United States
                    Environmental Protection
                    Agency
Air and Energy Engineering
Research Laboratory
Research Triangle Park, NC 27711
                    Research and Development
EPA/600/S7-88/011  Nov. 1 988
v°/EPA          Project  Summary
                    Development  of  a  Breadboard
                    CO2  Laser  Photoacoustic  Toxic
                    Vapor  Monitor
                    G.L. Loper, R.C. Corbin, M.L. Takayama, R.A. Clifton, J.A. Gelbwachs, and
                    S.M. Beck
                     This report describes the development
                    of a breadboard version of CO2 laser
                    photoacoustic detector. The CO2 laser
                    photoacoustic  technique  has been
                    demonstrated to be capable of detec-
                    ting, with high  specificity, a variety of
                    toxic compounds a low parts-per-billion
                    (ppb) levels in multicomponent air
                    samples. The technique can be used for
                    monitoring trace levels of various hazar-
                    dous compounds  in ambient  air
                    samples.
                     Key achievements during the program
                    included: (1) The determination of CO2
                    laser absorption cross-section data or
                    seven compounds of EPA concern that
                    are volatile constituents of hazardous
                    chemical waste. These data show that
                    the laser photoacoustic method could
                    detect these compounds in the ambient
                    air at levels well below their most
                    stringent threshold limit values. (2) The
                    development of an acoustic-frequency-
                    tracking device that allows the use of a
                    resonant photoacoustic cell for the first
                    time under field conditions of changing
                    temperature and humidity. (3) The iden-
                    tification of nonadsorptive materials for
                    use in air sampliong lines and for coating
                    the cell's interior to minimize sample ad-
                    sorption  and reaction losses.  (4) The
                    development of a pyro-electronic device
                    that automatically determines the wave-
                    length of a CO2 laser transition. This
                    device allows laser-wavelength selection
                    to be under closed-loop control. (5) The
                    placement of the breadboard detector
                    under microcomputer control such that
                    all wavelength  selection and the cal-
                    culation  and display of the unknown
                    concentrations  of the gases in the air
                    sample are automatic. (6) The analysis
of laboratory-prepared air mixtures to
determine the performance capability of
the instrument.
  Experiments on  the laboratory-
prepared mixtures showed that the fully
automatic breadboard instrument can
detect hydrazine, a toxic rocket fuel used
by the Air Force, at concentrations as
low as 5 ppb in the presence of three in-
terfering gases at  concentrations as
much as 600 times greater.
  This Project Summary was developed
by EPA's Air and Energy Engineering
Research Laboratory, Research Triangle
Park, NC, to announce key findings of the
research project that is fully documented
in a separate report of the same title (see
Project Report ordering information at
back).

Introduction
  A breadboard version of a CO2 laser
photoacoustic detector has been developed
for the U.S. Air Force  Space Division
(AFSD) and the Environmental Protection
Agency (EPA), Air and Energy Engineering
Research  Laboratory.  This detector can
automatically and simultaneously monitor
low parts-per-billion (ppb) level concentra-
tions of  several  gases  in  laboratory-
prepared air samples with high specificity.
  When fully developed, this detector will
be able to monitor areas that have poten-
tial hazards from toxic compounds will pro-
vide personnel protection not possible at
this time. The Air Force is interested in us-
ing a fully developed version of this instru-
ment for the  rapid detection,  at their
threshold-limit-values (TLVs), of various tox-
ic or carcinogenic compounds that may in-
advertently be present in air samples at
satellite launch sites.

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   Conclusions/Recommendations
   for Future Work
     Several key results were achieved in the
   program. (1) Resonant photoacoustic cell
   designs were shown to offer advantages
   over nonresonant cells in  terms of
   discriminating against window absorption
   and sample flow noise as well as minimiz-
   ing the adsorption of polar compounds. (2)
   Signal  risetime  experiments carried out
   with the photoacoustic detector using 1
   ppm hydrazine flows  indicated that TFE
   Teflon is suitable as a cell-coating-  and
   sampling-line-material to minimize adsorp-
   tion losses of sampled gases. (3) An elec-
   tronic device was developed that automati-
   cally maintains the modulation frequency
   of the laser at the acoustic resonance fre-
   quency of  a resonant photoacoustic  cell.
   This allows resonant  cell designs to be
   used for the first time in field environments
   where the sample gas temperature  and
   humidity may change often. (4) A pyroelec-
   tronic device was developed that can be us-
   ed to determine the CO2 laser wavelength.
   (5) This wavelength  verification device
   allowed the laser's grating and PZT drive
   to be placed under computer control such
   that sample  adsorbance measurements
   can be automatic at any desired set of laser
   tines. The computer can then use the ab-
   sorbence data at m different laser lines to
   calculate the concentrations of n < m com-
   ponents in a mixture using a matrix inver-
   sion program. The program employs a
   library of data containing absorption cross
   sections for the n compounds of interest at
   the m laser lines used for monitoring.
     It should also be possible to use the
   detector in multipoint  monitoring.
         Several areas require resolution before
        a prototype version of the instrument can
        be  developed for  use in  multipoint
        detection:
         (1)  The demonstrated feasibility of using
             CO2 laser photoacoustic detection for
             multipoint detection.
         (2)  Improvement of the response time of
             the instrument so that it can provide
             a 90% full scale response in  less
             than 2 minutes for two compounds of
             EPA concern at concentrations of 200
             ppb  in the   presence  of   two
             interferences.
         (3)  The effects of humidity on the instru-
             ment's detection limits.
         (4)  The effects of aerosols that may be
             present in the air at monitoring loca-
             tions on the instrument's detection
             limits.
(5) CO2 laser absorption cross-section
   data, if not previously determined, for
   new compounds of EPA concern and
   for unexpected interfering  com-
   pounds  that may be  present  at
   monitoring locations.
(6) Verification that the water continuum,
   aerosol, and unexpected interferent
   effects described in items (3) through
   (5), above, are adequately addressed.
(7) Results  of  analyses  of  mixtures
   prepared with air from a site selected
   by EPA.
(8) Field evaluations of the instrument at
   the EPA site.
           G. Loper, R,  Corbin, M, Takayama, R. Clifton, J. Gelbwachs, and S. Beck are
            with The Aerospace Corporation, £1 Segundo,  CA 90245.
           Merrill D. Jackson is the EPA Project Officer (see below).
           The complete  report,  entitled  "Development  of a Breadboard COz Laser
            Photoacoustic Toxic  Vapor Monitor," (Order No. PB 88-224 332/AS; Cost:
            $19.95. subject to change) will be available only from:
                   National Technical Information Service
                   5285 Port Royal Road
                   Springfield, VA 22161
                   Telephone: 703-487-4650
           The EPA Project Officer can be contacted at:
                   Air and Energy Engineering Research Laboratory
                   U.S. Environmental Protection Agency
                   Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
                                                                                                                 f? r
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