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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.
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 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
Nano zerovalent iron (nZVI) can be obtained from various 8 h of milling, the size of nZVI particles became 20 nm with 39 m2/
methods. Initially physical methods were used, such as grinding, g of surface area. These parameters are better in comparison to
abrasion, as well as lithography [1]. More popular at present are nZVI obtained through chemical reduction with sodium borohy-
through nucleation from homogeneous solutions or gas, separation dride [2,7]. The material is characterized by higher reactivity rela-
of phases, or annealing at elevated temperatures [1]. tive to chloroorganic contaminants such as trichloroethyelene
Apart from the physical methods mentioned above, chemical (TCE) [7]. Unfortunately, nZVI particles obtained with the method
methods for the synthesis of nZVI have been developed. The nZVI have irregular shape, which is related with their deformation and
can be obtained using sodium borohydride (NaBH4) as a reducing cracking as a result of contact with steel shot. Moreover, they
agent, according to the following reaction [2]: display a strong tendency of aggregation [7].
FeðH2 OÞ3þ 0
6 þ 3BH4 þ 3H2 O ! Fe # þ3BðOHÞ3 þ 10:5H2 ð1Þ
1.2. Carbothermal reduction
Another chemical method of obtaining nZVI is the reduction of
goethite (a-FeOOH) or hematite (a-Fe2O3) at elevated temperature, Another method of obtaining nZVI, that brings interesting
by H2 [3], and the decomposition of iron pentacarbonyl (Fe(CO)5) effects, is thermal reduction of iron compounds. In this method,
in organic solvents or in argon [4]. nanoparticles of iron oxide [11] or hydrous Fe2+ used in the form
Chemical reduction is the most frequently used method of of salts [8] are reduced to nZVI at elevated temperatures with
obtaining nZVI, mainly due to its simplicity. In addition, the pro- the use of thermal energy in the presence of gaseous reducing
duct obtained is characterized by a homogeneous structure that agents. The reducing agents applied are gases such as H2, CO2, or
displays high reactivity [5]. CO produced in the course of thermal decomposition of
There are other specific methods of obtaining nZVI currently carbon-based materials (carbon black, biochar, nanoparticles of
being studied in laboratory experiments. The primary objective carbon). The Fe0 is formed as a result of a high-temperature
of developing new methods for the production of nZVI is the reduc- endothermic reaction (>500 °C) in which only gaseous products
tion of production costs, which will permit more extensive applica- are present [12]. Such reactions can proceed according to the
tion of nZVI in practice. following Eqs. (2) and (3) [8].
All methods consisting of the diminution and processing of
input materials, leading to the production of nanoparticles, are FeðC2 H3 O2 Þ2 þ C ! Fe0 þ 2CH2 CO þ CO þ H2 O ð2Þ
referred to in the literature as top down. In turn, those involving
processes of nZVI production from the basics are bottom up [6]. Fe3 O4 þ 2C ! 3Fe0 þ 2CO2 ð3Þ
Table 1 presents the pros and cons of the methods of nZVI
production. Both of those are inexpensive methods of production, as carbon
Methods which at present are not in common use but which, materials, such as carbon black and biochar, are cheap and easily
due to their advantages, may soon become more popular, include available. Moreover, the material could be obtained from the fossil
precision milling, carbothermal reduction, ultrasound assisted fuel industry [12].
production, electrochemical generation, and green synthesis.
1.3. Ultrasound assisted method in synthesis of nZVI
1.1. Precision milling method
Ultrasonic waves can also be utilized for nZVI production, for
Precision milling consists of the milling of micro iron in a high- the enhancement of both the physical methods of diminution
speed rotary chamber with steel shot. The method does not require 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
sound for the reduction of particle size was first proposed by Tao and the formation of clusters. To counteract that phenomenon,
et al. [13]. In their study, it was demonstrated that the application cationic surfactants are used (7), act as a stabilizing agent, and
of ultrasound leads to small, uniform, and equal-axes grains of iron ultrasonic waves (20 kHz), which constitute a source of energy
with average size of 10 nm. As in the case of chemical reduction, necessary for fast removal of iron nanoparticles from the cathode.
