w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2

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Review

Magnetic nanoparticles: Essential factors for sustainable

environmental applications

Samuel C.N. Tang, Irene M.C. Lo*

Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Hong Kong, China

article info abstract

Article history: In recent years, there has been an increasing use of engineered magnetic nanoparticles for
Received 9 November 2012 remediation and water treatments, leading to elevated public concerns. To this end, it is
Received in revised form necessary to enhance the understanding of how these magnetic nanoparticles react with
6 February 2013 contaminants and interact with the surrounding environment during applications. This
Accepted 8 February 2013 review aims to provide a holistic overview of current knowledge of magnetic nanoparticles
Available online 4 March 2013 in environmental applications, emphasizing studies of zero-valent iron (nZVI), magnetite
(Fe3O4) and maghemite (g-Fe2O3) nanoparticles. Contaminant removal mechanisms by
Keywords: magnetic nanoparticles are presented, along with factors affecting the ability of contam-
Maghemite inant desorption. Factors influencing the recovery of magnetic nanoparticles are outlined,
Magnetic describing the challenges of magnetic particle collection. The aggregation of magnetic
Magnetite nanoparticles is described, and methods for enhancing stability are summarized. More-
Nanoparticles over, the toxicological effects owing to magnetic nanoparticles are discussed. It is possible
Remediation that magnetic nanoparticles can be applied sustainably after detailed consideration of
Zero-valent iron these discussed factors.
2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2614
2. Removal of contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2615
2.1. Contaminants removal by nZVI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2615
2.2. Contaminants removal by Fe3O4 and g-Fe2O3 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2615
2.3. Effects of environmental conditions on contaminant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2616
2.4. Effects of surface properties of magnetic nanoparticles on contaminant removal . . . . . . . . . . . . . . . . . . . . . . . . . 2617
3. Desorption of contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2617
3.1. Desorption from Fe3O4 and g-Fe2O3 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2620
3.2. Regeneration of nZVI? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2620
3.3. Desorption of contaminants in the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2621
4. Recovery of magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2621
4.1. Forces acting on magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2621

* Corresponding author. Tel.: 852 2358 7157; fax: 852 2358 1534.
E-mail address: cemclo@ust.hk (I.M.C. Lo).
0043-1354/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.watres.2013.02.039
2614 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2

4.2. Better recovery of magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2622

4.3. Questions in magnetic nanoparticles recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2622
5. Aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2623
5.1. Particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2623
5.2. Particle concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2623
5.3. Forces governing aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2623
5.4. Stabilize magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2623
5.5. Trade off between stability and reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2624
6. Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2624
6.1. Size and shape of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2625
6.2. Surface properties of magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2625
6.3. Nanoparticle concentration related to toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2626
6.4. Type of bacterial cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2626
6.5. Phytotoxicity of magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2626
6.6. Current limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2627
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2627
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2627
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2627

