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figure:copyright©2012IU

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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

www.cambridge.org© in this web service Cambridge University Press

http://www.cambridge.org/9780521887076

http://www.cambridge.org


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.






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






“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.






An Introduction to theChemistry of the SeaSecond Edition

MICHAEL E. Q. PILSONUniversity of Rhode Island






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.






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






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






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











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






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






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






Documents

IUPAC Periodic Table of the Elements - Assetsassets.cambridge.org/97805218/87076/frontmatter/9780521887076... · The chemical elements, IUPAC (2007) Name Symbol Atomic number Atomic