Marine Geochemistry,COMPANION WEBSITE,This book has a companion website. www wiley com go chester marinegeochemistry,with Figures and Tables from the book. Marine Geochemistry,Emeritus Professor Roy Chester. School of Environmental Sciences,The University of Liverpool. Liverpool UK,Professor Tim Jickells,School of Environmental Sciences. University of East Anglia,Norwich UK,A John Wiley Sons Ltd Publication. This edition first published 2012 2012 by Roy Chester and Tim Jickells. Blackwell Publishing was acquired by John Wiley Sons in February 2007 Blackwell s publishing. program has been merged with Wiley s global Scientific Technical and Medical business to form. Wiley Blackwell, Registered office John Wiley Sons Ltd The Atrium Southern Gate Chichester West Sussex PO19. Editorial offices 9600 Garsington Road Oxford OX4 2DQ UK. 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Chester R Roy 1936, Marine geochemistry Roy Chester and Tim Jickells 3rd ed. Includes bibliographical references and index, ISBN 978 1 118 34907 6 cloth ISBN 978 1 4051 8734 3 pbk 1 Chemical. oceanography 2 Marine sediments 3 Geochemistry I Jickells T D Tim D II Title. GC111 2 C47 2012,551 46 dc23,2012010712, A catalogue record for this book is available from the British Library. Wiley also publishes its books in a variety of electronic formats Some content that appears in print may. not be available in electronic books, Cover image Blue ocean waves from underwater Solvod Shutterstock com. Cover design by Simon Levy Associates, Set in 9 on 11 5 pt Sabon by Toppan Best set Premedia Limited. Preface to the third edition vii,1 Introduction 1,Part I The Global Journey Material Sources 7. 2 The input of material to the ocean reservoir 9, 3 The transport of material to the oceans the fluvial pathway 11. 4 The transport of material to the oceans the atmospheric pathway 52. 5 The transport of material to the oceans the hydrothermal pathway 83. 6 The transport of material to the oceans relative flux magnitudes 92. Part II The Global Journey The Ocean Reservoir 125. 7 Descriptive oceanography water column parameters 127. 8 Air sea gas exchange 154, 9 Nutrients oxygen organic carbon and the carbon cycle in seawater 163. 10 Particulate material in the oceans 208,11 Trace elements in the oceans 223. 12 Down column fluxes and the benthic boundary layer 253. Part III The Global Journey Material Sinks 271,13 Marine sediments 273. 14 Sediment interstitial waters and diagenesis 290. 15 The components of marine sediments 321, 16 Unscrambling the sediment forming chemical signals 352. Part IV The Global Journey Synthesis 389,17 Marine geochemistry an overview 391. Colour plate pages fall between pp 216 and 217,COMPANION WEBSITE. This book has a companion website,www wiley com go chester marinegeochemistry. with Figures and Tables from the book,This book is dedicated with great affection to. John Riley and Dennis Burton, Two great pioneers in the field of Marine Chemistry. Preface to the third edition, This edition of Marine Geochemistry has been in Chapter 6 to draw together the new understanding. created at a time when the role of the oceans in the of processes in these regions which are now evidently. Earth System is becoming ever more evident The of considerable importance to the marine geochemi. central role of ocean processes in climate change and cal cycle as well as being both of great societal value. indeed in all aspects of global change is increasingly while also under considerable pressure from human. important to all society The scientific understanding activity. of the role of the oceans and of how they function We are grateful to our publishers for their patience. has developed sufficiently over recent years to justify and support to Phil Judge for producing the new. a new edition of this book The revisions incorpo diagrams for this edition and to our respective insti. rated in this new edition are the result of the collabo tutions for allowing us the opportunity to develop. ration between the two authors following Roy s this and previous editions Our special thanks go to. retirement colleagues around the world who have published the. This edition has been updated to reflect recent science we attempt to summarize here. advances in the field of marine geochemistry In par Finally we would also like to thank Alison Chester. ticular new insights into nutrient cycling and the and Sue Jickells for their help and support with this. carbon cycle have led to a large scale reorganisation endeavour and for so much more including keeping. of Chapters 8 and 9 compared to previous editions us reasonably sane. The relatively recent recognition of the key role of. iron as a nutrient is discussed in Chapters 9 and 11 Roy Chester and Tim Jickells. In addition a section on shelf seas has been added. 1 Introduction, The fundamental question underlying marine geo framework within which marine geochemistry can be. chemistry is How do the oceans work as a chemical described in a manner that cannot only relate readily. system At present that question cannot be answered to the other oceanographic disciplines but also can. fully The past four decades or so however have seen accommodate future advances in the subject To. a number of quantum leaps in our understanding develop such a framework it is necessary to explore. of some aspects of marine geochemistry Three prin some of the basic concepts that underlie marine. cipal factors have made these leaps possible geochemistry. 