Aerosol Science and Technology

ISSN: 0278-6826 (Print) 1521-7388 (Online) Journal homepage: https://www.tandfonline.com/loi/uast20

Aerosol Absorption Measurement using

Photoacoustic Spectroscopy: Sensitivity,
Calibration, and Uncertainty Developments

Daniel A. Lack , Edward R. Lovejoy , Tahllee Baynard , Anders Pettersson & A.

R. Ravishankara

To cite this article: Daniel A. Lack , Edward R. Lovejoy , Tahllee Baynard , Anders Pettersson &
A. R. Ravishankara (2006) Aerosol Absorption Measurement using Photoacoustic Spectroscopy:
Sensitivity, Calibration, and Uncertainty Developments, Aerosol Science and Technology, 40:9,
697-708, DOI: 10.1080/02786820600803917

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Aerosol Science and Technology, 40:697–708, 2006
Copyright
c American Association for Aerosol Research
ISSN: 0278-6826 print / 1521-7388 online
DOI: 10.1080/02786820600803917
Aerosol Absorption Measurement using Photoacoustic
Spectroscopy: Sensitivity, Calibration, and Uncertainty
Developments
Daniel A. Lack,1,2 Edward R. Lovejoy,1 Tahllee Baynard,1,2 Anders Pettersson,1,2
and A. R. Ravishankara1
1
NOAA Earth System Research Laboratory, Boulder, Colorado, USA
2
Cooperative Institute for Research in the Environmental Sciences, University of Colorado, Boulder,
Colorado, USA
Light absorption by aerosols is one of the most uncertain pa-
rameters associated with the direct and indirect aerosol effects on
climate and is one of the most difficult quantities to measure. This
article describes the development of a sensitive method of mea-
suring aerosol absorption at 532 nm with excellent time response
(detection limit: 0.08 Mm−1 , 60 second average) using photoacous-
tic absorption spectroscopy. An accurate calibration method (ac-
curacy of 1–2%) at atmospherically relevant absorption levels and
independent validation of the photoacoustic technique is presented.
An upper limit to the instrument precision for aerosol absorption
measurement is ∼6% (2σ , 30 sec) while instrument accuracy is
calculated to be ∼5%. A standard for aerosol absorption measure-
ment techniques using well characterized absorbing aerosol is also
proposed.
1. INTRODUCTION
1.1. Aerosol Absorption and Climate
Uncertainties in current estimates of climate forcing are at the
core of the debate of climate science today. One of the largest
uncertainties in global radiative forcing is the contribution from
aerosols. Current estimates suggest (IPCC 2001; Penner et al.
2001) that the net cooling caused by the radiative forcing due to
direct and indirect effects of aerosol is potentially half to two-
thirds the warming caused by greenhouse gases. However the
uncertainties quoted for the aerosol contribution are as large as
or larger than the estimates themselves (IPCC 2001; Schwartz
Received 16 November 2005; accepted 5 January 2006.
This work was funded by NOAA’s Climate program. The authors
acknowledge Steven Ciciora, Bill Dubé, Richard McLaughlin, and Erik
Richards for help in design, development, and construction. Thanks to
Thomas Giddings at the University of Colorado for the TEM images.
Address correspondence to Daniel A. Lack, NOAA Earth Sys-
tem Research Laboratory, 325 Broadway, Boulder, CO 80305, USA.
E-mail: daniel.lack@noaa.gov
2004). Aerosols that scatter and absorb radiation can have a
cooling or warming effect depending on the magnitude of the ab-
sorption term and the albedo of the underlying surface. Whether
cooling or warming results, the magnitude of the effect is di-
rectly related to the quantity of light an aerosol absorbs. Aerosol
absorption is an important contributor to: (1) the aerosol sin-
gle scatter albedo (ωo ) or the ratio of aerosol scattering (σsp )
to total extinction (σep ), where σep is the sum of scattering and
absorption (σap ) and (2) Aerosol Optical Depth (AOD), the ver-
tical integration of extinction. Given its contribution to these
parameters, it is critical that the absorption term be measured
accurately.
1.2. Measuring Aerosol Absorption
The two most common techniques for measuring aerosol ab-
sorption are the so-called difference method, where absorption
is derived from the difference between extinction and scattering,
and from filter based methods that measure the attenuation of a
filter accumulating aerosol. An additional technique, although
not nearly as wide spread in its application, is photoacoustic
absorption spectroscopy. Here, these techniques are assessed
briefly.
The combination of instrumentation that provides the best
measure of absorption by difference is through cavity ring
down spectroscopy to measure aerosol extinction (with accu-
racies of 2% or better, Smith and Atkinson 2001; Strawa et al.
2003; Pettersson et al. 2004) and the integrating nephelome-
ter to measure scattering, which has a reported accuracy of
∼7% (Anderson and Ogren 1998; Bond et al. 1999). The major
disadvantage of this method is the large uncertainties derived
from the propagation of errors through the difference of the
two quantities, particularly at low absorption levels in the atmo-
sphere (Bond et al. 1999). Filter based methods, including the
aethelometer and Particle Soot Absorption Photometer (PSAP)
have found widespread application for field measurements of
absorption and have been evaluated using the σep –σsp calculated
697
698 D. A. LACK ET AL.

