Atmospheric Ozone: Proceedings of the Quadrennial Ozone Symposium held in Halkidiki, Greece 3–7 September 1984

868 Pages·1985·31.96 MB·English

by  A. Ghazi (auth.), A. Ghazi (eds.), C. S. Zerefos

Atmospheric Ozone
PROGRAM COMMITTEE:
C.L. Mateer, C.S. Zerefos (co-chairmen)
J.J. Barnett, R. Bojkov, G. Brasseur, J. Chang, H. U. Dutsch, P. Fabian,
A. Ghazi, R. Hudson, I. Isaksen, K.F. Kunzi, J. London, H. Mantis,
G. Megie, J.A. Pyle, C.D. Walshaw.
LOCAL ORGANIZING COMMITTEE:
Honorary Chairman: E.G. Mariolopoulos
Chairman: C.S. Zerefos
A. Anagnostopoulos, A. Ghazi, H.T. Mantis, D. Metaxas, C.C. Repapis,
G. Vassilikiotis.
CO-SPONSORS. American Meteorological Society
Commission of the European Communities
IAMAP
World Meteorological Organization
Ministry of Northern Greece
Chemical Industries of Northern Greece
HOSTS: Academy of Athens, Laboratory of Atmospheric Physics,
Thessaloniki and University of loannina, Greece
Publication arrangements: P.P. Rotondo,
Directorate-General Information Market and Innovation,
Commission of the European Communities, Luxembourg
International Ozone Commission
(IAMAP)
Atmospheric
Ozone
Proceedings of the Quadrennial Ozone Symposium
held in Halkidiki, Greece, 3-7 September 1984
Edited by
c. s. ZEREFOS
Laboratory ofA tmospheric Physics,
University of Thessaloniki, Greece
and
A. GHAZI
Commission of the European Communities,
Directorate-General for Science, Research and Development,
Brussels, Belgium
D. REIDEL PUBLISHING COMPANY
... 411
A MEMBER OF THE KLUWER " ACADEMIC PUBLISHERS GROUP
DORDRECHT/BOSTON/LANCASTER
for the
COMMISSION OF THE EUROPEAN COMMUNITIES
Library of Congress Cataloging in Publication Data
Main entry under title:
Ozone Symposium (1984 : Chalkidiki, Greece)
Atmospheric Ozone.
At head of title: International Ozone Commission, IAMAP.
Co-sponsors: American Meteorological Society and others.
1. Atmospheric ozone-Congresses. 1. Zerefos, C. S. (Christos S.)
II. Ghazi, A., 1940- III. Commission of the Europe}1D Communities.
IV. American Meteorological Society. V. Title.
QC879.7.G74 1984 551.5'112 85-1731
ISBN-13 :978-94-0 I 0-8847-3 e-ISBN-13:978-94-009-5313-0
DOI:IO.1007/978-94-009-5313-0
Publication arrangements by
Commission of the European Communities
Directorate-General Information Market and Innovation, Luxembourg
EUR 9574
© 1985 ECSC, EEC, EAEC, Brussels and Luxembourg
Softcover reprint of the hardcover 1s t edition 1985
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INTRODUCTION
This volume contains progress papers in atmospheric ozone research which were presen-
ted at the Ouadrennial Ozone symposium held in Greece from 3 to 7 September, 1984. These pa-
pers are grouped in nine chapters corresponding to the nine sessions of the symposium. The
Editors proVide the following summary of the highlights for each chapter; this summary has
been prepared after consulting the papers submitted for publication as well as session summa-
ries kindly provided by the following session chairmen: R. Bojkov, H. DOtsch, P. Fabian, J. Hai-
gh, I. Isaksen, L. Kaplan, K. KOnzi, J. London, H. Mantis, C. Mateer, A. Matthews, G. Megie and
J. Russell.
Chapter 1 entitled: Chemical - radiative - dynamical model calculations includes results
from recent developments in modeling techniques. The chapter begins with the results from a
two - dimensional model using isentropic coordinates. With prescribed diabatic heating rates
and a judicious choice of eddy diffusion coefficients this method can produce realistic fields of
several stratospheric species. Three dimensional model simulations come next which demon-
strate ozone transport by the stationary and transient components of the flow and emphasize
the role of wave transport of ozone during a sudden stratospheric warming.
The problem of chemical model validation is addressed in several different approaches.
