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REVIEWS  MINERALOGY
 GEOCHEMISTRY
Volume 82 2017
Non-Traditional Stable
Isotopes
EDITORS
Fang-Zhen Teng
University of Washington, USA
James Watkins
University of Oregon, USA
Nicolas Dauphas
The University of Chicago, USA
Front-cover: False-color image of a zoned olivine phenocryst (forsterite content) from the Kilauea
Iki lava lake, Hawaii. The black marks are spots where the Fe isotopic composition of the olivine
was measured by LA-MC-ICPMS and SIMS (Sio et al. 2013, Geochimica et Cosmochimica Acta
123, 302–321). In situ stable isotopic analyses of zoned minerals allow one to tell apart zoning
produced by diffusion from zoning produced by growth from an evolving medium.
Series Editor: Ian Swainson

MINERALOGICAL SOCIETY  AMERICA
GEOCHEMICAL SOCIETY
Reviews in Mineralogy and Geochemistry, Volume 82
Non-Traditional Stable Isotopes
ISSN 1529-6466
ISBN 978-0-939950-98-0
Copyright 2017
The MINERALOGICAL SOCIETY of AMERICA
3635 Concorde Parkway, Suite 500
Chantilly, Virginia, 20151-1125, U.S.A.
www.minsocam.org
The appearance of the code at the bottom of the first page of each chapter in this volume
indicates the copyright owner’s consent that copies of the article can be made for personal
use or internal use or for the personal use or internal use of specific clients, provided
the original publication is cited. The consent is given on the condition, however, that
the copier pay the stated per-copy fee through the Copyright Clearance Center, Inc. for
copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This
consent does not extend to other types of copying for general distribution, for advertising
or promotional purposes, for creating new collective works, or for resale. For permission
to reprint entire articles in these cases and the like, consult the Administrator of the
Mineralogical Society of America as to the royalty due to the Society.
Non-Traditional
Stable Isotopes
82 Reviews in Mineralogy and Geochemistry 82
FROM THE SERIES EDITOR

It has been a pleasure working with the volume editors and authors on this 82nd volume of
Reviews in Mineralogy and Geochemistry. Several chapters have associated supplemental figures
and or tables that can be found at the MSA website. Any future errata will also be posted there.
Ian P. Swainson, Series Editor
Vienna, Austria
PREFACE
Since the publication of Geochemistry of Non-Traditional Stable Isotopes in 2004 (volume 55
of Reviews in Mineralogy and Geochemistry), analytical techniques have significantly improved
and new research directions have emerged in non-traditional stable isotope geochemistry. Our
goal here is to review the current status of non-traditional isotope geochemistry from analytical,
theoretical, and experimental approaches to analysis of natural samples. In particular, important
applications to cosmochemistry, high-temperature geochemistry, low-temperature geochemistry,
and geobiology are discussed. The aim of this volume is to provide the most comprehensive
review on non-traditional isotope geochemistry for students and researchers who are interested
in both the theory and applications of non-traditional stable isotope geochemistry.
We take this opportunity to thank the timely contributions by authors of the individual
chapters and insightful reviews from the following scientists: Bridget Bergquist, Greg Brennecka,
Christopher Cloquet, Hans Eggenkamp, Toshiyuki Fujii, Sarah Gleeson, Doug Hammond,
Adrianna Heimann, Richard Hervig, Fang Huang, Timm John, Tom Johnson, Abby Kavner,
James Kubicki, Laura Lammers, Sheng-Ao Liu, Catherine Macris, Paul Mason, Ryan Mathur,
Vasileios Mavromatis, Fred Moynier, Kazuhide Nagashima, Philip Pogge Von Strandmann,
Martin Oeser, Noah Planavsky, Franck Poitrasson, John Reinfelder, Stephen Romaniello,
Mathieu Roskosz, Kate Scheiderich, Kathrin Schilling, Laura Sherman, Haolan Tang, Francois
Tissot, Paul Tomascak, Martin Tsz-Ki Tsui, Jim Van Orman, Xiangli Wang, Laura Wasylenki,
Dominik Weiss, Stefan Weyer, Jan Wiederhold, Martin Wille, Josh Wimpenny, Wei Yang,
Karen Ziegler, and many anonymous reviewers. We gratefully acknowledge the help from Don
DePaolo, Valarie Espinoza-Ross, and Kryshna Avina in organizing and hosting the workshop at
LBNL. We are also indebted to Ian Swainson, series editor, for all his work in producing this
volume, and Alex Speer at the MSA business office, for help in the preparation of the volume
and management of registrations and donations. We also thank Matt Kohn and Youxue Zhang
for sharing their experience in preparing a volume and workshop. Finally, the financial support
provided by Nu Instruments, Cameca and Ametek, Elemental Scientific, Geochemical Society,
Savillex, Depths of the Earth, and Thermo-Fisher are highly appreciated.
Fang-Zhen Teng, Seattle, Washington
James Watkins, Eugene, Oregon
Nicolas Dauphas, Chicago, Illinois
November 2016
1529-6466/17/0082-0000$00.00 http://dx.doi.org/10.2138/rmg.2017.82.0
Non-Traditional Stable
Isotopes
82 Reviews in Mineralogy and Geochemistry 82
TABLE OF CONTENTS
1 Non-Traditional Stable Isotopes: Retrospective and Prospective
Fang-Zhen Teng, Nicolas Dauphas, James M. Watkins
INTRODUCTION.....................................................................................................................1
THE δ NOTATION..................................................................................................................3
GUIDELINES FOR SELECTING REFERENCE MATERIALS.............................................4
EMERGING ISOTOPE SYSTEMS..........................................................................................6
Stable potassium isotope geochemistry..........................................................................7
Titanium isotope geochemistry......................................................................................8
Vanadium isotope geochemistry...................................................................................10
Stable rubidium isotope geochemistry.........................................................................11
Stable strontium isotope geochemistry.........................................................................11
Cadmium isotope geochemistry...................................................................................13
Tin isotope geochemistry.............................................................................................15
Antimony isotope geochemistry...................................................................................15
Stable tellurium isotope geochemistry.........................................................................16
Barium isotope geochemistry.......................................................................................16
Stable neodymium isotope geochemistry.....................................................................18
CONCLUSIONS......................................................................................................................20
ACKNOWLEDGMENTS........................................................................................................20
REFERENCES........................................................................................................................20
2 Equilibrium Fractionation of Non-traditional Isotopes:

a Molecular Modeling Perspective
Marc Blanchard, Etienne Balan, Edwin A. Schauble
INTRODUCTION...................................................................................................................27
THEORETICAL FRAMEWORK...........................................................................................28
Equilibrium fractionation theory..................................................................................28
Approximate formula based on force constants...........................................................33
MODELING APPROACHES..................................................................................................35
Quantum-mechanical molecular modeling..................................................................35
Theoretical studies of non-traditional stable isotope fractionation..............................37
iv
Non-Traditional Stable Isotopes ‒ Table of Contents
Modeling isotopic properties of liquid phases.............................................................40

Beyond harmonic approximation: Path integral molecular dynamics..........................43
MÖSSBAUER AND NRIXS SPECTROSCOPY....................................................................45
MASS-INDEPENDENT FRACTIONATION
AND VARIATIONS IN MASS LAWS...................................................................................47
Variability in mass laws for common fractionations....................................................48
Mass-independent fractionation in light elements (O and S).......................................50
Mass-independent fractionation in non-traditional elements (Hg, Tl, and U).............50
Mass-independent fractionation signatures in heavy elements,
versus light elements.................................................................................................53
Ab initio methods for calculating field shift fractionation factors................................53
Isomer shifts from Mössbauer spectroscopy................................................................55
CONCLUSIONS......................................................................................................................55
REFERENCES........................................................................................................................56
3 Equilibrium Fractionation of Non-Traditional Stable Isotopes:

an Experimental Perspective
Anat Shahar, Stephen M. Elardo, Catherine A. Macris
INTRODUCTION...................................................................................................................65
FACTORS INFLUENCING EQUILIBRIUM FRACTIONATION FACTORS......................66
PROOF OF EQUILIBRIUM IN ISOTOPE EXPERIMENTS................................................67
Time series....................................................................................................................67
Multi-direction approach..............................................................................................68
Three-isotope exchange method...................................................................................69
Kinetic effects...............................................................................................................72
EXPERIMENTAL METHODS...............................................................................................73
Low temperature experiments......................................................................................73
High temperature, low pressure experiments...............................................................74
High temperature and pressure experiments................................................................76
NRIXS and diamond anvil cell experiments................................................................78
POST-EXPERIMENT ANALYSIS.........................................................................................80
CONCLUSIONS......................................................................................................................80
REFERENCES........................................................................................................................81
4 Kinetic Fractionation of Non-Traditional Stable Isotopes

by Diffusion and Crystal Growth Reactions
James M. Watkins, Donald J. DePaolo, E. Bruce Watson
INTRODUCTION...................................................................................................................85
Organization of the article............................................................................................86
ISOTOPE FRACTIONATION BY DIFFUSION....................................................................86
Expressions for diffusive fluxes....................................................................................87
Isotopic mass dependence of diffusion in “simple” systems........................................87
Isotopic mass dependence of diffusion in aqueous solution........................................88
v
Isotopic mass dependence of diffusion in silicate melts..............................................90

Isotopic mass dependence of diffusion in minerals and metals...................................92
DIFFUSIVE BOUNDARY LAYERS IN THE GROWTH MEDIUM....................................94
ISOTOPE FRACTIONATION BY COMBINED REACTION AND DIFFUSION.............102
General framework for crystal growth from an infinite solution................................102
Crystal growth and kinetic isotope effects.................................................................105
Interpreting the model parameters..............................................................................107
Stable isotope fractionation during electroplating......................................................110
Stable isotope fractionation of trace elements............................................................113
THE ROLE OF THE NEAR SURFACE OF CRYSTALS....................................................115
The growth entrapment model (GEM).......................................................................116
The surface reaction kinetic model (SRKM), growth entrapment model (GEM),
and isotopes.............................................................................................................118
PERSPECTIVES...................................................................................................................120
ACKNOWLEDGMENTS......................................................................................................121
REFERENCES......................................................................................................................121
5 In Situ Analysis of Non-Traditional Isotopes by SIMS and

LA–MC–ICP–MS: Key Aspects and the Example of Mg Isotopes
in Olivines and Silicate Glasses
Marc Chaussidon, Zhengbin Deng, Johan Villeneuve, Julien Moureau, Bruce Watson,
Frank Richter, Frédéric Moynier
INTRODUCTION.................................................................................................................127
Notations used for Mg isotopes..................................................................................128
INSTRUMENTATION FOR IN-SITU STABLE ISOTOPE ANALYSIS.............................128
MC–SIMS analysis.....................................................................................................129
LA–MC–ICP–MS analysis.........................................................................................129
LIMITATIONS FOR IN-SITU STABLE ISOTOPES ANALYSIS.......................................130
Limitations due to the small amount of sample analyzed..........................................131
Limitations due to matrix effects on ion yield............................................................131
Limitations due to instrumental isotopic fractionation...............................................133
STANDARDS AND ANALYTICAL APPROACH USED FOR MG
IN THE PRESENT STUDY..................................................................................................136
Set of standards studied..............................................................................................136
MC–SIMS for Mg isotopic analysis...........................................................................137
LA–MC–ICP–MS for Mg isotopic analysis...............................................................138
Solution MC–ICP–MS for Mg isotopic analysis.......................................................138
MAGNESIUM ION EMISSION DURING IN SITU ANALYSIS.......................................140
Fundamental differences for Mg ion yield between SIMS and
laser ablation ICP–MS.............................................................................................140
Possible origin of the complex matrix effects on ion yield for SIMS .......................143
MAGNESIUM INSTRUMENTAL ISOTOPIC FRACTIONATION....................................145
Similarities and differences for Mg instrumental isotopic fractionation
between SIMS and laser ablation ICP–MS.............................................................145
Matrix effects during ionization of solutions in MC–ICP–MS .................................147
Matrix effects specific to in situ analysis...................................................................149
MEASUREMENT OF THE THREE MAGNESIUM ISOTOPES.......................................152
vi
The need for high-precision in situ three Mg isotopes analysis in cosmochemistry.. 152
The question of potential isobaric interferences.........................................................153
The question of the mass fractionation law used to correct for instrumental
isotopic fractionation...............................................................................................154
Mg instrumental mass fractionation law for MC–SIMS analyses..............................155
Mg instrumental mass fractionation law for LA–MC–ICP–MS analyses..................158
SUMMARY AND PERSPECTIVES....................................................................................158
REFERENCES......................................................................................................................159
6 Lithium Isotope Geochemistry

Sarah Penniston-Dorland,, Xiao-Ming Liu, Roberta L. Rudnick
INTRODUCTION.................................................................................................................165
LITHIUM SYSTEMATICS...................................................................................................167
Li in minerals..............................................................................................................168
Li partitioning.............................................................................................................168
Equilibrium Isotope Fractionation..............................................................................170
Diffusion and kinetic isotopic fractionation...............................................................174
METHODS............................................................................................................................176
Whole rock analyses...................................................................................................176
In situ analyses...........................................................................................................177
EXTRATERRESTRIAL LITHIUM RESERVOIRS.............................................................178
The interstellar medium and the Sun..........................................................................178
Meteorites and their components...............................................................................179
Moon..........................................................................................................................181
TERRESTRIAL LITHIUM RESERVOIRS..........................................................................181
Mantle peridotites.......................................................................................................181
Basalts........................................................................................................................188
Arc lavas.....................................................................................................................190
Continental crust.........................................................................................................191
Seawater.....................................................................................................................192
Rivers..........................................................................................................................193
Lakes..........................................................................................................................193
Groundwater...............................................................................................................194
Hydrothermal fluids....................................................................................................194
IGNEOUS PROCESSES.......................................................................................................195
Differentiation............................................................................................................195
Eruptive processes......................................................................................................196
METAMORPHIC PROCESSES...........................................................................................197
Dehydration................................................................................................................197
Redistribution of Li through fluid infiltration.............................................................198
Diffusion.....................................................................................................................199
CONTINENTAL WEATHERING PROCESSES..................................................................199
Weathering profiles.....................................................................................................201
Rivers..........................................................................................................................201
LITHIUM AS A TRACER OF CONTINENTAL WEATHERING
THROUGH TIME..............................................................................................................204
vii
FUTURE DIRECTIONS.......................................................................................................205
Weathering processes and Li fractionation experiments............................................205
Continental weathering through time.........................................................................205
Geospeedometry.........................................................................................................206
REFERENCES......................................................................................................................206
7 Magnesium Isotope Geochemistry