absorption (Bond et al. 1999; Weingartner et al. 2003; Sheridan understand the measurements produced from the current
et al. 2005). The PSAP and aethalometer measurements, hav- methods;
ing precision somewhere in the range of 20–25% (Bond et al. 2. Field instruments should be calibrated regularly in the field,
1999; Magi et al. 2003) and 30–35% (Weingartner et al. 2003; ideally with an absorbing aerosol standard. This is an impor-
Schmid et al. 2005) respectively, form the basis for most field tant step for filter based methods, so that the uncertainties in
absorption and albedo data. These filter based techniques re- these measurements can be further reduced.
quire many correction factors that limit the quality of the de-
In this manuscript, we describe further development and val-
rived data. The works by Bond et al. (1999), Anderson et al.
idation of a photoacoustic spectrometer (PAS) with optimized
(2003), Weingartner et al. (2003), Arnott et al. (2005a), Schmid
sensitivity and precision for atmospheric measurements that can
et al. (2005), and Virkkula et al. (2005) are important references
significantly reduce the uncertainties in measurements of ambi-
in understanding the strengths and weaknesses of these filter
ent aerosol absorption. We present a calibration at atmospheri-
based techniques. The corrections needed for filter based meth-
cally relevant absorption levels (<∼25 Mm−1 ) using ozone and
ods have been found to be source specific (Weingartner et al.
a potential aerosol absorption standard consisting of dyed mono-
2003; Schmid et al. 2005) and determination of these corrections
disperse polystyrene spheres. Combining the fast and sensitive
are not easily performed in the field and so general corrections
photoacoustic technique with fast and sensitive cavity ring down
calculated during inter-comparisons are usually applied to all
systems will provide a sensitive, well calibrated, low uncertainty
PSAP or aethalometer units.
instrument configuration to measure aerosol optical properties
The photoacoustic technique, which is a direct method that
with particular capabilities of measuring the single scatter albedo
can be easily calibrated, avoids the fundamental difficulties asso-
with reduced uncertainty.
ciated with filter based measurements or in situ measurements
using the difference of extinction and scattering. The photoa-
coustic technique has recently been developed into a stable 2. EXPERIMENTAL DETAILS
method of measuring aerosol absorption and is fast becoming an
2.1. Instrument Description
accepted standard for comparisons to the filter based methods
The photoacoustic principle is well described (e.g., Miklos
and the difference method (Moosmuller et al. 1998; Arnott et al.
et al. 2001) and significant work has been performed in the
1999, 2003, 2005a, 2005b; Schmid et al. 2005; Schnaiter et al.
application of the technique to gas phase absorption and also
2005; Sheridan et al. 2005). These photoacoustic systems have
describing its theoretical properties (Binjnen 1995; Raspet et al.
reported accuracies of 5–10% depending on laboratory or field
2003; Rey et al. 2005). Here, the method is summarized briefly.
locations and a number of methods of calibration. Excluding
When power modulated light is absorbed by a particle, the en-
the calibration methods used for black carbon mass monitors
ergy is released as heat creating pressure waves that propagate
(Petzold and Niessner 1995; Kramer et al. 2001) two types of
away from the particle. In a cavity, these waves resonate at the
calibrations have been used for photoacoustic instruments mea-
characteristic radial and longitudinal frequencies of the cavity.
suring aerosol absorption. Arnott et al. (2000) measured the
When the light source is modulated at a resonant frequency of
acoustic response to the light absorption of NO2 and compared
the cavity, the propagated sound wave is amplified and can be
this to the absorption measured using a transmittance measure-
detected by sensitive microphones.
ment. The photoacoustic signal can also be calculated using
Figure 1 shows a schematic of the photoacoustic system de-
a theoretical calibration which requires calibrated laser power,
scribed in this work. It takes aspects of the designs of Miklos
measured resonator quality factor and calibrated microphones as
et al. (2001), Kramer et al. (2001) and Nagele and Sigrist (2000).
described in Rosenwaig (1980). Probably the largest issue relat-
In this instrument 532 nm continuous wave (CW) laser light
ing to the application of the photoacoustic technique to aerosol
(200 mw) is introduced into a cavity consisting of two 150 mm
absorption is the potential to evaporate volatile species from the
long (1 /2 λ) 25 mm diameter tubes (resonators) machined into
aerosol. Under high RH conditions evaporation may result at
a 100 mm diameter aluminium rod. The sample flow passes
the expense of an acoustic response. Arnott et al. (2003) and
through both resonators while the light passes through one. Sen-
