ISSUES IN ENVIRONMENTAL SCIENCE

AND TECHNOLOGY
EDI TORS: R. E. HES TER AND R. M. HARRI SON
13
Chemistry in the
Marine
Environment
ISBN 0-85404-260-1
ISSN 1350-7583
A catalogue record for this book is available from the British Library
@ The Royal Society of Chemistry 2000
All rights reserved
Apart from any fair dealing for the purposes of research or private study, or criticism or review as
permitted under the terms of the UK Copyright, Designs and Patents Act, 1988, this publication may not
be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing
of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with
the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the
terms of the licences issued by the appropriate Reproduction Rights Organization outside the U K.
Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of
Chemistry at the address printed on this page.
Published by The Royal Society of Chemistry , Thomas Graham House,
Science Park, Milton Road, Cambridge C,B4 OWF, UK
For further information see our web site at www.rsc.org
Typeset in Great Britain by Vision Typesetting, Manchester
Printed and bound by Redwood Books Ltd., Trowbridge, Wiltshire
Preface
The oceans cover over 70% of our planet's surface. Their physical, chemical and
biological properties form the basis of the essential controls that facilitate life on
Earth. Current concerns such as global climate change, pollution of the world's
oceans, declining fish stocks, and the recovery of inorganic and organic chemicals
and pharmaceuticals from the oceans call for greater knowledge of this complex
medium. This volume brings together a number of experts in marine science and
technology to provide a wide-ranging examination of some issues of major
environmental impact.
The first article, by William Miller of the Department of Oceanography at
Dalhousie University in Nova Scotia, provides an introduction to the topic and
an overview of some of the key aspects and issues. Chemical oceanographic
processes are controlled by three principal concepts: the high ionic strength of
seawater, the presence of a complex mixture of organic compounds, and the sheer
size of the oceans. The organic chemistry of the oceans, for example, although
involving very low concentrations, influences the distribution of other trace
compounds and impacts on climate control via feedback mechanisms involving
primary production and gas exchange with the atmosphere. The great depth and
expanse of the oceans involve spatial gradients and the establishment of
distinctive zones wherein a diversity of marine organisms are sensitive to
remarkably small changes in their chemical surroundings. The impact of human
activities on marine biodiversity is of growing concern.
The second article, by Grant Bigg of the School of Environmental Sciences at
the University of East Anglia, is concerned with interactions and exchanges that
occur between ocean and atmosphere and which exert major influences on
climate. Through carbonate chemistry the deep ocean is a major reservoir in the
global carbon cycle and can act as a long-term buffer to atmospheric CO2 while
the surface ocean can act as either a source or sink for atmospheric carbon, with
biological processes tending to amplify the latter role. CO2 is, of course, a major
'greenhouse gas', but others such as N2O, CH4, CO and CH3Cl also are
generated as direct or indirect products of marine biological activity. Planktonic
photosynthesis provides an importan~ sink for CO2 and its effectiveness is
dependent on nutrient controls such as phosphate and nitrate and some trace
elements such as iron. Other gases in the marine atmosphere, such asdimethyl
sulfide, also have important climatic effects, such as influencing cloud formation.
v
Preface
In the third of the articles, Peter Swarzenski of the US Geological Survey
Center for Coastal Geology in St Petersburg, Florida, and his colleagues Reide
Corbett from Florida State University, Joseph Smoak of the University of
Florida, and Brent McKee of Tulane University, describe the use of ura-
nium-thorium series radionuclides and other transient tracers in oceanography.
The former set of radioactive tracers occur naturally in seawater as a product of
weathering or mantle emanation and, via the parent-daughter isotope relationships,
can provide an apparent time stamp for both water column and sediment
processes. In contrast, transient anthropogenic tracers such as the freons or CFCs
are released into the atmosphere as a byproduct of industrial/municipal activity.
Wet/dry precipitation injects these tracers into the sea where they can be used to
track such processes as ocean circulation or sediment accumulation. The use of
tracers has been critical to the tremendous advances in our understanding of
major oceanic cycles that have occurred in the last 10-20 years. These tracer
techniques underpin much of the work in such large-scale oceanographic
programmes as WOCE (World Ocean Circulation Experiments) and JGOFS
(Joint Global Ocean Flux Study).
The next article is by Raymond Andersen and David Williams of the
Departments of Chemistry and of Earth and Ocean Sciences at the University of
British Columbia, This is concerned with the opportunities and challenges
involved in developing new pharmaceuticals from the sea. Historically, drug
discovery programmes have relied on in vitro intact-tissue or cell-based assays to
screen libraries of synthetic compounds or natural product extracts for
pharmaceutically relevant properties. However, modern 'high-throughput screening'
methods have vastly increased the numbers of assays that can be performed, such
that libraries of up to 100 000 or more chemical entities can now be screened for
activity in a reasonable time frame. This has opened the way to exploitation of
natural products from the oceans in this context. Many of these marine natural
products have no terrestrial counterparts and offer unique opportunities for drug
applications. Examples of successful marine-derived drugs are given and the
potential for obtaining many more new pharmaceuticals from the sea is clearly
demonstrated.
The final article of the book is by Stephen de Mora of the International Atomic
Energy Agency's Marine Environment Laboratory in Monaco and is concerned
with contamination and pollution in the marine environment. The issues
addressed range from industrial and sewage discharges and the effects of elevated
nutrients from agricultural runoff in coastal zones to contamination of the deep
oceans by crude oil, petroleum products and plastic pollutants, as well as
wind-borne materials such as heavy metals. The use of risk assessment and
bioremediation methods is reviewed and a number of specific case studies
involving such problems as persistent organic pollutants and the use of
anti-fouling paints containing organotin compounds are detailed. An overview of
the economic and legal considerations relevant to marine pollution is given.
Taken together, this set of articles provides a wide-ranging and authoritative
review of the current state of knowledge in the field and a depth of treatment of
many of the most important issues relating to chemistry in the marine
environment. The volume will be of interest equally to environmental scientists,
VI
Preface
to chemical oceanographers, and to national and international policymakers
concerned with marine pollution and related matters. Certainly it is expected to
be essential reading for students in many environmental science and oceanography
courses.
Ronald E. Rester
Roy M. Harrison
VI]
Contents
Introduction and Overview 1
William L. Miller
1 Introduction 1
2 The Complex Medium Called Seawater 2
3 Spatial Scales and the Potential for Change 6
4 Summary 11
The Oceans and Climate 13
Grant R. Bigg
1 Introduction 13
2 Oceanic Gases and the Carbon Cycle 17
3 Oceanic Gases and Cloud Physics 25
4 Feedback Processes Involving Marine Chemistry and Climate 27
5 Future Prospects 30
The Use of U–Th Series Radionuclides and Transient Tracers in
Oceanography: an Overview 33
Peter W. Swarzenski, D. Reide Corbett, Joseph M. Smoak
and Brent A. McKee
1 Introduction 33
2 Radioactive Decay 35
3 Sources and Sinks 38
4 Oceanic Behavior 42
Pharmaceuticals from the Sea 55
Raymond J. Andersen and David E. Williams
1 Introduction 55
2 Opportunities in the Oceans 60
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
ix
3 Challenges Involved in Developing a ‘Drug from the Sea’ 68
4 Some Success Stories 72
5 Future Prospects 78
Contamination and Pollution in the Marine Environment 81
Stephen J. de Mora
1 An Overview of Marine Pollution 81
2 Selected Case Studies 83
3 Mitigation of Marine Pollution 89
4 Summary 92
Subject Index 93
Contents
Editors
Ronald E. Hester, BSc, DSc(London), PhD(Cornell), FRSC, CChem
Ronald E. Rester is Professor of Chemistry in the University of York. He was for
short periods a research fellow in Cam bridge and an assistant professor at Cornell
before being appointed to a lectureship in chemistry in Y orkin 1965. Hehas been a
full professor in York since 1983. His more than 300 publications are mainly in the
area of vibrational spectroscopy, latterly focusing on time-resolved studies of
photoreaction intermediates and on biomolecular systems in solution. He is active
in environmental chemistry and is a founder member and former chairman of the
Environment Group of the Royal Society ofChemistry and editor of'lndustry and
the Environment in Perspective' (RSC, 1983) and 'Understanding Our
Environment' (RSC, 1986). As a member of the Council of the UK Science and
Engineering Research Council and several of its sub-committees, panels and
boards, he has been heavily involved in national science policy and administra-
tion. He was, from 1991-93, a member of the UK Department of the Environment
Advisory Committee on Hazardous Substances and is currently a member of
the Publications and Information Board of the Royal Society of Chemistry.
Roy M. Harrison, BSc, PhD, DSc (Birmingham), FRSC, CChem, FRMetS, FRSH
Roy M. Harrison is Queen Elizabeth II Birmingham Centenary Professor of
Environmental Health in the University of Birmingham. He was previously Lecturer
in Environmental Sciences at the University ofLancaster and Reader and Director
of the Institute of Aerosol Science at the University Qf Essex. His more than 250
publications aremainlyin the field of environmental chemistry, although his current
work includes studies of human health impacts of atmospheric pollutants as well
as research into the chemistry of pollution phenomena. He is a past Chairman of
th~ Environment Group of the Royal Society ofChemistryfor whom he has edited
'Pollution: Causes, Effects and Control' (RSC, 1983; Third Edition, 1996) and
'Understanding our Environment: An Introduction to Environmental Chemistry
and Pollution' (RSC, Third Edition, 1999). He has a close interest in scientific and
policy aspects of air pollution, having been Chairman of the Department of Envi-
ronment Quality of Urban Air Review Group as well as currently being a member
of the DETR Expert Panel on Air Quality Standards and Photochemical Oxidants
Review Group, the Department ofHealth Committee on the Medical Effects of Air
Pollutants and Chair of the DETR Atmospheric Particles Expert Group.
XI
Contributors
R.J. Andersen, Department of Chemistry, 2036 Main Mall, University of British
Columbia, Vancouver, British Columbia V6T 1ZI, Canada
G. R. Bigg, School of Environmental Sciences, University of East Anglia, Norwich
NR4 7T1, UK
D. R. Corbett, Department of Oceanography, Florida State University, Tallahassee,
FL 32306, USA
S. J. de Mora, M arine Environment Laboratory, International Atomic Energy
Agency,4 Quai Antoine 1er, BP 800, MC 98012, Monaco
B.A. McKee, Department ofGeology, Tulane University, New Orleans, LA 70118,
USA
W.L. Miller, Department of Oceanography, Dalhousie University, Halifax, Nova
Scotia B3H 41/, Canada
J. M. Smoak, Department of Fisheries and Aquatic Sciences, University of Florida,
Gainesville, F L 32653, USA
P.W. Swarzenski, US Geological Survey, Centerfor Coastal Geology, 600 4th
Street South, St.Petersburg, FL 33701, USA
D. E. Williams, Department of Earth and Ocean Sciences, University of British
Columbia, Vancouver, British Columbia V6T 1ZI, Canada
XlII
Introduction and Overview
WILLIAM L. MILLER
1 Introduction
Why does Chemistry in the Marine Environment deserve separate treatment
within the Issues in Environmental Science and Technology series? Is it not true
that chemical principles are universal and chemistry in the oceans must therefore
simply abide by these well-known laws? What is special about marine chemistry
and chemical oceanography?
The long answer to those questions would probably include a discourse on
complex system dynamics, carefully balanced biogeochemical cycles, and
perhaps throw in a bit about global warming, ozone holes, and marine resources
for relevance. The short answer is that marine chemistry does followfundamental
chemical laws. The application of these laws to the ocean, however, can severely
test the chemist’s ability to interpret their validity. The reason for this relates to
three things: (1) the ocean is a complex mixture of salts, (2) it contains living
organisms and their assorted byproducts, and (3) it covers 75% of the surface of
the Earth to an average depth of almost 4000 metres. Consequently, for the
overwhelming majority of aquatic chemical reactions taking place on this planet,
chemists are left with the challenge of describing the chemical conditions in a high
ionic strength solution that contains an unidentified, modified mixture of organic
material. Moreover, considering its tremendous size, how can we reasonably
extrapolate from a single water sample to the whole of the oceans with any
confidence?
The following brief introduction to this issue will attempt to provide a
backdrop for examining some marine chemical reactions and distributions in the
context of chemical and physical fundamentals. The detailed discussions
contained in the chapters that follow this one will provide examples of just how
well (or poorly) we can interpret specific chemical oceanographic processes
within the basic framework of marine chemistry.
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
1
2 The Complex Medium Called Seawater
For all of the millions of years following the cooling of planet Earth, liquid water
has flowed fromland tothe sea. Beginning with the first raindropthat fell on rock,
water has been, and continues to be, transformed into planetary bath water as it
passes over and through the Earth’s crust. Rivers and groundwater, although
referred to as ‘fresh’, contain a milieu of ions that reflect the solubility of the
material with which they come into contact during their trip to the sea. On a
much grander scale even than the flow of ions and material to the ocean, there is
an enormous equilibration continually in progress between the water in the
ocean and the rock and sediment that represents its container. Both the
low-temperature chemical exchanges that occur in the dark, high-pressure
expanses of the abyssal plains and the high-temperature reactions occurring
within the dynamic volcanic ridge systems contribute controlling factors to the
ultimate composition of seawater.
After all those many years, the blendof dissolvedmaterials we call seawater has
largely settled into an inorganic composition that has remained unchanged for
thousands of years prior to now. Ultimately, while Na> and Cl are the most
concentrateddissolvedcomponents inthe ocean, seawater is muchmore complex
than a solution of table salt. In fact, if one works hard enough, every element in
the periodic table can be measured as a dissolved component in seawater. In
addition to this mix of inorganic ions, there is a continual flux of organic
molecules cycling through organisms into the ocean on timescales much shorter
thanthose applicable tosalts. Anyrigorous chemical calculationmust address both.
Salinity and Ionic Strength
The saltiness of the ocean is defined in terms of salinity. In theory, this term is
meant to represent the total number of grams of dissolved inorganic ions present
in a kilogram of seawater. In practice, salinity is determined by measuring the
conductivity of a sample and by calibration through empirical relationships to
the International Association of Physical Sciences of the Ocean (IAPSO)
Standard Sea Water. With this approach, salinity can be measured with a
precision of at least 0.001 parts per thousand. This is fortunate, considering that
75% of all of the water in the ocean falls neatly between a salinity of 34 and 35.
Obviously, these high-precision measurements are required to observe the small
salinity variations in the ocean.
So, why concern ourselves with such a precise measurement of salinity? One
physical consequence of salinity variations is their critical role in driving
large-scale circulation in the ocean through density gradients. As for chemical
consequences, salinity is directlyrelatedtoionic concentration andthe consequent
electrostatic interactions between dissolved constituents in solution. As salinity
increases, so does ionic strength. Because the thermodynamic constants relating
to any given reaction in solution are defined in terms of chemical activity (not
chemical concentration), high ionic strength solutions such as seawater can result
inchemical equilibria that are very different fromthat definedwiththermodynamic
constants at infinite dilution. This is especially true of seawater, which contains
W. L. Miller
2
substantial concentrations of CO
`
`, SO
"
`, Mg`>, and Ca`>. These doubly
charged ions create stronger electrostatic interactions than the singly charged
ions found in a simple NaCl solution.
Changes inactivitycoefficients (andhence the relationshipbetweenconcentration
and chemical activity) due to the increased electrostatic interaction between ions
in solution can be nicely modeled with well-known theoretical approaches such
as the Debye—Hu¨ ckel equation:
log
G
¬÷Az
G
`(I (1)
where is the activity coefficient of ion i, A is its characteristic constant, z is its
charge, and I is the ionic strength of the solution. Unfortunately, this equation is
onlyvalidat ionic strengthvalues less than about 0.01 molal. Seawater is typically
much higher, around 0.7 molal. Inclusion of additional terms in this basic
equation (i.e. the extended Debye—Hu¨ ckel, the Davies equation) can extend the
utility of this approach to higher ionic strength and works fine within an ion
pairing model for a number of the major and minor ions.¹ Ultimately, however,
this approach is limited by a lack of experimental data on the exceedingly large
number of possible ion pairs in seawater.
Another approach in the modeling of activity coefficient variations in seawater
attempts to take into account all interactions between all species. The Pitzer
equations present a general construct to calculate activity coefficients for both
chargedanduncharged species in solutionand formthe foundationof the specific
interactionmodel. This complex set of equations, coveredthoroughly elsewhere,``
is a formidable tool in the calculation of chemical activity for both charged and
uncharged solutes in seawater. Both the ion pairing and the specific interaction
models (or a combination of the two) provide valuable information about
speciation of both major and trace components in seawater."
Often chemical research in the ocean focuses so intently on specific problems
with higher public profiles or greater perceived societal relevance that the
fundamental importance of physicochemical models is overlooked. But make no
mistake; the inorganic speciation of salts in seawater represents the stage on
which all other chemistry in the ocean is played out. These comprehensive
inorganic models provide the setting for the specific topics in the following
chapters. While these models represent significant advances in the understanding
of marine chemistry, seawater, however, is such a complex mixture that on
occasioneven sophisticatedmodels fail to accurately describe observations in the
real ocean. In these cases, the marine chemist is left with empirical descriptions as
the best predictive tool. Sometimes this situation arises owing to processes such
as photochemistry or biochemical redox reactions that push systems away from
equilibrium. Other times it results from the presence of unknown and/or
¹ F. J. Millero and D. R. Schreiber, Am. J. Sci., 1982, 282, 1508.
` K. S. Pitzer, in Activity Coefficients in Electrolyte Solutions, ed. K. S. Pitzer, CRCPress, Boca Raton,
FL, 1991, p. 75.
` F. J. Millero, in Marine Chemistry: An Environmental Analytical Chemical Approach, ed. A.
Gianguzza, E. Pelizzetti and S. Sammartano, Kluwer, Dordrecht, 1997, p. 11.
" F. J. Millero, Geochim. Cosmochim. Acta, 1992, 56, 3123.
Introduction and Overview
3
uncharacterized compounds. Many of these latter compounds are of biological
origin.
Biological Contributions
In sharp contrast to the cool precision of the electrostatic equations used to
describe the inorganic interactions discussed above, the study of organic
chemistry in the ocean does not enjoy such a clear approach to the evaluation of
organic compounds in seawater. There is a boundless variety of both terrestrial
and marine organisms that contribute organic compounds to the sea. While their
initial contributions may be recognized as familiar biochemicals, much of this
material is quickly transformed by microbial and chemical reactions into a suite
of complex macromolecules with only a slight resemblance to their precursors.
Consequently, the starting point for evaluation of a general approach for organic
chemistryin the oceanis a situationwhere more thanhalf of the dissolvedorganic
carbon (DOC) is contained in molecules andcondensates that are not structurally
characterized; a mixture usually referred to as humic substances (HS). In other
words, for many of the organic reactions in the ocean, we simply do not knowthe
reactants.
Humic substances in the ocean are thought to be long lived and relatively
unavailable for biological consumption. They are found at all depths and their
average age in the deep sea is estimated in the thousands of years.` This suggests
that they are resilient enough to survive multiple complete trips through the
entire ocean system. The chromophoric (or coloured) dissolved organic matter
(CDOM), which absorbs most of the biologically damaging, high-energy
ultraviolet radiation (UVR) entering the ocean, is composed largely of HS.
Consequently, HS, through its light gathering role in the ocean, protects
organisms from lethal genetic damage and provides the primary photon
absorptionthat drives photochemistryinthe ocean. Since UVR-drivendegradation
of CDOM(and HS) both oxidizes DOCdirectly to volatile gases (primarily CO
`
and CO) and creates new substrate for biological degradation, the degree to
which HS is exposed to sunlight may ultimately determine its lifetime in the
ocean. Since DOCrepresents the largest organic carbon pool reactive enough to
respond to climate change on timescales relevant to human activity, its sources
and sinks represent an important aspect in understanding the relation between
ocean chemistry and climate change.
The presence of HS in seawater does more than provide a carbon source for
microbes and alter the UV optical properties in the ocean. It can also affect the
chemical speciation and distribution of trace elements in seawater. Residual
reactive sites within the highly polymerized mixture (i.e. carboxylic and phenolic
acids, alcohols, and aminogroups) can provide binding sites for trace compounds.
The chemical speciationof Cu in seawater is a good example of a potentially toxic
metal that has a distribution closely linked to that of HS and DOC. A very large
percentage of Cu is complexed to organic compounds in seawater and
consequently rendered non-toxic to most organisms since the free ion form of Cu
` P. M. Williams and E. R. M. Druffel, Nature, 1987, 330, 246.
W. L. Miller
4
is usually required for accumulation. One study of Cu in a sewage outfall area
within Narragansett Bay, RI, USA shows this effect dramatically.' As expected,
the highest total Cu concentrations were found in this most impacted area of the
estuary. Exactly coincident with high Cu concentrations, the researchers found
the lowest Cu toxicity due to high DOC concentrations and increased
complexation. Even thoughspecific organic ligands could not be identified, it was
clear that the presence of undefined organic compounds had turned a potentially
lethal Cu solution into a refuge from toxicity.
The compounds that are identifiable in the sea represent a vast array of
biochemicals attributable to the life and death of marine plants and animals.
They are generally grouped into six classes based on structural similarities:
hydrocarbons, carbohydrates, lipids, fatty acids, amino acids, and nucleic acids.
Because they represent compounds that can be quantified and understood for
their chemical properties and known role in biological systems, a great deal of
information has been accumulated over the years about these groups and the
specific compounds found within them.`
While each individual organic compound may exist in exceedingly low
concentrations, its presence in solution can be quite important. Organic carbon
leaking into solution from the death of organisms can serve as a potential food
source for a community of decomposers. Other compounds are intentionally
excreted into solution, potentially affecting both biological and chemical
surroundings. Certainof these compounds foundin marine organisms are unique
in their ability to elicit a particular biological or chemical effect. Some
biochemicals may serve to attract mates or repel predators and others have the
ability to sequester specific required nutrients, in particular, essential trace
metals. An excellent example of the ability of small concentrations of biochemicals
to significantly impact marine chemistry can be seen in a recent examination of
iron speciation in the ocean.`
Given the slightly alkaline pH of seawater, and relatively high stability
constants for Fe(III) complexes with hydroxide in seawater, it has long been
believed that the hydrolysis of Fe(III) represents the main speciation for iron in
the ocean. The low solubility of Fe(OH)
`
keeps total iron concentrations in the
nanomolar range. Consequently, calculations of iron speciation based on known
thermodynamic relationships have been extremely difficult to confirm experi-
mentally at natural concentrations. In recent years, the use of ultraclean
techniques with electrochemical titrations has turned the idea of a seawater iron
speciation dominated by inorganic chemistry on its ear. Working on seawater
samples from many locations, several groups"¹" have shown the presence of a
natural organic ligand (also at nanomolar concentrations) that specifically binds
to Fe(III). In fact, this ligand possesses conditional stability constants for
' W. G. Sunda and A. W. Hanson, Limnol. Oceanogr., 1987, 32, 537.
` J. W. Farrington, ‘Marine Organic Geochemistry: Review and Challenges for the Future’, Mar.
Chem., special issue 1992, 39.
` K. W. Bruland and S. G. Wells, ‘The Chemistry of Iron in Seawater and its Interaction with
Phytoplankton’, Mar. Chem., special issue, 1995, 50.
" E. L. Rue and K. W. Bruland, Mar. Chem., 1995, 50, 117.
¹" C. M. G. van den Berg, Mar. Chem., 1995, 50, 139.
Introduction and Overview
5
associationwiththe ferric ionthat are sohigh (K
'
:10`" M¹) that it completely
dominates the speciation of iron in the ocean. Calculations that include this
ligandpredict that essentially all of the iron inthe oceanis organicallycomplexed.
In view of the fact that Fe is an essential nutrient and can limit primary
productivity in the ocean, the chemistry associated with this Fe ligand represents
quite a global impact for such a seemingly insignificant concentration of a very
specific organic compound; a compound that was only discovered as a dissolved
constituent in seawater within the last 10 years.
3 Spatial Scales and the Potential for Change
As mentioned in the introduction to this chapter, the ocean is enormous. One
compilation¹¹ that includes all of the oceans and adjacent seas puts the volume of
seawater on the planet at 1.37 ;10" km` covering 3.61 ;10` km`. The Atlantic,
Pacific, and Indian oceans alone contain about 320 million km` (or 3 ;10`"
litres) of seawater. Consequently, when we consider a ubiquitous chemical
reaction in seawater, no matter how insignificant it may seem to our ordinary
scale of thinking, its extrapolation to such huge proportions can result in the
reaction taking on global significance. Conversely, chemical modifications that
create a considerable local impact may be of no consequence when considered in
the context of the whole ocean. The sheer size of the ocean forces a unique
approach when applying chemical principles to the sea.
Separation of the Elements
Because the ocean spreads continuously almost from pole to pole, there is a large
degree of difference in the heating of surface waters owing to varying solar
radiation. This causes variations in both temperature (obviously) and salinity
(from differential evaporation:precipitation ratios). These variations in heat and
salt drive a great thermohaline circulation pattern in the ocean that witnesses
cold, salty water sinking in the north Atlantic and in Antarctica’s Weddell Sea,
flowing darkly through the ocean depths, and surfacing again in the North
Pacific; a journey lasting approximately 1000 years. This deep, dense water flows
beneath the less dense surface waters and results in a permanent pycnocline
(density gradient) at about 1000 metres; a global barrier to efficient mixing
between the surface and deep oceans. The notable exceptions to this stable
situation are in areas of the ocean with active upwelling driven by surface
currents. On a large scale, the ocean is separated into two volumes of water,
largely isolated fromone another owing to differences insalinity and temperature.
As mentionedabove, bothof these variables will produce changes in fundamental
equilibrium and kinetic constants and we can expect different chemistry in the
two layers.
Another layering that occurs within the 1000 metre surface ocean is the
distinction between seawater receiving solar irradiation (the photic zone) and the
dark water below. The sun provides heat, UVR, and photosynthetically active
¹¹ J. A. Knauss, AnIntroductionto Physical Oceanography, Prentice Hall, EnglewoodCliffs, NJ, 1978, p. 2.
W. L. Miller
6
radiation (PAR) to the upper reaches of the ocean. Heat will produce seasonal
pycnoclines that are much shallower than the permanent 1000 metre boundary.
Winter storms limit the timescale for seasonal pycnoclines by remixing the top
1000 metres on roughly a yearly basis. Ultraviolet radiation does not penetrate
deeply into the ocean and limits photochemical reactions to the near surface
(metres to tens of metres depending on the concentration of CDOM). The visible
wavelengths that drive photosynthesis penetrate deeper than UVR but are still
generally restricted to the upper hundred metres.
At almost any location in the open ocean, the underlying physical structure
provides at least three distinct volumes of water between the air—sea interface and
the bottom. This establishes the potential for vertical separation of elements into
distinct chemical domains that occupy different temporal and spatial scales. In
fact, the biological productionof particles inthe photic zone throughphotosynthesis
acts to sequester a wide variety of chemical elements through both direct
incorporation into living tissue and skeletal parts and the adsorption of surface
reactive elements onto particles. Nutrients essential to marine plant growth like
N, P, Si, Fe, and Mnare strippedfromthe photic zone anddeliveredtodepthwith
particles. While most of the chemicals associated with particles are recycled by
microbial degradation in the upper 1000 metres, some percentage drop belowthe
permanent pycnocline and return to the dissolved components of the deep ocean
through microbial degradation and chemical dissolution. This flux of particles
from the surface ocean to deeper waters leads to vertical separation of many
chemical elements in the ocean.
The redistribution of essential biological elements away from where they are
needed for photosynthesis sets up an interesting situation. Marine plants, limited
to the upper reaches of the ocean by their need for light, are floating in a seawater
solution stripped of many of the chemicals required for growth. Meanwhile,
beneath them, in the deep ocean layers, exists the largest storehouse of plant
fertilizer on the planet; a reservoir that grows ever larger as it ages. The
mechanisms and rates of this particle-driven, chemical separation of the ‘fuel and
the fire’ are more closely examined by P. W. Swarzenski and co-authors later in
this book.
Diversity of Environments
Along with the great depth that leads to the vertical separation of water masses
with different density, the horizontal distribution of surface seawater across all
climates on Earth leads to a diversity of environments that is unlike any
terrestrial system. While terrestrial ecosystems often offer up physical barriers to
migration, the oceans are fluid and continuous. The mountains and trenches
found on the ocean floor present little or no barrier to organisms that have
evolved for movement and dispersal of offspring in three-dimensional space.
With enough time and biological durability, organisms thriving in any part of the
ocean could potentially end up being transported to any other part of the ocean.
The demarcations between different marine environments are often gradual and
difficult to define.
Ecological distinctions are easy to recognize when considering the ocean floor:
Introduction and Overview
7
muddy, sandy, or rocky bottoms result in very different benthic ecosystems. In
the majority of the ocean, however, organisms face pelagic distinctions that are
defined by varying physical and chemical characteristics of the solution itself.
Temperature is an obvious environmental factor. Most arctic organisms do not
thrive in tropical waters, although they may have closely related species that do.
A more subtle result of temperature variation involves the solubility of calcium
carbonate. The fact that calcium carbonate is less soluble in warm water than in
cold dictates the amount of energy required by plants and animals to build and
maintain calcium carbonate structures. This simple chemistry goes a long way
toward explaining the tropical distribution of massive coral reefs. Salinity, while
showing little variation in the open ocean, can define discrete environments
where rivers meet the sea. Chemical variations much more subtle than salinity
can also result in finely tuned ecological niches, some as transient as the sporadic
events that create them.
In the deep sea, entire ecosystems result from the presence of reduced
compounds like sulfur and iron in the water. These chemicals, resulting from
contact between seawater and molten rock deep within the Earth, spew from
vents within the superheated seawater. Their presence fuels a microbial
population that serves as the primary producers for the surrounding animal
assemblage, the only known ecosystem not supported by photosynthesis. Both
the reduced elements and the vents themselves are transient. Sulfide and Fe(II)
are oxidized and lost as the hot, reducing waters mix with the larger body of
oxygenated water. Vents are periodically shut down and relocated tens to
hundreds of kilometres away by volcanic activity and shifting of crustal rock. Yet,
these deep sea organisms have the intricate biochemistry to locate and exploit
chemical anomalies in the deep ocean.
Variable chemical distributions of specific elements inthe oceanpromote finely
tuned biological systems capable of exploiting each situation presented. For
example, the addition of Fe to open ocean ecosystems that are starved of this
micronutrient will cause population shifts from phytoplankton species that
thrive in low iron environments to those with higher Fe requirements. This shift
in plant speciation and growth can alter the survival of grazer populations and
their predators further up the food chain. It is important to note from this
example that chemical changes in the nanomolar range are certainly capable of
altering entire marine ecosystems.
In short, seemingly small chemical and physical gradients within seawater can
dictate the success or failure of organisms that possess only subtle differences in
biochemical machinery and will push marine ecosystems towards increased
biodiversity. The presence of a specific set of organisms in seawater will produce a
distinct chemical milieu via incorporation of required elements and excretion of
others. Salmon, returning from the ocean to spawn, can identify the set of
chemicals specific to the streams and rivers of their birth. The biochemistry of
marine organisms is very often finely evolved to exploit almost imperceptible
changes in ocean chemistry. Many other biochemical adaptations have resulted
in response to the intense competition among organisms to exploit these tiny
changes in their environment. Almost certainly, there are innumerable examples
that man has not yet even identified. Many of these specific compounds are being
W. L. Miller
8
discovered and their sources and prospects for exploitation are examined in the
chapter in this book by R. J. Andersen and D. E. Williams.
Impacts
Because their survival often depends directly on the ability to detect and respond
to infinitesimal changes in seawater chemistry, many marine organisms are
extremely sensitive to the presence of man-made contaminants in the ocean. As
mentioned above, it only requires nanomolar concentrations of Fe to change
entire marine ecosystems and potentially alter the chemical distribution of all
elements integral to the resulting biological processes. These intricate changes
may not be easily observable. The truth is, contamination may have already
alteredthe ocean in subtle ways that we currently knownothing about. The more
obvious examples of man’s impact on the ocean can be seen on smaller scales in
areas closer to anthropogenic activity, namely the coastal zone.
Our most vivid examples of man’s impact on marine systems often result from
catastrophic episodes such as oil spills and the visible results from marine
dumping of garbage. Oil drenched seabirds, seashores littered with dead fish, and
medical refuse on public beaches are the images that spring to mind when
considering marine pollution. While these things do represent the worst local
impact that man has been able to impose on the ocean, they probably do not
represent the largest threat to marine systems. Non-pointsource pollutionsuch as
terrestrial runoff of fertilizers and pesticides, discharge of long-lived industrial
chemical pollutants, daily spillage of petroleumproducts fromshippingactivities,
and increasing concentrations of atmospheric contaminants all reflect man’s
chronic contribution to ocean chemistry. These activities have the potential to
accumulate damage and affect the natural chemical and biological stasis of the
ocean. A subsequent chapter in this book by S. J. de Mora provides many more
details on the chronic and episodic modifications of marine chemistry that can
result from man’s activities.
As pointed out earlier, it is difficult to effect chemical change over the entire
ocean owing to its great size. Consequently, changes to the whole ocean system
are usually slow, only observable over hundreds to thousands of years. This is not
to say that long-term chemical changes cannot result from man’s activities.
Atmospheric delivery of anthropogenic elements can spread pollutants to great
distances and result in delivery of material to large expanses of the ocean. Outside
of the obvious impact of natural phenomena like large-scale geological events
and changes in solar insolation, the exchange of material between the ocean and
atmosphere represents one of the few mechanisms capable of producing oceanic
changes on a global scale. Examination of the exchange of material between
marine and atmospheric chemistry forces the collaboration of two disciplines:
oceanography and atmospheric science. Recent scientific enterprise directed at
the understanding of climate change and man’s potential role in that change has
led to a closer collaboration between these two disciplines than ever before. A
subsequent chapter in this book by G. R. Bigg goes into detail as to the workings
of ocean—atmosphere exchange.
Part of the requirement for interdisciplinary efforts in ocean—atmosphere
Introduction and Overview
9
exchange can be seen in a qualitative way by examining the dimethyl sulfide
(DMS) story.¹` It should be noted that development of many quantitative aspects
of this story are still on the drawing board and once these details are resolved, the
future telling of this story could very easily have a different plot and finale.
Regardless of the eventual details, the original DMS story reveals a glimpse into
the complex processes, reciprocal impacts, and feedback loops that must be
unearthed to understand the exact role of ocean—atmosphere exchange in climate
change.
The DMS story begins with the observation that in remote areas of the open
oceanthis trace gas is foundbothin the atmosphere and insurface waters with the
relative concentrations indicating an oceanic source. The intriguing part of the
story emerges when one considers the source of DMS in the ocean and its
eventual role in the remote atmosphere. Phytoplankton are responsible for the
precursors for DMS production in the surface ocean, where it fluxes into the
troposphere. Throughredox chemistry in the atmosphere, it appears that DMSis
capable, at least in part, of supplying the sulfate aerosols that serve as cloud
condensation nuclei. In other words, an organism that directly depends on solar
irradiance for its survival is the sole supplier of a compound that makes clouds.
This formation of clouds, in turn, changes the intensity and spectral quality of
light reaching the surface ocean. It is well known that phytoplankton growth,
with nutrients available, is directly regulated by the quantity and quality of
sunlight. Do phytoplankton population dynamics have a feedback mechanism
with cloud formation through the formation of DMS?
In another twist to the story, we know that many biological systems, with all
other growth parameters being equal, will operate at increased rates when
warmed. It is also known that white clouds have a higher albedo than ocean
water, thereby reflecting more sunlight back toward space. Does it then follow
that global warming will increase phytoplankton growth rates and result in
enhancedglobal DMS formation? Will this newelevatedDMS flux result in more
clouds over the ocean? If so, will the increased albedo cool the atmosphere and
serve as a negative feedback to global warming?
With the purposeful omission of the details in the DMS story as told here, it is
not possible to answer these questions. It is, however, possible to imagine that the
distribution and chemistry of a simple biogenic sulfur gas can have global
implications. Additionally, there are biogenic and photochemical sources of
other atmospherically significant trace gases in the ocean. Carbon monoxide,
carbonyl sulfide, methyl bromide, methyl iodide, and bromoform¹`¹" all have
oceanic sources to the atmosphere. In the end, it appears that this feedback
between processes in marine surface waters and atmospheric chemistry is an
integral part of climate control. Through this connection, it is quite possible that
man’s impact on the oceans can spread far beyond local events.
¹` R. J. Charlson, J. E. Lovelock, M. O. Andreae and S. G. Warren, Nature, 1987, 326, 655.
¹` R. M. Moore and R. Tokarczyk, Global Biogeochem. Cycles, 1993, 7, 195.
¹" P. S. Liss, A. J. Watson, M. I. Liddicoat, G. Malin, P. D. Nightingale, S. M. Turner and R. C.
Upstill-Goddard, in Understanding the North Sea System, ed. H. Charnock, K. R. Dyer, J.
Huthnance, P. S. Liss, J. H. Simpson and P. B. Tett, Chapman and Hall, London, 1993, p. 153.
W. L. Miller
10
4 Summary
The field of chemical oceanography/marine chemistry considers many processes
andconcepts that are not normally includedina traditional chemical curriculum.
While this fact makes the application of chemistry to the study of the oceans
difficult, it does not mean that fundamental chemical principles cannot be
applied. The chapters included in this book provide examples of important
chemical oceanographic processes, all taking place within the basic frameworkof
fundamental chemistry. There are three principal concepts that establish many of
the chemical distributions and processes and make the ocean a unique place to
practice the art of chemistry: (1) the high ionic strength of seawater, (2) the
presence of a complex mixture of organic compounds, and (3) the sheer size of the
oceans.
The physicochemical description of seawater must include the electrostatic
interactions between a multitude of different ions dissolved in the ocean. This
high ionic strength solution provides the matrix that contains and controls all
other chemical reactions in the sea. Much of the dissolved organic carbon that is
added to this milieu by biological activity is composed of a mixture of molecules
and condensates that are not yet identified, making a description of their
chemistry difficult. The identifiable organic compounds, while almost always
present at very low concentrations, can greatly affect the distribution of other
trace compounds and even participate in climate control via feedback to primary
production and gas exchange with the atmosphere.
A combination of water mass movement and the biological formation of
particles that strip chemicals from solution causes the physical separation of
many elements into vertical zones. Given the great depth and expanse of the
ocean, a spatial and temporal distribution of chemicals is established that
controls many biological and chemical processes in the sea. These spatial
gradients of chemical and physical seawater parameters encourage a diversity of
organisms that are sensitive to remarkably small changes in their chemical
surroundings. While the impact on the ocean by man’s activities is often local in
effect, the combinationof a carefully poisedchemistry, a populationof chemically
sensitive organisms, and the continued contribution of anthropogenic products
through atmospheric transport sets up the possibility of impact on a global scale.
The chapters contained in this book are just a few examples of the important
areas of marine chemistry that require understanding and evaluation in order to
fully grasp the role of the oceans within our planetary system.
Introduction and Overview
11
The Oceans and Climate
GRANT R. BIGG
1 Introduction
The ocean is an integral part of the climate system. It contains almost 96%of the
water in the Earth’s biosphere and is the dominant source of water vapour for the
atmosphere. It covers 71% of the planet’s surface and has a heat capacity more
than four times that of the atmosphere. With more than 97% of solar radiation
being absorbed that falls on the surface from incident angles less than 50° from
the vertical, it is the main store of energy within the climate system.
Our concern here is mainly with the chemical interaction between the ocean
and atmosphere through the exchange of gases and particulates. Through
carbonate chemistry the deep ocean is a major reservoir in the global carbon
cycle, and so can act as a long-termbuffer to atmospheric CO
`
. The surface ocean
can act as either a source or sink for atmospheric carbon, with biological
processes tending to amplify the latter. Biological productivity, mostly of
planktonic life-forms, plays a major role in a number of other chemical
interactions between ocean and atmosphere. Various gases that are direct or
indirect products of marine biological activity act as greenhouse gases once
releasedinto the atmosphere. These include N
`
O, CH
"
, COand CH
`
Cl. This last
one is also a natural source of chlorine, the element of most concern in the
destruction of the ozone layer in the stratosphere.
Other, sulfur-related, products of marine biological processes ultimately
contribute to production of cloud condensation nuclei (CCN). The physical loss
of salt particles to the atmosphere, particularly during wave-breaking, adds to the
atmospheric supply of CCN. The oceanic scavenging of atmospheric loadings of
some particulate material is also important in this chemical exchange between
ocean and atmosphere. Thus nitrates and iron contained in atmospheric dust are
fertilizers of marine productivity, and so can potentially act as limiting factors of
the biological pump’s climatic influence.
Thus the atmospheric component of the planet’s radiation budget is strongly
modulated by the indirect effects of oceanic gas and particle exchange. As will be
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
13
seen in the discussion of feedback processes, altering the radiation budget can
have profound impacts on all other aspects of the climate system.
There are also much longer timescales of chemical interaction between the
ocean and climate system. These are beyond the scope of this chapter but worth
identifying for completeness. The chemical weathering of land surfaces is a
mechanismby which changes in the atmospheric concentrationof CO
`
can occur
over millions of years. For example, slowerosion of the mountain ranges uplifted
over the past 20 million years, such as Tibet, the Rocky Mountains and the Alps,
sequesters atmospheric CO
`
in the ocean through the run-off of the dissolved
carbonate products of weathering.¹ Water andother climaticallyactive compounds
are also recycled fromthe ocean into the atmosphere through tectonic processes.
As oceanic plates are subducted under continental crust at destructive plate
margins, such as along the west coast of South America, trappedseawater, and its
salts, will boil off to become part of the molten crustal matrix that is re-injected
into the atmosphere by volcanic activity. These atmospheric inputs can be
climatically active, and the whole process helps to maintain the composition of
oceanic salinity over geological timescales.`
Physical Interaction
While this chapter is mainly concerned with the chemical interactions between
ocean and atmosphere, a few words need to be said about the physical
interactions, because of their general importance for climate. The main physical
interaction between the ocean and atmosphere occurs through the exchange of
heat, water and momentum,` although the presence of sea-ice acts to reduce all of
these exchanges to a greater or lesser extent.
Momentumis mostly transferredfromthe atmosphere to the ocean, having the
effect of driving the ocean circulation through the production of a wind-driven
flow. Of course, the resultant flowcarries heat and water, so contributing tofluxes
of these quantities to the atmosphere in ways that would not have occurred
without the establishment of the wind-driven circulation in the first place.
Heat is transferredin bothdirections, affecting the density of eachmedium, and
thus setting up pressure gradients that drive circulation. The ocean radiates
infrared radiation to the overlying atmosphere. This is a broadly similar flux
globally as it depends on the fourth power of the absolute temperature. In
contrast, the amount returned to the ocean through absorption and re-radiation
by, particularly, tropospheric water vapour is more variable. Evaporation from
the ocean surface, directly proportional to the wind speed as well as the
above-water humidity gradient, transfers large, and variable, amounts of latent
heat to the atmosphere. This does not warm the atmosphere until condensation
occurs, so may provide a means of heating far removed from the source of the
original vapour. Zones of concentrated atmospheric heating are also possible by
this mechanism, leadingtotropical andextra-tropical stormformation. Conduction
¹ M. E. Raymo, Paleoceanography, 1994, 9, 399.
` K. B. Krauskopf and D. K. Bird, Introduction to Geochemistry, McGraw-Hill, New York, 3rd edn.,
1995, ch. 21, p. 559.
` G. R. Bigg, The Oceans and Climate, Cambridge University Press, Cambridge, 1996, ch. 2, p. 33.
G. R. Bigg
14
and turbulent exchange also directly transfer heat from the warmer medium,
again in proportion to the wind speed. This tends to be much smaller in
magnitude than either of the other mechanisms. Latent heat transfer is thus the
most temporally and geographically variable heat exchange process, heating the
atmosphere at the ocean’s expense. Anomalous heating or cooling of the
atmosphere over regions of the ocean can lead to atmospheric circulation
changes, which in turn can feed back to the maintenance (or destruction) of the
originating oceanic anomaly. The El Nin o" phenomenon in the Pacific is linked
to such interactions, as is the North Atlantic Oscillation.`
As part of the process of latent heat transfer, water vapour is added to the
atmosphere. This not only leads to atmospheric heating through the release of
latent heat, but also to cloud formation and maintenance of the natural
greenhouse effect through the replenishment of atmospheric water vapour. In
exchange, water is added to the surface of the ocean via precipitation, run-off
from rivers and melting of icebergs. The local combination of evaporation and
addition of fresh water can alter the ocean’s surface density considerably. The
ocean circulation is a combination of (i) the wind-induced flow and (ii) a
larger-scale, deeper-reaching thermohaline circulation, the latter set up by
changes in temperature and salinity, and hence density, on both global and
regional scales. Altering the surface density regionally could thus have large
repercussions for the global ocean circulation, and hence the manner in which the
ocean contributes to the climate. Decreasing the salinity of the northern North
Atlantic, for example, could significantly slow the meridional overturning
circulation, or Conveyor Belt,' within the whole Atlantic, which, in turn, means
slowing, cooling and alteration of the path of the Gulf Stream extension across
the North Atlantic. This would have major climatic effects.` We will return to
such processes later in this chapter.
The Mechanics of Gas Exchange
The fundamental control on the chemical contribution of the ocean to climate is
the rate of gas exchange across the air—sea interface. The flux, F, of a gas across
this interface, into the ocean, is often written as
F¬k
'
(C
º
÷C
'
) (1)
where C
º
and C
'
are the respective concentrations of the gas in question in the
atmosphere and as dissolved in the ocean, and k
'
is the transfer velocity.
Sometimes this difference is expressed in terms of partial pressures`—in the case
of the water value this is the partial pressure that would result if all the dissolved
gas were truly in the gaseous state, in air at 1 atmosphere pressure. For gases that
" S. G. H. Philander, El Nino, La Nina and the Southern Oscillation, Academic Press, NewYork, 1990,
ch. 1, p. 9.
` J. M. Wallace and D. S. Gutzler, Mon. Weather Rev., 1981, 109, 784.
' G. R. Bigg The Oceans and Climate, Cambridge University Press, Cambridge, 1996, ch. 1, p. 1.
` S. Manabe and R. J. Stouffer, Nature, 1995, 378, 165.
` F. Thomas, C. Perigaud, L. Merlivat and J.-F. Minster, Philos. Trans. R. Soc. London, Ser. A, 1988,
325, 71.
The Oceans and Climate
15
Figure 1 The solubility of
the principal atmospheric
gases in seawater, as a
function of temperature.
Units are millilitres of gas
contained in a litre of
seawater of salinity 35 psu,
assuming an overlying
atmosphere purely of each
gas. Note that salinity is
defined in terms of a
conductivity ratio of
seawater to a standard
KCl solution and so is
dimensionless. The term
‘practical salinity unit’, or
psu, is often used to define
salinity values, however. It
is numerically practically
identical to the old style
unit of parts per thousand
by weight
are created through marine biological activity, C
'
is generally much larger than
C
º
so that the net flux towards the atmosphere is directly dependent on the
oceanic production rate of the gas. However, if a gas has a large atmospheric
concentration, or the ocean can act as a sink for the gas, as with CO
`
, then we
need to consider the solubility of our gas more carefully, as it is this that will
determine (C
º
÷C
'
). For gases that are chemically inert in seawater the solubility
is essentially a weak function of molecular weight. Oxygen is a good example of
such a gas, although its oceanic partial pressure can be strongly affected by
biological processes. For gases like CO
`
, however, which have vigorous chemical
reactions with water (as we will see in the next section), the solubility is much
increased, and has a different temperature dependence. For chemically inert gases
the solubility decreases by roughly a third in raising the water’s temperature from
0 °C to 24 °C, but for a reactive gas this factor depends on the relative reaction
rates. Thus, for CO
`
the solubility more than halves over this temperature range,
from 1437 mLL¹ to 666 mLL¹ (Figure 1).
The other major factor controlling gas exchange is the transfer velocity, k
'
.
This represents the physical control onexchange throughthe state of the interface
and near-surface atmosphere and ocean." A calm sea, and stable air, will only
allow slow exchange because the surface air mass is renewed infrequently and
there is largely only molecular diffusion across the interface in these conditions.
In very calm conditions the presence of surfactants slows this diffusion even
further.¹" Bigger molecules thus have lower values of k
'
in low-wave sea states,
because diffusion occurs more slowly. By contrast, rough seas and strong winds
allow frequent renewal of the surface air, and bubble formation during
wave-breaking actively bypasses the much slower molecular diffusion of gas.¹¹
The molecular size of the gas will also be less important in this strongly physically
controlledregime. Anabrupt change in transfer rate can be expectedwhenthe sea
state crosses the transition to breaking waves (Figure 2). Both bulk chemical
" P. S. Liss, A. J. Watson, M. I. Liddicoat, G. Malin, P. D. Nightingale, S. M. Turner and R. C.
Upstil-Goddard, Philos. Trans. R. Soc. London, Ser. A, 1993, 343, 531.
¹" R. Wanninkhof and W. R. McGillis, Geophys. Res. Lett., 1999, 26, 1889.
¹¹ D. M. Farmer, C. L. McNeil and B. D. Johnson, Nature, 1993, 361, 620.
G. R. Bigg
16
Figure 2 Variation of the
gas transfer velocity with
wind speed. The units of
transfer velocity are
equivalent to the number
of cm of the overlying air
column entering the water
per hour (Taken from
Bigg,`` with permission of
Cambridge University
Press)
measures of this exchange and micrometeorological-based eddy correlation
techniques¹` showsimilar rates of change of k
'
with wind speed, but they differ in
detail, with the eddy correlation technique tending to give somewhat higher rates
of exchange.
Afurther factor affecting k
'
is the air—sea temperature difference. When the sea
is colder than the air above it, the enhanced solubility of the gas in the water
(relative to the air temperature) tends to increase k
'
. This will occur in summer in
sub-polar waters and over upwelling regions. The opposite is also found, and
much of the ocean equatorward of 45° latitude is colder than the overlying air for
much of the year. However, air—sea temperature differences are generally less
than2—3°Csothat this effect results inaless than10%modulationof k
'
onaverage.
2 Oceanic Gases and the Carbon Cycle
Carbon dioxide is a major greenhouse gas within the atmosphere. Water vapour
is a greater contributor to the natural greenhouse effect (55—70% of the total
radiative absorption compared to CO
`
’s 25%). However, the large inherent
variability in atmospheric water vapour compared to the anthropogenically
¹` H. Dupuis, P. K. Taylor, A. Weill and K. Katsaros, J. Geophys. Res., 1997, 102, 21115.
The Oceans and Climate
17
Figure 3 Global carbon
reservoirs and annual
fluxes.¹` Units are gigatons
of carbon in the reservoirs
and Gt Cyr¹ for fluxes
driven steady rise in background atmospheric CO
`
levels from 280 ppmv to
360 ppmv over the last 200 years has led to concern that the magnitude of the
greenhouse effect may be increasing. The infrared absorption bands of the CO
`
molecule also occur in regions of the Earth’s electromagnetic spectrum where at
present moderate amounts of available energy escape to space.¹`
The largest reservoir of available carbon in the global carbon cycle, however, is
in the deep ocean, below the thermocline (Figure 3). This is the part of the ocean
that has essentially no thermal or dynamical link to direct atmospheric forcing.
The depth of the temperature barrier of the thermocline varies geographically
and temporally but the deep ocean can roughly be taken to be the entire ocean
deeper than 500 m from the surface. Here is stored the end results of the oceanic
carbonate chemistry, discussed below. As the overturning, or renewal, timescale
of the ocean is of the order of 1000 years, this deep reservoir is essentially isolated
fromshort-termchanges to the remainder of the cycle. Smaller reservoirs, but still
larger than that in the atmosphere, are found in the upper ocean and the
terrestrial biosphere. The upper ocean reservoir has both a chemical and a
biological component. While small elements of each of these surficial reservoirs
are sequestered into other reservoirs, 5—10%is recycled into the atmosphere each
year. Thus boththe upper oceanandthe terrestrial biosphere have the capacity to
interact, subject to a relatively small time lag, with anthropogenically driven
atmospheric change to CO
`
. As the focus here is on the oceanic involvement with
the carbon cycle, mechanisms to significantly alter the biological pump are
¹` D. Schimel, D. Alves, I. Enting and M. Heimann, in Climate Change 1995, ed. J. T. Houghton, L. G.
Meira Filho, B. A. Callander, N. Harris, A. Kattenberg and K. Maskell, Cambridge University
Press, Cambridge, 1996, ch. 2, p. 65.
G. R. Bigg
18
considered below. This mostly involves ways to alter primary productivity by
removing existing trace element controls such as nitrate or iron limitation. These
controls are very different in different oceanic regimes: coastal waters have
limitinglight levels, but excesses of nitrates and iron due to direct input fromriver
run-off or atmospheric deposition; in contrast, open ocean waters may have
limits inone nutrient or another depending onthe regional physical oceanography.
The ocean’s contribution to the carbon cycle has evolved over time, and still
changes with the growth and decline of glaciation. However, the deep component
of the cycle can also have climatic consequences. If the exchange of carbon shown
in Figure 3 is severed through changes to the physical overturning of the ocean as
a whole, or a substantial basin, this disconnection of the deep and upper ocean
reservoirs can lead to significant climatic change.
Carbonate Chemistry
The basic reason for the ocean being a major sink for CO
`
lies in the reaction of
the gas with water, and subsequent anion breakdown:
CO
`
(gas) ·H
`
O&H>·HCO
`
&2H>·CO
`
` (2)
The component reactions in eqn. (2) are very fast, and the system exists in
equilibrium. Additional carbon dioxide entering the sea is thus quickly converted
into anions, distributing carbon atoms between the dissolved gas phase,
carbonate and bicarbonate ions. This storage capacity is clear when the apparent
equilibrium constants for the two reactions in eqn. (2) are examined, namely
K
¹
¬
a
'
>
[HCO
`
]
[CO
`
]
(3)
for the gas to bicarbonate equilibrium (where [CO
`
] is the concentration of the
dissolved gas and a
'
>
is the activity of the hydrogen ion), and
K
`
¬
a
'
>
[CO
`
`]
[HCO
`
]
(4)
for the bicarbonate to carbonate equilibration. Note that these are different from
standard thermodynamic equilibrium constants because of the difficulty in
measuring some of the more usual quantities in seawater.¹" These constants
depend on temperature, pressure and salinity, most importantly increasing for
increasing temperature and pressure.¹` At Standard Temperature and Pressure,
and a salinity of 35 psu, K
¹
is several orders of magnitude greater than K
`
(K
¹
¬1 ;10' and K
`
¬7.69 ;10¹") so most carbon is in the intermediate,
bicarbonate, reservoir of reaction sequence (2).
More CO
`
can actually be absorbed chemically into the ocean than the above
reactionsequence suggests. Terrestrial weatheringof rocks containingcarbonate,
such as limestone, and subsequent aerial or riverine transport, means that the
ocean is enriched in carbonate. Keeping K
¹
and K
`
constant implies, through
eqns. (3) and (4), that enhancing the oceanic [CO
`
`] leads to a greater level of
¹" C. Merbach, C. H. Culberson, J. E. Hawley and R. M. Pytkowicz, Limnol. Oceanogr., 1973, 18, 897.
¹` W. S. Broecker and T.-H. Peng, Tracers in the Sea, Eldigio Press, New York, 1982, ch. 3, p. 110.
The Oceans and Climate
19
oceanic dissolved CO
`
. It is also worth noting that seawater’s pH is affected by
CO
`
dissolution, because hydrogen ions are released in both parts of eqn. (2).
Thus, if more carbon is pumped into the system, the greater is the ratio of
bicarbonate to carbonate ions, and the more hydrogen ions there are in solution.
Thus the pH falls. However, as the bicarbonate to carbonate reaction is so fast
(K
`
) the carbonate system acts as a pH buffer for the oceans.¹'
Another factor inthis reactionsequence is also subject toexternal modification,
namely, moderationof the basic oceanic dissolutionof CO
`
throughtemperature
dependence of its solubility, S. The latter is defined as:
S ¬
[CO
`
]
P
º
(CO
`
)
(5)
where P
º
(CO
`
) is the partial pressure of CO
`
gas in air equilibrated with a
particular sample of seawater. Combining eqns. (3), (4) and (5) gives:
P
º
(CO
`
) ¬
a
'
>
`[CO
`
`]
K
¹
K
`
S
(6)
Relative changes in the components of eqn. (6) mean that P
º
(CO
`
) should
decrease by about a factor of three between 25 °C and 0 °C.¹` However,
atmospheric concentrations of CO
`
are essentially uniform, so tropospheric
mixing clearly acts fast enough for this potential poleward gradient to be absent.
The Biological Pump
Oceanic biology is a sink for atmospheric CO
`
because of the involvement of the
aqueous form of this gas in planktonic photosynthesis. This complex process can
be summarized by
nCO
`
·nH
`
O`'''''° ''¨"'
æ
nO
`
·(CH
`
O)
L
(7)
where (CH
`
O)
L
represents a general carbohydrate. The reverse of this process, the
absorption of O
`
leading to the release of CO
`
, is known as respiration. Different
species preferentially absorb different wavelengths of visible light during
photosynthesis, and have maximal growth at different temperatures.¹` They can
also tolerate more or less intensity of radiation. Thus maximum photosynthesis
occurs below the surface and to a varying degree geographically, depending on
the environmental conditions and the species distribution.
Other limitations on phytoplankton growth are chemical in nature. Nitrogen,
in the formof nitrate, nitrite and ammoniumions, forms a basic building material
of a plankton’s cells. In some species silicon, as silicate, takes on this role.
Phosphorus, in the formof phosphate, is in both cell walls and DNA. Iron, in the
formof Fe(III) hydroxyl species, is an important trace element. Extensive areas of
the mixed layer of the upper ocean have low nitrate and phosphate levels during
¹' J. Wright and A. Colling, Seawater: its Composition, Properties and Behaviour, Pergamon Press,
Oxford, 1995, ch. 6, p. 85.