1 advances in sampling and analytical techniques Geochemical balance calculations show that a. 2 the development of theoretical concepts number of elements that could not have come from. 3 the setting up of large scale international oceano the weathering of igneous rocks are present at the. graphic programmes e g DSDP MANOP HEBBLE Earth s surface It is now generally accepted that. GEOSECS TTO VERTEX JGOFS SEAREX these elements which are termed the excess volatiles. WOCE which have extended the marine geochem have originated from the degassing of the Earth s. istry database to a global ocean scale interior The excess volatiles which include H and. O combined as H2O C Cl N S B Br and F are,especially abundant in the atmosphere and the. 1 1 Setting the background a unified, oceans It is believed therefore that both the atmos. process orientated approach to phere and the oceans were generated by the degas. marine geochemistry sing of the Earth s interior In terms of global cycling. Oceanography attracts scientists from a variety of Mackenzie 1975 suggested that sedimentary rocks. disciplines including chemistry geology physics are the product of a long term titration of primary. biology and meteorology A knowledge of at least igneous rock minerals by acids associated with the. some aspects of marine geochemistry is an essential excess volatiles a process that can be expressed as. requirement for scientists from all these disciplines. and for students who take courses in oceanography primary igneous rock minerals excess volatiles. at any level The present volume has been written sedimentary rocks oceans atmosphere. therefore with the aim of bringing together the,recent advances in marine geochemistry in a form. that can be understood by all those scientists who As this reaction proceeds the seawater reservoir is. use the oceans as a natural laboratory and not just continuously subjected to material fluxes which are. by marine chemists themselves Furthermore the delivered along various pathways from external. oceans are a key component of the Earth System so sources The oceans therefore are a flux dominated. an understanding of ocean geochemistry is central system Seawater however is not a static reservoir in. to understanding the functioning of the Earth as an which the material has simply accumulated over geo. integrated system Lenton and Watson 2011 One logical time otherwise it would have a very different. of the major challenges involved in doing this composition from that which it has at present for. however is to provide a coherent global ocean example the material supplied over geological time. Marine Geochemistry Third Edition Roy Chester and Tim Jickells. 2012 by Roy Chester and Tim Jickells Published 2012 by Blackwell Publishing Ltd. 2 Chapter 1, far exceeds the amount now present in seawater sediment and rock reservoirs as a unified system It. Further the composition of seawater appears not to is also apparent that one of the keys to solving. have changed markedly over very long periods of the question lies in understanding the nature of. time at least the last few million years and probably the chemical geological and biological biogeochem. longer Rather than acting as an accumulator there ical processes that control the composition of sea. fore the flux dominated seawater reservoir can be water and how these interact with the physical. regarded as a reactor Elements are intensively recy transport within the ocean system as this is the res. cled within the vast oceans by biological and chemi ervoir through which the material fluxes flow in the. cal processes although the extent of this recycling input internal reactivity output cycle In order. and the associated lifetime of components of the to provide a unified ocean framework within which. chemical system within the oceans vary enormously to describe the recent advances in marine geochem. It is the nature of the reactions that take place istry in terms of this cycle it is therefore necessary. within the reservoir that is the manner in which it to understand the nature and magnitude of the fluxes. responds to the material fluxes which defines the that deliver material to the oceans the input stage. composition of seawater via an input internal the reactive processes associated with the throughput. reactivity output cycle The system is ultimately of the material through the seawater reservoir the. balanced by the Earth s geological tectonic cycle that internal reactivity stage and the nature and magni. subducts ocean sediments into the Earth s interior tude of the fluxes that take the material out of sea. and returns them to the land surface water into the sinks the output stage. Traditionally there have been two schools of The material that flows through the system includes. thought on the overall nature of the processes that inorganic and organic components in both dissolved. operate to control the composition of seawater and particulate forms and a wide variety of these. 1 In the equilibrium ocean concept a state of chemi components will be described in the text In order to. cal equilibrium is presumed to exist between seawa avoid falling into the trap of not being able to see. ter and sediments via reactions that are reversible in the wood for the trees in the morass of data however. nature Thus if the supply of dissolved elements to it is essential to recognize the importance of the pro. seawater were to increase or decrease the equilib cesses that affect constituents in the source to sink. rium reactions would change in the appropriate cycle Rather than taking an element by element. direction to accommodate the fluctuations periodic table approach to marine geochemistry. 2 In the alternative steady state ocean concept it is the treatment adopted in the present volume will. assumed that the input of material to the system is involve a process orientated approach in which. balanced by its output that is the reactions involved the emphasis will be placed on identifying the key. proceed in one direction only In this type of ocean processes that operate within the cycle The treat. fluctuations in input magnitudes would simply result ment will include both natural and anthropogenic. in changes in the rates of the removal reactions and materials but it is not the intention to offer a special. the concentrations of the reactants in seawater would ized overview of marine pollution This treatment. be maintained does not in any way underrate the importance of. At present the generally held view supports the marine pollution Rather it is directed towards the. steady state ocean concept Whichever theory is concept that it is necessary first to understand. accepted however it is apparent that the oceans the natural processes that control the chemistry of. must be treated as a unified input output type of