Environmental and Resources Geochemistry of Earth System: Mass Transfer Mechanism, Geochemical Cycle and the Influence of Human Activity

257 Pages·2015·8.88 MB·English

by  Naotatsu Shikazono

Naotatsu Shikazono
Environmental
and Resources
Geochemistry of
Earth System
Mass Transfer Mechanism,
Geochemical Cycle and the Infl uence
of Human Activity
Environmental and Resources Geochemistry
of Earth System

Naotatsu Shikazono
Environmental and
Resources Geochemistry
of Earth System
Mass Transfer Mechanism, Geochemical
Cycle and the Influence of Human Activity
NaotatsuShikazono(deceased)
KeioUniversity
Tokyo,Japan
Dr.JamesWilkinson,colleagueandlongtimefriendofthelateProf.Shikazono,proofread
thisbookandcompiledthelistofsymbols.
CHIKYUUSISUTEMUNOKAGAKU
CHIKYUUSISUTEMUKANKYOUKAGAKU
©1997NaotatsuSHIKAZONO
©2010NaotatsuSHIKAZONO
Allrightsreserved
OriginalJapaneseeditionpublishedin1997and2010byUniversityofTokyoPress
EnglishtranslationrightsarrangedwithUniversityofTokyoPressthroughJapanUNI
Agency,Inc.,Tokyo
ISBN978-4-431-54903-1 ISBN978-4-431-54904-8(eBook)
DOI10.1007/978-4-431-54904-8
SpringerTokyoHeidelbergNewYorkDordrechtLondon
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Foreword
Thisbook‘EnvironmentalandResourceGeochemistryofEarthSystem’shouldbe
inthelibrariesofuniversitiesofferingcoursesinminingengineeringand/ormining
geology and should be read by mine managers and directors and concerned
politicians.
Chapter1providesanextensivediscussionofchemicalequilibriaastheypertain
to minerals. This covers in detail chemical equilibria of solids and aqueous solu-
tions, the solubility of various types of minerals, the weathering of silicate and
aluminosilicateminerals,thecompositionofgeothermalandgroundwater,hydro-
thermal alteration, oxidation and reduction reactions, and the partitioning of ele-
mentsbetweenaqueoussolutionsandcrystals.
Chapter 2 covers the partial chemical equilibria as they pertain to water–rock
interactioningeothermalareas.Thisincludesoxygenisotopevariations,formation
of minerals by boiling, due to mixing of fluids and due to mixing hydrothermal
solutionswithseawaterorgroundwater.
Chapter3providesadetaileddiscussionofmasstransfermechanisms.
Chapter4 presents detailed discussions of hydrothermal and seawater systems,
emphasizing the pertinent recharge, reservoir, and discharge zones, as well as the
pertinentchemicalreactions.
Chapter 5 provides a detailed discussion of the geochemical cycles of carbon,
sulfur,andoxygen,aswellasofarsenic,boron,barium,andotheroreelements.
Chapter 6 discusses in great detail the interaction between humans and the
atmosphere,hydrosphere,andsoils,aswellastheeffectsofhumanwasteemissions.
ItwasagreathonortobeinvitedtowritetheForewordtothisbookbythelate
Prof. Naotatsu Shikazono, who sadly did not live to see the completion of this
publication.Prof.Shikazonomadeextremelyvaluablecontributionstohisfieldand
willbegreatlymissedbyhisfriendsandcolleagues.
UlrichPetersen,Ph.D.
DepartmentofEarthandPlanetarySciences
HarvardUniversity,Cambridge
MA,USA
v

