View Article Online / Journal Homepage / Table of Contents for this issue

PERSPECTIVE www.rsc.org/pccp | Physical Chemistry Chemical Physics

Interaction of internally mixed aerosols with light

Naama Lang-Yona,a Ali Abo-Riziq,*a Carynelisa Erlick,b Enrico Segre,c
Miri Trainica and Yinon Rudicha
Received 2nd July 2009, Accepted 14th September 2009
First published as an Advance Article on the web 12th October 2009
DOI: 10.1039/b913176k

Atmospheric aerosols scatter and absorb solar radiation leading to variable effects on Earth’s
radiative balance. Aerosols individually comprising mixtures of different components (‘‘internally
mixed’’) interact differently with light than mixtures of aerosols, each comprising a different single
component (‘‘externally mixed’’), even if the relative fractions of the different components are
equal. In climate models, the optical properties of internally mixed aerosols are generally
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.

calculated by using electromagnetic ‘‘mixing rules’’, which average the refractive indices of the
individual components in different proportions, or by using coated-sphere Mie scattering codes,
which solve the full light scattering problem assuming that the components are divided into two
distinct layers. Because these calculation approaches are in common use, it is important to
validate them experimentally. In this article, we present a broad perspective on the optical
properties of internally mixed aerosols based on a series of laboratory experiments and theoretical
calculations. The optical properties of homogenously mixed aerosols comprised of non-absorbing
and weakly absorbing compounds, and of coated aerosols comprised of strongly absorbing,
non-absorbing, and weakly absorbing compounds in different combinations are measured using
pulsed and continuous wave cavity ring down aerosol spectrometry (CRD-AS). The success of
electromagnetic mixing rules and Mie scattering codes in reproducing the measured aerosol
extinction values is discussed.

1. Introduction materials (e.g., pollen, bacteria, etc.).1,2 Secondary aerosols

Atmospheric aerosols, small solid or liquid particles suspended
in the atmosphere, contain organic and inorganic compounds
from anthropogenic as well as natural sources. Aerosols can be
emitted directly into the atmosphere (primary aerosols) from
various sources, such as fossil fuel combustion, biomass
burning, soil and road dust, salt from sea spray, and biological
a
Department of Environmental Sciences, Weizmann Institute,
Rehovot, 76100, Israel
b
Department of Atmospheric Sciences, The Hebrew University of
Jerusalem, Jerusalem, 91904, Israel
c
Department of Physical Services, Weizmann Institute, Rehovot,
76100, Israel. E-mail: Ali.Abo-riziq@weizmann.ac.il
form in the atmosphere by condensation of gas phase compounds
onto pre-existing particles, homogeneous nucleation of
volatile or semi-volatile compounds to form nanometer-scale
particles, or by heterogeneous and multi-phase reactions.1,2
The latter two processes occur on aerosol surfaces, in the bulk
of the aerosol, as well as within cloud drops.1,3–6 The rate of
secondary aerosol formation is controlled by temperature,
relative humidity (RH), and the concentration of the nucleating
and condensing compounds.7
In the visible range, aerosols affect atmospheric radiation
balance, and hence climate, through three main processes: (1)
direct scattering and absorption of incoming solar radiation
(the direct effect), (2) by acting as cloud condensation nuclei

Naama Lang-Yona finished Ali Abo Riziq (PhD in

her MSc on optical properties Chemistry from University of
of aerosols in the Weizmann Santa Barbara California,
Institute of Science. She did UCSB, 2005) is a Staff
her BSc in Environmental Scientist at the Weizmann
Sciences at the Tel-Hai Institute of Science. He joined
College. Naama has just Prof. Yinon Rudich’s group at
started a PhD in atmospheric 2005 for postdoctoral work on
chemistry in the Weizmann developing different cavity
Institute of Science and will ring down aerosol spectro-
work on correlating fungi in meters. His main research
aerosols with allergies. interests are the optical
properties of aerosols.

Naama Lang-Yona Ali Abo-Riziq

This journal is 
c the Owner Societies 2010 Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 21

(CCN), which control cloud reflectivity, extent, and lifetime
(the indirect effect), and (3) by heating the atmosphere through
absorption of incoming solar radiation (the semi-direct
effect).8–20 While the direct and indirect effects generally lead
to a negative radiative forcing of climate or cooling by
reducing the amount of solar radiation reaching the Earth’s
surface, the semi-direct effect can lead to either cooling or
warming, depending on whether the atmospheric absorption
dominates (cooling the surface) or whether the corresponding
reduction in low cloud cover and liquid water path dominates
(warming the surface).21
Atmospheric aerosols contain a mixture of organic and
inorganic components.22 The chemical constituents that make
up atmospheric aerosols dictate their chemical and physical
properties (chemical reactivity, interaction with radiation,
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
hygroscopicity, optical properties, etc.). Aerosols that consist
mostly of inorganic matter (such as sea salt, sulfate,
nitrate)23,24 and non-absorbing organic compounds
(OC)25–27 tend to be scattering, affecting climate through the
direct effect. Aerosols that consist of elemental carbon (EC;
soot),10,28–31 mineral dust,32,33 and certain moderately absorbing
organics (‘‘brown carbon’’)27,34–37 tend to be absorbing, affecting
climate through the direct and semi-direct effects.18
Carynelisa Erlick (PhD
in Atmospheric Sciences,
University of Chicago) is a
senior lecturer at the Hebrew
University of Jerusalem,
Department of Atmospheric
Sciences. Her main research
interests are radiative transfer
in the Earth’s atmosphere and
climate forcing. Her recent
research involves accounting
for the effect of mixed compo-
sition and nonsphericity of
aerosol particles on their
Carynelisa Erlick radiative properties.
Miri Trainic is a PhD student
in atmospheric chemistry in
the Weizmann Institute of
Science. She did her BSc in
Chemistry and Environmental
Sciences in the Hebrew
University of Jerusalem and
her MSc in Environmental
Diagnosis, at the Imperial
College in London. Her
current PhD work focuses on
the optical properties of
organic aerosols.
Miri Trainic
22 | Phys. Chem. Chem. Phys., 2010, 12, 21–31
View Article Online
The scattering and absorbing properties of aerosol consti-
tuents are characterized by various physical parameters, the
most fundamental of which is the complex refractive index
(RI = n + ik), where the real part (n) describes the ability of
the constituent to reflect or scatter radiation, and the imaginary
part (k) describes the ability of the constituent to absorb
radiation. Both the real and the imaginary parts of the
complex RI are functions of wavelength (l).38 Knowing the
RI of aerosols enables the calculation of other radiative
parameters relevant to the climate and is therefore extremely
valuable for climate change modeling.13,39–43 These radiative
parameters include the scattering, absorption, and extinction
(attenuation) coefficients (describing the e-folding of radiative
intensity with distance: asca, aabs, and aext = asca + aabs,
respectively). Other optical parameters include the optical
depth (the extinction coefficient multiplied by the radiation
propagation distance; text), the phase function (describing the
angular pattern of scattered intensity for a single aerosol
scattering event; P(ysca), where ysca is the scattering angle),
the asymmetry parameter (the extent of forward scattering
relative to backward scattering; g), and the single scattering
albedo (describing the amount of scattering relative to total
extinction; $ = asca/(asca + aabs)).44
Enrico Segre (PhD in Physics
from the University of Turin,
Italy, 1994), is currently
a Staff Scientist at the
Weizmann Institute of Science
and was an assistant professor
at the Polytechnic of Turin
between 1995 and 2000. His
main scientific interests are in
non-linear aspects of fluid
dynamics and in microfluidics.
Enrico Segre
Yinon Rudich received his BSc
from Ben Gurion University
(1987) and MSc and PhD
degrees (honors) from the
Weizmann Institute (1994).
Following postdoctoral work
at the National Oceanic and
Atmospheric Administration
in Boulder, he joined the
Weizmann Institute of Science
where he is currently a
Professor in the Department
of Environmental Sciences
and Energy Research. His
Yinon Rudich research interests include the
chemistry and physics of
organic aerosols and of mineral dust, optical properties of
aerosols, aerosol–climate interactions and characterization
of ambient atmospheric aerosols.
This journal is 
c the Owner Societies 2010

