Environmental Science & Technology

M i l l e ro

Over the past ten years, a number of new large-scale oceanographic
programs have been initiated. These include the Climate Variability
Program (CLIVAR) and the recent initiation of the Geochemical Trace
Metal Program (GEOTRACES). These studies and future projects will
produce a wealth of information on the biogeochemistry of the world
oceans. Authored by Frank J. Millero, an acknowledged international
authority in the field, the fourth edition of Chemical Oceanography
maintains the stellar insight that has made it a favorite of students,
instructors, researchers, and other professionals in marine science,
geochemistry, and environmental chemistry. Reflecting the latest
updates on issues affecting the health of our environment, this text
• Supplies an in-depth treatment of ocean acidification, a key
emerging environmental problem
• Provides updated coverage on the carbonate system in the ocean
• Presents expanded information on oceanic organic compounds
• Contains updates on dissolved organic carbon, phosphate,
nitrogen, and metals in the ocean
• Offers a new definition of salinity and a new equation of the state
of seawater based on recent, original research
• Describes the new thermodynamic equation of the state of seawater
• Includes full-color graphs and photographs to assist readers in
visualizing the concepts presented
For more than two decades, this book has served as the "classic"
textbook for students and a valuable reference for researchers in the
fields of oceanography, environmental chemistry, and geochemistry.
Designed for both classroom use and self-study, this comprehensive
survey of essential concepts incorporates a wealth of state-of-the-art

reference data discovered on large-scale oceanographic studies
sponsored by the National Science Foundation and the National
Oceanographic and Atmospheric Administration.

K14907

Chemical Oceanography

FOU RTH E DITION

FOURTH EDITION

FO U RTH
E D ITI O N

Frank J. Millero


FOURTH EDITION

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FOURTH EDITION

Frank J. Millero

Boca Raton London New York

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Contents
Preface to the First Edition.............................................................................................................xi
Preface to the Second Edition..................................................................................................... xiii
Preface to the Third Edition.........................................................................................................xv
Preface to the Fourth Edition.................................................................................................... xvii
About the Author......................................................................................................................... xix
1. Descriptive Oceanography....................................................................................................1
1.1 Introduction....................................................................................................................1
1.2 Physical Characteristics of the Oceans.......................................................................2
1.3 Distribution of Temperature and Salinity for Ocean Waters..................................5
1.4 Circulation and Water Masses of the Oceans.......................................................... 16
1.4.1 Atlantic Ocean Waters.................................................................................... 18
1.4.2 Southern Ocean Waters.................................................................................. 25
1.4.3 Pacific Ocean Waters...................................................................................... 27
1.4.4 Indian Ocean...................................................................................................30
1.4.5 Arctic and Adjacent Seas............................................................................... 32
1.4.6 Closed Basins................................................................................................... 35
1.4.6.1 Mediterranean Sea.......................................................................... 35
1.4.6.2 Red Sea.............................................................................................. 35
1.4.6.3 Estuaries........................................................................................... 35
1.5 Use of Chemical Tracers in Oceanography.............................................................. 38
1.5.1 Carbon-14......................................................................................................... 38

1.5.2 Tritium and Helium-3.................................................................................... 40
1.5.3 Chlorofluorocarbons......................................................................................42
1.5.4 The Age of Water Masses............................................................................... 45
References and Further Reading.......................................................................................... 52
Descriptive Oceanography......................................................................................... 52
Carbon-14...................................................................................................................... 52
Tritium........................................................................................................................... 52
Helium-3........................................................................................................................ 52
Chlorofluorocarbons.................................................................................................... 53
Age of Water Masses.................................................................................................... 53
2. Composition of the Major Components of Seawater..................................................... 55
2.1 Introduction.................................................................................................................. 55
2.2 The Concept of Salinity............................................................................................... 57
2.3 Methods of Determination.........................................................................................64
2.3.1 Chloride............................................................................................................64
2.3.2 Sulfate...............................................................................................................65
2.3.3 Bromine............................................................................................................65
2.3.4 Fluorine............................................................................................................65
2.3.5 Bicarbonate and Carbonate...........................................................................65
2.3.6 Boric Acid and Borate.....................................................................................65
2.3.7 Magnesium......................................................................................................65
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2.3.8 Calcium............................................................................................................ 66
2.3.9 Potassium......................................................................................................... 66
2.3.10 Sodium............................................................................................................. 66
2.4 Composition and Stoichiometry of Average Seawater........................................... 66
2.5 Methods of Determining Salinity............................................................................. 69
2.6 Causes of the Major Components Not Being Conservative................................... 69
2.6.1 Estuaries........................................................................................................... 69
2.6.2 Evaporation in Isolated Basins...................................................................... 78
2.6.3 Admixture with Brines.................................................................................. 81
2.6.4 Precipitation and Dissolution........................................................................ 81
2.6.5 Submarine Volcanism.................................................................................... 81
2.6.6 Exchange between Atmosphere and Sea.................................................... 82
2.6.7 Anoxic Basins..................................................................................................84
2.6.8 Freezing............................................................................................................84
2.6.9 Interstitial Waters............................................................................................84
2.7 Isotopic Variations.......................................................................................................85
2.7.1 Hydrogen and Oxygen...................................................................................85
2.7.2 Deuterium........................................................................................................ 86
2.7.3 Oxygen-18......................................................................................................... 86
2.7.4 Isotopes of Sulfur............................................................................................ 87
References and Further Reading.......................................................................................... 87
3. Minor Elements in Seawater............................................................................................... 91
3.1 Classification of Elements........................................................................................... 91
3.1.1 d0 Cations......................................................................................................... 91
3.1.2 d10 Cations........................................................................................................ 92
3.1.3 Transition Metals between d0 and d10.......................................................... 97
3.2 Residence Times........................................................................................................... 98
3.3 Distribution of Trace Elements in the Oceans....................................................... 102
3.4 Biological Interactions............................................................................................... 109
3.5 Geochemical Balance of Elements........................................................................... 113

