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To cite this article: David J. Burleson , Michelle D. Driessen & R. Lee Penn (2004) On the Characterization of
Environmental Nanoparticles, Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and
Environmental Engineering, 39:10, 2707-2753, DOI: 10.1081/ESE-200027029
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JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH
Part A—Toxic/Hazardous Substances & Environmental Engineering
Vol. A39, No. 10, pp. 2707–2753, 2004
On the Characterization of
Environmental Nanoparticles
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ABSTRACT
The presence and release of nanoparticles into the environment has important
implications for human health and the environment. This article highlights and
describes techniques that are effective in the characterization of anthropogenic
and naturally occurring nanoparticles. Particle attributes like size, size distribu-
tion, shape, structure, microstructure, composition, and homogeneity are
critically important to determining the potential impact of such materials on
health and the environment. Many techniques yield data for a collection of
nanoparticles; while others yield data for individual nanoparticles; and still others
yield data showing the size, distribution of chemical species, and variations in
structure and microstructure for a single nanoparticle. All are important in the
context of environmental nanoparticles. Many of these techniques are comple-
mentary, and depending on the information required, the ideal characterization
usually employs multiple techniques.
2707
INTRODUCTION
Many common products and processes use and produce solid-state nanomater-
ials. The presence and release of such materials into the environment has important
implications for human health (Anastasio[1] and Cass et al.[2] and references
contained therein) and the environment. For example, common products containing
nanoparticulate components include cosmetics, sunscreens, pigments, catalysts,
pharmaceuticals, building materials, and electronic devices. Furthermore, much of
the reactive surface area on and near the Earth’s surface is comprised of
nanoparticles that are the products of physical and chemical weathering of rocks
and minerals, combustion, volcanic eruptions, biomineralization, and precipitation
reactions (e.g., Anastasio[1] and Banfield and Zhang[3]). While such nanoparticles
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represent only a tiny fraction of the Earth’s total mass, they represent a large fraction
of the surface area, which includes solid–solid, solid–liquid, and solid–gas interfaces.
The transport of anthropogenic and naturally occurring nanomaterials in the
environment and in living systems and how such materials facilitate or inhibit the
transport of chemical species is an understudied area that is full of opportunity. A
distinction must be made between anthropogenic nanomaterials, which are
manufactured materials, and naturally occurring nanomaterials. However, deter-
mining whether the source of a particular sample of nanoparticles was anthro-
pogenic or natural, or even biogenic or abiogenic, is often not straightforward.
A great deal of research over the last decade has been dedicated to studying
the health effects of airborne ultrafine particles. Many of these studies deal with
the size fraction commonly referred to as PM10, which usually refers to a mixture
of particulates (minerals, soot, biological particles, sea salt, and other solid-
state particles like ice and solid sulfuric acid) with an average aerodynamic size under
ten micrometers. Ultrafine usually refers to particulates with an aerodynamic size
under 100 nanometers. A major question in the field is whether the impact of
exposure to particles is size dependent, and several publications[4–7] specifically
suggest that health effects due to nanoparticle exposure are indeed size dependent.
For example, Brown et al. showed that lung inflammation resulting from the
inhalation of polystyrene nanoparticles was greatest for the smallest nanoparticles
used.[5]
In addressing the importance of nanoparticles in the environment, it is
important to understand the environment in which the nanoparticles are found or
used. For example, iron metal nanoparticles are finding use for the remediation of
sites contaminated with chlorinated hydrocarbons and other anthropogenic
contaminants.[8–10] In studying the mechanisms by which the nanoparticles are
involved in the chemical transformations of contaminants, it is important to examine
not only the chemical species before, during, and after reaction, but also the
nanoparticles before, during, and after reaction. For example, the reductive
transformation of anthropogenic contaminants like chlorinated hydrocarbons and
nitroaromatic compounds is accompanied by the oxidation of either dissolved
chemical species or solids (e.g., iron metal particles or naturally occurring materials).
Thus, to fully understand the mechanisms of such transformations, both the
molecular and solid-state products must be characterized. The focus of this article is
the characterization of solid nanoparticles.
ORDER REPRINTS
cantly lower than the melting temperature of bulk, crystalline gold.[18] For a nano-
particle that is five nanometers in diameter, nearly one half of the particle’s atoms
are located at or near the surface. Chemically, surface atoms and ions are distinct
from bulk atoms because they are either coordinatively undersaturated (e.g., in a
vacuum) or bonded to species from the surroundings (e.g., solution species, atoms
from adjacent solid material, or gas molecules) rather than bonded to the next layer
of bulk atoms. Furthermore, the atoms and ions near the surface layer are chemically
distinct from bulk atoms and ions because some of their nearest and next-to-nearest
neighbors are surface atoms.
Attributes such as particle size and shape impact how easily particles are
transported into and throughout the environment and living tissue. The vast
majority of reactions involving nanoparticles occur at the interface between the
nanoparticle and its environment (liquid, solid, or gas). Thus, surface area per unit
mass, porosity, and the condition of the surface (e.g., presence of adsorbates or
surface-bound water) are also significant. In addition, there is a growing body of
evidence that smaller particles are more reactive than larger particles, even when
rates of reaction are normalized to the total amount of surface area present.[19–21]
Furthermore, the crystal structure (e.g., anatase and rutile are two polymorphs of
titanium dioxide), crystallinity, and microstructure (e.g., type and concentration
of dislocations and stacking faults) can affect chemical reactivity. An example of
microstructure-controlled reactivity includes the formation of dissolution etch-pits
originating at dislocations contained at the interface between albite and orthoclase
aluminosilicates, which are two common minerals.[22] Thus, the characterization of
nanoparticle composition, surface area, shape, size, structure, and microstructure as
well as determining the distribution of species throughout a nanoparticle (including
the surface) are critical to evaluating the health and environmental impacts of
naturally occurring and anthropogenic nanoparticles.
placing a hydrated particle into a high vacuum system can dramatically alter both
the composition and structure of the particle. Furthermore, recent work has shown
that the crystal structure of nanoparticles can change as a result of changing the
solvent to which they are exposed.[23] An additional concern is how the particles
change with time. For example, phase transformations and particle growth of
ferrihydrite (a semi-crystalline iron oxyhydroxide mineral) nanoparticles stored in
aqueous suspension is observed even at 2 C.[24]
The quantity of material required can vary from femtograms to grams,
depending on the analysis methods performed and the information desired.