Fig. 1 Complex atmospheric aerosols (the combination of 1 and 2 in
the same environment represents externally mixed aerosols, 3–5
represent different types of coated particles, and 6 and 7 represent
different types of homogeneously mixed aerosols).
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
Related to aext, the extinction efficiency (Qext) is defined as
sext/pr2, where sext is the aerosol extinction cross section
(integrating the extinction cross section over the aerosol size
distribution gives aext).45,46 One way to obtain the complex RI
of an aerosol constituent is by measuring Qext as a function of
particle size for a homogeneous (spherical) aerosol comprised
of the same constituent. The complex RI can then be obtained
by fitting the measured Qext values to a Mie scattering curve,
computed with readily available numerical subroutines that
give the scattering solution to Maxwell’s equations as a
function of particle size and wavelength, following Gustav
Mie’s original derivation (see section 2).45,47
In addition to the RI values of the chemical constituents
that make up atmospheric aerosols, aerosol radiative parameter
values are strongly influenced by the physical configuration of
these constituents within the aerosol, i.e., by the aerosol
microstructure.45,48 As shown in Fig. 1, aerosols can appear
as externally mixed (particles 1 and 2), heterogeneously
internally mixed (i.e., coated particles; particles 3, 4, and 5),
or homogeneously internally mixed (particles 6 and 7).49–61
Homogeneous internally mixed aerosols form by processes
such as evaporation of droplets containing several species with
similar solubility and by simultaneous condensation of
semi-volatile species. They can be found in a variety of
combinations, including: (1) internal mixtures of several
non-absorbing components (e.g., sodium chloride (NaCl)
mixed with non-absorbing organics); (2) internal mixtures of
non-absorbing components (e.g., ammonium sulfate (AS))
Fig. 2 Internally mixed aerosols divided into homogeneously mixed aerosol (a) and heterogeneously mixed aerosols (coated particles) (b), with two
types of coated aerosol, constant core diameter with increasing shell thickness (i), and increasing core diameter with constant shell thickness (ii).
This journal is 
c the Owner Societies 2010
View Article Online
mixed with weakly absorbing components (e.g., humic-like
substances (HULIS)); and (3) internal mixtures of non-absorbing
components mixed with strongly absorbing components, such
as mineral elements, metals, or brown carbon.3,62–64
Coated particles can form by processes such as condensation
of semi-volatile species on pre-existing particles, evaporation
of droplets containing both soluble and insoluble components,
dehydration of droplets containing two species with substantially
different solubilities, and heterogeneous chemical reactions
(e.g., oxidation, radical reactions, photochemistry, etc.) on
aerosol surfaces, creating a shell with a different character.
Like homogeneously internally mixed aerosols, coated particles
can be found in a variety of combinations, including: (1)
a non-absorbing core (e.g., NaCl) coated with another
non-absorbing species (e.g., non-absorbing organics); (2) a
non-absorbing core coated with a weakly absorbing species
(e.g., HULIS); or (3) an absorbing core (e.g., soot or dust)
coated with a non- or weakly absorbing species (e.g.,
condensed organics).49,51–61,65 These different aerosol micro-
structures are visualized in Fig. 1.
The ratio of the coating to core diameter in coated particles
can also be an important factor. As shown in Fig. 2(b), two
coated particles with the same external diameter but different
core/coating diameter ratios will have different absorption and
scattering characteristics. Thus, we conducted each experiment
on coated particles twice, once with a constant core diameter
and increasing shell thickness (see Fig. 2(b),i), and again with
increasing core diameter whilst maintaining a constant shell
thickness (see Fig. 2(b),ii).
It is of great interest to understand how these micro-
structures affect aerosol optical properties and how well
theoretical calculations reproduce these characteristics in
order to achieve more reliable climate model simulations.
There are a number of approaches currently employed to
calculate the radiative properties of internally mixed aerosols
in climate models. For homogeneously internally mixed
aerosols, effective medium approximations or ‘‘mixing rules’’
are often used to calculate the particles’ effective RI, and then
a Mie scattering subroutine (for homogeneous spheres;
described above) is applied to calculate the aerosol optical
parameters. Mixing rules are derived assuming that pockets
(‘‘inclusions’’) of an aerosol constituent(s) exist within a
surrounding matrix comprised of another constituent(s). Each
inclusion is subjected to a local quasi-steady electromagnetic
Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 23

field averaged over the configuration of all of the other
inclusions, which contributes to a local polarizability. The
local polarizabilities are summed to compute the macroscopic
polarization of the entire aerosol, and the macroscopic
polarization is related to the effective dielectric constant of
the composite aerosol. (See Chýlek et al.48,66 for more detail.)
The combination of any mixing rule and a Mie scattering
subroutine for homogeneous spheres implicitly assumes that
either the constituents are truly homogeneously mixed or that
at least one constituent is randomly distributed throughout a
matrix comprised of the other constituents.
Examples of commonly used mixing rules include: (1) molar
refraction and absorption, in which the effective molar
refraction and effective molar absorption of the aerosol are
calculated by linearly averaging the molar refractions and
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
molar absorptions, respectively, of the RI of the aerosol matrix
and inclusions, weighted by their molar fractions38,67–69; (2) the
‘‘linear mixing rule’’, in which the effective RI of the aerosol is
calculated by linearly averaging the real and imaginary parts,
respectively, of the aerosol matrix and inclusions, weighted
by their volume fractions;45 (3) the Maxwell–Garnett rule,
according to which second-order effects due to neighboring
inclusions are neglected, and the dielectric constant of
Fig. 3 Illustration of the setup for generating mixed (a) and coated (b) aerosols, coupled to the continuous wave (CW) cavity ring down (CRD)
system (c).
24 | Phys. Chem. Chem. Phys., 2010, 12, 21–31
View Article Online
the aerosol matrix without inclusions determines the local
electromagnetic field that acts on the inclusions;45,70 (4) the
Bruggeman rule, according to which the aerosol matrix and
inclusions act symmetrically on one another;45,70 and (5)
extended effective medium approximations, according to
which terms of higher order than the electric dipole of the
inclusions are included.48,66,71,72
For coated particles, two approaches for calculating the
radiative properties are common. For aerosols coated with
water, a growth function—a parameterization describing the
change in scattering coefficient as a function of relative
humidity—is often used.39,73 Alternatively, a Mie scattering
subroutine for coated spheres can be used, which provides a
more explicit calculation, whether the coating consists of
water or of other aerosol constituents. Like Mie scattering
subroutines for homogeneous spheres, Mie scattering subroutines
for coated spheres give the scattering solution to Maxwell’s
equations as a function of particle size and wavelength, but
with extra boundary conditions at the interface between
the two layers.45,74,75 Since such subroutines are more
computationally intensive than mixing rules or growth
functions, they are often applied off-line in a look-up table
fashion,76 but they can also be applied on-line.67
This journal is 
c the Owner Societies 2010