1. Introduction performance, some researchers demonstrated the feasibility

In recent decades, various environmental challenges have
been mitigated due to a boom in nanotechnologies and
nanomaterials development. Nanoparticles have been widely
used in environmental applications and have shown prom-
ising performance in pollutant removal or toxicity mitigation
(Gavaskar et al., 2005; Tratnyek and Johnson, 2006). Among the
most widely used nanoparticles, magnetic nanoparticles,
mainly nano zero-valent iron (nZVI), magnetite (Fe3O4) and
maghemite (g-Fe2O3) nanoparticles, have sparked an
immense interest in research for engineering applications for
treatment of polluted water or subsurface environments (Hu
et al., 2004, 2005a,b; Li et al., 2006a,b; Shen et al., 2009;
Yantasee et al., 2007). One of the most famous examples is the
injection of nZVI into subsurface forming reactive treatment
zones (Gavaskar et al., 2005; Grieger et al., 2010). Heavy metals
such as arsenic and chromium, and organic pollutants like
chlorinated solvents, can be immobilized or reduced to less
toxic species by nZVI. The effectiveness of nZVI is not just
limited to laboratory findings. Many companies working on
the manufacturing of nZVI and its application for environ-
mental remediation have been established (Mueller et al.,
2012). In the U.S., numerous practical experience of site
remediation using nZVI has been reported (Comba et al., 2011;
Su et al., 2012). In Europe, although only three full scale ap-
plications were reported, there were many pilot test projects
with the application of nZVI for various contaminants
(Mueller et al., 2012). According to a case specific cost com-
parison of pump and treat, permeable reactive barrier and
nZVI technology on a site in New Jersey, it was estimated that
the cost for treating TCE and PCE with the application of nZVI
was far lower than the other two technologies (PARS
Environmental, 2013).
Moreover, a number of studies have also shown applica-
tion of Fe3O4 and g-Fe2O3 nanoparticles on heavy metals
removal from contaminated water (Hu et al., 2005a,b; Hu et al.,
2006; Xu et al., 2012). In addition to the great removal
of reusing magnetic nanoparticles by desorbing the contami-
nants and regaining the removal capacity in successive
treatment cycles (Hao et al., 2010; Hu et al., 2005a,b; Hu et al.,
2005a,b). However, there are numerous conditions influencing
the applicability of magnetic nanoparticles in a sustainable
treatment process.
These magnetic nanoparticles not only have a large
removal capacity, fast kinetics and high reactivity for
contaminant removal due to their extremely small particle
size and high surface-area-to-volume ratio, but also one more
important property, magnetism. This is a useful property for
water and wastewater treatment systems. The high reactivity
of the magnetic nanoparticles for pollutant removal, a
compact and efficient water or wastewater treatment system
can take advantage of this. It is expected that magnetic sep-
aration could be a more cost effective and convenient method
for separating such tiny particles than sophisticated mem-
brane filtration. Separation of magnetic nanoparticles from
solution with a low-gradient magnetic field or a hand-held
magnet has been frequently reported (Hu et al., 2004, 2007a;
Yantasee et al., 2007). However, although ample experimental
photographic results elsewhere (Bhaumik et al., 2011; Do et al.,
2011; Li et al., 2010a,b; Liu et al., 2010; Shin et al., 2011; Zhang
and Kong, 2011) showed the feasibility of separation and re-
covery of magnetic nanoparticles from water or wastewater,
no successful real applications of magnetic particles for water
or wastewater treatment have yet been reported. On top of the
high surface free energy, the magnetism of nanoparticles has
been suspected to enhance the aggregation of nanoparticles
and reduce the removal capacity (Petosa et al., 2010; Phenrat
et al., 2009a), so become a great hindrance to recover and
reuse magnetic nanoparticles.
Additionally, with extensive use of nanoparticles for a wide
spectrum of applications such as energy, electronics, and
personal care products, nanoparticles have been released to
the environment, heightening concern about the safety and
toxicity of nanoparticles (Borm et al., 2006; Brar et al., 2010;
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
Holsapple et al., 2005; Moore, 2006; Tsuji et al., 2006). Although
nanoparticles occur in nature, such as those originating from
volcanoes and combustion, artificially produced and released
engineered nanoparticles have been of a comparatively
tremendous amount (Hendren et al., 2011; Posner, 2009),
threatening natural environments and wastewater treatment
systems (Brar et al., 2010). Considering the direct applications
of these magnetic nanoparticles in the treatment technolo-
gies, their release into the environment is inevitable, hence
the assessment of their toxicity is of vital importance (Moore,
2006). To widely and wisely apply magnetic nanoparticles in
subsurface and water treatment processes, several major
concerns require further exploration.
In this article, influencing factors and mechanisms of
contaminant removal by magnetic nanoparticles are
reviewed, since their removal performance and associated
factors are the major considerations. To reduce the treatment
cost, the feasibility of reuse and recovery of magnetic nano-
particles are also discussed. In addition, concerns such as
their aggregation affecting capacity and reactivity as well as
their toxicity, are also addressed.
2. Removal of contaminants
The most popular magnetic nanoparticles are iron-based
nanoparticles, namely nZVI, Fe3O4 and g-Fe2O3. These nano-
particles are iron-based, but possess different chemical
properties originating from the oxidation states of iron. Their
capability and reactivity for contaminant removal are
different. Yet, the removal performance can be influenced by
various conditions, depending on the removal mechanisms
(Fig. 1). Knowing the removal mechanisms of these magnetic
nanoparticles can justify the applicability of them in envi-
ronmental applications.
2.1. Contaminants removal by nZVI
A number of laboratory studies and site application of nZVI
have shown that it is an effective remediation technology.
Since iron is a strong reducing agent, the strong reducing
property of nZVI brings about a degradation of wide range of
organic and inorganic pollutants. In particular, chlorinated
solvents, commonly found contaminants, can be degraded
through dechlorination to less harmful substances. The
reductive degradation rate increases dramatically compared
to the micro-sized counterparts (Wang and Zhang, 1997).
Numerous studies even showed that some persistence con-
taminants, such as polycyclic aromatic hydrocarbons (PAHs)
and pesticides, can be effectively degraded with highly reac-
tive nZVI (Chang and Kang, 2009; Li et al., 2006a,b). In addition,
surface sorption and co-precipitation of contaminants, espe-
cially heavy metals, also occur due to the formation of an iron
oxides/hydroxides shell when nZVI contacts with air or water.
This has been reported elsewhere and Cr(VI) is a widely-
studied example (Fang et al., 2011; Giasuddin et al., 2007;
Scott et al., 2011; Zhang, 2003). Previous studies demonstrated
that Cr(VI) can be reduced by nZVI, forming precipitates with
corrosion products. Furthermore, there are variations in nZVI
properties with different synthetic processes and coating. To
2615
Fig. 1 e Schematic model of magnetic nanoparticles (nZVI,
Fe3O4 and g-Fe2O3). Zero-valent iron in the core mainly
provides the reducing power for reactions with
contaminants. The oxide shell provides sites for sorption.
Adsorption is also occurred on the iron oxides (Fe3O4 and
g-Fe2O3) surface, while Fe3O4 possess reducing power.
date, nZVI is usually produced through reductive precipitation
of FeCl3 with NaBH4, or reduction of goethite and hematite
particles with H2 at high temperatures (200e600  C). Other
methods were mentioned by researchers (Crane and Scott,
2012). Preparation methods can greatly affect the removal
reactivity because of differences in iron phase, particle size
and shape (Liu et al., 2005; Nurmi et al., 2005). These studies
demonstrated that the reactivity of nZVI prepared by reduc-
tive precipitation of FeCl3 with NaBH4 was higher because of
its smaller particle size and larger surface area. Higher iron
content was also reported, resulting in rapid degradation of
pollutants (Liu et al., 2005; Nurmi et al., 2005). However, the
high reactivity of nZVI is a possible drawback for in-situ ap-
plications. It is because before reaching target pollutants,
reactive nZVI may react or be oxidized in water with dissolved
air, resulting in low longevity. When oxygen is present, nZVI is
easily oxidized to Fe2 and/or Fe3 ions. The conversion of
Fe2 to Fe3 is dominant under acidic and oxygenated envi-
ronments. The oxidation of nZVI in the presence of water can
also result in the production of hydrogen. Therefore, providing
surface coatings like a thin layer of Fe3O4 (Liu et al., 2005),
silica (Tang et al., 2006) or polymers (Wilson et al., 2004) could
alleviate this problem by reducing contact with oxygen,
thereby retaining the reactivity of nZVI. Addition of catalytic
metals (e.g., Pd, Pt, Ni) was also suggested for stabilizing nZVI
(Gunawardana et al., 2011). For in-situ remediation, the nZVI
slurry was prepared under a protected inert atmosphere. The
water for slurry preparation was also purged with inert gas,
usually nitrogen, before use (Elliott and Zhang, 2001).
2.2. Contaminants removal by Fe3O4 and g-Fe2O3
nanoparticles
For Fe3O4 nanoparticle, both physical and chemical adsorp-
tions of heavy metal were reported (Hu et al., 2004). In the
study of the removal of Cr(VI) with Fe3O4 nanoparticles (Hu
2616 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
et al., 2004), it was found that the crystalline structure of
FeCr2O4 on the surface of the nanoparticles was due to the
reduction of Cr(VI) to Cr(III), and the subsequent surface pre-
cipitation of Cr(III) onto the magnetic nanoparticles (Fig. 2).
This was also evidenced by the significantly low desorption
at high pH, indicative of chemical adsorption, while the ability
of desorption was attributed to physical adsorption. However,
the major contaminant removal mechanism of g-Fe2O3
nanoparticles is physical adsorption, without chemical
adsorption like Fe3O4 nanoparticles. The removal mechanism
was further revealed with spectroscopic studies, such as X-ray
photoelectron spectroscopy (XPS) and X-ray diffraction (XRD).
The crystallite structure of g-Fe2O3 nanoparticles did not
change after the pollutants were removed, indicating that the
removal mechanism did not involve chemical reactions (Hu
et al., 2005a,b). The pollutant removal by g-Fe2O3 nano-
particles has been recognized to be resulted from electrostatic
interactions. Oxygen atoms on the surface of iron oxides