application of ultrasound makes use of sodium borohydride [5],
according to the reaction: Cathode : Fe3þ þ 3e þ stabilizer ! nFe0 ð7Þ
Table 2
Summary of properties and applications of green nZVI.
nanoparticles [19]. One of the major drawbacks of using plant admixtures of other metals to nZVI (BnZVI), coating the surface
resources for nanoparticle synthesis is the destruction of plants of nZVI, emulsification of nZVI (EZVI), deposition of nZVI on a car-
and plant parts. rier, or trapping of nZVI in a matrix. An illustration of the methods
A possible way to avoid this is to employ agrowaste e.g. waste of modification of nano zerovalent iron is presented in Fig. 1.
of eucalyptus leaf [20] or extracts from various residues (skin, In addition, nZVI is not only a good material for the removal of
albedo, flesh) of such fruits as lemons, mandarins, limes, oranges contaminants from various matrices, but it also performs well in
or vine pomace [17,21]. Plant extracts reduce the metal ions in a the role of a modifier. It can be used as a material enhancing the
shorter time as compared to microbes. Depending upon plant type work of a catalyst based on titanium oxide (TiO2). Thanks to such
and concentration of phytochemicals, nanoparticles are synthe- an admixture the catalyst works more efficiently and the ‘‘life
sized within a few minutes or hours, whereas microorganism- span” of nZVI increases [28].
based methods require a longer time. The major drawback of
microbe-mediated nanoparticle synthesis is the obligatory con- 2.1. Doping of nZVI with other metals
straint of aseptic conditions, which requires trained staff, and
raises the scaling-up cost. All these reasons, along with the easy A very well documented method of improving the remediation
availability of plants in nature, make them more preferred biolog- properties of nano iron is the addition of another metal and cre-
ical resources than microbes [19]. ation of an alloy of iron-more noble metal, e.g. Pd, Pt, Ag, Cu, Ni
To date, green synthesized nZVI has been successfully used as a [12]. Small amounts of those metals applied on the surface of nZVI
Fenton catalyst for oxidizing monochlorobenzene (to 69%) [10] and causes an increased reactivity of the resultant particle and provides
for the reductive degradation of dye such as malachite green [22] good protection against passivation [6]. Among the transition met-
or bromothymol blue [18]. Previous studies have reported that als commonly studied as catalysts of the reaction of dehalogena-
green nZVI also can be used to degrade drugs (e.g. ibuprofen) in tion, Pd proved to be the best [44]. The most frequently
soils [21], Cr(VI) ions [23,24], nitrate [25] in aqueous solution or encountered in the scientific literature are studies on the removal
treatment of swine wastewater (of total N) [20]. of contaminants from water solution with the use of bimetallic
In spite of the numerous advantages of using this method, green nZVI. Few reports discuss a different matrix. As an example, Xu
synthesis is still not commonly accepted. This results from insuffi- et al. used Ni/Fe with a 15% admixture of nickel for the degradation
cient knowledge of the reactivity, physicochemical properties, and of 4-chlorophenol from water solution [45]. The effect achieved a
agglomeration of the nanoparticles produced [21]. The information 96% reduction of the compound within 60 min. Another example
available in the literature indicates that depending on the kind of of the use of bimetallic nZVI is the study conducted by Lai et al.
plant extract used for the production of nZVI, we obtain nanopar- who used Cu/Fe (Fe 47.1% by weight) for the degradation of p-
ticles with various sizes and values of specific surface area nitrophenol from water solution [46]. The effect was 98% removal
(Table 2). Green synthesis can also be limited by the incomplete of p-nitrophenol within 60 min. Huang et al. applied Pd/Fe (0.044%
reduction of iron to nZVI by plant extracts [23], resulting in of by weight), obtaining total degradation of tetrachlorobisphenol A
the formation of other forms of iron, e.g. iron oxides of hydroxides, from water solution after 60 min [47]. Also He et al. used Pd/Fe
in the course of the process [22]. (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
2. Modifications of nZVI achieved was not as good as the contaminant in water, attaining
only a removal level of 54% after 5 days. Nevertheless, it should
In spite of their effectiveness in the removal of contaminants, be emphasized that soil is a more difficult and a more demanding
nZVI have weaknesses including a lack of stability, difficult separa- matrix than water.
tion from the medium being purified, rapid passivation of the
material, and limited mobility of the particles due to the formation 2.2. nZVI surface coating
of agglomerates [26,27]. To counteract the negatives accompany-
ing the use of nZVI and to increase effectiveness of nZVI are being Modification of surface properties was one of the main
modified more and more frequently [6]. Examples of methods of approaches aimed at increasing nZVI dispersion in aqueous media
nZVI modification and the obtained results are presented in Table 3. and mobility in porous media. Surface coating causes a change of
The most frequent methods of modification of nZVI include 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]
624
Toxicity of nZVI on various organisms.