Only a few experimental studies of the optical properties of
complex aerosols have so far been conducted.53,66,77–89 Here, we
present new measurements of laboratory-generated aerosols
and theoretical calculations of their optical properties, along
with some of our previous studies of the optical properties
of internally mixed and coated aerosols. With respect to
homogeneously internally mixed aerosols, we consider three
combinations: (1) a mixture of two non-absorbers, glutaric acid
(an organic solid; Glu-A) and NaCl (an inorganic salt);80 (2) AS
(a non-absorbing salt) mixed with Suwannee River fulvic acid
(a weakly-absorbing organic compound with optical properties
similar to those of HULIS; SRFA);27,90 and (3) AS mixed with
Rhodamine-590 (a strong absorber in the visible range with an
absorption peak around 532 nm wavelength; Rh-590).80 Glu-A,
NaCl, and AS are common components of tropospheric aerosols,
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
while SRFA is a commonly-used proxy for HULIS.27,90 With
respect to coated aerosols, we consider three combinations: (1)
Nigrosin (a strong absorber) coated with Glu-A (a non-absorbing
organic solid); (2) polystyrene latex spheres (a non-absorbing
solid; PSL) coated with Glu-A; and (3) PSL coated with
b-carotene (a weakly absorbing organic compound; b-car).
In addition, we present some thoughts about the possible
implications of our results to atmospheric radiation balance
and climate.
2. Methodology
Aerosols were generated by the methods illustrated in Fig. 3,
described in detail in our previous publications.27,53,80,91,92
In short, an aqueous solution of the compound of interest is
nebulized with dry and pure nitrogen, dried in a silica gel
diffusion dryer, and charged by a neutralizer. Size selection
of the resulting polydisperse aerosol is achieved with a
differential mobility analyzer (DMA) (Fig. 3(a,b)), after which
the nearly monodisperse aerosol flow is directed into a pulsed
or continuous wave (CW) cavity ring down (CRD) system for
optical measurements. These systems are described in the next
section.
Homogenously mixed particles are created by nebulizing
aqueous mixtures, as shown in Fig. 3(a). Coated particles are
created by using size-selected aerosols as seeds. The seeds are
directed through a coating system, described in ref. 53 and
illustrated in Fig. 3(b). In short, the coating material is placed
in an oven in which the temperature and the flow rate control
the coating thickness. After exiting the coating oven and
cooling, the coated particles are size-selected in an additional
DMA before entering the CRD system. The second size
selection dictates the coating thickness that will be used.
Aerosol sphericity was checked using atomic force microscopy
in several cases.53
CRD spectroscopy is a sensitive method for spectroscopy of
gas phase species and for measuring optical properties of
aerosols.80,93–108 A pulsed or continuous laser beam enters a
high finesse cavity, performing multiple reflections between
two or three plano-concave mirrors.106 The exponential decay
time of the light exiting the cavity is measured, and differences in
this time are related to the internal losses. The particles exiting
the cavity are directed into a condensation optical counter
(CPC) in order to measure the particle number concentration.
This journal is 
c the Owner Societies 2010
View Article Online
In a CRD aerosol spectrometer, scattering and absorption
by the aerosol particles in the cavity lead to a reduction in the
exponential decay time of the light compared to that in the
empty cavity. From the reduction in decay time and the
particle number concentration, the extinction efficiency (Qext)
can be calculated for a specific wavelength and specific size
parameter x (ratio between the particle diameter, D, and the
laser wavelength, l; x = pD/l).80,100,102
Several pulsed laser CRD systems covering several wave-
length ranges were employed in this study.53,80 Although
pulsed systems often have lower sensitivities than CW systems,
they can achieve quite reliable measurements. Their biggest
advantage is their simplicity, making them easy to handle and
operate.91
In addition to the pulsed laser systems, we use in this study a
recently constructed CRD system employing a CW single
mode laser operating at 532 nm (see Fig. 3(c)).91 In the
portable system, an acousto-optic modulator (AOM) diffracts
the 532 nm single mode laser beam, and the first order beam is
directed into the cavity. The mirror at the light entrance side of
the cavity is mounted on a piezoelectric ring that moves back
and forth. This modifies the cavity’s length and hence its
longitudinal modes. Once mode matching between the CW
laser and the cavity is achieved, the light intensity in the cavity
builds up. This triggers the AOM and the laser beam is
deflected, leading to a single exponential decay of the light in
the cavity which is detected by a photomultiplier (PMT)
placed at one side of the cavity. The modulation frequency
of the AOM is triggered by the light intensity in the PMT and
is around 200 Hz. This new system improves the stability and
sensitivity as compared to pulsed laser systems;80,102 the
sensitivity of our CW-CRD system was 6.64  1010 cm1,91
compared to 3.77  109 cm1 in the pulsed CRD.80 We
present here experimental measurements obtained using both
pulsed and CW laser systems.
The complex RI of aerosols can be obtained using CRD
measurements of the extinction efficiency as a function of
particle size for a homogeneous spherical aerosol with the
same composition throughout the size distribution. The retrieval
algorithm compares the measured extinction efficiency as a
function of the size parameter, with the extinction efficiency
calculated using a Mie scattering subroutine for homogeneous
spheres, while simultaneously varying the real and imaginary
parts of the RI of the aerosols. The algorithm finds the
complex RI of the aerosol particles by minimizing the ‘‘merit
function’’, w2/N2, where w2 is
X
N 2
ðQext measured  Qext calculated Þi
w2 ¼ ; ð1Þ
e2i
i¼1
N is the number of particle sizes, and ei is the standard
deviation of the measurements of particle size
i.27,48,53,80,91,102 The minimization is performed using the
simplex search method109 and can be performed to any desired
resolution in RI values.
In addition to applying the retrieval algorithm to CRD
measurements of single component spherical aerosols, the
algorithm can essentially be applied to any aerosol configuration,
Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 25