¹` T. R. Parsons, M. Takahashi and B. J. Hargrave, Biological Oceanographic Processes, Pergamon
Press, Oxford, 1984, ch. 3, p. 65.
G. R. Bigg
20
periods of planktonic growth. Thus the lack of availability of these species,
collectively known as nutrients, can limit phytoplankton growth, and hence
marine CO
`
absorption. However, large areas of the ocean have high nutrient
levels, but low productivity. These include the Southern Ocean and part of the
equatorial seas. Here it is thought that iron is the limiting nutrient,¹` combined,
in cold-water environments, with light limitation. Iron is in short supply in the
ocean because of the poor dissolution of particles or colloidal material, which is
the most common state of marine iron. Field experiments and the marine
after-effects of the eruption of Mt. Pinatubo in 1991 have supported this so-called
‘iron’ hypothesis.¹"
Atmospheric inputs of the various potentially limiting nutrients are considerable
and may significantly affect the primary production of the ocean.`" While
globally, and in the long-term, nitrogeneous input from the atmosphere is
unlikely to be a major source of planktonic nitrogen, local and short-term effects
could be signficant. The major source of oceanic iron, however, is atmospheric.
The atmosphere delivers some 30 times more iron to the ocean than rivers, and
the sea floor also seems to be a negligible contributor to the overlying water
column. Areas far from land, or isolated from the airborne trajectories of major
sources of atmospheric dust, such as the Southern Ocean, may therefore be
fundamentally limited in their productivity by the lack of iron.`¹
Geographical Variation
The geographical distribution of the mean annual net marine flux of CO
`
to the
atmosphere`` shows the combined influence of physical, chemical and biological
effects on marine uptake of carbon (Figure 4). Polar waters tend to have net
increases in levels of CO
`
as a result of the united effects of both enhanced
solubility and biological production. The sub-tropical oceans are close to a state
of equilibrium with the atmosphere, because phytoplankton production is
limited by the weak winter upwelling of nutrients. Some such regions, nearby
eastern coasts, however, show high levels of CO
`
input to the atmosphere,
consistent with oceanic production of CO
`
rather than absorption. This is also
visible in equatorial regions. In both cases, such high values occur because water
upwells from deeper in the ocean, carrying water that has been at a higher
pressure. More carbon can exist as carbonate and bicarbonate ions at the greater
pressures at depth, but as the upwelled water’s pressure reduces, reaction (2) is
pushed to the left and CO
`
is formed. This effect outweighs the carbon
draw-down associated with the considerable phytoplankton production in these
areas caused by the continual upwelling of nutrients. The net effect is for the
ocean to be a source of CO
`
for the atmosphere in these areas.
¹` J. H. Martin and S. E. Fitzwater, Nature, 1988, 331, 341.
¹" A. J. Watson and P. S. Liss, Philos. Trans. R. Soc. London, Ser. B, 1998, 353, 41.
`" T. D. Jickells, Mar. Chem., 1995, 48, 199.
`¹ J. H. Martin, Paleoceanography, 1990, 5, 1.
`` T. Takahashi, R. A. Feely, R. F. Weiss, R. H. Wanninkhof, D. W. Chipman, S. C. Sutherland and
T. T. Takahashi, Proc. Natl. Acad. Sci. USA, 1997, 94, 8292.
The Oceans and Climate
21
Figure 4 Mean annual net CO
`
flux over the global oceans (in 10¹` grams of C per year per 5° square)``
G
.
R
.
B
i
g
g
2
2
Coastal regions are much greater sources of primary production than deeper
waters, because of the nearby source of terrestrial nutrients, which enter the sea
through both the air and rivers. It is also worth noting the strong seasonality of
carbon input to the oceans in regions dominated by the biological control, as
most such areas will have strongly enhanced carbon draw-down only during
periods of maximal primary production.
Marine Biology and Oceanic Greenhouse Gas Emissions
A number of biological processes result in the marine production of gases that
have a greenhouse role, similar to water vapour and CO
`
. In low oxygen
environments, of the sort discussed in the next section, methane is produced by
anaerobic bacterial decay:
2(CH
`
O)
L
'º°'°''º
æ
nCH
"
·nCO
`
(8)
The methane that escapes to the atmosphere, 1—2% of the global budget, largely
derives fromthe sub-surface oxygen minimumassociated with high productivity.
The Arabian Sea in summer is the best known of such environments. Another gas
produced through anaerobic decay is H
`
S. This can undergo oxidation in the air
tosulfate aerosols, but relatively little is likely toescape fromthe oceanbecause of
its high reactivity.
Incomplete respiration, that is respiration occurring where oxygen is limited
but not entirely absent and so CO
`
cannot be generated, also leads to the
production of a greenhouse gas, namely CO:
(CH
`
O)
L
·
n
2
O
`
;nCO·nH
`
O (9)
With the addition of CO caused by photochemical oxidation of methane, a
significant flux enters the atmosphere annually, but the principal global
contributions are terrestrial, anthropogenic and from atmospheric photolysis of
methane.``
Another important greenhouse gas is a product of phytoplankton oxidation of
ammonium. This reaction can follow two pathways:
2O
`
·NH
"
> ;NO
`
·H
`
O·2H> (10)
or, much more rarely (0.1% of the time):
2O
`
·2NH
"
> ;N
`
O·3H
`
O·2H> (11)
A product of the second pathway, N
`
O, is a significant greenhouse gas. About a
quarter of the annual input of N
`
O to the atmosphere comes from the ocean.
Ocean Anoxia
The back reaction of the photosynthesis equilibrium (7)—respiration—involves
the consumptionof oxygen and the productionof CO
`
. These dissolvedgases are
`` R. T. Watson, H. Rodhe, H. Oeschger and U. Siegenthaler, in Climate Change 1990, ed. J. T.
Houghton, G. J. Jenkins andJ. J. Ephraums, Cambridge UniversityPress, Cambridge, 1996, ch. 1, p. 1.
The Oceans and Climate
23
in the surrounding water, not within the phytoplankton cell. Thus while
photosynthesis both sequesters carbon and produces oxygen, the presence of
organisms at depths too deep for photosynthesis results in a depletion of the
oxygen levels in this water. This depletion can also occur higher in the water
columnif some, perhaps dynamical, mechanismconcentrates planktonat a depth
where onlylimitedphotosynthesis is possible; that is, belowthe compensationdepth.
Respirating organisms exist at all depths of the ocean, including the bottom
sediments, so below the euphotic zone the ocean’s supply of oxygen is slowly
depleted. At the surface, oxygen levels are always around saturation. The gradual
respirated depletion of oxygen as waters move away from the surface has been
one way to infer the spread of water deriving fromthe North Atlantic throughout
much of the deep waters of the global ocean.
If the replenishment of deep waters is slow, either through a particular basin
being isolated from a source of deep water formation or because the oxygen
utilization is faster than the re-supply of oxygenated water, then the deep water
can become anoxic. Such waters will then need to use sulfates rather than oxygen
in oxidizing reactions. In some regions the presence of anoxic deep water is an
important climatic signal. For instance, periodicallythe deepeasternMediterranean
has been anoxic, as is recorded in bottomsediment layers. This is thought to be a
result of enhanced surface run-off fromthe surrounding land masses reducing the
density of the surface waters, and so preventing winter cooling from raising
surface densities to a level comparable with intermediate or bottom waters and
thus causing deepconvection.`" The periodicity is probably related to the Earth’s
orbit, through the monsoonal rainfall variation associated with mid-latitude
insolationvariationcausedby the 20 000 year periodicityinthe Earth’s obliquity.
Anoxic deep water can help cause climatic change, as well as be a sign of it.
Large volumes of the deep ocean can be removed as potential storage zones for
carbon, because of the cessation of regional deep water formation or because an
ocean basin becomes isolated from global sources of deep water renewal. If less
carbon can be stored in the ocean, then more will remain in, or re-enter, the
atmosphere. The atmospheric greenhouse effect will then be enhanced and the
global temperature will rise. The Mediterranean is too small a basin for its
periodic anoxia to cause a major direct climatic change, although changes to the
exchange of water with the Atlantic caused by anoxically driven circulation
changes within the Mediterranean could have indirect climatic effects.`` A
long-term cessation of North Atlantic Deep Water formation, however, or a
tectonically induced isolation of a large ocean basin, could have a climatically
direct effect on atmospheric CO
`
. During the formation of the Atlantic Ocean,
several tropical basins remained isolated from the rest of the global ocean for
many millions of years and so this may have partially been responsible for the
high atmospheric CO
`
levels during the Cretaceous period.`'
`" E. J. Rohling, Mar. Geol., 1994, 122, 1.
`` R. G. Johnson, Earth and Planet. Sci. Lett., 1997, 148, 367.
`' J. E. Andrews, S. K. Tandon and P. F. Dennis, J. Geol. Soc., 1995, 152, 1.
G. R. Bigg
24
3 Oceanic Gases and Cloud Physics
Following the fate of a number of oceanically produced gases in the atmosphere
reveals one of the major ways by which the ocean chemically contributes to the
climate. Sulfates, sulfides and nitrogen oxides released by the ocean act as
condensation nuclei within clouds, either in the form in which they were emitted
from the ocean, or after undergoing chemical transitions. Sea salt, derived from
evaporation of water injected into the marine boundary layer, is also an
important source of cloud condensation nuclei (CCN). A greater abundance of
CCN means that cloud formation, and hence precipitation, is easier to initiate,
with clear implications for the surface climate. However, clouds are also major
reflectors of solar radiation, and absorbers of terrestrial infrared radiation. They
therefore play a fundamental role in the radiation balance of the planet. There are
many indirect and direct means by which clouds affect the radiation budget,``
some of which we will discuss in Section 4, but in general more cloud tends to
result in less net energy entering the climate system.
Breaking Waves and Sea Salt
In Section 1 we discussed the basic gas exchange mechanism and saw that a
transition region existed where release into the atmosphere was enhanced above
some critical wind speed (Figure 2). Breaking waves, physically injecting water
and its dissolved constituents into the atmosphere, cause this enhancement. In
addition to enhancing the upward flux of gases, this mechanism also effectively
injects sea salt into the air, through evaporation of the dispersed water droplets
before they return to the sea surface.
Sea salt particles are the biggest contributor by mass of particulate material
intothe marine atmosphere, with10"—10¹" tonnes cycledthroughthe atmosphere
annually. They tend to be relatively large, typically 0.1—1 m in diameter. This
large size means that there is a significant fall-out of particles within the marine
boundary layer (up to 90%). However, those that are carried by turbulence into
the free atmosphere in concentrations of typically several g m` are larger than
average CCN and so play a dominant role in the important coalescence mode of
rain formation.`` This role is enhanced by the strongly hygroscopic nature of the
largely NaCl sea salt aerosol. A relative humidity of only 75% is required for the
initiation of condensation around a NaCl nucleus. While some salts have even
lower thresholds—K
`
CO
`
at 44%, for instance—the abundance of atmospheric
sea salt makes this a significant source of cloud droplets.
Production Mechanisms for CCN Derived from Marine Gas
Emission
Biological decay mechanisms are responsible for the emission of gases that are
`` R. E. Dickinson, V. Meleshko, D. Randall, E. Sarachik, P. Silva-Dias and A. Slingo, in Climate
Change 1995, ed. J. T. Houghton, L. G. Meira Filho, B. A. Callander, N. Harris, A. Kattenberg and
K. Maskell, Cambridge University Press, Cambridge, 1996, ch. 4, p. 193.
`` G. R. Bigg, The Oceans and Climate, Cambridge University Press, Cambridge, 1996, ch. 3, p. 85.
The Oceans and Climate
25
Figure 5 Schematic
illustration of the sources
and sinks of DMS in the
marine boundary layer of
the atmosphere and the
oceanic mixed layer
(Taken from Bigg,`` with
permission of Cambridge
University Press)
precursors to CCN as well as for potential greenhouse gases. The decay of algal
cells releases methyl iodide, a precursor of methyl chloride that is a natural source
of chlorine, and hence ultimately involved in the chemistry of the stratosphere’s
ozone layer. Both dimethyl sulfide (DMS) and dimethyl sulfoniopropionate
(DMSP) are produced during the destruction of the cell walls of phytoplankton,
either through death, viral attack or grazing, although the exact mechanism is
under constant review.`" The production of DMSP, thought to be of importance
in limiting osmotic loss of algal cell material to the surrounding seawater, varies
significantly from one species to another. DMSP also oxidizes to form DMS.
DMShas beenobservedinthe marine boundary layer insignificant concentrations
of up to 0.25 g m` during plankton blooms.
Not all DMS released reaches the atmosphere. As can be seen from the
summarizing Figure 5, some undergoes photolytic oxidation`" within the sea
through the reaction
2(CH
`
)
`
S ·O
`
æ 2(CH
`
)
`
SO FJ (12)
A large proportion (30—90% in tropical waters) is absorbed by bacteria and
oxidized to H
`
S in order to allow the sulfur to be used by these organisms. Once
in the atmosphere, DMS is oxidized by various free radicals such as hydroxyl and
nitrate ions. In the presence of low concentrations of NO
V
the hydroxyl reaction
`" P. S. Liss, A. D. Hatton, G. Malin, P. D. Nightingale and S. M. Turner, Philos. Trans. R. Soc.
London, Ser. B, 1997, 352, 159.
`" P. Brimblecombe and D. Shooter, Mar. Chem., 1986, 19, 343.
G. R. Bigg
26
leads directly to sulfate aerosols, otherwise there is an acidic intermediate,
methanesulfonic acid (MSA). In either case the end result is an increase in the
atmosphere’s acidity and sulfate-based CCN concentration, and thus cloud
potential. The climatic feedback that could result fromthis natural marine sulfate
emission is discussed in Section 4.
4 Feedback Processes Involving Marine Chemistry and Climate
The climate system is very complex. Untangling how it works involves much
more than merely following the first-order energy fluxes between compartments,
such as the atmosphere, Earth’s surface and ocean, within the system. Feedbacks
are a key characteristic leading to difficulty in predicting howperturbationof one
part of the systemwill affect the whole. Feedbacks may be positive or negative, or
occasionally self-cancelling. Often the clear first-order feedback does not reveal
all the linked processes impacting on the particular feedback mechanism under
discussion. This may mean that the net effect of both direct and indirect links
opposes the first-order direct impact.
A major physically based feedback within the climate system is the ice albedo
feedback. Ice is highly reflective, so there is a strong inverse link between global
temperature and ice cover. The current increase in atmospheric concentrations of
greenhouse gases does not just trap more terrestrial radiation energy in the
troposphere, but warming the surface promotes more evaporation and so a
greater atmospheric concentration of the dominant greenhouse gas, water
vapour. However, among other effects, more clouds also result, warming affects
biological activity in the ocean, and gas exchange between the atmosphere and
oceanwill also change. We will consider some of these inter-linked, marine-related
feedbacks in more detail below.
First, however, we will consider another marine-related feedback potentially
implicated in the speed of deglaciation, a theme that will also appear in the next
section. This is the potential sea level and methane feedback. During glacial
periods the atmospheric concentration of methane has been significantly lower
than the current interglacial’s pre-industrial level. This is principally because so
much of the production occurs in anaerobic decay within sub-polar wetlands.
These are of lesser extent during glaciations owing to the greater spread of
permafrost. However, during deglaciation the rise of sea level leads to the
flooding of extensive areas of permafrost on the continental shelves of the Arctic,
eastern Canada and western Europe. The rapid thawing of the permafrost may
lead to a corresponding release of methane trapped within the ground since the
previous interglacial. As methane is a significant greenhouse gas, major, and
rapid, changes in its concentration could aid climatic warming. There is some
indication of such a link in Greenland ice cores,`¹ but recent work has tended to
weaken the likely impact of such a mechanism.``
`¹ J. Chappellaz, T. Blunier, D. Raynaud, J. M. Barnola, J. Schwander and B. Stauffer, Nature, 1993,
366, 443.
`` R. B. Thorpe, K. S. Law, S. Bekki, J. A. Pyle and E. G. Nisbet, J. Geophys. Res., 1996, 101, 28627.
The Oceans and Climate
27
Feedbacks within the Marine Segment of the Carbon Cycle
Carbon is an important part of both the physical chemistry and the biology of the
ocean. Feedbacks between the climate system and marine organisms are thought
tocool the globe byabout 1.7°Ctoday.¹" Changingthe atmospheric concentration
of CO
`
will therefore leadtoclimatic feedbacks involving the marine environment.
During glacial periods a drop in atmospheric concentrations of CO
`
by about a
third accompanied the methane decrease already mentioned. Such a decrease in
the second most important greenhouse gas, for thousands of years, will have
reduced atmospheric absorption of terrestrial radiation, and so assisted glacial
cooling. Most theories to explain this decline invoke the sequestration of carbon
within the marine carbon cycle. The cooling itself would promote greater oceanic
absorption, throughthe temperature dependence of solubilityand the conversion
of dissolved CO
`
to bicarbonate. This is a positive feedback. Nevertheless, the
enhancement of carbon draw-down associated with increased marine biological
activity is needed to reconcile the magnitude of the atmospheric decline.
There are various ways by which this may have been achieved and probably
more than one mechanism is required to explain the total change.¹" Increase in
the supply of nutrients to the ocean is one possibility. This can be done in various
ways. Atmospheric dust loadings were higher during the last glacial period. This
is likely to have meant additional supplies of airborne iron being deposited in the
ocean, particularly in the Southern Ocean, where winds may have been stronger
because of the greater meridional temperature gradient. Greater erosion of the
exposed continental shelves could have deposited more nutrients in coastal
waters. Changes in ocean circulation are likely to have expanded the cold, but
ice-free, regions of the North Atlantic, Southern Ocean and North Pacific. These
areas are currently the strongest marine carbon sinks and so may have played an
even more important role in glacial periods.
Anthropogenic change to today’s atmospheric CO
`
levels is also likely to have
climatic feedbacks with the ocean.```" These are summarized in Figure 6.
Surface warming will decrease CO
`
solubility—a positive feedback—but enhance
some species’ photosynthesis through the temperature dependence of the
maximal growth rate—a negative feedback through the promotion of CO
`
draw-down. Radical change in species distributions opens the possibility of
negating much of today’s biological carbon extraction through shift of the
organic carbon: CaCO
`
sinking ratio—a positive feedback.`" Increasedwarming
and greater precipitation, both predicted to be climatic changes in the 21st
century, will stabilize the upper oceanwater columnthroughreducing the surface
density. This, in turn, would lead to less convection transporting nutrients from
below the mixed layer into the euphotic zone—a positive feedback through
reducing productivity. In some, sub-tropical, regions there may be enhanced
evaporation, brought about by warming and increased wind speeds, which will
act in the opposite fashion—a negative feedback! Evaporation due to stronger
`` U. Siegenthaler and J. L. Sarmiento, Nature, 1993, 365, 119.
`" K. Denman, E. Hofmann and H. Marchant, in Climate Change 1995, ed. J. T. Houghton, L. G.
Meira Filho, B. A. Callander, N. Harris, A. Kattenberg and K. Maskell, Cambridge University
Press, Cambridge, 1996, ch. 10, p. 483.
G. R. Bigg
28
Figure 6 Schematic
illustration of the
mechanisms affecting
absorption of CO
`
in the
ocean (Taken from Bigg,``
with permission of
Cambridge University
Press)
winds would also cool the sea surface, through latent heat transfer, hence both
destabilizing the surface and enhancing CO
`
solubility—both negative feedbacks.
A final positive feedback is via the enhanced greenhouse effect’s predicted
reduction of the meridional overturning circulation within the Atlantic. This
currently removes large amounts of carbon from high latitude oceans, allowing
biological and physicochemical processes to remove further CO
`
from the
atmosphere.
The Marine Sulfur Cycle and the Charlson Hypothesis
DMS has been observed in the marine atmosphere since the early 1970s, but it
was not until the mid-1980s that there was interest in this gas as being a natural
source for sulfate CCN. Sulfate aerosols are, in number terms, the dominant
source of CCN. The major role clouds play in the climate systemleads to possible
climatic implications if changes to DMS production occurred. Furthermore, the
dependence of this production on environment conditions means that scope for a
feedback process arises; this feedback is called the Charlson hypothesis.``
This feedback is illustrated in Figure 7. An increase in DMS production within
the ocean leads, through oxidation of the emitted gas, to an increase in
atmospheric sulfate aerosols. This, in turn, means that a greater concentration of
CCN is available for any given cloud forming. Clouds will therefore have more
mid-size droplets—sea salt particles provide the majority of larger droplets.
Indeed, for a given cloudliquid water content, more condensationsites results, on
average, in smaller droplets beingproduced. As the cloud’s albedo depends onthe
surface areaexposedto the incident solar beam, andthe productionof more small
droplets tends to increase the net surface area of water droplets within the cloud,
less solar radiation will penetrate the cloud. Taken to global scale, this leads to a
lowering of the global temperature. The potential feedback mechanism now
appears. Cooling will both lower surface ocean temperatures, thus changing the
geographical distribution of where each plankton species may attain their
maximal growth rate, and reduce the solar flux required for photosynthesis.
`` R. J. Charlson, J. E. Lovelock, M. O. Andreae and S. G. Warren, Nature, 1987, 326, 655.
The Oceans and Climate
29
Figure 7 Diagram of the
feedback loop involving
climate and planktonic
production of DMS. The
( ¬?) under biological
production of DMS in the
ocean indicates the
uncertainty in the direction
of the net feedback loop
(Taken from Bigg,`` with
permission of Cambridge
University Press)
These changes will alter the rate of oceanic DMS production, but in a direction
not yet determined. One could argue that a negative feedback would arise owing
to restrictions in photosynthesis, and therefore plankton populations. However,
it is also possible that equatorward penetration of the productive, cooler-water
species wouldenhance global DMSproduction, giving rise toa positive feedback.
It is relevant here to note that the high DMS production in the equatorial Pacific
Ocean, one of the climatically most variable places in the world owing to the
Southern Oscillation, remained relatively constant over the period 1982 to 1996.
Some of the most dramatic, and prolonged, El Nin o events of this century
occurred during this interval. In the tropical Pacific, therefore, climate and
marine biological productivity may be self-stabilizing to a degree through the
above two opposite feedbacks.`'
An estimate has been made of the purely direct global cooling effect due to
DMS’s natural enhancement of cloud albedo that is possible in today’s
environment.¹" This suggests that marine DMS production may be currently
cooling the globe by 3.8 °C (roughly double the estimated impact of today’s
marine biological moderation of CO
`
), although error bars on this number are
large, and it does not take into account the indirect feedback mechanisms.
5 Future Prospects
The sensitivity of the ocean’s chemical role in climate is yet to be fully explored as
development of models for the carbon and biological components of oceanic
`' T. S. Bates and P. K. Quinn, Geophys. Res. Lett., 1997, 24, 861
G. R. Bigg
30
Table 1 Average annual
budget of CO
`
perturbations for
1980—1989.¹` Fluxes are
expressed in Gt Cyr¹;
error limits correspond to
a 90% confidence interval
1995 estimate
CO
`
sources
Fossil fuel emissions 5.5¬0.5
Tropical land-use change 1.6¬1.0
Reservoir change
Atmosphere 3.3¬0.2
Ocean 2.0¬0.8
Forest re-growth 0.5¬0.5
Other sinks 1.3¬1.5
climate lag behind the physical modelling. The latter itself still has significant
scope for improvement. Current estimates of the perturbation of the carbon cycle
owing to anthropogenic effects also have uncertainties. Table 1 shows annual
average estimates for the partitioning of carbon fluxes during the decade
1980—1989.¹` Without the ocean’s enhanced uptake, atmospheric CO
`
growth
would be considerably greater. Note, however, that a significant amount
(1.3 Gt Cyr¹) of the anthropogenically emitted carbon is not clearly withdrawn
from the atmosphere by a distinct mechanism. While there are a number of
potential terrestrial processes that can partially account for this, for example
fertilization due to higher CO
`
levels and additional nitrogen deposition, the
ocean could be responsible for more carbon withdrawal than current estimates
allow. Biological uptake is the largest uncertainty here. While more terrestrial
sinks are being identified,`` uncertainty still remains as oceanic estimates also
continue to be revised upwards.¹"``
Future climatic change due to increases in greenhouse gases will further alter
the ocean’s chemistry, and so climatic effect. Land clearance in the tropics and
sub-tropics is likely to increase the dust burden in the atmosphere, and thus may
lead to enhanced iron fertilization of the present High Nitrate but Low
Chlorophyll (HNLC) regions of the ocean. The African Sahel appears to be
already undergoing anincrease in dust productiondue tolong-termdessication.`"
There are other, atmospheric, mechanisms that result inan increased atmospheric
dust load which leads to cooling, but our arguments above show that there may
be a marine biologically induced cooling as well.
A number of current coupled ocean—atmosphere climate models predict that
the overturning of the North Atlantic may decrease somewhat under a future
warmer climate."" While this is not a feature that coupled models deal with well,
its direct impact on the ocean’s sequestration of carbon would be to cause a
significant decline in the carbon that is stored in the deep water. This is a positive
feedback, as oceanic carbon uptake would decline. However, the expansion of
area populated by the productive cool water plankton, and the associated decline
`` C. D. Keeling, J. F. S. Chin and T. P. Whorf, Nature, 1996, 382, 146.
`` R. L. Langenfelds, R. J. Francey, L. P. Steele, M. Battle, R. F. Keeling and W. F. Budd, Geophys.
Res. Lett., 1999, 26, 1897.
`" M. Hulme, Geophys. Res. Lett., 1996, 23, 61.
"" A. Kattenberg, F. Giorgi, H. Grassl, G. A. Meehl, J. F. B. Mitchell, R. J. Stouffer, T. Tokioka, A. J.
Weaver and T. M. L. Wigley, in Climate Change 1995, ed. J. T. Houghton, L. G. Meira Filho, B. A.
Callander, N. Harris, A. Kattenberg and K. Maskell, Cambridge University Press, Cambridge,
1996, ch. 6, p. 285.
The Oceans and Climate
31
in the extent of sub-polar HNLC zones, may well off-set this feedback, or
certainly diminish its size."¹ The greatest impact is likely to happen if
atmospheric CO
`
levels reach more than double present levels, as then the North
Atlantic’s thermohaline circulation is likely to cease almost completely. In that
case, recent model simulations suggest that there would be much less biological
modificationof the solubility-leduptake decrease due to surface warming."` This
magnifies the positive physical feedback.
Changes in surface temperature elsewhere in the globe are likely to have a
lesser impact on carbon or DMS production. For example, the warming that a
doubling of atmospheric CO
`
could produce in the Southern Ocean has been
modelledtoleadtodecreasedcarbonuptake, but enhancedbiological productivity,
due to the temperature effect on phytoplankton growth."` This would lead to an
approximately 5% increase in DMS production and a lesser increase in CCN.
There is thus a negative feedback here, but only of minor impact.
The role of oceanic physical chemistry and biochemistry in the enhanced
greenhouse future is still uncertain. We have discussed the mechanisms
generating a number of potential feedbacks, both positive and negative in their
impact. However, newinteractions are constantly beingdiscoveredinnature, and
model representation of them is a rapidly evolving science. At present what we
can say is that this is a young field of much intellectual and practical promise.
"¹ J. L. Sarmiento and C. Lequere, Science, 1996, 274, 1346.
"` F. Joos, G. K. Plattner, T. F. Stocker, O. Marchal and A. Schmittner, Science, 1999, 284, 464.
"` A. J. Gabric, P. H. Whetton, R. Boers and G. P. Ayers, Tellus B, 1998, 50, 388.
G. R. Bigg
32
The Use of U—Th Series Radionuclides and
Transient Tracers in Oceanography: an
Overview
PETER W. SWARZENSKI, D. REIDE CORBETT,
JOSEPH M. SMOAK, AND BRENT A. McKEE
1 Introduction
As we approach the 21st century, it is becoming increasingly evident that the
oceanplays a highly complexand critical role indefining our global environment.
For example, one of the most controversial issues is the complicated interplay
between the ocean and climate change, as well as our own undeniable signature
on such cycles. Exactly how the ocean influences short- and long-term climate
change through exchange of heat, water, or CO
`
are topics that are being
addressed in such large-scale oceanographic programs as WOCE (World Ocean
Circulation Experiments) and JGOFS (Joint Global Ocean Flux Study). These
studies benefit from the tremendous advances in our understanding of the
environmental behavior of trace elements and radionuclides in seawater that
have occurred just in the last 10—20 years. However, we still do not have an
adequate grasp of the complexity of major oceanic cycles that will hopefully
enable us to predict future trends in global climate change and sustainability. In
this chapter we will focus on two of the most useful groups of chemical tracers in
oceanography: the naturally occurring uranium- andthorium-series radionuclides
and the artificially introduced transient tracers.
In the marine environment, the numerous radionuclides can be classified into
three broad categories based on their production or origin: (1) those derived from
the weathering of continental rocks, the primordial radionuclides, (2) those
formed from cosmic radiation, the cosmogenic radionuclides, and (3) those
artificially introduced into nature, the anthropogenic or transient radionuclides
and tracers. The primordial radionuclides (e.g. ```U, ```Th, and ```U) were
incorporated during the Earth’s nucleogenesis and have half-lives that are long
enough to produce many shorter-lived daughter products, including isotopes of
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
33
Table 1 Physical constants
for some primordial
radionuclides
Isotopic abundance Half-life
Radionuclide (%) yr
""K 0.0117 1.26;10"
``Rb 27.83 4.88;10¹"
¹¹`In 95.72 4.4;10¹"
¹``Te 0.905 1.3 ;10¹`
¹``La 0.092 1.06;10¹¹
¹`"Hf 0.162 2 ;10¹`
¹``Re 62.60 4.2;10¹"
```Th 100 1.41;10¹"
```U 0.72 7.04;10`
```U 99.27 4.46;10"
Table 2 Major
radionuclides produced in
the atmosphere¹
Half-life Estimated production rate
Radionuclide (yr) (atoms m` yr¹)
`H 12.33 1.6;10¹¹
¹"Be 1.6 ;10' 1.26;10¹"
`"Ar 269 4.2;10¹¹
¹"C 5730 7 ;10¹¹
`'Al 7.2 ;10` 4.8;10`
``S 0.24 4.8;10`
`'Cl 3.01;10` 5 ;10`
`¹Kr 2.13;10' —
From Draganic`
radium, radon, polonium, bismuth, andlead. Alist of the primordial radionuclides
is givenin Table 1. We will, however, concentrate on ```U, ```U, ```Th, and a few
of their associated daughter products that collectively make up the U—Th decay
series. The uranium (```U) decay series includes important isotopes of radium,
radon, polonium, and lead. The uraniumdecay series begins with ```U(half-life,
t
¹`
¬4.46 ;10" yr) and ends with stable `"'Pb, after emission of eight alpha ()
and six beta () particles. The thorium decay series begins with ```Th
(t
¹`
¬1.41 ;10¹" yr) and ends with stable `"`Pb, after emission of six alpha and
four beta particles. Two isotopes of radium and ```Th are important tracer
isotopes in the thoriumdecay chain. The actiniumdecay series begins with ```U
(t
¹`
¬7.04 ;10` yr) and ends with stable `"`Pb after emission of seven alpha
and four beta particles. The actiniumdecay series includes important isotopes of
actinium and protactinium. These primordial radionuclides, as products of
continental weathering, enter the ocean primarily by the discharge of rivers.
However, as we shall see, there are notable exceptions to this generality.`
Cosmogenic radionuclides are formed in the upper atmosphere by the
interaction of cosmic rays, primarily from the sun, with elements present in the
atmosphere (e.g. ¹"N, ¹'O, and ""Ar). Their half-lives range from months to
¹ R. M. Key, R. F. Stallard, W. S. Moore and J. L. Sarmiento, J. Geophys. Res., 1985, 90, 6995.
` I. V. Draganic, Z. D. Draganic and J. Adloff, Radiation and Radioactivity on Earth and Beyond, 2nd
edn., CRC Press, Boca Raton, FL, 1993.
P. W. Swarzenski et al.
34
millions of years (Table 2) and their variable residence times in the atmosphere
are controlled by physicochemical processes. These nuclides enter the ocean
through wet/dry precipitation and, therefore, have a reasonably predictable
geographic distribution. Cosmogenic radionuclides are generally valuable
tracers for broad-scale marine processes, such as ocean circulation and water
mass residence time calculations.
Finally, anthropogenic radionuclides and tracers are introduced into the
environment either through nuclear reactions or industrial activity. Man-made
radionuclides are usually introduced into the environment by the fission of ```U
and/or the detonation of fission and fusion devices below ground or in the
atmosphere. These radionuclides [e.g. tritium (`H) and ¹``Cs] mark a specific
time event or series of events that can show up in a particular horizon within a
water column or a geologic record. Non-radioactive transient tracers are present
in the environment as a result of a specific, quantifiable input, such as the release
of chlorofluorocarbons (CFCs) to the atmosphere. Many of these tracers are
derived from refrigerant and aerosol propellant use and are thus more heavily
produced in the northern hemisphere. Man-made radioactive and transient
tracers provide a powerful suite of tools for gaining insight into varied
environmental processes. Both classes of tracers have unique attributes that
make them invaluable as geochronological tools that embrace a wide range of
timescales and rates of oceanic processes.
2 Radioactive Decay
The abundance of a trace element is often too small to be accurately quantified
using conventional analytical methods such as ion chromatography or mass
spectrometry. It is possible, however, topreciselydetermine verylowconcentrations
of a constituent by measuring its radioactive decay properties. In order to
understand how U—Th series radionuclides can provide such low-level tracer
information, a brief review of the basic principles of radioactive decay and the
application of these radionuclides as geochronological tools is useful.`" The
U—Th decay series together consist of 36 radionuclides that are isotopes (same
atomic number, Z, different atomic mass, M) of 10 distinct elements (Figure 1).
Some of these are very short-lived(t
¹`
1 min) and are thus not directly useful as
marine tracers. It is the other radioisotopes with half-lives greater than 1 day that
are most useful and are the focus of this chapter.
Radioactive decay can be expressed as the number of atoms (N) of an unstable
parent that remain at any time (t) compared to an original number of atoms (N
"
):
N¬N
"
eHR (1)
The decay constant, , defines the probability that a particular atom will decay
withina given time ( ¬ln2/t
¹`
). The half-life (t
¹`
) describes a time interval after
which N¬N
"
/2. The observed counting rate or activity (A) is equal to N.
Another way to describe radioactive decay is in terms of the mean life () of a
` M. Gascoyne, in Uranium Series Disequilibrium: Applications to Environmental Problems, ed. M.
Ivanovich and R. S. Harmon, Clarendon Press, Oxford, 1982, pp. 32—55.
" G. Faure, Principles of Isotope Geology, 2nd edn., 1991, Wiley, New York.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
35
Figure 1 Chart showing the decay chain of the U—Th decay series isotopes. Vertical arrows define alpha () decays while beta () decays
are illustrated by diagonal arrows
P
.
W
.
S
w
a
r
z
e
n
s
k
i
e
t
a
l
.
3
6
Figure 2 Exponential
decay of a hypothetical
radionuclide (N) to a
stable daughter (D) as
measured in half-lives (t
¹`
).
Note that as t approaches
-, N approaches 0 and D
approaches N
"
(Adapted
from Faure")
radionuclide, which simply describes the average ‘life expectancy’ of a radioactive
atom ( ¬¹). Radioactive decay can thus be described either in terms of a
half-life or a mean life, yet it is often more illustrative to present decay as a
functionof the half-life. The exponential decay of anunstable parent radionuclide
(Natoms) to a stable daughter (Datoms) is illustrated in Figure 2. The number of
daughter atoms produced by such decay can be expressed as:
D¬N
"
÷N and D¬N
"
(1 ÷eHR) (2)
These are the most basic equations needed in order to utilize U—Th series
radionuclides as time-dependent tracers. In turn, they can provide an ‘apparent
age’ of a process or a geochronological framework.
An understanding of the concept of secular equilibrium is also important for
suchage determinations using U—Thseries radionuclides. Owing to the longevity
of ```U, ```Th, and ```U, the number of parent atoms remains essentially
constant for several daughter half-lives. When the rate of decay of a daughter
radionuclide is equal to that of its parent, the systemis considered to be at secular
equilibrium (i.e.
¹
N
¹
¬
`
N
`
¬
`
N
`
¬. . .). This can be readily shown by the
natural decay of ``'Ra (t
¹`
¬1622 yr) and the ingrowth of its shorter-lived
daughters (e.g. `¹`Po, `¹"Pb, `¹"Bi, and `¹"Po). However, many biogeochemical
and physical processes, such as chemical weathering, precipitation/dissolution
reactions, and inorganic/organic scavenging, can readily disrupt these decay
chains. Separation of a parent radionuclide fromits progeny owing to differences
inchemical andphysical properties is termed isotopic fractionationor radioactive
disequilibrium. When this occurs, a radionuclide that has been separated fromits
radiogenic parent decays at a rate determined solely by its decay constant. U—Th
series disequilibrium dating methods have provided oceanographers with many
powerful tools to unravel both ancient (e.g. paleo-oceanographic) and modern
(e.g. scavenging, ocean circulation) processes.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
37
3 Sources and Sinks
The geochemical cycles in the ocean are controlled, in part, by the reversible
transfer of elements between the so-called dissolved (:0.4 m) and particulate
(90.4 m) phases.` It is through this process that the reactive elements, with
oceanic residence times of less than ca. 1000 years, are rapidly removed from
solution and ultimately deposited to the seabed. Some 25 years ago, Turekian'
eloquently described this cleansing capability of the oceans in terms of the ‘. . .
great particle conspiracy’. Knowledge of the partitioning of constituents between
dissolved and particulate phases in seawater is necessary for marine geochemists
to fully understand the ocean as a complete biogeochemical system. Marine
tracers can provide a means for tracking this partitioning or cycling of
constituents in seawater.
U–Th Series Radionuclides
Primordial or U—Th series radionuclides can be discharged into the ocean
through several possible pathways, illustrated schematically in Figure 3:
(a) Rivers are an important source for many radionuclides to the sea. Such
transport can involve the full particle size spectrum(fromparticles to ‘truly’
dissolved). Relatively soluble species such as uranium are usually in a
dissolved and/or colloidal-sized (defined loosely here as 0.4m) phase in
fresh water. In contrast, very little dissolved thorium is present in river
water. All three U—Th decay chains are represented in river water, albeit to
varying degrees of fractionation or disequilibrium.
(b) Highly particle-reactive thorium isotopes settling out of the water column
to the seafloor continually produce Ra—Rn isotopes. Coastal and offshore
marine sediments therefore constantly release Ra and Rn into bottom
waters, largely by diffusion/advection processes.
(c) Ground water (either fresh or recycled marine water) may discharge into
coastal waters where hydrologic gradients or tidal forcing are favorable. It
is possible that the advection of recently deposited sediments by such
ground water can release radium isotopes and their progeny into coastal
bottom waters.
(d) Autochthonous production of daughter isotopes by the radioactive decay
of a long-lived parent can be a major oceanic source, especially in deep
basins where water residence times are long.
(e) Wet/dry depositionis a final important source for cosmogenic radionuclides
(and transient tracers, see next section) to the surface ocean.
Cosmogenic Radionuclides
Cosmogenic radionuclides are produced in the upper atmosphere by spallation
reactions of cosmic rays with atmospheric elements. The most common
` W. S. Broecker and T. H. Peng, Tracers in the Sea, 1982, Eldigo Press, New York.
' K. K. Turekian, Geochim. Cosmochim. Acta, 1977, 41, 1139.
P. W. Swarzenski et al.
38
Anoxic basin
Run-off
U, Th
Source
Rock U, Th
232
Th
210
Pb
234
Th
238
U
234
U
230
Th
235
U
231
Pa
210
Pb
Sediment.
rates
Bioturbation
O
2
H
2
S
U
222
Rn
230
Th
231
Pa excess
210
Pb
210
Po
3
H, CFCs,
7,10
Be,
137
Cs, SF
6
Sed. rates
234
U
228,226
Ra
Pore waters
U
222
Rn
4
He,
238
U,
210
Pb
Hydrothermal vents
Near-shore Deep sea
water column scavenging
mixing
sedimentation rates
resuspension
redox-regulated processes
such as removal, precipitation
organic matter production
long-term sedimentation
exchange across the sediment/
water interface
growth of Mn-nodules
circulation
source of dissolved constituents
rare mineral deposits
unusual chemotrophic cycles
wet/dry fallout
decay
Ground water
222
Rn
228,226
Ra
226
Ra
222
Rn
Figure 3 Schematic cartoon depicting oceanic inputs and cycles of select U—Th series isotopes
T
h
e
U
s
e
o
f
U

T
h
S
e
r
i
e
s
R
a
d
i
o
n
u
c
l
i
d
e
s
a
n
d
T
r
a
n
s
i
e
n
t
T
r
a
c
e
r
s
i
n
O
c
e
a
n
o
g
r
a
p
h
y
3
9
atmospherically derived nuclides used as oceanographic tracers include `H, ¹"C,
`Be, and ¹"Be. Radioisotopes of hydrogen and carbon are of particular interest
because they are major biological elements, and thus can be used as both
chemical and biological tracers. Recently, particle reactive `Be (t
¹`
¬53.3 day)
has been utilizedas a valuable coastal tracer of short-termparticle depositionand
remobilization.`

"
Anthropogenic Tracers
Anthropogenic tracers are artificially produced, transient in nature, and may be
radioactive. The chlorofluorocarbons (CFCs) or freons are organic compounds
that are produced for a range of domestic and commercial purposes. CFC-11,
CFC-12, and CFC-113 have long residence times in the atmosphere (on the order
of 50, 180, and 90 years, respectively) and are thus evenly distributed over large
geographic expanses.¹" The partial pressures of these trace gases in the
atmosphere have been reconstructed fromknowledge of the world’s manufacture
of these products. Broecker and Peng` noted that since freons have no place to go
except the atmosphere and their rate of destruction is very low, a reconstruction
of the CFC partial pressures in the atmosphere should be valid. In general, CFC
partial pressures have steadily increased since the early 1960s. This feature is
critical in making transient analogs effective oceanographic mixing and current
tracers.¹¹
Radionuclides producedduring the testing of nuclear devices (e.g. `H, ""Sr, and
¹``Cs) may reach the sea surface within a few weeks after injection, or may also
travel a great distance from the source point, depending on their atmospheric
speciation and prevailing air currents. For example, the 1986 Chernobyl reactor
accident released various short-lived isotopes of Kr, Sr, Zr, Ru, I, Cs, Ce, Pu, and
Np into the atmosphere. While as much as 70%of the Chernobyl-released ¹``Cs
measuredinGreat Britainwas dissolvedandthus easilydispersible, awater-soluble
value of only 30% was measured in Prague, even though this city is much closer
to the accident site.¹`
The largest component of artificially derived radioactivity released into the
atmosphere occurred during extensive nuclear weapons testing that began in the
late 1940s and ended in early 1960s. Thus, these nuclides offer a pulse tracer to the
oceans that can yieldinsight intopatterns andrates of water mass circulation. It is
interesting to note that the utility of several valuable atmospheric tracers (e.g.
¹``Cs) is steadilydiminishing, simply owing to a constituent’s half-life and/or lack
of a modern input. Fortunately for chemical oceanographers, the atmospheric
release of other modern or longer-lived trace constituents such as ``Kr and SF
'
appears to show great promise.
` C. R. Olsen, N. H. Cutshall and I. L. Larsen, Mar. Chem., 1982, 11, 501.
` E. A. Canuel, C. S. Martens and L. K. Benninger, Geochim. Cosmochim. Acta, 1990, 54, 237.
" C. K. Sommerfield, C. A. Nittrouer and C. R. Alexander, Cont. Shelf Res., 1999, 19, 335.
¹" F. S. Rowland, Ambio, 1990, 19, 281.
¹¹ D. W. R. Wallace, P. Beining and A. Putzka, J. Geophys. Res., 1994, 99, 7803.
¹` G. Choppin, J. O. Liljenzinand J. Rydberg, Radiochemistry and Nuclear Chemistry, 2nd edn., 1995,
Reed Elsevier, Oxford.
P. W. Swarzenski et al.
40
Role of Particles/Surfaces
For a radionuclide to be an effective oceanic tracer, various criteria that link the
tracer to a specific process or element must be met. Foremost, the environmental
behavior of the tracer must closely match that of the target constituent. Particle
affinity, or the scavenging capability of a radionuclide to an organic or inorganic
surface site (i.e. distribution coefficient, K

), is one such vital characteristic. The
half-life of a tracer is another characteristic that must also coincide well with the
timescale of interest. This section provides a brief review of the role of various
surface sites in relation to chemical scavenging and tracer applications.
The biogeochemical processes that generally describe the interaction of
elements with particles are quite well known: dissolution, flocculation, ion
exchange, sorption, (co)precipitation, electron transfer, and biological uptake.¹`
In aquatic environments these reactions often occur simultaneously and
competitively. In order to utilize marine tracers effectively, we must understand
how elements are associated with particles and sediments.
It is widely recognized that surface sites of particles are the major sequestering
agent of dissolved trace elements and compounds in the aquatic environment.
However, the kinetic and thermodynamic mechanisms involved in this
dissolved-particulate partitioning are complex, rarely static, and generally still
not well understood. Particulate material consists of various chemical components
which are a result of natural chemical alterations (e.g. adsorption, flocculation,
complexation, and redox reactions) of weathered parent material during its
transport to the sea. Micro-organisms may also be important in waters that have
lower concentrations of inorganic suspendedmaterial, owing to the active and/or
passive incorporation of elements into soft tissues and fecal material.¹"¹`
Fine-grained particles and colloids generally occur as aggregates of intermeshed
or layered iron oxide coatings, manganese oxide particles, organic coatings, or
carbonates, and are associated predominantly with clay-sized particles.¹` These
reactive surface sites are thus a source or sinkfor dissolvedelements inthe aquatic
environment, depending on the chemical reactivity of a particular constituent
and the water mass residence time.
Elemental particle phase associations can be used to infer chemical reactivity
and oceanic behavior. The most important geochemical phase components
include iron and manganese (oxy)hydroxides, organic coatings and particles,
carbonates, sulfides, phosphates, and detrital clays and silicates.¹` The influence
of these mineral and organic components on the chemical reactivity of a
radionuclide is highly variable and related to the environmental setting. Typical
master variables such as pH, temperature, dissolved oxygen, salinity, alkalinity,
total CO
`
, and the degree of weathering play a critical role in defining the
efficiency of scavenging. For example, river-dominated coastal environments are
well-known sites for colloid/particle flocculation and particle aggregation. Such
areas are thus often sinks or depositional environments for many reactive
¹` W. Stummand J. J. Morgan, Aquatic Chemistry. Chemical Equilibria and Rates in Natural Waters,
3rd edn., 1995, Wiley, New York.
¹" D. N. Edginton, S. A. Gordon, M. M. Thommes andL. R. Almodovar, Limnol. Oceanogr., 1970, 15, 954.
¹` D. P. Kharkar, J. Thompson, K. K. TurekianandW. O. Forstner, Limnol. Oceanogr., 1976, 21, 294.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
41
Table 3 Historic trends in
concentrations (nM) of
some heavy metals in the
ocean¹`
Element 1963 1975 1983 1992 1995
Fe 180 36 0.7 0.6 0.02—1
Cu 50 8 2 2 0.5—4.5
Ag 3 0.3 0.03 0.02 0.001—0.023
Au 0.02 0.02 0.06 0.00015 0.00005—0.00015
Pb 0.2 0.2 0.005 0.005 0.003—0.150
Bi 0.1 0.1 0.05 0.00015 0.00002—0.0025
From Goldberg.¹`
From Brewer.¹"
From Quinby-Hunt and Turekian.`"
From Nozaki.`¹
From Donat and Bruland.``
inorganic and organic contaminants.¹' In many estuaries, one phase often does
not have a very large binding capacity, and so a variety of phases may compete
simultaneously, depending onlocal hydrological andphysicochemical conditions.
4 Oceanic Behavior
The first comprehensive effort to determine the elemental composition in the
world’s oceans was established by the 1872—1876 British Challenger Expedition.
Since then, marine geochemists have been continuously updating and expanding
this dataset with highly specialized oceanographic vessels, new analytical
instrumentation, contamination-free sampling protocols (Table 3), and large-scale
data intercomparisons. Only within the last decade have oceanographers been
able to reliably measure and agree upon trace concentrations of many dissolved
constituents in seawater. These most recent developments significantly advanced
our understanding of the oceanic behavior of U—Th radionuclides and enabled
their use as effective tracers and geochronological tools.
Uranium
In oxygenated seawater, uranium is thermodynamically predicted to be present
in a hexavalent (·6) oxidation state, but it can also exist as the tetravalent U(IV)
if conditions are sufficiently reducing. Reduced uranium in the ·4 oxidation
state is highly insoluble or particle reactive. In contrast, U(VI) is readily soluble
due to the rapid formation of stable inorganic carbonate complexes.`` According
¹' E. R. Sholkovitz, Geochim. Cosmochim. Acta, 1976, 40, 831.
¹` Y. Nozaki, in Deep Ocean Circulation, Physical and Chemical Aspects, ed. T. Teramoto, Elsevier,
Amsterdam, 1993, pp. 83—89.
¹` E. D. Goldberg, in The Sea, ed. M. N. Hill, Wiley-Interscience, New York, 1963, vol. 2, pp. 3—20.
¹" P. G. Brewer, in Chemical Oceanography, 2nd edn., ed. J. P. Riley and G. Skirrow, Academic Press,
London, 1975, vol. 1, pp. 415—496.
`" M. S. Quinby-Hunt and K. K. Turekian, Eos, 1983, 64, 130.
`¹ Y. Nozaki, Chikyukagaku, 1992, 26, 35.
`` J. R. Donat and K. W. Bruland, in Trace Elements in the Oceans, ed. B. Salbu and E. Steinnes, CRC
Press, Boca Raton, FL, 1995, pp. 247—281.
`` D. Langmuir, Geochim. Cosmochim. Acta, 1978, 42, 547.
P. W. Swarzenski et al.
42
Figure 4 Measurements of
(A) uranium activity ratios,
UARs (``"U: ```U) and U
concentrations (B) across a
salinity gradient off the
Amazon River mouth
(1996). UARs were
determined by thermal
ionization mass
spectrometry (TIMS) at
Caltech (D. Porcelli); U
concentrations by ICPMS
to thermodynamic calculations, in oxygenated, low pH waters, a phosphate
uranium complex [UO
`
(HPO
"
)
`
] might be an important species. However, at
higher pHs such as in seawater, the ubiquitous carbonate complex [e.g.
UO
`
(CO
`
)
`
] prevails. Recently there has been some evidence which suggests that
uranium may also exist as a peroxide complex in seawater under favorable
conditions. Such a complex could potentially participate in photo-oxida-
tion/reduction reactions, as has been shown for Mn(IV) and Fe(III).
Owing to the stability of the uranyl carbonate complex, uraniumis universally
present in seawater at an average concentration of ca. 3.2 g L¹ with a
daughter/parent activity ratio (``"U: ```U) of 1.14.`"`` In particulate matter and
bottomsediments that are roughly 1 ;10' years old, the ratio should approach
unity (secular equilibrium). The principal source of dissolved uranium to the
ocean is from physicochemical weathering on the continents and subsequent
transport by rivers. Potentially significant oceanic Usinks include anoxic basins,
organic richsediments, phosphorites and oceanic basalts, metalliferous sediments,
carbonate sediments, and saltwater marshes.`'

``
Removal of uranium from solution can take place by various mechanisms.
Calcareous and siliceous organisms can efficiently remove uranium from
`" D. L. Thurber, J. Geophy. Res., 1962, 67, 4518.
`` M. Baskaran, P. H. Santschi, L. Guo, T. S. Bianchi and C. Lambert, Cont. Shelf Res., 1996, 16, 353.
`' J. D. MacDougall, Earth Planet. Sci. Lett., 1977, 35, 65.
`` F. Aumento, Earth Planet. Sci. Lett., 1971, 11, 90.
`` T. M. Church, M. M. Sarin, M. Q. Fleisher and T. G. Ferdelman, Geochim. Cosmochim. Acta, 1996,
60, 3879.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
43
solution. Brewer`" reported a correlation between biogenic material from
sediment traps and uranium content, suggesting either active uptake by
organisms or passive incorporation. However, bioaccumulation of uranium
generally does not appear to be a dominant removal process in the open ocean
(paucity of surface sites). Particulate uranium can be also desorbed from oxide
surfaces by an increase in alkalinity or pH.`` Desorption of uranium from
suspended particles during estuarine mixing is thus geochemically feasible, and
has in fact been observed on the Amazon shelf`"`¹ (Figure 4). Langmuir`` also
reported a strong association between iron hydroxides and adsorbed uranium,
leading to speculation that this phase may be an important sink for U.````
Marine sediments can be both sources and sinks for U. Uranium has
repeatedlybeenshowntobe scavengedfromsolutionintoreducing sediments.`"

`"
This removal may also include diffusion of soluble U(VI) from seawater into the
sediment via pore water. Uranium—organic matter complexes are also prevalent
in the marine environment. Organically bound uraniumwas found to make up to
20%of the dissolved Uconcentration in the open ocean."" Uraniummay also be
enriched in estuarine colloids`"`¹ and in suspended organic matter within the
surface ocean.``"¹ Scott"` and Maeda and Windom"` have suggested the
possibility that humic acids can efficiently scavenge uranium in low salinity
regions of some estuaries. Finally, sedimentary organic matter can also efficiently
complex or adsorb uranium and other radionuclides.¹`""

"'
Global uranium flux calculations have typically been based on the following
two assumptions: (a) riverine-end member concentrations of dissolved uranium
are relatively constant, and (b) no significant input or removal of uraniumoccurs
in coastal environments. Other sources of uranium to the ocean may include:
mantle emanations, diffusion through pore waters of deep-sea sediments,
leaching of river-borne sediments by seawater,"` and remobilization through
reduction of a Fe—Mn carrier phase.`¹ However, there is still considerable debate
`" A. C. Sigleo and G. R. Helz, Geochim. Cosmochim. Acta, 1981, 45, 2501.
`" B. A. McKee, D. M. DeMaster and C. K. Nittrouer, Geochim. Cosmochim. Acta, 1987, 51, 2779.
`¹ P. W. Swarzenski, B. A. McKee and J. G. Booth, Geochim. Cosmochim. Acta, 1995, 59, 7.
`` R. T. Lowson, S. A. Short, B. G. Davey and D. J. Gray, Geochim. Cosmochim. Acta, 1986, 50, 1697.
`` C. Lienert, S. A. Short and H. R. von Gunten, Geochim. Cosmochim. Acta, 1994, 58, 5455.
`" C. E. Barnes and J. K. Cochran, Earth Planet. Sci. Lett., 1990, 97, 94.
`` C. E. Barnes and J. K. Cochran, Geochim. Cosmochim. Acta, 1993, 57, 555.
`' A. M. Giblin, B. D. Batts and D. J. Swaine, Geochim. Cosmochim. Acta, 1981, 45, 699.
`` J. K. Cochran, A. E. Carey, E. R. Sholkovitz and L. D. Surprenant, Geochim. Cosmochim. Acta,
1986, 50, 663.
`` R. F. Anderson, Geochim. Cosmochim. Acta, 1982, 46, 1293.
`" R. F. Anderson, Uranium, 1987, 3, 145.
"" K. Hirose and Y. Sugimura, J. Radiochem. Nucl. Chem. Art., 1991, 149, 83.
"¹ D. K. Mann and G. T. F. Wong, Mar. Chem., 1993, 42, 25.
"` M. Scott, in Uranium Series Disequilibria: Applications to Environmental Problems, ed. M.
Ivanovich and R. S. Harmon, Clarendon Press, Oxford, 1982, pp. 181—201.
"` M. Maeda and H. L. Windom, Mar. Chem., 1982, 11, 427.
"" G. N. Baturin and A. V. Kochenov, Geokhimya, 1973, 10, 1529.
"` Y. Kolodny and I. R. Kaplan, in Proceedings of the Symposium on Hydrogeochemistry,
Biogeochemistry and Hydrochemistry, Clark, Washington, 1973, pp. 418—442.
"' T. Mo, A. D. Suttle and W. M. Sackett, Geochim. Cosmochim. Acta, 1973, 37, 35.
"` S. G. Bhat and S. Krishnaswami, Proc. Indian Acad. Sci., 1969, 70, 1.
P. W. Swarzenski et al.
44
regarding the overall mass balance of uranium in the oceans.`"``"` Present
estimates for the flux of uraniumto the sea""

`¹ include large (factor of 2) margins
of uncertainty. These uncertainties result primarily froma poor understandingof:
(1) the variability in riverine-end member concentrations of uranium; (2) the
behavior of uraniumduring river/ocean mixing; and (3) the extent to which shelf
sediments may influence the net flux of uranium from coastal areas.
Because of these inherent uncertainties, estimates of oceanic uraniumresidence
times are still somewhat vague. Pioneering work on dissolved uranium in world
rivers suggested that the residence time of uranium in the oceans must be on the
order of 4 million years.`` As a consequence of having such long oceanic
residence times, uranium has been regarded as a relatively non-reactive
(conservative) element inseawater. Subsequent studies`"`¹```" have broadened
the data base for uranium concentrations in marine environments and current
estimates of seawater uranium residence times range from 200 000 to 400 000
years. These residence time calculations are constrained by the assumption that
the global riverine flux of dissolved uraniumis a reasonably accurate estimate of
total uranium input to the oceans.
If uranium is internally cycled in coastal environments or if the riverine
delivery of Ushows some variability, residence time estimates (regardless of their
precision) cannot be sensitive indicators of oceanic uraniumreactivity. Based on
very precise measurements of dissolved uraniumin the open ocean, Chen et al.``
concludedthat uraniummay be somewhat more reactive in marine environments
than previously inferred. Furthermore, recent studies in high-energy coastal
environments`"`¹`'`` indicate that uranium may be actively cycled and
repartitioned (non-conservative) from one phase to the next.
Thorium
Like many chemical species, thoriumexhibits a great affinity for particle surfaces
in the marine environment. These other species and thorium are referred to as
particle reactive because they are readily removed fromthe dissolved phase onto
the particulate phase. Thorium exists as a hydrolyzed species in seawater,
Th(OH)
L
'"L'>, andis thus extremelyparticle reactive. Because of its particle-reactive
nature, thorium has been used to examine scavenging as an analog for other
"` G. P. Klinkhammer and M. R. Palmer, Geochim. Cosmochim. Acta, 1991, 55, 1799.
"" J. K. Cochran, in Uranium Series Disequilibrium: Applications to Environmental Problems, ed. M.
Ivanovich and R. S. Harmon, Clarendon Press, Oxford, 1982, pp. 384—430.
`" W. M. Sackett, T. Mo, R. F. Spalding and M. E. Exner, in Symposium on the Interaction of
Radioactive Contaminants with the Constituents of the Marine Environment, Seattle, WA/IAEA,
Vienna, 1973, pp. 757—769.
`¹ A. Mangini, C. Sonntag, G. Berstch and E. Muller, Nature, 1979, 278, 337.
`` W. S. Moore, Earth Planet. Sci. Lett., 1967, 2, 231.
`` T. L. Ku, K. G. Knauss and G. G. Mathieu, Deep-Sea Res., 1977, 24, 1005.
`" K. K. Turekian and L. H. Chan, in Activation Analysis in Geochemistry and Cosmochemistry, ed.
A. O. Branfelt and E. Steinnes, Universitetsforlaget, Oslo, 1971, pp. 311—320.
`` J. H. Chen, R. L. Edwards and G. L. Wasserburg, Earth Planet. Sci. Lett., 1986, 80, 241.
`' J. Carroll and W. S. Moore, Geochim. Cosmochim. Acta, 1994, 58, 4987.
`` P. W. Swarzenski and B. A. McKee, Estuaries, 1998, 221, 379.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
45
particle-reactive species.``` Scavenging has a major influence on the marine
chemistry of many elements, including numerous metals and pollutants.
Recently, thorium isotopes have been examined as proxies of biogenic flux.`"


Once the particle-reactive species have been scavenged, subsequent packaging
and/or aggregation can result in the flux of particles and particle-reactive species
fromthe water column. Thoriumprovides a unique waytostudy the environmental
pathways and the biogeochemical processes that affect particle-reactive species.
The four useful thorium isotopes are ```Th (t
¹`
¬1.4;10¹" yr), ``"Th
(t
¹`
¬7.5 ;10" yr), ```Th (t
¹`
¬1.9 yr), and ``"Th (t
¹`
¬24.1 day).
Thorium-232 is the only non-radiogenic thorium isotope of the U/Th decay
series. Thorium-232 enters the ocean by continental weathering and is mostly in
the particulate form. Early measurements of ```Th were by alpha-spectrometry
and required large volume samples (ca. 1000 L). Not only did this make sample
collection difficult, but the signal-to-noise ratio was often low and uncertain.
Withthe development of a neutronactivationanalysis'` anda mass spectrometry
method``'` the quality of the data greatly improved, and the required volume
for mass spectrometry was reduced to less than a liter. Surface ocean waters
typically have elevated concentrations of dissolvedand particulate ```Th.¹```'`
Surface water enrichment is the result of aeolian and fluvial inputs, which are
thought to be the most important sources of ```Th to the ocean. Thorium-232
has been proposed as a link between the radiogenic thorium isotopes and trace
metals and anthropogenic pollutants.'` While the pathways are very different for
the radiogenic thorium isotopes, ```Th is delivered to the ocean in a fashion
similar to many pollutants and trace metals. For example, Guo et al.'" found
```Th distributions in the Gulf of Mexico and off Cape Hatteras in the North
Atlantic Ocean agreed well with the general distribution pattern of aluminum.
Thorium-230is suppliedtoseawater fromin situ decay of its parent, ``"U. Both
dissolved and particulate ``"Th activities increase with depth'`'' in water
columnprofiles. This increase with depthis the result of progressively more ``"Th
being scavenged onto particles as they sink through the water column. The
increase in the dissolved and particulate activity with depth indicates the
scavenging of ``"Th can be a reversible reaction. Decay is not a factor in the
``"Th water column distribution owing to its long half-life. Recently ``"Th
measurements have been coupled with ``¹Pa to examine particle fluxes.'`'`
Protactinium-231 and ``"Th are supplied by ```U and ``"U, respectively.
Protactinium has a weaker affinity for particles than ``"Th and is therefore
`` P. H. Santschi, Y.-H. Li and J. J. Bell, Earth Planet. Sci. Lett., 1979, 45, 201.
`" R. W. Eppley, in Productivity of the Ocean: Present and Past, ed. W. H. Berger, V. S. Smetacek and
G. Wefer, Wiley, New York, 1989, pp. 85—97.
'" K. O. Buesseler, M. P. Bacon, J. K. Cochran and H. D. Livingston, Deep-Sea Res., 1992, 39, 1115.
'¹ J. M. Smoak, W. S. Moore, R. C. Thunell and T. J. Shaw, Mar. Chem., 1999, 65, 177.
'` C.-A. Huh and M. P. Bacon, Anal. Chem., 1987, 57, 2138.
'` C.-A. Huh and T. M. Beasley, Earth Planet. Sci. Lett., 1987, 85, 1.
'" L. M. Guo, M. Baskaran, A. Zindler and P. H. Santschi, Earth Planet. Sci. Lett., 1995, 133, 117.
'` P. G. Brewer, Y. Nozaki, D. W. Spencer and A. P. Fleer, J. Mar. Res., 1980, 38, 703.
'' M. P. Bacon and R. F. Anderson, J. Geophys. Res., 1982, 87, 2045.
'` H. N. Edmonds, S. B. Moran, J. A. Hoff, J. N. Smith and R. L. Edwards, Science, 1998, 280, 405.
'` N. R. Kumar, R. Gwiazda, R. F. Anderson and P. N. Froelich, Nature, 1993, 362, 45.
P. W. Swarzenski et al.
46
susceptible tolateral transport. Thorium-230flux fromthe water columnroughly
balances its local rate of production. However, ``¹Pa fluxes have been observed
to increase with an increase in particle flux.'" In areas of high particulate flux,
``¹Pa: ``"Th ratios can exceed the production ratio. This technique has been
exploited in sediment cores to examine particle flux variability through time and
hence productivity.'`
The tworemaining thoriumisotopes have muchshorter half-lives. Thorium-228
has a half life of 1.91 years and is produced from ```Ra, with ```Ac as a very
short-lived intermediate daughter. The ```Th: ```Ra ratio can be used to
calculate residence times with respect to uptake on particles.` Thorium-228 is an
excellent tracer for intermediate timescale processes, while ``"Th is an ideal
tracer of short timescale processes because the half-life is 24.1 days and the only
source is the decay of ```U in seawater. Thorium-234 also has been used to
examine residence times with respect to uptake on particles and removal of
particles from the surface ocean.`" Thorium-234 was first measured in the ocean
by Bhat and Krishnaswami."` Thorium-234 generally is deficient with respect to
its parent ```U in surface waters as a result of the scavenging by particles and
particle flux. Below approximately 200 m in the water column, ``"Th and ```U
are typically in secular equilibrium and the uptake of ``"Th is balanced by the
loss from decay. In the open ocean, biogenic particles dominate the particle flux
and therefore are the scavengers of thorium. In a series of papers,`¹