Fang-Zhen Teng
INTRODUCTION.................................................................................................................219
MAGNESIUM ISOTOPIC ANALYSIS................................................................................221
Nomenclature.............................................................................................................221
Standard and reference materials...............................................................................222
Instrumental Analysis.................................................................................................229
Sample preparation.....................................................................................................229
MAGNESIUM ISOTOPIC SYSTEMATICS
OF EXTRATERRESTRIAL RESERVOIRS......................................................................230
Magnesium isotopic composition of chondrites.........................................................231
Magnesium isotopic composition of differentiated meteorites..................................232
Magnesium isotopic composition of the Moon..........................................................232
MAGNESIUM ISOTOPIC SYSTEMATICS OF THE MANTLE........................................234
Mantle xenoliths.........................................................................................................234
Oceanic basalts...........................................................................................................236
Abyssal peridotites and ophiolites..............................................................................237
Continental basalts.....................................................................................................239
MAGNESIUM ISOTOPIC SYSTEMATICS OF THE OCEANIC CRUST,
CONTINENTAL CRUST AND HYDROSPHERE............................................................241
Magnesium isotopic composition of the oceanic crust..............................................241
Magnesium isotopic composition of the continental crust.........................................243
Magnesium isotopic composition of the hydrosphere................................................247
MAGNESIUM ISOTOPIC SYSTEMATICS OF CARBONATES.......................................250
Abiogenic carbonates.................................................................................................250
Biogenic carbonates...................................................................................................254
Carbonate precipitation experiments and theoretical calculations.............................255
BEHAVIOR OF MAGNESIUM ISOTOPES
DURING MAJOR GEOLOGICAL PROCESSES.............................................................256
Behavior of Mg isotopes during biological processes................................................256
Behavior of Mg isotopes during continental weathering...........................................257
Behavior of Mg isotopes during magmatic differentiation........................................263
Behaviors of Mg isotopes during metamorphic dehydration.....................................264
HIGH-TEMPERATURE MAGNESIUM ISOTOPE FRACTIONATION............................267
High-temperature equilibrium inter-mineral Mg isotope fractionation......................267
Diffusion-driven kinetic Mg isotope fractionation.....................................................270
APPLICATIONS AND FUTURE DIRECTIONS.................................................................276
REFERENCES......................................................................................................................278
viii
8 Silicon Isotope Geochemistry

Franck Poitrasson
ELEMENT PROPERTIES.....................................................................................................289
NOMENCLATURE, REFERENCE MATERIALS AND
ANALYTICAL TECHNIQUES.........................................................................................290
ELEMENTAL AND ISOTOPIC ABUNDANCES IN MAJOR RESERVOIRS...................294
Extraterrestrial reservoirs...........................................................................................294
Terrestrial reservoirs...................................................................................................301
ELEMENTAL AND ISOTOPIC BEHAVIORS
DURING MAJOR GEOLOGICAL PROCESSES.............................................................317
Diffusion, condensation and evaporation...................................................................317
Igneous processes.......................................................................................................322
Metamorphic processes..............................................................................................325
Low temperature processes........................................................................................325
Biological processes...................................................................................................330
IMPORTANT IMPLICATIONS AND FUTURE DIRECTIONS.........................................333
REFERENCES......................................................................................................................337
9 Chlorine Isotope Geochemistry

Jaime D. Barnes, Zachary D. Sharp
INTRODUCTION.................................................................................................................345
CHLORINE ISOTOPE NOMENCLATURE AND STANDARDS......................................346
CHLORINE ISOTOPE ANALYTICAL METHODS ...........................................................346
Isotope ratio mass spectrometry (IRMS)....................................................................346
Thermal ionization mass spectrometry (TIMS).........................................................347
Secondary ion mass spectrometry (SIMS).................................................................348
Laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS).........348
ISOTOPIC FRACTIONATION.............................................................................................348
Equilibrium Cl isotope fractionation—theoretical constraints...................................348
Equilibrium Cl isotope fractionation—experimental constraints...............................349
Kinetic Cl isotope fractionation—Cl loss .................................................................351
CHLORINE ISOTOPIC COMPOSITION OF
VARIOUS GEOLOGIC RESERVOIRS ...............................................................................351
Mantle/OIB/mantle derived material..........................................................................351
Seawater and seawater-derived chloride.....................................................................353
Sediments...................................................................................................................355
Altered Oceanic Crust (AOC)....................................................................................355
Serpentinites...............................................................................................................357
Perchlorates................................................................................................................357
Extraterrestrial Materials............................................................................................358
CHLORINE ISOTOPES AS A TRACER .............................................................................364
Tracer through subduction zones................................................................................364
Crustal fluids ..............................................................................................................365
Tracer in ore deposits.................................................................................................368
ix
Environmental............................................................................................................370
SUMMARY...........................................................................................................................370
REFERENCES......................................................................................................................371
10 Chromium Isotope Geochemistry

Liping Qin, Xiangli Wang
INTRODUCTION.................................................................................................................379
Chemical properties of Cr..........................................................................................379
Research History of the Cr isotopic System...............................................................380
ANALYTICAL METHODS AND NOTATION....................................................................382
Analytical methods.....................................................................................................382
Notation......................................................................................................................385
CHROMIUM ISOTOPE COSMOCHEMISTRY..................................................................386
53
Mn–53Cr short-lived chronometer............................................................................386
54
Cr anomalies............................................................................................................387
CHROMIUM ISOTOPIC FRACTIONATION
IN HIGH-TEMPERATURE SETTINGS...........................................................................388
Bulk silicate earth and meteorites..............................................................................388
Serpentinization and metamorphism..........................................................................389
MECHANISMS OF CR ISOTOPIC FRACTIONATION
IN LOW-TEMPERATURE SETTINGS.............................................................................390
Reduction....................................................................................................................390
Equilibrium Cr isotopic fractionation and Cr(III)–Cr(VI) isotope exchange
in aqueous systems..................................................................................................397
Oxidation....................................................................................................................398
Adsorption..................................................................................................................398
Coprecipitation...........................................................................................................398
CHROMIUM ISOTOPIC VARIATIONS IN SURFACIAL ENVIRONMENTS..................399
Groundwater...............................................................................................................399
Weathering systems....................................................................................................399
Rivers and seawater....................................................................................................400
Cr isotope mass balance.............................................................................................401
The Cr isotope system as a paleo-redox proxy...........................................................403
CONCLUDING REMARKS AND OUTLOOK...................................................................407
ACKNOWLEDGEMENT.....................................................................................................408
REFERENCES......................................................................................................................408
11 Iron Isotope Systematics

Nicolas Dauphas, Seth G. John, Olivier Rouxel
INTRODUCTION.................................................................................................................415
METHODOLOGY................................................................................................................417
Rocks and solid samples.............................................................................................418
Water samples.............................................................................................................423
In situ analyses...........................................................................................................424
Isotopic anomalies and mass-fractionation laws........................................................428
x
KINETIC AND EQUILIBRIUM FRACTIONATION FACTORS.......................................429

Kinetic processes........................................................................................................430
Equilibrium processes................................................................................................433
IRON ISOTOPES IN COSMOCHEMISTRY.......................................................................451
Nucleosynthetic anomalies and iron-60.....................................................................451
Overview of iron isotopic compositions in extraterrestrial material..........................454
HIGH-TEMPERATURE GEOCHEMISTRY.......................................................................456
Partial mantle melting.................................................................................................462
Impact evaporation and core formation......................................................................464
Fractional crystallization, fluid exsolution, immiscibility, and thermal (Soret)
diffusion...................................................................................................................466
A new tool to improve on geospeedometry reconstructions in igneous petrology....469
IRON BIOGEOCHEMISTRY...............................................................................................470
Microbial cycling of Fe isotopes................................................................................470
Fe isotopes in plants, animals, and humans................................................................472
FLUID–ROCK INTERACTIONS.........................................................................................473
High- and low-temperature alteration processes at the seafloor.................................473
Rivers and soils...........................................................................................................475
Mineral deposits.........................................................................................................475
IRON BIOGEOCHEMICAL CYCLING IN THE MODERN OCEAN...............................477
The importance of iron in the global ocean................................................................477
Sources and sinks for Fe in the ocean........................................................................478
Using Fe isotopes to trace sources of Fe in the oceans..............................................482
Internal cycling of Fe isotopes within the ocean........................................................482
THE GEOLOGICAL RECORD AND PALEOCEANOGRAPHIC APPLICATIONS.........483
The ferromanganese crust record...............................................................................483
Oceanic anoxic events................................................................................................485
The Precambrian record.............................................................................................486
The archive of iron formations...................................................................................486
Black Shales and Sedimentary Pyrite Archives..........................................................490
CONCLUSION......................................................................................................................492
REFERENCES......................................................................................................................493
12 The Isotope Geochemistry of Ni

Tim Elliott, Robert C. J. Steele
INTRODUCTION.................................................................................................................511
Notation......................................................................................................................511
NUCLEOSYNTHETIC NI ISOTOPIC VARIATIONS.........................................................513
EXTINCT 60Fe AND RADIOGENIC 60Ni............................................................................520
MASS-DEPENDENT Ni ISOTOPIC VARIABILITY..........................................................526
Magmatic systems......................................................................................................526
Weathering and the hydrological cycle......................................................................532
Biological systems......................................................................................................534
OUTLOOK............................................................................................................................536
REFERENCES......................................................................................................................537
xi
13 The Isotope Geochemistry of Zinc and Copper

Frédéric Moynier, Derek Vance, Toshiyuki Fujii, Paul Savage
INTRODUCTION.................................................................................................................543
METHODS............................................................................................................................545
ZINC AND COPPER ISOTOPE FRACTIONATION FACTORS
FROM AB INITIO METHODS.........................................................................................548
ZINC AND COPPER IN EXTRA-TERRESTRIAL SAMPLES
AND IGNEOUS ROCKS...................................................................................................557
ZINC AND COPPER IN LOW TEMPERATURE GEOCHEMISTRY................................566
Experimental constraints on fractionation mechanisms.............................................568
Cu–Zn isotopes in the weathering–soil–plant system................................................576
The oceans: inputs, outputs and internal cycling of Cu and Zn isotopes...................581
Cu and Zn isotopes in the Anthropocene....................................................................589
REFERENCES......................................................................................................................591
14 Germanium Isotope Geochemistry

Olivier J. Rouxel, Béatrice Luais
INTRODUCTION.................................................................................................................601
METHODS............................................................................................................................602
Early methods to measure Ge isotope ratios..............................................................602
State of the art analytical methods.............................................................................603
Sample dissolution issues...........................................................................................605
Chemical purification of samples...............................................................................606
Hydride generation (HG) MC-ICPMS ......................................................................606
Interference issues......................................................................................................607
Notation......................................................................................................................607
Analytical precision ...................................................................................................608
Ge isotope standards and reference materials ...........................................................609
THEORETICAL CONSIDERATIONS AND EXPERIMENTAL CALIBRATIONS..........612
Equilibrium fractionation factors...............................................................................612
Kinetic processes........................................................................................................613
Diffusion of Ge in silicate melts.................................................................................614
HIGH-TEMPERATURE GEOCHEMISTRY.......................................................................616
Fundamentals of Ge high-temperature geochemistry................................................616
Cosmochemistry of Ge isotopes.................................................................................621
GERMANIUM ISOTOPE SYSTEMATICS IN IGNEOUS,
MANTLE-DERIVED ROCKS, AND METAMORPHIC ROCKS....................................626
The Ge isotopic composition of the Earth silicate reservoirs.....................................626
Germanium recycling into the mantle: an attempt to evaluate mantle homogeneity.628
Ore deposits................................................................................................................629
LOW-TEMPERATURE GEOCHEMISTRY.........................................................................631
Fundamentals of Ge low-temperature geochemistry..................................................631
Germanium isotope systematics in low-temperature marine environments...............634
Ge isotope fractionation during low temperature weathering....................................639
xii
Germanium isotope systematics of hydrothermal waters...........................................639

A preliminary oceanic Ge budget...............................................................................641
The potential for paleoceanography and the rock record...........................................644
CONCLUSION......................................................................................................................647
REFERENCES......................................................................................................................648
15 Selenium Isotopes as a Biogeochemical Proxy in Deep Time

Eva E. Stüeken
INTRODUCTION AND OVERVIEW..................................................................................657

NOMENCLATURE, REFERENCE MATERIALS AND ANALYTICAL TECHNIQUES.659
ELEMENTAL AND ISOTOPIC ABUNDANCES IN MAJOR RESERVOIRS...................661
Terrestrial and extraterrestrial igneous terrestrial reservoirs......................................661
Reservoirs at the Earth’s surface................................................................................663
SELENIUM IN BIOLOGY...................................................................................................666
ISOTOPIC FRACTIONATION PATHWAYS........................................................................667
GEOBIOLOGICAL APPLICATIONS..................................................................................670
Developing a mass balance for the modern ocean.....................................................670
Implications and predictions......................................................................................673
Selenium isotopes in deep time..................................................................................674
CONCLUSIONS AND FUTURE DIRECTIONS.................................................................677
REFERENCES......................................................................................................................677
16 Good Golly, Why Moly?

