EPA-650/3-74-002
June 1973
Ecological Research Series
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EPA-650/3-74-002
HAZE FORMATION:
ITS NATURE AND ORIGIN
1973
by
D. F. Miller, W. E. Schwartz, P. W. Jones
D. W. Joseph, C. W, Spicer, C. J. Riggle, and A. Levy
Battelle - Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
Contract No. 68-02-0276
Project No. 21AKB-03
Program Element No. 1A1008
EPA Project Officer: Ronald K. Patterson
Chemistry and Physics Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
Coordinating Research Council Inc.
30 Rockefeller Plaza
New York, N. Y. 10020
CAPA 6
and
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
June 1973
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This report has been reviewed by the Environmental Protection Agency and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Agency, nor does
mention of trade names or commercial products constitute endorsement
or recommendation for use.
11
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TABLE OF CONTENTS
INTRODUCTION 1
SCOPE AND STATUS OF PROGRAM 1
SUMMARY OF RESULTS 2
EXPERIMENTAL METHODS 3
Air-Quality Measurements 3
Aerosol Collections 6
Aerosol Inorganic Analyses 8
Organic Analyses of Aerosols 9
Solvent Extraction of Particulate 9
Determination of Weight Percent CHN 9
Infrared Spectroscopy 9
Nuclear Magnetic Resonance Spectroscopy 10
Sample Fractionation 10
Functional-Group Analyses 11
Determination of Alcohol 11
Determination for Carbonyl 12
SAMPLING SITES 12
Columbus, Ohio 13
Welfare Island - New York City 13
Pomona, California 13
RESULTS AND DISCUSSION 13
Air Quality 13
Inorganic Composition of Aerosols 20
Organic Composition of Aerosols 22
Solvent-Extractable Particulate Matter 23
Weight Percent C, H, and N 23
Infrared Spectra 25
Aromatic/Aliphatic Ratio 30
Acid/Base/Neutral Distribution 30
Functiotial-Group Concentrations 31
APPENDIXES
A. AIR-QUALITY DATA FROM COLUMBUS, OHlu, NEW YORK CITY,
AND POMONA, CALIFORNIA A-l
B. INORGANIC COMPOSITION OF SELECTED AEROSOLS B-l
C. INFRARED SPECTRA OF SOLVENT EXTRACTABLE PARTICULATE
MATTER_
111
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LIST OF TABLES
Page
Table 1. Analytical Instrumentation for Air-Quality Monitoring 5
Table 2. Summary of Air Quality - Columbus - July, 1972 14
TableS. Summary of Air Quality - New York - August, 1972 15
Table 4. Summary of Air Quality - Pomona - November, 1972 17
TableS. Average Aerosol Constituents at Three Localities 21
Table 6. Solvent Extraction of Particulate Matter 24
Table 7. Weight Percent Carbon, Hydrogen, Nitrogen, and
Oxygen in Solvent Extractable Matter 25
Table 8. Comparison of Infrared Spectroscopic Data and Weight Percent CHN Data . . 29
Table 9. Fourier Transform-NMR Analysis of Methylene Chloride Extractables .... 30
Table 10. Fractionation of Methylene Chloride Extractable Matter 31
Table 11. Functional Group Analyses of Methylene Chloride Neutral Fraction 32
LIST OF FIGURES
Figure 1. Battelle-Columbus' Mobile Air-Quality Laboratory 4
Figure 2. Schematic of Aerosol Samplers 7
Figures. Average Air Quality for Month of August, 1972; Welfare Island, New York . . 19
Figure 4. Infrared Spectra of Solvent-Extractable Matter 26
Figures. Infrared Spectra of Solvent-Extractable Matter 28
IV
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1
SECOND YEAR REPORT
on
HAZE FORMATION: ITS NATURE AND ORIGIN
to
COORDINATING RESEARCH COUNCIL INC.
(CAPA 6-68)
and
U.S. ENVIRONMENTAL PROTECTION AGENCY
(Contract No. 68-02-0276)
from
BATTELLE
Columbus Laboratories
June 15, 1973
INTRODUCTION
The objective of this project is to identify and analyze atmospheric haze in order to
distinguish between photochemical haze from automotive sources and that from nonautomotive
sources.
Historically, very little is known regarding the composition of atmospheric aerosols, partic-
ularly the composition of the organic constituency an area where photochemical processes
prevail in creating light-scattering aerosols. This program, currently in its second year at Battelle-
Columbus, has been devoted to characterizing the composition of aerosols by adaptations of
analytical techniques to microquantities and to the retrieval of detailed air-quality data simul-
taneously with aerosol collections. The report summarizes the results of research done in the
period June 6, 1972, to June 6, 1973.(1) In consultation with the CAPA-6 project group, it was
decided that the report contain a description of experimental methods, a complete presentation
of experimental data, and a brief discussion of experimental findings, with no attempt being
made to establish cause-effect relationships.
SCOPE AND STATUS OF PROGRAM
The overall program consists of three distinct phases involving field sampling, aerosol
analyses, and statistical and interpretive analyses. Work performed during this report period was
limited to the first two phases.
(1) Results of the first-year program are summarized in Battelle-Columbus' First Year Final Report to CRC and EPA, January 28,
1972.
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Field sampling was conducted in downtown Columbus during the latter half of July, 1972,
in New York City (Welfare Island) throughout August, and in Pomona, California, for 10 days in
mid-November. The sampling involved continuous monitoring of the meteorological conditions
and the gas-phase composition of the air (including CO, NO, NO2, SO2, ozone, methane,
ethylene, acetylene, and total hydrocarbon) concomitant with collecting aerosols and measuring
visibility reduction due to light scattering.
All aerosol samples were collected on a diurnal basis. To provide the aerosol mass needed
for organic analyses, three samplers operated continuously at 20 cfm, sampling 25 feet above
ground level. Because this project is devoted to small particles which cause light scattering, the
samplers were equipped with size-fractionating devices which provided particle separation (based
on aerodynamic size) near 2 jum diameter.
An analytical scheme was developed for determining the organic features of aerosols. In
addition to providing qualitative information concerning the broad chemical classes and func-
tional groups present in the organic fraction of aerosols, the scheme provides numerical data,
thereby permitting statistical treatment of organic compositional data together with data on air
quality and inorganic composition.
Numerical organic data describe the weight-percent solvent extractable (methylene chloride
and dioxane) components of the aerosols, weight-percent CHN in the extractables, infrared
spectroscopic band intensities for specified absorptions, aromatic/aliphatic ratios (by NMR) and
quantitative functional group analyses for total alcohol and total carbonyl in specified sample
fractions. The scheme has been applied to six aerosol samples; two diurnal samples collected at
each of the three sampling sites.
Inorganic analyses were performed on aerosols selected from 22 of the 43 sampling days at
the three sites. The analyses included trace metals by optical emission spectrometry, Cl, Br, S,
and Pb by X-ray fluorescence, and 804, NO^, NH^, and CHN by other chemical methods.
The third year of this program will initially be devoted to two activities: (1) detailed
interpretation and modeling of the ambient air-quality data and aerosol analytical results
currently available and (2) application of the organic analysis scheme to aerosols generated
photochemically from auto exhaust. Depending on the outcome of these tasks, the completion
of the third-year program will involve investigations among the following activities: (1) additional
field sampling, (2) additional chemical analyses of aerosols from previous sites and/or a new site,
and (3) a statistical analysis of the air quality and compositional data to identify relationships
between aerosols and their sources.