`` the link
between biogenic particles and removal of ``"Th was established. They showed
that ``"Th scavenging rates varied as a function of new biomass production.
Basedon this work it was proposedthat the flux of ``"Th out of the surface ocean
could be used to estimate new biomass production. More recently, Buesseler et
al.`"`` pioneered this work by measuring the depletion of ``"Th in the water
column to predict the flux of particulate organic carbon (POC). Buesseler’s
approach was to measure the ``"Th/POC ratio of sinking particles, then simply
multiply the export rate by the ratio. This approach has been widely used during
JGOFS.`'``
Radium
The historic discovery of radium in 1898 by Marie Curie initiated a remarkable
use of this isotope as an early oceanic tracer. Less than10 years after its discovery,
'" Y. Lao, R. F. Anderson, W. S. Broecker, H. J. Hofmann and W. Wolfli, Geochim. Cosmochim. Acta,
1993, 57, 205.
`" M. Baskaran, P. H. Santschi, G. Benoit and B. D. Honeyman, Geochim. Cosmochim. Acta, 1992, 56,
3375.
`¹ K. W. Bruland and K. H. Coale, in Dynamic Processes in the Chemistry of the Upper Ocean, ed. J. D.
Burton, P. G. Brewer and R. Chesselet, Plenum Press, New York, 1986, pp. 159—172.
`` K. H. Coale and K. W. Bruland, Limnol. Oceanogr., 1987, 32, 189.
`` K. H. Coale and K. W. Bruland, Limnol. Oceanogr., 1985, 30, 22.
`" K. O. Buesseler, L. Ball, J. Andrews, C. Benitez-Nelson, R. Belastock, F. Chai and Y. Chao,
Deep-Sea Res., 1998, 45, 2461.
`` K. O. Buesseler, Global Biogeochem. Cycles, 1998, 12, 297.
`' J. W. Murray, J. Young, J. Newton, J. Dunne, T. ChapinandB. Paul, Deep-SeaRes., 1996, 43, 1095.
`` M. M. Rutgers van der Loeff, J. Friedrich and U. V. Bathmann, Deep-Sea Res., 1997, 44, 457.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
47
Joly`` observedelevated ``'Ra activities in deep-sea sediments that he attributed
to water column scavenging and removal processes. This hypothesis was later
challenged with the first seawater ``"Th measurements (parent of ``'Ra), and
these newresults confirmedthat radiumwas instead activelymigrating across the
marine sediment—water interface. This seabed source stimulated much activity to
use radium as a tracer for ocean circulation. Unfortunately, the utility of Ra as a
deep ocean circulation tracer never came to full fruition as biological cycling has
been repeatedly shown to have a strong and unpredictable effect on the vertical
distribution of this isotope.
In the U—Th decay series there are four radium isotopes, ```Ra (t
¹`
¬11.4
day), ``"Ra (t
¹`
¬3.6 day), ```Ra (t
¹`
¬5.7 yr), and ``'Ra (t
¹`
¬1622 yr), with
half-lives that coincide well with the timescales of many coastal and oceanic
processes.`" Two important geochemical characteristics make radium ideal as a
marine tracer: (1) having highly particle-reactive thoriumas its direct radiogenic
parent which ties it directly to bottom sediments, and (2) exhibiting vastly
different environmental behavior in fresh water and saltwater systems. Both of
these criteria control the production and input of radium in marine systems. In
coastal waters, thorium is efficiently scavenged by particles/colloids and rapidly
removed to the seabed. In fresh water, radium is bound strongly onto particle
surfaces; however, as the ionic strength of a water mass increases during mixing
into seawater, desorption reactions and the general absence of particles in the
open ocean maintain radiumentirely in a dissolved phase."" Estuarine sediments
thus provide a continuous source for radium isotopes to coastal waters, and the
productionrate is defineddirectly by their individual isotopic decayconstants.`"`¹
Source functions for radium in an estuary may thus include the following
components: (1) riverine, (2) oceanic, (3) estuarine sediments, and (4) ground-
water.``

`" The relative significance of each of these source terms is definedby the
particular environmental constraints of an estuary.
Ground-water discharge, which can consist of recycled marine water or fresh
water, may enhance the diffusive/advective flux of dissolved radium from the
seabed to a coastal water column wherever the hydraulic gradients and sediment
transmissivities are favorable.`" In coastal systems where ground water is
discharged to coastal waters either continuously or ephemerally owing to tidal
forcing, a localized disequilibriumbetween ```Ra, ```Th, and ``"Ra can develop.
This disequilibrium occurs because dissolved radium will be rapidly advected
into the water column while thorium remains attached to bottom sediments. In
surficial sediments that are flushed by the upward movement of groundwater,
``"Ra: ```Ra activity ratios can become quite large as a result of this process and
can be used to model the flux across the sediment/water interface. Below this
diageneticallyactive surface sediment layer, one can expect secular equilibriumto
`` J. Joly, Philos. Mag., 1908, 15, 385.
`" P. W. Swarzenski, U.S. Geol. Surv. Circ., 1998, FS-065-99.
`" W. S. Moore and J. F. Todd, J. Geophys. Res., 1993, 98, 2233.
`¹ I. A. Webster, G. J. Hancock and A. S. Murray, Geochim. Cosmochim. Acta, 1995, 59, 2469.
`` M. S. Bollinger and W. S. Moore, Geochim. Cosmochim. Acta, 1993, 57, 2203.
`` Rama and W. S. Moore, Geochim. Cosmochim. Acta, 1996, 60, 4645.
`" W. S. Moore, Nature, 1996, 380, 612.
P. W. Swarzenski et al.
48
develop from ```Th down to ``"Ra. Such radioactive equilibrium in the ```Th
decay series requires approximately 20 years of sediment storage. Resuspension,
bioturbation, chemical dissolution as well as groundwater flow will allow these
two sediment layers to interact. Moore and colleagues have used such
disequilibria to derive a groundwater flux rate in a South Carolina salt
marsh.```` Finally, short-lived ``"Ra: ```Ra activity ratios may also be used to
derive apparent estuarine water mass ages; higher ratios generally imply younger
waters owing to the more rapid decay of radium.
Radon-222
Inert ```Rn is a unique marine tracer in that it should not interact in any
biogeochemical cycles. It has been used extensively for determining exchange
rates across both air—sea and sediment—water interfaces. In addition, ```Rn has
also been used as a tracer for evaluating coefficients of isopycnal and diapycnal
mixing in the deep sea``` and, more recently, for tracing submarine groundwater
discharge into the coastal zone.`'`` Radon is produced through the direct alpha
decay of ``'Ra and has a relatively short half-life of 3.85 days. With such a short
half-life, ```Rn is typically found in equilibrium with its parent away from the
air—water and sediment—water interfaces. However, near the air—water and
sediment—water interfaces, disequilibriaof radonwithrespect toits parent readily
prevail.
There are two main sources of ```Rn to the ocean: (1) the decay of
sediment-bound ``'Ra and (2) decay of dissolved ``'Ra in a water column.
Radon can enter the sediment porewater through alpha recoil during decay
events. Since radon is chemically inert, it readily diffuses from bottomsediments
into overlying waters. The diffusion of radon fromsediments to the water column
gives rise to the disequilibrium (excess ```Rn) observed in near-bottom waters.
Radon is also continuously being produced in the water column through the
decay of dissolved or particulate ``'Ra.
Loss of radon in the ocean occurs typically through radioactive decay
(producing four short-lived daughters before decaying to `¹"Pb) or loss to the
atmosphere at the air—sea interface. Loss of radon owing to turbulence or
diffusion at the air—sea interface leads to a depletion of radon with respect to
``'Ra, allowing for studies on gas exchange at this interface.`
Lead-210 and Polonium-210
The majority of published `¹"Pb reports address the utility of `¹"Pb as a
geochronological tool rather than as an element that is involved in complex
biogeochemical cycles. Nonetheless, some of these studies do provide insight into
the geochemical behavior of `¹"Pb and`¹"Po. Nearly all of the lead in the world’s
surface oceans is believedtobe of anthropogenic origin—derivedfromcombustion
`` J. L. Sarmiento and C. G. Rooth, J. Geophys. Res., 1980, 85, 1515.
`' J. Cable, W. Burnett, J. Chanton and G. Weatherly, Earth Planet. Sci. Lett., 1996, 144, 591.
`` D. R. Corbett, J. Chanton, B. Burnett, K. Dillon, andC. Rutkowski, Limnol. Oceanogr., 1999, 44, 1045.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
49
of leaded gasoline.`` Even the most remote areas of the world—the polar
caps—showa very clear effect of leadpollution. Recent measurements of polar ice
cores show that man’s activities have caused a 300-fold increase in Pb since the
beginning of the industrial revolution.`" Lead-210 and its indirect daughter
`¹"Po are both important radionuclides used in geochemical research. In broad
terms, the marine cycle of `¹"Pb is characterized by supply or production of
dissolved`¹"Pb which is then scavenged by solid surfaces and thus removed from
the water column. Lead-210 is delivered to the water column by three sources: (1)
atmospheric fallout from the decay of ```Rn, (2) from the in situ decay of ``'Ra
and ```Rn in the water column, and (3) from direct leaching of rocks and soils
during weathering.` Polonium-210 is a decay product of `¹"Pb and is produced
mainly by this source in the water column, but this isotope may also have an
atmospheric source term within surface waters. Lead-210 has been used
extensively as a tracer for particle-reactive elements as well as for geochronological
studies of lake, estuarine, and coastal sediments.
Lead-210 is rapidly removed by various processes in the water column and
deposited onto the seafloor during particle deposition and accumulation. The
mechanisms for removal may be similar to thorium scavenging, as studies in the
NewYork Bight indicate similar removal times for both `¹"Pb and ```Th."" Soil
profiles have shownorganic matter tobe effective inbinding `¹"Pb."¹ River water
is extremely depleted in dissolved `¹"Pb and ``"```Th under normal conditions.
In areas where pH may be low (e.g. where acid mines drain into water), elevated
`¹"Pb concentrations have been reported."` As this acid mine water is diluted
with natural waters, the sequential precipitation of iron oxides followed by
manganese oxides appears to completely scavenge `¹"Pb and other metals onto
suspended particles. In the ocean, sinking particles are adsorption sites for `¹"Pb
and, even here, iron and manganese oxides are important removal phases."`"" In
anoxic environments, `¹"Pb may be readily removed as a lead sulfide precipitate,
causing this mineral component to be of importance in sulfide-rich sediments.
Involvement in biological cycles may affect the distribution of both `¹"Pb and
`¹"Po. Santschi et al.`` noticed large seasonal variations of `¹"Pb and `¹"Po in
Narragansett Bay. This seasonal trendwas ascribedtotwofactors: remobilization
out of the sediments during the spring and early summer, or formation of organic
complexes. Polonium-210 appears to be somewhat more reactive than `¹"Pb in
seawater."` In a recent summary paper, Nozaki`¹ suggested that the removal of
``"Th, `¹"Pb, and `¹"Po from marine waters may be accelerated by biological
`` B. K. Schaule and C. C. Patterson, in Trace Metals in Sea Water, ed. C. S. Wong, E. Boyle, K. W.
Bruland, J. D. Burton and E. D. Goldberg, Plenum Press, New York, 1983, pp. 487—503.
`" A. Ng and C. C. Patterson, Geochim. Cosmochim. Acta, 1981, 45, 2109.
"" Y.-H. Li, P. H. Santschi, A. Kaufman, L. K. Benninger and H. W. Feely, Earth Planet. Sci. Lett.,
1981, 55, 217.
"¹ L. K. Benninger, D. M. Lewis andK. K. Turekian, inMarine Chemistryin the Coastal Environment,
ed. T. M. Church, ACS SymposiumSeries, no. 18, American Chemical Society, Washington, 1975,
pp. 202—210.
"` D. M. Lewis, Geochim. Cosmochim. Acta, 1977, 41, 1557.
"` L. S. Balistrieri, J. W. Murray and P. Paul, Geochim. Cosmochim. Acta, 1995, 59, 4845.
"" G. Benoit and H. F. Hemond, Geochim. Cosmochim. Acta, 1987, 51, 1445.
"` D. Kadko, J.Geophys. Res., 1993, 98, 857.
P. W. Swarzenski et al.
50
activity. Preferential biological uptake of `¹"Po relative to `¹"Pb in some
sediments may cause local disequilibria, which can affect the interpretation of
`¹"Pb-derived geochronologies."" Hodge et al."' demonstrated that Po, U, and
Pu have different uptake kinetics onto solid phases. They exposed different solid
phases to seawater to determine whether Po, U, or Pu could be removed by
inorganic material. Their results suggest that organic surface coatings may collect
particles, with their associated elements, at differing rates. Such variable uptake
rates led the authors to infer that particulate Pu, Po, and U may be associated
with different particulate phases.
CFCs
Since the early 1980s, chlorofluorocarbons (CFCs) have been used to trace
oceanic circulation and mixing processes. These compounds are ideally suited for
this purpose as they have no natural sources and the anthropogenic sources are
well understood. Some CFCs can be photochemically destroyed by UV light in
the stratosphere, but they are very stable in the troposphere and in the ocean.`"
CFCs have been increasing in the atmosphere since the onset of their production
and are well distributed in both hemispheres. This is due to their rather long
atmospheric lifetimes (970 years) and the rather short time of atmospheric
exchange between hemispheres (ca. 2 years). This worldwide distribution makes
these trace gases ideal tracers for oceanic studies at high latitudes, where
significant quantities of water are down-welled to form intermediate and deep
water masses. Unlike many other anthropogenic tracers, CFCs can be measured
at sea using a gas chromatograph (GC) equipped with an electron capture
detector (ECD) and a purge and trap system, providing results soon after sample
collection.
Two types of CFCs, CFC-11 (CCl
`
F) and CFC-12 (CCl
`
F
`
), have been
producedsince 1940. Their atmospheric histories are knownsince 1981 (Figure 5)
and have been reconstructedusing estimates of productionand releases obtained
from the Chemical Manufacturers Association (1983). Prior to 1940, the
atmosphere and ocean were CFC free. Upon atmospheric release, gas exchange
began delivering CFCs to the ocean. Therefore, recently ventilated waters
contain relatively high concentrations of CFCs. These CFC concentrations can
be used to deduce when a water mass was last in contact with the atmosphere.
Owing to mixing processes, CFC-enriched waters can become diluted with older,
CFC-free waters. For this reason, the CFC-11: CFC-12 ratio is used to estimate
the age of a givenwater mass since this ratiois unaffectedby dilution(Figure 6). In
some situations the CFC-enriched waters may mix with other waters containing
CFCs, with the result that the ratio will reflect an intermediate age. This age is
usually biased towards the younger component, which carries higher CFC
concentrations.¹¹
The atmospheric ratio of CFC-11: CFC-12 increased until 1975, when
regulation of the USAproduction of these compounds led to a reduction in their
rate of increase. Since this time, the ratiohas remainedfairly constant. This makes
"' V. F. Hodge, M. Koide and E. D. Goldberg, Nature, 1978, 277, 206.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
51
Figure 5 Atmospheric
concentrations for CFC-11,
CFC-12, CFC-113, SF
'
(pptv) and ``Kr (dpm
cm`). CFC data courtesy
of E. Busenberg and L. N.
Plummer (US Geological
Survey); atmospheric ``Kr
activities complied by
W. M. Smethie (LDEO)
(dpm¬disintegrations per
minute)
Figure 6 Atmospheric
ratios of CFC-11: CFC-12
and CFC-113: CFC-12
it difficult to distinguish between water masses that have formed since this time.
However, an additional CFC, CFC-113 (CCl
`
FCClF
`
), entered production
during the 1960s. This trace gas is used as a solvent in the electronics industry."`
Introduction of this gas into the atmosphere has led to a steadily increasing
CFC-113: CFC-11 ratio. This ratio provides a much finer resolution of a water
mass’s age for waters ventilated since 1977. In fact, it is possible to estimate an
apparent age with an error of less than a few years.
"` D. P. Wisegarver and R. H. Gammon, Geophys. Res. Lett., 1988, 15, 188.
P. W. Swarzenski et al.
52
Many studies have shown the usefulness of CFCs as tracers of the formation
and circulation of recently ventilated oceanic waters.¹¹"""`

¹"¹ These studies
have shown that water along the equator is relatively young (:15 years) at
shallow isopycnal surfaces of North Pacific intermediate water and becomes
older with depth and density (ca. 40 years). Intermediate waters are formed in
both hemispheres and have been studied with traditional physical tracers (i.e.
salinity and temperature) for many years. These studies show that these water
masses can be traced over time and space using CFCs. This newinformation has
generally supported previous studies of ocean circulation patterns but can
resolve them better through time. However, most studies have utilized CFC-11
and CF-12, underestimating the utility of CFC-13. Perhaps future work will
employ all three trace gases as transient tracers, potentially providing even more
precise information.
"` M. J. Warner and R. F. Weiss, Deep-Sea Res., 1992, 39, 2053.
"" M. J. Warner, J. L. Bullister, D. P. Wisegarver, R. H. Gammon and R. F. Weiss, J. Geophys. Res.,
1996, 99, 20 525.
¹"" Y. W. Watanabe, K. Harada and K. Ishikawa, J. Geophys. Res., 1994, 99, 25 195.
¹"¹ M. P. Meredith, K. A. VanScoy, A. J. WatsonandR. A. Locarinini, Geophys. Res. Lett., 1996, 23, 2943.
The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography
53
Pharmaceuticals from the Sea
RAYMOND J. ANDERSEN AND DAVID E. WILLIAMS
1 Introduction
There are a large number of life-threatening or chronically debilitating human
diseases such as solid tumor cancers, AIDS, antibiotic-resistant microbial
infections, asthma, and diabetes that urgently require improved medical
treatments. Drug therapy represents one well-established and still attractive
approach to treating these serious diseases. In order for the chemotherapeutic
approach to be more effective, there is a pressing need to discover and develop
new drugs that act against cancer cells, viruses, microbial pathogens, and other
molecular disease targets by novel biochemical mechanisms and have diminished
side effects. Secondary metabolites produced by the plants, animals, and
microorganisms living in the world’s oceans represent a vast and relatively
unexplored resource of structurally diverse low molecular weight organic
molecules that are ideal raw materials for the development of new drugs.
Exploitation of this extremely valuable molecular resource is a complex and
lengthy process that is shapedbymanyscientific, legal, business, andenvironmental
issues. The goal of this chapter is to highlight the tremendous opportunities and
the considerable challenges involvedin developingnewpharmaceuticals fromthe
sea.
The majority of human drugs (see Figure 1) are relatively lowmolecular weight
organic molecules with masses in the range of ca. 200 [aspirin (1): a pain killer] to
1500 [vancomycin (2): an antibiotic] Daltons.¹ Most of the drugs currently used
in the clinic come from two fundamentally different origins. One large group are
secondary metabolites, commonly called ‘natural products’, isolated from
terrestrial plants or cultures of soil microorganisms.` Two important examples
are paclitaxel (3), a clinically important anticancer drug that was originally
isolated from the Pacific Yew tree Taxus bevifolia, and penicillin G (4), an
antibiotic produced in culture by the fungus Penicillium notatum. In some
¹ S. Aldridge, Magic Molecules, HowDrugs Work, Cambridge University Press, Cambridge, 1998, ch.
2, p. 23.
` S. Grabley and R. Thiericke (ed.), Drug Discovery from Nature, Springer, Berlin, 1999.
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
55
Figure 1 Drugs derived
from natural products
instances, the plant or microbial metabolite is subjectedto synthetic modification
to give a semisynthetic derivative or else it serves as a model pharmacophore to
guide the synthesis of structural analogs that have enhanced drug properties.
Docetaxel (5) is a semisynthetic analog of paclitaxel that has also been approved
for clinical use as an anticancer drug and topotecan (6), an anticancer drug
currently in clinical trials, is a synthetic analog of the plant metabolite
camptothecin (7) isolated from the stem wood of Camptotheca acuminata, which
R. J. Andersen and D. E. Williams
56
itself has anticancer properties. The second group of drug molecules, which are
totally synthetic in origin, are not based on any naturally occurring template.
Prozac [fluoxetine (8)], a widely used antidepressant, is classic example of a
totally synthetic drug.
Historically, drug discovery programs have relied on in vitro intact tissue or
cell-based assays to screen libraries of synthetic compounds or natural product
extracts for pharmaceutically relevant properties. This screening approach
identifies compounds that elicit a desired cellular response such as antibacterial
or cytotoxic activity regardless of the mechanism of action. Cell-based or intact
tissue assays are relatively expensive and labor intensive, characteristics that
ultimately limit the total number of assays performed and the rate at which they
are executed in any drug screening program. An excellent example of a cell-based
screen is the US National Cancer Institute’s In Vitro Cell Line Screening Project
(IVCLSP) that was operational in the early 1990s.` This screen, which used 60
different human tumor cell lines, was designed to identify compounds that had
potential anticancer activity by looking for selective growth inhibition or cell
killing of particular cell lines. IVCLSP, which at its peak screened up to 20 000
pure compounds or natural product extracts per year, illustrates the typical scale
for traditional cell-based screens.
Research in molecular biology during the last two decades has provided
enormous advances in our understanding of many diseases at the gene or
molecular level. For example, there are now many well-documented genetic
differences between cancer cells and normal cells." The most commonly altered
gene products inhumansolidtumors include ErbB2/HER(amembrane-associated
tyrosine kinase), RAS (a GTP-binding protein), and proteins that affect
transcription, such as Myc, Rb, or p53. These and other genetically validated
protein targets have provided exciting newopportunities for developing selective
mechanism-based inhibitors of specific biochemical processes that are essential
to the malignant phenotype of cancer cells. They offer the hope of developing
anticancer drugs with low toxicity and, therefore, much improved therapeutic
margins. Similar situations exist for a whole range of other diseases.
It has been estimated that all the drugs in current clinical use target no more
than 420 receptors, enzymes, ion channels, and other as yet unknown proteins.`'
The Human Genome Project has the potential to identify a large number of
additional interesting drug targets. One conservative estimate has suggested that
for the 100—150 major diseases for which improved therapies are needed there are
perhaps 3000—10 000 new drug targets that will emerge from genomics. Once a
molecular target and its relevance for human therapy have been identified, its
large scale production for drug screening is usually carried out in a suitable
genetically engineered microbial expression system. This can be relatively
straightforward for some enzymes but may be considerably more difficult for
receptors and other complex proteins.
In a parallel development, there have recently been tremendous advances in
` M. R. Boyd and K. D. Paull, Drug Dev. Res., 1995, 34, 91.
" J. B. Gibbs and A. Oliff, Cell, 1994, 78, 193.
` J. Drews, Nat. Biotechnol., 1996, 14, 1516.
' J. Lehman et al., Nature, 1996, 384, suppl., 1.
Pharmaceuticals from the Sea
57
the robotic technology for screening chemical entities.` The fusion of molecular-
target-based screening and robotics has resulted in the current drug screening
paradigm known as ‘high-throughput screening’ (HTS).` HTS is the process by
which large numbers of compounds are tested in an automated fashion for
activity as inhibitors or activators of a particular molecular target such as a cell
surface receptor or metabolic enzyme. The bioassays used in HTS programs are
either in vitro screens against purified enzymes or receptors or cell-based assays
using engineered eukaryotic cells or microorganisms. HTS programs in major
drug companies can typically handle 3000 enzyme inhibition or 4800 engineered
cell-based assays per day, making it feasible to screen libraries of up to 100 000 or
more chemical entities in a reasonable time frame.` The primary role of HTS is to
identify ‘lead’ chemical structures that act against a particular molecular drug
target and supply directions for their structure—activity optimization.
Key elements in successful HTS programs are the judicious choice of validated
molecular targets and access to the greatest number and structural diversity of
compounds. Traditional directed-synthesis chemical libraries, combinatorial
chemistry libraries, and natural product extracts represent the most important
pools of chemical entities available for HTS programs. Each of these compound
pools brings different strengths to the drug discovery process. The directed
synthesis libraries found in all major pharmaceutical companies have been
accumulated through years of in-house medicinal chemistry programs. They
contain synthetic intermediates on pathways to, and structural analogs of,
biologically active target molecules. Advantages of lead compounds from these
libraries are that the structures are already well characterized and a synthetic
route to the compounds already exists. Combinatorial synthetic chemistry, which
has only emerged in the last decade, has the potential to generate very large
numbers of compounds and it is an extremely powerful tool for structure—activity
optimization.¹`` Initially, there was much enthusiasm for the idea that
combinatorial chemistry could replace the need for accessing all other sources of
chemical diversity, particularly natural product extracts. However, combinatorial
libraries will always be designed with ease and efficiency of synthesis in mind, so
they are likely to contain relatively simple structures. Living organisms, on the
other hand, pay little attention to synthetic efficiency and, as a result, they
contribute secondary metabolites with relatively complex structures, rich in
stereochemistry, concatenated rings, and reactive functional groups, to the pool
of chemical diversity.
The natural products chemical diversity pool, which is full of structural
surprises unbiased by human imagination, has a strong track record of
contributing to drug development. Terrestrial plant natural products (see
Figures 1 and 2) that are currently in clinical use include the anti-cancer drugs
paclitaxel (3) isolated from the Pacific Yew tree Taxus brevifolis and vincristine
(9) isolated from the rosy periwinkle" Catharanthus roseus, the analgesic
morphine (10) isolated from the poppy Papaver somniferum and the antimalarial
drug artemisinin (11) isolated from the Chinese plant Artemisica
` J. R. Borach and J. Thorner, Nature, 1996, 384, suppl., 14.
` J. C. Hogan, Nature, 1996, 384, suppl., 17.
" H.-K. Wang, IDrugs, 1998, 1, 92.
R. J. Andersen and D. E. Williams
58
Figure 2 Terrestrial plant
and soil microorganism
secondary metabolites
currently used as drugs
Pharmaceuticals from the Sea
59
annua.¹" Soil microbe natural products in clinical use include the anticancer
drug bleomycin (12), the antibiotic vancomycin (2), the immunosuppresants
cyclosporin (13) and FK 506 (14), and the cholesterol lowering agent lovastatin
(15).¹" The near-termfuture of natural products in drug discovery also continues
to look promising. A recent survey by National Cancer Institute scientists
showedthat natural products or synthetic analogs of natural products make up a
significant proportion (ca. 50%) of anti-cancer and anti-infective ‘lead’ compounds
currently in preclinical evaluation or clinical trials.¹¹ This promising pipeline of
drug candidates almost guarantees that new, clinically useful agents based on
natural product structures will continue to appear for the foreseeable future.
Despite the rich history of natural products contributing to drug development,
the emergence of HTS as the predominant drug development paradigm has
made most large pharmaceutical firms take a serious look at whether natural
products have any long-term role to play in this new approach.`' Their
evaluations have focused on the possibility that the large libraries of chemical
entities rapidly prepared by combinatorial chemistry have made natural product
screening obsolete. In order to address this issue in an unbiased and systematic
way, scientists at Bayer Pharma carried out a statistical analysis of the structural
complementarity of natural products and synthetic compounds. Their results led
to the conclusion that ‘the potential for new natural products is not exhausted
and natural products still represent an important source for the lead-finding
process’ in drug discovery.¹` What appears to be emerging, as a result of analyses
such as that carried out by the Bayer group and the accumulation of several
years worth of experience with the use of combinatorial libraries in HTS
programs, is the recognition that although combinatorial chemistry is indeed an
extremely powerful tool for drug discovery, it cannot completely replace natural
products as a source of chemical diversity.
2 Opportunities in the Oceans
Secondary metabolites (natural products) are so named because they are
apparently not essential for the primary metabolic activities involved in the
growth of the producing organism. It is often argued that they act as antifeedants
or toxins designed to reduce predation on the producing organism or that they
act to inhibit the growth of other species competing for the same pool of nutrients
or space. While these arguments are usually well founded, the reality is that for
most secondary metabolites there is no rigorous experimental proof for their
putative roles. In contrast to the almost universal occurrence of primary
metabolites such as amino acids, fatty acids, and nucleotides in all organisms
from microbes to mammals, the occurrence of any particular secondary
metabolite or natural product is normally restricted to only one or at most a few
species. It is also the case that not all living organisms make secondary
metabolites. A high proportion of higher plants and microorganisms do make
secondary metabolites while most vertebrates do not. The restricted taxonomic
¹" Y. Z. Shu, J. Nat. Prod., 1998, 61, 1053.
¹¹ G. M. Cragg, D. J. Newman and K. M. Snader, J. Nat. Prod., 1997, 60, 52.
¹` T. Henkel, H. Muller, R. M. Brunne and F. Reichel, Angew. Chem., Int. Ed. Engl., 1999, 38, 643.
R. J. Andersen and D. E. Williams
60
distribution of secondary metabolites means that for phyla known to be rich in
secondary metabolism, there is a rough correlation between species diversity and
chemical diversity. Consequently, drugscreeningprograms that are bioprospecting
for maximum structural diversity of natural products must try to access the
maximum available biodiversity.
Greater than 70% of the Earth’s surface is covered by oceans. The oceans are
much bigger volumetrically than inhabitable land surfaces so they provide much
more space in which organisms can live and diversify. The thermal buffering
capacity of seawater means that ocean temperatures are very stable in
comparison to those of freshwater and terrestrial environments. Furthermore,
the ions that contribute to the total salinity of seawater are in nearly the same
proportions throughout the oceans and their total concentrations in seawater are
very similar to their concentrations in physiological fluids, minimizing problems
of osmoregulation and ionic regulation. The very stable physical and chemical
environment in the oceans, the wide range of habitats extending from the very
deep abyssal plain to very shallow tidal pools, and the ready availability of
nutrients have been major factors in the development of the high biodiversity
found in the marine environment.
Marine biota are an extremely exciting potential source of novel natural
products not only because of the large number of species present in the oceans,
but also because many of these plants and animals are uniquely adapted to
marine habitats and have no terrestrial counterparts. Marine algae, for example,
live immersed in seawater, which requires a set of physiological adaptations for
accessing nutrients, exchanging metabolic gases, and reproduction that are very
different from those found in terrestrial vascular plants. In spite of their
physiological differences, one thing marine algae and terrestrial plants have in
common is an apparent ecological need for biologically active secondary
metabolites to deter herbivorous predators. Even though marine and terrestrial
plants are significantly different from each other, it is among the invertebrates
that there is the most striking difference between marine and terrestrial life forms.
There are approximately 100 000 species of marine invertebrates in the world’s
oceans and the true number is likely much higher because there are still many
undiscovered or undescribed species.¹` A number of the invertebrate phyla,
including the Coelenterata, Porifera, Bryozoa, andEchinodermata, are exclusively
aquatic and largely saline in habitat. Most of the animals in these phyla are
sessile, slow growing, brightly colored, and lack the physical protection of shells
or spines. Simple ecological arguments predict that organisms with exactly these
attributes might make extensive use of biologically active secondary metabolites
to defend themselves from predation by fishes, crabs, etc.
The field of marine natural products chemistry, which encompasses the study
of the chemical structures and biological activities of secondary metabolites
producedby marine plants, animals, and microorganisms, began in earnest in the
early 1960s.¹"¹` This is in stark contrast to the study of terrestrial plant natural
¹` R. C. Brusca and G. J. Brusca, Invertebrates, Sinauer Associates, Sunderland, MA, 1990, p. 4.
¹" P. J. Scheuer (ed.), Bioorganic Marine Chemistry, Springer, Heiderberg, 1987—92, vols. 1—6.
¹` D. J. Faulkner and R. J. Andersen, in The Sea, vol. 5, Marine Chemistry, ed. E. D. Goldberg,
Wiley-Interscience, New York, 1974, ch. 19, p. 679.
Pharmaceuticals from the Sea
61
products chemistry, which started almost a century and a half earlier with the
isolation of the well-known alkaloids morphine, strychnine, and quinine. The
relative inaccessibility of marine macroorganisms and difficulties associated with
culturing marine microorganisms, particularly phytoplankton, probably con-
tributed to the late bloom of marine natural products chemistry research.
Cousteau’s invention of SCUBA in 1943 dramatically increased the accessibility
of sessile marine invertebrates and algae. With this tool in hand, it became
practical for natural products chemists to make their own field collections of
marine organisms. Once sample collection was conveniently under the chemist’s
control, the way was open for active investigation of marine secondary
metabolism. Today, after nearly 40 years of research, there have been roughly
10 000 novel marine natural product structures described in the chemical
literature and the rate at which they are reported has increased to ca. 600 per year
in 1997 from ca. 250 per year in the decade 1977 to 1987.¹'
Several analyses of known marine natural products according to the phylumof
the source organism have revealed the richest sources of marine secondary
metabolism (Figure 3).¹`¹` It is clear from the data that marine algae and
invertebrates, which together account for more than 90% of all reported
compounds to date, have been the richest sources of novel natural products in the
oceans. This is in keeping with the rudimentary ecological arguments presented
above that these two groups of organisms might be expected to utilize chemical
defences to deter predators. Among the invertebrates, sponges, coelenterates (soft
corals and gorgonians), echinoderms, tunicates, and molluscs have yielded the
most compounds.
Interestingly, there has been a significant shift in emphasis during the last
decade. Inthe early days of marine natural products research, algae accountedfor
ca. 40%of new compounds, invertebrates ca. 60%, and microorganisms ca. 1%.
In the most recent analysis, algae account for only ca. 10% of the total,
invertebrates account for ca. 80%, and microorganisms account for ca. 10%.
Among the invertebrates, the proportion of sponge (26% in 1977—85; 43% in
1997) and tunicate (2.6% in 1977—85: ca. 10% in 1997) compounds have
significantly increased, while the proportion of coelenterate compounds (22%in
1977—85; 13% in 1997) has decreased. These shifts probably reflect the recent
focus of the field on drug discovery, particularly the active search for anti-cancer
drugs leads. A review of cytotoxic marine natural products showed that sponges
(44%of total) and tunicates (13%of total) were the most prolific marine sources
of compounds with this particular type of bioactivity, so it is not surprising that
interest in natural products from these phyla has increased.¹" The other major
shift has been the increase in reports of microbial metabolites (1% of total in
¹' D. J. Faulkner, Nat. Prod. Rep., 1998, 15, 113; and the previous reports in this series.
¹` C. Ireland, D. Roll, T. Molinski, T. McKee, M. Zabriske and J. Swersey, in Biomedical Importance
of Marine Organisms, ed. D. G. Fautin, California Academy of Sciences, San Francisco, 1988, p. 41.
¹` C. Ireland, B. Copp, M. Foster, L. McDonald, D. Radisky and C. Swersey, in Marine
Biotechnology, vol. 1, Pharmaceutical and Bioactive Natural Products, ed. D. Attaway and O.
Zaborsky, Plenum Press, New York, 1993, ch. 1, p. 1.
¹" F. J. Schmitz, B. F. Bowden and S. I. Toth, in Marine Biotechnology, vol. 1, Pharmaceutical and
Bioactive Natural Products, ed. D. Attaway and O. Zaborsky, PlenumPress, New York, 1993, ch.
7, p. 197.
R. J. Andersen and D. E. Williams
62
Figure 3 Distribution of
marine natural products
reported in 1997 according
to the phylum of the
source organism
1977—85: ca. 10% of total in 1997). This increase has been stimulated by the
results of several pioneering studies showing that cultures of microorganisms
uniquelyadaptedtothe marine environment are a rich but essentially unexplored
resource of novel bioactive secondarymetabolites,`"

