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nanoparticles (NPs) and their possible release in considerable amounts into the natural
aquatic environment have produced an increasing concern among the nanotechnology and
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
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
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
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
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
NT 8n3 6n2 3n
d na 0:565n
398
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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-
2.1.
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
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
2.1.2.
Carbon nanotubes
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.
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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.
2.2.2.
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2.2.3.
Titania nanoparticles
401
2.2.4.
Ceria nanoparticles
402
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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.
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2.3.2.
403
2.4.
404
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3.
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
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
406
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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-
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
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
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
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6.
Conclusions
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