Raspet et al. (2003) investigated this phenomenon for ambient
sitive microphones (Knowles Acoustics1 EK3132) are placed at
and theoretical aerosols, respectively, and suggest that aerosol
the center of each tube (anti-node of the sound wave), one de-
be dried below 65–70% RH to avoid evaporation biases.
tecting background noise, the other detecting background noise
We draw the following conclusions regarding the current state
and photoacoustic signal. The microphones are attached to a
of aerosol absorption measurements:
1
1. Uncertainties in the regular field measurement of aerosol ab- Certain commercial equipment, instruments, or materials are iden-
sorption need to be reduced so that the quality of related tified in this article in order to adequately specify the experimental
procedure. Such identification does not imply recognition or endorse-
quantities is improved. Continued development of fast, accu- ment by the National Oceanic and Atmospheric Administration, nor
rate, precise, and direct measurement techniques of aerosol does it imply that the material or equipment identified are necessarily
absorption is desired to achieve this end, and to further the best available for the purpose.
 PHOTOACOUSTIC INSTRUMENT DEVELOPMENT
FIG. 1. Schematic of laboratory PAS system.
short length of threaded rod which is screwed into the resonator
block. The microphones are orientated in the same position rel-
ative to one another while the back of the microphone plate is
in direct contact with the sample volume via a small channel to
allow for pressure equalization. The signals are subtracted and
amplified using a differential preamplifier–amplifier combina-
tion optimized for the 1–2 KHz region. The main cavity block
is capped on both ends with 1 /4 λ expanded volumes (75 mm in
length and diameter) which act as the boundary for the resonators
and as acoustic filters (total sample volume of the instrument is
∼750 cm3 ). The laser path length is increased through the use
of a Herriot cell multi-pass arrangement (Herriot and Schulte
1965) where spherical mirrors (reflectivity >99.5% at 532 nm,
1 m radius of curvature) are placed ∼85 cm apart in line with
the signal resonator. The multi-passed light (40-fold increase
in path) passes through this resonator. The Herriott cell optics
and the photoacoustic cell are separated by anti-reflective coated
quartz windows at the expanded volumes. The laser light passes
through these windows with a small loss of overall power (∼5%)
and negligible contribution to noise within the cell. The ampli-
tude of the laser is modulated electronically with a square wave
function at the resonant frequency of the resonator. Laser mod-
ulation and reading of the microphones are synchronized so that
user-defined sampling periods are triggered from a zero crossing
of the modulation signal. A Fast Fourier Transform is applied to
the signal and the resulting resonance peak is integrated in the
frequency domain.
2.2. Particle Generation
Two types of absorbing aerosol were used in this study. Ni-
grosin dye particles were generated in a collision type atomizer
(Liu and Lee 1975) using a solution of Nigrosin dye (C48 N9 H51 )
699
in deionized water. The particles were dried over 13X molecular
sieve. Downstream of the drying stage relative humidity (RH)
was monitored and for all experiments was ≤5%; well below
the RH at which any effects of evaporation on the acoustic sig-
nal are expected (Arnott et al. 2003). The size distribution was
varied by changing the concentration of the dye introducing an
absorbing component to the spheres. The particles were then
passed through a custom built Differential Mobility Analyzer,
DMA (Knutson and Whitby 1975) producing a size-selected
near-monodisperse size distribution. DMA flows were calibrated
initially and checked on a regular basis while the performance
of the DMA size selection capability was monitored regularly
by analysing a range of diameters of non-absorbing polystyrene
spheres. Particle concentrations for all experiments were mea-
sured using a Condensation Particle Counter. The CPC flow
was initially calibrated and then checked on a regular basis us-
ing a wet test meter. Number concentrations were stable (varia-
tions ≤ ± 5%) over the sampling periods (often ten minutes
or more). An initial sample of dried particles was deposited
on a conductive filter and analysed using Transmission Elec-
tron Microscopy (TEM). Figure 2 shows an example of the
micrographs of the atomized and dried Nigrosin solution. All
micrographs appeared to show spherical particles. Absorbing
Polystyrene Spheres (APSS) were obtained from Duke Scien-
tific.2 These aqueous solutions of monodisperse polystyrene
spheres are treated with an absorbing dye. Characterization of
the spheres is not provided. The aerosol is generated by atomiza-
tion of the solution. A range of sizes (nominally 150 nm, 300 nm,
450 nm, 600 nm, 800 nm, and 1020 nm) were obtained for this
analysis. Again, particles were dried over molecular sieve and
2
See footnote 1.
700 D. A. LACK ET AL.

