Geochemistry of Earth Surface Systems: A derivative of the Treatise on Geochemistry

689 Pages·2010·45.74 MB·English

by  Heinrich D Holland

GEOCHEMISTRY OF
EARTH SURFACE
SYSTEMS
FROM THE TREATISE ON GEOCHEMISTRY
Editors
H. D. Holland
UniversityofPennsylvania,Philadelphia,PA,USA
K. K. Turekian
YaleUniversity,NewHaven,CT,USA

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CONTENTS
Contents iii
Introduction v
Contributors vii
1 VolcanicDegassing 1
C.OPPENHEIMER,UniversityofCambridge,UK
2 HydrothermalProcesses 45
C.R.GERMAN,SouthamptonOceanographyCentre,Southampton,UK
K.L.VONDAMM*,UniversityofNewHampshire,Durham,NH,USA
3 TheContemporaryCarbonCycle 87
R.A.HOUGHTON,WoodsHoleResearchCenter,MA,USA
4 TheGlobalSulfurCycle 129
P.BRIMBLECOMBE,UniversityofEastAnglia,Norwich,UK
5 TheHistoryofPlanetaryDegass ingasRecordedbyNobleGases 167
D.PORCELLI,UniversityofOxford,UK
K.K.TUREKIAN,YaleUniversity,NewHaven,CT,USA
6 NaturalWeatheringRatesofSilicateMinerals 205
A.F.WHITE,USGeologicalSurvey,MenloPark,CA,USA
7 SoilFormation 241
R.AMUNDSON,UniversityofCalifornia,Berkeley,CA,USA
8 GlobalOccurrenceofMajorElementsinRivers 277
M.MEYBECK,UniversityofParisVI,CNRS,Paris,France
9 TraceElementsinRiverWaters 293
J.GAILLARDET,InstitutdePhysiqueduGlobedeParis,France
J.VIERSandB.DUPRE´,LaboratoiredesMe´canismesetTransfertsenGe´ologie,
Toulouse,France
*Deceased
iii
iv Contents
10 TheGeologicHistoryoftheCarbonCycle 341
E.T.SUNDQUISTandK.VISSER,USGeologicalSurvey,WoodsHole,MA,USA
11 OrganicMatterintheContemporaryOcean 389
T.I.EGLINTONandD.J.REPETA,WoodsHoleOceanographicInstitution,MA,USA
12 TheBiologicalPump 425
C.L.DELAROCHA,AlfredWegenerInstituteforPolarandMarineResearch,
Bremerhaven,Germany
13 TheBiologicalPumpinthePast 453
D.M.SIGMAN,PrincetonUniversity,NJ,USA
G.H.HAUG,GeoforschungszentrumPotsdam,Germany
14 TheOceanicCaCO Cycle 491
3
W.S.BROECKER,ColumbiaUniversity,Palisades,NY,USA
15 TheGlobalOxygenCycle 511
S.T.PETSCH,UniversityofMassachusetts,Amherst,MA,USA
16 TheGlobalNitrogenCycle 551
J.N.GALLOWAY,UniversityofVirginia,Charlottesville,VA,USA
17 EvolutionofSedimentaryRocks 579
J.VEIZER,RuhrUniversity,Bochum,Germanyand
UniversityofOttawa,ON,Canada
F.T.MACKENZIE,UniversityofHawaii,Honolulu,HI,USA
18 GenerationofMobileComponentsduringSubductionofOceanicCrust 617
M.W.SCHMIDT,ETHZu€rich ,Switzerland
S.POLI,UniversitadiMilano,Italy
Appendix1 643
Appendix2 644
Appendix3 648
Appendix4 649
Index
651
Introduction
ItisnowcommonparlancetorefertotheEarthasaphysical–chemical–biologicalsystem;butthisisa
relatively recent innovation. Until about 1950, geologists generally used the word ‘system’ to define
geologic periods, or the several crystal classes, or the physical chemistry of multicomponent mixtures.
Longbeforethen,theword‘system’initscurrentusagehadbeenapartofthevocabularyofanumberof
fields,includingcommunicationandcontrolengineering.Infact,thefirstsignificantpaperonfeedback
mechanisms in control systems was written by Clerk Maxwell in 1868. Its subject was governors
(mechanical, not political). In the 1930s and 1940s, Norbert Wiener of the Massachusetts Institute of
TechnologyandArturoRosenbluethoftheHarvardMedicalSchoolappliedcommunicationengineering
design to physiology, converted the field into a branch of statistical mechanics, and christened it
Cybernetics. Wiener’s book ‘Cybernetics, or Control and Communication in the Animal and the
Machine’(1948)introducedthesubjecttoawideaudience,which,happily,includedgeochemists.
Independently,Barth(1952)tookasteptowardtheuseofsystemsanalysisingeochemistrybyusing
theriverfluxoftheelementstotheoceanstocalculatetheir‘periodofpassage’throughtheoceans.In
1958hisresultswerelargelyconfirmedbyGoldbergandArrhenius.In1961Goldbergraisedimportant
questions about the operation of the ocean as a geochemical system. These were answered in part by
Broeckeretal’schapterinthesamevolumeasGoldberg’s.Intheir1975book,‘ChemicalCyclesandthe
Global Environment: Assessing Human Influences,’ Garrels, Mackenzie, and Hunt introduced the
concept of residence times, then the notion of fluxes and reservoirs, and finally, a description of the
Earthsystem.In1978,Ichosetobeginmybook‘TheChemistryoftheAtmosphereandOceans’witha
chapterontheEarthasachemicalsystem.Bythenthenewnomenclaturehadclearlyarrived.Itsadoption
signaledmorethanachangeinvocabulary.Therewasagreatlyexpandedapplicationofsystemsanalysis
totheEarthSciences.Extensivestudiesofreactionratesandreactionmechanismswereaddedtoanalyses

