Chemical Engineering Journal 287 (2016) 618–632

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Chemical Engineering Journal

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

Review

Review on nano zerovalent iron (nZVI): From synthesis to environmental

applications
Magdalena Stefaniuk a, Patryk Oleszczuk a,⇑, Yong Sik Ok b
a
Department of Environmental Chemistry, Maria Curie-Skłodowska University, 3 Maria Curie-Skłodowska Square, 20-031 Lublin, Poland
b
Korea Biochar Research Center & Department of Biological Environment, Kangwon National University, Chuncheon 200-701, Republic of Korea

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 prospects and risks related to use

of nano zerovalent iron (nZVI) are
reviewed.

A review of different synthesis and
modification methods of nZVI
particles is made.

Removal efficiencies of different
contaminants by nZVI are reported.

Toxicity of nZVI on various organisms
is presented.

Practical application of nZVI in
laboratory and macro scale are
reviewed.

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

Article history: For remediation of water and soil, various nanoparticles such as zeolites, metal oxides, carbon materials,
Received 6 August 2015 metals, or bimetallic nanoparticles (e.g. Fe/Pd, Fe/Ag) have been reported. However, the most extensively
Received in revised form 15 October 2015 applied nanoparticle is nano zerovalent iron (nZVI). It is due to properties and effectiveness of nZVI in the
Accepted 5 November 2015
removal of pollutants as well as its cost effectiveness of production. The aim of this work is to present the
Available online 22 November 2015
opportunities and risks arising from the use nZVI from its synthesis to environmental application.
Compared to the previous reviews, our paper shows, a new look on nZVI with the common (e.g. milling,
Keywords:
chemical reduction) and the latest methods of synthesis (e.g. green synthesis, ultrasound or electrochem-
Nanomaterials
Zerovalent iron
ical method) and modification of nZVI, whose number is increasing especially in recent years. Therefore,
Soil remediation refer to the new trends is very important when selecting nZVI for the treatment of various matrices. This
Water and wastewater treatment review also identifies problems that may occurs a result of changes in the physicochemical properties of
Toxicity nZVI due to their modification (e.g. other metal doping, coating the surface, or deposition on the support).
Research shows that modifications of the nZVI surface can help in their stabilization, reduction of aggre-
gation, and reduction of toxicity. However, the improvement of those properties may simultaneously lead
to the creation of other threats related with the application of nZVI. Finally, we present the latest exam-
ples of practical utilization of nZVI for the remediation of soil and water in large-scale application.
Research demonstrates that nZVI can be an effective and versatile tool for the purification of different
matrix and especially groundwater.
Ó 2015 Elsevier B.V. All rights reserved.

⇑ Corresponding author. Tel.: +48 81 5375515; fax: +48 81 5375565.

E-mail address: patryk.oleszczuk@poczta.umcs.lublin.pl (P. Oleszczuk).

http://dx.doi.org/10.1016/j.cej.2015.11.046
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632 619

Contents

1. Synthesis of nZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619

1.1. Precision milling method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
1.2. Carbothermal reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
1.3. Ultrasound assisted method in synthesis of nZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
1.4. Electrochemical method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
1.5. Green synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
2. Modifications of nZVI. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2.1. Doping of nZVI with other metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2.2. nZVI surface coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2.3. Emulsified nZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
2.4. Deposition on the support and encapsulated nZVI in matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
2.5. The impact on the transformation and fate of nZVI in the environment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
3. The impact of nZVI on living organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
3.1. The impact of nZVI on microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
3.2. The impact of nZVI on aquatic and soil organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
3.3. The impact of nZVI on plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
3.4. The impact of nZVI on mammalian cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
3.5. Toxicity assessment of nZVI – limitations and perspectives of application. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
4. Practical application of nZVI in macro scale. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629

1. Synthesis of nZVI
Nano zerovalent iron (nZVI) can be obtained from various
methods. Initially physical methods were used, such as grinding,
abrasion, as well as lithography [1]. More popular at present are
through nucleation from homogeneous solutions or gas, separation
of phases, or annealing at elevated temperatures [1].
Apart from the physical methods mentioned above, chemical
methods for the synthesis of nZVI have been developed. The nZVI
can be obtained using sodium borohydride (NaBH4) as a reducing
agent, according to the following reaction [2]:

FeðH2 OÞ3þ 0
6 þ 3BH4 þ 3H2 O ! Fe # þ3BðOHÞ3 þ 10:5H2
Another chemical method of obtaining nZVI is the reduction of
goethite (a-FeOOH) or hematite (a-Fe2O3) at elevated temperature,
by H2 [3], and the decomposition of iron pentacarbonyl (Fe(CO)5)
in organic solvents or in argon [4].
Chemical reduction is the most frequently used method of
obtaining nZVI, mainly due to its simplicity. In addition, the pro-
duct obtained is characterized by a homogeneous structure that
displays high reactivity [5].
There are other specific methods of obtaining nZVI currently
being studied in laboratory experiments. The primary objective
of developing new methods for the production of nZVI is the reduc-
tion of production costs, which will permit more extensive applica-
tion of nZVI in practice.
All methods consisting of the diminution and processing of
input materials, leading to the production of nanoparticles, are
referred to in the literature as top down. In turn, those involving
processes of nZVI production from the basics are bottom up [6].
Table 1 presents the pros and cons of the methods of nZVI
production.
Methods which at present are not in common use but which,
due to their advantages, may soon become more popular, include
precision milling, carbothermal reduction, ultrasound assisted
production, electrochemical generation, and green synthesis.
1.1. Precision milling method
Precision milling consists of the milling of micro iron in a high-
speed rotary chamber with steel shot. The method does not require
any toxic reagents, which is the case with the chemical methods of
nZVI synthesis, and can be easily applied on a large scale [7]. After
8 h of milling, the size of nZVI particles became 20 nm with 39 m2/
g of surface area. These parameters are better in comparison to
nZVI obtained through chemical reduction with sodium borohy-
dride [2,7]. The material is characterized by higher reactivity rela-
tive to chloroorganic contaminants such as trichloroethyelene
(TCE) [7]. Unfortunately, nZVI particles obtained with the method
have irregular shape, which is related with their deformation and
cracking as a result of contact with steel shot. Moreover, they
display a strong tendency of aggregation [7].
ð1Þ
1.2. Carbothermal reduction
Another method of obtaining nZVI, that brings interesting
effects, is thermal reduction of iron compounds. In this method,
nanoparticles of iron oxide [11] or hydrous Fe2+ used in the form
of salts [8] are reduced to nZVI at elevated temperatures with
the use of thermal energy in the presence of gaseous reducing
agents. The reducing agents applied are gases such as H2, CO2, or
CO produced in the course of thermal decomposition of
carbon-based materials (carbon black, biochar, nanoparticles of
carbon). The Fe0 is formed as a result of a high-temperature
endothermic reaction (>500 °C) in which only gaseous products
are present [12]. Such reactions can proceed according to the
following Eqs. (2) and (3) [8].
FeðC2 H3 O2 Þ2 þ C ! Fe0 þ 2CH2 CO þ CO þ H2 O ð2Þ
Fe3 O4 þ 2C ! 3Fe0 þ 2CO2 ð3Þ
Both of those are inexpensive methods of production, as carbon
materials, such as carbon black and biochar, are cheap and easily
available. Moreover, the material could be obtained from the fossil
fuel industry [12].
1.3. Ultrasound assisted method in synthesis of nZVI
Ultrasonic waves can also be utilized for nZVI production, for
the enhancement of both the physical methods of diminution
and the chemical methods of synthesis. The application of ultra-
620 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632

Table 1
Summary of reported methods for the synthesis of nZVI.

