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Endpaper
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Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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The chemical elements, IUPAC (2007)
Name Symbol
Atomic
number
Atomic
weight Name Symbol
Atomic
number
Atomic
weight
Actinium Ac 89 227 Molybdenum Mo 42 95.96
Aluminum Al 13 26.982 Neodymium Nd 60 144.242
Americium Am 95 243 Neon Ne 10 20.180
Antimony Sb 51 121.76 Neptunium Np 93 237
Argon Ar 18 39.948 Nickel Ni 28 58.693
Arsenic As 33 74.922 Niobium Nb 41 92.906
Astatine At 85 210 Nitrogen N 7 14.0067
Berkelium Bk 97 247 Osmium Os 76 190.23
Beryllium Be 4 9.012 Oxygen O 8 15.999
Bismuth Bi 83 208.980 Palladium Pd 46 106.42
Boron B 5 10.811 Phosphorus P 15 30.974
Bromine Br 35 79.904 Platinum Pt 78 195.084
Cadmium Cd 48 112.411 Plutonium Pu 94 244
Caesium Cs 55 132.905 Polonium Po 84 209
Calcium Ca 20 40.078 Potassium K 19 39.098
Californium Cf 98 251 Praseodymium Pr 59 140.908
Carbon C 6 12.0107 Promethium Pm 61 145
Cerium Ce 58 140.116 Protactinium Pa 91 231.036
Chlorine Cl 17 35.453 Radium Ra 88 226
Chromium Cr 24 51.996 Radon Rn 86 222
Cobalt Co 27 58.933 Rhenium Re 75 186.207
Copper Cu 29 63.546 Rhodium Rh 45 102.906
Curium Cm 96 247 Rubidium Rb 37 85.468
Dysprosium Dy 66 162.5 Ruthenium Ru 44 101.07
Erbium Er 68 167.259 Samarium Sm 62 150.36
Europium Eu 63 151.964 Scandium Sc 21 44.956
Fluorine F 9 18.998 Selenium Se 34 78.96
Francium Fr 87 223 Silicon Si 14 28.0855
Gadolinium Gd 64 157.25 Silver Ag 47 107.868
Gallium Ga 31 69.723 Sodium Na 11 22.990
Germanium Ge 32 72.64 Strontium Sr 38 87.62
Gold Au 79 196.967 Tantalum Ta 73 180.948
Hafnium Hf 72 178.49 Technetium Tc 43 98
Helium He 2 4.0026 Tellurium Te 52 127.6
Holmium Ho 67 164.930 Terbium Tb 65 158.925
Hydrogen H 1 1.00794 Thallium Tl 81 204.383
Indium In 49 114.818 Thorium Th 90 232.038
Iodine I 53 126.904 Thulium Tm 69 168.934
Iridium Ir 77 192.217 Tin Sn 50 118.71
Iron Fe 26 55.845 Titanium Ti 22 47.867
Krypton Kr 36 83.798 Tungsten W 74 183.84
Lanthanum La 57 138.905 Uranium U 92 238.029
Lead Pb 82 207.2 Vanadium V 23 50.942
Lithium Li 3 6.941 Xenon Xe 54 131.293
Lutetium Lu 71 174.967 Ytterbium Yb 70 173.054
Magnesium Mg 12 24.305 Yttrium Y 39 88.906
Manganese Mn 25 54.938 Zinc Zn 30 65.38
Mercury Hg 80 200.59 Zirconium Zr 40 91.224
Data from Wieser (2006), updates from IUPAC website. Where there is no figure after the decimal point
the element is man-made or the isotopic composition is variable so only the approximate weight of the
most stable or most important isotope is listed.
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
An Introduction to the Chemistry of the Sea
Engaging and clearly written, this new edition is an accessible introduction that
provides students in oceanography, marine chemistry and biogeochemistry with the
fundamental tools they need. It highlights geochemical interactions between the
ocean, solid earth, atmosphere, and climate, enabling students to appreciate the
interconnectedness of Earth’s processes and systems, and elucidates the huge vari-
ations in the oceans’ chemical environment, from surface waters to deep water.
• Fully updated to cover exciting recent developments in the field, including all-new
sections and expanded material ranging from estuaries and sediments to methane
hydrates and ligands.
• Now with a glossary, new end-of-chapter summaries, and questions for students to
review their learning and put the theory into practice.
• Appendices provide a useful detailed reference for students, and include seawater
properties, and key equations and constants for calculating oceanographic
processes.