The Stable Isotope Geochemistry of Molybdenum
Brian Kendall, Tais W. Dahl, Ariel D. Anbar
INTRODUCTION.................................................................................................................683
ANALYTICAL CONSIDERATIONS...................................................................................684
Data reporting.............................................................................................................684
Chemical separation...................................................................................................685
Mass Spectrometry.....................................................................................................686
CHEMICAL AND BIOLOGICAL CONTEXT....................................................................688
Aqueous geochemistry...............................................................................................688
Biology.......................................................................................................................690
FRACTIONATION FACTORS............................................................................................692
Adsorption to Mn oxides............................................................................................692
Adsorption to Fe oxides and oxyhydroxides..............................................................693
Sulfidic species...........................................................................................................694
Biological processes...................................................................................................694
High-temperature melt systems..................................................................................695
MOLYBDENUM ISOTOPES IN MAJOR RESERVOIRS...................................................696
Meteorites...................................................................................................................696
The mantle and crust..................................................................................................697
The oceans..................................................................................................................699
Lakes..........................................................................................................................706
xiii
APPLICATION TO OCEAN PALEOREDOX......................................................................706

Local depositional conditions.....................................................................................707
Reconstructing the oceanic Mo isotope mass balance...............................................708
Inferring seawater δ98Mo from sedimentary archives.................................................710
Tracing atmosphere–ocean oxygenation using Mo isotopes......................................712
Part 1: Searching for free O2 in the Archean surface environment.............................712
Part 2: Tracing global ocean oxygenation in the post-GOE world.............................714
APPLICATION TO NATURAL RESOURCES....................................................................717
Ore deposits................................................................................................................717
Petroleum systems......................................................................................................722
Anthropogenic tracing................................................................................................722
CONCLUSIONS....................................................................................................................723
REFERENCES......................................................................................................................724
17 Recent Developments in Mercury Stable Isotope Analysis

Joel D. Blum, Marcus W. Johnson
INTRODUCTION.................................................................................................................733
Element properties......................................................................................................734
Hg isotope nomenclature............................................................................................734
Reference materials....................................................................................................735
Analytical advances....................................................................................................735
Isobaric and molecular interferences..........................................................................737
Reagent blanks and sample carryover........................................................................740
Matrix effects and the need to remove matrix materials............................................741
Recommendations for analyses..................................................................................744
ISOTOPIC ABUNDANCES IN MAJOR RESERVOIRS.....................................................745
Isotopic behaviors during major geological processes...............................................748
NEW FRONTIERS IN HG ISOTOPE ANALYSIS...............................................................749
Isotopic composition of methyl mercury....................................................................749
Separation of Hg from low concentration waters.......................................................750
Separation of Hg from atmospheric gases..................................................................750
Even-mass MIF..........................................................................................................751
FUTURE DIRECTIONS.......................................................................................................752
REFERENCES......................................................................................................................753
18 Investigation and Application of Thallium Isotope Fractionation

Sune G. Nielsen, Mark Rehkämper, Julie Prytulak
ABSTRACT...........................................................................................................................759
INTRODUCTION.................................................................................................................760
METHODOLOGY................................................................................................................762
Mass spectrometry......................................................................................................762
Chemical separation of thallium.................................................................................762
Measurement uncertainties and standards..................................................................764
xiv
THALLIUM ISOTOPE VARIATION IN EXTRATERRESTRIAL MATERIALS..............765

The 205Pb–205Tl decay system......................................................................................765
Chondritic meteorites.................................................................................................766
Iron meteorites............................................................................................................767
Limitations of the 205Pb–205Tl chronometer................................................................770
THALLIUM ISOTOPE COMPOSITION OF THE SOLID EARTH...................................771
The primitive mantle..................................................................................................771
The continental crust..................................................................................................771
THALLIUM ISOTOPE COMPOSITION OF SURFACE RESERVOIRS...........................772
Volcanic degassing.....................................................................................................772
Weathering and riverine transport of Tl......................................................................773
Anthropogenic mobilization of Tl..............................................................................774
The isotope composition of seawater.........................................................................775
THE MARINE MASS BALANCE OF THALLIUM ISOTOPES........................................776
Thallium isotopes in marine input fluxes...................................................................776
Thallium isotope compositions of marine output fluxes............................................780
CAUSES OF THALLIUM ISOTOPE FRACTIONATION...................................................782
APPLICATIONS OF THALLIUM ISOTOPES....................................................................784
Studies of Tl isotopes in Fe–Mn crusts......................................................................784
Calculation of hydrothermal fluid fluxes using Tl isotopes in the ocean crust...........786
High temperature terrestrial applications...................................................................787
FUTURE DIRECTIONS AND OUTLOOK.........................................................................791
REFERENCES......................................................................................................................793
19 Uranium Isotope Fractionation

Morten B. Andersen, Claudine H. Stirling, Stefan Weyer
INTRODUCTION.................................................................................................................799
Uranium occurrence and properties...........................................................................799
Uranium isotopes........................................................................................................800
URANIUM ISOTOPE DETERMINATIONS.......................................................................803
Historical overview of 238U/235U measurements.........................................................803
Chemical preparation of U and mass spectrometric corrections................................804
Anthropogenic U contamination................................................................................804
238
U/235U nomenclature...............................................................................................805
EXPERIMENTAL EVIDENCE FOR URANIUM ISOTOPE FRACTIONATION
PROCESSES.......................................................................................................................806
Experimental studies for nuclear 235U enrichment......................................................806
Uranium isotopes and the nuclear field shift..............................................................806
Experimental evidence for kinetic and equilibrium 238U/235U fractionation...............807
238
U/235U IN COSMOCHEMISTRY......................................................................................809
Uranium isotopic anomalies and the search for extant 247Cm....................................809
Uranium isotope fractionation unrelated to 247Cm decay...........................................813
Pb–Pb chronometer....................................................................................................815
URANIUM ISOTOPE SYSTEMATICS IN HIGH TEMPERATURE
ENVIRONMENTS ON EARTH........................................................................................817
Bulk Earth 238U/235U....................................................................................................817
The mantle..................................................................................................................818
xv
The continental crust..................................................................................................819

URANIUM ISOTOPES IN ORE DEPOSITS.......................................................................820
Uranium ore types......................................................................................................821
Uranium isotope fractionation in ore deposits...........................................................821
Uranium isotopes as tracers of U mine remediation..................................................824
NEAR-SURFACE U CYCLING AND THE MARINE 238U/235U MASS BALANCE..........825
The 238U/235U in rivers and groundwater.....................................................................826
The 238U/235U of seawater............................................................................................827
The 238U/235U in reducing sediments...........................................................................827
The 238U/235U in marine carbonates.............................................................................831
The 238U/235U of altered oceanic crust.........................................................................832
The 238U/235U of ferromangenese oxides.....................................................................833
Isotopic constraints on the marine U cycle.................................................................834
U ISOTOPES AS A PALEO-REDOX PROXY.....................................................................837
Early Earth redox evolution........................................................................................838
Neo-Proterozoic and Phanerozoic..............................................................................839
OUTLOOK............................................................................................................................841
REFERENCES......................................................................................................................843
20 Medical Applications of Isotope Metallomics

Francis Albarède, Philippe Télouk, Vincent Balter
INTRODUCTION.................................................................................................................851
THE ISOTOPE EFFECT.......................................................................................................853
AN OVERVIEW OF Ca, Fe, Zn, Cu, AND S BIOCHEMISTRY AND HOMEOSTASIS...859
Calcium......................................................................................................................859
Iron.............................................................................................................................860
Zinc.............................................................................................................................861
Copper........................................................................................................................862
Sulfur..........................................................................................................................863
ISOTOPE COMPOSITIONS OF Fe–Zn–Cu–S IN THE BLOOD
OF HEALTHY INDIVIDUALS.........................................................................................864
CALCIUM AND BONE LOSS.............................................................................................867
GENETIC AND INFECTIOUS DISEASES.........................................................................868
ISOTOPE METALLOMICS IN CANCER...........................................................................869
ASSESSING THE POTENTIAL OF METAL ISOTOPES AS BIOMARKERS..................875
COMPARTMENTALIZED MODELS OF CELLULAR HOMEOSTASIS.........................877
PERSPECTIVES...................................................................................................................878
REFERENCES......................................................................................................................879
xvi
Reviews in Mineralogy & Geochemistry
Vol. 82 pp. 1-26, 2017 1
Copyright © Mineralogical Society of America
Non-Traditional Stable Isotopes:

Retrospective and Prospective
Fang-Zhen Teng
Isotope Laboratory
Department of Earth and Space Sciences
University of Washington
Seattle WA 98195
USA
fteng@uwashington.edu
Nicolas Dauphas
Origins Lab
Department of the Geophysical Sciences and Enrico Fermi Institute
The University of Chicago
Chicago IL 60637
USA
dauphas@uchicago.edu
James M. Watkins
Department of Earth Sciences
University of Oregon
Eugene OR 97403
USA
watkins4@uoregon.edu
INTRODUCTION
Traditional stable isotope geochemistry involves isotopes of light elements such as H, C,
N, O, and S, which are measured predominantly by gas-source mass spectrometry (Valley et al.
1986; Valley and Cole 2001). Even though Li isotope geochemistry was developed in 1980s based
on thermal ionization mass spectrometry (TIMS) (Chan 1987), the real flourish of so-called non-
traditional stable isotope geochemistry was made possible by the development of multi-collector
inductively coupled plasma mass spectrometry (MC-ICPMS) (Halliday et al. 1995; Marechal et
al. 1999). Since then, isotopes of both light (e.g., Li, Mg) and heavy (e.g., Tl, U) elements have
been routinely measured at a precision that is high enough to resolve natural variations (Fig. 1).
The publication of RIMG volume 55 (Geochemistry of Non-Traditional Stable Isotopes) in 2004
was the first extensive review of Non-Traditional Stable Isotopes summarizing the advances in
the field up to 2003 (Johnson et al. 2004). When compared to traditional stable isotopes, the
non-traditional stable isotopes have several distinctive geochemical features: 1) as many of these
elements are trace elements, their concentrations vary widely in different geological reservoirs;
2) these elements range from highly volatile (e.g., Zn and K) to refractory (e.g., Ca and Ti);
3) many of these elements are redox-sensitive; 4) many of them are biologically active; 5) the
bonding environments, especially for the metal elements, are different from those of H, C, N,
O and S; and finally, 6) many of these elements have high atomic numbers and more than two
stable isotopes. These features make the different elements susceptible to different fractionation
mechanisms, and by extension, make them unique tracers of different cosmochemical, geological
and biological processes, as highlighted throughout this volume.
1529-6466/17/0082-0001$05.00 http://dx.doi.org/10.2138/rmg.2017.82.1
2 Teng, Dauphas, & Watkins
Figure 1. Non-traditional stable isotope systems covered in this volume.
Large variations have been documented in both natural samples and laboratory experiments
for non-traditional stable isotopes (Fig. 2). These studies suggest that the following factors
control the degree of isotope fractionation in non-traditional stable isotopes during various
processes: the relative mass difference between isotopes, change of the oxidation state, biological
sensitivity, and volatility. Among these elements, Li displays the largest isotopic variation in
terrestrial samples, and since Li is not volatile during geological processes and is not sensitive
to redox reactions and biological processes, the large isotope fractionation is controlled mainly
by the large relative mass difference (Penniston-Dorland et al. 2017). For many of the other
elements, other factors may be equally, if not more, important. For example, Cl exhibits the
Figure 2. The terrestrial isotopic variation vs. the relative mass difference for non-traditional stable iso-
topes covered in this volume (Anderson et al. 2017; Barnes and Sharp 2017; Blum and Johnson 2017;
Dauphas et al. 2017; Elliott and Steele 2017; Kendall et al. 2017; Moynier et al. 2017; Nielsen et al. 2017;
Penniston-Dorland et al. 2017; Poitrasson 2017; Qin and Wang 2017; Rouxel and Luais 2017; Stueken
2017; Teng 2017). The Dmi−j = mi − mj, where i and j represent the two isotopes that are used to report the
isotopic variation, with i > j.
Retrospective and Prospective 3
second largest isotopic variation, which is due to kinetic isotope fractionation during volcanic
degassing (Barnes and Sharp 2017). Selenium isotopes also show large isotopic variations,
but this reflects redox-controlled Se isotope fractionation (Stueken 2017), while the large Hg
isotopic variations are mainly associated with biological processes (Blum and Johnson 2017).
In this chapter, we discuss guidelines and recommendations for reporting non-traditional
stable isotopic data and choosing reference materials. We then provide brief introductions
to some of the emerging isotope systems that are not covered as individual chapters in this
volume. As Ca isotope geochemistry has been recently reviewed in the book series on Advances
in Isotope Geochemistry (Gussone et al. 2016), and a similar book is also in preparation for
B isotope geochemistry, both Ca and B isotopes are not discussed in this volume. For the
basics of stable isotope geochemistry, we recommend prior RIMG volumes (Valley et al. 1986;
Valley and Cole 2001; Johnson et al. 2004; MacPherson 2008) and stable isotope geochemistry
textbooks (Criss 1999; Faure and Mensing 2005; Sharp 2007; Hoefs 2009).
THE δ NOTATION
The isotopic composition of a sample is commonly reported relative to an international
standard as defined by the δ notation. For example, for Mg isotopes:
 (26 Mg/ 24 Mg)sample 

=δ26 Mg  26 24
− 1 × 1000 (1)
 ( Mg/ Mg)DSM3 
where DSM3 is the international standard for reporting Mg isotopic data (Galy et al. 2003).
This definition of δ value has been used extensively for both non-traditional stable isotopes
(e.g., this volume, Johnson et al. 2004) and traditional stable isotopes (e.g., Valley et al. 1986).
Recently, a new δ notation without the factor of 1000 has been recommended by the
IUPAC for expression of stable isotope ratios (Coplen 2011). For example, the new guideline
would suggest a definition of δ for Mg isotopes as:
 (26 Mg/ 24 Mg)sample 

=
δ26 Mg  26 24
− 1 (2)
 ( Mg/ Mg)DSM3 
The rationale is that when isotopic data are reported, the ‰ symbol is commonly placed
following the value. Then, in the case that (26Mg/24Mg)sample/(26Mg/24Mg)DSM3 = 1.00025, the
d26Mg should be equal to + 0.25 in the traditional δ notation i.e., d26Mg = +0.25. If the ‰
symbol is added after the value i.e., d26Mg = +0.25‰, then mathematically, this means d26Mg
= +0.25‰ = +0.00025. In other words, (26Mg/24Mg)sample/(26Mg/24Mg)DSM3 = 1.00000025. If
the IUPAC δ notation is adopted, then when the (26Mg/24Mg)sample/(26Mg/24Mg)DSM3 = 1.00025,
the d26Mg = +0.00025 = +0.25‰.
While mathematically rigorous, the IUPAC recommendation goes against practices in the
field. Retaining the factor of 1000 in the δ notation is, in the view of many in the community,
critical to distinguish the δ, ε, and µ notations, which can be used concurrently in a paper.
In the literature on traditional and non-traditional stable isotopes, the δ notation (1) with
the factor of 1000 still prevails. For the purpose of being mathematically correct, an alternative
to the IUPAC recommendation is to keep the traditional δ notation with the factor of 1000 and
omit the ‰ symbol after the δ value, e.g., d26Mg = +0.25, which means (26Mg/24Mg)sample/
(26Mg/24Mg)DSM3 = 1.00025. This expression is also consistent with the usage of the ε notation
where the part per 10000 is not added after any ε value.
Another alternative is to adopt the original δ notation as defined by Craig (1957). For Mg
isotopes:
 (26 Mg/ 24 Mg)sample 

