Ecological Research Series
APPLICATION OF FOURIER TRANSFORM
SPECTROSCOPY TO AIR POLLUTION PROBLEMS
Interim Report - 1976
Computer-Generated Long-Path
Air Spectra
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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EPA-600/3-77-026
March 1977
APPLICATION OF FOURIER TRANSFORM SPECTROSCOPY TO AIR POLLUTION PROBLEMS
Interim Report- 1976
Computer-Generated Long-Path Air Spectra
by
R. J. Nordstrom
J. H. Shaw
W. R. Skinner
J. G. Calvert
W. H. Chan
W. M. Uselman
The Ohio State University
Research Foundation
Columbus, Ohio 43212
Grant Number R803868-1
Project Officer
John Spence
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U. S..Environmental Protection Agency and approved for
publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U. S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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ABSTRACT
An atlas of computer-generated infrared transmission spectra of the atmosphere
for low humidity (29 percent relative humidity) and high humidity (6 percent
relative humidity) air samples is presented. These spectra extend from 700
cm to 3000 cm , and were computed with a resolution of approximately 0.25
cm . The simulated path length is 3 km through an environment at 1013 mbar
and 296 K.
111
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INTRODUCTION
Analysis of high-resolution infrared spectra of long path lengths of air
samples is a specific and highly sensitive technique for determining the pre-
sence of trace atmospheric gases. However, because of the presence of ab-
sorption lines of naturally occurring gases, especially H~0 throughout the
region from 2-20 ym, it is often difficult to identify features of trace
pollutants umambiguously.
A number of techniques have been used to reduce the spectral interference
due to the permanent gases. In one approach, spectra of air samples which
are known to be "clean" are recorded and spectra of other samples are com-
pared with these. This comparison can be accomplished very quickly if the
absorption due to the permanent gases is nearly the same in both spectra
and if the spectra are recorded digitally with data points of the spectral
transmittance made at the same frequencies in each spectrum. Under these
conditions, dividing one spectra transmission by the other will remove all
of the absorption features which are the same in both spectra and leave only
those features which differ. This technique is especially suitable for
computer manipulation of data collected by the method of Fourier transform
spectroscopy.
The principal requirements for this ratio method are that the spectral resolu-
tions of both spectra be the same; that the temperatures, pressures and path
lengths of both samples be the same; and that the composition of the back-
ground sample be known accurately. For most in_ situ applications of infrared
spectroscopy, however, a background spectrum is difficult (if not impossible)
to record. Fluctuations in the concentrations of CO, C0?, and H_0 make the
ratioing technique near the regions of their infrared bands ambiguous.
Furthermore, if spectral features of a potential atmospheric contaminant are
present in the background spectrum, the pollutant will not be observed in the
ratioed spectrum.
An alternate technique to the direct method of ratioing is to perform a visual
comparison of collected atmospheric transmission spectra to a spectrum which
is calculated from the AFCRL Atmospheric Absorption Line Parameters Compila-
tion. This compilation, which is on magnetic tape, includes the vibration-
rotation and pure rotation transitions of H-O, 0 , CO, C02, CH., N_0, and
0_. Pollutants are not included. Therefore, a spectrum of any desired path
length through an unpolluted atmosphere can be calculated and used as a
reference spectrum.
R.A. McClatchey, W.S. Benedict, S.A. Clough, D.E. Burch, R.F. Calfee, K. Fox,
L.S. Rothman, and T. S. Caring, "AFCRL Atmospheric Absorption Line Parameters
Compilation," AFCRL-TR-73-0096, Air Force Cambridge Research Laboratories
Environmental Research Papers, No. 434 (1973).
-------
There are several laboratory facilities where path lengths of 1.5 km or
better can be obtained in multiple traversal cells. However, no path lengths
in excess of 2 km of synthetic spectra of permanent atmospheric gases have
been reported even though direct in_ situ measurements of 3 km are planned
(P. Hanst, private communication) for a variety of urban atmospheric con-
ditions.
This atlas of infrared transmission spectra is intended to be used in con-
junction with actual long-path spectra. It is hoped that this atlas will not
only help to reveal absorption features which may be due to other atmospheric
constituents, but also will reveal inadequacies in the present knowledge of
the absorption spectra of the permanent molecules in the atmosphere.