Unfortunately, many nanoparticle characterization methods are destructive, and
the application of some ‘‘nondestructive’’ techniques results in subtle changes in the
sample that can significantly impact results of subsequent analyses. Thus, holistic
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Imaging
Table 1. Techniques used for nanoparticle characterization, organized according to their appearance in this article.
2712
Spatial resolution,
Main minimum particle size, Sample
Acronym(s) Meaning informationa or detection limit requirementsb Notes:
Nanometer length-scale
STEM Scanning Transmission I, S, D, P, APS <0.1 nm spatial resolution Sub-mg, a In combination with EELS/EDS: C,
Electron Microscopy Ox, and CB is possible. Can
quantify the size of an individual
particle
TEM Transmission Electron I, S, D, P, APS >0.1 nm spatial resolution Sub-mg, b In combination with EELS/EDS: C,
Microscopy Ox, and CB is possible. Can
quantify the size of an individual
ORDER
particle
HRTEM High-Resolution TEM I, S, D, P, APS 0.1 nm spatial resolution Sub-mg, b In combination with EELS/EDS: C,
Ox, and CB is possible. Can
quantify the size of an individual
particle
REPRINTS
SAED Selected Area Electron D, P, S 0.1 mm diameter area Sub-mg, b Scattering volume is selected by use of
Diffraction a selected area aperture
CBED Convergent Beam Electron D, P, S 1 nm diameter area Sub-mg, a Scattering volume is selected by
Diffraction focusing the electron beam
EELS Electron Energy Loss C, Ox, CB 0.5 nm spatial resolution Sub-mg, b Smallest volume analyzable is
Spectroscopy determined by the size of the
electron probe. Single atom
detection possible with some
elements
EDS Energy Dispersive C 0.5 nm spatial resolution Sub-mg, b Smallest volume analyzable is slightly
Spectroscopy Also larger than the projected volume
EDX, XEDS defined by the size of the electron
probe
Burleson, Driessen, and Penn
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EFTEM Energy-Filtered TEM I, S, D, P, C, Ox, CB 0.5 nm for C, Ox, and CB Sub-mg, b Energy-filtered images are formed
using electrons that have lost a
specified amount of energy by
coupling EELS with TEM
HAADF High-Angle Annular Dark I, S, D, C 0.1 nm Sub-mg, a Also known as Z-contrast imaging.
Field Single heavy atom imaging is
possible using HAADF
AEM Analytical Electron I, S, D, P, C, Ox, CB, APS 0.5 nm spatial resolution Sub-mg, b AEM refers to the combination of
Microscopy for analyses, 0.1 nm for imaging nd analytical techniques
imaging (e.g., EELS and EDS)
ETEM Environmental TEM I, S, D, P, C, Ox, CB >0.1 nm spatial resolution Sub-mg, stable under Semi- in situ measurements possible
ORDER
(continued)
2713
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Table 1. Continued.
2714
Spatial resolution,
Main minimum particle size, Sample
Acronym(s) Meaning informationa or detection limit requirementsb Notes:
Micrometer length-scale
SEM Scanning Electron I, APS 1 nm–1 mm spatial resol- Sub-mg, semicon- Can quantify the size of larger
Microscopy ution depending on signal ductive or con- individual particles. In combination
monitored ductive with Auger Spectroscopy: C, Ox,
and CB. In combination with EDS:
C. In combination with EBSD: S, P
SE Secondary Electrons I, APS 1 nm spatial resolution SE are commonly detected in SEM.
SE intensity maps yield mainly
ORDER
topographical information
BSE Back-scattered Electrons I, some C 1 mm spatial resolution BSE are commonly detected in SEM.
BSE intensity maps yield mainly
atomic number (Z) contrast
EBSD Electron Back-scatter S, P, crystal 1 mm3 Used in combination with SEM: S, P
REPRINTS
Diffraction orientation
AES Auger Electron C, Ox, CB 1–2 nm spatial resolution Sub-mg, semicon- Extremely surface sensitive technique.
Spectroscopy possible. ductive or con- Often used in combination with
ductive SEM. Mostly used for C
ESEM Environmental SEM I, APS 3–4 nm spatial resolution Same as above Semi- in situ measurements possible
(sample chamber at 1–10 Torr
pressure)
PIXE Particle Induced X-ray C 1 mm3 Sub-mg Trace element detection limits on the
Emission order of 1015 g In situ
measurements possible
XPS X-ray Photoelectron C, Ox, CB 1 mm spatial resolution Sub-mg Extremely Surface Sensitive Technique
Spectroscopy possible
Burleson, Driessen, and Penn
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Bulk analyses (These methods produce an average result for a sample of nanoparticles)
AA Atomic Absorption Also C 10–100 ppb detection limit Sub-mg Average compositional analysis.
AAS (see text) Sample prep. generally requires
sample dissolution
AES Atomic Emission Spectros- C 10–100 ppb detection limit Sub-mg Average compositional analysis.
copy Sample prep. generally requires
sample dissolution
ICP-AES Inductively Coupled Plasma C 1–100 ppb detection limit Sub-mg Average compositional analysis.