=
δ26 Mg(‰)  26 24
− 1 × 1000 (3)
 ( Mg/ Mg)DSM3 
which would read “d26Mg expressed in ‰ is equal to [(26Mg/24Mg)sample/

(26Mg/24Mg)DSM3 − 1] × 1000”. Under this definition, it is also mathematically correct to
place the ‰ symbol after the value, e.g., d26Mg = +0.25‰, which means (26Mg/24Mg)sample/
(26Mg/24Mg)DSM3 = 1.00025.
Although both notations (2) and (3) are mathematically correct, we recommend the
notation (3) as it ensures that new publications are consistent with past practices. More
important, it is the original definition of δ notation since the beginning of stable isotope
geochemistry (Craig 1957). We did not enforce this notation in the present volume but
recommend it be used in future publications.
Regardless of which notation is used, it is still correct, as often done by the community,
to write sentences like “the 26Mg/24Mg varies 1‰ in water samples from Chicago and Seattle”
or “The water sample from Chicago is enriched in heavy Mg isotopes by 1‰ relative to that in
Seattle”, or “The water sample from Chicago is 1‰ heavier than that from Seattle”.
GUIDELINES FOR SELECTING REFERENCE MATERIALS

The field of non-traditional stable isotope geochemistry is confronted with the same
issues as traditional stable isotope geochemistry regarding the selection of isotope reference
materials (IRMs; Carignan et al. 2004; Vogl and Pritzkow 2010). The recurring problem is
that standards used in laboratories either run out or are not readily available. This is the case
for reference materials distributed by official organizations as well as in-house standards.
For instance, IRMM-014, which is used in iron isotope geochemistry and distributed by
the Institute for Reference Materials and Measurements (IRMM), is no longer available.
Similarly, JMC Lyon Zn and DSM3, which are used in Zn and Mg isotope geochemistry,
are not readily available. These issues need to be addressed because systematic errors arise
when measurements are carried out against secondary standard solutions. Below, we propose
some guidelines for selecting isotopic reference materials used in isotope geochemistry. These
are informed by discussions with members of the community as well as our analysis of best
practices in traditional and non-traditional stable isotope geochemistry.
Guideline #1: The isotopic composition of the reference material should be demonstrably
homogeneous given current analytical precision and its preparation should be such that
future isotopic analyses will be unlikely to reveal isotopic heterogeneities when the
precision improves.
We, as a community, should be forward-thinking in designing preparation protocols that
minimize the possibility that reference materials will prove to be heterogeneous as analytical
capabilities improve. The purified Mg metal isotopic standard NIST SRM 980, which was
made and distributed by National Institute of Standards and Technology (NIST), was deemed
to be isotopically homogeneous when it was created in 1966 (Catanzaro et al. 1966). However,
subsequent higher precision measurements showed that it was isotopically heterogeneous,
and it was replaced by a Mg solution made from dissolution of pure Mg metal from Dead
Sea Magnesium Ltd, i.e., DSM3 (Galy et al. 2003). Some steps can be taken to ensure that the
maximum level of homogeneity is achieved (i.e., stable solutions, quenched glasses, stable metal
sheets or bars are likely to be isotopically homogeneous to a high degree). The processes that can
potentially cause heterogeneities in isotopic composition and should be avoided are evaporation,
chemical diffusion, the Soret effect, and precipitation/crystallization (e.g., Richter et al. 2009).
Guideline #2: The reference material should be pure elements or chemical compounds
that are either in diluted acids or can be easily dissolved into diluted acids.
Any unnecessary processing performed in the lab has the potential to induce systematic
errors. For example, incomplete digestion and precipitation can induce isotope fractionation, as
can chemical purification of analytes in the lab. Although some of these issues can be mitigated
using a double-spike approach, it is advantageous to have the reference material in a pure form or
a form in which the other elements can be quantitatively removed (e.g., by drying after digestion).
Guideline #3: The reference material should have an isotopic composition that falls
within the range of natural variability, and ideally is representative or similar to a major
geological reservoir.
For non-traditional stable isotope systems, Guideline #2 imposes the reference material be
purified by a third party, often at an industrial scale. A benefit is that it ensures that the reference
material is available in large quantities and is unlikely to be exhausted. The process of purification
can, however, induce significant isotope fractionation, such that the synthetic material can have
extreme isotopic composition and may not be representative of any geochemically relevant
reservoir. This can lead to all natural isotopic compositions being systematically shifted either
to the negative or positive side. Therefore, the reference material should have an isotopic
composition that falls within the range of natural variability and ideally is representative of a
major geological reservoir for the element investigated. This can be achieved by first surveying
aliquots of industrially purified material to find a batch whose isotopic composition approaches
that of a geologically relevant reservoir. For example, IRMM-014 coincidentally has an iron
isotopic composition that is indistinguishable from chondrites (Craddock and Dauphas 2011).
Guideline #4: The isotopic composition of the reference material should be characterized
at high-precision for all its isotopes to ensure that no measurable anomalies are present
that would complicate studies of mass-independent effects and mass-fractionation laws.
To first order, isotopic variations follow the rules of mass-dependent fractionation,
meaning that the variations in isotopic ratios scale as the differences in mass of the isotopes
involved. However, it is now possible to discern clear departures from mass-dependent
fractionation produced by nuclear field-shift or magnetic effects, and it is also possible to
precisely define the laws of mass dependent-fractionation (Dauphas and Schauble 2016).
Large-scale purification processes that would fractionate isotopes would impart a certain
mass-fractionation law that would complicate comparison between naturally occurring mass
fractionation laws. Furthermore, it has been shown previously that some purification processes,
notably the Mond-process used in purifying Ni, can create spurious isotopic anomalies (Steele
et al. 2011). Characterization of mass-independent effects and mass-fractionation laws is a
growing field in geochemistry (Dauphas and Schauble 2016) and it is essential that attention be
paid to this issue by documenting whether the material displays spurious isotopic anomalies.
Guideline #5: The choice of a reference material against which to report isotopic
analyses should be a community-led effort and should be consistent.
Once a standard has reached a certain level of acceptance (e.g., when more than 20
publications report isotopic compositions relative to that standard; if two reference materials
have achieved this status, whichever has been more extensively used), that standard should
be used in subsequent publications. If it is exhausted, a secondary reference material may
be defined and an offset be applied to the isotopic analyses such that the original reference
material can still be used to report isotopic compositions. For example, JMC Zn-Lyon is
not readily available but future Zn isotopic analyses should still be reported relative to this
standard even if new reference materials are used such as IRMM-3702 (Cloquet et al. 2006a;
Ponzevera et al. 2006; Moeller et al. 2012) or NIST SRM-683 (Tanimizu et al. 2002; Chen et
al. 2016). The secondary reference material used during the measurement should be specified
when the δ-notation is defined. For example, one would write: “The Zn isotopic composition
is expressed as, d66Zn = [(66Zn/64Zn)std / (66Zn/64Zn)JMC Lyon − 1] × 1000, where the isotopic
analyses were measured relative to IRMM-3702 to which a systematic offset of − 0.29 was
applied (Moeller et al. 2012) for conversion to the JMC Lyon d66Zn scale”.
The exception to this guideline is that if the standard is proven to be isotopically
heterogeneous as analytical capabilities improve, then a new reference material should be used
to report isotopic compositions (see guideline # 1). Ideally, this new standard should have an
isotopic composition that is similar to the original reference material used to define the d scale.
Guideline #6: The reference materials should be widely available. This implies that lab-
defined and owned reference materials should be transferred to organizations that do not
have a conflict of interest.
The role of certification institutes such as IRMM or NIST is to characterize the reference
materials that they distribute and ensure that they are available. In many instances, there has
been a disconnect between the needs of the geochemical community and what these certification
institutes can provide. This is probably due, in part, to the fact that non-traditional stable
isotope geochemistry has grown at a rapid pace while preparation of certified materials can
take a long time (Vogl and Pritzkow 2010). Part of the certification involves characterization
of absolute isotopic abundances using gravimetrically prepared isotope mixtures. In non-
traditional stable isotope geochemistry, knowing the absolute ratios is not particularly useful.
To cope with the shortage or unavailability of isotopic reference materials, in-house isotopic
standards have become the reference materials against which isotopic analyses are reported
(DSM3 for Mg, Zn-Lyon for Zn, OL-Ti for Ti). An issue with this practice is the availability
of those materials, and conflicts of interest may arise that are detrimental to the advancement
of science. Investigator-controlled distribution systems do not work. Moving forward, some
organizations/companies could take over that role and distribute (perhaps against a modest
fee) the reference materials created by the community. Taking titanium as an example, the bar
of pure Ti used to define the OL-Ti standard (Millet and Dauphas 2014; Millet et al. 2016) will
be transferred to SARM (Nancy, France), where it will be available to end-users upon request.
Another aspect regarding availability is the preparation of a large enough stock so
that the reference material can be used for decades and the material remains stable in time.
Aqueous solutions are appealing as they ensure homogeneity (Vogl and Pritzkow 2010) but
the concentration is limited by solubility constraints and long-term stability may be an issue.
Solids alleviate this issue and are more cost effective for the end user.
Several isotopic systems are, or will be, in crisis if no action is taken to remediate the
shortage of isotopic reference materials that can be used by newcomers to the field. There is no
committee or working group overseeing the important issues related to standards and we take
the opportunity of writing this chapter to propose the establishment of such a working group.
EMERGING ISOTOPE SYSTEMS

The recent advances in instrumentation have made high-precision isotopic analysis
possible for almost all elements on the periodic table. Besides those systems reviewed in
individual chapters of this volume, there are numerous emerging systems that show great
potential as briefly summarized for some of them below.
Stable potassium isotope geochemistry

Table 1. K (atomic number = 19) isotopes and typical natural abundance.
Isotope Abundance (%)
39
K 93.2581
40
K 0.0117
41
K 6.7302
Isotopic abundance data are from Berglund and Wieser (2011).
Potassium (K) is a volatile, lithophile, incompatible and fluid-mobile element (McDonough
and Sun 1995). It is a major cation in both seawater and river water (Pilson 2013), and is well
mixed in the ocean because of its long residence time of ~7 Myr (Li 1982). Potassium has three
isotopes, 39K, 40K and 41K (Table 1). Among them, 40K is radioactive and exhibits a branched
decay scheme to 40Ca and 40Ar, with a half-life of 1.25 × 109 years (Faure and Mensing 2005).
The stable 39K and 41K isotopes have > 5% mass difference, which can potentially lead to
large K isotope fractionations. Indeed, fractionation of K isotopes during chemical processes
has been well known and was documented as early as 1938. Taylor and Urey (1938) found
a 10% variation in 41K/39K when K was incompletely eluted by an aqueous solution from a
zeolite ion exchange column, with 39K preferentially eluted from the exchange medium. This
indicates that natural processes such as water-rock interactions could potentially fractionate
K isotopes, and generate isotopically distinct reservoirs. Humayun and Clayton (1995a,b)
found that both extraterrestrial samples (chondrites, eucrites, SNC meteorites, ureilites, and
some lunar highland and mare igneous samples) and terrestrial samples (peridotites, basalts,
granites, carbonatites, biotite schists and seawater) have similar K isotopic compositions
within ± 0.5‰, despite variable levels of volatile element depletion among those bodies.
This has been explained by vaporization under a high vapor pressure, as opposed to free
evaporation. Indeed, under such conditions, evaporation would take place in an equilibrium
rather than a kinetic regime (Richter et al. 2009 and references therein). Chondrules also
revealed limited K isotope fractionation, again suggesting that evaporation took place under
equilibrium conditions, presumably because chondrule melting and vaporization took place
when the density of chondrules was high enough for a high partial pressure of K to build up
around them (Alexander et al. 2000; Alexander and Grossman 2005).
The advent of high-resolution mass spectrometry has made it possible to measure K
isotopes with higher precision (from ± 0.1‰ to < ±0.05‰, 2SE by MC-ICPMS) (Morgan et
al. 2014; Li et al. 2016; Wang and Jacobsen 2016a,b) and TIMS (Wielandt and Bizzarro 2011;
Naumenko et al. 2013).
Stable K isotopic compositions are reported in the δ notation:
 ( 41K/ 39K) 
δ41K(‰)  41 39 sample − 1 × 1000
=
 ( K/ K)std 
where the standard (std) is either NIST SRM 3141a (Li et al. 2016) or commercial ultrapure
potassium nitrate (Wang and Jacobsen 2016a,b). There is a slight difference between these
two standards based on the same geostandard and seawater data published from these two
groups. Further studies are needed to better quantify the difference and to select one standard
for reporting high-precision K isotopic data.
To date, >1.4‰ variation in 41K/39K has been reported for terrestrial and extraterrestrial
samples (Fig. 3). Morgan et al. (2014) found 0.4‰ K isotopic variation in a diverse range of
whole rocks and mineral separates that formed at high temperatures, which is 10 times greater
than the analytical uncertainty of < ±0.05‰ (2SE). Wang and Jacobsen (2016a,b) found that
Plant
Seawater
Sylvite
Igneous rock
Tectite
Moon
Chondrite
-1.5 -1.2 -0.9 -0.6 -0.3 0 0.3