SUMMARY OF RESULTS
Although much of the significance of the data contained in this report will be brought out
only through next year's work (third-year program), there are a number of observations regarding
air quality and aerosol properties which stand out from only casual review of the data. Some of
these observations are:
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Air-quality data taken at Welfare Island, New York City, indicate that the contribu-
tion of automotive exhaust emissions to the hydrocarbon burden in that area is <10
percent.
Photochemical aerosol formation was quite moderate in New York in spite of the
substantial development of other photochemical-smog manifestations, particularly
ozone.
A high, positive correlation was found between nephelometry data (light scattering)
and aerosol mass concentration data for aerosols <2 /zm in diameter.
The chemical composition of aerosols <2 ,um in diameter is vastly different from
that of aerosols >2 pm in diameter.
Organic compounds and sulfate compounds are major constituents of the <2-;um
aerosols in Columbus, New York, and Pomona; in Pomona, nitrate compounds are
also major constituents in that size range.
In the size range >2 jum, most of the aerosol matter comprises carbonate and
metallic compounds. Lead and zinc compounds, however, were predominantly in the
<2 p.m size range.
A dual-solvent extraction procedure was necessary to extract organics from aerosols
(<2 jum) having wide ranges of polarity and solubility.
Correspondence has been observed between results of CHN analyses and those of
infrared spectroscopic analyses. For example, there is an apparent correlation be-
tween the weight percent nitrogen in the organic sample and the relative intensity of
tentatively identified nitrate bands.
The techniques adapted for micro-functional-group analyses provide unambiguous
molar values for alcohol and carbonyl content of specified sample fractions.
EXPERIMENTAL METHODS
Air-Quality Measurements
Battelle-Columbuc Mobile Air-Quality Laboratory, pictured in Figure 1, was used in
Columbus and New York to monitor meteorological conditions, integrated light scattering,
solar-irradiation intensity, and the gas-phase composition of the air while simultaneously collecting
aerosols for chemical analyses. In Pomona, only the aerosol samplers were used; air-quality data
were made available through the County of Los Angeles Air Pollution Control District and
Brackett Field Airport, La Verne, California.
Pertinent instrumentation used in collecting the data in Columbus and New York is
indicated in Table 1.
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a. View of Exterior
'
'
b. View of Interior
FIGURE 1. BATTELLE-COLUMBUS' MOBILE AIR-QUALITY LABORATORY
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TABLE 1. ANALYTICAL INSTRUMENTATION FOR AIR-QUALITY MONITORING
Analysis
Instrument
Wind speed and direction
Temperature
Relative humidity
Global radiation intensity
Light scattering
NO
NOX
NOo (by difference)
THC
CH4
CO
S02
C2H2
C2H4
MRI, Model 1074-2 sensor
MRI, Model 802 sensor
MRI, Model 907 sensor
Eppley Lab., Inc., 180° pyrheliometer
MRI integrating nephelometer
REM, Model 612 chemiluminescence monitor
Bendix, Model 8101-B chemiluminescence NO-NOX analyzer,
gold/carbon catalyst converter
Union Carbide, Model 3020 analyzer
Battelle-Columbus built; Tracer Instruments flame
photometer detector
Varian Series 1200 gas chromatograph
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The meteorological station was calibrated by MRI. The integrating nephelometer was zeroed
and electronically spanned each day; a calibration with Freon 12 (Du Pont) was performed
weekly.
Chemiluminescence instruments were used for monitoring O3, NO-NOX, and SO2. The
ozone instrument was calibrated against the wet chemical KI method(2) and a constant ozone
source (McMillan Series 1000 ozone generator). Calibration was performed before and after
monitoring periods. In the field, the ozone instrument was zeroed each day. A Hopcalite catalyst
was used to destroy the ethylene effluent from the ozone instrument. The NO-NOX analyzer was
calibrated daily using an NO span bottle whose concentration was determined using an NO-O3
titration procedure/3) Charcoal was used to destroy the O3 effluent. The SO2 (total sulfur)
analyzer was calibrated using an SO2 permeation tube (Metronics, Inc.) and appropriate
apparatus.
The FID analyzer for total hydrocarbon (THC), CH4, and CO was calibrated each day,
using a span bottle of known CO and CH4 concentrations. The CH4 span concentrations were
validated against other standards in the Battelle-Columbus laboratory.
Porapak N and Q packed columns were used to chromatograph C2H4, C2H6, and C2H2.
Only the C2H4 and C2H2 areas were quantitated. The sample volume was 1 ml. With ultrapure
hydrogen, 1 ppb C sensitivity was achieved. The same span bottle used for calibrating the
THC-CH4-CO analyzer was used to calibrate the gas chromatograph each day.
Aerosol Collections
All aerosol samples were collected on a diurnal (23 hour) basis. To provide the aerosol mass
needed for analytical purposes, three high-volume samplers operated continuously at 20 cfm.
Samples were collected from about 25 feet above ground and directed through 6-inch-diameter
aluminum stacks to the filters located within the laboratory (see Figure 1).
Because in this program the interest is primarily in characterizing the small particles that
cause light scattering and are respired (particles having aerodynamic sizes <2jum), the samplers
were equipped with size-fractionation devices. Andersen 2000 Inc. Hi-Vol impactor heads were
used with two of the samplers and a cyclone was used for the third sampler. Particle fractiona-
tion with the Andersen heads provided particle precollection in the size range 7 jum and above,
3.3 to 7 jum, and 2.0 to 3.3 jum and backup filter collection of particles <2 jum in diameter. The
configuration of the aerosol samplers and impaction stages is shown schematically in Figure 2.
It is estimated that, because of the design of the interface plate (Figure 2), about 50
percent of the particles in the size range 1 to 2 jum were inadvertently impacted on this plate
rather than being collected on the backup filter. However, the amount of aerosol thereby lost
was apparently small compared with the total amount of material collected on the backup filter
as evidenced by the "nearly" identical mass loadings that were obtained using the cyclone
sampler, which collected all particles <2 //m in diameter. Furthermore, if the size distribution of
atmospheric aerosols analyzed in the Los Angeles area are representative of distributions in other
(2) "Air Quality Criteria for Photochemical Oxidants", USUHEW-PHS, National Air Pollution Control Administration, Publication
No. AP-63, Washington, D.C., March, 1970.
(3) Hodgeson, J. A., Baumgardner, R. E., Martin, B. E., and Rehme, K. A., Analytical Chemistry, 43 (8) (July, 1971).
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Neoprene
gaskets
Jet plates
Interface plate
L
Air flow, 20 cfm
Aluminum stack
Millipore filter, 47mm
To pump
Critical orifice
,
4 \
P 1 * 1
11 '
D *
4
<
t i
* 1 °
I
, ' o
1
1 i
*
Collection membrane, >7 micron
Collection membrane, 3-7 micron
Collection membrane, 2-3 micron
D
To manometer
Calibrated orifice
Millipore filter, 47mm
I^=> To pump
Critical orifice
Quartz filter, < 2 micron
-SS screen
To pump
FIGURE 2. SCHEMATIC OF AEROSOL SAMPLERS
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8
»
urban areas, one might not expect that a substantial fraction of the particles <2 pm would have
been lost owing to the design under consideration. According to the size-distribution study by
Whitby(4), the aerosol volume associated with particle sizes of 1 to 2 nm is fairly small (~12
percent) compared with the total volume for aerosols <2 /urn.
