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Aerosol Science and Technology

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Fourier Transform Infrared

Spectroscopy of Aerosol
Collected in a Low Pressure
Impactor (LPI/FTIR): Method
Development and Field
Calibration
a a a
David T. Allen , Edward J. Palen , Mitchell I. Haimov
b c
, Susanne V. Hering & James R. Young
a
Department of Chemical Engineering , University of
California , Los Angeles, CA, 90024-1592
b
Aerosol Dynamics , 2329 Fourth Street, Berkeley, CA,
94720
c
Southern California Edison , 2244 Walnut Grove
Avenue, Rosemead, CA, 91770
Published online: 12 Jun 2007.

To cite this article: David T. Allen , Edward J. Palen , Mitchell I. Haimov , Susanne
V. Hering & James R. Young (1994) Fourier Transform Infrared Spectroscopy of
Aerosol Collected in a Low Pressure Impactor (LPI/FTIR): Method Development
and Field Calibration, Aerosol Science and Technology, 21:4, 325-342, DOI:
10.1080/02786829408959719

To link to this article: http://dx.doi.org/10.1080/02786829408959719

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 Fourier Transform Infrared Spectroscopy of
Aerosol Collected in a Low Pressure Impactor
(LPI / FTIR): Method Development and
Field Calibration
Downloaded by [Memorial University of Newfoundland] at 01:33 01 August 2014
David T. Allen,* and Edward J. Palen,t and Mitchell I. ~ a i m o v '
Department of Chemical Engineering, Uniuersity of California, Los Angeles, CA 90024-1592
Susanne V. Hering
Aerosol Dynamics, 2329 Fourth Street, Berkeley, CA 94720
James R. Young
Southern California Edison, 2244 Walnut Groce Avenue, Rosemead, CA 91 770
A method for determining the loadings of organic and
inorganic functional groups in size segregated ambient
aerosol has been developed and demonstrated. The
method uses a Hering Low Pressure Impactor (LPI),
equipped with ZnSe impaction surfaces, to sample the
aerosol. The aerosol samples are analyzed directly,
without extraction, using transmission infrared spec-
troscopy. The resulting spectra of aerosol size fractions
are used to determine loadings of sulfate ion, nitrate
1. INTRODUCTION
Determining the composition of atmos-
pheric aerosol, as a function of aerosol
size, is a challenging problem. The chal-
lenge is due in part to the complex nature
of atmospheric aerosols, which are mix-
tures of inorganic salts, metals, organic
"Author to whom correspondence should bc ad-
dressed.
'Current address: Hughes Aircraft Company, P.O.
Box 902, El Segundo, CA 90245.
'Current address: South Coast Air Quality Man-
agement District, 21865 East Copley Drive, Diamond
Bar. CA 91765-4182.
Aerosol Science and Technology 21:325-342 (1994)
Q 1994 Elsevier Science Inc.
ion, aliphatic carbon, carbonyl and organonitrate
groups, using calibration factors developed in field and
model compound studies. This paper describes, in de-
tail, the data interpretation and calibration methods
used to obtain these functional group loadings from the
infrared spectra. The functional group loadings, par-
ticularly the size distributions of organic compound
classes, provide new insights into the composition of
atmospheric aerosol.
compounds and water. Additional chal-
lenges are provided by the difficulties of
size resolved sampling. Despite these dif-
ficulties, a number of methods have been
developed to determine the loadings of
inorganic species in size resolved aerosol.
Ion chromatography interfaced with im-
pactors (John et al., 1989~1,1989b) proton
induced x-ray emission (Cahill et al., 1989;
Ouimette and Flagan, 1982) and x-ray
fluorescence (Groblicki et al., 1981; On-
dov et al., 1990) are just a few of the
available methods. In contrast, methods
for analysis of organics in size segregated
aerosol are limited, and most of the meth-
ods that are available rely on organic and
 326
elemental carbon analysis (McMurry and
Zhang, 1989; Turpin et al., 1989a, b), or
on extraction followed by mass spectro-
scopic analysis, which requires large sam-
ple mass (Mazurek et al., 1989; Rogge
et al., 1993). This paper will describe the
development, use and field calibration of
a method for the analysis of size segre-
gated aerosol based on infrared spec-
troscopy. The method described in this
Downloaded by [Memorial University of Newfoundland] at 01:33 01 August 2014
work has a number of advantages relative
to more traditional methods of aerosol
analysis. First, it is a nondestructive meth-
od of analysis, requiring no extractions.
Second, as will be demonstrated in this
paper, the method accounts for a large
fraction of the inorganic and organic
aerosol mass. Third, due to the high mass
sensitivity of the method, short sampling
runs are possible. Finally, in contrast to
analysis of carbonaceous aerosol for or-
ganic and elemental carbon, infrared
methods provide data on the compound
classes present in the aerosol, not merely
on the total carbon loadings. Balancing
these advantages is the fact that individ-
ual organic species are not identified, only
compound classes. Overall, however, the
chemical insight provided by infrared
spectroscopy represents a significant ad-
vance in the analysis of size segregated
aerosol.
The use of infrared spectroscopy in
aerosol analysis is not new. Infrared spec-
troscopy was used extensively in the 1970s
and early 1980s to probe the composition
of atmospheric aerosol (Blanco and Mc-
Intyre, 1972; Cunningham et al., 1974,
1976; Kellner, 1978; Bogard et al., 1982);
however, these methods were largely
abandoned because of difficult sample
collection, lack of sensitivity, and the
semiquantitative nature of infrared spec-
tra. Recent advances in infrared optics
and detectors have now overcome many
of these problems and it is now possible
to directly analyze picogram quantities of
sample with little or no sample prepara-
D. T. Allen et al.
tion (Kellner and Malissa, 1989). A com-
plete review of recent advances in aerosol
analysis by infrared spectroscopy has been
presented by Allen and Palen (1989). This
work will focus on the use of infrared
spectroscopy as an analysis tool for aerosol
samples collected in a Low Pressure Im-
pactor (LPI). Sample collection, spectral
interpretation and the quantification of
infrared absorbance bands will be dis-
cussed. Both organic and inorganic in-
frared absorbances will be addressed and
the calibration results will demonstrate
that infrared spectroscopy can be used to
determine the composition of the majority
of the mass found in fine atmospheric
aerosol.
2. SAMPLE COLLECTION AND ANALYSIS
2.1 Particle Collection
This work describes the use of infrared
spectroscopy to analyze aerosol samples
collected in a Low Pressure Impactor
(Hering et al., 1978, 1979). The Hering
LPI has eight stages with cutpoints at
aerodynamic diameters of 4.0, 2.0, 1.0, 0.5,
0.26, 0.12, 0.075, and 0.05 pm. Each stage
has a single, circular orifice, which gener-
ally results in a single, circular aerosol
deposit on the impaction surface. The first
four stages operate at near atmospheric
pressure, while the final four stages
(0.26-0.05 p m cutpoint diameters) segre-
gate particles at reduced pressures
(140-24 torr). A critical orifice placed be-
tween the fourth and fifth stages controls
the volumetric flow rate through the im-
pactor at 1.05 L/min.
A sintered stainless steel disk coated
with silicone oil is used as the impaction
surface in the first LPI stage (4.0 p m
cutpoint). This stage serves as a coarse
particle precut and is not analyzed. Un-
greased, optically polished, zinc selenide
(ZnSc) disks are used as impaction sub-
strates in stages 2-8 (cutpoints of 2.0-0.05
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol 327

