SPECIAL
TECHNICAL
Nanoparticle Aggregation: Challenges to Understanding Transport and Reactivity
in the Environment
Ernest M. Hotze, Tanapon Phenrat, and Gregory V. Lowry* Carnegie Mellon University
Unique forms of manufactured nanomaterials, nanoparticles,
and their suspensions are rapidly being created by manipulating
properties such as shape, size, structure, and chemical
composition and through incorporation of surface coatings.
Although these properties make nanomaterial development
interesting for new applications, they also challenge the ability
of colloid science to understand nanoparticle aggregation in
the environment and the subsequent eects on nanomaterial
transport and reactivity. This review briey covers aggregation
theory focusing on Derjaguin-Landau-Verwey-Overbeak
(DLVO)-based models most commonly used to describe
the thermodynamic interactions between two particles in a
suspension. A discussion of the challenges to DLVO posed by
the properties of nanomaterials follows, along with examples
from the literature. Examples from the literature highlighting
the importance of aggregation eects on transport and reactivity
and risk of nanoparticles in the environment are discussed.
Copyright 2010 by the American Society of Agronomy, Crop Science
Society of America, and Soil Science Society of America. All rights
reserved. No part of this periodical may be reproduced or transmitted
in any form or by any means, electronic or mechanical, including pho-
tocopying, recording, or any information storage and retrieval system,
without permission in writing from the publisher.
J. Environ. Qual. 39:19091924 (2010)
doi:10.2134/jeq2009.0462
Published online 20 May 2010.
Received 18 Nov. 2009.
*Corresponding author (glowry@andrew.cmu.edu).
ASA, CSSA, SSSA
5585 Guilford Rd., Madison, WI 53711 USA
1909
SUBMISSIONS
REPORTS
A s of the submission date of this review, approximately
4700 articles on nanoparticle (NP)-related topics have been
published in the calendar year 2009 alone (Thompson Reuters,
2009). Many of these papers discuss novel particles, and applica-
tions of nanomaterials along with their use in consumer products
are expanding rapidly (Project on Emerging Nanotechnologies,
2009). For example, nanomaterials are used for environmental
clean-up and biomedical applications (Alivisatos, 2001; Liu et al.,
2005). This expansion in applications, and the incorporation of
nano ingredients into products that may be released during the
life cycle of those products, will increase the occurrence of manu-
factured nanomaterials in the environment. For example, the
leaching of silver NPs used as antimicrobial agents in cloth was
recently reported (Benn and Westerho, 2008). Unintentionally
or intentionally, manufactured NPs might come into contact with
biological receptors. For this reason, the risk of nanomaterials to
humans and to the environment garners attention from the scien-
tic community, governmental agencies, and public stakeholders.
Nanoparticless in engineered or environmental systems could
be thought of as dispersions of primary particles. However, pri-
mary NPs tend to aggregate into clusters up to several microns
in size (Brant et al., 2007; Chen and Elimelech, 2007; Jiang et
al., 2009; Limbach et al., 2005; Phenrat et al., 2008). Therefore,
NP aggregation plays an important role in determining reactivity,
toxicity, fate, transport, and risk in the environment. The critical
role of aggregation in environmental implications had occasion-
ally been ignored (Baveye and Laba, 2008), but many recent stud-
ies have begun applying colloid science principles, based around
Derjaguin-Landau-Verwey-Overbeak (DLVO) theory, to under-
stand NP aggregation under various conditions. Manufactured
NPs challenge the limits of colloid science, however, due to their
small size, variable shape, structure, composition, and poten-
tial presence of adsorbed or grafted organic macromolecules.
Laboratory aggregation studies, which are covered in detail in this
review, have demonstrated that these challenges, acting simulta-
neously, will ultimately aect how NPs behave in the environ-
ment. Additionally, particles released to the environment undergo
Center for Environmental Implications of NanoTechnology (CEINT) and Deps. of Civil
& Environmental Engineering, Carnegie Mellon Univ., Pittsburgh, PA 15213-3890.
Assigned to Associate Editor Dionysios Dionysiou.
Abbreviations: CT, carbon tetrachloride; Df, fractal dimension; DLVO, Derjaguin-Landau-
Verwey-Overbeak; EDL, electrostatic double layer; MWCNT, multi-walled carbon
nanotubes; NOM, natural organic matter; NP, nanoparticle; NZVI, nano zero valent iron;
PZC, point of zero charge; ROS, reactive oxygen species; Velas, elastic-steric potential; VOSM,
osmotic potential; XDLVO, extended Derjaguin-Landau-Verwey-Overbeak.
chemical and physical transformations and encounter a multi-
tude of solution conditions important for aggregation, includ-
ing solution pH, dissolved ions, naturally occurring organic
matter, clays, and biocolloids.
This review focuses on three questions: (i) Can basic colloid
science predict the behavior of nanomaterials in the environ-
ment? We provide a brief overview of colloid science. Several
excellent resources are available for additional information
on colloid science (Evans and Wennerstrom, 1999; Hiemenz
and Rajagopalan, 1997; Bue et al., 1998; Elimelech and
OMelia, 1990; OMelia, 1980). (ii) Where are challenges to
existing theory posed by manufactured nanomaterials? We
discuss the intrinsic NP properties that raise these challenges.
(iii) How will these challenges aect studies of fate and trans-
port, reactivity, and risk to the environment? We describe
several case studies examining environmental implications of
nanomaterial aggregation.
Colloid Science and Aggregation
Colloid science is dened as a branch of chemistry dealing with
colloids, heterogeneous systems consisting of a mechanical
mixture of dispersion (colloids) and dispersant. When particles
are dispersed, sizes range between 1 nm and 1 m in a continu-
ous medium. Above this size range, particles begin to sediment
out of suspension. Several theories to explain aggregation of
submicrometer spherical particles have been developed and
experimentally studied for decades, the most common being
DLVO (Derjaguin and Landau, 1941; Verwey et al., 1948)
(an alternative approach is statistical thermodynamics; see
Hermansson [1999] and Koponen [2009]). By denition, the
size range of colloidal particles overlaps the size range of manu-
factured nanomaterials (i.e., <100 nm). Therefore, theories in
colloid science should be applicable to manufactured nanoma-
terials, but, due to the novelty of nanomaterial properties, sev-
eral studies have found that this is not always the case (He et
al., 2008; Kozan et al., 2008; Phenrat et al., 2008). However,
colloid science is fundamental to understanding and develop-
ing theories for nanomaterials systems. This section, therefore,
provides a very brief review of the types of aggregation and
DLVO theory.
Types of Aggregation and Aggregate Structure
Aggregation of colloidal particles occurs when physical pro-
cesses bring particle surfaces in contact with each other and
short-range thermodynamic interactions allow for particle
particle attachment to occur. For particles <100 nm in size,
Brownian diusion controls the long-range forces between
individual nanoparticles, causing collisions between particles.
When contact occurs, it can result in attachment or repul-
sion. Short-range thermodynamic interactions that control
this can be understood in the context of DLVO theory. There
are two types of aggregation relevant to manufactured NPs in
the environment: homoaggregation and heteroaggregation.
Homoaggregation refers to aggregation of two similar par-
ticles (i.e., NPNP attachment). This is observed in homo-
geneous suspensions of particles that are typically studied in
the laboratory to make useful correlations with DLVO theory.
Heteroaggregation refers to aggregation of dissimilar particles
1910
(e.g., NPclay particle attachment). Real environmental sys-
tems contain natural particles (e.g., clay particles) in numbers
far greater than the number of manufactured NPs, so heteroag-
gregation is an important fate process for manufactured NPs.
The probability that two particles attach is given by a stick-
ing coecient, also known as the attachment eciency ()
(i.e., when = 1, sticking occurs 100% of the time; when =
0.5, sticking occurs 50% of the time). Particles attaching at rst
contact ( = 1) form large dendritic aggregates, whereas par-
ticles sticking only after several collisions ( < 1) form denser
and less dendritic aggregates (Bue and Leppard, 1995). The
concept of fractal dimension is used to describe aggregate struc-
ture. Fractal dimension (Df ) can range from 1 (a line) to 3 (a
sphere). These are limits that come from Euclidean dimension,
where 1 is a straight line (e.g., x1), 2 is a at surface (e.g., x2),
and 3 is a volume (e.g., x3). Fractal dimensions are those that
lie between Euclidean dimensions. Ideal fractal structures are
self-similar throughout. Homoaggregation under controlled
laboratory conditions produces aggregates of reasonably pre-
dictable fractal dimension (Barbot et al., 2010; Chakraborti
et al., 2003; Hansen et al., 1999), whereas heteroaggregation
typically forms natural fractals (statistically self-similar over a
limited range of length scales), making aggregation state more
dicult to predict. The physical dimensions of the aggregates
formed can aect the reactive surface area, reactivity, bioavail-
ability, and toxicity. Aggregate structure must therefore be
determined and considered when interpreting fate, transport,
and toxicity data.
Derjaguin-Landau-Verwey-Overbeak and Extended
Derjaguin-Landau-Verwey-Overbeak
According to the classical DLVO theory of aggregation, the
sum of attractive and repulsive forces determines attachment
(Derjaguin and Landau, 1941; Verwey et al., 1948). This
theory maintains that only two forces dominate interactions
between particles: van der Waals (vdW) attractive and electro-
static double layer (EDL) forces. Table 1 lists an expression for
the vdW attraction experienced by two spheres in suspension
(Stumm and Morgan, 1996). Expressions for vdW commonly
calculate the attraction between two spherical particles; how-
ever, due to unique NP shapes and compositions, expanded
theoretical approaches may be needed (Gatica et al., 2005).
An EDL has a charge that reects not only the surface that it
surrounds but also the solution chemistry of the surrounding
media. Ionic strength, which is a measure of the amount of
ions present, controls the extent of the radius of the diuse
layer from the surface. Low ionic strength means the EDL ion
cloud extends far out from the particle; high ionic strength
conditions compress the EDL. Table 1 lists an expression for
the EDL experienced by two charged spheres in suspension
(Stumm and Morgan, 1996).
Classical DLVO simplies thermodynamic surface inter-
actions and predicts the probability of two particles stick-
ing together by simply summing van der Waals and electric
double-layer potentials to determine if forces are net attractive
(VT) or net repulsive (+VT). For example, in Fig. 1, van der
Waals and electric double-layer potentials are plotted as a func-
tion of separation distance between the particles. Summing
Journal of Environmental Quality Volume 39 NovemberDecember 2010
Table 1. Derjaguin-Landau-Verwey-Overbeak and extended Derjaguin-Landau-Verwey-Overbeak forces in aggregation.
Force X/DLVO Equations Origin References
van der Waals DLVO interactions of Stumm and Morgan
attraction V VDW A 2a 2 2a 2 s (4a + s ) electrons in particles (1996)
= + + ln
kT 6kT s (4a + s ) (2a + s )2
(2a + s )2

