Table Of ContentAIR POLLUTION RESEARCH REPORT 18
MONITORING OF GASEOUS POLLUTANTS
BY TUNABLE DIODE LASERS
The Symposium was organized in collaboration with the Concerted Action
"Physico-Cllemical Behaviour of Atmospheric Pollutants" COST 611,
Commission of the European Communities,
Directorate-General "Science, Research and Development"
Commission of the European Communities
MONITORING OF
GASEOUS POLLUTANTS BY
TUNABLE DIODE LASERS
Proceedings of the International Symposium
held in Freiburg, F.R.G. 17-18 October 1988
organized by the Fraunhofer Institut
fUr Physikalische Messtechnik (Freiburg)
under the auspices of
the Commission of the European Communities
Edited by
R. GRISAR, G. SCHMIDTKE, M. TACKE
Fraunho/er Institutfor Physikalische Messtechnik, Freiburg, F.R.G.
and
G.RESTELLI
Commission o/the European Communities,
loint Research Centre, Ispra, Italy
KLUWER ACADEMIC PUBLISHERS
DORDRECHT I BOSTON I LONDON
ISBN-13: 978-94-010-6934-2 e-ISBN -13: 978-94-009-0989-2
DOl: 10.1007/978-94-009-0989-2
Publication arrangements by
Commission of the European Communities
Directorate-General Telecommunications, Infonnation Industries and Innovation,
Scientific and Technical Communications Unit, Luxembourg
EUR 11956
© 1989 ECSC, EEC, EAEC, Brussels and Luxembourg
Softcover reprint of the hardcover 1st edition 1989
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INTRODUCTION
In 1986, an International Symposium on Monitoring of Gaseous Pollut
ants by Tunable Diode Lasers was organized by the Fraunhofer-Institut fuer
Physikalische Messtechnik in Freiburg, FRG, and held at this institution
on November 13-14, 1986.
The papers presented at that occasion extensively covered the applications
of tunable diode laser spectroscopy (TDLS) to the analysis of trace and
exhaust gases together with the latest improvements brought to the tech
niques used.
It was generally consented by the participants that meetings of this kind
are of major importance and should take place on a regular basis.
The organizers were thus encouraged to plan a Second International Sympo
sium on Monitoring of Gaseous Pollutants by Tunable Diode Lasers which was
held two years later on October 17-18, 1988, again in Freiburg. In addi
tion to the main subjects treated in the first Symposium, the Scientific
Programme this time presented a session on the development of lead chalco
genide lasers. Once more, only a limited attention was given to applica
tions in high resolution molecular spectroscopy. In order to complete the
update, sessions on components and techniques were included in the Pro
gramme. As for the previous Symposium, some space was also given to alter
native optical techniques. This time, in particular contributions on laser
photoacoustic detection were included.
The volume contains the 29 papers presented at the Symposium, grouped
in four sections:
- Atmospheric Trace Gas and Exhaust Gas Analysis:
- Lead Chalcogenide Diode Laser Development:
- Components and Techniques:
- Special Applications.
Let us try to briefly summarize the results of this symposium and in
particular to answer the questions: what is the state of the art and where
do the trends go?
As for the first symposium in 1986, the sessions on trace gas and exhaust
gas analysis were the central part of the meeting and of central impor
tance.
The highlights of these sessions clearly Showed, in parallel to the demon
strated capability of these devices to perform trace gas measurements in
ambient air, a trend towards "applications in industrial environments".
Hazardous gases were detected by open path techniques achieving surveil
lance of large areas or waste deposits even with operation of TDL instru
ments in adverse environments. On the other hand the performance of in
struments for gas exhaust analysis were shown validated by functional
tests executed in the industry.
The status of TDLS is characterised by a wide range of activities. Indus
trial applications are being established, but at the same time much effort
is spent on fundamental research in the laboratories as was illustrated in
the sessions on components and techniques and on special applications. The
trend will be certainly towards an increasing number of applications
whereas the overall spectrum of projects will change only gradually.
-v-
This situation is exemplified by the review presented on the imple
mentation of FM spectroscopy. This promising technique introduced to TDLS
only recently was in fact also critically commented on the present limita
tions of TDLS in general.
The overall impression is that TDLS has technically reached a high stan
dard, but a number of improvements both on techniques and components can
still be expected.
The key component, which is the diode laser, is still the obj ect of in
tense efforts. In a session devoted exclusively to this subject, invited
talks by members of the three major groups working in this field in the
USA, in Japan and in the FRG reported on the progress in lead chalcogenide
diode laser technology and resulting laser improvements. Molecular beam
epitaxy consistently led to higher cw operating temperatures above 170 K
in all three laboratories. Pulsed operation up to 290 K was reported. At
this stage, liquid-nitrogen cooling of diode lasers seems more and more
attractive for a number of applications and even thermoelectric cooling
could be envisaged for particular cases. Further trends aim at better con
trolled mode quality and beam geometry which were stressed to be essential
for achieving ultimate sensitivity in trace gas analysis.