The trajectory method allows a direct comparison of the change in concentration of ozone but
the coverage of satellite ozone observations is such that ozone concentration in the same
mass of air are obtained only at 8 to 10 day intervals. Validation of model predictions is of
course dependent on the accuracy of computed trajectories. The other methods compare point
calculations with measurements. Using the same set of reaction rates, all three methods prod-
uce lower values for ozone than are measured, indicating inconsistencies in the derived fields
of other species (particularly of the NOy family) and suggesting that some of the reaction rates
might be reassessed. In addition to the chemical model validation, two new approaches to cal-
culating photochemical acceleration coefficients are given.
In a two - dimensional analysis of the quasi-biennial oscillation (OBO) of ozone it was as-
sumed that the ozone OBO is forced by the tropical stratospheric OBO wind circulation which
is modeled from observations. The derived amplitude and phase of the ozone qBO compares
well with satellite observations. Another presentation shows how inclusion of a representation
of the semi-annual oscillation in a two - dimensional model improves the derived fields of CH.
and Np. A study of the effect of EI Chichon volcanic cloud on ozone and temperature demon-
strates that the inclusion of volcanic aerosol in a two - dimensional model can produce tempe-
rature increases in the lower stratosphere with strong latitudinal gradients and hence implica-
tions for changes in zonal wind structure. The model predicts an approximate 2% depletion of
globally averaged total ozone following the eruption.
The chapter includes two other groups of papers; diagnostic methods and applications of
the 'Limb Infrared Monitor of the Stratosphere' (LlMS) data and analysis of past and future
trends in atmospheric ozone changes. The need for simultaneously measured data on multiple
species, for evaluating the theory of ozone chemistry is emphasized and it is shown that to a
large extent the LlMS data set is consistent with current photochemical theory. There remains
the difficulty of explaining the low level of HN03 in the upper stratosphere as observed by LlMS
and other in situ measurements, and the need for better understanding of polar winter dyna-
mics.
The first chapter concludes with papers concerned with estimating ozone trends both past
and present and projectiAg man's impact on future trends via multiple scenarios. The choices
of estimated trends for CD2, CH., NP, NOx and CFC's are the dominating factors in these ana-
lyses. Trends in both the total ozone amount and its vertical distribution are reported to be in a-
greement with the most recent statistical analysis of ground - based data, although upper stra-
tospheric temperature changes appear to be smaller than observed. The nonlinear dependence
of ozone column to changes of CIO an NO are also studied in multiple scenarios. Future ozo-
ne trends depend heavily on the assumedXtrends in many trace species, especially nitrogen
containing species. It is clear that projections of future trends in the trace species are required.
Another nonlinear effect predicted with large chlorine increases is a significant long-term ozo-
ne decrease, although near term changes may be small.
Ozone Symposium - Greece 1984 -v-
Chapter 2 includes recent results on the climatic effects of secular changes in trace spe-
cies as estimated from one - dimensional model calculations with radiative - convective ad-
justments and fixed cloudiness_ The importance of taking into account coupling effects of tem-
perature, trace gas concentrations, photochemistry and radiation, which has largely been igno-
red in recent impact simulation studies, is stressed. The combined calculated effects on sur-
face temperature of expected anthropogenic increases in CH 4, Np and Freon II and 12 in-
cluding the resultant redistribution of ozone between the years 1980 and 2010 are found to be
equal to that calculated for expected increases in CO 2, The approximate equality between the
greenhouse effect from CO 2 increase and that of the other combined anthropogenic gases is
stressed in all three papers in this chapter.
Details of the differences between the results of various models could be attributed to
their different scenarios and differences in their physical parameterizations. Feedback interac-
tions with clouds, include the possibility that the effect of increased cloudiness can be to red-
uce the net heating, rather than enhance it, as generally believed. In addition to the feedback
coupling of the various physical processes, it is shown that volcanic aerosols can affect the
ozone indirectly by altering the atmospheric temperature structure and thus the photochemical
coupling. The resulting radiative effects would in turn modify the initial temperature changes
due to increased CO2 and volcanic aerosols.
Chapter 3 includes the results of measurements on key stratospheric constituents obtai-
ned by different observational systems in ground - based, balloon, rocket and satellite experi-
ments. There have been a number of recent extensive intercomparison campaings namely the
MAP - Globus in southwestern Europe and the Balloon Intercomparison Campaign (BIG) in the
U.S. Although the data from the MAP-GLqBUS compaign have become available only recently,
initial inter comparisons show agreement of NP, CH4 and CFCI3 from cryogenic samplers. The
time variability of nitric oxide from several experiments which are remarkably consistent over
several hours, suggest that the variability is real. The next MAP-GLOBUS campaign. in 1985 will
be a smaller effort focused on NO compounds.