of the thermodynamics of Earth materials. The consequences of positive and negative feedbacks,
singularities, tipping points, chaos theory, and the linking of geochemical cycles were explored. All
thisledtoconsiderableprogressinourabilitytounderstandtheworkingsofnear-surfacesystems,where
temperaturesaregenerallylowandmanyreactionsareslow,evenongeologictimescales.Theneedto
understandandtopredicttheconsequencesofmankind’sperturbationsoftheEarth’ssurfaceandnear-
surface environments has lent a strong sense of urgency and greatly increased funding for studies of
nonsteadystatesystems.
The Earth’s near-surface systems have always been subjected to inputs of mass and energy. The
intensityandthefrequencyoftheseinputshavevariedwidely.Manyinputshavebeencyclic,somehave
beensingular,andseveralhaveevolvedmoreorlessunidirectionallyduringthecourseofEarthhistory.
Volcanoes (Chapter 1) and oceanic hydrothermal vents (Chapter 2) have been the major sources of
volatiles for near-surface systems, although these inputs are now dwarfed by the effects of fossil fuel
burning and other human activities (Chapters 3 and 4). Volcanic rocks have been the most important
terrestrial and marine resurfacing agents, and magmatic intrusions have continually underplated the
Earth’ssurface.Sporadically,meteoritesandpossiblycometshavebeenquantitativelyimportantsources
ofmassanddevastation,particularlyduringtheearliestpartsofEarthhistory.
Sunlight has been by far the largest source of energy for the Earth’s near-surface environments,
although these have been shaped to a surprisingly large extent by the small supply of energy from the
v
vi Introduction
Earth’s interior. The internal energy is responsible for the large supply of volatiles that are now and
alwayshavebeenaddedtotheEarth’snear-surfacesystems.Mostofthesevolatileshavebeen‘digested’
andremovedtomorepermanentquartersongeologicallyshorttimescales.Theheavierraregasesarean
exception.Heliumescapesintointerplanetaryspaceonatimescale ofabout106years,butmostofthe
Ne,Ar,Kr,andXethathasescapedfromtheEarth’sinteriorhasaccumulatedintheatmosphere(Chapter5).
Water, the most abundant of the volcanic volatiles, rapidly becomes a participant in the hydrologic
cycle and enters the oceans, where it has accumulated to form the largest of the Earth’s near-surface
systems. It is a critical actor in weathering (Chapter 6), in the formation of soils (Chapter 7), and in
the release of the dissolved constituents of rivers that become the major solute inputs to the oceans
(Chapters 8 and 9). Together with carbon and nitrogen, water cycles rapidly through the biosphere.
Without these elements the Earth would not be a habitable planet. Next to water, CO is the most
2
abundant of the degassed volatiles. It is an important greenhouse gas, the most important of the
weathering acids (Chapter 6), and an essential participant in photosynthesis (Chapter 3). In the oceans
itisthebasisofmarinephotosynthesis,andhencethesourceofmuchoftheorganicmatterintheoceans
(Chapter11).OrganicmatterandmarineCaCO arecycledthroughtheoceansbythemarinebiological
3
pump(Chapters12and13)andviathemarineCaCO cycle(Chapter14).Smallresiduesbecomepartsof
3
marinesediments.PhotosynthesisviaphotosystemIIgeneratesO ,theonlymajoratmosphericconstitu-
2
entthatisnotadevolatilizedgas(Chapter15).Itshistoryislinkedbothtotheevolutionofvolcanicgases,
particularlytheirH ,CO ,andSO content(Holland,2009),andtotheevolutionofthebiosphere.
2 2 2
Ofall the biologically important gases emitted by volcanoes,N isthe only constituentwhosenear-
2
surfacechemistryissimilartothatoftheraregases.Ithasaccumulatedintheatmospherelargelybecause
allofthecommoncompoundsofNO(cid:1),NO(cid:1),andNHþarehighlysoluble(Chapter16).Bycontrast,the
3 2 4
removal of carbon from the near-surface reservoirs is and has been speeded considerably by
the precipitation of CaCO and CaMg(CO ) . Similarly the removal of sulfur has been speeded by the
3 3 2
precipitationofFeS andCaSO .Thesemineralsandresidualorganicmatter,togetherwiththeterrestrial
2 4
detritusdeliveredtotheoceansandthemarinevolcanicinputs,havecombinedtoformmostofthelarge
variety of marine sediments and their diagenetic products, the sedimentary rocks (Chapter 17). The
metamorphism and the melting of sedimentary rocks in subduction zones have closed the geochemical
cycle. They have been accompanied by the release of volatiles. These, together with the primordial
volatiles, have been the major volatile volcanic and hydrothermal inputs to the Earth surface systems
(Chapter18).Themembersofthebiospherehavebothrespondedtoandmoldedtheirenvironment.The
moldinghasbecomeparticularlyintensesincethearrivalofmankind.
H.D.Holland