References and Further Reading........................................................................................ 127
4. Ionic Interactions................................................................................................................. 129
4.1 Introduction................................................................................................................ 129
4.2 Water, the Unique Solvent......................................................................................... 130
4.3 Review of the Structure of Water............................................................................. 134
4.3.1 Uniformist (Average) Models...................................................................... 135
4.3.2 Mixture Models............................................................................................. 135
4.3.2.1 Ice-­Like Models............................................................................. 136
4.3.2.2 Cluster Theories............................................................................ 137
4.3.2.3 Clathrate Cage Models................................................................. 138
4.3.2.4 Significant Structure Theory and Eucken’s Polymer Model.... 139
4.4 Ion–Water Interactions.............................................................................................. 141
4.4.1 Electrostriction.............................................................................................. 145
4.4.2 Proton Structure in Aqueous Solutions..................................................... 152
4.5 Ion–Ion Interactions................................................................................................... 153
4.5.1 Ion-­Pairing Model......................................................................................... 161
4.5.2 Specific Interaction Model........................................................................... 166

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4.6 Physical Properties of Seawater............................................................................... 175
References and Further Reading........................................................................................ 180
5. Atmospheric Chemistry..................................................................................................... 183
5.1 Introduction................................................................................................................ 183
5.1.1 Composition of the Atmosphere................................................................. 189

5.2 Nitrogen Gases........................................................................................................... 192
5.3 Greenhouse Gases...................................................................................................... 198
5.4 Effects of Global Change........................................................................................... 207
5.4.1 Effects of Global Warming on the Oceans................................................ 209
5.5 Loss of Ozone............................................................................................................. 210
5.6 The Global Sulfur Cycle............................................................................................ 219
5.7 Atmospheric Aerosols............................................................................................... 221
References and Further Reading........................................................................................225
6. Dissolved Gases Other than CO2..................................................................................... 227
6.1 Introduction................................................................................................................ 227
6.2 Composition of the Atmosphere.............................................................................. 227
6.3 Dissolution of Gases in Seawater............................................................................. 229
6.4 Air–Sea Exchange...................................................................................................... 232
6.5 Nonreactive Gases..................................................................................................... 237
6.6 Dissolved Oxygen in Seawater................................................................................ 242
6.7 Other Nonconservative Gases.................................................................................. 252
6.8 Structural Aspects of the Solubility of Gases........................................................ 255
References and Further Reading........................................................................................ 257
7. The Carbonate System........................................................................................................ 259
7.1 Introduction................................................................................................................ 259
7.2 Acid–Base Equilibria in Seawater............................................................................ 264
7.3 Equilibria of Carbonate Species............................................................................... 269
7.4 Parameters of the CO2 System in Seawater............................................................ 274
7.5 Distribution of Carbonate Species........................................................................... 281
7.5.1 pCO2. .............................................................................................................. 281
7.5.2 pH.................................................................................................................... 286
7.5.3 Total Alkalinity............................................................................................. 288
7.5.4 Total CO2........................................................................................................ 291
7.6 CaCO3 Dissolution in Seawater................................................................................ 295
7.7 Fossil Fuel CO2 Input to the Oceans........................................................................ 307