“This second edition is a welcome updating of Pilson’s classic text. The book treats
the broad range of aspects of marine chemistry for advanced undergraduates and
graduate students, but even seasoned researchers will find it a valuable resource. The
inclusion of a historical perspective throughout the book is particularly useful.”
– Professor J. Kirk Cochran
School of Marine and Atmospheric Sciences, Stony Brook University
“Contains an enormous wealth of information, presenting marine chemistry in a way
that even non-chemists will be able to grasp. Pilson has taken great care to explain
the basics as well as the state-of-the-art. It is a book that any marine scientist (from
undergraduate through to professor) will benefit from having close to hand.”
– Professor David Thomas
School of Ocean Sciences, Bangor University;
UK & Finnish Environment Institute, Marine Research Centre, Helsinki;
Finland & Arctic Research Centre, Aarhus University, Denmark
“This book is unique and clearly presented: not just a textbook for courses on ocean
chemistry, but definitely a great reference book for coastal ecosystems and freshwater
bodies as well.” – Dr. Yushun Chen
Director of Environmental Quality and Ecosystems Health Research
Laboratory Aquaculture and Fisheries Center, University of Arkansas
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
“This new edition of Pilson’s classic textbook has been brought up to date with
regard to the latest analytical techniques and scientific insights of modern marine
chemistry. With its broad scope and light narrative style it will likely remain the
foundation of many excellent graduate and advanced undergraduate courses for
years to come.”
– Dr. Johan Schijf
University of Maryland Center for
Environmental Science / Chesapeake Biological Laboratory
Michael E. Q. Pilson is Emeritus Professor of Oceanography at the Graduate School
of Oceanography, University of Rhode Island, and has taught a course on chemical
oceanography for most of the past 40 years. For some years, he directed the Marine
Ecosystems Research Laboratory at Rhode Island, conducting experimental study of
biogeochemistry in shallow coastal waters. Professor Pilson has published around 90
papers on chemical, physical, biological, ecological, and geological aspects of ocean-
ography and has advised students in chemical and biological areas. His broad range
of experience has shaped his oceanography course to be accessible and interesting to
students with diverse backgrounds, interests and professional goals.
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
An Introduction to theChemistry of the SeaSecond Edition
MICHAEL E. Q. PILSONUniversity of Rhode Island
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
cambridge university press
Cambridge, New York, Melbourne, Madrid, Cape Town,Singapore, Sao Paulo, Delhi, Mexico City
Cambridge University Press
The Edinburgh Building, Cambridge CB2 8RU, UK
Published in the United States of America by Cambridge University Press, New York
www.cambridge.orgInformation on this title: www.cambridge.org/9780521887076
First edition published by Prentice Hall (Pearson Education Inc.), UK, 1998,as An Introduction to the Chemistry of the Sea
First edition # Prentice Hall Inc. 1998Second edition # Michael E. Q. Pilson 2013
This publication is in copyright. Subject to statutory exceptionand to the provisions of relevant collective licensing agreements,no reproduction of any part may take place without
the written permission of Cambridge University Press.
Printed and bound in the United Kingdom by the MPG Books Group
A catalogue record for this publication is available from the British Library
Library of Congress Cataloging-in-Publication Data
Pilson, Michael E. Q.
An introduction to the chemistry of the sea / Michael E. Q. Pilson,University of Rhode Island. – Second edition.
pages cm
Includes bibliographical references and index.ISBN 978-0-521-88707-61. Chemical oceanography. I. Title.GC111.2.P55 2013
551.4606–dc23 2012028896
ISBN 978-0-521-88707-6 Hardback
Additional resources for this publication at www.cambridge.org/pilson
Cambridge University Press has no responsibility for the persistence oraccuracy of URLs for external or third-party internet websites referred toin this publication, and does not guarantee that any content on such
websites is, or will remain, accurate or appropriate.
Cover illustration (front): phytoplankton bloom in the Barents Sea, 31 Aug 2010. NASAimage courtesy of Norman Kuring, NASA Ocean Color Group. (back inset, graph): The
seawater in equilibrium with the atmosphere has a temperature of 18 �C, a salinity of 35%,and a total alkalinity of 2.32 mmol kg�1, close to the current global averages for thesurface ocean. This graph is updated from one that appeared on the cover of the 1998
edition of this book.