AES Sample prep. generally requires
sample dissolution
ICP-MS ICP Mass Spectrometry C 1–10 ppt detection limit micrograms Average compositional analysis.
Sample prep. generally requires
sample dissolution
XRD X-ray Diffraction S, D, P, APS 1–3 wt % detection limit Milligrams Ideal for crystalline nanoparticles.
ORDER
sample
EXAFS Extended X-ray Absorption S, CB 5–10 mg XAS method: ideal for probing the
Fine structure arrangement, number, and identity
of nearest neighbor atoms around
the absorbing element
XANES X-ray Absorption Near Edge C, Ox, CB Milligrams XAS method: sensitive to the
Structure oxidation state and symmetry
around the absorbing element
SEXAFS Surface Extended X-ray C, Ox, CB, S Thin film Surface sensitive (probes outer 1 nm
Absorption Fine Structure of material)
IR, FTIR Infrared Spectroscopy; P, CB Milligrams Vibrational spectroscopy.
Fourier Transform IR Incompatible with wet systems
Raman Raman Spectroscopy P, CB Milligrams Vibrational spectroscopy. Compatible
with aqueous suspension and wet
nanoparticle samples
2715
(continued)
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Table 1. Continued.
2716
Spatial resolution,
Main minimum particle size, Sample
Acronym(s) Meaning informationa or detection limit requirementsb Notes:
Magnetic Mössbauer Spectroscopy P, APS, Ox P 10 mg tens of mg These methods are useful for the
properties Magnetometry characterization of iron rich
environmental nanoparticles, even
in extremely heterogeneous samples
BET Brunauer, Emmett, and Total surface area Up to thousands of m2/g 100 mg Method is most sensitive for high
Teller surface area materials (small particle
size). Method can also be used to
characterize porosity of
ORDER
nanoparticles
PCS Photon Correlation APS 3 nm–mm particle size Sub-mg in liquid Average particle size and size
Spectroscopy or DLS suspension distribution obtainable in situ
Single particle analyses
ATOFMS Aerosol Time of Flight Mass APS, C 3 nm–mm particle size <pg Can analyze a single nanoparticle for
REPRINTS
fact that electrons have wave character. Diffraction contrast depends on the
orientation of a crystal with respect to the electron beam. At certain orientations
(e.g., when the Bragg condition is satisfied, see below), scattering due to diffraction is
very strong, which produces dark regions in the TEM image. Phase contrast is the
consequence of phase shifts in the electron beam as a result of interacting with
the sample (e.g., Fig. 1). The contrast observed in atomic structure images and lattice
fringe images belongs to this category. When atomic structure images are compared
to image simulations, direct information about the distribution of atoms in a sample
can be obtained. Image simulations are produced by modeling imaging conditions
(e.g., focus, stigmation, beam tilt, sample tilt, and aperture selections), the
microscope specifications (e.g., spherical aberration constant), and the structure of
the sample. Through careful comparison of the experimental and simulated images,
which can be performed quantitatively, it is possible to determine which features in
an image correspond to actual positions of atoms and/or clusters of atoms.
Using TEM images, particle size, size distribution, and morphology can be
evaluated. In general, measuring particle sizes using TEM images can be performed
with some accuracy (5%) when good standards are employed.[27] At the highest
ORDER REPRINTS
Diffraction
The electron diffraction pattern originates from the volume of sample traversed
by the electron beam. The wave character of electrons means they can be diffracted.
The electron diffraction pattern is similar to an X-ray diffraction pattern (discussed
below) in that diffraction occurs when the Bragg condition is satisfied. The Bragg
equation (n ¼ 2 d sin ) relates the wavelength () of the electrons, the angle () of
the electron beam with respect to a set of diffracting planes, and the spacing (d)
between those planes, which is determined by the crystal structure of the material
examined. One challenge when working with electron diffraction is that electrons are
often multiply scattered by the sample, which can complicate the interpretation of
electron diffraction patterns.
Using electron diffraction, it is possible to distinguish between amorphous and
crystalline materials and often possible to identify crystalline materials by measuring
d-spacings and examining the symmetry of the pattern. Furthermore, a diffraction
pattern can be obtained from an individual nanoparticle or, in some cases, from
a portion of a nanoparticle. The diffracting volume can be limited by using selected-
area electron diffraction (SAED), which employs an aperture in order to limit the
volume of sample from which the pattern is generated, or convergent beam electron
diffraction (CBED), which involves focusing the electron beam into a narrow beam
(as narrow as a fraction of one nanometer in diameter). A major advantage of
electron diffraction in the TEM is that it is possible to directly image the particle or
portion of a particle from which a diffraction pattern is taken. In addition, by using
imaging and diffraction, the size and size distribution of crystalline nanoparticles
along specific crystallographic directions can be evaluated.
Spectroscopy
energy difference between the two electron energy levels, and it is characteristic of
the element ionized. Furthermore, the primary electron loses an amount of energy
that is equal to the energy required to remove the inner shell electron.
EDS (or XEDS or EDX) measures the intensity and energy of X-rays generated
from the specimen. The EDS detector is positioned very close to the sample and
typically kept at liquid nitrogen temperature and under vacuum. Thus, a window is
often employed in order to prevent condensation of gaseous species onto the detector
semiconductor. A consequence of using a window is substantially reduced sensitivity
to characteristic X-rays from the lighter elements. The detection limits can be as low
as sub-parts per thousand for elements heavier than sodium and for which very little
EDS peak overlap is observed.[27,31] Quantitative results can be obtained by
generating k-factors, which relate the intensity of the EDS peak to concentration
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Advanced Techniques
Figure 2. High-resolution zero-loss TEM images of coating material prepared using a gentle
abrasion method to remove ‘‘iron oxide’’ coatings from sand grains from Oyster Bay Virginia.