7.7.1 Ocean Acidification...................................................................................... 314
7.7.2 Effect of Ocean Acidification on the Speciation of Metals in Seawater.... 317
References and Further Reading........................................................................................ 329
8. Micronutrients in the Oceans........................................................................................... 335
8.1 Introduction................................................................................................................ 335
8.2 Phosphorus in Seawater............................................................................................ 335
8.2.1 Determination of Phosphate.......................................................................340
8.2.2 Distribution of Phosphate............................................................................340
8.3 Nitrogen Compounds in Seawater..........................................................................342
8.3.1 Determination of Nitrogen Compounds...................................................343
8.3.2 Distribution of Nitrogen Compounds.......................................................345

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8.3.3 Dissolved Organic Nitrogen and Phosphate............................................ 352
8.3.4 Nitrogen–Phosphorus Ratio........................................................................354
8.4 Silicon in Seawater..................................................................................................... 359
8.4.1 Determination of Silicon.............................................................................. 360
8.4.2 Distribution of Dissolved SiO2.................................................................... 362
8.5 Use of Nutrients as Water Mass Tracers................................................................. 362
References and Further Reading........................................................................................ 365
Phosphorus................................................................................................................. 365
Nitrogen....................................................................................................................... 365
Silicon........................................................................................................................... 366
Use of Nutrients......................................................................................................... 366

9. Primary Production in the Oceans.................................................................................. 367
9.1 Primary Production................................................................................................... 367
9.1.1 Phytoplankton Production.......................................................................... 369
9.1.2 Standing Crop or Biomass........................................................................... 370
9.1.3 The O2 Liberation Method of Measuring Primary Productivity........... 370
9.1.4 Uptake of CO2 Method of Measuring Primary Productivity................. 372
9.1.5 Determining New Production.................................................................... 372
9.1.6 Factors Affecting the Growth of Phytoplankton...................................... 374
9.1.6.1 Light................................................................................................ 374
9.1.6.2 Temperature................................................................................... 375
9.1.6.3 Salinity............................................................................................ 375
9.1.6.4 Micronutrients and Trace Metals................................................ 375
9.1.6.5 Organic Factors.............................................................................. 376
9.1.7 Growth and Distribution of Phytoplankton in the Sea........................... 376
9.1.8 Remote Sensing Techniques........................................................................ 380
9.2 The Iron Hypothesis.................................................................................................. 383
9.2.1 IRONEX I Study............................................................................................ 387
9.2.2 Galapagos Plume Study............................................................................... 391
9.2.3 IRONEX II Study........................................................................................... 397
9.2.4 SOFeX Study.................................................................................................. 398
9.3 Microbial Transformations....................................................................................... 403
9.4 Dissolved and Particulate Organic Compounds in Seawater.............................405
9.4.1 Sources of Organic Matter........................................................................... 406
9.4.1.1 Terrestrial Input by Rivers........................................................... 406
9.4.1.2 Terrestrial Input from the Atmosphere..................................... 407
9.4.1.3 Additional Sources of Organic Matter.......................................408
9.4.2 Dissolved and Particulate Organic Matter................................................ 409
9.4.2.1 Dissolved Organic Matter............................................................ 413
9.4.2.2 Particulate Organic Matter.......................................................... 415
9.4.3 Kinds of Organic Compounds in Seawater.............................................. 416

9.4.3.1 Carbohydrates................................................................................ 417
9.4.3.2 Amino Acids and Proteins.......................................................... 419
9.4.3.3 Hydrocarbons................................................................................ 419
9.4.3.4 Carboxylic Acids........................................................................... 419
9.4.3.5 Humic Substances......................................................................... 420
9.4.3.6 Steroids........................................................................................... 420

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ix

Contents

References and Further Reading........................................................................................ 421
Primary Productivity................................................................................................. 421
Iron Limitation............................................................................................................422
Organics in Seawater.................................................................................................423
10. Processes in the Oceans.....................................................................................................425
10.1 Photochemical Processes in Seawater.....................................................................425
10.1.1 Principles........................................................................................................425
10.1.2 Formation of Hydrogen Peroxide............................................................... 431
10.1.3 The •OH Radical........................................................................................... 439
10.2 Hydrothermal Vent Chemistry................................................................................ 441
10.3 Anoxic Waters............................................................................................................. 453
10.3.1 The Black Sea................................................................................................. 459
10.3.2 Cariaco Trench.............................................................................................. 466
10.3.3 Framvaren Fjord............................................................................................ 478
10.3.4 The Kinetics Oxidation of Hydrogen Sulfide in Natural Waters........... 495
References and Further Reading........................................................................................ 502