the ocean system because it is largely these same. system in which materials stored in the seawater the processes that affect the cycles of the anthropogenic. sediment and the rock reservoirs interact sometimes constituents. via recycling stages to control the composition of Since the oceans were first formed sediments have. seawater stored material and thus have recorded changes. It is clear therefore that the first requirement nec in environmental conditions The emphasis in the. essary to address the question How do the oceans present volume however is largely on the role that. work as a chemical system is to treat the seawater the sediments play in controlling the chemistry of the. Introduction 3, oceans The diagenetic changes that have the most the role played by particles in the sequestration of. immediate effect on the composition of seawater take reactive elements during every stage in the transport. place in the upper few metres of the sediment column cycle from source to marine sink. For this reason attention will be focused on these Ultimately therefore it is the transfer of dissolved. surface deposits and their role in biogeochemical constituents to the particulate phase and the subse. cycles The role played by sediments in recording quent sinking of the particulate material that is. palaeooceanographic change will be touched upon responsible for the removal of the dissolved constitu. only briefly It is however important to recognize ents from seawater to the sediment sink The biologi. that the oceans play a key role in the Earth System cal production and consumption of particles by. a role that evolves over geological time and the the ocean microbial community and its predators is. oceans also record the history of the evolution of the central to this process It must be stressed however. Earth System and its climate e g Emerson and that although dissolved particulate transforma. Hedges 2008 Lenton and Watson 2011 tions are the driving force behind the removal of most. In order to rationalize the process orientated elements to the sediment sink the transformations. approach special attention will be paid to a number themselves involve a wide variety of biogeochemical. of individual constituents which can be used to elu processes For example Emerson and Hedges 2008. cidate certain key processes that play an important and Stumm and Morgan 1996 identified a number. role in controlling the chemical composition of sea of chemical reactions and physicochemical processes. water In selecting these process orientated constitu that are important in setting the chemical composi. ents it was necessary to recognize the flux dominated tion of natural waters at a fundamental physico. nature of the seawater reservoir The material fluxes chemical level These processes included acid base. that reach the oceans deliver both dissolved and par reactions oxidation reduction reactions complexa. ticulate elements to seawater It was pointed out tion reactions between metals and ligands adsorp. above however that the amount of dissolved mate tion processes at interfaces the precipitation and. rial in seawater is not simply the sum of the total dissolution of solid phases gas solution processes. amounts brought to the oceans over geological time and the distribution of solutes between aqueous and. This was highlighted a long time ago by Forchham non aqueous phases The manner in which reactions. mer 1865 when he wrote and processes such as these and those specifically. Thus the quantity of the different elements in sea associated with biota interact to control the compo. water is not proportional to the quantity of ele sition of seawater will be considered throughout the. ments which river water pours into the sea but is text For the moment however they can be grouped. inversely proportional to the facility with which simply under the general term particulate dis. the elements are made insoluble by general chemi solved reactivity The particulate material itself is. cal or organo chemical actions in the sea delivered to the sediment surface mainly via the. our italics According to Goldberg 1963 this down column sinking of large sized organic aggre. statement can be viewed as elegantly posing the gates as part of the oceanic global carbon flux. theme of marine chemistry and it is this facility with Thus within the seawater reservoir reactive elements. which the elements are made insoluble and so are undergo a continuous series of dissolved particu. removed from the dissolved phase which is central late transformations which are coupled with the. to our understanding of many of the factors that transport of biologically formed particle aggregates. control the composition of seawater This was high to the sea bed Turekian 1977 aptly termed this. lighted more recently by Turekian 1977 In an influ overall process the great particle conspiracy In. ential geochemical paper this author formally posed the flux dominated ocean system the manner in. a question that had attracted the attention of marine which this conspiracy operates to clean up seawater. geochemists for generations and may be regarded is intimately related to the oceanic throughput of. as another expression of Forchhammer s statement externally transported and internally generated par. that is Why are the oceans so depleted in trace ticulate matter Further it is apparent that several. metals Turekian concluded that the answer lies in important aspects of the manner in which this. 4 Chapter 1, throughput cycle operates to control the inorganic The steps involved in the three stage global journey. and organic compositions of both the seawater reser are illustrated schematically in Fig 1 1 This is not. voir and the sediment sink can be assessed in terms meant to be an all embracing representation of res. of the oceanic fates of reactive trace elements and ervoir interchange in the ocean system but is simply. organic carbon intended to offer a general framework within which. Many of the most important thrusts in marine to describe the global journey By directing the. geochemistry over the past few years have used journey in this way the intention therefore