Method Short description Pros Cons Diameter Surface area [m2/g] References
[nm]
Top down
Lithography Break down bulk iron materials Inexpensive method Limited control over N.A. N.A. [1]
Grinding particle size
distribution and
morphology
Precision The rotary chamber with steel beads Elimination of toxic 10–50 39.0 [7]
milling reagents, short processing
method time, low energy
consumption
Bottom up
Chemical Reduction of the iron salts using reducing Simple and easy to use in The use of toxic 1–100 33.5 [2]
reduction agent any laboratory reducing agent
Carbothermal Fe2+ are reduced to nZVI at elevated Spherical iron particles, Not well known 20–150 130, (C was used as a [8]
reduction temperatures with the use of thermal cheap reducing agent – matrix and created Fe0/
energy in the presence of gaseous H2, CO2, CO C had better
reducing agents properties)
Ultrasound Application of ultrasound waves and The creation of small The use of toxic 10 34.0–42.0 [5]
method reducing agent nanoparticles reducing agent
Electrochemical Reduction of the iron salt in the presence Inexpensive method Tendency to form 1–20 25.4 [9]
method of the electrodes and electrical nZVI clusters
Green synthesis Biosynthesis of nanoparticles using plant Replacing toxic reducing Irregular shape 20–120 5.8 [10]
extracts agent

N.A. – not available.

sound for the reduction of particle size was first proposed by Tao
et al. [13]. In their study, it was demonstrated that the application
of ultrasound leads to small, uniform, and equal-axes grains of iron
with average size of 10 nm. As in the case of chemical reduction,
application of ultrasound makes use of sodium borohydride [5],
according to the reaction:
and the formation of clusters. To counteract that phenomenon,
cationic surfactants are used (7), act as a stabilizing agent, and
ultrasonic waves (20 kHz), which constitute a source of energy
necessary for fast removal of iron nanoparticles from the cathode.
Cathode : Fe3þ þ 3e þ stabilizer ! nFe0 ð7Þ

 þ The nZVI produced with the use of ultrasonication can be

4Fe2þ 0
ðaqÞ þ BH4ðaqÞ þ 3H2 O ! 3Fe þ H3 BO3ðaqÞ þ 7HðaqÞ ð4Þ
between 1 and 20 nm and have a specific surface area of 25 m2/g
However, beside the main reaction of nZVI production, oxida- [9].
tion of the nZVI can simultaneously take place (5). Another method of effective plating with iron nanostructures is
cathode plating with alumina nano templates formed as a result of
Fe0 þ 2Hþ ! Fe2þ þ H2 " ð5Þ anodizing of high-purity aluminum foil in sulfuric acid. The sizes of
the iron nanostructures obtained can be strictly controlled by the
That is an unfavourable however, as it causes a reduction of the
size of pores of the coating applied, current intensity, and duration
process efficiency. For its elimination, the method presented
of the process. That method was used by Yoo et al. for the produc-
includes the use of an addition of ammonium hydroxide to the
tion of zerovalent iron nanowires [15].
solution of NaBH4. The reaction then proceeds according to the fol-
lowing equation:
1.5. Green synthesis
 þ
4Fe2þ 0
ðaqÞ þ BH4ðaqÞ þ 7NH4 OH ! 4Fe # þH3 BO3ðaqÞ þ 7NH4ðaqÞ þ 4H2 O

