1 s2.0 S0048969708006943 Main

SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 0 ( 2 00 8 ) 3 9 64 14
a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m
w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v
Manufactured nanoparticles: An overview of their chemistry,

interactions and potential environmental implications
Yon Ju-Nam, Jamie R. Lead
Division of Environmental Health and Risk Management, School of Geography, Earth and Environmental Sciences, University of Birmingham,
Edgbaston, Birmingham, B15 2TT, UK
AR TIC LE I N FO
ABS TR ACT
Article history:
The industrial scale production and wide variety of applications of manufactured
Received 24 June 2008
nanoparticles (NPs) and their possible release in considerable amounts into the natural
Accepted 24 June 2008
aquatic environment have produced an increasing concern among the nanotechnology and
Available online 19 August 2008
environmental science community. In order to address this issue, it is important to

understand NP chemistry, preparation, reactivity and possible mechanisms involved in
Keywords:
their interaction with the naturally occurring aquatic components, particularly natural
Manufactured nanoparticles
colloids and NPs present in the aquatic systems. In this review, an overview of the chemistry
Natural aquatic colloids
of both manufactured and natural aquatic NPs is outlined. This review discusses the
Fullerenes
physico-chemical aspects of both type of NPs as an essential point to assess possible routes
Carbon nanotube
involved in manufactured NP fate in the natural aquatic environment and their toxicity. Key
Metal oxides
advances related to the characterisation of the manufactured NPs and natural colloids.
Quantum dots
1.
Introduction
Nanoscience involves the study of materials on the nanoscale

level between approximately 1 and 100 nm (Rotello, 2003) and
involves study of how to control the formation of two- and
three-dimensional assemblies of molecular scale building
blocks into well-defined nanostructures or nanomaterials
(Rosi an Mirkin, 2005). In general, these NPs can be categorised
into carbon-based materials such as fullerenes and carbon
nanotubes and inorganic nanoparticles including the ones
based on metal oxides (zinc oxide, iron oxide, titanium dioxide
and cerium oxide etc), metals (gold, silver and iron) and
quantum dots (cadmium sulfide and cadmium selenide).
Mixtures of different phases are also manufactured. In
addition, these nanomaterials also present different interesting morphologies such as spheres, tubes, rods and prisms.
Nanotechnology includes the integration of these nanoscale
structures into larger material components and systems,
keeping the control and construction of new and improved
materials at the nanoscale (Roco and Brainbridge, 2001).
2008 Elsevier B.V. All rights reserved.
Among these novel nanomaterials, nanoparticles (NPs, with

all three dimensions between 1 and 100 nm) play an important
role in nanotechnology advances. The unusual properties of
NPs have accelerated growth in the production of nanoscale
materials and the rapid increase of their applications in many
areas has captured the attention of researchers, government
and industry worldwide. Manufactured NPs are currently used
in different areas such as electronics, biomedicine, pharmaceuticals, cosmetics, environmental analysis and remediation, catalysis and material sciences, due to the relative ease
with which they can be prepared and manipulated, their
generally high reactivity and surface area and the tuneable
nature of their optical and other properties (Niemeyer, 2001;
Poole and Owen, 2003; Schmid, 2004).
Increasingly, study of their fate and impact in the
environment is becoming important due to the discharges
already occurring to the environment, the likely increase in
discharges as the industry grows dramatically, the known
toxicity of NPs and the immense gaps in our knowledge
leading to difficulties in risk assessment and management
Corresponding author. Tel.: +44 121 414 8147; fax: +44 121 414 5528.
E-mail address: j.r.lead@bham.ac.uk (J.R. Lead).
0048-9697/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2008.06.042
397
S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 0 ( 2 00 8 ) 3 9 64 14
(Handy et al., 2008a,b). Despite some recently acquired

knowledge on the effects of nanoparticles on human toxicology and to a lesser extent in ecotoxicology, very little is known
about mechanisms of biological uptake and toxicity modes of
action, about transport in and between environmental and
biological compartments and their chemical behaviour in the
environment. Currently, there is no information on background concentrations and physical-chemical form of NPs in
the environment due to limitations in separation and
analytical methodologies. Some laboratory based studies
are addressing this lack currently. However, this information
is urgently required and a major advance in knowledge would
come through the development of accurate and robust
methodologies for the measurement of NP concentration
and form under realistic conditions.
Previous reviews (Biswas and Wu, 2005; Handy et al.,
2008a,b; Nowack and Bucheli, 2007) have focussed on
ecotoxicological effects and environmental transport generally. In the present review, an overview of the chemistry of
NPs, both in the laboratory and the aquatic and terrestrial
environments is presented. The focus is primarily on
manufactured NPs due to their current importance and the
lack of knowledge in the general environmental field of these
important contaminants.
2.
Manufactured nanoparticles
The design of novel NPs has been the basis of many advances
in technology for the last decade. In general, manufactured
NPs can be classified according to their chemical composition
and properties. They can be produced by a huge range of
procedures which can be grouped into top-down and bottomup strategies (Fig. 1). Top-down approaches are defined as
those by which NPs or well-organised assemblies are directly
generated from bulk materials via the generation of isolated
atoms by using various distribution techniques (Niemeyer,
2001). The majority of the top-down strategies involve
physical methods such as milling or attrition, repeated
quenching and photolithography (Gao, 2004). Bottom-up
strategies involve molecular components as starting materials
linked with chemical reactions, nucleation and growth
Fig. 1 Top-down and bottom-up strategies.
Table 1 Number of atoms on the surface NS, and

percentage of atoms on the surface of different GaAs
nanoparticle sizes (nm) (taken from Poole and Owens,
2003, Introduction to Nanotechnology)
N
Size
na
(nm)
Total
number of
atoms
2
3
4
5
6
10
15
25
50
100
1.13
1.70
2.26
2.83
3.39
5.65
8.48
14.1
28.3
56.5
94
279
620
1165
1962
8630
2.84 104
1.29 105
1.02 106
8.06 106
Number of
surface atoms
48
108
192
300
432
1200
2700
7500
3.0 104
1.2 105
Percent of
atoms on
surface
51.1
38.7
31.0
25.8
22.0
13.9
9.5
5.8
2.9
1.5
process to promote the formation of more complex clusters

(Gao, 2004; Rotello, 2003).
NPs differ from larger materials in that the number of
atoms at the surface and their physical properties are different
from those of bulk materials (Poole and Owens, 2003). Properties associated with the bulk materials are averaged properties, such as density, resistivity and magnetisation and the
dielectric constant. Critically, however, many properties of
these materials change over at the NP scale (Daniel and
Astruc, 2004; Niemeyer, 2001). These differences arise from the
small size and large number of surface atoms of the particles
and related effects. For instance, in the case of the gallium
arsenide (GaAs) NPs, if the initial cube has a face-centered
cubic shape (unit cell) and nanostructures containing n3 of
these unit cells are built up, then it can be shown that the
number of atoms NS on the surface, the total number of atoms
NT, and the size or dimension d of the cube are given by the
following equations:
Ns 12n2
NT 8n3 6n2 3n
d na 0:565n
where a = 0.565 nm is the lattice constant of GaAs (Poole and