Photochemistry........................................................................................................... 502
Hydrothermal Vents.................................................................................................. 503
Anoxic Basins.............................................................................................................. 503
Black Sea......................................................................................................................504
Cariaco Trench............................................................................................................504
Framvaren Fjord.........................................................................................................505
Kinetics Oxidation of Hydrogen Sulfide in Natural Waters................................505
Glossary of Chemical Oceanography Terms......................................................................... 507
Descriptive Oceanography....................................................................................... 507
I.
II.
Major Components of Seawater............................................................................... 512
III. Minor Elements in Seawater..................................................................................... 514
Ionic Interactions in Seawater.................................................................................. 518
IV.
V.
Atmospheric Chemistry............................................................................................ 521
VI. Dissolved Gases Other than CO2. ........................................................................... 523
VII. The Carbonate System............................................................................................... 523
VIII. Micronutrients in the Oceans................................................................................... 525
IX. Primary Production in the Oceans.......................................................................... 526
Organic Compounds................................................................................................. 527
X.
Processes in the Oceans............................................................................................ 529
Photochemical Processes........................................................................................... 529
Hydrothermal Vent Chemistry................................................................................ 530
Anoxic Waters............................................................................................................. 531
Appendix 1................................................................................................................................... 533
Appendix 2................................................................................................................................... 537
Appendix 3................................................................................................................................... 539

Appendix 4................................................................................................................................... 541
Appendix 5...................................................................................................................................543
Appendix 6...................................................................................................................................545
Index.............................................................................................................................................. 547

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Preface to the First Edition
This book is the result of a course that I have taught over the last 20 years at the University
of Miami. Shortly after I arrived in Miami in 1966 from a short stint in industry, I was
asked to teach a graduate course in chemical oceanography. At the time I knew little about
the oceans and found it necessary to do a lot of reading. Luckily J. P. Riley and G. Skirrow
(1965) had just edited a two-volume book on chemical oceanography. The book contained
chapters written by a number of authors that described the basic areas of the field. I used
these volumes as a source for my first course and the present book is patterned after these
volumes. My early reading included the classical text The Oceans by Sverdrup, Johnson,
and Fleming and the book Oceanography edited by M. Sears (1961). I used the text Marine
Chemistry by Horne (1969), and the text Introduction to Marine Chemistry by Riley and
Chester (1971) for some time, but they became outdated. The volumes of The Sea: Ideas and
Observations, edited by Hill and others (1963, 1974, 1977) were used as a source of supplemental material. The second edition of Chemical Oceanography by Riley and Skirrow (1975)
and later volumes by Riley and Chester (1976, 1978, 1983) and by Riley (1989) are still used
to keep the course up to date.
In 1980 I started teaching an undergraduate course in chemical oceanography and found
the need for a textbook. The text Chemical Oceanography by Broecker (1971) was used for a
time, but it did not cover the classical areas that were more familiar to me. The more recent
Tracers in the Sea by Broecker and Peng (1982) was better, but the undergraduate students

found it difficult to follow. Although graduate students can probe the volumes of Chemical
Oceanography and current literature references, undergraduate students need a more fundamental approach to the field. The present text is my attempt to put together my views of
the field. It is largely descriptive and is biased by my strong mechanistic feelings as a physical chemist. Since it is meant to be an undergraduate text, I have not given all the original
references. I have mentioned by name many of my colleagues who have contributed to
the field—I apologize for any omissions. Since my background and interests in organic
chemistry are rather meager, I asked May Sohn to join me as co-author. She has been very
helpful in correcting some of my mistakes and wrote the chapter on organic chemistry.
As with most endeavors, I owe thanks to a number of people: my many students, both
graduate and undergraduate who have struggled through my courses; Mrs. Rita Marvez
who has typed and re-typed the many drafts of this book; Mrs. Sara Sotolongo who has
drawn many of the figures; and Kara Kern, who carefully proofed the final copy. The
support of my research from the National Science Foundation and the Office of Naval
Research should also be acknowledged. These agencies provided me with research funds
to probe the thermodynamics and kinetics of processes occurring in the oceans.
I am sure the book has some flaws, but I hope it will prove useful to those wishing to get
an introduction to the field of chemical oceanography. Some of the books that have shaped
my views of the field are given below.
The Oceans, H. U. Sverdrup, M. W. Johnson, and R. H. Fleming, Prentice-Hall, Englewood Cliffs, New
Jersey (1942).
The Chemistry and Fertility of Seawater, H. W. Harvey, Cambridge University Press, London (1955).
Oceanography, M. Sears, Ed., Pub 67, A.A.A.S., Washington, D.C. (1961).
The Sea: Ideas and Observations, M. N. Hill, Ed., Vol. 2, John Wiley & Sons, New York (1963).
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Preface to the First Edition