ð6Þ Due to several limitations of conventional methods, research

It was observed that under ultrasound, depending on their fre-
quency, nZVI can be obtained with different morphology, from
spherical to plate and needle types [14]. The structure obtained
is probably a result of Fe2+ growth inhibition in the presence of
acoustic waves. The ultrasonic intensity can also be described as
the power density of the acoustic wave (W) applied to a unit area
of the medium (square centimeter). In addition, the application of
ultrasound permits the production of nZVI with smaller particle
size (10 nm) than without their use (34 nm) and greater specific
surface area [14].
1.4. Electrochemical method
The next method of producing nZVI is with electrolysis, which
uses solution containing Fe2+/Fe3+ salts, electrodes (cathode and
anode), and electric current [9]. The method is extremely simple,
cheap, and fast [12] in comparison to chemical reduction [15].
Atoms of iron produced are gradually deposited on the cathode,
but they often display a strong tendency towards aggregation
focus has recently shifted towards the development of clean and
eco-friendly synthesis protocols. Nanoparticles can also be biosyn-
thesized (green synthesis), based on the use of plant extracts which
are responsible for the reduction of metal compounds to suitable
nanoparticles. Green synthesis is not only environmentally
friendly, but also inexpensive. Because there is no need to use high
temperatures, pressure, or additional energy inputs, it is easy to
implement on a large scale [16,17]. Green synthesis to produce
nZVI was first applied by VeruTEK and US EPA [18]. The method
included the preparation of a polyphenolic solution by heating
plant extracts (coffee, green tea, black tea, lemon, balm, sorghum,
bran, grape etc.) in water to a temperature close to the boiling
point. Extract prepared in that way is separated from the plant
residue and then mixed with a solution of Fe2+. The iron ions in
the presence of polyphenols were reduced to nZVI [18]. This green
synthesis procedure for producing iron nanoparticles is considered
as the most environmental friendly process and is still currently
widely used. Another new methods e.g. hydrothermal synthesis
with plant extracts, synthesis with plant biomass or biotemplate-
assisted synthesis are more common in the synthesis of iron oxide
 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
Table 2
Summary of properties and applications of green nZVI.
Plants Diameter [nm] Surface
area [m2/g]
Camellia sinensis 5–15 N.A.
Tea extracts: green tea, oolong tea, black 40–50 2.6–5.8
tea
Black tea, grape marc and vine leaves 15–45 N.A.
Green tea 20–40 and 80–120 5.82
Eucalyptus leaves, Green tea 20–80 N.A.
Syzygium aromaticum, Mentha spicata, N.A. N.A.
Punica granatum
Eucalyptus leaf 20–80 N.A.
Camellia sinensis, Syzygium aromaticum, 5–60 N.A.
Mentha, spicata Punica granatum juice
Red Wine
N.A. – not available.
nanoparticles [19]. One of the major drawbacks of using plant
resources for nanoparticle synthesis is the destruction of plants
and plant parts.
A possible way to avoid this is to employ agrowaste e.g. waste
of eucalyptus leaf [20] or extracts from various residues (skin,
albedo, flesh) of such fruits as lemons, mandarins, limes, oranges
or vine pomace [17,21]. Plant extracts reduce the metal ions in a
shorter time as compared to microbes. Depending upon plant type
and concentration of phytochemicals, nanoparticles are synthe-
sized within a few minutes or hours, whereas microorganism-
based methods require a longer time. The major drawback of
microbe-mediated nanoparticle synthesis is the obligatory con-
straint of aseptic conditions, which requires trained staff, and
raises the scaling-up cost. All these reasons, along with the easy
availability of plants in nature, make them more preferred biolog-
ical resources than microbes [19].
To date, green synthesized nZVI has been successfully used as a
Fenton catalyst for oxidizing monochlorobenzene (to 69%) [10] and
for the reductive degradation of dye such as malachite green [22]
or bromothymol blue [18]. Previous studies have reported that
green nZVI also can be used to degrade drugs (e.g. ibuprofen) in
soils [21], Cr(VI) ions [23,24], nitrate [25] in aqueous solution or
treatment of swine wastewater (of total N) [20].
In spite of the numerous advantages of using this method, green
synthesis is still not commonly accepted. This results from insuffi-
cient knowledge of the reactivity, physicochemical properties, and
agglomeration of the nanoparticles produced [21]. The information
available in the literature indicates that depending on the kind of
plant extract used for the production of nZVI, we obtain nanopar-
ticles with various sizes and values of specific surface area
(Table 2). Green synthesis can also be limited by the incomplete
reduction of iron to nZVI by plant extracts [23], resulting in of
the formation of other forms of iron, e.g. iron oxides of hydroxides,
in the course of the process [22].
2. Modifications of nZVI
In spite of their effectiveness in the removal of contaminants,
nZVI have weaknesses including a lack of stability, difficult separa-
tion from the medium being purified, rapid passivation of the
material, and limited mobility of the particles due to the formation
of agglomerates [26,27]. To counteract the negatives accompany-
ing the use of nZVI and to increase effectiveness of nZVI are being
modified more and more frequently [6]. Examples of methods of
nZVI modification and the obtained results are presented in Table 3.
The most frequent methods of modification of nZVI include
621
Effect References
Higher iron concentrations accelerated the degradation of bromothymol [18]
blue
The XRD pattern indicated green-Fe NPs contain iron oxide, iron [22]
oxohydroxide and nZVI
Remove ibuprofen (54–66% of the initial amount) in aqueous solutions [21]
and in sandy soils
Green nZVI tends to form irregular spherical particles, indicating a chain [10]
structure which is the same with chemically synthesized nZVI
Strong stability even after being aged in air for 2 months [25]
The highest reduction of Fe(III) and Cr(VI) was achieved by Punica [23]
granatum
Treatment of swine wastewater of total N [20]
Punica granatum and Red Wine were the most efficient agents for nano [24]
iron production
admixtures of other metals to nZVI (BnZVI), coating the surface
of nZVI, emulsification of nZVI (EZVI), deposition of nZVI on a car-
rier, or trapping of nZVI in a matrix. An illustration of the methods
of modification of nano zerovalent iron is presented in Fig. 1.
In addition, nZVI is not only a good material for the removal of
contaminants from various matrices, but it also performs well in
the role of a modifier. It can be used as a material enhancing the
work of a catalyst based on titanium oxide (TiO2). Thanks to such
an admixture the catalyst works more efficiently and the ‘‘life
span” of nZVI increases [28].
2.1. Doping of nZVI with other metals
A very well documented method of improving the remediation
properties of nano iron is the addition of another metal and cre-
ation of an alloy of iron-more noble metal, e.g. Pd, Pt, Ag, Cu, Ni
[12]. Small amounts of those metals applied on the surface of nZVI
causes an increased reactivity of the resultant particle and provides
good protection against passivation [6]. Among the transition met-
als commonly studied as catalysts of the reaction of dehalogena-
tion, Pd proved to be the best [44]. The most frequently
encountered in the scientific literature are studies on the removal
of contaminants from water solution with the use of bimetallic
nZVI. Few reports discuss a different matrix. As an example, Xu
et al. used Ni/Fe with a 15% admixture of nickel for the degradation
of 4-chlorophenol from water solution [45]. The effect achieved a
96% reduction of the compound within 60 min. Another example
of the use of bimetallic nZVI is the study conducted by Lai et al.
who used Cu/Fe (Fe 47.1% by weight) for the degradation of p-
nitrophenol from water solution [46]. The effect was 98% removal
of p-nitrophenol within 60 min. Huang et al. applied Pd/Fe (0.044%
by weight), obtaining total degradation of tetrachlorobisphenol A
from water solution after 60 min [47]. Also He et al. used Pd/Fe
(0.05%) for the reduction of the content of 2,20 ,3,4,40 ,5,50 -hepta
chlorobiphenyl in soil [29]. In that case, however, the effectiveness
achieved was not as good as the contaminant in water, attaining
only a removal level of 54% after 5 days. Nevertheless, it should
be emphasized that soil is a more difficult and a more demanding
matrix than water.
2.2. nZVI surface coating
Modification of surface properties was one of the main
approaches aimed at increasing nZVI dispersion in aqueous media
and mobility in porous media. Surface coating causes a change of
surface charge of nZVI, which prevents electrostatic attraction of
Table 3

622
Summary of reported modification methods for nZVI.

Modifying agent Type of particles The role of the modifying agent The amount of Other References
modifier
Bimetallic nZVI (BnZVI)
Pd nZVI Increase reactivity of nZVI 0.05% wt 54% removal of 2,20 ,3,4,40 ,5,50 -heptachlorobiphenyl [29]
in soil after 5 days
Coating the surface of nZVI
Carboxymethylcellulose (CMC) Pd/Fe (0.1% wt) < 17.2 nm Reduce the aggregation of nanoparticles, 0.2% wt Complete reduction of TCE after 40 min [30]
reactivity of nZVI increase, improve
mobility in soil
Copolymer (vinyl alcohol–vinyl nZVI 10–100 nm Improve the surface properties, increase 5–10% wt 98% removal of TCE after 3 h [4]
acetate, itaconic acid) (PV3A) the stability and reduce the particle size
(<10 nm)
Starch Pd/Fe (0.1% wt) Reduce the aggregation of nanoparticles, 0.2% wt 98% and 80% removal of TCE and PCBs [31]
improve dechlorination of contaminants
Poly(methylmethacrylate) in anizole nZVI Retards oxidation of nZVI and reduction of N.A. A coating of PMMA/anisole reduces the efficiency of [32]

M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632

(PMMA)/anisole agglomeration removal of dye in comparison to BnZVI
Ca(OH)2 nZVI Reduce the aggregation of nanoparticles 10% wt Improve the mobility of nZVI in porous media [33]
nZVI
Emulsified nZVI (EZVI)
Emulsion oil in water (O/W) Crystalline nano-iron (RNIP) Increase stability of nZVI suspension in 0.25% wt EZVI is easily transported by sand media [34]
40–60 nm aqueous and non-aqueous media
Deposition nZVI on the support or encapsulated in matrix
Granular activated carbon (GAC) Pd/Fe Allow to achieve a high surface area 11.0–14.0% Fe 90% removal of 2-chlorobiphenyl after 2 days, the [35]
(358 m2/g) necessary to the physical 0.65% Pd 85.0% residue contaminants was adsorbed on the surface
adsorption of contaminants GAC of the Pd/Fe/GAC
Montmorillonite (Mont) nZVI Increase the surface area from 24.3 to N.A. More effective reduction of Cr(VI) by HDTMA-Mont/ [36]
Montmorillonite 28.7 m2/g and 38.1 m2/g, reduce nZVI compared to Mont/nZVI
hexadecyltrimethylammonium aggregation and size of the nanoparticles
(HDTMA-Mont)
Silica fume 60–80 nm (85% SiO2) nZVI 20–110 nm Reduce aggregation N.A. Effective removal of Cr(VI) [37]
Silica RNIP Reduce aggregation, improve mobility in N.A. Silica particles functionalized alkyl groups are very [38]
soil effective at adsorbing TCE
Ca-alginate nZVI 10–90 nm Improve mobility in water N.A. 85–100% removal of arsenic after 2 h [39]
Bamboo nZVI Retards oxidation of nZVI, reduce N.A. 79.6% removal of methylene blue dye in aqueous [40]
aggregation, easier recovery after the solution
application
Rice hull derived biochar nZVI Increase the surface area N.A. 99.4% removal of TCE [41]
Graphene nZVI Use of a stable support N.A. Efficient removal of phosphate from aqueous [42]
solutions
Chitosani fibers nZVI Immobilization of nZVI using fibers with a N.A. The material was effectively used in As(III) and As [43]
large specific surface area (V) uptake from aqueous systems

N.A. – not available.