`` andparallel demonstrations
that many of the exciting bioactive compounds isolatedfrommarine invertebrate
extracts are actually metabolites of associated microorganisms.``
The underlying assumption driving marine natural products chemistry
research is that secondary metabolites produced by marine plants, animals, and
microorganisms will be substantially different from those found in traditional
terrestrial sources simply because marine life forms are very different from
terrestrial life forms and the habitats which they occupy present very different
physiological and ecological challenges. The expectation is that marine organisms
will utilize completely unique biosynthetic pathways or exploit unique variations
on well established pathways. The marine natural products chemistry research
conducted to date has provided many examples that support these expectations.
Red algae were some of the first organisms to attract serious attention from
marine natural product chemists.`" The typical metabolites of red algae are
mono-, sesqui-, anddi-terpenoids andpolyketides. What makes these compounds
unique to marine plants is the high degree of substitution with chlorine and
bromine atoms and the large number of unprecedented terpenoid carbon
skeletons. Redalgae in the genera Laurencia and Plocamiumhave beenthe richest
source of halogentated algal terpenoids and polyketides. Some typical Laurencia
terpenoids (see Figure 4) include pacifenol (16), perforatane (17), oppositol (18),
andneoirieone (19), and some typical Laurencia polyketides include laurepinnacin
`" W. Fenical, Chem. Rev., 1993, 93, 1673.
`¹ B. S. Davidson, Curr. Opin. Biotechnol., 1995, 6, 284.
`` V. S. Bernan, M. Greenstein and W. M. Maiese, Adv. Appl. Microbiol., 1997, 43, 57.
`` C. A. Bewley and D. J. Faulkner, Angew. Chem., Int. Ed. Engl., 1998, 37, 2162.
`" K. L. Erickson, in Marine Natural Products, Chemical and Biological Perspectives, ed. P. J.
Scheuer, Academic Press, New York, 1983, vol. 5, ch. 4, p. 132.
Pharmaceuticals from the Sea
63
Figure 4 Halogenated
terpenoid and polyketide
metabolites isolated from
red algae in the genera
Laurencia and Plocamium
(20) and okamurallene (21). The dibromotrichloro acyclic compound 22 and the
tetrachloro monocyclic compound 23 are typical Plocamium monoterpenoids.
It has been postulated that the biosynthesis of halogenated red algal
metabolites involves a variation on the well-known terpenoid and polyketide
pathways. The introduction of halogen atoms into the molecular skeletons is
thought to arise from initial reaction of an electrophilic halonium ion (formally
Br> or Cl>) species with a nucleophilic alkene or alkyne bond to generate
intermediate carbocations that can lose a proton, undergo ring cyclization
reactions, or be trapped by bromide, chloride, or oxygennucleophiles as shownin
Figure 5 for the sesquiterpenoid nidificine (24). In terrestrial plant biosynthesis,
the analogous cyclizations of acyclic terpenoid precursors are initiated by the
electrophilic species H> rather than by halonium ions. The incorporation of
halogen atoms into red algal metabolites is a typically marine biosynthetic
variationonthe basic terpenoidandpolyketide pathways that takes advantage of
the relatively high concentrations of chloride and bromide ions in seawater.
Dinoflagellates, a group of planktonic unicellular marine plants, make a
remarkable group of extremely toxic polyketides (see Figure 6) that have no
terrestrial counterparts.`` Maitotoxin (25), produced by the dinoflagellate
Gambierdiscus toxicus, is one of the toxins (LD¬50 ng/kg, mouse, ip) responsible
for ciguatera seafood poisoning.`' It is the largest (molecular weight ¬3422
Daltons) non-biopolymer natural product knownand it features a linear skeleton
containing142 carbonatoms that has beenelaboratedintomultiple units of fused
cyclic ethers. Okadaic acid and the related compound DTX-4 (26), biosynthetic
products of dinoflagellates in the genera Prorcentrum and Dinophysis, are
`` T. Yasumoto and M. Murata, Chem. Rev., 1993, 93, 1897.
`' M. Sasaki, N. Matsumori, T. Maruyama, T. Nonomura, M. Murata, K. Tachibana and T.
Yasumoto, Angew. Chem., Int. Ed. Engl., 1996, 35, 1672.
R. J. Andersen and D. E. Williams
64
Figure 5 Proposed
mechanism for biosynthetic
introduction of bromine
and chlorine atoms into
the Laurencia
sesquiterpenoid nidificine
(24)
Figure 6 Toxic polyketide
metabolites of marine
dinoflagellates members of the family of compounds that are responsible for causing diarrhetic
shellfish poisoning.
Biosynthetic investigations of DTX-4 (26) have revealed that the molecule is
formed via a polyketide pathway, but one that involves a number of unusual
features.`` These include the use of glycolate as a starter unit, the formation of
pendant methyl groups and exomethylene groups fromC-2 of acetate, cleavage of
the polyketide chain via a Baeyer—Villiger-like oxidation, and deletion of
individual carbons fromthe polyketide chainvia a Favorskii-type rearrangement
followedby decarboxylationas showninFigure 7. While there is no experimental
`` J. L. C. Wright, T. Hu, J. L. McLachlan, J. Needhamand J. A. Walter, J. Am. Chem. Soc., 1996, 118,
8757.
Pharmaceuticals from the Sea
65
Figure 7 Proposed
biological Favorskii-like
reaction involved in
DTX-4 biosynthesis. —
denotes incorporation of
intact units of
¹`CH
`
—¹`CO
`
H in a
biosynthetic feeding
experiment
Figure 8 Sponge
terpenoids containing the
rare isocyanide,
isothiocyanide, and
dichloroimine functional
groups
evidence yet to verify that these same polyketide modifications are involvedin the
formation of other dinoflagellate polyether toxins, structural features found in
other compounds of this class suggest that these rare and interesting variations
onthe polyketide pathway maybe a commonfeature of dinoflagellate biosynthesis.
Many marine invertebrate metabolites also have biosynthetic origins without
known terrestrial counterparts. Two examples frommarine sponges will serve as
illustrations. Terpene isocyanides, isothiocyanides and dichloroimines are some
of the most distinctive metabolites of marine sponges (see Figure 8).
Diisocyanoadociane (27) from Amphimedon terpenensis, axisonitrile-3 (28) and
axisothiocyanate-3 (29) from Acanthella cavernosa, the dichloroimine 30 from
Stylotella aurantiumand 2-thiocyanoneopupukeanane (31) from an Axinyssa sp.
are representative examples. Biosynthetic feeding studies have shown that the
isocyanide and isothiocyanide functionalities in these compounds arise from
direct incorporation of inorganic cyanide and thiocyanate, presumably by
reaction with terpene carbocation biosynthetic intermediates.`` This is in direct
contrast to the biosynthesis of the small number of isocyanide containing
metabolites known from terrestrial microorganisms, where the isocyanide
functionality arises from modification of an amino acid nitrogen.
Sponges in the order Haplosclerida have been the source of a family of more
than 100 3-alkylpiperidine alkaloids (see Figure 9) that all appear to have been
formed via a common biosynthetic pathway which is unique to marine
`` J. S. Simpson and M. J. Garson, Tetrahedron Lett., 1999, 40, 3909.
R. J. Andersen and D. E. Williams
66
Figure 9 3-Alkylpiperidine
alkaloids isolated from
sponges in the order
Haplosclerida
Figure 10 Proposed
biogenesis of
3-alkylpiperidine alkaloids
Pharmaceuticals from the Sea
67
sponges.`" Manzamine A (32) isolated from a Haliclona sp., petrosin A (33)
isolated fromPetrosia seriata, halicyclamine A(34) also isolated froma Haliclona
sp., along with ingenamine (35) and madangamine A (36) isolated from
Xestospongia ingens are representative examples.
It has been proposed that the basic building blocks involved in the biogenesis
of all the 3-alkylpiperidine alkaloids are ammonia, a three-carbon unit such as
propenal, and a long-chaindialdehyde as shown in Figure 10. These units are first
assembled into a 3-alkylpiperidine monomer that can either polymerize to give
the oligomeric halitoxins or dimerize to give a bis(3-alkylpiperidine) macrocycle.
Bis(3-alkylpiperidine) macrocycles canundergovarious transformations, including
intramolecular [4 ·2] cycloaddition reactions, to generate the polycyclic
skeletons found in many of these complex alkaloids. There is no terrestrial
counterpart tothe proposedbiogenetic pathwaytothese complex3-alkylpiperidine
sponge alkaloids.
The selected examples described above serve to illustrate that marine natural
products are indeedsignificantly different fromthe natural products traditionally
isolated fromterrestrial plants and microorganisms. Numerous excellent reviews
of the marine natural products literature are full of many additional examples.
This marine pool of novel chemical diversity, which contains many remarkably
complex molecules that are often imbued with exquisitely potent biological
activities, represents an extremely valuable molecular resource for the ‘lead
finding’ process incontemporary HTSdrug discovery programs. The opportunity
to exploit this valuable resource and the resulting rewards are waiting for those
who are willing to meet the significant challenges required to bring a marine
natural product ‘lead’ compound to the clinic.
3 Challenges Involved in Developing a ‘Drug from the Sea’
The process of developing any new drug is a lengthy and very costly business.
Typically it takes 12—15 years to bring a drug to market fromthe time of its initial
discovery and the total bill is more than $350 million (US). The failure rate is also
enormous. In the initial stages, thousands of chemical entities are evaluated to
find one or more ‘lead’ compounds that merit extra evaluation and only a very
small percentage of these ‘lead’ compounds ever make it into the clinic. These
timeline, cost, and failure rate barriers to drug development exist regardless of
whether the ‘lead’ compoundcomes froma synthetic or natural product chemical
diversity pool. However, there are a number of unique challenges to developing a
drug based on a natural product from a marine plant or animal source.
The first step in discovering a marine natural product ‘lead’ compound
involves accumulating collections of the source organisms. Ideally the collections
would include as many species as possible collected from a large number of sites
reflecting the wide diversity of habitats found in the world’s oceans. The
development of SCUBA and both manned and remotely operated (ROV)
submersibles has providedthe technology requiredto effectively collect algae and
invertebrate specimens frommost marine habitats. Consequently, the major issue
`" R. J. Andersen, R. W. M. Van Soest and F. Kong, in Alkaloids: Chemical &Biological Perspectives,
ed. S. W. Pelletier, Pergamon, New York, 1996, vol. 10, ch. 3, p. 301.
R. J. Andersen and D. E. Williams
68
in collecting marine specimens now involves securing permission to collect from
the countries whose territorial waters encompass the desired collecting sites.
There are two issues that must be addressed when securing collecting permits.
The first relates to the possible environmental impact of collecting marine
specimens. Many jurisdictions require collecting permits that are much like
fishing licenses in an attempt to control the excessive removal of marine
specimens by SCUBA, dredging, or submersibles. Sometimes the regulations
cover entire coastlines, other times they only cover protected areas like marine
parks and reserves or high profile tourist destination dive sites. Fortunately,
modern HTS assays require very small quantities of crude extracts, so initial
collections of specimens for screening purposes can usually be limited to less than
500g. Recent advances in isolation and structure elucidation technology have
also dramatically reduced the quantities of crude extract required to identify the
chemical structures of bioactive hits. Therefore, the total biomass of a specimen
currently required for HTS screening and compound identification is quite small
and collection of this quantity should normally have no environmental impact. A
carefully documented case along these lines is usually adequate to obtain a
collecting permit where environmental issues are the concern.
The second, more complex issue involvedin obtaining collecting permits has to
dowithintellectual property rights, licensingfees, androyalties. Twointernational
documents deal with this issue. The first is the Conventionof Biological Diversity
that was signed by 140 nations at the 1992 Earth Summit in Rio de Janeiro (as of
1997, only 30 countries have ratified the document). In the convention, ethical
concerns regarding the intrinsic value of biodiversity were addressed, but the
mainfocus was to establishsovereignrights over biological resources, developing
mechanisms for their sustainable use, and ensuring equitable distribution of the
resulting benefits.`" The convention acknowledgedthat, in general, international
assistance would have to be provided to developing countries to pursue
biodiversity protection efforts, and acknowledged the rights of countries to
obtain compensation for access to their genetic resources, including transfer of
relevant technologies and equitable sharing of researchresults and other benefits.
However, many of the provisions of the convention are quite vague and
contradictory, particularly with regard to intellectual property rights and the
compensation arrangements that should be applied to transactions involving
genetic resources. Essentially, countries are left to decide for themselves what
constitutes compliance.`"
TRIPS, the Trade Related Aspects of Intellectual Property Rights agreement
of the World Trade Organization, which came into effect in 1995, is the second
international document that deals with intellectual property rights arising from
biodiversity. This document is in sharp conflict with the basic premise endorsing
the concept of nations holding property rights to their indigenous species as
outlined in the Rio Accord. The TRIPS assumptions are that excessive
government control of resources is to be avoided as an obstacle to economic
growth. Such obstacles include the ability of individuals to negotiate market
`" A. Artuso, Drugs of Natural Origin: Economic and Policy Aspects of Discovery, Development, and
Marketing, The Pharmaceutical Products Press, New York, 1997, p. 142.
Pharmaceuticals from the Sea
69
prices of biological resources that the Biodiversity Convention allows.`¹ The
Organization of African Unity’s task force on access to genetic resources has
argued that TRIPs should comply with the Biodiverity Convention, and not the
other way round, and that member countries may refuse to recognize any patent
fromnatural products found in Africa unless it acknowledges the ‘ownership’ and
contribution of the relevant community to the new product.`¹
The National Institute of Health (NIH) in the USAhas taken a leadership role
in this area by making sure that collections of marine specimens made in foreign
waters using NIHfunds are conducted only under agreements that recognize the
rights of the country of origin of the biological materials. The responsibilities of
the collectors and the benefits to the country of origin will usually be formalized
in a Memorandum of Understanding (MOU). MOUs spell out how the
collections and ensuing research will be conducted and how proceeds from
intellectual property rights will be shared. There is an emphasis on involvinglocal
scientists in the research, promoting technology transfer, and encouraging
educational exchanges as well as negotiating equitable formulas for sharing
licensing fees and royalty payments.
Once extracts have been obtained, they have to be screened for bioactivity and
the chemical structures of the active constituents have to be elucidated.
Contemporary HTS programs have been designed to speed up the process of
identifying ‘lead’ structures in an attempt to shorten the timeline for drug
development. Campaigns will often be mounted to screen full libraries of up to
several hundred thousand compounds against a particular molecular target with
the intent of identifying a complete suite of ‘lead’ structures in a period of no more
than a few weeks or months. Combinatorial and directed synthetic libraries are
ideally suited to this purpose, because they provide immediate ‘lead’ structures
once hits have been identified by HTS. In contrast, a hit in a natural product
crude extract provides no immediate structural information and, furthermore,
the time required for bioassay-guided fractionation and structure elucidation,
which can be days, months, or years, is highly variable from extract to extract.
The delay in providing an active structure and the unpredictability of the process
are hurdles that natural product extracts must overcome to be compatible with
HTS. Ideally the time for assay-guided fractionation and chemical structure
elucidation must be shortened to a fewweeks or probably, at most, three months.
Technological advances in NMR, MS, and HPLC, and the emergence of
powerful hyphenated analytical techniques such as HPLC-MS, HPLC-NMR,
and HPLC-CD,`` have partially solved this problem by greatly accelerating the
rate of routine structure elucidation. Other approaches to solving this problem
involve preliminary purification of crude extracts before they are submitted to
HTS and the creation of libraries of purified and identified natural products that
can then compete directly with synthetic libraries.``
After a bioactive marine natural product ‘lead’ structure has been identified,
`¹ C. MacLlwain, Nature, 1998, 392, 535: ibid., 1998, 392, 525; E. Masood, ibid., 1998, 392, 537.
`` G. Bringmann, K. Messer, M. Wohlfarth, J. Kraus, K. Dumbuya, M. Ruckert, Anal. Chem., 1999,
71, 2678.
`` C. Koch, T. Neumann, R. Thiericke and S. Grabley, in Drug Discovery fromNature, ed. S. Grabley
and R. Thiericke, Springer, Berlin, 1999, ch. 3, p. 51.
R. J. Andersen and D. E. Williams
70
either by HTS or other traditional screening approaches, the issues of short-term
small-scale and long-term manufacturing-scale supply become the determining
factors in its further progress towards development. In the short term, 10s to 100s
of milligrams of the compound are required to test for activity in secondary
assays that probe such issues as activity in whole cells, in vivo efficacy in animal
models, maximum tolerated doses and minimum effective doses in animals, and
pharmacokinetics. Demonstration of in vivo activity is an absolute requirement
before development can proceed.
Obtaining 10s or 100s of milligrams of many marine natural products for
secondary assays represents a considerable challenge. This usually involves
recollection of significant quantities of the source organismandthe environmental
impact of these larger collections must be carefully evaluated since many of the
source organisms are rare species. The shift of emphasis towards marine
microorganisms is partly aresult of the supply issues since laboratory fermentation
of a marine microorganism represents a sustainable supply of an interesting
metabolite. It also reflects the emerging recognition that many interesting
compounds isolated from marine invertebrate extracts are actually biosynthetic
products of associated microorganisms.`` The ability to culture the producing
microorganism would provide a suitable supply of the desired compound both
for secondary assays and ultimate commercial production.
Moving a promising marine natural product fromthe demonstration of in vivo
activity insecondaryassays to a genuine drugdevelopment project is a major step
because of the required commitment of both financial and human resources. In
order for a large pharmaceutical company to proceed, they must first determine
that there is potential market niche for the compound that will return their
development investment and, second, they must be assured of a reliable and
economical source of the compound. Organic synthesis represents the ideal
industrial source of a drug. Many marine natural products with promising in vivo
activity have very complex chemical structures, making them attractive targets
for academic synthetic programs. While academic syntheses prove that a
particular compound can be made in the laboratory and often provide valuable
structure—activity data, few of them are short enough or use reagents that are
cheap or safe enough to become economical large-scale industrial syntheses.
For marine natural products that are too complex tobe producedcommercially
by total synthesis, there are still several supply options. The first option is to use
the natural product as a ‘lead’ structure for a synthetic medicinal chemistry
program that identifies simpler synthetically accessible analogs that contain the
samepharmacophore. Biological productionof the natural product viafermentation
or aquaculture represents a second potential solution to the supply problem.
Manydrugs are producedbyindustrial-scale fermentations of soil microorganisms,
so conceptually this should be straightforward for a metabolite of a marine
microorganism. The only difference is the need to solve the technical problems
associated with preparation of large volumes of seawater-based fermentation
mediumand the incompatibility of the high concentration of salts in the medium
with currently available stainless-steel fermentation equipment. Industrial-scale
production of complex marine invertebrate metabolites by aquaculture of the
producing organism under controlled conditions is an exciting prospect. While
Pharmaceuticals from the Sea
71
this technology is still in its infancy, the feasibility of the approach has recently
been demonstrated by the production of anti-cancer compounds in the
bryostatin family using controlled cultures of the bryozoan Bugula neritina.`"
4 Some Success Stories
The number of marine natural product derived drugs currently in clinical use is
still very small; however, there are many promising marine natural products or
synthetic analogs in clinical or pre-clinical trials, so the expectation that new
drugs based on marine natural products will appear in the clinic in the next few
years is genuine. Two products (see Figure 11) based on marine natural products
that have already reached the market are the anti-cancer drug ara C (37) and the
anti-inflammatory pseudopterosin diterpenoids [i.e. pseudopterosin A(38)]. Ara
C (37) (trade name Cytarabine) is a synthetic material based on the ‘lead
structures’ providedby isolation of spongothymidine (39) andspongouridine (40)
fromthe sponge Cryptotethya crypta in the 1950s.`` It is currently the most active
anti-metabolite in clinical use for inducing remissions in acute non-lymphocytic
leukemia inadults andpediatric patients.`' Incombinationwithother anti-cancer
agents, such as anthracyclines, ara C treatment leads to complete remission in
60—70%of treated patients. It can be viewedas a first generation‘Pharmaceutical
from the Sea’ that emerged from the classical model of using a bioactive natural
product as a ‘lead structure’ for the development of a synthetic drug.
The pseudopterosins, isolatedfromthe Caribbeansoft coral Pseudopterogorgia
elisabethae, are potent inhibitors of inflammation and its associated pain.`` They
have potential applications in a number of conditions including arthritis,
psoriasis, and inflammatory bowel disease. The skin care company Este´ e Lauder
is currently using a ‘pseudopterosin-containing’ natural extract of P. elisabethae
in a product line called ‘Resilience’. The natural extract produces reduction of
skin inflammationfromsunburn or irritation, and it also reduces degeneration of
the skin. In this instance, the ability to obtain the active pseudopterosins as part
of a ‘natural marine extract’ as opposedto making them‘synthetically’ appears to
be an important part of the marketing strategy.
Manoalide (41) was originally isolatedfromthe Indo-Pacific sponge Laffariella
variabilis and its chemical structure was reported without any mention of
biological activity.`` Subsequently, it was discovered that manoalide had
exciting anti-inflammatory properties.`" The anti-inflammatory activity of
manoalide apparently results fromits ability to inhibit the enzyme phospholipase
A
`
(PLA
`
). This ubiquitous enzyme catalyzes the hydrolysis of the ester in the
sn-2 position of phospholipids, resulting in the release of arachadonic acid, the
biosynthestic precursor of prostaglandins and leukotrienes in the arachadonic
`" M. Jaspars, Chem. Ind. (London), 1999, January, p. 51.
`` W. Bergmann and D. C. Burke, J. Org. Chem., 1956, 21, 226.
`' V. I. Avramis, in A Clinician’s Guide to Chemotherapy, Pharmacokinetics and Pharmacodynamics,
ed. L. B. Growchow and M. M. Ames, Williams and Wilkins, Baltimore, 1998, ch. 9, p. 209.
`` A. M. S. Mayer, P. B. Jacobson, W. Fenical, R. S. Jacobs and K. B. Glaser, Life Sci., 1998, 62, 401.
`` E. D. de Silva and P. J. Scheuer, Tetrahedron Lett., 1980, 21, 1611.
`" B. C. Potts, D. J. Faulkner and R. S. Jacobs, J. Nat. Prod., 1992, 55, 1701.
R. J. Andersen and D. E. Williams
72
Figure 11 Anti-
inflammatory or
anti-cancer marine natural
products and synthetic
analogs that are in
commercial use or in
clinical and preclinical
evaluation
Pharmaceuticals from the Sea
73
acid cascade. The prostaglandins are well-known mediators of inflammation and
pain. Many anti-inflammatory drugs interfere with the archadonic acid cascade
but, at the time of discovery, manoalide was the only one that worked by
interfering with PLA
`
. While not sold as a drug, manoalide (41) has been
developed as a commercial reagent for basic studies of PLA
`
. It is widely used
throughout the pharmaceutical industry and it may well result, throughsynthetic
drug design, in a new class of anti-inflammatory agents. It is a good example of
how a marine natural product can also play an important indirect role in drug
development by helping to identify new disease-relevant molecular targets that
can be used in HTS screens to find mechanistically related but structurally
unrelated ‘lead’ compounds.
Contignasterol (42), a steroid with a number of novel structural features that
include the ring  and  hydroxylation pattern, the cis / ring junction, and the
hemiacetal functionality in the side chain, was isolated from the sponge Petrosia
contignatacollectedinPapua NewGuinea."" It was foundtoinhibit the release of
histamine from rat mast cells stimulated with anti-Ige in a dose-dependent
manner, a property that suggested it had potential as an anti-asthma agent.
Histamine is one of the mediators of asthma that causes smooth muscle
contraction, leading to bronchial constrictionanddifficulty in breathing. Further
testing showedthat contignasterol (42) was very effective at preventingasthma-like
symptoms in standard guinea pig models."¹ Inflazyme Pharmaceuticals has
made a synthetic analog of contignasterol designated IPL-576-092, that is
currently in Phase I clinical trials in Europe as a new anti-asthma agent. Unlike
other cortisone-based steroidal anti-asthma drugs, IPL-576-092 is orally active
and it does not appear to bind to the steroid receptors that are responsible for
long-term toxic side effects in the current generation of inhaled anti-asthma
drugs. Inflazyme is currently exploring other anti-inflammatory indications for
IPL-576 analogs of contignasterol and expects to define additional therapeutic
targets for this class of compounds.
The majority of promising drug candidates emerging from marine natural
products research to date are potential cancer treatments. Six anti-cancer
compounds that are either marine natural products or synthetic analogs of
marine natural products have made it to clinical trials. The first of these
compounds to enter clinical trials was didemnin B (43), one of a family of cyclic
depsipetides isolated from the Caribbean tunicate Trididemnum solidum."`
Didemnin B was advanced to Phase II clinical trials for treatment of small cell
lung cancer, myeloma, prostate cancer, and melanoma. Unfortunately, no
favorable responses were found so the compound has been withdrawn."` Crude
extracts of another Caribbean tunicate, Ecteinascidia turbinata, showedextremely
"" D. L. Burgoyne, R. J. Andersen and T. M. Allen, J. Org. Chem., 1992, 57, 525.
"¹ A. M. Bramley, J. M. Langlands, A. K. Jones, D. L. Burgoyne, Y. Li, R. J. Andersen and H. Salari,
Br. J. Pharmacol., 1995, 115, 1433.
"` K. L. Rinehart, T. G. Holt, N. L. Fregeau, P. A. Keifer, G. R. Wilson, T. J. Perun, R. Sakai, A. G.
Thompson, J. G. Stroh, L. S. Shield, D. S. Seigler, D. H. Li, D. G. Martin and G. Gade, J. Nat.
Prod., 1990, 53, 771.
"` For one example, see: S. K. Williamson, M. K. Wolf, M. A. Eisenberger, M. O’Rourke, W. Brannon
and E. D. Crawford, Invest. New Drugs, 1995, 13, 167.
R. J. Andersen and D. E. Williams
74
promising tumor inhibitory properties. Two groups simultaneously succeeded in
isolating and elucidating the structures of members of the ecteinascidin family of
tetrahydroisoquinoline alkaloids that were responsible for the cytotoxicity of the
crude extracts."""` One member of this family of compounds, ecteinascidin 743
(44), is currently in clinical trials.¹" The material required for clinical trials was
obtained from harvest of wild specimens.
Two additional marine natural product structural classes that have led to
anti-cancer drug candidates in clinical trials have come from bryozoan and
mollusc extracts. The bryostatins are a family of potently cytotoxic macrolides
isolated fromthe bryozoan Bugula neritina."' Bryostatin 1 (45) is currently in late
Phase I andearly Phase II clinical trials in Europe for the treatment of melanoma.
The supply of bryostatin 1 (45) required for preclinical testing came fromharvest
of wild specimens; however, the generally low yield and large variability from
collectionto collection make this a non-viable source for commercial production
should a compound in this family make it to the clinic. An aquaculture approach
to producing the bryostatins that is capable of generating a sufficient and
sustainable supply for clinical use has been developed by CalBioMarine. The
dolastatins are a family of cyclic and linear peptides isolated from the sea hare
Dolabella auricularia collected in the Indian Ocean."' Isolation and structure
elucidation of the potently cytotoxic dolastatins was hampered by their very low
yields in the D. auricularia crude extracts. Several large collections of the animals
that exceeded 1500 kg wet weight in total were processed in order to obtain the
milligramquantities of individual compounds required for structure elucidation
and preliminary biological testing. Subsequently, many of the dolastatins and a
wide variety of structural analogs have been synthesized in order to confirm the
structures of the natural product and provide material for further biological
evaluation. Two linear peptides, dolastatin 10 (46) and dolastatin 15 (47), which
have been found to be potent anti-mitotic agents that inhibit the polymerization
of tubulin, have emerged as the most promising ‘lead’ compounds in the family.
Dolastatin 10 (46) and a synthetic analog auristatin PE, along with dolastatin 15
(47) and a water soluble synthetic analog LU-103793, are all in phase I clinical
trials.¹""`
In addition to the compounds that have already moved to clinical trials, there
are a number of very exciting marine natural products (see Figure 12) that are in
pre-clinical evaluation as potential anti-cancer agents. Many of these turn out to
be anti-mitotic agents that interfere with tubulin dynamics either by inhibiing
polymerization or by stabilizing microtubules. Halichondrin B (48), a complex
macrolide initially isolated from the Japanese sponge Halichondria okadai, is a
potent inhibitor of tubulin polymerization that shows very promising in vivo
"" K. L. Rinehart, T. G. Holt, N. L. Fregeau, J. G. Stroh, P. A. Keifer, F. Sun, L. H. Li and D. G.
Martin, J. Org. Chem., 1991, 56, 1676.
"` A. E. Wright, D. A. Forleo, G. P. Gundawardana, S. P. Gunasekera, F. E. Koehn, O. J. McConnell,
J. Org. Chem., 1990, 55, 4508.
"' G. R. Pettit, J. Nat. Prod., 1996, 59, 812—821.
"` H. C. Pitot, E. A. McElroy, J. M. Reid, A. J. Windebank, J. A. Sloan, C. Erlichman, P. G.
Bagniewski, D. L. Walker, J. Rubin, R. M. Goldberg, A. A. Adjeu and M. M. Ames, Clin. Cancer
Res., 1999, 5, 525.
Pharmaceuticals from the Sea
75
Figure 12 Some promising
marine natural product
‘lead’ compounds
R. J. Andersen and D. E. Williams
76
activity against a number of human cancer cell lines in mouse xenografts."` The
promising anti-tumor activity, but very limited supply, of halichondrin B has
prompted the development of a method of producing the compound by in situ
aquaculture of the New Zealand sponge Lissodendoryx. The recent introduction
of the plant natural product paclitaxel into clinical use has prompted many
researchers to search for other natural product structural classes that, like
paclitaxel, also kill cells by stabilizing microtubules. Eleutherobin (49), a
diterpenoidglycoside isolatedfromthe Western Australiansoft coral Eleutherobia
sp.,"" discodermolide (50), a polyketide isolated from the Caribbean sponge
Discodermia dissoluta,`" and laulimalide (51), isolated from the South Pacific
sponge Cacospongia mycofijiensis,`¹ are three novel marine natural products that
mimic paclitaxel’s ability to stabilize microtubules. All three compound classes
are currently the focus of extensive chemical and biological research aimed at
evaluating their clinical potential.
The anti-inflammatory and anticancer ‘lead’ compounds discussed above were
all discovered by screening programs that used traditional whole cell or
tissue-based assays and all come fromextracts of marine invertebrates. Manoalide
and the pseudopterosins were discovered using a mouse ear edema assay and all
of the anti-cancer compounds were initially isolated because they showed potent
in vitro cytotoxicity against either murine or human cancer cell lines. The recent
shift in screening paradigms towards more focused molecular targets, using
purified enzymes and receptors or engineered cell lines, is also taking place in
marine natural products drug discovery research. This has resulted in reports of
some exciting new activities for marine natural product chemotypes.
Dysidiolide (52) isolated fromthe Caribbean sponge Dysidea etheria is the first
naturally derived inhibitor of cdc25A protein phosphatase, an enzyme involved
in the activation of the G2/M transition of the cell cycle.`` Dysidiolide shows
micromolar in vitro inhibition of A-549 human lung carcinoma, presumably
owing to its inhibition of cdc25A, making it an exciting ‘lead compound’ for
development of a mechanism-of-action-based anti-cancer drug. Granulatimide
(53) and isogranulatimide (54), metabolites of the Brazilian tunicate Didemnum
granulatum, are the first G2 cell-cycle checkpoint inhibitors discovered by
rational screening.`` When used in combination with either a chemical DNA
damaging agent or radiation, alkaloids 53 and 54 enhance the killing of cancer
cells, missing the tumor suppressor gene (i.e. p53÷ cells) relative to cells that
"` O. Fodstad, K. Breistol, G. R. Pettit, R. H. Shoemaker and M. R. Boyd, J. Exp. Ther. Oncol., 1996,
1, 119.
"" T. Lindel, P. R. Jensen, W. Fenical, B. H. Long, A. M. Casazza, J. Carboni, C. R. Fairchild, J. Am.
Chem. Soc., 1997, 119, 8744.
`" E. ter Haar, R. J. Kowalski, E. Hamel, C. M. Lin, R. E. Longley, S. P. Gunasekera, H. S.
Rosenkranz and B. W. Day, Biochemistry, 1996, 35, 243.
`¹ S. L. Mooberry, G. Tien, A. H. Hernandez, A. Plubrukarn and B. S. Davidson, Cancer Res., 1999,
59, 653.
`` S. P. Gunasekera, P. J. McCarthy, M. Kelly-Borges, E. Lobovsky and J. Clardy, J. Am. Chem. Soc.,
1996, 118, 8759.
`` M. Roberge, R. G. S. Berlinck, L. Xu, H. Anderson, L. Lim, D. Curman, C. M. Stringer, S. H.
Friend, P. Davies, I. Vincent, S. J. Haggarty, M. T. Kelly, R. Britton, E. Piers and R. J. Andersen,
Cancer Res., 1998, 58, 5701.
Pharmaceuticals from the Sea
77
contain the tumor suppressor gene (i.e. p53· cells). This combination therapy
approach offers the hope of a greatly improved therapeutic index for the
approximately one half of all human solid tumors that are known to be missing
the tumor suppressor gene p53. Lamellarin I (55), another polycyclic aromatic
alkaloid isolated from tunicates in the genus Didemnum, has been found to
effectivelyreverse multi-drug resistance incancer cells by inhibiting P-glycoprotein
mediated drug efflux.`" The potency of lamellarin I as a MDR modulator was 9-
to 16-fold higher than that of the benchmark compound verapamil.
Another promising recent development is the increase in reports of interesting
‘lead’ compounds isolated from cultures of marine microorganisms. Two
examples illustrate the trend. A family of anti-fungal compounds named 15G256
(56), , and have been isolated from the mangrove derived fungus Hypoxylon
oceanicumby scientists at Wyeth Ayerst.`` These compounds have been patented
and they are being evaluated for potential use against human fungal infections.
CyclomarinA(57), aheptapeptide obtainedfromcultures of a marine actinomycete,
has been patented as an anti-inflammatory agent.`' The use of molecular target
assays and investigations of marine microorganism secondary metabolites
represent important trends for the future in marine natural products drug
discovery research.
5 Future Prospects
Nearly four decades of marine natural products chemistry investigations have
demonstrated that organisms living in the world’s oceans are an incredibly rich
storehouse of novel lowmolecular weight chemical entities. The natural products
chemical diversity pool present in marine algae and invertebrate extract libraries
has virtually no overlap with the chemical diversity pools present in traditional
synthetic libraries, combinatorial synthetic libraries, or terrestrial plant and
microorganism natural product extract libraries. Many of the compounds
already known exhibit potent biological activities that are relevant to treating
human diseases. Therefore, marine natural products represent a unique and
extremely valuable molecular resource for drug discovery programs using either
traditional or HTS screening paradigms.
A large number of very promising compounds from the marine natural
products chemical pool are currently in the pre-clinical and clinical stages of
development, leading to the clear expectation that newpharmaceuticals fromthe
sea will emerge for clinical use in the next decade. In order to keep the
development pipeline full, researchers in the field will have to make marine
extracts compatible with HTS discovery paradigms and they will have to
continue to find creative ways to solve the supply issues. When the next
generationof marine derived drugs do appear, it will represent the culminationof
a new type of harvest from the bounty of the oceans. The ideal outcome of a
marine natural product drug discovery effort is identification of a bioactive ‘lead’
`" A. R. Quesada, M. D. Garcia Gravalos and J. L. Fernandez Puentes, Br. J. Cancer, 1996, 74, 677.
`` D. Albaugh, G. Albert, P. Bradford, V. Cotter, J. Froyd, J. Gaughran, D. Kirsch, M. Lai, A. Rehnig,
E. Sieverding and S. Silverman, J. Antibiot., 1998, 51, 317.
`' W. H. Fenical, R. S. Jacobs and P. R. Jensen, US Patent 5 444043, 1995.
R. J. Andersen and D. E. Williams
78
structure that can be developed into a clinically useful synthetic entity. In this
scenario, organisms in the ocean are yielding only knowledge about new
pharmacophores rather than the more traditional harvests of biomass. This
intellectual harvest is environmentally benign, it has the potential to greatly
benefit all humans by leading to better treatments for serious diseases, and it can
result in significant sustainable economic benefits to the countries where the
relevant biological specimens were collected and where the advanced stages of
development work have taken place.
Pharmaceuticals from the Sea
79
Contamination and Pollution in the Marine
Environment
STEPHEN J. DE MORA
1 An Overview of Marine Pollution
Both contamination and pollution entail the perturbation of the natural state of
the environment by anthropogenic activity. The two terms are distinguishable by
the severity of the effect: pollution induces the loss of potential resources.¹
Additionally, a clear cause—effect relationshipmust be established for a substance
to be classified as a pollutant towards a particular organism.
In the marine environment, human-induced disturbances take many forms.
Owing to source strengths and pathways, the greatest effects tend to be in the
coastal zone. Waters and sediments in such regions bear the brunt of industrial
and sewage discharges and are subject to dredging and spoil dumping.
Agricultural runoff may contain pesticide residues and elevated nutrients, the
latter of which may over-stimulate biological activity, producing eutrophication
in the water column or anoxic conditions in underlying sediments. However, the
deep sea has not escaped contamination. The most obvious manifestations
comprise crude oil, petroleum products, and plastic pollutants, but also include
the long-range transport of long-lived radionuclides from continental sources.
Additionally, the aeolian transport of heavy metals has enhanced natural fluxes
of some elements, particularly lead.
In the 1960s, the global problems related to the wide-scale application of
pesticides first accentuatedthe possible difficulties associatedwith utilizing useful
and apparently benign compounds. The lesson supposedly learned with DDT
has been reinforced in the past decade with tributyltin (TBT) compounds in the
marine environment. TBT, a ‘modern contaminant’, is the main active ingredient
in a range of organotin-based marine anti-fouling paints owing to its appreciable
toxicity towards a wide range of organisms. In effect, TBT is a broad-spectrum
pesticide and herbicide, with all the ensuing problems one might expect, that had
been unwittingly introduced and popularized in a pesticide-aware culture. The
¹ E. Goldberg, Mar. Pollut. Bull., 1992, 25, 45.
Issues in Environmental Science and Technology No. 13
Chemistry in the Marine Environment
© The Royal Society of Chemistry, 2000
81
widespread deleterious influence of TBT on non-target organisms, including
those of commercial value, has resulted in the rapid regulation of TBT in many
countries and international regulations to ban TBT are under consideration.
However, the case history of TBT has demonstrated the difficulties associated
with assuming stewardship of the global environment.`
The concept of marine pollution has undergone a continual evolution. Three
key factors in such a re-evaluation pertain to the nature of the pollutants and the
processes by which contamination is investigated and, more recently, controlled.
Firstly, the understanding of what constitutes a threat tothe marine environment,
once perceived to entail essentially just chemical contaminants, has been
broadened in scope. Thus, pollution by such agents as metals, pesticides, and oil
continues tofeature prominentlyin environmental impact studies. More recently,
one could add organometals, radionuclides, and endocrine disrupters to the list
of chemicals. However, other agents of anthropogenic change are now being
investigated. Hence, non-chemical causes for concern include the heat associated
with the emission of cooling waters from power plants, exotic biota from ship
ballast waters and hulls, and enhanced sediment discharge as a result of
accelerated soil erosion caused by deforestation and urban development.
Secondly, the research process to investigate contaminants has changed.
Biogeochemical practices have ensured that understanding the behaviour of
contaminants in the marine environment requires a multidisciplinary strategy.
This takes into appreciation the role of hydrodynamics in pollutant transport
processes at one extreme and elucidating biochemical responses at a sub-cellular
level at the other. The development of more sensitive instrumentation has
facilitated the creation of a better database of pollutant distributions. However,
of greater significance is the realization that marked biological responses can be
induced at extremely low contaminant concentrations. Sensitive assays now
allow the investigation of sub-lethal effects of pollutants on cellular components
and processes. Thus, several compounds have been shown to act as endocrine
disrupters and, accordingly, ecotoxicology comprises a part of the spectrum of
marine pollution studies.
Finally, recognition of the deleterious effects of marine pollution has led to a
variety of control strategies. These strategies can be legal or technological in
nature, but have usually been reactive responses to a pollution event. Thus, there
is a notable ongoing effort to develop technologies to remediate polluted marine
environments, particularly following oil spills. In the same vein, legislation has
been introduced, both nationally and internationally, to limit known sources of
contamination. The efforts by the International Maritime Organization (IMO)
are notable in this regard with respect to limiting pollution fromships. However,
the approach has been changing to become proactive in character. Essentially,
the hard-learned lessons fromDDT and TBT have instilled caution, for instance
in the introduction of new antifouling agents in marine paints. This cautionary
approach places greater reliance on risk assessment procedures and cost—benefit
analyses. Present and future challenges rest with the need to identify the
` S. J. de Mora (ed.), Tributyltin: Case Study of an Environmental Contaminant, Cambridge University
Press, Cambridge, 1996.
S. J. de Mora
82
acceptable limits of pollution based on environmental, social, economic, and
legal criteria. Marine pollution, perhaps once considered the domain of chemists
and biologists, now impinges and relies on numerous other disciplines.
2 Selected Case Studies
There are numerous examples and instances of pollution in the marine
environment and a comprehensive coverage would be beyond the scope of a
single article. Only a few case studies are presented here. They are global in
character and represent examples where public and scientific concern has been
sufficient to provoke strategies to mitigate and/or prevent such pollution.
Oil Slicks
Major releases of oil have been caused by the grounding of tankers (e.g. Torrey
Canyon, Southwest England, 1967; Argo Merchant, Nantucket Shoals, USA,
1976; Amoco Cadiz, Northwest France, 1978, Exxon Valdiz, Alaska, 1990) or by
the accidental discharge fromoffshore platforms (e.g. Chevron MP-41C, Mississippi
Delta, 1970; Ixtox I, Gulf of Mexico, 1979). Because oil spills receive considerable
public attention and provoke substantial anxiety, oil pollution must be put into
perspective. Crude oil has habitually beenintroducedintothe marine environment
from natural seeps at a rate of approximately 340 ;10' Lyr¹. Anthropogenic
activity has recently augmented this supply by an order of magnitude; however,
most of this additional oil has originated from relatively diffuse sources relating
to municipal run-off and standard shipping operations. Exceptional episodes of
pollutionoccurred in the Persian Gulf in 1991 (910 ;10' L) and due to the Ixtox
I well in the Gulf of Mexico in 1979 (530 ;10' L). In contrast to such mishaps,
the Amoco Cadiz discharged only 250 ;10' L of oil in 1978, accounting for the
largest spill froma tanker. The cumulative pollution fromtanker accidents on an
annual basis matches that emanating from natural seepage. Nevertheless, the
impacts can be severe when the subsequent slick impinges on coastal ecosystems.
Regardless of the source, the resultant oil slicks are essentially surface
phenomena that are affected by several transportation and transformation
processes.` With respect to transportation, the principal agent for the movement
of slicks is the wind, but length scales are important. Whereas small (i.e. relative to
the slick size) weather systems, such as thunderstorms, tend to disperse the slick,
cyclonic systems can move the slick essentially intact. Advection of a slick is also
affected by waves and currents. To a more limited extent, diffusion can also act to
transport the oil.
Transformation of the oil involves phase changes and/or degradation. Several
physical processes can invoke phase changes. Evaporation of the more volatile
components is a significant loss mechanism, especially for light crude oil. Oil
slicks spread as a buoyant lens under the influence of gravitational forces, but
generally separate into distinctive thick and thin regions. Such pancake
formation is due to the fractionation of the components within the oil mixture.
` S. Murray, in Pollutant Transfer and Transport in the Sea, ed. G. Kullenberg, CRC Press, Boca
Raton, FL, 1982, vol. 2, p. 169.
Contamination and Pollution in the Marine Environment
83
Sedimentation can play a role in coastal waters when rough seas bring dispersed
oil droplets into contact with suspended particulate material and the density of
the resulting aggregate exceeds the specific density of seawater. Colloidal
suspensions can consist of either water-in-oil or oil-in-water emulsions, which
behave distinctly differently. Water-in-oil emulsification creates a thick, stable
colloidthat can persist at the surface for months. The volume of the slickincreases
and it aggregates into large lumps known as ‘mousse’, thereby acting to retard
weathering. Conversely, oil-in-water emulsions comprise small droplets of oil in
seawater. This aids dispersion and increases the surface area of the slick, which
can accelerate weathering processes.
Chemical transformations of oil are evoked through photochemical oxidation
and microbial biodegradation. Not only is the latter more important in nature,
but strategies can be adopted to stimulate biological degradation, consequently
termed bioremediation. All marine environments contain microorganisms
capable of degrading crude oil. Furthermore, most of the molecules in crude oils
are susceptible to microbial consumption. Oil contains little nitrogen or
phosphorus, and as a result, microbial degradation of oil tends to be nutrient
limited. Bioremediation often depends upon on the controlled and gradual
delivery of these nutrients, while taking care to limit the concurrent stimulationof
phytoplanktonactivity. Approaches that have been adoptedare the utilizationof
slow-release fertilizers, oleophilic nutrients, and a urea-foam polymer fertilizer
incorporating oil-degrading bacteria. Bioremediation techniques were applied
successfully in the cleanup of Prince William Sound and the Gulf of Alaska
following the Exxon Valdez accident. Alternative bioremediation procedures
relying on the addition of exogenous bacteria have still to be proved. Similarly,
successful bioremediation of floating oil spills has yet to be demonstrated.
Source apportionment of crude oil in seawater and monitoring the extent of
weathering and biodegradationconstitute important challenges inenvironmental
analytical chemistry. As the concentration of individual compounds varies from
one sample of crude oil to another, the relative amounts define a signature
characteristic of the source. Compounds that degrade at the same rate stay at
fixed relative amounts throughout the lifetime of an oil slick. Hence, a ‘source
ratio’, which represents the concentration ratio for a pair of compounds
exhibiting such behaviour, remains constant. Conversely, a ‘weathering ratio’
reflects the concentration ratio for two compounds that degrade at different rates
and consequently this continually changes. Oil spill monitoring programmes
conventionally determine four fractions:"
E Volatile hydrocarbons
E Alkanes
E Total petroleum hydrocarbons
E Polycyclic aromatic hydrocarbons (PAHs)
The volatile hydrocarbons, albeit comparatively toxic to marine organisms,
evaporate relatively quickly and hence serve little purpose as diagnostic aids. The
" G. S. Douglas, A. E. Bence, R. C. Prince, S. J. McMillenand E. L. Butler, Environ. Sci. Technol., 1996,
30, 2332.
S. J. de Mora
84
Figure 1 Plot of
weathering ratio
(C3-dibenzothiophenes: C3-
chrysenes) versus source
ratio (C3-dibenzothio-
phenes: C3-phenanthrenes)
for fresh and degraded oil
samples from three
different crude oil spills
(Reprinted with permission
from Environ. Sci. Technol.,
30, 2332. © 1996 American
Chemical Society)
alkanes and total petroleum hydrocarbons make up the bulk of the crude oil.
They can be used to some extent for source identification and monitoring
weathering progress. The final fraction, the PAHs, comprises only about 2% of
the total content of crude oil but includes compounds that are toxic. Moreover,
these components exhibit marked disparities in weathering behaviour due to
differences inwater solubility, volatility, andsusceptibility towards biodegradation.
As demonstratedinFigure 1, bothaD3/P3source ratio(C3-dibenzothiophenes: C3-
phenanthrenes) and a D3/P3 weathering ratio (C3-dibenzothiophenes: C3-
chrysenes) have been defined from amongst such compounds that enable the
extent of crude oil degradationto be estimatedin the marine environment, as well
as for subtidal sediments and soils."
Litter and Debris
The increasing accumulation of litter along shorelines epitomizes a general
deterioration of environmental quality of the marine environment. Such
degradation extends to the high seas, being manifest as floating debris. The
material originates not only fromcoastal sources, but also arises fromthe ancient
custom of dumping garbage from ships. Thus, high concentrations of floating
rubbish have been observed near fishing grounds and in shipping lanes. Drilling
rigs and offshore production platforms have similarly acted as sources of
contamination. Some degree of protection in recent years has accrued fromboth
the London Dumping Convention (LDC) and the International Convention for
the Preventionof Pollution fromShips (MARPOL) which outlawsuch practices.
However, the problem of seaborne litter remains global in extent and not even
Antarctica has been left unaffected.`
The floating debris and beach litter consists of many different materials that,
tending to be non-degradable, endure in the marine environment for many years.
` M. R. Gregory and P. G. Ryan, in Marine Debris: Sources, Impacts and Solutions, ed. J. M. Coe and
D. B. Rogers, Springer, New York, 1996, p. 49.
Contamination and Pollution in the Marine Environment
85
Figure 2 Quantities of
debris per trawling tow
(30 min) collected on the
continental shelf and
adjacent canyon of the
Gulf of Lyons (Reprinted
from Mar. Pollut. Bull., 30,
713. © 1995, with
permission from Elsevier
Science)
The most notorious are the plastics (e.g. bottles, sheets, fishing gear, packaging
materials, and small pellets). Numerous other materials have been observed, such
as glass bottles, tin cans, and lumber. This litter constitutes an aesthetic eyesore
on beaches, but more importantly can be potentially lethal to marine organisms.
Deleterious impacts on marine birds, turtles, and mammals result from
entanglement and ingestion. While this floating material can have the apparently
benignconsequence of acting as a habitat for opportunistic colonizers, this allows
the introduction of exotic species into newterritories, with all the latent problems
that such invasions can cause. Lost or discarded plastic fishing nets remain
functional and can continue ‘ghost fishing’ for several years.
Perhaps more startling is the unseenpollutionthat has largely gone undetected
on the sea floor. Bottom trawls in the northwest Mediterranean Sea found that
litter was essentially ubiquitous in the region (see Figure 2).' The highest
concentrations occurred in the vicinity of metropolitan areas, but canyons also
tended to be sites of preferential accumulation. Again plastics dominated the
material found, with up to 90% of the litter at a site near Marseilles comprising
plastic bags. Plastic debris settlingon soft and hardbottoms can smother benthos
and limit gas exchange with pore waters. On a different note, traps and pots that
go astray can continue to catch benthic animals.
' F. Galgani, S. Jaunet, A. Campillo, X. Guenenen and E. His, Mar. Pollut. Bull., 1995, 30, 713.
S. J. de Mora
86
Tributyltin
Tributyltin (TBT) provides an interesting case study of a pollutant in the marine
environment.` Because TBT compounds are extremely poisonous and exhibit
broad-spectrum biocidal properties, they have been utilized as the active
ingredient in marine anti-fouling paint formulations. Its potency and longevity
ensures good fuel efficiencies for ship operations and guarantees a long lifetime
between repainting. TBT-based paints have been used on boats of all sizes, from
small yachts to supertankers, ensuring the global dispersion of TBT throughout
the marine environment, from the coastal zone to the open ocean.
Notwithstanding such benefits, the extreme toxicity and environmental
persistence has resulted in a wide range of deleterious biological effects on
non-target organisms. TBT is lethal to some shellfish at concentrations as lowas
0.02g TBT-SnL¹. Lower concentrations result in sub-lethal effects, such as
poor growth rates and reducedrecruitment leading to the decline of shellfisheries.
The most obvious manifestations of TBT contamination have been shell
deformation in Pacific oysters (Crassostrea gigas) and the development of
imposex (i.e. the imposition of male sex organs on females) in marine gastropods.
The latter effect, an example of TBT acting as an endocrine disrupter, has caused
dramatic population decline of gastropods at locations throughout the world.
TBT has been observed to accumulate in fish and various marine birds and
mammals, with as-yet unknown consequences. Although it has not been shown
to pose a public health risk, one recent study reported measurable butyltin
concentrations in human liver.`
The economic consequences of the shellfisheries decline led to a rapid political
response globally. The first publication suggesting TBT to be the causative agent
appearedonly in 1982,` but already the use of TBT-basedpaints has been banned
in some countries, including New Zealand. Other nations have imposed partial
restrictions, its use being permitted only on vessels 925 m in length or on those
with aluminium hulls and outdrives. This has certainly had the effect of
decreasing the TBTflux to the marine environment, as manifestedin sedimentary
TBTprofiles. Oyster aquaculture in Arcachon Bay benefited immediately, with a
notable decline in shell deformations and TBT-body burdens and the complete
recoveryof productionwithintwoyears (see Figure 3)." Comparable improvements
in oyster conditions have been reported for Great Britain and Australia.
Similarly, there have been many reported instances of restoration of gastropod
populations at previously impacted locations. However, large ships continue to
act as a source of TBT to the marine environment. It should be of concern that
imposexed gastropods have been observed at sites (e.g. North Sea and Strait of
Malacca) where the source of TBT can only be attributed to shipping.
TBT exists in solution as a large univalent cation and forms a neutral complex
with Cl or OH. It is extremely surface active and so is readily adsorbed onto
suspendedparticulate material. Such adsorption and depositionto the sediments
limits its lifetime in the water column. Degradation, via photochemical reactions
` K. Kannan and J. Falandysz, Mar. Pollut. Bull., 1997, 34, 203.
` C. Alzieu, M. Heral, Y. Thibaud, M. J. Dardignac andM. Feuillet, Rev. Trav. Inst. Marit., 1982, 45, 100.
" C. Alzieu, Mar. Environ. Res., 1991, 32, 7.
Contamination and Pollution in the Marine Environment
87
Figure 3 Annual oyster
(Crassostrea gigas)
production in Arcachon
Bay, 1978—85; restrictions
on TBT use were first
applied in January 1982
(Data taken from Alzieu")
or microbially mediated pathways, obeys first-order kinetics. Several marine
organisms, as diverse as phytoplankton to starfish, debutylate TBT. Stepwise
debutylationproduces di- and mono-butyltin moieties, which are much less toxic
in the marine environment than is TBT. As degradation lifetimes in the water
column are of the order of days to weeks, degradation is slow relative to
sedimentation. Thus, TBT accumulates in coastal sediments where degradation
rates are much slower, with the half-life being of the order of years.¹"
Furthermore, concentrations are highest in those areas, such as marinas and
harbours, which are most likely to undergo dredging. The intrinsic toxicity of
TBT, its persistency in the sediments, and its periodic remobilization by
anthropogenic activity are likely to retard the long-term recovery of the marine
ecosystem. One recent study¹¹ has estimated that the residence time of TBT in
oligotrophic waters may also be of the order of years. This may, in part, help to
explain the measurable quantities of TBT in squid and marine mammals
collected in the open sea.
Recapitulating, the unrestricted use of TBT has ended in many parts of the
world but significant challenges remain. For the most part, the coastal tropical
ecosystems remain unprotected and the sensitivity of its indigenous organisms is
relativelypoorlyevaluated. TBTendures insediments globally, withconcentrations
usually greatest in environments most likely to be perturbed. The widespread
introduction of TBT into seawater continues from vessels not subject to
legislation. Organisms in regions hitherto considered to be remote nowmanifest
TBTcontamination and effects. Such observations imply that further restrictions
on the use of organotin-based paints are required. Indeed, the International
Maritime Organization has undertaken to draft a global, legally binding
convention that would prohibit the application of TBT-based paints after
January 1, 2003, and ban the presence of TBT on ship hulls as from January 1,
2008. Of course, the prescribed dates will provoke considerable debate. However,
¹" C. Stewart and S. J. de Mora, Environ. Technol., 1990, 11, 565.
¹¹ P. Michel and B. Averty, Environ. Sci. Technol., 1999, 33, 2524.
S. J. de Mora
88
the paramount lesson learned from TBT should be that potential replacement
compounds must be properly investigated prior to their introduction in order to
avoid another global pollution experiment.
3 Mitigation of Marine Pollution
As indicated above, national policies and international conventions have been
invoked to curb known, and usually obvious, sources of marine pollution.
National legislation is used to control coastal discharges of contaminants. A
major problem remains owing to the inadequate treatment of sewage prior to
emission from land-based sources. The most important deleterious effects in this
case are with respect to microbial water quality. This can have a direct influence
on bathing criteria and result in beach closures during contamination episodes.
An additional problem from land-based sources pertains to transboundary
effects, whereby pollution may inadvertently be exported from one country to
another.
A series of international conventions have been negotiated, especially to
control pollution from ship-based sources. Numerous restrictions apply to the
release of rubbish and oil discharges. Similarly, the role of ships as a source of
biological contaminants has become appreciated. Thus, adequate control of
sewage discharges andballast water is increasingly advocated. The environmental
threat posed by antifoulants has become widely recognized owing to TBT-based
paints. As noted above, such material should become prohibited in the near
future. Replacement compounds will needtobe showntobe more environmentally
friendly. Althoughthis is anobvious sentiment, the criteria to judge (or rank) such
biocidal compounds remain contentious. The desired attributes are usually
consideredto be a highdegradationrate, leading to non-toxic products and a low
bioaccumulation potential (possibly manifest by a low water—octanol partition
coefficient). Anegative consequence of the use of biocides other than TBTmay be
the enhanced capacity for shipping to act as a transportation vector for the
invasion of exotic species into new territory.
Economic Controls
Althougheconomic forces have oftenbeenviewedtobe anagent of environmental
degradation, the perception and role of market forces in preventing and
mitigating pollution is changing. Garrod and Whitmarsh¹` have appraised
governmental and economic methods of controlling pollution in the marine
environment. They suggested that economic controls to pollution control have
been gaining favour over ‘command and control’ strategies, but the role of
governmental action is not likely to become redundant.
As background, Garrod and Whitmarsh¹` describe market failure with respect
to protecting the marine environment. Particular difficulties arise because of the
diverse and perhaps conflicting exploitation of the sea and its resources. Thus,
pollutants maybe released into the marine environment by one sector or industry
¹` B. Garrod and D. Whitmarsh, Mar. Pollut. Bull., 1995, 30, 365.
Contamination and Pollution in the Marine Environment
89
but the environmental costs are born by society and/or other users. Property
rights are usually so poorly defined that the polluter cannot readily identify the
party to whom compensation should be paid.
Government interventionfor environmental protectionis not without criticism.
‘Standard setting’ solutions can have a proclivity towards over-regulation and
may be unable to distribute appropriately or adequately the associated costs and
compensations. Some policies may favour specific sectors of industry, to the
extent where regulations promote the industry at the expense of customers,
society, or other industrial sectors. As an alternative, governments can promote
economic approaches. Taxes and charges may be levied in an attempt to ensure
that the true costs of production are borne by the industry. The ‘polluter pays’
adage of the 1980s thereby transfers the financial burden of environmental
damage from society to the producer, with the incentive that reducing pollution
activities may realise cost benefits. An alternative tactic is to impose a system of
tradable pollution permits. Again, the incentive then rests with the producer to
minimize environmental damage and associated costs.
Corporate environmentalism is an evolving concept for environmental
protection. In this case, business takes a pro-active stance independent of
regulatory authorities. This can be in recognition of social responsibilities, but is
more successful when compelled by competitionin the market place. Thus, a firm
can conscientiously target environmentally aware consumers (throughmarketing
environmentally friendly products or processes) or can be better placed for
financial support from ethical investment funding bodies.
Despite the attractions of economic forces driving environmental protection,
some cautions and failures have been noted.¹` Firstly, the export of hazardous
waste to countries where costs for treatment are lower enhances environmental
risks during transport and has the potential for transboundary export in the
event of pollution. At the same time, the loss of raw material may deprive the
home market of an adequate supply of feedstock for the home-based industry.
Secondly, there is considerable scepticism that self-regulation of TBT-based
antifoulants could be achieved in a timely manner by the shipping industry. This
is an instance where the cost benefits to one industry are born by another
commercial sector, notablyaquaculture. Thus, protectionof the marine environment
is likely to be aided by economic factors but the role of government, via taxation
and standard setting, is not likely to be usurped. Public education and, in turn,
pressure, can promote and support corporate environmentalism.
Bioremediation
Legislation and economic factors may aim to prevent marine pollution.
Nevertheless, contaminationis inevitable andtechnological solutions tomitigating
the impacts have been developed. This is especially the case for oil pollution,
which inevitably receives considerable press attention. Accidental oil spills at sea
do occur and frequently impact shoreline environments. Petroleum pollutants
can be removed by microbial degradation. Although bacteria and fungi capable
of degrading many oil components exist in the marine environment, natural rates
of hydrocarbon biodegradation are usually limited by abiotic environmental
S. J. de Mora
90
factors. Numerous strategies to accelerate oil biodegradation rates have been
developed over the last 20 years and in situ bioremediation has become an
established oil spill countermeasure.¹`
Bioremediation refers to the addition of substances or modification of habitat
at contaminated sites to accelerate biodegradation. Two approaches have been
used. In bioaugmentation, oil-degrading bacteria are introduced to supplement
the existing microbial population. However, oil-degrading microflora naturally
increase in numbers following exposure to oil. Moreover, laboratory and field
trials have failed to provide convincing evidence of consistent success. The
cost-effective application of such technology remains controversial and not well
justified. In contrast, biostimulation involves the addition of nutrients or
growth-enhancing co-substrates and/or improvements in habitat quality to
enhance the growth of indigenous oil-degrading bacteria. Several different
strategies have been tested.
Firstly, giventhat nutrient availabilityoftenlimits microbial activity, fertilization
with nitrogen and phosphorus has been used. To prevent rapid dilution and to
maintain a sufficient concentration of nutrients to support the maximal oil
biodegradation rates, they generally are incorporated into oleophilic nutrient
formulations or microemulsions, which are retained in interfacial regions (e.g.
air—sea interface or on the surfaces of sediments in beaches). Its efficacy during
actual response operations has beendemonstratedoncobble beaches contaminated
by the Exxon Valdez spill in Alaska.¹" Secondly, diverse means to oxygenate
sedimentary environments have been attempted because anoxic conditions
dramatically limit microbial oil degradation rates. Deeper penetration of oxygen
and nutrient supplements can be achieved with tilling and raking. Alternatively,
chemical oxidants, such as hydrogen, calcium, and magnesium peroxides, can
alleviate oxygen deficiency within sediments. Transplantation may aerate the
rhizosphere and serve as a means to stimulate aerobic oil biodegradation. The
introduced plants also may take up oil and release exudates and enzymes that
further stimulate microbial activity. This technique, known as phytoremediation,
has potential application in delicate and sensitive salt marsh environments that
are the most difficult to clean. Finally, methods to increase the surface area of the
oil—water interface have been applied, this being where microbial oil degradation
principally occurs. Thus, chemical dispersants, surface agents such as powdered
peat, and fertilizers supplemented with biosurfactants have all been used as
bioremediation agents.
Recommendedfor use followingthe physical removal of bulkoil, bioremediation
has an operational advantage in that it breaks down and/or removes the residual
contaminants in place. This technology is relatively cost-effective, not requiring a
large number of personnel or highlyspecializedequipment. Laboratoryexperiments
andfield trials have demonstratedthe feasibility and success of bioremediationto
enhance bacterial degradation of oil on cobble, sand beach, and salt marsh
environments. Terminationof treatment should be implemented when: (1) it is no
longer effective; (2) the oil has degraded to acceptable biologically benign
concentrations; or (3) toxicity due to the treatment is increasing.
¹` K. Lee and S. J. de Mora, Environ. Technol., 1999, 20, 783.
¹" R. C. Prince, Crit. Rev. Microbiol., 1993, 19, 217.
Contamination and Pollution in the Marine Environment
91
4 Summary
Marine pollution takes many forms. A few case examples have been described
here with the objective to portray the diversity of contamination. Many types,
locations, and impacts can be contemplated, but some characteristics are
universal. On a positive note, there are many mechanisms for preventing
pollutionand mitigating long-termadverse effects. Thus, national legislationand
international conventions provide considerable protection from both land- and
sea-based sources of pollution. Economic forces can be used to control pollution,
either via governmental interventioninthe formof taxationor throughcorporate
environmentalism. In the inevitable consequence of marine pollution events,
bioremediation strategies have successfully aided shoreline recovery from oil
spills. This field is still evolving, with the major challenge of cleaning spills at sea
still remaining.
S. J. de Mora
92
aerobic oil, 91
hydrocarbon,90
microbial, 84
Biodiversity, 8, 61, 69
Convention, 70
Biogenic flux, 46
Biogeochemical processes, 41
Biological pump, 20
Bioremediation, 84, 90
Biostimulatio~, 91
Biosurfactants, 91
Biosynthetic pathways, 63
Bismuth,34
Bleomycin, 60
British Challenger Expedition, 42
Bryostatin 1, 72, 75
Butyltin concentrations in human liver,
87
Actinium, 34
Activity coefficients, 3
Africa, 70
African Sahel, 31
Air-sea interface, 15
Algae, 62
red, 62-64
Alkaloids, 62, 67-68
sponge, 68
Amazon River, 43
Amino acids, 5
Ammonium ions, 20
Amoco Cadiz, 83
Anoxic deep water, 24
Anthropogenic activity, 9, 81
Anthropogenic effects, 31
Anti-cancer activity, 57
Anti-cancer drugs, 57
Anti-cancer marine natural products, 73
Antifouling agents in marine paints, 82,
87
Anti-inflammatory marine natural
products, 73
Aquaculture, 71
Ara C, 72
Arabian Sea, 23
Arctic, 27
Argo Merchant, 83
Artemisinin, 58
Bicarbonate, 19-20, 28
Bioactive secondary metabolites, 63
Bioaugmentation,91
Biodegradation
Calcium carbonate, 8
Camptothecin, 56
Cape Hat teras, 46
Carbohydrates, 5
Carbon
cycle, 18, 19, 28, 31
flux, 31
reservoirs, 18
Carbonate, 14, 19-20
chemistry, 18
Carbon dioxide, 13-14, 16-21, 23-24,
28-29, 32-33
flux, 22
solubility, 20, 29
sources, 31
93
Subject Index
Thorium, 34
U- Th, 34, 35, 48
Deep convection, 24
Deep water, 24
Deep ocean circulation tracer, 48
Deep-sea sediments, 48
Deglaciation, 27
Degradation
biological, 84
microbial, 90
microbial oil, 91
Didemnin B, 74
Dimethyl sulfide (DMS), 10, 26
production, 30
Dimethyl sulfoniopropionate (DMSP),
26
Discodermolide, 77
Dissolved organic carbon (DOC), 4, 11
Diversity, chemical, 68
pool, 58
Docetaxel, 56
Dolastatin, 75
Drugs
anti-cancer, 56
derived from natural products, 56
development, 71
discovery, 58
discovery programs, 68
from the sea, 68
screening, 58
therapy, 55
Dumping garbage from ships, 85
Dysidiolide, 77
Carbon monoxide, 13, 23
CFCs
as tracers, 53
partia] pressures in the atmosphere, 40
Char]son Hypothesis, 29
Chemica] activity, 2-3
Chemica] diversity, 58, 68
Chernoby], 40
Ch]orofluorocarbons, see also CFCs, 35,
40, 51, 53
Chomophoric dissolved organic matter
(CDOM),4
Circulation in the ocean, 2
Climate, 13-15
change, 24, 31, 33
control, 10
system, 27-28
Cloud
condensation nuc]ei (CCN), 13, 25
physics, 25
Combinatorial chemistry, 60
libraries, 58
Contamination, 81
Contignasterol, 74
Continental crust, 14
Convention of Biological Diversity, 69
Conveyor belt, 15
Coral reefs, 8
Corporate environmentalism, 90
Cosmic rays, 38
Cyc]omarin A, 78
Cyclosporin, 60
Cytarbine, 72
Cytotoxic marine natural products, 62
Daughter isotopes, 37
Davies equation, 3
DDT,81
Debris, 85
Debye-Hiickel equations, 3
Decay
anaerobic, 27
bacterial, 23
constant, 35
radioactive, 35, 37
rate of, 37
Decay series
Earth Summit in Rio de Janiero, 69
Economic controls on maritime
pollution, 89
Ecosystems
benthic, 8
marine, 8-9
Ecteinascidin 743, 75
Eddy correlation technique, 17
El Nino, 15, 30
Eleutherobin, 77
Emulsification of water-in-oil, 84
Emulsions, oil-in-water, 84
Endocrine disrupters, 82, 87
Subject Index
Estuarine colloids, 44
Esuarine sediments, 48
Euphotic zone, 24, 28
Exxon Valdez, 83-84,91
Humic substances (HS), 4
Hydrocarbons, 5
Hydrogen sulfide, 23
Hyphenated analytical techniques, 70
Fatty acids, 5
Feedback, 27-28, 32
climatic, 28
ice albedo, 27
loop, 30
methane, 27
Fertilizers
slow-release, 84
urea-foam polymer, 84
Fission, 35
Fluoxetine, 57
Freons, 40
Fusion, 35
Imposex in marine gastropods, 87
In Vitro Cell Line Screening Project
(IVCLSP), 57
Inorganic composition, 2
Intellectual property rights, 69
International Association of Physical
Sciences of the Ocean (IAPSO),
2
International Convention for the
Prevention of Pollution from
Ships (MARPOL), 85
International Maritime Organization,
88
Invertebrates, 61, 62
Ionic strength, 2-3, 11
Iron, 19-20
fertilization, 31
hypothesis, 21
limiting nutrient, 21
speciation in the ocean, 5
Isogranulartimide, 77
Isotopes
radium, 48
thorium, 38, 46
U- Th series, 39
Isotopic fractionation, 37
Joint Global Ocean Flux Study
(JGOFS}, 33
Gas exchange, 15
Gas transfer velocity, 17
Genomics, 57
Geochemical cycles, 38
Geochronological tools, 35
Ghost fishing, 86
Glacial period, 28
Global cooling, 30
Global warming, 10
Granulatimide, 77
Greenhouse effect, 15, 17, 24
gases, 13, 17,23,26-28
Greenland ice cores, 27
Gulf of Alaska, 84
Gulk of Mexico, 46, 83
Laulimalide, 77
Lea, 34, 49
pollution, 50
Leukemia, 72
Limestone, 19
Lipids, 5
Litter, 85
London Dumping Convention {LDC),
85
Lovastatin, 60
Half-life, 37
Halichondrin B, 75
Halogenated terpenoid and polyketide
metabolites, 64
Heavy metals, 42
Herbicides, 81
High nitrate but low chlorophyll
{HNLC), 31
High-throughput screening, 58
Human drugs, 55
Human Genome Project, 57
Humic acids, 44
Maitotoxin, 64
0"
Subject Index
Nitrite, 20
Nitrogen oxides, 13, 23, 25
North Atlantic, 24
Deep Water, 24
Oscillation, 15
Nuclear weapons testing, 40
Nucleic acids, 5
Nutrients, 7, 21, 23, 28
oleophilic, 84, 91
Manoalide, 72, 74
Marine
algae, 61
and invertebrates, 62
biological activity, 13
biota,61
chemistry, 1
invertebrates, 61
extracts, 71
metabolites, 66
microorganisms, 71
natural products
chemistry, 61
distribution, 63
'lead' compounds, 76
structures, 62
plants and animals, 5
pollution, 82
sediments, 44
sponges, 66
sulfur cycle, 29
tracers, 38, 41
Mass spectrometry, 46
Medicinal chemistry, 58
Mediterranean Sea, 24, 86
Memorandum of Understanding
(MOU), 7
Meridional overturning circulation, 15,
29
Methane, 13, 23, 28
Methanesufonic acid (MSA), 27
Methyl chloride, 13, 26
Microorganisms, 62
Mitigation of maritime pollution,
89
Morphine, 58
Oceanography, chemical, 1
Oceans
-atmosphere climate models, 31
circulation, 14, 28, 35, 51
cycles, 33, 39
OMS production, 30
inputs, 39
plates, 14
Southern, 28
temperatures, 61
uranium residence times, 45
Oil slicks, 83
Oil spills, 82
countermeasures,91
at sea, 90
Organic chemistry in the ocean, 4
Organic matter
sedimentary, 44
suspended, 44
Organization of African Unity's task
force, 70
Organotin-based marine anti-fouling
paints, 81, 82, 87
Oxygen, 24
Oysters
aquaculture, 87
Pacific, 87
production in Arcachon, 88
Ozone layer, 13
Narragnansett Bay, 50
National Cancer Institute, 60
National Institute of Health (NIH),
70
Natural products, 55, 60
Neutron activation analysis, 46
New York Bight, 50
New Zealand, 87
Nidificine, 64-65
Nitrates, 19-20
Paclitaxel, 55-56, 58, 77
Paints, anti-fouling, 81, 82, 87
Particulate material, 41
Particulate organic carbon {POC),
47
Penicillin G, 55
Persian Gulf, 83
96
Subject Index
u- Th series, 38
Radium, 34, 37
in marine systems, 48
Radon, 34, 49
Ratio
source, 84-85
weathering, 84-85
Remotely operated (ROY) submersibles,
68
Respiration, 20, 23
Rio Accord, 69
Robotic technology, 58
Pesticides, 81
pH
buffer, 20
of seawater, 5
Pharmaceuticals from the sea,
55-79
Phosphate, 20
Photic zone, 6- 7
Photochemical oxidation of methane,
23
Photosynthesis, 7, 20, 24, 29- 30
Photosynthetically active radiation
(P AR), 6
Phytoplankton,8, 10, 20, 24, 26, 62
growth, 21, 32
oxidation, 23
Phytoremediation, 91
Pinatubo, 21
Pitzer equations, 3
Plankton see also Phytoplankton
blooms, 26
cool water, 31
growth, 21
nitrogen, 21
photosynthesis, 20
populations, 30
species, 29
Plastics, 86
Polar ice cores, 50
'Polluter pays', 90
Pollution, 81
Polonium, 34, 49
Polyketide metabolites, 65
Practical salinity unit, 16
Prince William Sound, 84
Protactinium, 34, 46
Prozac, 57
Pseudoptersoin A, 72
Pycnoclines, 7
Radiation budget, 13, 25
Radiactive disequilibrium, 37
Radionuclides, 33-35, 37
anthropogenic, 33
cosmogenic, 33-35, 38
'primordial, 33-34
transient, 33
Salinity, 2, 8, 14, 15
of seawater, 61
variations in the ocean, 2
SCUBA, 62, 68-69
Sea salt, 25
aerosol, 25
Seawater
composition, 2
physicochemical description, 11
Secondary metabolites, 55, 60-61
currently used as drugs, 59
Secular equilibrium, 37
Sessile marine invertebrates and algae,
62
Sewage discharges, 89
Shellfisheries, 87
Silicates, 20
Silicon, 20
Size of the ocean, 6
Solar radiation, 13
Solubility, 16
South Caroline salt marsh, 49
Southern Oscillation, 30
Spatial gradients, 11
Speciation
of copper, 5
of iron in the ocean, 6
Sponge terpenoids, 66
Spongothymidine, 72
Spongouridine, 72
Standard Sea Water, 2
Sulfate aerosols, 29
Sulfates, 25
Sulfides, 25
97
Subject Index
Tumour suppressor gene p 53, 78
Ultraviolet radiation, 4
Uranium,42
activity ratios, 43
bioaccumulation of, 44
concentrations in marine
environment, 45
organic matter complexes, 44
particulate, 44
Uranyl carbonate complex, 43
U- Th series radionuclides, 33
Vancomycin,60
Vincristine, 58
Volcanic activity, 8, 14
Water mass residence times, 35
Weddell Sea, 6
World Ocean Circulation Experiments
(WOCE), 33
World Trade Organization, 69
TBT see tributyltin
Tectonic processes, 14
Thermocline, 18
Thermohaline circulation, 6, 15
in North Atlantic, 32
Thorium, 45
Topotecan,56
Torrey Canyon, 83
Trace elements in seawater, 4, 33, 35
Tracers, 35
anthropogenic, 40, 51
half-life of, 41
in oceanography, 33,41
isotopes, 34
Tradable pollution permits, 90
Trade Related Aspects of Intellectual
Property Rights agreement,
69
Transfer velocity, 16-17
Tributyltin (TBT), 81,87,88
TRIPS, 69
Tropospheric water vapour, 14
98