pm). These stages are analyzed by in-
frared spectroscopy. The ZnSe disks are
transparent to infrared radiation in the
range of 1-18 pm, allowing for direct
analysis by FTIR transmission spectro-
scopy. The ZnSe disks do not degrade
when exposed to water and may be cleaned
with ordinary organic solvents, but they
are brittle and must be handled with care.
The impacted aerosol samples are con-
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ble of sampling the entire aerosol deposit
were employed.
For the sample analysis, a Digilab FTS-
60 spectrometer was used, with a liquid
nitrogen cooled mercury-cadmium-tel-
luride (MCT) wide band detector. Before
each analysis, the sample compartment
was thoroughly purged with bone dry ni-
trogen. The aerosol deposits on the ZnSe
disks were placed in the path of the spec-

centrated in a small area, 2-3 mm in trometer's modulated IR beam. A 3-mm

diameter, directly underneath the single circular sample mask was placed on the
circular impaction jet. The concentration side of the disk not containing the aerosol
of the aerosol in a single deposit facili- deposit and was used to block the part of
tates direct analysis by infrared spectro- the IR beam not passing through or close
scopy. Concentric rings indicative of parti- to the impacted aerosol. The background
cle bounce are observed infrequently in spectrum was of the clean ZnSe disk with
ambient aerosol sampling. sampling mask in place. The spectrometer
was run at a resolution of 2 cm-', over
the spectrum of 4000 to 575 cm-'. Signal
acquisition time averaged 5 minutes, which
2.2 Sample Analysis: FTIR Spectroscopy at a scan speed of 10 kHz represented 128
After sample collection, ZnSe disks from scans. A resolution of 2 cm-' was suffi-
stages 2-8 are analyzed directly using ei- cient to detect most spectral features of
ther conventional Fourier Transform In- interest.
frared (FTIR) spectroscopy or using FTIR
microscopy. Although FTIR n~icroscopy
can provide mass sensitivities in the high 2.3 Ambient Sampling
picogram to low nanogram range (Allen Size segregated aerosol samples were col-
and Palen, 1989) it is not yet a convenient lected at Claremont and Duarte, Califor-
method for determining absolute mass nia, during the 1987 Southern California
loadings of compound classes in size seg- Air Quality Study (SCAQS). Claremont is
regated aerosol, because of the limited located in the northeast section of the
area that can be sampled by the focused Southern California Air Basin, approxi-
infrared beam. Typically, the area that mately 43 miles from the Pacific Coast.
can be sampled by an infrared microscope Duarte is a foothill receptor site located
is 0.0001-0.1 mm2. In comparison, the 13 miles west of Claremont. Sampling at
area of the deposit in the Hering impactor Claremont occurred in the summer during
is of order 10 mm2. Thus, in order to 12 days of high pollutant concentrations.
quantitatively measure the infrared ab- Claremont was a SCAQS "A" site, where
sorptions associated with an entire aerosol extensive measurements were made con-
deposit on a single stage of the impactor, currently by other research groups. The
it would be necessary to collect roughly data of other research teams will be used
100 spectra using infrared microscopy, be- for sampling method comparisons. During
ing very careful not to sample any part of each of the 12 sampling days, four LPI
the deposit more than once. Such experi- samples were collected. Sampling periods
mental methods are clearly impractical, so were from 0600 to 0950, 1000 to 1350,
in this work, less sensitive methods capa- 1400 to 1750, and 1800 to 0550 PDT. '
 D. T. Allen et al.

Sampling at Duarte occurred during 58

I
I
I
- I
NH4+
A
I

days of varying pollutant and meteorologi-

cal conditions during the summer and
early fall of 1987. Each sample was col-
lected over a 24-h period starting at 0600
h. The Claremont site impactors sampled
ambient air approximately 3 m above
ground level. At Duarte the LPI was set
up on the roof of the City of Hope hos-
pital. In both cases the impactors were
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shaded from direct sunlight in order to

reduce sampling artifacts.
After sample collection, the ZnSe disks
were placed in plastic holders and stored
in a desiccator out of direct sunlight. All
samples were analyzed within 8 h of sam-
ple collection. Calibration experiments es-
tablished that the samples could be stored
for approximately 3 days before any sig-
nificant degradation of the resulting spec-
tra occurred. Previous investigators (Mc-
Clenny et al., 1985), found &3% repro-
ducibility of sulfate absorption areas for
filter samples that had been desiccated for
24 hours.

3. SPECTRAL INTERPRETATION
A typical set of infrared spectra is shown
in Figure 1. These spectra are for a single
sample collected by the Low Pressure Im-
pactor and analyzed using FTIR spec-
troscopy (LPI/FTIR). There are seven
spectra per sample, representing stages
2-8. Converting these spectra into esti-
mates of aerosol composition involved as-
signing absorption peaks to aerosol func-
tional groups and converting absorbance I
areas into estimates of functional group 0.000
4000.0
I
2000.0
I
10000 !
Wovenumbers
loadings. This section will consider peak
assignments. By comparing the spectra of (b)
ambient aerosol to the spectra of model
FIGURE 1. (a) Spectra of ambient Los Angeles
compounds, it was possible to confirm ei- aerosol (taken at Duarte, 8/19/87); each sample
ther the presence or the absence of cer- consisted of seven size fractions and a spectrum
tain compounds or compound classes in was obtained for each size fraction; all of the
atmospheric aerosol. Both inorganic and spectra are plotted on the same absorbance scale.
organic functionalities will be considered, b) enlarged view of a spectrum of a typical size
beginning with the inorganics. fraction.
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol 329