 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
Fig. 1. The schematic presentation of nZVI modification methods. (A) Other metal
doping, (B) coating the surface of the stabilizing compound, (C) emulsified nZVI
(EZVI), (D) encapsulated in matrix, and (E) nZVI deposition on the support.
molecules [48] and reduces their aggregation. For that purpose,
natural and modified polymers, anionic surface-active agents,
and other organic coatings were tested [49]. The application of
biopolymers is especially interesting due to their availability, low
cost, and environmental safety. Among biopolymers, the use of
starch [50], carboxymethyl cellulose (CMC) [50–52] and guar
gum [53] proved to be particularly successful.
Xiong et al. studied the ability of reducing the content of per-
chlorates in an aqueous medium [50]. Perchlorates are completely
soluble in water, which constitutes a serious problem with their
removal. Nanoparticles stabilized with starch or CMC removed per-
chlorates from water samples 1.8-and 3.3-fold faster, respectively,
compared to non-modified nZVI [50]. In their study, Naja et al. used
CMC for the stabilization of nZVI [51]. Modification of nZVI with
CMC caused good dispersion of nZVI in water, and the reduction
of RDX was 40-fold higher than when using metallic nano-iron.
Similarly, Qiu et al., in the course of purification of river waters
contaminated with Cr(VI) using nZVI stabilized with CMC (0.5%
by weight), observed an effective removal of the metal [52]. The
nZVI modified with CMC was characterized by low aggregation
and absence of toxicity towards microorganisms. Tiraferri et al.
used guar gum for the stabilization of nZVI [53]. Guar gum formed
negatively charged coating on the surface of nZVI, thus preventing
the aggregation of nZVI. The starched nanoparticles displayed
much less agglomeration but 4 times greater dechlorination pow-
der than those prepared without a stabilizer. While starched
nanoparticles remained suspended in water for days, non-
starched agglomerated and precipitated within minutes [31].
Other polymer used for modification of surface of nZVI is
polyacrylic acid (PAA). Research show that presence of this poly-
mer enhance mobility of nZVI in carbonate porous media. The
cause of mobility increase was strong repulsion between PAA/nZVI
and the carbonate matrix [54]. Additionally, demonstrated that
mobility of PAA/nZVI in classic Ca2+ concentration of groundwater
was superior to CMC/nZVI [55]. Therefore, PAA/nZVI has the poten-
tial to become an effective material for in situ groundwater
remediation.
Furthermore, the research show that using polymers as a pro-
tecting agent for zerovalent iron nanoparticles drastically increases
their applicability [56]. By synthesizing magnetic nanoparticles in
623
the presence of different varieties of poly(ethylene glycol) (PEG),
it has been shown that the formation and agglomeration of the
nanoparticles are controlled by the polymer concentration and
the geometry and terminal group of the PEG. Additionally, pres-
ence of layer PEG caused increase levels of magnetization particles,
which highlights their potential use in biomedical applications
such as targeted drug delivery, cancer detection and chemotherapy
[57].
A novel way of coating a nZVI surface is also a simple thermal
deposition to coat a Ca-based layer on the particle surface. This
coating can effectively protect the nZVI against corrosion and
greatly improve the stability during storage, transportation and
application. Beside the Ca(OH)2/nZVI particles are a low cost and
environmentally friendly materials [33].
2.3. Emulsified nZVI
Emulsification of nZVI is based on the formation of emulsions of
the type water-in oil-in water (W/O/W) [58], or oil-in water (O/W)
[34]. In the case of producing W/O/W, a hydrophobic membrane is
formed (oil film), that separates particles of nZVI contained in
water droplets with sizes of 10–20 lm from the remaining med-
ium [58].
Another type of emulsion is O/W, which consists in the place-
ment of nZVI in a non-polar substance, e.g. soybean oil, which
not only causes a reduction of aggregation, but also passivation
of the nanomaterial. The results of the study by Berge and Rams-
burg demonstrated that oil droplets (1–2 lm) containing nanopar-
ticles of iron are easily transported by sandy media and participate
actively in the reaction of dechlorination [34].
2.4. Deposition on the support and encapsulated nZVI in matrix
One of the problems resulting from the application of nZVI, and
related to its small size, is the difficult separation of nano iron from
the purified matrix. This can be counteracted through the use of
such materials supporting nZVI as silica, activated carbon, zeolites,
or polymer membranes [6,48], which, apart from immobilizing
nZVI, can affect its physicochemical properties. The immobilization
of nZVI by of the above carriers can be achieved through the fixing
of nZVI on their surface or trapping inside their pores.
Li et al. conducted a study on the removal of Cr(VI) in ground
water with the use of nZVI deposited on silica dust [37]. The end
effect was 22.5% more effective in metal removal compared to
the use of non-modified nZVI. It was also found that nZVI fixed
on silica reduces the aggregation of nanoparticles with simultane-
ous preservation of their high reactivity. Apart from silica, other
natural materials also proved to be good carriers of nZVI, such as
bentonite, kaolinite [59], or palygorskite (also known as atta-
pulgite) [60].
High effectiveness of complexes of those materials with nZVI in
the removal of heavy metals and bisphenol A from waters was
demonstrated [59,60].
In turn, Zhu et al. [61] and Chen et al. [62] demonstrated that
nZVI adsorbed on the surface of activated carbon permits effective
removal of As(III) and As(V) and, is also effective in dechlorination
[63,64] when activated carbon is substituted by graphite oxide or
montmorillonite.
Apart from activated carbon, nZVI can be deposited on other
carbon carriers. In this area, materials studied so far included bio-
char [41,65], graphene [42], and carbon nanotubes [66]. The bio-
char supported nZVI was applied successfully for the removal of
TCE, heavy metals, and dyes from waters [41,65]. Apart from the
effect of nZVI, the high effectiveness in reducing the content of
those contaminants is probably related with the large specific sur-
face area and the numerous surface functional groups of biochar,
Table 4

624
Toxicity of nZVI on various organisms.

Test organisms Type of nZVI Dose of nZVI Toxic effect References

Microorganisms
Dehalococcoides culture nZVI 100 mg/l Biostimulation of bacteria in the presence of nZVI [90]
Nitrate-reducing culture nZVI 5 g/l Increase microbial reduction of nitrate in the presence of nZVI [91]
Escherichia coli nZVI 1.2–110 mg/l Bactericidal effect of nZVI towards E. coli [92]
Escherichia coli nZVI, nFe3O4, nFe2O3 7.0–700 mg/l With increasing concentration of Fe0 and Fe2+ the mortality of [93]
E. coli raised, the presence of Fe3+ did not induce cytotoxicity
Escherichia coli PAP-nZVI, PSS-nZVI, NOM-nZVI N.A. The presence of polymer coating or adsorbed organic matter on [94]
nZVI caused reduced toxicity compared to the bare nZVI
Viruses nZVI 4.0 g/l Most of the viruses removed from solution were either inactivated [95]
or irreversibly adsorbed on iron
Soil and water organisms
Folsomia candida CMC–nZVI 1.0–10 g/l Total mortality of F. candida in soil after 7 days after application [83]
nZVI, complete inhibition of reproduction of F. candida in soil after
30 days after application nZVI