pulsed 532 nm laser whereas the PAS system uses a CW 532 nm

laser at slightly different wavelength (λ = 0.1 nm). Ozone
was chosen as the calibration gas because its broadband absorp-
tion structure around 532 nm minimizes any potential absorp-
tion differences derived from the two lasers (calculated to be
∼0.1% difference using cross section data from Burkholder and
Talukdar 1994). Also, the ozone calibration technique is suit-
able for field application because ozone is easy to generate (a
commercially available mercury lamp generator was used in this
study) and quantify.

3.1.1. Resonant Frequency and Quality Factor

The resonant frequency of the photoacoustic cavity changes
as temperature and gas density change. In this laboratory system,
oxygen and ozone are introduced into the cell and the amplitude
of the photoacoustic response due to ozone absorption is mea-
sured across a frequency range surrounding the expected funda-
mental resonant frequency (FR ). Figure 3 shows these measure-
ments and pinpoints the resonant frequency during an ozone cal-
ibration as 932 Hz. The resonant cavity quality factor (Q = FR ÷
FWHM) is determined to be 52. This Q is low for a resonant
FIG. 2. TEM image of atomized and dried nigrosin dye showing spherical cavity and hence the acoustic signal sensitivity to changes in
particles. temperature and composition of the sample is small. Using the
relation outlined in Miklos et al. (2001) a 1◦ C change in temper-
the humidity monitored (always ≤5% RH) prior to size selection ature will cause just less than a 1% change in measured signal
and interrogation by the instrumentation. for this resonator. It was also calculated that RH changes of 10%
will cause a 1% change to the measured signal (due to gas den-
2.3. Uncertainties sity changes). For this study, the resonant frequency was stable;
Uncertainties in the voltage applied to the DMA, DMA pres-
sure, sheath flows, and sample flows were included in particle
size calculations. Cumulatively, there is estimated to be about
±3% uncertainty in the calculated diameter. Uncertainties in ex-
tinction measurements were included and PAS calibration un-
certainties were also considered. Uncertainties in the particle
number concentrations generated in the atomizer (measured by
the CPC) and CPC flow rate calibration (±5%) were consid-
ered, as were uncertainties in temperature (±0.25◦ C) and pres-
sure (±1 Torr). The contributions of multiply charged particles
that exit the DMA with the singly charged particles of inter-
est was quantified using a method similar to that described in
Hoppel (1978) and their optical effect was accounted for in the
analysis. Although laser power within the PAS system was not
monitored, the repeated stability of gas phase calibrations and
monodisperse aerosol over many months of operation indicated
a very stable light source.