(Fe3O4 and g-Fe2O3) can be polarized under various pH values.
Particularly, when the pH value is below the zero point of
charge (pHZPC), the surface of the iron oxides possesses posi-
tive charges, attracting negatively charged pollutants (e.g.,
Cr(VI) and As(V)) (Chowdhury and Yanful, 2010; Hu et al.,
2007b; Yean et al., 2005). It is evident that the removal per-
formance of Fe3O4 and g-Fe2O3 nanoparticles was highly pH
dependent (Hu et al., 2004, 2007b; Yang et al., 2010; Yantasee
et al., 2007). Since electrostatic attraction is a weak
Fig. 2 e XPS (a) and XRD (b) images of Fe3O4 nanoparticles
after Cr(VI) adsorption, indicative of chemisorption and
incorporation of Cr onto Fe3O4 (Hu et al., 2004).
interaction compared with chemical adsorption, environ-
mental conditions, especially pH values, dramatically affect
the removal performance. A charged nanoparticle surface is
preferred for the removal of charged contaminants. Ion ex-
change was also proposed to elucidate the removal mecha-
nism. Hu et al. (2005a,b) demonstrated that Cr(VI) was also
removed when the solution pH was higher than the pHZPC of
g-Fe2O3 nanoparticles. The negative charges on hydroxylated
iron oxide surface can exchange with Cr(VI) for adsorption.
Although the pollutant removal is based on the mecha-
nisms discussed, environmental conditions that may alter
magnetic nanoparticles performance include background
ions, humic substances, and pH. The aquatic chemistry and
groundwater composition vary from site to site. The strategic
deployment of magnetic nanoparticles must consider various
operational parameters. When magnetic nanoparticles are
applied to wastewater treatment, high ionic strength and
extreme pH are usually concerned. The variables of the
properties of magnetic nanoparticles are also discussed
below.
2.3. Effects of environmental conditions on contaminant
removal
In real engineering applications, magnetic nanoparticles face
a complex environment, teeming with a wide spectrum of
dissolved organic and inorganic compounds. Since electro-
static interaction has been proven to be one of the major
removal mechanisms of magnetic nanoparticles, studies to
date have usually taken background electrolytes into account
for determination of removal performance (Chowdhury and
Yanful, 2010; Hu et al., 2004, 2005a,b; Yang et al., 2010).
These researchers reported that the background electrolytes
insignificantly affected the removal performance, when the
affinity of pollutants to the nanoparticles was higher than that
of background electrolytes. For example, chloride and nitrate
(100 mg/L) did not affect Cr(VI) removal by maghemite nano-
particles (Hu et al., 2005a,b); the background electrolytes in
groundwater did not significantly affect As(V) removal by
magnetite and maghemite nanoparticles (Chowdhury and
Yanful, 2010). However, some researchers found that partic-
ular ions competed with target pollutants. One of the widely
studied heavy metals, arsenic, is a good example. Although
As(V) exists as anions in a normal aquatic environment, some
common anions, such as sulphate and chloride, showed little
effect on the removal of As(V) (Biterna et al., 2007; Chowdhury
and Yanful, 2010; Sun et al., 2006). Competition of phosphate
was clearly demonstrated in previous studies (Chowdhury
and Yanful, 2010; Dong et al., 2012), which was probably due
to the similar molecular structure and properties under the
same group in the periodic table.
Other researchers also found that natural organic matters
(NOM), like humic acid, influenced removal performance,
causing lower capacity and slower kinetics (Chen et al., 2011;
Giasuddin et al., 2007; Liu et al., 2008), due to the occupancy of
sorption sites by humic acid, and the formation of the disor-
dered structure of the humic acid layer on the surface of
nanoparticles. On the other hand, an enhancement of As(V)
removal was reported with the addition of Zn(II). In this case, a
ternary surface complex formation was proposed to be the
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
mechanism (Yang et al., 2010). More studies are still required
to reveal the whole picture.
Even though the pH value of the natural environment is
considerably steady, pH values of industrial wastewater alter a
lot. Since pH value dramatically affects the reduction of nZVI and
adsorption performance of Fe3O4 and g-Fe2O3 nanoparticles,
various approaches have been applied to magnetic nano-
particles to alleviate these influences. Coating with organic
surfactants or polymers is one of the methods for changing the
surface properties of magnetic nanoparticles (Ge et al., 2012; Hao
et al., 2010; Hu et al., 2011; Huang and Chen, 2009). The removal
mechanism still remains electrostatic interaction regarding the
surface modifications as discussed in the section below. On the
contrary, Hu et al. (2006) suggested another way to make use of
the surface property of magnetic nanoparticles, moving from
limitation to opportunity. In industrial wastewater, various
heavy metals usually co-exist and make the composition more
complicated than synthetic solutions in laboratory. An effective
treatment with magnetic nanoparticles was experimented by
changing the pH values, so that the surface charge of the mag-
netic nanoparticles was manipulated for adsorption anions (i.e.,
Cr(VI)) and cations (i.e., Cu(II) and Ni(II)) selectively with specific
pH values. The optimal pH for selective removal of Cr, Cu, and Ni
was determined to be 2.5, 6.5, and 8.5, respectively. Thus, these
useful heavy metals can be separated and recovered by a simple
process with magnetic nanoparticles by alternating pH values
(Hu et al., 2006).
2.4. Effects of surface properties of magnetic
nanoparticles on contaminant removal
The large contaminants removal capacity and fast reaction
rate of the magnetic nanoparticles are the major advantages.
The total surface area of particles with the same mass in-
creases tremendously (can up to a thousand times), when the
particle size decreases to nano-scale (Tratnyek and Johnson,
2006). Due to the high surface-area-to-volume ratio, thus in-
crease of active sites for the reaction, the mass required for
treatment processes can be less than the case using the
micron-sized counterparts. Various studies showed that the
removal capacity and reactivity of nanoparticles are highly
size dependent (Nurmi et al., 2005; Rivero-Huguet and
Marshall, 2009; Yean et al., 2005). Shen et al. (2009) reported
that the removal capacity of Fe3O4 nanoparticles (8 nm) was
about seven times higher than that of coarse-grained coun-
terparts (50 mm). The reactivity of ZVI was found to be 50e90
times higher when the particle size was reduced from around
500 to 100 nm (Lin et al., 2008). Although the capacity increases
with decreasing particle size, some researchers reported that
the removal capacity normalized by surface area is not much
different when the particle size changes (Tratnyek and
Johnson, 2006; Yean et al., 2005). This is because all physical
or chemical reactions occur at the liquidesolid interface. To
increase the surface area, synthesizing smaller particles
seems to be a way to produce an effective treatment tool.
Indeed, despite the large capacity and high reactivity origi-
nating from the small particle size, it has been found that the
smaller the particles are, the higher the tendency of aggre-
gation stemming from a high surface free energy, which re-
duces the removal capacity and reactivity (Hao et al., 2010; Li
2617
et al., 2006a,b). The applicability of smaller particles related
to possibility of aggregation of magnetic nanoparticles is dis-
cussed in another section.
Considering the fact that the removal capacity and reac-
tivity of magnetic nanoparticles is highly surface area
dependent, an alternative method for providing larger surface
area is engineering a porous structure, such as activated car-
bon (Jiao et al., 2006). It was demonstrated by Wang and Lo
(2009) that mesoporous g-Fe2O3 particles with around
200 nm were synthesized and applied for Cr(VI) removal. The
surface area of mesoporous g-Fe2O3 particles, and the result-
ing removal capacity and reactivity, was comparable to that of
g-Fe2O3 nanoparticles (10 nm). But its large particle size
showed a greater potential for magnetic separation than g-
Fe2O3 nanoparticles. However, the synthesis of mesoporous
structure was much more complicated, and the improvement
on the removal capacity was still limited.
Studies to date have mostly focused on the removal perfor-
mance of magnetic nanoparticles, and impressive percentage
results (e.g., 98% removal) have usually been reported. However,
more attention should be paid to the experimental conditions for
reflecting the real situation. The removal performance may be
overestimated if just focusing on reporting percentage (Gupta
et al., 2012; Hao et al., 2010). The experimental conditions
require more thorough consideration to reflect the actual situ-
ation precisely. Parameters, such as dosage of nanoparticles,
concentration of pollutants or other electrolytes, should be
carefully decided. For example, a competition effect of other
contaminants may be studied with a corresponding equivalent
concentration of the target pollutant. This is also related to the
mechanism of removal and capacity of the nanoparticles. If the
applied nanoparticles offer a removal capacity that is far beyond
the saturation limit for the target pollutants, the competition
effect could not be concluded.
As mentioned above, different mechanisms are involved in
the contaminant removal by different magnetic nano-
particles. The removal performance is considerably related to
the surface properties of the magnetic nanoparticles. In gen-
eral, contaminants can be removed by g-Fe2O3 and Fe3O4
nanoparticles via physical adsorption, so the desorption of
contaminants and regeneration of nanoparticles are feasible.
However, relatively irreversible chemical adsorption for Fe3O4
nanoparticles, and chemical reduction and coprecipitation for
nZVI were also reported. The recent findings on contaminant
removal are summarized in Table 1.
3. Desorption of contaminants
When considering the applicability of magnetic nanoparticles
for treatment technologies, another major consideration is
the reusability of magnetic nanoparticles. To maintain reac-
tivity, physical and chemical properties of the nanoparticle
products, the synthesis and manufacturing process of nano-
particles require meticulous control of conditions. The treat-
ment cost of applying nanoparticles is relatively high,
compared with traditional treatments. For instance, the price
of 1 kg of g-Fe2O3 nanoparticles is ranging from USD 180 to 380,
depending on the particle size, purity and methods of syn-
thesis (MKnano, 2012; NANOSHEL, 2012; SkySpring
 2618
Table 1 e Magnetic nanoparticles for contaminant removal.
MNPsa Db (nm) SAc (m2/g) pHZPC Surface coating Target Cd Key findings Ref.e
contaminants

