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![1.3 The Crustal-Ocean-Atmosphere Factory 7
that a specified unit of a substance spends in a particular reservoir is called its residence
time. This steady-state residence time is given by
Residence time =
Total amount of a substance in a reservoir
Total rate of supply to or removal of the
substance from the reservoir
=
MC
Jin or Jout
(1.2)
In the case of water,
Residence time =
Total volume of water in the ocean
Annual volumetric rate of water input
=
VSW
QRW
(1.3)
As shown in the next chapter, the average molecule of water spends 3800 years in the
ocean before being removed, mostly via the process of evaporation.
The steady-state concentration of a chemical with an oceanic residence time much
longer than that of water can be predicted if it is assumed that its removal rate is directly
proportional to its abundance in seawater, i.e.,
Jout = kM = kCSSWVSW (1.4)
where k is a removal rate constant and CSSW is the steady-state concentration of C in
seawater. Since river input is the major source of most elements to seawater,
Jin = QRWCRW (1.5)
where CRW is the concentration of C in riverwater. Substituting Eqs. 1.3 and 1.4 into
Eq. 1.1 and solving for CSSW yields
[C ]SSW =
[C ]RW
RT × k
(1.6)
where RT is the residence time of water in the ocean. Equation 1.5 indicates that the
steady-state concentration of a given chemical is dependent on the relative magnitudes
of its k and [C ]RW. Steady-state concentrations can shift given a sustained change in k
and/or [C ]RW. In many biogeochemical cycles, changes in the steady-state concentration
are difficult to achieve because natural systems tend to have feedbacks that act to reduce
the effects of rate and/or concentration changes and, hence, stabilize biogeochemical
cycles against perturbations.
Equation 1.6 is built upon the assumption that each of the removal processes that
C undergoes follows first-order behavior. If these are chemical reactions, a first-order
rate law can be written for each (individual) process in which
Rate of change of C due to reaction i = −
d [C ]SW
dt
i
= ki [C ]SW (1.7)
where ki is the first-order reaction rate constant that has a positive value if C is lost
from the ocean through chemical reaction. These rate constants are additive so the k
used in Eq. 1.7 can be computed as the sum of the individual reaction rate constants:
k =
n
i
ki (1.8)
First-order chemical behavior is commonly assumed because reaction rate laws are gen-
erally not known. Although this approach is accepted as a reasonable and practical](https://image.slidesharecdn.com/20823-250228035914-278a63f9/75/Introduction-to-marine-biogeochemistry-2ed-Edition-Libes-S-27-2048.jpg)
![24 CHAPTER 2 The Waters of the Sea
2.3 WATER: A PHYSICALLY REMARKABLE LIQUID
Water is an unusual liquid. For example, solids tend to be denser than their liquid phase,
whereas ice floats in its liquid. Another oceanographically relevant behavior is that water
is nearly incompressible. This causes seawater at great depths to have nearly the same
density and viscosity as surface seawater of matching temperature and salinity. Water
also has a relatively high heat capacity, making it a large heat reservoir that effectively
moderates weather and climate. In comparison to other hydrides of the group VI ele-
ments, the hydride of oxygen, H2O, has a relatively high boiling (100
◦
C) and freezing
point (0
◦
C). Given the temperature range on Earth’s surface, water is commonly found in
its liquid form, making it the most common naturally occurring liquid. Another interest-
ing characteristic of liquid water is its high surface tension. This is exploited by aquatic
insects to keep them atop water’s surface. All of these unusual behaviors of water can be
traced back to its tendency to form hydrogen bonds between adjacent water molecules,
which is in turn a consequence of water’s polar intramolecular bonds.
2.3.1 The Molecular Structure of Water
The molecular structure of water is shown in Figure 2.2. Each atom of hydrogen is
covalently bonded to a central oxygen atom, with two electrons shared between the
atoms. This sharing is not equal because the eight protons in the nucleus of the oxygen
atom exert a stronger force of electrostatic attraction than does the single proton in
the hydrogen nucleus. The magnitude of the force of this attraction (F in Newtons [N])
between oppositely charged particles is given by Coulomb’s law:
F = k
q1q2
r2
(2.1)
where q1 is the negative charge on an electron, q2 is the positive charge on a proton,
both 1.602 × 10−12
coulombs (C), r is the distance of separation (in meters) between
the charges, and k is a constant (8.99 × 10
9
N m
2
C
2
).
Water molecule
104.58
Electron } negative charge (2)
Nucleus } positive charge (1)
d2
d1 1d
FIGURE 2.2
The Lewis structure and molecular geometry of the water molecule.](https://image.slidesharecdn.com/20823-250228035914-278a63f9/75/Introduction-to-marine-biogeochemistry-2ed-Edition-Libes-S-44-2048.jpg)
![Married in Haste, 19th cent., H. J. Byron.
Married Libertine (The), 1761, Macklin. F.
Married Life, 1834, Buckstone. C.
Married Man (The), 1789, Inchbald. C.
Martha, 1858, Flotow. O.
Martyr of Antioch, 1821, Milman. T.
Martyrs (Les), 1840, Donizetti. O. (from Corneille’s Polyeucte).
[Mary] Queen of Scots, 1684, Banks. T.
Mary Queen of Scots, 1807, Grahame. T.
Mary Queen o’ Scots, 1874, Wills. H.Pl.
Mary (Queen), 1877, Tennyson. T.
Mary Stuart, 1840, Haynes. T.
Mary Stuart, 1881, Swinburne. T. (See “Maria ...” and “Evasion
de....”)
Mary Tudor, 1833, Victor Hugo. T.
Mary Tudor, 1847, Vere. T.
Mary Tudor, 1876, Miss Dickinson. H.Pl.
Masaniello, 1814, Ingemann. T.
Masaniello, about 1820, Carafa. O.
Masaniello, 1828, Auber. O. (libretto by Scribe). Often called La
Muette de Portici. (See “Massaniello.”)
Masks and Faces (1817-1880), Tom Taylor. C.
Masnadieri (I), 1847, Verdi. O.
Masque (The), 1612, Beaumont and Fletcher. C.
Masque de Velours, 1860, Delaporte. D.
Masque of Calisto, 1676, Crowne. M.](https://image.slidesharecdn.com/20823-250228035914-278a63f9/75/Introduction-to-marine-biogeochemistry-2ed-Edition-Libes-S-63-2048.jpg)
![Menæchmi, or The Brothers Menæchmus who were Exactly Alike
(B.C. 254-184), Plautus. C. (Latin). Translated into blank verse by
Messrs. Thornton, Rich, Warner and Colman, 1769-74. It was
translated by W. W[arner] in 1595, and furnished Shakespeare
with the scheme, etc., of his Comedy of Errors. (See below.)
Ménage en Ville, 1864, Barrière. Pl.
Ménechmes, 1637, Rotrou. C. (imitated from the Menæchi of
Plautus).
Ménechmes (Les), 1705, Régnard. C.
Menteur, 1642, Corneille. C. (See “Liar.”)
Mercator, or The Merchant (B.C. 254-184), Plautus. C. (Latin,
adapted from a Greek play by Philemon). Translated into blank
verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74.
Merchant Pirate, 19th cent., Stirling. D.
Merchant of Bruges, before 1830, Kinnaird. Pl. (altered from
Beaumont and Fletcher).
Merchant of Venice, 1598, Shakespeare. D. (See “Jew of Malta.”)
Mercurius Britannicus, 1641, Braithwait. T.C. (From the French.)
Mère Coupable (La), 1792, Beaumarchais. D.
Méridien, 1852, Deslandes. D.
Merlin in Love, 1759, Hill. C.
Mérope, 1713, Maffei. T.
Mérope, 1738, Voltaire. T.
Merope, 1749, Jefferys or Hill (ascribed to both). T.
Merope, 1783, Alfieri. T. (translated by C. Lloyd, 1815).
Merope, 1858, Matthew Arnold. Cl.T.
Merry Devil of Edmonton (The), 1608, Brewer. C.](https://image.slidesharecdn.com/20823-250228035914-278a63f9/75/Introduction-to-marine-biogeochemistry-2ed-Edition-Libes-S-66-2048.jpg)
Introduction to marine biogeochemistry 2ed Edition Libes S.
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- 5. Introduction to marinebiogeochemistry 2ed Edition Libes S. Digital Instant Download Author(s): Libes S. ISBN(s): 9780120885305, 0120885301 Edition: 2ed File Details: PDF, 15.20 MB Year: 2009 Language: english
- 7.
- 8. To adopt thisbook for course use, visit http://textbooks.elsevier.com Companion Web Site: http://elsevierdirect.com/companions/9780120885305 ELSEVIER science & technology books Resources for Professors: • All figures from the book available in color (if applicable) as PowerPoint slides • Study guide and homework problems for students • Suggestions for supplemental readings, many of which are Web accessible • Two chapters and nine appendices available only on the Web • Full reference list Introduction to Marine Biogeochemistry, Second Edition by Susan Libes ACADEMIC PRESS TOOLS ALL TEACHING FOR YOUR NEEDS textbooks.elsevier.com
- 9. Introduction to Marine Biogeochemistry SecondEdition Susan Libes College of Natural and Applied Sciences Coastal Carolina University Conway, South Carolina AMSTERDAM • BOSTON • HEIDELBERG • LONDON NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Academic Press is an imprint of Elsevier
- 10. Academic Press isan imprint of Elsevier 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA 525 B Street, Suite 1900, San Diego, California 92101-4495, USA 84 Theobald’s Road, London WC1X 8RR, UK This book is printed on acid-free paper. ∞ Copyright © 2009, by Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopy, recording, or any information storage and retrieval system, without permission in writing from the publisher. Permissions may be sought directly from Elsevier’s Science Technology Rights Department in Oxford, UK: phone: (+44) 1865 843830, fax: (+44) 1865 853333, E-mail: [email protected]. You may also complete your request on-line via the Elsevier homepage (http://elsevier.com), by selecting “Support Contact” then “Copyright and Permission” and then “Obtaining Permissions.” Library of Congress Cataloging-in-Publication Data APPLICATION SUBMITTED British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. ISBN: 978-0-12-088530-5 For information on all Academic Press publications visit our Web site at www.books.elsevier.com Printed in the United States of America 09 10 11 12 9 8 7 6 5 4 3 2 1
- 11. Contents Preface . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix How to Use This Book . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii PART I THE PHYSICAL CHEMISTRY OF SEAWATER 1 CHAPTER 1 The Crustal-Ocean-Atmosphere Factory 3 CHAPTER 2 The Waters of the Sea 21 CHAPTER 3 Seasalt Is More Than NaCl 41 CHAPTER 4 Salinity as a Conservative Tracer 65 CHAPTER 5 The Nature of Chemical Transformations in the Ocean 101 CHAPTER 6 Gas Solubility and Exchange across the Air-Sea Interface 147 PART II THE REDOX CHEMISTRY OF SEAWATER 169 CHAPTER 7 The Importance of Oxygen 171 CHAPTER 8 Organic Matter: Production and Destruction 207 CHAPTER 9 Vertical Segregation of the Biolimiting Elements 221 CHAPTER 10 Horizontal Segregation of the Biolimiting Elements 237 CHAPTER 11 Trace Elements in Seawater 259 CHAPTER 12 Diagenesis 299 v
- 12. vi Contents PART IIITHE CHEMISTRY OF MARINE SEDIMENTS 325 CHAPTER 13 Classification of Sediments 327 CHAPTER 14 Clay Minerals and Other Detrital Silicates 351 CHAPTER 15 Calcite, Alkalinity, and the pH of Seawater 373 CHAPTER 16 Biogenic Silica 403 CHAPTER 17 Evaporites 423 CHAPTER 18 Iron-Manganese Nodules and Other Hydrogenous Minerals 441 CHAPTER 19 Metalliferous Sediments and Other Hydrothermal Deposits 471 CHAPTER 20 Global Pattern of Sediment Distribution 515 CHAPTER 21 Why Seawater Is Salty but Not Too Salty 525 PART IV ORGANIC BIOGEOCHEMISTRY 559 CHAPTER 22 Marine Biogeochemistry: An Overview 561 CHAPTER 23 The Production and Destruction of Organic Compounds in the Sea 609 CHAPTER 24 The Marine Nitrogen and Phosphorus Cycles 661 CHAPTER 25 The Marine Carbon Cycle and Global Climate Change 709 CHAPTER 26 The Origin of Petroleum in the Marine Environment 759 CHAPTER 27 Organic Products from the Sea: Pharmaceuticals, Nutraceuticals, Food Additives, and Cosmoceuticals 761
- 13. Contents vii PART VMARINE POLLUTION 763 CHAPTER 28 Marine Pollution: The Oceans as a Waste Space 765 APPENDICES 853 1 The Periodic Table of the Elements . . . . . . . . . . . . . . . . . . . . . . . 853 2 Common Names and Chemical Formulae . . . . . . . . . . . . . . . . . . . 855 3 Metric Units and Equivalents . . . . . . . . . . . . . . . . . . . . . . . . . . . 857 4 Symbols, Constants, and Formulae . . . . . . . . . . . . . . . . . . . . . . . 861 5 Geologic Time Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863 Glossary 865 Index 893 Please visit http://elsevierdirect.com/companions/9780120885305 for supplementary web materials.
- 14. This page intentionallyleft blank
- 15. Preface Seawater covers nearly71% of Earth’s surface making the oceans, at least to us humans, the dominant feature of Planet Earth. International interest in utilizing and conserving this vast resource has given rise to undergraduate and graduate degree programs in oceanography. Most rely on curricula built upon a set of core courses that individually provide surveys of marine biology, geology, physics and chemistry. This text is designed for a one-semester survey in marine chemistry at the advanced undergraduate or intro- ductory graduate level. Students are expected to have completed foundational course work in basic chemistry, biology, physics, and calculus along with an introductory course in marine science. Segregating oceanographic disciplines for educational purposes has grown increas- ingly confining as research continues to confirm the importance of a multidisciplinary understanding of ocean processes. This has led to an appreciation of the critical role that the oceans play in regulating atmospheric and thereby, terrestrial processes. Of all the subdisciplines of oceanography, marine chemistry relies most heavily on a multidisci- plinary approach, now referred to as marine biogeochemistry. This makes formulation of a suitable introductory textbook challenging given the enormous diversity of important topics and complexity of approaches now in use. To capture the multidisciplinary nature of marine chemistry, this text highlights the ocean’s role in the global biogeochemical cycling of elements that are key to regula- tion of climate and marine biology. The impact of humans on the oceans and climate is given special emphasis, as are some of the practical triumphs of applied marine biogeochemistry, namely petroleum prospecting and the development of marine nat- ural products, such as drugs and food additives. Part I covers the hydrological cycle and basic physico-chemical processes including chemical speciation. Part II provides an introduction to redox chemistry in the context of microbial ecology. Part III considers how marine processes result in the formation of sediments and the role of the sedi- ments in regulating the chemistry of seawater. Part IV constitutes a survey of the field of marine organic chemistry including coverage of the molecular composition, sources and sinks of organic compounds along with a discussion of the elemental cycling of car- bon, nitrogen, oxygen, sulphur, and phosphorus. A comprehensive discussion of marine pollution is the subject of Part V. Special features of the text include: (1) a thematic emphasis on the marine cycling of iron to exemplify marine biogeochemical processes that provide feedbacks regulating global climate and that are thereby linked to terres- trial processes, (2) basic details on introductory chemical principles including equilibria, rate laws, redox energetics, and organic chemistry on an as needed basis, (3) advances in paleoceanographic reconstructions of past ocean chemistry, biology, sedimentology and climate, and (4) human impacts on the ocean including climate change and marine pollution. By focusing on the “hot” areas of research in marine chemistry, I have attempted to communicate the sense of excitement and discovery that is an essential characteristic of ix
- 16. x Preface this relativelyyoung and growing science. The nature of the “hot” topics has changed a bit since my writing of the first edition. Namely, the singular impacts of marine microbes on elemental cycling have come to be recognized as so powerful as to play a critical role in regulating climate and hence, indirectly, ocean circulation and terrestrial ero- sion rates. Conversely, physical processes, including oceanic circulation, hydrothermal activity, the production of flood basalts, and mountain building, have come to be rec- ognized as having key impacts on ocean chemistry. These phenomena are now thought to have triggered important evolutionary shifts amongst the marine biota, including the Precambrian explosion of metazoans. This book also includes a few aspects of marine analytical chemistry to address the operational nature of much of our data collection. This includes the use of remote sens- ing, such as satellite imagery, and in-situ sensing. Exciting advances in the latter include the use of submerged chemical detectors, such as mass spectrometers, and devices pow- ered by natural redox processes, such as those occurring in marine sediments. Examples are provided of a particularly powerful and widespread approach—the use of naturally occurring stable and radioactive isotopes as tracers of biogeochemical processes. Arti- ficial radionucludes, such as those introduced by bomb testing, have also proven to be excellent tracers of ocean circulation. This text seeks to give the reader enough of a background to pursue a more detailed study of this complicated topic. Research efforts are now being urgently directed at understanding and mitigating the impacts of humans on the oceans as we have come to appreciate the truly global scope and scale of marine pollution and anthropogenically-driven climate change. The field of marine biogeochemistry is uniquely suited to help in this respect and hence represents a critical frontier of knowledge that can help us sustain ourselves and other life forms on planet Earth.