δ41K (‰)
Figure 3. Natural variations in the stable K isotopic composition relative to NIST SRM 3141a. The
vertical line and shaded area represent the bulk Earth as represented by igneous rock standards, with
δ41K = 0.50 ± 0.04‰ (2SD). Data from Wang and Jacobsen (2016a,b) are normalized to NIST SRM 3141a
by subtracting 0.58. Data are from the literature (Li et al. 2016; Wang and Jacobsen 2016a,b).
seawater samples are ~ 0.6‰ heavier than terrestrial basalts whereas sylvite samples from two
evaporate deposits have heterogeneous K isotopic compositions and overall are also heavier
than basalts. Wang and Jacobsen (2016b) reported for the first time that lunar samples are
enriched in heavy K isotopes relative to the Earth and chondrites. The isotopically heavy Moon
was interpreted as a result of evaporation-driven kinetic K isotope fractionation during the
Moon-forming giant impact. Li et al. (2016) documented the largest K isotopic variation in
natural samples, with δ41K (relative to NIST SRM 3141a) ranging from − 1.3 in plants to ~ 0‰
in seawater. Though the underlying processes for large K isotopic variations require further
investigation, the large fractionations make K isotope geochemistry a promising avenue for
tracing geological and biological processes.
Stable K isotope geochemistry might also play a significant role in refining the 40K–40Ar
and K–40Ca dating as these methods are based on the assumption that K isotopic composition
40
does not vary in nature to an important degree. As discussed in Naumenk et al. (2013), the
40
K/K isotopic abundance is the largest contributor to the total K–Ar age uncertainty.
Titanium isotope geochemistry
Table 2. Ti (atomic number = 22) isotopes and typical natural abundance.
46
Ti 8.25
47
Ti 7.44
48
Ti 73.72
49
Ti 5.41
50
Ti 5.18
Titanium (Ti) shares many geochemical similarities with other high field strength
elements Hf, Zr, Nb, and Ta. In particular, it has very low solubility in aqueous medium, such
that it is largely insusceptible to low temperature aqueous alteration. Titanium is also a highly
refractory element that condensed from solar nebula gas early in the condensation sequence
(Lodders 2003). For example, refractory inclusions in meteorites (also known as Calcium-
Aluminum-rich Inclusions—CAIs) contain significant amounts of Ti. In natural settings, Ti
is usually present as Ti4+ but significant amounts of Ti3+ can be present under low oxygen
fugacity conditions, such as those that prevailed during condensation of CAIs.
Titanium has 5 stable isotopes, 46Ti, 47Ti, 48Ti, 49Ti and 50Ti (Table 2). In meteorites and
their components, significant departures from mass-dependent fractionation (i.e., isotopic
anomalies) have been documented (Dauphas and Schauble 2016). Hibonite inclusions from
CM chondrites and CAIs display large enrichments in 50Ti that correlate with anomalies in
another neutron-rich isotope, 48Ca (see Fig. 9 and its caption in Dauphas and Schauble 2016
for details). The anomalies measured in hibonite grains can reach ~2500 for ε50Ti (25%). Bulk
meteorites also display isotopic anomalies affecting primarily 50Ti but the effects are subtler,
ranging from ~−2 to +4 ε-units (Trinquier et al. 2009; Zhang et al. 2012). Zhang et al. (2012)
measured the ε50Ti value of lunar rocks and found that they were affected by cosmogenic
effects, more specifically neutron capture effects arising from interactions between galactic
cosmic rays and lunar rocks. They were able to correct for these effects by using collateral
neutron capture effects on Sm and Gd. After correction, they found that lunar and terrestrial
rocks have identical ε50Ti values within ± 0.04, despite the 6 ε-unit span of the meteorites.
This suggests that either most of the Moon came from the protoEarth or the Moon-forming
impactor had very similar isotopic composition to the Earth.
The mass-dependent Ti isotopic variations, similar to other non-traditional stable isotopes,
are also reported in the traditional δ notation. Nonetheless, no officially certified Ti isotopic
standard is available and the measurements published thus far are reported relative to a bar of
high-purity metal Ti: OL-Ti (Millet and Dauphas 2014). Millet and Dauphas (2014) showed that
different part of the OL-Ti reference material had indistinguishable Ti isotopic compositions.
Furthermore, the Ti isotopic compositions of basalts measured by a double spike technique yield
a δ49Ti value of + 0.004 ± 0.062‰, relative the OL-Ti reference material. Millet et al. (2016)
used this technique to measure a more extensive array of mantle-derived magmas and found that
they have approximately uniform isotopic compositions (variations can be found but they span
less than 0.05‰). Lunar rocks also have Ti isotopic compositions very similar to the Earth. The
Figure 4. Trend of magmatic Ti isotope fractionation in igneous rocks (modified from

Millet et al. 2016).
isotopic composition of OL-Ti is thus representative of an important geochemical reservoir. This

reference material fulfills the guidelines highlighted above and we recommend that this standard
continue to be used in future studies to facilitate inter-laboratory comparisons.
The available high-precision Ti isotopic data are still limited but suggest a great
potential for understanding magmatic differentiation (Miller et al. 2016). Millet et al. (2016)
discovered that magmatic differentiation of silicic rocks can fractionate Ti isotopes, producing
rocks that have δ49Ti values as high as ~+0.3‰ (Fig. 4). Such enrichment could reflect Ti
isotope fractionation during magmatic differentiation, possibly associated with equilibrium
fractionation between oxides (e.g., ilmenite) and melt.
Vanadium isotope geochemistry
Table 3. V (atomic number = 23) isotopes and typical natural abundance.
50
V 0.250
51
V 99.750
Vanadium (V) is a biologically active trace element with multiple redox states. The ratio
of V to another non-redox element of similar geochemical behavior (e.g., Sc) can provide
direct information on the oxygen fugacity during magmatic processes. This approach has been
used to examine the redox state of the mantle in the Archean (Canil 1997; Li and Lee 2004)
and various other settings (the source of mid-ocean ridge basalts; the sub-arc mantle; Lee et
al. 2005). The conclusion is that the redox conditions of melting did not change drastically
with time (Canil 1997; Li and Lee 2004). Similarly, there does not appear to be much spatial
heterogeneity in the present mantle (Lee et al. 2005). Those results have been questioned
recently (Kelley and Cottrell 2009; Aulbach and Stagno 2016) and it is important to develop
new proxies of the redox condition of Earth’s mantle. Vanadium isotope fractionation could
provide clues on that. Indeed, it has been shown that in magmas and minerals relevant to
mantle petrology, significant isotope fractionation was present between the two redox states of
iron (Dauphas et al. 2014; Roskosz et al. 2015). Similar equilibrium isotope fractionation may
be present for V between for example V4 + and V5+.
Not much work has been done on V isotope geochemistry because it possesses only two
stable isotopes, 50V and 51V (Table 3), so a double spike technique cannot be applied and
quantitative recovery is required during purification. This element is also not straightforward
to purify from other elements. An additional complication arises from the fact that there is a
large contrast between the abundances of 51V and 50V (51V/50V = ~400), so that it is difficult
to measure its isotopic composition by mass spectrometry. Nielsen et al. (2011) addressed
those difficulties and designed a protocol to measure the V isotopic composition of natural
rocks. Prytulak et al. (2011) applied this technique to the analysis of igneous geostandards
PCC-1, BHVO-2, BCR-2, BIR-1a, GSP-2, and AGV-2 as well as the Allende chondrite and
found ~1.2‰ isotopic variation. A later comprehensive study of 64 mafic and ultramafic rocks
revealed 1.6‰ V isotopic variation, and yielded a silicate Earth δ51V value of − 0.7 ± 0.2‰,
where the reference material is a pure V solution distributed by Alfa Aesar (Prytulak et al. 2013).
In this δ reference frame, all samples measured so far have markedly negative values. Nielsen
et al. (2014) measured the V isotopic composition of meteorites (various chondrites, some HED
meteorites, and one martian meteorite). They found that those meteorites have a δ51V value of
around − 1.7‰, meaning that they are lower than the terrestrial composition by 1‰. The cause
for this shift is uncertain but could be related to irradiation from the young Sun, which can
produce enrichments in 50V relative to 51V (i.e., it can shift δ51V towards lower values).
More recently, Wu et al. (2015) calculated V isotope fractionation factors using first-
principle techniques for V species in solution or adsorbed on goethite surface. They suggested
that V isotopes could record past redox conditions in seawater. Wu et al. (2016) reported on a new
measurement protocol for V isotopes that yields a precision of better than ± 0.1 ‰. Schuth et al.
(2016) presented measurements by femtosecond laser ablation MC-ICPMS of V-rich minerals
and found a range in 51V/50V of ~1.5‰. Overall, V isotopes show a lot of promise as a tracer of
metabolic pathways as well as redox conditions in the mantle and possibly in the ocean.
Stable rubidium isotope geochemistry
Table 4. Rb (atomic number = 37) isotopes and typical natural abundance.
85
Rb 72.17
87
Rb 27.83
Rubidium (Rb), similar to K, belongs to the alkali metal group and is a volatile, lithophile,
incompatible, and fluid-mobile element. Rb has two isotopes, 87Rb and 85Rb (Table 4). Between
them, 85Rb is stable and 87Rb is radioactive and decays to 87Sr, with a half-life of 48.8 billion
years (Faure and Mensing 2005). In 87Rb–87Sr dating, the isotopic composition of Rb is often
measured to determine the concentration of Rb in the rocks or minerals by isotope dilution but
the demand on the precision of those isotopic analyses is not very stringent because other sources
of error contribute to the overall error (Waight et al. 2002). To date, high precision Rb isotopic
measurements in the literature are still limited. This is presumably due to two difficulties.
One is that Rb behaves very similarly to K during most chromatography procedures, so that
separating the two can be difficult. The second difficulty is that Rb possesses only two stable
isotopes, so that high yield is needed to avoid isotope fractionationation during purification.
Achieving both requirements (effective separation from K and high yield) is difficult. Nebel
et al. (2005) developed a protocol to purify Rb and analyzed its isotopic composition. The
publication does not give details on the degree of separation between Rb and K, other than
after processing the K/Rb ratio is < 5. The isotopic analyses are corrected for instrumental
mass bias using Zr doping and the precision of the analyses is on the order of ± 0.5‰. Nebel et
al. (2011) applied this technique to the Rb isotopic analysis of chondrites and found that if any,
the isotopic variations were limited to ±1‰ around the terrestrial value. Rb is significantly
more volatile than K but improvements in precision are needed to tell whether its isotopic
composition was affected by vaporization in the solar system.
Stable strontium isotope geochemistry
Table 5. Sr (atomic number = 38) isotopes and typical natural abundance.
84
Sr 0.56
86
Sr 9.86
87
Sr 7.00
88
Sr 82.58
Strontium (Sr) is an alkaline earth element, with four isotopes (Table 5). Of them, 87Sr
is the decay product of 87Rb, with a half-life of 48.8 billion years (Faure and Mensing 2005).
The 87Rb–87Sr decay scheme has been extensively used as a chronometer and fingerprint of
mantle source regions (Faure and Powell 1972; Faure and Mensing 2005). Because of the
small relative mass difference, the stable Sr isotope ratios are often treated as invariable,
with 88Sr/86Sr = 8.375209. This value has been used to calibrate instrumental fractionations
for high-precision Sr isotopic analyses.
With the developments in high precision mass spectrometry using MC-ICPMS and TIMS,
significant stable isotope fractionation has been found for Sr in natural samples. The large
fractionation has important implications for the measurement and application of radiogenic Sr
isotopes, as well as great potential to trace various geological processes.
Stable Sr isotopic compositions are often reported in the δ notation:
 (88Sr/ 86Sr) 
δ88Sr(‰)  88 86 sample − 1 × 1000
=
 ( Sr/ Sr)std 
where the standard (std) is the NIST SRM 987.

Sable Sr isotopic compositions have been measured on both TIMS and MC-ICPMS.
Double spike methods are usually used for TIMS (DS-TIMS) (Krabbenhoft et al. 2009;
Shalev et al. 2013) and some MC-ICPMS (Shalev et al. 2013), though more MC-ICPMS
protocols have adopted the standard-sample bracketing method (SSB-MC-ICPMS) (Fietzke
and Eisenhauer 2006; Moynier et al. 2010; Charlier et al. 2012; Ma et al. 2013a). In general,
the DS-TIMS yield the highest precision and accuracy (±0.02 for δ88Sr, 1SD), followed by
DS-MC-ICPMS and SSB-MC-ICPMS. To date, significant stable Sr isotope fractionation has
been observed for both high-T and low-T geological processes, with the overall variation in
δ88Sr greater than 1.1‰ in terrestrial materials (Fig. 5).
Plant
Seawater
Fresh water
Barite
Biogenic
carbonate Abiogenic
carbonate
Serpentinite
Sediment
Igneous
rock
Mars
Moon
Achondrite
Chondrite
Allende matrix
CAI & chondrule
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8

δ88Sr (‰)
Figure 5. Natural variations in the stable Sr isotopic composition relative to the standard SRM987. The
δ88Sr range of CAI and chondrule extends down to −1.73‰. The vertical line and shaded area represent the
mantle, with δ88Sr = 0.29 ± 0.07‰ (2SD) (Charlier et al. 2012). Data are from literature (Fietzke and Eisen-
hauer 2006; Halicz et al. 2008; Ohno et al. 2008; Ruggeberg et al. 2008; de Souza et al. 2010; Krabbenhoft
et al. 2010; Moynier et al. 2010; Bohm et al. 2012; Charlier et al. 2012; Ma et al. 2013a; Raddatz et al.
2013; Wei et al. 2013; Stevenson et al. 2014, 2016; Vollstaedt et al. 2014; Widanagamage et al. 2014, 2015).
Studies of extraterrestrial and terrestrial materials reveal significant Sr isotope fractionation.

Chondrites have heterogeneous Sr isotopic compositions, with d88Sr ranging from +0.12 to
+0.35‰, reflecting the mixing of different proportions of isotopically light CAIs and chondrules
with the isotopically heavy matrix materials during nebular processes (Moynier et al. 2010;
Charlier et al. 2012). The terrestrial mantle has an average d88Sr value of +0.29 ± 0.07‰ (2SD),
similar to carbonaceous chondrites, angrites, eucrites and martian meteorites (Moynier et al.
2010; Charlier et al. 2012). By contrast, differentiated igneous rocks from the Earth and Moon
have light Sr isotopic compositions, likely resulting from the crystallization of isotopically
heavy plagioclase during magmatic differentiation (Charlier et al. 2012).
Large stable Sr isotopic variation has also been observed in biogenic and inorganic
carbonates (Fietzke and Eisenhauer 2006; Ruggeberg et al. 2008; Krabbenhoft et al. 2010;
Bohm et al. 2012; Raddatz et al. 2013; Stevenson et al. 2014; Vollstaedt et al. 2014), barite
precipitation (Widanagamage et al. 2014; 2015) and weathered residues (Halicz et al. 2008; de
Souza et al. 2010; Krabbenhoft et al. 2010; Wei et al. 2013; Stevenson et al. 2016), indicating
the potential of using Sr isotopes as a tracer of continental weathering, marine Sr cycle, and
paleoceanographic studies. In general, carbonates tend to have light Sr isotopic compositions
relative to seawater, which has a homogenous d88Sr of 0.387 ± 0.002‰ (2SE mean) (Shalev
et al. 2013). The large Sr isotope fractionation correlates with factors such as growth rate and
temperature (e.g., Ruggeberg et al. 2008; Bohm et al. 2012; Stevenson et al. 2014). River waters
draining carbonates and silicates tend to have distinct Sr isotopic compositions, reflecting the
control of source lithologies (isotopically light carbonates vs. heavy silicates) (e.g., Wei et al.
2013). Stable Sr isotopes have also been used in archaeology for paleodietary studies, as there
are systematic mass-dependent variations with increasing trophic level (Knudson et al. 2010).
Cadmium isotope geochemistry
Table 6. Cd (atomic number = 48) isotopes and typical natural abundance.