nZVI 10e90 25 e Amphiphilic TCE 1.5e3 g/L 89% removal of 30 mg/L TCE; Krajangpan
polysiloxane TCE degradation rate with et al., 2012
graft copolymer APGC-coated nZVI was
(APGC) comparable to bare nZVI;
Chemical reactivity of
APGC-coated nZVI
remained for 6 months
nZVI w50 e e e TCE 1 g/L The presence of Suwanneee Chen et al., 2011
River humic acid reduced the
reactivity towards TCE and
mitigated toxicity of nZVI
nZVI 50e100 33.5  4.2 e e Cu(II), Pb(II), 2.5 g/L Cu(II) enhanced the TCE Lien et al., 2007
As(V), dechlorination;

w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
Cr(VI), TCE Cr(VI) decreased the TCE
dechlorination rate
nZVI w100 8.1  0.1 Iron oxides NO
3 1.42 g/L Iron oxides coating protected Sohn et al., 2006
the inner ZVI from further
corrosion and thus maintained
reactivity
nZVI with 20e40 35 e Iron oxides Cr(VI) 0.1e0.6 g/L 99.9% removal of 50 mg/L Cr(VI) Fang et al., 2011
Ni (0.011%) at pH 4.82 with 0.6 g/L nZVI;
and Zn (0.002%) Maximum removal
capacity 182  2 mg/g;
The presence of Ni and Zn
improved removal efficiency
nZVI 20e100 14.8 e e U(VI) 0.25 g/L nZVI removed >98% of U Crane et al., 2011
Fe3O4 20e50 52.5 e e to <10 mg/L, but Fe3O4 failed
to achieve >20% U
removal;
U re-release was observed in
solution treated with nZVI
due to the presence
of ligands (carbonate)
Fe3O4 6e10 4.5f; Succinic acid (SA); Cr(III), Co(II), 1.25 g/L Metal ions were captured Singh et al., 2011
4.7g; Ethylenediamine (EDA); Ni(II), Cu(II), by forming chelate complexes
veh 2,3-dimercaptosuccinic Cd(II), Pb(II), or ion exchange process or
acid (DMSA) As(III) electrostatic interaction,
depending on the surface
functionality;
All metal ions showed 80e85% of
desorption ratio using 0.1 M HCl
Fe3O4 w5 178.48 e Ascorbic acid As(V), As(III) 60 mg/L Maximum removal Feng et al., 2012
capacity 16.56 mg/g for As(V);
46.06 mg/g for As(III) at pH 7
and 300 K
Fe3O4 w10 62; 6; Humic acid (HA) Hg(II), Pb(II), 100 mg/L HA coated Fe3O4 was able to Liu et al., 2008
64 (with HA) 2.3 (with HA) Cd(II), Cu(II) remove >99% of Hg(II) and Pb(II),
and >95% of Cu(II) and Cd(II) in
natural and tap water with 1 mg/L
of metal ions at wpH 7;
The presence of Ca2 and PO3 4 had
no effect on the sorption of
heavy metals
Fe3O4 10 198 8.3 e Cr(VI) 5 g/L Cr(VI) removal was governed by Hu et al., 2004
physico-chemical adsorption;
The adsorption process was pH and
temperature dependent
Fe3O4 and g-Fe2O3 20e40 49 e e As(V), As(III), 0.4 g/L Maximum removal Chowdhury and
Cr(VI) capacity 3.71 mg/g for As(V); Yanful, 2010
3.69 mg/g for As(III) at pH 2;
2.4 mg/g for Cr(VI) at pH 2;
The presence of phosphate reduced

w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
the removal of As and Cr
g-Fe2O3 10 198 6.3 e Cr(VI), Cu(II), 5 g/L Metals can be selectively removed Hu et al., 2006
Ni(II) from wastewater depending on pH;
Metal removal capacity of g-Fe2O3
can be regenerated by 0.05 M HCl or
0.01 M NaOH
g-Fe2O3 10 178 6.3 e Cr(VI) 5 g/L 19.2 mg/g for Cr(VI) at pH 2e3 and 298 K; Hu et al., 2005a
Competition from common coexisting
ions such as Na, Ca2, Mg2, Cu2,
Ni2, NO 
3 , and Cl was ignorable
g-Fe2O3 15 120e180 8.5 d-FeOOH Cr(VI) 5 g/L 25.8 mg/g for Cr(VI), which is higher Hu et al., 2007b
than that of pure g-Fe2O3 (19.4 mg/g);
The nanoparticles can be regenerated
by 0.01 M NaOH

a MNPs Magnetic nanoparticles.

b D particles size.
c SA surface area.
d C Particle concentration.
e Ref. Reference.
f Fe3O4 nanoparticles coated with SA.
g Fe3O4 nanoparticles coated with EDA.
h Fe3O4 nanoparticles coated with DMSA possessing negatively charged in the studied pH range.