Ne;"" results, based on cry~genic in-situ sampling of stratospheric halocarbon com-
pounds, show a very rapid decrease of chlorinated compounds with altitude between 20 and 30
km. This large decrease is not predicted in model calculations and may be due to a problem ei-
ther in I-D model calculations of vertical transport or to instrummental bias. The latter is less
likely since the same results are reported independently by different groups. An additional no-
teworthy cryogenic sampler result is the observation that molecules with higher flourine con-
tent decrease less rapidly with altitude than those with less flourine, suggesting that these mo-
lecules reside for longer times in the stratosphere.
In addition to the results from the international campaigns, the LlMS experiment on board
Nimbus 7 spacecraft provided the basis for constructing a stratosphere - mesosphere climato-
logy of N0
2 in both hemispheres for the period November 1978 through May 1979. Column N02
amounts are considerably larger in the summer than in the winter hemisphere Steep latitudinal
gradients occur in winter high latitudes in situations where the height field is dominated by
wave number one. Results are next given from recent flights with the Oxford balloon - borne
pressure modulator radiometer which measures stratosphere NO and N02 by sensing emission
from the atmospheric limb.
The global distribution of NO is retrieved from whole spectrum scans of the SBUV in-
strument on board Nimbus 7. The NO vertical column above the 1m b level is almost constant in
the summer hemisphere and increases towards the winter pole. Another paper estimates that a
thermospheric NO source of up to 50 ppbv at the 2 mb level is required to match rocket ozone
profiles observed in the upper stratosphere and mesosphere. New measurements on N02 and
N0 provided satisfactory comparison with modelled diurnal variation of these important spe-
3
cies. In another paper an unknown N03 sink in the lower stratosphere was proposed to explain
the rapid decrease of N03 below 30 Km.
New ground - based microwave data of stratospheric chlorine monoxide (CIO) show that
CIO disappears faster in the lower stratosphere than in the upper stratosphere. This variation
and its magnitude is in good agreement with current models suggesting that to first order the
chemistry is quite well understood.
The chapter also includes reports of several campaigns of intercomparisons of measure-
ments of trace species by various observational techniques.
-vi -
Chapter 4 deals with the analyses of ozone observations from various data sets and on va-
rious times scales. It seems that backscattered UV measurements will be the major source of
long term global information on total ozone and on ozone profiles. There are now about 15
years of satellite ozone data available which need proper interpretation. In general, the agree-
ment between different satellite ozone measurements is good and a further improvement in
such agreement is expected from reprocessing of satellite data incorporating new absorption
coefficients.
Analyses of ozonesonde, umkehr and of satellite ozone data show evidence of stratosphe-
ric ozone decrease following the erruption of EI Chichon. In fact the behaviour of total ozone at
mid - latitudes is shown to be anomalous after the volcanic eruption and the first half of 1983 is
probably a period of extremely low values of total ozone over middle and high latitudes of the
northern hemisphere. However, there is no convincing physical explanation for this anomalous
ozone behaviour. In addition to these real ozone decreases there are also errors caused by the
volcanic cloud to ozone measurements by the Umkehr method. New evidence has been present-
ed on a strong anticorrelation between the volcanic aerosol and columnar S02 amounts its phy-
sical explanation being presently under study.
Periodic and long-term variations of ozone and temperature are examined in two papers. A
homogeneous ozonesonde data set does not show any statistically significant trends in strato-
spheric column ozone above 15 mb in the 1970's. During the same period significant upward
trends in tropospheric ozone are observed in agreement with model predictions. Important ad-
dition to the worldwide effort in monitoring the vertical ozone distribution are the new ozone-
sonde sounding programme in the equatorial region and the rocket ozone soundings program-
me in the tropics.
Stratosphere fields of temperature and ozone are examined in this chapter. In a compari-
son between these two fields from independent satellite observations the coefficient of varia-
tion between the two parameters is used to diagnose the relative importance of transport and
photochemistry in determining the ozone distribution.
The development of ground-based Lidar for detailed vertical ozone profiles is used to provi-
de examples of stratospheric ozone intrusions into the troposphere. A detailed discussion of
the sources of error and their correction for the electrochemical ozsmesonde are next dis-
cussed as well as the relative quality and performance of GOp.S. The chapter concludes with
the development of a European climatology of ozone as derived from the Nimbus - 7 Total Ozone
Mapping Spectrometer.
Chapter 5 includes recent developments in observational techniques and begins with the
implementation of a 7 - station network of automated Dobson spectrophotometers which will
allow routine measurements of the ozone vertical profile using the Umkehr technique for the
purpose of detection of long term ozone trends in the 40 km altitude range. The importance of
calibration level, statistical evaluation, operating mode and data analysis for the Dobson spec-
trophotometer network is emphasized in subsequent papers with special attention being paid
to possible interferences due to aerosol particles or S02.