Electrostatic DLVO charged surfaces Delgado et al.

VEDL 64n kT ( a + )
2 2
double layer ze d ( s 2 ) (2007), Stumm and
= tanh exp
kT ( s + 2a ) 4kT Morgan (1996)
1
N 2 2 2
e z i ni
= i
rs 0kT

Magnetic XDLVO aligning electron Phenrat et al. (2007)

8o M S2 a 3
attraction VM = 3
spins
s
9 + 2
a

Hydrophobic (Lewis XDLVO entropic penalty of Hoek and Agarwal

VAB s s
acid-base) = G sAB exp 0 separating hydrogen (2006), Wu et al.
surface area 0
bonds in water (1999)

Osmotic XDLVO V concentration of Fritz et al. (2002),

repulsion 2d s OSM = 0 ions between two Ortega-Vinuesa et
kT particles (Fig. 4) al. (1996), Phenrat
et al. (2008),
V s
2 Romero-Cano
a 4 2 1
d s < 2d OSM = p d et al. (2001)
kT v1 2 2

V a 4 2 1 s 1 s
s < d OSM = p d 2 ln
kT v1 2 2d 4 d

Elastic-steric XDLVO V molecules on (Fritz et al., 2002;

repulsion d s elas = 0 particle surfaces Ortega-Vinuesa et
kT resist loss of entropy al., 1996; Phenrat
due to compaction et al., 2008; Romero-
2 a s s 3 s d
2 Cano et al., 2001)
V
d > s elas = p d 2 p ln
kT MW d d 2
3s d s
6 ln + 3 1 +
2 d

Bridging XDLVO NA surface molecules Chen and Elimelech

attraction bridge to other (2007), Domingos
particles et al. (2009)

DLVO, Derjaguin-Landau-Verwey-Overbeak; EDLVO, extended Derjaguin-Landau-Verwey-Overbeak.

A, Hamaker Constant; a, average particle radius; , Flory-Huggins solvency parameter; d, thickness of brush polymer layer (~); G sAB :free energy of
0
acid base interaction between particles at distance s0; , Stern layer thickness; , relative permittivity of water (=78.5 C V1 m1); o, permittivity of a vacuum
(=8.854 10 ); e, elementary charge of an electron; , inverse Debye length; k, Boltzmann constant; , decay length for acidbase interactions (=0.6
12

nm); Ms, saturation magnetization; o, vacuum permeability; MW, molecular weight of polyelectrolyte; n, number concentration of ion pairs; p, density
of polymer; d diffuse potential (~zeta potential); s, distance between interacting surfaces; s0, minimum equilibrium separation distance (=0.158 nm); T,
absolute temperature; p, volume fraction of polymer in brush; v1, volume of solvent molecule; z, electrolyte valence,
Refer to referenced publications for details of equation derivations and constraints.

these curves (VT) demonstrates that particles can have a net gated, whereas particles in the secondary well are reversibly
attraction in a primary or secondary minimum (well). Particles aggregated (i.e., re-entrainment is possible if shear forces are
in the primary well are considered to be irreversibly aggre- exerted) (Hahn et al., 2004). Figure 1 also shows something

Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity 1911


Fig. 1. van der Waals force (dashed line), electrostatic double layer (EDL) force (gray
line), total Derjaguin-Landau-Verwey-Overbeak (DLVO) forces, and elastic force plotted
together to find total potential as a function of separation distance. XDLVO, extended
Derjaguin-Landau-Verwey-Overbeak. V/KT, potential energy divided by Boltzmanns
constant and absolute temperature.
that is commonly the case with manufactured NPs having an
organic coating: Classical DLVO forces alone are not sucient
to accurately predict aggregation behavior. Steric repulsion
forces (VT + VELAS) resulting from adsorbed polymer or poly-
electrolyte coatings or natural organic matter (NOM) makes it
so these particles may only have a net attraction in a second-
ary minimum. Coated NPs may therefore aggregate reversibly
(Graf et al., 2009), and aggregation reversibility has signicant
consequences regarding the fate, transport, bioavailability, and
eects of NPs in the environment. These additional forces are
collectively known as extended DLVO (XDLVO).
In addition to steric repulsion forces (VT + VELAS) due to NP
coatings, other XDLVO forces have been invoked to match
experimental data for various types of aggregating primary
particles (Chen and Elimelech, 2007; Fritz et al., 2002; Hoek
and Agarwal, 2006; Ortega-Vinuesa et al., 1996; Phenrat et
al., 2007; Phenrat et al., 2008; Romero-Cano et al., 2001; Wu
et al., 1999). This means that additional short-range forces are
operating on an equivalent magnitude as vdW attraction and
EDL. These forces can include bridging (Chen and Elimelech,
2007), osmotic (Fritz et al., 2002; Ortega-Vinuesa et al., 1996;
Phenrat et al., 2008; Romero-Cano et al., 2001), steric (Fritz
et al., 2002; Ortega-Vinuesa et al., 1996; Phenrat et al., 2008;
Romero-Cano et al., 2001), hydrophobic Lewis acid-base (Wu
et al., 1999) (Hoek and Agarwal, 2006), and magnetic forces
(Phenrat et al., 2007). Table 1 summarizes these forces. The rel-
evant force type depends on the system tested, and frequently
more than one XDLVO force is important. Moreover, forces
are not completely independent of one another. In the case of
nanomaterials, understanding aggregation using a DLVO- or
XDLVO-based theory presents many challenges.
Nanoparticle Challenges to Derjaguin-
Landau-Verwey-Overbeak
Colloid science demonstrates that several forces with dier-
ent natures and origins govern the kinetics and extent of par-
ticle aggregation. This section elaborates how manufactured
NPs present a combination of challenges to two predominant
1912
theories in colloid science, DLVO and XDLVO.
Among these challenges are shape, size, structure,
composition, and adsorbed or grafted organic
macromolecules (e.g., coatings or NOM) (Fig.
2). Although particles not classied as nano
(i.e., <100 nm) also present some of these chal-
lenges, manufactured NPs are often designed
with the intention of amplifying these properties.
Examining some early studies demonstrating these
challenges can inform our discussion in the previ-
ous section on implications of NP aggregation on
their transport and reactivity in the environment.
Particle Size
The small size of most NPs conicts with a funda-
mental assumption of DLVO. Equations describ-
ing EDL are mathematically incorrect if this
assumption does not hold (Delgado et al., 2007).
This is because when a particle reaches a small
enough size, its surface curvature is too substantial
to assume it is at (i.e., when the assumption of
*a >>1 no longer applies). Therefore, this is one of the pri-
mary challenges when considering NP aggregation in a DLVO
framework. Aside from this, vdW and EDL forces (Table 1)
scale similarly with particle size (Evans and Wennerstrom,
1999; Hiemenz and Rajagopalan, 1997; Israelachvili, 1991),
so moving from microscale to nanoscale particles should theo-
retically aect a change on vdW and EDL forces to a similar
degree. However, as a particle decreases in size, a greater per-
centage of its atoms exist on the surface. Electronic structure,
surface charge behavior, and surface reactivity can be altered as
a result. Recent studies suggest that redistribution and chang-
ing coordination environment of charge and atoms at the sur-
faces of NPs strongly inuences their reactivity (Hochella et al.,
2008). He et al. (2008) reported that as the particle size became
smaller, the particles became more susceptible to surface charge
titration. They found an inverse correlation between particle
size and the measured point of zero charge (PZC); 12, 32, and
65 nm hematite particles had PZCs of 7.8, 8.2, and 8.8 pH
units, respectively (He et al., 2008). These hematite NPs were
synthesized using the same method so they would be identi-
cal in every aspect except for size. However, for these particles,
at pH 7 the smaller particles are less charged than larger par-
ticles, leading to lower EDL repulsion forces and subsequently
greater aggregation tendency. Indeedgiven the same ionic
strengthsmaller hematites have faster aggregation rates than
larger ones (He et al., 2008). This suggests that size polydisper-
sity in manufactured NPs aects their aggregation behavior.
Polydispersion is the reality in large-scale applications. For
example, reactive nano-scale zerovalent iron (NZVI) particles
used for environmental remediation are highly polydisperse
(Liu et al., 2005; Phenrat et al., 2007; Phenrat et al., 2009a).
Unlike van der Waals attraction, long-range magnetic attrac-
tion between two NZVI particles increases with particle radius
to the sixth power (Table 1). Polydispersity and particle size
therefore greatly aected the aggregation of NZVI having par-
ticle sizes ranging from 15 to 260 nm, with aggregation being
proportional to the fraction of large particles in the dispersion
(Phenrat et al., 2009a).
Journal of Environmental Quality Volume 39 NovemberDecember 2010
Fig. 2. Derjaguin-Landau-Verwey-Overbeak (DLVO) frames particle aggregation by modeling two solid spheres approaching in suspension. The
sum of van der Waals (VDW) force and electrostatic double layer (EDL) force determines if the particles attach or repulse. Nanoparticles present
challenges to DLVO frameworks because of shape, structure, composition, size, and macromolecule considerations. Not drawn to scale.

Another example of a size eects is halo stabilization,
where nano sized materials can control electrostatic repulsion
between two approaching micrometer-sized particles, hinder-
ing their occulation by keeping them separated beyond the
range of DLVO attractive forces (Fig. 3). Tohver et al. (2001)
found that adding 6-nm zirconia NPs to a dispersion of unsta-
ble submicron silica particles (0.6 m in diameter) stabilized
the mixture (Tohver et al., 2001). The same phenomenon was
observed for bimodal magnetorheological uids consisting of
micrometer sized magnetite particles (1.45 m in diameter)
and magnetite NPs (8 nm diameter) (Viota et al., 2007). Size
and resultant polydispersity, therefore, present a large challenge
to understanding how NP dispersions behave because these
parameters can enhance or diminish aggregation.
Chemical Composition
Colloid science captures the eect of chemical composition on
aggregation through the Hamaker constant, which governs van
der Waals attraction; saturation magnetization, which control
magnetic attraction; hydrophobicity, which controls hydro-
phobic interaction (Wu et al., 1999); and surface charge, which
governs electrostatic double layer (EDL) interaction (Table 1)
(Evans and Wennerstrom, 1999).
Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity
Particles with a high Hamaker constant have greater aggre-
gation tendency compared with particles with a low Hamaker
constant at the same solution and surface chemistry. Because
the origin of van der Waals attraction is permanent or induced
dipoles, a bulk material with electronic or molecular structure
that favors generation of permanent or induced dipoles nor-
mally has a large Hamaker constant value. For example, the
Hamaker constants of gold, silver, and polystyrene are 45.3,
39.8, and approximately 9.8 1020 J, respectively (Hiemenz
and Rajagopalan, 1997). van der Waals attraction forces are
approximately ve times stronger for gold particles in compari-
son with polystyrene (see equation in Table 1). In addition to
controlling van der Waals attraction, some materials can origi-
nate forces that challenge the DLVO framework, including
magnetic and hydrophobic interactions that promote aggrega-
tion. For example, ferromagnetic and ferrimagnetic materials,
such as zerovalent iron and magnetite, can cause long-range
magnetic attraction without an applied magnetic eld (Table
1) (Elena et al., 2009; Phenrat et al., 2007). This magnetic
force contributes to abnormally rapid aggregation. Moreover,
carbon-based nanomaterials, such as C60 or CNTs, have hydro-
phobic surfaces in aqueous environments. Interaction of all-
carbon surfaces with water molecules involves a signicant
entropic penalty driving an aggregation process that might
1913