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) 618–632 625
which is of fundamental importance in the processes of adsorption sedimentation on bottoms of water reservoirs, or become carriers
of contaminants. of other contaminants.
On the other hand, the fixing of nZVI on graphene [42] and car- Under natural environmental conditions, nanoparticles are
bon nanotubes [66] permitted effective removal of phosphate ions affected the most significantly by pH, ionic strength, and content
and nitrates from waters, which in the future may be utilized for of organic matter and clay minerals [79]. It is well known that nat-
the reduction of eutrophication of waters. ural organic substances are easily adsorbed on the surface of solids
To increase the effectiveness of water purification, nZVI can be and nanoparticles, which may cause a change in the surface elec-
included in polymer membranes [48]. The main advantages of trochemistry of nZVI [79]. Depending on the kind of modification
membranes is the fact that it is built on existing membrane tech- applied, that phenomenon can amplify or attenuate aggregation
nology. There are some disadvantages i.e. it’s very fragile – high of nZVI. Research shows that in ground water, in the case of starch
water pressure can cause rapture of membrane, another one is that and Tween-20 used as nZVI coatings, there are strong interactions
it can’t be reused or recycled [48]. of the stabilizers with humic acids, causing an increase of agglom-
The most common way of incorporation of NZVI on the mem- eration, followed by sedimentation of nanoparticles [80]. Depend-
branes is to submerge a mat of fibers in an aqueous solution of iron ing on the matrix, increased agglomeration of particles may lead to
salt, then the excess of salt is rinsed, and the ions are chemically the clogging of soil pores and to inhibition of transport of the nZVI
reduced by using sodium borohydride, to form the zerovalent iron [81] through the accumulation of nZVI and of the nZVI-
nanoparticles [43]. So far the literature provides descriptions of the contaminant complex in the soil or on the bottom of water reser-
use of such materials as PGE/nylon 66, PGE/PVDF [67], chitosan voirs. On the other hand, all modifications leading to a reduction
fibers [43], polyaniline [68–70] and PAA/PVA deposited on carbon of aggregation are basically conducive to nZVI scattering in the
nanotubes [71]. Membranes with nZVI deposited on their surface environment and to contamination of other areas, not directly con-
found an application for the removal of chloroorganic compounds, nected with the source of the contaminant [81]. For example, Dong
As(III), As(V), Cr(VI) ions, and dyestuffs. In addition, a study by [67] et al. noted that after nZVI stabilization with PAA, there was a lack
confirm that as a result of deposition of nZVI its properties may of interaction of the nZVI with humic acids as well as good disper-
change depending on the kind of membrane used. In the presence sion of those particles in water [80].
of nylon 66 nanoparticles of Ni/Fe are characterized by lower Various composites of nZVI-organic matrix can constitute a spe-
agglomeration and smaller particle size than in the case of PVDF. cial threat. The most popular ones include composites of nZVI with
In additionally, recent research showed that pre-deposition of nZVI CNT or with biochar [41,66]. Due to their large adsorption surface
on PVDF could enhance the performance of membrane by decreas- area, those materials can adsorb contaminant, which can then be
ing the transport of pollutants getting to the membrane surface transported to other locations or accumulated in the matrix where,
and blocking the membrane pores. Presence of nZVI layer results due to the strong adsorption, they may not undergo biodegrada-
in successful removal of humic acid and increase of membrane flux tion. It should also be stressed that in the case of a change of con-
[72]. Membranes containing reactive nanoparticles (Fe and Fe/Pd) ditions (e.g. pH) the contaminants can be released back to the
immobilized in a polymer film (PAA/PVDF) were prepared with environment [82], causing secondary contamination.
