The Role of Air-Sea Exchange in Geochemical Cycling

554 Pages·1986·24.78 MB·English

by  Roland Wollast (auth.), Patrick Buat-Ménard (eds.)

The Role of Air-Sea Exchange
in Geochemical Cycling
NATO ASI Series
Advanced Science Institutes Series
A series presenting the results of activities sponsored by the NATO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The series is published by an international board of publishers in conjunction with the
NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical D. Reidel Publishing Company
and Physical Sciences Dordrecht, Boston, Lancaster and Tokyo
D Behavioural and Social Sciences Martinus Nijhoff Publishers
E Engineering and The Hague, Boston and Lancaster
Materials Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York and Tokyo
Series C: Mathematical and Physical Sciences Vol. 185
The Role of Air-Sea Exchange
in Geochemical Cycling
edited by
Patrick Buat-Menard
Centre des Faibles Radioactivites,
Laboratoire Mixte CNRS-CEA,
Gif-sur-Yvetle, France
D. Reidel Publishing Company
Dordrecht / Boston / Lancaster / Tokyo
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Study Institute on
The Role of Air-Sea Exchange in Geochemical Cycling
Bombannes, France
16-27 September 1985
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute on the Role of Air-Sea Exchange in Geochemical Cycling
(1985 : Bombannes, France)
The role of air-sea exchange in geochemical cycling.
(NATO ASI series. Series C, Mathematical and physical sciences; vol. 185)
"Proceedings of the NATO Advanced Study Institute on the Role of Air-Sea Exchange
in Geochemical Cycling, Bombannes, France, 16-27 September, 1985"-T.p. verso.
Companion vol. to: Air-sea exchange of gases and particles / edited by Peter S. Liss
and W. George N. Slinn. Dordrecht; Boston :D. Reidel Pub. Co., c1983.
"Published in cooperation with NATO Scientific Affairs Division."
Includes bibliographies and index.
1. Ocean-atmosphere interaction-Congresses. 2. Sea-water-Composition-
Congresses. 3. Geochemistry-Congresses. I. Buat-MElnard, Patrick, 1946-
II. North Atlantic Treaty Organization. Scientific Affairs Division. III. Title. IV. Series:
NATO ASI series. Series C, Mathematical and physical sciences; vol. 185.
GC190.2.N16 1985 551.46'.01 86-17678
ISBN -13: 978-94-010-8606-6 e-ISBN -13: 978-94-009-4738-2
DOl: 10.1 007/978-94-009-4738-2
Published by D. Reidel Publishing Company
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All Rights Reserved
© 1986 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover 1st edition 1986
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CONTENTS
PREFACE - P. Buat-Menard xiii
ACKNOWLEDGEMENTS xv
BASIC CONCEPTS IN GEOCHEMICAL MODELLING - R. Wollast 1
1. Introduction 1
2. First Order Models 3
2.1. First order decay reaction 3
2.2. Instantaneous perturbation in a first order decay
model 8
2.3. First order production model 9
3. Heterogeneous Catalysis and Enzymatic Type Reactions 10
4. Reversible Reactions 12
5. Model with Coupled Components in the Reservoir 19
6. Second Order Reactions 25
7. Periodic Fluctuations 27
8. Coupling of Reservoirs 30
9. Conclusions 33
ATMOSPHERIC PATHWAYS TO TIlE OCEANS - J. T. Merrill 35
1. Introduction 35
2. Atmospheric Structure and Transports 36
2.1. Boundary layer 37
2.2. Cloud scale transport 41
2.3. Storms and midlatitude circulation 42
2.4. Global scale exchange 47
3. Variability and Representativeness 49
3.1. Seasonal and interannual variability 50
3.2. Representativeness of observations 52
4. Modeling of Atmospheric Transport 53
4.1. Source identification models 53
4.2. Mechanistic models 56
4.3. Tropospheric chemistry system models 57
MODELING OCEANIC TRANSPORT OF DISSOLVED CONSTITUENTS -
J.L. Sarmiento 65
1. Introduction 65
2. Box Models 66
3. Advection-Diffusion Models 71
4. Equations of Motion 78
5. Conclusion 80
CONTENTS
VERTICAL TRANSPORT OF PARTICLES WITHIN THE OCEAN -
J.C. Brun-Cottan 83
1. Introduction 83