M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632

Heterocypris incongruens Total mortality of F. candida
Larvaes Oryzias latipes CMC–nZVI, aged nanoscale iron oxides 1.0–100 mg/l Toxic effects of all the tested compounds against larvae of O. [96]
(nFe-oxides), ferrous ion (Fe2+) latipes fish, nFe-oxides caused the smallest harmful effect
Eisenia fetida, Lumbricus rubellus CMC–nZVI 0–2000 mg/kg A negative impact on both test organisms P500 mg CMC–nZVI/kg [97]
of soil, inhibition of reproduction P100 mg CMC–nZVI/kg soil
Plants
Lolium perenne, Hordeum vulgare, Linum usitatissimum nZVI 300–5000 mg/l Observed negative effect on germination and root growth [98]
inhibition of test plants at concentration of nZVI P500 mg/l and
P200 mg/l, total inhibition of germination occurred at
concentration greater than 1000 mg nZVI/L
Typha latifolia, Populous deltoids  Populous nigra nZVI 0–1000 mg/l Toxic effect of nZVI on T. latifolia and hybrid poplars at [99]
concentrations >200 mg nZVI/L, increase the growth of T. latifolia,
and no change in hybrid poplars <50 mg nZVI/L
Flax, barley CMC–nZVI N.A. Inhibition of germination and root growth of the test plants in [100]
comparison to control
Mammalian cells
Rodent microglial cells, neurons nZVI, aged nZVI, Fe3O4 oraz SM-nZVI N.A. Fresh nZVI was the most toxic iron compound tested, the coating [101]
of SM resulted in the reduction of nZVI toxicity
2+
Human bronchial epithelial cells nZVI, Fe N.A. The nZVI and Fe2+ dissolved in physiological saline showed [102]
equivalent negative impact on tested cells

