Chemical events in the atmosphere

CHEMICAL EVENTS IN
THE
ATMOSPHERE
AND
THEIR IMPACT ON
THE
ENVIRONMENT
PONTIFICIAE ACADEMIAE SCIENTIARVM SCRIPTA VARIA
56
STUDY
WEEK
ON
:
CHEMICAL EVENTS IN THE
ATMOSPHERE AND THEIR
IMPACT ON THE ENVIRONMENT
November
7-11,
1983
EDITED BY
G.
B.
MARINI-BETTOLO
PONTI
F
IC
IA
ACADEMIA
ScIENTIARvM
EX AEDIBVS ACADEMICIS

IN
CIVITATE VATICANA
-
MCMLXXXVI
STUDIES IN ENVIRONMENTAL SCIENCE
26
CHEMICAL EVENTS
IN
THE
ATMOSPHERE AND THEIR
IMPACT
ON
THE
ENVIRONMENT
PROCEEDINGS
OF
A
STUDY
WEEK
AT
THE
PONTIFICAL ACADEMY
OF
SCIENCES
November
7-11,
1983
EDITED
BY
G.B.

MARINI-BETTOLO
ELSEVIER
AMSTERDAM
-
OXFORD
-
NEW
YORK
-
TOKYO
1986
0
COPYRIGHT
1986
PONTIFICIA
ACADEMIA
SCIENTIARUM
-
CITTA
DEL
VATICANO
Elsevier Science Publishers
Sara
Burgerhartstraat
25
P.O.
Box
211, 1000
AE Amsterdam, The Netherlands
Elsevier Science Publishing Company, Inc.

52
Vanderbilt Avenue
New York, NY
10017,
U.S.A.
Library
of
Congress
Cataloging
in
Publication Data
Study Week on:
Chemical Events in the Atmosphere and Their Impact on the
Environment
(1983:
Pontifical Academy
of
Sciences)
Chemical events in the atmosphere ant their impact on the environment.
(Studies in environmental science;
26)
(Pontificiae Academiae Scientiamm
Bibliography
:
p
.
Includes index.
1.
Atmospheric chemistry
-

Environmental aspects
-
Congresses.
2.
Environ-
mental chemistry
-
Congresses.
I.
Marini-Bettblo,
G.
B. (Giovanni Battista).
11.
Pon-
tificia Accademia delle scienze.
111.
Title. IV. Series.
V.
Series: Pontificiae Academia-
Scientiarum scripta varia;
56.
TD193.S78 1983 551.5'11 86-2465
scripta varia;
56)
ISBN
0-444-99513-7
(Vol.
26)
ISBN
0-444-41696-X

(Series)
Printed in Italy
Other uolumes in
this
series
1
2
3
4
5
6
7
8
9
10
11
12
13
1
4
15
16
17
18
19
20
21
22
23
24

Atmospheric Pollution
1978
edited by
M.M.
Benarie.
Air Pollution Reference Measurement Methods and Systems
edited by
T. Schneider, H.W. de Koning and L.J. Brasser.
Biogeochemical Cycling of Mineral-Forming Elements
edited by P.
A.
Truciinger and D.J. Swaine.
Potential Industrial Carcinogens and Mutagens
by
L.
Fishbein.
Industrial Waste Managements
by S.E. Jergensen.
Trade and Environment:
A
Theoretical Enquiry
by H. Siebert, J. Eichber-
ger,
R.
Gronych and
R.
Pethig.
Field Worker Exposure during Pesticide Application
edited by W.F. Tordoir
and E.A.H. van Heemstra-Lequin.