3.1 Inorganic Absorption Assignments wavenumber with changing ammonium

Ammonium sulfate and ammonium ni-
trate absorptions dominated the spectra
of ambient fine aerosol. These compo-
nents represent a significant portion of
fine aerosol mass (John et al., 1989a,
1989b; Gray et al., 1984; Pratsinis et al.,
1984; Grosjean and Friedlander, 1975).
Absorptions due to silicates and particu-
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nitrate to ammonium sulfate ratios, and
with the presence of other cations such as
sodium ions. Bisulfate ions of NH,HSO,
absorb at 580-590, 867, 1029, and 1180
cmpl. The sulfate and bisulfate absorp-
tions are separable; the bisulfate absorb-
ances appear as low and high frequency
shoulders on the strong sulfate ab-
sorbance at 1103-1135 cm- (Palen, '

late water are also present, although they

are not as strong as the ammonium sul-
fate and ammonium nitrate absorptions.
Absent from the spectra are absorptions
due to sulfite, nitrite, carbonate, and chlo-
rides. A summary of inorganic absorb-
ances observed in this study is given in
Table 1. Details of the peak assignments
are described below.
3.1.1 Sulfate and Bisulfate Absorptions.
Absorptions due to sulfate ions, in
(NH,),SO,, peak at 612-615 cm-' and
1103-1 135 cmpl. The higher frequency
(higher wavenumber) absorption varies in
1991). These shoulders are seen in the
spectra of 0.075-0.12 p m and 1.0-4.0 p m
Los Angeles aerosol, shown in Figure 1.
The 867-cmpl bisulfate ion absorption is
also distinguishable, but weak, in these
spectra.
To quantify the sulfate ion and bisul-
fate ion loadings, the absorptions that
peaked at 612-615 cmpl and 580-590
cm-' were integrated over the wavenurn-
ber range of 580-635 c m p l . Even though
this spectral region contains both sulfate
and bisulfate absorbances, they were con-
sidered as a single absorbance. This did

TABLE 1. Inorganic Absorbances Observed in Spectra of Ambient Aerosol

Absorbance Band
Abqorpt~on Chosen for Presence in Los Angeles Aerosol
Frequencies Quantification Sampled in This Work
Functionality (cm-' ) (cm-') Superm~cron Submicron
INORGANICS
sulfate ions 580-635 always always
bisulfate ions 580-635 occasionally occasionally
calcium sulfate none occasionally never
nitrate ions 818-838 always only for d, > 0.5
sodium nitrate none occasionally Pm
silicate ions always only for d, > 0.5
silica Pm
ammonium ions none always always