with the Mie scattering subroutine for homogeneous spheres
being replaced by some other appropriate theoretical calculation.
For homogeneously internally mixed aerosols, a mixing rule
computation can be inserted before the Mie scattering subroutine
calculation, while for coated particles, a Mie scattering subroutine
for coated spheres (‘‘core/shell’’) can be put in place of that for
homogeneous spheres. Again, the complex RI of one or more
of the aerosol constituents can be retrieved, or the merit
function can be used simply to ascertain which theoretical
approach best matches the measurements for a given set of
(known) RI.80
3. Laboratory measurements of complex aerosols
Homogeneously internally mixed aerosols
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
The Qext of laboratory-generated aerosols comprised of
internal mixtures of NaCl and Glu-A with molar ratios 1 : 1
and 1 : 2 was measured in ref. 80 with a pulsed CRD aerosol
spectrometer employing a 532 nm Nd : YAG laser. These
homogeneously internally mixed aerosols mimic aerosols
comprised of inorganic and organic mixtures often detected
above urban and polluted areas.22 The aerosol RI retrieval
algorithm was then used to test which mixing rule provides the
best match to the measurements, given values of the RI of the
pure constituents that make up the mixture as retrieved using
the same system (RI = 1.546 + i0.003 for pure NaCl and
RI = 1.41 + i0.00 for pure Glu-A). The level of agreement
between the mixing rules and the experimental data was
determined using the merit function (eqn (1)); the smaller the
merit function, the better the agreement. The results are shown
in Fig. 4. The linear mixing rule provides the best match to the
experimental Qext values; for a 1 : 1 mixture of Glu-A and
NaCl, the merit function value for the linear mixing rule is 0.14
as compared to 0.15–2.65 for the other mixing rules, and for a
1 : 2 mixture of of Glu-A and NaCl, the merit function value
for the linear mixing rule is 0.14 as compared to 0.14–2.80 for
Fig. 4 Extinction efficiency of mixed particles of NaCl and Glutaric
acid (Glu-A) in mass ratios 1 : 1 and 1 : 2, respectively, along with
the Mie curves corresponding to the effective refractive indices
calculated with the volume-weighted ‘‘linear mixing’’ rule at 532 nm
wavelength.
26 | Phys. Chem. Chem. Phys., 2010, 12, 21–31
View Article Online
the other mixing rules, when all particle sizes are included.80
We surmise that the high solubility of both compounds in the
aqueous solution ensured thorough mixing. This, combined
with the fact that the two constituents exhibit very little
absorption, allows such good agreement with the simple linear
mixing rule.
In a new set of mixing experiment, the Qext of aerosols
comprised of internal mixtures of AS (non-absorbing) and
SRFA (weakly absorbing material) with molar ratio 1 : 1 was
measured using an optical parametric oscillator (OPO) pulsed
laser system at 390 nm wavelength. These homogeneously
internally mixed aerosols again mimic aerosols comprised of
inorganic and organic mixtures often detected in urban and
polluted areas.22 The wavelength 390 nm was chosen for
several reasons. First, SRFA absorbs better at shorter
wavelengths than at 532 nm, as implicit in the imaginary
part of its RI (RI = 1.602 + i0.098 at 390 nm, while
RI = 1.634 + i0.004 at 532 nm).27 Second, near ultraviolet
wavelengths are often employed in satellite measurements of
aerosol absorption.110
The mixed aerosol RI retrieval algorithm was then used
to test which mixing rule provides the best match to
the measurements, given values of the RI of the pure
constituents that make up the mixture, which were previously
retrieved using the same system (RI = 1.525 + i0.0008 for
pure AS and RI = 1.602 + i0.098 for pure SRFA). The results
are shown in Fig. 5. The linear mixing rule provides the
best match to the experimental Qext values, but all of the
mixing rules tested provide reasonable results; for a 1 : 1
mixture of AS and SRFA, the merit function value for the
linear mixing rule is 0.11 as compared to 0.11–0.18 for
the other mixing rules. We conclude that for homogeneous
internal mixtures of non-absorbing and weakly absorbing
constituents, Qext is not overly sensitive to how the interaction
between the electromagnetic fields of the constituents is
described.
Fig. 5 Extinction efficiency of mixed ammonium sulfate (AS) and
Suwannee River fulvic acid (SRFA) particles with a 1 : 1 mass ratio,
along with the Mie curves corresponding to the effective refractive
indices calculated with the volume–weighted ‘‘linear mixing’’ rule at
390 nm wavelength.
This journal is 
c the Owner Societies 2010

However, when one of the constituents in the homogeneous
internal mixture is strongly absorbing, the situation changes.
In ref. 80 the Qext of laboratory-generated aerosols comprised
of internal mixtures of AS and Rh-590 was also measured
with the Nd : YAG pulsed CRD aerosol spectrometer
running at 532 nm wavelength. Due to the low solubility of
Rh-590 in water, the aqueous solution of the mixture was
diluted with 10% ethanol. The aerosol RI retrieval algorithm
was then used to test which mixing rule provides the best
match to the measurements. We found that for low volume
fractions of Rh-590, the Mie scattering subroutine for
coated spheres, rather than one of the mixing rules, provides
the best agreement with measurements; for a 1 : 500 mixture
of Rh-590 and AS, the merit function value for the Mie
scattering subroutine for coated spheres, including particle
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
sizes starting from 350 nm, is 3.29 as compared to 3.90–4.26
for the mixing rules. The lack of success of the mixing rules
for low volume fractions of the strong absorber could be
attributed to residue of ethanol, which, unlike water, may
not have completely evaporated in the diffusion drier.
Additionally, AS has a different solubility in water than
Rh-590, which might have caused the final molar ratios of
the two constituents to differ from their original molar ratios
in the solution or might have led to the formation of a more
heterogeneous internal mixture akin to a coated particle.
Alternatively, the coated sphere model might better represent
the interaction between the electromagnetic fields of the
constituents in the case of a strong absorber with low volume
fraction even if they are truly homogeneously mixed. For
higher volume fractions of Rh-590 in the mixture, we found
that the extended effective medium approximation provides
the best agreement with measurements; for a 1 : 10 mixture of
Rh-590 and AS, the merit function value for the extended
effective medium approximation, including particle sizes from
350 nm and inclusion size 10 nm, is 2.95 as compared to
5.85–9.57 for the other mixing rules and as compared to 31.72
for the Mie scattering subroutine for coated spheres. The
success of the extended effective medium approximation for
high volume fractions of the strong absorber is likely connected
to the fact that, among all of the mixing rules, the extended
effective medium approximation retains the highest order
representation of the electromagnetic fields, allowing the highest
order description of the interaction between internal scattering
and absorption.
In addition to testing the theoretical calculation approaches
against extinction measurements, we also performed calculations
of the single scattering albedo (see section 1; $) and the direct
radiative forcing efficiency (RFE; the difference in radiative
flux at the top of the atmosphere with and without aerosols per
unit optical depth) for a pollution-type aerosol containing
ammonium sulfate, absorbing organic carbon (HULIS),
and soot.27 Our calculations suggest that accounting for
absorption by HULIS leads to a significant decrease in $
(more atmospheric absorption) and to a significant increase in
aerosol RFE (heating) as compared to pollution-type aerosols
containing only non-absorbing organic aerosol constituents.
Therefore, an additional conclusion is that HULIS and similarly
absorbing organic constituents are important contributors to
This journal is 
c the Owner Societies 2010
View Article Online
Fig. 6 Extinction efficiency of Nigrosin coated with glutaric acid
(Glu-A), along with the Mie curves for coated spheres at 532 nm
wavelength. Blue curve and symbols: constant core diameter with
increasing shell thickness; green curve and symbols: increasing core
diameter with constant shell thickness.
the radiative balance in the atmosphere and to the climate in
polluted environments.
Heterogeneously mixed (coated) aerosols
In ref. 53, measurements of the Qext of laboratory-generated
aerosols comprised of Nigrosin coated with Glu-A performed
with the Nd : YAG pulsed CRD at 532 nm wavelength were
reported. The aerosol retrieval algorithm was then used to test
the accuracy of the Mie scattering subroutine for coated
spheres, and the results are shown in Fig. 6. As can be seen,
the Mie scattering subroutine is successful at predicting the
aerosol Qext for thin coatings (constant shell thickness of
20 nm; compare the green curve to the green dots). However,
it is less successful at predicting the aerosol Qext for thicker
coatings (increasing shell thickness; compare the blue curve to
the blue dots), with the Mie calculation over-predicting the
extinction by a greater extent as the shell thickness increases.
The same discrepancy occurred when the coating was switched
to diethyl-hexyl-sebacate (a non-absorbing organic liquid;
DEHS53), which is liquid at room temperature rather
than solid like Glu-A. In ref. 53, we suggested that these
discrepancies result from either a lack of perfect sphericity in
the generated aerosols or from changes in the dielectric
constant of the coating near the interface between the core
and coating. However, no theoretical representations of
such physical effects that we tested completely resolved the
discrepancy. Since then, we have conducted further sensitivity
tests, systematically reducing the RI of the coating in the
theoretical calculations. A reduction in RI corresponding to
a mixture of air with Glu-A with mass ratio 1 : 5 (representing,
for example, pockets of air in the coating) calculated with the
linear mixing rule does bring the calculations more in line
with the measured extinction. Although Guenther (1984)111
did suggest that small distortions can occur at the interface
between the surface of the core and coating when physical
Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 27
 View Article Online