2619
2620 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2

60

Fraction of desorbed As (%)

pH=9

Relative desorbed As (%)

pH=5 pH=7
50

40 phosphate=0.5 mg/L (as P)

phosphate=1.0 mg/L (as P)
30 phosphate=3.0 mg/L (as P)

20

10

0
5 10 20 5 10 20 5 10 20
Initial As(V) concentration (mg/L) Initial As(V) concentration (mg/L) Initial As(V) concentration (mg/L)

Fig. 3 e Fraction of desorbed As from As(V)-sorbed-nZVI as induced by phosphate of various concentrations (Dong et al.,
2012).

Nanomaterials, 2012). Reuse of nanoparticles would substan-
tially reduce the treatment cost. Regeneration is a common
practice to regain the removal capacity of adsorbents, whilst
feasibility of regeneration of magnetic nanoparticles is closely
related to their removal mechanism.
3.1. Desorption from Fe3O4 and g-Fe2O3 nanoparticles
Although the pollutant removal mechanism of Fe3O4 nano-
particles involves physical and chemical adsorption in which
chemical bonding formation limits the regeneration of nano-
particles, various approaches have been adopted for devel-
oping reusable magnetic nanoparticles, for instance, surface
coating with organic functionalized surfactants (Badruddoza
et al., 2011; Bhaumik et al., 2011), humic acid (Liu et al.,
2008), and silicate (Fan et al., 2012; Hakami et al., 2012).
These coatings prevent the magnetic core, Fe3O4 nano-
particles, from chemical adsorption and redox reaction to
form non-magnetic minerals (e.g., a-Fe2O3), thus maintaining
magnetism. In addition, the surface coatings usually possess
specialized functional groups for adsorption of target pollut-
ants. Taking Hg removal as an example, Hakami et al. (2012)
prepared Fe3O4 nanoparticles functionalized with thiol
groups by adding (3-mercaptopropyl) trimethoxysilane on
silica-coating. According to the Pearsons hard-soft acids-
bases theory (Pearson, 1968), the sulfur atoms in thiol moieties
served as ligands to bind with soft metal cations like Hg. Due
to the increase of binding sites provided by the surface
coating, the removal capacity and affinity of the magnetic
nanoparticles were massively improved. This was also sup-
ported by findings from another research group (Yantasee
et al., 2007). The reported approach of desorption was also
different from simply using acid or alkaline, particularly
considering the property of ligands, and interaction between
ligands and pollutants to promote the desorption process.
Eventually, adopting the hard-soft acids-bases theory, thio-
urea was added to facilitate desorption of Hg because of the
presence of sulfur atoms. Moreover, amino moieties were re-
ported as having a novel capability for sorption of metal cat-
ions and anions under various pH values, derived from
positive charges after protonation or coordination with lone
pair of electrons of nitrogen atoms without protonation (Hu
et al., 2011; Huang and Chen, 2009). This property has impor-
tant implications for developing magnetic nanoparticles with
an ability for regeneration by alternating pH.
Another approach to endow with the ability of regeneration
and maintain the magnetism of nanoparticles is to oxidize Fe3O4
to g-Fe2O3 delicately under well controlled conditions. Since the
removal mechanism by g-Fe2O3 nanoparticles has been deter-
mined to be electrostatic interactions (Hu et al., 2005a,b; Hu
et al., 2006) and g-Fe2O3 is a chemically stable form of iron
oxide, the adsorbed pollutants can be desorbed by changing the
pH, and thus the surface charges. The most important param-
eter to be determined is the pHZPC of the g-Fe2O3 nanoparticles.
Numerous studies (Afkhami and Moosavi, 2010; Hao et al., 2010;
Hu et al., 2005a,b; Hu et al., 2006) supported that simple inorganic
acid or alkaline can be applied for effective regeneration of g-
Fe2O3 nanoparticles, and for surface modified g-Fe2O3 nano-
particles (Bee et al., 2011). This process not only can regenerate
the exhausted magnetic nanoparticles and restore the removal
capacity, but also recover valuable components, like heavy
metals, useful in many industrial processes, from the adsorbed
phase. Hu et al. (2006) demonstrated that heavy metals can be
separated and recovered selectivity from a complex solution
with a careful pH adjustment.
Although the ability of g-Fe2O3 nanoparticles was proven to
be regenerated and reused for successive treatment cycles,
the stability of the magnetic nanoparticles has to be taken into
consideration (Ge et al., 2012; Liu et al., 2008; Yantasee et al.,
2007). Acid have been suggested for regeneration in
numerous studies, while acid and alkaline can also enhance
the dissolution of magnetic nanoparticles, especially in HCl
and HNO3, hence diminishing the reusability of magnetic
nanoparticles. One should note that desorption of contami-
nants with strong acid or alkaline may lead to nanoparticle
dissolution (Yantasee et al., 2007).
3.2. Regeneration of nZVI?
Although regenerating nanoparticles through the desorption of
pollutants is one of the crucial considerations of practicability,
nZVI can hardly be regenerated because of its irreversible
reductive property. Pollutants such as Cr(VI) are reduced, co-
precipitated or sorbed on the nZVI, specifically the iron oxide
layer, indicating that desorption of the pollutants may require
disruption of the chemical structure (Fang et al., 2011; Li et al.,
2006a,b; Scott et al., 2011). This depends on the stability and
solubility of the compounds, and the presence of ligands. Dong
et al. (2012) found that the adsorbed As(V) on nZVI was further
sorbed onto the crystalline structure of iron oxyhydroxides
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
with aging time, and thus became more strongly bonded.
However, Sohn et al. (2006) suggested that nZVI can be reused
several times, and the removal performance maintained. The
nZVI particles were used for six cycles of nitrate reduction with
successive complete removal. During the consecutive re-
ductions, transformation of nZVI particles occurred, and the
size of the iron core reduced, indicating a decreasing lifespan of
the nZVI particles. Actually, the reactivity of nZVI may not be
exhausted after reaction, but passivated by the iron oxide layer
formed (Liu et al., 2005). The iron oxide layer blocks electron
transfer from the iron core. The reactivity can even be exploited
and enhanced by acid-washed to disrupt the iron oxide
passivation layer (Sun et al., 2011).
3.3. Desorption of contaminants in the environment
Using magnetic nanoparticles for contaminant removal was
proven to be a highly efficient technology, but most of the
results were based on conditions with simple synthetic solu-
tions, usually containing only one target pollutant. Desorption
is desirable for controlled applications like wastewater treat-
ment. But this can lead to a disaster of pollutant migration and
spreading out if desorption occurs when the spent magnetic
nanoparticles are released into the environment. Studies
showed that uranium can be re-oxidized (Dickinson and Scott,
2010) or chemically complexed with ligands like carbonate
(Crane et al., 2011), resulting in the increase of solubility and
re-release of uranium. Desorption of arsenic was also reported
(Dong et al., 2012; Jackson and Miller, 2000; Peryea, 1991; Yin
et al., 2012) offering the possibility that phosphate and hy-
droxide anions had the greatest competition effects for the
sorption sites (Fig. 3). Indeed, Nordstrom (2002) pointed out
that high concentrations of phosphate, bicarbonate, silicate,
and/or organic matter in groundwater can enhance the solu-
bility of arsenic. Leaching and remobilizing of chromium by
low pH condition and presence of competition anions like
phosphate (Jing et al., 2006; Mandiwana, 2008) were also
demonstrated. And it was reported that humic acid exerted an
influence on the removal of heavy metals because of an
enhancement in solubility and mobility of heavy metals by
complexation (Dries et al., 2005; Liu and Lo, 2011; Mak et al.,
2011). Since heavy metals can only be immobilized or trans-
formed to less harmful states, but not degraded like organic
contaminants, the migration or remobilization of heavy
metals is intractable, crucially depending on the environ-
mental conditions. The mechanism of heavy metal re-release
was attributed to complexation or competition of other con-
stituents in natural waters. Site characteristics should not be
overlooked, especially the pH and the high concentration of
particular dissolved ions and NOM. As a result, the magnetic
nanoparticles with different coatings and functionalizations,
showing various reactivity and surface properties, should be
tested under site-specific conditions before application.
4. Recovery of magnetic nanoparticles
One of the most fascinating characteristics of magnetic
nanoparticles, showing advantage over other nanoparticles, is
their magnetism. Abundant evidence showed that magnetic
2621
properties of particles alter when particle size reaches nano-
scale (Sundaresan and Rao, 2009). In particular, the magnetic
property of Fe3O4 and g-Fe2O3 changed from ferromagnetic to
superparamagnetic (Chatterjee et al., 2003). This property of-
fers an encouraging option, satisfying requirements of high
accessibility as well as reusability. Most water or wastewater
treatment systems require a settling, filtration or centrifuge
process to separate solids like sludge. However, magnetic
nanoparticles can be separated and recovered with an external
magnetic field due to the intrinsic magnetic characteristic of
the nanoparticles, aiding in prominent nanoparticles recovery
without a filtration process. Magnetic separation is a widely
adopted method for collecting or separating magnetic sub-
stances from flowing streams (Yavuz et al., 2009).
High-gradient magnetic separation (HGMS) is a widely used
technique for magnetic separation process (de Vicente et al.,
2010; Hoffmann and Franzreb, 2004a, 2004b; Svoboda, 2001).
A stack of magnetically susceptible metal wires is installed
inside an electromagnetic system in an HGMS. To generate
large field gradients around the wires, a magnetic field from the
electromagnetic system is applied across the wires, distrib-
uting the magnetic field, and attracting magnetic particles to-
ward the surfaces of wires. The generation of great magnetic
field gradients is the one of crucial factors for particle collec-
tion. The size and magnetic properties of particles, and the
area of magnetized surfaces also play the important roles. For
effective collection of magnetic particles by magnetic separa-
tion, the magnetic force attracting particles must dominate the
gravitational, inertial, fluid drag and diffusion forces when the
particle suspension flows through the separation unit.
4.1. Forces acting on magnetic nanoparticles
Generally, magnetic separation is caused by the feature of
magnetic fields exerting a force on matter with magnetic
properties. The involved magnetic force, Fm, can be expressed
as
Fm m0 Vp Mp DH (1)
where m0 denotes the permeability constant of the vacuum, Vp
is the particle volume, Mp is the particle magnetization and DH
is the gradient of magnetic field strength at the position of the
particle. The particle magnetization may be expressed by the
magnetic volume susceptibility c and the magnetic field
strength H, where the volume susceptibility is a constant for
diamagnetic and paramagnetic substances, and a function
among others of particle shape and size as well as field
strength for the ferromagnetic or ferrimagnetic substances.
Mp cH (2)
Other competing forces in the magnetic separation process
include gravitational force, Fg,
 