NOM – natural organic matter, PSS – poly(styrene sulfonate), PAP, SM – poly(aspartate), N.A. – not available.
 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
which is of fundamental importance in the processes of adsorption
of contaminants.
On the other hand, the fixing of nZVI on graphene [42] and car-
bon nanotubes [66] permitted effective removal of phosphate ions
and nitrates from waters, which in the future may be utilized for
the reduction of eutrophication of waters.
To increase the effectiveness of water purification, nZVI can be
included in polymer membranes [48]. The main advantages of
membranes is the fact that it is built on existing membrane tech-
nology. There are some disadvantages i.e. it’s very fragile – high
water pressure can cause rapture of membrane, another one is that
it can’t be reused or recycled [48].
The most common way of incorporation of NZVI on the mem-
branes is to submerge a mat of fibers in an aqueous solution of iron
salt, then the excess of salt is rinsed, and the ions are chemically
reduced by using sodium borohydride, to form the zerovalent iron
nanoparticles [43]. So far the literature provides descriptions of the
use of such materials as PGE/nylon 66, PGE/PVDF [67], chitosan
fibers [43], polyaniline [68–70] and PAA/PVA deposited on carbon
nanotubes [71]. Membranes with nZVI deposited on their surface
found an application for the removal of chloroorganic compounds,
As(III), As(V), Cr(VI) ions, and dyestuffs. In addition, a study by [67]
confirm that as a result of deposition of nZVI its properties may
change depending on the kind of membrane used. In the presence
of nylon 66 nanoparticles of Ni/Fe are characterized by lower
agglomeration and smaller particle size than in the case of PVDF.
In additionally, recent research showed that pre-deposition of nZVI
on PVDF could enhance the performance of membrane by decreas-
ing the transport of pollutants getting to the membrane surface
and blocking the membrane pores. Presence of nZVI layer results
in successful removal of humic acid and increase of membrane flux
[72]. Membranes containing reactive nanoparticles (Fe and Fe/Pd)
immobilized in a polymer film (PAA/PVDF) were prepared with
the use also of tea extract. The membrane-supported nanoparticles
were used for the degradation of a common and highly important
pollutant, trichloroethylene (TCE) [73].
Another method of immobilization of nZVI is their ‘‘trapping” in
a matrix. Calcium alginate [39,74–76], chitosan [77] and gum Ara-
bic [78] can be an examples. Calcium alginate is environment-
friendly and has pores large enough for trapping nZVI. Contami-
nants diffusing into the pores undergo either adsorption or reduc-
tion by nZVI. The method has been applied for the effective
removal of nitro compounds, [74], trichloroethylene [75], As(V)
[39], and Cr(VI) [76] from water solutions. Research has shown that
alginate does not reduce the activity of nZVI. In addition, recent
studies show that both chemically (chemical reduction) and bio-
logically (green synthesis) synthesized nZVI immobilized alginate
beads characterized by similar level of removal efficiency of Cr
(VI) from aqueous solution [76]. Entrapment of nZVI in chitosan
beads also has high efficiency removal of Cr(VI) (80%). In addition-
ally, the results [77] indicate that there is no significant difference
between the reaction rates of bare nZVI and entrapped nZVI. In
turn, nZVI encapsulated in gum Arabic within the soybean oil
was used to degradation of TCE. The use of gum Arabic represents
an advance in stabilizing nZVI-in-oil-in-water emulsions [78].
2.5. The impact on the transformation and fate of nZVI in the
environment
Various modifications are used for the purpose of more effective
delivery of reactive nanoparticles to the purification zone
[6,34,48,49,51]. Modifications of nZVI increased stability, reactiv-
ity, mobility, and reduced aggregation or passivation of nZVI. How-
ever, modifications of nZVI may lead to the creation of materials
that not only eliminate contaminants more effectively, but also
accumulate in living organisms, migrate over large distances,
625
sedimentation on bottoms of water reservoirs, or become carriers
of other contaminants.
Under natural environmental conditions, nanoparticles are
affected the most significantly by pH, ionic strength, and content
of organic matter and clay minerals [79]. It is well known that nat-
ural organic substances are easily adsorbed on the surface of solids
and nanoparticles, which may cause a change in the surface elec-
trochemistry of nZVI [79]. Depending on the kind of modification
applied, that phenomenon can amplify or attenuate aggregation
of nZVI. Research shows that in ground water, in the case of starch
and Tween-20 used as nZVI coatings, there are strong interactions
of the stabilizers with humic acids, causing an increase of agglom-
eration, followed by sedimentation of nanoparticles [80]. Depend-
ing on the matrix, increased agglomeration of particles may lead to
the clogging of soil pores and to inhibition of transport of the nZVI
[81] through the accumulation of nZVI and of the nZVI-
contaminant complex in the soil or on the bottom of water reser-
voirs. On the other hand, all modifications leading to a reduction
of aggregation are basically conducive to nZVI scattering in the
environment and to contamination of other areas, not directly con-
nected with the source of the contaminant [81]. For example, Dong
et al. noted that after nZVI stabilization with PAA, there was a lack
of interaction of the nZVI with humic acids as well as good disper-
sion of those particles in water [80].
Various composites of nZVI-organic matrix can constitute a spe-
cial threat. The most popular ones include composites of nZVI with
CNT or with biochar [41,66]. Due to their large adsorption surface
area, those materials can adsorb contaminant, which can then be
transported to other locations or accumulated in the matrix where,
due to the strong adsorption, they may not undergo biodegrada-
tion. It should also be stressed that in the case of a change of con-
ditions (e.g. pH) the contaminants can be released back to the
environment [82], causing secondary contamination.
Apart from the determination how a modification of nZVI can
affect its behavior in the environment and its physicochemical
properties, it is also important to determine the effect of the mod-
ification on living organisms. At present, research concerning the
modification of nZVI is focused mainly on increasing the effective-
ness of their contaminant-elimination capacity [6,37,51,50]. Less
frequent in the literature are studies of the physicochemical behav-
ior of nZVI after modification [80], and even less frequent are stud-
ies that verify the effectiveness of the method with the use of
ecotoxicological tests [83], which is the case in relation to other
methods of purification [84]. It is known that nZVI can penetrate
cellular membranes and enter into living cells [81], which can lead
to accumulation of nanoparticles in living organisms. At present
there is little information concerning the actual bioaccumulation
of nZVI particles in various organisms [81]. However, it cannot
be excluded that modifications of nZVI may have an effect on the
intensity of bioaccumulation of nZVI in organisms. The presence
of surfactants, polymers, or various functional groups attached to
the surface of nanoparticles can cause changes in the physico-
chemical properties of those materials, affecting their cytotoxicity
[85]. Therefore, the presence of modified nZVI may either cause the
appearance of a toxic effect or a reduction of toxicity towards var-
ious organisms, depending on the modification [83,86].
In relation to the above improvements and limitations, one
should be very careful when choosing the modification of nZVI
that, depending on the kind of contaminants removed or the geo-
chemical conditions, can behave differently and exert diverse
effects on the environment. In addition, one should take into
account that environmental factors may transform modified nZVI,
i.e. physical, chemical, and biological changes [87], which can alter
their properties, and the form structures that so far have never
appeared in the environment and have unknown or unusual prop-
erties and effects on the environment.
626 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
3. The impact of nZVI on living organisms
Apart from the advantages resulting from the application of
nanoparticles in environmental remediation, there is also a threat
caused by the insufficiently elucidated toxicity of nZVI towards liv-
ing organisms. The toxicity of nanoparticles can be caused by a
variety of factors, largely convergent with those which are respon-
sible for their high reactivity.
In the literature, there is a relative scarcity of reports concern-
ing the toxicity of nZVI. A majority of the studies [88,89] relate
to nanomaterials based on carbon and oxides of metals. The avail-
able information on nZVI is focused mainly on their effect on
microorganisms and, to a lesser extent, on crustaceans, fish larvae,
arthropods, annelids, plants, and occasionally mammalian cells.
The determination of the effect of nZVI is of particular importance
because of the increasingly popular use of those materials in the
purification of waters and remediation of soils. Table 4 provides
a compilation of available literature data concerning the effect of
nZVI on various groups of organisms (microorganisms, aquatic
and soil organisms, plants and mammalian cells).
3.1. The impact of nZVI on microorganisms
Studies show that nZVI can be adsorbed on cell membranes of
bacteria, or penetrate through them, which often leads to distur-
bances in the functioning of the cell [93]. Nanoparticles adsorbed
on cell membranes can block cellular ducts, cause structural
changes to the membranes, or inhibit mobility and nutrient intake
and result in death of the bacteria [90]. Another cause of the neg-
ative effect of nZVI on microorganisms is the formation, as a result
of its oxidation, of reactive oxygen species (ROS) apart from iron
ions, according to the following reactions [93]:
Fe0 þ O2 þ 2Hþ ! Fe2þ þ H2 O2 ð8Þ
Fe0 þ H2 O2 ! Fe2þ þ 2OH ð9Þ
Fe2þ þ H2 O2 ! Fe3þ þ OH þ OH ð10Þ
The ROS formed in that way may cause peroxidation of lipids and
damage to DNA [103,104], as well as the death of cells [105]. Studies
show that the application of polymer-based coatings or surfactants
on nZVI may reduce of the toxicity towards bacteria [86]. This is
related with minimization of the response of cells to oxidative
stress and a limitation of disturbances related with the functioning
of cell membranes as compared to non-coated nZVI [106]. It should
be emphasized, however, that so far the studies that estimate the
toxicity of nZVI towards microorganisms were focused mainly on
Escherichia coli. Those bacteria are characterized by greater sensitiv-
ity to the presence of Fe2+ and nZVI than Pseudomonas fluorescens,
Table 5
List of commercially available nZVI reported in the literatures [115,118–120].
Name of companies Location Type of nanoparticles
Nano iron Czech Republic nZVI powder nZVI
suspension nZVI modified
Toda kogyo corp. Japan RNIP(mainly iron oxides)
Polyflon USA, Florida nZVI powder
Gotthart Maier Metallpulver GmbH Germany mZVI powder (contains
traces of other metals)
Toyo ink mfg. Co. Ltd Japan mZVI suspension
MKnano Canada nZVI powder
Sky spring Nanomaterials, Inc. USA, Houston nZVI powder
Nanostructured & Amorphous Materials, Inc. USA, Houston nZVI powder
N.A. – not available, DM – dry matter.
Bacillus subtilis, or Staphylococcus aureus. This indicates that the
strain of bacteria has a significant effect on their bactericidal sensi-
tivity or tolerance to oxidative stress, which has been confirmed
[107]. That phenomenon is highly important for generalization of
the toxic effect of nZVI on microorganisms. However, research
shows that the potential undesirable changes caused to the compo-
sition of microbial populations under the effect of nZVI may revert
to the initial status after the termination of the purification [108]. In
addition, certain studies indicate that apart from the negative effect
of nZVI on microorganisms, a positive effect can also be noted. Such
a positive effect of nZVI on microorganisms was observed by Shin
and Cha [91], who found that in the presence of nZVI, there was
an increase in the reduction of nitrates by microbial activity. Eco-
toxicological studies conducted by Němeček et al. on the basis of
tests with bacteria Vibrio fischeri and psychrophilic bacteria also
confirmed the absence of a negative effect of nZVI on the organisms
studied. In addition, the authors observed a stimulation of the
growth of Gram (+) bacteria in soils [109].
3.2. The impact of nZVI on aquatic and soil organisms
Studies of the effect of nZVI and modified nZVI on aquatic and
soil organisms are scarce in the literature. Heterocypris incongruens
proved to be highly sensitive to the presence of nZVI stabilized
with CMC, both in soil and in aquatic environments. As suggested
by El-Temsah and Joner, the high toxicity of nZVI resulted from
limited availability of oxygen in the studied environment, as that
had been used for the processes of oxidation of nZVI [83]. Similar
conclusions were arrived at by Chen et al. who studied the toxic
effects of CMC–nZVI and the products of its oxidation in the pres-
ence of larvae of Oryzias latipes [96]. In addition, the authors noted
a significant effect of Fe(II), Fe(III) and ROS on increasing the toxi-
city of nZVI towards the test organisms. The negative effect of
nanoparticles on the reproduction and mortality of soil organisms
Folsomia candida is also attributed to the effect of noxious reactive
oxygen radicals formed during the oxidation of CMC–nZVI [83]. In
turn, the effect of CMC/nZVI and nZVI on, respectively, earthworms
(Eisenia fetida, Lumbricus rubellus) and nematodes (Caenorhabditis
elegans) was studied [97,110]. In the case of C. elegans, an absence
of mortality or an inhibition of growth of the test organisms was
noted, even at a dose of 17 g nZVI/kg of soil [110]. A negative effect
on reproduction, body mass and mortality was noted in relation to
E. fetida and L. rubellus at nZVI-CMC concentrations above 100 mg/
kg of soil [97]. It should be noted, however, that such levels of nZVI
in soil are values that occur only during direct application of nZVI.
3.3. The impact of nZVI on plants
The evidence of the toxicity of nZVI towards plants is ambigu-
ous [86,98,99]. It is assumed that the phytotoxicity of nZVI, similar
Size of particles Surface area [m2/g] Price
20–100 nm 20–25 120 euro/kg – (powder) 25–65
(suspension – 20% DM) euro/kg
100 nm 23 25–33 (powder) euro/kg
100–200 nm 37–58 N.A.
0–80 lm N.A. 1.2 euro/kg
2 lm N.A. N.A.
25 nm N.A. 144 $/100 g
20 nm 40–60 337 $/100 g
40–60 nm 6–13 244 $/100 g
60–80 nm 7 215 $/100 g
25 nm 40–60 330 $/100 g
 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632 627

References
to other magnetic nanoparticles, depends on the plant species, the
concentration of nZVI, and nZVI properties such as particle size,
[126]
surface properties, and the experimental method used [86]. El-
[124]

[125]

[123]

[129]
[129]
[58]

[27]

[27]
[27]
Temsay and Joner described an inhibiting effect of nZVI on the ger-
mination and growth of Lolium perenne, Hordeum vulgare, and

255 thousand USD

259 thousand USD
290 thousand EUR

360 thousand EUR

300 thousand EUR
Linum usitatissimum [98]. The negative effect of nZVI on plants is
attributed to the blocking of water and nutrient uptake by plant
roots as a result direct deposition and accumulation of nZVI parti-
cles on root surface [98,99]. Ma et al. demonstrate that nZVI can
Cost

N.A.