Owens, 2003). Table 1 tabulates NS, NT, d, and the fraction of
atoms on the surface NS/NT, for various values of n. The large
percentage of atoms on the surface for small n is one of the
principal factors that differentiate properties of nanostructures from those of the bulk material (Poole and Owens,
2003).
In the case of spherical NPs, such as gold based particles, a
similar tendency to those GaAs NPs can be observed. Indeed,
one of the most important attributes of all NPs is their high
surface area per unit mass. As result of this feature, the
surface of NPs possesses a considerable surface energy
(Feldheim and Colby, 2002). Indeed, if the surface of the NPs
is not protected with a molecule, a so-called capping agent,
interactions between particles will generally occur in such a
way so as to reduce this high surface energy and this generally
398
results in aggregation. Capping agents can be organic molecules, polymers, or biological molecules. Capping agents
generally work by either charge or steric stabilisation mechanisms, which prevent further aggregation. In addition to
stabilisation, capping agents can be carriers of specific
functionalities for further applications (Poole and Owens,
2003; Rotello, 2003). The capping agents are thus an integral
component of most NPs and consideration of NP behaviour
without understanding the chemistry of the capping agent
will lead to misunderstandings of their properties.
For the production of manufactured NPs, the main objective
is not simply to obtain nanoscale materials. For most real
world applications, experimental conditions need to be tightly
controlled in order to obtain NPs with at least the following
characteristics: identical particles in terms of size (a uniform
size distribution), shape or morphology, chemical composition
and crystal structure (ideally, core and surface composition
must be the same, unless specifically designed for other
purposes), and monodispersity (no aggregation) (Rotello,
2003). This is important in terms of current environmental
research, which tends to use off-the-shelf materials, purchased from suppliers, often unpurified and without discrete
size distributions and other properties. Understanding the
purely nano effects of nanomaterials and testing of hypotheses about nano behaviour in the environment, becomes
much more difficult in these circumstances. Additionally,
given these developments and likely industrial uses, currently
available materials with poorly defined properties will be less
realistic in terms of potential future release scenarios and may
not reflect the true behaviour of nanomaterials in environmental systems. Future research in the environmental area
should use NPs produced for specific purposes to exacting
specifications and with detailed physico-chemical characterisation. The effects of relevant environmental solution conditions on the NPs need to be quantified.
Another consideration important to environmental studies is that NPs are not one class of potential pollutant. Just
as there are many trace metals and many trace organic
pollutants, so NPs contain a wide range of different materials
with different physical, chemical and toxicological properties. NPs should thus be broken down into a series of classes
and not considered as a single homogeneous group. NPs are
usually defined by their core materials i.e. organic and
inorganic. Organic NPs can be further defined as fullerenes
(C60 and C70 and derivatives) and carbon nanotubes (multiwalled or single walled CNTs), while inorganic NPs can be
divided into metal oxides (of iron, zinc, titanium, cerium etc),
metals (mainly silver and gold) and quantum dots (such as
cadmium selenides). Other classifications and terminologies
are also used in the literature to refer some specific groups of
nanomaterials i.e. nanocrystals (single crystal nanoparticles) and different morphologies such as spheres, pyramids
and cubes. Some of these NPs, such as the ones based on
metals and fullerenes, offer the possibility of manipulating
their surfaces in order to introduce specific functionalities
for further applications (Yang et al., 2007). If we take into
account different surface chemistries (including from capping agents, surfactants or co-solvents), sizes and other
properties then it is easy to see the range of possible
nanomaterials is vast and they have many different proper-
ties which will impact on their environmental behaviour

substantially.
2.1.
Fullerenes and carbon nanotubes
Carbon-based fullerenes and nanotubes are carbon anisotropes with nanometer-scaled structures and this part of the
review, the synthesis and physical and chemical properties
will briefly be discussed below.
2.1.1.
Fullerenes
In general, fullerenes are molecules with 60 atoms of carbon,

commonly denoted as C60. This Buckminsterfullerene C60
possesses a spherical molecular structure where the carbon
atoms are positioned at the vertices of a regular truncated
icosahedron structure (Kroto et al., 1985). There are also higher
mass fullerenes with different geometric structures, such as,
C70, C76, C78 and C80 (Kikuchi et al., 1992). However, the most
widely studied is the C60 molecule.
The physical method of production involves the use of an
arc discharge between graphite electrodes in 200 Torr of He
gas (Krtschmer et al., 1990) and is one of the most popular
techniques to obtain carbon fullerenes. It consists in the
generation of fullerenes through the heat produced at the
contact point between the electrodes. The evaporation of the
carbon at this point promotes the formation of soot. The latter
normally contains approximately 15% of fullerenes (13% of
C60 and 2% of C70). Generally, the mixture of fullerenes is
separated from the soot by using liquid chromatography
(Millar et al., 1993; Jinno et al., 1993; Zarzycki et al., 2006). A
large number of applications of fullerenes in optics (Singh and
Roy, 2004), electronics (Otsubo et al., 2005; Diederich, 2005)
and biomedicine (Yang et al., 2007) makes this molecule of
importance and promise in the nanotechnology field.
Finding realistic applications of fullerenes has been a
major area of research for the past 20 years. However, the
direct use of these molecules in high impact applications, for
instance in biological ones, is restricted by their poor
solubility in aqueous media (Kadish and Ruoff, 2000). C60 is
soluble in a small range of organic solvents but almost
insoluble in water limiting its utilisation in biological
applications. In order to overcome this problem, two different
strategies to increase their solubility have been reported in
the literature: (1) non-covalent encapsulation of fullerene
molecules into soluble polymeric or host molecules (Andersson et al., 1992; Yamakoshi et al., 1994; Atwood et al., 1994), (2)
covalent functionalisation of fullerenes by introduction of
hydrophilic groups by chemical modification (Chiang et al.,
1996). The second strategy has attracted more interest as
these novel building blocks can be used for further molecular
constructions. Yang and co-workers have reported the
syntheses and characterisation of a series of fullerenederivatised amino acids, [60] fullerene-substituted phenylalanine and lysine derivatives, suggesting that the incorporation of fullerene-based amino acids into proteins, peptides or
antibodies could lead to new applications in medicinal
chemistry (Yang et al., 2007).
In water, unmodified fullerenes are largely insoluble
forming large aggregates of tens to hundreds of nm (or
larger). Dispersion in water as NPs has been achieved in two
ways: solvent exchange (Deguchi et al., 2001, Andrievsky

et al., 1995) and ultrasonication and stirring in water (Brant
et al., 2005, Deguchi et al., 2006) in order to promote the
formation of smaller clusters. The mechanism of this
process is not currently clear. However, it has been assumed
that the self-assembly of the fullerene molecules occurs
during the formation of the NPs, and aggregations of C60 have
been observed in different solvents. In addition, measured
zeta potentials of these fullerenes show a negative charge,
although differing mechanisms have been suggested about
how a negative potential is acquired (Brant et al., 2005).
Interesting differences in C60 (usually termed nC60 when
aggregated in water) between the co-solvent and waterstirred varieties have been observed including generally
greater toxicities in bacteria, fish and invertebrates (Lyon
et al., 2005 and 2006; Kashiwada, 2006) when dissolved with
co-solvent. Again, the mechanism needs clarifying, although
the direct impact of the co-solvent or solvent contamination
on toxicity have been suggested (Oberdrster, 2004; Henry
et al., 2007). One author (JRL) is currently involved in research
into toxicological response in fish, which has found significant and substantial up and down regulation of genes
involved in a wide variety of physiological processes, when
fish were exposed to water-stirred fullerenes i.e. biological
response not related to solvent (manuscripts in prep.). In
addition, in most studies physico-chemical characteristics
have not been measured fully and until this is performed
alongside toxicity studies, our lack of understanding of C60
toxicity will persist.
2.1.2.
Carbon nanotubes
Ijima and co-workers were pioneers in the synthesis of CNTs