2. Determination of the Lognormal Coefficients L, cr
and of N 86
2.1. Particle size data collection 86
2.2. Calculation of the coefficients L, cr and N
from data 87
3. Determination of Suspended Particulate Matter Physical
Properties using Lognormal coefficients 90
3.1. Surface area concentration 90
3.2. Mass concentration 90
3.3. Vertical fluxes 92
3.4. Residence time 96
3.5. Application to the open sea 97
4. Suspended Particulate Matter Sedimentation with
Dissolution Process 99
4.1. Sedimentation at steady state 99
4.2. Sedimentation at non steady state 102
5. Conclusion 105
6. Appendix 106
6.1. Specific properties of the lognormal law 106
6.2. Evaluation of the lognormal coefficients 107
AIR-SEA GAS EXCHANGE RATES: INTRODUCTION AND SYNTHESIS -
P.S. Liss and L. Merlivat 113
1. Introduction 113
2. Basic Principles 114
3. Models 115
3.1. Film model 115
3.2. Surface renewal models 115
3.3. Boundary-layer models 116
4. Laboratory (Wind Tunnel) Studies 116
4.1. Smooth surface regime 118
4.2. Rough surface regime 118
4.3. Breaking wave (bubble) regime 118
5. Field Measurements 118
5.1. Box method 119
5.2. Dissolved gas balance method 119
5.3. Micrometeorological techniques 119
5.4. Natural and bomb-produced 14C 120
5.5. The radon deficiency method 120
5.6. Sulphur hexafluoride 121
5.7. Summary 121
6. Synthesis 122
6.1. Comparison with field data 125
CONTENTS vii
THE OCEAN AS A SOURCE FOR ATMOSPHERIC PARTICLES - E.C. Monahan 129
1. Introduction 129
2. The W aE/ar Model 130
3. The VI a2E/at ar Model 135
W
4. Comparison of aE/ar and W a2E/at ar Models 139
5. Oceanic Whitecap Coverage 146
6. Global Sea-to-Air Salt Flux 152
7. Toward a Comprehensive Marine Aerosol Generation Model 155
THE OCEAN AS A SINK FOR ATMOSPHERIC PARTICLES - P. Buat-Menard 165
1. Overview 165
2. Assessement of Wet Deposition 167
3. Field Approach to Dry Deposition 172
4. Accurate Deposition Measurements do not Guarantee
Accurate Net Air to Sea Transfer Rates 177
5. Relative Importance of Wet and Dry Removal Rates 179
6. Conclusion 181
ATMOSPHERIC, OCEANIC, AND INTERFACIAL PHOTOCHEMISTRY AS FACTORS
INFLUENCING AIR-SEA EXCHANGE FLUXES AND PROCESSES - D.C. Zafiriou 185
1. Introduction 185
2. Environmental Photochemistry 186
2.1. Stratospheric photochemistry 186
2.2. Homogeneous tropospheric photochemistry 187
2.3. Heterogeneous tropospheric photochemistry 191
2.4. Seawater photochemistry 194
2.5. Soil photochemistry 198
3. Interaction of Photochemistry with Air-Sea Exchange
Processes 198
3.1. Air-sea gas exchange 198
3.2. Rainout-washout deposition processes 201
3.3. Dry deposition 202
3.4. Marine aerosol generation 203
4. Summary 203
CARBON DIOXIDE: ITS NATURAL CYCLE AND ANTHROPOGENIC PERTURBATION -
U. Siegenthaler 209
1. Introduction 209
2. The Natural Cycle of Carbon Dioxide 210
2.1. Reservoirs, fluxes, residence times 210
2.2. Air-sea exchange of CO 213
2
2.3. Regional variability of air-sea fluxes 215
2.4. Marine carbonate chemistry 219
2.5. The oceanic carbon cycle 220
viii CONTENTS
2.6. The cycle of oxygen 221
3. Anthropogenic Increase of Atmospheric CO2 223
3.1. Observations and airborne fraction 223
3.2. Modelling the oceanic response to carbon cycle
perturbations 225
3.3. CO2 release from the terrestrial biosphere and the
"missing CO2 sink" 229
3.4. Scenarios for future CO2 concentrations 231
3.5. Carbone isotope perturbations 233
4. Climatic Effects of CO2 Increase 234
5. Natural CO2 Variations 239
5.1. Seasonal variations 239
5.2. Correlation with El Nino 240
5.3. Glacial/interglacial changes 242
CO2 AIR-SEA EXCHANGE DURING GLACIAL TIMES: IMPORTANCE OF DEEP
SEA CIRCULATION CHANGES - J.C. Duplessy 249
1. Introduction 249
2. Evidence from Polar Ice Cores 249
2.1. Data 249
2.2. Discussion: is the ocean able to absorb the
missing CO2? 250
3. Evidence from Deep Sea Sediments 250
3.1. Data 250
3.2. Various hypotheses explaining the sedimentary
record 251
3.3. Cadmium as a proxy-indicator for past phosphate 252
4. Broecker's two box Model for the CO2 Cycle 253