- 17. How to Usethis Book The study of marine chemistry is challenging but highly satisfying as you will use many of the skills and concepts learned in your basic science and math courses. Please be patient – true mastery takes time. Consider this text as a future reference book that you can return to long after graduation. Useful features in the text include: (1) a glossary that defines technical terms, abbreviations, and acronyms, whose first appearance in the text is shown in italic font, (2) appendices containing various constants, equations, and conversion fac- tors, and (3) a thorough index. Because we learn best from doing, this text has a companion website with resources to support a variety of active learning strategies (http://elsevierdirect.com/companions/9780120885305). Online features include: (1) a study guide, (2) homework problems, (3) supplemental content material, (4) a set of lengthy appendices containing geochemical and physical constants and other computa- tional details, (5) color versions of figures as noted in the text’s captions, and (6) a list of the full citations for works referenced in the text. The supplemental content material available at the companion website is briefly described in the text at the relevant locations. For example, information on the evolution of the global carbon cycle over geologic time is briefly presented in Section 25.4 of the text as part of Chapter 25. A lengthier version of Section 25.4 is available online, and is so noted in the text. Text references to figures and tables that are available only online are labeled with a “W”. For example, Figure W25.14 is available only in the online supplemental material for Section 25.4. xi
- 18. This page intentionallyleft blank
- 19. Acknowledgements Many others, besidesme, spent long hours working on this textbook. My heartfelt thanks go to them and to my students who provided me with the necessary teach- ing experience as well as to my fellow faculty members who have been enthusiastic supporters and best friends. Coastal Carolina University has provided a stable and sup- portive environment since my arrival in 1983. Many administrators and staff have been instrumental in providing essential resources, particularly Paul Gayes, Rob Young, Pete and Betsy Barr, and CCU’s librarians. My thanks also go to the editors and publisher of the first edition, John Wiley Sons. The editors of the second edition, Frank Cynar, Philip Bugeau, Laura Kelleher, and Linda Versteeg of Elsevier Press, provided critical support including an unlimited online subscription to Science Direct! The following colleagues served as reviewers: Tom Tisue, Ron Kiene, Erin Burge, Kevin Xu, Brent Lewis, Paul Haberstroh, Margareta Wedborg, and Courtney Burge. Important motivation for undertaking this second edition came from numerous highly vocal users of the first edition who have variously threatened and cajoled me since 2003. This effort turned out to be far more of an undertaking than anticipated and required drafting various family members into service, namely Lennie, who proof- read what she could understand and even stuff she couldn’t, Sol, who kept me in functioning computers, Don, who served as my book agent, Prashant, who checked all the math and left me alone for very long periods of time, and last but not least, the three best kitties in the world, Prem, Kali and Moti. My personal interest in marine biogeochemistry stems from my experiences in the early 1980s as a graduate student in the Massachusetts Institute of Technology/Woods Hole Oceanographic Institution Joint Program in Oceanography and Ocean Engineering where I had first-hand contact with many of the most active researchers in the field. My thanks and admiration goes to them all, as well as to all the researchers and publishers who generously granted permission to use their copyrighted figures and tables herein. It has truly been an honor and a pleasure to summarize and present to the next generation of biogeochemists, the depth and breadth of research now being conducted around the world by an increasingly numerous, diverse, sophisticated and highly dedicated group of marine biogeochemists. Susan Libes 6/17/08 xiii
- 20. This page intentionallyleft blank
- 21. 1 PART The Physical Chemistryof Seawater
- 22. This page intentionallyleft blank
- 23. 1 CHAPTER The Crustal-Ocean-Atmosphere Factory All figuresare available on the companion website in color (if applicable). 1.1 INTRODUCTION The study of marine chemistry encompasses all chemical changes that occur in seawa- ter and the sediments. The ocean is a place where biological, physical, geological, and chemical processes interact, making the study of marine chemistry very interdisciplinary and more appropriately termed marine biogeochemistry. Chemical approaches are now commonly used by marine biologists, marine geologists, and physical oceanographers in support of their research efforts. Likewise, oceanographers recognize the intercon- nectedness of Earth’s hydrosphere with its atmosphere and crust, requiring that a true understanding of the ocean include consideration of its interactions with the rest of the planet. Also important are extraterrestrial forces, such as changes in solar energy and meteorites. For these reasons, this textbook covers topics that range far beyond the margins of the seashore and seafloor, as well as the boundaries of a classical study of chemistry. 1.2 WHY THE STUDY OF MARINE BIOGEOCHEMISTRY IS IMPORTANT Most of the water on Earth’s surface is in the ocean; relatively little is present in the atmosphere or on land. Because of its chemical and physical properties, this water has had a great influence on the continuing biogeochemical evolution of our planet. Most notably, water is an excellent solvent. As such, the oceans contain at least a little bit of almost every substance present on this planet. Reaction probability is enhanced if the reactants are in dissolved form as compared with their gaseous or solid phases. Many of the chemical changes that occur in seawater and the sediments are mediated by marine organisms. In some cases, marine organisms have developed unique biosynthetic pathways to help them survive the environmental conditions found only in the oceans. Some of their metabolic products have proven useful to humans as pharmaceuticals, nutraceuticals, food additives, and cosmeceuticals. 3
- 24. 4 CHAPTER 1The Crustal-Ocean-Atmosphere Factory Another important characteristic of water is its ability to absorb a great deal of heat without undergoing much of an increase in temperature. This enables the ocean to act as a huge heat absorber, thereby influencing weather and climate. Thus through many means, water sustains life, both marine and terrestrial. Scientific evidence supports the hypothesis that on Earth, life first evolved in a wet environment, such as an early ocean or submarine hydrothermal system. In turn, biological activity has had important effects on the chemical evolution of the planet. For example, the photosynthetic metabolism of plants is responsible for the relatively high concentration of oxygen gas (O2) in our present-day atmosphere. Most of this oxygen was originally present as CO2 emitted onto Earth’s surface as part of volcanic gases. Over the millennia, photosynthesizers, such as marine phytoplankton, have converted this CO2 into O2 and organic matter (their biomass). Burial of their dead biomass (organic matter) in marine sediments has enabled O2 to accumulate in the atmosphere. In this way, microscopic organisms have effected a global-scale transformation and transport of chemicals. This in only one example of many in which microscopic organisms serve as global bioengineers. In studying the ocean, marine biogeochemists focus on exchanges of energy and material between the crust, atmosphere, and ocean. These exchanges exert a central influence on the continuing biogeochemical evolution of Earth. Particular concern is currently focused on the role of the ocean in the uptake and release of greenhouse gases, such as CO2. As part of the atmosphere, these gases influence solar heat reten- tion and, hence, influence important aspects of climate, such as global temperatures, the hydrological cycle, and weather, including tropical storms. Exchanges of material between the land and sea control the distribution of marine life. For example, transport of nutrients from the nearby continents causes marine organisms to grow in greater abundance in coastal waters than in the open ocean. The exchange rates of many sub- stances have been or are being altered by human activities. Thus, the study of marine chemistry has great practical significance in helping us learn how to use the ocean’s vast mineral and biological resources in a sustainable fashion to ensure its health for future generations of humans and other organisms. 1.3 THE CRUSTAL-OCEAN-ATMOSPHERE FACTORY AND GLOBAL BIOGEOCHEMICAL CYCLES As illustrated in Figure 1.1, the planet can be viewed as a giant chemical factory in which elements are transported from one location to another. Along the way, some undergo chemical transformations. These changes are promoted by the ubiquitous presence of liquid water, which is also the most important transporting agent on Earth’s surface. It carries dissolved and particulate chemicals from the land and the inner earth into the ocean via rivers and hydrothermal vents. Chemical changes that occur in the ocean cause most of these materials to eventually become buried as sediments or diffuse across the sea surface to accumulate in the atmosphere. Geological processes uplift marine sediments to locations where terrestrial weathering followed by river transport
- 25. 1.3 The Crustal-Ocean-AtmosphereFactory 5 ATMOSPHERE Precipitation plants Formation of soils, humus and fresh waters LITHOSPHERE uplift of crystallines uplift of sediments weathering products detritus ALGAE photo- synthesis hv co2 o2 sedimentary sediments crystalline fluid phases volcanic emanations evaporator org. ligands reductants H2 O1 salt OCEAN NO NO2 SO2 HCI CO2 (CH3)2S oven distillation column FIGURE 1.1 The crustal-ocean-atmosphere factory. Source: Stumm, W. and J. J. Morgan (1996) Aquatic Chemistry, 3rd ed. Wiley-Interscience, p. 874. returns the chemicals to the ocean. The mobility of chemicals within the crustal-ocean- atmosphere factory is strongly affected by partitioning at interfaces. In the ocean, these include the air-sea and sediment-water interfaces, as well as the contact zone between seawater and suspended or sinking particulate matter. Thus, the ocean acts as a giant stirred flow-through reactor in which solutes and solids are added, transformed, and removed. The representation of the ocean presented in Figure 1.1 is not a complete descrip- tion of the ocean but serves to illustrate aspects important to the discussion at hand. Scientists refer to these simplified descriptions as a model. Models are useful ways of summarizing knowledge and identifying avenues for further study. Those that include mathematical information can be used to make quantitative predictions. The model illustrated in Figure 1.1 is a mechanistic one that emphasizes the flow of materials between various reservoirs. Because most material flows appear to follow closed circuits (if observed for long enough periods of time), the entire loop is referred to as a biogeo- chemical cycle. Such a cycle can be defined for any particular substance, whether it be an element, molecule, or solid. An example of the latter, the rock cycle, is given in Figure 1.2. This type of depiction is called a box model because each reservoir, or form that a substance occurs in, is symbolized by a box (e.g., sedimentary rock). The flow
- 26. 6 CHAPTER 1The Crustal-Ocean-Atmosphere Factory compaction cementation burial transport weathering de ep bu ria l Soil Volcanic Plutonic Igneous Rocks Volcanic Plutonic Igneous Rocks erosion erosion weathering MANTLE deep burial melting Sedimentary Rocks Metamorphic Rocks deep burial uplift subduction melting above subduction zones Sedimentary Rocks Sediment Ions Dissolved in Ocean Water bio-precipitation burial, compaction, cementation OCEANS CONTINENTS THE ROCK CYCLE subduction at trenches u p l i f t uplift erosion, weathering, transport melting at mid- ocean ridges Erosion, weathering, transport FIGURE 1.2 The global rock cycle. Source: After Bice, D. Exploring the Dynamics of Earth Systems: Modeling Earth’s Rock Cycle. http://www.carleton.edu/departments/geol/DaveSTELLA/ Rock%20Cycle/rock cycle.htm. of materials between reservoirs is indicated by arrows that point from the source of a substance to its sink. The magnitude of the exchange rates and sizes of the reservoirs are often included in these diagrams. For some substances, such as carbon and nitrogen, humans have significantly altered exchange rates and reservoir sizes. In these cases, the box model approach has proven valuable in assessing current impacts of human activ- ities. These insights are used to predict how the crustal-ocean-atmosphere factory is likely to respond in the future, enabling a cost-benefit analysis of various environmental management strategies. 1.3.1 Steady State, Residence Times, and Turnover Times If the size of a reservoir remains constant over time, the combined rates of input ( Jin) to each box must equal the combined rates of output ( Jout): − dMC dt = 0 = Jin − Jout (1.1) where MC is the amount of material, C, in the reservoir, and J has the units of amount per unit time.1 This condition is referred to as steady state. The average period of time 1 Typically, Mc has units of mass.
- 27. 1.3 The Crustal-Ocean-AtmosphereFactory 7 that a specified unit of a substance spends in a particular reservoir is called its residence time. This steady-state residence time is given by Residence time = Total amount of a substance in a reservoir Total rate of supply to or removal of the substance from the reservoir = MC Jin or Jout (1.2) In the case of water, Residence time = Total volume of water in the ocean Annual volumetric rate of water input = VSW QRW (1.3) As shown in the next chapter, the average molecule of water spends 3800 years in the ocean before being removed, mostly via the process of evaporation. The steady-state concentration of a chemical with an oceanic residence time much longer than that of water can be predicted if it is assumed that its removal rate is directly proportional to its abundance in seawater, i.e., Jout = kM = kCSSWVSW (1.4) where k is a removal rate constant and CSSW is the steady-state concentration of C in seawater. Since river input is the major source of most elements to seawater, Jin = QRWCRW (1.5) where CRW is the concentration of C in riverwater. Substituting Eqs. 1.3 and 1.4 into Eq. 1.1 and solving for CSSW yields [C ]SSW = [C ]RW RT × k (1.6) where RT is the residence time of water in the ocean. Equation 1.5 indicates that the steady-state concentration of a given chemical is dependent on the relative magnitudes of its k and [C ]RW. Steady-state concentrations can shift given a sustained change in k and/or [C ]RW. In many biogeochemical cycles, changes in the steady-state concentration are difficult to achieve because natural systems tend to have feedbacks that act to reduce the effects of rate and/or concentration changes and, hence, stabilize biogeochemical cycles against perturbations. Equation 1.6 is built upon the assumption that each of the removal processes that C undergoes follows first-order behavior. If these are chemical reactions, a first-order rate law can be written for each (individual) process in which Rate of change of C due to reaction i = − d [C ]SW dt i = ki [C ]SW (1.7) where ki is the first-order reaction rate constant that has a positive value if C is lost from the ocean through chemical reaction. These rate constants are additive so the k used in Eq. 1.7 can be computed as the sum of the individual reaction rate constants: k = n i ki (1.8) First-order chemical behavior is commonly assumed because reaction rate laws are gen- erally not known. Although this approach is accepted as a reasonable and practical
- 28. 8 CHAPTER 1The Crustal-Ocean-Atmosphere Factory accommodation, marine scientists are careful to acknowledge any computed results as “first approximations” or “back-of-the-envelope estimates.” Equation 1.2 assumes that the concentration of C is constant throughout the ocean, i.e., that the rate of water mixing is much faster than the combined effects of any reaction rates. For chemicals that exhibit this behavior, the ocean can be treated as one well-mixed reservoir. This is generally only true for the six most abundant (major) ions in seawater. For the rest of the chemicals, the open ocean is better modeled as a two-reservoir system (surface and deep water) in which the rate of water exchange between these two boxes is explicitly accounted for. Another useful measure of biogeochemical processing is the fractional residence time or turnover time of a material in a reservoir. Computation of this “time” is similar to that of a residence time except that some subset of the input or output processes is substituted into the denominator of Eq. 1.2. The resulting turnover time represents how long it would take for that subset of processes by itself to either supply or remove all of the material from the reservoir. Turnover times can be calculated for reservoirs that are not in steady state. As will be shown in Chapter 21, the residence time can be computed by summing the reciprocals of the turnover times. Using the rock cycle as an example, we can compute the turnover time of marine sed- iments with respect to river input of solid particles from: (1) the mass of solids in the marine sediment reservoir (1.0 × 10 24 g) and (2) the annual rate of river input of par- ticles (1.4 × 1016 g /y).2 This yields a turnover time of (1.0 × 10 24 g)/(1.4 × 10 16 g /y) = 71 × 106 y. On a global basis, riverine input is the major source of solids buried in marine sediments; lesser inputs are contributed by atmospheric fallout, glacial ice debris, hydrothermal processes, and in situ production, primarily by marine plankton. As shown in Figure 1.2, sediments are removed from the ocean by deep burial into the seafloor. The resulting sedimentary rock is either uplifted onto land or subducted into the mantle so the ocean basins never fill up with sediment. As discussed in Chapter 21, if all of the fractional residence times of a substance are known, the sum of their reciprocals provides an estimate of the residence time (Equation 21.17). 1.4 CONSIDERATION OF TIME AND SPACE SCALES Box models are limited in their ability to show temporal and spatial variability. In the case of the former, rates and reservoir sizes are liable to change over time. For example, plankton distributions tend to fluctuate on a seasonal, and even a daily, basis. Climate change appears to be causing rate and abundance changes over longer time periods, such as decades. This temporal variability is difficult to show in the box model format. One approach is to provide a range of values for the rate or reservoir size. Likewise, 2 Pre-anthropocene suspended load carried by rivers as estimated by Syvitski, J. P. M, et al. (2005). Science, 308: 376–380.