The third sampler incorporated a specially designed cyclone which served as a precollector
for particles >2.0 p.m. With all samplers, 6-inch high-purity quartz-fiber membranes were used as
backup filters. In addition, two 47-mm Millipore filters were used to collect aerosols for metals
analyses. These filters were located above and below the Andersen impactors, thereby providing
samples of total aerosol and aerosol <2jum diameter.
The mass gain on each filter was determined gravimetrically with a Cahn electrobalance. The
filters were equilibrated to a constant humidity (30 percent at 25 C) before and after weighings;
24 hours were allowed for equilibration.
Aerosol Inorganic Analyses
Four analytical methods were used to analyze the inorganic constituents of the aerosols. A
brief description of each follows:
Optical emission spectrometry (OES) was used for determining traces and major
elemental distributions on membrane filters (Millipore cellulose). The filter and
sample are ashed by burning in ethyl alcohol which, by moderating the combustion,
prevents sample loss. The ashed product is mixed with graphite and shot by the
DC-arc technique.
X-Ray fluorescence (XRF) was used for determining Pb, S, Cl, and Br. Aerosol
samples collected on quartz fiber were subjected directly to the XRF method, and
the collected intensities were compared with those of secondary standards consisting
of simulated samples previously analyzed by other methods.
Wet-chemical analyses were used for inorganic ions collected on quartz tissue. Upon
extraction in water, sulfate ions were precipitated as barium sulfate and weighted
quantitatively. Ammonium ions were determined by distillation and titration. An
aliquot was treated to reduce nitrate ions to ammonia which was treated as
described for ammonium only. The difference of the two titrations corresponds to
the nitrate ion.
CHN elemental analyzers were used to determine CHN by pyrolysis of the sample
and subsequent detection by thermal conductivity.
(4) Whitley, K. T., Husar, R. B., and Liu, B.Y.H., "Aerosol Size Distribution of the Los Angeles Smog", J. Colloid and Interface
Sci., 39, 177 (April, 1972).
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Organic Analyses of Aerosols
Solvent Extraction of Particulate
Aerosols collected on quartz-fiber filters were subjected to Soxhlet extraction, first with
methylene chloride (20 hours) and then with dioxane (44 hours). Throughout, only high-purity*
solvents were used, and dioxane was redistilled before use. For each sampling day, three quartz
filters (Qi, Q2> and Q3) were combined. That is, samples simultaneously collected using the two
Andersen samplers and the cyclone-equipped sampler were combined for extraction. Approxi-
mately 100ml of each solvent was used per set of filters. The volume of each methylene
chloride extract was reduced to approximately 1 ml by vacuum distillation (10 in Hg at 35 C pot
temperature) using a Kuderna-Danish fractionating column. The weight of methylene chloride
extractables was determined by taking an aliquot of the concentrate (~5 percent) and evapo-
rating the solvent on a light (~5 mg) aluminum weighing pan. Pans were tared and reweighed
using a Cahn electrobalance, and aliquot weights were determined to ±2 jug. From these data, the
total weight of the methylene chloride extractable material was calculated. Use of this procedure
obviated the necessity for taking the entire sample to dryness. This is desirable in that the
methylene chloride extract can be expected to contain the more volatile (nonpolar) sample
components. Taking the entire sample to dryness might compromise the sample with respect to
such components. The dioxane extracts, containing the more polar, less volatile components,
were reduced by lyophilization (freeze drying). Solvent and filter blanks were carried through the
reflux and concentration procedures. In calculating the weight percent solvent extractable, values
due to such solvent and filter background were subtracted. Data concerning blanks are presented
in the Results and Discussion section. Values for weight percent methylene chloride extractable
and weight percent dioxane extractable were calculated as follows:
, . . . , , ,, (Weight of extracted matter, corrected) inr>
Weight percent solvent extractable = x 100 .
(Weight of total particulate)
In order to demonstrate that the dioxane does not extract significant quantities of inorganic
salt from the filters, I00-ml portions of dioxane were stirred with ammonium sulfate, ammonium
nitrate, lead nitrate, sodium carbonate, and sodium chloride. The suspensions were filtered and
the dioxane filtrates were lyophilized in tared flasks. Salt residues were only barely visible, and
did not exceed 0.3 mg.
Determination of Weight Percent CHN
Determinations of we'^ht percent C, H, and N were conducted using a Perkin-Elmer Model
240 elemental analyse*- with gas purification accessory. The instrument performs automated
Pregel-Dumas determinations. Values shown for weight percent oxygen [O] were calculated by
difference from the CHN data. Approximately I mg of sample was used for each determination.
Infrared Spectroscopy
Infrared spectra were obtained using a Perkin-Elmer Model 521 grating infrared spectropho-
tometer. Spectra were obtained of thin films of sample on a sodium chloride plate.
""'Distilled in-glass" solvents obtained from Burdick and Jackson, Muskegon, Michigan.
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Reduction of spectroscopic results to numerical form was performed by calculating relative
peak intensities for specified absorptions. Values of relative peak intensity were obtained by
calculating the ratio of the optical density for the specified absorption to that observed for the
CH stretching vibration at 2920 cm'1; i.e.,
. . . ., (O.D. - specified absorption)
Relative intensity =
(O.D. - 2920 cm-i)
Nuclear Magnetic Resonance Spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy was performed using a modified Varian
Associates 60 MHz spectrometer. The instrument is equipped to perform Fourier-transform (FT)
spectroscopy. Instrument control, data acquisition, and reduction in the Fourier-transform mode
are accomplished using a Digilab digital computer interfaced with the spectrometer. Fourier-
transform spectroscopy permits the rapid generation of spectra, consequently allowing the
generation of a large number of spectra in a relatively short period of time. Computer time
averaging a series of such spectra leads to enhanced signal-to-noise ratio and permits acquisition
of useful spectra not obtainable by conventional techniques. The current application required the
use of FT-NMR to obtain adequate spectra. Spectra were obtained using ~l-mg samples of
extractable matter. Methylene chloride extractables were analyzed in deutero-chloroform solution
and dioxane extractables were analyzed in deutero-dioxane solution. From the spectra obtained,
aromatic/aliphatic ratios were obtained. These values are expressed as proton-percent aromatic,
and were calculated on the basis of the integrated resonances for methyl and methylene protons
and the integrated resonances for aromatic protons.
Sample Fractionation
The methylene chloride extractable matter was fractionated as noted in the scheme shown
below. The material was fractionated first into water-soluble and water-insoluble components by
partitioning the methylene chloride solution against distilled water. All extractions were con-
ducted in conical centrifuge tubes agitated by means of a Vortex-Genie mechanical mixer. This
procedure permits convenient centrifugation of emulsions prior to separation of phases, and
minimizes sample losses. Water was removed by lyophilization, and the weight of the water-
soluble fraction was determined.
Methylene Chloride Extractable Matter
Water-Soluble Fraction Water-Insoluble Fraction
1
Acid
Fraction
Nei
tral
Fraction
Basic
Fraction
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The water-insoluble material remaining in methylene chloride solution was next fractionated
into acid, basic, and neutral components. The solution was extracted using first 2N aqueous
sodium hydroxide and then 2N hydrochloric acid. Material remaining in methylene chloride
solution after extractions with both aqueous sodium hydroxide and hydrochloric acid is defined
as the water-insoluble neutral fraction.
The sodium hydroxide extract (containing organic-acid salts) was brought to pH ~0.8, and
the free acid was extracted into methylene chloride using a continuous liquid/liquid extractor.