N.A.

N.A.

N.A.

N.A.
also lead to an inhibition of growth of young leaves and to the
decay of older ones [99]. In addition, in certain cases, nanoparticles
of Fe oxides, formed as a result of oxidation of nZVI, can be assim-
80% – TCE in soil samples,
mobility during the field

57–100% – TCE in water

ilated by cells and contribute to their death [111]. Low solubility of

CMC/nZVI showed good

nZVI in water additionally allows particles of nZVI to persist in bio-

40% and 61% – PCE,

logical systems and cause long-term effects that include a muta-

TCE 87% – PCBs

genic effect on organisms [111]. Another by product formed as a

Effectiveness

result of application of nZVI is FeO(OH). That compound has been

samples

Ok. 80%
50–99%

60–75%

demonstrated to cause damage to cell DNA and peroxidation of

96%

90%

90%

90%
test

lipids [104]. Another factor negatively affecting plants, can be

boron occurring on the surface of nZVI as a residue after the pro-
CMC/nZVI in the soil matrix

cess of nZVI production through chemical reduction of ions of iron

A few km2, 16–22 m depth
Pilot study on mobility of

in the presence of sodium borohydride. The negative effect of

boron can be avoided by washing out BH 4 and the products of its
clean groundwater
200 m2, it tries to

2.5 km2 + 1.2 km2

oxidation with water prior to the application of nZVI [100].

7.2 km2, 3–10 m
2 km2, 20–35 m

As in the case of bacteria, a positive effect of nZVI on plant

Scale of test

growth was observed. Even at low nZVI concentrations Ma et al.

0.6 km2

noted a stimulation of the growth of Typha latifolia, which may

N.A.

N.A.

N.A.

suggest that suitably chosen concentrations of nZVI can be used

for the remediation of the environment without any harmful
effects on the surroundings [99].
670 l EZVI at different
month 150 L (1.0 g/l)
150 L (0.2 g/l), after

3.4. The impact of nZVI on mammalian cells

380 kg (1.0 g/l)

55 kg (0.2 g/l)
Dose of nZVI

The literature provides little information on the effect of nZVI

on mammalian cells [101,102]. Human bronchial epithelium cells
1 t nZVI
depths
180 kg

150 kg
150 kg
2 t ZVI
300 kg

died in the presence of nZVI dissolved in physiological saline

60 kg

[101,102]. In addition, it was noted that dissolved Fe2+ ions have

2t

the same negative effect on the cells. Research demonstrates that

nZVI can cause neurotoxic effects in rodent and neuron microglia
Polychlorinated biphenyls

[101]. Modification of nZVI, e.g. as a result of nZVI coating with

Perchlorethylene (PCE)
Trichlorethylene (TCE)

polyasparaginate, reduces the toxicity of nZVI by limiting direct

Chlorinated ethylenes

PCE. TCE. 1.1.1-TCA

Vinyl chloride (VC)

contact of nanoparticles with cells [101].

PCE, TCE, DCE

TCE, PCE, DCE

Contaminants

3.5. Toxicity assessment of nZVI – limitations and perspectives of

application
(PCBs)

Cu(II)
N.A.

TCE

PCE

Summing up, it can be stated that nZVI can have a harmful

effect on microorganisms, animal cells, plant cells, and human
cells. This may inspire questions for their common use in environ-
oil, 1.5% wt surfactant, 17.0% wt
EZVI (44.3% wt water, 37.2% wt
Summary of pilot-scale and field-scale applications of nZVI.

mental remediation. The process of remediation should be con-

CMC/Pd/nZVI (0.1% wt, 0.6%

ducted under controlled conditions, taking all possible

precautions so as to reduce the possibility of nZVI migration
Pt/nZVI (0.5–1.0% wt)

CMC/nZVI (0.8% wt)

beyond the remediated area. It should be emphasized, however,

Type of particles

that in most of the cases observed the toxicity of nZVI is below

wt/0.1% wt)

the level observed for other nanoparticles [112]. The reason for
nZVI, ZVI

the lower toxicity of nZVI is probably because iron is a common

nZVI)

element occurring in soil and a necessary element for correct

nZVI

nZVI
nZVI

nZVI
nZVI

development of all organisms [97].The determination of the toxic-

ity of nZVI is very difficult as it is affected, apart from its physico-
Horice Czech Republic
The South of the USA

chemical properties, by the test organism species, the dose of nZVI,

Bornheim Germany

N.A. – not available.

Jacksonville USA

and the environmental conditions. Therefore, for the toxicity of

Ontario, Canada

Piasecna Czech

Lakehurst USA

nZVI to be fully understood one should perform an in-depth anal-

Florida, USA

Republic
Field-scale
Pilot-scale

ysis of all potential factors that may have an effect on it [113].

Taiwan

However, it is worth noting that the application of suitable modi-

Place
Table 6

N.A.