- 29. 1.4 Consideration ofTime and Space Scales 9 spatial variability is also difficult to depict. Reservoirs in box models are assumed to be homogenous, i.e., having uniform composition. In reality, most reservoirs have some degree of heterogeneity or nonuniformity. For example, surface-water concentrations of nutrients tend to be much lower than deep-water concentrations, and coastal waters tend to have much higher concentrations than open-ocean waters. One approach to dealing with spatial variability is to partition reservoirs into sub- reservoirs, such as into surface, deep-water, and coastal-water boxes. Sediments also tend to exhibit great horizontal and vertical variability. For example, most of the solid particles carried by rivers into the ocean are deposited nearshore on the continental margin. In the open ocean, most of the input of particles to the sediments is from atmospheric fallout of dust particles and in situ production of calcareous hard parts by plankton. Thus, calcareous oozes are common on mid-ocean ridges and rare on continental shelves. These examples of temporal and spatial variability highlight the important role of marine organisms in controlling chemical distributions. In turn, their biological activity and spatial distributions are greatly influenced by physical processes such as water movement, gravity, gas diffusion, and heat exchange. In many cases, chemical distributions can be used to trace the pathways and rates of these physical processes. As illustrated in Figure 1.3, these biogeochemical and physical phenomena occur over a wide range of time and space scales in the crustal-ocean-atmosphere factory. Some are restricted to short time and space scales, whereas others are important only over long time and/or space scales. This requires that oceanographers sample strategically to ensure that their measurements of rates, concentrations, and amounts are truly representative. Because of the complex nature of variability in the marine environment, statistical techniques are now commonly used to design these strate- gic sampling plans. The goal of these plans is to most effectively target limited resources by adequately covering the temporal and spatial scales over which the processes of interest operate. In some cases, the best approach is to collect large num- bers of small samples. In other cases, it is more cost effective to collect very large samples. Temporal variability in the crustal-ocean factory can disrupt or prevent attainment of steady-state conditions for a given element. Examples of catastrophic events that can perturb global biogeochemical cycles include: (1) meteorite impacts, (2) changes in the rate and pattern of plate tectonic activity, and (3) climate change induced by fluc- tuations in delivery of solar radiation. Fortunately, many of the biogeochemical cycles seem to have an inherent structure that drives them back toward a steady-state condi- tion. This stabilizing effect is the result of interactions among the transport processes that constitute the biogeochemical cycles. For example, a perturbation that causes an increase in the rate of supply of some element will be countered by an ensuing increase in the rate of its removal. In this way, the steady state is reestablished, although most likely at a new setpoint concentration. This type of interconnected response is termed a negative feedback loop. Unfortunately, some perturbations can induce a positive feedback response in which perturbations are amplified. For example, the warming associated with global climate
- 30. 10 CHAPTER 1The Crustal-Ocean-Atmosphere Factory Radiatively active gases Atmosphere and ocean composition Global weather systems Climate Petroleum generation Ore formation Ocean/crustal exchanges: Plate Tectonics Ocean/sediment exchanges Ocean/atm osphere exchanges 2 4 6 8 10 12 14 16 Log (seconds) 10,000 1000 100 10 1 Local Minute Day Year Century Time 1 million years 1 billion years Space (km) Ocean/particle exchanges Ocean photochemistry Second FIGURE 1.3 Time- and space-scales of processes in the crustal-ocean-atmosphere factory. Source: From Bard, A., et al. (1988). Applied Geochemistry 3, 5. change is reducing ice cover, which is in turn reducing Earth’s ability to reflect, rather than absorb, incoming solar radiation, thereby enhancing global warming. Geological evidence documents that Earth has experienced numerous catastrophic changes throughout its history, leading to at least five major extinction events dur- ing which a majority of species died off. After each extinction event, a repopulation occurred of life forms that were able to adapt to changed environmental conditions. Over the long term, this has lead to a steady chemical evolution of Earth’s surface from a hot, acidic, rocky, airless place to one with a moderate climate, soils, an atmosphere that absorbs UV radiation, and an oxygenated atmosphere and ocean. Much of this evo- lution is attributable to the effects of marine microbes and algae, some of which have endured for billions of years. Others, such as the diatoms and coccolithophorids, are relative newcomers whose recent evolution has added important stabilizing structure to many of the global biogeochemical cycles. Some scientists consider that these neg- ative feedback loops have conferred upon Earth self-regulatory functions akin to those exhibited by an organism. In this view, called the Gaia hypothesis, Earth’s biota and its abiotic environment interact so as to maintain the atmosphere, land, and ocean in a
- 31. 1.5 The Historyof the Study of Marine Biogeochemistry 11 steady state that favors the survival of life. Although direct evidence for the existence of such a high level of organization has not yet been found, a significant body of data support the existence of various negative feedbacks. Some are discussed in this text. 1.5 THE HISTORY OF THE STUDY OF MARINE BIOGEOCHEMISTRY Marine chemistry became a formal subdiscipline of chemistry in the early 1900s, with the advent of scientists who focused all their research efforts in this field and with the development of doctoral degree programs. Prior to the 1900s, the study of marine chemistry focused on investigations of the composition of the salts in seawater. The first such work was published in 1674 by the English chemist Robert Boyle, the dis- coverer of Boyle’s law, which describes the behavior of ideal gases. Many other notable early chemists chose to focus their efforts on seawater and, in so doing, discovered new elements, established important new principles, and developed new investigative techniques. In 1772, the French chemist Antoine Lavoisier published the first analysis of seawater based on a method of evaporation followed by solvent extraction. Twelve years later, the Swedish chemist Olaf Bergman also published results of the analysis of seawater. To make his measurements, Bergman developed the method of weighing pre- cipitated salts. Through their efforts, the field of analytical chemistry was born. Between 1824 and 1836, the technique of volumetric titrimetry was developed by Joseph Louis Gay-Lussac. Using this method of analysis, Gay-Lussac determined that the salt content of open-ocean seawater is nearly geographically constant. This conclusion was con- firmed in 1818 by John Murray and in 1819–1822 by Alexander Marcet, who proposed that seawater contained small quantities of all soluble substances and that the rela- tive abundances of some were constant. This hypothesis is now known as Marcet’s principle. The concept of salinity was introduced by Georg Forchhammer in 1865. From exten- sive analyses of seawater samples, he was able to demonstrate the validity of Marcet’s principle for the most abundant of the salt ions: chloride, sodium, calcium, potassium, magnesium, and sulfate. Thus, he recognized that the salinity of seawater could be inferred from the easily measurable chloride concentration or chlorinity. The details of this relationship were worked out by Martin Knudsen, Carl Forch, and S. P. L. Sorenson between 1899 and 1902. With the international acceptance of their equation relating salinity to chlorinity (S‰ = 1.805 Cl‰ + 0.030), the standardization necessary for hydro- graphic research was provided. A slight revision in this equation (S‰ = 1.80655 Cl‰) was made in 1962 by international agreement. The modern era of oceanography began in 1876 with the Challenger Expedition. This voyage of exploration was the first undertaken for purely scientific reasons. The results from the analysis of 77 seawater samples collected during this cruise were published by William Dittmar in 1884 and supported Marcet’s principle. During the remainder of the 19th century, progress was made in the development of analytical methods for
- 32. 12 CHAPTER 1The Crustal-Ocean-Atmosphere Factory the measurement of trace constituents, such as dissolved oxygen (O2) and nutrients. With this information, attention shifted to the investigation of the chemical controls on marine life. The study of oceanography grew increasingly more sophisticated during the period from 1925 to 1940, with the initiation of systematic and dynamic surveys. The most famous was performed by the R / V Meteor, in which echo sounding was first used to map seafloor topography. Oceanography and the field of marine chemistry entered a new era in the 1940s, primarily as a result of submarine activity during World War II. This was a period of rapid development in technology and instrumentation. Analytical methods were developed for the measurement of trace constituents, such as metals, isotopes and organic matter, with detection levels dropping to subnanomolar levels. The salinity and temperature of seawater became recognized as a powerful tracer of large-scale water movements, including surface and deep ocean currents. Salinity and temperature were also employed to determine the density of seawater for the purposes of correcting sonar and computing geostrophic current velocities. Modern oceanography is presently characterized by multidisciplinary research projects conducted collaboratively by large groups of scientists often from different research institutions. This approach is necessitated by the complexity of studying marine processes, such as ones that involve global scales, like climate change. This current era was initiated in 1958 with the International Geophysical Year, which was orga- nized by the United Nations’ UNESCO General Assembly. For marine chemistry, the first multi-investigator, multi-institution project was the Geochemical Ocean Sections Study (GEOSECS) that ran from 1968 to 1978 during the National Science Foundation’s Inter- national Decade for Ocean Exploration (IDOE). Its goal was to determine the pathway of deep-ocean circulation using radioisotopes, such as radiocarbon, as tracers of water movement. This work was continued in the Transient Tracers in the Ocean (TTO) pro- gram, which ran from 1980 to 1983. Both programs sought to take advantage of the global injection of artificial radionuclides into the ocean from fallout generated during the nuclear weapons testing conducted in the 1950s and 1960s. The Joint Global Ocean Flux Study,3 which ran from 1987 to 2003, investigated fluxes of chemicals, primarily carbon and other biogenically controlled elements, to bet- ter understand linkages to global climate change. This international program was one of the first core projects of the International Geosphere-Biosphere Programme (IGBP) developed by the Scientific Committee on Oceanic Research (SCOR), a committee of the International Council for Science (ICSU). An important component of JGOFS was the establishment of time-series measurements at two sites, HOTS (Hawaii Ocean Time Series) and BATS (Bermuda Atlantic Time Series Study), to provide interannual and sea- sonal resolution of biogeochemical variability. Sampling at the BATS site was initiated in 1978 by Dr. Werner Deuser at the Woods Hole Oceanographic Institution as part of the Oceanic Flux Program (OFP) and is the longest time series of its kind; recording 3 http://www.uib.no/jgofs/
- 33. 1.6 New Technologies,New Approaches 13 temporal variability in the delivery of sinking biogenic detritus to the seafloor. JGOFS was also notable in its use of remote sensing data collected by satellites. Data from GEOSECS, TTO, BATS, and HOTS and other major oceanographic research projects, such as the WOCE (World Ocean Circulation Experiment) are available online.4 The GEOSECS, TTO, and WOCE datasets are part of the Java Ocean Atlas, which pro- vides a graphic exploration environment for generating vertical profiles, cross-sections, and property-property plots.5 Many of the data presented in this text were obtained from this source. The research ships that supported these major projects were largely managed by the University-National Oceanographic Laboratory System (UNOLS),6 a consortium of 64 academic institutions established in 1971. UNOLS now coordinates schedules of 28 research vessels ranging in size from 20 to 85 m that are operated by 20 different member organizations, including universities, research institutions, and federal agencies. Ship time is available to all federally funded oceanographers. Deep-sea submersibles and remotely operated vehicles (ROVs) schedules are also coordinated through UNOLS. This technology has played a major role in the study of hydrothermal vents and cold- water seeps. The vents were first discovered in 1977, providing marine chemists with direct observations of large sources and sinks of materials associated with venting along submarine plate boundaries. It also lead to the discovery of a new food web based on chemosynthetic bacteria. An increasing focus of ongoing work is directed at understanding anthropogenic impacts on the crustal-ocean-atmosphere factory: not just climate change, but also the long-range transport and fate of pollutants. Of particular interest are processes that occur at interfaces, such the fate of river input after it mixes with seawater, the effect of sunlight on the photochemistry of surface water, and the role of organisms in the for- mation and solubilization of particles. Much of the work involving particles and the fate of pollutants relies on research into very small-scale phenomena, namely the role of phy- toplankton and microbes, such as bacteria and viruses, in translocating and transforming chemicals. 1.6 NEW TECHNOLOGIES, NEW APPROACHES The next step in obtaining a true systems-level understanding of the crustal-ocean- atmosphere factory requires establishment and maintenance of a global-scale, long-term observational program. For marine scientists, this requires switching from short- duration, ship-based expeditions in which discrete samples are collected and brought back to shore for lab-based analysis to one that relies on continuous data collection using 4 http://whpo.ucsd.edu/index.html 5 http://odf.ucsd.edu/joa 6 http://www.unols.org