Similarly, the hydrochloric acid extract (containing organic-basi salts) was brought to pH ~13,
and the free base was extracted into methylene chloride, again using a continuous liquid/liquid
extractor. The methylene chloride solutions containing the acid, basic, and neutral fractions were
dried by refluxing the solutions over a 3 A molecular sieve. Drying the solutions directly with
anhydrous magnesium sulfate or molecular sieve was found to be unsatisfactory because of
irreversible adsorption of organics upon the drying agent.
The dried solutions were concentrated to a volume of ~1 ml using a Kuderna-Danish
fractionating column. The weight of organic matter in the concentrated solutions was determined
by taking an aliquot of the concentrate (~5 percent) and evaporating the solvent on a light
(~5 mg) aluminum weighing pan. Pans were tared and reweighed using a Cahn electrobalance,
and aliquot weights were determined to ±2 /xg. Using vdues determined for the weights of the
various fractions, weight percent values were calculated.
Functional-Group Analyses
Quantitative functional-group analyses for alcohol and for carbonyl were performed using
the water-insoluble neutral fraction of the methylene chloride extractable matter. Isolation of this
fraction was described above. Procedures for determining micromolar quantities of carbonyl have
been described in the literature.*5 * The procedure selected for use in this program*6} is based
upon the colorimetric determination of 2,4-dinitrophenylhydrazones, and is described below. In
contrast, micro-functional-group analysis for alcohols has not been reported. Thus, during this
report period, an existing macroscale procedure*7'8' was adapted to the microchemical require-
ments of this application. Details of the method are presented below.
The procedure for determination of alcohols is subject to interference from carboxylic
acids, phenols, and amines. Thus, the analysis is conducted on the neutral fraction. Although the
carbonyl determination is not subject to the interferences that limit the alcohol analysis, the
carbonyl determination is applied to the neutral fraction in order that a comparison can be made
between alcohol and carbonyl content in the same sample fraction.
Determination o" Alcohol. The method selected for adaptation is based on the reaction of
lithium aluminum hydride with the hydroxyl group. Although amines, carboxylic acids, and
phenols also react, these compounds are not present in the neutral fraction, and hence do not
interfere. It is expected that a modified version of the procedure could be adapted to determine
(5) Siggia, S., Quantitative Organic Analysis, John Wiley (1963).
(6) Lappin, G. R., and Clark, L. C, Anal. Chem., 23, 541 (1951).
(7) Weiss, F. T, Determination of Organic Compounds: Methods and Procedures, Wiley-Interscience (1970), p 124.
(8) Gaylord, N. G., Reduction With Complex Mftal Hydrides, Interscience (1956).
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12
hydroxy acids in the acid fraction. This would involve treatment of the acid, fraction with
diazomethane to yield methyl esters and methyl-aryl ethers of the carboxylic acids and phenols,
respectively. By performing duplicate analyses before and after diazomethane treatment, values
could be calculated for both total acid-associated alcohol and total acid hydrogen.
Procedures utilizing the lithium aluminum hydride reaction for large-scale alcohol determina-
tions are well documented, and involve the collection of evolved hydrogen in a gas burette.(7>8)
In the procedure modified for this microchemical application, the sample is treated with hydride
in a micro reaction vessel (~200 /ul) which is plumbed directly to the inlet of a gas chromato-
graph. The evolved hydrogen is swept onto a 1 ft x 2 mm alumina column, and is quantitated
using a thermal conductivity detector. As presently employed, the method has been demon-
strated to be reproducible over the range 10'8 to 10~5 mole of alcohol, and linear calibrations
were obtained over this range. The sensitivity of the method is well within that required for this
application. For example, a 1-mg sample containing 1 x 10'8 mole of alcohol corresponds to a
concentration of 0.016 weight percent alcoholic oxygen.
Determination for Carbonyl. Of the methods available for the quantitative determination of
carbonyl, the colorimetric method involving the formation of 2,4-dinitrophenylhydrazone is most
suitable for the current application.(5'6) The colored derivative formed is stable for several
hours. Further, the molar absorbances of hydrazones formed from different carbonyl compounds
varies so little that the method is well suited to the determination of "total carbonyl". The
method is most useful in the range of carbonyl concentration from 10~4 to 10'6 M. This is well
within the sensitivity range required for the current application. For example, if a 1-mg sample
containing 1 x 10'8 mole of carbonyl is dissolved in 1 ml of solvent for analysis, the solution is
1 x 10~5 M. in carbonyl. Such a sample contains 0.016 weight percent carbonyl oxygen.
Calibrations were carried out using 5 x 10"2 molar solutions of n-heptaldehyde and
2-heptanone; 1 to 25 /ul of these solutions were added to 1 ml of carbonyl-free methyl alcohol.
A linear calibration over the range 10'7 to 10-6 mole of carbonyl against optical density was
obtained.
SAMPLING SITES
Columbus, Ohio
The geographic fe;vures of the Columbus region range from the Ohio till plain and central
lowland to the Appalachian Plateau. The hills on the eastern and southeastern edge of this region
are generally <200 feet high. Climatology is typically Midwest and is classified as humid
continental, long summer phase. The City of Columbus, along with the heavier manufacturing
area of the town, is located in a dish-shaped basin in comparison with the rest of the
countryside. The result of this feature is a slightly more stable air mass and more persistent
morning inversions. The mean wind speeds are the second lowest in the state for major cities,
and the wind direction is primarily south to southwest.
The mobile air-quality laboratory was located in an open area at an abandoned Army Post,
Fort Hayes, just northeast of the downtown area. The site was ideally situated for sampling aged
downtown air masses, without the influence of any point-source emissions.
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13
Welfare Island - New York City
Climatology in the New York region is changeable, with variable wind speed and direction.
The laboratory was located on the northern tip of Welfare Island in the East River (saltwater).
The Island is situated between Manhattan, about 200 yards to the West, and Queens, about
200 yards to the East. The sampling site was parallel with Central Park in Manhattan. There was
very little activity on the island, and the air sampled was representative of well-mixed, aged, and
diluted air masses which flow back and forth among the Boroughs, and from New Jersey to the
West.
Pomona, California
Aerosol collections in California were performed at the Los Angeles County Fairground in
Pomona, California. The town of Pomona lies approximately 45 miles due east of downtown Los
Angeles, 30 miles west of San Bernardino, 5 to 10 miles south of the San Gabriel Mountains and
about 5 miles north of the Puente Hills. With the mountains to the north and the hills to the
south, the site is in a long valley which opens into the L.A. basin to the west. The area within 5
miles to the west is mostly undeveloped and consists of recreational areas, small airfields, and
some small colleges. The closest industry is 10 to 15 miles to the southwest in the City of
Industry.
RESULTS AND DISCUSSION
Air Quality
Air-quality data from each of the three sampling sites are summarized in Tables 2 through
4. More comprehensive air-quality data appear in Appendix A. Diurnal profiles of the data are
displayed there, together with meteorological conditions and tabulations of 24-hour averages and
hourly maximums of gas-phase pollutants (CO, NO, NO2, SO2, O3, THC, CH4, C2H2, and
C, H4) and light scattering.
Referring to the aerosol mass loading data in Tables 2 through 4, the mass concentration of
aerosols <2/^m in dh -;aer should be comparable for quartz and Millipore filters. Other than
experimental error, tKre is no apparent reason for the differences in the mass data obtained on
the two media. In those tables, the data headed by Millipore-B/A represent the fraction of the total
aerosol mass which was in the <2/xm size range on a given day.