in 1991 (Ijima, 1991), reporting the formation of these
nanotubes by using a carbon cathode and the arc discharge
technique. However, the discovery of the structure of these
nanomaterials took place a few years after their first synthesis
(Ijima and Ichihashi, 1993, Bethune et al., 1993). There are two
main forms of manufactured CNTs, the single-walled or
SWCNT, and multi-walled or MWCNT. In terms of structure,
the SWCNT is a single-layer graphene sheet rolled-up as
cylindrical shapes, with a diameter of approximately 1 nm and
a length of several micrometers, whereas the MWCNT
contains two or more concentric layers with various lengths
and diameters (Gao, 2004).
Carbon nanotubes are generated by arc evaporation
(Ebbesen, 1994), laser ablation (Paradise and Goswami, 2007),
pyrolysis (Endo et al., 1993), and electronic methods (Hsu et al.,
1995). Ebbensen and co-workers demonstrated that CNTs can
be generated in bulk amounts by varying arc-evaporation
conditions, (Ebbesen and Ajayan, 1992). Ijima and co-workers
also showed that the synthetic yield of SWCNT preparation
can be improved by adding cobalt or other transition metals
such as nickel, iron, and molybdenum, with the graphite in the
arc vaporisation process (Ijima and Ichihashi, 1993). Generally,
in all the carbon nanotube synthetic methods, generation of
carbon atoms from the carbon-bearing sources in an inert
atmosphere at 6001200 C and the utilisation of a catalytic
metal are involved (Nikolaev et al., 1999). The proposed
mechanism for the carbon nanotube growth assumes that
the nanotubes are always capped (Endo et al., 1993).
399
CNT products contain non-nanotube carbon and substantial amounts of metal impurities. These are removed by postmanufacturing treatments, and three basic methods have
been reported for purification: gas phase (Tsang et al., 1993),
liquid phase (Hiura et al., 1995) and intercalation techniques
(Ikazaki et al., 1994). Clearly, the presence of such metal
impurities might lead to a variety of adverse biological endpoints. The similarity in structure with asbestos suggests that
CNTs may behave as these fibres do when considering their
toxicology. Recent evidence (Poland et al., 2008), where a
variety of CNT morphologies has suggested in rat models that
this may be the case, with long, thin and biopersistent CNTs
causing pathologies similar to asbestos. A second order effect
appeared to be likely due to metal contamination. CNTs
appeared to be more hazardous than asbestos, but in these
studies producing CNT aerosols appeared to be difficult, so
their impact on human health through this route is still
unknown.
Properties of carbon nanotubes have been widely investigated and SWCNTs possess important mechanical, thermal,
photochemical and electrical properties (Arepalli et al., 2001)
which are industrially useful. MWCNTs contain several
SWCNTs in their structure, and therefore, they possibly have
analogous physicochemical properties to those corresponding
to SWCNTs. These nanomaterials are robust and stiff but
flexible and they have been reported as the strongest of all the
synthetic fibres (Arepalli et al., 2001, Kumar, 2006), although
practical experience suggests there are a wealth of different
properties and batch to batch (and even within batch)
variability is significant. Materials containing CNTs may,
however, be strong enough to build spacecrafts, space
elevators, artificial muscles, and land and sea vehicles
(Kumar, 2006). SWCNTs can conduct twice the electricity of
copper, making these materials excellent electrical conductors
(Kumar, 2006), and may also be used to improve rechargeable
batteries and fuel cell production, for instance (Kumar, 2006).
They also have a distinctive electron-transport property and
commonly in a manufactured material bulk sample ca 30% of
the SWCNTs are conductors and 70% are semiconductors
(Watts et al., 2002).
In humans, as discussed, CNTs may act like fibres (such as
asbestos) and this effect s also likely to be a problem in
environmental organisms, although little is known about
possible exposures and exposure routes. Current risk assessments suggest that CNTs may be of limited concern, although
our understanding is still very poor. In aquatic systems, Smith
and co-workers obtained evidence of oxidative injury in
rainbow trout (Oncorhynchus mykiss) exposed to SWCNTs
(Smith et al., 2007). They concluded that CNTs acted as
respiratory toxicants in rainbow trout. A significant concern
of investigations of CNT toxicity is inadequate assessment of
purity and physico-chemical form to ensure that nanoparticles are free from contaminants, particularly the metal
catalysts used during fabrication, which can be present in
materials obtained from commercial suppliers (Kagan et al.,
2006; Pulskamp et al., 2007; Handy et al., 2008a,b). For instance,
toxicity in zebrafish embryos exposed to SWCNTs has been
attributed to the presence of Co and Ni catalysts used in the
preparation of the SWCNTs (Cheng et al., 2007), although this
remains to be confirmed.
400
2.2.
Metal oxide nanoparticles
Metal oxide nanoparticles are extensively used in a considerable number of applications in food, material, chemical and
biological sciences (Aitken et al., 2006). It is well known that
bulk materials based on TiO2, SiO2 and aluminium and iron
oxides have been massively produced for many years. More
recently, nanoparticulate versions of these metal oxides have
been manufactured and introduced in commercial products
such as cosmetics and sunscreens (TiO2, Fe2O3 and ZnO)
(Nowack and Bucheli, 2007), fillers in dental fillings (SiO2)
(Balamurugan et al., 2006), in catalysis (TiO2) (Aitken et al.,
2006), and as fuel additives (CeO2) (Laosiripojana et al., 2005).
Several of the most commercially important NPs will be
discussed below.
2.2.1.
and specific binding sites (Dyal et al., 2003; Willner and Katz,
2003). Another functionalisation method of iron oxide NPs is
ligand exchange. In this method the NPs dispersed in an
organic phase are converted into water soluble particles by
using a highly water-soluble ligand and vigorous stirring
(Frankamp et al., 2006). Despite their high usage, it is unlikely
that these materials present significant environmental problems. Indeed, iron oxides are generally present in high
concentrations in the environment and are often limiting
nutrients. In seawater especially, iron is an essential limiting
nutrient (Turner and Hunter, 2001) and addition of iron has
been suggested as a means of stimulating marine algal growth
and drawing down atmospheric carbon dioxide from the
atmosphere to potentially slow down CO2-driven climate
change. Iron oxide NPs may have a useful role to play in this
process if it proved feasible.
Iron oxide nanoparticles
These NPs have been widely used for biological applications

and manufacturing pigments (Cornell and Schwertmann,
1996). Iron oxide NPs, Fe3O4 and Fe2O3 have been synthesised
with a number methods involving different compositions and
phases (Neveu et al., 2002; Grasset et al., 2002; Sun and Zeng,
2002). During the last few years, many publications describing
efficient synthetic methods to obtain shape-controlled, highly
stable, and monodisperse magnetic NPs have been produced.
Co-precipitation (Willis et al., 2005; Cushing et al., 2004),
thermal decomposition and/or reduction (Park et al., 2004),
and hydrothermal synthesis (Wang et al., 2005) techniques are
among the most used methods and also easily scalable with
high synthetic yields.
Steric and electrostatic repulsion are the interactions
involved in the stability of the colloidal iron oxide NPs
manufactured by the previously mentioned techniques.
Their stability depends on the stabilizers, such as fatty acids
or amines, and the polarity of the solvent used. In the case of
the synthesis of the iron oxide NPs in an aqueous medium
through the co-precipitation method, NPs are stabilised by
repulsive electrostatic forces due to positively charge on
particles (Lu et al., 2007), dependent on pH and ionic strength
(Baalousha et al., in press), whereas, NPs obtained by the
thermal decomposition technique are often sterically stabilised in an organic solvent by fatty acids or surfactant (Sun
et al., 2004).
However, due to the increasing interest of these nanomaterials to be used as potential devices for biomedical applications, water soluble iron oxide NPs are more attractive. For this
reason, a simple one-pot synthesis of water-soluble iron
oxide NPs has been recently reported. The preparation of these
NPs were carried out by the addition of ,-dicarboxylterminated poly(ethylene glycol) as the capping agent and
under reflux conditions (245 C) (Li et al., 2005; Hu et al.,
2006a, b). Different particles in terms of size were obtained
varying the reflux time, with 4, 12, and 60 nm particles obtained
when the reflux time was 1, 10, and 24 h respectively. These NPs
have been reported to possess potential application in the
cancer diagnosis as magnetic resonance imaging agents.
Stabilisation with capping agents does not only help to
protect the iron oxide NPs against degradation, it can also be
used for the introduction of specific functional groups into the
NP surface, such as catalytically active species, various drugs
2.2.2.
Zinc oxide nanoparticles
The remarkable properties of zinc oxide (ZnO) have attracted

the interest of many researchers in the past few years. ZnO is a
direct band gap semiconductor with band gap energy of
3.36 eV at room temperature, high exciton binding energy of
60 meV and high dielectric constant (Singh et al., 2007). Hence,
the luminescent properties of ZnO have attracted considerable
attention due to its potential application in ultraviolet light
emitting devices. This band-gap semiconductor has numerous potential applications, particularly in the form of thin
films, nanowires, nanorods or nanoparticles (Starowicz and
Stypula, 2008) and can be introduced to optoelectronic and
electronic devices. They also can be used in the production of
chemical sensors and solar cells (Singh et al., 2007). One of the
most remarkable commercial applications of 20100 nm ZnO
nanoparticles is their used in the production of sunscreens
and cosmetics, due to their property of blocking broad UV-A
and UV-B rays (Huang et al., 2008). This is a potentially
important diffuse source of NP contamination, due to washoff from individuals into the environment.
Several methods for the synthesis of ZnO nanoparticles
have been developed. Solid-state pyrolysis (Wang et al., 2003),
solgel chemistry (Haase et al., 1988), magnetic sputtering,
chemical vapour deposition (CVD) (Gorla et al., 1999) and
molecular beam epitaxy (Agashe et al., 2004) are some of the
methods reported in the literature. Recently, Singh and Gopal
(2008) have reported the synthesis of ZnO nanoparticles by
pulsed laser ablation of zinc target in aqueous media with
simultaneous flow of pure oxygen gas. With this approach,
smaller particles of ca 14 and a narrow size distribution were
obtained as compared to those produced by other conventional methods (Singh and Gopal, 2008).
ZnO nanoparticles are believed to be non-toxic, biosafe and
biocompatible nanomaterial (Zhou et al., 2006), although a few
reports have reported some toxicological activity of ZnO
nanoparticles e.g. in algae (Adams et al., 2006). It has been
shown that they cause membrane damage in the E. coli,
possibly due to oxidative stress mechanisms (Zhang et al.,
2007). More recently, Huang and coworkers (2008) have
investigated the possible interactions that govern the bactericidal activity of 60100 nm polyvinyl alcohol (PVA)-ZnO
nanoparticles against S. agalactiae and S. aureus. In their
preliminary studies, the results showed that low concentrations
of ZnO nanoparticles did not induce any cellular damage, as