- 34. 14 CHAPTER 1The Crustal-Ocean-Atmosphere Factory in situ and remote-sensing technologies. The latter is referred to as operational oceanog- raphy. In the United States, implementation of these approaches is being directed through the National Aeronautics and Space Administration (NASA), National Oceanic and Atmospheric Administration (NOAA), the Joint Oceanographic Institutions (JOI), and the Consortium for Oceanographic Research and Education (CORE). In 2004, these groups established the Ocean Research Interactive Observatory Networks (ORION) Pro- gram to coordinate development and operation of large-scale ocean observatories.7 Examples include NOAA’s seafloor observatories, such as the Aquarius, an underwa- ter laboratory moored at 20 m in the Florida Keys National Marine Sanctuary since 1993, and the Long-term Ecosystem Observatory (LEO-15) established in 1996. LEO-15 is located in 15 m of water over a 30 × 30 km 2 area on the inner continental shelf of New Jersey.8 In 2001, LEO-15 was expanded into the New Jersey Shelf Observing Sys- tem (NJSOS), which covers a 300 × 300 km 2 area. More than a dozen different sensors have been deployed at this site, carried by autonomous underwater vehicles (AUVs), ROVs, and human-occupied vehicles (HOVs). Another example of such a comprehensive approach to ocean monitoring is the High Latitude Time Series Observatory, which is located in the NW Pacific. This obser- vatory was established in 2001 by the Joint North Pacific Research Center to study what appears to be a site of major CO2 uptake. It is a collaborative effort between the Woods Hole Oceanographic Institution and two Japanese groups, Mutsu Institute for Oceanog- raphy and the Japan Marine Science and Technology Center. An innovative technology being used at this site is moored geochemical profilers that shuttle 200 times a year between the mixed layer and deep zone, providing in situ measurements of conduct- ivity, temperature, depth, and 3D current velocity.9 Also deployed are automated sam- plers that collect experiments conducted on filtered water, sediment and plankton in automated incubators. In the mixed layer, an optical sensor continuously measures flu- orescence, chlorophyll, and particles to depths of 35 m. These measurements are being coordinated with remote sensing obtained from the ADEOS-II, a satellite launched by the National Space Development Agency of Japan (NSDA). Space-based earth observations began in 1960 with NASA’s Television Infrared Obser- vation Satellite (TIROS). In the United States, NOAA and NASA have since developed sensors to measure sea surface temperature, winds, and topography. The first experi- mental effort to obtain remotely sensed color data was made in 1978 with the launch of the Coastal Zone Color Scanner (CZCS) aboard the Nimbus-7 satellite. The first effort to collect biogeochemical data began in 1997 with NASA’s SEAWIFS (Sea-viewing Wide Field of View Sensor) Project, which relies on an ocean color sensor to provide an esti- mate of phytoplankton production by estimating in vivo fluorescence from chlorophyll. These data were designed to help assess the oceans’ role in the global carbon cycle, and were by JGOFS. In 1999, NASA began its Earth Observing System (EOS) program 7 http://www.orionprogram.org. 8 NURP; http://www.nurp.noaa.gov 9 http://Jpac.whoi.edu/hilats/strategy/instruments.html
- 35. 1.7 The Futureof Marine Biogeochemistry 15 with the launch of the Terra satellite, which contains an upgraded color sensor called the Moderate Resolution Imaging Spectroradiometer (MODIS). MODIS has 36 spectral channels, as compared to SEAWIFS’ eight, enabling it to collect information on colored dissolved organic matter (CDOM) and detritus at a resolution of 0.25 to 1 km. A sec- ond MODIS satellite, Aqua, was launched in 2002. Near real-time imagery from MODIS sensors is available online.10 The NOAA Polar Orbiting Environmental Satellites (POES) also carry a multispectral sensor called an Advanced Very High Resolution Radiometer (AVHRR). As shown in Table 1.1, many other countries have launched satellites with ocean color sensors. Plans have been made to fly a new high-resolution multispectral sensor, Visi- ble/Infrared Imager/Radiometer Suite (VIIRS), aboard the National Polar-Orbiting Oper- ational Environmental Satellite System (NPOESS). The Navy also has plans to send a Coastal Ocean Imaging Spectrometer (COIS) with a resolution of 30 m aboard the Navy Earth Map Observer (NEMO). This sensor is designed to enable detection of oil spills and plankton blooms from spectral signatures. In addition to improving spectral coverage and spatial resolution, future efforts will be directed at increasing temporal resolution. Satellites have been deployed by other countries than the United States. For example, Japan’s Advanced Earth Observing Satellite (ADEOS), launched in 2002, carries a Global Imager (GLI) with resolution of 250 m in some of its 36 spectral channels. An interna- tional group, the Committee on Earth Observation Satellites (CEOS), was formed in 1984 to coordinate and enhance productivity of space-related earth observation activities. With 100 new satellites expected to be launched over the next decade, this technology can be expected to play an increasingly important role in oceanographic research. 1.7 THE FUTURE OF MARINE BIOGEOCHEMISTRY Operational oceanography is a first step in the direction of obtaining a systems-level understanding of the crustal-ocean-atmosphere factory. The next step is integrating oceanography with other earth sciences and translating our new understanding into a form that can be used to protect resources and humans. Formal work toward this end began at the First Earth Observation Summit held in July 2003. At its conclusion, thirty countries agreed to support the development of a Global Earth Observation System of Systems (GEOSS). GEOSS currently includes a land-based component, the Global Terres- trial Observing System (GTOS), a satellite-based component (CEOS), and an ocean-based component, the Global Ocean Observing System (GOOS). A systems approach will facil- itate integration of data collection with data processing, database management, and data delivery conducted via query-based web pages to provide open access. Forty countries are now participating in GEOSS. In the United States, GOOS will be implemented through a new Integrated Ocean Observing System (IOOS) run by a new organization, Ocean.US, the National Office 10 http://rapidfire.sci.gsfc.nasa.gov/
- 36. 16 CHAPTER 1 The Crustal-Ocean-Atmosphere Factory Table 1.1 Summaryof Recent and Current Satellite Ocean Color Sensors. Sensor Agency Satellite Operating Dates Resolution Number Spectral Ref. (m) of Bands Coverage (nm) CZCS NASA (USA) Nimbus-7 (USA) 24/10/78–22/06/86 825 6 433–12500 a OCTS NASDA (Japan) ADEOS (Japan) 17/08/96–01/07/97 700 12 402–12500 b POLDER-1 CNES (France) ADEOS (Japan) 17/08/96–01/07/97 6000 9 443–910 c MOS DLR (Germany) IRS P3 (India) Launched 21/03/96 500 18 408–1600 d SeaWiFS NASA (USA) OrbView-2 (USA) Launched 01/08/97 1100 8 402–885 e OCI NEC (Japan) ROCSAT-1 (Taiwan) Launched Jan 1999 825 6 433–12500 f OCM ISRO (India) IRS-P4 (India) Launched 26/05/99 350 8 402–885 g MODIS-Terra NASA (USA) Terra (USA) Launched 18/12/99 1000 36 405–14385 h OSMI KARI (Korea) KOMPSAT (Korea) Launched 20/12/99 850 6 400–900 i MERIS ESA (Europe) ENVISAT-1 (Europe) Launched 01/03/02 300/1200 15 412–1050 j MODIS-Aqua NASA (USA) Aqua (EOS-PM1) Launched 04/05/02 1000 36 405–14385 h CMODIS CNSA (China) Shen Zhou-3 (China) 25/03/02–15/09/02 400 34 403–12500 k COCTS CNSA (China) HaiYang-1 (China) Launched 15/05/02 1100 10 402–12500 k CZI CNSA (China) HaiYang-1 (China) 15/05/02–01/12/03 250 4 420–890 k GLI NASDA (Japan) ADEOS-II (Japan) 14/12/02–25/10/03 250/1000 36 375–12500 l POLDER-2 CNES (France) ADEOS-II (Japan) 14/12/02–25/10/03 6000 9 443–910 m Data used courtesy of the International Ocean Color Coordinating Group, http://www.ioccg.org/sensorshttp://www.ioccg.org/sensors. a: http://daac.gsfc.nasa.gov/DATASET DOCS/czcs dataset.html. http://daac.gsfc.nasa.gov/DATASET DOCS/czcs dataset.html. b: http://www.eoc.nasda.go.jp/guide/satellite/sendata/octs e.html. http://www.eoc.nasda.go.jp/guide/satellite/sendata/octs e.html. c: http://smsc.cnes.fr/POLDER. http://smsc.cnes.fr/POLDER. d: http://www.ba.dlr.de/NE-WS/ws5/mos home.html. http://www.ba.dlr.de/NE-WS/ws5/mos home.html. e: http://seawifs.gsfc.nasa.gov. http://seawifs.gsfc.nasa.gov. f: http://rocsat1.oci.ntou.edu.tw/en/oci/index.htm. http://rocsat1.oci.ntou.edu.tw/en/oci/index.htm. g: http://www.isro.org/programmes.htm. http://www.isro.org/programmes.htm. h: http://modis.gsfc.nasa.gov. http://modis.gsfc.nasa.gov. i: http://kompsat.kari.re.kr/english/index.asp. http://kompsat.kari.re.kr/english/index.asp. j: http://envisat.esa.int/instruments/meris. http://envisat.esa.int/instruments/meris. k: http://www.cnsa.gov.cn/main e.asp. http://www.cnsa.gov.cn/main e.asp. l: http://www.eoc.nasda.go.jp/guide/satellite/sendata/gli e.html. http://www.eoc.nasda.go.jp/guide/satellite/sendata/gli e.html. m: http://polder-mission.cnes.fr. http://polder-mission.cnes.fr. Source: From Pinkerton, M. H. et al. (2005). Remote Sensing of Environment 97, 382–402.
- 37. 1.7 The Futureof Marine Biogeochemistry 17 for Integrated and Sustained Ocean Observations. The goals of IOOS are to benefit humans by (1) improving predictions of climate change and weather and their effects on coastal communities and the nation; (2) improving the safety and efficiency of maritime operations; (3) more effectively mitigating the effects of natural hazards; (4) improving national and homeland security; (5) reducing public health risks; (6) more effectively protecting and restoring healthy coastal ecosystems; and (7) enabling the sustained use of ocean and coastal resources. IOOS is split into an ocean and a coastal component. The coastal component is divided into 10 Regional Coastal Ocean Observing Systems (RCOOS), each run by a Regional Association (RA). The National Federation of Regional Associations (NFRA) is charged with producing an integrated network by coordinating efforts of the RCOOSs. One interesting challenge lies in linking the existing freshwa- ter observational framework, such as gaging stations maintained by the U.S. Geological Survey (USGS), to downstream efforts in estuaries. Several RCOOSs have seafloor obser- vatories, such as LEO-15, which will continue to be coordinated through the ORION. One of the important challenges of these initiatives is in developing strategies for cop- ing with large data streams generated by multiple sensors and instruments, including providing power, high-speed data transmission, and two-way, shore-to-seafloor commu- nications. Another important initiative is the development of telepresence at sea in which an advanced type of videoconferencing is used to transmit video and digital data between ship and shore in near real time using satellite links to the Internet. Through telepresence, the science command center for an expedition can be located on land, thereby reducing costs and scheduling problems amongst the lead scientists. A notable example of a GOOS program is the broad-scale global array of tempera- ture/salinity profiling floats, known as Argo. Deployments began in 2000, with the final array to be composed of 3000 floats that will generate 100,000 vertical profiles of tem- perature, salinity and velocity measurements per year at an average 3-degree spacing. Sensor technology is improving rapidly, enabling in situ measurement of other parame- ters such as dissolved oxygen, nitrate, in vivo chlorophyll fluorescence, CDOM, turbidity, pH, photosynthetically active radiation (PAR), and redox potential (ORP). At present, long-term deployments of these sensors are rare because of biofouling and calibration issues. An interesting short-term deployment technique uses towed undulating ROVs. Depth and GPS sensors provide location information used by an onboard computer to produce horizontal maps, cross-sectional depth profiles, and property-property plots. A new generation of in situ sensors using a wet chemistry approach for measuring nutri- ents and iron in seawater is now commercially available, but the need for a larger variety of in situ sensors for identifying and quantifying a wide range of gases, organic com- pounds, and plankton, including microbes, is great. Future approaches will likely seek to create instrument packages that carry sophisticated chemical instrumentation such as high-pressure liquid chromatographs (HPLCs), UV-VIS spectrophotometers, mass and Raman spectrometers, and even DNA analyzers.11 11 http://www.whoi.edu/institutes/oli/activities/short report.pdf
- 38. 18 CHAPTER 1The Crustal-Ocean-Atmosphere Factory Though great progress has been made in the past four decades, many gaps remain in our understanding of the chemical processes that occur in the sea. There are several reasons for this. First, except for water and the six major ions, all the other substances in seawater are present at very low concentrations. The combination of trying to detect low concentrations in the presence of large amounts of salts makes measurement of the trace constituents in seawater very difficult. To make matters even more complicated, most elements are present in several different forms, or species, in seawater. The speci- ation of an element determines its reactivity. Thus, the concentration of each species of an element must be known to fully understand the chemical behavior of that element. Another great challenge in furthering our understanding of the ocean lies in improv- ing our theoretical approach to the ocean. Marine chemists have traditionally resorted to assuming that the chemical reactions of interest attain equilibrium. This greatly simpli- fies computations, but provides limited insight into the wide variety of biogeochemical processes controlled by marine organisms. Since living organisms are themselves not at equilibrium, neither are the reactions they mediate. Some attempts have been made at kinetic descriptions of marine processes, with most relying on an assumption of first-order rate behavior. Higher-order rate laws are more likely to be the rule and are thought to confer stability on biological systems. Marine chemistry has traditionally been divided into two fields. One seeks to under- stand the chemistry of organic substances in the ocean. The other investigates inorganic substances. Because of analytical difficulties, more is known about the latter than the former. Continuing methodological advances are causing this gap to close rapidly. Our growing recognition of the ubiquitous influence of marine organisms has also blurred the distinction between the two fields. This has direct impact on how research is now being conducted to elucidate the controls on ocean fertility, namely assessing the role of trace metals, such as iron, in supporting the growth of phytoplankton. Understand- ing ocean fertility will help better manage fisheries and cope with pollution problems. Related areas of research include (1) establishing the molecular structure and reactivity of dissolved and particulate organic matter, (2) elucidating the role of marine organisms in packaging materials into solids that settle and become buried in marine sediments, and (3) quantifying material inputs to the ocean from the coastal ocean, atmosphere, and hydrothermal vents. Other efforts are directed at exploring the recovery of min- eral resources from the seabed and the discovery of marine natural products. Many of these research areas are characterized by multidisciplinary approaches, making it dif- ficult to separate chemical studies from biological, geological, physical, atmospheric, and even aquatic work. As a result, biogeochemists are being increasingly common and can be found working in laboratories and departments of biology, geology, physics, atmospheric, space, and environmental science! Biogeochemistry has been particularly useful in efforts to study the ocean’s past. This subdiscipline is called paleoceanography. Because of the linkages among the crust, ocean, and atmosphere, the field of paleoceanography also provides insight into past cli- mate and terrestrial conditions. Much of the geochemical reconstruction of the ocean’s past has relied on compositional analysis of marine microfossils recovered from long sediment cores. These cores are collected by specialized drill ships. The first of these
- 39. 1.7 The Futureof Marine Biogeochemistry 19 was the Glomar Challenger, deployed in 1966 as part of the Deep Sea Drilling Project (DSDP). In 1984, DSDP was transformed into the Ocean Drilling Program (ODP) and acquired a new vessel, the Resolution, operated by JOIDES ( Joint Oceanographic Insti- tutions for Deep Earth Sampling). In 2003 this program was retooled as the Integrated Ocean Drilling Program (IODP) that now involves 22 countries, including the United States, Japan, and the European Union.12 IODP has a new drill ship, the Japanese Chikyu, and an annual budget of $160 million! IODP’s goals include elucidating the history of global climate change and discovering new energy resources and microbes. The ocean covers most of Earth’s surface, contains half the planet’s biota, and controls our climate. Thus the story of the ocean’s past is truly the story of Earth’s past. Using information about the causes and behavior of such phenomena as ice ages and plate tectonics, paleoceanographers hope to predict the future of our ocean and planet. This goal is of more than academic interest. Humans have greatly accelerated the transport rates of some materials into the atmosphere and ocean. These changes are so profound that they have arguably launched planet Earth into a new geological epoch, dubbed the Anthropocene.13 It is critical to our own continued existence on this planet that we predict the effects of our own actions so we can take appropriate actions to protect our home, planet Earth. 12 http://www.iodp-usio.org 13 Geologists have deemed it necessary to recognize this new epoch because sediments now accumu- lating on the seafloor are chemically distinct from those whose origins predate human impacts on the crustal-ocean-atmosphere factory.