The Sea: Ideas and Observations, E. D. Goldberg, Ed., Vol. 5, John Wiley & Sons, New York (1974).
The Sea: Ideas and Observations, E. D. Goldberg, I. N. McCave, J. J. O’Brien, and J. H. Steel, Eds., Vol. 6,
John Wiley & Sons, New York (1977).
Marine Chemistry, R. A. Horne, Wiley-Interscience, New York (1969).
Introduction to Marine Chemistry, J. P. Riley and R. Chester, Academic Press, New York (1971).
Chemical Oceanography, W. S. Broecker, Harcourt, Brace and Jovanovich Inc., New York (1971).
Chemical Oceanography, J. P. Riley and G. Skirrow, Vols. 1 and 2, 1st ed., Academic Press, New York (1965).
Chemical Oceanography, J. P. Riley and G. Skirrow, Vols. 1 to 4, 2nd ed., Academic Press, New York (1975).
Chemical Oceanography, J. P. Riley and R. Chester, Vols. 5 and 6, 2nd ed., Academic Press, New York (1976).
Chemical Oceanography, J. P. Riley and R. Chester, Vol. 7, 2nd ed., Academic Press, New York (1978).
Chemical Oceanography, J. P. Riley and R. Chester, Vol. 8, 2nd ed., Academic Press, New York (1983).
Chemical Oceanography, J. P. Riley, Vols. 9 and 10, 2nd ed., Academic Press, New York (1989).
Tracers in the Sea, W. S. Broecker and T. H. Peng, Eldigio Press, Palisades, NY (1982).

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Preface to the Second Edition
In 1992 the first edition of this book was published as a result of my teaching a course
in chemical oceanography at the University of Miami over the last 25 years. This edition is an updated version of this book which I hope is improved due to the comments
of undergraduate and graduate students that have struggled through my first attempt.
I have deleted the chapter on organic chemistry largely due to my ignorance of this field
and the problems my students had getting through this area. I discuss the organic compounds that are related to primary production in a separate chapter. This chapter also
includes a discussion on the iron hypothesis that has been examined in recent years. The
other chapters have been updated as new areas have been discussed in the literature. As
with the first edition of the book, it is meant to be used as an upper level undergraduate
course or a first year graduate course in chemical oceanography. At the graduate level it
can be supplemented with the volumes of Chemical Oceanography and current literature
references. It remains biased with my views of the field. It is largely descriptive and is

biased by my strong mechanistic feelings as a physical chemist. Since it is meant to be
an undergraduate text, I have not given all the original references. I have mentioned by
name many of those colleagues of mine that have contributed to the field— I apologize
for any omissions.
As with most endeavors, I owe thanks to a number of people: my many students,
both graduate and undergraduate, who have struggled through my courses; Mrs. Sara
Sotolongo, Elizabeth Degler, Meridith Galanter, and Danny Madina who have drawn
many of the figures; and Gay Ingram for proofing the book. The support of the National
Science Foundation and the Office of Naval Research of my research work should also be
acknowledged. These agencies provided me with research funds to probe the thermodynamics and kinetics of processes occurring in the oceans.
I am sure the book still has some flaws, but I hope it will prove useful to those wishing
to get an introduction to the field of chemical oceanography.

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Preface to the Third Edition
This third edition of the book has been updated based on recent literature. It is still
based on undergraduate and graduate courses I have taught for the past 39 years at the
University of Miami. Over the past 10 years a number of large-scale oceanographic programs have been completed. These programs have examined the physical, chemical,
and biological systems in the oceans. These include the Joint Global Ocean Flux Study
(JGOFS) and the World Ocean Climate Experiment (WOCE). These studies have provided
a wealth of maps and sections of properties of the oceans and are available on the web.
Some of the sections for nutrients and carbonate parameters have been given. A number of iron addition experiments have been made in the southern ocean in recent years
(SOIREE, Southern Ocean Iron RElease Experiment, EisenEx, “Iron” Experiment, and

the SOFEX, Southern Ocean Iron Experiment). These studies have led to a vast amount
of new data that have been used to examine the biogeochemical processes occurring in
the oceans. In the new revision, I have attempted to discuss some of this latest material.
The section of the book on the carbonate system in the oceans has been expanded to
examine the input of fossil fuel CO2 into the oceans and the effect it will have on the pH
of the world oceans.
As with earlier editions of the book, several students and coworkers have helped to
redo a number of the figures and proof the text. Much of this was done by Mr. Taylor
Graham, who has been with my group as an undergraduate from the University of Miami
and has stayed on as a research assistant before he enters graduate school. I also wish to
acknowledge the help of Gay Ingram, my secretary, as well as my student Hector Bustos
Serrano, who did some proofreading of the book. A number of readers have sent me corrections for typos in the last edition. I have attempted to correct all of these errors as well
as others pointed out by my students taking my undergraduate class in chemical oceanography. Over the years much of the content of the book has been put into PowerPoint
presentations. I hope to make these presentations available to those using the book as a
text. I also have a number of Quick Basic programs that can be used to calculate the properties of seawater, carbonate parameters, and the speciation of metals in natural waters
that are available upon request.