system at 532 nm wavelength, and the aerosol RI retrieval

algorithm was used to retrieve the RI of b-car, given the
previously retrieved/known RI for PSL (RI = 1.590 + i0.000).
The retrieved value for b-car is RI = 1.455 + i0.090, with a
merit value of 2.38. To the best of our knowledge, the RI of
b-car at 532 nm has not previously been reported in the
literature. The real part of the retrieved RI is in good
agreement with values for typical organic compounds
(B1.4), while the imaginary part was validated by measuring
the absorption of b-car dissolved in dichloromethane (CH2Cl2)
with a spectrophotometer (CARY 100 Bio UV-Visible spectro-
photometer, Varian). The imaginary part of the RI of b-car
derived from the spectrophotometer measurements according
to the formulation in Jacobson et al.112 is 0.075  0.001, a
difference of 0.025 from our retrieved value. This difference,
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.

though not very large, may be inherent in the different

Fig. 7 Extinction efficiency of PSL coated with glutaric acid (Glu-A), methods of measurement or could be caused by interactions
along with the Mie curves for coated spheres at 532 nm wavelength.
of dissolved b-car with the solvent. Either way, we take the
Blue curve and symbols: constant core diameter with increasing shell
thickness; green curve and symbols: increasing core diameter with
retrieved value of 0.090 to be reliable.
constant shell thickness. The red and black lines are Mie fits for The results of the measurements for PSL coated with b-car
measured points using the same system. The green and blue lines are are shown in Fig. 8. As can be seen, there are differences
the results of the coated sphere Mie calculation, using the retrieved RIs between the measurements and the calculated extinction
as input parameters. (calculated using the retrieved RI for b-carotene and the Mie
scattering subroutine for coated spheres) that increase with
vapor deposition is used to generate the coating, and that increasing particle size. However, the differences are not
these distortions can develop into narrow air pockets, we systematic; at times, the theoretical calculations over-predict
have no evidence that such pockets exist in our coatings. The the extinction, and at other times they under-predict the
mechanism by which Glu-A vapors condense onto the core extinction. This is true for the experiment with constant shell
particle in the coating oven needs to be examined more thickness of 40 nm (compare the green curve to the green dots
thoroughly. and see Table 1; the differences are up to 10%) and for the
To investigate whether coated particles presenting different experiment with increasing shell thickness (compare the blue
optical properties exhibit the same discrepancy, we present curve to the blue dots). The differences between the measurements
new measurements of Qext of laboratory-generated aerosols and the calculated extinction in the case of PSL coated with
comprised of PSL coated with Glu-A recently measured with b-car as compared to PSL coated with Glu-A may result from
the new CW-CRD system at 532 nm wavelength. The results the more rigid molecular structure of b-car, leading to a less
are compared with calculations using the same Mie scattering organized shell around the core PSL.
subroutine for coated spheres, as shown in Fig. 7. As can be
seen, the Mie scattering subroutine is successful at predicting
the aerosol extinction for both thin coatings (constant shell
thickness of 40 nm; compare the green curve to the green dots)
and thicker coatings (increasing shell thickness; compare the
blue curve to the blue dots). Although surface (interface)
effects should be more stable in the case of Nigrosin coated
by Glu-A (due to hydrogen bonds, compared to mostly
van der Waals in the case of PSL coated by Glu-A), we found
that PSL coated by Glu-A can be well described by the core
plus shell model. A possible explanation for these results might
be the existence of a mixed layer in the interface between the
Nigrosin core and the Glu-A shell. In this case, a different
model needs to be applied, and again, a more thorough
investigation on the mechanism by which Glu-A vapors
condense onto the core particle in the coating oven is needed.
In the next experiment, non-absorbing particles with a
weakly absorbing coating were examined. b-Carotene was Fig. 8 Extinction efficiency of PSL coated with b-carotene (b-car),
chosen as the coating material because it is more stable at along with the Mie curves for coated spheres at 532 nm wavelength.
high temperatures than other absorbers such as Nigrosin. The Blue curve and symbols: constant core diameter with increasing shell
Qext of laboratory-generated aerosols comprised of PSL thickness; green curve and symbols: increasing core diameter with
coated with b-car was measured with the new CW-CRD constant shell thickness.

28 | Phys. Chem. Chem. Phys., 2010, 12, 21–31 This journal is 

c the Owner Societies 2010
 View Article Online

Table 1 Percentage error between the measured and calculated Qext for PSL coated with glutaric-acid (Glu-A) and with b-carotene (b-car) in both
models (constant core diameter with increasing shell thickness and increasing core diameter with constant shell thickness)

Coated diameter/nm Size parameter (x) Qext calculated Qext measured Error/%
PSL–Glu-A: const. core diameter (350 nm)
350 2.067 2.510 2.506 0.143
370 2.185 2.532 2.511 0.821
390 2.303 2.616 2.672 2.170
410 2.421 2.768 2.949 6.510
430 2.539 2.992 3.050 1.916
450 2.657 3.239 3.288 1.531
470 2.775 3.421 3.463 1.223
490 2.894 3.495 3.679 5.253
510 3.012 3.494 3.605 3.197
PSL–Glu-A: const. shell thickness (40 nm)
280 1.653 1.279 1.165 8.860
340 2.008 2.250 1.989 11.593
390 2.303 2.616 2.601 0.573
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.

440 2.598 3.475 3.371 2.971

490 2.894 3.794 3.689 2.767
540 3.189 3.916 3.821 2.426
PSL–b-car: const. core diameter (350 nm)
390 2.303 2.681 2.523 5.875
410 2.421 2.843 2.747 3.359
440 2.598 3.100 3.102 0.048
470 2.775 3.255 3.510 7.837
500 2.953 3.296 3.539 7.376
PSL–b-car: const. shell thickness (40 nm)
340 2.008 2.270 2.094 7.775
390 2.303 2.681 2.445 8.807
440 2.598 3.430 3.492 1.796
490 2.894 3.750 3.917 4.440
540 3.189 3.914 3.587 8.335
600 3.543 4.309 4.258 1.167