The white arrow in the left-hand image serves to highlight an agglomerate of goethite
(a-FeOOH) nanoparticles. EDX and electron diffraction results demonstrate that the
agglomerates are composed of goethite nanoparticles. The middle image shows the
agglomerate at higher magnification. The right-hand image is a micrograph of a different
agglomerate in which a significant degree of preferred orientation of the primary goethite
nanoparticles is observed. The inset in the right-hand image is a fast-fourier transform, which
serves to highlight the preferred orientation of the primary nanoparticles. These images were
taken using a 300 kV FEI CM300 FEG TEM-STEM.
STEMs only operate in this mode, and the achievable image resolution in STEM
mode is superior to the achievable image resolution in TEM mode. STEM can be
combined with spectroscopic methods (EELS or EDS) to produce spectrum images
(e.g., Fig. 2) and HAADF (high-angle annular dark field) to produce ‘‘Z-contrast’’
images. Spectrum images are four-dimensional images that contain, in addition to
contrast information, a spectrum at each pixel. Z-contrast imaging takes advantage
of mass thickness contrast to produce images in which the contrast is directly related
to the atomic weight of the atoms scattering the electron beam. Images of individual
heavy atoms on low atomic weight materials can be produced. Electron holography
is a specialized TEM technique that can produce images with enhanced
resolution.[27,36,37] Lorentz microscopy is yet another specialized TEM or STEM
technique that enables the user to directly image the magnetic microstructure of the
sample.[27,38]
Sample Preparation
the support film. One alternative is to use holey or lacey films, which have many
small holes, in the hope that some particles will either adhere to the side of a hole or
partially overlap with a hole.
Particles can be deposited onto the grid by several methods. An easy method
involves suspending particles in a solvent that does not dissolve the support film and
dipping the grid into the suspension or placing a single drop of the suspension onto
the grid (on the support film side) and then allowing solvent to evaporate. Another
method is to place the grid in an aerosol stream. Ideally, the amount of coverage
should be approximately 10% or less, and the ideal suspension concentration or time
in the particle stream can usually be estimated. Still another method is to dip the grid
into a dried powder of nanoparticles and shake the excess off. The preparation
method of choice will depend on the sample and the information desired. It is
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important to pay close attention to the sample preparation method used since many
methods can introduce substantial artifacts (e.g., aggregate fragmentation upon
impact with support film or precipitation of salts and nanoparticle aggregation upon
drying a droplet of suspension on support film). Lastly, the ideal TEM sample is less
than 200 nm thick, which is usually not a concern with nanoparticle samples.
However, in the event that the particles are fairly large, they can be suspended in an
epoxy, and mechanical polishing or ion milling of the resulting particle mount can be
used to prepare an electron transparent sample. Additional and more complex
methods of sample preparation are available (e.g., ion millers and dimplers), and the
reader is referred to Williams and Carter for additional details.[27]
Sample preparation techniques to avoid or minimize aggregation include the
addition of a volatile acid or base (e.g., acetic acid or ammonia) to an aqueous
suspension prior to dipping or drop placement. If a volatile acid or base is used, then
the acid or base will evaporate along with the water. Care must be taken that the acid
or base selection is appropriate for the nanoparticles to be examined (e.g., solubility
considerations). This can reduce aggregation if the pH of the solution can be moved
significantly away (at least two or three pH units) from the average isoelectric point
of the nanoparticles (for a discussion of isoelectric points, the reader is referred to
Hiemenz and Rajagopalan.[39]). In addition, if one must prepare a suspension from a
dry powder, sonication can be used to help break up aggregates.
If aggregation of particles is observed in TEM images, it does not necessarily
imply that the particles were strongly aggregated in situ. Also, if particle aggregates
are fragmented on the TEM grid, it does not necessarily imply that the aggregates
are fragmented in situ. For example, aerosol soot particles that were deposited from
an aerosol stream onto a TEM grid fragmented upon collision with the support film
(Fig. 3 and Park[40]). Thus the average aggregate size measured using TEM was
substantially smaller than the in situ aggregate size.
One of the major disadvantages of TEM for the characterization of
nanoparticles is that it is inherently an ex situ method. The sample must be dried
and inserted into a high vacuum, which makes the study of materials sensitive to
vacuum conditions (e.g., hydrated materials) challenging. Both sample preparation
and insertion into the TEM can introduce artifacts that must be considered. In fact,
Zhang et al. recently demonstrated that the crystal structure of zinc sulfide nano-
particles changes as a result of changing the nature of the molecules surrounding the
particle.[23] They showed that the binding of water molecules to zinc sulfide
ORDER REPRINTS
Figure 3. TEM images of mobility-classified soot nanoparticle (220 nm mobility size, John
Deere engine, 50% load, 1400 rpm, EPA fuel (360 ppm S)). White arrowheads in the left-hand
image serve to highlight ‘‘fragments’’ that were produced as a result of particle impact onto the
carbon film support. The right-hand image is a higher magnification image of two such
fragments. This image was taken using a JEOL 1210 TEM and at a slight underfocus in order
to highlight particle edges. Images are courtesy of Kihong Park.
The primary SPM discussed here is atomic force microscopy (AFM) because it is
the most commonly applied SPM for environmental nanoparticles. The AFM
measures the forces of interaction between a sharp tip (radius of curvature
usually 10 nm) and the sample by rastering the tip over the sample surface or
rastering the sample beneath the tip (using piezoelectric tubes). Force measurements,
force maps, and topographic images with vertical and lateral resolutions in the sub-
nanometer range can be obtained. AFM is useful for imaging the size, shape, and
topography of nanoparticles in situ and, with modified AFM tips, measuring the
forces of interaction between nanoparticles as a function of environment.