particulate water none always always

ORGANICS
C-H aliphatic carbons 1452-5, 2800-3000 2800-3000 rarely always
C =O carbonyl carbons 1640-1850 1640-1850 only for d, < 2 always
Pm
CONO, organonitrates 856, 1278, 1631 1255-1296 never always
COH alcohols 3500-3750 none occasionally occasionally
 330
not pose a significant problem since the
bisulfate ion was never the dominant form
of sulfate observed. The higher-frequency
sulfate ion absorptions were not used for
quantification due to difficulty in determi-
nation of spectral baselines and due to
overlapping silicate absorptions.
3.1.2 Nitrate Absolptions. Nitrate ions,
in NH4N0,, absorb at 825-835 cm-' and
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1318-35 cm-'. Pure salt spectra of
NH,NO, also exhibit additional sharp,
but weak absorptions peaking at 713,1040,
and 1752 cm-', which were not seen in
ambient spectra. The sharp absorbance
peaking at 825-835 em-' was chosen for
quantification of ambient aerosol nitrate
ion loadings. This absorption was inte-
grated over the approximate range of
818-838 cm-' The higher frequency ab-
sorption (1318-1335 cm-' ) was not cho-
sen for quantification due to severe over-
lap with ammonium ion absorptions, which
peaked at 1410-1435 cm-', and due to
difficulties in defining baselines of broad
absorptions.
A sharp absorption at 1786 cm-' due
to NaNO, was observed in the spectra of
some large aerosol size fractions (2.0-4.0
pm), as shown in Figure 1. The nitrate
ions in NaNO, also absorbed at 835 cm-'
and were included in total nitrate ion
quantifications. Molar absorptivities of
the nitrate ion in the 818-838 cm-' reg-
ion were relatively constant for the nitrate
salts of ammonium, potassium, sodium,
calcium, and magnesium (Bogard et al.,
1982). Sodium nitrate had previously been
found together with ammonium nitrate
in 3.3-11 p m aerosols (Kadowaki, 1977;
Wall et al., 1988).
3.1.3 Ammonium Absorptions. Ammo-
nium ion absorptions were observed in
infrared spectra of all ambient aerosol
size ranges (0.05-4.0 prn). Submicron am-
monium ion absorptions were associated
primarily with (NH4), SO, and NH4HS04.
D. T. Allen et al.
Supermicron ammonium ion absorptions
also included N H 4 N 0 , contributions.
Ammonium ion absorptions in these salts
are strong at 1250-1540 cm-' peaking at
1410-1435 cm-'. The precise frequency
of the absorption depends upon mixing
ratio and anion type (Palen, 1991). Addi-
tional absorptions were present in the
2700-3390 cm-' region peaking around
3020 cm-' and 3210 cm-', and weakly
around 2840 cm-'.
3.1.4 Silicate Absorbances. Silicate ion
and silica absorptions can be due to a
number of minerals. Blanco and McIntyre
(1972) identified quartz and kaolinite to
be the major species in coarse atmo-
spheric aerosol samples. Quartz (SiO,)
absorbs most strongly around 1090 cm-'
a n d 7 3 0 c m - ', a n d k a o l i n i t e
(Al,(OH),(Si,O,)) around 1010 cm- . Sil-'
icate ion library spectra exhibited strong
absorptions peaking at 990-1140 cm-'.
Cunningham et al. (1974) assigned strong
absorptions at 1035 cm-' and weaker ab-
sorptions at 780 and 800 cm-' to SO:-.
Stelson and Seinfeld (1981) reported Los
Angeles aerosol to contain high concen-
trations of silica.
The spectra obtained using the LPI-
FTIR method clearly exhibited silicate ab-
sorptions at 772-812 cm-' peaking at 789
cm-' in the largest size fraction (2.0-4.0
pm), as shown in Figure 1. Silicate ab-
sorptions are weak in 0.5-2.0 p m aerosol
spectra and are not present in smaller
aerosols. Higher frequency absorptions of
silicates overlapped sulfate absorptions
and protruded above the overlap at 1035
cm-'.
3.1.5 Particulate WaterAbsolptions. Wa-
ter strongly bound to aerosol salts absorbs
at 1600-1700 cm-', peaking at 1620-1655
cm-'. Water absorptions at roughly 1620
cm- were observed in all ambient aerosol
spectra, but were strongest in supermi-
cron aerosol, as shown in Figure 1. Since
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol
aerosol samples were stored and analyzed
at 0% relative humidity, it can be as-
sumed that this particulate water was due
to strongly bound water in salt hydrates.
Salt hydrates also absorb broadly at 3100--
3600 cm-' peaking at 3350-3450 cm-'.
These high frequency absorptions can be
seen in supermicron aerosol spectra as a
weak absorption on the 3220 cm-' edge
of the broad, strong ammonium ion ab-
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sorptions, particularly in the largest size
fraction.
3.1.6 Sulfite and Nitrite Absorptions.
Sulfur functional groups other than sul-
fate can be distinguished by their sharp
absorptions. For sulfite these are at 925,
945, or 965 cm-' and 620 cm-'. None of
these absorptions were observed in spec-
tra of fine Los Angeles aerosol. Nitrite
ions absorb strongly at 1220-1280 cm-'.
This nitrite absorption is broad and would
be easily recognized in the absorption
minimum between the strong and broad
sulfate absorption at 900-1200 cm-', and
the nitrate ion or ammonium ion absorp-
tions at 1150-1450 cmP1 and at 1300-
1470 cm-'. This nitrite ion absorption was
not observed in any of the ambient Los
Angeles aerosol spectra.
3.1.7 Carbonate Ion and Phosphate Ion
Absorptions. Calcium carbonate was the
main carbonate species identified in
coarse aerosol by Blanco and McIntyre
(1972). Carbonate ions absorb strongly and
broadly at 1433 cm-', and with a slightly
weaker but sharper peak at 877 cm-'.
The lower frequency absorption can be
used to characterize CaCO, in ambient
aerosol. This 877-cm-' absorption was not
observed for any sub-4.0-pm ambient Los
Angeles aerosol. Phosphate absorptions
were not consistently identified in our am-
bient aerosol spectra. The largest aerosol
size fraction (2.0-4.0 pm) spectra did
contain weak sharp absorptions at 670
and 916 cm-l, which could be due to
331
calcium phosphate if strong absorptions at
950 and 1235 cm-' had also been ob-
served. Since these absorptions were not
observed, it was concluded that fine aero-
sol phosphate ion loadings were negligi-
ble.
3.1.8 Ammonium Chloride Absorptions.
Ammonium chloride can be distinguished
by an absorption of moderate strength
and breadth at 1760 cm-l, and a strong
absorption at 1400-1404 cm-'. The for-
mer absorption would be distinguishable
on the high-frequency shoulder of car-
bonyl carbon absorptions which peak at
about 1714 cm-l, but was not seen in any
aerosol spectra. No shifts of ammonium
ion absorptions to 1400 cm-', indicative
of NH,Cl, were observed. It was con-
cluded that ammonium chloride was not
present in Los Angeles fine aerosol in
significant quantities.
3.2 Organic Absorption Assignments
Organic absorptions in ambient aerosol
are due to a complex hydrocarbon mix-
ture of hundreds of different compounds
(Schuetzle et al., 1975; Appel et al., 1979;
Mazurek et al., 1989; Rogge et al., 1993).
These absorptions differ from inorganic
absorbances in that a single organic ab-
sorption, e.g., a C = 0 absorption, will
contain contributions from many different
molecular species each of which has a
slightly different frequency and intensity.
The variety of potential organic ab-
sorbance~considerably complicates data
interpretation, and, as a result, interpreta-
tion of the spectra will be limited to just a
few absorbances. Aliphatic carbon, car-
bonyl carbon and organonitrate absorb-
ances will be examined. Absorbances due
to alkenes, aromatics and nitro groups are
near or below current detection limits. A
summary of the major organic ab-
sorbance~observed in this work is given in
Table 1.
 332
3.2.1 Aliphatic Carbon Absorptions. Ali-
phatic carbon absorptions are observed at
2800-3000 cm-', peaking at 2850-2853,
2924, and 2958 cm-'. The 2958-cm-I ab-
sorption is due to CH, aliphatic carbon
bond absorptions, and the absorptions at
2924 and 2850-2853 cm-' are due to
CH, bonds (Nakanishi, 1962). Weaker ab-
sorption peaks are also observed at 2870
cm-' due to CH,, and at 2890 cm-' due
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to the weakly absorbing methine (CH)
aliphatic groups. A lower frequency ab-
sorption, peaking at 1452-1455 cm-' in-
cludes contributions from CH, and CH,
aliphatic carbon bonds. In the spectra of
ambient aerosol, the strength of the 2924-
and 2850-cm-' absorptions relative to the
other aliphatic carbon groups indicates
that aliphatic carbon loadings are domi-
nated by CH, bonds. This conclusion is
agreement with GC and GC/MS data
indicating the presence of high molecular
weight paraffins (Mazurek et al., 1989;
Rogge et al., 1993).
Both the high- and low-frequency ali-
phatic carbon absorptions were superim-
posed on ammonium ion absorptions. The
higher-frequency absorptions of 2800-
3000 cm-' were distinct and easily sepa-
rated from the smooth broad ammonium
ion absorption of 2700-3320 cm-'. The
lower frequency absorptions at 1452-1455
cm-', however, were superimposed on a
steep slope of the ammonium ion absorp-
tion, making this aliphatic carbon absorp-
tion area difficult to quantify. Therefore,
the high-frequency aliphatic carbon ab-
sorptions of 2800-3000 cm-' were used
to quantify this functional group. For very
short sampling times, this absorption was
not always distinguished above spectra
noise levels.
3.2.2 Carbonyl Absorptions. Carbonyl
carbon absorptions were the most com-
plex of the organic absorbances to inter-
pret. The carbonyl complex absorbed over
the broad range of 1640-1850 cm-', gen-
I).T. Allen et al.
erally peaking at about 1714 cm-l. This
carbonyl absorption may have included
contributions from ketones, aldehydes,
and carboxylic acids. Each of these car-
bony1 species has a characteristic absorp-
tion frequency, but this characteristic fre-
quency can be shifted due to intermolecu-
lar and intramolecular interactions, mak-
ing the carbonyl absorbance appear as a
single, smooth broad peak. No single,
strong carbonyl absorptions due to single
species were identified.
3.2.3 Organonitrate absorptions. Organ-
onitrate absorptions peaking at 1631,1278,
and 856 cm-' were observed in the aero-
sol spectra. The 1631-cm-' absorption was
the strongest and the 1278-cm-' absorp-
tion was the sharpest. Water absorptions
overlapped with the 1631-cm-' peak, and
so the 1278-cm-' peak was chosen for
quantification due to its sharpness and
relative isolation. It was integrated from
'
1255-1296 cm- . Organonitrate absorp-
tions are were rarely detected in aerosols
larger than 1.0 p m in aerodynamic diam-
eter.
3.2.4 Alcohol Absorptions. Weak, high-
frequency alcohol absorptions were ob-
served in the 3500-3750-cm-' region.
This broad absorption is due to free O H
stretching and hydrogen-bonding of alco-
hol groups (Nakanishi, 1962). Lower fre-
quency alcohol absorptions at 1000-1200
cm-' due to a C - 0 stretch were washed
out by strong sulfate ion absorptions in