fication, suitable method of synthesis, or a suitably selected dose,

the negative effect of nZVI on the environment can be minimized.
628 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
4. Practical application of nZVI in macro scale
The effectiveness of nZVI in the elimination of various contam-
inants has been demonstrated successfully on the laboratory scale
[114]. Studies of this type mainly involve the performance of col-
umn tests, sedimentation tests, and batch tests [115].
The results of laboratory experiments, however, do not always
reflect the natural conditions in which the effectiveness of
nanoparticles. For practical application of nZVI, it is necessary to
conduct experiments in real conditions.
In addition, practical application of nZVI requires prior consid-
eration of all possibilities, limitations, and threats which are insep-
arably related with the application of nZVI. The potential benefits
of the use of nZVI in environmental remediation include increased
effectiveness and efficiency of purification of soils or ground
waters in comparison to macro iron particles used earlier. A dis-
tinct difficulty in the practical application of nZVI is its insufficient
mobility in the environment. Research conducted by Elliot and
Zhang showed that only 1.5% of nZVI introduced into ground water
reached the remediation location at the depth of 6 m [116]. There-
fore, from the practical point of view, it is necessary to increase the
mobility of nZVI. That, however, causes certain environmental con-
sequences. On one hand increased mobility of nZVI will reduce the
possibility of controlling the nZVI (mobile particles can propagate
more easily in the environment and more to undesirable locations)
[81,117]. On the other hand, modification of nZVI increasing
hydrophilicity will lead to increased or easier accumulation by
organisms.
Another important aspect is the cost related with the applica-
tion of nZVI to the environment and its availability on an industrial
scale. There are a lot of companies (Table 5) that are involved in the
production of nZVI on a large scale. The companies differ from one
another as to the kind of nZVI produced (mainly particle size and
specific surface area), their form (suspension, powder), type of
modification and product price.
It is difficult to estimate the total costs of a technology involving
the use of nZVI because it depends on numerous factors, e.g. the
kind of product, amount ordered, and costs of transportation. In
addition to the cost related with the purchase of nZVI, one should
also account for the costs of additional laboratory and field exper-
iments, including hydrogeological and geochemical studies, and of
conducting a pilot test on a contaminated area [111]. This results
from the fact that at a field scale there may exist additional factors
with significant effect on the transport and reactivity of nZVI, and
thus on the effectiveness of its application [121]. The effect of dis-
tribution, level of water resources, or the properties of under-
ground waters may have a significant importance for the
migration of nZVI particles [27].
A pilot study is the preliminary activity aimed at acquiring prac-
tical information necessary for conducting an efficient and effec-
tive process of remediation. It permits the determination of the
amount of suspension required, mobility of the nZVI, time during
which the nZVI particles remain active, and a preliminary estimate
of the expected reduction of contaminants. After such a prelimi-
nary study, the remediation work is conducted, which in the case
of purification of ground waters consists of the following stages:
(1) installation of injection and monitoring wells, (2) analysis of
samples of underground waters collected from the wells, (3) dos-
ing of nZVI with simultaneous monitoring of parameters of the
environment (e.g. pH, temperature, injection pressure, rate of flow
of solutions of reactive particles, concentration of iron suspension),
and (4) analysis of samples of underground waters after the appli-
cation of nZVI solution to estimate the effectiveness of the opera-
tion [122]. Apart from the monitoring of those parameters and of
the level of contaminants, analysis of other factors is conducted
to estimate the effect of the nZVI injection on the geochemistry
of the matrix.
Those parameters include e.g. the content of oxygen, nitrates
and sulfates, redox potential measurements, and the total content
of Fe(II) and Fe0 [115]. Table 6 presents examples of pilot projects
conducted in real conditions, in which nZVI was used for the purifi-
cation of waters. Depending on the kind of nZVI used, or the type of
contaminant to be eliminated, the achieved effectiveness of con-
taminant elimination varied from 40% to as much as 100%. In the
case of most of the pilot tests the changes in the level of contami-
nants resulting from the application of nanoparticles constitute
highly important information permitting the estimation of the
effectiveness of nZVI, but only in the test site. Comparison of pilot
tests is difficult because of the diversity of prevailing conditions at
the test sites. The size of the remediation zone and the duration of
the remediation are also very important elements [6].
The first pilot tests of the use of nZVI was conducted in the sum-
mer of 2000 in Trenton (USA). For the purification of ground waters
contaminated with, among other things, TCE, PCE, VC, and chloro-
form, 2.5 kg of modified Pd/nZVI was applied at concentration of
1 g/l. After 4 weeks of remediation a 96.5% reduction of chloroor-
ganic contaminants was obtained [116]. In pilot tests, both normal
nZVI and various modified nZVI were used.
Non-modified nZVI was also applied for the removal of Cu2+
ions from industrial wastewaters [123]. In the final effect, apart
from the elimination of Cu2+, a composite composed of iron and
copper was obtained (20–25%), and the copper could be recovered
during the recycling of the nZVI. The pilot tests demonstrated a
high elimination of chloroorganic compounds by modified nZVI
(CMC/nZVI, BnZVI, EZVI) [58,124–126].
Good results obtained in pilot tests cause more and more
attempts of water and soils remediation with full-scale application
of nZVI. That is additionally facilitated by greater availability of
nZVI in industrial amounts.
Moreover, the suppliers of nZVI often provide also geotechnical
services for the implementation of new methods of contaminant
elimination [127]. At present large scale application of nZVI is used
primarily for the elimination of chloroorganic contaminants,
mainly from ground water (Table 6).
The literature shows that the largest number of both pilot and
full scale tests have been conducted in North America [128]. The
US EPA (American Environmental Protection Agency) compiled a
list of 25 sites in the USA where nZVI was tested or applied on a
large scale for soil remediation. The data show that in 56% of cases
the load of contaminants was reduced (with a distinct decreasing
trend of concentration by an average of ca. 70%). Non-modified
nZVI was used most (40%), followed by bimetallic (32%), and emul-
sified (16%) nZVI. The suspension concentration that was most fre-
quently applied was 8 g/l (in a range of 0.2–30 g/l) [115].
As an example, remediation of contaminated soils by of nZVI
was conducted in areas of US Navy installations, such as the Naval
Air Station (Jacksonville, FL) and the Naval Air Engineering Station
near Lakehurst (NJ). Those areas were contaminated with 1,1,1-
TCA, DCE, TCE, and PCE. During those studies it was observed that
if b-elimination of chlorine compounds takes place, the dehalo-
genation proceeds faster and smaller amounts of by products are
produced. It was also noted that to ensure optimum remediation
conditions iron should be applied at the weight ratio of 0.004 to
the mass of the soil being remediated, and the injection of nZVI
should be conducted with the minimum use of water which con-
tains large amounts of oxidants and causes the passivation of iron
[129].
In Europe nZVI was applied for the first time in 2007 for full
scale elimination of chloroorganic contaminants, in Bornheim
(Germany). The area was contaminated with PCE from the aero-
 M. Stefaniuk et al. / Chemical Engineering Journal 287 (2016) 618–632
space industry. The contamination spread over an area of several
square kilometers down to a depth of 20 m.
The application of steam extraction for the remediation of that
area did not produce satisfactory results. During 14 years only
5 tons of PCE were eliminated, which cost about 1 million EUR.
The lack of satisfactory effectiveness in PCE removal and the high
costs of the remediation led to the decision to change the method
of remediation by nZVI (with particle size of 70 nm and stabilized
with polycarboxylic acid). Within a short period of time over 90%
elimination of the contaminant was achieved, at lower cost. What
is more, after 2 years from the application of nZVI, further reduc-
tion of the level of contaminants was observed [27].
The Czech Republic was the next European country to used ZVI
on a macro scale. At the Horice and Pisecna, on areas of approxi-
mately 7 and 2 km2, 82 injection wells were constructed, to which
300 kg of nZVI were injected. The reduction of contamination var-
ied from 60% to 90% [27].
5. Conclusion
The application of nanoparticles in the remediation of the envi-
ronment not only reduced the concentration of potential noxious
substances, but also reduced the costs of large scale remediation
and of the duration of the process. As research demonstrates, nZVI
can be an effective and versatile tool for the purification of waters
and soils. In view of the interest in nZVI, numerous studies have
been under taken in recent years, aimed at innovation of the tech-
niques of production, physicochemical functionality, and enhanced
stability and mobility of those particles. However, the potential
threats resulting from the application of modified and non-
modified nZVI to various matrices are rather poorly recognized.
Nevertheless, the actual number of applications of the nanoparti-
cles is constantly growing. It is necessary to conduct research that
will take into account not only the toxicity of nZVI prior to the pro-
cess of remediation, but also address the consequences resulting
from the application of nZVI. Of particular importance here would
be studies involving various groups of organisms, at various stages
of development, and at various degrees of transformation of mod-
ified and non-modified nZVI. Another important aspect in the esti-
mation of the safety of application of nZVI is to determine how the
various methods of modification will affect the fate of nZVI and
their effect on living organisms. Also important are the interactions
between nZVI and other contaminants, and the stability of those
complexes in relation to variable environmental conditions and
in relation to the degree of transformation of nZVI.
Acknowledgement
The project was funded by the National Science Centre – Poland
granted on the basis of the decision number DEC-2012/07/E/
ST10/00572.
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