The AFM tip is attached to a cantilever with an extremely small spring constant,
and the cantilever deflects when the tip is attracted to or repulsed from the sample
surface. The deflection is sensed using an optical lever, which usually consists of a
red laser reflected off the back-side of the cantilever and onto a position sensitive
photodiode. Deflection is monitored as a function of position, and topographic and
force maps can be produced. In contrast to electron beam methods, AFM can be
routinely performed in situ and with both conductive and non-conductive samples.
For detailed discussions of the construction, theory, and operation of an AFM, the
reader is referred to excellent discussions by Maurice,[44] Friedbacher and Fuchs,[45]
and Sarid.[46]
In general, AFMs can be operated in three modes: contact, noncontact tapping,
and contact tapping modes. In contact mode, the tip is essentially dragged across the
surface, and a topographic map is generated. In tapping mode, the cantilever is
oscillated near its first bending mode resonance frequency with an amplitude of
approximately one to 200 nm. In noncontact mode, this oscillating tip is rastered at a
distance of approximately 10 nm above the surface, and the oscillation amplitude is
ORDER REPRINTS
usually 1–10 nm. In contact tapping mode, the amplitude of tip oscillation is
significantly larger, 20–200 nm, and the tip makes contact with the sample at the
bottom of each oscillation. Tip sample interactions result in measurable changes in
the amplitude and phase of the oscillation as well as the resonant frequency of the
oscillation. All can be measured and used to generate force and topographic maps of
a sample surface. By monitoring different modes of tip deflection, properties like
relative adhesion, hardness, and, in some cases, chemical composition can be
characterized. If the interfacial area between tip and surface and the spring constant
of the cantilever are known, quantitative force measurements can also be performed.
Atomic force microscopy is capable of imaging at sub-nanometer spatial
resolution, and, under ideal conditions (e.g., sharp tip, clean surface), it is theoretically
possible to image the atomic structure of a surface. In terms of particle size and shape
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measurements, the shape of the tip must be well known and good standards must be
employed. Tip shape can be determined by imaging a sharp object. If, for example,
the radius of curvature is very large, then the sharp object will appear large in the
AFM image. If, for example, the tip has a double apex, then the sharp object will be
doubly imaged. Furthermore, if a nanoparticle detaches from the substrate and
attaches to the tip, substantial artifacts will be introduced into the AFM force
measurements and topographic maps. This is usually marked by a sudden loss in
resolution in the AFM image or a dramatic change in force measurements. Tapping
mode is particularly useful in imaging nanoparticles because it minimizes the lateral
force between tip and sample, which reduces the chance that particles will be moved by
the tip. Finally, significant damage can occur to samples that are substantially softer
than the tip, especially when the AFM is operated in contact mode. Conversely,
significant tip damage can occur when imaging materials that are substantially
harder than the tip. The use of tapping modes can substantially reduce such damage.
When imaging in air, capillary forces (due to surface sorbed water) can be
substantial. The most effective method of avoiding complications due to capillary
forces is to image using a fluid cell. The environment of the fluid cell can be
controlled (e.g., anaerobic conditions, choice of solvent) and the fluid composition
varied over time (flow through construction). Thus, dynamic changes in surfaces
undergoing reaction can be quantitatively measured. For example, Nagy et al.
examined the kinetics of gibbsite (Al(OH)3) growth on various substrates using
AFM[47]; Sutheimer et al. measured the dissolution rates of well and poorly
crystallized kaolinite particles in aqueous solutions[48]; and Teng et al. examined
calcite growth in various aqueous solutions.[49]
A major drawback of AFM is chemical information cannot be obtained from
AFM images directly. However, relative differences in chemistry can be determined
by using chemically modified AFM tips, and this method is often termed chemical
force microscopy.[50–52] In magnetic force microscopy (MFM), the tip is coated with
a magnetic material, which enables the user to characterize the magnetic domain
structure of a sample. For example, Proksch et al. used MFM to characterize
magnetic nanoparticles in a magnetotactic bacterial cell.[53] Lateral force microscopy
refers to monitoring the twisting motion of the cantilever as the tip is scanned over
the surface, which enables the user to characterize variations in friction between the
sample and the tip. Furthermore, a relatively new tapping technique looks at the
phase shift in the oscillation of the cantilever in comparison to the applied oscillation
ORDER REPRINTS
and enables the user to characterize some specific materials properties like visco-
elasticity.[54] Lastly, near-field scanning optical microscopy (NSOM or SNOM) is
a more recent scanning probe technique that uses light channeled through a
small aperture at the end of a quartz AFM tip.[55–58] Transmitted or fluorescent
light can be used to obtain chemical information and image the sample with better
spatial resolutions (down to 1 nm in some cases) than normal (far-field) optical
microscopy.
A related technique is scanning tunneling microscopy (STM), which monitors
the tunneling current between a conductive tip (usually a sharp metal tip) and a
conductive or semiconductive sample as the tip is rastered over the sample. STM is
capable of achieving molecular- to atomic-scale resolution and is sensitive to the
chemical identity of the atoms and molecules at the surface.[45,59]
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Sample Preparation
This section presents three techniques that can access length-scales intermediate
between the nanometer and bulk scales. The first, SEM (Scanning Electron
ORDER REPRINTS
Microscopy), fits into both the nanometer and micrometer length-scale groups. It is
ideal for imaging particles in the tens of nanometers to micrometers range and, when
equipped with the appropriate detector, can often be used to perform chemical
analyses at a spatial resolution in the sub-micron range. The second, PIXE (Proton
Induced X-ray Emission), is less common but is ideal for performing trace chemical
analyses down to a spatial resolution of approximately one micrometer. The third,
XPS (X-ray Photoelectron Spectroscopy) is also less common but is ideal for
performing chemical analyses and obtaining information about the chemical state
(e.g., oxidation state) of elements in a sample.