Preface
TheEarthsystemconsistsoftheatmosphere,hydrosphere,lithosphere(geosphere),
biosphere,andhumans,andeachsubsysteminteractswithotherbodieswithregard
to mass and heat (Fig. 1). The interactions between humans and the other sub-
systems are becoming the most important problems for humans. The interaction
betweenhumansandnatureposesdifficultiesbecausecurrentmethodologiesdonot
yetoffersolutionstoitsproblems.Forinstance,peopletodayarefacingissuesrelated
to Earth’s resources and environmental problems (e.g., depletion of resources;
pollutionofthe atmosphere,hydrosphere, andsoils; extinctionofbiomass; global
warming;acidrain;anddestructionoftheozonelayer).
Toresolvetheenvironmentalandresourcesproblems,ascientificunderstanding
of the Earth system is the first step. Particularly, mechanisms of mass and energy
transport and circulation among the subsystems (water, atmosphere, rocks, i.e.,
minerals) should be scientifically understood. Among the various processes,
the water–rock interactions near the Earth’s surface significantly influence the
formations of Earth’s resources, the generation of environmental pollution, and
elementalandmasstransportneartheEarth’ssurfaceenvironment.
Inthisbook weconsider(1) water–soils–rockreaction,(2) waste–groundwater
reaction,(3)formationofmetallicoredeposits,(4)masstransferinthehydrother-
mal system, and (5) the global geochemical cycle. To interpret these processes,
thermodynamics, dissolution-precipitation kinetics, fluid flow, diffusion and
coupling of these mechanisms, mass transfer, and geochemical modeling (e.g.,
dissolution-kinetics fluid flow modeling) are used. In addition to dissolution,
precipitation reactions, ion exchange reaction, adsorption, and biomineralization
arebrieflydescribed.Theanalysesofglobalgeochemicalcyclesofcarbon,sulfur,
andotherelementsarebasedontheboxmodel.
This book has arisen from several courses on Environmental and Resources
GeochemistryofEarthandPlanetarySystemSciencesforundergraduateandgrad-
uate students at Keio University and also from many classes at other universities
(TheUniversityofTokyo,AkitaUniversity,ChibaUniversity,IbarakiUniversity,
Hiroshima University,Yamaguchi University, NihonUniversity,Tokushima Uni-
versity, Yamagata University, Kyoto University, Shizuoka University, Tsukuba
vii
viii Preface
Fig. 1 Earth system consisting of subsystems such as atmosphere, biosphere, hydrosphere,
humansandgeosphere.Subsystemsareinteractingeachotherwithregardtomassandheats
University,TohokuUniversity,Waseda University,GakushuinUniversity,Tokyo
Gakugei University). In these courses during the last 30 years, I received many
comments, questions, and responses from numerous undergraduate and graduate
students.Discussionswiththemhaveallowedmetodevelop andclarifytheideas
presented here. In writing this book I am greatly indebted to many people in the
DepartmentofAppliedChemistryofKeioUniversity,theGeologyDepartmentof
The Universityof Tokyo, the Geology Department of Tokyo Gakugei University,
andtheDepartmentofEarthandPlanetaryScienceofHarvardUniversity.Iexpress
mygreatappreciationforthelateprofessorsT.Tatsumi,oftheUniversityofTokyo,
T. Fuji of Tsukuba University, A. Tsusue of Kumamoto University, and H. D.
HollandandU.PetersenofHarvardUniversityforteachingmeeconomicgeology,
environmental geochemistry, thermodynamics and kinetics. Dr. K. Fujimoto and
Dr.N.Takenoreadthemanuscriptandgavemeusefulcriticalcomments.Ithank
Ms.M.Aizawa,Ms.N.Katayama,Ms.K.Suga,Ms.N.Takeuchi,Ms.A.Takeuchi,
andMr.Y.Sugafortheirskillfulandpatientwordprocessingandfiguredrawing.
Ms.M.ShimizuandMs.M.KomatsuofTheUniversityofTokyoPressandMr.Ken
Kimlicka of Springer Japan edited with care the manuscripts for the Japanese
version of the books Chemistry of Earth System and Environmental Chemistry of
EarthSystemandtheEnglishversionofEnvironmentalandResourcesGeochemis-
tryofEarthSystem(thepresentvolume),respectively.
I want to dedicate this book to my wife, Midori Shikazono, and my two
daughters, Chikako and Hisako Shikazono; and to my parents, Yoshiko and
NaoharuShikazono,whohavepatientlyprovidedunderstandingandmoralsupport
duringthemorethan45yearsofmyacademicresearchandteaching.
Tokyo,Japan NaotatsuShikazono
Contents
1 ChemicalEquilibrium.. . . . . . . .. . . . . . . .. . . . . . . .. . . . . . . .. . . 1
1.1 ChemicalEquilibriumModel. . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 ThermochemicalStabilityofSolidPhase
inSolid-AqueousSolutionSystem. . . . . . . . . . . . . . . . . . . . . . . 3
1.3 SolubilityofMinerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 OxidesandHydroxides. . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.2 Silicates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.3 Carbonates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4 ChemicalWeatheringandSilicateandAluminosilicate
Mineralogy. .. . . . . . .. . . . . . .. . . . . . .. . . . . . .. . . . . . .. . . 15
1.5 AnalysisofMulti-Component–Multi-PhaseHeterogeneous
System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.6 InterpretationofChemicalCompositionsofGeothermal
WaterinTermsofChemicalEquilibriumModel. . . . . . . . . . . . 18
1.7 HydrothermalAlteration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.8 InterpretationofChemicalCompositionofGroundWater
inTermsofInverseMassBalanceModel. . . . . . . . . . . . . . . . . . 25
1.9 Oxidation-ReductionCondition. . . . . . . . . . . . . . . . . . . . . . . . . 33
1.9.1 OxygenFugacity(fO )-pHDiagram. . . . . . . . . . . . . . . 33
2
1.9.2 H–S–OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.9.3 Fe–S–O–HSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.9.4 EstimateofOxygenFugacity(f )forHydrothermal
O
2
OreDeposits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.9.5 Sulfides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.10 PartitioningofElementsBetweenAqueousSolution
andCrystal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
1.10.1 PartitioningofElementBetweenAqueous
SolutionandSolidSolutionMineral. . . . . . . . . . . . . . . 44
1.10.2 RayleighFractionation. . . . . . . . . . . . . . . . . . . . . . . . . 48
CitedLiterature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
ix