the use also of tea extract. The membrane-supported nanoparticles Apart from the determination how a modification of nZVI can
were used for the degradation of a common and highly important affect its behavior in the environment and its physicochemical
pollutant, trichloroethylene (TCE) [73]. properties, it is also important to determine the effect of the mod-
Another method of immobilization of nZVI is their ‘‘trapping” in ification on living organisms. At present, research concerning the
a matrix. Calcium alginate [39,74–76], chitosan [77] and gum Ara- modification of nZVI is focused mainly on increasing the effective-
bic [78] can be an examples. Calcium alginate is environment- ness of their contaminant-elimination capacity [6,37,51,50]. Less
friendly and has pores large enough for trapping nZVI. Contami- frequent in the literature are studies of the physicochemical behav-
nants diffusing into the pores undergo either adsorption or reduc- ior of nZVI after modification [80], and even less frequent are stud-
tion by nZVI. The method has been applied for the effective ies that verify the effectiveness of the method with the use of
removal of nitro compounds, [74], trichloroethylene [75], As(V) ecotoxicological tests [83], which is the case in relation to other
[39], and Cr(VI) [76] from water solutions. Research has shown that methods of purification [84]. It is known that nZVI can penetrate
alginate does not reduce the activity of nZVI. In addition, recent cellular membranes and enter into living cells [81], which can lead
studies show that both chemically (chemical reduction) and bio- to accumulation of nanoparticles in living organisms. At present
logically (green synthesis) synthesized nZVI immobilized alginate there is little information concerning the actual bioaccumulation
beads characterized by similar level of removal efficiency of Cr of nZVI particles in various organisms [81]. However, it cannot
(VI) from aqueous solution [76]. Entrapment of nZVI in chitosan be excluded that modifications of nZVI may have an effect on the
beads also has high efficiency removal of Cr(VI) (80%). In addition- intensity of bioaccumulation of nZVI in organisms. The presence
ally, the results [77] indicate that there is no significant difference of surfactants, polymers, or various functional groups attached to
between the reaction rates of bare nZVI and entrapped nZVI. In the surface of nanoparticles can cause changes in the physico-
turn, nZVI encapsulated in gum Arabic within the soybean oil chemical properties of those materials, affecting their cytotoxicity
was used to degradation of TCE. The use of gum Arabic represents [85]. Therefore, the presence of modified nZVI may either cause the
an advance in stabilizing nZVI-in-oil-in-water emulsions [78]. appearance of a toxic effect or a reduction of toxicity towards var-
ious organisms, depending on the modification [83,86].
2.5. The impact on the transformation and fate of nZVI in the In relation to the above improvements and limitations, one
environment should be very careful when choosing the modification of nZVI
that, depending on the kind of contaminants removed or the geo-
Various modifications are used for the purpose of more effective chemical conditions, can behave differently and exert diverse
delivery of reactive nanoparticles to the purification zone effects on the environment. In addition, one should take into
[6,34,48,49,51]. Modifications of nZVI increased stability, reactiv- account that environmental factors may transform modified nZVI,
ity, mobility, and reduced aggregation or passivation of nZVI. How- i.e. physical, chemical, and biological changes [87], which can alter
ever, modifications of nZVI may lead to the creation of materials their properties, and the form structures that so far have never
that not only eliminate contaminants more effectively, but also appeared in the environment and have unknown or unusual prop-
accumulate in living organisms, migrate over large distances, 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 Bacillus subtilis, or Staphylococcus aureus. This indicates that the
strain of bacteria has a significant effect on their bactericidal sensi-
Apart from the advantages resulting from the application of tivity or tolerance to oxidative stress, which has been confirmed
nanoparticles in environmental remediation, there is also a threat [107]. That phenomenon is highly important for generalization of
caused by the insufficiently elucidated toxicity of nZVI towards liv- the toxic effect of nZVI on microorganisms. However, research
ing organisms. The toxicity of nanoparticles can be caused by a shows that the potential undesirable changes caused to the compo-
variety of factors, largely convergent with those which are respon- sition of microbial populations under the effect of nZVI may revert
sible for their high reactivity. to the initial status after the termination of the purification [108]. In
In the literature, there is a relative scarcity of reports concern- addition, certain studies indicate that apart from the negative effect
ing the toxicity of nZVI. A majority of the studies [88,89] relate of nZVI on microorganisms, a positive effect can also be noted. Such
to nanomaterials based on carbon and oxides of metals. The avail- a positive effect of nZVI on microorganisms was observed by Shin
able information on nZVI is focused mainly on their effect on and Cha [91], who found that in the presence of nZVI, there was
microorganisms and, to a lesser extent, on crustaceans, fish larvae, an increase in the reduction of nitrates by microbial activity. Eco-
arthropods, annelids, plants, and occasionally mammalian cells. toxicological studies conducted by Němeček et al. on the basis of
The determination of the effect of nZVI is of particular importance tests with bacteria Vibrio fischeri and psychrophilic bacteria also
because of the increasingly popular use of those materials in the confirmed the absence of a negative effect of nZVI on the organisms
purification of waters and remediation of soils. Table 4 provides studied. In addition, the authors observed a stimulation of the
a compilation of available literature data concerning the effect of growth of Gram (+) bacteria in soils [109].