previously demonstrated by other research groups (Feldmann,
2003). However, they observed cellular damage when the PVAcoated ZnO nanoparticle concentrations are higher than 0.016 M
in the ethylene glycol (EG) medium containing the cells. And
after the contact of these cells with PVA-coated ZnO nanoparticles, a significant change in the ZnO nanoparticle crystal
structure was observed (Huang et al., 2008). Heinlaan and
coworkers investigated the toxicity of ZnO nanoparticles to
bacteria Vidrio fischeri and crustaceans Daphnia magna and
Thamnocephalus platyurus and allowed discerned the toxic effects
of metal oxides and solubilised metal ions (Heinlaan et al., 2008).
They showed the metal oxide nanoparticles do not necessarily
have to enter to the cells to cause damage in the cell membrane.
In fact, the contact between the particle and the cell wall or
crustacean gut environment may cause changes in the vicinity
of organism-particle contact area and also may increase the
solubilisation of metals (Heinlaan et al., 2008). It has been also
demonstrated that the release of metal ions from the ZnO NP i.e.
from the solubilisation, was responsible for toxicity in lung cell
lines (Brunner et al., 2006), while under realistic environmental
conditions, similar results on algae have been reported (Franklin
et al., 2007). Indeed, as a general point, free metal ion toxicity
needs to be considered for all inorganic NPs and this appears to
be particularly so for the highly soluble ZnO.
2.2.3.
Titania nanoparticles
In general, titania (TiO2) is considered an excellent band-gap

semiconductor due to its large energy gap (Eg = 3.2 eV). This
nanostructurated material requires the use of near UV light in
order to be photoactivated (Bellardita et al., 2007; Lihitkar
et al., 2007; Reijnders, 2008). Consequently, photocatalysis
using TiO2 nanoparticles has recently become very important.
The use of TiO2 nanoparticles has improved the photodegradation process and the complete mineralization of toxic
organic pollutants. In fact, TiO2 nanoparticles have been
successfully used in environmental technology for the treatment of waste water and groundwater, the removal of
benzothiophene from diesel fuel and the degradation of air
pollutants, specifically nitrogenoxide, sulforoxides and volatile organic compounds (Kominami et al., 2002; Matsuda and
Hatano, 2005; Toma et al., 2006; Yu et al., 2006; Inaba et al.,
2006). Although TiO2 nanoparticles possess large specific
surface area, commercial applications have not been developed rapidly due to their tendency to aggregate and coalesce
very easily forming larger particles which is an undesirable
effect on the catalyst efficiency, and also the difficulties in the
separation and recovery of TiO2 particles from the reactant
mixture (Yu et al., 2002). Nevertheless, TiO2 is used widely, as
with ZnO, in sunscreens, because of its photoactivity.
TiO2 exists in three main crystallographic structures e.g.
anatase, rutile and brookite (Li et al., 2004a; Arami et al., 2007),
of which the first two are usually considered the most
important in the environment. Each of these forms presents
different properties and therefore, different applications and
environmental impacts. The phase-specific environmental
effects have not been much studied due to the difficulties of
producing phase-pure NPs. It is also well-known that it is
more difficult to obtain TiO2 nanoparticles with good crystallinity and high surface area from the rutile than anatase
401
crystalline form. This evidence can be attributed to the

thermodynamic stability which is size dependent. Indeed,
anatase is more stable that rutile at particle diameters below
14 nm (Zhang and Banfield, 2000). Apart from the applications
of TiO2 as a catalyst support (Matsuda and Kato, 1986;
Djenadic et al., 2007), semiconductor photocatalyst (Grtzel,
2001) and sensors (Ruiz et al., 2003), there is also a great
interest in the development of synthetic methods to obtain
TiO2 nanoparticles with high morphological specificity, such
as nanofibers, nanowires, nanorods and nanotubes (Chen
et al., 2002; Wu et al., 2006) due to their potential applications
in solar energy conversion, photocatalysis, photovoltaic
devices, and carrier for metallic nanoparticles (Zhu et al.,
2005). Different production methods to obtain anatase titania
nanostructures have been reported in the literature including
solgel (Li et al., 2004b), deposition with templates (Liu et al.,
2002b), anodic oxidation of titanium (Tsuchiya et al., 2005),
but most the hydrothermal method in which TiO2 particles
are added to a highly concentrated alkaline solution, such as
NaOH, KOH, and then transferred into a autoclave and treated
at different temperatures (from 100 C to 200 C) (Kasuga,
2006) and varying time (from 10 h to 1 week) (Wu et al., 2006).
By controlling experimental parameters such as temperature,
time, cooling and washing, nanostructures with different
morphologies can be obtained. As mentioned before, there
are a few drawbacks associated to the utilisation of this TiO2
in practical and commercial applications. In order to overcome these issues, several studies have been recently
performed to enhance the photocatalytical efficiency including impurity doping (Elahifard et al., 2007), metallization
(Sunada et al., 2003) and sensitisation (Hu et al., 2006a, b; Liu
et al., 2002a).
In addition to the discussion above, microorganisms in the
presence of light (Oberdrster et al., 2007) are adversely
affected by TiO2 NPs due to the production of reactive oxygen
species (ROS) (Hirano et al., 2005). This experimental evidence
suggests that these nanoparticles can produce oxidative stress
in aquatic organisms. This has been confirmed in rainbow
trout, where inflammatory injury and respiratory distress
were observed after the exposure to TiO2 NPs (Federici et al.,
2007; Reijnders, 2008).
2.2.4.
Ceria nanoparticles
Ceria nanoparticles (CeO2) of b10 nm have been the focus of

most of the advances involving the use of these nanomaterials
and also it is well-known that the distinct properties are
strongly size-dependent and would show significant quantum
size effects (Xu et al., 2008). Hence, the development of
methodologies for the synthesis of monodispersed CeO2
nanoparticles of different ands well-controlled sizes is the
ultimate aim in this field. These nanoparticles have been
synthesised using many preparation routes such as solgel (Li
et al., 2001), thermal decomposition (Kamruddin et al., 2004),
coprecipitation (Muccillo et al., 2004), solvothermal oxidation
(Kobayashi et al., 2006), microemulsion methods (Lee et al.,
2005), flame electrospray pyrolysis (Oh and Kim, 2007) and
microwave-assisted solvothermal process (Zawadzki, 2008).
However, the main issue of the all the methods previously
mentioned is the size control of the CeO2 nanoparticles to
obtain particles of less than 10 nm. Xu and coworkers have
402
recently developed a synthetic method to obtain homogeneous CeO2 nanoparticles of 2 nm in average size, simply
mixing cerium sulfate and ammonia solution at room
temperature (Xu et al., 2008).
CeO2 can exist as both Ce(III) and Ce(IV) forms (Robinson
et al., 2002) and the ratio of the two oxidation states appears to
be size dependent (Zhang et al., 2002), with increasing Ce(III) at
the lower size. CeO2 has been used as an oxygen sensor
(Robinson et al., 2002) and as a fuel additive, increasing fuel
efficiency. The latter use, with its potential to distribute NPs
widely in the environment from diesel exhausts, is of
potential concern. More recently, CeO2 nanoparticles have
been used to reduce oxidative stress in biological systems as a
free radical scavenger (Chung, 2003; Niu et al., 2007), although
they might also cause oxidative stress under different conditions. The evidence suggests that toxicity is low in humans
(Park et al., 2008) and that positive effects occur, such as
reduction in the particle number concentration of ultrafine
particles form diesel combustion, but further work is required
to give more definitive responses. Negative effects of CeO2 on
E. coli has been reported (Thill et al., 2006), where the NPs can
be adsorbed on the E coli outer membrane.
2.3.
Metal nanoparticles
Metal nanoparticles are potentially useful for sensing, catalysis, transport, and other applications in biological and
medical sciences (Daniel and Astruc, 2004; Murphy et al.,
2008; Tao et al., 2008). One of the most exciting areas of
nanotechnology is the use of nanomaterials to carry out
particle-specific functions. Despite the considerable variety of
NPs, this part of literature review will focus on the synthesis
and stabilization of gold, silver and zero-valent iron NPs, and
various types of assemblies, their physical and chemical
properties, and finally their potential applications and
problems.
2.3.1.
Gold and silver nanoparticles
Metal systems are expected to form the basis of new