The state of development of the performance of the automated Brewer spectrophotometer
has been reviewed in routine comparisons with the Dobson instrument which confirm its high
quality. This instrument is gradually being introduced in the world ozone network. The develop-
ment of a new instument to replace the M-83 in the USSR network (the M-124) was also repor-
ted.
Results of measurements of ozone and water vapour in the stratosphere and mesosphere
with microwave radiometers are also presented in addition to the Lidar measurements. Poten-
tialities for a spaceborne instrument (UARS) are also underlined and calibration and validation
in both the UV and the IR wavelength ranges give an insight as to the accuracy'Of such mea-
surements.
Ozone profiles obtained with Brewer-Mast ozonesondes are in good agreement with the
profiles by differential absorption Lidar. On the other hand however the comparison of results
obtained from different instruments shows much larger differences than is to be expected from
the quoted errors of individual instruments. It is therefore most important that more intercom-
parison campaigns similar to BOIC, MAP-GLOBUS and WINE, be continued in order to establish
the absolute accuracy of different sensors.
- vii-
Results of new UV-absorption ozone in situ sensors, in situ mass spectrometry and spec-
trophotometry in other regions of the spectrum are presented together with a modification of
ECC ozonesondes for operation to 40 Km altitude. The chapter also includes measurements of me-
sospheric ozone from satellite observation of the 1.27 11m airglow emission and a gas-gas che-
miluminescent technique for measuring 0 and 0 3 in the middle atmosphere.
Chapter 6 includes studies concerned with the interaction of ozone and circulation using
ozone and temperature data derived from satellites and 1 or the Global Air Sampling Program
(GASP). Radiative damping coefficients derived from SAGE indicate coupling between ozone
and temperature which can produce significant variations in the damping rate which in turn,
critically depends on the vertical structure of the planetary waves. Data from the same satellite
confirm that while in the lower stratosphere temperature and ozone waves are nearly in-phase,
they are out-of-phase in the upper stratosphere with an in-between transition region, confirm-
ing the results of earlier Umkehr analyses. Furthermore tracking the extremes of the ozone field
derived from satellites can give a measure of the displacement of the winds. It is also demon-
strated that over tropical latitudes very low ozone values occur in the upper troposphere (less
than 20 ppbv) associated with the rising arm of the Walker circulation. While the transport due
to the meridional circulation driven by diabatic processes is nearly constant during the winter,
the portions due to transient waves and the uncompensated transport by eddies vary rapidly
with time the effects of transport being in moderate agreement with the observed ozone chan-
ges.
Large ozone variations (4 to 10 ppm) have been observed during the month of January pre-
ceeding sudden stratospheric warming and the efficiency of the northward ozone transport by
the flow pattern can be examined from combined ground-based and satellite soundings. It is al-
so shown that the seesaw structure of the aBO can be explained by the modulation of tropo-
spheric dynamical forcing associated with the location of the zero zonal wind critical surface.
In addition the meridional and vertical transport of ozone by planetary waves depends on their
vertical structure, their orientation and magnitude. Considering the effect of temperature wa-
ves it is estimated that a 20% enhancement of the zonal mean ozone in the photochemical
equilibrium region of the upper stratopshere can be produced by temperature wave of 15° K am-
plitude which is typical of winter conditions.
Finally, three days of aircraft sampling in spring over Scotland indicate the presence of
turbulent mixing processes which suggest that the exchange between the stratosphere and
troposphere is not confined only to tropopause folding.
Chapter 7 contains new results and recommendation concerning the ultraviolet absor-
ption cross-section of ozone. The chapter starts with a detailed description of the temperature
dependence of the UV ozone absorption spectrum and the magnitude of resulting correction to
ozone measurements based on previous cross section data. The impact of using the recom-
mended ozone cross - sections on BUV satellite and Dobson total ozone measurements is also
reported. For the SBUV satellite experiment, which gives total ozone values about 8% lower
than the Dobson with presently - used cross - sections, the difference is essentially reduced to
zero with the new coefficients. The Dobson values are reduced by 4% and the SBUV satelltie
values are increased by 4%. However concerning the BUV and TOMS satellite experiments, for
which the calibration is not as well determined as the SBUV calibration, differences up to 2-3 %
still exist. The chapter includes also other interesting new results including an evaluation of
collision broadened and oxygen as the perturbing gases and the result from a newly developed
air-borne actinometer to measure the photolYSis frequency of Np at various heights and zenith
angles.