nZVI on various groups of organisms (microorganisms, aquatic
and soil organisms, plants and mammalian cells). 3.2. The impact of nZVI on aquatic and soil organisms
3.1. The impact of nZVI on microorganisms Studies of the effect of nZVI and modified nZVI on aquatic and
soil organisms are scarce in the literature. Heterocypris incongruens
Studies show that nZVI can be adsorbed on cell membranes of proved to be highly sensitive to the presence of nZVI stabilized
bacteria, or penetrate through them, which often leads to distur- with CMC, both in soil and in aquatic environments. As suggested
bances in the functioning of the cell [93]. Nanoparticles adsorbed by El-Temsah and Joner, the high toxicity of nZVI resulted from
on cell membranes can block cellular ducts, cause structural limited availability of oxygen in the studied environment, as that
changes to the membranes, or inhibit mobility and nutrient intake had been used for the processes of oxidation of nZVI [83]. Similar
and result in death of the bacteria [90]. Another cause of the neg- conclusions were arrived at by Chen et al. who studied the toxic
ative effect of nZVI on microorganisms is the formation, as a result effects of CMC–nZVI and the products of its oxidation in the pres-
of its oxidation, of reactive oxygen species (ROS) apart from iron ence of larvae of Oryzias latipes [96]. In addition, the authors noted
ions, according to the following reactions [93]: 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
Fe0 þ O2 þ 2Hþ ! Fe2þ þ H2 O2 ð8Þ nanoparticles on the reproduction and mortality of soil organisms
Folsomia candida is also attributed to the effect of noxious reactive
Fe0 þ H2 O2 ! Fe2þ þ 2OH ð9Þ 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
Fe2þ þ H2 O2 ! Fe3þ þ OH þ OH ð10Þ
elegans) was studied [97,110]. In the case of C. elegans, an absence
The ROS formed in that way may cause peroxidation of lipids and of mortality or an inhibition of growth of the test organisms was
damage to DNA [103,104], as well as the death of cells [105]. Studies noted, even at a dose of 17 g nZVI/kg of soil [110]. A negative effect
show that the application of polymer-based coatings or surfactants on reproduction, body mass and mortality was noted in relation to
on nZVI may reduce of the toxicity towards bacteria [86]. This is E. fetida and L. rubellus at nZVI-CMC concentrations above 100 mg/
related with minimization of the response of cells to oxidative kg of soil [97]. It should be noted, however, that such levels of nZVI
stress and a limitation of disturbances related with the functioning in soil are values that occur only during direct application of nZVI.
of cell membranes as compared to non-coated nZVI [106]. It should
be emphasized, however, that so far the studies that estimate the 3.3. The impact of nZVI on plants
toxicity of nZVI towards microorganisms were focused mainly on
Escherichia coli. Those bacteria are characterized by greater sensitiv- The evidence of the toxicity of nZVI towards plants is ambigu-
ity to the presence of Fe2+ and nZVI than Pseudomonas fluorescens, ous [86,98,99]. It is assumed that the phytotoxicity of nZVI, similar
Table 5
List of commercially available nZVI reported in the literatures [115,118–120].