Fg rp  rg Vp g (3)
where rp is spherical particle density, rg and g are density of
fluid and acceleration due to gravity; hydrodynamic drag
force, Fd, can be calculated with Stokes Law,


Fd 6phb vf  vp (4)
2622 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
where h is the dynamic viscosity of the fluid, b is a constant
that depends on the properties of the fluid and the dimensions
of the particle, and nf and np are velocities of the fluid and
particle respectively.
Ample of results showed that magnetic nanoparticles can
be effectively separated from the aqueous phase, even with a
hand-held magnet (Bhaumik et al., 2011; Do et al., 2011; Fan
et al., 2012; Feng et al., 2012; Li et al., 2010a,b; Liu et al., 2010;
Shen et al., 2011; Shin et al., 2011; Wang et al., 2010a,b; Zhang
and Kong, 2011). However, no industrial application of mag-
netic separation for magnetic nanoparticles has yet been re-
ported, although there have been some for microparticles.
Although the magnetic properties of the particles are un-
doubted with evidence of vibrating sample magnetometer
(VSM) measurements, those photographic results shown in
literature, magnetic separation within the vials or beakers by a
magnet, may be misleading. A vial or beaker is not a large
container, usually only a few centimeters in diameter. The
magnetic field provided by a hand-held magnet would be
strong enough to provide sufficient magnetic force on the
magnetic nanoparticles in the vial. But magnetic field drops
substantially with distance away from the source, following
an inverse cube law. On the other hand, when the particle size
is reduced to nano-scale, a much greater magnetic field is
required to provide sufficient attraction to compete with other
forces, such as drag, buoyancy, and even Brownian motion
(Tratnyek and Johnson, 2006). From the equations mentioned
above, the magnetic force depends on the particle size. Since
there is a limited magnetic field gradient for distant particles,
even a few centimeters more, the magnetic nanoparticles
cannot be attracted, but stay suspended in solution, without
taking into consideration of velocity and drag force from the
flowing stream.
4.2. Better recovery of magnetic nanoparticles
Particle size is one of the variables which can be manipulated
for better recovery, but increase in particle size leads to
decrease in reactivity and removal capacity. Moreover, the
magnetic separation efficiency is not just influenced by the
particle size (Chatterjee et al., 2003; Papaefthymiou, 2009;
Sundaresan and Rao, 2009), but also the synthesis methods of
magnetic nanoparticles (Badruddoza et al., 2011; Hakami
et al., 2012), and fluid properties (Hayashi et al., 2011). To
strike a balance between effective recovery and high removal
performance, an optimum particle size, considering the
magnetic properties of different nanoparticles and fluid
properties, is required to be studied. Yavuz et al. (2006)
Fig. 4 e Schematic representation of electrostatic, steric and electrosteric stabilized magnetic nanoparticles.
suggested that the optimal particle size of Fe3O4 for HGMS is
around 12 nm with a superparamagnetic property. Crane and
Scott (2012) pointed out that particle size of nZVI larger than
20 nm is more practical due to the exceedingly high reactivity
of tiny particles.
In order to economically recover the magnetic nano-
particles from water and wastewater treatment, another op-
tion can be the adoption of a greater magnetic field. Usually,
the magnetic source in magnetic separators like HGMS is
electromagnets, which consist of solenoids of electrical con-
ducting wires generating a magnetic field during electric cur-
rent passage. However, this magnetic field provided by
electromagnets is limited to magnetic microparticle separa-
tion (Ohara et al., 2001). A stronger magnetic field is required
for magnetic nanoparticles; superconducting magnets are
required. The coil conductor of a superconducting magnet is
operated under cryogenic temperatures in the super-
conducting state. Since there is very little energy lost due to
resistance, a much greater magnetic field is produced when a
large current passes through (Iacob et al., 2002). On the other
hand, the concern is the capital and operation cost of the
superconducting magnet which is related to the design and
materials (Iacob et al., 2002; Iwasa, 2009; Li et al., 2007).
4.3. Questions in magnetic nanoparticles recovery
With the conceptual possibility of magnetic nanoparticles
recovery using magnetic separation, a reduction of removal
capacity and reusability of magnetic nanoparticles raises a
question because of aggregation. Although numerous evi-
dence have shown the feasibility of magnetic separation and
reuse of nanoparticles, magnetic nanoparticles aggregation
under magnetic field attraction, resulting from collision
among nanoparticles, is still in question (Mandel and Hutter,
2012). Quick magnetic separation with a hand-held
magnet also implied that aggregate formed, while the aggre-
gation is suggested to be reversible (Yantasee et al., 2007;
Yavuz et al., 2006), hence the magnetic nanoparticles are
recoverable. Nevertheless, more in-depth study to reveal
nanoparticle interactions under magnetic field is necessary.
Magnetic nanoparticles may be held on the magnetic surface
strongly, and hardly recovered (Yavuz et al., 2006). Dispersion
of the magnetic nanoparticles to let as much surface area of
the nanoparticle as possible for reaction is still essential,
although the aggregation is expected to be reversible.
Considering the high surface free energy of the nanoparticles,
re-dispersion such as by sonication (Huber, 2005; Wassel et al.,
2007) is recommended before application. Surface coating,
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
especially by steric and electrosteric stabilization, can prevent
aggregation of magnetic nanoparticles, discussed further in
the section below.
5. Aggregation
Nanoparticles with a high surface free energy tend to aggre-
gate, achieving a stabilized state. The smaller particles have
higher tendency of aggregation due to the lower energy bar-
riers (Petosa et al., 2010). Formation of aggregate decreases the
surface area of the magnetic nanoparticles. This reduces the
removal capacity and reactivity, thereby limiting the treat-
ment performance. Aggregation also undermines the effec-
tiveness of magnetic nanoparticles during remediation
because of the loss of mobility. Several conditions leading to
the aggregation of magnetic nanoparticles are highlighted
including the particle size distribution, particle concentration,
solution composition, surface chemistry, and certainly the
magnetism of the nanoparticles (Hu et al., 2010; Petosa et al.,
2010; Phenrat et al., 2009a; Yin et al., 2012).
5.1. Particle size
Theoretically, compared to that of particles with the same
size, differential sized particles show a higher aggregation
rate, following the Eq. (5) (Petosa et al., 2010). Larger particles
have a higher attractive force, especially for magnetic nano-
paritcles (Phenrat et al., 2009a). There is an unbalanced force
among particles, so polydispersed nanoparticles have a
greater tendency to aggregate due to differential sedimenta-
tion (Dickinson and Scott, 2010). Thus, polydispersed nano-
particles are relatively less stable.