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- 41. 2 CHAPTER The Waters ofthe Sea All figures are available on the companion website in color (if applicable). 2.1 INTRODUCTION What is the most abundant substance in the ocean? Water! Not only does water con- stitute approximately 97 percent of the mass of seawater, but it has some very unusual and important physical characteristics. Because water has a relatively high boiling point, it occurs mostly in the liquid phase. In fact, water is the most common liquid on our planet. Water is essential for life processes largely because of its unique ability to dissolve at least a little bit of virtually every substance. Water is also important because it plays a major role in controlling the distribution of heat on the planet. As water moves through the global hydrological cycle, it transports solutes, gases, and particles, including orga- nisms. In this chapter, the physical and chemical features of water are discussed along with the processes by which this important substance is transported around our globe. 2.2 THE HYDROLOGICAL CYCLE Among the planets of our solar system, Earth is unique in its great abundance of free water.1 On Earth’s surface, most of this water currently resides in the oceans. The origin of this water is still a matter of debate. The favored hypothesis is that most came from the degassing of the planet’s interior during the early stages of Earth’s formation. Other potential sources that could still be supplying water include (1) radiogenic processes within Earth’s mantle followed by volcanic emission and (2) vaporization from small water-rich comets or asteroids as they enter the upper atmosphere. The latter was first observed in the 1980s from satellite imagery. The comets appear to be striking at a rate 1 Geochemists distinguish free water from bound water based on the degree to which the water is physically or chemically associated with particles, such as mineral or organic surfaces. Examples of binding forces are Van der Waals interactions and hydrogen bonding. They cause bound water to exhibit physical characteristics that are markedly different from those found in free water. 21
- 42. 22 CHAPTER 2The Waters of the Sea Metamorphism Metamorphism Weathering ATMOSPHERE 0.0013107 km3 Compaction 0.18 Porewater advection Comets 0.2 to 0.4 Photolysis followed by escape of H2 8.7 31025 Precipitation 119,000 Carried in wind 47,000 Evaporation 72,000 Precipitation 458,000 Evaporation 505,000 Runoff 2,122 to 4,244 Runoff 35,000 to 43,000 Subduction 1.03 to 1.83 LAND Ice Snow 2.413107 km3 Groundwater 2.343107 km3 Lakes 0.023107 km3 Swamp 0.001310 7 km3 River 0.0002 3107 km3 MANTLE 517 3107 km3 CRYSTALLINE ROCK ??? 3107 km3 SEDIMENTARY ROCK 1.5 3107 km3 Mixed Layer 113107 km3 Deep Zone 126 3107 km3 Sediments 5.3 3107 km3 OCEAN Degassing 0.51 Downwelling 1.08 x 10 6 Upwelling 1.08 x 10 6 Porewater burial 0.18 Degassing via volcanism Extraterrestrial Biological 0.00013107 km3 FIGURE 2.1 The global hydrological cycle. Rates are in units of km3/y and reservoir volumes in km3. Note that global estimates of rates and reservoirs are still a matter of uncertainty leading to the ranges reported in the figure. Sources: (1) Gleick, P. M. (1993). Water in Crisis. Oxford University Press, p. 14. (2) Frank, L. A. Small Comets and Our Origins. University of Iowa. http://sdrc.lib.uiowa.edu/ preslectures/frank99/. (3) Bounama, C., et al. (2001). Hydrology and Earth System Sciences 5(4), 569–575. (4) Jarrard, R. D. (2003). Geochemistry, Geophysics Geosystems 4(5), 15. (5) Burnett, W. C., et al. (2003). Biogeochemistry 66, 3–33. of approximately 5 to 30 per minute with each one carrying 20 to 40 tons of water into Earth’s upper atmosphere. As shown in Figure 2.1, the free water on Earth’s surface is now transported between the land, atmosphere, ocean, and mantle through a global hydrological cycle. From
- 43. 2.2 The HydrologicalCycle 23 the perspective of the ocean, water is supplied from direct precipitation, river runoff, groundwater seepage, and mantle degassing. If the volume of the ocean remains con- stant over time, these inputs must be balanced by an equal amount of output. Water is largely removed from the ocean by evaporation. A small amount is buried as part of the sediments that accumulate on the seafloor. Some of this buried water is subducted into the mantle, where it can be returned to the atmosphere by various geological means, including subaerial volcanism and terrestrial weathering. Ninety percent of the water that evaporates from the ocean is returned in the form of rainfall. The rest is transported over land, where it is rained out onto the continents. River runoff and groundwater seeps carry this missing 10 percent back to the sea. At the rates that precipitation and runoff (including seeps) deliver water, it would take 3800 y to cycle the amount of water in the ocean through the atmosphere and back into the sea. This is probably a good estimate of the residence time of water in the ocean, assuming the cometary source of water is small and that the ocean’s volume is in a steady state. Because rivers and groundwater are the major transport agents of dissolved and solid materials into the ocean, the turnover time of the marine reservoir of water with respect to these processes (30,000 y) is a more geochemically interesting measure than the residence time. In comparison, one mixing cycle of the ocean is approximately 1000 y. Planet Earth acquired an ocean early in its history, probably by 3.8 billion years before present. Most of the water is thought to have been released during the process of differentiation in which density-driven convection and cooling caused the still-molten planet to separate into layers of decreasing density, i.e., core, mantle, crust, and atmo- sphere. Once the crust had cooled sufficiently, gaseous water condensed to form a permanent ocean. Most depictions of the hydrological cycle, such as Figure 2.1, indicate that on time scales experienced by humans, the volume of the ocean remains constant. The most recent significant changes in ocean volume occurred during the Ice Ages of the Pleis- tocene Epoch. During the last Ice Age, which ended 18,000 y ago, 4.2 × 10 7 km 3 of seawater was transformed into glacial ice, reducing the ocean’s volume by 3% and lowering sea level about 120 m below that of present day. On longer time scales, continuing mantle and extraterrestrial processes will likely cause shifts in the sizes of the reservoirs. In the case of the former, subduction into the mantle is large enough to be causing a net loss. As the planet continues to cool, this rate will diminish. On the other hand, as the Sun’s luminosity increases, the rate of photodissociation of atmospheric water into H2 and O2, followed by escape of H2 to outer space, will increase. In a billion years or so, this process will have stripped all the surface water from Earth. On time scales of greater import to humans is a pre- dicted intensification of the global hydrological cycle associated with global climate change, some of which is natural and some of which is driven by human activities. This is predicted to lead to an increase in the frequency and intensity of floods and droughts that could then alter reservoir sizes in the hydrological cycle, at least region- ally. Some evidence already exists for an increase in global runoff rates over the last century.
- 44. 24 CHAPTER 2The Waters of the Sea 2.3 WATER: A PHYSICALLY REMARKABLE LIQUID Water is an unusual liquid. For example, solids tend to be denser than their liquid phase, whereas ice floats in its liquid. Another oceanographically relevant behavior is that water is nearly incompressible. This causes seawater at great depths to have nearly the same density and viscosity as surface seawater of matching temperature and salinity. Water also has a relatively high heat capacity, making it a large heat reservoir that effectively moderates weather and climate. In comparison to other hydrides of the group VI ele- ments, the hydride of oxygen, H2O, has a relatively high boiling (100 ◦ C) and freezing point (0 ◦ C). Given the temperature range on Earth’s surface, water is commonly found in its liquid form, making it the most common naturally occurring liquid. Another interest- ing characteristic of liquid water is its high surface tension. This is exploited by aquatic insects to keep them atop water’s surface. All of these unusual behaviors of water can be traced back to its tendency to form hydrogen bonds between adjacent water molecules, which is in turn a consequence of water’s polar intramolecular bonds. 2.3.1 The Molecular Structure of Water The molecular structure of water is shown in Figure 2.2. Each atom of hydrogen is covalently bonded to a central oxygen atom, with two electrons shared between the atoms. This sharing is not equal because the eight protons in the nucleus of the oxygen atom exert a stronger force of electrostatic attraction than does the single proton in the hydrogen nucleus. The magnitude of the force of this attraction (F in Newtons [N]) between oppositely charged particles is given by Coulomb’s law: F = k q1q2 r2 (2.1) where q1 is the negative charge on an electron, q2 is the positive charge on a proton, both 1.602 × 10−12 coulombs (C), r is the distance of separation (in meters) between the charges, and k is a constant (8.99 × 10 9 N m 2 C 2 ). Water molecule 104.58 Electron } negative charge (2) Nucleus } positive charge (1) d2 d1 1d FIGURE 2.2 The Lewis structure and molecular geometry of the water molecule.
- 45. 2.3 Water: APhysically Remarkable Liquid 25 Because of the stronger pulling power of the larger atom, the bonding electrons spend more time closer to the oxygen atom. This unequal sharing of electrons is referred to as a polar covalent bond. It is characterized by a small net positive charge at the hydrogen end of the molecule and a small net negative charge at the oxygen end. Since these net charges are significantly weaker than those associated with ions and ionic bonds, they are represented by the symbols ␦ − and ␦+ . In a water molecule, the oxygen atom shares its valence electrons with two hydrogen atoms. This electron sharing causes the oxygen atom to have four pairs of valence elec- trons. Two of the pairs form the polar covalent bonds found between oxygen and each hydrogen atom. The other two pairs are nonbonding. If all four pairs were distributed equally through three-dimensional space, the water molecule would exhibit tetrahedral geometry with bonding angles of 109.5 ◦ . This is not observed because the two electrons in the nonbonding pairs exert a net repulsive force that reduces the bonding angle between the H–O–H bonds to 104.5 ◦ . The two nonbonding pairs also contribute to the small net negative charge that is present on the oxygen end of the water molecule. 2.3.2 The Phases of Water Water is one of the few substances on the planet that naturally occurs in three phases. Gaseous water is usually referred to as steam or water vapor. This phase is characterized by a relatively random arrangement of molecules. Like any gas, a quantity of steam has no definite shape or size. For example, one can put some gas in a balloon and then change the size and shape of the gas just by manipulating the size and shape of the balloon. Some gases, such as steam and oxygen (O2), are composed of molecules, while others, such as the noble gases, are composed of separate atoms. In the gas phase, these particles of matter are less tightly packed together than in either the liquid or solid phases. The relative compactness of the phases of matter is shown in Figure 2.3. The degree of compactness can be expressed as the density of a substance, which is defined as Density = Mass Volume (2.2) The SI unit of density is kg/m 3 . Oceanographers more commonly use units of g/cm 3 and kg/L. The density of pure liquid water at 4 ◦ C is exactly 1 g/cm 3 . Thus, a cube of liquid water, measuring exactly 1 cm on all sides, has a mass of exactly 1 g. This is how the unit of a gram was originally defined. Density is an intrinsic property of matter. It remains constant regardless of the amount of substance being measured. For example, at 4 ◦ C both 1000 kg and 10 mg of pure water have a density of exactly 1 g/cm 3 . The density of a substance gives important information on its behavior. For example, oil floats on liquid water because oil has a lower density than water. A rock will sink in liquid water because the rock has the higher density. The liquid phase of matter is denser than the gaseous phase and has a more orderly arrangement of particles. A liquid has a definite volume, but no definite shape. So a cup of liquid water can take on the shape of its container, whether it be a cylinder or a box. Water in the solid phase is referred to as ice. Solids possess the most orderly arrangement
- 46. 26 CHAPTER 2The Waters of the Sea Solid Liquid Gas FIGURE 2.3 Particle distributions in the solid, liquid, and gaseous phases of matter. Source: From Chang, R. (1994). Chemistry, 5th ed. McGraw-Hill, Inc, 994 pp. of particles. As shown in Figure 2.4, which uses a grain of sodium chloride salt as an example, crystalline solids possess such an orderly arrangement that the positions of the particles can be predicted over long distances. Because of this long-range order, solids are mechanically rigid and thus have a size and shape that is independent of any container. The dimensions of any given chunk of crystalline solid are determined by the envi- ronmental conditions under which it solidifies or is mechanically fractured. In the case of table salt, an average grain (0.1 mm 3 ) contains about 10 13 atoms of Na and Cl. Thus, it is not possible to write one molecular formula that describes all grains of crystalline sodium chloride. Instead, chemists use an empirical formula that indicates the combining ratios of the atoms. For crystalline sodium chloride, this empirical formula is NaCl(s). If the pressure on a substance is kept constant, its phase can be changed simply by adding or removing heat. For water, specific names are given to each phase change. The transition from solid to liquid state is termed melting and its reverse is freezing. If the water temperature is held at 0 ◦ C in a closed container held at 1 atm pressure,2 the two phases will coexist and interconvert as represented by the following equation: H2O(s) H2O( l ) (2.3) The two phases are said to be in equilibrium when the rate at which water molecules entering the solid state is exactly matched by rate entering the liquid state. The temper- ature at which this occurs is called the melting point, or freezing point, of water. Note that true phase changes are not considered to be chemical reactions as no intramolecular bonds are broken or formed. 2 SI units for atmospheres are pascals where 1 atm = 101325 Pa = 1.01325 bar. Most oceanographers use bars when referring to pressures at depth below the sea surface.
- 47. 2.3 Water: APhysically Remarkable Liquid 27 Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI Na FIGURE 2.4 Crystal lattice of NaCl. The transition from the liquid to the gaseous state is called evaporation or vaporiza- tion. The reverse is referred to as condensation or, in terms of rainfall, precipitation. If heated to 100 ◦ C in a closed container at 1 atm pressure, the two phases of water will coexist in the equilibrium given in Eq. 2.4. H2O( l ) H2O( g ) (2.4) This temperature is called the normal boiling point of water. If the container were to be opened, some of the gas molecules would escape. To replace the missing water, the phase change represented by Eq. 2.4 would be driven toward the products until all of the liquid water evaporated. The direct transition from the solid to the gaseous phase is termed sublimation. Ice will sublime under arid conditions, especially in polar climates. Heat transfer causes phase transitions by changing the average kinetic energy of the particles.3 When heated, particles move faster and, if unconfined, farther apart. In so doing, thermal energy (heat) is transformed into kinetic energy. By driving the particles apart, the density of a substance is lowered. When heat is removed from a substance, the particles slow down. In this lower energy state, they come closer together, causing an increase in density. 3 The generic term particle is used to refer to either atoms or molecules.
- 48. 28 CHAPTER 2The Waters of the Sea From this discussion, we would predict that given sufficient cooling, a liquid should be transformed into a solid, more dense phase. Why, then, does ice float in liquid water? Some force must keep the water molecules far enough apart in ice so as to cause its density to be lower than that of liquid water. It is somewhat ironic that the most abundant and important of liquids on our planet is the only one to exhibit this anomalous density behavior. 2.3.3 Hydrogen Bonding in Water The force that influences the orientation of water molecules in ice is called hydrogen bonding. This is somewhat of a misnomer because hydrogen bonding is an inter- molecular force rather than a true chemical bond, which is an intramolecular force. Hydrogen bonding is caused by the electrostatic attraction of the negatively charged end of a water molecule for the positively charged end of a neighboring molecule. As shown in Figure 2.5, this attraction causes the unshared electron pairs on the oxy- gen end of each water molecule to orient themselves toward the hydrogen atoms of neighboring water molecules. The strength of a hydrogen “bond” is on the order of 5 kcal/mol. In comparison, the energy of a typical single covalent bond ranges from 50 to 110 kcal/mol (depending on the molecular setting). So hydrogen bonds are weaker than true intramolecular bonds. In ice, all of the water molecules have formed the maximum number of hydrogen bonds, which is four per molecule. This creates the hexagonal pattern illustrated in Figure 2.6. As shown in Figure 2.7, liquid water also contains some degree of hydrogen bonding. Although the details of the structure of liquid water are not well understood, it is thought to be composed of transitory clusters of four to five molecules held together by multiple hydrogen bonds. Since the molecules have a high kinetic energy in the H H O H O O O H H H H H FIGURE 2.5 Hydrogen bonding between water molecules. Hydrogen bonds are represented by dashed lines.
- 49. 2.3 Water: APhysically Remarkable Liquid 29 FIGURE 2.6 The crystalline structure of fully hydrogen-bonded water in ice. Hydrogen bonds are represented by dashed lines. Solid (Crystalline structure is three-dimensional) Liquid Gas FIGURE 2.7 A comparison of hydrogen bonding in the solid, liquid, and gaseous phases of water. Source: From Thurman, H. V., (1988). Introductory Oceanography, 5th ed., Merrill Publishing Company, p. 150.
- 50. 30 CHAPTER 2The Waters of the Sea liquid state, these intermolecular “bonds,” and, hence, clusters, are rapidly broken and reformed.4 This results in regions of varying density in liquid water, with some greater than that found in ice. 2.3.4 The Effect of Hydrogen Bonding on the Physical Behavior of Water Hydrogen bonding is not restricted to water. A few other hydrides, such as NH3 and HF, have polar covalent bonds with large enough charge differences to support hydro- gen bonding. But these substances are gases at the temperatures and pressures usually encountered on this planet. Therefore hydrogen bonding is of little importance to their environmental chemistry, except when they are dissolved in water. Hydrogen bond- ing also occurs between biochemicals, such as proteins and DNA, and helps define their three-dimensional molecular structure, which in turn affects their chemical sta- bility and reactivity. In water, hydrogen bonding plays a large role in determining a variety of unusual physical and chemical properties as summarized in Table 2.1 and discussed next. First, water has a relatively high boiling and freezing point. As illustrated in Figure 2.8, extrapolation of the molecular weight trends established by the Group VIA hydrides suggests that the boiling and freezing points of H2O should be −68◦ C and −90 ◦ C, respectively. Instead, water has a boiling point of 100 ◦ C. A higher tem- perature is needed to give water enough kinetic energy to overcome the hydrogen bonds and thus enable the water molecules to separate and escape into the gas phase. The anomalously high freezing point (0 ◦ C ) is caused by the formation of hydrogen bonds as water cools. This extra force helps organize the molecules into the long- range order necessary to produce a solid. Thus, less heat removal is required to freeze water. Second, water has a relatively high heat capacity, which is a measure of how much heat can be absorbed per unit of temperature increase. As shown in Figure 2.9, the temperature of 1 g of liquid water is increased by 1 ◦ C for every calorie of heat energy added. In other words, the heat capacity of liquid water is 1 cal ◦ C−1 g−1 . The heat capacities of ice and steam are 0.51 and 0.48 cal ◦ C−1 g−1 , respectively.5 The cause of the relatively high heat capacity of liquid water is similar to that which produces the anomalously high boiling point. Because of the presence of hydrogen bonds, heat that would otherwise go to increasing the motion of the water molecules instead goes into breaking the hydrogen bonds. Once the hydrogen bonds have been disrupted, the added heat energy is expressed solely as an increase in molecular motion. It is this increased motion that is measured as a temperature rise by a thermometer. 4 Experimental evidence and theoretical modeling suggest that these clusters involve several to several hundred water molecules. 5 These heat capacities vary slightly with temperature and pressure. For example, the heat capacity of liquid water increases from 1.000 cal ◦ C −1 g −1 at 14 ◦ C to 1.007 cal ◦ C −1 g −1 at 100 ◦ C under 1 atm pressure.