3. RESULTS AND DISCUSSION

3.1. PAS Calibration
We have used the Cavity Ring-Down Aerosol Extinction
Spectrometer (CRD-AES) system developed by Pettersson et al.
(2004) to measure the gas phase absorption of ozone and cali-
brate the photoacoustic response. The CRD-AES system uses a
FIG. 3. PAS resonance response giving the resonant frequency (FR ) of 932 Hz
at 620 Torr and 295 K and the resonator Q factor (FR /FWHM) of the system of
∼52.
 PHOTOACOUSTIC INSTRUMENT DEVELOPMENT
temperatures did not vary more than ±0.25◦ C and the RH of the
system varied less than ±2%.
3.1.2. PAS Response Calibration
The photoacoustic system was calibrated with ozone at
known optical absorption levels measured with the cavity ring
down technique. Ozone loss through the CRD-AES and PAS
systems was negligible (<1% loss through instrument surfaces
and plumbing). The CRD-AES system measured extinction to
an accuracy and precision of better than 1%; this sensitivity en-
abled accurate calibration of the PAS system across 3 orders of
magnitude down to levels approaching the instrument sensitiv-
ity. Figure 4 depicts the calibration using the CRD-AES system
and shows a linear response of the PAS system across this large
absorption range. The precision in this calibration (2σ in the cal-
culated slope) is 0.09% across the full range and 0.39% across
the atmospherically relevant range (<∼25 Mm−1 ). Combining
this precision for the gas phase calibration and the accuracy in
the CRD-AES measurement gives a total accuracy for the PAS
instrument, for the gas phase calibration of 1 to 2%.
Arnott et al. (2000) calibrated their aerosol photoacoustic in-
strument by measuring the light transmission through the pho-
toacoustic cell and the photoacoustic response in the presence of
NO2 . They used NO2 concentrations that gave gas phase absorp-
tion levels of ∼1.5 × 105 Mm−1 . This method assumes linearity
in the calibration down to the detection limit of the instrument.
They have also compared their calibration method to the differ-
ence between aerosol extinction and scattering (Sheridan et al.
FIG. 4. Ozone calibration of PAS System. Each point is an average of 30 1 second data points.
701
2005) and the theoretical calibrations outlined by Rosenwaig
(1980). The agreement between these three methods provides
confidence in the gas phase absorption calibration and that sat-
uration at high levels used for calibration and other potential
sources of non-linear dependencies are minimal. The calibration
presented here covers a range extending from near the instrument
detection limit up through atmospherically relevant values, and
confirms the linear dependence at levels nearing the detection
limits of the currently available instrumentation. The precision
of the calibration is also a significant advance in minimizing un-
certainties in absorption measurements. This calibration method
can also utilize other methods of measuring ozone if a CRD-
AES system is not available. Limited calibration trials using a
commercial ozone monitor were performed and compared to
the CRD-AES calibration. These calibrations were similar sug-
gesting that commercial ozone monitors for calibration could be
used for calibrations (ozone absorbs at 0.007 Mm−1 /ppb at STP
using cross section data of Burkholder and Talukdar (1994)).
3.2. Sensitivity
Using the calibration from Figure 4 the PAS laboratory sensi-
tivity was determined (defined as 2σ in background signal). The
instrument sensitivity was measured for a range of integration
times and flow rates between 1 to 5 LPM. Figure 5 shows a mod-
ified Allan Variance plot, where variance has been converted to
absorption using the calibration from Figure 4. The small vari-
ability around the fitted slope indicates long term (3 months) sta-
bility in microphone response, small differences in laboratory
702 D. A. LACK ET AL.

√
FIG. 5. Modified Allan Variance plot showing PAS sensitivity relative to other techniques. Dashed line shows theoretical profile of noise scaled to 1/ N.
Numbered points indicate literature sensitivities values for various instruments measuring aerosol absorption. 1: PSAP (Bond et al. 1999), 2: multi-angle absorption
photometer (MAAP) (Petzold et al. 2005), 3: Photoacoustic (Arnott et al. 1999), 4: Photoacoustic (Arnott et al. 2006).

ambient noise and PAS insensitivity to sample flows up to 5
LPM. Figure 5 indicates a PAS sensitivity of ∼0.8 Mm−1 for
a 1 second integration time and ∼0.08 Mm−1 for a 60 second
integration time. Figure 5 also shows some reported sensitivi-
ties for other instrumentation measuring aerosol absorption. A
significant contribution to the improvement in sensitivity for
this instrument, compared to literature values 1, 2, and 3 from
Figure 5, is the effective laser power. This system uses 40 passes
of a 200 mW laser, resulting in 8 W of effective power. The large
mass surrounding the resonators, expanded volumes and dif-
ferential measurement also combine to improve sensitivity by
significantly reducing ambient noise. Under conditions where
ambient noise was minimized as much as possible, flow noise
from flows up to 5 LPM contributed about 15% of the noise while
the background electronic noise of the microphones (∼80%) ap-
peared to limit the instrument sensitivity. Amplifier electronic
noise contributed the remaining 5%. Arnott et al. (2006, point
4 in Figure 5) reported uncertainties of 0.4 Mm−1 for a 1 sec-
ond integration time for their most recent photoacoustic system.
This improvement relative to their previous system was due to
increases in laser power.
3.3. Validation Using Nigrosin Dye
Nigrosin is a water soluble black dye (C48 N9 H51 ) that has
been used previously to generate absorbing aerosol for instru-
ment comparisons (Bond et al. 1999) and has a reported refrac-
tive index of 1.67 + 0.26i (Garvey and Pinnick 1983). The PAS
response was validated using atomized and dried water soluble
Nigrosin dye particles and a laboratory technique similar to that
employed by Pettersson et al. (2004). First, the performance
of the experimental configuration, source generation and size
selection was confirmed using CRD-AES and non-absorbing
polystyrene spheres. The tests performed showed results con-
sistent with the published refractive index for polystyrene (Real
RI of 1.59, Boundy et al. 1952) and Mie theory. The size depen-
dence of extinction and absorption for Nigrosin particles was
measured by size selecting Nigrosin aerosol and passing this
flow through the CRD-AES, PAS, and CPC system.
Figure 6 shows the linear correlation between aerosol extinc-
tion (Figure 6a) (absorption (Figure 6b)) and number concentra-
tion (αep = σep Nep ; (αap = σap Np )) for three selected Nigrosin
particles sizes. Individual extinction and absorption values are
the average of 30 points of 1 second data. Table 1 shows the
 PHOTOACOUSTIC INSTRUMENT DEVELOPMENT 703