4. Conclusions fraction of the absorber. For low absorber mass fractions,

We have summarized and reviewed experiments and theoretical
calculations of optical properties of complex aerosols.
Specifically, we focused on the impact of aerosol microstructure
on the effective refractive index of aerosols composed of
internal mixtures of components with different optical properties.
In the atmosphere, most aerosols are multi-component, and
therefore detailed understanding and modeling of their
complex refractive index will reduce the uncertainty related
to energy balance and climate change modeling.
By controlling the aerosol microstructure and the mass
ratios of the components and knowing the RI of one or more
of the separate components that make up the aerosols at the
wavelength of interest, through our experiments we were able
to validate different theoretical approaches used for evaluating
the optical properties of complex aerosols. Our approach also
allowed us to retrieve the aerosol’s Qext and/or the RI of one
or more of the components.
We conclude that the effective RI of homogeneously mixed
aerosols comprised of two non-absorbing materials with
similar water solubilities can be accurately calculated with
the simple mass or concentration based ‘‘linear mixing’’ rule.
In the case of a non-absorbing material homogeneously mixed
with weakly absorbing compounds, we conclude that all
mixing rules provide a reasonable estimate, but the coated
sphere Mie calculation does not always perform as well. In the
case of a strong absorber ‘‘homogeneously’’ mixed with a
non-absorber (with different solubilities in water), the success
of the different theoretical approaches varies with the mass
surprisingly, the coated sphere Mie calculation provides the
best estimate, while for high absorber mass fractions, the
extended effective medium approximation provides the best
estimate. Given the above, we conclude that the microstructure is
actually dissimilar for high and low mass fractions of the
absorbing compound. In order to generalize this statement for
other absorbers, we first need to eliminate the influence of the
solubility difference on the results.
Regarding coated particles, we find that the coated sphere
Mie subroutine gives an accurate calculation of Qext for
aerosols comprised of a non-absorber coated by another
non-absorber. However, for aerosols comprised of a strong
absorber coated by a non-absorber or of a non-absorber
coated by a weak absorber, discrepancies of up to 10%
between the measurements and theoretical calculations were
documented. These discrepancies await further investigation
with more advanced instrumentation in order to understand
their origin. Several such tools can be considered. Multiwave-
length CRD could provide a comprehensive view of the
wavelength dependence of the refractive index for the internally
mixed particles. Measuring the absorption coefficient with a
photo-acoustic spectrophotometer (PAS) coupled to the CRD
system could provide direct and independent measurements of
the extinction and absorption of aerosols and hence direct
measurement of the single scattering albedo of the aerosol and
more accurate values of the imaginary part of the complex
index of refraction. A new approach, that was recently developed
by Thompson et al., is the albedometer.113 This instrument
combines CRD within an integrating sphere nephelometer.

This journal is 
c the Owner Societies 2010 Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 29