REFERENCES
BarthT.W.F.(1952)TheoreticalPetrology.NewYork,NY:Wiley.
BroeckerW.S.,GerardR.D.,EwingM.,andHeezenG.C.(1961)Geochemistryandphysicsofoceancirculation.In:SearsM.(ed.)
Oceanography,pp.301–322.Washington,DC:AmericanAssociationfortheAdvancementofScience,PublicationNo.67.
GarrelsR.M.,MackenzieF.T.,andHuntC.(1975)ChemicalCyclesandtheGlobalEnvironment:AssessingHumanInfluences.
LosAltos,CA:WilliamKaufmann.
Goldberg E. D. (1961) Chemistry in the oceans. In: Sears M. (ed.) Oceanography, pp. 583–597. Washington, DC: American
AssociationfortheAdvancementofScience,PublicationNo.67.
GoldbergE.D.andArrheniusG.O.S.(1958)ChemistryofPacificpelagicsediments.GeochimicaetCosmochimicaActa13,
153–212.
HollandH.D.(1978)TheChemistryoftheAtmosphereandOceans.NewYork,NY:Wiley-Interscience.
HollandH.D.(2009)Whytheatmospherebecameoxygenated:Aproposal.GeochimicaetCosmochimicaActa73,5241–5255.
MaxwellJ.C.(1868)OnGovernors.ProceedingsoftheRoyalSociety(London)16,270–283.
WienerN.(1948)Cybernetics,orControlandCommunicationintheAnimalandtheMachine.Cambridge:TheMITPress.
CONTRIBUTORS
R.Amundson
UniversityofCalifornia,Berkeley,CA,USA
P.Brimblecombe
UniversityofEastAnglia,Norwich,UK
W.S.Broecker
ColumbiaUniversity,Palisades,NY,USA
C.L.DeLaRocha
AlfredWegenerInstituteforPolarandMarineResearch,Bremerhaven,Germany
B.Dupre´
LaboratoiredesMe´canismesetTransfertsenGe´ologie,Toulouse,France
T.I.Eglinton
WoodsHoleOceanographicInstitution,MA,USA
J.Gaillardet
InstitutdePhysiqueduGlobedeParis,France
J.N.Galloway
UniversityofVirginia,Charlottesville,VA,USA
C.R.German
SouthamptonOceanographyCentre,Southampton,UK