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Preface to the Fourth Edition
This fourth edition of the book has been updated based on recent literature. It is still
based on undergraduate and graduate courses I have taught for the past 45 years at the
University of Miami. Over the past 10 years a number of new large-scale oceanographic
programs have been initiated. This includes The Climate Variability Program (CLIVAR)

and the recent initiation of the Geochemical Trace Metal Program (GEOTRACES). This
program is aimed at understanding the biogeochemical cycles of trace elements in the
oceans. The initial studies have already shown the input of Fe and Pb from hydrothermal
vents and the redox behavior of metals in low oxygen waters. These recent and future
studies will produce a wealth of information on the biogeochemistry of the world oceans.
The increasing CO2 in the atmosphere from the burning of fossil fuels continues to affect
the atmosphere and the oceans. The increased temperature of surface waters is causing
stratification in the oceans. This has led to areas of low oxygen regions in coastal waters.
Each year oceanographers contribute to the expanding knowledge of the oceans. I have
tried to build and update this introduction to Chemical Oceanography with new understanding and concepts. The dissolution of CO2 in the waters is lowering the pH (called
ocean acidification). This lower pH will affect calcifiers in the oceans and biogeochemical
processes such as equilibrium and rates of reactions. New research in the field of ocean
acidification has been added as well as information on the new standards developed by
the SCOR/IAPSO working group to describe the properties of seawater for researchers to
report their measurements. Standardization of measurements in the literature leads to a
clearer understanding and less confusion in reporting the processes in the oceans. More
research will come over the next ten years and I will try to add any new and exciting
changes in the oceans in my PowerPoint Lecture that I update each year. I hope the new
edition covers some of the areas that were missing and gives a reasonable review of the
basic concepts of the field.
There are a number of graduate and undergraduate students that have contributed to the
updating of this book. This summer I was fortunate to have Sara Denka, a junior majoring
in marine science/biology at the University of Miami, assist me in editing this fourth edition of Chemical Oceanography. She took my undergraduate course and was familiar with
the content of the earlier version. From 2005-2012, my Ph.D. students Yanxin Luo, William
Hiscock, Mareva Chanson, John Michael Trapp, Hector Bustos Serrano, Jason Waters, Ryan
Woosley, Benjamin Ditrolio, and Carmen Rodriguez provided additional comments and
corrections to the text. Gay Ingram, my right hand, has also edited the various versions of
my papers and books over the years.
The continual support of the National Science Foundation and the National
Oceanographic and Atmospheric Administration provided the research funds for our

work. Without the financial backing from these two U.S. government agencies our research
would be seriously curtailed. We thank them for their interest in the common good and
advancement of scientific knowledge.

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About the Author
Dr. Frank J. Millero was born in Greenville, Pennsylvania, in 1939. He received his B.S.
(1961) from Ohio State University and his M.S. (1964) and Ph.D. (1965) from Carnegie-Mellon
University in physical chemistry. After a brief interval in industry, he came to the Rosenstiel
School of the University of Miami in 1966. He has been a professor in marine and physical
chemistry since that time. During 1986 to 2006 he was the Associate Dean of Academic
Affairs and Research at the school. His research focuses on the application of physical
chemical principles to natural waters. He uses chemical models to understand how ionic
interactions affect the thermodynamics and kinetics of processes occurring in the oceans.
These studies have resulted in numerous research cruises in the Indian, Pacific, Atlantic,
and Southern oceans and the Arabian Sea. Millero’s research group is presently studying
the carbonate system in the world oceans as part of the CLIVAR (Climate Variability) project to determine the changes in the flux of CO2 across the air–sea interface in the oceans
and ocean acidification. Over the years, he has received a number of awards for his teaching and research accomplishments. These include the Office of Naval Research Educator
Award (1991-1995), Sigma Xi Professor of the Year (1989), Florida Academy of Science Medal
(1991), Sigma Xi Professor of the Year (1989), Florida Academy of Science Medal (1991), and
a Gold Medal from Rudjer Boskovic Institute, Zabreb, Croatia, in recognition of contributions to marine chemistry (1988). He was selected as a member of his Warren, Ohio, High
School Distinguished Alumni Hall of Fame and won the Carnegie Mellon Distinguished
Achievement Award (2003). He received the Distinguished Faculty Scholar Award from