106
Cd 1.25
108
Cd 0.89
110
Cd 12.49
111
Cd 12.80
112
Cd 24.13
113
Cd 12.22
114
Cd 28.73
116
Cd 7.49
Cadmium (Cd) is a highly volatile, chalcophile, moderately incompatible and biologically

active trace element with a single oxidation state (Cd2+) in the Earth (McDonough and Sun
1995). Cadmium, together with Hg and Zn, belongs to the group-IIB element, and is toxic and
widely distributed in the hydrosphere, biosphere, crust, mantle and extraterrestrial rocks. Cd
has eight stable isotopes (Table 6), with a large (>9%) relative mass difference, which could
lead to large mass-dependent isotope fractionation.
Stable Cd isotopic compositions are reported in either d notation:
 ( Cd/ Cd)sample 
114 x
=
δ114/x Cd(‰)  114 x
− 1 × 1000
 ( Cd/ Cd)std 
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"Well," said Louise, laughing, "it is true; I cannot get away from her; her life
seems so forlorn, somehow. I can't help being sorry for her. She is losing her
girlhood almost before it is time for it to bloom. I have been wondering and
wondering all day what there was that we could do for her; and I find the real
life being worked out before our eyes so engrossing, that it is hard to come
back to the dead lives of Shakespeare."
Her husband closed the book, putting his finger between the leaves to mark
the place.
"I have studied that problem somewhat, Louise," he said earnestly, "in the
days gone by. I didn't succeed in making much of it. It is true, as you say, that
she is slipping away from girlhood, almost without knowing that she has been
a girl. Sometimes I think that she will have only two experiences of life—
childhood and old womanhood. Mother cannot realize that she is yet any more
than a child, to be governed, and to obey; and one of these mornings it will be
discovered that she is no longer a child, but has passed middle life. Her future
looks somewhat dreary to me, I confess."
"We must not let it grow dreary," Louise said, with a determined tone, and a
positive setting of her small foot—a curious habit that she had when very
much in earnest. "What sense is there in it? She is young, and in good health,
and has a sound brain; why should she not make her life what it ought to be?
Why shouldn't we help her in a hundred ways?"
"Yes; but come down to actual, practical truth. What is there that she can do
for herself, or that we can do for her? You see, Louise, our family is peculiar;
there is no use in shutting one's eyes to that fact. It is not because father is a
farmer that we find ourselves situated just as we are; other farmers have very
different experiences. We are surrounded on all sides with men who get their
living by cultivating the fields, whose sons and daughters are in college, or
seminary, and in society, and who, in every way, take as good a position, and
have as many advantages, as town-bred people—at the expense, it is true, of
some inconvenience and special labour. Of course, it is also true that some of
the sons and daughters do not choose to accept all the advantages for
cultivation; and equally, of course, there are some who are unable to furnish
the means for what they would like their children to enjoy; but no greater
proportion of that class in the country than in town, I think. My father does not
belong to any of these classes; he is, as I said, peculiar."
At this point both husband and wife stopped to laugh over the associations
connected with that word "peculiar;" it bringing to the minds of both reminders
of Gough and Dickens, as well as many more common characters which
those two geniuses have caricatured.
"It is true, nevertheless," Lewis said, the laugh over. "Let me see if I can
explain. In the first place, both father and mother had, in their youth, lives of
grinding toil and poverty. Both were shrewd, clear-headed people, with, I think,
much more than the average share of brains. The result is that, despite
drawbacks and privations, they made their way, acquiring, not thorough
educations, it is true, but a very fair degree of knowledge on all practical
subjects. The amount of information which my mother, for instance, possesses
about matters concerning which she would be supposed to know nothing
would surprise you. Perhaps the result of all this is natural; anyhow, it is
evident. They believe that the rubbing process is decidedly the best way to
secure education or anything else needed in this world. If one makes his way
in spite of obstacles, they believe it is because the grit is in him, and must find
its end."
"Had Dorothy, for instance, pushed her determination to attend school in town,
and get a thorough education; pushed it persistently—what you would call
doggedly—against argument and opposition, and everything but absolute
command—she would have won the prize, and both father and mother would
have, in a certain sense, respected her more than they do now. But Dorothy
was not of that mould. She wanted to go on with her studies. Had everything
been smooth before her, she would, doubtless, have gone on, and made a fair
scholar; but to stem a current, with so much against her, required more effort
of a certain kind than she knew how to make."
"I conclude," said his wife, smiling brightly on him, "that you were one of those
who can push persistently."
He answered her smile, partly with a laugh, and partly with a shrug of his
handsome shoulders.
"I did push—most vehemently some of the time; worked my way part of the
time besides, as you know; but in the end I gained. Both father and mother
have a degree of pride in my persistence; it reminds them of their own rugged
natures."
"I wonder that Dorothy, crossed in her natural ambitions, did not run into the
extremes, on the question of dress and society, and, well—and aimless going
generally, without regard to quality or consequence. That is the rock on which
so many girls shipwreck."
"I think she would have done just that thing had she been given opportunity. I
think it is what both my father and mother were afraid of. It has made them
draw the reins of family government very tightly. They simply commanded that
singing-schools, and country school debating societies, and social gatherings,
should be ignored. We were all under that command; so that the consequence
is, we are almost as isolated from our neighbours as though we had none. My
mother did not feel the need of society. She could not understand why any
one should feel that need; consequently, she has no society. There are good
and pleasant people around us, people whom it would be a pleasure to you to
meet; but they never come near us, because we have, as a family, given them
to understand that we have nothing to do with common humanity."
"What a strange idea! Do you know, I have wondered why it was that your
neighbours didn't call on me? I thought it must be that they had a
preconceived dislike for me, somehow."
"They have a preconceived belief that you will not care to see them. You
would be amused to see how this withdrawal from all friendships has been
translated. If father were a poor man, having a struggle to get along, it would
be set down as a dislike to mingling with those who were better off in this
world's goods than ourselves; but with his farm stretching before their eyes in
so many smiling acres, and with his barns the finest and best stocked in the
neighbourhood, we are looked upon as a family too aristocratic to mingle with
country people; which is simply funny, when you take into consideration the
fact that we have never been other than country people ourselves, and that
we live much more plainly than any of our neighbours. But you can readily see
the effect on Dorothy; she has, in a degree, dropped out of life. The
occasional going to church on a pleasant Sunday, and going to market with
mother when both can, on rare occasions, be spared from home, being her
two excitements. She has hardly a speaking acquaintance with the
neighbours about us, and no associates whatever."
"Poor girl!" said Louise, and there was more than compassion in her voice;
there was a curious undertone of determination, which made her husband
smile, and wonder what this little woman, in whose capabilities he thoroughly
believed, would do.
"Haven't I established the validity of our claim to being 'peculiar'?" he asked

her.
"I should think you had! What has been the effect of the 'peculiarities' on
John?"
Her husband's face instantly sobered, and there was a note of pain in his
voice.
"John has broken loose from the restraints in a degree—in a painful degree.
He has made his own associates; and they are of a kind that he wouldn't care
to bring home, if he had an opportunity. He is away very frequently of
evenings, it is difficult to tell where; but the daily decrease of anything like
manliness attests the unfortunate result. I am more than suspicious that he is
learning to drink something stronger than cider; and I am sure that he
occasionally, at least, smokes—two vices that are my father's horror. He looks
on with apparently mingled feelings of anger and dismay. His pet theories of
family government have failed. He honestly desired to shield his children from
evil influences; he is comparatively satisfied with the result both in Dorothy's
case and mine. He doesn't know what to think of John. He has spells of great
harshness and severity connected with him, thwarting everything that he
undertakes in what must seem to John an utterly unreasonable way; and yet I
believe it is done with a sore heart, and with an anxious desire for his good.
And when my mother's face is most immovable, I have learned to know that
she is trying to quiet the frightened beatings of her heart over the wrong-
doings of her youngest boy."
"Lewis," his wife said, interrupting the next word, and with intense earnestness
and solemnity in her voice, "we must save John for Christ, and his father and
mother."
"Amen. But how, dear, how?"
"Lewis, let's go right downstairs. They are all at home; I noticed it as I came
through the room; and they look so gloomy. Why shouldn't we all have a
pleasant evening together? Did you ever read anything to them? I thought not.
Now, don't you know they can't help enjoying your reading? I mean to try it
right away."
"Read Shakespeare?" her husband asked dryly, albeit there was also dismay
in his voice. To talk earnestly over a state of things, to wish that all was
different, was one thing; and to plunge right into the midst of existing things,
and try to make them differ, was quite another. His wife answered his question
with a bright little laugh.
"No, I don't believe they would enjoy Shakespeare yet, though I am by no

means sure that we can't have some good readings from him some time. But
let me see; I have a book that I am certain they will all like. You never read it,
and you ought to; it is worth any one's while to read it." And she let fall spool
and scissors, and went in eagerness to the old-fashioned swinging-shelves,
where she had arranged some of her favourite books, selecting one from
among them. "Here it is," she said; "Estelle and I enjoyed this book
wonderfully; so did papa. We read it while mamma was away one winter,
when we were dreary without her. John will certainly be interested in the bear
hunt; being a boy, he can't help it; and I know mother will like to hear about
that poor mother down behind the beans."
"Behind the beans! What an extraordinary place for a mother to be! What was
she doing there?"
"Wait until you read it, my dear. You will like the book; people of good sense
always do."
"Thank you. But, Louise dear, do you think it a wise thing to try? Remember
what a disastrous failure I made on Sabbath. I don't believe I am fitted for
aggressive movements."
"I don't believe anybody but Christ knows yet whether your Sabbath effort was
all a failure, Lewis; and I don't believe that you and I have any right with the
results, if we did what we could. Besides, this is different. I know you can read.
Come."
"I can't see to read from the light of a tallow candle; I always despised them."
"We will take the lamp," she said, with a defiant little nod of her head toward
the pretty bronze figure that held a shapely kerosene lamp of newest pattern
and improved burner, Lewis having searched the lamp-stores over for just the
right sort of offering for his bride. "We will set it right beside mother, where it
will throw just the right angle of light on her work, and yet be shaded from her
eyes; and we will not hint, by word or glance, that she may possibly see better
than she does by her candle. Come, Lewis, carry it; it is too heavy for me. I
will bring the book and my work-basket."
"Mother despises dressing-gowns," her husband said, rising slowly, and

casting regretful looks at Shakespeare, the open fire, and his lounging-chair,
though it was neither the chair nor yet the book that held him, but a horrible
shrinking from this attempt at innovation, and an almost certainty of disastrous
failure.
"No, she doesn't; she only thinks so, because she isn't used to them, and
doesn't realize how much they save coats. I'm going to make John one for
Christmas, and a pair of slippers like those Estelle gave you last year, and she
will like them very much; you see if she doesn't. Now we're ready."
CHAPTER IX.
A NEW CHAMPION.
IF the Sunday callers to the kitchen had astonished the family group, this
descent upon them with work-basket, book, and, above all, lamp, fairly took
from them the power of utterance—at least after Dorothy's first startled
exclamation, when she retired into flushed silence.
"Lewis was going to read to me," explained Louise, in a tone intended to

convey the idea that their proceeding was the most natural and ordinary one
imaginable, "and I thought it was a pity to waste a new book on one person;
so we came down for you all to hear. May I sit by you, mother?"
Without waiting for answer, the artful daughter-in-law took her pretty bronze
lamp from her husband's hand, and, setting it in "just the right angle," drew
one of the wooden-seated chairs, and settled herself near it before the
audience had time to recover from its surprise.
"Now, Lewis, we're ready," she added, in complacent tone. She had resolved
not to venture on the doubtful question as to whether they desired to hear any
reading. If their consent was taken for granted, what could they do but listen?
Nevertheless John seemed resolved not to be taken by guile; he drew himself