2
2kB T ai aj
kij
3h0 ai aj
where kij is perikinetic aggregation rate constant between
dissimilar-size particles, kB is Boltzman constant, T is absolute
temperature, h0 is absolute viscosity of fluid, ai and aj are
particle radii. According to the equation, the stability of
nanoparticles in aquatic environments is not solely depen-
dent on particle properties, but also on fluid properties. The
influence of fluid properties can be observed from ferrofluids,
which contains well-dispersed magnetic nanoparticles. There
is a high concentration of surfactants in ferrofluids, suffi-
ciently coating on the nanoparticles, thus preventing aggre-
gation. However, this may not be feasible in environmental
applications because of dilution. Once the ferrofluid apply in
the treatment processes, leading to inadequate stability from
diluted surfactants and probably aggregate.
5.2. Particle concentration
Aggregation increases with an increase in concentration of
magnetic nanoparticles, resulting from more frequent colli-
sion and particleeparticle interactions (Baalousha, 2009;
Maximova and Dahl, 2006). Previous research reported that a
low concentration of nanoparticles (30 mg/L) was mobile in a
porous medium (Phenrat et al., 2009a), indicative of a
2623
minimum aggregation. Extensive aggregation of nanoparticles
(i.e., hematite) was observed at high concentrations (>50 mg/
L) in a wide range of pH, especially near pH values of the pHZPC
of nanoparticles (Baalousha, 2009). Under higher particle
concentrations, formation of the stable sized agglomerates
occurs rapidly, reaching a steady state. The size of the
aggregate formed was suggested to be similar as force balance
dominant the control of aggregate size, independent of par-
ticle concentration (Phenrat et al., 2009a).
5.3. Forces governing aggregation
In aquatic environments, aggregation of nanoparticles,
controlled by particleeparticle interactions, has been conven-
tionally described by DerjaguineLandaueVerweyeOverbeek
(DLVO) theory (Baalousha, 2009; Petosa et al., 2010; Phenrat
et al., 2009a; Saleh et al., 2008). The traditional DLVO theory
described colloidal stability considering the total interaction
energy on a particle with another particle. The major interac-
tion energy can be estimated and calculated as the sum of van
der Waals and electrical double layer interactions. The theory
explains rapid nanoparticle aggregation at pH values near
pHZPC, as well as a direction for improving stability with sur-
face modifications. The charges on the magnetic nanoparticles
can be neutralized under certain pH environments, reaching
pH values of pHZPC. Hence, electrostatic repulsions among
nanoparticles diminish leading to aggregation. On top of the
DLVO theory, steric and magnetic forces, regarded as non-
DLVO forces, also play a key role in magnetic nanoparticle
aggregation. These factors were discussed in detail with gov-
erning equations (Petosa et al., 2010).
Magnetic nanoparticles have an intrinsic permanent
magnetic dipole moment with a saturation magnetization
(Ms), even in the absence of an applied magnetic field, which is
related to the iron content. It was reported that Ms increased
(5) with the iron content and particle size, following an empirical
relationship (Phenrat et al., 2008). In addition, since magnetic
force is a long-range attractive interaction, compared with
van der Waals and electrical double layer interactions, ag-
gregation may result from the unbalanced force due to the
domination of magnetic force, especially for nZVI (Petosa
et al., 2010; Phenrat et al., 2009a). This was also evident by
comparing to use of non-magnetic hematite nanoparticles
with similar surface treatment, which showed a greater sta-
bility than nZVI (Phenrat et al., 2009a).
5.4. Stabilize magnetic nanoparticles
Surface coating can significantly enhance the stability of
magnetic nanoparticles suspension. A number of methods
and chemicals for stabilization have been applied and studied
for providing steric, electrostatic, or electrosteric stabilization
(Fig. 4). Some natural polyelectrolytes like humic acid and
starch have been proven the ability of stabilization (Dickson
et al., 2012; Kim et al., 2003; Mikhaylova et al., 2004; Xiong
et al., 2007). There are numerous moieties on these marco-
molecules providing different functions. For example, the
phenyl groups and carbon chains can provide steric repulsion
between magnetic nanoparticles. The functional groups
complexing and bonding onto the surface of iron/iron oxides
2624 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
nanoparticles were identified to be carboxylic acid (eCOOH),
instead of thiol group (eSH) (Hakami et al., 2012; Sirk et al.,
2009; Yantasee et al., 2007). These findings are useful for an
engineering design of surface coating to provide specific
functions and properties for magnetic nanoparticles. More-
over, modifications can also be performed on some surface
coating such as chitosan and silica (Chang and Chen, 2005;
Geng et al., 2009a, 2009b; Wang et al., 2010a,b). Xanthate (Zhu
et al., 2012), ethylenediamine (Hu et al., 2011), and thiourea
(Zhou et al., 2009) were used to further modify the surface
coating of chitosan to increase the adsorption ability and
selectivity towards metal ions.
In addition to these findings, some researchers have tried
various functional polymers for synthesizing magnetic
nanoparticles with specific functions. Modifications with
poly(acrylic acid) (Chen and Huang, 2004; Huang et al., 2006;
Liao et al., 2004; Mahdavian and Mirrahimi, 2010) and car-
boxymethyl cellulose (CMC) (He et al., 2010; Phenrat et al.,
2008; Wang et al., 2010a,b; Zhang et al., 2011a) have been
widely studied, showing a significant promotion of collide
stability of magnetic nanoparticles. Block copolymer in
another type of polyelectrolyte can be used to develop a multi-
functional architecture with different block copolymers. The
surface properties of magnetic nanoparticles, such as hydro-
phobic/hydrophilic, surface charge, and even addition of
chelating/complexation moieties can be manipulated with
special design block copolymer architecture (Sirk et al., 2009).
This modification not only maintains the magnetic nano-
particles in a dispersed condition, but also reduces the contact
of magnetic nanoparticles with bacteria. This may prevent
toxic effects on microorganisms. The toxicological effect is
discussed in another section.
Although a surface coating can assist the dispersion of
magnetic nanoparticles, the coating may not be permanent.
Surface modified magnetic nanoparticles have usually been
prepared in a high concentration of surface modifiers (e.g.,
humic acid, polymers, surfactants). These surface modifiers
adsorbed onto the surface of magnetic nanoparticles, some
anchoring tightly through complexation with iron oxide
surface, because of the concentration gradient. However, the
adsorption of surface modifiers may be reversible in the
environment with diluted surface modifiers, extreme pH and
ionic strength, or after reaction of nanoparticles. It was
found that humic acid can be desorbed from humic acid
coated magnetic nanoparticles (Liu et al., 2008), especially
under low pH values and high ionic strength. The stability of
magnetic nanoparticles can be influenced once the coating
desorbed. In contrast, Kim et al. (2009) have reported the
stability and mobility of surface modified nZVI maintained
for about 8 months, and the desorption of surface modifiers
was not significant. Some efforts should be made on study-
ing the stability of coatings, especially under extreme
conditions.
5.5. Trade off between stability and reactivity
To effectively apply magnetic nanoparticles in remediation
and water treatments, it is necessary to avoid aggregation of
magnetic nanoparticles, yet maintain the advantages of rapid
reaction and high removal capacity. Nevertheless, research on
Fig. 5 e Schematic model of potential cell damage after
exposure to magnetic nanoparticles. Magnetic
nanoparticles adsorb onto the cell wall or cell membrane,
subsequent internalization. The adsorbed magnetic
nanoparticles limit the mobility, block membrane channel,
or disrupt the membrane of bacteria. Fe2D, releasing from
magnetic nanoparticles, reacts with hydrogen peroxide
through Fentons reaction, generating OH radical and
causing lipid/protein oxidation.
surface modifications usually focuses on advancement in
stability and mobility of magnetic nanoparticles, rather than
on reaction with contaminants. A thick layer of surface
modifiers may limit the access to the surface of magnetic
nanoparticles where reactions occur. On the other hand, some
studies reported that reaction rate was reduced due to the
coating of humic acid (Chen et al., 2011; Liu et al., 2008), but
removal capacity was enhanced with increase of active sites
contributed from surface modifications. Some active sites on
the magnetic nanoparticles could also be blocked during
surface coating. To comprehensively evaluate the surface
modified magnetic nanoparticles, the effect on both removal
performance including capacity and kinetics, as well as sta-
bility and mobility, should be intensively studied.
6. Toxicity
Nanoparticles surreptitiously enter the environment through
water, soil, and air during various human activities. However,
the application of nanoparticles for environmental treatment
deliberately injects or dumps engineered nanoparticles into
the soil or aquatic systems. This has resultantly attracted
increasing concern from all stakeholders (Brar et al., 2010;
Posner, 2009). The advantages of magnetic nanoparticles like
their small size, high reactivity and great capacity, could
become potential lethal factors by inducing adverse cellular
toxic and harmful effects, unusual in micron-sized counter-
parts. Studies also illustrated that nanoparticles have the
ability to enter organisms during ingestion or inhalation
(Holsapple et al., 2005), and can translocate within the body to
various organs and tissues (Borm et al., 2006) where the
nanoparticles have the possibility to exert the reactivity being
toxicology effects. Although some studies have also addressed
the toxicological effects of nanoparticles on animal cells
(Iversen et al., 2011; Moore, 2006), plants and plant cells
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
(Navarro et al., 2008; Miralles et al., 2012), the toxicological
studies with magnetic nanoparticles on plants to date is still
limited. In this section, the main focus is on the effects upon
bacteria, while the effects upon plants are briefly discussed.
Inactivation of bacteria by magnetic nanoparticles has
been observed, especially for nZVI, resulting from the inter-
action between nanoparticles and bacteria. Adsorption of
magnetic nanoparticles on the bacteria membrane surface,
and the reactions internally in cytoplasm of bacteria were
reported to be the causes of bactericidal effect (Auffan et al.,
2008; Lee et al., 2008; Tsuji et al., 2006). However, the mecha-
nism of toxicity is still unclear and biocompatibility varies
depending on numerous parameters, such as nanoparticle
size and shape, surface property, applied nanoparticle con-
centration, type of cell and nanomaterial.
6.1. Size and shape of nanoparticles
Several studies indicated that when the size of particles was
reduced to nanoscale, bactericidal effects can be observed.
The size of magnetic nanoparticles can be manipulated with
synthesis methods and these provide varying performance in
contaminant removal and aggregation, discussed above.
Similar to the effect of aggregation, the smaller size of nano-
particles was found to have a higher tendency to be adsorbed
onto bacteria (Zhang et al., 2011b). Higher particle mobility
and lower energy barriers in the interaction energy of small
size nanoparticles were attributed to fast adsorption kinetics
and high in the adsorbed number of particles on the bacterial
surface. Further, it was proven that adsorption of nano-
particles to a bacterial surface is a primary step for bacteri-
cidal effects to be exhibited (Iversen et al., 2011; Simon-
Deckers et al., 2009; Verma and Stellacci, 2010). The nano-
particles with the size of 20e50 nm can be effectively taken up
by cells. This is also supported by the low toxicity of particles
with a larger size, less associated with bacteria (Lee et al.,
2008). Moreover, spherical particles showed higher cellular
uptake rate and toxicity than rod-shape particles, despite the
research focus being spherical magnetic nanoparticles. This is
speculated to be because of the higher wrapping time
requirement of the cell membrane for elongated particles
(Nair et al., 2009; Simon-Deckers et al., 2009). However, some
studies found that carbon nanotubes cause injury in mice
during inhalation exposure (Lam et al., 2004; Poland et al.,
2008). To evaluate the toxicity of magnetic nanoparticles, the
polydispersity of particle size and the possibility of aggrega-
tion should be taken into account, since particle size is one of
the crucial parameters. The toxic effects may be reduced if
aggregation occurs.
6.2. Surface properties of magnetic nanoparticles
As discussed in previous sections, surface properties of mag-
netic nanoparticles influence the removal and aggregate per-
formance. The effect on nanoparticleecell interactions is
highlighted in this section. Magnetic nanoparticles possess a
great adsorption capacity and reactivity. The high reducing
potential of nZVI can readily reduce various organic contam-
inants, similar to the components of cell membrane. Some
investigators reported that bare nZVI adsorbed onto or
2625
penetrate cell membrane, leading to cell disruption due to the
chemical interactions between the nZVI and cells (Auffan
et al., 2008; Lee et al., 2008). The disruption of cell mem-
branes further resulted in leakage of the intracellular con-
tents, cytoplasm, and elevated exposure of nZVI or other
reactive species (e.g., Fe2), causing inactivation. This is
probably due to reductive decomposition of cell membrane in
which the proteins and polysaccharides maintain the integ-