The significance of separating the aerosols according to size will become apparent when
comparing the chemical composition of the two size fractions. Statistical analyses of the mass
loading data indicate that 2 /um is a satisfactory cutoff size for particles significantly influencing
atmospheric visibility due to light scattering. In Columbus and New York where integrated light
scattering was determined, the linear correlation coefficient between scattering and mass concen-
tration of aerosols <2 /urn in diametei was 0.94. On the other hand, the correlation of scattering
with total mass concentration (all sizes) was only 0.59.
-------
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18
The air-quality data obtained in Columbus and Pomona are too limited to permit making
generalizations about the average or typical air quality of these localities. In New York, however,
it appears that a large enough data base was obtained to permit an assessment of air quality
there during a sustained period of good ventilation.
Figures 3A and 3B profile the average diurnal air quality existing during the 1-month
sampling period on Welfare Island. Referring to Figure 3A, at about 7 a.m. there is a pronounced
increase in NO followed by the typical photochemical transformation to NO2. The buildup of
NO2 in the evening results from the reaction of newly emitted NO with the O3 that accumu-
lated during the day. The average level of ozone provides further evidence of the formation of
photochemical smog in the area. Ozone exceeded the 1-hour maximum standard (0.08 ppm) on
15 of the 21 sampling days.
In spite of the apparent photochemical activity, light scattering was generally quite low
(average bscat ~3 x 10'4 nr1 corresponding to visibility distance of ~10 miles). Also surprising is
the absence of a noontime or afternoon peak in light scattering typical of pronounced photo-
chemical aerosol formation. During the daylight hours, the maximum in light scattering occurred
during the morning rush hours (7 to 9 a.m.). During the evening, light scattering appears to be
strongly influenced by humidity, as indicated in Figure 3A.
The profiles in Figures 3A and 3B show another interesting result; the nonmethane
hydrocarbon (NMHC) curve is not significantly influenced by obvious trends in motor-vehicle
activity, although other automotive emissions (CO, NO, C2H2, and C2H4) correspond to such
trends. It is conceivable that the NMHC profiles reflect inputs from stationary combustion
sources and/or from New Jersey refining operations. This is a controversial finding, however, and
requires further clarification.
An assessment of the vehicle-exhaust contribution to NMHC can be made by examining
changes in vehicle-related emissions during the period of greatest increase in automotive activity:
from 7 to 9 in the morning. According to data in Figures 3A and 3B, the following average
increases in concentrations were determined during those 2 hours.
PPM
CO 0.64
NO 0.022
C2H2 0.0020
C2H4 0.0025
The magnitude of these increases, together with approximations of vehicle-exhaust composition,
can be used to predict the increase in NMHC during the period in question. Assume the
following exhaust-emission composition relative to nonmethane hydrocarbon:
CO/NMHC 13
NO/NMHC 0.4
C2H2/NMHC 0.06
C2H4/NMHC 0.12
-------
19
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20
Applying these ratios to the respective changes in emission levels noted above yields the
following predictions of 2-hour increases in hydrocarbons due to automotive exhaust:
Predicted Increase
Predictor in NMHC, ppm C
CO 0.049
NO 0.055
C2H2 0.033
C2H4 0.021
These predicted hydrocarbon concentrations are virtually insignificant compared with the total
NMHC level (2.5 to 3.0 ppm C), and are consistent with the absence of a maximum in the actual
NMHC curve during the morning rush hours. Even if the assumptions in exhaust composition
made in this exercise are in error by a ridiculous factor of 5, the automotive exhaust contribu-
tion to NMHC would be <10 percent.
Inorganic Composition of Aerosols
Detailed inorganic compositions of selected aerosol samples appear in Appendix B. Ele-
mental analyses of aerosols collected on Millipore filters are presented in Table B-l. Analyses for
total C, H, N, S, 804, NOj, NHj, Cl", Br", and Pb on quartz filters are presented in Table B-2.
Compositions of aerosols by element categories are summarized in terms of weight percent in
Table B-3.
Similarities and/or differences in composition of aerosols between sampling sites and
between aerosol size fractions (< 2 jum >) are apparent from the summary data in Table 5. The
compositions of aerosols <2 jiim diameter presented are the averages of samples from 5 days in
Columbus, 1 1 days in New York, and 6 days in Pomona. Data for aerosols >2 jtxm are averages
from 11 days in Columbus and 27 days in New York; no large aerosols were collected in
Pomona.
As indicated in Table 5, nearly all the metallic compounds are associated with large
particles; of all the metals, only lead and zinc were found to predominate in the small aerosol
size range. Nearly all of the carbon of the large particles is inorganic (presumably carbonate), as
borne out by the small amount of hydrogen in that size range. In New York, chlorine was the
predominant halogen its concentration is attributed primarily to sea salt. In each city, sulfate
was a major contributor to the mass of small particles. Although not indicated in Table 5, there
was a considerable amount of nonsulfate sulfur in the small particles.
Nitrate was found in both particle size ranges; the significant finding for nitrate is the
order-of-magnitude greater concentration in the Pomona aerosols compared with that in
Columbus and New York aerosols. Ammonium was found almost exclusively in the small particle
size range.
In total, the categories included in Table 5 account for 50 to 80 percent of the total
aerosol mass determined at the time of collection. Other components, particularly water, oxygen,
and nonsulfate sulfur are thought to account for the remaining fractions.
-------
21
TABLE 5. AVERAGE AEROSOL CONSTITUENTS AT THREE LOCALITIES
Weight Percent According to Aerosol Size
Columbus
Aerosol diameter (Aim):
Constituent
Metals
Carbon
Hydrogen
Halogen
Sulfate
Nitrate
Ammonium
Total
<2
1
17
6
0
19
1
6
50
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36
17
1
1
2
2
0
59
New York
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2
26
6
1
22
4
7
68
>2
37
16
1
6
4
3
0
69
<2
2
25
5
2
14
24
9
81
Pomona
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NC
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(a) NC: large aerosols not collected.
-------
22
Organic Composition of Aerosols
The organic analyses adapted for use in this study provide information concerning the broad
chemical classes and functional groups present in the organic fraction of air particulate. Two
major factors determined the nature of the analyses undertaken:
(1) The statistical treatment of the results ultimately required
i
(2) The limited quantities of sample available for analysis.
Since the results are to be treated statistically, the analyses must be quantitative or
semiquantitative. This application requires numerical data points for the organic composition
comparable to those more commonly obtained for the gas phase, and for the inorganic com-
ponents of particulate. Further, the number of discrete samples analyzed must be large enough
to permit statistical treatment of the results. This puts a practical limitation on the time and cost
that may be expended analyzing each day's sample. Detailed fractionation and analysis can be
expected to provide needed insight into the nature and origin of haze formation. Such analysis,
however, is best applied to carefully selected samples. The basis for such selection can be
developed using a broad-scale analytical scheme applied to a large number of daily samples. The
scheme developed and applied during this report period fulfills, in part, this need for broad-scale
characterization leading to numerically expressible results.
Diurnal sampling limited the quantities of sample available for analysis. Although three
simultaneously operating 20-cfrn sampling systems were used, the organic material extracted from
the <2 Mm aerosols averaged about 14mg per extraction. Within these limitations, both spectro-
scopic and wet-chemical analyses were conducted. In considering the results of the analytical
studies it should be pointed out that the number of data points available at this time is too small
to permit firm interpretation. The results presented should serve, however, to illustrate the types
of numerical data that can be developed for the organic composition, and the types of questions
that a more complete data set of this type might serve to answer. The results are presented
under the following headings:
Solvent-Extractable Particulate Matter
Weight Percent C, H, and N
Infrared Spectra
Aromatic/Aliphatic Ratio
Acid/Base/Neutral Distribution
Functional Group Concentrations.