Atmospheric Pollution
1980
edited by M.M. Benarie.
Energetics and Technology of Biological Elimination of Wastes
edited by
G. Milazzo.
Bioengineering, Thermal Physiology and Comfort
edited by K. Cena and
J.A.
Clark.
Atmospheric Chemistry. Fundamental Aspects
by E. Mkszaros.
Water Supply and Health
edited by
H.
van Lelyveld and B.C.J. Zoeteman.
Man under Vibration. Suffering and Protection
edited by
G.
Bianchi,
K.V.
Frolov and
A.
Oledzki.
Principles of Environmental Science and Technology
by S.E. Jergensen
and
I.
Johnsen.
Disposal

of
Radioactive Wastes
by
Z.
Dlouhf.
Mankind and Energy
edited by
A.
Blanchpierre.
Quality of Groundwater
edited by
W.
van Duijvenbooden, P. Glasbergen
and
H.
van Lelyveld.
Education and Safe Handling in Pesticide Appkation
edited by E.A.H.
van Heemstra-Lequin and W.F. Tordoir.
Physicochemical Methods for Water and Wastewater Treatment
edited by
L. Pawlowski.
Atmospheric Pollution
1982
edited by
M.M.
Benarie.
Air Pollution by Nitrogen Oxides
edited by T. Schneider and L. Grant.
Environmental Radioanalysis

by H.A. Das,
A.
Faanhof and H.A. van der
Sloot.
Chemistry for Protection of the Environment
edited by L. Pawlowski,
A.J.
Verdier and W.J. Lacy.
Determination and Assessment of Pesticide Exposure
edited by
M.
Sie-
wierski.
The Biosnhere: Problems and Solutions
edited bv T.N. VeziroGh.
Address
:
"
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INDEX
CARLOS CHAGAS:
Foreword
.
List of Participants
.
Pontifical Audience
.
INTRODUCTION
G.B. MARINI-BETT~LO: Chemical Events in the Atmosphere and

Their Impact on the Environment (Introductory Remarks)
I.
STRUCTURE,
COMPONENTS
AND
PRIMARY PROCESSES
IN
THE
ATMOSPHERE
D.
PHILLIPS:
Photochemical Reactions in the Atmosphere
.
Discussion
.
A.
PULLMAN:
Quantum-Mechanical Studies on the Binding Pro-
Discussion
.
perties
of
Small Atmosphere Molecules
.
V.M. CANUTO,
J.S.
LEVINE, C.L.
IMHOFF, I.
GOLDMAN,
T.R.

AUGUSTSSON and
0.
HUBICKYJ:
The Young Sun, the Early
Earth and the Photochemistry
of
Oxygen, Ozone and
For-
maldehyde in the Early Atmosphere
.
Discussion
.
XI11
xv
XXI
3
7
23
25
45
51
99
X
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F.
ARNOLD: Atmospheric Ions
.
.
103
Discussion
.
*
135
J.R. WIESENFELD: Oxygen Cycle in the Atmosphere
.
.
143
Discussion
.
.
173
C. BROSSET: The Global Sulfur Budget
. .
179
Discussion
. .
197
C.
J.
HOWARD:
Laboratory Studies of Atmospheric Radical
Reactions
.
203

Discussion
. .
217
11.
ATMOSPHERE
AND
THE SECONDARY PROCESSES:
THE EFFECT
OF
GEOLOGICAL AND ANTHROPIC COMPONENTS
W.L.
CHAMEIDES and
D.D. DAVIS:
The Photochemistry of Tro-
pospheric Trace Species: the Central Role of Radicals and
Their Possible Variability
.
.
227
Discussion
. .
255
G.
FIOCCO:
Perturbations
of
the Atmosphere and of the Climate
System Induced by Volcanic Eruptions: Relevance
of
Some

Specific Processes
.
.
261
Discussion
.
.
279
K.Ya. KONDRATYEV, V.A.
IVANOV,
D.V.
POZDNYAKOV
and M.A.
PROKOFYEV:
Natural and Anthropogenic Aerosols: a Com-
parative Analysis
.
,
281
F.S.
ROWLAND, D.R. BLAKE, S.C.
TYLER
and Y. MAKIDE: In-
creasing Concentrations of Perhalocarbons, Methylchloro-
form and Methane in the Atmosphere
. .
305
Discussion
. .
335

CHEMICAL EVENTS
IN
THE ATMOSPHERE AND THEIR IMPACT
ON
THE ENVIRONMENT
XI
J.G.
ANDERSON: Role and Fate
of
Ozone in the Atmosphere
341
Discussion
.
.
379
.
111.
THE EFFECTS ON THE ENVIRONMENT
OF
CHEMICAL REACTIONS IN THE ATMOSPHERE
T.F.
MALONE: Toward a Better Understanding of Atmospheric
Chemistry
.
.
391
Discussion
.
.
401

R. REVELLE: Carbon Dioxide and Other Greenhouse Gases in
Ocean, Atmosphere, and Biosphere, and Future Climatic
Impacts
.
405
F.K.
HARE:
Carbon Dioxide and Environment
.
.
429
Discussion
. .
443
P.J.
CRUTZEN apd
I.E.
GALBALLY:
Atmospheric Conditions After
a Nuclear War
. .
457
Discussion
.
.
503
A.
LIBERTI:
Atmospheric Acidity
. .