up, with a shuffling noise, and was evidently making ready for flight. Her
husband telegraphed a significant glance at Louise, which said, as plainly as
words could, that encouraging sentence, "I told you so; John won't stay." But
she saw the whole, and, while her heart beat for the success of her scheme,
her voice was prompt and assured.
"O John! Have you got to go to the barn so soon? Well, never mind, we'll wait
for you. I selected this book on purpose, because I was so sure you would like
it; it is a special favourite of mine."
Thus addressed, John, who had had no intention of going to the barn, but
simply of escaping, sat down again, for very astonishment; and Lewis, who
was both amazed and amused at his wife's boldness, promptly seized the
opportunity to commence his book without further introduction.
It was nearly eight o'clock when the reading commenced, the usual hour for
the family to separate, but for an unbroken hour Lewis Morgan's voice went
steadily on. The shade of embarrassment which he felt at first speedily lost
itself in his genuine interest in the book, new to him; and perhaps he never
showed his reading powers to better advantage. Louise, to whom the story
was an old one, had leisure to watch its effect on the group, and was more
than satisfied with the hushed way in which Mother Morgan laid down her
great shears on the uncovered stand, and finally transferred them to her lap,
that their clatter might not make her lose a word; at the knitting which dropped
from Dorothy's fingers, and lay unheeded, while she, unchid by mother, fixed
what were certainly great hungry eyes on the reader, and took in every
sentence; at the unwinking eyes of Father Morgan, who did not interrupt the
hour by a single yawn; but, above all, at the gleam of intense satisfaction in
John's face when the young minister came off victor. Besides, did she, or did
she not, hear a quick, suddenly suppressed sigh coming from the mother's
heart, as she listened to the story of that other mother's wrestlings in prayer in
her closet, "down behind the beans." The loud-spoken clock, as it clanged out
the hour of nine, was the first interruption to the reading since it struck eight;
and Louise, mindful of the unwisdom of carrying her experiment too far,
hastened to change the programme.
"Why, Lewis, it is nine o'clock! It won't do to read any more."
And Lewis, who had many an evening read until ten, and occasionally until
eleven, to that other family group in the old home, looked up with obtuseness
exactly like a man, and was about to ask, "Why not?" but the warning look in
her eyes brought him back to the level of present experiences; and, despite
Dorothy's hungry eyes and John's utter stillness indicating that he was entirely
willing to hear more, the book was promptly closed.
"Well," said Farmer Morgan, drawing a long breath, "that minister in the book
was a most likely chap as ever I heard of; if more of 'em acted like that, I
should have a higher opinion of them than I do. It's a very well told story; now,
that's a fact."
"A pack of lies, the whole of it." This from Mother Morgan; not said severely,
but in a deprecatory tone, as though she felt herself obliged to say it, as a sort
of punishment for having allowed herself to become interested.
"Well, now," said Farmer Morgan, dropping his head to one side, with a
thoughtful air, "I don't know about that; there is nothing so dreadfully unlikely
about it. And that smart chap had a streak of good luck and a streak of
common sense; and I've known, myself, exactly such a family as that set of
boys, father and all, hard as they were. Whether it is lies or not, it is told
exactly as though it all might have happened. I don't object to hearing it,
anyhow. It takes up the time, though; I had no idea it was nine o'clock."
"Nine o'clock isn't late," ventured Dorothy. "Stuart's folks sit up till ten nearly
every evening; I always see a light in their front room when I go to bed."
"Yes, and they don't get up till long after daylight, and don't have breakfast
until it's almost time for dinner. I never brought my children up to habits of that
kind, thank fortune."
There was a good deal of sharpness in the mother's tone by this time. The
reaction was coming over her; she was growing vexed to think she had
allowed her heart to throb in sympathy with the trials of a mother whose
experience was only a "pack of lies," forgetting for the moment that touches of
the bitterness of that mother's experience over her youngest born had already
come to her. If only she would make the experience of prayer her own!
Louise arose promptly; she was satisfied with her experiment, and judged it
wise to beat an immediate retreat.
"Come, Lewis," she said, her hand on the pretty lamp; "if I am late to breakfast
to-morrow morning, father will think it is a bad book. Isn't that a dainty design
for a lamp-handle, mother?"
"It's a dangerous thing to carry around," the mother said grimly, meaning the
lamp, and not the handle. "I never take up the paper that I don't read about an
accident of some sort with kerosene lamps. If I could have had my way, there
should never one of them have come into this house."
"Oh, but this is a new patent; if Lewis should stumble and drop it, the light
would go instantly out. Look I just a little motion, such as, of course, the lamp
would get if it fell, and the light is gone." Suiting the action to the word, the
flame was instantly extinguished.
"There!" Lewis said, "now we are in darkness."
"I didn't mean to have it go quite out," Louise answered, laughing. "I was only
going to move it a little, to show mother. Never mind, John will get us a candle;
won't you, John?"
Thus appealed to, John arose slowly from his corner, went slowly to the high
mantel, where shone several beautifully polished candlesticks, took from the
paper-holder a paper match, applied it to his mother's candle, solemnly lighted
the other candle, and as solemnly handed it to Louise; really performing the
first act of simple courtesy for a lady that he had ever done in his life.
"Thank you," she said, quite as a matter of course; yet it was actually the first
"thank you" of his grown-up life!
There were certainly two sides to John's gruffness. Louise would have been
amazed to know how that simple "thank you" thrilled him! He looked after the
bright vision on which the stair-door closed, and had strange stirrings in his
heart, the name of which he did not know.
"If I had dared," began Louise, as soon as they were in the privacy of their
own room, "I would have substituted that big, old Bible for this book during the
last ten minutes, and asked you to read a chapter, and pray with us all. I
believe your father would have liked it. I don't believe he is as indifferent to
these things as he seems."
"It is well you don't dare," her husband said gravely; "I am afraid I should have
disappointed you. Louise, I don't believe I could have done that; it looks to me
like an almost impossible thing."
"Why, Lewis, you led at family worship at home right before papa and mamma
and Estelle; and, sometimes, when the house was full of company!"
"That was a very different thing," he answered earnestly. "I felt then that the
head of the house was in sympathy with me, and joined in the reading and the
praying. It was like a company of brothers and sisters talking together with
their father; but here it is different. My father's tendency would be to make light
of the whole thing."
"I don't believe it," she said positively. "I can't believe that he would make light
of an earnest, simple prayer, such as you would offer. It is the profession of
godliness, and an absence of the fruit that he naturally expects to see in lives,
which inclines him to ridicule. That sounds harsh, Lewis, but I don't mean
harshness. What I mean is, that he evidently expects great things of
Christians, and their lives, naturally enough, disappoint him. How do you
know, dear, but that your very silence, or reserve, toward him on these
subjects leads him to question the degree of anxiety you have for his
conversion?"
Whatever Lewis Morgan thought of this direct question he made no definite

answer, and the subject dropped.
All things considered, Louise was well pleased with the result of one evening's
sacrifice; for to give up the delightful privacy of their own room, and their own
plans, and listen to a book that she had read before, was of course somewhat
of a sacrifice. Its result elated her; she felt that her position in the family was
on a more assured footing, and looked forward to the accomplishment of other
little plans with a greater degree of certainty of success than she had felt
heretofore. What a pity that her complacent feelings should have been put to
rout through the intervention of a boiled dinner!
A victim to old-fashioned dinners of that type once explained to a novice the

method of making them after this fashion: "You take a few of everything that
grows in the garden, and dump them all together, with some slab-sided beef
and a little pork, and let them boil for hours and hours, sending a remarkable
odour through the house, which penetrates through every tightly-closed door
and window; and then serve with quarts of slush!" Whether this recipe would
be acknowledged by the lovers of such dinners or not, it exactly describes the
state of nerves with which a few people sit down to them. Now, I beg you will
not fall into the mistake of supposing my friend Louise to be an epicure, or of
being unreasonably dainty as to the food which she ate. On the contrary, if her
friends had but known it, she had the comfortable natural appetite which a
healthy condition of stomach and brain are likely to produce. She was not one
of those unhappy beings to whom the sight and smell of food which they do
not happen to like is positive torture; on the contrary, Mother Morgan might
have had a boiled dinner three days out of every week, had she chosen; and
so long as the bread-tray was piled high with generous slices of good, sweet,
home-made bread, and the butter-dish held its roll of hard, yellow, glistening
butter, and the generous-sized pitcher brimmed with creamy milk, Louise
would have made a dinner fit for a queen, in her own estimation. For when
was a healthy city maiden other than rejoiced over real country butter and
cream?
The trouble lay in the fact that poor Mother Morgan herself had nerves. Albeit
she despised the name, and considered all such matters as modern
inventions of fashionable society, it was just as surely an over-wrought and
undisciplined state of nerves which caused her to visit hard-voiced displeasure
on certain innocent tastes differing from her own, as though she had
expressed it with a burst of tears. Did you ever have for a hostess one who
accepted it as a personal insult if you declined any dish of her preparing? If
not, you are fortunate. But just such an one was Mother Morgan: Her family
had, for years and years, partaken, with a fair degree of relish, of cabbage
and turnip and potato and beets and beef and parsnips and pork, all dwelling
in friendly nearness in the same large pot. Nay, they had appreciated
sometimes in addition, little round, yellow balls, known to the initiated to be
meal balls, but tasting to the ignorant like nothing so much as sawdust wetted
up with a little pork gravy.
With a feeling nearly akin to dismay did Louise watch the lading of the plate
which she knew was intended for her. How was she ever to dispose of that
mass, which, from the unmeshed turnip down to the yellow cannon-balls, she
disliked? If she might only say, "No, thank you," and betake herself to the
inviting-looking bread and butter and milk! Why need people have nerves
leading straight to their palates, and, in this world of infinite variety, take the
trouble to be aggrieved because tastes differ? Meekly she received the well-
laden plate, meekly she sliced bits of potato and minced at the turnip, even
taking delicate nibbles of the stump of cabbage, which she detested. All to no
purpose. Mrs. Morgan was watching her with jealous eyes. What right had she
to presume to dislike so savoury a dinner? Presently her indignation found
vent in words.
"I don't see but we shall have to set a separate table for you; it seems you
can't stand the dishes we are used to. I don't want you to starve on our hands,
I'm sure."
Despite the fact that Louise had just received a letter full of tenderness from
the dear mother at home—a tenderness which made this mother a sharp
contrast—she was enabled to laugh, as she answered, pleasantly,—
"Oh, mother, I'm in no danger of starving. It seems to me that I like your bread
and butter better than any I ever tasted. I suppose I am somewhat peculiar in
my tastes; but I always find plenty to eat."
If people could see into each other's hearts, or if people could keep still when
they ought, it might yet have been well. But it chanced that life had gone awry
with the young husband that morning. A discussion had arisen between his
father and himself concerning certain farming plans, and a decided difference
of opinion had developed, during which the son expressed himself warmly and
positively; and the father, waxing indignant, had sharply informed him that
going to college and Australia, and marrying a fine lady for a wife, didn't make
a farmer. Had Lewis found a moment's leisure and privacy with his wife, and
he had spoken his thoughts, they would have been somewhat after this
fashion:
"I am discouraged with the whole thing; we never can assimilate. If it were not
for you, I should be miserable; you are the joy of my heart, and my rest." Then
Louise would have comforted and encouraged him.
As it was, believing in her wholly, and being just then desirous that she should
appear perfect in the eyes of his father, he addressed her in a disturbed, not
to say almost vexed tone, albeit it was a low one,—
"Do, Louise, pretend to eat something, whether you accomplish it or not."
Louise could never understand how it was; she had not supposed herself one
of the nervous sort; but just then and there arose such a lump in her throat,
that to have taken another mouthful would have been impossible; and, to her
dismay and chagrin, there rushed into her eyes actual tears!
Then up rose John to the emergencies of the situation.
"Why, in the name of common sense, can't you all let folks eat what they like,
without nagging at them all the time? I never touch cabbage, and won't no
more than I will touch a frog, and you let me alone; why can't you her?"
Whereupon Dorothy was so amazed, that she continued pouring milk into the
bowl long after it had brimmed, her eyes fixed, meantime, on her younger
brother's face. As for Lewis, he seemed stricken with remorse for his words,
apparently realizing at this moment how they sounded. But Louise was so
pleased with John's evident desire to champion her, and so amused that it
should seem to be necessary to shield her on a question of cabbage or not
cabbage, that the ludicrous side of the matter came uppermost, and, as she
laughed, the lump in her throat vanished.
"Thank you," she said gaily to John; "don't you like cabbage, either? I'm glad
of it. We'll form a compact to stand by each other for freedom without
cabbage."
Something approaching to a smile hovered over John's face, and Dorothy

giggled outright.
CHAPTER X.
FISHING.
SUNDAY morning dawned at last, with as bright a sunshine as ever May

produced. The air was crisp and clear, and the level road was frozen hard.
Look which way he would, Farmer Morgan would have found it hard to
produce an excuse why the family should not appear in church. To be sure, he
often said that he didn't "feel like going;" and as John wouldn't go, that had
heretofore settled the matter for the mother and Dorothy, whether they would
or not. But on this morning, Louise and Lewis came from their room evidently
dressed for the day; and Louise, with confident air, remarked—
"What a nice morning for a ride! if one didn't care for church-going, it would be
pleasant to get out to-day."
In Lewis's mind were some doubts as to who of the family could go, as the
small spring-waggon would not accommodate more than four; but Farmer
Morgan settled it by saying in positive voice—
"You'll have to go to-day, John, and drive. I've got a stiff neck, and I don't feel
like going out."
"I guess Lewis hasn't forgot how to drive," John began sullenly: "I ain't going
to church."
"You can go to church or not, just as you like, when you get down there, I
s'pose; but you will have to drive the horses, for the colt has got to go, and
she isn't used to Lewis, and I won't have him drive her. It would look more
decent to go to church, I think; but you've got so you don't care much about
decency, and I s'pose you'll do as you please.—You going, mother?"
"No!" said Mrs. Morgan promptly; "I'll get the dinner. Dorothy can go, if she
likes."
And the instant glow on Dorothy's cheek told that she "liked." Only John was
sullen; he did not recover during the entire ride; spoke only to the horses,
save when Dorothy gave little frightened jumps when the colt seemed to her
not to be moving with propriety; then the driver snappishly directed her to "sit
still and not act like a simpleton."
Arrived at the church door, he sat still, allowing Lewis to alight and wait on the
ladies.
"Let us wait for John," Louise said, as her husband turned from the waggon;
"it is nicer to all go in together."
John opened his lips, and if ever lips were going to say, "John isn't coming,"
his were; but he hesitated, looked down at the young, earnest face turned with
a confident air toward him, then turned away, snapped his whip, and said
nothing.
"You'll be here in a minute, won't you, John?"
"Yes," he said, or rather snapped, as though he was disgusted with himself for
the answer; then giving the colt a smart touch with the whip, she curveted
around the corner in a style which would surely have made Dorothy scream
had she been behind her.
"That is only a little short of a miracle," Lewis said in surprise. "I never knew
John to compromise his dignity by going to church after he had announced
that he wasn't going, and that announcement is the rule rather than the
exception."
"I felt as though he must come to church this morning, somehow," Louise
made answer in a low tone. "I couldn't give it up; it has been the burden of my
prayer all the morning."
To which remark Lewis Morgan had no reply to make; he remembered, with a