Recall that six aerosol samples were analyzed: two each from New York City, Pomona,
California, and Columbus, Ohio. Five of the six samples were discrete daily samples. The sixth, a
Pomona sample, was a composite of particulate pooled from three similar days. For each of the
three sites, one sample was collected during a period of relatively high mass loading and the
other during a period of relatively low mass loading. The atmospheric data for these sampling
days are summarized in Tables 2 through 4.
-------
23
Solvent-Extractable Particulate Matter
Sequential Soxhlet extraction using methylene chloride followed by dioxane was used in
order to obtain a wider range of organics than are extractable using the more commonly applied
single-solvent procedure. Dioxane can be expected to dissolve the polar, relatively oxidized
organics normally left behind by benzene or chlorinated solvents. The data shown in Table 6
indicate that the dioxane extractables do indeed represent a significant fraction of the total
extractable organic matter.
As noted in the Experimental Methods section of this report, an experiment was conducted
to verify that dioxane does not extract significant quantities of inorganic salt from the filters.
Several salts were stirred individually with dioxane, and the filtered solvent was lyophilized in
tared flasks. The data indicate that such inorganic salts do not correspond to more than 4
percent of the dioxane extractable matter, and that most likely this value is less than 1 percent
of the dioxane-extractable matter.
Throughout the course of the determinations, solvent and filter blanks were carried through
the reflux and concentration procedure. In calculating the values shown in Table 6, blanks due to
solvent and filter background have been subtracted. Typically, three 6-inch-diameter quartz-fiber
filters were extracted using 100 ml of solvent. Blanks were determined as 0.09 mg (±0.01 mg) per
disk for methylene chloride extractions, and 0.8 mg (±0.3 mg) per disk for dioxane extractions.
The magnitude and variability of the dioxane blank is such that data concerning the dioxane-
extractable matter should be interpreted cautiously. Nevertheless, it is felt that these values are
not entirely spurious, and that they demonstrate that a significant fraction of atmospheric
particulate matter consists of relatively oxidized organic matter. This assertion is supported by
data for weight percent C, H, and N determined for methylene chloride and dioxane-extractable
matter. Although these data are considered more fully in the section below (Table 7), values for
weight percent N in the dioxane-extractable matter roughly parallel those observed for the
methylene chloride-extractable matter. Moreover, CHN analysis of a dioxane-blank residue reveals
only trace N, 44.1 weight percent C, 6.4 weight percent H, and 0.1 weight percent N. Thus,
although there is some doubt as to the precision and reliability of values for weight percent
dioxane-extractable matter, these data are included in the hope that they may be helpful within
the specified limitations.
Considering the data in Table 6 more closely, there appears to be an interesting trend
within the three pairs of days. Notice that for each pair of days, the day with the higher mass
loading has the lower value for weight percent methylene chloride extractable. For two of the
three sites (New York and Pomona), as the weight percent methylene chloride extractable
decreases, the weight percent dioxane extractable increases. A statistically significant trend of
this type would suggest that on days of high mass loading, the organic constituents of particulate
are relatively oxidized ir. comparison with particulate for low-mass-loading days.
Data obtained from infrared spectroscopy and CHN analysis are useful in assessing the
relative composition of the methylene chloride- and dioxane-extractable fractions, and they are
considered below.
Weight Percent C, H, and N
Values of weight percent C, H, N, and [Ol for the methylene chloride and dioxane
extractables are shown in Table 7. The values for weight percent [O] were calculated by
difference from the Pregel-Dumas determination of C, H, and N. As expected, weight percent
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[O] is significantly higher for the dioxane extractables than for the methylene chloride extract-
ables. Overall, the incorporation of oxygen could be a useful indicator of the tendency of a given
atmosphere to oxidize gas-phase or suspended organics. In the statistical tasks planned for the
third-year study, correlation of this parameter will be investigated with various elements of the
gas-phase data.
The data for weight percent C, H, N, and [O] correlate well with results of the infrared
spectroscopic analysis. These results are considered in the following section.
TABLE 7. WEIGHT PERCENT CARBON, HYDROGEN, NITROGEN
AND OXYGEN IN SOLVENT EXTRACTABLE MATTER
Methylene Chloride
Extractables,
weight percent
Site
Columbus
New York
Pomona
Date
July 21
July 26
Aug. 23
Aug. 1 1
Nov. 18
Nov. 10-
13
C
69.3
73.0
69.1
68.8
61.6
69.3
H
9.5
10.2
9.1
9.0
7.7
8.9
N
0.8
0.9
1.1
1.3
1.9
1.3
[0]
20.4
15.9
20.7
20.9
28.8
20.5
Dioxane
Extractables,
weight percent
C
44.4
47.2
54.4
46.6
39.1
50.6
H
6.1
6.0
4.8
5.5
5.0
5.9
N
0.8
0.8
1.6
2.2
1.9
1.6
[0]
48.7
46.0
39.2
45.7
54.0
41.9
Infrared Spectra
Infrared spectroscopic analysis has provided both qualitative and quantitative results. Before
presenting numerical data, the relative composition of various samples will be considered from
the qualitative standpoint.
In the previous section, relative compositions of the methylene chloride and dioxane
extractables were considered. Continuing along these lines, infrared spectra are shown in Figure 4
for methylene chloride and dioxane extractables of particulate collected in Pomona on November
18. Note that the absorbance due to C-H stretching, near 2900 cm'1, is relatively strong for the
methylene chloride extractables and relatively weak for the dioxane extractables. Absorbances
near 1100cm'1 may be assigned to C-O stretching for a variety of compounds including ethers,
lactones, and esters. This region shows significantly stronger absorption with the dioxane
extractables. Both samples show strong absorptions for carbonyl compounds in the region above
IVOOcnr1. These spectra indicate that the dioxane extractables consist of the relatively oxidized
aerosol constituents compared with the less oxidized methylene chloride extractables. It is clear
that with dual extraction, the range of organics being obtained is wider than that obtained with
the usual single-solvent extraction. This is especially significant with regard to determination of
the organic/inorganic ratio. The difficulties associated with determining this ratio are well known.
Data presented earlier in this report indicate that only negligible quantities of inorganic salt are
-------
26
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dissolved by dioxane. The infrared data indicate that the dioxane-extractable organics are indeed
highly oxygenated, polar compounds. Thus, values for total solvent-ex tractable material shown in
Table 6 may closely approximate values for the true percent organic in particulate matter.
The spectra of the methylene chloride extractables suggest some apparent trends in peak
position and intensity. For example, a subtle shift in the position of the carbonyl band appears
to be related to the weight percent oxygen in the sample. Samples with high weight percent
oxygen display a subtle shift of the carbonyl peak to slightly higher frequency. This may be seen
in the spectra shown in Figure 5 (carbonyl peaks are noted with Marker B). This effect is
consistent with a greater population of diketones, keto acids, and keto aldehydes in the samples
having higher oxygen incorporation. As shown in Table 7, the November 18 sample has 28.8
weight percent oxygen, while the November 10-13 sample has 20.5 weight percent oxygen. The
complete set of infrared spectra is included in Appendix C.