507
Discussion
.
.
533
J.
LAG': Effects on Soils
of
Chemical Events in the Atmosphere
537
Discussion
. .
547
IV.
THE EFFECTS ON LIFE OF CHEMICAL EVENTS
IN THE ATMOSPHERE
W.
KNABE:
Effects
of
Chemical Air Pollution on Forests and
Other Vegetation
.
.
553
Discussion
. .
595
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G.B. MARINI-BETT~LO: Chemical Reactions in the Atmosphere
.
and Their Impact on Human Health and Animal Life 607
Discussion
. .
619
E.
SALATI
and P.B. VOSE: The Water Cycle in Tropical Forests,
With Special Reference
to
the Amazon
.
.
623
S.O.
WANDIGA: Effects
of
Chemical Events on Environment in
Africa
. .
649
Discussion
. .

665
FINAL CONSIDERATIONS
AND CONCLUSIONS
Final Considerations and Conclusions
. .
677
SUBJECT INDEX
.
AUTHOR INDEX
.
693
.
701
FOREWORD
It is
a
great honour and joy for me to present this volume of
Scripta Varia
which contains the papers presented during the Study Week
on
“Chemical Events in the Atmosphere and their Impact
on
the
Environment” held
at
the seat of the Academy from the 7th to the 11th
of November,
1983.
The discussions which followed each presentation
are included in the volume. These proceedings are of great interest;

they touch
on
problems which may seem diverse for
a
non-knowledgeable
person, or insignificant to those who flee the reality of our present world.
Nevertheless, the problems dealt with are
a
menace to mankind and
challenge our future. Only those who
are
not aware of the questions
raised herein are not preoccupied by the picture we see around
us.
These
problems are
a
part of our daily life but they are not visible to the
general public, either because they are hidden by concealed interests or
because they have such slow effects that even their additive results are
difficult to perceive.
The danger of
a
nuclear war after the dropping of the atomic bombs
on
Hiroshima and Nagasaki leads
us
easily to fear for the future and
gives
us

the desire to act in any way in order to avoid
a
global nuclear
catastrophe. The subtle effect
on
the biosphere of the chemical events
occurring in the atmosphere, because they are not instantaneous, cannot
easily be perceived; unless an event of great proportions occupies the
front page of our daily paper for
a
few
days
it is scarcely noticed. Yet,*
the effect of these chemical events in the atmosphere could in
a
not-so-
distant future destroy the quality of life, or life itself. Should we be
pessimistic? Yes, certainly, unless we can change the mentality of many
of the developmental processes of our society. This can be done only
if
scientists, technologists, sociologists and economists working together
can change many of the priorities of our present times and, by recognition
of the facts, convince policy makers and the industrialists of the urgency
to take measures to prevent the every-day increasing menace of slow
destruction of the wonders of our world, which
if
protected will conserve
XIV
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the joy everyone experiences when admiring the blue sky, the smoke-free
air,
the clear water of
a
waterfall, the greenness of our mountains, prairies
and forests.
The success of
our
Study Week was due to the hard work Giovanni
Battista Marini-Bettdo put into its preparation,
a
zeal which was felt by
all participants, and which he has applied in editing this volume. As always,
Professor Marini-Betthlo brought perfection to his actiuity. It is my
honour to express to my colleague my deep gratitude.
I
wish also to
extend my thanks to Father Enrico
di
Rovasenda, Madame Michelle
Porcelli, Mrs. Gilda Massa and Siluio Devoto.
It
is only through their
devotion to the work of the Academy that
our