IS S U E S IN E N V IR O N M E N T A L S C IE N C E AND TEC HNOLOGY
EDITORS:
R. E. HES TER AND R. M. HARRISON

13 Chemistry in the Marine Environment

ISBN ISSN

0-85404-260-1 1350-7583

A catalogue record for this book is available from the British Library @ The Royal Society of Chemistry 2000
All rights Apart from permitted reserved any fair dealing for the purposes in any form of research or private study, or criticism or review as under the terms of the UK Copyright, stored or transmitted, Society of Chemistry, Designs and Patents Act, 1988, this publication the prior permission may not in writing with with the the U K. Society of

be reproduced, of The Royal terms

or by any means, without Licensing Agency

or in the case of reprographic Reproduction

reproduction Rights

only in accordance outside

the terms of the licences issued by the Copyright of the licences concerning issued by the appropriate reproduction outside on this page. Enquiries Chemistry

in the UK, or in accordance Organization

the terms stated here should be sent to The Royal

at the address printed

Published by The Royal Society of Chemistry , Thomas Graham House, Science Park, Milton Road, Cambridge C,B4 OWF, UK For further information see our web site at www.rsc.org Typeset in Great Britain by Vision Typesetting, Manchester Printed and bound by Redwood Books Ltd., Trowbridge, Wiltshire

The second article. although involving very low concentrations. the presence of a complex mixture of organic compounds. and the recovery of inorganic and organic chemicals and pharmaceuticals from the oceans call for greater knowledge of this complex medium. The organic chemistry of the oceans. is concerned with interactions and exchanges that occur between ocean and atmosphere and which exert major influences on climate. CH4. such asdimethyl sulfide. chemical and biological properties form the basis of the essential controls that facilitate life on Earth. The great depth and expanse of the oceans involve spatial gradients and the establishment of distinctive zones wherein a diversity of marine organisms are sensitive to remarkably small changes in their chemical surroundings. Other gases in the marine atmosphere. Current concerns such as global climate change. Planktonic photosynthesis provides an importan~ sink for CO2 and its effectiveness is dependent on nutrient controls such as phosphate and nitrate and some trace elements such as iron. with biological processes tending to amplify the latter role. declining fish stocks. influences the distribution of other trace compounds and impacts on climate control via feedback mechanisms involving primary production and gas exchange with the atmosphere. v . of course. and the sheer size of the oceans. The impact of human activities on marine biodiversity is of growing concern. Through carbonate chemistry the deep ocean is a major reservoir in the global carbon cycle and can act as a long-term buffer to atmospheric CO2 while the surface ocean can act as either a source or sink for atmospheric carbon. This volume brings together a number of experts in marine science and technology to provide a wide-ranging examination of some issues of major environmental impact. such as influencing cloud formation. Chemical oceanographic processes are controlled by three principal concepts: the high ionic strength of seawater. also have important climatic effects.Preface The oceans cover over 70% of our planet's surface. provides an introduction to the topic and an overview of some of the key aspects and issues. The first article. CO2 is. by William Miller of the Department of Oceanography at Dalhousie University in Nova Scotia. a major 'greenhouse gas'. by Grant Bigg of the School of Environmental Sciences at the University of East Anglia. for example. Their physical. pollution of the world's oceans. CO and CH3Cl also are generated as direct or indirect products of marine biological activity. but others such as N2O.

as well as wind-borne materials such as heavy metals. The use of risk assessment and bioremediation methods is reviewed and a number of specific case studies involving such problems as persistent organic pollutants and the use of anti-fouling paints containing organotin compounds are detailed. The issues addressed range from industrial and sewage discharges and the effects of elevated nutrients from agricultural runoff in coastal zones to contamination of the deep oceans by crude oil. The final article of the book is by Stephen de Mora of the International Atomic Energy Agency's Marine Environment Laboratory in Monaco and is concerned with contamination and pollution in the marine environment. Florida. Joseph Smoak of the University of Florida. Examples of successful marine-derived drugs are given and the potential for obtaining many more new pharmaceuticals from the sea is clearly demonstrated. and his colleagues Reide Corbett from Florida State University. Many of these marine natural products have no terrestrial counterparts and offer unique opportunities for drug applications. petroleum products and plastic pollutants. drug discovery programmes have relied on in vitro intact-tissue or cell-based assays to screen libraries of synthetic compounds or natural product extracts for pharmaceutically relevant properties. this set of articles provides a wide-ranging and authoritative review of the current state of knowledge in the field and a depth of treatment of many of the most important issues relating to chemistry in the marine environment. This has opened the way to exploitation of natural products from the oceans in this context. This is concerned with the opportunities and challenges involved in developing new pharmaceuticals from the sea. Historically. Peter Swarzenski of the US Geological Survey Center for Coastal Geology in St Petersburg. These tracer techniques underpin much of the work in such large-scale oceanographic programmes as WOCE (World Ocean Circulation Experiments) and JGOFS (Joint Global Ocean Flux Study). Taken together. transient anthropogenic tracers such as the freons or CFCs are released into the atmosphere as a byproduct of industrial/municipal activity. VI . such that libraries of up to 100 000 or more chemical entities can now be screened for activity in a reasonable time frame. The volume will be of interest equally to environmental scientists. describe the use of uranium-thorium series radionuclides and other transient tracers in oceanography. can provide an apparent time stamp for both water column and sediment processes. modern 'high-throughput screening' methods have vastly increased the numbers of assays that can be performed. The use of tracers has been critical to the tremendous advances in our understanding of major oceanic cycles that have occurred in the last 10-20 years. However. The next article is by Raymond Andersen and David Williams of the Departments of Chemistry and of Earth and Ocean Sciences at the University of British Columbia.In contrast. and Brent McKee of Tulane University. The former set of radioactive tracers occur naturally in seawater as a product of weathering or mantle emanation and.Preface In the third of the articles. Wet/dry precipitation injects these tracers into the sea where they can be used to track such processes as ocean circulation or sediment accumulation. An overview of the economic and legal considerations relevant to marine pollution is given. via the parent-daughter isotope relationships.

Rester Roy M. Harrison VI] . and to national and international policymakers concerned with marine pollution and related matters. Ronald E.Preface to chemical oceanographers. Certainly it is expected to be essential reading for students in many environmental scienceand oceanography courses.

Swarzenski.Contents Introduction and Overview William L. D. Andersen and David E. 2000 ix . Miller 1 2 3 4 Introduction The Complex Medium Called Seawater Spatial Scales and the Potential for Change Summary 1 1 2 6 11 13 13 17 25 27 30 The Oceans and Climate Grant R. 13 Chemistry in the Marine Environment © The Royal Society of Chemistry. Williams 1 Introduction 2 Opportunities in the Oceans Issues in Environmental Science and Technology No. Joseph M. Reide Corbett. Bigg 1 2 3 4 5 Introduction Oceanic Gases and the Carbon Cycle Oceanic Gases and Cloud Physics Feedback Processes Involving Marine Chemistry and Climate Future Prospects The Use of U–Th Series Radionuclides and Transient Tracers in Oceanography: an Overview Peter W. McKee 1 2 3 4 Introduction Radioactive Decay Sources and Sinks Oceanic Behavior 33 33 35 38 42 55 55 60 Pharmaceuticals from the Sea Raymond J. Smoak and Brent A.

de Mora 1 2 3 4 An Overview of Marine Pollution Selected Case Studies Mitigation of Marine Pollution Summary 68 72 78 81 81 83 89 92 93 Subject Index .Contents 3 Challenges Involved in Developing a ‘Drug from the Sea’ 4 Some Success Stories 5 Future Prospects Contamination and Pollution in the Marine Environment Stephen J.

BSc. 1996) and 'Understanding our Environment: An Introduction to Environmental Chemistry and Pollution' (RSC. FRSC. having been Chairman of the Department of Environment Quality of Urban Air Review Group as well as currently being a member of the DETR Expert Panel on Air Quality Standards and Photochemical Oxidants Review Group. His more than 250 publications aremainlyin the field of environmental chemistry. the Department ofHealth Committee on the Medical Effects of Air Pollutants and Chair of the DETR Atmospheric Particles Expert Group. Harrison is Queen Elizabeth II Birmingham Centenary Professor of Environmental Health in the University of Birmingham. BSc. Rester is Professor of Chemistry in the University of York. 1983. Third Edition. CChem Ronald E. 1983) and 'Understanding Our Environment' (RSC. He has a close interest in scientific and policy aspects of air pollution. He was. PhD. 1986). FRMetS. Hester. CChem. He was previously Lecturer in Environmental Sciencesat the University ofLancaster and Reader and Director of the Institute of Aerosol Science at the University Qf Essex. latterly focusing on time-resolved studies of photoreaction intermediates and on biomolecular systems in solution. a member of the UK Department of the Environment Advisory Committee on Hazardous Substances and is currently a member of the Publications and Information Board of the Royal Society of Chemistry. DSc(London). panels and boards. Third Edition. although his current work includes studies of human health impacts of atmospheric pollutants as well as research into the chemistry of pollution phenomena. Harrison. Effects and Control' (RSC. Roy M. DSc (Birmingham). from 1991-93. 1999). He is a past Chairman of th~ Environment Group of the Royal Society ofChemistryfor whom he has edited 'Pollution: Causes.Editors Ronald E. FRSH Roy M. he has been heavily involved in national science policy and administration. He was for short periods a research fellow in Cam bridge and an assistant professor at Cornell before being appointed to a lectureship in chemistry in Y orkin 1965. XI . Hehas been a full professor in York since 1983. He is active in environmental chemistry and is a founder member and former chairman of the Environment Group of the Royal Society ofChemistry and editor of'lndustry and the Environment in Perspective' (RSC. PhD(Cornell). FRSC. As a member of the Council of the UK Science and Engineering Research Council and several of its sub-committees. His more than 300 publications are mainly in the area of vibrational spectroscopy.

MC 98012. Department of Oceanography. Department of Earth and Ocean Sciences. de Mora. Vancouver. USA W. Nova Scotia B3H 41/. Department of Oceanography. F L 32653. M arine Environment Laboratory. Swarzenski. University of British Columbia. University of East Anglia. University of Florida. 2036 Main Mall. BP 800. R. Dalhousie University. Florida State University. Tulane University. US Geological Survey. McKee. Halifax. International Atomic Energy Agency.Petersburg.Contributors R. St. Bigg. School of Environmental Sciences. University of British Columbia. R. Canada J. Andersen.L. USA P.W. Department ofGeology. LA 70118. USA D. Norwich NR4 7T1. Gainesville. Department of Chemistry.4 Quai Antoine 1er. Tallahassee. J. Corbett. Monaco B. Department of Fisheries and Aquatic Sciences. British Columbia V6T 1ZI. Williams. British Columbia V6T 1ZI. M.J. FL 33701. Miller. Canada G. Vancouver. FL 32306. 600 4th Street South.A. Smoak. E. New Orleans. UK D. Canada XlII . USA S. Centerfor Coastal Geology.

and perhaps throw in a bit about global warming. Consequently. Issues in Environmental Science and Technology No. Moreover. The application of these laws to the ocean. how can we reasonably extrapolate from a single water sample to the whole of the oceans with any confidence? The following brief introduction to this issue will attempt to provide a backdrop for examining some marine chemical reactions and distributions in the context of chemical and physical fundamentals. (2) it contains living organisms and their assorted byproducts. and (3) it covers 75% of the surface of the Earth to an average depth of almost 4000 metres. and marine resources for relevance. however. ozone holes. carefully balanced biogeochemical cycles. 2000 1 . The detailed discussions contained in the chapters that follow this one will provide examples of just how well (or poorly) we can interpret specific chemical oceanographic processes within the basic framework of marine chemistry.Introduction and Overview WIL LI AM L . chemists are left with the challenge of describing the chemical conditions in a high ionic strength solution that contains an unidentified. modified mixture of organic material. considering its tremendous size. 13 Chemistry in the Marine Environment © The Royal Society of Chemistry. can severely test the chemist’s ability to interpret their validity. for the overwhelming majority of aquatic chemical reactions taking place on this planet. MI L LE R 1 Introduction Why does Chemistry in the Marine Environment deserve separate treatment within the Issues in Environmental Science and Technology series? Is it not true that chemical principles are universal and chemistry in the oceans must therefore simply abide by these well-known laws? What is special about marine chemistry and chemical oceanography? The long answer to those questions would probably include a discourse on complex system dynamics. The reason for this relates to three things: (1) the ocean is a complex mixture of salts. The short answer is that marine chemistry does follow fundamental chemical laws.

salinity is determined by measuring the conductivity of a sample and by calibration through empirical relationships to the International Association of Physical Sciences of the Ocean (IAPSO) Standard Sea Water. Because the thermodynamic constants relating to any given reaction in solution are defined in terms of chemical activity (not chemical concentration).W. After all those many years. With this approach. every element in the periodic table can be measured as a dissolved component in seawater. these high-precision measurements are required to observe the small salinity variations in the ocean. this term is meant to represent the total number of grams of dissolved inorganic ions present in a kilogram of seawater. As salinity increases. water has been. Salinity and Ionic Strength The saltiness of the ocean is defined in terms of salinity.001 parts per thousand. This is especially true of seawater. Rivers and groundwater. high ionic strength solutions such as seawater can result in chemical equilibria that are very different from that defined with thermodynamic constants at infinite dilution. considering that 75% of all of the water in the ocean falls neatly between a salinity of 34 and 35. In fact. there is an enormous equilibration continually in progress between the water in the ocean and the rock and sediment that represents its container. This is fortunate. L. why concern ourselves with such a precise measurement of salinity? One physical consequence of salinity variations is their critical role in driving large-scale circulation in the ocean through density gradients. while Na> and Cl\ are the most concentrated dissolved components in the ocean. Both the low-temperature chemical exchanges that occur in the dark. Miller 2 The Complex Medium Called Seawater For all of the millions of years following the cooling of planet Earth. Beginning with the first raindrop that fell on rock. high-pressure expanses of the abyssal plains and the high-temperature reactions occurring within the dynamic volcanic ridge systems contribute controlling factors to the ultimate composition of seawater. salinity can be measured with a precision of at least 0. In addition to this mix of inorganic ions. In practice. the blend of dissolved materials we call seawater has largely settled into an inorganic composition that has remained unchanged for thousands of years prior to now. As for chemical consequences. although referred to as ‘fresh’. So. transformed into planetary bath water as it passes over and through the Earth’s crust. so does ionic strength. Obviously. On a much grander scale even than the flow of ions and material to the ocean. seawater is much more complex than a solution of table salt. In theory. liquid water has flowed from land to the sea. there is a continual flux of organic molecules cycling through organisms into the ocean on timescales much shorter than those applicable to salts. contain a milieu of ions that reflect the solubility of the material with which they come into contact during their trip to the sea. Ultimately. which contains 2 . and continues to be. if one works hard enough. Any rigorous chemical calculation must address both. salinity is directly related to ionic concentration and the consequent electrostatic interactions between dissolved constituents in solution.

Another approach in the modeling of activity coefficient variations in seawater attempts to take into account all interactions between all species. Pelizzetti and S. Am.e. 282. SO \. and Ca>. around 0. Millero. ed. But make no mistake. ed. in Activity Coefficients in Electrolyte Solutions. S. Changes in activity coefficients (and hence the relationship between concentration and chemical activity) due to the increased electrostatic interaction between ions in solution can be nicely modeled with well-known theoretical approaches such as the Debye—Huckel equation: ¨ log : 9 Az (I G G (1) where is the activity coefficient of ion i. J. Boca Raton.. 1991. 3 . Sometimes this situation arises owing to processes such as photochemistry or biochemical redox reactions that push systems away from equilibrium. Sci. Acta. Dordrecht. this approach is limited by a lack of experimental data on the exceedingly large number of possible ion pairs in seawater. 56. 1982. however. While these models represent significant advances in the understanding of marine chemistry. the inorganic speciation of salts in seawater represents the stage on which all other chemistry in the ocean is played out. Seawater is typically much higher. 1997. Mg>. Both the ion pairing and the specific interaction models (or a combination of the two) provide valuable information about speciation of both major and trace components in seawater. Unfortunately. p. 3123. R. J. Inclusion of additional terms in this basic equation (i. the extended Debye—Huckel. Pitzer. Often chemical research in the ocean focuses so intently on specific problems with higher public profiles or greater perceived societal relevance that the fundamental importance of physicochemical models is overlooked. Gianguzza. however. Geochim. In these cases.  K. z is its charge. Schreiber. Pitzer. J. 75. These doubly   charged ions create stronger electrostatic interactions than the singly charged ions found in a simple NaCl solution. FL. 11. CRC Press. 1508.  F. Millero. These comprehensive inorganic models provide the setting for the specific topics in the following chapters. p. seawater.01 molal. the marine chemist is left with empirical descriptions as the best predictive tool.7 molal. Cosmochim. in Marine Chemistry: An Environmental Analytical Chemical Approach. A. A is its characteristic constant. is such a complex mixture that on occasion even sophisticated models fail to accurately describe observations in the real ocean.Introduction and Overview substantial concentrations of CO \. Other times it results from the presence of unknown and/or  F. covered thoroughly elsewhere.  is a formidable tool in the calculation of chemical activity for both charged and uncharged solutes in seawater. the Davies equation) can extend the ¨ utility of this approach to higher ionic strength and works fine within an ion pairing model for a number of the major and minor ions. E. this equation is only valid at ionic strength values less than about 0. Sammartano. Kluwer. 1992. S. This complex set of equations. The Pitzer equations present a general construct to calculate activity coefficients for both charged and uncharged species in solution and form the foundation of the specific interaction model. Ultimately.  F. K. Millero and D. J. and I is the ionic strength of the solution.

M. Humic substances in the ocean are thought to be long lived and relatively unavailable for biological consumption. M. protects organisms from lethal genetic damage and provides the primary photon absorption that drives photochemistry in the ocean. Miller uncharacterized compounds. Since DOC represents the largest organic carbon pool reactive enough to respond to climate change on timescales relevant to human activity. They are found at all depths and their average age in the deep sea is estimated in the thousands of years. 4 . much of this material is quickly transformed by microbial and chemical reactions into a suite of complex macromolecules with only a slight resemblance to their precursors. It can also affect the chemical speciation and distribution of trace elements in seawater. Williams and E. Consequently. carboxylic and phenolic acids. While their initial contributions may be recognized as familiar biochemicals. R. through its light gathering role in the ocean. and amino groups) can provide binding sites for trace compounds. Consequently. Nature. high-energy ultraviolet radiation (UVR) entering the ocean. HS. alcohols. Biological Contributions In sharp contrast to the cool precision of the electrostatic equations used to describe the inorganic interactions discussed above. Many of these latter compounds are of biological origin. the degree to which HS is exposed to sunlight may ultimately determine its lifetime in the ocean. a mixture usually referred to as humic substances (HS). The presence of HS in seawater does more than provide a carbon source for microbes and alter the UV optical properties in the ocean.e. A very large percentage of Cu is complexed to organic compounds in seawater and consequently rendered non-toxic to most organisms since the free ion form of Cu  P. for many of the organic reactions in the ocean. Residual reactive sites within the highly polymerized mixture (i. The chromophoric (or coloured) dissolved organic matter (CDOM). This suggests that they are resilient enough to survive multiple complete trips through the entire ocean system. 246. which absorbs most of the biologically damaging. is composed largely of HS. 1987. the starting point for evaluation of a general approach for organic chemistry in the ocean is a situation where more than half of the dissolved organic carbon (DOC) is contained in molecules and condensates that are not structurally characterized. its sources and sinks represent an important aspect in understanding the relation between ocean chemistry and climate change. 330.W. Druffel. the study of organic chemistry in the ocean does not enjoy such a clear approach to the evaluation of organic compounds in seawater. L. There is a boundless variety of both terrestrial and marine organisms that contribute organic compounds to the sea. The chemical speciation of Cu in seawater is a good example of a potentially toxic metal that has a distribution closely linked to that of HS and DOC. we simply do not know the reactants. In other words. Since UVR-driven degradation of CDOM (and HS) both oxidizes DOC directly to volatile gases (primarily CO  and CO) and creates new substrate for biological degradation.

 While each individual organic compound may exist in exceedingly low concentrations. W. Sunda and A.  K. 1995. Oceanogr. W. Mar. Certain of these compounds found in marine organisms are unique in their ability to elicit a particular biological or chemical effect. amino acids. 50. fatty acids. Mar. Consequently. Rue and K. Working on seawater samples from many locations.  E. essential trace metals. USA shows this effect dramatically. G.  J.. calculations of iron speciation based on known thermodynamic relationships have been extremely difficult to confirm experimentally at natural concentrations. its presence in solution can be quite important. and relatively high stability constants for Fe(III) complexes with hydroxide in seawater. ‘The Chemistry of Iron in Seawater and its Interaction with Phytoplankton’.. ‘Marine Organic Geochemistry: Review and Challenges for the Future’.  C. They are generally grouped into six classes based on structural similarities: hydrocarbons. 537. Chem. One study of Cu in a sewage outfall area within Narragansett Bay.. 1995. potentially affecting both biological and chemical surroundings. 39. Limnol. Bruland and S.. it was clear that the presence of undefined organic compounds had turned a potentially lethal Cu solution into a refuge from toxicity. Chem. carbohydrates. Even though specific organic ligands could not be identified. Chem. it has long been believed that the hydrolysis of Fe(III) represents the main speciation for iron in the ocean. 50. several groups  have shown the presence of a natural organic ligand (also at nanomolar concentrations) that specifically binds to Fe(III). 32. W. 1987.. W. In recent years. Mar. G. Hanson. Organic carbon leaking into solution from the death of organisms can serve as a potential food source for a community of decomposers. lipids. M. van den Berg. The low solubility of Fe(OH) keeps total iron concentrations in the  nanomolar range. Chem. Given the slightly alkaline pH of seawater. special issue 1992. Wells. The compounds that are identifiable in the sea represent a vast array of biochemicals attributable to the life and death of marine plants and animals. Farrington. Some biochemicals may serve to attract mates or repel predators and others have the ability to sequester specific required nutrients. G. As expected. the use of ultraclean techniques with electrochemical titrations has turned the idea of a seawater iron speciation dominated by inorganic chemistry on its ear. Bruland. Other compounds are intentionally excreted into solution. Because they represent compounds that can be quantified and understood for their chemical properties and known role in biological systems. a great deal of information has been accumulated over the years about these groups and the specific compounds found within them. RI. 139. Exactly coincident with high Cu concentrations. special issue. Mar. In fact. 1995. and nucleic acids. the highest total Cu concentrations were found in this most impacted area of the estuary. L. An excellent example of the ability of small concentrations of biochemicals to significantly impact marine chemistry can be seen in a recent examination of iron speciation in the ocean. 117.Introduction and Overview is usually required for accumulation. the researchers found the lowest Cu toxicity due to high DOC concentrations and increased complexation. in particular. 5 . 50. this ligand possesses conditional stability constants for  W.

UVR. a journey lasting approximately 1000 years. and surfacing again in the North Pacific. Conversely. chemical modifications that create a considerable local impact may be of no consequence when considered in the context of the whole ocean.61 . the ocean is separated into two volumes of water. a compound that was only discovered as a dissolved constituent in seawater within the last 10 years. Another layering that occurs within the 1000 metre surface ocean is the distinction between seawater receiving solar irradiation (the photic zone) and the dark water below. L. no matter how insignificant it may seem to our ordinary scale of thinking. Prentice Hall. p. An Introduction to Physical Oceanography. 2. The sheer size of the ocean forces a unique approach when applying chemical principles to the sea. These variations in heat and salt drive a great thermohaline circulation pattern in the ocean that witnesses cold. flowing darkly through the ocean depths. when we consider a ubiquitous chemical reaction in seawater. and photosynthetically active  J. In view of the fact that Fe is an essential nutrient and can limit primary productivity in the ocean. 6 . 10 km covering 3. salty water sinking in the north Atlantic and in Antarctica’s Weddell Sea. its extrapolation to such huge proportions can result in the reaction taking on global significance. the ocean is enormous. One compilation that includes all of the oceans and adjacent seas puts the volume of seawater on the planet at 1. As mentioned above. 3 Spatial Scales and the Potential for Change As mentioned in the introduction to this chapter.W. 10 km. Consequently. Calculations that include this ligand predict that essentially all of the iron in the ocean is organically complexed. NJ. both of these variables will produce changes in fundamental equilibrium and kinetic constants and we can expect different chemistry in the two layers. Knauss. there is a large degree of difference in the heating of surface waters owing to varying solar radiation.37 . Englewood Cliffs. Pacific. This causes variations in both temperature (obviously) and salinity (from differential evaporation:precipitation ratios). Miller association with the ferric ion that are so high (K : 10 M\) that it completely * dominates the speciation of iron in the ocean. and Indian oceans alone contain about 320 million km (or 3 . A. 1978. This deep. The sun provides heat. The notable exceptions to this stable situation are in areas of the ocean with active upwelling driven by surface currents. largely isolated from one another owing to differences in salinity and temperature. a global barrier to efficient mixing between the surface and deep oceans. dense water flows beneath the less dense surface waters and results in a permanent pycnocline (density gradient) at about 1000 metres. The Atlantic. On a large scale. 10 litres) of seawater. the chemistry associated with this Fe ligand represents quite a global impact for such a seemingly insignificant concentration of a very specific organic compound. Separation of the Elements Because the ocean spreads continuously almost from pole to pole.

limited to the upper reaches of the ocean by their need for light. Si. the horizontal distribution of surface seawater across all climates on Earth leads to a diversity of environments that is unlike any terrestrial system. In fact. Swarzenski and co-authors later in this book. At almost any location in the open ocean. Fe. Ultraviolet radiation does not penetrate deeply into the ocean and limits photochemical reactions to the near surface (metres to tens of metres depending on the concentration of CDOM). are floating in a seawater solution stripped of many of the chemicals required for growth. organisms thriving in any part of the ocean could potentially end up being transported to any other part of the ocean. Diversity of Environments Along with the great depth that leads to the vertical separation of water masses with different density. and Mn are stripped from the photic zone and delivered to depth with particles. The mountains and trenches found on the ocean floor present little or no barrier to organisms that have evolved for movement and dispersal of offspring in three-dimensional space. The visible wavelengths that drive photosynthesis penetrate deeper than UVR but are still generally restricted to the upper hundred metres. the biological production of particles in the photic zone through photosynthesis acts to sequester a wide variety of chemical elements through both direct incorporation into living tissue and skeletal parts and the adsorption of surface reactive elements onto particles. exists the largest storehouse of plant fertilizer on the planet. W. The mechanisms and rates of this particle-driven. This flux of particles from the surface ocean to deeper waters leads to vertical separation of many chemical elements in the ocean. While terrestrial ecosystems often offer up physical barriers to migration. the underlying physical structure provides at least three distinct volumes of water between the air—sea interface and the bottom. a reservoir that grows ever larger as it ages. in the deep ocean layers. Nutrients essential to marine plant growth like N. The redistribution of essential biological elements away from where they are needed for photosynthesis sets up an interesting situation. beneath them. Winter storms limit the timescale for seasonal pycnoclines by remixing the top 1000 metres on roughly a yearly basis. The demarcations between different marine environments are often gradual and difficult to define.Introduction and Overview radiation (PAR) to the upper reaches of the ocean. Meanwhile. P. chemical separation of the ‘fuel and the fire’ are more closely examined by P. While most of the chemicals associated with particles are recycled by microbial degradation in the upper 1000 metres. Heat will produce seasonal pycnoclines that are much shallower than the permanent 1000 metre boundary. the oceans are fluid and continuous. Marine plants. some percentage drop below the permanent pycnocline and return to the dissolved components of the deep ocean through microbial degradation and chemical dissolution. With enough time and biological durability. This establishes the potential for vertical separation of elements into distinct chemical domains that occupy different temporal and spatial scales. Ecological distinctions are easy to recognize when considering the ocean floor: 7 .

W. The biochemistry of marine organisms is very often finely evolved to exploit almost imperceptible changes in ocean chemistry. Temperature is an obvious environmental factor. This shift in plant speciation and growth can alter the survival of grazer populations and their predators further up the food chain. Chemical variations much more subtle than salinity can also result in finely tuned ecological niches. Salinity. can define discrete environments where rivers meet the sea. Miller muddy. Most arctic organisms do not thrive in tropical waters. A more subtle result of temperature variation involves the solubility of calcium carbonate. there are innumerable examples that man has not yet even identified. These chemicals. resulting from contact between seawater and molten rock deep within the Earth. It is important to note from this example that chemical changes in the nanomolar range are certainly capable of altering entire marine ecosystems. sandy. Many of these specific compounds are being 8 . however. seemingly small chemical and physical gradients within seawater can dictate the success or failure of organisms that possess only subtle differences in biochemical machinery and will push marine ecosystems towards increased biodiversity. In short. Vents are periodically shut down and relocated tens to hundreds of kilometres away by volcanic activity and shifting of crustal rock. The presence of a specific set of organisms in seawater will produce a distinct chemical milieu via incorporation of required elements and excretion of others. Almost certainly. although they may have closely related species that do. Many other biochemical adaptations have resulted in response to the intense competition among organisms to exploit these tiny changes in their environment. Both the reduced elements and the vents themselves are transient. This simple chemistry goes a long way toward explaining the tropical distribution of massive coral reefs. In the deep sea. Their presence fuels a microbial population that serves as the primary producers for the surrounding animal assemblage. For example. L. entire ecosystems result from the presence of reduced compounds like sulfur and iron in the water. reducing waters mix with the larger body of oxygenated water. or rocky bottoms result in very different benthic ecosystems. Variable chemical distributions of specific elements in the ocean promote finely tuned biological systems capable of exploiting each situation presented. these deep sea organisms have the intricate biochemistry to locate and exploit chemical anomalies in the deep ocean. spew from vents within the superheated seawater. The fact that calcium carbonate is less soluble in warm water than in cold dictates the amount of energy required by plants and animals to build and maintain calcium carbonate structures. while showing little variation in the open ocean. organisms face pelagic distinctions that are defined by varying physical and chemical characteristics of the solution itself. the only known ecosystem not supported by photosynthesis. returning from the ocean to spawn. some as transient as the sporadic events that create them. Yet. the addition of Fe to open ocean ecosystems that are starved of this micronutrient will cause population shifts from phytoplankton species that thrive in low iron environments to those with higher Fe requirements. Sulfide and Fe(II) are oxidized and lost as the hot. Salmon. In the majority of the ocean. can identify the set of chemicals specific to the streams and rivers of their birth.

R. seashores littered with dead fish. daily spillage of petroleum products from shipping activities. A subsequent chapter in this book by G. This is not to say that long-term chemical changes cannot result from man’s activities. Non-pointsource pollution such as terrestrial runoff of fertilizers and pesticides. namely the coastal zone. Andersen and D. they probably do not represent the largest threat to marine systems. Atmospheric delivery of anthropogenic elements can spread pollutants to great distances and result in delivery of material to large expanses of the ocean. Impacts Because their survival often depends directly on the ability to detect and respond to infinitesimal changes in seawater chemistry. J. J. Examination of the exchange of material between marine and atmospheric chemistry forces the collaboration of two disciplines: oceanography and atmospheric science. Williams. and increasing concentrations of atmospheric contaminants all reflect man’s chronic contribution to ocean chemistry. it only requires nanomolar concentrations of Fe to change entire marine ecosystems and potentially alter the chemical distribution of all elements integral to the resulting biological processes. changes to the whole ocean system are usually slow. discharge of long-lived industrial chemical pollutants. the exchange of material between the ocean and atmosphere represents one of the few mechanisms capable of producing oceanic changes on a global scale. and medical refuse on public beaches are the images that spring to mind when considering marine pollution. Oil drenched seabirds. Consequently. A subsequent chapter in this book by S. only observable over hundreds to thousands of years. These intricate changes may not be easily observable. Outside of the obvious impact of natural phenomena like large-scale geological events and changes in solar insolation. While these things do represent the worst local impact that man has been able to impose on the ocean. As pointed out earlier. many marine organisms are extremely sensitive to the presence of man-made contaminants in the ocean. contamination may have already altered the ocean in subtle ways that we currently know nothing about. E. The more obvious examples of man’s impact on the ocean can be seen on smaller scales in areas closer to anthropogenic activity. Bigg goes into detail as to the workings of ocean—atmosphere exchange. it is difficult to effect chemical change over the entire ocean owing to its great size. As mentioned above. Recent scientific enterprise directed at the understanding of climate change and man’s potential role in that change has led to a closer collaboration between these two disciplines than ever before.Introduction and Overview discovered and their sources and prospects for exploitation are examined in the chapter in this book by R. The truth is. These activities have the potential to accumulate damage and affect the natural chemical and biological stasis of the ocean. de Mora provides many more details on the chronic and episodic modifications of marine chemistry that can result from man’s activities. Our most vivid examples of man’s impact on marine systems often result from catastrophic episodes such as oil spills and the visible results from marine dumping of garbage. Part of the requirement for interdisciplinary efforts in ocean—atmosphere 9 .

G. London.  R. Simpson and P. Chapman and Hall. M. Upstill-Goddard. Additionally. possible to imagine that the distribution and chemistry of a simple biogenic sulfur gas can have global implications. Turner and R. in Understanding the North Sea System. ed. D. methyl bromide. p. Carbon monoxide. where it fluxes into the troposphere. 326. Charlson. in turn. and feedback loops that must be unearthed to understand the exact role of ocean—atmosphere exchange in climate change. L. 153. In the end. Do phytoplankton population dynamics have a feedback mechanism with cloud formation through the formation of DMS? In another twist to the story.W. Through this connection. however. there are biogenic and photochemical sources of other atmospherically significant trace gases in the ocean. It is also known that white clouds have a higher albedo than ocean water. Malin. Liss. it appears that this feedback between processes in marine surface waters and atmospheric chemistry is an integral part of climate control. Liss. Global Biogeochem. This formation of clouds. The DMS story begins with the observation that in remote areas of the open ocean this trace gas is found both in the atmosphere and in surface waters with the relative concentrations indicating an oceanic source. S. 1993. C. Tett. and bromoform  all have oceanic sources to the atmosphere. It should be noted that development of many quantitative aspects of this story are still on the drawing board and once these details are resolved. thereby reflecting more sunlight back toward space. Does it then follow that global warming will increase phytoplankton growth rates and result in enhanced global DMS formation? Will this new elevated DMS flux result in more clouds over the ocean? If so. P. Phytoplankton are responsible for the precursors for DMS production in the surface ocean. the original DMS story reveals a glimpse into the complex processes. it appears that DMS is capable. of supplying the sulfate aerosols that serve as cloud condensation nuclei. A. methyl iodide. 1993. It is well known that phytoplankton growth. changes the intensity and spectral quality of light reaching the surface ocean. carbonyl sulfide. at least in part. Tokarczyk. Watson. Through redox chemistry in the atmosphere. reciprocal impacts. M. Nightingale. will operate at increased rates when warmed. 195. 7. H. It is. we know that many biological systems. Dyer. E. In other words. S. H. Huthnance. 10 .  P. R. with nutrients available. K. J. I. Nature. P. 655. M. S. Lovelock. J. Charnock. an organism that directly depends on solar irradiance for its survival is the sole supplier of a compound that makes clouds. Liddicoat. Warren. Cycles. J. Moore and R. is directly regulated by the quantity and quality of sunlight. B. with all other growth parameters being equal. will the increased albedo cool the atmosphere and serve as a negative feedback to global warming? With the purposeful omission of the details in the DMS story as told here. Miller exchange can be seen in a qualitative way by examining the dimethyl sulfide (DMS) story. 1987.  R. Andreae and S. The intriguing part of the story emerges when one considers the source of DMS in the ocean and its eventual role in the remote atmosphere. Regardless of the eventual details. G. J. O. J. it is not possible to answer these questions. the future telling of this story could very easily have a different plot and finale. M. it is quite possible that man’s impact on the oceans can spread far beyond local events.

it does not mean that fundamental chemical principles cannot be applied. (2) the presence of a complex mixture of organic compounds. The physicochemical description of seawater must include the electrostatic interactions between a multitude of different ions dissolved in the ocean. Much of the dissolved organic carbon that is added to this milieu by biological activity is composed of a mixture of molecules and condensates that are not yet identified. While this fact makes the application of chemistry to the study of the oceans difficult. and the continued contribution of anthropogenic products through atmospheric transport sets up the possibility of impact on a global scale. These spatial gradients of chemical and physical seawater parameters encourage a diversity of organisms that are sensitive to remarkably small changes in their chemical surroundings. while almost always present at very low concentrations. The identifiable organic compounds. all taking place within the basic framework of fundamental chemistry. 11 . The chapters included in this book provide examples of important chemical oceanographic processes. can greatly affect the distribution of other trace compounds and even participate in climate control via feedback to primary production and gas exchange with the atmosphere. a population of chemically sensitive organisms. There are three principal concepts that establish many of the chemical distributions and processes and make the ocean a unique place to practice the art of chemistry: (1) the high ionic strength of seawater. and (3) the sheer size of the oceans.Introduction and Overview 4 Summary The field of chemical oceanography/marine chemistry considers many processes and concepts that are not normally included in a traditional chemical curriculum. A combination of water mass movement and the biological formation of particles that strip chemicals from solution causes the physical separation of many elements into vertical zones. a spatial and temporal distribution of chemicals is established that controls many biological and chemical processes in the sea. Given the great depth and expanse of the ocean. While the impact on the ocean by man’s activities is often local in effect. The chapters contained in this book are just a few examples of the important areas of marine chemistry that require understanding and evaluation in order to fully grasp the role of the oceans within our planetary system. making a description of their chemistry difficult. This high ionic strength solution provides the matrix that contains and controls all other chemical reactions in the sea. the combination of a carefully poised chemistry.

The Oceans and Climate GR AN T R . Biological productivity. Thus nitrates and iron contained in atmospheric dust are fertilizers of marine productivity. This last    one is also a natural source of chlorine. As will be Issues in Environmental Science and Technology No. the element of most concern in the destruction of the ozone layer in the stratosphere. sulfur-related. it is the main store of energy within the climate system. plays a major role in a number of other chemical interactions between ocean and atmosphere. Thus the atmospheric component of the planet’s radiation budget is strongly modulated by the indirect effects of oceanic gas and particle exchange. It contains almost 96% of the water in the Earth’s biosphere and is the dominant source of water vapour for the atmosphere. Other. B I GG 1 Introduction The ocean is an integral part of the climate system. with biological processes tending to amplify the latter. adds to the atmospheric supply of CCN. Through carbonate chemistry the deep ocean is a major reservoir in the global carbon cycle. 2000 13 . and so can potentially act as limiting factors of the biological pump’s climatic influence. CO and CH Cl. The surface ocean  can act as either a source or sink for atmospheric carbon. These include N O. The oceanic scavenging of atmospheric loadings of some particulate material is also important in this chemical exchange between ocean and atmosphere. Various gases that are direct or indirect products of marine biological activity act as greenhouse gases once released into the atmosphere. It covers 71% of the planet’s surface and has a heat capacity more than four times that of the atmosphere. mostly of planktonic life-forms. The physical loss of salt particles to the atmosphere. particularly during wave-breaking. CH . 13 Chemistry in the Marine Environment © The Royal Society of Chemistry. Our concern here is mainly with the chemical interaction between the ocean and atmosphere through the exchange of gases and particulates. products of marine biological processes ultimately contribute to production of cloud condensation nuclei (CCN). With more than 97% of solar radiation being absorbed that falls on the surface from incident angles less than 50° from the vertical. and so can act as a long-term buffer to atmospheric CO .

Of course. Cambridge. K. so contributing to fluxes of these quantities to the atmosphere in ways that would not have occurred without the establishment of the wind-driven circulation in the first place. Conduction  M. 399. 559. McGraw-Hill. and thus setting up pressure gradients that drive circulation. such as Tibet. and its salts. so may provide a means of heating far removed from the source of the original vapour. the Rocky Mountains and the Alps. Zones of concentrated atmospheric heating are also possible by this mechanism. E. 33. 2. affecting the density of each medium. There are also much longer timescales of chemical interaction between the ocean and climate system. transfers large. directly proportional to the wind speed as well as the above-water humidity gradient. Water and other climatically active compounds are also recycled from the ocean into the atmosphere through tectonic processes.G. Cambridge University Press. These atmospheric inputs can be climatically active. tropospheric water vapour is more variable. In contrast. For example. the resultant flow carries heat and water. 1996.. New York. sequesters atmospheric CO in the ocean through the run-off of the dissolved  carbonate products of weathering.  G. and variable. p. Physical Interaction While this chapter is mainly concerned with the chemical interactions between ocean and atmosphere. 9. The Oceans and Climate. Introduction to Geochemistry. B. slow erosion of the mountain ranges uplifted over the past 20 million years. 3rd edn. although the presence of sea-ice acts to reduce all of these exchanges to a greater or lesser extent. This is a broadly similar flux globally as it depends on the fourth power of the absolute temperature. Evaporation from the ocean surface. This does not warm the atmosphere until condensation occurs. 1995. Raymo. trapped seawater. will boil off to become part of the molten crustal matrix that is re-injected into the atmosphere by volcanic activity. Bigg. such as along the west coast of South America.  K. ch. Paleoceanography. Bird. a few words need to be said about the physical interactions. ch. 21. amounts of latent heat to the atmosphere. R. As oceanic plates are subducted under continental crust at destructive plate margins. Bigg seen in the discussion of feedback processes. Krauskopf and D. R. The main physical interaction between the ocean and atmosphere occurs through the exchange of heat. water and momentum. and the whole process helps to maintain the composition of oceanic salinity over geological timescales. particularly. 1994. Heat is transferred in both directions. leading to tropical and extra-tropical storm formation. having the effect of driving the ocean circulation through the production of a wind-driven flow. The chemical weathering of land surfaces is a mechanism by which changes in the atmospheric concentration of CO can occur  over millions of years. because of their general importance for climate. the amount returned to the ocean through absorption and re-radiation by. The ocean radiates infrared radiation to the overlying atmosphere. Momentum is mostly transferred from the atmosphere to the ocean. 14 . altering the radiation budget can have profound impacts on all other aspects of the climate system. These are beyond the scope of this chapter but worth identifying for completeness. p.

deeper-reaching thermohaline circulation. Manabe and R. run-off from rivers and melting of icebergs. as is the North Atlantic Oscillation. 15 .  G. p. 1996. As part of the process of latent heat transfer. Gutzler. again in proportion to the wind speed. 9.  J. L. Perigaud. The flux. Soc. on both global and regional scales. Cambridge.  F. This tends to be much smaller in magnitude than either of the other mechanisms. for example. means slowing. Bigg The Oceans and Climate. but also to cloud formation and maintenance of the natural greenhouse effect through the replenishment of atmospheric water vapour. Altering the surface density regionally could thus have large repercussions for the global ocean circulation. G. 1990. or Conveyor Belt. 1981.. could significantly slow the meridional overturning circulation. 1. and hence density. Academic Press. Ser. This not only leads to atmospheric heating through the release of latent heat. Latent heat transfer is thus the most temporally and geographically variable heat exchange process. the latter set up by changes in temperature and salinity. 109. 325. p. Weather Rev. El Nino. Philos. The ocean circulation is a combination of (i) the wind-induced flow and (ii) a larger-scale.  S. of a gas across this interface. Nature. J. which. which in turn can feed back to the maintenance (or destruction) of the originating oceanic anomaly. in air at 1 atmosphere pressure. Stouffer. 1988. 1. 1. Decreasing the salinity of the northern North Atlantic.The Oceans and Climate and turbulent exchange also directly transfer heat from the warmer medium. within the whole Atlantic. and k is the transfer velocity. In exchange. into the ocean. Thomas. cooling and alteration of the path of the Gulf Stream extension across the North Atlantic. R. Merlivat and J. M. 165. is often written as F : k (C 9 C ) 2  (1) where C and C are the respective concentrations of the gas in question in the  atmosphere and as dissolved in the ocean. heating the atmosphere at the ocean’s expense. C. The Mechanics of Gas Exchange The fundamental control on the chemical contribution of the ocean to climate is the rate of gas exchange across the air—sea interface. Philander. 784. La Nina and the Southern Oscillation. 2 Sometimes this difference is expressed in terms of partial pressures—in the case of the water value this is the partial pressure that would result if all the dissolved gas were truly in the gaseous state. Trans. Mon. H. water vapour is added to the atmosphere. and hence the manner in which the ocean contributes to the climate. 71. Anomalous heating or cooling of the atmosphere over regions of the ocean can lead to atmospheric circulation changes. New York. This would have major climatic effects. London.-F. For gases that  S. Wallace and D. water is added to the surface of the ocean via precipitation. Minster. R. Cambridge University Press.   ch. F. 378. 1995. The local combination of evaporation and addition of fresh water can alter the ocean’s surface density considerably. A. We will return to such processes later in this chapter. The El Nino phenomenon in the Pacific is linked  to such interactions. S. in turn. ch.

. Res. Note that salinity is defined in terms of a conductivity ratio of seawater to a standard KCl solution and so is dimensionless. however. G. is often used to define salinity values. Upstil-Goddard. C. Malin. assuming an overlying atmosphere purely of each gas. 26. and bubble formation during wave-breaking actively bypasses the much slower molecular diffusion of gas. 620. It is numerically practically identical to the old style unit of parts per thousand by weight are created through marine biological activity. Turner and R. Farmer. 361. Bigg Figure 1 The solubility of the principal atmospheric gases in seawater. The molecular size of the gas will also be less important in this strongly physically controlled regime. C is generally much larger than  C so that the net flux towards the atmosphere is directly dependent on the oceanic production rate of the gas. 1993. The term ‘practical salinity unit’. Liss.  D. if a gas has a large atmospheric concentration. 2 This represents the physical control on exchange through the state of the interface and near-surface atmosphere and ocean. Units are millilitres of gas contained in a litre of seawater of salinity 35 psu. The other major factor controlling gas exchange is the transfer velocity. which have vigorous chemical  reactions with water (as we will see in the next section).G. and has a different temperature dependence. 1889. R. For gases that are chemically inert in seawater the solubility  is essentially a weak function of molecular weight. McNeil and B. I. Ser. For gases like CO . Soc. An abrupt change in transfer rate can be expected when the sea state crosses the transition to breaking waves (Figure 2). J. Bigger molecules thus have lower values of k in low-wave sea states. Both bulk chemical  P. 16 . however. as it is this that will determine (C 9 C ). as a function of temperature. Wanninkhof and W. However. for CO the solubility more than halves over this temperature range. R. Trans. By contrast. Oxygen is a good example of such a gas. but for a reactive gas this factor depends on the relative reaction rates. 531. M. C. Thus. S. D. will only allow slow exchange because the surface air mass is renewed infrequently and there is largely only molecular diffusion across the interface in these conditions. S. D. 1999. Johnson. 343. or the ocean can act as a sink for the gas. P. London. or psu.  from 1437 mL L\ to 666 mL L\ (Figure 1). then we  need to consider the solubility of our gas more carefully. A. rough seas and strong winds allow frequent renewal of the surface air. A calm sea. k . as with CO .  R. Geophys. the solubility is much increased. R. Philos. In very calm conditions the presence of surfactants slows this diffusion even further. and stable air. Watson. For chemically inert gases the solubility decreases by roughly a third in raising the water’s temperature from 0 °C to 24 °C. M. although its oceanic partial pressure can be strongly affected by biological processes. 2 because diffusion occurs more slowly. McGillis. Nightingale. M. Lett. 1993. A. L. Liddicoat. Nature.

The Oceans and Climate
Figure 2 Variation of the gas transfer velocity with wind speed. The units of transfer velocity are equivalent to the number of cm of the overlying air column entering the water per hour (Taken from Bigg, with permission of Cambridge University Press)

measures of this exchange and micrometeorological-based eddy correlation techniques show similar rates of change of k with wind speed, but they differ in 2 detail, with the eddy correlation technique tending to give somewhat higher rates of exchange. A further factor affecting k is the air—sea temperature difference. When the sea 2 is colder than the air above it, the enhanced solubility of the gas in the water (relative to the air temperature) tends to increase k . This will occur in summer in 2 sub-polar waters and over upwelling regions. The opposite is also found, and much of the ocean equatorward of 45° latitude is colder than the overlying air for much of the year. However, air—sea temperature differences are generally less than 2—3 °C so that this effect results in a less than 10% modulation of k on average. 2

2 Oceanic Gases and the Carbon Cycle
Carbon dioxide is a major greenhouse gas within the atmosphere. Water vapour is a greater contributor to the natural greenhouse effect (55—70% of the total radiative absorption compared to CO ’s 25%). However, the large inherent  variability in atmospheric water vapour compared to the anthropogenically 
H. Dupuis, P. K. Taylor, A. Weill and K. Katsaros, J. Geophys. Res., 1997, 102, 21115.

17

G. R. Bigg
Figure 3 Global carbon reservoirs and annual fluxes. Units are gigatons of carbon in the reservoirs and Gt C yr\ for fluxes

driven steady rise in background atmospheric CO levels from 280 ppmv to  360 ppmv over the last 200 years has led to concern that the magnitude of the greenhouse effect may be increasing. The infrared absorption bands of the CO  molecule also occur in regions of the Earth’s electromagnetic spectrum where at present moderate amounts of available energy escape to space. The largest reservoir of available carbon in the global carbon cycle, however, is in the deep ocean, below the thermocline (Figure 3). This is the part of the ocean that has essentially no thermal or dynamical link to direct atmospheric forcing. The depth of the temperature barrier of the thermocline varies geographically and temporally but the deep ocean can roughly be taken to be the entire ocean deeper than 500 m from the surface. Here is stored the end results of the oceanic carbonate chemistry, discussed below. As the overturning, or renewal, timescale of the ocean is of the order of 1000 years, this deep reservoir is essentially isolated from short-term changes to the remainder of the cycle. Smaller reservoirs, but still larger than that in the atmosphere, are found in the upper ocean and the terrestrial biosphere. The upper ocean reservoir has both a chemical and a biological component. While small elements of each of these surficial reservoirs are sequestered into other reservoirs, 5—10% is recycled into the atmosphere each year. Thus both the upper ocean and the terrestrial biosphere have the capacity to interact, subject to a relatively small time lag, with anthropogenically driven atmospheric change to CO . As the focus here is on the oceanic involvement with  the carbon cycle, mechanisms to significantly alter the biological pump are 
D. Schimel, D. Alves, I. Enting and M. Heimann, in Climate Change 1995, ed. J. T. Houghton, L. G. Meira Filho, B. A. Callander, N. Harris, A. Kattenberg and K. Maskell, Cambridge University Press, Cambridge, 1996, ch. 2, p. 65.