sudden sting of conscience, that he had not so much as thought of his
brother's name in prayer that morning. Reasoning upon common sense
principles, how much could he have desired his presence in the church?
It was a quiet little village church, looking natural enough to the eyes of the
usual worshippers; but what a strange feeling it gave Louise! She was
accustomed to broad, soft-carpeted aisles; richly carved and upholstered
seats; costly pulpit furnishing; massive organ, with solemn tones filling the
church. Here her feet trod on bare floors, and the old-fashioned pew, to which
she was ushered, had neither footstool nor cushion, though it was high
enough to demand the one and hard enough to suggest the other. The red
and yellow tassels, which depended from the pulpit cushion, were frayed and
faded; the sun streamed in unpleasantly from windows that boasted of neither
shades nor blinds; and there was a general air of dilapidation about
everything. She looked around with curious eyes on the congregation: their
appearance was not in keeping with the surroundings; they looked well-
dressed and well-bred, as if the most of them might have come out from
comfortable homes to spend this hour together. To all such, what a painful
contrast between the comforts and the luxuries of their own homes must the
house of God have presented; while to those who came from desolate homes,
if there were any such, what attractions did the place offer? "It isn't even
clean," the new-comer said to herself, her lip almost curling as she saw the
stray bits of paper and card scattered over the floor, and the dust lying loosely
everywhere. "If they care for the church at all, why don't they keep it in order?"
When the service commenced the feeling of discomfort was not removed. The
little choir, perched high in air away at the back of the church, would not at
that distance and height have been able to "lead the congregation," had they
been so disposed. Their voices were clear and in fair tone, and the little
parlour organ was originally sweet-voiced, but the whole was so marred by a
high-keyed, distressing squeak, that Louise found it difficult to keep back the
frowns. She bowed her head during the prayer, and succeeded in getting into
the spirit of communion; then waited eagerly for the sermon. The words of the
text rang with a suggestive thought: "The life is more than meat, and the body
more than raiment." But alas for the sermon! What was the matter with it? It
was true; it was well written and well read; it was carefully logical; it sought to
impress upon the minds of his hearers what a wonderful and glorious and
endless thing was life. And John and Dorothy, those two for whom Louise had
most anxious desire, listened—or appeared to listen—to the wonderful
possibilities of this life and the wonderful certainties of the future, and were as
indifferent to the one as the other, neither serving to lift the bored look from
their faces.
As Louise watched, and saw how little they were getting, Satan appeared to
her, suggesting to her heart that perplexing and harassing question with which
he delights to weary those who have tried: "What good," said he, "will it do to
have those two young people come to this church and listen to this sermon?
Do you believe they have gotten a single new idea or aspiration? Don't you
feel nearly certain that they will go home less impressible than they came?
Because you must remember that every presentation of the truth either helps
or hardens. Of what use were all your plans and prayers? What availed your
little thrill of thanksgiving over the success of your scheme? Don't you see it
will amount to less than nothing?" Is not it strange that the followers of Christ
will go on, year after year, bending a listening ear to Satan, while he rings the
changes of that old, long ago vanquished falsehood, "If thou be the Son of
God"? "If the Lord had cared anything about your efforts to serve him," said
the tempter on this Sunday morning, "wouldn't he have planned this whole
service differently? You believe that he could have done it; why didn't he? You
know very well that there hasn't been a thing said that would be in the least
likely to help these two persons."
What should Louise do? Here she was, in the house of God, and here was
this tempting demon at her elbow. Who was it that said, "Whoever else stays
away from church, Satan never does"? Whoever said it, the thought flashed
over this tried soul suddenly, and she bowed her head to speak a word to that
triumphant Conqueror who passed through the conflict centuries ago, and is
"able to succour them that are tempted." Did he speak again the word of
command, "Get thee hence, Satan"? Assuredly he came himself and stood
beside her, and she was enabled to remember that her part was to plant and
water as she could, the fruit thereof being God's part, and his unchangeable
"doubtless" was added to the promise of success. In the hymn and prayer that
followed heart and spirit joined, and as Louise Morgan raised her head after
the benediction, she felt that this was indeed the house of God and the gate of
heaven. He had verified his promise yet again, and met her in his temple.
Nevertheless, her first spoken words after the service would not have seemed
to many to be in keeping with the hour—
"John, what on earth is the matter with that organ?"
Despite the habitual frown on John's face, he was betrayed into a laugh, there
was so much intensity in the questioner's voice.
"Why, it needs a drop or two of oil," he said promptly; "and has needed it ever
since I can remember. Anybody would think they considered the squeak an
addition to the music, by the way they hang on to it."
"Is it possible that a little oil is all that is needed to stop that horrible sound?
Why don't you fix it?"
"I?" said John, turning full, astonished eyes on her, surprised out of his
reserve and his frowns.
"Why, certainly; how can you endure it for so long? Do, John, fix it before next
Sunday; it spoils the music. I could hardly enjoy even the words, because of
that dreadful sound. How many things there are that ought to be done here.
Why do they leave the church in this shape? Isn't there a sexton?"
"Why, yes," said John, "I suppose so. Of course there must be; he rings the
bell and makes the fires."
"But never sweeps," added Louise, smiling, "nor dusts. John, if you can
prevail on him to do some sweeping this week, I'll come down with you, when
you come to oil that organ, and do the dusting. Wouldn't that be an
improvement?"
"When you come to oil that organ!" The sentence had so strange a sound that
John repeated it to himself. Was it possible that he was coming to oil the
church organ? She spoke very confidently, quite as though it were a settled
matter. And yet he would almost as soon have expected to see himself
coming to preach the sermon! What would the people think of his going into
the church on a week day? No one remembered better than he that of late his
presence on the Sabbath had been a rarity. He had been on the verge of
telling her that he had not been hired to keep the church in order, but neither
had she been hired to dust it; and he was quick-witted enough to see that
after the dusting scheme was proposed his subterfuge would not do.
"Oh well," he said to himself, "she'll forget it. Catch me oiling the church organ!
If it groaned loud enough to be heard ten miles off I wouldn't touch it!" And he
honestly thought he would not; he had a vindictive feeling for that old organ.
This conversation had consumed much less time than it has taken me to give
it. They were passing down the aisle, John having been withheld from his
usual habit of rushing out the instant the Amen was spoken by the sudden
question that had been put to him. Now Louise turned his thoughts into
another channel. Her husband had been waylaid by a gentleman who seemed
anxious to have his opinion on some church matter; she was therefore at
leisure to fish for John.
"I don't want to go home without being introduced to the minister," she said.
"There he comes now. Will you introduce me, John?"
"I don't know him," answered John shortly. The tone added, "And I don't want
to."
"Don't you? Oh, he's a new-comer. Well, then, let's introduce ourselves."
He was just beside them now, and aided her plans, holding out his hand with
a genial "Mrs. Morgan, I believe." He was a young, bright-faced man, cheery
of voice and manner, and more winning, apparently, anywhere else than he
was in the pulpit. Louise returned his hand-clasp cordially, and hastened to
say—
"My brother, Mr. Morgan; my sister, Miss Morgan. We are all strangers
together, I believe. You have been here but a short time, I understand?"
"Why, yes," the minister said, flushing slightly—he was comparatively a new-
comer—remembering, meantime, the embarrassing fact that he had been
there quite long enough to get acquainted with that portion of his flock which
seemed to him worth cultivating. "I have not gotten out to Mr. Morgan's yet,
but I hope to do so this week. What day will you be most at leisure, Mrs.
Morgan?"
"Oh," said Louise brightly, "we shall be glad to see you at any time; suppose
you come on Tuesday," thinking, meantime, of one or two little pet schemes of
her own. "Shall we expect you to tea?—John, we would like to have him take
tea with us, wouldn't we? You haven't an engagement for Tuesday, have
you?"
Thus appealed to, what was there for John but to stammer out an answer,
over which he ruminated half the way home. Was it possible that he had
engaged to be at home on Tuesday, to meet the minister, and had actually
seconded his invitation to tea? How came he to do it? What were the words
he said? How happened he to say them? He felt very much bewildered,
somewhat vexed, and just a very trifle interested. There was certainly nothing
in the minister to like, and he did not like him; moreover, he did not mean to
like him. What was it, then, that interested him? He did not quite know. He
wondered what loophole of escape he could find for Tuesday; also he
wondered whether he really and truly was determined to escape. Altogether,
John did not understand his own state of mind.
"O Lewis," said Mrs. Morgan, just as they were nearing home, "do you
suppose anybody would object if you were to cut those dreadful-looking
yellow tassels from the pulpit and tack a neat little braid, such as upholsterers
use, around it? John and I are going down there, some day this week, to fix up
things, and you may go along and upholster the pulpit if you want to."
"John and you!"

The astonishment in her husband's voice made Louise's eyes laugh; but her
tones were steady. "Yes, he is going to stop that dreadful squeak in the organ;
isn't that terrible? It just spoiled the music, and it would have been good but
for that. I've promised to dust if there can be some sweeping done. O John,
did you speak to the sexton? No? Well, I am not sure that it is very Sunday
work; but when can you see him?"
Then Dorothy roused to the occasion—
"The sexton comes every morning to get a can of milk for some of his
customers at the village."
"Oh, does he? Then you can see him. John, you will attend to it to-morrow
morning, won't you? And have it done before Wednesday, because then the
church will be warmed for prayer-meeting, and we can get it ready more
comfortably. I wonder if those lamps don't smoke? They look as if they might."
"They used to smoke fiercely enough when I knew them last," her husband
said. "I haven't been down in the evening since I came home from Australia."
Here was certainly a revelation to Louise. Her husband had not been to the
church prayer-meeting since he came from Australia, eight months before! But
she made no comment. Dorothy, having once determined to speak, had more
to say—
"They look as though they hadn't been washed for forty years! I never saw
such black things in my life!"
"Suppose you enlist with us, Dorothy? Go down on Wednesday, and let's put
the lamps in order. We'll let Lewis buy some wicks and chimneys for his share.
I saw that two of the chimneys were broken; those two lamps will smoke, of
course."
John laughed outright.
"I believe you saw every crack and corner of the church," he said, speaking
almost good-naturedly.
And Dorothy spoke her troubled thought—
"I don't know anything about kerosene lamps. I don't suppose I could fix one
to save my life."
"I know all about them; papa used to have one in his office that I took care of,
and mamma used one for sewing. I can show you all about them in five
minutes. Will you go?"
"Well," said Dorothy, veiling her eagerness as well as she could, "I'd be willing,
but I don't believe mother will."
"Yes, she will; I'll look out for that."
It was neither Lewis nor Louise that made this startling promise, but John
himself!
"Was it quite according to Sunday observance to make all those plans?"

Louise asked her husband, smiling, but a shade of trouble, nevertheless, in
her voice. "Sometimes those things trouble me. I had Sunday plans at heart,
but I'm afraid they didn't show very plainly."
"Well, I don't know: to brighten the church, so that it shall be a more tolerable
spot, is important, certainly. It is a very desirable thing to accomplish, Louise.
But I don't see how you coaxed John into it."
"I want the church to look better, it is true," Louise said, thoughtfully; "but, after
all, that is secondary. Lewis, I want John and Dorothy."
CHAPTER XI.
GRACE SUFFICIENT.
MRS. MORGAN, senior, with her long check apron, reaching to within an inch
of the hem of her dress, her sleeves rolled to her elbow, her arms akimbo,
stood in the kitchen door, and regarded Dorothy with an air of mute
astonishment for about two minutes, then her thoughts found vent in words:—
"And did she invite him to tea her own self?"

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Non Traditional Stable Isotopes 1st

Edition Fang-Zhen Teng

Production of Platform Chemicals from Sustainable

Production of Materials from Sustainable Biomass

Food forensics : stable isotopes as a guide to

Food Forensics: Stable Isotopes as a Guide to

Ecotoxicology and genotoxicology non traditional

Non-Traditional and Advanced Machining Technologies 2nd

Ecotoxicology and Genotoxicology Non traditional

Non-Traditional and Advanced Machining Technologies:

Series Editor: Ian Swainson

FROM THE SERIES EDITOR

2 Equilibrium Fractionation of Non-traditional Isotopes:

Modeling isotopic properties of liquid phases.............................................................40

3 Equilibrium Fractionation of Non-Traditional Stable Isotopes:

4 Kinetic Fractionation of Non-Traditional Stable Isotopes

Isotopic mass dependence of diffusion in silicate melts..............................................90

5 In Situ Analysis of Non-Traditional Isotopes by SIMS and

6 Lithium Isotope Geochemistry

7 Magnesium Isotope Geochemistry

8 Silicon Isotope Geochemistry

9 Chlorine Isotope Geochemistry

10 Chromium Isotope Geochemistry

11 Iron Isotope Systematics

KINETIC AND EQUILIBRIUM FRACTIONATION FACTORS.......................................429

12 The Isotope Geochemistry of Ni

13 The Isotope Geochemistry of Zinc and Copper

14 Germanium Isotope Geochemistry

Germanium isotope systematics of hydrothermal waters...........................................639

15 Selenium Isotopes as a Biogeochemical Proxy in Deep Time

INTRODUCTION AND OVERVIEW..................................................................................657

16 Good Golly, Why Moly?

APPLICATION TO OCEAN PALEOREDOX......................................................................706

17 Recent Developments in Mercury Stable Isotope Analysis

18 Investigation and Application of Thallium Isotope Fractionation

THALLIUM ISOTOPE VARIATION IN EXTRATERRESTRIAL MATERIALS..............765

19 Uranium Isotope Fractionation

The continental crust..................................................................................................819

20 Medical Applications of Isotope Metallomics

Non-Traditional Stable Isotopes:

Figure 1. Non-traditional stable isotope systems covered in this volume.

 (26 Mg/ 24 Mg)sample 

 (26 Mg/ 24 Mg)sample 

 (26 Mg/ 24 Mg)sample 

which would read “d26Mg expressed in ‰ is equal to [(26Mg/24Mg)sample/

GUIDELINES FOR SELECTING REFERENCE MATERIALS

EMERGING ISOTOPE SYSTEMS

Stable potassium isotope geochemistry

-1.5 -1.2 -0.9 -0.6 -0.3 0 0.3

Figure 4. Trend of magmatic Ti isotope fractionation in igneous rocks (modified from

isotopic composition of OL-Ti is thus representative of an important geochemical reservoir. This

where the standard (std) is the NIST SRM 987.

CAI & chondrule

-0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8

Studies of extraterrestrial and terrestrial materials reveal significant Sr isotope fractionation.

Table 6. Cd (atomic number = 48) isotopes and typical natural abundance.

Cadmium (Cd) is a highly volatile, chalcophile, moderately incompatible and biologically

"Haven't I established the validity of our claim to being 'peculiar'?" he asked

"Amen. But how, dear, how?"

"No, I don't believe they would enjoy Shakespeare yet, though I am by no

"Mother despises dressing-gowns," her husband said, rising slowly, and

"Lewis was going to read to me," explained Louise, in a tone intended to

Nevertheless John seemed resolved not to be taken by guile; he drew himself