A second interesting effect concerns a shoulder near 1770 cm"1 (Marker A). The intensity
of this absorption is more intense for the more oxidized sample in a pair of samples collected at
the same site. The shoulder may be assigned to peroxides, organic carbonates, anhydrides or
lactones. It is most probable for alkyl/aryl peroxides and carbonates.
o o o
II II II
R-C-O-O-C-Ar R-O-C-O-Ar
Peroxide Carbonate
A relatively limited variety of anhydrides or lactones would exhibit this absorption, principally
five- or six-membered strained cyclic species. Thus, this absorption is probably due to peroxides
or carbonates. Organic peroxides might be formed via the free-radical decomposition of per-
oxyacyl nitrates. Since this absorption cannot be unambiguously assigned, we will refer to it as
the "percarbonyl" peak. This is meant to refer to the relatively oxidized character of the
candidate compound types, especially the peroxides and carbonates.
As described in the Experimental Methods section of this report the relative intensity for
various absorbances has been reduced to numerical form. This was done for the carbonyl peak
and the percarbonyl shoulder. Calculated values are shown in Table 8. In each pair of days at a
given site, the sample having the higher weight percent oxygen exhibits stronger carbonyl and
percarbonyl absorptions. For the two samples collected in New York there is a relatively small
difference in weight percent oxygen. This is reflected in correspondingly small differences in the
carbonyl and percarbonyl band intensities for the two samples.
Interesting trends in peak intensity were also observed for absorptions at 1630cm"1 and
1275cm"1 (FigureS, Markers C and D). According to Colthup, et al.,(9) organic nitrates
(RONO2) display strong bands near 1660 to 1625cm"1 (NO2 asymmetric stretching) and
1285 to 1270 cm"1 (NO2 symmetric stretching). Broad absorptions observed at 850cm"1 are
also consistent with organic nitrates. The observed bands, however, might also be attributed to
aromatic amines. Nevertheless, the group frequencies for aromatic amines are quite broad. For
example, the band due to C-N stretching could appear in the region of 1250 to 1380 cm"1. Most
(9) Colthup, N. B., Daly, L. H., and Wiberly, S. E., Introduction to Infrared and Raman Spectroscopy, Academic Press, New York
(1964), p 286.
-------
28
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TABLE 8. COMPARISON OF INFRARED SPECTROSCOPIC DATA AND WEIGHT
PERCENT CHN DATA
Data presented are for methylene chloride extracts.
Site
Pomona
New York
Columbus
Site
Pomona
New York
Columbus
Date
Nov. 18
Nov. 10-13
Aug. 11
Aug. 23
July 21
July 26
Date
Nov. 18
Nov. 10-13
Aug. 11
Aug. 23
July 21
July 26
Weight,
percent [0]
28.8
20.5
20.9
20.7
20.4
15.9
Nitrate Band
(1630cm-1
Weight Relative
Percent N Intensity
1.9 0.43
1.3 0.29
1.3 0.25
1.1 0.19
0.8 0.17
0.9 0.15
Carbonyl Band
Relative Intensity
0.64
0.51
0.50
0.47
0.58
0.38
l Nitrate Band ll
) (1275 cm'1)
Relative
Intensity
0.37
0.24
0.28
0.22
0.19
0.15
Percarbonyl Band^'
Relative Intensity
0.06
0.03
0.13
0.14
0.16
0.07
Average
Intensity,
Bands I and II
0.40
0.27
0.27
0.21
0.18
0.15
(a) Refer to text.
(b) Tentative assignments.
-------
30
primary amines have an NH2 deformation band at 1650 to 1590 cm"1, while secondary aromatic
amines have an NH bending absorption near 1510 cm"1. Most aliphatic secondary amines have no
significant NH bending band above 1470 cm"1. Thus, although various aromatic amines could
give rise to the observed bands at 1275 cm'1 and 1630 cm"1, these absorptions are more
generally assignable to organic nitrates. In considering the data further, we will refer to the
observed absorptions as "tentatively assigned" nitrate bands. The relative intensities for these
bands are also shown in Table 8. There appears to be a correlation between the weight percent
nitrogen in the methylene chloride extractables, and the relative intensity of the bands. This
correlation is of interest even if the observed bands arise from aromatic amines.
Aromatic/Aliphatic Ratio
Aromatic/aliphatic ratio data are expressed as proton-percent aromatic in Table 9. For the
New York and Pomona samples, particulate collected during a period of high mass loading has a
relatively high aromatic content, while that collected during a period of comparatively low mass
loading has an aromatic content below the level of detection (~1 proton percent).
TABLE 9. FOURIER TRANSFORM-NMR ANALYSIS OF
METHYLENE CHLORIDE EXTRACTABLES
Site
Columbus
New York
Pomona
Date
July 21
July 26
Aug. 23
Aug. 1 1
Nov. 18
Nov. 10-13
Mass Loading,
/jg/m3
69.5
34.6
53.4
34.3
52.4
17.5
Proton Percent
Aromatic
9
10
11
<1
13
<1
Data for the aromatic content of the dioxane extractables has been omitted. It was
observed that upon standing, a fine precipitate formed in the concentrated deutero-dioxane
solutions, leading to irregular results.
Acid/Base/Neutral Distr.,* Jon
The acid/b
-------
31
TABLE 10. FRACTIONATION OF METHYLENE CHLORIDE EXTRACTABLE MATTER
Mass Distribution, weight percent
Water Insoluble Fraction Water-Soluble Fraction,
Site
New York
Date
Aug. 11
Aug. 23
Acid
26
30
Neutral
52
50
Base
4
5
Total
18
15
Typically, about 5 mg of sample was subjected to fractionation, and an overall recovery of
approximately 60 percent was achieved. Wet chemical analysis of small samples inevitably results
in some random handling losses. The recovery observed here is consistent with the quantity of
sample used and the nature of the analytical procedure applied. The losses incurred are
acceptably random, and the distribution data obtained appear valid, within confidence limits of
approximately 15 percent of reported values.
Functional-Group Concentrations
The determinations for carbonyl and alcohol were conducted using the neutral fraction of
the methylene chloride extracts. Results of functional group analyses are most often expressed in
terms of some molar value; i.e., total moles, moles per milligram of sample, etc. This is ideal for
the current application, in which an unambiguous measure of specified organic functionalities is
desired. To further clarify the results, the molar values for carbonyl and alcohol have been
converted to a single common basis, and expressed in terms of weight percent oxygen. This was
calculated as shown in the following example:
... . , . , , (mg [O] present as carbonyl) ,,_
Weight percent carbonyl oxygen = / - x 100 .
(mg sample)
Expression of the data in this form permits a direct comparison between weight percent carbonyl
oxygen, weight percent alcoholic oxygen, and weight percent oxygen obtained from the CHN
determination performed on the unfractionated extract. The data expressed in this form are
shown in Table 11. In considering the results of the CHN determination, it was noted that
incorporation of oxygen into organic particulate may be a useful indicator of the tendency for a
given atmosphere to oxidize gas-phase or suspended organics. In seeking statistical correlations
between oxygen incorporation and gas-phase data, it will be valuable to consider oxygen
incorporation into specific functionalities. In terms of fundamental atmospheric reactions, for
example, incorporation of oxygen to yield carbonyl compounds might be related to ozonolysis
of olefins while incorporation of oxygen to yield alcohols might be related to free radical
reactions. In any event, interpretation of the functional-group-analysis data will have to await
forthcoming statistical tasks.