rity of the cell (Sevc
u et al., 2011). The adsorbed nanoparticles
on the cell membrane may also block the cellular channels, or
cause structural changes of cell membrane, or limit the
mobility and nutrient uptake of bacteria, and finally leading to
bacterial death (Xiu et al., 2010).
Another inactivation mechanism proposed has been
oxidative damage through Fenton reaction, regarding as
oxidative stress. The major component of nZVI is iron,
regardless of the preparation methods and storage conditions.
With oxidation in water, iron reacts according to the following
equations:
2Fe0 O2 2H2 O/2Fe2 4OH (6)
Fe0 O2 2H /Fe2 H2 O2 (7)
Even without oxygen, iron can still be oxidized:
Fe0 2H2 O/Fe2 H2 2OH (8)
Ferrous ions generated following the above equations acti-
vate Fenton reaction with the reactive oxygen species (ROS)
(e.g., OH and H2O2) and enhance the production of ROS, leading

to cellular injury and death (Sevc 
u et al., 2011). ROS are normally
produced during metabolism in cells as a by-product of aerobic
respiration. The validity of these proposed mechanisms was
supported by a number of experiments. The decrease of
bactericidal effects of oxidized nZVI and nZVI under aerobic
condition indicated that the key role of chemical reactivity of
nZVI (Lee et al., 2008; Li et al., 2010a,b). The similar inactivation
results of the presence of Fe2 illustrated the possible inacti-
vation pathway of Fenton reaction (Lee et al., 2008).
Other magnetic nanoparticles (Fe3O4 and g-Fe2O3) showed
much lower bactericidal effects. However, the release of Fe2
from Fe3O4 and g-Fe2O3 nanoparticles causing cytotoxicity
was reported (Auffan et al., 2008; Niu et al., 2011), despite the
fact that it is less harmful than nZVI due to their more stable
chemical state, particularly for g-Fe2O3. Based on the toxico-
logical results, iron oxides magnetic nanoparticles, or partially
oxidized nZVI are preferred over fresh nZVI, regardless of the
rapid reduction for contaminants. The bactericidal in-
teractions of magnetic nanoparticles are illustrated in Fig. 5.
In order to depress the toxic effects of magnetic nano-
particles, various surface coatings have been employed. This
can greatly reduce the contact of magnetic nanoparticles with
bacteria. Similar to the enhancement in stability, surface
coatings provide steric, electrostatic, or electrosteric barriers
showing satisfactory results on elimination of bactericidal ef-
fects. A number of surfactants and polymers were applied to
mitigate the bactericidal effect, such as poly(styrene sulfonate)
(PSS) (Rayavarapu et al., 2010), poly(aspartate) (PAP) (Phenrat
et al., 2009b), and NOM (Li et al., 2010a,b). Studies found that
anionic surfactants provide a better toxicity mitigation (Li et al.,
2010a,b; Verma and Stellacci, 2010), but only Escherichia coli, a
2626 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
gram-negative bacterium, has been usually used as the model
bacteria (Chen et al., 2011; Li et al., 2010a,b). Extensive studies
on NOM coated magnetic nanoparticles have been conducted,
because NOM is ubiquitous in natural environments and can
readily adsorb onto magnetic nanoparticles during environ-
mental applications. The toxicity of magnetic nanoparticles
was reduced even when the particles were not pretreated with
NOM (Chen et al., 2011). It is suggested that the mitigation was
due to the electrosteric hindrance of NOM. NOM possesses a
negative charge in the pH range of natural environments for
electrostatic repulsion, and provides abundant alkyl and aro-
matics functional groups with steric barriers.
However, some other studies on interactions between
nanoparticles and animal cells showed that neutral charge
polymers can provide better biocompatibility than charged
particles like with coating of biocompatible ligands (Liu et al.,
2009; Verma and Stellacci, 2010), polyethylene glycol or poly-
ethylene oxide. Since these coatings lowered protein adsorp-
tion and decrease cell recognition, the uptake rate of magnetic
nanoparticles by cells was reduced. More than the molecular
weight, functional groups, or the charge of surface coatings on
magnetic nanoparticles, the spatial configuration of coated
polymer also affected the interactions between cells (Hu et al.,
2007; Sant et al., 2008).
6.3. Nanoparticle concentration related to toxicity
Iron oxide (Fe3O4 and g-Fe2O3) nanoparticles are more stable,
but still exert certain toxic effects on bacteria. It was found
that E. coli can withstand high concentration of iron oxide
nanoparticles (up to 350 mg/L of Fe3O4 and 700 mg/L of g-
Fe2O3) (Auffan et al., 2008; Lee et al., 2008), while the toxicity
due to nZVI was significant with less than 10 mg/L. Bacteria
can still be damaged by surface coated magnetic nano-
particles (Singh et al., 2011). Other bacteria were also studied
and showed greater resistance to exposure of nZVI, even at a
higher concentration (Xiu et al., 2010). Although Fajardo et al.
(2012) reported there was no toxicity toward a gram negative
strain, even with high dose of nZVI, the nZVI used in their
study was stabilized with surfactants, and other types of
bacteria were affected. In contrast, there was little toxic effect
of nZVI with 100 mg/L on the diversity and structure of a
natural bacterial community in river water (Barnes et al.,
2010b). The natural river water may contain NOM lowering
the toxicity of nZVI, or other dissolved electrolytes complexed
with Fe2 reducing oxidation stress.
6.4. Type of bacterial cell
Apart from the toxicological effects of magnetic nanoparticles,
both inhibition and promotion of bacterial reaction by mag-
netic nanoparticles in contaminants removal were reported.
Shin and Cha (2008) found that the microbial reduction of ni-
trate was promoted with the presence of nZVI, and no lag
phase was observed. Compared with the findings from appli-
cations of nZVI with microorganisms for dechlorination of TCE
(Barnes et al., 2010a; Xiu et al., 2010), an inhibitory effect of nZVI
was demonstrated. Although the study (Xiu et al., 2010) indi-
cated that H2 generated from corrosion of nZVI was consumed
by the dechlorinating bacteria, the TCE degradation rate was
lower than the system with only bacteria. There was a lag
phase in the nZVI-bacteria system, suggesting that nZVI may
be passivated over time, or the bacteria may require time to
adjust and recover; however, insufficient data after the lag
phase have been presented. Despite inclusive findings about
whether nZVI promote removal of contaminants, nZVI can
provide H2 as an electron donor for bacterial reduction (An
et al., 2009; Barnes et al., 2010a; Xiu et al., 2010), without sig-
nificant bactericidal effects, such as that utilized by sulfate
reducing and methanogenic bacteria. To facilitate biological
treatment, magnetic nanoparticles with surface coating can
also be adsorbed onto bacteria by offering the advantage of
magnetic separation (Li et al., 2009). The researchers pointed
out that oleate-modification provided hydrophobic in-
teractions towards the bacterial cell wall, in addition to solely
nanoparticle adsorption; therefore, the modified magnetic
nanoparticles were difficult to be washed off. This demon-
strates that a careful design of surface coating not only miti-
gates the toxicity of nanoparticles, but also combines the
advantages for novel environmental applications.
6.5. Phytotoxicity of magnetic nanoparticles
The research data on the environmental effects and
bioavailability of magnetic nanoparticles is still limited,
especially on phytotoxicity, although the toxicological effects
of several other types of nanoparticles, such as fullerenes,
carbon nanotubes, titanium dioxide and silver, have been
widely studied (Barrena et al., 2009; Miralles et al., 2012;
Navarro et al., 2008; Scown et al., 2010). Since plants are
essential constituents in ecosystems, and probably a pathway
for magnetic nanoparticles transport and bioaccumulation
along food chain, the recent findings on phytotoxicity of
magnetic nanoparticles are discussed below.
Various experimental methods such as in vitro study with
isolated plant cells, a whole plant, or seeds as well as various
experimental setups such as water, soft agar medium, and
nature soil were applied (Miralles et al., 2012). The evidence on
the phytotoxicity of nanoparticles is yet conclusive because it
likely depends on the plant species, composition, concentra-
tion, size and surface properties of the nanoparticles, and
experimental methods.
Although diverging results of the phytotoxicology of the
magnetic nanoparticles were reported, a comparatively
conclusive finding showed that the presence of soil or sand
reduced the impacts of magnetic nanoparticles on plants. The
magnetic nanoparticles tend to attach or deposit on soil or
sand grains, leading to a reduction of availability of magnetic
nanoparticles (El-Temsah and Joner, 2012; Zhu et al., 2008).
Several recent research papers reported the uptake of mag-
netic nanoparticles from aqueous medium by different plant
species, such as pumpkin (Cucurbita maxima) (Zhu et al., 2008),
cattail (Typha latifolia) and hybrid poplars (Populous
deltoids  Populous nigra) (Ma et al., 2013). Barrena et al. (2009)
observed low toxicity of Fe3O4 in germination, biolumines-
cent and anaerobic toxicity tests, while El-Temsah and Joner
(2012) reported the inhibitory effects of germination and
shoot growth on ryegrass (Lolium perenne), barley (Hordeum
vulgare), and flax (Linum usitatissimum) by nZVI at various
concentrations. The inhibitory effects could be due to physical
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 1 3 e2 6 3 2
deposition and accumulation on the root surface (Ma et al.,
2013), leading to blockage for moisture and nutrients uptake,
or due to chemical toxicity resulting from potential dissolu-
tion and anoxic conditions caused by reductive reactions (El-
Temsah and Joner, 2012; Ma et al., 2010). The magnetic
nanoparticles can also lead to little growth of leaves and death
of older leaves (grown before dosing of nanoparticles) (Ma
et al., 2013). On the contrary, It was also reported that the
magnetic nanoparticles could be taken up and translocated in
plants (Zhu et al., 2008) without any apparent visual impact,
and could even enhanced the plant growth at low concen-
tration (Ma et al., 2013).
Taken together with the toxicology effects on bacteria,
surface modifiers can reduce degree of toxicity on both plants
and bacteria, probably due to reduction of attachment, and
thus bioavailability. Moreover, the attachment of magnetic
nanoparticles to soil medium resulted in lower the toxic im-
pacts, suggesting that magnetic nanoparticles at low concen-
tration could be used for environmental engineering
applications without pernicious effects on plants and bacteria.
6.6. Current limitations
The research findings on the toxic effects of magnetic nano-
particles have generally focused on clean particles. Howev-
er, during environmental applications of magnetic
nanoparticles, various contaminants could interact with the
particles and alter their physiochemical properties. Magnetic
nanoparticles may act as contaminant carriers, if the used
magnetic nanoparticles are internalized by cells. A synergistic
toxic effect could be a consequence in this ternary system,
cells-contaminants-magnetic nanoparticles, where the
bioavailability of loaded magnetic nanoparticles and its af-
finity towards bacterial cells have yet to be studied. One
should also note that the type of bacteria plays a critical role
on bactericidal effects, since different bacteria have a different
tolerance on oxidative stress and exposure to nanoparticles.
For instance, autotrophic bacteria can utilize chemical energy
which can probably withstand the high reactivity of nano-
particles (Shin and Cha, 2008; Yu et al., 2006). The strain of
bacteria, gram positive or negative, also exhibits varying re-
sistances to magnetic nanoparticles where electrostatic in-
teractions may be taken into account (Diao and Yao, 2009;
Fajardo et al., 2012). Other microbes like fungi have a more
robust structure and are less sensitive to the environmental
disturbance than bacteria (Diao and Yao, 2009). These are also
abundant in natural environments. In addition, the bacteri-
cidal ability of magnetic nanoparticles can be utilized in a
beneficial way as a disinfecting and sedimentation agent (Diao
and Yao, 2009; You et al., 2005). More attention should also be
paid to assess the potential phytotoxicity of magnetic nano-
particles, because plants are critical and elemental parts of
ecosystems. To better understand the toxicity of magnetic
nanoparticles, all these factors should be considered for a
comprehensive study before being widely applied.
Since there is no standard method for measuring bacteria
activity and phytotoxicity in the presence of nanoparticles, the
diverging results from these findings may be attributed to the
ample variables in magnetic nanoparticles and the experi-
mental setups. The inactivation or toxicological effects on
2627
bacteria and plants strongly depend on the types of bacteria or
plant species, iron oxidation state, surface coatings, concen-
tration and size of magnetic nanoparticles, culture medium,
and the determination methods of bacteria population or ac-
tivity or parameters for phytotoxicity assays. During the
sampling and measurement of bacteria activity, the nano-
particles may be oxidized, aggregate, or react with extracted
bacterial DNA, thereby influencing the results. For phytotox-
icity, different impacts of nanoparticles can be observed at
varying stages of plant growth for different species, so more in-
depth research and frequent review are required.
7. Conclusions
Five major concerns about magnetic nanoparticles for envi-
ronmental applications have been summarized and high-
lighted. The surface chemistry of engineered magnetic
nanoparticles is complex and plays a crucial role in various
interactions. Magnetic nanoparticles readily interact with
other magnetic nanoparticles, contaminants, and microbial
communities, thus further increasing the difficulty of inves-
tigation. Given the advantages of magnetic nanoparticles, a
systematic understanding of surface modifications and syn-
thesis of magnetic nanoparticles is important to boost prac-
ticability in environmental technology. Although the smaller
particle size contributes to their larger removal capacity and
higher reactivity, there is a tradeoff between recovery
magnetically, stability, and toxicity. Surface modifications can
help in stabilization and reduction of toxicity, but the active
surface of magnetic nanoparticles may be sacrificed. Further
modifications may be required to enhance the number of
active sites for contaminant removal. Studies of toxicity have
had controversial results, originating from the difference be-
tween various natural environments and simplified experi-
mental conditions. A more comprehensive and reliable
approach to determination of bacterial activity with the
presence of magnetic nanoparticles is desirable. However, to
reveal the whole picture of magnetic nanoparticles in the
environment, a close collaboration among scientists and en-
gineers with different backgrounds is required. Modification
on magnetic nanoparticles is essential to balance effects on
their reactivity, capacity, reusability and biocompatibility, and
thus would aid their environmental applications.
Acknowledgements
The authors wish to thank the Research Grants Council of the
HKSAR Government for providing financial support under
General Research Fund 617309 and FSGRF12EG28.
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