is to treat. tracers to identify the processes that drive the the seawater sediment and rock phases as integral. system and to establish the rates at which they parts of a unified ocean system. operate Broecker and Peng 1982 These tracers In addition to the advantages of treating the oceans. will be discussed at appropriate places in the text as a single system the treatment adopted here is. The tracer approach however also has been adopted important in order to assess the status of the marine. in a much broader sense in the present volume in that environment in terms of planetary geochemistry. special attention will be paid to the trace elements For example according to Hedges 1992 there is a. and organic carbon in the source input internal complex interplay of biological geological and. reactivity sink output transport cycle Both stable chemical processes by which materials and energy. and radionuclide trace elements e g the use of Th are exchanged and reused at the Earth s surface. isotopes as a time clock for both transport and These interreacting processes which are termed. process indicators are especially rewarding for the biogeochemical cycles are concentrated at interfaces. study of reactivity within the various stages of the and modified by feedback mechanisms The cycles. cycle and organic carbon is a vital constituent with operate on time scales of microseconds to eons and. respect to the oceanic biomass the down column occur in domains that range in size from a living cell. transport of material to the sediment sink and sedi to the entire ocean atmosphere system and inter. ment diagenesis faces in the oceans play a vital role in the biogeo. To interpret the source input internal reactiv chemical cycles of some elements The chemistry of. ity sink output transport cycle in a coherent and the vast oceans is ultimately profoundly shaped by. systematic manner a three stage approach will be their internal biological processes which are domi. adopted which follows the cycle in terms of a global nated by tiny organisms microorganisms less than. journey In Part I the movements of both dissolved 1 mm in diameter The carbon fixed from the atmos. and particulate components will be tracked along phere and transformed within the water column by. a variety of transport pathways from their original these organisms affects the chemistry of the oceans. sources to the point at which they cross the interfaces and sustains most of the biological life within the. at the land sea air sea and rock sea boundaries In oceans The exchanges of CO2 associated with these. Part II the processes that affect the components processes also play a critical role in the global carbon. within the seawater reservoir will be described In cycle and in the habitability of the whole planet. Part III the components will be followed as they are The volume has been written for scientists of all. transferred out of seawater into the main sediment disciplines To contain the text within a reasonable. sink and the nature of the sediments themselves will length a basic knowledge of chemistry physics. be described The treatment however is concerned biology and geology has been assumed and the. mainly with the role played by the sediments as fundamental principles in these subjects which are. marine sinks for material that has flowed through readily available in other textbooks have not been. the seawater reservoir In this context it is the pro reiterated here As the volume is deliberately designed. cesses that take place in the upper few metres of the with a multidisciplinary readership in mind however. sediments that have the most immediate effect on the an attempt has been made to treat the more advanced. composition of seawater For this reason attention chemical and physical concepts in a generally descrip. will be restricted mainly to the uppermost sediment tive manner with appropriate references being given. sections and no attempt will be made to evaluate the to direct the reader to the original sources One of. status of the whole sediment column in the history the major aims of marine geochemistry in recent. of the oceans years has been to model natural systems on the basis. Introduction 5,Atmospheric,River Surface Glacial,input ocean input. Hydrothermal,Sediment inputs and,water outputs,Basement rock. Fig 1 1 A schematic representation of the source major sediment sink mainly as particulate matter largely by. input seawater internal reactivity sink output global biological processes The removal of dissolved material to the. journey The large open arrows indicate transport from sediment sink therefore usually requires its transformation to. material sources and the large filled arrows indicate transport the particulate phase This is shown by the p d term The. into material sinks relative flux magnitudes are not shown intention here however is simply to indicate that internal. The small arrows indicate only that the strengths of the fluxes particulate dissolved reactivity occurs within the seawater. can be changed as they cross the various interfaces in the reservoir and it must be stressed that a wide variety of. system thus g and n represent gross and net inputs or chemical reactions and physicochemical processes are involved. outputs respectively Material is brought to the oceans in both in setting the composition of the water phase see text For. particulate and dissolved forms but is transferred into the convenience coastal zones are not shown. of theoretical concepts To follow this approach it is redox reactions and the diffusion of solutes in inter. necessary to have a more detailed understanding of stitial waters In others however the emphasis is. the theory involved and for this reason a series of placed on modelling a variety of geochemical systems. Worksheets have been included in the text Some of these using where possible actual examples from litera. Worksheets are used to describe a number of basic ture sources for example the topics covered include. geochemical concepts for example those underlying a sorptive equilibrium model for the removal of trace.
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