Fig. 3. Without nanoparticles present, microscale particles aggregate because net forces are
attractive. Nanoparticles (NPs) create a halo effect that increases electrostatic double layer
repulsive forces and causes net forces between microscale particles to be unattractive.
be understood through the use of XDLVO frameworks that
model hydrophobic Lewis acidbase interactions (Wu et al.,
1999). These types of XDLVO frameworks have yet to be
developed for carbon-based nanomaterials.
Unique NP composition and morphology (e.g., core-shell
NPs) and environmental transformations of NPs will chal-
lenge DLVO explanations of aggregation. Particles with a high
surface potential have lower aggregation tendencies compared
with particles with a low surface potential given the same
solution chemistry. Nanoparticle chemical composition alters
surface potential by dissociation or ion adsorption by surface
atoms (Evans and Wennerstrom, 1999; Israelachvili, 1991).
Surface charge of uncoated NPs is therefore governed in part
by the type of atoms at the surface of the particles. However,
the core of core-shell particles, which are common, can inu-
ence the charge of the surface atoms. For example, uncoated
Fe0/Fe3O4 core-shell NPs have a zeta potential near 32 mV (in
1 mmol L1 NaHCO3 at pH 7.5), but as the Fe0 core of the par-
ticles oxidizes to magnetite, the surface charge becomes more
like that of magnetite (Phenrat et al., 2007). Gold NPs (syn-
thesized via citrate reduction) have a charge of around 55 mV
(Kim et al., 2009), presumably due to citrate acid adsorbed on
the surface. Multiwall carbon nanotubes (MWCNTs) treated
with a mixture of sulfuric acid and nitric acid (3:1) together
with ultrasonication have zeta potential around 55 mV (Kim
and Sigmund, 2004) due to carboxylation of the surface of the
MWCNTs (Smith et al., 2009). Brant et al., Cheng et al., and
Chen et al. have shown that stable fullerene clusters with nega-
tive charge of approximately 40 to 80 mV (from pH 2 to
12) were formed from mixing fullerene clusters in water for a
period of several weeks (Brant et al., 2005; Chen and Elimelech,
2009; Cheng et al., 2004). The nature of these charges is under
investigation. These examples demonstrate that core-shell
structures, the presence of coatings, and chemical transforma-
tions impart charges to NP surfaces. These charge sources, or
combinations thereof, are not accounted for in colloid science.
Understanding the fate of NPs in the environment therefore
requires a fundamental comprehension of the types of trans-
formations that the NPs may undergo during manufacturing,
under commercial use, and after release into the environment
(as discussed later in this review).
1914
Complex Crystal Structures
Complex NP crystal structures can present
challenges to colloid science because changes
in the crystal structure can alter Hamaker con-
stants and surface charges in ways not explain-
able by theory. Additionally, defects in the
crystal lattice can alter surface charge (Evans
and Wennerstrom, 1999; Israelachvili, 1991).
The crystal structure of materials with the same
atomic composition can play a large role in
determining surface charge. Nano-sized TiO2,
for example, has three dierent polymorphs:
rutile, anatase, and brookite, each with a unique
crystal structure. The zeta potential is approxi-
mately 20 mV (French et al., 2009) when
anatase and brookite structures are predomi-
nant and is approximately 35 mV (Lebrette et
al., 2004) when the rutile phase is predominant
(both measured at pH 7.5). This is consistent with ndings
that the dielectric constant can be altered by annealing pure
anatase-phase TiO2 to the rutile phase (Kim et al., 2005). The
Hamaker constant is a function of dielectric constant (Tabor
and Winterton, 1969); therefore, the Hamaker constant also
can depend on the crystal structure of NPs. This is important
to consider for NP systems containing mixtures of phases or
where crystal structures are altered for applications, such as
photocatalysis with TiO2.
Shape
In DLVO modeling, one of the primary assumptions is that
particles are spherical. This assumption is reasonable for ideal
latex particles and some ideal colloidal systems. Manufactured
NPs, however, come in a variety of nonspherical shapes.
Triangles, icosahedrons, ellipses, rhombohedrons, spindle,
rod, and tube shapes are possible (AgNPs [Moon et al., 2009],
Fe2O3NPs [Wang et al., 2009], and Ag2S [Ma et al., 2007]),
thereby complicating traditional DLVO and XDLVO.
Both vdW and EDL forces are aected by changes in
shape. Several researchers have investigated these changes
(Bhattacharjee and Elimelech, 1997; Montgomery et al., 2000;
Vold, 1954). At a separation distance smaller than the mean
diameter (v1/3, where v is the volume of particles), the attrac-
tion between anisometric particles, such as plates, rectangu-
lar rods, and cylinders, is larger than for spherical particles of
equal volume because a greater number of atoms are in close
proximity (Vold, 1954). The attraction between spheres, rods
(and cylinders), and platelets varies as s1, s2, and s3, respec-
tively, where s is separation distance (Vold, 1954). For cylindri-
cal particles, parallel orientation is energetically favored over a
perpendicular orientation at small distances. For rectangular
rods or platelets, an orientation with the largest faces oppo-
site each other is the most favorable energetically. Electrostatic
double-layer forces of cylindrical particles are theoretically a
function of particle orientation (Vold, 1954). These results
imply that shape can theoretically control aggregation under
some favored orientations. For example, Kozan et al. (2008)
studied the aggregation of tungsten trioxide (WO3) nanowire
suspensions of dierent types (uneven, single, or bundled in
Journal of Environmental Quality Volume 39 NovemberDecember 2010
diameter) and dimensions (diameter of 40200 nm and nomi- Surfactants and Macromolecular Surface Coatings
nal lengths of 2, 4, 6, and 10 m) in various polar solvents
Nanomaterials are commonly manufactured with surface
and compared the aggregate morphology of the nanowires with
coatings (e.g., surfactants, polymers, and polyelectrolytes) to
that of spherical WO3 NPs (40 nm in diameter) (Kozan et al.,
enhance dispersion stability or to provide specic functionality
2008). The aggregates of spherical WO3 NPs were more com-
(He et al., 2007; Hezinger et al., 2008; Hydutsky et al., 2007;
pact and more spherical in shape (Df ~ 2.6 and Rg ~3.8 m)
Mayya et al., 2003; Phenrat et al., 2008; Saleh et al., 2008;
than aggregates of nanowires with diameter of 200 nm (Df ~
Saleh et al., 2005; Zhang et al., 2002). Table 2 summarizes
2.3 and Rg ~2.2 m). Moreover, aggregation of the nanow-
some examples of surface-coated NPs and their applications.
ires for 7 d in a quiescent environment resulted in no signi-
Adsorbed or covalently bound surfactants prevent aggregation
cant Rg increase but an increase in Df (Kozan et al., 2008).
and enhance dispersion stability of NPs by increasing surface
This reorganization is related to the theoretical prediction that
charge and electrostatic repulsion or by reducing interfacial
anisometric particles are likely to aggregate under a secondary
energy between particle and solvent (Rosen, 2004). Coulombic
minimum (Vold, 1954). The degree of secondary minimum
attractions (Rosen, 2004; Vaisman et al., 2006; Wang et al.,
aggregation is dependent on shape and is most favorable for
2004), hydrophobic interactions (Vaisman et al., 2006), and
platelets, less favorable for rods and cylinders, and least favor-
surfactant concentration (Vaisman et al., 2006) aect the
able for spherical NPs (Vold, 1954). Loose aggregates formed
adsorbed surfactant mass and layer conformation and hence
in the secondary minimum might gradually restructure into
the ability of a surfactant to stabilize a NP against aggrega-
denser aggregates in the primary minimum. Nanoparticless
tion. Table 3 summarizes the properties of surfactants that
designed with a myriad of unique shapes (Cai and Sandhage,
aect their ability to stabilize NPs against aggregation. Low-
2005; Kawano and Imai, 2008; Sanchez-Iglesias et al., 2009)
molecular-weight surfactants reversibly adsorb on particle sur-
therefore challenge colloid science to understand their aggrega-
faces (Rosen, 2004), so, without a strong interaction between
tion behavior in the environment because of the model com-
the surfactant and NP surface, the surfactant may desorb or be
plexity of understanding these shapes in a DLVO framework.
displaced by higher-molecular-weight natural polymers such as
Although nonconventional theories, such as surface element
NOM when the particles are released into the environment.
integration (Bhattacharjee and Elimelech, 1997), may account
Therefore, changes in the stability of surfactant-coated NPs are
for interfacial forces in irregular shapes (e.g., ellipsoids), these
expected on release to the environment.
theories are dicult to apply to the unique (e.g., helical) and
Polymers are organic macromolecules consisting of repeti-
diverse types of nanomaterial shapes.
tions of smaller monomer chemical units (Fleer et al., 1993).
Table 2. Examples of surface coated nanoparticles and their applications.
Particle type Surface modifier Purpose References
Quantum dots amphiphilic alkyl-modified alter particle hydrophilicity and modify quantum Luccardini et al. (2006)
polyacrylic acid dot interactions with other biological compounds
Titanium dioxide polyacrylic acid stabilize dispersions and modify surface Kanehira et al. (2008)
chemistry allowing attachment of an antibody
for a substrate selective photocatalytic system
Fe0/Fe-oxide poly(styrene sulfonate), polyaspartate, inhibition of aggregation, decreasing adhesion He et al. (2009), Kanel et al. (2008),
carboxymethyl cellulose, or triblock to solid surfaces, increasing mobility in the Phenrat et al. (2008), Phenrat et
copolymers subsurface, and targeting specific pollutants al. (2009c), Phenrat et al. (2009a),
Saleh et al. (2005)
Carbon nanotubes various kinds of anionic, cationic, individually stabilized, single-walled carbon Moore et al. (2003)
nonionic surfactants and polymers nanotubes
Silver daxad 19 (sodium salt of a high- stabilize dispersions silver nanoparticles Sondi et al. (2003)
molecular-weight naphthalene
sulfonate formaldehyde condensate)

Table 3. Examples of surfactant properties and their relationship to particle stabilization.