Advanced Techniques
Sample Preparation
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A major limitation of SEM is that the electron beam can cause the reduction of
hydrocarbons, which then deposit as a layer of carbonaceous material on the imaged
area that, in turn, reduces image contrast. Thus, it is important that samples are
clean and that preparation materials (e.g., adhesives and epoxies) do not outgas
upon insertion into the microscope. The high vacuum requirements can be detri-
mental to samples that contain volatile components such as water. For inadequately
coated specimens, charging can lead to image distortion, artifacts, or sudden
discharges. Lastly, samples can be damaged or altered upon exposure to the electron
beam.
Hydrated specimens or samples that charge easily but cannot be coated can be
imaged by a newer subset of SEM called environmental SEM (ESEM). In ESEM,
the sample compartment is maintained between 1–10 Torr while the electron source
chamber is maintained at high vacuum by a series of differential pumping stages
along the column. The main disadvantage of ESEM is that its maximum resolution is
only 3–4 nm due to substantial electron scattering by the presence of gas molecules.
Ebert et al. used ESEM to examine the morphological changes and deliquescence of
aerosol particles as a function of relative humidity.[73] They found that ESEM was an
ideal technique for examining the hygroscopic behavior of aerosol particles because,
unlike other available techniques, it allowed them to directly image the aerosol
particles at a range of H2O partial pressures.
Because SEM can accept a wide variety of sample sizes and has a large depth-
of-field, it is an ideal technique for imaging particles ranging in size from 50 nm up
to several mm. While SEM can image nanoparticles smaller than 50 nm, TEM is
ORDER REPRINTS
much better suited for imaging such small particles. Recent applications of SEM
(and its complementary technique EDS) in the literature include examining the size,
morphology, and composition of aerosol particles collected from refineries and
urban environments as well as aerosol particles prepared in the laboratory.[74–77]
PIXE is a less commonly used method that is useful for the compositional
analysis of major, minor, and trace constituents of nanoparticles. Trace analysis
(e.g., heavy metals) of atmospheric aerosols can be used to establish the relationship
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between the source (e.g., anthropogenic vs. crustal) and the fate and transport of
such particles.[78] In PIXE, a fixed 2–3 MeV beam of protons or a-particles impinges
on a sample, knocking out core electrons. As in EDS, a characteristic X-ray can be
emitted as the result of an outer shell electron relaxing into the orbital from which
the electron was ejected. PIXE is more bulk sensitive than EDS due to the greater
sample penetration depth of protons and a-particles as compared to electrons.
For a particularly good treatment of the background and application of this
technique the reader is referred to the text of Johansson et al.[79] and two recent
papers that specifically discuss the use of PIXE for the analysis of atmospheric
aerosols.[78,80,81]
While the information obtained from PIXE is very similar to EDS, it has several
advantages over EDS. Most importantly, PIXE spectra do not have the strong
Bremsstrahlung radiation background found in EDS. This makes PIXE an excellent
technique for trace elemental analysis with detection limits on the order of 1015 g
because low intensity X-ray peaks are less obscured by background signal.
The biggest disadvantage of PIXE is that it requires a high-energy particle
accelerator, which means PIXE equipment is large and expensive. Additional
limitations of PIXE are similar to EDS, including the ability to detect only elements
where Z > 4, the low sensitivity to light elements (Z 10), and beam heating of the
sample. Analysis of samples is normally performed under high vacuum to minimize
the scattering of the particle beam by gas molecules. However, for samples that are
large or contain volatile components, it is possible to use a modified PIXE apparatus
to perform external-beam PIXE at atmospheric pressure.[79]
Micro-PIXE is a recent PIXE variation in which a focused particle beam is
rastered across a sample surface to perform elemental mapping.[82–84] Micro-PIXE
can not compete with the spatial resolution of EDS for thin samples. However, for
thicker samples (1 mm), the spatial resolution of the two techniques is comparable
(0.5–1 mm).
PIXE and micro-PIXE are often used for trace elemental analysis of aerosol
particles.[81,85–87] For particles and aggregates that are larger than a micron in dia-
meter, it is possible to perform elemental mapping with micro-PIXE. Unfortunately,
elemental mapping of nanoparticles by micro-PIXE is not possible because its spatial
resolution is larger than the typical particle. This limits the elemental information to
an average of a single isolated particle or group of particles.
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incident X-ray photons are used to determine the binding energy of the ejected
elections, which is related to the identity of the elements and their oxidation state and
bonding environment. The ideal sample is conductive, but there are techniques
available for overcoming problems with charging for insulating samples (e.g., low
energy electron flood gun directed at the sample or the use of an internal standard
for which XPS peak positions are known).[88] An example of using XPS to
characterize nanoparticles is recent work by Anschutz and Penn, in which XPS was
used to characterize iron(III) oxyhydroxide nanoparticles, which are common at and
near the Earth’s surface, before and after reaction with a reducing agent. Those
results showed a significant shift in the iron peaks (to weaker binding energies),
which demonstrated that the surface material had been reduced to contain
significant Fe2þ.[89] Lastly, XPS imaging techniques can achieve spatial resolutions
on the order of 1 mm.[90]
Chemical Composition
Structure
The major advantages of XRD are: (1) crystalline materials can be identified
quickly; (2) amorphous and crystalline materials can be distinguished; (3) XRD
patterns are additive; (4) the method is quick and relatively inexpensive; (5) particle
size and size distribution information can be obtained for crystalline particles; and
(6) it’s possible to perform the analysis using controlled atmosphere chambers (e.g.,
anaerobic conditions or controlled humidity). Major weaknesses include: (1) trace
components (< 1 mass %) can be difficult to detect; (2) elements cannot be directly
identified; (3) the pattern is an average over all particles in the scattering volume; and
(4) peak shapes can be difficult to interpret.