Further contributions dealt with the improvement of TDL components or
operational techniques: this is the case of the design and realisation of
a high precision White cell and of a sophisticated computer controlled
spectrometer. The situation in regard to the important goal of establish
ing frequency calibration tables for TDL was also reviewed. Special appli
cations in the study of transient molecules and of combustion gases were
also presented.
Finally some light was shed on techniques competing with TDLS in trace gas
detection as e.g. laser magnetic resonance or photoacoustic detection with
high power IR lasers, thus demonstrating that in view of sensitivity TDLS
may well be complemented by other methods in some cases.
In conclusions, this book joins the previous one containing the
papers presented at the First Symposium and represents once more an up
dated state of the art covering the most important aspects in the develop
ment of components and techniques as well as in the design and operation
of instruments for the measurement of trace gases by tunable diode lasers.
THE EDITORS
The Proceedings of the First International Symposium were published in
1987 in this same Series under the CEC sponsorship:
Air Pollutant Research Reports
Monitoring of Gaseous Pollutants by Tunable Diode Lasers
R. Grisar, H. Preier, G. Schmidtke and G. Restelli Editors.
D. REIDEL Publ. Co. 1987.
- vi-
CONTENTS
INTRODUCTION v
I. ATMOSPHERIC TRACE GAS AND EXHAUST GAS ANALYSIS
Long-path diode laser measurement of industrial air pollution 3
R.H. PARTRIDGE and I.H. CURTIS
National Physical Laboratory, Teddington, Middlesex,
U.K.
Measurements of atmospheric HCl and NH3 with a mobile tunable 16
diode laser system
D.J. BRASSINGTON
Central Electricity Generating Board ,Central
Electricity, Research Laboratories, Leatherhead,
Surrey, U.K.
Atmospheric trace gas measurement on the Schauinsland 25
surveying station
G. SCHMIDTKE, U. KLOCKE, M. KNOTHE, W. KOHN,
W.J.RIEDEL and H. WOLF
Fraunhofer-Institut fur Physikalische Messtechnik,
Freiburg, FRG.
Tunable diode laser absorption spectrometry as a reference 36
method for tropospheric measurements
H.I.SCHIFF and G.I.MACKAY
Unisearch Associates, Limited, Concord, Ontario,
CANADA.
Functional testing of a multi.component diode laser 46
spectrometer (DIOLA) in comparison with the conventional
technology
G. LACH, H. LUF and J. WINCKLER
Volkswagen A.G., Wolfsburg, FRG.
Dynamic car exhaust gas analysis using tunable IR diode 61
lasers
H. WOLF, R. GRISAR, U. KLOCKE, W. J. RIEDEL and
R. WISSLER
Fraunhofer-Institut fur Physikalische Messtechnik,
Freiburg, FRG.
Measurement of trace species in the remote maritime boundary 68
layer using TDLAS
G.W. HARRIS, J.P. BURROWS, D. KLEMP and T. ZENKER
Max-Planck-Institute for Chemistry, Mainz, FRG.
II. LEAD CHALCOGENIDE DIODE LASER DEVELOPMENT
Development of lead chalcogenide lasers at Fujitsu 77
K. SHINOHARA
Fujitsu Laboratories Ltd., Atsugi, JAPAN.
Status of lead salt diode laser development at Spectra 85
Physics
H. PREIER, Z. FElT, J. FUCHS, D. KOSTYK, W. JALENAK
and J. SPROUL
Laser Analytics, Inc., Bedford, MA, USA.
Recent results in lead-salt laser development at the IPM 103
M. TACKE
Fraunhofer-Institut fur Physikalische Messtechnik,
Freiburg, FRG.
III. COMPONENTS AND TECHNIQUES
High frequency modulation spectroscopy with a lead salt diode 121
laser
P. WERLE, F. SLEMR and M. GEHRTZ
Fraunhofer Institut fur Atmospharische
Umweltforschung, Garmisch-Partenkirchen,FRG
Ch. BRAUCHLE
Institut fur Physikalische Chemie der Universitat
Munchen, Munchen, FRG.
Current status of frequency calibration tables (0 to 122
3000 cm-1) for tunable diode lasers from heterodyne
frequency measurements
J.S. WELLS and M.D.VANEK
Time and frequency Division, National Institute
of Standards and Technology (former National
Bureau of Standards), Boulder, USA.
A.G. MAKI
Molecular Spectroscopy Division, National
Institute of Standards and Technology,
Gaithersburg, USA.
M. SCHNEIDER and A. HINZ
Institut fur Angewandte Physik der Universitat
Bonn, Bonn, FRG.
Oxygen measurement with GaAIAs diode lasers 138
R.GRISAR, Th.PFANDLER and W.J.RIEDEL
Fraunhofer-Institut fur Physikalische Messtechnik,
Freiburg, FRG.