FIG. 6. Nigrosin Aerosol Extinction (a) and Absorption (b). Response to Aerosol Number Concentrations. Particle sizes presented here are 850 nm (•), 650 nm
(
), 450 nm (⊗). Aerosol number concentration ranges were dictated by atomization of the dye solution.
704 D. A. LACK ET AL.
TABLE 1
Precision in extinction and absorption data for nigrosin aerosol using 30 seconds of data for both extinction and absorption
Measured optical
Measured cross section, σ
diameter (Mm−1 /cm−3 ) or (1 × 10−8 cm2 )
(nm) extinction/absorption
149.3 (±4.5) 0.030 (±0.001)/0.020 (±0.0006)
243.6 (±7.3) 0.126 (±0.002)/0.064 (±0.002)
346.4 (±10.4) 0.303 (±0.008)/0.145 (±0.004)
482.4 (±14.5) 0.618 (±0.005)/0.290 (±0.005)
535.3 (±16.1) 0.723 (±0.02)/0.325 (±0.007)
668.7 (±20.1) 1.120 (±0.009)/0.510 (±0.006)
762.8 (±22.9) 1.36 (±0.03)/0.67 (±0.02)
851.8 (±25.5) 1.56 (±0.03)/0.76 (±0.02)
950.3 (±28.5) 1.94 (±0.03)/0.99 (±0.03)
1050.3 (±31.6) 2.33 (±0.05)/1.13 (±0.05)
linear regression analysis of each size particle interrogated. The
slope of these weighted linear regressions represent the averaged
extinction (σep ) or absorption (σap ) optical cross section for that
size particle. The standard deviation (σ ) of these cross sections
is also shown in brackets next to the cross section value. The pre-
cision within each of these cross sections (2σ ) is also shown in
Table 1 and gives a representation of PAS instrument precision.
This precision value incorporates the precision from the gas
phase calibration and aerosol number concentration measure-
ments. For large particles, generating stable and sufficient num-
ber concentrations is difficult, thus creating larger measurement
uncertainties. For particles up to 950 nm diameter the precision
of PAS was 6% or better. This reported precision (2σ , 30 sec)
is considered an upper limit for measuring aerosol absorption
using PAS as it is dominated by the uncertainty from aerosol
number concentrations (ozone calibration contributes a small
uncertainty). Aerosol extinction and aerosol absorption optical
cross sections obtained from the slopes of the linear fits (e.g.,
Figure 6) were converted to Q values; the efficiency of a particle
to absorb, scatter or extinguish light relative to its geometri-
cal cross sectional area. Optical cross sections were divided by
the geometrical cross section of the particles to calculate QEXT
and QABS , after the effect of multiply charged particles was re-
moved. Figure 7 shows the experimental QEXT and QABS values
measured for dry Nigrosin dye particles. The TEM microscopy
of the Nigrosin particles appeared to show particles that were
spherical (Figure 2). Using this as the basis for assuming spher-
ical particles, Mie theory was used to find the best fit values
of the real (RIREAL ) and imaginary (RIIMAG ) refractive index
that fit the QEXT data. Chi square minimization with RIREAL and
RIIMAG as the only free parameters returned a best fit refractive
index of 1.70 (±0.04) + 0.31i (±0.05i). Quoted uncertainties
are one standard deviation (1σ ) calculated from the chi square
minimization as detailed in Press et al. (1986, p. 533). A non-
spherical particle is known to “wash out” the resonance structure
Precision in measured
optical cross section
(2σ as %) R2
extinction/absorption extinction/absorption
1.41/0.55 0.9983/0.9663
2.51/4.24 0.9978/0.9915
5.12/5.90 0.9895/0.9794
1.71/3.64 0.9980/0.9880
4.62/4.17 0.9900/0.9917
1.60/2.40 0.9990/0.9975
4.56/4.23 0.9980/0.9893
3.98/6.00 0.9930/0.9816
2.60/4.94 0.9880/0.9574
4.23/9.27 0.7390/0.8887
in extinction and scattering and the deviations between exper-
imental and theoretical QEXT at larger diameters is consistent
with a small non-spherical component to the aerosol at these
sizes. The best fit refractive index compares favorably to the
previously reported RI of 1.67 + 0.26i reported by Garvey and
Pinnick (1983), although no uncertainties in these values were
reported. The similarity in the refractive indices provides further
confidence in the CRD-AES system and allows us to base fur-
ther analysis on the CRD-AES. Using the best fit RI values, Mie
theory was used to calculate the expected QABS . This is overlaid
against the experimental QABS values in Figure 7 and shows ex-
cellent agreement and is an independent validation of the photoa-
coustic technique as applied to aerosol absorption. The average
deviation of the experimental QABS from the modeled QABS gives
an indication of PAS accuracy related to measurement of aerosol
absorption. This provides an accuracy value of 4.5% although
this value is dominated (50%) by one large deviation at the small-
est diameter. The source of this deviation is unknown, although
the corrections for multiply charged particles are largest at this
diameter.
3.4. Standardized Absorbing Aerosol
An ideal calibration for any method of measuring aerosol
absorption would be well characterized and easily generated
absorbing aerosol. Most instrumentation for measuring aerosol
absorption use calibration methods that do not initially involve
aerosol and are then compared to other methods using a com-
mon aerosol, usually laboratory generated black carbon. This
method has provided the basis for many inter-comparisons.
However, the fractal nature of the particles and lack of char-
acterizability of the particles prior to use limits it ability to re-
duce uncertainties in absorption measurements. In an effort to
develop a direct absorbing aerosol standard and simplify the
calibration of absorbing aerosol instrumentation, and perhaps
 PHOTOACOUSTIC INSTRUMENT DEVELOPMENT 705