Two spectra have been compiled. The first spectrum represents the spectral
transmission through a 3 km path length of air with a relative humidity of
29 percent (7970 ppm). The second spectrum represents the same path length
through an atmosphere with a relative humidity of 65 percent (17,860 ppm).
The concentrations of other atmospheric gases are listed in Table I. For
both spectra the temperature was taken to be 296 K and the pressure was one
atmosphere (1013 mbar).
TABLE I. Physical Parameters Used in Computation of Spectra
Pressure = 1013 mbar
Temperature = 296 K
Concentration
Molecule (by volume)
C02 330 ppm
0* 0.025 ppm
N_0 0.27 ppm
CO 0.075 ppm
CH. 1.6 ppm
Each page of this atlas shows a 28 cm" region. The two spectra are pre-
sented on facing pages, so comparison of the two spectra can be made easily.
The low-water-vapor spectrum appears on thejieft hand pages. The spectra
have a resolution of approximately 0.25 cm . This was accomplished by first
computing a spectrum with infinite resolution, and then numerically conolving
this spectrum with a triangular slit function with a 0.25 cm width. The
atmosphere is opaque for 3 km path lengths in the., spectral regions from
1375 cm" to 1800 cm" from 2275 cm" to 2375 cm" and these regions are
not reproduced.
Synthetic spectra for shorter path lengths than these shown in this atlas
are in excellent agreement with actual air spectra of similar path lengths.
A compilation of actual and synthetic spectra of homogeneous paths up to 1 km
and of slant path solar spectra is being prepared (Nordstrom et^ aiU, in pre-
paration) .
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This atlas of air spectra includes absorptions due to individual spectral
lines up to 20 cm from the line center. Continuum attenuation by H20
absorption, aerosol absorption, and scattering have been neglected. Futher-
more, the pressure-induced absorption by N2 near 2500 cm~ has also been
neglected. For an actual atmospheric sample the fractional transmittances
will be less than is shown in these spectra.
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Fi \' E N J M B E R
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TECHNICAL REPORT DATA
(Please read iHS&uctions on the reverse before completing)
1.
4.
REPORT NO.
EPA-600/3-77-026
TITLE AND SUBTITLE
2.
APPLICATION OF FOURIER TRANSFORM SPECTROSCOPY TO
AIR POLLUTION PROBLEMS
Interim Report -
1976
Computer-Generated Long -Path Air Spectra
7.
AUTHOR(S)
R.J. Nordstrom, J. H. Shaw, W. R. Skinner, J. G.
9.
Calvert, W. H. Chan, and
W. M. Uselman
PERFORMING ORGANIZATION NAME AND ADDRESS
The Ohio State University Research Foundation
1314 Kinnear Road
Columbus, Ohio 43212
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory- RTP, NC
Office of Research £ Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
3. RECIPIENT'S ACCESSIOt»NO.
5. REPORT DATE
March 1977
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1AA603
11. CONTRACT/GRANT NO. '
R803868-1
-. . '
13. TYPE OF REPORT AND PERIOD COVERED
Interim
14. SPONSORING AGENCY CODE
EPA/60Q/09
, * ' ;;" ' "
15. SUPPLEMENTARY NOTES ...... ...... '-,.-.
16. ABSTRACT . '. -
An atlas of computer-generated infrared transmission spectra of the atmosphere
for low humidity (29 percent relative humidity) and high humidity (65 percent; ,
relative humidity) air samples is presented. These spectra extend
from 700
cm . to 3000 cm , and were computed with a resolution of approximately 0:. 25
cm . The simulated path length is 3 km
17
a.
and 296 K.
through an environment at
1013 mbar
':,'- -.-'- ' ". -:> " "
i.- . ' V - 1 "
'. I . .
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
* Air pollution
* Infrared spectra
* Humidity
* Computerized simulation
18
. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b.lDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS {This Report)
UNCLASSIFIED
20. SECURITY CLA;
UNCLASSIFI
ZStThispage)
Hi/
c. COSATI Field/Group
13B
20F
04B
14B
21. NO. OF PAGES
150
22. PRICE
EPA Form 2220-1 (9-73)
146
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