Property Findings References
Surfactant A linear relationship exists between the surfactant chain length and the logarithm of Dederichs et al. (2009)
chain length the dispersion concentration (cdc), where cdc is defined as the lowest concentration of a
surfactant necessary to disperse hydrophobic particles.
Molecular weight Stabilization of CNT with nonionic surfactants increased with molecular weight (e.g., Brij Moore et al. (2003)
78 [MW = 1198 g mole1] stabilized 4.3% of CNT, while Brij 700 [MW = 4670 g mole1] could
stabilize 6.4% of CNT)
Type of ionic At similar molecular weight, cationic surfactants such as dodecyltrimethylammonium Moore et al. (2003)
head groups bromide (MW = 308 g mole1) and cetyltrimethylammonium bromide (MW =
364 g mole1) were slightly more effective in stabilizing CNT than anionic sodium
dodecylbenzenesulfonate (MW = 348 g mole1).
Self-assembly Sodium dodecyl sulfate, anionic surfactant, forms cylindrical micelles as helices or double OConnell et al. (2002), Richard
structure helices and hemicellar structures on CNT. Random adsorption of surfactants on CNT et al. (2003), Yurekli et al. (2004)
hypothesized to enhance stabilization of the CNT dispersions.

CNT, carbon nanotube.

Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity 1915

They can be synthetic (e.g., polyethylene glycol) or naturally
occurring (e.g., biomacromolecules, such as proteins and poly-
saccharides) (Brewer et al., 2005; Jain et al., 2005; Liu et al.,
2006). They also are surface active agents but are generally of
higher molecular weight than surfactants discussed previously.
Unlike surfactants, the repeating monomer units can adsorb
to NPs at multiple places along the polymer chain, making
polymer adsorption stronger than surfactant adsorption and
relatively irreversible. For example, Kim et al. (2009) modi-
ed NZVI by physisorption of various types of strong and
weak polyelectrolytes and found that <30% by mass of poly-
mer desorbed from the NPs over a period of 4 mo (Kim et al.,
2009). Polyelectrolytes are charged polymers. Their charge is
derived from ionizable groups built into the polymer structure
(e.g., from -COO, -SO4, or -SO3 groups) (Fleer et al., 1993).
Adsorbed polymers and polyelectrolytes provide electrosteric
repulsions that prevent NP aggregation. These repulsive forces
have osmotic (VOSM) and elastic-steric (Velas) components due
to their charge and large molecular weight, respectively (Fig.
4). The magnitude of the electrosteric repulsion is governed
by the surface excess (adsorbed mass of polymers per unit sur-
face area of a NP), polymer molecular weight, polymer den-
sity, adsorbed layer thickness, and solution composition (see
expressions in Table 1 and examples in Tables 4 and 5) (Fritz
et al., 2002; Ortega-Vinuesa et al., 1996; Phenrat et al., 2008;
Romero-Cano et al., 2001).
Fig. 4. Osmotic plus elastic repulsive forces (VOSM + Velas) of polyelectro-
SurfactantNP and polymerNP interactions are extremely lytes are dependent on surface layer thickness.
complex and often kinetically controlled rather than being
in thermodynamic equilibrium. The science describing or summarizes some of the environmental interactions of NPs
predicting adsorbed mass and adsorbed layer conformation that aect or are aected by aggregation and are discussed next.
is immature, and the adsorbed mass and layer conformation
depends on NP properties and solution conditions (pH, ionic Effect of Solution Chemical Composition on
strength, ionic composition). Therefore, predicting the eects Aggregation: pH and Ionic Solutes
of adsorbed surfactants, polymers, or polyelectrolytes on NP
pH and dissolved ionic solutes play crucial roles on aggregation
behavior in the environment is challenging.
of NPs in engineered and natural systems. These parameters can
be controlled in laboratory settings but may vary spatially and
Effect of Nanoparticle Aggregation on temporally in natural systems. Spatial heterogeneity of miner-
Applications and Implications als in the subsurface alters the concentration of ionic species
present in dierent systems (e.g., groundwater versus surface
for the Environment water). Variation in aquatic environment pH stems from the
Understanding NP aggregation under well controlled solution same phenomenon. A better understanding of how pH and dis-
conditions in the laboratory is dicult because NP properties solved ionic solutes aect the behavior of organic macromol-
present challenges for colloid science. However, ultimately we eculecoated NPs in the environment is needed. Surface charge
would like to comprehend the fate, transport, reactivity, and titration and EDL screening are the two primary ways that
risks associated with manufactured NPs released into the envi- pH and ionic solutes promote NP aggregation. Most NP sur-
ronment. How do these intrinsic challenges in understanding faces have surface functional groups (e.g., hydroxide and oxide
aggregation aect our understanding of NP fate, transport, and groups) that are titratable by H+ or OH. Excess of H+ (low
eects in more complicated environmental settings? Figure 5 pH) normally results in a positively charged particle surface,

Table 4. Examples of polymer properties and their relationship to particle stabilization.

Polymer property Findings References
Adsorbed layer thickness and surface excess Correlate to dispersion stability of polymer modified Fe0Fe Phenrat et al. (2008)
oxide nanoparticles.
Molecular weight Dispersion stability of carbon nanotubes increased as the Moore et al. (2003)
molecular weight of Pluronic increased.
Condition of polymer adsorption: heat treatment Adsorption of polyacrylic acid on TiO2 enhanced at 150C Kanehira et al. (2008)
versus 20C. This resulted in the enhanced dispersion stability.
Condition of polymer adsorption: solvent property More polyacrylic acid adsorbed on TiO2 in dimethylformamide Kanehira et al. (2008)
than in water.

1916 Journal of Environmental Quality Volume 39 NovemberDecember 2010

Table 5. Examples of particle stabilization and destabilization by natural organic matter and biomolecules.
System
TiO2 (positively charged)
at pH 2 to 6 with 1 mg L1 FA
TiO2 (negatively charged)
pH > PZC with 1 mg L1 FA
C60 or CNT with HA (CaCl2
concentration <40 mmol L1)
C60 with HA (CaCl2 concentration
>40 mmol L1)
AuNPs with BSA
AuNPs with lysozymes
Findings References
Disaggregation of TiO2, resulting in a smaller particle size (3 nm) than the Domingos et al. (2009)
original bare TiO2 obtained from the manufacturer (10 nm).
Flocculation of TiO2 due to bridging FA was observed. Aggregation decreased Domingos et al. (2009)
with increasing ionic concentration. High ionic concentration screened the
negative charges of FA and TiO2, resulting in greater FA adsorption onto TiO2
promoting stabilization, not bridging.
Humic acid as low as 1 mg L1 increased dispersion stability of C60 up to 5 mg L1. Chappell et al. (2009),
Humic acid concentrations increased the dispersion stability of CNTs from 5 to Chen and Elimelech (2007)
300 mg L1.
Unadsorbed HA aggregated through intermolecular bridging via calcium Chen and Elimelech (2007)
complexation. Aggregates subsequently bridged C60, resulting in flocculation.
Gold nanoparticles coated with BSA were stable as colloids at the PZC of bare Brewer et al. (2005)
AuNPs, suggesting steric stabilization due to adsorbed BSA layers.
Enhanced aggregation of lysozymeAuNP assemblies at physiological pH Zhang et al. (2009)
at very low lysozyme concentrations (16 nmol L1). Au nanoparticles were
found embedded in the lysozyme matrix.