this region. Alcohol absorptions are shown
in Figure 1 for 0.12-4.0 p m aerosols.
3.2.5 Elemental Carbon Absorptions.
The infrared analysis was not able to de-
tect elemental carbon, which absorbs con-
tinuously across the infrared spectrum.
Pollard et al. (1990) quantified elemental
carbon loadings on filters by relating ele-
mental carbon loading to scattering in the
650-666-cm-' spectral region, where the
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol
filter samples had no overlapping absorb-
ances. Quantifying elemental carbon by
measuring scattering would be difficult us-
ing the sample collection methods of this
work. The scattering is likely to be a func-
tion of the precise geometry of the im-
paction deposit and establishing a refer-
ence spectrum for each impaction sub-
strate would be necessary.
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3.2.6 Alkenes, Aromatics, and Nitro
Groups. Alkenes absorb strongly and
sharply at 1640-1650 cm-', and aromatics
absorb most strongly around 3030 cm-I.
These absorptions were not generally de-
tected in fine ambient aerosol spectra be-
cause of overlapping absorbances, low
molar absorptivities and, in some cases,
low concentrations. Aliphatic nitro groups
absorb most strongly around 1540-1570
cm-', and aromatic nitro groups around
1530 cm-'. No strong aliphatic or aro-
matic nitro group absorptions were de-
tected in the ambient spectra, as shown in
Figure 1. The spectra did show a very
weak absorbance near 1530 cm-' and this
may be due to nitroaromatics present at
levels of approximately a few nanograms
per cubic meter. Such levels are consis-
tent with predictions of nitroaromatic
concentrations based on ambient loadings
of polyaromatic hydrocarbons and yields
of nitroaromatics from these compounds
(Atkinson, 1990; Raval, 1993). Gordon
et al. (1988) have also detected small
quantities of nitroaromatic compounds in
Southern California fine aerosol as indi-
cated by absorptions at 1524 cm-', after
liquid chromatographic separation of
aerosol filter samples. These relatively mi-
nor absorbances will be examined in fu-
ture work.
3.3 Summary of Spectral Interpretation
Dozens of infrared absorbances can be
detected in ambient Los Angeles aerosol,
however, only a few of these absorbances
333
are suitable for detailed quantification.
To be useful in determining the concen-
tration of compound classes or ions in
ambient aerosol, an absorbance must be
sharp, intense and relatively isolated from
other strong absorbances. Due to these
constraints, only five of the dozens of
observed absorbances will be quantified.
These absorbances are due to sulfate ions,
nitrate ions, aliphatic carbon, carbonyl
groups, and organonitrate groups. Re-
stricting quantification to these groups is
not a serious limitation, since, as the re-
mainder of this work will show, these ab-
sorbance~account for a significant frac-
tion of the mass in Los Angeles aerosol.
4. FUNCTIONAL GROUP LOADINGS IN
AMBIENT AEROSOL: CALIBRATION AND
REPRESENTATIVE SIZE DISTRIBUTIONS
The previous section has described the
functional groups that are responsible for
the absorptions observed in the infrared
spectra of ambient aerosol. This section
will examine the quantitative interpreta-
tion of five of those absorptions, absorp-
tions due to sulfate, nitrate, aliphatic
carbon, carbonyl, and organonitrate. Cali-
bration factors, converting infrared ab-
sorption areas into functional group load-
ings, will be established for each of the
five groups. To validate the methods and
calibration factors, the loadings estimated
using infrared spectroscopy will be com-
pared to functional group loadings mea-
sured in parallel, using other analytical
techniques.
4.1 Sulfate and Bisulfate Calibration
Sulfate and bisulfate absorbances were
calibrated in field sampling. Two identical
Hering Low Pressure Impactors were run
side by side. In one impactor, aerosol was
deposited onto Vaseline coated stainless
steel strips which were then analyzed for
total sulfur content using a flash volatili-
 334
zation/flame photometric technique (Ro-
berts and Friedlander, 1976). Details of
these measurements are described else-
where (Allen, 1989; Allen and Hering,
1989). In the other impactor, aerosol was
collected on uncoated ZnSe disks for in-
frared analysis. The infrared spectra ob-
tained using these samples were inte-
grated in the region from 580 to 635 cm-'.
This region included both sulfate and
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bisulfate absorbances, and so the absorp-
tion area was representative of total sul-
fate loading. In addition, since no evi-
dence of sulfite was detected in the spec-
tra and since organic sulfur is not antici-
pated in the samples examined in this
work, it can be assumed that almost all of
the sulfur was present as sulfate. Thus,
the combined sulfate and bisulfate ab-
sorption areas were calibrated against the
sulfur measurement from the flash volatil-
ization flame photometric experiment. The
calibration data are given in Figure 2 and
a calibration equation is given below. It
should be noted that this calibration, as
well as the others reported in this work,
are instrument dependent.
Sulfate ion loading ( pg/m3)
sulfate absorbance area
-
-
m3 of ambient air sampled
0.34 p g sulfate
X source of uncertainty in the calibration
area unit
The average deviation from the linear
calibration was 24%. The bias was 2%.
Potential causes of uncertainty in the cali-
bration include molar absorptivity varia-
tions with changes in particle size and
differences in sampling procedures for the
LPI/FTIR and LPI/flash volatilization
flame photometric method. The particle
size variations are assumed to be small.
This assumption is based on theoretical
calculations of scattering in the infrared
region by layers of super and sub-micron
particles (Duyckaerts, 1959). The scatter-
D. T. Allen et al.
0
o O ! 4' 8I 1I2 16
I
Absorbance area per m3 (LPVFTIR)
20
FIGURE 2. Comparison of total sulfur loadings
obtained using the flame photometric technique
and total sulfate absorbance area observed in the
infrared spectra.
ing calculations indicate a constant molar
absorptivity for sub-micron particles. For
super-micron particles with diameters less
than 4 pm, scattering may be a problem
at the shorter mid-infrared wavelengths.
Fortunately, however, the bands used to
quantify material in the super-micron
stages were relatively long wavelengths.
Consequently, changes in molar absorptiv-
ity with particle size should not be a prob-
lem in this work.
For the sulfate calibration, the greatest
had to do with sampling times. The sam-
pling times for the LPI-FTIR and the
flame photometric sulfur measurements
did not overlap completely. The flame
photometric sulfur measurement required
only 30 minutes of sample to produce
measurable loadings, while the LPI-FTIR
analyses required four hours of sampling.
So, in a typical calibration run, 3 or 4
flame photometric samples were collected
during each four hour LPI-FTIR sampling
period. The 3-4 flame photometric runs
were averaged to yield a loading to com-
pare to the LPI-FTIR run. Thus, the cali-
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol
bration is based on an average of 3-4 half
hour samples (a total of 1.5-2 h of sam-
pling), compared to a LPI/FTIR sample
collected over 4 h. If sulfate loadings were
changing over the 4 h, significant uncer-
tainties in the calibration could result.
Therefore, the calibration was based only
on runs where the sulfur loadings seemed
stable over the 4-h sampling period.
The detection limit for sulfate and bi-
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sulfate absorption was approximately 0.01
area units. For sulfate and bisulfate, this
corresponds to 1-2 ng/m3 for a 4-h sam-
ple.
4.2 Nitrate Calibration
Nitrate ion absorptivity was based on the
sulfate calibration, and the ratio of nitrate
to sulfate ion absorptivities. The ratio of
nitrate absorption to sulfate absorption
was measured using laboratory generated,
polydisperse NH4N0,/(NH4),S04 aero-
sol impacted onto ZnSe disks. The salt
aerosols were generated from aqueous so-
lutions of known molarity. The 830-cm-'
nitrate absorptivity was found to be an
order of magnitude weaker than the 614
cm-' sulfate absorption area on a molar
basis. The detection limit was approxi-
mately 15 ng/m%nd the calibration fac-
tor for nitrate was
Nitrate loading ( pg/m3)
nitrate absorbance area
= i(
m3 of ambient air sampled
4.0 p g nitrate
area unit
4.3 Aliphatic Carbon Calibration
Aliphatic carbon absorptions include con-
tributions from CH,, CH,, and C H
groups. Since all aliphatic molecules will
contain these groups, the absorbances will
include contributions from n-alkanes,
branched alkanes, carbonyl containing
molecules, alkenes, and aromatics with
335
aliphatic substituents (e.g., methyl-benzo-
pyrene). Aliphatic carbon absorptivities
were determined using two methods. The
first method relied on liquid cell measure-
ments of the absorptivities of octanoic
acid, octanol, 3-octanone, octyl aldehyde,
and octyl nitrate. Liquid cell absorbances
were used to establish the calibration fac-
tors because it was very difficult to place a
known, microgram quantity of a calibra-
tion compound on the ZnSe impaction
surface. In contrast, it was straightforward
to prepare dilute solutions of model com-
pounds in CC1,. The only disadvantage of
using a calibration based on liquid cell
measurements is the different scattering
characteristics of the liquid cell and the
deposited aerosol. Differences in scatter-
ing could result in differences in absolute
absorptivity, so a second method for de-
termining absolute C-H absorptivity was
employed. This method involved a com-
parison of "organic" carbon (McMurry
and Anderson, 1989; McMurry and Zhang,
1989) to parallel measurements of carbon
containing functional groups as deter-
mined using LPI-FTIR The comparison
relied exclusively on samples collected
from 0600-1000 PDT during the Southern
California Air Quality Study (SCAQS).
During these morning periods, aliphatic
carbon dominated the spectra of the aero-
sol, presumably because of a strong auto-
motive contribution (Pickle et al., 1990).
The calibration factor determined us-
ing the liquid cell was 1 x 10"rea
per mole of C-H bonds while that based
units
on the parallel measurements of organic
carbon was 3 x 10' area units per mole of
C-H bonds. Given the uncertainties asso-
ciated with liquid cell and aerosol deposit
scattering characteristics, the agreement
is reasonable. The calibration factor based
on the organic carbon measurements was
chosen for future work, although it should
be clear from this discussion that signifi-
cant uncertainties remain in this calibra-
tion.
 D. T. Allen et al.