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- 52. Les 20,000 francs,1832, Boule. D. Lesson for Ladies (1802-1879), Buckstone. C. Lethe, 1743, Garrick. L’Étoile de Seville, 1842, Balfe. O. L’Étourdi, 1653, Molière. C. Leucothe, 1756, Bickerstaff. C. Liar (The), 1762, Foote. F. (See “Menteur.”) Libertine (The), 1676, Shadwell. C. Liberty Asserted, 1704, Dennis. D. Life (1765-1841), Reynolds. C. Life-Buoy (The), (1566-1638), Hoskins. D. Life-Drama (The), 1852, A. Smith. D.Pm. Light Heart (1574-1637), Jonson. Lighthouse (The), 1855, Wilkie Collins. D. Like will to Like, 1568, Fulwel. Int. L’Ile du Prince Touton, 1854, Dennery. Lily of Killarney, 1862, Benedict. O. Lily of the Desert (The), 1859, Stirling. R.D. Limherham, 1679, Dryden. Linda di Chamourni, 1842, Donizetti. O. Lindamira, 1805, Foote. Lingua, or The Five Senses, 1580, printed 1607, Brewer. Alleg.Pl. (Cromwell, on one occasion, acted the part of Tactus.) Lionel and Clarissa, 1768, Bickerstaff. O. (music by Dibdin). Little Em’ly (1830-1877), Halliday. Little French Lawyer, 1647, Beaumont and Fletcher. C.
- 53. Little Rebel (The),1805-1868, Coyne. Little Red Riding-Hood (1817-1880), Taylor. Little Toddlekins (1803-1878), C. T. Mathews. Loan of a Lover, (The), 1833, Planché. V. Lock and Key (1755-1834), Hoare (music by Shield). Locrine, 1595, Tylney. T. Lodoiska, 1791, Kemble. Mu.D. (music by Storace). Lodoiska, 1800, Mayer. Mu.D. Lodowick Sforza, 1628, Gomersall. T. Lohengrin, 1848, Wagner. O. Lombardi, 1843, Verdi. O. London Assurance, 1841, Boucicault. C. London Florentine (The), 1602, Chettle and Heywood. Pl. London Prodigal (The), 1605 (ascribed by some to Shakespeare). Long Strike, 19th cent., Boucicault. D. Longer Thou Livest the More Foole Thou Art (time, Queen Elizabeth), Wager. C. Looking-Glasse for London, etc., 1594, Greene and Lodge. T.C. (The Looking-Glass is Nineveh.) Lord Cromwell, 1602, Anon. H.Pl. (See “Cromwell.”) Lord Dacre, * Mrs. Gore. Lord Dundreary Married and Done For, 1859, H. J. Byron and Sothern. C. Lord of the Manor, before 1833, C. Dibdin, junior. C.O. (altered from Burgoyne, 1783; music by Jackson). Lord of the Manor, 1783, Burgoyne. C.
- 54. Lord’s Warmingpan (The),1825 (same as Colman’s Heir-at-Law). Lorenzo (1755-1798), Merry. T. Lost Lady (The), 1639, Berkeley. T.C. Lost at Sea, 19th cent., Boucicault. D. Louis IX., 1819, Ancelot. T. Louis XI., 1832, Delavigne. H.D. (An English version in 1846 by Boucicault). Louise de Lignerolles, 1838, Legouvé. D. Love, 1840, Knowles. D. Love-Chase (The), 1837, Knowles. C. Love Crowns the End, 1657, Tatham. T.C. Love Laughs at Locksmiths, 1803, Colman. F. Love, Law and Physic (1772-1849), Kenney. C. Love Makes a Man, 1700, Cibber. C. Love-Riddelig, 1816, Ingemann. D. Love Tricks, 1667, Shirley. C. (originally called The Schoole of Complement, 1631). Love Triumphant, 1694, Dryden. C. Love à-la-Mode, 1759, Macklin. C. Love and a Bottle, 1698, Farquhar. C. Love and Fortune, 1859, Planché. C. Love and Friendship, 1666, Killigrew. Pl. Love and Honor, 1649, Davenant. C. Love and Police, 19th cent., Herz. V. Love and Revenge, 1675, Settle. T. Love and War, 1658, Meriton. T.
- 55. Love and War,1792, Jephson. F. Love at First Sight (1730-1805), King. C. Love at a Loss (1679-1749), Mrs. Cockburn. C. Love at a Venture, 1706, Centlivre. C. Love for Love, 1695, Congreve. C. Love for Money, or The Boarding School, 1691, D’Urfey. C. Love in a Blaze, 1800, Atkinson. C. Love in a Camp, 1798, O’Keefe. C. Love in a Forest, 1721, C. Johnson. C. (based on Shakespeare’s As You Like It). Love in a Hurry, 1709, Aston. C. Love in a Maze, 1844, Boucicault. C. Love in a Riddle (1671-1757), C. Cibber. C. Love in a Tub, 1664, Etherege. C. Love in a Veil, 1718, Savage. C. Love in a Village, 1762, Bickerstaff. O.F. (music by Arne). Based on Johnson’s Village Opera. Love in a Wood, 1672, Wycherly. C. Love in a Wood (1686-1744), G. Jacob. C. Love in Several Masques, 1728, Fielding. C. Love in the City, 1767, Bickerstaff. C. (See “The Romp.”) Love of Arcadia, 1860, Miss Braddon. Cdta. Love of King David, etc., 1599, Peele. S.D. Love will find out the Way, 1661, by T. B. (Shirley’s Constant Maid reset). C. Love’s Contrivances, 1703, Centlivre. C.
- 56. Love’s Cruelty, 1640,Shirley. T. Love’s Cure, 1647, Beaumont and Fletcher. C. Love’s Disguises, 1838, Knowles. C. Love’s Dominion, 1654, Flecknoe. D. Love’s Kingdom. 1664, Flecknoe. P.T.C. (same as “Love’s Dominion,” slightly altered). Love’s Labor’s Lost, 1594, Shakespeare. C. (printed 1598). Love’s Last Shift, 1695, Cibber. C. Love’s Metamorphosis, 1601, J. Lyly. Myt.D. Love’s Mistress, 1636, Heywood. C. Love’s Pilgrimage, 1647, Beaumont and Fletcher. Love’s Riddle, 1638, A. Cowley. P.C. Love’s Sacrifice, 1633, Ford. T. (It resembles Shakespeare’s Othello.) Love’s Stroke of Genius, 19th cent., Herz. V. Love’s Triumph, 1630, Johnson. M. Love’s Triumph, 1860, Wallace. O. Love’s Victorie, 1653, Shirley. Pl. Love’s Victory, 1658, Chamberlayne. T.C. Loves of Arcadia (The), 1860, Miss Braddon. Cdta. Lover (The), 1730, T. Cibber. C. Lover Lost (The), 1696, Mrs. Manley. C. Lover’s Melancholy (The), 1628, Ford. T. (This play contains the exquisite description of a contest of song between a musician and a nightingale). Lovers’ Progress, 1647, Beaumont and Fletcher.
- 57. Lovers’ Quarrels (1730-1805),King. Int. (See “Mistake.”) Lovers’ Vows, 1800, Inchbald. Pl. (Kotzebue’s play, 1798, Anglicized). Lover’s Watch (The), 1686, Mrs. Behn. C. Lovesick Court (The), 1653, Brome. C. Lovesick King (The), 1655, Brewer. C. Loyal Brother (The), 1682, Southerne. T. Loyal Subject, 1618, Fletcher (Beaumont died 1616). Based on Heywood’s Royal King and Loyal Subject. L.S.D., 1872, A. W. A’Beckett. C. Lucia di Lammermoor, 1835, Donizetti. O. Lucidi (I), 1539, Angelo. C. Lucio Silla, 1773, Mozart. O. Lucius, 1717, Mrs. Manley. T. Lucius Junius Brutus. (See “Brutus.”) Lucky Chance (The), 1687, Mrs. Behn. C. Lucretia Borgia, 1831, Victor Hugo. R.T. Lucrezia di Borgia, 1834, Donizetti. O. Lucretius, 19th cent., Tennyson. D.Mon. Luisa Miller, 19th cent., Verdi. O. Luke, the Laborer, 1828, Buckstone. Mel. Luria, 19th cent., R. Browning. T. Lurline, 1860, Wallace. O. Lust’s Dominion, 1593, Marlowe. T. (finished by Dekker, 1617). Lusty Juventus (time, Henry VIII.), Anon. Mo. Lying Lover (The), 1704, Steele. C.
- 58. Lying Valet, 1740,Garrick. F. Lysistrata, B.C. 411, Aristophanes. C. (Greek). Translated by Mitchell, 1820-22; Hickie, 1853; Rudd, 1867. Ma Tante Aurore, 1802, Boieldieu. O. Macbeth, 1606, Shakespeare. T. (music by Lock, 1672). Macbeth, 19th cent., Verdi. O. Mad as a Hatter, 1863, Marshall. F. Mad Couple well matched, 1653, Brome. C. Mad Lover, 1617, Fletcher (Beaumont died 1616). Mad Lover, 1637, Massinger. Mad Lovers (The), 1732, S. Johnson. C. Mad World, 1608, Beaumont and Fletcher. Mad World, My Masters, 1608, Middleton. C. Madam Fickle, 1677, D’Urfey. C. Madame Diogène, etc., 1854, Desarbres. C. Madame Favart, 1878, Offenbach. C.O. Madame Du Barry, 1836, Ancelot. V. Madame du Châtelet, about 1834, Ancelot. V. Madcap Prince (A), 1874, *. Maestro di Capella, 1797, Dellamaria. Magician no Conjuror (1755-1798), Merry. C. Magicienne (La), 1799-1860, Halévy. O. Magnetic Lady, 1632, Jonson. C. Magnifique (Le), 1672-1731, Lamotte. C. Magnifycence (time, Henry VII.), Skelton. Mo.
- 59. Mahomet, 1738, Voltaire.T. (done into English by Miller, 1740). Maid Marian (The), 1822, Bishop. O. (libretto by Planché). Maid and the Magpie, 1792-1852, Payne. C. Maid in the Mill, 1647, Beaumont and Fletcher, or Rowley and Fletcher. C. Maid of Artois, 1836, Balfe. O. Maid of Bath, 1771, Foote. F. Maid of Honor, 1632, Massinger. T.C. Maid of Honor, 1847, Balfe. O. Maid of Lockling, 1801, W. Richardson. L.D. Maid of Mariendorpt, 1838, Knowles. D. Maid of Milan (Clari, the), 1822, Payne. Mu.D. (music by Bishop). Maid of Orleans, 1801, Schiller. T. (See “Joan of Arc.”) Maid of Saxony, 1842, George Morris. O. Maid of the Mill, 1765, Bickerstaff. O.F. (music by Arnold). (See “Maid in the Mill.”) Maid of the Oaks (The), 1779, Burgoyne. D.E. Maid’s Metamorphoses. (See “Maydes Metamorphoses.”) Maid’s Revenge (The), 1639, Shirley. T. Maid’s Tragedy, 1610, Beaumont and Fletcher. T. (Waller altered the fifth act.) Maids and Bachelors (1768-1850), Skeffington. C. Maids as They Are, etc., 1797, Inchbald. C. Maiden Queen (The), 1667, Dryden. H.Pl. Maidenhead. (See “Maydenhead.”) Maire du Palais (Le), 1823, Ancelot. T.
- 60. Maître en Droit(Le), 1760, Monsigny. O.C. Malade Imaginaire (Le), 1673, Molière. C. (See “Dr. Last in His Chariot,” and “Robert, the Invalid.”) Malati and Madhava, 8th cent., Bhavabhouti. R.T. (translated by Wilson in his Indian Theatre). Malcontent (The), 1604, Marston and Webster. T.C. Male Coquette, 1758, Garrick. F. Mamilia, 1593, Greene. Man Bewitched, 1710, Centlivre. C. Man o’ Airlee, 1866, Wills. Pl. Man of Honor, 19th cent., Boucicault. C. Man of Mode (The), 1676, Etherege. C. Man of the World, 1764, Macklin. C. (Its original title was The Freeborn Scotchman.) Man’s the Master (The), 1668, Davenant. C. Management (1765-1841), Reynolds. C. Manfred, 1817, Byron. T. Manfredi, 1825, Monti. T. (A version in French, by Duplissis, 1854.) Maniac (The), 1810, Bishop. O. Mankind (time, Henry VI.), Hynghus. Mo. Manlius Capitolinus, 1684, Lafosse. T. (imitated from Otway’s Venice Preserved). Manteau (Le), 1826, Andrieux. C. Mantuan Revels, 1812, Chenevix. C. Manuel, 1817, Maturin. T. Maometto Secundo, 1822, Rossini. O.
- 61. Marciano, or TheDiscovery, 1663, Clerke. T.C. Maréchal Ferrent (Le), 1726-1795, Philidor. O.C. Maréchaux de l’Empire (Les), 1856, Anicet Bourgeois. D. Margaret of Anjou (1727-1812), Jerningham. T. Margery, or The Dragoness, 1738, Carey. F. (sequel to The Dragon, q.v.). Margherita d’Anjou, 1822, Meyerbeer. O. (See “Margaret....”) Marguerite d’Anjou, 1810, Guilbert de Pixérécourt. D. Mari dans du Coton, 1862, Thiboust. C. Mari Impromptu, 1836, Duval. C. Mari Retrouve, 1662, Dancourt. C. Mari qui Lance sa Femme, 1864, Deslande or Labiche (it is attributed to both). C. Maria Padilla, 1838, Ancelot. T. Maria Stuarda, 1785, Alfieri. T. (translated by C. Lloyd, 1815). (See “Mary Stuart.”) Maria Stuart, 1800, Schiller. T. (See “Mary Queen of Scots,” “Mary Stuart,” etc.). Mariage Fait et Rompu, 1721, Dufresny. C. Mariage Forcé, 1664, Molière. C. (See “Forced Marriage.”) Mariage Infantin (Le), before 1822, Scribe. Pt.Pc. Mariage d’Argent (Le), 1827, Scribe. C. Mariage de Figaro, 1784, Beaumarchais. C. (See “Nozze....”) Mariage de Rien (Le), 1640-1685, Ant. J. Montfleury. C. Mariages Samnites (Les), 1741-1813, Grétry. O. Mariamne, 1623, Hardy. T.
- 62. Mariamne, 1640, P.T. L’Ermite. T. Mariamne, 1724, Voltaire. T. Marian, the Faire Queen of Jewry, 1613, Lady Elizabeth Carew. T. Marian, 1788, Miss Brooke. Pl. Marian (1754-1829), Shield. O. Marianne, 1718, Fenton. T. Marie de Brabant, 1825, Ancelot. D.Pm. Marino Faliero, 1821, Byron. T. Marino Faliero, 1829, Delavigne. T. Marino Faliero, 1835, Donizetti. O. Marion Delorme, 1829, Victor Hugo. R.D. Maritana (a mosaic, by Wallace, of Ruy Bias and Notre Dame), 1845. O. Marius, 1791, Arnault. T. Marius (Caius), 1680, Otway. T. Marius and Sylla, 1594, Lodge. H.Pl. Marmaduke Maxwell (Sir), 1827, Cunningham. C. Marplot, 1711, Centlivre. C. Marquis Caporal, 1864, Sejour. D. Marquis d’Argencourt, 1857, Dupenty. D. Marquis de Kénilis, 1879, Lomon. Marriage à-la-Mode, 1672, Dryden. C. Marriage-Hater Matched, 1692, D’Urfey. C. Marriage Night (The), 1664, H. Carey, Lord Falkland. T. Marriage of Witte and Science (The), about 1559, Anon. Mo. Married for Money (1803-1878), C. J. Mathews.