diagnostic biosensor technologies and novel therapeutic
agents, and the most widely studied systems are based on
gold and silver (Drexler, 1992; Langer and Tirrell, 2004; Liu and
Lin, 2007). AgNPs have been widely use in commercial
applications in cosmetics and as bacteriocides in fabrics and
other consumer products (Jeon et al., 2003; Kim et al., 2007) and
are perhaps the most worrying of produced nanoparticles
because of this inherent toxicity and these consumer products
are undoubtedly a source of NPs to the environment (Eckelman and Graedel, 2007). These NPs, especially Au, have
interesting properties such as their stability, inertness and
size-related and tuneable electronic, magnetic and optical
properties. Furthermore, metal NPs have the advantages of
easy preparation and the possibility of chemical modification
of the surface (Brust and Kiely, 2002; Schmid and Corain, 2003;
Haick, 2007) by a variety of capping agents.
The number of procedures for generating metal NPs is
extensive. There are two main approaches to synthesize metal
NPs: physical and chemical. Physical methods are defined as
those by which NPs are directly generated from bulk metal via
the generation of NPs by various distribution techniques,
whereas chemical routes use metal salts as a starting

material, linked with chemical reduction steps (Frens, 1973;
Brust et al., 1994; Turkevitch et al., 1951; Schmid and Corain,
2003; Bajpai et al., 2007). An important aspect of both
approaches is the stabilization of the particles to avoid
coalescence. This stabilization can occur in many different
ways but primarily based on electrostatic repulsion or steric
hindrance as with many metal oxides.
The basic concept of chemical synthesis of gold and silver
NPs is that a salt of the metal is dissolved in an appropriate
solvent and then reduced to the zero valence state. The
problem is that the lifetime of the atoms in the solution is
short, and they tend to coalesce into large aggregates. The
crucial step in the process is then to determine when to stop
the growth and thus prevent the formation of large aggregates.
In many cases the use of ligand molecules such as citrate has
been found to be effective in stopping bulk formation. These
ligands coordinate strongly with the surface atoms of the
growing NP (Daniel and Astruc, 2004; Templeton et al., 1998).
Among the most used ligands are sodium citrate (13100 nm in
particle size) (Frens, 1973; Brown et al., 2000; Doty et al., 2005)
and alkanethiols (510 nm in particle size) (Brust et al., 1994;
Hostetler et al., 1998). In interpreting the environmental
impacts of NPs, it is essential, as discussed, to bear in mind
the potential role of these intimately associated capping
agents. Potentially, the correct choice of organic moieties has
the potential to reduce or increase toxicity, providing one
possibility for designing NPs with lower toxicity in environmental systems (and fewer impacts on human health).
An important property which metal NPs exhibit is the
resonance effect, the so-called surface plasmon resonance
(SPR), which is caused by the interaction with the incident
light and the free electrons in the materials (Noguez, 2007).
This resonance effect depends on a number of properties such
shape, surface chemistry, aggregation state and size. In
general, the aqueous solutions of gold NPs stabilised with
citrate are red colloidal solutions which present a surface
plasmon band (SPB) at 550 nm (Grabar et al., 1997; Daniel and
Astruc, 2004; Noguez, 2007), whereas the corresponding silver
NPs have an SPB at 414 nm (Doty et al., 2005). This behaviour is
an important analytical tool in the synthesis and is potentially
important in environmental applications and environmental
detection, with the surface. The surface plasmon has been
used to quantify the changes in gold NP properties upon
interaction with natural organic macromolecules, such as
humic substances (HS), which absorb maximally at ca 254 nm
(Diegoli et al., 2008).
AgNPs (and also dissolved silver) are known to have
significant antibacterial properties, and are used in fabrics
and cosmetic and have medical uses. Ag is used in dental resin
composites (Herrera et al., 2001), in synthetic zeolites (Faghihian and Kamali, 2003), and in coatings of medical equipments
such as catheters, infusion systems and medical textiles
(Bosetti et al., 2002; Markarian, 2006) The antibacterial activity
of silver ion (Ag+) and related silver species, and to a lesser
extent Ag NPs have been studied (Pal et al., 2007; Sondi and
Salopek-Sondi, 2004; Morones et al., 2005; Shahverdi et al.,
2007; Shrivastava et al., 2007; Yoon et al., 2007), although the
exact mode of action is not fully known. The catalytic
oxidation by metallic silver and reaction with dissolved
monovalent silver ion likely contribute to its bactericidal

effect. The antibacterial mechanism of silver-containing
products possibly ends in a long term release of silver ions
(Ag+) by oxidation of zero-valent metallic silver Ag0 in contact
with water (Kumar et al., 2005) and it has been shown, for
instance, that the Ag+ ion inhibits the enzymes for the P, S, and
N cycles of nitrifying bacteria (Ratte, 1999). Additionally, Ag+
can block DNA transcription, interrupt bacterial respiration
and adenosine triphosphate (ATP) production and react with
proteins by combining the SH groups of enzymes which leads
to the inactivation of the proteins (Jeon et al., 2003). When this
metal is in a nanostructurated form, higher antimicrobial
activity is expected due to its larger specific surface area (Yoon
et al., 2007) at least in comparison to the bulk. Our own work
(manuscripts in prep) indicates that dissolved silver has a
higher antibacterial effects compared with. Ag NPs (2050 nm,
citrate stabilised), but that the NPs have a different toxicity
mechanism compared to dissolved ions, a finding backed up
by recent work on Cu NPs in fish (Griffitt et al., 2007).
A number of detailed studies have investigated Ag toxicity
to bacteria (Sondi and Salopek-Sondi, 2004; Shahverdi et al.,
2007; Elechigerra et al., 2005; Pal et al., 2007). Ag NPs have been
shown to increase antibacterial activity of antibiotics such as
vancomycin and amoxicillin when used on S. aureus and E. coli
(Shahverdi et al., 2007). Both size and shape (Morones et al.,
2005; Pal et al., 2007) have been shown to affect antibacterial
properties, with smaller sized NPs having more effect. In
addition, triangular plates had improved anti bacterial efficiency compared with spherical and rod-shaped NPs. Along
with Ag+ (i.e. AgNO3), triangular nanoplates show the strongest biocidal action. A number of these studies also observed
aggregation of silver nanoparticles and larger effects on
bacteria on agar plates compared with bacteria grown in a
culture medium. This effect was most likely due to the
increased dose and certain experimental conditions such as,
temperature, pH, and mixing speed (Pal et al., 2007).
2.3.2.
Zero-valent ion nanoparticles
Among the most relevant zero-valent metal nanoparticles to

environmental systems, zero-valent iron nanoparticles have
received great attention due to their potential applications in
the remediation of contaminated groundwater (Wang and
Zhang, 1997; Elliott and Zhang, 2001; Quinn et al., 2005).
Several studies have shown that these iron nanoparticles
possess the capacity of transforming or sorbing a wide range
of common environmental contaminants including chlorinated organic solvents (Zhang, 2003; Elliott and Zhang, 2001;
Nutt et al., 2005), organic dyes (Liu et al., 2005), various
inorganic compounds (Alowitz and Scherer, 2002; Cao et al.,
2005), including metals (Xu et al., 2005; Kanel et al., 2005).
Several synthetic methods have been developed for the iron
nanoparticles production including the reduction of Fe(III) or
Fe(II) to Fe0 with sodium borohydride (Sun et al., 2006; Zhang,
2003; Wang and Zhang, 1997; Sun et al., 2007; elebi et al.,
2007), or through decomposition of iron pentacarbonyl (Fe
(CO)5) in organic solvents or in argon (Karlsson et al., 2005, Sun
et al., 2006), and reduction of iron oxides using hydrogen (Sun
et al., 2006). These nanoparticles can be also prepared with a
top-down approach which involves ball-milling larger iron
particles (Wiesner et al., 2006). As with other metal and oxide
403
particles, the surfaces of zero-valent iron nanoparticles can be