Name of companies Location Type of nanoparticles Size of particles Surface area [m2/g] Price
Nano iron Czech Republic nZVI powder nZVI 20–100 nm 20–25 120 euro/kg – (powder) 25–65
suspension nZVI modified (suspension – 20% DM) euro/kg
Toda kogyo corp. Japan RNIP(mainly iron oxides) 100 nm 23 25–33 (powder) euro/kg
Polyflon USA, Florida nZVI powder 100–200 nm 37–58 N.A.
Gotthart Maier Metallpulver GmbH Germany mZVI powder (contains 0–80 lm N.A. 1.2 euro/kg
traces of other metals)
Toyo ink mfg. Co. Ltd Japan mZVI suspension 2 lm N.A. N.A.
MKnano Canada nZVI powder 25 nm N.A. 144 $/100 g
Sky spring Nanomaterials, Inc. USA, Houston nZVI powder 20 nm 40–60 337 $/100 g
40–60 nm 6–13 244 $/100 g
60–80 nm 7 215 $/100 g
Nanostructured & Amorphous Materials, Inc. USA, Houston nZVI powder 25 nm 40–60 330 $/100 g
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
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
Ok. 80%
50–99%
60–75%
90%
90%
90%
test
N.A.
N.A.
55 kg (0.2 g/l)
Dose of nZVI
150 kg
150 kg
2 t ZVI
300 kg
Cu(II)
N.A.
TCE
PCE
the level observed for other nanoparticles [112]. The reason for
nZVI, ZVI
nZVI
nZVI
nZVI
nZVI
Piasecna Czech
Lakehurst USA
Republic
Field-scale
Pilot-scale
N.A.
4. Practical application of nZVI in macro scale to estimate the effect of the nZVI injection on the geochemistry
of the matrix.
The effectiveness of nZVI in the elimination of various contam- Those parameters include e.g. the content of oxygen, nitrates
inants has been demonstrated successfully on the laboratory scale and sulfates, redox potential measurements, and the total content
[114]. Studies of this type mainly involve the performance of col- of Fe(II) and Fe0 [115]. Table 6 presents examples of pilot projects
umn tests, sedimentation tests, and batch tests [115]. conducted in real conditions, in which nZVI was used for the purifi-
The results of laboratory experiments, however, do not always cation of waters. Depending on the kind of nZVI used, or the type of
reflect the natural conditions in which the effectiveness of contaminant to be eliminated, the achieved effectiveness of con-
nanoparticles. For practical application of nZVI, it is necessary to taminant elimination varied from 40% to as much as 100%. In the
conduct experiments in real conditions. case of most of the pilot tests the changes in the level of contami-
In addition, practical application of nZVI requires prior consid- nants resulting from the application of nanoparticles constitute
eration of all possibilities, limitations, and threats which are insep- highly important information permitting the estimation of the
arably related with the application of nZVI. The potential benefits effectiveness of nZVI, but only in the test site. Comparison of pilot
of the use of nZVI in environmental remediation include increased tests is difficult because of the diversity of prevailing conditions at
effectiveness and efficiency of purification of soils or ground the test sites. The size of the remediation zone and the duration of
waters in comparison to macro iron particles used earlier. A dis- the remediation are also very important elements [6].
tinct difficulty in the practical application of nZVI is its insufficient The first pilot tests of the use of nZVI was conducted in the sum-
mobility in the environment. Research conducted by Elliot and mer of 2000 in Trenton (USA). For the purification of ground waters
Zhang showed that only 1.5% of nZVI introduced into ground water contaminated with, among other things, TCE, PCE, VC, and chloro-
reached the remediation location at the depth of 6 m [116]. There- form, 2.5 kg of modified Pd/nZVI was applied at concentration of
fore, from the practical point of view, it is necessary to increase the 1 g/l. After 4 weeks of remediation a 96.5% reduction of chloroor-
mobility of nZVI. That, however, causes certain environmental con- ganic contaminants was obtained [116]. In pilot tests, both normal
sequences. On one hand increased mobility of nZVI will reduce the nZVI and various modified nZVI were used.