18

The Oceans and Climate considered below. This mostly involves ways to alter primary productivity by removing existing trace element controls such as nitrate or iron limitation. These controls are very different in different oceanic regimes: coastal waters have limiting light levels, but excesses of nitrates and iron due to direct input from river run-off or atmospheric deposition; in contrast, open ocean waters may have limits in one nutrient or another depending on the regional physical oceanography. The ocean’s contribution to the carbon cycle has evolved over time, and still changes with the growth and decline of glaciation. However, the deep component of the cycle can also have climatic consequences. If the exchange of carbon shown in Figure 3 is severed through changes to the physical overturning of the ocean as a whole, or a substantial basin, this disconnection of the deep and upper ocean reservoirs can lead to significant climatic change.

Carbonate Chemistry
The basic reason for the ocean being a major sink for CO lies in the reaction of  the gas with water, and subsequent anion breakdown:
CO (gas) ; H O & H> ; HCO \ & 2H> ; CO \     (2)

The component reactions in eqn. (2) are very fast, and the system exists in equilibrium. Additional carbon dioxide entering the sea is thus quickly converted into anions, distributing carbon atoms between the dissolved gas phase, carbonate and bicarbonate ions. This storage capacity is clear when the apparent equilibrium constants for the two reactions in eqn. (2) are examined, namely
a [HCO \]  K : &>  [CO ]  (3)

for the gas to bicarbonate equilibrium (where [CO ] is the concentration of the  dissolved gas and a > is the activity of the hydrogen ion), and &
a [CO \]  K : &>  [HCO \]  (4)

for the bicarbonate to carbonate equilibration. Note that these are different from standard thermodynamic equilibrium constants because of the difficulty in measuring some of the more usual quantities in seawater. These constants depend on temperature, pressure and salinity, most importantly increasing for increasing temperature and pressure. At Standard Temperature and Pressure, and a salinity of 35 psu, K is several orders of magnitude greater than K   (K : 1 ; 10\ and K : 7.69 ; 10\) so most carbon is in the intermediate,   bicarbonate, reservoir of reaction sequence (2). More CO can actually be absorbed chemically into the ocean than the above  reaction sequence suggests. Terrestrial weathering of rocks containing carbonate, such as limestone, and subsequent aerial or riverine transport, means that the ocean is enriched in carbonate. Keeping K and K constant implies, through   eqns. (3) and (4), that enhancing the oceanic [CO \] leads to a greater level of  
C. Merbach, C. H. Culberson, J. E. Hawley and R. M. Pytkowicz, Limnol. Oceanogr., 1973, 18, 897.  W. S. Broecker and T.-H. Peng, Tracers in the Sea, Eldigio Press, New York, 1982, ch. 3, p. 110.

19

The Biological Pump Oceanic biology is a sink for atmospheric CO because of the involvement of the  aqueous form of this gas in planktonic photosynthesis. atmospheric concentrations of CO are essentially uniform. S. the greater is the ratio of bicarbonate to carbonate ions. nH OæÆ   . However. R. Combining eqns. (6) mean that P (CO ) should  decrease by about a factor of three between 25 °C and 0 °C. namely. if more carbon is pumped into the system. (3). because hydrogen ions are released in both parts of eqn. so tropospheric  mixing clearly acts fast enough for this potential poleward gradient to be absent.  Another factor in this reaction sequence is also subject to external modification. (4) and (5) gives: a [CO \]  P (CO ) : &>  K K S   (6) Relative changes in the components of eqn. Thus the pH falls. as the bicarbonate to carbonate reaction is so fast (K ) the carbonate system acts as a pH buffer for the oceans. (2). Bigg oceanic dissolved CO .  Thus. However. It is also worth noting that seawater’s pH is affected by  CO dissolution. and the more hydrogen ions there are in solution. moderation of the basic oceanic dissolution of CO through temperature  dependence of its solubility.G. The latter is defined as: S: [CO ]  P (CO )  (5) where P (CO ) is the partial pressure of CO gas in air equilibrated with a   particular sample of seawater. This complex process can be summarized by nCO .

.

in the form of Fe(III) hydroxyl species.  T. Oxford. p. takes on this role. Other limitations on phytoplankton growth are chemical in nature. is known as respiration. is in both cell walls and DNA. Parsons. Oxford. ch. Nitrogen. depending on the environmental conditions and the species distribution. Colling. Phosphorus. The reverse of this process. Extensive areas of the mixed layer of the upper ocean have low nitrate and phosphate levels during  J. 1995. forms a basic building material of a plankton’s cells. 6. ch. In some species silicon. 85. nitrite and ammonium ions. Different   species preferentially absorb different wavelengths of visible light during photosynthesis.  nO . Pergamon Press. Takahashi and B. Hargrave. the  L absorption of O leading to the release of CO . is an important trace element. 1984. (CH O)   æ   L (7) where (CH O) represents a general carbohydrate. Wright and A. Biological Oceanographic Processes. as silicate. Properties and Behaviour. M. 3. Seawater: its Composition. in the form of nitrate. 20 . J. Pergamon Press. and have maximal growth at different temperatures. Iron. p. in the form of phosphate. R. They can also tolerate more or less intensity of radiation. 65. Thus maximum photosynthesis occurs below the surface and to a varying degree geographically.

The major source of oceanic iron. While globally. such as the Southern Ocean. 5. Wanninkhof. Jickells. In both cases. T. F. R. 353.. USA. Martin and S. T. W. 1. Geographical Variation The geographical distribution of the mean annual net marine flux of CO to the  atmosphere shows the combined influence of physical. Mar. Soc. which is the most common state of marine iron. R. Chem. local and short-term effects could be signficant. H.  consistent with oceanic production of CO rather than absorption. Natl. and in the long-term. but low productivity. 1995. nearby eastern coasts. collectively known as nutrients. Nature. 1990. because phytoplankton production is limited by the weak winter upwelling of nutrients. The atmosphere delivers some 30 times more iron to the ocean than rivers. reaction (2) is pushed to the left and CO is formed. 199. 1988. E. 21 . The sub-tropical oceans are close to a state of equilibrium with the atmosphere. R. T. however. Sutherland and T. Watson and P. Here it is thought that iron is the limiting nutrient. but as the upwelled water’s pressure reduces. The net effect is for the ocean to be a source of CO for the atmosphere in these areas. is atmospheric. show high levels of CO input to the atmosphere. and hence marine CO absorption. C. and the sea floor also seems to be a negligible contributor to the overlying water column. Pinatubo in 1991 have supported this so-called ‘iron’ hypothesis. A. 94. D. Takahashi. 341. S. J. with light limitation. Sci. may therefore be fundamentally limited in their productivity by the lack of iron. Polar waters tend to have net increases in levels of CO as a result of the united effects of both enhanced  solubility and biological production. Field experiments and the marine after-effects of the eruption of Mt. J. D. However. B. Feely. 41. Liss. S. 8292. such high values occur because water upwells from deeper in the ocean. Martin. in cold-water environments. This is also  visible in equatorial regions. Fitzwater. These include the Southern Ocean and part of the equatorial seas. 1998. Atmospheric inputs of the various potentially limiting nutrients are considerable and may significantly affect the primary production of the ocean. combined. 331. Takahashi. R. however. Thus the lack of availability of these species.The Oceans and Climate periods of planktonic growth. Weiss. Iron is in short supply in the ocean because of the poor dissolution of particles or colloidal material. H. Chipman. This effect outweighs the carbon  draw-down associated with the considerable phytoplankton production in these areas caused by the continual upwelling of nutrients. London. Acad. Trans. H. large areas of the ocean have high nutrient  levels. or isolated from the airborne trajectories of major sources of atmospheric dust. Areas far from land. nitrogeneous input from the atmosphere is unlikely to be a major source of planktonic nitrogen. carrying water that has been at a higher pressure. Some such regions. Ser. Paleoceanography. Proc.       J. chemical and biological effects on marine uptake of carbon (Figure 4). 1997. A. can limit phytoplankton growth. More carbon can exist as carbonate and bicarbonate ions at the greater pressures at depth. Philos. 48.

G. Bigg 22 Figure 4 Mean annual net CO flux over the global oceans (in 10 grams of C per year per 5° square)  . R.

largely derives from the sub-surface oxygen minimum associated with high productivity. N O. methane is produced by anaerobic bacterial decay: 2(CH O) æÆ  L  nCH . ch.The Oceans and Climate Coastal regions are much greater sources of primary production than deeper waters. This can undergo oxidation in the air  to sulfate aerosols. H O . J. similar to water vapour and CO . namely CO: n (CH O) . anthropogenic and from atmospheric photolysis of methane. much more rarely (0. N O . In low oxygen  environments. nCO . Rodhe. nH O  L 2   (9) With the addition of CO caused by photochemical oxidation of methane. because of the nearby source of terrestrial nutrients. Siegenthaler. The Arabian Sea in summer is the best known of such environments. Oeschger and U. of the sort discussed in the next section. Jenkins and J. that is respiration occurring where oxygen is limited but not entirely absent and so CO cannot be generated. Ephraums. but the principal global contributions are terrestrial. 2H>     (11) A product of the second pathway. a significant flux enters the atmosphere annually. About a  quarter of the annual input of N O to the atmosphere comes from the ocean. 23 . It is also worth noting the strong seasonality of carbon input to the oceans in regions dominated by the biological control. 2NH > . This reaction can follow two pathways: 2O . NH > .  Ocean Anoxia The back reaction of the photosynthesis equilibrium (7)—respiration—involves the consumption of oxygen and the production of CO . 2H>     (10) or. These dissolved gases are   R. H. but relatively little is likely to escape from the ocean because of its high reactivity. Cambridge. 3H O . ed.1% of the time): 2O . 1. is a significant greenhouse gas. Marine Biology and Oceanic Greenhouse Gas Emissions A number of biological processes result in the marine production of gases that have a greenhouse role. Cambridge University Press. p. as most such areas will have strongly enhanced carbon draw-down only during periods of maximal primary production. Another gas produced through anaerobic decay is H S. which enter the sea through both the air and rivers. Incomplete respiration. J. in Climate Change 1990. J. 1—2% of the global budget. G. Another important greenhouse gas is a product of phytoplankton oxidation of ammonium. 1. NO \ . 1996. Watson. nCO   (8) The methane that escapes to the atmosphere. H. T. also leads to the  production of a greenhouse gas. O . Houghton. T.

 several tropical basins remained isolated from the rest of the global ocean for many millions of years and so this may have partially been responsible for the high atmospheric CO levels during the Cretaceous period. The periodicity is probably related to the Earth’s orbit.. Thus while photosynthesis both sequesters carbon and produces oxygen. 24 . below the compensation depth. In some regions the presence of anoxic deep water is an important climatic signal. A long-term cessation of North Atlantic Deep Water formation. 152. the presence of organisms at depths too deep for photosynthesis results in a depletion of the oxygen levels in this water. 1995. The atmospheric greenhouse effect will then be enhanced and the global temperature will rise. Mar. During the formation of the Atlantic Ocean. so below the euphotic zone the ocean’s supply of oxygen is slowly depleted. perhaps dynamical.. Anoxic deep water can help cause climatic change. R. that is. Bigg in the surrounding water. This is thought to be a result of enhanced surface run-off from the surrounding land masses reducing the density of the surface waters. Large volumes of the deep ocean can be removed as potential storage zones for carbon. including the bottom sediments.   E. 367. Johnson. could have a climatically direct effect on atmospheric CO . This depletion can also occur higher in the water column if some. 1. Dennis. Respirating organisms exist at all depths of the ocean. K..  R. or a tectonically induced isolation of a large ocean basin. however.G. If less carbon can be stored in the ocean. mechanism concentrates plankton at a depth where only limited photosynthesis is possible. Soc. then the deep water can become anoxic. F. 1. the atmosphere. The Mediterranean is too small a basin for its periodic anoxia to cause a major direct climatic change. through the monsoonal rainfall variation associated with mid-latitude insolation variation caused by the 20 000 year periodicity in the Earth’s obliquity. as well as be a sign of it. as is recorded in bottom sediment layers. Geol. J. Lett. Earth and Planet. S. Geol. For instance. Andrews. If the replenishment of deep waters is slow. not within the phytoplankton cell. or re-enter. then more will remain in. J. Such waters will then need to use sulfates rather than oxygen in oxidizing reactions. E.  J. Tandon and P. oxygen levels are always around saturation. and so preventing winter cooling from raising surface densities to a level comparable with intermediate or bottom waters and thus causing deep convection. because of the cessation of regional deep water formation or because an ocean basin becomes isolated from global sources of deep water renewal. G. although changes to the exchange of water with the Atlantic caused by anoxically driven circulation changes within the Mediterranean could have indirect climatic effects. 1997. 148. The gradual respirated depletion of oxygen as waters move away from the surface has been one way to infer the spread of water deriving from the North Atlantic throughout much of the deep waters of the global ocean. At the surface. 1994. periodically the deep eastern Mediterranean has been anoxic. Sci. Rohling. either through a particular basin being isolated from a source of deep water formation or because the oxygen utilization is faster than the re-supply of oxygenated water. 122.

typically 0. B. with 10—10 tonnes cycled through the atmosphere annually. In addition to enhancing the upward flux of gases. D. However. 3. 1996. for instance—the abundance of atmospheric   sea salt makes this a significant source of cloud droplets. While some salts have even lower thresholds—K CO at 44%. Production Mechanisms for CCN Derived from Marine Gas Emission Biological decay mechanisms are responsible for the emission of gases that are  R. p. ed. Breaking Waves and Sea Salt In Section 1 we discussed the basic gas exchange mechanism and saw that a transition region existed where release into the atmosphere was enhanced above some critical wind speed (Figure 2). and hence precipitation. Slingo. V. ch. 4. A greater abundance of CCN means that cloud formation. N. clouds are also major reflectors of solar radiation. is also an important source of cloud condensation nuclei (CCN). cause this enhancement. The Oceans and Climate.The Oceans and Climate 3 Oceanic Gases and Cloud Physics Following the fate of a number of oceanically produced gases in the atmosphere reveals one of the major ways by which the ocean chemically contributes to the climate. E.  G. This large size means that there is a significant fall-out of particles within the marine boundary layer (up to 90%). Callander. and absorbers of terrestrial infrared radiation. Meleshko. Sea salt particles are the biggest contributor by mass of particulate material into the marine atmosphere. Meira Filho. However. but in general more cloud tends to result in less net energy entering the climate system. Houghton. either in the form in which they were emitted from the ocean. Harris. 25 . J. 85. 1996. T. in Climate Change 1995. sulfides and nitrogen oxides released by the ocean act as condensation nuclei within clouds. L. Dickinson. Randall. They tend to be relatively large. R. ch. p. A relative humidity of only 75% is required for the initiation of condensation around a NaCl nucleus. some of which we will discuss in Section 4. Maskell. Cambridge University Press. A. 193. Cambridge. E. this mechanism also effectively injects sea salt into the air. There are many indirect and direct means by which clouds affect the radiation budget. This role is enhanced by the strongly hygroscopic nature of the largely NaCl sea salt aerosol. Kattenberg and K. Sulfates. Bigg. physically injecting water and its dissolved constituents into the atmosphere. with clear implications for the surface climate. Sea salt. those that are carried by turbulence into the free atmosphere in concentrations of typically several g m\ are larger than average CCN and so play a dominant role in the important coalescence mode of rain formation. through evaporation of the dispersed water droplets before they return to the sea surface. derived from evaporation of water injected into the marine boundary layer. Breaking waves. is easier to initiate. G.1—1 m in diameter. Cambridge. A. Silva-Dias and A. or after undergoing chemical transitions. Cambridge University Press. They therefore play a fundamental role in the radiation balance of the planet. Sarachik. P.

D.. P. although the exact mechanism is under constant review. In the presence of low concentrations of NO the hydroxyl reaction V  P. Hatton. 352. DMSP also oxidizes to form DMS. Ser. Bigg Figure 5 Schematic illustration of the sources and sinks of DMS in the marine boundary layer of the atmosphere and the oceanic mixed layer (Taken from Bigg. The production of DMSP. B. 26 . R. Philos. a precursor of methyl chloride that is a natural source of chlorine.G. thought to be of importance in limiting osmotic loss of algal cell material to the surrounding seawater. Turner. O æÆ FJ 2(CH ) SO    (12) A large proportion (30—90% in tropical waters) is absorbed by bacteria and oxidized to H S in order to allow the sulfur to be used by these organisms. with permission of Cambridge University Press) precursors to CCN as well as for potential greenhouse gases. Shooter. 19. DMS is oxidized by various free radicals such as hydroxyl and nitrate ions. 1986. Mar. M. some undergoes photolytic oxidation within the sea through the reaction 2(CH ) S . As can be seen from the summarizing Figure 5. Once  in the atmosphere. viral attack or grazing. The decay of algal cells releases methyl iodide. 1997. Brimblecombe and D. G. D. Trans. 159. Liss. S. R. and hence ultimately involved in the chemistry of the stratosphere’s ozone layer. Both dimethyl sulfide (DMS) and dimethyl sulfoniopropionate (DMSP) are produced during the destruction of the cell walls of phytoplankton. Chem. Not all DMS released reaches the atmosphere.25 g m\ during plankton blooms. Malin. varies significantly from one species to another. A. DMS has been observed in the marine boundary layer in significant concentrations of up to 0. London. Nightingale and S. 343. Soc. either through death.  P.

within the system. more clouds also result. J. Thorpe. so there is a strong inverse link between global temperature and ice cover. A. and gas exchange between the atmosphere and ocean will also change. 27 . methanesulfonic acid (MSA). a theme that will also appear in the next section. Barnola. among other effects.. 28627. warming affects biological activity in the ocean. Ice is highly reflective. Stauffer. and thus cloud potential. We will consider some of these inter-linked. S. 4 Feedback Processes Involving Marine Chemistry and Climate The climate system is very complex. First. The rapid thawing of the permafrost may lead to a corresponding release of methane trapped within the ground since the previous interglacial. or occasionally self-cancelling. Untangling how it works involves much more than merely following the first-order energy fluxes between compartments. However. 1996. M. Law. J. J. The climatic feedback that could result from this natural marine sulfate emission is discussed in Section 4. This is principally because so much of the production occurs in anaerobic decay within sub-polar wetlands. This may mean that the net effect of both direct and indirect links opposes the first-order direct impact. 366. changes in its concentration could aid climatic warming. J. Feedbacks may be positive or negative. water vapour. The current increase in atmospheric concentrations of greenhouse gases does not just trap more terrestrial radiation energy in the troposphere. marine-related feedbacks in more detail below. during deglaciation the rise of sea level leads to the flooding of extensive areas of permafrost on the continental shelves of the Arctic. eastern Canada and western Europe. Raynaud. otherwise there is an acidic intermediate. such as the atmosphere. S. Chappellaz. D. T. Geophys. In either case the end result is an increase in the atmosphere’s acidity and sulfate-based CCN concentration. Schwander and B. and rapid. we will consider another marine-related feedback potentially implicated in the speed of deglaciation. This is the potential sea level and methane feedback. K. A major physically based feedback within the climate system is the ice albedo feedback. G. 1993. however. There is some indication of such a link in Greenland ice cores. Feedbacks are a key characteristic leading to difficulty in predicting how perturbation of one part of the system will affect the whole. major. During glacial periods the atmospheric concentration of methane has been significantly lower than the current interglacial’s pre-industrial level. However. These are of lesser extent during glaciations owing to the greater spread of permafrost. but warming the surface promotes more evaporation and so a greater atmospheric concentration of the dominant greenhouse gas. Often the clear first-order feedback does not reveal all the linked processes impacting on the particular feedback mechanism under discussion. As methane is a significant greenhouse gas. Nisbet. Blunier. B.  J. but recent work has tended to weaken the likely impact of such a mechanism.  R. Res. Earth’s surface and ocean. 101. Nature. Bekki. Pyle and E. 443.The Oceans and Climate leads directly to sulfate aerosols.

p. Increased warming  and greater precipitation. This is likely to have meant additional supplies of airborne iron being deposited in the ocean. Southern Ocean and North Pacific. Anthropogenic change to today’s atmospheric CO levels is also likely to have  climatic feedbacks with the ocean. which will act in the opposite fashion—a negative feedback! Evaporation due to stronger  U. In some.G. in Climate Change 1995. and so assisted glacial cooling. the  enhancement of carbon draw-down associated with increased marine biological activity is needed to reconcile the magnitude of the atmospheric decline. sub-tropical. particularly in the Southern Ocean. ed. A. J. but ice-free.  During glacial periods a drop in atmospheric concentrations of CO by about a  third accompanied the methane decrease already mentioned. 365. Increase in the supply of nutrients to the ocean is one possibility. Marchant. regions there may be enhanced evaporation. Maskell. through the temperature dependence of solubility and the conversion of dissolved CO to bicarbonate. 28 . Changes in ocean circulation are likely to have expanded the cold. regions of the North Atlantic. Bigg Feedbacks within the Marine Segment of the Carbon Cycle Carbon is an important part of both the physical chemistry and the biology of the ocean. Kattenberg and K. This is a positive feedback. There are various ways by which this may have been achieved and probably more than one mechanism is required to explain the total change.7 °C today. Denman. Most theories to explain this decline invoke the sequestration of carbon within the marine carbon cycle. Meira Filho. R. brought about by warming and increased wind speeds. where winds may have been stronger because of the greater meridional temperature gradient. Atmospheric dust loadings were higher during the last glacial period. Cambridge University Press. Surface warming will decrease CO solubility—a positive feedback—but enhance  some species’ photosynthesis through the temperature dependence of the maximal growth rate—a negative feedback through the promotion of CO  draw-down. in turn. B. would lead to less convection transporting nutrients from below the mixed layer into the euphotic zone—a positive feedback through reducing productivity. Nature. ch. both predicted to be climatic changes in the 21st century. Radical change in species distributions opens the possibility of negating much of today’s biological carbon extraction through shift of the organic carbon: CaCO sinking ratio—a positive feedback. G. Greater erosion of the exposed continental shelves could have deposited more nutrients in coastal waters. 1993. T. This can be done in various ways. N. 1996.  K. Nevertheless. Changing the atmospheric concentration of CO will therefore lead to climatic feedbacks involving the marine environment. Harris. Cambridge. E. 10. A. Such a decrease in the second most important greenhouse gas.  These are summarized in Figure 6. 483. Feedbacks between the climate system and marine organisms are thought to cool the globe by about 1. for thousands of years. 119. L. will stabilize the upper ocean water column through reducing the surface density. Callander. The cooling itself would promote greater oceanic absorption. These areas are currently the strongest marine carbon sinks and so may have played an even more important role in glacial periods. L. Houghton. This. will have reduced atmospheric absorption of terrestrial radiation. Siegenthaler and J. Sarmiento. Hofmann and H.

on average. means that a greater concentration of CCN is available for any given cloud forming. This currently removes large amounts of carbon from high latitude oceans. the dominant source of CCN. thus changing the geographical distribution of where each plankton species may attain their maximal growth rate. more condensation sites results. with permission of Cambridge University Press) winds would also cool the sea surface. Warren. Lovelock. the dependence of this production on environment conditions means that scope for a feedback process arises. through oxidation of the emitted gas. Clouds will therefore have more mid-size droplets—sea salt particles provide the majority of larger droplets. to an increase in atmospheric sulfate aerosols. O.The Oceans and Climate Figure 6 Schematic illustration of the mechanisms affecting absorption of CO in the  ocean (Taken from Bigg. in smaller droplets being produced. this feedback is called the Charlson hypothesis. Indeed. Taken to global scale. Furthermore. Nature. through latent heat transfer. 655. J.  A final positive feedback is via the enhanced greenhouse effect’s predicted reduction of the meridional overturning circulation within the Atlantic. This feedback is illustrated in Figure 7. This. Charlson. The potential feedback mechanism now appears. this leads to a lowering of the global temperature. and the production of more small droplets tends to increase the net surface area of water droplets within the cloud. hence both destabilizing the surface and enhancing CO solubility—both negative feedbacks. Sulfate aerosols are.  R. Andreae and S. for a given cloud liquid water content. Cooling will both lower surface ocean temperatures. 326. The major role clouds play in the climate system leads to possible climatic implications if changes to DMS production occurred. The Marine Sulfur Cycle and the Charlson Hypothesis DMS has been observed in the marine atmosphere since the early 1970s. An increase in DMS production within the ocean leads. E. 1987. in number terms. and reduce the solar flux required for photosynthesis. less solar radiation will penetrate the cloud. M. allowing biological and physicochemical processes to remove further CO from the  atmosphere. but it was not until the mid-1980s that there was interest in this gas as being a natural source for sulfate CCN. in turn. 29 . As the cloud’s albedo depends on the surface area exposed to the incident solar beam. J. G.

Lett. one of the climatically most variable places in the world owing to the Southern Oscillation. it is also possible that equatorward penetration of the productive. This suggests that marine DMS production may be currently cooling the globe by 3. with permission of Cambridge University Press) These changes will alter the rate of oceanic DMS production. El Nino events of this century  occurred during this interval. Geophys. S. giving rise to a positive feedback. Bigg Figure 7 Diagram of the feedback loop involving climate and planktonic production of DMS. although error bars on this number are  large. Res. One could argue that a negative feedback would arise owing to restrictions in photosynthesis. 24. It is relevant here to note that the high DMS production in the equatorial Pacific Ocean.G. climate and marine biological productivity may be self-stabilizing to a degree through the above two opposite feedbacks. Quinn. cooler-water species would enhance global DMS production. therefore. and prolonged. remained relatively constant over the period 1982 to 1996. K. 5 Future Prospects The sensitivity of the ocean’s chemical role in climate is yet to be fully explored as development of models for the carbon and biological components of oceanic  T. An estimate has been made of the purely direct global cooling effect due to DMS’s natural enhancement of cloud albedo that is possible in today’s environment. and it does not take into account the indirect feedback mechanisms. However. Bates and P. 861 30 . R. In the tropical Pacific. 1997.. The ( < ?) under biological production of DMS in the ocean indicates the uncertainty in the direction of the net feedback loop (Taken from Bigg. and therefore plankton populations. but in a direction not yet determined.8 °C (roughly double the estimated impact of today’s marine biological moderation of CO ). Some of the most dramatic.

its direct impact on the ocean’s sequestration of carbon would be to cause a significant decline in the carbon that is stored in the deep water. p. While more terrestrial sinks are being identified. Callander. A. for example fertilization due to higher CO levels and additional nitrogen deposition. error limits correspond to a 90% confidence interval 1995 estimate CO sources  Fossil fuel emissions Tropical land-use change Reservoir change Atmosphere Ocean Forest re-growth Other sinks 5. P. This is a positive feedback. G. 382. atmospheric CO growth  would be considerably greater. and the associated decline  C. F. Meira Filho. ed. Keeling.3 < 0. N. While this is not a feature that coupled models deal with well. Mitchell.3 < 1.  R. 31 .5 climate lag behind the physical modelling. the expansion of area populated by the productive cool water plankton. R. J.2 2. Table 1 shows annual average estimates for the partitioning of carbon fluxes during the decade 1980—1989. Current estimates of the perturbation of the carbon cycle owing to anthropogenic effects also have uncertainties. Res. mechanisms that result in an increased atmospheric dust load which leads to cooling. There are other. 1999. 26. 1996. Chin and T.8 0. Land clearance in the tropics and sub-tropics is likely to increase the dust burden in the atmosphere.5 1. Houghton. R.The Oceans and Climate Table 1 Average annual budget of CO  perturbations for 1980—1989. T.. A. A. Giorgi. D. ch. Kattenberg and K.5 < 0. 1996. that a significant amount (1.3 Gt C yr\) of the anthropogenically emitted carbon is not clearly withdrawn from the atmosphere by a distinct mechanism. Biological uptake is the largest uncertainty here.6 < 1. Keeling and W. B. Fluxes are expressed in Gt C yr\. Without the ocean’s enhanced uptake. L. F. Cambridge University Press. F. Battle. Stouffer.0 3. A. Weaver and T. S. Geophys. L. J. T. J. M. However.  A. Lett. Francey. uncertainty still remains as oceanic estimates also continue to be revised upwards. R. The African Sahel appears to be already undergoing an increase in dust production due to long-term dessication. but our arguments above show that there may be a marine biologically induced cooling as well. the  ocean could be responsible for more carbon withdrawal than current estimates allow. 6. L.5 < 0. 1996. Geophys. Res. Note. Lett.5 1. Maskell. atmospheric. Kattenberg. 1897. Hulme.  M.. Cambridge. 146. J. as oceanic carbon uptake would decline. Grassl. J. F. M. Tokioka. however. Steele. J. G. Langenfelds. Meehl. B. A number of current coupled ocean—atmosphere climate models predict that the overturning of the North Atlantic may decrease somewhat under a future warmer climate.0 < 0. in Climate Change 1995. Nature. 23. H. and thus may lead to enhanced iron fertilization of the present High Nitrate but Low Chlorophyll (HNLC) regions of the ocean. F. L. P. Harris. 285. Whorf. Budd. and so climatic effect.  Future climatic change due to increases in greenhouse gases will further alter the ocean’s chemistry. Wigley. The latter itself still has significant scope for improvement. While there are a number of potential terrestrial processes that can partially account for this. 61.

1999. Science. This would lead to an approximately 5% increase in DMS production and a lesser increase in CCN.G. as then the North  Atlantic’s thermohaline circulation is likely to cease almost completely. Bigg in the extent of sub-polar HNLC zones.  A. G. K. Sarmiento and C. This magnifies the positive physical feedback. P. Gabric. 1998. 284. Lequere. Schmittner. Plattner. 32 . the warming that a doubling of atmospheric CO could produce in the Southern Ocean has been  modelled to lead to decreased carbon uptake. Tellus B. Marchal and A. Science.  J. At present what we can say is that this is a young field of much intellectual and practical promise. H. 274. but only of minor impact. new interactions are constantly being discovered in nature. both positive and negative in their impact. or certainly diminish its size. Ayers. O. However. Joos. The role of oceanic physical chemistry and biochemistry in the enhanced greenhouse future is still uncertain. There is thus a negative feedback here. For example. recent model simulations suggest that there would be much less biological modification of the solubility-led uptake decrease due to surface warming.  F. Whetton. L. P. 1996. 388. We have discussed the mechanisms generating a number of potential feedbacks. due to the temperature effect on phytoplankton growth. but enhanced biological productivity. Changes in surface temperature elsewhere in the globe are likely to have a lesser impact on carbon or DMS production. and model representation of them is a rapidly evolving science. 1346. Stocker. R. 50. F. The greatest impact is likely to happen if atmospheric CO levels reach more than double present levels. Boers and G. 464. R. may well off-set this feedback. In that case. T. J.

U. RE I D E C O R BE T T. In the marine environment.and long-term climate change through exchange of heat. 13 Chemistry in the Marine Environment © The Royal Society of Chemistry.g. the numerous radionuclides can be classified into three broad categories based on their production or origin: (1) those derived from the weathering of continental rocks. (2) those formed from cosmic radiation. the anthropogenic or transient radionuclides and tracers.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography: an Overview PE T ER W. including isotopes of Issues in Environmental Science and Technology No. In this chapter we will focus on two of the most useful groups of chemical tracers in oceanography: the naturally occurring uranium. These studies benefit from the tremendous advances in our understanding of the environmental behavior of trace elements and radionuclides in seawater that have occurred just in the last 10—20 years. water. as well as our own undeniable signature on such cycles. SW A R Z EN SKI . A ND B RE NT A. the cosmogenic radionuclides. However. For example. 2000 33 . Exactly how the ocean influences short. SMO AK . JOS EP H M. or CO are topics that are being  addressed in such large-scale oceanographic programs as WOCE (World Ocean Circulation Experiments) and JGOFS (Joint Global Ocean Flux Study). Th. one of the most controversial issues is the complicated interplay between the ocean and climate change. and (3) those artificially introduced into nature. D .and thorium-series radionuclides and the artificially introduced transient tracers. the primordial radionuclides. Mc KEE 1 Introduction As we approach the 21st century. we still do not have an adequate grasp of the complexity of major oceanic cycles that will hopefully enable us to predict future trends in global climate change and sustainability. it is becoming increasingly evident that the ocean plays a highly complex and critical role in defining our global environment. and U) were incorporated during the Earth’s nucleogenesis and have half-lives that are long enough to produce many shorter-lived daughter products. The primordial radionuclides (e.

0117 27. 10 0.8 . Sarmiento.33 1.2 . concentrate on U.41 .6 .27 Half-life (yr) 12.4 . The uranium (U) decay series includes important isotopes of radium.01 .13 .04 . N. Swarzenski et al.. 10 7.06 . 10 4. Their half-lives range from months to  R. 10 5 .24 3.26 . 10 yr) and ends with stable Pb. 10 4. 1985. Radiation and Radioactivity on Earth and Beyond. radon. after emission of six alpha and  four beta particles. 10 yr) and ends with stable Pb. Th. however. 10 1. 10 4. enter the ocean primarily by the discharge of rivers. V. polonium.60 100 0.41 .46 . primarily from the sun. bismuth.092 0.162 62.88 . 10 1. A list of the primordial radionuclides is given in Table 1. polonium. Key. 34 . R. after emission of eight alpha ( )  and six beta ( ) particles. M. Cosmogenic radionuclides are formed in the upper atmosphere by the interaction of cosmic rays. 10 2. as products of continental weathering. Adloff. and Ar). FL.72 0. Geophys.2 . Boca Raton. Res. O. 10 4. Stallard. Two isotopes of radium and Th are important tracer isotopes in the thorium decay chain. 10 2 . J.83 95. 10 7 . Draganic.26 .72 99.P.6 . 10 Half-life yr 1. However. U.2 . with elements present in the atmosphere (e. 10 4. W. 10 269 5730 7.8 . t : 4. These primordial radionuclides. The actinium decay series begins with U (t : 7. 2nd edn. CRC Press. The actinium decay series includes important isotopes of actinium and protactinium. 10 4. 10 1. Table 1 Physical constants for some primordial radionuclides Radionuclide K Rb In Te La Hf Re Th U U Isotopic abundance (%) 0. 10 1. 10 yr) and ends with stable Pb after emission of seven alpha  and four beta particles. as we shall see. there are notable exceptions to this generality.3 . radon. 10 4.. Draganic and J.  I. Moore and J. 6995. and lead.905 0. D.g. L. and lead.46 . F. 1993. 90. 10 Estimated production rate (atoms m\ yr\) 1.04 . 10 — Table 2 Major radionuclides produced in the atmosphere Radionuclide H Be Ar C Al S Cl Kr From Draganic radium. The thorium decay series begins with Th (t : 1. W. S. We will. and a few of their associated daughter products that collectively make up the U—Th decay series. Z. The uranium decay series begins with U (half-life.

35 . The half-life (t ) describes a time interval after   which N : N /2. tritium (H) and Cs] mark a specific time event or series of events that can show up in a particular horizon within a water column or a geologic record. pp. Radioactive decay can be expressed as the number of atoms (N) of an unstable parent that remain at any time (t) compared to an original number of atoms (N ):  N : N e\HR  (1) The decay constant. defines the probability that a particular atom will decay within a given time ( : ln 2/t ). M) of 10 distinct elements (Figure 1). Both classes of tracers have unique attributes that make them invaluable as geochronological tools that embrace a wide range of timescales and rates of oceanic processes. Oxford. a brief review of the basic principles of radioactive decay and the application of these radionuclides as geochronological tools is useful. Z. Non-radioactive transient tracers are present in the environment as a result of a specific. Cosmogenic radionuclides are generally valuable tracers for broad-scale marine processes. Faure. such as ocean circulation and water mass residence time calculations. 2 Radioactive Decay The abundance of a trace element is often too small to be accurately quantified using conventional analytical methods such as ion chromatography or mass spectrometry. Ivanovich and R. such as the release of chlorofluorocarbons (CFCs) to the atmosphere. Wiley.g.  The U—Th decay series together consist of 36 radionuclides that are isotopes (same atomic number. It is possible.  Another way to describe radioactive decay is in terms of the mean life ( ) of a  M. The observed counting rate or activity (A) is equal to N. 1982. Principles of Isotope Geology. in Uranium Series Disequilibrium: Applications to Environmental Problems. In order to understand how U—Th series radionuclides can provide such low-level tracer information.  G. . Finally. ed. It is the other radioisotopes with half-lives greater than 1 day that are most useful and are the focus of this chapter. Some of these are very short-lived (t  1 min) and are thus not directly useful as  marine tracers. 32—55. different atomic mass. Harmon. Clarendon Press.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography millions of years (Table 2) and their variable residence times in the atmosphere are controlled by physicochemical processes. S. These nuclides enter the ocean through wet/dry precipitation and. These radionuclides [e. have a reasonably predictable geographic distribution. Many of these tracers are derived from refrigerant and aerosol propellant use and are thus more heavily produced in the northern hemisphere. M. therefore. quantifiable input. Man-made radioactive and transient tracers provide a powerful suite of tools for gaining insight into varied environmental processes. Gascoyne. New York. however. Man-made radionuclides are usually introduced into the environment by the fission of U and/or the detonation of fission and fusion devices below ground or in the atmosphere. anthropogenic radionuclides and tracers are introduced into the environment either through nuclear reactions or industrial activity. to precisely determine very low concentrations of a constituent by measuring its radioactive decay properties. 1991. 2nd edn..

W. 36 Figure 1 Chart showing the decay chain of the U—Th decay series isotopes. Vertical arrows define alpha ( ) decays while beta ( ) decays are illustrated by diagonal arrows .P. Swarzenski et al.

The number of daughter atoms produced by such decay can be expressed as: D : N 9 N and D : N (1 9 e\HR)   (2) These are the most basic equations needed in order to utilize U—Th series radionuclides as time-dependent tracers. precipitation/dissolution reactions. ocean circulation) processes.g. scavenging. Owing to the longevity of U. and inorganic/organic scavenging. Separation of a parent radionuclide from its progeny owing to differences in chemical and physical properties is termed isotopic fractionation or radioactive disequilibrium.g. many biogeochemical and physical processes. the system is considered to be at secular equilibrium (i. a radionuclide that has been separated from its radiogenic parent decays at a rate determined solely by its decay constant. The exponential decay of an unstable parent radionuclide (N atoms) to a stable daughter (D atoms) is illustrated in Figure 2. they can provide an ‘apparent age’ of a process or a geochronological framework. such as chemical weathering. Th. N approaches 0 and D approaches N (Adapted  from Faure) radionuclide. When the rate of decay of a daughter radionuclide is equal to that of its parent.).e. An understanding of the concept of secular equilibrium is also important for such age determinations using U—Th series radionuclides. This can be readily shown by the       natural decay of Ra (t : 1622 yr) and the ingrowth of its shorter-lived  daughters (e. can readily disrupt these decay chains. and U. Pb. 37 . However. Po. and Po). which simply describes the average ‘life expectancy’ of a radioactive atom ( : \). Bi. paleo-oceanographic) and modern (e. . U—Th series disequilibrium dating methods have provided oceanographers with many powerful tools to unravel both ancient (e.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography Figure 2 Exponential decay of a hypothetical radionuclide (N) to a stable daughter (D) as measured in half-lives (t ). In turn.g. . When this occurs. the number of parent atoms remains essentially constant for several daughter half-lives. Radioactive decay can thus be described either in terms of a half-life or a mean life. yet it is often more illustrative to present decay as a function of the half-life.  Note that as t approaches -. N : N : N : .

Acta. illustrated schematically in Figure 3: (a) Rivers are an important source for many radionuclides to the sea. Cosmogenic Radionuclides Cosmogenic radionuclides are produced in the upper atmosphere by spallation reactions of cosmic rays with atmospheric elements. are rapidly removed from solution and ultimately deposited to the seabed. Swarzenski et al. Peng. albeit to varying degrees of fractionation or disequilibrium. The most common  W. (e) Wet/dry deposition is a final important source for cosmogenic radionuclides (and transient tracers. in part. 3 Sources and Sinks The geochemical cycles in the ocean are controlled. It is possible that the advection of recently deposited sediments by such ground water can release radium isotopes and their progeny into coastal bottom waters. Relatively soluble species such as uranium are usually in a dissolved and/or colloidal-sized (defined loosely here as 0. Such transport can involve the full particle size spectrum (from particles to ‘truly’ dissolved). K. Coastal and offshore marine sediments therefore constantly release Ra and Rn into bottom waters. Some 25 years ago. 1977. Turekian eloquently described this cleansing capability of the oceans in terms of the ‘. (d) Autochthonous production of daughter isotopes by the radioactive decay of a long-lived parent can be a major oceanic source. see next section) to the surface ocean. by the reversible transfer of elements between the so-called dissolved (:0.4 m) phase in fresh water. Broecker and T. New York. Eldigo Press. 1139. very little dissolved thorium is present in river water. great particle conspiracy’. Cosmochim. (b) Highly particle-reactive thorium isotopes settling out of the water column to the seafloor continually produce Ra—Rn isotopes. especially in deep basins where water residence times are long. It is through this process that the reactive elements. 41. largely by diffusion/advection processes. .  K. U–Th Series Radionuclides Primordial or U—Th series radionuclides can be discharged into the ocean through several possible pathways. 1982.4 m) phases. . Marine tracers can provide a means for tracking this partitioning or cycling of constituents in seawater. Turekian. Tracers in the Sea.P. with oceanic residence times of less than ca. W. H. 1000 years. (c) Ground water (either fresh or recycled marine water) may discharge into coastal waters where hydrologic gradients or tidal forcing are favorable. S. 38 . Geochim.4 m) and particulate (90. Knowledge of the partitioning of constituents between dissolved and particulate phases in seawater is necessary for marine geochemists to fully understand the ocean as a complete biogeochemical system. In contrast. All three U—Th decay chains are represented in river water.

Th U. rates 210Pb Bioturbation U 234U 228. rates 238U 234Th 235U 234U 231Pa 230Th 231Pa excess 222Rn 228. 238U. 7. 137Cs. precipitation organic matter production Deep sea long-term sedimentation exchange across the sediment/ water interface growth of Mn-nodules circulation Hydrothermal vents source of dissolved constituents rare mineral deposits unusual chemotrophic cycles 39 Figure 3 Schematic cartoon depicting oceanic inputs and cycles of select U—Th series isotopes . Th 232Th 210Pb Sediment.226Ra 222Rn 230Th 226Ra 222Rn 4He.226Ra Pore waters Near-shore water column scavenging mixing sedimentation rates resuspension Anoxic basin redox-regulated processes such as removal. SF 6 210Pb 210Po decay The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography 222Rn wet/dry fallout Run-off Source Rock U. 210Pb Ground water U O2 H2S Sed.10Be.3H. CFCs.

19. Cs) is steadily diminishing. Thus. particle reactive Be (t : 53. For example. Fortunately for chemical oceanographers. CFC partial pressures have steadily increased since the early 1960s. G.. Sr. the atmospheric release of other modern or longer-lived trace constituents such as Kr and SF  appears to show great promise. This feature is critical in making transient analogs effective oceanographic mixing and current tracers. Geochim. C. H. Radionuclides produced during the testing of nuclear devices (e. 40 . Oxford. and thus can be used as both chemical and biological tracers. Broecker and Peng noted that since freons have no place to go except the atmosphere and their rate of destruction is very low. depending on their atmospheric speciation and prevailing air currents. respectively) and are thus evenly distributed over large geographic expanses. F. 1990. K. J. Olsen. atmospherically derived nuclides used as oceanographic tracers include H. K. R. A. C. transient in nature. Beining and A. 1982. P. A. Ambio. Mar.P. Res. Shelf Res. and CFC-113 have long residence times in the atmosphere (on the order of 50. In general. H. E. C. Larsen.. 1990. Wallace. 54.       C. these nuclides offer a pulse tracer to the oceans that can yield insight into patterns and rates of water mass circulation. Geophys. D. CFC-11. Canuel. 281.3 day)  has been utilized as a valuable coastal tracer of short-term particle deposition and remobilization. It is interesting to note that the utility of several valuable atmospheric tracers (e. CFC-12.. I. N. Swarzenski et al. Rydberg. and Np into the atmosphere. Radioisotopes of hydrogen and carbon are of particular interest because they are major biological elements. Cs. Putzka. or may also travel a great distance from the source point. Choppin. Rowland. C. the 1986 Chernobyl reactor accident released various short-lived isotopes of Kr. Sr. Ru. J. and Be. even though this city is much closer to the accident site. Recently. Pu. 1995. R.— Anthropogenic Tracers Anthropogenic tracers are artificially produced. 11. W. a water-soluble value of only 30% was measured in Prague. Martens and L. 335. Acta. 2nd edn. and Cs) may reach the sea surface within a few weeks after injection. 99. Nittrouer and C. simply owing to a constituent’s half-life and/or lack of a modern input. Cosmochim. While as much as 70% of the Chernobyl-released Cs measured in Great Britain was dissolved and thus easily dispersible. and may be radioactive. Zr. 1994.g. 7803. S. Benninger. Radiochemistry and Nuclear Chemistry. Cutshall and I. W. Cont. 237. and 90 years. 19. S. The chlorofluorocarbons (CFCs) or freons are organic compounds that are produced for a range of domestic and commercial purposes. Liljenzin and J. Sommerfield. L. 501. a reconstruction of the CFC partial pressures in the atmosphere should be valid. Ce. 180.g. Be. The partial pressures of these trace gases in the atmosphere have been reconstructed from knowledge of the world’s manufacture of these products. The largest component of artificially derived radioactivity released into the atmosphere occurred during extensive nuclear weapons testing that began in the late 1940s and ended in early 1960s. Alexander. O.. 1999. Reed Elsevier. R. Chem.

1995. rarely static. flocculation. 21. Almodovar. or carbonates. S.e. M. Chemical Equilibria and Rates in Natural Waters. Typical master variables such as pH. Oceanogr. 954. Turekian and W. depending on the chemical reactivity of a particular constituent and the water mass residence time. Forstner. owing to the active and/or passive incorporation of elements into soft tissues and fecal material. Elemental particle phase associations can be used to infer chemical reactivity and oceanic behavior. However. various criteria that link the tracer to a specific process or element must be met. (co)precipitation.. and generally still not well understood. alkalinity. In aquatic environments these reactions often occur simultaneously and competitively. Oceanogr. Aquatic Chemistry. or the scavenging capability of a radionuclide to an organic or inorganic surface site (i. P. salinity. 15.. total CO . and are associated predominantly with clay-sized particles. we must understand how elements are associated with particles and sediments. carbonates. 41 . flocculation. Micro-organisms may also be important in waters that have lower concentrations of inorganic suspended material. 1970. Limnol. and biological uptake. K ).  Fine-grained particles and colloids generally occur as aggregates of intermeshed or layered iron oxide coatings. R. is one such vital characteristic. Limnol.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography Role of Particles/Surfaces For a radionuclide to be an effective oceanic tracer. It is widely recognized that surface sites of particles are the major sequestering agent of dissolved trace elements and compounds in the aquatic environment. M. 1976. organic coatings.  D. Edginton. A. manganese oxide particles. dissolved oxygen.g. 3rd edn. These reactive surface sites are thus a source or sink for dissolved elements in the aquatic environment. Particle affinity. 294. phosphates. and detrital clays and silicates. distribution coefficient. O. Thommes and L. complexation. sulfides. Particulate material consists of various chemical components which are a result of natural chemical alterations (e.. and redox reactions) of weathered parent material during its transport to the sea. the kinetic and thermodynamic mechanisms involved in this dissolved-particulate partitioning are complex. Gordon. Stumm and J. Foremost.  D. This section provides a brief review of the role of various surface sites in relation to chemical scavenging and tracer applications. and the degree of weathering play a critical role in defining the  efficiency of scavenging. The biogeochemical processes that generally describe the interaction of elements with particles are quite well known: dissolution. For example. J. New York. Thompson. The most important geochemical phase components include iron and manganese (oxy)hydroxides. sorption. electron transfer. river-dominated coastal environments are well-known sites for colloid/particle flocculation and particle aggregation. In order to utilize marine tracers effectively. K. Morgan. the environmental behavior of the tracer must closely match that of the target constituent. Wiley. The influence of these mineral and organic components on the chemical reactivity of a radionuclide is highly variable and related to the environmental setting. K. Such areas are thus often sinks or depositional environments for many reactive  W. temperature. Kharkar. The half-life of a tracer is another characteristic that must also coincide well with the timescale of interest. organic coatings and particles. J. N. adsorption. ion exchange.

Acta. 2. Hill.4 oxidation state is highly insoluble or particle reactive.001—0. 42 . Elsevier. Academic Press.02 0. inorganic and organic contaminants.1 1983 0. N. Geochim. 547.  D.  P. Cosmochim. D. in Deep Ocean Circulation. Turekian.06 0.5 0. Acta. 40. In contrast.02—1 0. B. ed. Teramoto. 64. From Nozaki.02 0. Sholkovitz. Nozaki. Swarzenski et al. Chikyukagaku. one phase often does not have a very large binding capacity. Reduced uranium in the . T. Riley and G. Since then.00005—0. depending on local hydrological and physicochemical conditions.005 0.0025 From Goldberg.1 1975 36 8 0. 1993. 1992. From Donat and Bruland. ed. Quinby-Hunt and K.02 0.  Y. Cosmochim. marine geochemists have been continuously updating and expanding this dataset with highly specialized oceanographic vessels.3 0. Skirrow.005 0. pp. vol. These most recent developments significantly advanced our understanding of the oceanic behavior of U—Th radionuclides and enabled their use as effective tracers and geochronological tools.  Y. 1976. From Brewer. 247—281. Langmuir. London. in The Sea. 1995. 35.7 2 0.P.00015 0.2 0.6 2 0.  J. P. pp. ed.  E. uranium is thermodynamically predicted to be present in a hexavalent (. contamination-free sampling protocols (Table 3). in Chemical Oceanography. R. Physical and Chemical Aspects.00015 1995 0. 130.00015 0. 415—496. vol. Boca Raton. Geochim. Table 3 Historic trends in concentrations (nM) of some heavy metals in the ocean Element Fe Cu Ag Au Pb Bi 1963 180 50 3 0. pp. K. 2nd edn. and so a variety of phases may compete simultaneously. W. Nozaki. S. Goldberg. Brewer. Amsterdam.03 0. Wiley-Interscience. Salbu and E. 1983. 83—89. Uranium In oxygenated seawater. but it can also exist as the tetravalent U(IV) if conditions are sufficiently reducing. Only within the last decade have oceanographers been able to reliably measure and agree upon trace concentrations of many dissolved constituents in seawater.2 0. Eos. 1978.. 42. U(VI) is readily soluble due to the rapid formation of stable inorganic carbonate complexes. FL. ed. 1. pp. 26. Steinnes.5—4. In many estuaries. 1975. From Quinby-Hunt and Turekian.003—0. and large-scale data intercomparisons. Bruland. G. M. According  E. 4 Oceanic Behavior The first comprehensive effort to determine the elemental composition in the world’s oceans was established by the 1872—1876 British Challenger Expedition.6) oxidation state.00002—0.150 0. R. W. J.05 1992 0. in Trace Elements in the Oceans.  M. New York. 831. Donat and K.023 0. 1963. CRC Press. new analytical instrumentation. 3—20.

16. Cont.14. the ratio should approach unity (secular equilibrium). 4518.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography Figure 4 Measurements of (A) uranium activity ratios. Aumento. S. low pH waters. Res. UARs (U: U) and U concentrations (B) across a salinity gradient off the Amazon River mouth (1996). F. Santschi. Owing to the stability of the uranyl carbonate complex.  In particulate matter and bottom sediments that are roughly 1 . 90. Lett. carbonate sediments. Porcelli). 3. 1996. 1977. T. 60. Such a complex could potentially participate in photo-oxidation/reduction reactions. the ubiquitous carbonate complex [e. Potentially significant oceanic U sinks include anoxic basins. H. 1962. 1971. 353. Calcareous and siliceous organisms can efficiently remove uranium from      D. Q.— Removal of uranium from solution can take place by various mechanisms. 35. Recently there has been some evidence which suggests that   uranium may also exist as a peroxide complex in seawater under favorable conditions. Geophy.. L... G. and saltwater marshes. organic rich sediments.. Earth Planet. 43 . at   higher pHs such as in seawater. M. L. Lambert. UO (CO ) ] prevails. as has been shown for Mn(IV) and Fe(III). Shelf Res.g. J. Sci. Ferdelman. D. phosphorites and oceanic basalts. However. Baskaran. a phosphate uranium complex [UO (HPO ) ] might be an important species. Earth Planet. Guo. The principal source of dissolved uranium to the ocean is from physicochemical weathering on the continents and subsequent transport by rivers. 3879. Sci. J. Thurber. Church. Cosmochim. 67. Fleisher and T. in oxygenated. M. Sarin. 11. M. U concentrations by ICPMS to thermodynamic calculations. metalliferous sediments. Geochim. M. Acta. 1996. M.2 g L\ with a daughter/parent activity ratio (U: U) of 1. P. 10 years old. UARs were determined by thermal ionization mass spectrometry (TIMS) at Caltech (D. 65. Bianchi and C. uranium is universally present in seawater at an average concentration of ca. Lett. MacDougall. T.

Geochim. Sugimura. Desorption of uranium from suspended particles during estuarine mixing is thus geochemically feasible. D. Maeda and H. D. However. Lowson. bioaccumulation of uranium generally does not appear to be a dominant removal process in the open ocean (paucity of surface sites). 94. F. 70. and has in fact been observed on the Amazon shelf  (Figure 4). diffusion through pore waters of deep-sea sediments. Cosmochim. Kolodny and I. Sholkovitz and L. Swaine. 663. Chem. R. Nucl. Acta. 1987. Short. C. Chem. Other sources of uranium to the ocean may include: mantle emanations. G.. Washington. 149. Cosmochim. G. W. Short and H. A. C. Uranium may also be enriched in estuarine colloids  and in suspended organic matter within the surface ocean. Krishnaswami. L. — Global uranium flux calculations have typically been based on the following two assumptions: (a) riverine-end member concentrations of dissolved uranium are relatively constant. Uranium has repeatedly been shown to be scavenged from solution into reducing sediments. A. Lett. in Proceedings of the Symposium on Hydrogeochemistry. Anderson. 7. Harmon. R. P. 50.. Carey. Brewer reported a correlation between biogenic material from sediment traps and uranium content. R. 1986. Helz. Bhat and S. Sigleo and G.  Scott and Maeda and Windom have suggested the possibility that humic acids can efficiently scavenge uranium in low salinity regions of some estuaries. G. C. pp. S. K. Baturin and A. 45. A. G. Cosmochim. A. Acta. Geochim. 1529. 1973. 1982. ed. McKee. Sackett. F. Acta. Indian Acad. 1981. Acta. J. S. 699. K. 1991. 1697. Geochim. 1982. Hirose and Y. T. However. Nittrouer. B. leading to speculation that this phase may be an important sink for U. Sci. Chem. 2501. 3. 57. Anderson. 181—201. Organically bound uranium was found to make up to 20% of the dissolved U concentration in the open ocean. Geochim. 10. Cosmochim. T. M. pp. Mann and G. B. 35. in Uranium Series Disequilibria: Applications to Environmental Problems. 97. Geochim. Wong. 1990. Geochim. 25. K. Cosmochim. 427. Swarzenski et al. solution. Cochran. Acta. 45. Giblin. 5455. Davey and D. 1973. K. E. Cosmochim.. Cochran. Cosmochim. 51. leaching of river-borne sediments by seawater. 1. K. Particulate uranium can be also desorbed from oxide surfaces by an increase in alkalinity or pH. A. Geochim. 1981.P. 37. 1973. M. Kaplan. T. M. and remobilization through reduction of a Fe—Mn carrier phase. M. Art. Mar. DeMaster and C. D. 58. Oxford. E. W. Lienert. 59. Cosmochim. Geochim. A. Acta. Finally. A. D. R. R. J. Uranium. N. D. B. 42. 1995. there is still considerable debate                    A. R. B. 1293. Acta. 418—442. 555. Suttle and W. Earth Planet. J. S. Proc. Gray. Kochenov. 1987. Langmuir also reported a strong association between iron hydroxides and adsorbed uranium. 1994. Radiochem. Uranium—organic matter complexes are also prevalent in the marine environment. 83. Barnes and J.. Mar. Acta. 1982. 145. E.  Marine sediments can be both sources and sinks for U. 46. Ivanovich and R. sedimentary organic matter can also efficiently complex or adsorb uranium and other radionuclides. Barnes and J. Geochim. C. Clark. 1969. Sci.— This removal may also include diffusion of soluble U(VI) from seawater into the sediment via pore water. M. suggesting either active uptake by organisms or passive incorporation. Batts and D. 50. K. Acta. Surprenant. McKee and J. Y. von Gunten. Mo. Scott. Cochran. 11. R. Clarendon Press. Acta. V. S. Booth. 44 . 1993.. Biogeochemistry and Hydrochemistry. 1986. Cosmochim. Cosmochim. and (b) no significant input or removal of uranium occurs in coastal environments. Windom. J. M. F. 2779. Swarzenski. E. Geochim. 1993. Geokhimya.