modified (Khalil et al., 2004; Elliott and Zhang, 2001) and much
effort has gone towards reducing aggregation and improving
transport. Despite the apparent lack of risk from iron itself (see
argument above related to iron oxide NPs), zero-valent iron
provides the only known (to the authors) example of a fieldbased study showing adverse environmental impacts of NPs.
Zhang (2003) showed that these NPs reduced high concentrations of solvents to nearly zero within days but at the same
time oxygen levels were reduced making the groundwater
anoxic and pH levels changed significantly (Zhang, 2003). No
further analyses were performed in this study, although
presumably there were at least substantial short term effects
on groundwater ecology. In the absence of further applications
it is also likely that conditions returned to their previous state
within a relatively short period of time, but continued
application may have had a prolonged effect.
2.4.
Other manufactured nanoparticles
Among the other relevant manufactured NPs, the ones based

on CdS, CdSe and CdTe, also known as semiconductor
quantum dots have been reported in the literature (Wang
et al., 2007). These NPs have attracted a special interest for
their promising applications in molecular biology, medicine
and information technology (Gao, 2004; Chen, 2008), although
given their composition e.g. Cd, they are likely to be inherently
highly toxic and large-scale use need to be viewed with
caution. Quantum dots are small assemblies of semiconductor
materials in the range between 210 nm, and they possess
unique electronic, optical, magnetic and catalytic properties
(Wang et al., 2007). They have been referred as artificial atoms
due to their unusual structures as they are considered to
possess neither a solid structure nor a single molecular unit
(Schmid, 2004). The most used methods to synthesise
semiconductor quantum dots are based on the wet chemical
colloidal procedures. They can emit light, and this can also be
adjusted to a selected wavelength by varying the particle size
through accurate control of the growth and nucleation
processes (Roco and Brainbridge, 2001; Rotello, 2003; Schmid,
2004; Jamieson et al., 2007).
The ecotoxicity of quantum dots have only recently gained
interest (Moore, 2006). For instance, the toxicity of CdTe may
be linked to the leaching of toxic heavy metals from the
colloidal form, and derived from the intrinsic properties of the
size and surface chemistry of the CdTe QDs (Clapp et al., 2004).
In theory, they could transfer energy to nearby oxygen
molecules and lead to the formation of ROS, which may lead
to cell inflammation, damage and death. In fact, Choi and
coworkers showed that quantum dots can induce cell death by
lipid peroxidation of human neuroblastoma cells (Choi et al.,
2007). More recently, the ecotoxicological effects of CdTe QDs
to freshwater mussel Elliptio complanata have been reported
showing that these NPs are immunotoxic to freshwater
mussels and can cause oxidative stress in gills and can
cause DNA damage (Gagn et al., 2008).
In summary, several types of NPs have been considered
which may have important impacts in the environment such
as fullerenes, carbon nanotubes, metals oxides and metals of
various types and quantum dots. Each of these classes is
404
composed of a vast range of different chemistries, size and

shapes making a bewildering range of possible materials. A
number of studies have shown potential impacts on a range of
aquatic organisms with a lesser focus on terrestrial and other
organisms and their toxicity can be related to dissolution,
surface properties or to size. Currently, it is questionable
whether discharges are sufficient in volume or intensity to
cause severe environmental problems and current modelling
studies suggest that risk is negligible for many NPs (Zhao et al.,
2007). Nevertheless, given the scale of the industry, future
growth and our limited knowledge in this area, concern is
warranted.
3.
Natural aquatic colloids and nanoparticles
Both natural aquatic colloids and NPs have significant effects

on pollutant, nutrient and pathogen chemistry, transport and
bioavailability. Knowledge of their chemistry and environmental impact will be highly useful for better understanding
of the fate, behaviour and toxicity of manufactured NPs in the
environment, as it has been to understand the fate and
behaviour of trace elements and trace organic pollutants. A
fuller discussion of natural colloids can be found in Lead and
Wilkinson (2006a and 2006b). In addition, further knowledge in
this area will help put in perspective the potential risk from
manufactured NPs. NPs have always been present in the
environment and in high concentrations compared with likely
concentrations of manufactured NPs. Nevertheless, some of
these natural NPs can cause deleterious effects (Nowack and
Bucheli, 2007) and the risk from manufactured NPs comes
from their novelty i.e. potentially having quite different
structure and activity compared with natural NPs and their
highly structured nature.
Natural aquatic colloids are normally classified by their
particle size and in general, they are referred to materials in a
range of 1 nm1 m in dimension, whereas particles are N1 m
(Buffle and van Leeuwen, 1992; Lead and Wilkinson, 2006a).
Natural NPs in the environment are commonly referred to as
particles b100 nm in size, in analogous fashion to manufactured NPs, and there are suggestions that this group should be
studied separately from all colloids due to their novel properties (Wigginton et al., 2007). In addition, some data suggest that
particles below 1025 nm are of particular importance with
novel properties (Madden and Hochella, 2005; Madden et al.,
2006; Lyven et al., 2003), in terms of trace element binding,
redox behaviour and surface chemistry. These colloids may be
inorganic such as iron and manganese oxides, humic substances (HS, partially stable degradation products form plants
and algae) and macromolecules such as polysaccharides,
peptidoglycans and aggregates of these materials (Fig. 2)
(Lead and Wilkinson, 2006a; Nowack and Bucheli, 2007). In
the colloidal and particulate range, concentrations may reach
several tens to hundreds of milligrams per litre, although the
smallest fraction only contains 110% of this total.
There are a variety of aquatic colloids including iron (Plaschke
et al., 2002; Lead et al., 2005; Lyven et al., 2003) and manganese
(Lienemann et al., 1997; Ferreira et al., 1997) oxyhydroxides,
aluminosilicates (Benedetti, 2006), humic substances (Milne
et al., 2001; Weber et al., 2006), viruses (Daughney et al., 2002,
Daughney et al., 2004) and bacteria (Boyanov et al., 2003). These

colloids and NPs are known to be generated by a variety of
different natural processes such as weathering of minerals and
microbial activity (Lead and Wilkinson, 2006b; Wigginton et al.,
2007). For instance, iron oxide (Glasauer et al., 2002; Banfield et al.,
2000) and manganese oxide (Villalobos et al., 2005) nanocrystals
may be consequences of metal redox reactions promoted by
microorganisms. Once natural colloids and NPs are formed, they
can also undergo aggregation and other changes in part due to
microbial action (Buffle and Leppard, 1995), with consequent
effects on fate and transport in both surface waters and in porous
media. Natural colloids and NPs can undergo aggregation due to
the interactions with other natural NPs or larger particles. This
aggregation can be produced by several physical processes such
as Brownian diffusion, fluid motion and differential sedimentation (OMelia, 1980; Mackay et al., 2006). Natural colloids and NPs
can also facilitate the transport of contaminants in surface
waters and through porous media such as groundwaters
(McGechan and Lewis, 2002; Sen and Khilar, 2006), including
potentially the transport of NPs. The movement of natural
aquatic colloids and NPs in these media is obstructed by straining
or physical filtration where the particle is larger than the pore
and is trapped and removed from solution by interception,
diffusion and sedimentation. However, particles removed from
Fig. 2 Size distributions of various types of environmental

colloids and particles and several of the analytical techniques
used to characterize them. Abbreviations employed:
FFF = field-flow fractionation; FCS = fluorescence correlation
spectroscopy; LIBD = laser induced breakdown detection.
Taken from Lead and Wilkinson (copyright 2006, JohnWiley
and Sons).
Fig. 3 TEM micrograph of fullerene aggregate in the

presence of humic acid (1 mg/L TOC) and 40 mM CaCl2 at
pH 7.58.5. Arrows indicate some of the humic acid aggregates
bridging the fullerene nanoparticles. (Taken from: K. L. Chen
and M. Elimelech, Journal of Colloid and Interface Science, 309
(2007) 126134).
suspension by such processes may be become resuspended upon

changes in the chemical or physical conditions such as pH, ionic
strength and flow rate (Sen and Khilar, 2006). The controlling
behaviour on colloids in aquatic and terrestrial environments is
thus identical to the controlling behaviour on manufactured NPs:
aggregation. Given the much higher concentrations of the
natural material (Lead and Wilkinson, 2006b), it might be
expected that natural colloids will control the behaviour of
manufactured NPs.
4.
Interactions between manufactured
nanoparticles and natural aquatic colloids
Clearly, natural colloids and (nano)particulate material present in the environment at the mg L 1 level (Lead and
Wilkinson, 2006b), will have a major impact on manufactured
NPs, present at g L 1 levels (Boxall et al., 2007). The behaviour
of natural colloids is dominated by aggregation (Lead and
Wilkinson, 2006a) and understanding these areas is essential
to understanding NP behaviour. It is useful to investigate this
potential behaviour in detail, although little work is available
under environmentally realistic conditions. The majority of
currently available studies have investigated the interactions
of several different types of NPs with extracted humic
substances (HS) only, under a variety of solution conditions
(pH ionic strength) and concluded that HS will likely stabilise
NPs in general, although not under all conditions.
Chen and Elimelech (2006, 2007) studied the influence of
humic substances (HS), pH and monovalent and divalent
electrolyte solutions on the aggregation kinetics of fullerene
(C60) by electrophoretic mobility measurements, DLS and TEM.
They observed that the aggregation was generally consistent
with the classic DerjaguinLandauVerweyOverbeek (DLVO)
theory which explains the colloidal stability (Amal et al., 1992;
Kihira et al., 1992; Tiller and OMelia, 1993). However, bridging
reactions between HS, Ca and C60 was observed (Fig. 3) and
405
steric repulsion invoked to fully explain the data (Chen and