The CRD resonator was built using the integrating sphere by
mounting the CRD mirrors on opposite sides of the sphere.
The light scattered by the aerosols inside the sphere is collected
by the inner side of the sphere to a separate PMT from the
CRD PMT. The main advantage of this method is the
simultaneous determination of the extinction and scattering
in a single instrument utilizing two very sensitive methods. In
addition, combining the methods in a single instrument would
minimize the errors in the measurements due to different
sample conditions in different instruments.
Acknowledgements
This work was partially supported by the Israel Science
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
Foundation (grants 1527/07 and 196/08). Y.R. acknowledges
financial support by the Helen and Martin Kimmel Award for
Innovative Investigation. We thank H. E. Levy for programming
support, and A. Moroz and M. Tzemach for helpful suggestions
regarding surface/interface effects in coated particles.
References
1 B. J. Finlayson-Pitts and J. Pitts, Jr., Chemistry of the Upper and
Lower Atmosphere, Academic Press, CA, 1999.
2 J. H. Seinfeld and S. N. Pandis, Atmospheric Chemistry and
Physics, 2nd edn, John Wiley & Sons Inc, 2006.
3 P. U. Poschl, Angew. Chem., Int. Ed., 2005, 44, 7520.
4 Y. Rudich, N. M. Donahue and T. F. Mentel, Annu. Rev. Phys.
Chem., 2007, 58, 321–352.
5 M. C. Jacobson, H. C. Hansson, K. J. Noone and R. Charlson,
Rev. Geophys., 2000, 38, 267–294.
6 Y. Rudich, Chem. Rev., 2003, 103, 5097–5124.
7 M. Kulmala, H. Vehkamaki, T. Petaja, M. Dal Maso, A. Lauri,
V. M. Kerminen, W. Birmili and P. H. McMurry, J. Aerosol Sci.,
2004, 35, 143–176.
8 B. T. Johnson, K. P. Shine and P. M. Forster, Q. J. R. Meteorol.
Soc., 2004, 130, 1407–1422.
9 U. Lohmann and J. Feichter, Geophys. Res. Lett., 2001, 28, 159.
10 S. Menon, J. Hansen, L. Nazarenko and Y. Luo, Science, 2002,
297, 2250–2253.
11 U. Lohmann and J. Feichter, Atmos. Chem. Phys., 2005, 5, 715.
12 D. Y. Kim and V. Ramanathan, J. Geophys. Res.-Atmos., 2008,
113.
13 S. Solomon, D. Qin, M. Manning, R. B. Alley, T. Berntsen,
N. L. Bindoff, Z. Chen, A. Chidthaisong, J. M. Gregory,
G. C. Hegerl, M. Heimann, B. Hewitson, B. J. Hoskins,
F. Joos, J. Jouzel, V. Kattsov, U. Lohmann, T. Matsuno,
M. Molina, N. Nicholls, J. Overpeck, G. Raga,
V. Ramaswamy, J. Ren, M. Rusticucci, R. Somerville,
T. F. Stocker, P. Whetton, R. A. Wood and D. Wratt, Technical
Summary, in Climate Change 2007: The Physical Science Basis.
Contribution of Working Group I to the Fourth Assessment Report
of the Intergovernmental Panel on Climate Change, Cambridge
University Press, Cambridge, 2007.
14 Y. J. Kaufman, I. Koren, L. A. Remer, D. Rosenfeld and
Y. Rudich, Proc. Natl. Acad. Sci. U. S. A., 2005, 102,
11207–11212.
15 V. Ramanathan, C. Chung, D. Kim, T. Bettge, L. Buja,
J. T. Kiehl, W. M. Washington, Q. Fu, D. R. Sikka and
M. Wild, Proc. Natl. Acad. Sci. U. S. A., 2005, 102, 5326–5333.
16 Y. J. Kaufman and I. Koren, Science, 2006, 313, 655–658.
17 I. Koren, L. A. Remer, Y. J. Kaufman, Y. Rudich and
J. V. Martins, Geophys. Res. Lett., 2007, 34.
18 I. Koren, J. V. Martins, L. A. Remer and H. Afargan, Science,
2008, 321, 946–949.
19 D. Rosenfeld, U. Lohmann, G. B. Raga, C. D. O’Dowd,
M. Kulmala, S. Fuzzi, A. Reissell and M. O. Andreae, Science,
2008, 321, 1309–1313.
30 | Phys. Chem. Chem. Phys., 2010, 12, 21–31
View Article Online
20 H. Moosmuller, R. K. Chakrabarty and W. P. Arnott,
J. Quant.Spectrosc. Radiat. Transfer, 2009, 110, 844–878.
21 C. Erlick, V. Ramaswamy and L. M. Russell, J. Geophys. Res.,
2006, 111, D06204.
22 Q. Zhang, J. L. Jimenez, M. R. Canagaratna, J. D. Allan, H. Coe,
I. Ulbrich, M. R. Alfarra, A. Takami, A. M. Middlebrook,
Y. L. Sun, K. Dzepina, E. Dunlea, K. Docherty,
P. F. DeCarlo, D. Salcedo, T. Onasch, J. T. Jayne, T. Miyoshi,
A. Shimono, S. Hatakeyama, N. Takegawa, Y. Kondo,
J. Schneider, F. Drewnick, S. Borrmann, S. Weimer,
K. Demerjian, P. Williams, K. Bower, R. Bahreini, L. Cottrell,
R. J. Griffin, J. Rautiainen, J. Y. Sun, Y. M. Zhang and
D. R. Worsnop, Geophys. Res. Lett., 2007, 34.
23 K. Chamaillard, S. G. Jennings, C. Kleefeld, D. Ceburnis and
Y. J. Yoon, J. Quant. Spectrosc. Radiat. Transfer, 2003, 79–80,
577–597.
24 J. T. Kiehl, T. L. Schneider, P. J. Rasch and M. C. Barth,
J. Geophys. Res., 2000, 105, 1441–1457.
25 C. E. Lund Myhre and C. J. Nielsen, Atmos. Chem. Phys.
Discuss., 2004, 4, 3013.
26 S. F. Maria, L. M. Russell, M. K. Gilles and S. C. B. Myneni,
Science, 2004, 306, 1921–1924.
27 E. Dinar, A. A. Riziq, C. Spindler, C. Erlick, G. Kiss and
Y. Rudich, Faraday Discuss., 2008, 137, 279–295.
28 M. O. Andreae, Nature, 2001, 409, 671–672.
29 T. C. Bond, D. G. Streets, K. F. Yarber, S. M. Nelson, J. H. Woo
and Z. Klimont, J. Geophys. Res., 2004, 109, D14203.
30 B. F. Henson, J. Geophys. Res., 2007, 112, D24S16.
31 L. Liua and M. I. Mishchenkoa, J. Quant. Spectrosc. Radiat.
Transfer, 2007, 106, 262–273.
32 Z. Li, P. Goloub, L. Blarel, B. Damiri, T. Podvin and
I. Jankowiak, Appl. Opt., 2007, 46, 1548–1553.
33 I. N. Sokolik and O. B. Toon, Nature, 1996, 381, 681–683.
34 M. O. Andreae and A. Gelencser, Atmos. Chem.Phys. Discuss.,
2006, 6, 3419–3463.
35 S. F. S. Decesari, M. C. Facchini, M. Mircea, L. Emblico,
F. Cavalli, W. Maenhaut, X. Chi, G. Schkolnik, A. Falkovich,
Y. Rudich, M. Claeys, V. Pashynska, G. Vas, I. Kourtchev,
R. Vermeylen, A. Hoffer, M. O. Andreae, E. Tagliavini,
F. Moretti and P. Artaxo, Atmos. Chem. Phys., 2006, 6, 375.
36 A. Hoffer, A. Gelencser, P. Guyon, G. Kiss, O. Schmid,
G. P. Frank, P. Artaxo and M. O. Andreae, Atmos. Chem. Phys.,
2006, 6, 3563–3570.
37 H. L. Sun, L. Biedermann and T. C. Bond, Geophys. Res. Lett.,
2007, 34.
38 M. Born and E. Wolf, Principles of optics, 7th edn, Cambridge
University Press, 1999.
39 T. S. Bates, T. L. Anderson, T. Baynard, T. Bond, O. Boucher,
G. Carmichael, A. Clarke, C. Erlick, H. Guo, L. Horowitz,
S. Howell, S. Kulkarni, H. Maring, A. McComiskey,
A. Middlebrook, K. Noone, C. D. O’Dowd, J. Ogren,
J. Penner, P. K. Quinn, A. R. Ravishankara, D. L. Savoie,
S. E. Schwartz, Y. Shinozuka, Y. Tang, R. J. Weber and
Y. Wu, Atmos. Chem. Phys., 2006, 6, 1657–1732.
40 N. Bellouin, O. Boucher, J. Haywood and M. S. Reddy, Nature,
2005, 438, 1138–1141.
41 W.-T. Chen, R. A. Kahn, D. Nelson, K. Yau and J. H. Seinfeld,
J. Geophys. Res., 2008, 113.
42 Y. J. Kaufman, Nature, 2002, 419, 215.
43 Y. J. Kaufman and R. S. Fraser, Science, 1997, 277, 1636–1639.
44 G. W. Petty, A First Course in Atmospheric Radiation, Sundog
publishing, Madison, Wisconsin, 2004.
45 C. F. Bohren and D. R. Huffman, Absorption and Scattering of
Light by Small Particles, Wiley, New York, 1983.
46 G.-h. Dai, Z.-b. Ren, Q. Sun and J. Liu, Proc. SPIE–Int. Soc.
Opt. Eng., 2006, 602723.
47 G. Mie, Ann. Phys., 1908, 25, 377–445.
48 C. Erlick, J. Atmos. Sci., 2006, 63, 754–763.
49 G. Lesins, P. Chylek and U. Lohmann, J. Geophys. Res., 2002,
107, 4094.
50 C. Marcolli, B. P. Luo, T. Peter and F. G. Wienhold, Atmos.
Chem. Phys., 2004, 4, 2593–2599.
51 F. Parungo, in Atmos. Aerosol. Nucleat., 1988, p. 269.
52 F. P. Parungo, C. T. Nagamoto, J. Rosinski and
P. L. Haagenson, J. Atmos. Chem., 1986, 4, 199.
This journal is 
c the Owner Societies 2010