One of the uncertainties involves con- 4.4 Carbonyl

verting the number of C-H bonds into an
The carbonyl absorption contains contri-
estimate of aliphatic group loading in the
butions from ketones, aldehydes and acids
aerosol. This conversion requires an as-
present in the aerosol. Since the molar
sumption concerning the relative concen-
absorptivity of C = 0 in acids is approxi-
tration of CH, CH,, and CH, groups. In
mately 2-3 times stronger than the ab-
this work, the average aliphatic carbon
sorbance for ketones and aldehyde in this
composition was taken to be CH, because
region, determination of a calibration fac-
the CH, absorption bands of 2924 and
tor depends on the relative concentration
2850 cm-' dominated aliphatic carbon
of ketones, aldehydes and acids. Determi-
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absorptions (section 3.2.1), and because

CH, represents the majority of aerosol
aliphatic carbon cited in literature (see,
for example, Mazurek et al., 1989; Rogge
et al., 1993). The calibration can be sum-
marized by the following equation:
Aliphatic carbon loading ( pg C/m2)
C-H absorbance area
= [ m3 of ambient air sampled
1 mol aliphatic C-H bonds
3 X 106 area units
1 mol aliphatic carbon
2 moles C-H bonds
nation of the relative ratios of ketones,
aldehydes and acids that should be used
in the overall carbonyl calibration factor
was based on a comparison of model com-
pound and ambient spectra. Table 2 sum-
marizes the individual compounds used to
model the carbonyl absorptions observed
in Southern California aerosols (Palen,
1991).
To understand the basis for determin-
ing the overall carbonyl calibration, it is
important to note the ratio of C-H/C =
0 absorbances. For ketones, ester and
aldehyde model compounds, this ratio was
greater than 1. For acids and diacids, the

( 12 X 1 0 pg aliphatic carbon
ratio was considerably less than 1. In com-
parison, the C-H/C = 0 ratios for ambi-
ent Los Angeles aerosol averaged less than
mole aliphatic carbon
0.2 and ranged from 0 to 0.7. If ketones or
The detection limit was 0.08 pg/m3 for a aldehydes were present in significant
4-h sample. quantities in the ambient aerosol, the

TABLE 2. Calibration Compounds Used in Carbonyl Absorbance Calibration

C-H/C = 0
Carbon Absorption
Fraction Functionality Number Reference Compound Area Ratio
Neutral ketone 10 2-decanone 1.5
Neutral ketone 19 10-nonadecanone 2.2
Neutral ester 16 methyl pentadecanoate 1.5
Neutral ester 18 methyl heptadecanoate 1.3
Acid monofunctional 16 palmitic acid 0.44
Acid monofunctional 18 stearic acid 0.45
Acid monofunctional 24 tetracosanoic acid 0.76
Acid monofunctional 26 hexacosanoic acid 0.89
Acid diacid 2 oxalic acid 0.00
Acid diacid 4 succinic acid 0.01
Acid diacid 6 adipic acid 0.07
Acid diacid 8 phthalic acid 0.04
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol 337