possibility of controlling the nZVI (mobile particles can propagate Non-modified nZVI was also applied for the removal of Cu2+
more easily in the environment and more to undesirable locations) ions from industrial wastewaters [123]. In the final effect, apart
[81,117]. On the other hand, modification of nZVI increasing from the elimination of Cu2+, a composite composed of iron and
hydrophilicity will lead to increased or easier accumulation by copper was obtained (20–25%), and the copper could be recovered
organisms. during the recycling of the nZVI. The pilot tests demonstrated a
Another important aspect is the cost related with the applica- high elimination of chloroorganic compounds by modified nZVI
tion of nZVI to the environment and its availability on an industrial (CMC/nZVI, BnZVI, EZVI) [58,124–126].
scale. There are a lot of companies (Table 5) that are involved in the Good results obtained in pilot tests cause more and more
production of nZVI on a large scale. The companies differ from one attempts of water and soils remediation with full-scale application
another as to the kind of nZVI produced (mainly particle size and of nZVI. That is additionally facilitated by greater availability of
specific surface area), their form (suspension, powder), type of nZVI in industrial amounts.
modification and product price. Moreover, the suppliers of nZVI often provide also geotechnical
It is difficult to estimate the total costs of a technology involving services for the implementation of new methods of contaminant
the use of nZVI because it depends on numerous factors, e.g. the elimination [127]. At present large scale application of nZVI is used
kind of product, amount ordered, and costs of transportation. In primarily for the elimination of chloroorganic contaminants,
addition to the cost related with the purchase of nZVI, one should mainly from ground water (Table 6).
also account for the costs of additional laboratory and field exper- The literature shows that the largest number of both pilot and
iments, including hydrogeological and geochemical studies, and of full scale tests have been conducted in North America [128]. The
conducting a pilot test on a contaminated area [111]. This results US EPA (American Environmental Protection Agency) compiled a
from the fact that at a field scale there may exist additional factors list of 25 sites in the USA where nZVI was tested or applied on a
with significant effect on the transport and reactivity of nZVI, and large scale for soil remediation. The data show that in 56% of cases
thus on the effectiveness of its application [121]. The effect of dis- the load of contaminants was reduced (with a distinct decreasing
tribution, level of water resources, or the properties of under- trend of concentration by an average of ca. 70%). Non-modified
ground waters may have a significant importance for the nZVI was used most (40%), followed by bimetallic (32%), and emul-
migration of nZVI particles [27]. sified (16%) nZVI. The suspension concentration that was most fre-
A pilot study is the preliminary activity aimed at acquiring prac- quently applied was 8 g/l (in a range of 0.2–30 g/l) [115].
tical information necessary for conducting an efficient and effec- As an example, remediation of contaminated soils by of nZVI
tive process of remediation. It permits the determination of the was conducted in areas of US Navy installations, such as the Naval
amount of suspension required, mobility of the nZVI, time during Air Station (Jacksonville, FL) and the Naval Air Engineering Station
which the nZVI particles remain active, and a preliminary estimate near Lakehurst (NJ). Those areas were contaminated with 1,1,1-
of the expected reduction of contaminants. After such a prelimi- TCA, DCE, TCE, and PCE. During those studies it was observed that
nary study, the remediation work is conducted, which in the case if b-elimination of chlorine compounds takes place, the dehalo-
of purification of ground waters consists of the following stages: genation proceeds faster and smaller amounts of by products are
(1) installation of injection and monitoring wells, (2) analysis of produced. It was also noted that to ensure optimum remediation
samples of underground waters collected from the wells, (3) dos- conditions iron should be applied at the weight ratio of 0.004 to
ing of nZVI with simultaneous monitoring of parameters of the the mass of the soil being remediated, and the injection of nZVI
environment (e.g. pH, temperature, injection pressure, rate of flow should be conducted with the minimum use of water which con-
of solutions of reactive particles, concentration of iron suspension), tains large amounts of oxidants and causes the passivation of iron
and (4) analysis of samples of underground waters after the appli- [129].
cation of nZVI solution to estimate the effectiveness of the opera- In Europe nZVI was applied for the first time in 2007 for full
tion [122]. Apart from the monitoring of those parameters and of scale elimination of chloroorganic contaminants, in Bornheim
the level of contaminants, analysis of other factors is conducted (Germany). The area was contaminated with PCE from the aero-
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