fitting protocol can provide quantitative measurements of both the type and
percentage of phases present. Recent work has used EXAFS to characterize hydrous
iron oxide nanoparticles, which are important materials in the biogeochemical
cycling of chemical species in the environment, formed in the presence of zinc[118] and
arsenate.[119] Figure 5 shows Fe K-edge EXAFS spectra, and the corresponding
Fourier transforms, of iron oxyhydroxide nanoparticles aged at 90 C from 0–25
days. Comparison of the experimental spectra to reference spectra and the observed
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Figure 5. Fe K-edge EXAFS spectra (a) and corresponding Fourier transforms (b) of iron
oxyhydroxide nanoparticles aged at 90 C for 0–25 days. On the left-hand figure, the x-axis (k)
represents energy converted to momentum space following the normalization of the EXAFS
data to a fixed point in energy space, and the y-axis (C(k)k3) is a k-cubed weighted expression
of the EXAFS function. The Fourier transforms are similar to radial distribution functions
and have as their x-axis the radial distance (þ phase shift) in Angstroms and as the y-axis the
Fourier transform peak magnitude, which is a function of the coordination number, identity
of scattering neighbors, and degree of structural disorder as identified by the Debye-Waller
factor. Model compound spectra are also presented (labeled ferrihydrite and goethite) to show
the structural change from ferrihydrite to goethite as a function of aging time. This is
demonstrated by changes in the position or intensity of various EXAFS features (two sets of
peaks are highlighted by grey vertical guidelines). An increase in the amplitude of Fourier
transform features between 2.2–3.2 Å (Fe–Fe interactions) also accompanies the transition
from ferrihydrite to goethite. Figure courtesy of C. Kim and G. Waychunas at Berkeley
National Laboratories.
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shifts in peak intensities, position, and shape as a function of aging time demonstrate
that ferrihydrite transforms to goethite over time.
Increasingly bright synchrotron sources can now conduct spatially resolved
EXAFS analysis with spot sizes as small as 1 1 mm. While this is not yet small
enough to effectively map nanoparticles, it does minimize the total amount of sample
needed to collect a usable EXAFS spectrum. For example, for pure phases (e.g., the
iron oxyhydroxide samples highlighted in Fig. 5) 5–10 mg of sample is sufficient.
XANES refers to the portion of the spectrum with X-ray energies ranging from
just below (pre-edge) to just above (post-edge) the absorption edge and is a sensitive
probe of valence and site symmetry for many elements. It is more sensitive but less
quantitative than EXAFS. Pre-edge features are the result of electronic transitions
and provide information about valence and bonding environment of the absorbing
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element. Post-edge features near the absorption edge provide information about the
symmetry around the absorbing element.[112,116,117] Figure 6 shows Cr K-edge
XANES spectra for Cr(III) and Cr(VI) species,[116] illustrating how XANES spectra
can be used to determine the oxidation state of the absorbing element. SEXAFS is a
surface sensitive technique that provides information about nanoparticle surfaces
and the way adsorbed species are bonded to surfaces. In SEXAFS, the X-ray
absorption coefficient is usually determined indirectly by monitoring fluorescence,
Auger electron emission, or total or partial electron yield. For a detailed treatment of
the theory and application of SEXAFS, the reader is referred to Cheng et al.,[120]
Lagarde,[121] Norman,[122] and Stor.[123]
Figure 6. Cr K-edge XANES specta for Cr(III) and Cr(VI) species, illustrating how
NEXAFS spectra can be used to determine the oxidation state of the absorbing element.
Reprinted with permission from Fendorf et al.[116]
ORDER REPRINTS
determined; (6) surface sensitive measurements can be obtained; and (7) hetero-
geneous samples can be characterized. Major disadvantages include: (1) synchrotron
radiation is required; (2) data interpretation is complicated; and (3) results are an
average over all particles present.
Vibrational Spectroscopy
thermore, fluorescence from the sample, which is the result of electronic transitions
caused by the absorption of incident photons, can complicate data collection. In
general, the use of a lower frequency source can eliminate fluorescence. For general
discussions of Raman spectroscopy see Ingle et al.[124] or Skoog et al.[106] For specific
applications of Raman spectroscopy to solid materials see Lyon et al.,[127]
Pelletier,[128] Weber and Merlin,[129] or Mulvaney and Keating.[130] Specific
applications of Raman spectroscopy to environmental particles include works by
Tarassov et al.[110] and de Faria et al.[131] Tarrasov examined the incorporation of
tungsten in environmental goethite and hematite nanoparticles from Bulgaria in
order to elucidate the mechanism by which tungsten is incorporated into these
mineral particles.[110] De Faria used Raman spectroscopy in order to characteriza-
tion iron oxide and oxyhydroxide phases.[131]
The two major differences between IR and Raman spectroscopy lie in the exci-
tation source, the signal monitored, and the selection rules for observed vibrational
modes as mentioned above. Some IR-active vibrational modes are not Raman-active,
and not all vibrational modes are active for even one of the two techniques. For
instance, the strong absorption of infrared radiation by water makes IR difficult to use
for the characterization of wet samples. Raman spectroscopy, on the other hand, is
not sensitive to the presence of water and therefore well-suited to monitor reactions
that occur in aqueous environments. Lastly, Raman is better suited for characterizing
lower energy vibrational modes such as metal-oxygen bonds, whereas IR is better
suited for higher energy vibrational modes such as carbon-hydrogen bonds.
Lastly, while no vibrational spectroscopy is inherently surface sensitive, the large
surface area-to-volume ratios of nanoparticles means that surface-bound species can
often be characterized, especially if the species of interest occurs only at the surface.