activity is made possible.
CARLOS CHAGAS
President
of
the Pontifical Academy of Sciences
LIST
OF
PARTICIPANTS
This Page Intentionally Left Blank
JAMES
G.
ANDERSON, Harvard University, Center
of
Earth and
Planetary Physics, Cambridge, USA.
FRANK ARNOLD, Max-Planck-Institut
fiir
Physik, Heidelberg, Federal
Republic
of
Germany.
CYRILL BROSSET, Swedish Water and Air Pollution Research
Institute, Goteborg, Sweden.
VITTORIO CANUTO, NASA Institute for Space Studies, New York,
USA.
WILLIAM
L.
CHAMEIDES
,
School

of
Geophysical Sciences, Georgia
Institute
of
Technology, Atlanta, USA.
PAUL
CRUTZEN, Max-Planck-Institut fir Chemie,
Maim,
Federal
Republic
of
Germany.
GIORGIO
FIOCCO,
Dipartimento di Fisica, Universith Roma, La Sa-
pienza
-
Rome, Italy.
F.
KENNETH
HARE,
Trinity College, Toronto, Canada.
CARLETON
J.
HOWARD,
Environmental Research Laboratories, NOOA,
Boulder, Colorado, USA.
WILHELM
KNABE,
Landesanstalt

fiir
Okologie, Recklinghausen,
Federal Republic
of
Germany.
J.
LAG, Institutt for Jordbunnslaere med Statens Jordundersskelse,
AS-
NLH, Norway.
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ARNALDO LIBERTI, Dipartimento di Chimica, Universiti Roma
La
Sapienza
-
Rome, Italy.
THOMAS
F.
MALONE, Holcomb Research Institute, Indianapolis, USA.
G.B. MARINI-BETTOLO, Pontifical Academician, Universiti di Roma
La Sapienza and Istituto di Chimica Universiti Cattolica del
S.
Cuore,
Rome, Italy.
DAVID

PHILLIPS, The Royal Institution, London, England.
ALBERTE PULLMAN, Institut
de
Biologie Physico-Chimique, Paris,
France.
SILVIO RANZI, Honorary Pontifical Academician, Department
of
Biology, University
of
Milan, Italy.
ROGER REVELLE, University of California, San Diego, La Jolla, USA.
F.S.
ROWLAND, University of California, Department
of
Chemistry,
Irvine, USA.
ENEAS
SALATI, Centro de Energia Nuclear na Agricultura,
Siio
Paulo,
Brazil.
SHEM
0.
WANDIGA, University
of
Nairobi, Department
of
Chemistry,
Nairobi, Kenya.
JOHN

WIESENFELD, Cornell University, Department
of
Chemistry,
Ithaca,
N.Y.,
USA.
VERONICA
M.
BIERBAUM, as Scientific Secretary, University
of
Colorado, Boulder, CO., USA.
Patidpants in
the
Study
Week.
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PONTIFICAL AUbIENCE
On November 12,
1983,
His Holiness John Paul
I1
granted
an
Audience in the “Sala Regia”
of
the Apostolic Palace in the Vatican to
45
Members of the Pontifical Academy of Sciences gathered in Plenary
Session to discuss the subject “Science in the Service of Peace”, to 20
scientists participating in the Study Week organized by the Academy on

“Chemical Events in the Atmosphere and their Impact on the Environ-
ment”, and to
15
scientists
of
a Working Group convened
by
the Academy
to discuss
“
Specificity in Biological Interactions
”.
His Holiness John
Paul
I1
addressed to the participants an important
speech on the role of Science
for
Peace and in particular the role of
scientific community extended to
all
nations, concluding:
Gentlemen, as men
of
thought and sciknce, as pilgrims of the truth,
as explorers in the different branches of science and knowledge, about
man and the universe, who submit yourselves to the labour of observing,
thinking, searching,
so
that man may be ever more man and may find

in nature the proper environment for his development:
I
ask you to
work
for justice, love and peace, and
to
believe that today more than
ever the Catholic Church is your ally, this Church which loves true
science and right thinking, this Church which prays for you and which
in my person, respecting your beliefs, invokes upon each one of you the
blessing of God.
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SCIENTIFIC PAPERS
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