FIG. 7. Experimental QEXT () and QABS () measured using CRD-AES and PAS, respectively. Solid line through QEXT data indicates the best fit to the real
and imaginary refractive index using Mie Theory (1.70 + 0.31i). Solid line through QABS data is the independent Mie Theory calculated QABS from the QEXT best
fit. Dashed lines indicate QEXT and QABS calculated using the literature refractive indices for Nigrosin from Garvey and Pinnick (1983).

improve the accuracy of calibrations, samples of dyed mono-
disperse polystyrene spheres were obtained (APSS). Solutions
were atomized and passed through the DMA producing a nearly
monodisperse absorbing aerosol. The CRD-AES, PAS, and CPC
system was used to measure total aerosol extinction, absorp-
tion and number concentrations. Again, comparisons between
aerosol number concentration and PAS absorption (Figure 8)
show a linear correlation with a maximum precision (2σ , 30
sec) of 6.7%, within the linear fit across the diameter range of
150–800 nm. This includes uncertainties due to aerosol num-
ber concentrations and sampling fluctuations. Table 2 shows the
optical cross sections derived from the weighted linear regres-
sions and the measured precision in the measurements. QEXT
values were again calculated and used in a refractive index fit-
ting analysis similar to that used for Nigrosin dye particles. In
this analysis, a single refractive index that provided a good fit
the Q data (real and imaginary) could not be determined. This
suggested that the dye did not penetrate completely through the
larger particles, indicating a refractive index that varied with par-
ticle size. Despite this, the absorption optical cross sections for
each particle size can be repeatabley measured to high precision
which could then be used individually to calibrate the PAS or
any other absorption measurement instrument. Also, the range
of single scatter albedo values across the particle size range
(presented in Table 2) will be of value in investigating possible
albedo dependence of some absorption measurement methods.
This calibration tool is tied to the original CRD-AES/PAS ozone
calibration, and will be dependant on the particular APSS batch
from the manufacturer. This method will allow for assessment of
instrument response to aerosol rather than a gas or mass calibra-
tion. Considering the high precision in the ozone calibration, it is
anticipated that any calibration using DMA size-selected APSS
will be limited by uncertainties in the particle number concen-
trations. Non-size-selected APSS could very easily be used as
a comparative tool between other instruments. The advantage
of these procedures would be to allow laboratory standardized
APSS that can be simply generated, to be used for regular field
calibrations of instrumentation measuring absorption. The APSS
would also have the following advantages: (1) allows calibration
using particles. The APSS aerosol eliminates any uncertainties
that may be introduced due to volatile species on soot particles,
the fractal nature of soot or the subtle differences in soot op-
tical properties produced from different fuels and fuel ratios.
(2) Allows interrogation of the absorption, scattering and ex-
tinction response of instrumentation using Mie theory, given the
characterized spherical particles. This may aid in investigations
into scattering corrections (including particle stacking) for filter
based methods.
4. SUMMARY
A fast, sensitive and direct method of measuring aerosol
absorption has been developed using the photoacoustic tech-
nique. The instrument has been calibrated using ozone and a
cavity ring down aerosol extinction spectrometer (CRD-AES).
706 D. A. LACK ET AL.