Elimelech, 2007). Thus, HS may promote or reduce aggregation, dependent on conditions. A similar result was observed
with HS and iron oxide NPs (Baalousha et al., in press), where
nanoscale HS surface film formation induced greater stability,
but higher concentrations of added HS increased aggregation
significantly. The point of zero charge and pH at which
maximum aggregation occurred differed between the iron
oxide NP alone and the iron oxide NP with HS. Both studies
showed that the presence of added HS also altered the
aggregation mechanism compared with the nanoparticle
alone. Increased stability has been observed on 20 nm acrylate
and citrate stabilised gold nanoparticles (Diegoli et al., 2008)
due to replacement of the capping agent with HS and
subsequent surface film formation. Red and blue shifts in
the surface plasmon, under different conditions, supported
the replacement of capping agents by HS and surface film
formation, while TEM and PCS measurements quantified
aggregation. Effects on NP stability were only seen at low
and high pH, due to the intrinsic charge on the stabiliser at
circum-neutral pH values, but steric repulsion seemed the
main mechanism of stabilisation. The same effect was
observed with multi-walled carbon nanotubes in different
aqueous suspensions. Fig. 4 shows stabilised CNT in the
presence of Suwannee River natural organic matter (SR-NOM)
and 1% sodium dodecyl sulphate (SDS, commonly used
surfactant to stabilise carbon nanotubes in aqueous phase)
(Hyung et al., 2007). Initially, SR-NOM did not affect stabilisation of the MWNT in the presence of SDS. However, the NOM
appeared to stabilise the CNTs over longer periods of time
(days) and this was attributed to interactions between
CNT and NOM (Hyung et al., 2007).
Taken together, the little information available suggests a
complex interaction between natural (organic HS) colloids and
manufactured NPs of different types. The observed effects
include aggregation, disaggregation and surface film formation and are all dependent on conditions. Further work using
other colloidal fractions, such as fibrillar material, which
might be expected to induce aggregation (Buffle et al., 1998).
Longer term data to study kinetics of aggregation and more
Fig. 4 TEM image of multi-walled nanotubes stabilised in

the Suwannee River-natural organic matter solution (taken
from: H Hyung, J. D. Fortner, J. B. Hughes, J-H Kim,
Environmental Science & Technology, 41 (2007) 179184).
406
realistic experimental designs such as mesocom or in-field

work is also now required.
5.
Characterisation methods
Methods developed and used for the detection and characterisation of manufactured and natural aquatic NPs overlap to a
great extent. Several papers have reviewed this topic have
been recently published (Dresselhaus et al., 1996; Feldheim
and Colby, 2002; Terranova et al., 2006; Lead and Wilkinson,
2006b; Handy et al., 2008a,b), and the following is only a brief
account. In order to quantify the concentration and changes to
the physico-chemical form of these materials, a large number
of parameters must be measured, including size and size
distribution, specific surface area, shape and chemistry.
The enormous progress in microscopy since the inception
of electron microscopy (EM), force microscopy (FM) in the
1930 s and 1980 s, respectively, along with other methods has
allowed the extensive characterisation of manufactured and
natural NPs. There are microscopic techniques, such as
scanning (SEM) and transmission (TEM) electron microscopes
offering nanometre resolution, and scanning probe microscopy (SPM) in which the images can be obtained at atomic
resolution (Poole and Owens, 2003).
The most common characterization technique for manufactured NPs is high-resolution transmission electron microscopy
(HRTEM) (Giersig and Mulvaney, 1993; Hasan et al., 2002), from
which an electron micrograph of the NPs can be obtained.
However, their dimensions can be determined by a number of
other methods including scanning tunnelling microscopy (STM)
(Grabar et al., 1997), atomic force microscopy (AFM) (Junno et al.,
1998; Li et al., 2003), small-angle X-ray scattering (SAXS)
(Nakamura et al., 2003), and X-ray diffraction (Leff et al., 1995).
By counting a suitable number of particles (either manually or
automatically) size distributions of these NPs gives relevant
information on the dispersity of the NPs (Giersig and Mulvaney,
1993). TEM, with appropriate detectors and software, also gives a
range of other data such as fractal dimensions, elemental
composition and chemistry (bonding and redox activity).
When using TEM (and a number of other techniques such as
BET to measure specific surface area) for the analysis of aquatic
colloids, dehydration, due to ultra high vacuum (UHV) conditions, must be considered, as major structural changes can occur
due to this process (Mavrocordatos et al., 2006). This point
towards a general problem of sample handling in this area
applies to both manufactured and natural nanoparticles and
their combination. Data accuracy depends on suitable sample
preparation probably to a greater extent than correct use and
choice of instrumentation. Instruments are sophisticated and
expensive but are automated, software controlled and usually
come with highly experienced users and technicians. Preparation is a much more low-tech affair and less considered and is
often a weak link in the analysis.
The problems of dehydration have been overcome by
specialised methods for EM (Mavrocordatos et al., 2006) and
the use of other techniques. Atomic force microscopy (AFM)
and environmental scanning electron microscopy (ESEM) are
techniques which allow imaging samples under ambient
conditions at lower relative humidity to some extent circum-
vent these problems. However, the ESEM has difficulties