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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CONTENTS
Preface page ix
Acknowledgments xi
1 Introduction 11.1 Scope of chemical oceanography 2
1.2 History of chemical oceanography 5
1.3 Major features of ocean circulation 12
2 The water in seawater 202.1 Physical properties of water 20
2.2 Isotopes of hydrogen and oxygen 29
2.3 Clathrate compounds 41
3 Salinity, chlorinity, conductivity, and density 463.1 Need for accurate determination of salinity and density 46
3.2 Salinity 48
3.3 Chlorinity 51
3.4 Relationships between chlorinity and salinity 52
3.5 Conductivity and salinity 53
3.6 Salinity and density 59
4 Major constituents of seawater 664.1 Concentrations 66
4.2 Residence times 69
5 Simple gases 745.1 General considerations 74
5.2 Simple gas laws 75
5.3 Solubility in water 76
5.4 Sources and sinks within the ocean 80
5.5 Atmospheric exchange by diffusion 81
5.6 Air injection 90
6 Salts in solution 956.1 Solubility of salts 95
6.2 Freezing point and boiling point 97
6.3 Osmotic pressure 97
6.4 Activity coefficients 101
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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6.5 Electrostriction 105
6.6 Absorption of sound 107
6.7 A note on pH 110
7 Carbon dioxide 1147.1 Reservoirs of carbon dioxide 115
7.2 Relationships in solution 116
7.3 Calcium carbonate 136
7.4 Anthropogenic carbon dioxide 150
7.5 Longer-term issues 173
8 Nutrients 1768.1 Phosphorus 176
8.2 Nitrogen 186
8.3 Silicon 199
8.4 Other nutrients 209
8.5 Quantitative relationships 212
8.6 Initial nutrients 220
9 Trace metals and other minor elements 2289.1 Analytical considerations 228
9.2 Various patterns of distribution 231
9.3 Mercury, an interesting special case 243
9.4 Speciation 249
9.5 Iron, another special case 253
9.6 Trace elements in sediments 257
10 Radioactive clocks 26110.1 Radioactivity 262
10.2 Radionuclides in seawater 267
10.3 The uranium series 270
10.4 Carbon-14 278
11 Organic matter in the sea 28711.1 Historical note 288
11.2 Primary production 289
11.3 Other sources of organic matter 294
11.4 Fate of the primary product 296
11.5 Measurement of organic carbon in seawater 304
11.6 Concentration and age of marine organic matter 305
11.7 Nature of marine organic matter 308
12 Anoxic marine environments 32712.1 Rates of oxygen consumption 327
12.2 Anoxic oxidation 330
12.3 The Black Sea 333
vi Contents
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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13 Exchanges at the boundaries 34213.1 River input 343
13.2 Air–sea exchange 345
13.3 Hot rocks 347
13.4 Sediment–water exchange 356
13.5 Warm clay 361
13.6 Residence times 365
14 Chemical extraction of useful substances from the sea 36814.1 Salt 368
14.2 Evaporation of seawater 370
14.3 Rock salt 372
14.4 Magnesium 374
14.5 Bromine 375
14.6 Gold 376
14.7 Water 377
15 Geochemical history of the oceans 37915.1 Illustrative rates 380
15.2 Early history of the ocean volume 381
15.3 Glacially caused changes in ocean volume 387
15.4 Mass of salt in the ocean 387
15.5 Composition of sea salt 389
15.6 Oxygen 392
15.7 Strontium isotopes 393
15.8 The churning of the Earth 395
Appendices 398A The chemical elements 398
B Symbols, units, and nomenclature 400
C Physical properties of seawater 404
D Gases 414
E Carbon dioxide 430
F Dissociation constants and pH scales 441
G Solubility of calcium carbonate 450
H Effects of pressure 453
I Radioactive decay 456
J Geochemical reservoirs, and some rates 459
K Sound absorption 466
Epilogue 467
Questions for chapters 471
Glossary 479
References 483
Index 516
vii Contents
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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PREFACE
This textbook grew out of a set of class notes developed for teaching an introductory
course on the chemistry of the sea to successive classes of beginning graduate
students in oceanography, and to a few undergraduates. Students enter marine
science from a wide variety of disciplines; I have not assumed an advanced know-
ledge of chemistry nor, indeed, of any single science. The book is intended to be
accessible to anyone with some exposure to chemistry, physics, and biology (such as
would be the case for most people with a degree in a natural science), as well as a little
geology. It might be helpful if the reader has previously seen one or more of the many
excellent books that provide a general description of the oceans or has otherwise
acquired a similar overview.
