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AP-107

Digitally signed by K.

K. Jagannathan
DN: CN = K.
Jagannathan, C = IN, MEASUREMENTS OF CHEMICAL EMISSIONS
Jagann O = VIT, OU =
Department of Physics USING FTIR SPECTROSCOPY
Date: 2005.10.17
athan 17:36:10 +05'30'

by Hue Phan and Jerry Auth

Introduction

Recently, toxic volatile organic air pollution has become a source of major health concern because
of its widespread presence in the atmosphere. Chemical dump sites, landfills, industrial sites,
chemical spills, auto and rocket exhaust are the usual sources of volatile organic compounds (VOC).
There is growing interest in monitoring ambient air for these toxic compounds. Among the many
instrumental techniques that have been developed for environmental monitoring, FTIR spectroscopy
is one that has unique advantages. This paper describes the application of open path Fourier
Transform Infrared Spectroscopy (FTIR) for measurements of ambient air volatile organic
compounds. It is important to have a stable spectrometer system with high sensitivity so that the
compounds of interest may easily be identified and quantified. This experiment focuses on
measuring the controlled release of volatile gas over a grass covered athletic field at the University
of Kansas. The instrument used was a Midac portable emission spectrometer. This paper describes
the Midac open path FTIR spectrometer for on-site pollution analysis and presents various IR gas
traces that were measured using a long path configuration.

Instrumentation
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The FTIR instrument used in this experiment was the Midac Outfielder (M2400) portable emission
spectrometer. It is the combination of a Midac interferometer and a liquid nitrogen cooled mercury
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cadmium telluride (MCT) detector. The Midac spectrometer is capable of 0.5cm resolution and is
controlled by an IBM compatible AT computer. The optical unit was mounted on a basic tripod
which was placed on the sampling path at the athletic field of the University of Kansas. The
infrared source (a 1660K silicon carbide glower) was located across the field about 100 meters away
from the spectrometer. The beam was collimated into the optical unit and subsequently through
the interferometer to the detector. For this test, a telescope was not used in conjunction with the
spectrometer system. However, for infrared measurement with pathlengths longer than 100 meters,
coupling a telescope with the spectrometer system is recommended. The signal-to-noise ratio of
the spectral data would increase by a factor of two with the use of a telescope (a 10 inch
Newtonian telescope). The source and FTIR spectrometer setup was aligned by hand; the source
was moved using the sighting scope until the center of the beam struck the spectrometer. The
spectrometer was then aligned by adjusting the position of the gear head mounted on the tripod.
This fine alignment was being done while the spectrometer was continuously scanning (Spectra
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Calc's "align" mode). A series of 200 scans was collected for each run. The samples were collected
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at 1cm resolution. The data acquisition

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time for each run was approximately 5 minutes. All sample collection and spectral data processing
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were handled using Galactic's Spectra Calc software.

Experiment

The experiment was conducted on an athletic field at the University of Kansas. The device used for
generating the gases and releasing them was designed and constructed at the University of Kansas.
This device may be set to release a known concentration of gas over a predetermined time interval.
This gas emitter was located about 50 meters away from the sampling line. Figure 1 shows a
generalized diagram of the equipment set up.

Figure 1. Sampling setup on the open field.

The instrumental emission reference and a background were measured before the gases were
released. Both single compounds and mixtures were generated for gas releases. The standard gases
studied were trichloroethylene, trichloroethane, dichloromethane and trichlorotrifluoroethane. The
emission rates of gases at unknown concentrations varied from 100ml/min to 200ml/min. The VOCs
generator was operated in a 20 minute cycle throughout the day: 10 minutes of gas release and a
10 minute pause. The sample measurements were obtained consecutively over 5 minute intervals
throughout the day. The instrumental emission reference was subtracted from the background and
sample spectra to eliminate the emission that is not due to the IR source. Applying the
instrumental emission correction can increase the absorbance significantly for lower frequencies,
producing more correct absorbances. The sample single beam spectra were then ratioed against the
background. The absorbance spectra of unknown VOC release with a pathlength of 100 meters are
presented on figures 2 through 7. The concentration and identification of the gas spectrum is
shown on each plot which were determined by using the Infrared Analysis' Hanst Quantitative
Reference Spectra Library. The calculated

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concentrations range from 50 to 400ppb.