AuNP, gold nanoparticle; BSA, bovine serum albumin; CNT, carbon nanotubes; FA, fulvic acid; HA, humic acid; PZC, point of zero charge.

Fig. 5. Hypothesized effects of the environment on nanoparticle aggregation and how aggregation state could alter nanoparticle (NP) environ-
mental interactions. (A) pH and ions. Increasing acidity can lead to charge neutralization at the point of zero charge. Increasing ionic strength
reduces the size of the electrostatic double layer and repulsive forces. Certain ions (e.g., Ca2+) can bridge functional groups on the surface of
nanoparticles. (B) Heteroaggregation. Macromolecules present in the environment coat nanomaterials leading to a steric effect. Larger mac-
romolecules trap NPs in a mesh or gel causing stabilization or destabilization. Nanoparticles also associate with other particles such as clays or
biocolloids. Nanoparticles flow through porous media depending on their aggregation state. (C) Biological interactions. Cells activate phagocy-
tosis mechanisms depending on if a particle is aggregated or not. Nanoparticles containing metals aggregate at the surface of organisms and
release metal ions at varying rates. (D) Transformations. Oxidants or sunlight degrade particle coatings or the particles themselves. Aggregated
photoactive NPs only have the outside particles active.

Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity 1917

whereas excess of OH (high pH) normally yields a negatively
charged surface. For each particular system, the pH at which
the H+ and OH concentration causes suspended particles to
have a neutral charge is called the PZC. As pH moves toward
this point, the EDL repulsion decreases, and aggregation is pro-
moted by vdW attraction (Fig. 5A). Charge reversal (i.e., from
negatively charged to positively charged particles) is also possi-
ble. This change would dramatically aect NP behavior because
most surfaces in the environment are negatively charged at near
neutral pH. As for the ionic species eect, high ionic concen-
tration decreases the Debye length (1) (see Table 1 for calcu-
lation of EDL using DLVO), resulting in the decrease of the
extent of EDL repulsion (Fig. 5A). The ionic concentration
where the repulsive energy barrier is completely screened and
rapid aggregation occurs is known as the critical coagulation
concentration. Table 6 summarizes factors governing nanoma-
terial critical coagulation concentration and dispersion sensitiv-
ity toward electrolytes. In many cases, surface titration and EDL
screening eects occur in NP dispersions as they occur for large
colloidal particles. However, there are notable exceptions where
the pHPZC depends on the NP size. Table 7 summarizes param-
eters altering nanoparticle PZC.
Heteroaggregation and Deposition
The environment is a complex system with multiple primary
molecules and particles as well as solution compositions.
Straightforward DLVO theory is dicult to apply to these sys-
tems, and typically XDLVO forces are brought into models to
improve results (Wu et al., 1999). At best, DLVO + XDLVO
provides qualitative information about aggregation and deposi-
tion, but this information is useful for understanding the inu-
ence of various parameters on aggregation and deposition.
Nanoparticle Interaction with Naturally Occurring Organic Matter,
Biomolecules, and Biomacromolecules
As with synthetic surface coatings used on NPs (e.g., polyelec-
trolytes), naturally occurring organic macromolecules (e.g.,
NOM) in the environment can signicantly alter the aggre-
gation behavior of NPs. Even without fully dened structure,
due to its macromolecular nature, NOM is expected to prevent
aggregation and deposition presumably due to electrosteric sta-
bilization (Amirbahman and Olson, 1993; Amirbahman and
Olson, 1995). Natural organic matter consists of mainly fulvic
and humic substances. Fulvic compounds typically make up 40
to 80% of NOM compounds, and, due to their small size (1
kDa), they can coat the surfaces of particles. Fulvic compounds
alter the surface charge and have been shown to stabilize with
an eect similar to surfactants (Domingos et al., 2009). In fact,
NOM may stabilize MWCNTs better than surfactants com-
monly used for laboratory suspensions of MWCNTs (Hyung et
al., 2007). However, enhanced dispersion stability due to elec-
trosteric forces and destabilization due to bridging have been
experimentally observed, and it is not often possible to predict
these interactions. Natural organic matter attaches to the sur-
face of particles in a variety of ways. For example, irreversible
adsorption onto the surfaces of iron oxide via ligand exchange
between carboxyl/hydroxyl functional groups of humic acid
and iron oxide surfaces (Gu et al., 1994) or hydrophobic inter-
actions with carbon based nanomaterials (Hyung et al., 2007)
have been reported. Whether or not attachment results in stabi-

Table 6. Factors governing nanomaterial critical coagulation concentration and dispersion sensitivity toward electrolyte concentration (ionic
strength).
Parameter Findings References
Type of ionic Regardless of particle type, CCC for divalent ions (e.g., CaCl2 or MgCl2) Chen and Elimelech (2007), Evans and
species is lower than for monovalent ions (e.g., NaCl). Wennerstrom (1999), Saleh et al. (2008)
Particle size Values of CCC increase with increasing particle size (e.g., CCC values of Fe2O3 with He et al. (2008)
diameter of 12, 32, and 65 nm have CCCs of 45, 54, and 70 mmol L1 NaCl, respectively).
Type of particles The CCC of carbon nanomaterials such as fullerene appears to be higher than that of Chen and Elimelech (2007),
metal oxide such as Fe2O3 [e.g., CCC of C60 [dp = 60 nm] is around 120 mmol L1 NaCl, He et al. (2008)
whereas that of Fe2O3 [dp = 65 nm] is 70 mmol L1 NaCl). This is presumably due to
stronger van der Waals attractions of Fe2O3 in comparison to C60, making the stability
of metal oxide nanoparticles more sensitive to screening effects.
Particle shape The CCC of carbon nanotubes is lower than C60 particles. Van der Waals attraction is Chen and Elimelech (2007),
greater and EDL repulsion is lower for rod-like shapes than for spherical shapes. Saleh et al. (2008)
Surface modifier Due to steric repulsions polymeric surface modification decreases the sensitivity Kanehira et al. (2008)
of aggregation induced by ionic species. NZVI (dp = 162 nm) modified by guar-gum
prevented aggregation at ionic concentrations up to 0.5 mmol L1. TiO2 modified
by PAA prevented aggregation in ionic concentrations up to 0.5 mol L1 NaCl.

CCC, critical coagulation concentration; EDL, electrostatic double layer; NZVI, nano zero valent iron; PAA, polyacrylic acid.

Table 7. Parameters altering nanoparticle point of zero charge.

Parameter
Chemical composition
Surface modification
Particle size
Particle transformation
Findings References
PZCs of metal NPs, metal oxides, and carbon nanomaterials have a wide range Brant et al. (2005), Kim et al. (2009),
and need to be measured for each material and preparation method. Kosmulski (2009), Sirk et al. 2009
Surface modification using anionic polyelectrolytes shifts PZC toward lower Kim et al. (2009), Sirk et al. (2009)
values (e.g., ~3 pH units for Fe0/Fe-oxide nanoparticles).
PZCs for hematite nanoparticles of diameter 12, 32, and 65 nm are ~7.5, 7.8, He et al. (2009)
and 8.5, respectively.
Aged Fe0/Fe oxide nanoparticles have lower PZC than fresh NPs by ~3 pH Kim et al. (2009)
units, presumably due to surface oxidation and hydrolysis.