- 63. Married in Haste,19th cent., H. J. Byron. Married Libertine (The), 1761, Macklin. F. Married Life, 1834, Buckstone. C. Married Man (The), 1789, Inchbald. C. Martha, 1858, Flotow. O. Martyr of Antioch, 1821, Milman. T. Martyrs (Les), 1840, Donizetti. O. (from Corneille’s Polyeucte). [Mary] Queen of Scots, 1684, Banks. T. Mary Queen of Scots, 1807, Grahame. T. Mary Queen o’ Scots, 1874, Wills. H.Pl. Mary (Queen), 1877, Tennyson. T. Mary Stuart, 1840, Haynes. T. Mary Stuart, 1881, Swinburne. T. (See “Maria ...” and “Evasion de....”) Mary Tudor, 1833, Victor Hugo. T. Mary Tudor, 1847, Vere. T. Mary Tudor, 1876, Miss Dickinson. H.Pl. Masaniello, 1814, Ingemann. T. Masaniello, about 1820, Carafa. O. Masaniello, 1828, Auber. O. (libretto by Scribe). Often called La Muette de Portici. (See “Massaniello.”) Masks and Faces (1817-1880), Tom Taylor. C. Masnadieri (I), 1847, Verdi. O. Masque (The), 1612, Beaumont and Fletcher. C. Masque de Velours, 1860, Delaporte. D. Masque of Calisto, 1676, Crowne. M.
- 64. Masque of Heroes,1619, Middleton. M. Massacre of Paris, 1590, Marlowe. T. Massacre of Paris, 1690, Lee. T. Massacre de Syrie, 1860, Sejour. T. Massaniello, 1699, D’Urfey. T. (Originally two plays, but compressed into one by T. Walker, in 1700.) Massaniello, 1829, Kenney. (See “Masaniello.”) Match at Midnight, 1633, Rowley. C. Match for a Widow (A), 1787, Atkinson. C. Match mee in London, 1631, Day. T.C. Matilda, 1775, T. Franklin. T. Matilda of Hungary, 1847, Wallace. O. Matrimonial Troubles, (1624-1673), Margaret, Duchess of Newcastle. Pt. i. C. Pt. ii. T. Matrimonio Segreto (Il), 1793, Cimarosa. O. Matrimony, 1804, Kenney. C. Maud, 1855, Tennyson. D.Pm. Maures d’Espagne (Les), 1804, Guilbert de Pixérécourt. D. Maximian, 1800, Lady S. Burrell. T. (from Corneille). May Day, 1611, Chapman. C. May Queen (1802-1879), Buckstone. Maydenhead Well Lost (A), 1634, Heywood. C. Maydes Metamorphoses, 1600, J. Lyly. Myt.D. Mayor of Garratt, 1763, Foote. F. Mayor of Quinborough, 1661, Middleton. C.
- 65. Meadows of St.Gervaise (The), * Ware. F.C. (translated from the French). Measure for Measure, 1603, Shakespeare. C. (based on Promos and Cassandra, 1578, by Whetstone; acted at Whitehall, 1604). Medea, B.C. 431, Euripides. T. (Greek). Translated by Potter, 1781; Wodhull, 1782; Morgan, 1865; Giles, 1865; Lee, 1867; Webster, 1868; Williams, 1871. Medea (B.C. 58-32), Seneca. T. (Latin). Adapted by J. Studley, 1566; translated by E. Sherburne, 1648. Medea, 1761, Glover. T. Medea, 1795, Cherubini. O. Medea, about 1820, Mayer. O. Médecin Malgré Lui, 1666, Molière. C. (See “Mock Doctor.”) Médecins (Les), 1863, Nus. D. Médée, 1635, Corneille. T. Médée, 1695, Longpierre. T. Médée, 1853, Legouvé. T. Médus, 1739, Deschamps. T. Méduse (1677-1758), Lagrange. O. Mélanie, 1770, Laharpe. T. Melanthe, 1614, printed 1615, Brookes. P. Méléagre (1677-1758), Lagrange. T. Mélicerte, 1666, Molière. C. Mélite, 1629, Corneille. C. (translated 1776). Memorable Maske of the Two Hon. Inns-of-Court (The), 1614, Chapman. M.
- 66. Menæchmi, or TheBrothers Menæchmus who were Exactly Alike (B.C. 254-184), Plautus. C. (Latin). Translated into blank verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74. It was translated by W. W[arner] in 1595, and furnished Shakespeare with the scheme, etc., of his Comedy of Errors. (See below.) Ménage en Ville, 1864, Barrière. Pl. Ménechmes, 1637, Rotrou. C. (imitated from the Menæchi of Plautus). Ménechmes (Les), 1705, Régnard. C. Menteur, 1642, Corneille. C. (See “Liar.”) Mercator, or The Merchant (B.C. 254-184), Plautus. C. (Latin, adapted from a Greek play by Philemon). Translated into blank verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74. Merchant Pirate, 19th cent., Stirling. D. Merchant of Bruges, before 1830, Kinnaird. Pl. (altered from Beaumont and Fletcher). Merchant of Venice, 1598, Shakespeare. D. (See “Jew of Malta.”) Mercurius Britannicus, 1641, Braithwait. T.C. (From the French.) Mère Coupable (La), 1792, Beaumarchais. D. Méridien, 1852, Deslandes. D. Merlin in Love, 1759, Hill. C. Mérope, 1713, Maffei. T. Mérope, 1738, Voltaire. T. Merope, 1749, Jefferys or Hill (ascribed to both). T. Merope, 1783, Alfieri. T. (translated by C. Lloyd, 1815). Merope, 1858, Matthew Arnold. Cl.T. Merry Devil of Edmonton (The), 1608, Brewer. C.
- 67. Merry Play betweenJohan ..., Tyb. ... and Johan, the Prester, 1533, Heywood. C. Merry Wives of Windsor, 1596, Shakespeare. C. (printed 1602). (See “Comical Gallant.”) Mery Play between the Pardoner and the Frere (A), 1533, J. Heywood. C. Mesogonus, 1560, Thomas Rychardes. C. (only four acts extant). Messalina, 1640, Richards. T. Messiah (The), 1741, Handel. Or. (libretto by Jennens). Metamorphosed Gypsies (1574-1637). Jonson. C. Métamorphoses de l’Amour, 19th cent., Brohan. C. (See “Love’s Metamorphoses.”) Metamorphosis of Pygmalion’s Image, 1598, Marston. C. Métromanie ou Le Poete, 1738, Piron. C. (said to be the best comedy in the French language). Michaelmas Term, 1607, Middleton. Michael et Cristine, before 1822, Scribe. Pt.Pc. Microcosmus, 1637, Nabbes. M. Midas, 1592, J. Lyly. Myt.D. Midas, 1764, O’Hara. Blta. Midas (Jugement de), 1741-1813, Grétry. O. Midnight Hour (The), 1793, Inchbald. Pt.C. Midsummer Night’s Dream, 1592, Shakespeare. Fy.C. (printed 1600). Midsummer Night’s Dream, 1843, Mendelssohn. Milês (B.C. 254-184), Plautus. C. (Latin). Translated into blank verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74.
- 68. Milkmaid (The), 1771-1841,Dibdin. Mu.D. Miller and His Men, 1813, Pocock. Mel. (music by Bishop). Miller of Mansfield (The), 1737, Dodsley. D.E. (The second part is Sir John Cockle at Court.) Mind, Will and Understanding (time, Henry VI.), Anon. Mo. (In MS. only.) Minerva’s Sacrifice, 1653, Massinger. Mines de Pologne (Les), 1803, Guilbert de Pixérécourt. Minister (The), 1797, Lewis. T. (adapted from Schiller). Minna von Barnhelm, 1767, Lessing. C. Minor (The), 1760, Foote. F. Mirandola, 1821, Procter. T. Mirra, 1783, Alfieri (translated by C. Lloyd, 1815). Mirror. (See “Myrrour.”) Mirza, 17th cent., R. Baron. T. Misanthrope, 1666, Molière. C. Misanthropy and Repentance, 1797, Kotzebue. D. (called in English The Stranger). Miser (The), 1672, Shadwell. (See below.) Miser (The), 1732, Fielding. C. (from L’Avare, by Molière, 1667). Misérables (Les), 1864, Hugo, junior. D. (his father’s novel dramatized). Misfortunes of Arthur, 1587, Hughes. T. Misogonist (The), 1780, Lessing. D. Misogonus, 1560, printed 1577, Rychardes. C. (one of our earliest plays).
- 69. Miss Sarah Samson,1755, Lessing. T. (music by Mendelssohn and Nicolay). Miss in Her Teens, 1747, Garrick. F. Mistake (The), 1672-1726, Vanbrugh. C. (altered by King into Lovers’ Quarrels). Mistakes (The), or The Happy Resentment, 1758, Lord Hyde. C. Mithridate, 1673, Racine. T. (imitated from Euripidês). Mithridate, 1770, Mozart. O. Mithridates, 1674, Lee. T. Mock Doctor (The), 1732, Fielding. F. (This is Le Médecin Malgré Lui of Molière, 1666, converted into a farce.) Mock Officer (The), 1733, T. Cibber. C. Mock Tempest (The), 1675, Duffett. C. Modern Antiques, 1798, O’Keefe. C. Modern Husband (The), 1735, Fielding. C. Modern Prophet, 1709, D’Urfey. C. Mœurs de Temps (Les), 1750, Saurin. C. Mogul Tale (The), 1785, Inchbald. F. Moise in Egitto, 1818, Rossini. O. Mon Gigot et Mon Gendre, 1861, Antier. Monastère Abandonna, 1816, Guilbert de Pixérécourt. Money, 1840, Lytton. C. Money in an Asse, 1668, Jordan. C. Mons. D’Olive, 1606, Chapman. C. Mons. le Duc, 1869, Val Prinsep. Pl. Mons. Ragout, about 1669, Lacy. C.
- 70. Mons. Thomas, 1619,Fletcher (Beaumont died 1616). C. Mons. Tonson, 1767, Moncrieff or Taylor (attributed to both). F. Montargis. (See “Chien.”) Montezuma, 1772, Sacchini. O. Montezuma, 1878, Verdi. O. Montfort (De), 1798, Baillie. T. (the passion of “hate”). Montoni, 1820, Sheil. Montrose (1782-1835), Pocock. Monument of Honor (The), 1624, Webster. Moonstone (The), 1877, Wilkie Collins (his novel dramatized). Morando, 1584, Greene. More Dissemblers besides Women, 1657, Middleton. C. More Ways than One, 1785, Mrs. Cowley. C. Mort d’Abel, 1792, Legouvé. T. (imitated from Gesser and Klopstock). Mort de Calas, 1791, Chénier. T. Mort de Henri IV., 1806, Legouvé. T. Mostellaria, or The Haunted House (B.C. 254-184), Plautus. C. (Latin). Translated into blank verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74; and imitated by Regnard, Addison and others. Mother Bombie, 1594, J. Lyly. Ct.E. Mother Goose (1771-1841), Dibdin. Pn. Mother Pantom (1771-1841), Dibdin. C. Mother Shipton (no date), about 1670, Thompson. C. Mount Sinai, 1831, Neukomm. Or.
- 71. Mountain Sylph (The),1834, Barnett. O. Mountaineers (The), 1793, Colman. C. Mourning Bride, 1697, Congreve. T. Mousquetaires (Les), 19th cent., Halévy. O.C. M.P., 1870, T. W. Robertson. C. M.P., or The Blue Stocking, 1811, Moore. Mu.C. Mucedorus (no date), about 1590, Greene. F. Much Ado about Nothing, 1600, Shakespeare. C. Muet (Le), 1691, De Brueys. C. Muette de la Fôret, 1828, Antier. Muette de Portici (La). (See “Masaniello.”) Mulberry Garden (The), 1668, Sedley. Pl. Murderous Michael, 1578, Anon. T. Muse in Livery, 1732, Dodsley. C. Muses in Mourning, 1749, Hill. C. Muses’ Looking-Glass (The), 1638, Randolph. C. Mustapha, 1609, F. Greville, Lord Brooke. T. Mustapha, 1739, Mallet. Pl. Mutius Scævola, 1801, Ireland. H.D. Mutual Deception, 1795, Atkinson. C. (altered by Colman into Tit for Tat). My Awful Dad (1803-1878), C. J. Mathews. My Grandmother and Other Fairies (1755-1834), Hoare. My Lord and My Lady, 1861, Planché. My Spouse and I (1771-1841), Dibdin. O.F. My Wife’s Daughter (1805-1868), Coyne.
- 72. My Wife’s Mother(1803-1878), C. J. Mathews. Myrrha, 1783, Alfieri. T. (Translated by C. Lloyd, 1815). Mystères d’Udolphe (Les), 1798, Guilbert de Pixérécourt. Mel. Mysterious Husband (The), 1783, Cumberland. C. Mysterious Mother, 1768, Walpole. T. Naaman, 1864, Costa. Or. Nabob (The), 1772, Foote. F. Nabob (The), 1879, Burnard (an English version of Les Trente Millions de Gladiateurs, by Labiche and Gille). Nabucco, 1842, Verdi. O. Nabucodonosor, 19th cent., Verdi. O. Nancy, 1739, Carey. Nanine, 1749, Voltaire. C. Narbonne. (See “Count of Narbonne.”) Nathan the Wise, 1778, Lessing. D. Nations (Les), 1851, Banville. O. Native Land, 1823, Bishop. O. Natural Daughter (The), 1792, Goethe. C. Natural Son (The), 1786, Cumberland. C. (See “Fils Natural.”) Natural Son (The), 1799, Anne Plumtree. Pl. (from Kotzebue). Nature, 1490, H. Medwell. Int. Naufragium Joculare, 1638, Cowley. C. (translated by C. Johnson, and called Fortune in her Wits, 1705). Neck or Nothing, 1766, Garrick or King (ascribed to both). F. Ne’er-do-Weel (The), 1878, Gilbert. C. Negro Slaves, 1796. H.Pc. (from Kotzebue).
- 73. Nell (1830-1877), Halliday.C. Nell Gwynne, 1832, Jerrold. C. Nero, 1675, Lee. T. Nerone, 1700, Handel. O. Nervous Man, 19th cent., B. Bernard. C. Nest of Ninnies (A), 1608, Armyn. C. Never too Late, 1590, Greene. C. Never too Late to Mend (It’s), 1878, Reade. C. New Academy (The), 1653, Brome. C. New Droll (A), 1660, Jordan. M. New Hippocrates (The), 1761, Hiffernan. D. New Inn (The), 1630, Jonson. C. New Men and Old Acres (1817-1880), T. Taylor. C. New Peerage (The), 1830, Miss Lee. C. New Tricke to Cheat the Divell, 1639, R. Davenport. C. New Way to Pay Old Debts, 1625, printed 1633, Massinger. C. New Wonder, a Woman Never Vext, 1532, Rowley. C. Nice Firm (A), 19th cent., Tom Taylor. Nice Valour, 1647, Beaumont and Fletcher. C. Nice Wanton (The), 1560, Anon. Mo. Nicholas Flam, 19th cent., Buckstone. Nicholas Nickleby (1830-1877), Halliday (C. Dickens’s novel dramatized). Nicodemus (time, Edward III.), Anon. Mir.Pl. (founded on chap. xvi. of the “Gospel of Nicodemus”). Nicomède, 1670, P. Corneille. T.C.
- 74. Nicomedes, 1671, J.Dancer. T.C. (from the Nicomède of Corneille). Niebelungen, 1850, Wagner. O. Night Walkers, 1633, Beaumont and Fletcher. C. Night Watcher (The), * Körner. C. Nine Points of the Law, 1859, Tom Taylor. Ninette à la Cour (1710-1792), Favart. O.C. Ninus II., 1814, Brifant. T. No Cure no Pay, 1794, H. Rowe. Mu.F. No Song no Supper, 1790, Hoare. Mu.E. (music by Storace). No Wit like Woman’s 1657, Greene or Middleton. C. Noah’s Flood, 1679, Ecclestone. Or. Noble Choice, 1653, Massinger. Noble Gentleman, 1647, Beaumont and Fletcher. Noble Heart (The), 1850, Lewes. T. Noble Ingratitude, 1659, Lower. P.T. Nobleman (The), 17th., cent., Tourneur. T.C. (The Manuscript of this play was destroyed by the cook of Mr. Warburton, the Somerset herald). Nobody and Somebody, 1606, Trundell. C. Noces de Gamache, 1827, Mendelssohn. O. Nonjuror (The), 1717, Cibber. C. (from Molière’s Tartuffe). (See “Hypocrite.”) Nonne Sanglante, 1854, Delavigne. O. (music by Gounod). Norma, 1831, Bellini. O. (libretto by Romani). Northern Lass (The), 1632, Brome. C. Northward Hoe! 1607, Dekker.