the University of Miami (1966). In 2011 Millero received the Geochemical Society Victor
Moritz Goldschmidt Award for distinguished research in geochemistry and the Florida
Award (Florida section of the American Chemical Society (FLACS). He is a Fellow of
the 1) American Geophysical Union (1999); 2) Geochemical Society and the European
Association for Geochemistry (2000); and 3) American Association for the Advancement
of Science (2009).
He has served on the National Academy of Sciences Ocean Science Board (1981–1983) and
is a member of a number of chemical and oceanographic societies. He also served on the
National Academies Committee on the Development of an Integrated Science Strategy for
Ocean Acidification Monitoring, Research and Impacts Assessment (2009-10). In addition,
he serves as an associate editor for a number of journals and is presently editor-in-chief
of Marine Chemistry. Professor Millero has authored more than 550 juried publications in
75 different journals and numerous book chapters and has published two major books on
marine chemistry.
At the university he has taught courses in chemical oceanography and marine physical chemistry at the graduate and undergraduate level for 45 years. He is proud to have
published papers with 8 high school students, 21 undergraduate students, and 43 graduate students over the years. Many have become successful chemists, engineers, and
other professionals.

xix

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1
Descriptive Oceanography

1.1 Introduction

Before we discuss the chemistry of the oceans, it is useful to review some descriptive features of the oceans. Oceanography is the scientific study of the oceans and can be divided
into four major areas:





1.Physical oceanography: the study of the physics of the oceans and their interactions with the atmosphere
2.Biological oceanography: the study of the biology of the oceans
3.Geological oceanography: the study of the geology and geophysics of the oceans
4.Chemical oceanography: the study of the chemistry of the oceans

The basic goal of oceanography is to obtain a clear and systematic description of the
oceans. It is hoped that an increased knowledge of the oceans will lead to a better understanding of how they control the climate of the earth and how they can be used as a source
of food, chemicals, and energy.
The goal of the physical oceanographer is to obtain a systematic and quantitative description of ocean waters and their movements. The ocean currents circulate continuously with
small-­scale variations from tides and waves generated by winds and earthquakes. This
physical study of the oceans has been examined by



1.The descriptive approach: Observations are made of specific features and reduced
to a single characterization of the general features.
2.The dynamic approach: The known laws of physics are applied to the oceans.
An attempt is made to solve the mathematical equations for the motion of a body
acted on by forces.

This chapter gives a brief review of descriptive physical oceanography of the oceans. It
is important to understand these descriptive features since the movement of ocean waters
affects the biogeochemical processes that occur in the oceans. Much of the material covered in the earlier editions of the book was taken from books by Pickard and Emery (1982),

Dietrich et al. (1980), and Tchernia (1980). Lynne Tally, George Pickard, and Wilmer Emery
and James Smith (2011) have written a sixth edition of the earlier Pickard and Emery (1982)
book. It is up to date and should be referred to for further details.
The field of physical oceanography has expanded in recent years due to a number of
large-­scale research programs, including the following:
1

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Chemical Oceanography, 4th Edition



1.The Geochemical Oceans Sections Study (GEOSECS) from 1970 to 1980



2.The World Ocean Circulation Experiment (WOCE) from 1990 to 2000



3.The Climate Variability and Predictability (CLIVAR) project from 2001 to the present

Early theoretical studies of surface tides were made by Newton and Laplace and of
waves by Gerstner and Stokes. The Scandinavian meteorologists Bjerknes, Ekman, and
Helland-­Hansen developed the field of dynamic oceanography. Recent studies have examined coastal processes, western boundary currents (such as the Gulf Stream), and small-­
scale fluctuations, eddies or rings, bottom water movement, and the use of tracers to study

large-­scale mixing processes. Currently, physical and chemical oceanographers are participating in CLIVAR. This study is a continuation of the WOCE program. This global
study includes a reoccupation of some of the long lines that were studied as part of the
Joint Global Ocean Flux Study (JGOFS) and Ocean–Atmosphere Carbon Exchange Study
(OACES) CO2 programs, which are discussed further elsewhere in this book. Future oceanography will have a strong component dealing with satellites and remote sensing techniques utilizing moored arrays of instruments in the oceans. This global ocean observing
system (GOOS) will be concerned with making continuous physical and chemical measurements of the global ocean. It should also be pointed out that a new International Study
of Marine Biogeochemical Cycles of Trace Elements and Their Isotopes has been initiated.
It is called GEOTRACES. These studies should provide a wealth of information on the
effect that trace metals have on biogeochemical processes in the oceans.