Chapter 8 begins with results of recent measurements of solar spectral irradiance from So-
lar Mesosphere Explorer (SME) satellite. It is shown that solar UV irradiance variations for the
two year period 1982/83 were about + 15% at Ly-a, + 4% at 175-190 nm and less than + 1 % for
the spectral interval 240-260 nm. The accuracy of present methods of solar irradiance measure-
ments in the spectral interval 290-450 nm is next reviewed.
-viii-
Various aspects of solar activity and ozone variations are also discussed including the evi-
dence of a short period (27 days) and long period solar cycle relationship between solar UV and
ozone. The importance of solar proton events and solar faculae areas in solar activity - ozone
relationships are also discussed.
Two papers deal with applications of the Brewer spectrophotometer to measurements of
the solar UV radiation at the earth's surface. The zenith sky is (in contrast to the situation of vi-
sible wavelengths) brighter than the horizon. The sulfur dioxide concentrations in an urban env-
ironment are found to significantly deplete the solar UV beam so as to alter estimates of increa-
sed UV-B with projected anthropogenic decrease in ozone. The extent of the influence of strato-
spheric aerosols on ozone is also examined through the sensitivity of the ozone photodissocia-
tion rates, the radiative energy budgets and the perturbed thermal structure. Finally calcula-
tions are given of the variability of Ly-a absorption in the mesosphere and atmospheric tran-
smittances.
The last chapter deals with recent results on the processes governing the background ozo-
ne concentration in the troposphere. Nitrogen oxides and hydrocarbons transported to the higtl
latitudes during wintertime in the northern hemisphere seem to play an important role for tro-
pospheric ozone production over middle and high latitudes during springtime. Furthermore, in-
creases in the release rate of the precursors may lead to an ozone increase at mid and high la-
titudes of the order of 1 % per year.
Increasing trends in troposphere ozone are of major concern both because of their possi-
ble influences on climate via alteration in the IR radiation field and in the transmission of U\t-B.
However there is considerable disagreement in the papers of this chapter as to the rate of in-
crease of tropospheric ozone (which so far seems to be confined to the northern hemisphere)
because of unresolved problems with the observing systems (differences between ozone son-
des and the information content of Umkehr observations with respect to troposphe-
ric ozonej. The observed increase is undoubtedly a consequence of the anthropog~nic emis-
sion of trace gases leading to photochemical ozone production. Therefore the ozone increase
is greatest in the boundary layer around the main industrial centers and appears to be sprea-
ding over the whole northern hemisphere.
In addition to photochemical processes, ozone transport from the stratosphere and dry de-
position at the ground play an important role in the tropospheric ozone budget. In this context
the increase of dry deposition over mountainous terrain due to the effect of local wind system
is of importance both with respect to ozone itself and certain other trace substances.
These proceedings are published by the sponsorship of CEC in the framework of its R&D
programme Environment.
The Editors
Christos S. Zerefos
Anver Ghazi
-ix-
CON TEN T S
Introduction v
The Editors, Christos S. ZEREFOS, Anver GHAZI
Pres i dent i a 1 address 3
C.L. MATEER
Sir Charles Normad - In Memoriam 9
C.D. WALSHAW, Department of Atmospheric Physics,
Clarendon Laboratory, Oxford, UK
Implementation of the WMO ozone project (1980-84) 11
R.D. BOJKOV, Member of the Ozone Commission-
1i ai son with WMO
C HAP T E R CHEMICAL-RADIATIVE-DYNAMICAL MODEL CALCULATIONS
Simulation of 03 distribution using a two-dimensional
zonal-mean model in isentropic coordinate 19
M. KO, D. WEISENSTEIN and NIEN OAK SZE Atmospheric
and Environmental Research Inc.; Massachusetts, USA,
KA-KIT TUNG, Department of Mathematics, Massachusetts
Institute of Technology, Cambridge, USA
A GCM study of the transport of heat, momentum and
ozone in the stratosphere 24
D. CARIOLLE and M. DEQUE, Centre National de
Recherches Meteorologiques, EERM, Toulouse, France
Ozone during sudden stratospheric warming: a three-
dimensional simulation 28
K. ROSE, Institut fUr Meteorologie Freie
Universitat Berlin - FRG; G. BRASSEUR, Institut
d'Aeronomie Spatiale, Brussels, Belgium
A matrix method for calculating photochemical acceleration 33
J.D. HAIGH, Centre for Remote Sensing,
Imperial College of Science and Technology,
London, UK
Photochemical acceleration 38
C. GAY, Centro de Ciencias de la Atmosfera; J.L. BRAVO,
Instituto de Geofisica, U.N.A.M., Ciudad Uriversitaria,
Mexico
~ xi