- 75. Not so Badas we Seem, 1851, Lord Lytton. C. Not such a Fool as he Looks, 1869, H. J. Byron. Notaire Obligeant, 1650, Dancourt. C. Note of Hand, or Trip to Newmarket, 1777, Cumberland. C. Notoriety (1765-1841), Reynolds. C. Notre Dame, 19th cent., Victor Hugo. D. Nouveau Pourceaugnac, before 1822, Scribe. Pt.Pc. Nouveau Seigneur du Village, 1813, Boieldieu. O. Novella, 1653, Brome. C. Nozze di Figaro, 1786, Mozart. O. (See “Mariage de Figaro.”) Sir H. Bishop altered this opera. Nuit Blanche (Une), 19th cent., Offenbach. O.Bf. Nuit de Noël (La), 1848, Reber. O. Nuits Terribles, 1821, St. Georges. O.C Nuptials of Peleus and Thetis, 1654, Howell. M. and C. Oberon, 1616, Jonson. C. Oberon, 1626, Weber. O. (libretto by Planché). Oberto di Bonifazio, 1839, Verdi. O. Obstinate Lady (The), 1657, Cokaine. C. Octavia (B.C. 58-32), Seneca. T. (Latin). Adapted by T. Nuce, 1566; acted 1581. Octavia, 1783, Alfieri. T. (translated by C. Lloyd, 1815). (See “Virtuous Octavia.”) Octavius (1761-1819), Kotzebue. H.D. Octoroon, 1861, Boucicault. D. Oden (1756-1829), Lèopold. T.
- 76. Odette, 1832, Déaddé.D. O’Dowd (The), 1880, Boucicault (a version like “The Porter’s Knot” of Les Crochets du Père by Cormon and Grange). Œdipe, 1659, Corneille. T. Œdipe, 1718, Voltaire. T. Œdipe, 1781, Sacchini. O. Œdipe Rol, 1798, Chénier. T. Œdipe à Colone, 1796, Chénier. T. Œdipe chez Admète, 1778, Ducis. T. Œdipus (B.C. 58-32), Seneca. T. (Latin). Adapted by A. Nevyle, 1560. Œdipus, 1679, Dryden and Lee. T. Œdipus at Colonus, about B.C. 407, Sophocles. T. (Greek). Translated by G. Adams, 1729; Potter, 1788; Dale, 1824; Plumptre, 1865. Œdipus Tyrannus, about B.C. 425, Sophocles. T. (Greek). Translated by L. Theobald, 1715; G. Adams, 1729; Potter, 1788; G. S. Clarke, 1791; Dale, 1824; F. H. Doyle, 1849; Plumptre, 1865. Œdipus Tyrannus, etc., 1820, P. B. Shelley. T. Œnone, 1804, Kalkbrenner. O. Œuvres du Démon (Les), 1854, Boule. D. Old Bachelor, 1693, Congreve. C. Old City Manners, 1777, Mrs Lennox. C. (This is Eastward Hoe reset.) Old Couple, before 1641, May. C. Old Fortunatus. (See “Fortunatus.”) Old Heads and Young Hearts, 1843, Boucicault. C.
- 77. Old Law (The),1599, printed 1656, Middleton and Rowley. C. (altered by Massinger). Old Maid (The), 1761, Murphy. F. Old Maids, 1841, Knowles. C. Old Martin’s Trials, 19th cent., Stirling. Dom.D. Old Mode (The) and the New, 1709, D’Urfey. C. Old Sailors, 1874, H. J. Byron. C. Old Troop, 1672, Lacy. C. Old Wives’ Tale, 1590, Peele. C. (Milton’s Comus is indebted to this comedy.) Oldcastle (Sir John), 1600, Munday and Drayton. T. (one of the “spurious plays” of Shakespeare). Olimpiade, 1719, Leo. O. Olive (D’). (See “Mons. D’Olive.”) Olivia, 1878, W. G. Wills. C. Ollanta, 1871, Markham. D. Olympiade, 1761, Piccini. O. Olympic Revels, 1831, Planché. Olympie, 1800, Kalkbrenner. O. Olympie, 1820, Brifaut. O. (music by Spontini). Omba, 1853, Bigsby. D.R. Oncle Valet, 1798, Dellamaria. O.C. Ondine, 1816, Hoffmann. O. On Bail, 1877, Gilbert. On Strike, 1873, A. W. A’Beckett. One, or a Monarchy, 1805, Alfieri. C. Translated by C. Lloyd, 1815.
- 78. One o’clock, orThe Wood Demon, 1811, Lewis. G.O.R. One Snowy Night, * Ware. C. Opera Comique, 1799, Dellamaria. O.C. Opera di Camera of Jessy Lea, 1863, Macfarren. O. Opportunity (The), 1640, Shirley. C. Oraloosa (1803-1854), Bird. T. Orators (The), 1762, Foote. F. Ordeal by Touch (The), 1872, R. Lee. D. Order of the Garter (The), 1742, West. D.Pm. Ordinary (The), 1647, printed 1651, Cartwright. C. Oreste, 1750, Voltaire. T. Oreste et Pylade, 1695, Lagrange. T. Orestes, B.C. 408, Euripides. T. (Greek). Translated by Banister, 1780; Potter, 1781; Wodhull, 1782. Orestês, 1783, Alfieri. T. (translated by C. Lloyd. 1815). Orestes, 1802, Sotheby. T. Orestes, 1871, Warren. Met.D. Orfeo, 1483, Poliziano. (See “Orpheus.”) Orfeo, 1764, Glück. O. (libretto by Calzabigi). Orientales (Les), 1828, V. Hugo. R.D. Originaux (Les), 1693, Lamotte. Orlandino, 1526, Folengo. B. Orlando Furioso, 1594, Greene. (See “Bombastes Furioso.”) Ormasdes (1612-1690), Henry Killigrew. Oronooko, 1696, Southerne. T. (Mrs. Behn’s novel dramatized). Orphan (The), 1680, Otway. T.
- 79. Orphan of China(The), 1761, Murphy. T. (Voltaire’s L’Orphelin de la Chine). Orphan of the Frozen Sea, 1856, Stirling. N.D. Orphée (1677-1758), Lagrange. O. Orphée aux Enfers, 1858, Offenbach. O.Bf. Orphelin de la Chine (L’), 1760, Voltaire. T. Orpheus and Eurydice, 1705, Dennis. T. (See “Orfeo.”) Orpheus and Eurydice (1730-1805), King. Orti Esperidi (Gli), 1722, Metastasio. O. (music by Porpora). Oscar and Malvina (1754-1829), Shield. O. Osmond the Great Turk, 1657, Carlell. Pl. Otello, 1816, Rossini. O. Othello, 1602, Shakespeare. T. Otho the Great (1796-1821), Keats and Brown. T. Othon, 1664, Corneille. T. Oulita, the Serf, 1858, Helps. Pl. Our American Cousin, 1858, Tom Taylor. C. (It was greatly altered by Sothern.) Our Boys, 1878, H. J. Byron. C. Our Clerks, 1852, Tom Taylor. C. Our Mary Anne (1802-1879), Buckstone. C. Our New Governess (1815-1874), C. S. Brooks. D. Ours, 1866, Robertson. C. Ours et la Pacha (Les), before 1822, Scribe. Pt.Pc. Outtara-Rama-Tscheritra, 8th cent., Bhavabhouti. Myt.D. (translated by Wilson in his Indian Theatre).
- 80. Overland Route, 1860,Tom Taylor. C. Ovin, 1662, Cockaine. T. Padlock (The), 1768, Bickerstaff. O.F. Page (The), 1765-1841, Reynolds. C. Page of Plymouth (time, Queen Elizabeth). Anon. T. Palace of Truth, 1870, Gilbert. Fy.C. Palamon and Arcyte, 1566, Edwards. C. Palestine (1775-1847), Crotch. Or. Pallantus and Eudora, 1653, T. Killigrew. T. (same as The Conspiracy). Pamela, 1742, Love. C. Pammachius, 1544, Anon. C. (Latin). Pandora, 1664, Sir W. Killigrew. Pl. Panel (The), 1757-1823, Kemble. (This is Bickerstaff’s comedy of ’Tis Well ’tis no Worse, reset.) Pan’s Anniversary, 1625, B. Jonson. M. Panurge, 1785, Grétry. O. Papal Tyranny, 1745, Cibber. T. Paracelsus, 1836, R. Browning. D.Pm. Parasitaster, or The Fawn, 1606, Marston. C. Paria (Le), 1821, Delavigne. T. Paria (The), 1826, Beer. T. (the above in English). Paride e Elena, 1770, Glück. O. (libretto by Calzabigi). Paris et Londres, 1827, Dartois. C. Parisien (Le), 1838, Delaporte. C. Parisina, 1833, Donizetti. O.
- 81. Parliament of Love,1625, Massinger. C. Parolle et Izidora (1703-1758), Theo. Cibber. C. Parson’s Wedding (The), 1663, Killigrew. C. Parted (1799-1838), Reeve. C. Pasquale (Don), 1843, Donizetti. O. Pasquin, 1736, Fielding. C. Passionate Lovers (The), 1655, Carlell. T.C. Passions (Plays of the), 1798-1812, J. Baillie. C. and T. Past Ten o’clock (1771-1841), Th. Dibdin. F. Pastorale Comique, 1666, Molière. Pastor Fido (Il), 1590, Guarini. P. (See “Faithful Shepherdess.”) Pathomachia, or The Battle of the Affections, 1630, Constable. D. Patient Grizzell, 1603, Chettle and Dekker. C. Patrician and Parvenu (The), 1835, Poole. C. Patrician’s Daughter, 1841, W. Marston. T. Patriot (The), 1784, Charles Hamilton. T. Patron (The), 1764, Foote. F. Patter v. Clatter (1803-1878), C. J. Mathews. Pattie and Peggie, 1730, Th. Cibber. Bd.O. (Allan Ramsay’s Gentle Shepherd reset.) Paul, 1836, Mendelssohn. Or. Paul Lafarge, 1870, Boucicault. Paul Pry, 1825, Poole. F. Paul and Virginia (1756-1818), Cobb. Mu.E. Paul and Virginia (1755-1837), Favieres. T. Paul and Virginia (1768-1844), Mazzhingi. O.
- 82. Pauline, 1841, Labrousse.C. Payable on Demand (1817-1880), Tom Taylor. Peace, B.C. 419, Aristophanes. C. (Greek). Translated by Mitchell, 1820-22; Hickie, 1853; Rudd, 1867. Pédre (Don), 1857, Cormon. D. Pedro de Portugal (Don), 1828, Gily Zarate. D. Peep Behind the Curtain, 1767 (ascribed to Garrick and to King). F. Pelayo (1749-1811), Jovellanos. T. Pèlerin Blanc (Le), 1811, Guilbert de Pixérécourt. Pélopides, 1763, Voltaire. T. Pénélope, 1785, Marmontel. O. Percy, 1777, Hannah More. T. Père de Famille, 1758, Diderot. C. Pericles Prince of Tyre, 1609, Shakespeare. T. Perjured Husband, 1700, Centlivre. C. Perkin Warbeck, 1634, Ford. H.D. Perle Noire, 1862, Sardou. Perouse (La), 1799, B. Thompson. D. Perplexed Couple (The), 1706-1767, Molloy. C. Perplexed Lovers, 1712, Centlivre. C. Perplexities (The), 1767, Hull. C. (The Adventures of Five Hours, 1663, reset.) Persa, or The Persian (B.C. 254-184), Plautus. C. (Latin). Translated into blank verse by Messrs. Thornton, Rich, Warner and Colman, 1769-74. Persian Prince (The), 1682, Southerne. T.
- 83. Persian Princess (The)1711, Theobald. T. Persians (The), B.C. 472, Æschylus. T. (Greek). Translated by otter, 1777; Buckley, 1849; Plumptre, 1869. Pertharite, 1693, Corneille. T. Peter and Paul (1788-1841), Hook. Pewterer (The), 1747, Holbery. B.C. Phædra and Hippolytus, 1708, E. Smith. T. Phaeton, 1597, Daniel or Dekker. T. Pharamond, 17th cent., Calprenède. T. (translated by Phillips, 1677). Pharamond, 1736, Cahusac. T. Phèdre, 1677, Racine. T. Phèdre et Hippolyte, 1677, Pradon. T. Philaster, or Love Lies a-Bleeding, 1620, Fletcher (Beaumont died 1616). T. Philenzo and Hippolyta, 1653, Massinger. Philip II., 1783, Alfieri. T. (translated by C. Lloyd, 1815). Philip von Artevelde, 1834, H. Taylor. D.Pm. Phillippe II., (1764-1881), Chénier. D. Phillis of Seyros, 1655, Shirley. Pl. Philoctète, 1783, Laharpe. T. Philoctetes, about B.C. 415, Sophocles. T. (Greek). Translated by T. Sheridan, 1725; G. Adams, 1729; Potter, 1788; Dale, 1824; Plumptre, 1865. Philoctetes, 1871, Warren. Met.D. Philosophe sans le Savoir (Le), 1765, Sedaine. C. Philosopher’s Stone (The), 1850, Tom Taylor.
- 84. Philotas, 1597, acted1607, Daniel. T. Philtre (Le), 1830, Scribe. O. Phœnisssæ (B.C. 480-406), Euripides. T. (Greek). Translated by Banister, 1780; Potter, 1781; Wodhull, 1782; Morgan, 1805; Giles, 1865. (See “Thebais.”) Phœnix (The), 1607, Middleton. Phœnix in Her Flames (The), 1639, Lower. T. Phormio, B.C. 162, Terence. C. (Latin). Translated by Bentley, 1726; Colman the Elder, 1765; Barry, 1857; etc. Phrenologist, 1835, Coyne. C. Phrontisterion, or Oxford in the Nineteenth Century, 1852, Mansel. D. (unfinished). Phrosine et Mélidor, 1794, Méhul. O.C. Physic Lies a-Bleeding, 1697, Th. Brown. C. Piccolino, 1875, Guiraud. O. (libretto by Sardou). Picture (The), 1630, Massinger. T.C. Pierce Penniless (Supplication of) 1592, Nash. Pierre et Catherine, 1829, St. Georges. Pierre le Grand, 1854, Meyerbeer. O. Piety in Pattens, 1773, Foote. F. Pilgrim (The), 1621, Fletcher. Pilot (The), 19th cent., Fitzball. N.Blta. Pinafore (H.M.S.), 1878, Gilbert and Sullivan. N.C.Opta. Pinner of Wakefield, 1560-1592, R. Greene. C. Piperman’s Predicaments, * Ware. F. Pippa Passes, 1842, R. Browning. D.
- 85. Pirata (Il), 1806-1835,Bellini. O. Pirate (The), 1792-1851, Davenport. Pl. Pirates (1763-1796), Storace. Mu.D. Piso’s Conspiracy, 1676, Lee. T. (same as Nero). Pizarro, 1799, Sheridan. T. (from Kotzebue’s drama The Spaniard in Peru, 1797). Plaideurs (Les), 1668, Racine. C. (imitated from the Wasps of Aristophanês). Plain Dealer, 1677, Wycherly. C. Plain Dealer (The), 1766, Bickerstaff. C. Platonic Love, 1707, Centlivre. C. Platonic Lovers, 1636, Davenant. T.C. Play (1829-1871), Robertson. C. Play betwene the Pardoner and the Frere, printed 1533, J. Heywood. Int. Play called the Four P’s (The), printed 1569, J. Heywood. Pl. Play of Love (The), 1533, Heywood. Int. Play of the Wether (The), 1533, Heywood. Int. Plot and No Plot (A), 1697, Dennis. C. Plot and Passion, 1852, Tom Taylor, etc. Plotting Sisters (The), 1676, D’Urfey. C. Plus Beau Jour de la Vie (Le), before 1822. Scribe. Pl.Pc. Plutus, B.C. 408, Aristophanês. C. (Greek). Translated by Randolph, 1651; Fielding and Young, 1812; Mitchell, 1820-22; Cunningham, 1826; Rudd, 1857. Pœrulus (B.C. 254-184), Plautus. C. (Latin).
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