C-H/C = 0 absorbance ratios would

have been higher than the observed 0.2.
Thus, it can be assumed that the carbonyl
absorbance is mainly due to acids and
diacids. Diacids may dominate, since
monoacid model compounds had a C-H/
C = 0 absorbance ratio of approximately
0.6. Additional support for the domina-
tion of diacids comes from their ab-
sorbance peak shapes. The complex car-
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bony1 carbon absorption shapes seen in

ambient aerosol spectra were the same as
for the diacid calibration spectra, as shown
in Figure 3. Both have C = 0 absorptions
which peak at 1713-1714 cm-' and have
a high frequency shoulder around 1735
cmpl. Both absorptions are broad and
smooth. Based on all the spectral evi-
dence, the calibration factor for carbonyl
groups was based on the molar absorptivi-
ties of diacid model compounds. A cali-
bration factor of 3 x lo7 area units per
mole of C = 0 bonds was selected, and
the calibration is summarized in the fol-
lowing equation:
Carbonyl carbon loading ( p g C/m3)
C = 0 absorbance area
Diocid model
compound
absorbance ------
Wavenumbers (cm-I)
FIGURE 3. Comparison of ambient carbonyl
peak shape to peak shape for diacid model com-
pound mixture.
tra, however, indicated little variability in
molar absorptivity from compound to
compound. For octyl nitrate, the 1280
cm-' absorptivity was found to be 2 X 107
absorbance area units per mole of
CONO,. This corresponds to a detection
limit of 0.1 p g C - O - N O , / ~ ~ for a 4-h

= ( m3 of ambient air samples

1 mole C = 0 bonds
sample. The calibration was
Organonitrate loading ( pg/m3)
C-0-NO, absorbance area
3 x lo7 area units
[ 12 x l o 6 p g carbonyl carbon
m3 of ambient air samples
1 mole C-0-NO,
mole carbonyl carbon
2 X lo7 area units
Detection limits were approximately 0.02
pg/m"or a 4-h sample.

4.5 Organonitrate Calibration

In contrast to the aliphatic carbon and
carbonyl calibrations, the organonitrate
calibration was determined with a single
reference compound, octyl nitrate. Only a
single compound was used because very
few organonitrate reference compounds
are commercially available. Library spec-
4.6 Comparison of Functional Group
Loadings with Other
Analytical Measurements
The total low pressure cascade impactor/
Fourier transform infrared (LPI/ FTIR)
sulfate mass loadings (d, < 2.0 p m ) mea-
sured for each sampling period were com-
 338
pared with the corresponding Bemer cas-
cade impactor/ ion chromatography (BI/
IC) values reported by John et al. (1989a,
1989b). The sulfate loadings determined
by the LPI/FTIR average 93% of the
sub-4-pm sulfate loadings measured by
BI/ IC (Palen, 1991). The LPI/ FTIR and
BI/IC nitrate loadings were also com-
pared. They did not agree as well as did
the sulfate loadings. The LPI/FTIR ni-
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trate loadings average 74% of the sub-4-
p m nitrate values reported by John et al.
(1989a, b). This may be due to volatiliza-
tion of nitrate in the low pressure stages
of the Hering Impactor, since the agree-
ment with the data of John et al. (1989a,
b) was good for the high pressure stages,
but poor for the low pressure stages.
Specifically, John et al. (1989a, b) found
that aerosol smaller than 0.4 p m ac-
counted for 25% of the sub-2.0-pm ni-
trate, while our work, using the Hering
impactor, found only 4%-7% of the ni-
trate in sub 0.5 p m aerosol. Thus,
volatilization losses in the low pressure
stages may result in losses on the order of
20% of the nitrate (Palen, 1991). A de-
tailed analysis of artifacts for Low Pres-
sure Impactors has been given by Biswas
et al. (1987) and Jalapathy (1992) while
those for the Berner impactor have been
given by Wang and John (1988).
The LPI/FTIR carbonyl loadings were
compared with the organic carbon load-
ings of McMurry and Anderson (1989)
that were not used in establishing the
calibration factor. Recall that only sam-
ples collected from 0600-1000 during the
Southern California Air Quality Study
were used in the calibration. For the other
sets of samples, collected from 1000-1400,
1400-1800, and 1800-0600 PDT, the esti-
mated loadings of carbon in carbonyl
groups was 40% of McMurry's total or-
ganic carbon during daylight hours and
10% of McMurry's organic carbon during
the overnight sampling period. This is in
reasonable agreement with estimates by
D. T. Allen et al.
Rogge et al. (1993) of the ratio of car-
bony1 groups to total organic carbon. Vol-
atilization losses may also influence or-
ganic loadings. Calculations by Jalapathy
(1992) indicate that losses may be severe
in the low pressure stages for organics
with vapor pressures greater than
atrn.
These comparisons show that the inor-
ganic LPI/FTIR functional group load-
ings are in reasonable agreement with
corresponding loadings as determined by
dissimilar sampling and analysis protocols.
Much uncertainty remains for the abso-
lute loadings of organic groups, but the
approximate loading as determined by
LPI-FTIR, seem reasonable.
5. SIZE DISTRIBUTION OF SELECTED
FUNCTIONAL GROUPS IN
LOS ANGELES AEROSOL
The LPI-FTIR method was used to ana-
lyze aerosol composition as a function of
particle size during the Southern Califor-
nia Air Quality Study (SCAQS). Describ-
ed below are some of the sulfate, nitrate,
aliphatic carbon, carbonyl and organoni-
trate size distributions measured at Clare-
mont and Duarte.
5.1 Sulfate Size Distributions
Daytime ambient sulfate concentrations,
as determined using LPI-FTIR method,
ranged from 2 to 13 pg/m? This range is
only about half as wide as the range ob-
served in the samples analyzed using the
flash volatilization sulfur method (1-23
pg sulfate/m", since the relatively short
(30 minutes) flash volatilization sampling
duration allowed more temporal fluctua-
tions to be observed in the measured sul-
fur loadings. The FTIR samples mask-
ed these sulfate fluctuations by averaging
them over longer sampling periods (four
hours). Typical sulfate size distributions
are presented in Figure 4.
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol 339

and almost 7 pg/m3 between 6 0 0 pm

and 6:00 am. The highest concentrations
were observed on August 27, 28 and 29
with daytime values reaching 19 pg/m3.
Virtually all ambient nitrate was found in
particles having aerodynamic diameters
ranging from 0.5 to 4.0 pm, with 50 to
75% of the mass falling between 2.0 and
4.0 pm. Typical nitrate size distributions
are presented in Figure 5.
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5.3 Aliphatic Size Distributions

The highest concentrations of aliphatic
carbon were measured on July 13 and 14.
The peak concentrations were approxi-
Particle Diameter, DP (pm) mately 11 pg/m3 on the 13th (afternoon)
and the 14th (morning). The ambient ali-
FIGURE 4. Aerosol sulfate size distributions de-
termined using the LPI-FTIR method. (a) Data
from sample collected on July 27, 1000-1400 h at
Claremont. This sample had the highest loading
observed during the study. (b) Data from sample
collected from September 3, 1800 h to Septem-
ber 4, 0600 h at Claremont. This sample had the
lowest loading observed during the study.