5. Evidence for Deep Water Circulation during the Last
Climatic Cycle 253
5.1. Geochemical basis 253
5.2. Glacial to interglacial contrasts 258
5.3. Disappearance of North Atlantic Deep Water during
the glacial to interglacial transition 263
5.4. Enhanced North Atlantic Deep Hater formation
during the inception of the glaciation 263
6. Conclusion 265
EXCHANGE OF CO AND H2 BETWEEN OCEAN AND ATMOSPHERE - R. Conrad
and W. Seiler 269
1. Introduction 269
2. Determination of the Supersaturation Factors of
CO and H2 270
3. Spatial and Temporal Changes of dissolved CO and H2 272
4. Processes Sustaining CO and H2 Concentrations
in Surface Water 274
4.1. Production processes 274
CONTENTS IX
4.2. Consumption processes 276
4.3. Transport processes 277
5. Calculation of Fluxes by the "Laminar Film Model" 278
6. Role of Oceans in the budget of atmospheric CO and H2 280
THE AIR-SEA EXCHANGE OF LOW HOLECULAR WEIGHT HALOCARBON GASES -
P.S. Liss 283
1. Introduction 283
2. Gases for which the Oceans are a net Source for the
Atmosphere 284
2.1. Alkyl (mainly Hethyl) halides 284
2.2. Haloforms 287
2.3. Other organo-halides 289
3. Gases for which the Oceans are a net Sink for the
Atmosphere 289
4. Summary 290
SEA-AIR EXCHANGE OF HIGH-MOLECULAR WEIGHT SYNTHETIC ORGANIC
COHPOUNDS - E. Atlas and C.S. Giam 295
1. Introduction 295
2. Compounds of Interest 296
3. Sampling/Analytical Aspects of Trace Organics 296
4. Distribution of High Molecular Weight Organics in
the Marine Environment 297
4.1. Water and organisms 297
4.2. Atmospheric concentrations 300
4.3. Atmospheric deposition 303
5. Air-Sea Exchange Hechanisms for Synthetic Organics 303
5. 1. Dry deposition 305
5.2. Wet deposition 310
5.3. Adsorption and partitioning in surface waters 311
6. Air-Sea Fluxes in the North Pacific 314
7. Relative Importance of Atmospheric Deposition to the
CHC Cycle 319
8. Summary and Conclusions 321
THE OCEAN AS A SOURCE OF ATMOSPHERIC SULFUR COHPOUNDS -
M.D. Andreae 331
1. Sources of Sulfur to the Atmosphere: an Overview 331
2. Seaspray and the Production of Aerosol Sulfate 332
3. Sulfate Reduction by Geological and Biological Processes 334
4. Assimilatory Sulfate Reduction 336
5. Biosynthesis of Dimethylsulfide 338
6. Marine Chemistry and Distribution of Dimethylsulfide 338
7. Estimating the Air/Sea Flux of Dimethylsulfide 343
x CONTENTS
8. Chemical Reactions and Transformations of Dimethylsulfide
in the Marine Atmosphere 346
9. A Model of the Cycle of Biogenic Sulfur over the Oceans 349
10. Carbonyl Sulfide 352
10.1. Photochemical production of COS 352
10.2. Air/Sea exchange of COS 353
11. Formation and Emission of other Sulfur Species: Hydrogen
Sulfide, Carbon Disulfide, Methylmercaptan,
Dimethyldisulfide etc... 354
11.1. Hydrogen sulfide 354
11.2. Carbon disulfide 355
11.3. Methylmercaptan, dimethyldisulfide and other
sulfur compounds 356
12. Conclusion 356
CYCLING OF MERCURY BETWEEN THE ATMOSPHERE AND OCEANS -
W.F. Fitzgerald 363
1. Introduction 363
2. Global Models 364
3. Physico-Chemical Models 367
4. Atmospheric Hg Determinations 370
4.1. Total gaseous Hg 370
4.2. Volatile Hg species 371
5. Hg Analysis in Seawater and Rainwater 371
5.1. Reactive and Total Hg 372
5.2. Volatile H2 372
5.3. Determinations of Hg in rain 372
6. Air-Sea Exchange of Hg 373
6.1. Preliminary studies 373
6.2. Present status 375
6.3. Summary 382
7. Ocean Sources of Hg 382
7.1. Hg evasion from the Equatorial Pacific Ocean: 1980 382
7.2. Hg evasion from the Equatorial Pacific Ocean: 1984 386
8. Hg Deposition to the Sea Surface 393
8.1. Precipitation 393
8.2. Dry depositional Hg flux to the Equatorial
Pacific Ocean 396
8.3. Air-sea exchange in the Equatorial Pacific Ocean 396
8.4. Physico-chemical aspects 397
9. Atmospheric Cycling of Hg over the Oceans:
Global Perspectives 397
THE AIR-SEA EXCHANGE OF PARTICULATE ORGANIC MATTER: THE SOURCES AND
LONG-RANGE TRANSPORT OF LIPIDS IN AEROSOLS - R.B. Gagosian 409
1. Introduction 409
1.1. Background 409