FIG. 8. Absorption Response of Absorbing Polystyrene Spheres to Aerosol Number Concentrations. Particle sizes presented here are 800 nm (•), 600 nm (
),
300 nm (⊗).

The calibration spans 3 orders of magnitude in signal and in-
cludes levels of aerosol absorption most commonly observed
in the atmosphere (<∼25 Mm−1 ). This calibration explicitly
shows the linear dependence between absorption and photoa-
coustic response at these absorption levels, and provides a gas
phase calibration accuracy of 1–2%. The sensitivity of the sys-
tem has been calculated to be 0.08 Mm−1 for 60 seconds of
integration. Here, the photoacoustic technique for measuring
aerosol absorption has been independently validated using dry
size selected absorbing Nigrosin dye aerosol. The PAS instru-
ment responded to this aerosol as Mie theory predicted. This
validation also provides confidence that the mechanism of gen-
erating acoustic signal from gas phase species is comparable to
that producing acoustic signal from aerosol. The validation step
also provides an estimation of the upper limit of the precision of
aerosol absorption measurements, and is in the order of 6 % (2σ ,
30 sec). This is believed to be dominated (2–3%) by uncertain-
ties in aerosol number concentrations. This validation step also
provided an estimate of the overall instrument accuracy, with re-
spect to aerosol absorption, of about 5%. This compares to filter
methods having precision of 20–35% (not inclusive of filter scat-
tering response). The validated photoacoustic system was used
to calibrate mono-disperse absorbing polystyrene spheres. These
measurements confirmed the precision range of the instrument
derived from the Nigrosin trials. These calibrated monodisperse
dyed polystyrene spheres, can be used as a calibration standard
for laboratory and field studies, independent of the refractive in-
dex. The precision and sensitivity improvements of this system

TABLE 2
Measured extinction and absorption for absorbing polystyrene spheres
Measured optical Precision in measured
Measured cross section, σ optical cross section
diameter (Mm−1 /cm−3 ) or (1 × 10−8 cm2 ) (2σ as %) R2 Single scatter
(nm) extinction/absorption extinction/absorption extinction/absorption Albedo ωo
158.8 (±4.8) 0.01743 (±0.0003)/0.00377 (±0.00004) 3.63/2.17 0.9970/0.9980 0.784
315.1 (±9.5) 0.227 (±0.002)/0.0250 (±0.0005) 1.36/3.71 0.9996/0.9940 0.890
457.8 (±13.7) 0.688 (±0.001)/0.0792 (±0.0003) 0.37/0.74 0.9998/0.9993 0.885
623.4 (±18.7) 1.206 (±0.006)/0.174 (±0.002) 1.06/2.74 0.9990/0.9920 0.856
811.1 (±24.3) 1.77 (±0.01)/0.39 (±0.01) 1.60/6.72 0.9973/0.9680 0.780
1107.0 (±33.2) 1.76 (±0.04)/0.51 (±0.05) 4.11/19.70 0.9938/0.7454 0.710
 PHOTOACOUSTIC INSTRUMENT DEVELOPMENT
compared to current methods of measuring aerosol absorption
will contribute significantly to reducing the uncertainty in mea-
sured aerosol absorption. This system incorporates a number of
features that enhances its applicability to aerosol systems. The
large diameter resonators reduce the resonator quality (Q) which
reduces signal sensitivity to changes in temperature and gas com-
position. This reduces signal sensitivity, although this sensitiv-
ity is returned and further enhanced using a Herriot multi-pass
arrangement. This multi-pass configuration provides enhanced
sensitivity (8 Watts of effective laser power) while providing
only 200 mW of laser power onto a single particle. This mini-
mizes the possibility of evaporation of adsorbed species. Also,
the volume sampled by the multi-passed laser increases sam-
pling volume, which contributes to reducing issues with aerosol
sampling uncertainties. This instrument has been modified for
field measurements and will be used in tandem with a field ver-
sion of the cavity ring down aerosol extinction spectrometer to
significantly improve the quality of absorption and single scatter
albedo measurements.
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