The coverage is intended to provide an introduction appropriate for most students
of marine science, as well as a general base from which the professional marine
chemist can go forward to specialized studies. A rather large number of references
provides an entree to reviews, textbooks, and more specialized literature. Tables of
numerical values and constants, provided in the Appendix, will be useful to ocean-
ographers and other environmental scientists.
Every branch of oceanography draws to some extent upon the others, and this
interaction often passes through a common link in the chemistry of seawater. The
chemistry of the sea affects and is affected by numerous physical, biological, and
geological processes. Much of the knowledge of physical processes comes from
chemical measurement, and in turn the great flows and mixings in the sea influence
the distribution of chemical substances. The biota influence many aspects of the
chemistry of the sea and in turn are controlled in part by the chemistry of the medium
in which they float or swim. The sediments of the sea floor are partly the product of
chemical and biological processes, and finally the chemistry of the sea is ultimately
controlled in large part by geological processes. I have endeavored to point out or
draw upon these linkages, when I have had the strength to do so.
Some subjects are covered more completely than others. For example, in Chapter 7,
the subject of carbon dioxide is presented in considerable detail, for several reasons.
The carbon dioxide system itself touches on or is deeply intertwined with most areas of
marine science. Air–sea gas exchange, solubility of gases, physical chemistry of sea-
water, ionic reactions, biological production and respiration, precipitation and dissol-
ution of minerals in seawater, ocean circulation, isotopic tracers and the dating of
seawater, and the history of ancient climates are all subjects where knowledge of the
carbon dioxide system is important as a base or contributes to the analysis. Further-
more, one of the major impacts by humans on the biogeochemistry of Earth is caused
by the discharge of carbon dioxide. The role of CO2 in climate change and the role of
the oceans in modulating the concentration of CO2 in the atmosphere are so important
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
that it seemed useful to make this section as thorough as a reasonable balance of space
would allow.
When it seemed interesting or illuminating, I have provided a brief recounting of
the history of a subject, for I think that science textbooks too often present the state
of a field as if it is rather fixed, with too little appreciation of how we got to where we
are. Sometimes the sense of where we are now in the development of our understand-
ing can only be gained by a little familiarity with the rhythm and pace of scientific
discovery. In a few cases I have included early figures from the literature, rather than
figures derived from better modern data, because often the general principle involved
in some process was initially fixed into our minds by a glance at that early figure.
Many subjects touched on in this book are active fields of research. Every month
the journals coming into the library bring relevant facts to enhance our knowledge or
new insights to change in some detail the way we view the chemistry of the sea. Those
who would maintain a current knowledge of the field must keep reading the journal
literature. The material covered here will help to prepare the reader to read those
journals. I will be most grateful to those who make substantive suggestions or report
the inevitable errors.
x Preface
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
www.cambridge.org© in this web service Cambridge University Press
ACKNOWLEDGMENTS
I thank all the many students, colleagues, and others (some of whom I know only
from what they have written) who have helped or stimulated me over many years.
I especially acknowledge Dana Kester, John Knauss, Jim Quinn, and Dave Schink.
A great many helpful comments on the manuscript were received from David
R. Schink, Texas A & M University; Douglas E. Hammond, University of Southern
California; James G. Quinn, University of Rhode Island; Theodore C. Loder III,
University of New Hampshire; and Kent A. Fanning, University of South Florida.
The organizers of each of the Gordon Conferences in Chemical Oceanography are
also due special thanks, beginning with Norris Rakestraw and Victor Linnenbom
who initiated the series. Without these excellent and stimulating conferences, held at
intervals since 1969, this book might not have been written. Early drafts of the first
edition were typed by my wonderfully competent secretary, Evelyn Dyer.
The preparation of the second edition has been substantially aided by the many
suggestions from several dozen students and other colleagues of several institutions.
I am grateful to all.
Lastly, our present understanding of the chemistry of the sea has been won by the
cleverness and dedication of only a few hundred investigators inquiring into the
processes at work in Earth’s environment, especially the oceans. As sciences go, it
is a relatively small, but, for me, a very special group of people.
Michael E. Q. Pilson
Graduate School of Oceanography
University of Rhode Island
Cambridge University Press978-0-521-88707-6 - An Introduction to the Chemistry of the Sea: Second EditionMichael E. Q. PilsonFrontmatterMore information
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