53 A. A. Riziq, M. Trainic, C. Erlick, E. Segre and Y. Rudich,
Atmos. Chem. Phys., 2008, 8, 1823–1833.
54 A. H. Falkovich, G. Schkolnik, E. Ganor and Y. Rudich,
J. Geophys. Res., 2004, 109, D02208.
55 S. A. Guazzotti, J. R. Whiteaker, D. Suess, K. R. Coffee and
K. A. Prather, Atmos. Environ., 2001, 35, 3229.
56 Q. Zhang, M. R. Canagaratna, J. T. Jayne, D. R. Worsnop and
J. L. Jimenez, J. Geophys. Res.-Atmos., 2005, 110.
57 G. B. Ellison, A. F. Tuck and V. Vaida, J. Geophys. Res., 1999,
104, 11633–11641.
58 V. Vaida, A. F. Tuck and G. B. Ellison, Phys. Chem. Earth Pt.
C-Solar-Terr. Planet. Sci., 2000, 25, 195–198.
59 A. Laskin, D. J. Gaspar, W. H. Wang, S. W. Hunt, J. P. Cowin,
S. D. Colson and B. J. Finlayson-Pitts, Science, 2003, 301,
340–344.
60 V. H. Grassian, Int. Rev. Phys. Chem., 2001, 20, 467–548.
61 M. Posfai, J. R. Anderson, P. R. Buseck and H. Sievering,
J. Geophys. Res., 1999, 104, 21685–21693.
62 K. Karar, A. Gupta, A. Kumar and A. Biswas, Environ. Monit.
Published on 12 October 2009. Downloaded on 19/10/2015 20:40:30.
Assess., 2006, 120, 347.
63 U. Panne, R. E. Neuhauser, M. Theisen, H. Fink and
R. Niessner, Spectrochim. Acta, Part B, 2001, 56, 839.
64 M. H. Shah, N. Shaheen and M. Jaffar, J. Chem. Soc. Pak., 2007,
29, 598–604.
65 H. X. Xue, A. F. Khalizov, L. Wang, J. Zheng and R. Y. Zhang,
Environ. Sci. Technol., 2009, 43, 2787–2792.
66 P. Chylek, G. Videen, D. J. W. Geldart, J. S. Dobbie and H. C.
W. Tso, Effective medium approximations for heterogeneous
particles in: Light scattering by nonspherical particles, theory,
measurements and application, Academic Press, 2000.
67 M. Z. Jacobson, J. Geophys. Res., 2002, 107.
68 A. W. Stelson, Environ. Sci. Technol., 1990, 24, 1676–1679.
69 I. N. Tang, J. Geophys. Res., 1997, 102.
70 P. Chylek, V. Ramaswamy and R. J. Cheng, J. Atmos. Sci., 1984,
41, 3076–3084.
71 A. Sihvola and R. Sharma, Microwave Opt. Technol. Lett., 1999,
22, 229–231.
72 M. Z. Jacobson, J. Phys. Chem. A, 2006, 110, 6860–6873.
73 M. R. Beaver, R. M. Garland, C. A. Hasenkopf, T. Baynard,
A. R. Ravishankara and M. A. Tolbert, Environ. Res. Lett., 2008,
3, 045003.
74 R. E. Danielson, D. R. Moore and H. C. van de Hulst, J. Atmos.
Sci., 1969, 26, 1078–1087.
75 T. P. Ackerman and O. B. Toon, Appl. Opt., 1981, 20,
3661–3667.
76 J. E. Penner, C. C. Chuang and K. Grant, Clim. Dyn., 1998, 14,
839.
77 O. Mohler, S. Benz, H. Saathoff, M. Schnaiter, R. Wagner,
J. Schneider, S. Walter, V. Ebert and S. Wagner, Environ. Res.
Lett., 2008, 3, 025007.
78 O. Mohler, S. Buttner, C. Linke, M. Schnaiter, H. Saathoff,
O. Stetzer, R. Wagner, M. Kramer, A. Mangold, V. Ebert and
U. Schurath, J. Geophys. Res., 2005, 110, D11210.
79 M. Schnaiter, C. Linke, O. Mohler, K. H. Naumann, H. Saathoff,
R. Wagner, U. Schurath and B. Wehner, J. Geophys. Res., 2005,
110, D19204.
80 A. A. Riziq, C. Erlick, E. Dinar and Y. Rudich, Atmos. Chem.
Phys., 2007, 7, 1523–1536.
81 K. Adachi and P. R. Buseck, Atmos. Chem. Phys., 2008, 8,
6469–6481.
This journal is 
c the Owner Societies 2010
View Article Online
82 P. J. Sheridan, W. P. Arnott, J. A. Ogren, E. Andrews,
D. B. Atkinson, D. S. Covert, H. Moosmuller, A. Petzold,
B. Schmid, A. W. Strawa, R. Varma and A. Virkkula, Aerosol
Sci. Technol., 2005, 39, 1–16.
83 A. F. Khalizov, H. Xue, L. Wang, J. Zheng and R. Zhang,
J. Phys. Chem. A, 2009, 113, 1066–1074.
84 P. Chylek, V. Srivastava, R. G. Pinnick and R. T. Wang, Appl.
Opt., 1988, 27, 2396.
85 G. Videen, D. Ngo and P. Chlek, Opt. Lett., 1994, 19, 1675.
86 G. Videen and P. Chlek, Opt. Commun., 1998, 158, 1.
87 M. J. Wolff, G. C. Clayton and S. J. Gibson, Astrophys. J., 1998,
503, 815–830.
88 J. E. Spanier and I. P. Herman, Phys. Rev. B., 2000, 61, 10437.
89 L. Kolokolova and B. S. Gustafsonm, J. Quant. Spectrosc.
Radiat. Transfer, 2001, 70, 611.
90 E. R. Graber and Y. Rudich, Atmos. Chem. Phys. Discuss., 2006,
5, 9801.
91 N. Lang-Yona, Y. Rudich, E. Segre, E. Dinar and A. Abo-Riziq,
Anal. Chem., 2009, 81, 1762–1769.
92 C. Spindler, A. Abo Riziq and Y. Rudich, Aerosol Sci. Technol.,
2007, 41, 1011–1017.
93 A. O. Keefe and D. A. G. Deacon, Rev. Sci. Instrum., 1988, 59,
2544–2555.
94 D. Romanini, A. A. Kachanov, N. Sadeghi and F. Stoeckel,
Chem. Phys. Lett., 1997, 264, 316–322.
95 M. D. Wheeler, S. M. Newman and A. J. Orr-Ewing, J. Chem.
Phys., 1998, 108, 6594–6605.
96 S. S. Brown, H. Stark, S. J. Ciciora, R. J. McLaughlin and
A. R. Ravishankara, Rev. Sci. Instrum., 2002, 73, 3291–3301.
97 M. Mazurenka, A. J. Orr-Ewing, R. Peverallb and and G. A.
D. Ritchieb, Annu. Rep. Prog. Chem., Sect. C, 2005, 101, 100–142.
98 M. Pradhan, R. E. Lindley, R. Grilli, I. R. White, D. Martin and
A. J. Orr-Ewing, Appl. Phys. B, 2008, 90, 1–9.
99 G. Berden, R. Peeters and G. Meijer, Int. Rev. Phys. Chem., 2000,
19, 565.
100 V. Bulatov, M. Fisher and I. Schechter, Anal. Chim. Acta, 2002,
466, 1–9.
101 H. Moosmuller, R. Varma and W. P. Arnott, Aerosol Sci.
Technol., 2005, 39, 30–39.
102 A. Pettersson, E. R. Lovejoy, C. A. Brock, S. S. Brown and
A. R. Ravishankara, J. Aerosol Sci., 2004, 35, 995–1011.
103 A. D. Sappey, E. S. Hill, T. Settersten and M. A. Linne, Opt.
Lett., 1998, 23, 954–956.
104 J. D. Smith and D. B. Atkinson, Analyst, 2001, 126, 1216–1220.
105 A. W. Strawa, R. Castaneda, T. Owano, D. S. Baer and
B. A. Paldus, J. Atmos. Oceanic Technol., 2003, 20, 454–465.
106 T. J. A. Butler, J. L. Miller and A. J. Orr-Ewing, J. Chem. Phys.,
2007, 126, 174302.
107 J. J. Scherer, J. B. Paul, A. O’Keefe and R. J. Saykally, Chem.
Rev., 1997, 97, 25–52.
108 S. M. Ball and R. L. Jones, Chem. Rev., 2003, 103, 5239–5262.
109 J. C. Lagarias, J. A. Reeds, M. H. Wright and P. E. Wright,
SIAM J. Optim., 1998, 9, 112–147.
110 O. Torres, A. Tanskanen, B. Veihelmann, C. Ahn, R. Braak,
P. K. Bhartia, P. Veefkind and P. Levelt, J. Geophys. Res., 2007,
112, D24S47.
111 K. H. Guenther, Appl. Opt., 1984, 23, 3806.
112 M. Z. Jacobson, J. Geophys. Res., 1999, 104, 3527–3542.
113 J. E. Thompson, N. Barta, D. Policarpio and R. DuVall, Opt.
Express, 2008, 16, 2191–2205.
Phys. Chem. Chem. Phys., 2010, 12, 21–31 | 31