in removing relatively high concentrations of contaminants.
and polychlorophenols can be produced during the chlorination
However, conclusions drawn from the lab experiments may
process of drinking water [153]. U.S. EPA listed phenol as a priority
not reflect the performances at contaminated sites. There is a
pollutant and the European Union also regarded several phenols
need to perform more large-scale field studies and to explore
as priority pollutants. Waters containing phenolic compounds are
the practical utility of ZVI on commercial scale. As the effluents
highly toxic to most aquatic life. Therefore, the removal of phe-
contain several other pollutants, researchers are encouraged
nol from wastewater is of environmental interest. Because some
to work on actual effluents which have more practical signifi-
phenol derivatives may also be COCs, chlorinated phenols are not
cance.
included in this part.
(4) More research on the combination of ZVI with other technolo-
The removal of phenol by ZVI was investigated and • OH radicals
gies should be explored to conduct since only ZVI method is
concentration was quantified to confirm the removal of phenol via
practically difficult to treat actual wastewater or groundwater.
Fenton reaction besides adsorption/precipitation [18]. Fenton reac-
(5) Most of the studies on ZVI PRBs deal with experimental param-
tion was mainly responsible for the removal of phenol and TOC at
eter optimizations in order to develop more effective ZVI forms.
pH 3. To reduce the presence of ferrous ion in solution in Fenton-
Although ZVI PRBs are useful in situ remediation for some
based homogeneous advanced oxidation processes, the removal of
sites, the major issues hindering further development of PRBs
phenol by heterogeneous photo-electro Fenton-like based on nZVI
was also studied [154]. Besides, advanced Fenton process combined
with ultrasound was used to mineralize phenol [19,155]. For exam-
ple, Segura et al. [19] reported advanced Fenton process coupling
a short input of ultrasonic irradiation can successfully mineralize
phenol (up to 90% mineralization over 24 h).

4. Suggestions/remarks on ZVI based technology for the

remediation/treatment of contaminants from groundwater
and wastewater

The use of ZVI for the treatment of toxic contaminants in

groundwater and wastewater has received wide attention and
encouraging treatment efficiencies have been documented. How-
ever, many challenges exist. The following recommendations are
suggested for future work.

(1) As shown in this review, ZVI has been applied to remediate

a range of contaminants from groundwater and wastewater.
However, the reaction mechanism of ZVI with contaminants
varies with the contaminants (Fig. 2) and is rather complex
since oxidation, reduction, adsorption, surface precipitation,
surface complexation, and co-precipitation may be involved.
More studies should be performed to reveal the reaction mech-
anism between ZVI and contaminants. Fig. 2. Schematic model of reaction mechanism of ZVI with different contaminants.
202 F. Fu et al. / Journal of Hazardous Materials 267 (2014) 194–205
technology are that the use of ZVI alone as reactive medium
demonstrated limitations and deteriorating performance of
PRBs after installation [118]. In order to solve these problems
and to optimize the use of ZVI, the use of mixtures of ZVI with
other less expensive materials or combination of ZVI process
with other technologies is encouraged.
5. Conclusions
There is an increasing interest in the use of ZVI for the removal
of contaminants from groundwater and wastewater. ZVI has been
successfully applied for the remediation/treatment of groundwater
and wastewater contaminated with chlorinated organic com-
pounds, nitroaromatic compounds, arsenic, heavy metals, nitrate,
dyes, and phenol. ZVI can be combined with other technologies
such as ultrasonic irradiation, Fenton process, advanced Fenton
and microwave to remove contaminants and an evident syner-
gistic effect was often observed in such integrated processes. ZVI
PRBs have received increasing attention for in situ remediation of
groundwater contaminated by many kinds of contaminants. The
review shows that there is a need for more detailed systematic stud-
ies on contaminants removal mechanism and also some technical
improvements in preparing and utilizing ZVI.
Acknowledgments
The authors thank the financial supports from National Natu-
ral Science Foundation of China (No. 51008084), Guangzhou Pearl
River Nova Program (No. 2012J2200097) and State Scholarship
Fund (No. 201308440001). D. D. Dionysiou acknowledges support
for his involvement in this study to Cyprus Research Promotion
Foundation through Desmi 2009–2010 which is co-funded by the
Republic of Cyprus and the European Regional Development Fund
of the EU under contract number NEA IPODOMI/STRATH/0308/09.
Professor Dionysiou is UNESCO Co-Chair Professor of “Water Access
and sustainability” at the University of Cincinnati.
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