1.2 Physical Characteristics of the Oceans
Some general physical features of the oceans to keep in mind are the following:


1.Of the earth’s surface, 71% is covered by the oceans (361 × 106 km2).



2.The deepest trench is 11,022 m (Mariana); the highest mountain on land is 8848 m
(Mt. Everest).



3. The Southern Hemisphere has the largest percentage of water (80.9%) in the oceans.



4. The world oceans are made up of 50% Pacific, 29% Atlantic, and 21% Indian Oceans
by volume.

5.The major depth zone of the ocean (74%) lies between 3 and 6 km.



6.Of ocean waters, 50% have a temperature range between 1.3 and 3.8°C and salinity
(grams of salt in 1 kg of seawater) between 34.6 and 34.8.



7.The mean depth of the oceans is 3.7 km; the mean temperature is 3.5°C, and the
mean salinity is 34.7.

The major features of the ocean floor are shown in Figure 1.1. Continental margins show
a wide range of unique features, and a number of studies have been conducted of seamounts that occur in deep-­sea basins. The detailed structure has been examined for the
midocean ridge systems (see Figure 1.2).
The shore is the part of the land mass close to the sea that has been modified by the
sea. The continental shelf is seaward from the shore and has a gradient or slope of 1 to

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3

Descriptive Oceanography

Island Arc
Trench

Sea

Mount

e
Slop

Shore

Continent

High Water
Sea Level
Low Water
Break in Slope
Shelf

Basin
Deep Sea Bottom

Figure 1.1
Structure of the ocean floor.

S.Explorer Ridge
Juan de Fuca Ridge

Azores

Gorda Ridge

Lau Basin
Havre

Trough

Southeast Indian Ridge

Mid

Atl
ant
ic

Galápagos Rift

Ch

ile

R is

e
Scotia
Plate

Pacific Atlantic Ridge

Central
Indian
Ridge

Ridge

Manus & Woodlark
Basins
N. Fiji Basin

Red
Sea

Guaymas Basin

Mariana Trough

East Pacific Rise

Okinawa
Trough

Bouvet
T.J.

Rodrigues
T.J.

ian

d
. In
S.W

Rid

ge
SE Indian
Ridge

E. Scotia Ridge

Locations of known hydrothermal activity along the global mid-ocean ridge system
= Known active sites
= Active sites indicated by midwater chemical anomalies

Figure 1.2
Active ridge systems in the oceans.

500 and an average width of 65 km. The break in slope is the outer limit of the shelf and
has a slope of about 1 to 20 and an average depth of 130 m. The continental slope is about
4000 m from the shelf to the deep-­sea bottom. In some places, it extends as much as 9000 m
vertically over a relatively short horizontal distance (e.g., off the western coast of America).
The deep-­sea bottom represents the most extensive topographic area (76% of ocean basins)

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Chemical Oceanography, 4th Edition

Sediment Types

Volcanic and Continental
Weathering Products

Meteorites

World
Dissolved
Phases

Pore
Solutions

Hydrogenous

Ocean
Particulate
Phases

Biogenous

Lithogenous

Cosmogenous

Sediment Components
Figure 1.3
Types of ocean sediments.

and has a depth between 3 and 6 km. This area is not completely flat but is characterized
by welts, furrows, swells, and basins.
The bottom sediments contain material both formed in the sea (pelagic) and brought
from the land by rivers and the atmosphere (nonpelagic). The components of sediments

can be divided into a detrital fraction transported as a solid and a nondetrital, or authigenic, fraction transported as dissolved matter. Sediments can be divided into four types
(see Figure 1.3):





1.Hydrogenous: formed by reactions (precipitation and adsorption) in the water
2.Biogenous: produced by living organisms from the parts of shells and skeletons
3.Lithogenous: produced from the weathering of the earth’s surface and transported
by rivers and winds to the oceans
4.Cosmogenous: produced from extraterrestrial sources
Examples of the various types include





1.Hydrogenous: aragonite (CaSO3) in the form of “whitings” on the Bahama Banks;
manganese (MnO2) nodules in the deep Pacific; iron hydroxides (Fe2O3); sulfates
(CaSO4); and phosphates, Ca3(PO4)2
2.Biogenous: calcite (CaCO3) from foraminifera and cocoliths, aragonite from pteropods, silica (SiO2) from radiolarians and diatoms

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