55. K. R. 231. and is thus extremely particle reactive. A. Steinnes.  T. S. in Symposium on the Interaction of Radioactive Contaminants with the Constituents of the Marine Environment. Estuaries. Thorium exists as a hydrolyzed species in seawater.  K. WA/IAEA. Carroll and W. Acta. Chan. L. 1979. thorium exhibits a great affinity for particle surfaces in the marine environment. C.  A. Spalding and M. 1971. Chen et al. Moore. Cochran. Oslo. Wasserburg. 384—430. Mangini. Muller. As a consequence of having such long oceanic residence times. H. 1982. 278. These uncertainties result primarily from a poor understanding of: (1) the variability in riverine-end member concentrations of uranium. Furthermore. in Uranium Series Disequilibrium: Applications to Environmental Problems. Ku. thorium has been used to examine scavenging as an analog for other  G. McKee. 1973. Swarzenski and B. Vienna. Geochim. Thorium Like many chemical species. E. Th(OH) \L >.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography regarding the overall mass balance of uranium in the oceans. 379. Turekian and L. G. Sci. Cosmochim. 58.  P. ed. Exner. G. F. 80.  J. pp.  W. K. Moore. 757—769. pp. 241.  J. Seattle. Pioneering work on dissolved uranium in world rivers suggested that the residence time of uranium in the oceans must be on the order of 4 million years. G. Branfelt and E. 45 . H. S. Palmer. uranium has been regarded as a relatively non-reactive (conservative) element in seawater. Cosmochim. Sonntag. 221. Chen. Acta. Lett. L. (2) the behavior of uranium during river/ocean mixing. Based on very precise measurements of dissolved uranium in the open ocean. Because of its particle-reactive L nature.. 337. 24. 1986. 2. R. These residence time calculations are constrained by the assumption that the global riverine flux of dissolved uranium is a reasonably accurate estimate of total uranium input to the oceans. pp. Oxford. 1977. Geochim. Sackett. 1799. W. These other species and thorium are referred to as particle reactive because they are readily removed from the dissolved phase onto the particulate phase. 1994. Knauss and G. P. Lett. Ivanovich and R. residence time estimates (regardless of their precision) cannot be sensitive indicators of oceanic uranium reactivity. Deep-Sea Res. Earth Planet. S. concluded that uranium may be somewhat more reactive in marine environments than previously inferred. Clarendon Press. K. Earth Planet. 311—320. Harmon. ed.  W. estimates of oceanic uranium residence times are still somewhat vague. Klinkhammer and M. M. 1998. 4987. 1967. Nature. Because of these inherent uncertainties.. A. Mo. O.   Present estimates for the flux of uranium to the sea— include large (factor of 2) margins of uncertainty. Berstch and E. in Activation Analysis in Geochemistry and Cosmochemistry. Sci. 1991. 1005. If uranium is internally cycled in coastal environments or if the riverine delivery of U shows some variability. T. Universitetsforlaget. and (3) the extent to which shelf sediments may influence the net flux of uranium from coastal areas. R. Edwards and G..  J. Subsequent studies    have broadened the data base for uranium concentrations in marine environments and current estimates of seawater uranium residence times range from 200 000 to 400 000 years. M. L. Mathieu. recent studies in high-energy coastal environments    indicate that uranium may be actively cycled and repartitioned (non-conservative) from one phase to the next.

Surface ocean waters typically have elevated concentrations of dissolved and particulate Th. Hoff.  C. Earth Planet. Smith and R. Wiley. J. Buesseler. Spencer and A. respectively. Shaw. K.4 . Bacon and R. Bell. Fleer. Recently Th measurements have been coupled with Pa to examine particle fluxes. Res. Anal.  L. The four useful thorium isotopes are Th (t : 1. B. Th is delivered to the ocean in a fashion similar to many pollutants and trace metals. Edmonds. Res. J. Livingston. and the required volume for mass spectrometry was reduced to less than a liter. Mar.  M. O. N..— Once the particle-reactive species have been scavenged. 1979. 362. N. Deep-Sea Res.   Surface water enrichment is the result of aeolian and fluvial inputs. Cochran and H. A. New York. Thorium-230 is supplied to seawater from in situ decay of its parent. W.9 yr). M. 1980. Lett. Huh and M.. Th (t : 1. Y. N. M. 85.-A. 10 yr). 38. Science. P. G. V. 177. H. ed. Earth Planet. 85—97. Lett. Nature. in Productivity of the Ocean: Present and Past. R. Swarzenski et al. F.. Froelich. While the pathways are very different for the radiogenic thorium isotopes. 45. 2045. Thorium-232 has been proposed as a link between the radiogenic thorium isotopes and trace metals and anthropogenic pollutants. Th  (t : 7. 1993. Sci. P. Li and J. Gwiazda.. Sci.  J. D. 280. For example. R. U. pp. 1115. 133.-H. Wefer. Y. found Th distributions in the Gulf of Mexico and off Cape Hatteras in the North Atlantic Ocean agreed well with the general distribution pattern of aluminum. Chem. 1987. Recently. Eppley. M. Lett.-A. W. D. Berger. Bacon. 1989. J. 45. 65. Earth Planet.  Scavenging has a major influence on the marine chemistry of many elements. Thorium-232 enters the ocean by continental weathering and is mostly in the particulate form. Bacon.  Protactinium-231 and Th are supplied by U and U. Anderson. 10 yr). Moore. F. S.  P. M. and Th (t : 24. Moran. but the signal-to-noise ratio was often low and uncertain. thorium isotopes have been examined as proxies of biogenic flux.  K. Guo. Baskaran. Brewer. Anderson and P. Sci. Nozaki. 1999.5 . 1992. Early measurements of Th were by alpha-spectrometry and required large volume samples (ca. Geophys. Mar. L. Smetacek and G. Both dissolved and particulate Th activities increase with depth  in water column profiles. particle-reactive species. J. which are thought to be the most important sources of Th to the ocean. P. H. 2138. R. With the development of a neutron activation analysis and a mass spectrometry method  the quality of the data greatly improved. Smoak. Kumar. 405. Not only did this make sample collection difficult. Decay is not a factor in the Th water column distribution owing to its long half-life. 1000 L). 46 . J. J.. 703.  H. R. Santschi. 1995.  C.1 day). 57. including numerous metals and pollutants. S. Santschi.. Edwards. This increase with depth is the result of progressively more Th being scavenged onto particles as they sink through the water column. 201.. 117. Thunell and T. S. 87. Beasley. 1.. Protactinium has a weaker affinity for particles than Th and is therefore  P. Zindler and P. Huh and T.  N. H.  R. Guo et al.P. 1987. 1998. J. 39. M. 1982.    Thorium-232 is the only non-radiogenic thorium isotope of the U/Th decay series. W. Thorium provides a unique way to study the environmental pathways and the biogeochemical processes that affect particle-reactive species. P. C. W. subsequent packaging and/or aggregation can result in the flux of particles and particle-reactive species from the water column. The increase in the dissolved and particulate activity with depth indicates the scavenging of Th can be a reversible reaction. A. Chem. W.

Limnol. 32. biogenic particles dominate the particle flux and therefore are the scavengers of thorium. 12. 1996. This approach has been widely used during JGOFS. 1985. 205. Hofmann and W. 1993.  K. 1998.  M. D. Broecker. Geochim. F. 189. H. Buesseler. Chao. Coale and K. ed. Pa: Th ratios can exceed the production ratio. Deep-Sea Res.. 47 . M. Thorium-228 is an excellent tracer for intermediate timescale processes. Based on this work it was proposed that the flux of Th out of the surface ocean could be used to estimate new biomass production. 44.  K. Brewer and R.. Pa fluxes have been observed to increase with an increase in particle flux. P. Cosmochim. Cosmochim. 56. Less than 10 years after its discovery.  Y. 2461. Deep-Sea Res. Belastock. O. F. In the open ocean. Bathmann. J.  J. H.. 1987. Rutgers van der Loeff. Thorium-234 also has been used to examine residence times with respect to uptake on particles and removal of particles from the surface ocean. H. Thorium-230 flux from the water column roughly balances its local rate of production. Dunne. J. 1997. pp. Thorium-234 was first measured in the ocean by Bhat and Krishnaswami. H. 1986.1 days and the only source is the decay of U in seawater.  M. Global Biogeochem. Thorium-234 generally is deficient with respect to its parent U in surface waters as a result of the scavenging by particles and particle flux. Geochim. Limnol.91 years and is produced from Ra. W. R. J. Below approximately 200 m in the water column. T. 22. Newton. Cycles. Santschi. while Th is an ideal tracer of short timescale processes because the half-life is 24. Burton. J. New York.. The Th: Ra ratio can be used to calculate residence times with respect to uptake on particles. Friedrich and U. 457. 1992. J.  Radium The historic discovery of radium in 1898 by Marie Curie initiated a remarkable use of this isotope as an early oceanic tracer. Buesseler. R.  pioneered this work by measuring the depletion of Th in the water column to predict the flux of particulate organic carbon (POC). Buesseler’s approach was to measure the Th/POC ratio of sinking particles.  K. Oceanogr. S. Chesselet. 3375. The two remaining thorium isotopes have much shorter half-lives. Paul. V. 1998. G. 297. O. Coale. However. More recently. P. J. C. Bruland and K. Anderson. Plenum Press. Honeyman. then simply multiply the export rate by the ratio. Benoit and B. 159—172.. L. 1095. 43. Acta. Coale and K. Bruland. They showed that Th scavenging rates varied as a function of new biomass production. G. Benitez-Nelson. In areas of high particulate flux. Murray. H. 30. W. Th and U are typically in secular equilibrium and the uptake of Th is balanced by the loss from decay. Thorium-228 has a half life of 1.  K. Bruland. Buesseler et al. in Dynamic Processes in the Chemistry of the Upper Ocean. Lao.  K. Baskaran. This technique has been exploited in sediment cores to examine particle flux variability through time and hence productivity. Oceanogr. Chapin and B. Deep-Sea Res.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography susceptible to lateral transport.— the link between biogenic particles and removal of Th was established. D. 45. 57. J. In a series of papers. W. W. Chai and Y. Andrews. with Ac as a very short-lived intermediate daughter. Ball. Acta. Young. W. Wolfli.

Both of these criteria control the production and input of radium in marine systems. Geophys. Circ. 2469. 1998. 48 . Joly observed elevated Ra activities in deep-sea sediments that he attributed to water column scavenging and removal processes. W. 1908. may enhance the diffusive/advective flux of dissolved radium from the seabed to a coastal water column wherever the hydraulic gradients and sediment transmissivities are favorable. Th. 2233. 59. Ra: Ra activity ratios can become quite large as a result of this process and can be used to model the flux across the sediment/water interface. I. and the production rate is defined directly by their individual isotopic decay constants. M. 15. Moore. with    half-lives that coincide well with the timescales of many coastal and oceanic processes. Unfortunately. In coastal waters. Cosmochim. (3) estuarine sediments. Two important geochemical characteristics make radium ideal as a marine tracer: (1) having highly particle-reactive thorium as its direct radiogenic parent which ties it directly to bottom sediments. F. Cosmochim. (2) oceanic. Todd. FS-065-99. 4645. U.— The relative significance of each of these source terms is defined by the particular environmental constraints of an estuary. and (2) exhibiting vastly different environmental behavior in fresh water and saltwater systems. S. thorium is efficiently scavenged by particles/colloids and rapidly removed to the seabed. Geochim. Webster. Geochim. Ra (t : 3. 2203.6 day). Res. Geochim.4  day). Rama and W. W. 98. W. Surv. radium is bound strongly onto particle surfaces. Below this diagenetically active surface sediment layer. Moore. This hypothesis was later challenged with the first seawater Th measurements (parent of Ra). Acta. 60.P. A. In surficial sediments that are flushed by the upward movement of groundwater. Hancock and A. and Ra (t : 1622 yr). Acta. Ra (t : 11. Estuarine sediments thus provide a continuous source for radium isotopes to coastal waters. Mag. Ra (t : 5. and these new results confirmed that radium was instead actively migrating across the marine sediment—water interface. desorption reactions and the general absence of particles in the open ocean maintain radium entirely in a dissolved phase. G. 57. P. Bollinger and W. Joly. This disequilibrium occurs because dissolved radium will be rapidly advected into the water column while thorium remains attached to bottom sediments. Moore and J. J. Ground-water discharge. one can expect secular equilibrium to        J. Moore. Cosmochim. 1995. Swarzenski.  Source functions for radium in an estuary may thus include the following components: (1) riverine.S.. 385. a localized disequilibrium between Ra. S. Philos.. In fresh water. Swarzenski et al. which can consist of recycled marine water or fresh water. Murray.7 yr). Acta. as the ionic strength of a water mass increases during mixing into seawater. W. S. J. This seabed source stimulated much activity to use radium as a tracer for ocean circulation. however. 1993. Geol. the utility of Ra as a deep ocean circulation tracer never came to full fruition as biological cycling has been repeatedly shown to have a strong and unpredictable effect on the vertical distribution of this isotope. In coastal systems where ground water is discharged to coastal waters either continuously or ephemerally owing to tidal forcing. 1996.. Nature. and Ra can develop. S. 380. In the U—Th decay series there are four radium isotopes. 612. 1993. S. 1996. and (4) groundwater. S.

Res. J. Cable. 1045. Geophys. W. With such a short half-life. Radon can enter the sediment porewater through alpha recoil during decay events. L. Chanton. J. Loss of radon owing to turbulence or diffusion at the air—sea interface leads to a depletion of radon with respect to Ra. Rn has also been used as a tracer for evaluating coefficients of isopycnal and diapycnal mixing in the deep sea  and. for tracing submarine groundwater discharge into the coastal zone. Rn is typically found in equilibrium with its parent away from the air—water and sediment—water interfaces. In addition. Radon-222 Inert Rn is a unique marine tracer in that it should not interact in any biogeochemical cycles. Chanton and G. Such radioactive equilibrium in the Th decay series requires approximately 20 years of sediment storage. short-lived Ra: Ra activity ratios may also be used to derive apparent estuarine water mass ages. Rooth. 49 . Corbett. some of these studies do provide insight into the geochemical behavior of Pb and Po. 1996. Earth Planet. Loss of radon in the ocean occurs typically through radioactive decay (producing four short-lived daughters before decaying to Pb) or loss to the atmosphere at the air—sea interface. bioturbation. The diffusion of radon from sediments to the water column gives rise to the disequilibrium (excess Rn) observed in near-bottom waters.  J. B. disequilibria of radon with respect to its parent readily prevail. Lead-210 and Polonium-210 The majority of published Pb reports address the utility of Pb as a geochronological tool rather than as an element that is involved in complex biogeochemical cycles. Radon is also continuously being produced in the water column through the decay of dissolved or particulate Ra. Limnol. it readily diffuses from bottom sediments into overlying waters. There are two main sources of Rn to the ocean: (1) the decay of sediment-bound Ra and (2) decay of dissolved Ra in a water column. Rutkowski. Moore and colleagues have used such disequilibria to derive a groundwater flux rate in a South Carolina salt marsh. Resuspension. 1515. 591. Since radon is chemically inert.. K. J.  Radon is produced through the direct alpha decay of Ra and has a relatively short half-life of 3. R. Nonetheless. 85. and C.. Burnett. Weatherly. Sarmiento and C.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography develop from Th down to Ra. Oceanogr. It has been used extensively for determining exchange rates across both air—sea and sediment—water interfaces. Sci. However. chemical dissolution as well as groundwater flow will allow these two sediment layers to interact. Burnett. 144. 44.  Finally. Nearly all of the lead in the world’s surface oceans is believed to be of anthropogenic origin—derived from combustion  J. Lett. near the air—water and sediment—water interfaces. allowing for studies on gas exchange at this interface. 1999. Dillon. higher ratios generally imply younger waters owing to the more rapid decay of radium. 1980.85 days.  D. more recently.. G.

Patterson. Cosmochim. 51. Goldberg. H. and coastal sediments. Hemond. American Chemical Society.  Y. P. and (3) from direct leaching of rocks and soils during weathering. Washington. of leaded gasoline.P. J. M. 1557. M. Res. Ng and C. Paul.  D. Earth Planet. in Trace Metals in Sea Water. Even the most remote areas of the world—the polar caps—show a very clear effect of lead pollution. 217. 41. D. 2109.. Sci. Pb may be readily removed as a lead sulfide precipitate. Swarzenski et al. L. 1987. Soil profiles have shown organic matter to be effective in binding Pb. (2) from the in situ decay of Ra and Rn in the water column. Geochim. 1977.  In anoxic environments. iron and manganese oxides are important removal phases. In broad terms.  A. Nozaki suggested that the removal of Th. 1975. Pb. Li.  L.  L. and Po from marine waters may be accelerated by biological  B.g. River water is extremely depleted in dissolved Pb and  Th under normal conditions. 1983. but this isotope may also have an atmospheric source term within surface waters. Boyle. W. Kadko. Acta. Santschi. Turekian. causing this mineral component to be of importance in sulfide-rich sediments..-H. J. 55. 4845. Acta. D. 487—503. where acid mines drain into water). Lewis. Patterson. W. S. Balistrieri. Benoit and H. K.  G. elevated Pb concentrations have been reported. Lewis and K. Geochim. 1981. As this acid mine water is diluted with natural waters. Wong. Lett. Plenum Press. even here. In areas where pH may be low (e. 1981. in Marine Chemistry in the Coastal Environment. The mechanisms for removal may be similar to thorium scavenging. Lead-210 is rapidly removed by various processes in the water column and deposited onto the seafloor during particle deposition and accumulation. C.  D. Polonium-210 appears to be somewhat more reactive than Pb in seawater.Geophys. C. K. 50 . Geochim. noticed large seasonal variations of Pb and Po in Narragansett Bay. W. D. W. C. Cosmochim. New York. Murray and P. Kaufman. Lead-210 has been used extensively as a tracer for particle-reactive elements as well as for geochronological studies of lake. Cosmochim. estuarine. the marine cycle of Pb is characterized by supply or production of dissolved Pb which is then scavenged by solid surfaces and thus removed from the water column. 1445. 18. Feely. pp. K. Church. Acta. Acta. Benninger and H. Schaule and C. This seasonal trend was ascribed to two factors: remobilization out of the sediments during the spring and early summer. 98. T. Burton and E. Benninger. 857. ACS Symposium Series. 45. ed. 1993. Polonium-210 is a decay product of Pb and is produced mainly by this source in the water column. F. In the ocean. K. 1995. Lead-210 and its indirect daughter Po are both important radionuclides used in geochemical research. Santschi et al. or formation of organic complexes. the sequential precipitation of iron oxides followed by manganese oxides appears to completely scavenge Pb and other metals onto suspended particles. S. Recent measurements of polar ice cores show that man’s activities have caused a 300-fold increase in Pb since the beginning of the industrial revolution. A. Geochim. E. K. as studies in the New York Bight indicate similar removal times for both Pb and Th. Lead-210 is delivered to the water column by three sources: (1) atmospheric fallout from the decay of Rn. J. 59. ed. Cosmochim. Involvement in biological cycles may affect the distribution of both Pb and Po. 202—210. M. sinking particles are adsorption sites for Pb and. Bruland. pp. In a recent summary paper. no.

providing results soon after sample collection. D. which carries higher CFC concentrations. Therefore. but they are very stable in the troposphere and in the ocean. M. Some CFCs can be photochemically destroyed by UV light in the stratosphere. CFC-enriched waters can become diluted with older. Koide and E. These CFC concentrations can be used to deduce when a water mass was last in contact with the atmosphere. Po. These compounds are ideally suited for this purpose as they have no natural sources and the anthropogenic sources are well understood. F. with their associated elements. Such variable uptake rates led the authors to infer that particulate Pu. and U may be associated with different particulate phases. Nature. In some situations the CFC-enriched waters may mix with other waters containing CFCs. the ratio has remained fairly constant. CFCs Since the early 1980s. the CFC-11: CFC-12 ratio is used to estimate the age of a given water mass since this ratio is unaffected by dilution (Figure 6). This worldwide distribution makes these trace gases ideal tracers for oceanic studies at high latitudes. 1978. CFCs can be measured at sea using a gas chromatograph (GC) equipped with an electron capture detector (ECD) and a purge and trap system. Hodge. This age is usually biased towards the younger component. Unlike many other anthropogenic tracers. 206. CFCs have been increasing in the atmosphere since the onset of their production and are well distributed in both hemispheres. This makes  V. This is due to their rather long atmospheric lifetimes (970 years) and the rather short time of atmospheric exchange between hemispheres (ca. U. CFC-free waters. The atmospheric ratio of CFC-11: CFC-12 increased until 1975. Preferential biological uptake of Po relative to Pb in some sediments may cause local disequilibria. chlorofluorocarbons (CFCs) have been used to trace oceanic circulation and mixing processes. the atmosphere and ocean were CFC free. Hodge et al. at differing rates. Their atmospheric histories are known since 1981 (Figure 5) and have been reconstructed using estimates of production and releases obtained from the Chemical Manufacturers Association (1983). recently ventilated waters contain relatively high concentrations of CFCs. Since this time.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography activity. gas exchange began delivering CFCs to the ocean. Owing to mixing processes. demonstrated that Po. which can affect the interpretation of Pb-derived geochronologies. 51 . Their results suggest that organic surface coatings may collect particles. Two types of CFCs. where significant quantities of water are down-welled to form intermediate and deep water masses. 277. Goldberg. when regulation of the USA production of these compounds led to a reduction in their rate of increase. have been    produced since 1940. 2 years). and Pu have different uptake kinetics onto solid phases. or Pu could be removed by inorganic material. Upon atmospheric release. CFC-11 (CCl F) and CFC-12 (CCl F ). For this reason. U. Prior to 1940. with the result that the ratio will reflect an intermediate age. They exposed different solid phases to seawater to determine whether Po.

an additional CFC. atmospheric Kr activities complied by W. This ratio provides a much finer resolution of a water mass’s age for waters ventilated since 1977. W. Swarzenski et al. Plummer (US Geological Survey). Res. CFC-113. CFC data courtesy of E. 188. it is possible to estimate an apparent age with an error of less than a few years. Busenberg and L. 52 . CFC-113 (CCl FCClF ). SF  (pptv) and Kr (dpm cm\). In fact. H. 15. Geophys.P. Figure 5 Atmospheric concentrations for CFC-11. However. P.. Smethie (LDEO) (dpm : disintegrations per minute) Figure 6 Atmospheric ratios of CFC-11: CFC-12 and CFC-113: CFC-12 it difficult to distinguish between water masses that have formed since this time. This trace gas is used as a solvent in the electronics industry. CFC-12. entered production   during the 1960s.  D. N. 1988. Introduction of this gas into the atmosphere has led to a steadily increasing CFC-113: CFC-11 ratio. M. Gammon. Wisegarver and R. Lett.

Wisegarver. J. J. 39. 53 . 20 525. 2053.e. J. 1994. However. Van Scoy. Res. K. 1992. Warner and R. A. salinity and temperature) for many years. Weiss. F. Lett. H.. R. Geophys. Bullister. P. W.  M. A. P. most studies have utilized CFC-11 and CF-12. 23. Geophys. L. Meredith. underestimating the utility of CFC-13. 1996.  — These studies have shown that water along the equator is relatively young (:15 years) at shallow isopycnal surfaces of North Pacific intermediate water and becomes older with depth and density (ca.. Gammon and R. Weiss. Harada and K. 99. J. Res.  Y.  M. Warner. Ishikawa. Watanabe. Res. F. Intermediate waters are formed in both hemispheres and have been studied with traditional physical tracers (i. J. These studies show that these water masses can be traced over time and space using CFCs.. D. 1996.  M.The Use of U—Th Series Radionuclides and Transient Tracers in Oceanography Many studies have shown the usefulness of CFCs as tracers of the formation and circulation of recently ventilated oceanic waters. 40 years). J. Geophys. Deep-Sea Res.. This new information has generally supported previous studies of ocean circulation patterns but can resolve them better through time. 25 195. Perhaps future work will employ all three trace gases as transient tracers. K. A. Watson and R. potentially providing even more precise information. 99. 2943. Locarinini.

 S. commonly called ‘natural products’. there is a pressing need to discover and develop new drugs that act against cancer cells. A N D ER S EN A N D D A V I D E. a clinically important anticancer drug that was originally isolated from the Pacific Yew tree Taxus bevifolia. antibiotic-resistant microbial infections. Aldridge. Exploitation of this extremely valuable molecular resource is a complex and lengthy process that is shaped by many scientific. In some  S. The majority of human drugs (see Figure 1) are relatively low molecular weight organic molecules with masses in the range of ca. and environmental issues. legal. asthma. isolated from terrestrial plants or cultures of soil microorganisms. In order for the chemotherapeutic approach to be more effective. 1999. Two important examples are paclitaxel (3). Cambridge University Press. p.). Issues in Environmental Science and Technology No. 1998. and other molecular disease targets by novel biochemical mechanisms and have diminished side effects. and penicillin G (4). Berlin. Drug therapy represents one well-established and still attractive approach to treating these serious diseases. microbial pathogens. business. Thiericke (ed. 13 Chemistry in the Marine Environment © The Royal Society of Chemistry. Cambridge. and diabetes that urgently require improved medical treatments. ch. 200 [aspirin (1): a pain killer] to 1500 [vancomycin (2): an antibiotic] Daltons. One large group are secondary metabolites. Springer. an antibiotic produced in culture by the fungus Penicillium notatum. viruses. animals. 2000 55 . Magic Molecules. Grabley and R. AIDS.Pharmaceuticals from the Sea RA Y MO ND J. WI L L I A MS 1 Introduction There are a large number of life-threatening or chronically debilitating human diseases such as solid tumor cancers. and microorganisms living in the world’s oceans represent a vast and relatively unexplored resource of structurally diverse low molecular weight organic molecules that are ideal raw materials for the development of new drugs. Secondary metabolites produced by the plants. Drug Discovery from Nature. 2. How Drugs Work. Most of the drugs currently used in the clinic come from two fundamentally different origins. The goal of this chapter is to highlight the tremendous opportunities and the considerable challenges involved in developing new pharmaceuticals from the sea. 23.

the plant or microbial metabolite is subjected to synthetic modification to give a semisynthetic derivative or else it serves as a model pharmacophore to guide the synthesis of structural analogs that have enhanced drug properties.R. J. an anticancer drug currently in clinical trials. Andersen and D. Docetaxel (5) is a semisynthetic analog of paclitaxel that has also been approved for clinical use as an anticancer drug and topotecan (6). Williams Figure 1 Drugs derived from natural products instances. is a synthetic analog of the plant metabolite camptothecin (7) isolated from the stem wood of Camptotheca acuminata. which 56 . E.

  The Human Genome Project has the potential to identify a large number of additional interesting drug targets. 1995. Research in molecular biology during the last two decades has provided enormous advances in our understanding of many diseases at the gene or molecular level. Boyd and K. Nature. These and other genetically validated protein targets have provided exciting new opportunities for developing selective mechanism-based inhibitors of specific biochemical processes that are essential to the malignant phenotype of cancer cells. 1996. 1996. 1. illustrates the typical scale for traditional cell-based screens. Drews. 1516. This screen. enzymes. characteristics that ultimately limit the total number of assays performed and the rate at which they are executed in any drug screening program. They offer the hope of developing anticancer drugs with low toxicity and. Cell-based or intact tissue assays are relatively expensive and labor intensive. B. is classic example of a totally synthetic drug. drug discovery programs have relied on in vitro intact tissue or cell-based assays to screen libraries of synthetic compounds or natural product extracts for pharmaceutically relevant properties. Similar situations exist for a whole range of other diseases.. Nat. 78. its large scale production for drug screening is usually carried out in a suitable genetically engineered microbial expression system. Drug Dev. 14. suppl. 1994. 384. This screening approach identifies compounds that elicit a desired cellular response such as antibacterial or cytotoxic activity regardless of the mechanism of action. are not based on any naturally occurring template. and other as yet unknown proteins. Gibbs and A. Once a molecular target and its relevance for human therapy have been identified. This can be relatively straightforward for some enzymes but may be considerably more difficult for receptors and other complex proteins. J. 34. much improved therapeutic margins. 57 . D.. RAS (a GTP-binding protein). a widely used antidepressant. such as Myc. Paull. was designed to identify compounds that had potential anticancer activity by looking for selective growth inhibition or cell killing of particular cell lines. Biotechnol. The most commonly altered gene products in human solid tumors include ErbB2/HER (a membrane-associated tyrosine kinase). The second group of drug molecules. which at its peak screened up to 20 000 pure compounds or natural product extracts per year.Pharmaceuticals from the Sea itself has anticancer properties. Rb. which are totally synthetic in origin. J. Res. In a parallel development.. therefore. IVCLSP. For example. It has been estimated that all the drugs in current clinical use target no more than 420 receptors. Cell. Oliff. One conservative estimate has suggested that for the 100—150 major diseases for which improved therapies are needed there are perhaps 3000—10 000 new drug targets that will emerge from genomics. Historically. and proteins that affect transcription. there are now many well-documented genetic differences between cancer cells and normal cells.. or p53. which used 60 different human tumor cell lines. there have recently been tremendous advances in     M. 193. R. ion channels. An excellent example of a cell-based screen is the US National Cancer Institute’s In Vitro Cell Line Screening Project (IVCLSP) that was operational in the early 1990s. Prozac [fluoxetine (8)]. 91. Lehman et al. J.

R. J. Andersen and D. E. Williams the robotic technology for screening chemical entities. The fusion of moleculartarget-based screening and robotics has resulted in the current drug screening paradigm known as ‘high-throughput screening’ (HTS). HTS is the process by which large numbers of compounds are tested in an automated fashion for activity as inhibitors or activators of a particular molecular target such as a cell surface receptor or metabolic enzyme. The bioassays used in HTS programs are either in vitro screens against purified enzymes or receptors or cell-based assays using engineered eukaryotic cells or microorganisms. HTS programs in major drug companies can typically handle 3000 enzyme inhibition or 4800 engineered cell-based assays per day, making it feasible to screen libraries of up to 100 000 or more chemical entities in a reasonable time frame. The primary role of HTS is to identify ‘lead’ chemical structures that act against a particular molecular drug target and supply directions for their structure—activity optimization. Key elements in successful HTS programs are the judicious choice of validated molecular targets and access to the greatest number and structural diversity of compounds. Traditional directed-synthesis chemical libraries, combinatorial chemistry libraries, and natural product extracts represent the most important pools of chemical entities available for HTS programs. Each of these compound pools brings different strengths to the drug discovery process. The directed synthesis libraries found in all major pharmaceutical companies have been accumulated through years of in-house medicinal chemistry programs. They contain synthetic intermediates on pathways to, and structural analogs of, biologically active target molecules. Advantages of lead compounds from these libraries are that the structures are already well characterized and a synthetic route to the compounds already exists. Combinatorial synthetic chemistry, which has only emerged in the last decade, has the potential to generate very large numbers of compounds and it is an extremely powerful tool for structure—activity optimization.   Initially, there was much enthusiasm for the idea that combinatorial chemistry could replace the need for accessing all other sources of chemical diversity, particularly natural product extracts. However, combinatorial libraries will always be designed with ease and efficiency of synthesis in mind, so they are likely to contain relatively simple structures. Living organisms, on the other hand, pay little attention to synthetic efficiency and, as a result, they contribute secondary metabolites with relatively complex structures, rich in stereochemistry, concatenated rings, and reactive functional groups, to the pool of chemical diversity. The natural products chemical diversity pool, which is full of structural surprises unbiased by human imagination, has a strong track record of contributing to drug development. Terrestrial plant natural products (see Figures 1 and 2) that are currently in clinical use include the anti-cancer drugs paclitaxel (3) isolated from the Pacific Yew tree Taxus brevifolis and vincristine (9) isolated from the rosy periwinkle Catharanthus roseus, the analgesic morphine (10) isolated from the poppy Papaver somniferum and the antimalarial drug artemisinin (11) isolated from the Chinese plant Artemisica 
J. R. Borach and J. Thorner, Nature, 1996, 384, suppl., 14.  J. C. Hogan, Nature, 1996, 384, suppl., 17.  H.-K. Wang, IDrugs, 1998, 1, 92.

58

Pharmaceuticals from the Sea
Figure 2 Terrestrial plant and soil microorganism secondary metabolites currently used as drugs

59

R. J. Andersen and D. E. Williams annua. Soil microbe natural products in clinical use include the anticancer drug bleomycin (12), the antibiotic vancomycin (2), the immunosuppresants cyclosporin (13) and FK 506 (14), and the cholesterol lowering agent lovastatin (15). The near-term future of natural products in drug discovery also continues to look promising. A recent survey by National Cancer Institute scientists showed that natural products or synthetic analogs of natural products make up a significant proportion (ca. 50%) of anti-cancer and anti-infective ‘lead’ compounds currently in preclinical evaluation or clinical trials. This promising pipeline of drug candidates almost guarantees that new, clinically useful agents based on natural product structures will continue to appear for the foreseeable future. Despite the rich history of natural products contributing to drug development, the emergence of HTS as the predominant drug development paradigm has made most large pharmaceutical firms take a serious look at whether natural products have any long-term role to play in this new approach.  Their evaluations have focused on the possibility that the large libraries of chemical entities rapidly prepared by combinatorial chemistry have made natural product screening obsolete. In order to address this issue in an unbiased and systematic way, scientists at Bayer Pharma carried out a statistical analysis of the structural complementarity of natural products and synthetic compounds. Their results led to the conclusion that ‘the potential for new natural products is not exhausted and natural products still represent an important source for the lead-finding process’ in drug discovery. What appears to be emerging, as a result of analyses such as that carried out by the Bayer group and the accumulation of several years worth of experience with the use of combinatorial libraries in HTS programs, is the recognition that although combinatorial chemistry is indeed an extremely powerful tool for drug discovery, it cannot completely replace natural products as a source of chemical diversity.

2 Opportunities in the Oceans
Secondary metabolites (natural products) are so named because they are apparently not essential for the primary metabolic activities involved in the growth of the producing organism. It is often argued that they act as antifeedants or toxins designed to reduce predation on the producing organism or that they act to inhibit the growth of other species competing for the same pool of nutrients or space. While these arguments are usually well founded, the reality is that for most secondary metabolites there is no rigorous experimental proof for their putative roles. In contrast to the almost universal occurrence of primary metabolites such as amino acids, fatty acids, and nucleotides in all organisms from microbes to mammals, the occurrence of any particular secondary metabolite or natural product is normally restricted to only one or at most a few species. It is also the case that not all living organisms make secondary metabolites. A high proportion of higher plants and microorganisms do make secondary metabolites while most vertebrates do not. The restricted taxonomic 
Y. Z. Shu, J. Nat. Prod., 1998, 61, 1053.  G. M. Cragg, D. J. Newman and K. M. Snader, J. Nat. Prod., 1997, 60, 52.  T. Henkel, H. Muller, R. M. Brunne and F. Reichel, Angew. Chem., Int. Ed. Engl., 1999, 38, 643.

60

61 . and reproduction that are very different from those found in terrestrial vascular plants. including the Coelenterata. which requires a set of physiological adaptations for accessing nutrients. drug screening programs that are bioprospecting for maximum structural diversity of natural products must try to access the maximum available biodiversity. 1990. Andersen. Porifera. and lack the physical protection of shells or spines. etc. C. Heiderberg. Wiley-Interscience. 679. Bioorganic Marine Chemistry. In spite of their physiological differences. Brusca. are exclusively aquatic and largely saline in habitat. Even though marine and terrestrial plants are significantly different from each other. but also because many of these plants and animals are uniquely adapted to marine habitats and have no terrestrial counterparts.  P. J. Marine Chemistry. Greater than 70% of the Earth’s surface is covered by oceans. one thing marine algae and terrestrial plants have in common is an apparent ecological need for biologically active secondary metabolites to deter herbivorous predators. Invertebrates. A number of the invertebrate phyla. 1974. Furthermore.  This is in stark contrast to the study of terrestrial plant natural  R. Goldberg. Scheuer (ed. slow growing. animals. and Echinodermata. E. exchanging metabolic gases. The field of marine natural products chemistry. J. 4. J. Faulkner and R. There are approximately 100 000 species of marine invertebrates in the world’s oceans and the true number is likely much higher because there are still many undiscovered or undescribed species. p. for example. the ions that contribute to the total salinity of seawater are in nearly the same proportions throughout the oceans and their total concentrations in seawater are very similar to their concentrations in physiological fluids. there is a rough correlation between species diversity and chemical diversity. vols. MA. in The Sea. Brusca and G. live immersed in seawater. Sunderland. it is among the invertebrates that there is the most striking difference between marine and terrestrial life forms. D. ch. minimizing problems of osmoregulation and ionic regulation.  D. Simple ecological arguments predict that organisms with exactly these attributes might make extensive use of biologically active secondary metabolites to defend themselves from predation by fishes.Pharmaceuticals from the Sea distribution of secondary metabolites means that for phyla known to be rich in secondary metabolism. 5. Bryozoa. and the ready availability of nutrients have been major factors in the development of the high biodiversity found in the marine environment. Most of the animals in these phyla are sessile. the wide range of habitats extending from the very deep abyssal plain to very shallow tidal pools. Marine algae. vol. Springer. 1987—92. crabs. Consequently. and microorganisms. New York. which encompasses the study of the chemical structures and biological activities of secondary metabolites produced by marine plants. ed. began in earnest in the early 1960s. The thermal buffering capacity of seawater means that ocean temperatures are very stable in comparison to those of freshwater and terrestrial environments. 19. 1—6. Sinauer Associates. The very stable physical and chemical environment in the oceans. J. brightly colored. The oceans are much bigger volumetrically than inhabitable land surfaces so they provide much more space in which organisms can live and diversify.). p. Marine biota are an extremely exciting potential source of novel natural products not only because of the large number of species present in the oceans.

E. p. This is in keeping with the rudimentary ecological arguments presented above that these two groups of organisms might be expected to utilize chemical defences to deter predators. algae accounted for ca. 15. ed. and the previous reports in this series. M. Radisky and C. 197. These shifts probably reflect the recent focus of the field on drug discovery. In the early days of marine natural products research. echinoderms. New York. it became practical for natural products chemists to make their own field collections of marine organisms. algae account for only ca. D. J. I.  C. p. Williams products chemistry. 1. Zabriske and J. invertebrates account for ca. Toth. The relative inaccessibility of marine macroorganisms and difficulties associated with culturing marine microorganisms. Pharmaceutical and Bioactive Natural Products. Ireland. so it is not surprising that interest in natural products from these phyla has increased. particularly phytoplankton. 1988. which together account for more than 90% of all reported compounds to date.  C. vol. D. Today. Ireland. Several analyses of known marine natural products according to the phylum of the source organism have revealed the richest sources of marine secondary metabolism (Figure 3). and molluscs have yielded the most compounds. sponges. 1998. 80%. With this tool in hand. Copp. San Francisco. Faulkner. Among the invertebrates. Bowden and S. 1%. In the most recent analysis. invertebrates ca. Schmitz. the way was open for active investigation of marine secondary metabolism. 60%. 10% in 1997) compounds have significantly increased. M. there have been roughly 10 000 novel marine natural product structures described in the chemical literature and the rate at which they are reported has increased to ca. while the proportion of coelenterate compounds (22% in 1977—85. the proportion of sponge (26% in 1977—85. A review of cytotoxic marine natural products showed that sponges (44% of total) and tunicates (13% of total) were the most prolific marine sources of compounds with this particular type of bioactivity. J. McDonald. in Marine Biotechnology. The other major shift has been the increase in reports of microbial metabolites (1% of total in  D. probably contributed to the late bloom of marine natural products chemistry research. 1993. 1. 10% of the total. Andersen and D. there has been a significant shift in emphasis during the last decade. particularly the active search for anti-cancer drugs leads. ch. Prod. Among the invertebrates. Molinski.. and quinine. Nat. G. and microorganisms ca. 43% in 1997) and tunicate (2. New York. B. Pharmaceutical and Bioactive Natural Products. in Biomedical Importance of Marine Organisms. 41. 600 per year in 1997 from ca. Once sample collection was conveniently under the chemist’s control. after nearly 40 years of research. 62 . tunicates. have been the richest sources of novel natural products in the oceans. D. Foster. coelenterates (soft corals and gorgonians). J. Plenum Press. ed. 113. Attaway and O.6% in 1977—85: ca. Fautin. L. 1993. ch.  F. Cousteau’s invention of SCUBA in 1943 dramatically increased the accessibility of sessile marine invertebrates and algae. 7. B. p. Plenum Press. 250 per year in the decade 1977 to 1987. 40% of new compounds. in Marine Biotechnology. F. and microorganisms account for ca. 13% in 1997) has decreased. 1. Swersey. Zaborsky. vol. Swersey. D. McKee. 1. strychnine. California Academy of Sciences. ed. Attaway and O. Zaborsky. Rep. T. Roll. Interestingly. T. D. which started almost a century and a half earlier with the isolation of the well-known alkaloids morphine.R. 10%.  It is clear from the data that marine algae and invertebrates.

and microorganisms will be substantially different from those found in traditional terrestrial sources simply because marine life forms are very different from terrestrial life forms and the habitats which they occupy present very different physiological and ecological challenges. 93. Engl. sesqui-. Greenstein and W. The typical metabolites of red algae are mono-. Bernan. The underlying assumption driving marine natural products chemistry research is that secondary metabolites produced by marine plants. 10% of total in 1997). 5. 1995.— and parallel demonstrations that many of the exciting bioactive compounds isolated from marine invertebrate extracts are actually metabolites of associated microorganisms. Scheuer. New York. ch. Rev. 1993. A. Microbiol. What makes these compounds unique to marine plants is the high degree of substitution with chlorine and bromine atoms and the large number of unprecedented terpenoid carbon skeletons. Biotechnol. Red algae in the genera Laurencia and Plocamium have been the richest source of halogentated algal terpenoids and polyketides. 37. animals. B. Some typical Laurencia terpenoids (see Figure 4) include pacifenol (16).Pharmaceuticals from the Sea Figure 3 Distribution of marine natural products reported in 1997 according to the phylum of the source organism 1977—85: ca. 1673. This increase has been stimulated by the results of several pioneering studies showing that cultures of microorganisms uniquely adapted to the marine environment are a rich but essentially unexplored resource of novel bioactive secondary metabolites. 1998. Davidson. L. Chem. M. 2162. Curr. vol. Int. Fenical. ed. The expectation is that marine organisms will utilize completely unique biosynthetic pathways or exploit unique variations on well established pathways. Angew. in Marine Natural Products. and some typical Laurencia polyketides include laurepinnacin      W. S. M. Chemical and Biological Perspectives. 284. Bewley and D. Erickson. and neoirieone (19). The marine natural products chemistry research conducted to date has provided many examples that support these expectations.. 43. S. Adv.. Chem. C. Opin. J. Ed. 63 . P. 132. 1997. K. and di-terpenoids and polyketides. p. 1983. Academic Press. 4. J. perforatane (17).. V. Maiese.. 6. Red algae were some of the first organisms to attract serious attention from marine natural product chemists.. Appl. 57. Faulkner. oppositol (18).

1996. Chem. Chem. N. Murata. Engl. undergo ring cyclization reactions. T. Nonomura. the analogous cyclizations of acyclic terpenoid precursors are initiated by the electrophilic species H> rather than by halonium ions. The dibromotrichloro acyclic compound 22 and the tetrachloro monocyclic compound 23 are typical Plocamium monoterpenoids.. 35.. Williams Figure 4 Halogenated terpenoid and polyketide metabolites isolated from red algae in the genera Laurencia and Plocamium (20) and okamurallene (21). In terrestrial plant biosynthesis. produced by the dinoflagellate Gambierdiscus toxicus. are  T. a group of planktonic unicellular marine plants. Rev. Maruyama. Ed. Maitotoxin (25). 1993. Int. Angew. make a remarkable group of extremely toxic polyketides (see Figure 6) that have no terrestrial counterparts. or be trapped by bromide. Tachibana and T. E. is one of the toxins (LD : 50 ng/kg. Andersen and D. 64 . 93.. The incorporation of halogen atoms into red algal metabolites is a typically marine biosynthetic variation on the basic terpenoid and polyketide pathways that takes advantage of the relatively high concentrations of chloride and bromide ions in seawater. Yasumoto. J. Sasaki. Yasumoto and M. M. Murata. It has been postulated that the biosynthesis of halogenated red algal metabolites involves a variation on the well-known terpenoid and polyketide pathways. 1897. Matsumori. Dinoflagellates. biosynthetic products of dinoflagellates in the genera Prorcentrum and Dinophysis.R. Okadaic acid and the related compound DTX-4 (26). chloride. T. It is the largest (molecular weight : 3422 Daltons) non-biopolymer natural product known and it features a linear skeleton containing 142 carbon atoms that has been elaborated into multiple units of fused cyclic ethers. mouse. The introduction of halogen atoms into the molecular skeletons is thought to arise from initial reaction of an electrophilic halonium ion (formally Br> or Cl>) species with a nucleophilic alkene or alkyne bond to generate intermediate carbocations that can lose a proton. or oxygen nucleophiles as shown in Figure 5 for the sesquiterpenoid nidificine (24). 1672. K. ip) responsible for ciguatera seafood poisoning.  M.

. Needham and J. Biosynthetic investigations of DTX-4 (26) have revealed that the molecule is formed via a polyketide pathway. A. While there is no experimental  J. the formation of pendant methyl groups and exomethylene groups from C-2 of acetate. and deletion of individual carbons from the polyketide chain via a Favorskii-type rearrangement followed by decarboxylation as shown in Figure 7. 65 . J. McLachlan. Soc. 118. J. L. Walter.Pharmaceuticals from the Sea Figure 5 Proposed mechanism for biosynthetic introduction of bromine and chlorine atoms into the Laurencia sesquiterpenoid nidificine (24) Figure 6 Toxic polyketide metabolites of marine dinoflagellates members of the family of compounds that are responsible for causing diarrhetic shellfish poisoning. Chem. cleavage of the polyketide chain via a Baeyer—Villiger-like oxidation. J. C. T. L. Am. These include the use of glycolate as a starter unit. Wright. Hu. 8757. 1996. but one that involves a number of unusual features.

presumably by reaction with terpene carbocation biosynthetic intermediates. Andersen and D. Williams Figure 7 Proposed biological Favorskii-like reaction involved in DTX-4 biosynthesis. J.R. the dichloroimine 30 from Stylotella aurantium and 2-thiocyanoneopupukeanane (31) from an Axinyssa sp. axisonitrile-3 (28) and axisothiocyanate-3 (29) from Acanthella cavernosa. 66 . and dichloroimine functional groups evidence yet to verify that these same polyketide modifications are involved in the formation of other dinoflagellate polyether toxins. Simpson and M. Garson. are representative examples. This is in direct contrast to the biosynthesis of the small number of isocyanide containing metabolites known from terrestrial microorganisms. isothiocyanide. Diisocyanoadociane (27) from Amphimedon terpenensis. 1999.. Two examples from marine sponges will serve as illustrations. Many marine invertebrate metabolites also have biosynthetic origins without known terrestrial counterparts.  — denotes incorporation of intact units of CH —CO H in a   biosynthetic feeding experiment Figure 8 Sponge terpenoids containing the rare isocyanide. J. Biosynthetic feeding studies have shown that the isocyanide and isothiocyanide functionalities in these compounds arise from direct incorporation of inorganic cyanide and thiocyanate. 40. S. Terpene isocyanides. isothiocyanides and dichloroimines are some of the most distinctive metabolites of marine sponges (see Figure 8). Tetrahedron Lett. Sponges in the order Haplosclerida have been the source of a family of more than 100 3-alkylpiperidine alkaloids (see Figure 9) that all appear to have been formed via a common biosynthetic pathway which is unique to marine  J. E. structural features found in other compounds of this class suggest that these rare and interesting variations on the polyketide pathway may be a common feature of dinoflagellate biosynthesis. where the isocyanide functionality arises from modification of an amino acid nitrogen. 3909.

Pharmaceuticals from the Sea Figure 9 3-Alkylpiperidine alkaloids isolated from sponges in the order Haplosclerida Figure 10 Proposed biogenesis of 3-alkylpiperidine alkaloids 67 .

Numerous excellent reviews of the marine natural products literature are full of many additional examples. New York. Pelletier. represents an extremely valuable molecular resource for the ‘lead finding’ process in contemporary HTS drug discovery programs. 3 Challenges Involved in Developing a ‘Drug from the Sea’ The process of developing any new drug is a lengthy and very costly business. thousands of chemical entities are evaluated to find one or more ‘lead’ compounds that merit extra evaluation and only a very small percentage of these ‘lead’ compounds ever make it into the clinic. R. Pergamon. p. 1996. 301. 2] cycloaddition reactions. 3. However. M. The failure rate is also enormous. vol. In the initial stages. Andersen. There is no terrestrial counterpart to the proposed biogenetic pathway to these complex 3-alkylpiperidine sponge alkaloids. The first step in discovering a marine natural product ‘lead’ compound involves accumulating collections of the source organisms. to generate the polycyclic skeletons found in many of these complex alkaloids. The development of SCUBA and both manned and remotely operated (ROV) submersibles has provided the technology required to effectively collect algae and invertebrate specimens from most marine habitats. Ideally the collections would include as many species as possible collected from a large number of sites reflecting the wide diversity of habitats found in the world’s oceans. These timeline. a three-carbon unit such as propenal. S. petrosin A (33) isolated from Petrosia seriata. Van Soest and F. halicyclamine A (34) also isolated from a Haliclona sp. there are a number of unique challenges to developing a drug based on a natural product from a marine plant or animal source. Manzamine A (32) isolated from a Haliclona sp. J.. 68 . J. It has been proposed that the basic building blocks involved in the biogenesis of all the 3-alkylpiperidine alkaloids are ammonia. including intramolecular [4 . Kong. These units are first assembled into a 3-alkylpiperidine monomer that can either polymerize to give the oligomeric halitoxins or dimerize to give a bis(3-alkylpiperidine) macrocycle. W. and a long-chain dialdehyde as shown in Figure 10. E. The selected examples described above serve to illustrate that marine natural products are indeed significantly different from the natural products traditionally isolated from terrestrial plants and microorganisms.R. in Alkaloids: Chemical & Biological Perspectives. which contains many remarkably complex molecules that are often imbued with exquisitely potent biological activities. Bis(3-alkylpiperidine) macrocycles can undergo various transformations. ed. ch. cost. along with ingenamine (35) and madangamine A (36) isolated from Xestospongia ingens are representative examples. This marine pool of novel chemical diversity. Andersen and D.. the major issue  R. Williams sponges. 10. Consequently. W. and failure rate barriers to drug development exist regardless of whether the ‘lead’ compound comes from a synthetic or natural product chemical diversity pool. Typically it takes 12—15 years to bring a drug to market from the time of its initial discovery and the total bill is more than $350 million (US). The opportunity to exploit this valuable resource and the resulting rewards are waiting for those who are willing to meet the significant challenges required to bring a marine natural product ‘lead’ compound to the clinic.

The first relates to the possible environmental impact of collecting marine specimens. Development. more complex issue involved in obtaining collecting permits has to do with intellectual property rights. 1997. The second. the total biomass of a specimen currently required for HTS screening and compound identification is quite small and collection of this quantity should normally have no environmental impact. ethical concerns regarding the intrinsic value of biodiversity were addressed. including transfer of relevant technologies and equitable sharing of research results and other benefits. dredging. The Pharmaceutical Products Press. international assistance would have to be provided to developing countries to pursue biodiversity protection efforts. This document is in sharp conflict with the basic premise endorsing the concept of nations holding property rights to their indigenous species as outlined in the Rio Accord. Essentially. Such obstacles include the ability of individuals to negotiate market  A. A carefully documented case along these lines is usually adequate to obtain a collecting permit where environmental issues are the concern. Drugs of Natural Origin: Economic and Policy Aspects of Discovery. There are two issues that must be addressed when securing collecting permits. Therefore. p. the Trade Related Aspects of Intellectual Property Rights agreement of the World Trade Organization. or submersibles. Many jurisdictions require collecting permits that are much like fishing licenses in an attempt to control the excessive removal of marine specimens by SCUBA. Fortunately. in general. and acknowledged the rights of countries to obtain compensation for access to their genetic resources. Sometimes the regulations cover entire coastlines. and ensuring equitable distribution of the resulting benefits. Two international documents deal with this issue. licensing fees. many of the provisions of the convention are quite vague and contradictory. is the second international document that deals with intellectual property rights arising from biodiversity. The first is the Convention of Biological Diversity that was signed by 140 nations at the 1992 Earth Summit in Rio de Janeiro (as of 1997. countries are left to decide for themselves what constitutes compliance. and royalties. Artuso. New York. particularly with regard to intellectual property rights and the compensation arrangements that should be applied to transactions involving genetic resources. 69 . In the convention. developing mechanisms for their sustainable use. which came into effect in 1995. The TRIPS assumptions are that excessive government control of resources is to be avoided as an obstacle to economic growth. However. but the main focus was to establish sovereign rights over biological resources. and Marketing. only 30 countries have ratified the document).Pharmaceuticals from the Sea in collecting marine specimens now involves securing permission to collect from the countries whose territorial waters encompass the desired collecting sites. modern HTS assays require very small quantities of crude extracts. The convention acknowledged that. Recent advances in isolation and structure elucidation technology have also dramatically reduced the quantities of crude extract required to identify the chemical structures of bioactive hits. so initial collections of specimens for screening purposes can usually be limited to less than 500 g. 142. TRIPS. other times they only cover protected areas like marine parks and reserves or high profile tourist destination dive sites.

Springer. R. a hit in a natural product crude extract provides no immediate structural information and.  C. Berlin. Technological advances in NMR.. and encouraging educational exchanges as well as negotiating equitable formulas for sharing licensing fees and royalty payments. Williams prices of biological resources that the Biodiversity Convention allows. 1999. 1998. and HPLC.. The delay in providing an active structure and the unpredictability of the process are hurdles that natural product extracts must overcome to be compatible with HTS. Wohlfarth. 51. 3. and HPLC-CD. furthermore. Ruckert. Thiericke. Kraus. ed. Koch. Anal. 1998. The responsibilities of the collectors and the benefits to the country of origin will usually be formalized in a Memorandum of Understanding (MOU). MacLlwain. Masood. J. in Drug Discovery from Nature. ch. E. they have to be screened for bioactivity and the chemical structures of the active constituents have to be elucidated. is highly variable from extract to extract. and the emergence of powerful hyphenated analytical techniques such as HPLC-MS. The National Institute of Health (NIH) in the USA has taken a leadership role in this area by making sure that collections of marine specimens made in foreign waters using NIH funds are conducted only under agreements that recognize the rights of the country of origin of the biological materials. at most. Dumbuya. In contrast. Thiericke and S. and not the other way round. 1998. E. T. 525. 71. Grabley. After a bioactive marine natural product ‘lead’ structure has been identified.R. three months.. Neumann. M. Messer. p. Nature. K. 70 . 2678. Ideally the time for assay-guided fractionation and chemical structure elucidation must be shortened to a few weeks or probably. M. There is an emphasis on involving local scientists in the research.  C. months. MS. Chem. have partially solved this problem by greatly accelerating the rate of routine structure elucidation. ibid. Other approaches to solving this problem involve preliminary purification of crude extracts before they are submitted to HTS and the creation of libraries of purified and identified natural products that can then compete directly with synthetic libraries. HPLC-NMR. because they provide immediate ‘lead’ structures once hits have been identified by HTS. Andersen and D. which can be days. The Organization of African Unity’s task force on access to genetic resources has argued that TRIPs should comply with the Biodiverity Convention. 392. J. 537. 392. Once extracts have been obtained. Campaigns will often be mounted to screen full libraries of up to several hundred thousand compounds against a particular molecular target with the intent of identifying a complete suite of ‘lead’ structures in a period of no more than a few weeks or months. Combinatorial and directed synthetic libraries are ideally suited to this purpose. Contemporary HTS programs have been designed to speed up the process of identifying ‘lead’ structures in an attempt to shorten the timeline for drug development. MOUs spell out how the collections and ensuing research will be conducted and how proceeds from intellectual property rights will be shared. S. promoting technology transfer. K. 392. 1999.  G. and that member countries may refuse to recognize any patent from natural products found in Africa unless it acknowledges the ‘ownership’ and contribution of the relevant community to the new product. or years. the time required for bioassay-guided fractionation and structure elucidation. Grabley and R. 535: ibid. Bringmann.