G.H.Haug
GeoforschungszentrumPotsdam,Germany
R.A.Houghton
WoodsHoleResearchCenter,MA,USA
F.T.Mackenzie
UniversityofHawaii,Honolulu,HI,USA
M.Meybeck
UniversityofParisVI,CNRS,Paris,France
C.Oppenheimer
UniversityofCambridge,UK
S.T.Petsch
UniversityofMassachusetts,Amherst,MA,USA
vii
viii Contributors
S.Poli
UniversitadiMilano,Italy
D.Porcelli
UniversityofOxford,UK
D.J.Repeta
WoodsHoleOceanographicInstitution,MA,USA
M.W.Schmidt
ETHZu¨rich,Switzerland
D.M.Sigman
PrincetonUniversity,NJ,USA
E.T.Sundquist
USGeologicalSurvey,WoodsHole,MA,USA
K.K.Turekian
YaleUniversity,NewHaven,CT,USA
J.Veizer
RuhrUniversity,Bochum,Germanyand
UniversityofOttawa,ON,Canada
J.Viers
LaboratoiredesMe´canismesetTransfertsenGe´ologie,Toulouse,France
K.Visser
USGeologicalSurvey,WoodsHole,MA,USA
K.L.VonDamm*
UniversityofNewHampshire,Durham,NH,USA
A.F.White

USGeologicalSurvey,MenloPark,CA,USA
*Deceased
1
Volcanic Degassing
C. Oppenheimer
University of Cambridge, UK
NOMENCLATURE 2
1.1 INTRODUCTION 2
1.1.1 EarthOutgassing,AtmosphericEvolutionandGlobalClimate 2
1.1.2 MagmaEvolutionandDynamics,andVolcanicEruptions 4
1.1.3 VolcanicHazardsandVolcanoMonitoring 4
1.2 ORIGIN,SPECIATION,ANDABUNDANCEOFVOLATILES 6
1.2.1 SourcesandAbundancesofVolatilesinMagmas 6
1.2.2 SolubilityandSpeciationofVolatiles 8
1.3 DEGASSING 9
1.3.1 Saturation 9
1.3.2 SupersaturationandNucleation 10
1.3.3 BubbleGrowthandMagmaAscent 10
1.3.4 BubbleCoalescence 10
1.3.5 GasSeparation 11
1.3.6 Fragmentation 12
1.3.7 ExcessDegassing 12
1.4 EMISSIONS 13
1.4.1 StylesofSurfaceEmissions 13
1.4.1.1 Noneruptiveemissions 14

1.4.1.2 Eruptiveemissions 16
1.4.2 ChemicalCompositionofVolcanicGases 16
1.4.3 MeasurementofVolatiles 16
1.4.3.1 Insitusamplingandanalysis 17
1.4.3.2 Portableremotesensingsystems 18
1.4.3.3 Satelliteremotesensing 19
1.4.3.4 Petrologicalmethods 19
1.4.3.5 Icecores 20
1.4.3.6 Applicationofgeochemicalsurveillancetovolcanomonitoring 21
1.5 FLUXESOFVOLCANICVOLATILESTOTHEATMOSPHERE 23
1.5.1 Sulfur 24
1.5.2 CarbonandWater 26
1.5.3 Halogens 26
1.5.4 TraceMetals 27
1.6 IMPACTS 27
1.6.1 StratosphericChemistryandRadiativeImpactsofVolcanicPlumes 28
1.6.1.1 Formationofstratosphericsulfateaerosolveil 28
1.6.1.2 Impactsonozonechemistry 28
1.6.1.3 Opticalandradiativeeffects 30
1.6.2 ClimaticImpactsofMajorVolcanicEruptions 31
1.6.2.1 Intermediatetosiliciceruptions 31
1.6.2.2 Maficeruptions 33
1