analysing the smallest NPs. Visualisation of both types of
NPs can be achieved by using AFM (Lead et al., 1999a; Maurice
and Nemjesnik-Dejanovic, 1999; Plaschke et al., 1999) under
humid or fully hydrated conditions. The technique is still not
fully exploited and as with EM, sample preparation is still a
crucial issue in order to obtain the required results.
In the case of the metal NPs UVvisible spectroscopy can be
used in order to determine the presence of NPs in solution and the
position of the surface plasmon band (Daniel and Astruc, 2004;
Doty et al., 2005), which contains information about size, aggregation and surface chemistry. In addition, spectral separation of
mixtures of gold NPs and humic substances has been achieved
(Diegoli et al., 2008), although other techniques such as photon
correlation spectroscopy (PCS, otherwise known as dynamic light
scattering, DLS), TEM and electrophoresis measurements were
used to fully interpret data. A second general point in characterisation studies is the need to use a variety of methods to give greater
accuracy, reduce bias and give a fuller picture of the physicochemical status of NPs. Also for metal NPs, the average surface
coverage by capping agent ligands can be calculated by elemental
analysis (Brust et al., 1995; Brust and Kiely, 2002; Jana et al., 2001), Xray photoelectron spectroscopy (XPS) (Battistoni et al., 1982) and
thermogravimetric analysis (TGA) (Templeton et al., 2000). Many
other spectroscopic and microscopic techniques can and should be
used to characterise a variety of different manufactured NPs.
PCS is a frequently used method for characterisation of
manufactured NPs, but less used in natural samples (and then
only after pre-fractionation) due to its inability to adequately
analyse polydisperse samples. Larger particles or aggregates
will mask the presence of NPs and cause difficulty in
interpretation. Nevertheless PCS remains an important method
and can give useful information on size and aggregation status
with suitable sample pre-treatment and data analysis.
Due to the complexity and polydispersity of natural colloids
and NPs, samples are generally size fractionated using cross
flow filtration (CFF) (Doucet et al., 2004; Vignati et al., 2005), fieldflow fractionation (FFF) (Baalousha and Lead, 2007a and 2007b;
Stolpe et al., 2005), ultrafiltration (Benoit and Rozan, 1999) and
centrifugation (Lead et al., 1999b, Doucet et al., 2004) to reduce
sample complexity and also provide information on different
sized fractions including the truly dissolved phase. These
methods will be very useful in examining the behaviour of
manufactured NPs in natural waters.
Ultrafiltration, along with traditional filtration, is the standard
technique used in the aquatic colloid and NP separation, and the
produced fractions can be characterised later in a variety of ways
(Guo and Santschi, 2006). Much of the information currently in
the literature on colloidal and NP binding of trace elements
comes from the combination of filtration and ultrafiltration and
metal analysis (ICP-MS or GFAAS). The particular role of
ultrafiltration in the area of manufactured NPs is to separate
the dissolved phase metal from the NP metal (for inorganic NPs),
either due to the synthesis or from re-dissolution of the NP over
time. Both dialysis and field flow fractionations (FFF) are useful
for this also (Franklin et al., 2007, Baalousha et al., in press). Flow
FFF (FlFFF) is a chromatography-like technique where separation
is effected in a thin channel (Hassellv et al., 2006) and this
fractionation technique offers higher size resolution (Lead et al.,
1999b) in the nano range below 100 nm and is ideal for
separating and characterising these NPs. However, the requirement for sample pre-concentration is a severe disadvantage
(Gimbert et al., 2005; Ranville et al., 2005; Hassellv et al., 2006)
and can promote aggregation. FlFFF has also been coupled with
different detection methods such as inductively coupled plasma
mass spectroscopy (ICPMS) for trace element analysis (Lyven
et al., 2003; Hassellv et al., 2006; Siripinyanond et al., 2005) and
this coupled technique perhaps represents the most promising
methodology for quantifying manufactured NPs in natural
samples. FlFFF has also been combined with electron microscopy
for single particle structural and chemical analysis (Baalousha
et al., 2006; Eum et al., 2007; Gimbert et al., 2006 and 2007). It has
recently been shown that the FlFFF and AFM are highly
complementary for the quantification of the structure (permeability and sphericity) of nanoscale natural colloids (Baalousha
and Lead, 2007a and 2007b), as can be seen in Fig. 5, and requires
further exploration for analysis of manufactured NPs.
A particular problem in understanding NP toxicology and
ecotoxicology which relates to characterisation is the quantifi-
407
cation of dose and two important points need to be addressed

fully in further studies and are significant gaps in our understanding of NP effects. Firstly, as is reasonably well-known, we
need to develop the correct metrics for quantifying dose i.e.
should we use mass, particle number or specific surface area.
Both a priori and with supporting experimental data (e.g. Duffin
et al., 2007) number and surface area are likely to be the key
parameters, although generally mass is specified as the dose
metric. There are a number of ways of measuring these doses
such as TEM (Chen and Elimelech, 2007) and laser induced
breakdown detection (LIBD) (Kim and Walther, 2006) but these
tend to be time consuming and/or relatively exotic methods, not
widely available. Secondly, during the time of exposure to an
organism, either in a laboratory test or in the environment, the
actual dose is likely to change for a number of reasons. For
instance, in a 24 h exposure to a selected organism in an aquatic
system, individual NPs will likely aggregate and sediment to the
bottom of the experimental tank. Aggregation and sedimentation will usually be rapid in laboratory experiments as high ionic
Fig. 5 AFM images and the corresponding particle size distribution of the FlFFF fraction b25 nm (a, d) Vale Lake, (b, e) Bailey
Brook and (c, f) Tern River, image width is 2 m (taken from M. Baalousha and J. R. Lead, Science of the Total Environment 386
(2007) 93102).
408
strength conditions are frequently chosen in such ecotoxicology

exposures so as to maintain optimal organism health in
unexposed solutions. In this example, dose to pelagic species
will decrease over time but will increase to benthic organisms.
In both cases, the dose to the organism will change over time
and to date this change is unquantified in any study. Similar
difficulties apply to preparing sediments dosed with NPs.
6.
Conclusions
The rapid growth of nanotechnology is directly related to the

ability to design novel materials at the nanoscale level alongside recent innovations in analytical and imaging technologies
for measuring and manipulating nanomaterials. This has led
to the rapid development of commercial applications which
involve the use of a wide variety of manufactured NPs.
Nanotechnologies hold great promise for reducing the production of wastes, reducing industrial contamination and improving the efficiency of energy production and use. However, the
production, use and disposal of manufactured NPs will
inevitably lead to discharges to air, soils and aquatic systems.
Therefore, it is crucial to investigate their transport into and
through the environment and their impacts on environmental
health. Currently, our knowledge is poor under realistic
conditions and the need for further understanding is urgent.
Adverse effects are likely and quantification and minimisation
of these effects is necessary, both for environmental protection
and to ensure the long term sustainability of the nanotechnology industry, with its associated benefits. Accurate knowledge
of concentration and physico-chemical properties of manufactured NPs under realistic conditions is essential in understanding their fate, behaviour and toxicity in the natural
aquatic environment and a necessary first step in this process.
The aquatic colloid and atmospheric ultrafine particle literature both offer important evidence as to the likely behaviour
and impacts of manufactured NPs, but further direct evidence
is required. In all environments, the ability to detect concentrations of NPs at natural levels is an immediate research
priority to provide baseline data on which to benchmark
further studies. Techniques are not currently available to
provide this data and need to be developed, validated and used
as a matter of urgency.
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SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 0 ( 2 00 8 ) 3 9 64 14

Manufactured nanoparticles: An overview of their chemistry,

The industrial scale production and wide variety of applications of manufactured

Received 24 June 2008

Accepted 24 June 2008

Available online 19 August 2008

environmental science community. In order to address this issue, it is important to

Natural aquatic colloids

Nanoscience involves the study of materials on the nanoscale

2008 Elsevier B.V. All rights reserved.

Among these novel nanomaterials, nanoparticles (NPs, with

(Handy et al., 2008a,b). Despite some recently acquired

Fig. 1 Top-down and bottom-up strategies.

Table 1 Number of atoms on the surface NS, and

process to promote the formation of more complex clusters

where a = 0.565 nm is the lattice constant of GaAs (Poole and

ties which will impact on their environmental behaviour

Fullerenes and carbon nanotubes

In general, fullerenes are molecules with 60 atoms of carbon,

ways: solvent exchange (Deguchi et al., 2001, Andrievsky

Ijima and co-workers were pioneers in the synthesis of CNTs

Metal oxide nanoparticles

Iron oxide nanoparticles

These NPs have been widely used for biological applications

Zinc oxide nanoparticles

The remarkable properties of zinc oxide (ZnO) have attracted

of ZnO nanoparticles did not induce any cellular damage, as

In general, titania (TiO2) is considered an excellent band-gap

crystalline form. This evidence can be attributed to the

Ceria nanoparticles (CeO2) of b10 nm have been the focus of

Gold and silver nanoparticles

Metal systems are expected to form the basis of new

whereas chemical routes use metal salts as a starting

monovalent silver ion likely contribute to its bactericidal

Zero-valent ion nanoparticles

Among the most relevant zero-valent metal nanoparticles to

particles, the surfaces of zero-valent iron nanoparticles can be

Other manufactured nanoparticles

Among the other relevant manufactured NPs, the ones based

composed of a vast range of different chemistries, size and

Natural aquatic colloids and nanoparticles

Both natural aquatic colloids and NPs have significant effects

Daughney et al., 2004) and bacteria (Boyanov et al., 2003). These

Fig. 2 Size distributions of various types of environmental

Fig. 3 TEM micrograph of fullerene aggregate in the

suspension by such processes may be become resuspended upon

steric repulsion invoked to fully explain the data (Chen and

Fig. 4 TEM image of multi-walled nanotubes stabilised in

realistic experimental designs such as mesocom or in-field

vent these problems. However, the ESEM has difficulties

cation of dose and two important points need to be addressed

strength conditions are frequently chosen in such ecotoxicology

The rapid growth of nanotechnology is directly related to the

Andersson T, Nilsson K, Sundahl M, Westman G, Wennerstrom O.

in aqueous suspensions. Environ Sci Technol

application to shallow acidic lakes and wetlands in Kejimkujik

nanoparticles with an atomic force microscope. Appl Phys Lett

Lead JR, Hamilton-Taylor J, Davison W, Harper M. Trace metal

Madden AS, Hochella MFJ. A test of geochemical reactivity as a

Oberdrster G, Stone V, Donaldson K. Toxicology of nanoparticles:

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