NP, nanoparticle; PZC, point of zero charge.

1918 Journal of Environmental Quality Volume 39 NovemberDecember 2010

lization or destabilization depends on several factors, including
type of NOM, NOM concentration, and solution chemistry
(Chen and Elimelech, 2007; Chen et al., 2006; Diegoli et al.,
2008; Domingos et al., 2009). Stabilization usually results from
NOM forming a charged stabilizing layer on the outside of the
particle. Destabilization, on the other hand, results from par-
ticles being bridged by larger NOM molecules, such as rigid
biopolymers (Fig. 5B, left). This occurs for relatively large-sized
NOM (~10100 kDa) and can dominate interactions between
nanoparticles (Bue et al., 1998). Large-molecular-weight bio-
molecules and biomacromolecules, including proteins, poly-
peptides, and amino acids (McKeon and Love, 2008; Moreau
et al., 2007; Vamunu et al., 2008), aect aggregation of NPs in
aquatic environments similarly. Table 5 summarizes reports of
NP stabilization and destabilization aorded by the presence of
NOM and biomacromolecules reported in literature.
Nanoparticle Interaction with Inorganic and Biocolloids
Nanoparticles released to the environment can interact with
inorganic colloids (e.g., clays, aluminoscilicates and iron oxy-
hydroxides) and biocolloids (e.g., bacteria), altering the disper-
sion stability of engineered NPs via heteroaggregation (Fig.
5B). Heteroaggregation with bacteria can prevent aggregation
or promote disaggregation of NPs. Cerium oxide NPs were
reported to attach the surface of bacteria at the maximum
adsorption capacity of 15 mg of CeO2 m2 due to electrostatic
attraction (Thill et al., 2006). Holden et al. (2009c) showed
that TiO2 NPs were disaggregated in the presence of micro-
organisms (unpublished data). Heteroaggregation of NZVI
and bacteria also increases dispersion stability when com-
pared with dispersions containing no bacteria (Li et al., 2010).
Heteroaggregation with bacteria, NOM, or mobile colloids
(e.g., clay particles) could enhance NP stability, but heteroag-
gregation to large enough particles could also destabilize NP
dispersions. A complete understanding of the impacts of het-
eroaggregation on NP behavior requires more experimentation.
Effect of Aggregation on Deposition and Sedimentation
Aggregation of NPs aects their fate and transport in ground
and surface waters (Fig. 6). In the subsurface, aggregation aects
deposition processes; in surface waters, aggregation drives sedi-
mentation processes. Homoaggregation of NPs mostly leads to

Fig. 6. Nanoparticles are hypothesized to transport differently in the environment depending on their homo- or heteroaggregation state.
Homoaggregated particles are more likely to attach to surfaces and be removed in porous media. Homoaggregation can also lead to the forma-
tion of aggregates that are large enough to be settled out of surface waters by gravitational forces. Heteroaggregation may lead to surface particle
coatings that enhance transport in porous media. Heteroaggregation can also lead to stabilization or destabilization effects in surface waters (e.g.,
with bacteria or natural organic matter).

Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity 1919

high deposition rates in porous media because of increased col-
lisions between NP clusters and aquifer materials via sedimenta-
tion and interception as opposed to relying only on Brownian
motion. For example, NZVI injected into the subsurface at high
particle concentrations (110 g L1) aggregate rapidly, and their
mobility in the subsurface suers as a result (Kanel et al., 2008;
Phenrat et al., 2007; Saleh et al., 2007) (i.e., they do not trans-
port far from their injection point).
There are numerous studies that suggest prevention of
aggregation improves transport in porous media. Polymeric
surface modication has been used to decrease NZVI aggrega-
tion and therefore deposition (Kanel et al., 2008; Kim et al.,
2009; Phenrat et al., 2009c; Phenrat et al., 2008; Saleh et al.,
2008). He et al. (2009) and Tiraferri and Sethi (2009) observed
enhanced mobility of NZVI modied with adsorbed carboxy-
methyl cellulose and guar gum (He et al., 2009; Tiraferri and
Sethi, 2009). Phenrat et al. (2009a) demonstrated that NZVI
transport was limited specically by NP aggregation during
transport in porous media by comparing the transport of non-
aggregating hematite NPs and aggregating NZVI of the same
size and surface chemistry. When NP deposition is interpreted
by classical ltration theory (i.e., assuming no aggregation
during particle transport in porous media), the eect of aggre-
gation is neglected and can lead to error in the reported attach-
ment coecient. This makes comparisons between dierent
experiments and systems dicult.
In contrast to homoaggregation, heteroaggregation with
mobile, natural colloidal particles (e.g., clay) and with natu-
ral particles that have low density (e.g., microorganisms) can
enhance transport of NPs in porous media by decreasing the
particle collision rate. For example, the presence of 20 mg
L1 NOM enhanced NZVI transportability in porous media
(Johnson et al., 2009). Clay particles were also used as NZVI
supports to enhance NZVI mobility (Hydutsky et al., 2007),
which indicates that heteroaggregation between clay and NZVI
enhances NZVI mobility.
In surface waters, homoaggregation can enhance sedimen-
tation if aggregates or agglomerates reach a size where gravity
forces acting on the particles becomes signicant compared
with Brownian diusion (OMelia, 1980). Nanoparticles with
low dispersion stability therefore tend to accumulate in the
sediment near their source (Fig. 6). Heteroaggregation, with
low-density natural colloids, may facilitate stabilization or dis-
aggregation of NPs, which would increase their residence times
in water bodies (Fig. 6). Stabilizing or destabilizing NPs against
aggregation can have far-reaching eects. For example, cerium
oxide NPs stabilized with surfactant remained dispersed as col-
loids and were not eectively removed by an activated sludge
system (Limbach et al., 2008). Additionally, the removal e-
ciency of functionalized versus nonfunctionalized fullerene
NPs by alum coagulation was compared. Increased steric sta-
bilization by surface functionalization prevented aggregation
and attraction with alum ocs (Hyung and Kim, 2009). In
contrast, surface coatings, such as Tween 20 on SiO2 NPs,
have been shown to enhance their occulation and removal
during water treatment, whereas uncoated SiO2 NPs were not
removed (Jarvie et al., 2009). The ability to predict the aggre-
gation eects of adsorbed or grafted organic macromolecular
coatings on NP surfaces is not possible with current DLVO
1920
or XDLVO theory and is an important area of environmental
nanotechnology research.
Effect of Aggregation on Nanoparticle Reactivity
and Effect of Reactivity on Aggregation State
Aggregation can alter NP reactivity, and NP aggregation state
can be altered by chemical or photochemical environmen-
tal processes (Fig. 5D). Several types of NPs are photoactive
(e.g., C60, quantum Dots, and TiO2) and can produce reactive
oxygen species (ROS). A relationship between Df and photoac-
tivity indicates that the structure of the aggregates formed has a
role in determining ROS production and subsequent reactivity.
Fullerene (C60) is a photoactive carbon-based class of NP that
forms crystalline aggregates in water with high Df (i.e., closely
packed aggregates). This aggregation promoted triplettriplet
annihilation and self-quenching due to close contact between
cages and severely reduced the quantum yield of C60 (Hotze
et al., unpublished data). Fullerol (hydroxylated fullerene),
which has a lower theoretical quantum yield than C60 produced
greater amounts of ROS than C60 under identical solution con-
ditions because fullerol formed aggregates with lower Df (less
closely packed fractal aggregates), which decreased the amount
of triplettriplet annihilation and increased ROS yield relative
to C60 (Hotze et al., unpublished data).
Aggregation has been shown to decrease the rate of dissolu-
tion of lead sulde (PbS) NPs (Liu et al., 2008). The dissolu-
tion rate of 240 nm aggregates of PbS NPs (4.7 1010 mol m2
s1) was an order of magnitude lower than for monodisperse
14-nm primary PbS NPs (4.4 109 mol m2 s1) and also
lower than for micrometer-sized particles of the same materi-
als. In addition to aggregation decreasing available surface area
for dissolution, they attributed the retarded dissolution to inhi-
bition in the highly conned space between the particles in
the aggregates. In conned space, water molecules arrange dif-
ferently than in the bulk, increasing viscosity at the interface.
Enhanced viscosity in conned space decreases the diusion
rate of water to the surface and therefore the dissolution rate.
They also hypothesized that the overlap of the diusion layer
between two adjacent particles in an aggregate can reduce the
concentration gradient (i.e., the driving force for dissolution)
from NP surfaces to bulk solution.
Another example of aggregation decreasing NP reactivity
is the dechlorination of carbon tetrachloride (CT) by 9-nm-
diameter magnetite NPs (Vikesland et al., 2007). The CT
dechlorination rate decreased as the degree of aggregation
of the magnetite NPs increased. By promoting aggregation
through addition of dierent concentrations of monovalent
or divalent cations, an inverse relationship between aggre-
gate size (measured by DLS) and the CT dechlorination rate
was established.
Although aggregation can aect NP reactivity, NP reactiv-
ity can also aect aggregation. Clusters of C60 also undergo
photochemical oxidation and subsequent disaggregation in
water (Hou and Jafvert, 2009; Lee et al., 2009). For exam-
ple, Hou and Jafvert (2009) reported that the photochemical
transformation of aqueous C60 clusters in sunlight decreased
mean aggregate size from 500 to 160 nm and produced
unidentied soluble reaction products after 65 d of exposure
Journal of Environmental Quality Volume 39 NovemberDecember 2010
to natural sunlight (Hou and Jafvert, 2009). Lee et al. (2009)
observed similar transformations under UV light exposure
(Lee et al., 2009). Photochemical transformations of C60
also took place during heteroaggregation with NOM (Li et
al., 2009) and enhanced the dispersion stability of NOM-
coated C60 in comparison to nonilluminated samples (Li et
al., 2009). Enhanced dispersion appeared to be due to a sur-
face erosion or dissolution-recrystallization process catalyzed
by sunlight, rather than a simple breakage of C60 from clus-
ters (Li et al., 2009). Therefore, NPs designed to be reactive
under photoilluminated conditions (e.g., C60 or TiO2) could
have their aggregation properties altered by long-term sun-
light exposure.
Chemical oxidation could act in a similar manner by alter-
ing surface coatings or the underlying NP so that the particles
gain or lose stability against aggregation (Fig. 5D). For exam-
ple, ozone reacts with C60 (Fortner et al., 2007) and CNTs,
breaking the carbon cage structure and altering the stability of
the NPs against aggregation in aqueous suspension. This ozo-
nation process has been demonstrated to render the oxidized
C60 more photoactive than its unoxidized parent aggregates
(Cho et al., 2009). Additionally, surfactants and coatings are
susceptible to these same types of oxidation processes possi-
bly decreasing the stability of NPs in the environment due to
loss of the stabilizing coating. A better understanding of the
biological and abiotic reactions aecting NP stability against
aggregation is needed to predict their fate in the environment.
Effects of Aggregation on Biological Impacts
from Nanoparticles
Aggregation of NPs can alter their biological eects by aecting
ion release from the surface, if and where particles collect inside
an organism, and the reactive surface area of NPs (Fig. 5C).
Calculation of metal ux at cell surfaces is important for deter-
mining the bioavailability and ecotoxicity of nanomaterials. This
is especially true in the case of silver NPs where silver ion release
plays an important role in the inhibition of bacterial growth
(Taurozzi et al., 2008; Ju-Nam and Lead, 2008). Ion release
may also prove to be important for determining the impacts of
quantum dots and iron NPs, among others. Heteroaggregation
can confound understanding of metal ux because the metal
can also bind to surfaces and internal sites of naturally occur-
ring colloids of various sizes and compositions (Bue et al.,
2007). Solution chemistry (e.g., ionic strength and the amount
and type of NOM) controls the fractal dimension of NP aggre-
gates, with lower Df (1.32.0) formed in solutions with high
NOM, and higher Df (2.32.7) formed in solutions without
signicant NOM present (Zhang et al., 2007). Aggregate struc-
ture plays an important role in how metal ions diuse inside of
the ocs where the kinetics of metal association and dissociation
from binding sites is slowed by orders of magnitude compared
with rates expected for free ions in solution (Bue et al., 2007).
Understanding mechanisms by which aggregate structure aects
the dissolution and release of ions and resulting ecotoxicity (e.g.,
from silver NPs) will improve insights into the potential impacts
of such particles in the environment.
Aggregation alters the NP size distribution, in turn aect-
ing the fate of NPs in biological systems as well as their toxic-
Hotze et al.: Nanoparticle Aggregation: Environmental Transport and Reactivity
ity. For example, 20-nm NPs were found to deposit mostly in
the alveolar region, whereas 5- to 10-nm particles deposited
in tracheobronchial region, and particles smaller than 10 nm
accumulate mostly in the upper respiratory tract (Heyder et
al., 1986; Oberdorster et al., 2007; Swift et al., 1994). This
indicates that aggregation can alter exposure locations or
exposure pathways. Nanoparticle aggregation was also shown
to aect the mode of cellular uptake of NPs and subsequent
biological responses. For example, phagocytosis by macro-
phages and giant cells is a mechanism used by cells to clear
particles of a few microns or less (Oberdorster et al., 2007).
Phenrat et al. (2009b) found that aggregation aected uptake
of bare and polymer-modied NZVI particles by mammalian
glial cells. Although the primary particle sizes of bare NZVI
particles (20100 nm) are smaller than the optimal size range
(12 m) for phagocytosis, the NZVI loosely aggregated to
micrometer-sized clusters in the physiological buer, trigger-
ing phagocytosis and subsequent uptake. Biological eects,
therefore, vary depending on whether or not a particle is
aggregated, among other confounding factors (e.g., endotox-
ins, adsorption of biomacromolecules, etc.). Given this fact,
understanding aggregation in biological systems is essential
for elucidating mechanisms of toxicity.
Conclusions
The ability to manipulate atoms allows scientists to create
NPs with signicantly dierent reactivity than their micro-
sized analogs (He et al., 2008; Kanehira et al., 2008).
Reports on NP behavior and eects to date indicate that
the aggregation behavior of the NPs will signicantly aect
their fate, transport, reactivity, bioavailability, and eects in
environmental systems. Fortunately, the science of aggrega-
tion is well developed. Unfortunately, the translation of that
science into the regime of nanomaterials remains a challenge
due their unique physical and chemical properties (e.g., size,
shape, composition, and reactivity). The presence of organic
macromolecular coatings on NPs including those engineered
as part of the NP, or those that are acquired in the environ-
ment (e.g., adsorption of NOM), further complicate analysis
of NP behavior by traditional colloid science. Nanomaterial
aggregation studies, therefore, aim to take into account
how these types of novel surface properties will alter what
is already understood about aggregation science. Ultimately,
this will guide scientists grasp of how nanomaterials and
NPs will occur in and aect environmental systems. Much
work remains to gain a full understanding of NP aggregation
and how to apply these principles to create better applica-
tions and lower impacts of nanomaterials.
Acknowledgments
This material is based on work supported by the National Science
Foundation (NSF) and the Environmental Protection Agency (EPA)
under NSF Cooperative Agreement EF-0830093, Center for the
Environmental Implications of NanoTechnology (CEINT). Any
opinions, ndings, conclusions or recommendations expressed in this
material are those of the author(s) and do not necessarily reect the
views of the NSF or the EPA. This work has not been subjected to
EPA review, and no ocial endorsement should be inferred.
1921
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Journal of Environmental Quality Volume 39 NovemberDecember 2010