-------
32
TABLE 11. FUNCTIONAL GROUP ANALYSIS OF METHYLENE
CHLORIDE NEUTRAL FRACTION
Site
Columbus
New York
Pomona
Date
July 21
July 26
Aug. 23
Aug. 1 1
Nov. 18
Nov. 10-13
Wt%
[01
MeCl2
Extract
20.4
15.9
20.7
20.9
28.8
20.5
Alcoholic
Oxygen,
wt % in
neutral
fraction
19.3
5.0
3.0
4.6
4.0
4.4
Carbonyl
Oxygen,
wt % in
neutral
fraction
4.9
5.5
4.2
5.2
7.3
3.2
Total
Oxygen,
Alcoholic
Plus
Carbonyl,
wt %
24.2
10.5
7.2
9.8
11.3
7.6
-------
A-l
APPENDIX A
AIR QUALITY DATA FROM COLUMBUS, OHIO,
NEW YORK CITY, AND POMONA, CALIFORNIA
Sampling Site: Fort Hayes, Columbus, Ohio
Sampling Period: July 19, through July 29, 1972
Comments:
(1) The period July 19-21, 1972 was marked by
an unusual inversion in the area, the re-
maining period was more typical of summer
conditions.
(2) Data obtained prior to July 26 was not
suitably formatted for the profile routine.
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B-4
TABLE B-2. ANALYSES OF AEROSOLS «2 A2 /im)
New York (>2 Aim)
Pb
380
90
240
175
140
125
160
150
300
125
200
310
500
325
150
200
440
200
350
325
0.2
0.3
Br
220
102
180
110
120
55
50
30
130
43
35
40
70
50
43
140
80
141
200
150
Composite of
0.06
0.08
Cl
40
75
20
60
20
125
20
75
125
140
200
120
140
80
20
100
120
360
200
175
Large Aerosols
0.8
6.2
S
16,300
13,500
14,000
4,000
11,000
5,500
14,500
4,500
10,000
7,500
6,500
6,600
16,000
6,500
10,000
4,500
6,600
1,100
2,500
2,800
(>2 Aim),
4.8
8.2
soy
13,500
15,650
11,200
1,550
7,800
1,550
15,300
8,000
12,150
7,450
8,450
12,000
15,100
12,200
6,500
1,300
1,500
4,400
6,500
weight percent
2.2
4.0
filter
NOJ
390
195
150
435
600
2,100
550
350
480
500
390
1,200
950
2,400
240
400
2,250
8,000
10,500
1.6
3.3
NHj
3,700
4,200
4,200
460
2,600
850
4,200
1,900
2,450
1,600
2,150
4,000
4,200
3,600
1,800
600
750
3,300
4,400
0.07
0.12
(a)
Analyses for Pb, Br, Cl, S by X-ray fluorescence. Analyses for 504, NO3, NH^ by wet chemistry. Sample
volume ~750 m .
-------
B-5
TABLE B-3. COMPOSITION OF AEROSOLS «2 Jim) BY ELEMENT CATEGORIES
Sample
Date
Mo - Day
Columbus
7-20
7-21
7-22
7-26
7-28
New York
8-11
8-13
8-14
8-18
8-22
8-23
8-24
8-25
8-26
8-29
8-30
Pomona
11-10-13
11-18
11-19
Percents of Total Mass Loading
Metals
1.1
0.9
0.5
1.8
1.1
1.8
1.3
2.0
1.7
0.8
1.8
1.7
1.4
1.1
0.9
1.1
3.7
1.1
0.7
Carbon
13.7
14.7
15.6
23.7
17.2
25.8
21.7
31.0
24.8
25.2
19.4
25.5
22.6
19.2
21.2
30.7
30.5
22.3
21.5
Hydrogen
4.6
4.7
6.4
5.0
9.3
6.2
6.7
7.2
5.1
5.5
3.5
9.2
5.1
4.5
4.3
7.1
3.6
5.6
4.6
Nitrogen
5.8
7.8
7.9
3.0
7.6
4.9
8.9
7.4
7.4
6.1
5.6
7.9
7.6
7.2
4.8
3.6
13.5
18.1
20.6
Sulfur
23.1
24.9
26.7
14.1
31.1
20.6
30.5
15.4
23.1
22.2
15.6
24.2
27.5
13.1
26.0
13.1
10.3
8.0
7.6
Halogen
0.4
0.2
0.4
0.6
0.4
0.6
0.1
0.4
0.4
0.5
0.6
0.3
0.3
0.3
0.2
0.7
4.7
1.3
0.9
Sum of Percents
of Total Mass Total Mass
Oxygen'3'
13.1
19.9
14.9
5.2
16.3
10.1
22.7
19.2
19.8
16.0
14.6
16.5
18.9
20.4
12.0
26.8
9.8
29.5
33.7
Loading
61.8
73.1
72.4
53.4
83.0
70.0
91.9
82.6
82.3
76.3
61.1
85.3
83.4
65.8
69.4
83.1
76.1
85.9
89.6
Loading, ng/m^
90.7
69.5
66.2
34.6
45.4
34.3
60.9
37.4
55.6
43.2
53.4
69.8
74.6
63.4
49.3
43.0
13.7
40.0
46.4
(a) Calculated from the oxy n of nitrate and sulfate only.
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Sample Collected Aug. 23
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C-7
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-650/3-74-002
3. RECIPIENT'S ACCESSIOt*NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
Haze Formation: Its Nature and Origin
June 15. 1973
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
D.F. Miller, W.E. Schwartz, P.M. Jones, D.W. Joseph,
C.M. Spicer. C.J. Riaale. and A. Levy
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle, Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-0276
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency, Research Triangle Park,
North Carolina 27711,
Coordinating Research Council, 30 Rockefeller Plaza,
New York. New York 10020 .
13. TYPE OF REPORT AND PERIOD COVERED
Second Year
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Supplement - First Year Report, PB 212609
16-ABSTRACT Aerosol analyses have been carried out on samples collected in downtown
Columbus in July, in New York City (Welfare Island) in August, and in Pomona, Califor-
nia in November, 1972. Along with the collection of aerosol samples continuous moni-
toring of meteorological conditions and gas-phase composition of the air (CO, N02, S02,
ozone, methane, ethylene, acetylene, and total hydrocarbon) and light scattering were
carried out. Aerosol collection and analysis was primarily concerned with the < 2 ym
diameters particles. An analytical scheme was developed for determining the organic
features of aerosols. Organic data describe the weight-percent solvent extractable
components of the aerosols, weight-percent CHN, IR band intensities, aromatic/aliphatic
ratios, and quantitative functional group analyses for total alcohol and total carbony
Inorganic analyses include trace metals plus Cl, Br, S, Pb, sulfate, nitrate, ammonium
and CHN. Some of the observations suggest: small contributions of automotive emissiorl
to the hydrocarbon burden in New York City, moderate photochemical aerosol formation
in New York, a high positive correlation between light scattering and aerosol mass
centration (<2 ym), significantly different chemical composition for aerosols above
and below 2 ym, predominance of metallic compounds in > 2 ym aerosols, predominance of
organic compounds and sulfates in < 2 ym aerosol in Columbus and New York.
KEY WORDS AND DOCUMENT ANALYSIS
DESCR',JTORS
Air pollution, aerosols, light scattering,
haze, ozone, New York City, Columbus, Ohio,
dioxane and methylene chloride extractions,
automotive, total hydrocarbon.
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
13. DISTRIBUTION STATEMENT
Unlimited
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UNCLASSIFIED
21. NO. OF PAGES
178
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
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C-8
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-------
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