These can either be the species that terminate the bulk structure, for example,
hydroxyl groups at the surface of many metal oxides, or adsorbed species. For
examples of infrared spectroscopy used to characterize surface bound species, see
work by Driessen et al.[132–134] In addition, Khaleel and Dellinger used FTIR to
characterize nanophase alumina catalyst that was used in the chemical transforma-
tion of carbon tetrachloride. Their results showed that there was a significant
concentration of surface hydroxyls before and after heat treatment. In addition, they
used the method to monitor the concentrations of the gaseous products of the
carbon tetrachloride transformations.[135]
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Magnetic Measurements
trace amounts and even when extremely heterogeneous mixtures of nanoparticles are
analyzed.
Mössbauer, or g ray spectroscopy, is a nondestructive technique that probes
transitions in nuclei in order to characterize magnetic properties and obtain
information on the oxidation state, coordination number, and bonding environment
around the absorbing atom. It is also used to identify magnetic components in
heterogeneous samples. Monochromatic g rays are used to irradiate the sample, and
the incident g ray energy is varied by translating the source (i.e., the Doppler shift).
The transmitted radiation is monitored, and absorption is plotted vs. the velocity of
the source translation (positive for towards the source and negative for away from
the source).[136,139,140] One limitation of Mössbauer spectroscopy is that the analysis
is most commonly limited to Fe and Sn due to availability of appropriate g ray
sources. Several examples of using Mössbauer spectroscopy include the character-
ization of iron containing aerosols[139] and sediments.[125]
The BET surface area method measures the volume of gas required to adsorb a
single monolayer of gas molecules (or atoms) to the accessible surface area of a given
mass of sample.[71,141] Usually, nitrogen is the gas of choice. The total accessible
surface is calculated using the BET equation, which was named for and developed by
ORDER REPRINTS
Brunauer, Emmett, and Teller and which relates the monolayer volume of gas
adsorbed, the size of the gas molecules, and the mass of the sample to the total
surface area per mass.[142]
The BET surface area method is inexpensive and relatively easy to perform, and
the method directly and quickly measures the accessible surface area per mass of
sample. Furthermore, it requires little sample preparation other than to ensure that
the sample particles are dry, degassed, and well-separated before performing
measurements. If particles are not adequately degassed and well-separated, surface
area measurements will be artificially low. Unfortunately, no information about the
size and shape distributions is obtained. In addition, more complicated data analysis
enables the characterization of porous materials. When used in combination with
another method, such as electron microscopy, a description of particle size, size
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distribution, and accessible surface area can be produced. Recent studies have used
BET surface area measurements to examine the surface area change of iron oxide
nanoparticles during phase changes[143] and the calcination of tin oxide and titanium
dioxide nanoparticles.[144,145]
disperse, electron microscopy results can produce a small particle size distribution
dataset that can be used as a starting model for the distribution determined from the
autocorrelation function collected using DLS. In addition, if the particles appear
aggregated in the electron microscope, DLS could be used to determine whether the
particles might also have been aggregated in solution.
A differential mobility analyzer (DMA) can be used to measure the particle size
distribution of an aerosol sample and to size-select aerosol particles for subsequent
ORDER REPRINTS
with a wide range of diameters (2–1000 nm) can be analyzed in real time with little to
no sample preparation. In addition, samples that are already aerosols require little to
no sample preparation except the addition of a carrier gas to dilute the particles and
carry them through the DMA. Particle suspensions and dry powders can also be
analyzed. Particles suspended in volatile liquids can be converted into solid aerosol
particles by nebulizing the liquid suspension and then drying the resulting droplets
in a carrier gas. A wide range of powdered materials can be converted into aerosols
by various dry dispersion methods.[165] Lastly, a DMA can size-select particles
for analysis using other instrumentation by directing the exit flow to a second
instrument (e.g., mass spectrometer) or by collecting the particles on a support
medium.
The primary limitations of a DMA are that the samples must be aerosols with
concentrations between 1 and 108 particles cm3 and that DMA does not directly
provide chemical or structural information. In addition, as particle size decreases, a
smaller percentage of particles are charged by the neutralizer. Therefore, the DMA
has a lower sensitivity to smaller particles because only charged particles with the
correct mobility leave the device through the exit slit for a particular potential
setting. Finally, the particle diameter measured by the DMA is a mobility diameter,
which is equivalent to the diameter of a spherical particle with the same surface area
as the particle analyzed. Since particles are often irregularly shaped, the actual
particle size and mobility diameter are frequently quite different. Thus, the DMA by
itself gives no direct information about particle shape or aggregation.
When a DMA is used to size-select particles, exiting particles can either be
collected for further analysis (e.g., electron microscopy) or passed directly into
another analytical instrument. In work by Weber et al., silver particle agglomeration
was studied by DMA, ICP-AES, SEM, and TEM.[167] In their work, DMA size-
selected particles were sent directly into an ICP-AES to determine the amount of
silver (in the form of particle agglomerates) exiting the DMA. A portion of the size-
selected particles were also collected on a filter and then analyzed by SEM and TEM
to determine particle morphology. The DMA and the various techniques that can be
coupled to it have many direct applications to nanoparticles, especially atmospheric
nanoparticles. DMAs have been coupled to mass spectrometers in order to obtain
simultaneous size and chemical information of soot nanoparticles.[168] Tandem
DMA (TDMA) systems send a stream of particles through a DMA to size-select
the particles and then direct those size-selected particles through a reaction zone
ORDER REPRINTS
(with heating or oxidizing conditions) and into a second DMA in order to determine
the final particle size distribution. TDMA systems have been used to study the
hygroscopicity and oxidation of soot and other atmospheric aerosol particles by
measuring particle size changes as a result of heat treatment in the presence of a
variety of gasses (e.g., inert gas vs. oxygen).[169–172]
CONCLUSION
ACKNOWLEDGMENTS
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