Figure 2 shows the gas spectrum which was determined as trichloroethylene at 370ppb
concentration. The spectra of pure compounds were easily identified by confirming with the
reference standards. The concentration of each gas trace obtained was quantified using Hanst
Quantitative Reference spectra. Figure 3 shows the gas trace of trichloroethane with the
concentration measured at 172ppb using the same method. The spectrum of dichloromethane
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shown on figure 4 was easily recognizable by two major absorbances at 760cm and 1270cm . A
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series of sharp bands overlapping around the 1270cm band were due to water vapor. The negative
absorbance bands of water vapor shown on figures 5, 6 and 7 are due to a decrease in water vapor.

Figure 2. Spectrum of unknown VOC release.


Compound: trichloroethylene relative concentration: 370ppb

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Figure 3. Spectrum of unknown VOC release.
Compound: Trichloroethane
Relative concentration: 172ppb

Figure 4. Spectrum of unknown VOC release.


Compound: Dichloromethane
Relative concentration: 300ppb

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Figure 5. Spectrum of unknown VOC release.
Compound, Conc.: Dichloromethane, 194ppb
Tetrachloroethylene, 84ppb

Figure 6. Dichloromethane subtracted spectrum


(spectrum #5 - spectrum #4)
==> Compound: tetrachloroethylene, 84ppb

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Figure 7. Spectrum of unknown VOC release.
Compound, Conc.: Trichlorotrifluoroethane, 86ppb
Trichloroethane, 90ppb

These negative bands are commonly seen from the fluctuations of the amount of water vapor
and/or carbon dioxide (CO2) in ambient air.

Figure 5 presents one of the gas mixture spectra. The dichloromethane component in this mixture
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was positively identified by the assigned absorbance bands at about 760cm and 1270cm .
Typically, the classical approach to the analysis of a mixture prior to spectral interpretation involves
absorbance subtraction of any known components from the mixture. The spectrum of the
recognized dichloromethane compound obtained earlier was subtracted from this gas mixture
spectrum. The difference spectrum is shown on figure 6 which was then identified as
tetrachloroethylene by standard spectral search method. These components were then quantified
using Hanst quantitative reference spectra data base. Similar calculations were applied to the gas
mixture spectrum shown on figure 7. The components were identified as trichlorotrifluoroethane
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and trichloroethane at 86ppb and 90ppb respectively. The absorbance bands at 725cm and
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1090cm marked on the spectral trace are due to trichloroethane component. All other bands are
due to the trichlorotrifluoroethane component. This compound can also be easily identified by
band assignments.

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Conclusions

The field portable FTIR spectrometer system has been developed for on-site monitoring of ambient
air for toxic volatile organic compounds. This paper has presented a description of the FTIR
spectroscopy technique and its application to the analysis of the toxic chemical emissions in the
atmosphere. The results have demonstrated the performance of the open path FTIR spectrometer
system and its ability to measure atmospheric trace gases at ambient concentrations. The analysis
of compounds can be made at ppb levels. Qualitative and quantitative results were obtained for
both single component samples and mixtures at 100 meters path length. Using a longer path
length would increase the detection sensitivity. However, in such a case, the intense absorbances
due to water vapor and CO2 would complicate the spectral data in some wavelength regions. In
addition, a telescope would improve sensitivity. As mentioned earlier, the Midac spectrometer
system and the IR source used in this experiment was set up without using a telescope. If a
telescope had been used, the signal-to-noise ratio would be increased significantly. The results of
this study have demonstrated the feasibility of using open path FTIR spectrometry for the real time
detection of trace organic compounds in ambient air. Furthermore, the effects of other variables
on the measured concentrations such as wind velocity, wind direction, ambient temperature and
humidity also need to be studied in more detail.

Acknowledgments

The work described in this paper was performed at the University of Kansas in cooperation with the
Civil Engineering Environmental Health Laboratory at University of Kansas