Absorption spectrometry for atmospheric methane:techniques 146
for higher sensitivity.
R.KOGA
Department of Electricity and Electronics, Facul ty of
Engineering,Okayama University, Tsushima ,Okayama, Japan.
Computer controlled diode, laser spectrometer 156
R. BRUGGEMANN, M. PETRI and W. URBAN
Institut fur Angewandte Physik, Universitat Bonn,
Bonn, FRG.
-viii -
fin anastigmatic White cell for IR diode laser spectroscopy 165
W.J.RIEDEL, M.KNOTHE, W. KOHN and R.GRISAR
Fraunhofer-Institut fur Physikalische Messtechnik,
Freiburg, FRG.
CO-laser-magnetic -resonance facility for sensi ti ve detection 172
of radical trace gases (NOX' H02?)
W. BOHLE and W. URBAN
Institut fur Angewandte Physik, Universitat Bonn,
Bonn, FRG.
High-sensitivity frequency modulation spectroscopy with lead 180
salt diode lasers.
D. E. COOPER and C. B. CARLISLE
SRI International, Menlo Park. California, USA.
On the adsorption properties of ammonia to various surfaces 196
H. SAUREN, H. JALINK and D. BICANIC
Dept. of Physics and Meteorology, Agricultural
University, Wageningen, NL.
B. VAN HOVE and W. TONK
Dept. of Plant Physiology, Agricultural University,
Wageningen, NL.
IV. SPECIAL APPLICATIONS
Application of tunable diode lasers to laboratory studies of 205
atmospheric chemistry : kinetics of the reaction N03+N02 -->
NO+N02+02
J. HJORTH, F. CAPPELLANI, C. NIELSEN and G. RESTELLI
Commission of the European Communities, Joint Research
Centre, Ispra Establishment, Ispra, I.
Monitoring of metal oxides in low pressure flames 219
H.G. HEDDERICH and C.E. BLOM
Physikalisch-Chemisches Institut, Justus Liebig
Universitat, Giessen, FRG.
Diode laser spectroscopy of transient species in electric 225
discharges
P.B. DAVIES, S.A. JONHSON, P.M. MARTINEAU and
R.J. STICKLAND
Department of Chemistry, University of Cambridge,
Cambridge, U.K.
Diode laser application for meaEurements of foreign-gas 240
broadening of v2 band in NH3
G. BALDACCHINI
ENEA - DIP.TIB, U.S. Fisica Applicata, eRE Frascati,
Frascati, Roma, I.
G. BUFFA and O. TARRINI
Dipartimento di Fisica, Universita di Pisa, Pisa, I.
-ix-
Carbon monoxide concentrations and temperature measurements 246
in combustion gases
B. ROSIER, P. GICQUEL and D.HENRY
Office National d' Etude et de Recherche Aerospatiale,
Chatillon, F.
D. COPPALLE
Universite de Rouen, Mont Saint-Aignan, F.
V. PHOTOACOUSTICS
Line strength measurement using optoacoustic spectroscopy 263
K.STEPHAN and W. HURDELBRINK
Insti tut fur Technische Thermodynamik und Thermische
Verfahrenstechnik der Universitat Stuttgart,
Stuttgart,FRG.
A novel wide temperature range photoacoustic cell for 274
molecules in the vapour phase
H. JALINK and D. BICANIC
Department of Physics and Meteorology, Agricultural
University, Wageningen, NL.
Photoacoustic investigation of pesticides 280
D. BICANlC, H. JALINK and H. 3AUREN
Photoacoustic Laboratory, Dept. of Physics and
Meteorology, Agricultural University, Wageningen, NL.
F. HARREN and J. REUSS
Dept. of Molecular and Laser Physics, Catholic
University, Nijmegen, NL.
B. ZUIDBERG
Dept. of Physics, Gadjad Mada University, Yogjakarta,
Indonesia.
E. WOLTERING
Sprenger Institute, Ministry of Agriculture and
Fischeries, Wageningen, NL.
Sensitive photoacoustic trace detection of ethylene 289
F. HARREN, F. BIJNEN, C. LINDSNBAUM and J. REUSS
Dept. of Molecular and Laser Physics, Catholic
University, Nijmegen, NL.
L.A.C.J. VOESENEK and C.W.P.M. BLOM
Dept. of Experimental Botany, Catholic University,
Nijmegen, NL.
Photoacoustic detection of ethylene evolution in emasculated 294
Cymbidium and Oncidium orchid flowers.
E.J. WOLTERING
Sprenger Institute, Ministry of Agriculture and
Fisheries, Wageningen, NL.
F. HARREN
Dept. of Molecular and Laser Physics, Uni versi ty of
Nijmegen, NL.
LIST OF PARTICIPANTS 297
INDEX OF AUTHORS 305
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