Biological production of the natural product via fermentation or aquaculture represents a second potential solution to the supply problem. In order for a large pharmaceutical company to proceed. making them attractive targets for academic synthetic programs. so conceptually this should be straightforward for a metabolite of a marine microorganism. 10s to 100s of milligrams of the compound are required to test for activity in secondary assays that probe such issues as activity in whole cells. Many marine natural products with promising in vivo activity have very complex chemical structures. While academic syntheses prove that a particular compound can be made in the laboratory and often provide valuable structure—activity data. the issues of short-term small-scale and long-term manufacturing-scale supply become the determining factors in its further progress towards development. This usually involves recollection of significant quantities of the source organism and the environmental impact of these larger collections must be carefully evaluated since many of the source organisms are rare species.Pharmaceuticals from the Sea either by HTS or other traditional screening approaches. they must be assured of a reliable and economical source of the compound. Obtaining 10s or 100s of milligrams of many marine natural products for secondary assays represents a considerable challenge. in vivo efficacy in animal models. For marine natural products that are too complex to be produced commercially by total synthesis. While 71 . few of them are short enough or use reagents that are cheap or safe enough to become economical large-scale industrial syntheses. second. Many drugs are produced by industrial-scale fermentations of soil microorganisms. they must first determine that there is potential market niche for the compound that will return their development investment and. The only difference is the need to solve the technical problems associated with preparation of large volumes of seawater-based fermentation medium and the incompatibility of the high concentration of salts in the medium with currently available stainless-steel fermentation equipment. The shift of emphasis towards marine microorganisms is partly a result of the supply issues since laboratory fermentation of a marine microorganism represents a sustainable supply of an interesting metabolite. It also reflects the emerging recognition that many interesting compounds isolated from marine invertebrate extracts are actually biosynthetic products of associated microorganisms. maximum tolerated doses and minimum effective doses in animals. and pharmacokinetics. Moving a promising marine natural product from the demonstration of in vivo activity in secondary assays to a genuine drug development project is a major step because of the required commitment of both financial and human resources. Organic synthesis represents the ideal industrial source of a drug. Industrial-scale production of complex marine invertebrate metabolites by aquaculture of the producing organism under controlled conditions is an exciting prospect. The ability to culture the producing microorganism would provide a suitable supply of the desired compound both for secondary assays and ultimate commercial production. In the short term. there are still several supply options. Demonstration of in vivo activity is an absolute requirement before development can proceed. The first option is to use the natural product as a ‘lead’ structure for a synthetic medicinal chemistry program that identifies simpler synthetically accessible analogs that contain the same pharmacophore.

Scheuer. Baltimore. S. P. Mayer. Subsequently. ara C treatment leads to complete remission in 60—70% of treated patients. 9.  V. In this instance. Ames. Ara C (37) (trade name Cytarabine) is a synthetic material based on the ‘lead structures’ provided by isolation of spongothymidine (39) and spongouridine (40) from the sponge Cryptotethya crypta in the 1950s. 401. W. Williams and Wilkins. Jacobs and K. This ubiquitous enzyme catalyzes the hydrolysis of the ester in the   sn-2 position of phospholipids. 72 . 1611. are potent inhibitors of inflammation and its associated pain. Chem. Jacobs. M.. Bergmann and D. p. Tetrahedron Lett. ed. I. Manoalide (41) was originally isolated from the Indo-Pacific sponge Laffariella variabilis and its chemical structure was reported without any mention of biological activity. and inflammatory bowel disease.e. Avramis. Org. They have potential applications in a number of conditions including arthritis. so the expectation that new drugs based on marine natural products will appear in the clinic in the next few years is genuine. 4 Some Success Stories The number of marine natural product derived drugs currently in clinical use is still very small. 1980. however. it was discovered that manoalide had exciting anti-inflammatory properties. Andersen and D. S. and it also reduces degeneration of the skin. 21. D. Chem.  B. 51. the ability to obtain the active pseudopterosins as part of a ‘natural marine extract’ as opposed to making them ‘synthetically’ appears to be an important part of the marketing strategy. S. 21. isolated from the Caribbean soft coral Pseudopterogorgia elisabethae. M. Potts. In combination with other anti-cancer agents. Glaser. The anti-inflammatory activity of manoalide apparently results from its ability to inhibit the enzyme phospholipase A (PLA ). Jacobson. psoriasis. January. there are many promising marine natural products or synthetic analogs in clinical or pre-clinical trials. Williams this technology is still in its infancy.  E. 1999. J.  A. 1998. (London).. Growchow and M. the feasibility of the approach has recently been demonstrated by the production of anti-cancer compounds in the bryostatin family using controlled cultures of the bryozoan Bugula neritina. Burke. L. The natural extract produces reduction of skin inflammation from sunburn or irritation. D. J. de Silva and P. elisabethae in a product line called ‘Resilience’. pseudopterosin A (38)]. Ind. Prod. The pseudopterosins. resulting in the release of arachadonic acid. It is currently the most active anti-metabolite in clinical use for inducing remissions in acute non-lymphocytic leukemia in adults and pediatric patients. Jaspars.R. p. B. C. ch. E. in A Clinician’s Guide to Chemotherapy.. Life Sci. Nat. Fenical. The skin care company Estee Lauder ´ is currently using a ‘pseudopterosin-containing’ natural extract of P. B. Two products (see Figure 11) based on marine natural products that have already reached the market are the anti-cancer drug ara C (37) and the anti-inflammatory pseudopterosin diterpenoids [i. the biosynthestic precursor of prostaglandins and leukotrienes in the arachadonic  M. 1992. 1956. C. 62. J. 1998. J.  W. 209. R. 226. J. such as anthracyclines. Pharmacokinetics and Pharmacodynamics. Faulkner and R. B. 1701.. 55. It can be viewed as a first generation ‘Pharmaceutical from the Sea’ that emerged from the classical model of using a bioactive natural product as a ‘lead structure’ for the development of a synthetic drug.

Pharmaceuticals from the Sea Figure 11 Antiinflammatory or anti-cancer marine natural products and synthetic analogs that are in commercial use or in clinical and preclinical evaluation 73 .

Williamson. 74 . Y. A. A. manoalide was the only one that worked by interfering with PLA . Ecteinascidia turbinata. see: S. a steroid with a number of novel structural features that include the ring  and  hydroxylation pattern. A. R. Li. Prod. 115. R. and melanoma. It is a good example of how a marine natural product can also play an important indirect role in drug development by helping to identify new disease-relevant molecular targets that can be used in HTS screens to find mechanistically related but structurally unrelated ‘lead’ compounds. A. 1992. L. Rinehart. Salari. Inflazyme is currently exploring other anti-inflammatory indications for IPL-576 analogs of contignasterol and expects to define additional therapeutic targets for this class of compounds. 1995. 57. M. Shield. R. The majority of promising drug candidates emerging from marine natural products research to date are potential cancer treatments. It is widely used  throughout the pharmaceutical industry and it may well result. 525. K. Wolf. K. New Drugs. S. at the time of discovery. Many anti-inflammatory drugs interfere with the archadonic acid cascade but. Perun. Six anti-cancer compounds that are either marine natural products or synthetic analogs of marine natural products have made it to clinical trials. 13. K. It was found to inhibit the release of histamine from rat mast cells stimulated with anti-Ige in a dose-dependent manner. O’Rourke. Unlike other cortisone-based steroidal anti-asthma drugs. Chem. Crude extracts of another Caribbean tunicate. Contignasterol (42). R. 1995. manoalide (41) has been  developed as a commercial reagent for basic studies of PLA . Inflazyme Pharmaceuticals has made a synthetic analog of contignasterol designated IPL-576-092. W. Burgoyne. J. no favorable responses were found so the compound has been withdrawn. and the hemiacetal functionality in the side chain. D. J. Crawford.  For one example. Andersen and T. S. G.. Williams acid cascade. Jones. Langlands. Seigler. Nat.. The first of these compounds to enter clinical trials was didemnin B (43). J. a property that suggested it had potential as an anti-asthma agent. G. J. M. Gade. showed extremely  D. 53. G. Martin and G. M. prostate cancer.. Burgoyne. Org.  K. Andersen and D. IPL-576-092 is orally active and it does not appear to bind to the steroid receptors that are responsible for long-term toxic side effects in the current generation of inhaled anti-asthma drugs. Holt. L. 771. Eisenberger. T. Sakai. 167. Keifer. Wilson. D. Stroh. J. the cis / ring junction. Invest. E. Histamine is one of the mediators of asthma that causes smooth muscle contraction. L. one of a family of cyclic depsipetides isolated from the Caribbean tunicate Trididemnum solidum. H. The prostaglandins are well-known mediators of inflammation and pain. Thompson. J. Pharmacol. J. that is currently in Phase I clinical trials in Europe as a new anti-asthma agent. N. D. Andersen and H. Li. J. Didemnin B was advanced to Phase II clinical trials for treatment of small cell lung cancer. D. myeloma. in a new class of anti-inflammatory agents. T. Brannon and E. L. M. G. J. L.  A. Further testing showed that contignasterol (42) was very effective at preventing asthma-like symptoms in standard guinea pig models. While not sold as a drug. Bramley. leading to bronchial constriction and difficulty in breathing.R. D. 1433. was isolated from the sponge Petrosia contignata collected in Papua New Guinea. P. G. M. Allen. through synthetic drug design. 1990. Unfortunately. M. Fregeau. Br.

An aquaculture approach to producing the bryostatins that is capable of generating a sufficient and sustainable supply for clinical use has been developed by CalBioMarine. 1996. 525. G. M.  One member of this family of compounds. C. H.  G. Nat.. Dolastatin 10 (46) and a synthetic analog auristatin PE. A. Two additional marine natural product structural classes that have led to anti-cancer drug candidates in clinical trials have come from bryozoan and mollusc extracts. 4508. E. P. S. 1991. Adjeu and M. L. 56. 1990. Halichondrin B (48). Wright. M.  A. Pitot. A. Pettit. D. P.. The supply of bryostatin 1 (45) required for preclinical testing came from harvest of wild specimens. J. Chem. L. Rubin. A. The bryostatins are a family of potently cytotoxic macrolides isolated from the bryozoan Bugula neritina.  In addition to the compounds that have already moved to clinical trials. Cancer Res. J. however. Several large collections of the animals that exceeded 1500 kg wet weight in total were processed in order to obtain the milligram quantities of individual compounds required for structure elucidation and preliminary biological testing. Prod. is currently in clinical trials. Keifer. A. McConnell. Walker. The material required for clinical trials was obtained from harvest of wild specimens. many of the dolastatins and a wide variety of structural analogs have been synthesized in order to confirm the structures of the natural product and provide material for further biological evaluation. Two groups simultaneously succeeded in isolating and elucidating the structures of members of the ecteinascidin family of tetrahydroisoquinoline alkaloids that were responsible for the cytotoxicity of the crude extracts. Koehn. The dolastatins are a family of cyclic and linear peptides isolated from the sea hare Dolabella auricularia collected in the Indian Ocean. O. 1999. Chem. P. Two linear peptides. 5.  H. the generally low yield and large variability from collection to collection make this a non-viable source for commercial production should a compound in this family make it to the clinic. Gunasekera. Erlichman. Many of these turn out to be anti-mitotic agents that interfere with tubulin dynamics either by inhibiing polymerization or by stabilizing microtubules. Gundawardana. A. Stroh. have emerged as the most promising ‘lead’ compounds in the family. Holt. J. Martin. R. 75 . Ames. a complex macrolide initially isolated from the Japanese sponge Halichondria okadai. J. J. Clin. F. Fregeau. auricularia crude extracts.. J. F. C. there are a number of very exciting marine natural products (see Figure 12) that are in pre-clinical evaluation as potential anti-cancer agents. G. P. Sloan. which have been found to be potent anti-mitotic agents that inhibit the polymerization of tubulin. are all in phase I clinical trials. dolastatin 10 (46) and dolastatin 15 (47). ecteinascidin 743 (44). 812—821. Windebank. Bryostatin 1 (45) is currently in late Phase I and early Phase II clinical trials in Europe for the treatment of melanoma. N. is a potent inhibitor of tubulin polymerization that shows very promising in vivo  K. E. G.. Bagniewski. L.Pharmaceuticals from the Sea promising tumor inhibitory properties. M. 59. Rinehart. G. J. A. Goldberg. Org. Sun. T. D. G. 1676. Isolation and structure elucidation of the potently cytotoxic dolastatins was hampered by their very low yields in the D. Reid. McElroy. Forleo. along with dolastatin 15 (47) and a water soluble synthetic analog LU-103793. J. Subsequently. J. 55. Li and D. L. E. R. A. Org.

R. Williams Figure 12 Some promising marine natural product ‘lead’ compounds 76 . E. Andersen and D. J.

p539 cells) relative to cells that  O. 1996. Friend. M. 1. S. P. Lin. W. When used in combination with either a chemical DNA damaging agent or radiation. alkaloids 53 and 54 enhance the killing of cancer cells. J. Roberge. H. Fenical. P. Xu. Kowalski. The anti-inflammatory and anticancer ‘lead’ compounds discussed above were all discovered by screening programs that used traditional whole cell or tissue-based assays and all come from extracts of marine invertebrates. Vincent. J. Clardy. Plubrukarn and B. 118. The recent introduction of the plant natural product paclitaxel into clinical use has prompted many researchers to search for other natural product structural classes that. Fodstad. M. Chem. Anderson. is also taking place in marine natural products drug discovery research. J. S. The recent shift in screening paradigms towards more focused molecular targets. 5701. Mooberry. P. an enzyme involved in the activation of the G2/M transition of the cell cycle. Cancer Res. Davies. 653. All three compound classes are currently the focus of extensive chemical and biological research aimed at evaluating their clinical potential. C. Soc.. 119. Casazza. Cancer Res. Berlinck. J. a polyketide isolated from the Caribbean sponge Discodermia dissoluta. S. Rosenkranz and B.. C. McCarthy. missing the tumor suppressor gene (i. Carboni. 1996. are three novel marine natural products that mimic paclitaxel’s ability to stabilize microtubules. Gunasekera. R. Piers and R. J. 243. A. Dysidiolide shows micromolar in vitro inhibition of A-549 human lung carcinoma. M. are the first G2 cell-cycle checkpoint inhibitors discovered by rational screening. K. Soc. J. R. Day. L. W. H.Pharmaceuticals from the Sea activity against a number of human cancer cell lines in mouse xenografts. H. Fairchild. M. Eleutherobin (49). of halichondrin B has prompted the development of a method of producing the compound by in situ aquaculture of the New Zealand sponge Lissodendoryx. Oncol. Dysidiolide (52) isolated from the Caribbean sponge Dysidea etheria is the first naturally derived inhibitor of cdc25A protein phosphatase. metabolites of the Brazilian tunicate Didemnum granulatum. B. 119.. 58. This has resulted in reports of some exciting new activities for marine natural product chemotypes.  S. Lim. Hernandez. S. and laulimalide (51). Davidson.. Manoalide and the pseudopterosins were discovered using a mouse ear edema assay and all of the anti-cancer compounds were initially isolated because they showed potent in vitro cytotoxicity against either murine or human cancer cell lines. E. using purified enzymes and receptors or engineered cell lines. Tien. Gunasekera. G. T. E. Breistol. E. E. R. D. S. like paclitaxel. Shoemaker and M. H. 1997. 8744. M. 1996. 59. ter Haar. R. but very limited supply. L. L. Lindel.  M. P. presumably owing to its inhibition of cdc25A.e. Chem. Biochemistry. Am. Ther. Andersen. C. Granulatimide (53) and isogranulatimide (54)..  E. a diterpenoid glycoside isolated from the Western Australian soft coral Eleutherobia sp. R. Kelly-Borges. G. discodermolide (50). P. Longley. I. A. 1999. Pettit. also kill cells by stabilizing microtubules. Jensen. making it an exciting ‘lead compound’ for development of a mechanism-of-action-based anti-cancer drug. Stringer. 35. 8759. R.  T. H. Hamel.. The promising anti-tumor activity. Boyd. A. J. H. 1998. R. R. Britton. Curman. J. Haggarty. Kelly. S. Lobovsky and J. 77 . Am. R. Exp.  S. G. Long. isolated from the South Pacific sponge Cacospongia mycofijiensis.

marine natural products represent a unique and extremely valuable molecular resource for drug discovery programs using either traditional or HTS screening paradigms. 1996. Sieverding and S. E. or terrestrial plant and microorganism natural product extract libraries. Quesada. Silverman. p53. Gaughran. The use of molecular target assays and investigations of marine microorganism secondary metabolites represent important trends for the future in marine natural products drug discovery research. R. Albaugh. 74. Cancer. has been found to effectively reverse multi-drug resistance in cancer cells by inhibiting P-glycoprotein mediated drug efflux. This combination therapy approach offers the hope of a greatly improved therapeutic index for the approximately one half of all human solid tumors that are known to be missing the tumor suppressor gene p53. Jensen. Albert.. Kirsch. 51. researchers in the field will have to make marine extracts compatible with HTS discovery paradigms and they will have to continue to find creative ways to solve the supply issues.R. Andersen and D. 317.  D. leading to the clear expectation that new pharmaceuticals from the sea will emerge for clinical use in the next decade. J. The natural products chemical diversity pool present in marine algae and invertebrate extract libraries has virtually no overlap with the chemical diversity pools present in traditional synthetic libraries. V. Many of the compounds already known exhibit potent biological activities that are relevant to treating human diseases. S. Cyclomarin A (57). Lai. Cotter. another polycyclic aromatic alkaloid isolated from tunicates in the genus Didemnum. . D. M. Fernandez Puentes. Therefore. Williams contain the tumor suppressor gene (i. P. a heptapeptide obtained from cultures of a marine actinomycete. Lamellarin I (55). Rehnig. Garcia Gravalos and J. R. it will represent the culmination of a new type of harvest from the bounty of the oceans. M. Br. and have been isolated from the mangrove derived fungus Hypoxylon oceanicum by scientists at Wyeth Ayerst. J. 1995. Another promising recent development is the increase in reports of interesting ‘lead’ compounds isolated from cultures of marine microorganisms.  W. Two examples illustrate the trend. D. R. The ideal outcome of a marine natural product drug discovery effort is identification of a bioactive ‘lead’  A. 5 Future Prospects Nearly four decades of marine natural products chemistry investigations have demonstrated that organisms living in the world’s oceans are an incredibly rich storehouse of novel low molecular weight chemical entities. A family of anti-fungal compounds named 15G256 (56). In order to keep the development pipeline full. A. A large number of very promising compounds from the marine natural products chemical pool are currently in the pre-clinical and clinical stages of development. When the next generation of marine derived drugs do appear. 677. 1998. G. Fenical. cells). Jacobs and P. Bradford. L. Froyd. has been patented as an anti-inflammatory agent. The potency of lamellarin I as a MDR modulator was 9to 16-fold higher than that of the benchmark compound verapamil. These compounds have been patented and they are being evaluated for potential use against human fungal infections. 78 . E.e. US Patent 5 444 043. H. J. combinatorial synthetic libraries. J. Antibiot. J.

it has the potential to greatly benefit all humans by leading to better treatments for serious diseases. In this scenario. and it can result in significant sustainable economic benefits to the countries where the relevant biological specimens were collected and where the advanced stages of development work have taken place. organisms in the ocean are yielding only knowledge about new pharmacophores rather than the more traditional harvests of biomass. This intellectual harvest is environmentally benign. 79 .Pharmaceuticals from the Sea structure that can be developed into a clinically useful synthetic entity.

13 Chemistry in the Marine Environment © The Royal Society of Chemistry. Additionally. 2000 81 . 45. Additionally. Mar. and plastic pollutants. In the 1960s. TBT. producing eutrophication in the water column or anoxic conditions in underlying sediments. 25. Pollut. Agricultural runoff may contain pesticide residues and elevated nutrients. the deep sea has not escaped contamination. In the marine environment. In effect. the latter of which may over-stimulate biological activity. the aeolian transport of heavy metals has enhanced natural fluxes of some elements. The  E. However. Waters and sediments in such regions bear the brunt of industrial and sewage discharges and are subject to dredging and spoil dumping. particularly lead. Issues in Environmental Science and Technology No. a ‘modern contaminant’. Bull. petroleum products. Goldberg.. the greatest effects tend to be in the coastal zone.Contamination and Pollution in the Marine Environment ST EP HE N J. The most obvious manifestations comprise crude oil. The two terms are distinguishable by the severity of the effect: pollution induces the loss of potential resources. 1992. with all the ensuing problems one might expect. TBT is a broad-spectrum pesticide and herbicide. DE MO RA 1 An Overview of Marine Pollution Both contamination and pollution entail the perturbation of the natural state of the environment by anthropogenic activity. Owing to source strengths and pathways. is the main active ingredient in a range of organotin-based marine anti-fouling paints owing to its appreciable toxicity towards a wide range of organisms. that had been unwittingly introduced and popularized in a pesticide-aware culture. human-induced disturbances take many forms. but also include the long-range transport of long-lived radionuclides from continental sources. a clear cause—effect relationship must be established for a substance to be classified as a pollutant towards a particular organism. the global problems related to the wide-scale application of pesticides first accentuated the possible difficulties associated with utilizing useful and apparently benign compounds. The lesson supposedly learned with DDT has been reinforced in the past decade with tributyltin (TBT) compounds in the marine environment.

both nationally and internationally. J. non-chemical causes for concern include the heat associated with the emission of cooling waters from power plants. Three key factors in such a re-evaluation pertain to the nature of the pollutants and the processes by which contamination is investigated and. has resulted in the rapid regulation of TBT in many countries and international regulations to ban TBT are under consideration. recognition of the deleterious effects of marine pollution has led to a variety of control strategies. de Mora (ed. Essentially. ecotoxicology comprises a part of the spectrum of marine pollution studies. there is a notable ongoing effort to develop technologies to remediate polluted marine environments. one could add organometals. the case history of TBT has demonstrated the difficulties associated with assuming stewardship of the global environment. including those of commercial value. Hence. the approach has been changing to become proactive in character. Present and future challenges rest with the need to identify the  S. the understanding of what constitutes a threat to the marine environment. controlled. particularly following oil spills. accordingly. The efforts by the International Maritime Organization (IMO) are notable in this regard with respect to limiting pollution from ships. However. the research process to investigate contaminants has changed. Sensitive assays now allow the investigation of sub-lethal effects of pollutants on cellular components and processes. pollution by such agents as metals. other agents of anthropogenic change are now being investigated. This takes into appreciation the role of hydrodynamics in pollutant transport processes at one extreme and elucidating biochemical responses at a sub-cellular level at the other. Cambridge. J. but have usually been reactive responses to a pollution event. Finally. This cautionary approach places greater reliance on risk assessment procedures and cost—benefit analyses. and enhanced sediment discharge as a result of accelerated soil erosion caused by deforestation and urban development. Cambridge University Press. Biogeochemical practices have ensured that understanding the behaviour of contaminants in the marine environment requires a multidisciplinary strategy. 82 . several compounds have been shown to act as endocrine disrupters and. However. However. In the same vein. legislation has been introduced. Thus. more recently. the hard-learned lessons from DDT and TBT have instilled caution. has been broadened in scope. de Mora widespread deleterious influence of TBT on non-target organisms. and oil continues to feature prominently in environmental impact studies. 1996. for instance in the introduction of new antifouling agents in marine paints. Firstly. Tributyltin: Case Study of an Environmental Contaminant. More recently. The concept of marine pollution has undergone a continual evolution. exotic biota from ship ballast waters and hulls. However. Thus. once perceived to entail essentially just chemical contaminants. pesticides. radionuclides.). The development of more sensitive instrumentation has facilitated the creation of a better database of pollutant distributions. and endocrine disrupters to the list of chemicals. of greater significance is the realization that marked biological responses can be induced at extremely low contaminant concentrations. to limit known sources of contamination. Secondly.S. Thus. These strategies can be legal or technological in nature.

tend to disperse the slick. In contrast to such mishaps.g. social. USA. 1967. and legal criteria. Transformation of the oil involves phase changes and/or degradation. the impacts can be severe when the subsequent slick impinges on coastal ecosystems. Boca Raton. most of this additional oil has originated from relatively diffuse sources relating to municipal run-off and standard shipping operations. Several physical processes can invoke phase changes. Chevron MP-41C. 10 L of oil in 1978. 1976. 2. 83 . economic. Murray. oil pollution must be put into perspective. Mississippi Delta. accounting for the largest spill from a tanker. Oil Slicks Major releases of oil have been caused by the grounding of tankers (e. perhaps once considered the domain of chemists and biologists. the principal agent for the movement of slicks is the wind. Nevertheless. CRC Press. however. Torrey Canyon. Southwest England. relative to the slick size) weather systems. in Pollutant Transfer and Transport in the Sea. They are global in character and represent examples where public and scientific concern has been sufficient to provoke strategies to mitigate and/or prevent such pollution. Only a few case studies are presented here. p. 10 L) and due to the Ixtox I well in the Gulf of Mexico in 1979 (530 . Crude oil has habitually been introduced into the marine environment from natural seeps at a rate of approximately 340 . 1978. especially for light crude oil. cyclonic systems can move the slick essentially intact. Northwest France.  S. 1990) or by the accidental discharge from offshore platforms (e. Such pancake formation is due to the fractionation of the components within the oil mixture. Whereas small (i. Anthropogenic activity has recently augmented this supply by an order of magnitude. but length scales are important. Oil slicks spread as a buoyant lens under the influence of gravitational forces. Nantucket Shoals. such as thunderstorms. Gulf of Mexico. FL. Evaporation of the more volatile components is a significant loss mechanism. the resultant oil slicks are essentially surface phenomena that are affected by several transportation and transformation processes. but generally separate into distinctive thick and thin regions. 1979). Advection of a slick is also affected by waves and currents.e. 10 L). Regardless of the source. Marine pollution. 169. Exxon Valdiz. Alaska. 2 Selected Case Studies There are numerous examples and instances of pollution in the marine environment and a comprehensive coverage would be beyond the scope of a single article. Amoco Cadiz. Exceptional episodes of pollution occurred in the Persian Gulf in 1991 (910 . The cumulative pollution from tanker accidents on an annual basis matches that emanating from natural seepage. With respect to transportation. Ixtox I. Kullenberg. 1970. now impinges and relies on numerous other disciplines. Argo Merchant. 10 L yr\. G. Because oil spills receive considerable public attention and provoke substantial anxiety. 1982. diffusion can also act to transport the oil. To a more limited extent. vol.g. the Amoco Cadiz discharged only 250 . ed.Contamination and Pollution in the Marine Environment acceptable limits of pollution based on environmental.

S. Compounds that degrade at the same rate stay at fixed relative amounts throughout the lifetime of an oil slick. Conversely. Alternative bioremediation procedures relying on the addition of exogenous bacteria have still to be proved. McMillen and E. Water-in-oil emulsification creates a thick. J. Chemical transformations of oil are evoked through photochemical oxidation and microbial biodegradation. the relative amounts define a signature characteristic of the source. evaporate relatively quickly and hence serve little purpose as diagnostic aids. Source apportionment of crude oil in seawater and monitoring the extent of weathering and biodegradation constitute important challenges in environmental analytical chemistry. but strategies can be adopted to stimulate biological degradation. and as a result. successful bioremediation of floating oil spills has yet to be demonstrated. L. while taking care to limit the concurrent stimulation of phytoplankton activity. Not only is the latter more important in nature. The volume of the slick increases and it aggregates into large lumps known as ‘mousse’.. albeit comparatively toxic to marine organisms. Furthermore. stable colloid that can persist at the surface for months. most of the molecules in crude oils are susceptible to microbial consumption. Colloidal suspensions can consist of either water-in-oil or oil-in-water emulsions. which represents the concentration ratio for a pair of compounds exhibiting such behaviour. A. 84 . Approaches that have been adopted are the utilization of slow-release fertilizers. C. 2332. consequently termed bioremediation. Similarly. 30. All marine environments contain microorganisms capable of degrading crude oil. S.S. 1996. oil-in-water emulsions comprise small droplets of oil in seawater. R. Butler. which behave distinctly differently. As the concentration of individual compounds varies from one sample of crude oil to another. Technol. a ‘source ratio’. Bioremediation often depends upon on the controlled and gradual delivery of these nutrients. and a urea-foam polymer fertilizer incorporating oil-degrading bacteria. The  G. Hence. Prince. J. Bioremediation techniques were applied successfully in the cleanup of Prince William Sound and the Gulf of Alaska following the Exxon Valdez accident. Oil spill monitoring programmes conventionally determine four fractions: E E E E Volatile hydrocarbons Alkanes Total petroleum hydrocarbons Polycyclic aromatic hydrocarbons (PAHs) The volatile hydrocarbons. which can accelerate weathering processes. Bence. Sci. Conversely. remains constant. a ‘weathering ratio’ reflects the concentration ratio for two compounds that degrade at different rates and consequently this continually changes. microbial degradation of oil tends to be nutrient limited. Oil contains little nitrogen or phosphorus. de Mora Sedimentation can play a role in coastal waters when rough seas bring dispersed oil droplets into contact with suspended particulate material and the density of the resulting aggregate exceeds the specific density of seawater. Environ. This aids dispersion and increases the surface area of the slick. thereby acting to retard weathering. E. oleophilic nutrients. Douglas.

 Litter and Debris The increasing accumulation of litter along shorelines epitomizes a general deterioration of environmental quality of the marine environment. Gregory and P. Such degradation extends to the high seas. 49. Impacts and Solutions. 2332. G. Ryan. being manifest as floating debris. the problem of seaborne litter remains global in extent and not even Antarctica has been left unaffected. Some degree of protection in recent years has accrued from both the London Dumping Convention (LDC) and the International Convention for the Prevention of Pollution from Ships (MARPOL) which outlaw such practices. M. © 1996 American Chemical Society) alkanes and total petroleum hydrocarbons make up the bulk of the crude oil. as well as for subtidal sediments and soils. and susceptibility towards biodegradation. The floating debris and beach litter consists of many different materials that.  M. 1996. Sci. 85 . Rogers.. J. ed. the PAHs. Thus. p. However. The material originates not only from coastal sources. Moreover. tending to be non-degradable. Drilling rigs and offshore production platforms have similarly acted as sources of contamination. Coe and D. both a D3/P3 source ratio (C3-dibenzothiophenes: C3phenanthrenes) and a D3/P3 weathering ratio (C3-dibenzothiophenes: C3chrysenes) have been defined from amongst such compounds that enable the extent of crude oil degradation to be estimated in the marine environment. volatility. New York. Springer. high concentrations of floating rubbish have been observed near fishing grounds and in shipping lanes. but also arises from the ancient custom of dumping garbage from ships. comprises only about 2% of the total content of crude oil but includes compounds that are toxic. The final fraction.Contamination and Pollution in the Marine Environment Figure 1 Plot of weathering ratio (C3-dibenzothiophenes: C3chrysenes) versus source ratio (C3-dibenzothiophenes: C3-phenanthrenes) for fresh and degraded oil samples from three different crude oil spills (Reprinted with permission from Environ. B. They can be used to some extent for source identification and monitoring weathering progress. Technol. endure in the marine environment for many years. R. in Marine Debris: Sources. these components exhibit marked disparities in weathering behaviour due to differences in water solubility. 30. As demonstrated in Figure 1.

Again plastics dominated the material found. The highest concentrations occurred in the vicinity of metropolitan areas. 30. turtles. but more importantly can be potentially lethal to marine organisms. such as glass bottles. J. de Mora Figure 2 Quantities of debris per trawling tow (30 min) collected on the continental shelf and adjacent canyon of the Gulf of Lyons (Reprinted from Mar. This litter constitutes an aesthetic eyesore on beaches. X. Jaunet. While this floating material can have the apparently benign consequence of acting as a habitat for opportunistic colonizers. Pollut.  F. Campillo. Pollut. Bull. and small pellets). this allows the introduction of exotic species into new territories. Guenenen and E. Deleterious impacts on marine birds. A. His. 86 . 30. sheets. 713.. Bull. Mar. Lost or discarded plastic fishing nets remain functional and can continue ‘ghost fishing’ for several years. On a different note. 713. tin cans. with permission from Elsevier Science) The most notorious are the plastics (e. © 1995. Plastic debris settling on soft and hard bottoms can smother benthos and limit gas exchange with pore waters. fishing gear.S. S. Galgani. and lumber. traps and pots that go astray can continue to catch benthic animals. Bottom trawls in the northwest Mediterranean Sea found that litter was essentially ubiquitous in the region (see Figure 2). bottles.. and mammals result from entanglement and ingestion. but canyons also tended to be sites of preferential accumulation. with all the latent problems that such invasions can cause. Numerous other materials have been observed. packaging materials. with up to 90% of the litter at a site near Marseilles comprising plastic bags.g. Perhaps more startling is the unseen pollution that has largely gone undetected on the sea floor. 1995.

Feuillet. Dardignac and M. Environ. Res. 203. North Sea and Strait of Malacca) where the source of TBT can only be attributed to shipping. Notwithstanding such benefits. Falandysz. TBT is lethal to some shellfish at concentrations as low as 0.g. 34. The latter effect. Although it has not been shown to pose a public health risk. M. the imposition of male sex organs on females) in marine gastropods. However. Such adsorption and deposition to the sediments limits its lifetime in the water column. as manifested in sedimentary TBT profiles. the extreme toxicity and environmental persistence has resulted in a wide range of deleterious biological effects on non-target organisms. The first publication suggesting TBT to be the causative agent appeared only in 1982.  C. 87 . 45. TBT-based paints have been used on boats of all sizes. Alzieu.Contamination and Pollution in the Marine Environment Tributyltin Tributyltin (TBT) provides an interesting case study of a pollutant in the marine environment. there have been many reported instances of restoration of gastropod populations at previously impacted locations. with as-yet unknown consequences. Thibaud.  C. TBT exists in solution as a large univalent cation and forms a neutral complex with Cl\ or OH\. Kannan and J. Because TBT compounds are extremely poisonous and exhibit broad-spectrum biocidal properties. Oyster aquaculture in Arcachon Bay benefited immediately. This has certainly had the effect of decreasing the TBT flux to the marine environment. Pollut. Heral. large ships continue to act as a source of TBT to the marine environment. Trav.. but already the use of TBT-based paints has been banned in some countries. Lower concentrations result in sub-lethal effects. Mar. Its potency and longevity ensures good fuel efficiencies for ship operations and guarantees a long lifetime between repainting. 1991. ensuring the global dispersion of TBT throughout the marine environment. its use being permitted only on vessels 925 m in length or on those with aluminium hulls and outdrives. Bull. Alzieu.02 g TBT-Sn L\. 32. Similarly.e. It should be of concern that imposexed gastropods have been observed at sites (e. The economic consequences of the shellfisheries decline led to a rapid political response globally. The most obvious manifestations of TBT contamination have been shell deformation in Pacific oysters (Crassostrea gigas) and the development of imposex (i. Mar. Comparable improvements in oyster conditions have been reported for Great Britain and Australia. J. from the coastal zone to the open ocean. Y. 1982. an example of TBT acting as an endocrine disrupter. including New Zealand. has caused dramatic population decline of gastropods at locations throughout the world. It is extremely surface active and so is readily adsorbed onto suspended particulate material. 7. such as poor growth rates and reduced recruitment leading to the decline of shellfisheries. with a notable decline in shell deformations and TBT-body burdens and the complete recovery of production within two years (see Figure 3). one recent study reported measurable butyltin concentrations in human liver. Other nations have imposed partial restrictions. M. via photochemical reactions  K. Rev. 1997. Inst.. Marit. they have been utilized as the active ingredient in marine anti-fouling paint formulations. from small yachts to supertankers. 100. TBT has been observed to accumulate in fish and various marine birds and mammals.. Degradation.

Indeed. which are much less toxic in the marine environment than is TBT. 2008. J. Stepwise debutylation produces di. the International Maritime Organization has undertaken to draft a global. as diverse as phytoplankton to starfish. For the most part. Furthermore. legally binding convention that would prohibit the application of TBT-based paints after January 1. de Mora Figure 3 Annual oyster (Crassostrea gigas) production in Arcachon Bay. help to explain the measurable quantities of TBT in squid and marine mammals collected in the open sea. Michel and B. the prescribed dates will provoke considerable debate.. Several marine organisms. Such observations imply that further restrictions on the use of organotin-based paints are required. Sci. However..  C. with the half-life being of the order of years. 2003. in part. Of course. One recent study has estimated that the residence time of TBT in oligotrophic waters may also be of the order of years. Thus.S. Environ. which are most likely to undergo dredging. The intrinsic toxicity of TBT. 1990. de Mora. 33. obeys first-order kinetics. its persistency in the sediments. TBT endures in sediments globally. This may. 2524. 11. and its periodic remobilization by anthropogenic activity are likely to retard the long-term recovery of the marine ecosystem. degradation is slow relative to sedimentation. the coastal tropical ecosystems remain unprotected and the sensitivity of its indigenous organisms is relatively poorly evaluated. with concentrations usually greatest in environments most likely to be perturbed. TBT accumulates in coastal sediments where degradation rates are much slower. 1999. Environ. debutylate TBT.  P. such as marinas and harbours. and ban the presence of TBT on ship hulls as from January 1. concentrations are highest in those areas. Averty. 565. Organisms in regions hitherto considered to be remote now manifest TBT contamination and effects. Stewart and S. J. Technol. The widespread introduction of TBT into seawater continues from vessels not subject to legislation. 1978—85. Technol. the unrestricted use of TBT has ended in many parts of the world but significant challenges remain. Recapitulating. 88 .and mono-butyltin moieties. As degradation lifetimes in the water column are of the order of days to weeks. restrictions on TBT use were first applied in January 1982 (Data taken from Alzieu) or microbially mediated pathways.

Whitmarsh.Contamination and Pollution in the Marine Environment the paramount lesson learned from TBT should be that potential replacement compounds must be properly investigated prior to their introduction in order to avoid another global pollution experiment.. An additional problem from land-based sources pertains to transboundary effects. Thus. and usually obvious. 365. national policies and international conventions have been invoked to curb known. Although this is an obvious sentiment. A series of international conventions have been negotiated. such material should become prohibited in the near future. This can have a direct influence on bathing criteria and result in beach closures during contamination episodes. 30. Bull. Similarly. 3 Mitigation of Marine Pollution As indicated above. As noted above. sources of marine pollution. National legislation is used to control coastal discharges of contaminants. 1995. The environmental threat posed by antifoulants has become widely recognized owing to TBT-based paints. Garrod and Whitmarsh describe market failure with respect to protecting the marine environment. They suggested that economic controls to pollution control have been gaining favour over ‘command and control’ strategies. Economic Controls Although economic forces have often been viewed to be an agent of environmental degradation. 89 . Numerous restrictions apply to the release of rubbish and oil discharges. pollutants may be released into the marine environment by one sector or industry  B. Pollut. but the role of governmental action is not likely to become redundant. Thus. A negative consequence of the use of biocides other than TBT may be the enhanced capacity for shipping to act as a transportation vector for the invasion of exotic species into new territory. leading to non-toxic products and a low bioaccumulation potential (possibly manifest by a low water—octanol partition coefficient). The most important deleterious effects in this case are with respect to microbial water quality. As background. the perception and role of market forces in preventing and mitigating pollution is changing. whereby pollution may inadvertently be exported from one country to another. adequate control of sewage discharges and ballast water is increasingly advocated. Mar. Replacement compounds will need to be shown to be more environmentally friendly. the role of ships as a source of biological contaminants has become appreciated. especially to control pollution from ship-based sources. Garrod and Whitmarsh have appraised governmental and economic methods of controlling pollution in the marine environment. The desired attributes are usually considered to be a high degradation rate. A major problem remains owing to the inadequate treatment of sewage prior to emission from land-based sources. Particular difficulties arise because of the diverse and perhaps conflicting exploitation of the sea and its resources. Garrod and D. the criteria to judge (or rank) such biocidal compounds remain contentious.

In this case. Property rights are usually so poorly defined that the polluter cannot readily identify the party to whom compensation should be paid. society. contamination is inevitable and technological solutions to mitigating the impacts have been developed. The ‘polluter pays’ adage of the 1980s thereby transfers the financial burden of environmental damage from society to the producer. in turn. a firm can conscientiously target environmentally aware consumers (through marketing environmentally friendly products or processes) or can be better placed for financial support from ethical investment funding bodies. Bioremediation Legislation and economic factors may aim to prevent marine pollution. An alternative tactic is to impose a system of tradable pollution permits. Firstly. This can be in recognition of social responsibilities. but is more successful when compelled by competition in the market place. ‘Standard setting’ solutions can have a proclivity towards over-regulation and may be unable to distribute appropriately or adequately the associated costs and compensations. Taxes and charges may be levied in an attempt to ensure that the true costs of production are borne by the industry. to the extent where regulations promote the industry at the expense of customers. Corporate environmentalism is an evolving concept for environmental protection. Petroleum pollutants can be removed by microbial degradation. Despite the attractions of economic forces driving environmental protection. Although bacteria and fungi capable of degrading many oil components exist in the marine environment. notably aquaculture.S. protection of the marine environment is likely to be aided by economic factors but the role of government. This is especially the case for oil pollution. Accidental oil spills at sea do occur and frequently impact shoreline environments. the loss of raw material may deprive the home market of an adequate supply of feedstock for the home-based industry. Thus. there is considerable scepticism that self-regulation of TBT-based antifoulants could be achieved in a timely manner by the shipping industry. business takes a pro-active stance independent of regulatory authorities. Thus. the export of hazardous waste to countries where costs for treatment are lower enhances environmental risks during transport and has the potential for transboundary export in the event of pollution. governments can promote economic approaches. Secondly. via taxation and standard setting. which inevitably receives considerable press attention. J. Government intervention for environmental protection is not without criticism. de Mora but the environmental costs are born by society and/or other users. As an alternative. Nevertheless. At the same time. Some policies may favour specific sectors of industry. some cautions and failures have been noted. Public education and. with the incentive that reducing pollution activities may realise cost benefits. natural rates of hydrocarbon biodegradation are usually limited by abiotic environmental 90 . can promote and support corporate environmentalism. or other industrial sectors. the incentive then rests with the producer to minimize environmental damage and associated costs. pressure. is not likely to be usurped. Again. This is an instance where the cost benefits to one industry are born by another commercial sector.

 K.g. This technology is relatively cost-effective. Environ. or (3) toxicity due to the treatment is increasing. 91 . oil-degrading microflora naturally increase in numbers following exposure to oil. Rev. Two approaches have been used. C. fertilization with nitrogen and phosphorus has been used. air—sea interface or on the surfaces of sediments in beaches). Bioremediation refers to the addition of substances or modification of habitat at contaminated sites to accelerate biodegradation. Prince. 19. chemical dispersants. Transplantation may aerate the rhizosphere and serve as a means to stimulate aerobic oil biodegradation. not requiring a large number of personnel or highly specialized equipment. and salt marsh environments. 1993.Contamination and Pollution in the Marine Environment factors.  R. such as hydrogen. 783. Recommended for use following the physical removal of bulk oil. has potential application in delicate and sensitive salt marsh environments that are the most difficult to clean. This technique. Termination of treatment should be implemented when: (1) it is no longer effective. sand beach. de Mora. (2) the oil has degraded to acceptable biologically benign concentrations. this being where microbial oil degradation principally occurs. Numerous strategies to accelerate oil biodegradation rates have been developed over the last 20 years and in situ bioremediation has become an established oil spill countermeasure. known as phytoremediation. which are retained in interfacial regions (e. Deeper penetration of oxygen and nutrient supplements can be achieved with tilling and raking. bioremediation has an operational advantage in that it breaks down and/or removes the residual contaminants in place. J. The introduced plants also may take up oil and release exudates and enzymes that further stimulate microbial activity. biostimulation involves the addition of nutrients or growth-enhancing co-substrates and/or improvements in habitat quality to enhance the growth of indigenous oil-degrading bacteria. surface agents such as powdered peat. Secondly. Firstly. diverse means to oxygenate sedimentary environments have been attempted because anoxic conditions dramatically limit microbial oil degradation rates. given that nutrient availability often limits microbial activity. can alleviate oxygen deficiency within sediments. Several different strategies have been tested. 20. Finally. oil-degrading bacteria are introduced to supplement the existing microbial population. they generally are incorporated into oleophilic nutrient formulations or microemulsions. The cost-effective application of such technology remains controversial and not well justified. To prevent rapid dilution and to maintain a sufficient concentration of nutrients to support the maximal oil biodegradation rates. Technol. Alternatively. laboratory and field trials have failed to provide convincing evidence of consistent success.. Moreover. Thus. Lee and S. Crit. and magnesium peroxides. methods to increase the surface area of the oil—water interface have been applied. In contrast. Laboratory experiments and field trials have demonstrated the feasibility and success of bioremediation to enhance bacterial degradation of oil on cobble. 1999. Microbiol. However. In bioaugmentation. and fertilizers supplemented with biosurfactants have all been used as bioremediation agents.. chemical oxidants. Its efficacy during actual response operations has been demonstrated on cobble beaches contaminated by the Exxon Valdez spill in Alaska. calcium. 217.

This field is still evolving. locations. On a positive note. Thus. bioremediation strategies have successfully aided shoreline recovery from oil spills. J. either via governmental intervention in the form of taxation or through corporate environmentalism. Many types. there are many mechanisms for preventing pollution and mitigating long-term adverse effects. In the inevitable consequence of marine pollution events. A few case examples have been described here with the objective to portray the diversity of contamination. 92 .and sea-based sources of pollution. with the major challenge of cleaning spills at sea still remaining. de Mora 4 Summary Marine pollution takes many forms.S. Economic forces can be used to control pollution. but some characteristics are universal. national legislation and international conventions provide considerable protection from both land. and impacts can be contemplated.

23-24. 31 93 . 72. 63 Bioaugmentation. 18 Carbonate. 70 Biogenic flux. 13-14. 31 Air-sea interface. 75 Butyltin concentrations in human liver. 57 Anti-cancer drugs. 70 African Sahel. 56 Cape Hat teras. 91 hydrocarbon. 61. 31 reservoirs. 84. 87 Anti-inflammatory marine natural products. 29 sources. 28.Actinium. 24 Anthropogenic activity. 31 Anti-cancer activity. 46 Carbohydrates. 83 Anoxic deep water. 82. 58 Bicarbonate. 31 flux. 14. 8. 81 Anthropogenic effects. 23 Arctic. 62-64 Alkaloids. 19-20 chemistry. 87 Calcium carbonate. 27 Argo Merchant. 46 Biogeochemical processes. 28 Bioactive secondary metabolites. 8 Camptothecin. 68 Amazon River. 18. 19. 20 Bioremediation. 57 Anti-cancer marine natural products. 72 Arabian Sea. 18 Carbon dioxide. 62. 73 Antifouling agents in marine paints. 71 Ara C. 9. 84 Biodiversity. 42 Bryostatin 1. 5 Ammonium ions. 16-21. 83 Artemisinin. 32-33 flux. 91 Biosurfactants. 5 Carbon cycle. 60 British Challenger Expedition. 41 Biological pump.90 microbial. 20 Amoco Cadiz. 63 Bismuth. 3 Africa. 43 Amino acids. 62 red. 28-29.91 Biodegradation aerobic oil. 15 Algae. 90 Biostimulatio~. 73 Aquaculture. 22 solubility. 20.34 Bleomycin. 19-20. 67-68 sponge. 34 Activity coefficients. 69 Convention. 91 Biosynthetic pathways.

24. 89 Ecosystems benthic. 27-28 Cloud condensation nuc]ei (CCN). 77 Dissolved organic carbon (DOC). 56 development. 51. 37 Decay series Thorium. 34. 90 microbial oil. 53 partia] pressuresin the atmosphere. 11 Diversity. 30 Dimethyl sulfoniopropionate (DMSP). 48 Deep-sea sediments. 33 control. 4. 30 Eleutherobin. 68 screening. 8 Corporate environmentalism. 55 Dumping garbage from ships. 35 radioactive. 26 Discodermolide. 84 Emulsions. oil-in-water.Subject Index Carbon monoxide. 35. 37 Davies equation. 13-15 change. 84 Endocrine disrupters.4 Circulation in the ocean. 58 discovery programs. 26 production. 68 from the sea. 35. 8 marine. 24 Deep ocean circulation tracer. 10. 71 discovery. 56 derived from natural products. 69 Economic controls on maritime pollution. 77 Earth Summit in Rio de Janiero. 72 Cytotoxic marine natural products. 84 microbial. 23 CFCs as tracers. 82. 25 Combinatorial chemistry. 8-9 Ecteinascidin 743. 62 Daughter isotopes. 40 Char]son Hypothesis. 13. 17 El Nino. 40.Th. 56 Dolastatin. 75 Eddy correlation technique. 74 Continental crust. 40 Ch]orofluorocarbons. 38 Cyc]omarin A.81 Debris. 58 Contamination. 25 physics. 68 pool. 48 Deep convection. 2 Climate. seealso CFCs. 91 Didemnin B. 29 Chemica] activity. 15 Coral reefs. 87 . 75 Drugs anti-cancer. 60 Cytarbine. 35. 58. 48 Deglaciation. 69 Conveyor belt. 68 Chernoby]. 14 Convention of Biological Diversity. 85 Dysidiolide. 3 DDT. 24 Deep water. 27 Degradation biological. 58 Docetaxel. 78 Cyclosporin. 13. chemical. 90 Cosmic rays. 3 Decay anaerobic. 2-3 Chemica] diversity. 58 therapy. 27 bacterial. 10 system. 53 Chomophoric dissolved organic matter (CDOM). 31. 85 Debye-Hiickel equations. 81 Contignasterol. 74 Dimethyl sulfide (DMS). 15. 77 Emulsification of water-in-oil. 60 libraries. 34 U. 23 constant. 37 rate of.

27 loop. 48 thorium. 77 Greenhouse effect. 85 Lovastatin. 77 Isotopes radium. 83 Half-life. 2 International Convention for the Prevention of Pollution from Ships (MARPOL). 84 Gulk of Mexico. 30 Global warming. 28 ice albedo. 83-84. 64 Heavy metals.Subject Index Estuarine colloids. 17 Genomics. 40 Fusion. 11 Iron. 30 methane. 28 Exxon Valdez. 77 Lea. 5 Litter. 2 Intellectual property rights. 69 International Association of Physical Sciencesof the Ocean (IAPSO). 5 Hydrogen sulfide. 27-28. 57 Humic acids. 24 gases. 37 Halichondrin B. 84 Fission. 5 Isogranulartimide. 39 Isotopic fractionation. 48 Euphotic zone. 75 Halogenated terpenoid and polyketide metabolites. 35 Fluoxetine. 35 Ghost fishing. 33 Laulimalide. 55 Human Genome Project. 44 Esuarine sediments.Th series. 60 Maitotoxin. 42 Herbicides. 17. 58 Human drugs. 72 Limestone. 38. 27 Gulf of Alaska. 5 Feedback. 50 Leukemia. 23 Hyphenated analytical techniques. 81 High nitrate but low chlorophyll {HNLC). 62 Ionic strength. 17. 87 In Vitro Cell Line Screening Project (IVCLSP). 84 urea-foam polymer. 35 Gas exchange. 64 0" . 24. 88 Invertebrates. 70 Imposex in marine gastropods. 13. 85 London Dumping Convention {LDC). 34. 49 pollution. 10 Granulatimide. 19 Lipids. 61.91 Fatty acids. 19-20 fertilization. 15 Gas transfer velocity. 31 High-throughput screening. 28 Global cooling. 32 climatic. 85 International Maritime Organization. 37 Joint Global Ocean Flux Study (JGOFS}. 21 limiting nutrient. 27 Fertilizers slow-release. 38 Geochronological tools. 31 hypothesis.23. 46. 44 Humic substances (HS). 57 Freons. 21 speciation in the ocean. 57 Geochemical cycles. 4 Hydrocarbons. 46 U. 57 Inorganic composition.26-28 Greenland ice cores. 2-3. 15. 86 Glacial period.

28 Methanesufonic acid (MSA). 66 sulfur cycle. 62 biological activity. 13. 87 production in Arcachon. 14 Southern. 23. 61 distribution. 83 Oil spills. 15 Nuclear weapons testing. 55. 60 National Institute of Health (NIH). 55-56. 61 extracts. 23. 4 Organic matter sedimentary. 71 metabolites. 13. 81. 70 Organotin-based marine anti-fouling paints. 83 . 87 Oxygen. 46 Medicinal chemistry. 40 Nucleic acids. 24 Oysters aquaculture. 1 invertebrates. 7 Meridional overturning circulation. 62 Mitigation of maritime pollution. 24 Oscillation. 72. 19-20 96 Nitrite. 58 Narragnansett Bay. 51 cycles. 82. 24. 30 inputs. 44 Organization of African Unity's task force. 60 Neutron activation analysis. 46 New York Bight. 29 Methane. 90 Organic chemistry in the ocean. 44 sponges. 91 Oceanography. 76 structures. 58 Mediterranean Sea. 35. 26 Microorganisms. 28 oleophilic. 62 plants and animals. 28. 77 Paints. chemical. 44 suspended. anti-fouling. 31 circulation. 87 Nidificine.Subject Index Manoalide. 45 Oil slicks. 66 microorganisms. 13 Paclitaxel. 5 Nutrients. 13 biota. 70 Natural products. 61 and invertebrates. 89 Morphine.91 at sea. 41 Particulate organic carbon {POC). 5 pollution. 24 Deep Water. 29 tracers. 20 Nitrogen oxides. 87 Pacific. 82 sediments. 88 Ozone layer. 38. 82. 14. 82 countermeasures. 86 Memorandum of Understanding (MOU). 41 Mass spectrometry. 63 'lead' compounds. 23. 84. 1 Oceans -atmosphere climate models. 71 natural products chemistry. 61 uranium residence times. 39 OMS production. 50 National Cancer Institute. 81. 28 temperatures. 64-65 Nitrates. 58. 87 Particulate material. 13. 39 plates. 47 Penicillin G. 25 North Atlantic. 33. 74 Marine algae. 7. 27 Methyl chloride. 21. 15.61 chemistry. 55 Persian Gulf. 50 New Zealand.

81 Polonium. 37 anthropogenic. 25 aerosol. 20. 37 in marine systems. 87 Silicates. 29 Plastics. 62. 72 Pycnoclines.Subject Index Pesticides. 21 Pitzer equations. 89 Shellfisheries. 38 Radium. 6. 24. 33 cosmogenic. 25 Sulfides. 2. 60-61 currently used as drugs. 30 Spatial gradients. 26 cool water. 66 Spongothymidine. 72 Spongouridine. 37 Sessile marine invertebrates and algae. 10. 26. 59 Secular equilibrium. 61 variations in the ocean. 68-69 Sea salt.8. 5 of iron in the ocean. 20. 30 species. 3 Plankton see also Phytoplankton blooms. 7. 33-34 transient. 13. 37 Radionuclides. 29 Sulfates. 46 Prozac. 33-35.7 Photochemical oxidation of methane. 23 Rio Accord. 6 Sponge terpenoids. 13 Solubility. 34.30 Photosynthetically active radiation (P AR). 6 Phytoplankton. 49 Polyketide metabolites. 34. 50 'Polluter pays'. 25 Radiactive disequilibrium. 62 growth. 48 Radon. 16 South Caroline salt marsh. 65 Practical salinity unit. 2 SCUBA. 33-35. 20. 2 Sulfate aerosols. 16 Prince William Sound. 72 Standard Sea Water. 21 photosynthesis. 14. 29. 20 of seawater. 86 Polar ice cores. 58 Salinity. 62 Sewage discharges. 11 Secondary metabolites. 55. 81 pH buffer. 23 Photosynthesis. 33 u. 91 Pinatubo. 55-79 Phosphate. 7 Radiation budget. 15 of seawater. 20 Size of the ocean. 11 Speciation of copper. 49 Ratio source. 84 Protactinium. 57 Pseudoptersoin A. 5 Pharmaceuticals from the sea. 84-85 Remotely operated (ROY) submersibles. 20 Silicon. 23 Phytoremediation. 49 Southern Oscillation. 24. 38 'primordial. 20 Photic zone. 84-85 weathering. 31 growth. 25 Seawater composition. 90 Pollution. 68 Respiration. 69 Robotic technology. 8. 21. 25 97 . 34. 2 physicochemical description.Th series. 34. 6 Solar radiation. 20 populations. 32 oxidation. 21 nitrogen.

60 Vincristine.Subject Index TBT see tributyltin Tectonic processes. 4. 16-17 Tributyltin (TBT). 69 Transfer velocity. 14 Thermocline.Th series radionuclides. 45 organic matter complexes. 15 in North Atlantic. 69 Tropospheric water vapour. 40.87. 69 98 .42 activity ratios. 51 half-life of. 83 Trace elements in seawater. 6 World Ocean Circulation Experiments (WOCE). 78 Ultraviolet radiation. 18 Thermohaline circulation. 45 Topotecan. 35 Weddell Sea. 43 bioaccumulation of.88 TRIPS. 6. 33. 81. 8. 44 particulate. 14 Tumour suppressor gene p 53. 32 Thorium. 33. 90 Trade Related Aspects of Intellectual Property Rights agreement. 58 Volcanic activity. 4 Uranium. 44 Uranyl carbonate complex. 33 Vancomycin.41 isotopes. 33 World Trade Organization. 35 Tracers. 14 Water mass residence times.56 Torrey Canyon. 41 in oceanography. 43 U. 34 Tradable pollution permits. 44 concentrations in marine environment. 35 anthropogenic.

Master your semester with Scribd & The New York Times

Special offer for students: Only $4.99/month.

Master your semester with Scribd & The New York Times

Cancel anytime.