Of the 12 days when sampling was

performed during the SCAQS program,
September 2, September 3, and July 13
were the days of lowest sulfate levels. The
maximum loading occurred on August 29
between 2:00 pm and 6 0 0 pm. Stage 4
(0.5-1.0 pm) was the dominant size frac-
tion for sulfate, although significant load-
ings were observed in all size fractions. A
secondary mode was frequently observed, Particle Diameter, DP (pm)
peaking in either the 0.075-0.12 p m or
the 0.12-0.26 p m ranges, with the latter FIGURE 5. Aerosol nitrate size distributions de-
being more common. termined sing the LPI-FTIR method. (a) Data
from sample collected on August 29, 1000-1400
h at Claremont. This sample had the highest
5.2 Nitrate Size Distributions loading observed during the study. (b) Data from
sample collected on September 2, 0600-1000 h at
The day of lowest ambient nitrate load- Claremont. This sample had the lowest loading
ings during the SCAQS sampling periods observed during the study (note that volatiliza-
was September 2, which had concentra- tion of nitrate from the sub-0.5-pm stages is
tions of about 1 pg/m3 during the day significant).
 340 D. T. Allen et al.

phatic concentration typically demon- aerodynamic diameters below half a mi-

strated two maxima each day correspond- cron. Typical aliphatic size distributions
ing to the morning and evening rush hours. are presented in Figure 6.
This indicates a strong primary automo-
tive source for aliphatic carbon although
other sources are also present (Pickle 5.4 Carbony' Size Distributions
et al., 1990). Aliphatic carbon is predomi- June 19 was the day of lowest ambient
nantly found in the size fractions with carbonyl concentrations with concentra-
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$
2
m
$0
40
Carbonyl Groups

16 40
' 3
5/28/87
fF l
r-9
i :
20
16

f Aliphatic Carbon

9 2

0 0

f Carbonyl Groups

20
16
C, 30 I2 30

Aliphatic Corbon

K
0 2

Organonitrates
l{-v-m~---35

'L.1:. 4

0
IWO-14OOhr

0
10-2 10-1 lo0 lo1
Aerodynamic Diameter, Dp ( ~ 1

FIGURE 6. Carbonyl group, aliphatic carbon and organonitrate

size distributions determined using the LPI-FTIR method.
Loadings are in (pg-C/m" for the carbonyl and aliphatic
groups; for the organonitrates loadings are in pg-0-N0,/m3.
The size distributions are for August 28 and 29, at Claremont.
 FTIR Spectroscopy of Low-Pressure Impactor Aerosol
tions between 2 and 6 p g c / m 3 in the
morning and evening and 8 pg C/m3
during midday. The highest atmospheric
loadings occurred August 27-29. The car-
bonyl concentrations peaked in the after-
noons (between 2:00 and 6:OO) at levels
as high as 15 p g c/m3. These afternoon
peaks are an indicator of the carbonyl
aerosol's photochemical nature. The dom-
inant carbonyl size fraction had aerody-
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namic diameters in the 0.5-1.0 p m range.
A significant secondary peak was found in
the 0.12-0.26 p m range fairly often, how-
ever. Typical size distributions for car-
bonyl are presented in Figure 6 (Pickle
et al., 1990).
5.5 Organonitrate Size Distributions
Loadings of the organonitrate group (C-
0-NO,) during the SCAQS intensive pe-
riods ranged between 0.3 and 1.7 pg
0-NO,/ m3. The loading correlated
strongly with carbonyl absorbances, indi-
cating that many of the molecules con-
taining the organonitrate group may be
difunctional (Mylonas et al., 1991). Smog
chamber studies have also indicated that
difunctional species containing organoni-
trates are formed in the atmosphere
(07Brien et al., 1975a, b). Typical size
distributions for the organonitrate group
are shown in Figure 6. During periods of
high photochemical activity, the size dis-
tributions show maxima in the 0.05-0.075
p m and the 0.12-0.26-pm size fractions.
During periods of low to moderate photo-
chemical activity, the size distributions
were shifted to slightly larger sizes, with
maxima appearing in the 0.075-0.12 p m
and the 0.5-1.0 p m size fractions.
CONCLUSION
Infrared spectroscopy can be used to
characterize the organic and inorganic
species present in size segregated atmo-
spheric aerosol. Organics, sulfates, ni-
341
trates, ammonium, and some trace species
can be detected using infrared methods.
The estimates of sulfate and nitrate load-
ings based on the infrared spectra agreed
well with other, more established methods
of analysis. For the organics, aliphatic car-
bon, carbonyl, and organonitrates can cur-
rently be detected, providing new chemi-
cal insights into the compound classes
present in atmospheric aerosol. If detec-
tion limits are improved by making mod-
est changes to the designs of the impactor
and the infrared optics, it may be possible
to detect additional organic groups such
as nitro-aromatics and alkenes.
Preparation of this manuscript was supported by
Southem California Edison as part of the Los Angeles
Aerosol Characterization and Source Allocation Study.
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Allen, D. T. (1989). Final Report to the Coordinating
Research Council on Contract SCAQS-4-4, 219
Perimeter Center, Parkway, Atlanta, GA 30346.
Appel, B. R., Hoffer, E. M., Kothny, E. L., Wall, S. M.,
and Haik, M. (1979). Enuiron. Sci. Tech. 13:98-104.
Atkinson, R. (1990). Atmos. Enuiron. 24A:l-41.
Biswas, P., Jones, C. L., and Flagan, R. C. (1987).
Aerosol Sci. Technol. 7:231-246.
Blanco, A. J. and McIntyre, R. G. (1975). Atmos.
Enuiron. 65.57.
Bogard, J. S., Johnson, S. A., Kumar, R., and Cunning-
ham, P. T. (1982). Enuiron. Sci. Tech. 16:136-140.
Cahill, T., Matsumura, R., Wakabayashi, P., and
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Received September 13, 1993