UNIVERSITE PARIS 7 - Denis DIDEROT UFR des Sciences Physiques de la Terre INSTITUT DE PHYSIQUE DU GLOBE DE PARIS

DOCTORAT Gochimie

Accrtion et diffrenciation des plantsimaux et des plantes telluriques: Contraintes apportes par le systme 182Hf-182W
Accretion and differentiation of planetesimals and terrestrial planets: constraints from the 182Hf-182W system

Mathieu Touboul
Thse dirige par: Bernard Bourdon

Soutenance le 19 novembre 2008 en prsence du jury compos de MM. : Max Schmidt, professeur (ETH Zrich) Prsident Francis Albarde, professeur (ENS Lyon) Rapporteur Alex Halliday, professeur (Universit dOxford) Rapporteur Jean-Louis Birck, professeur (IPGP) Examinateur Bernard Bourdon, professeur (ETH Zrich) Directeur de thse Thorsten Kleine, directeur de recherche (ETH Zrich) Directeur de thse

Front cover: Artists view of the giant impact. The hot debris ejected during this event re-accreted to form the Moon . Credit: James Garry, FastLight.

Sommaire - List of contents

Rsum-Abstract .. 11

Chapitre 1

Introduction - Introduction ..15

1.1 Introduction - Intoduction.. 17 1.2 Le chronomtre 182Hf-182W courte priode 182 Hf-182W short-lived chronometer... 19 1.2.1 1.2.2 Notations - Notations..... 20 Ages Hf-W des mtorites - Hf-W ages of meteorites... 20 1.2.2.1 1.2.2.2 1.2.2.3 1.2.3 Isochrone interne et age relatif Internal isochron and relative age..20 Calibration sur une chelle de temps absolu Calibration onto an absolute timescale...22 Temprature de fermeture du systme Closure temperature of the system..24

Datation de la differenciation plantaire Hf-W ages of planetary differentiation.......26 1.2.3.1 Systmatiques 182Hf-182W des chondrites et des objets plantaires totaux 182 Hf-182W systematics of chondrites and bulk planetary objects ... 26 Ages Hf-W de formation du noyau Hf-W ages of core formation...27 Ages Hf-W de differentiation mantellique Hf-W ages of mantle differentiation29

1.2.3.2 1.2.3.3

1.3 Contenu de la thse - Contents of the thesis..30 Rfrences - Reference.33

Chapitre 2

Techniques analytiques analytical techniques..39

2.1 Introduction - Introduction...41

2.2 Prparation des chantillons - Sample preparation......... 42 2.2.1 2.2.2 2.2.3 Roches totales - Whole rocks..... 42 Sparation magntique - Magnetic separation...42 Sparation des plagioclases danorthosites lunaires Plagioclase separation from lunar anorthosites....43

2.3 Procdures chimiques - Chemical procedures..... 43 2.3.1 2.3.2 2.3.3 Procdure sur les mtaux -Procedure for metals... 44 Procdure sur des silicates et roches totales Procedure for silicate fractions and whole rocks.. 45 Procdure particulire dveloppe pour les plagioclases danorthosites lunaires Procedure for plagioclases from lunar anorthosites. 47

2.4 Spectromtrie de masse - Mass spectrometry.. 49 2.4.1 2.4.2 2.4.3 Protocole de mesure des compositions isotopiques du W Measurements of W isotopic composition..50 Discrimination de masse instrumentale et interfrences Mass bias and interferences.......51 Reproductibilit externe et justesse des mesures External reproductibility and accuracy..... 53

2.5 Mesure de concentrations par dilution isotopique Concentration measurements by isotope dilution...... 54 2.6 Conclusions - Conclusions....56 Rfrences -References.... 57

Chapitre 3

Thermochronomtrie Hf-W des mtorites: Contraintes sur laccrtion et lvolution thermique des corps parents Thermochonometry of meteorites : Constraints on the accretion anf thermal evolution of parent bodies................. 59

3.1 Accretion and thermal history of the acapulcoite-lodranite parent body inferred from Hf-W thermochronometry. 61 3.1.1 3.1.2 Introduction.... 64 Samples and analytical techniques.65 3.1.2.1 3.1.2.2 3.1.3 3.1.4 Samples65 Analytical techniques.. 68

Results.... 70 Discussion.. 73 3.1.4.1 3.1.4.2 3.1.4.3 3.1.4.4 Hf-W isochron ages for acapulcoites and lodranites...73 Closure temperature for the Hf-W system in acapulcoites and lodranites..75 Accretion and cooling history of the acapulcoitelodranite parent body...77 Bulk Hf-W systematics of the acapulcoite-lodranite parent body nebular vs. parent body processes 82

3.1.5

Conclusions 84

References.. 87 3.2 HfW thermochronometry: Closure temperature and constraints on the accretion and cooling history of the H chondrite parent body..... 93 3.2.1 3.2.2 3.2.3 3.2.4 Introduction.... 95 Analytical methods.....96 Results.... 98 Discussion.. 99 3.2.4.1 3.2.4.2 3.2.4.3 3.2.4.4 3.2.4.5 3.2.5 Hf-W isochron ages for H chondrites. 99 Closure temperature for the Hf-W system in equilibrated H chondrites...100 Significance of the Hf-W ages...102 Constraints on the accretion and cooling history...104 Hf-W fractionation among chondrite parent materials in the solar nebula..105

Conclusions.. 105

References.... 106

Chapitre 4

Chronomtrie Hf-W de la Lune: Contraintes sur limpact gant et la cristallisation de locan magmatique lunaire Hf-W chronometry of the Moon: Constraints on the giant impact and the crystallization of the lunar magma ocean................. 109

4.1 Late formation and prolonged differentiation of the Moon inferred from W isotopes in lunar metals. 111 4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 Main text.. 112 Methods summary 121 Acknowledgements...... 122 References 122 Supplementary information..126 4.1.5.1 4.1.5.2 4.1.5.3 Lunar metals..126 Analytical methods....126 Cosmogenic effects on W isotope ratios in lunar samples.127 4.1.5.3.1 4.1.5.3.2 4.1.5.4 4.1.5.5 Correction for W isotope data obtained in this study.127 Correction of W isotope data obtained in earlier studies..129

Hf/W fractionation in the crystallizing lunar magma ocean.131 Supplementary references..132

4.2

Hf-182W systematics of ferroan anorthosites and the lifetime of the lunar magma ocean..135 4.2.1 4.2.3 4.2.4 Introduction ................................................................................. 137 Results ......................................................................................... 141 Discussion.................................................................................... 144 4.2.4.1 4.2.4.2 4.2.5 Tungsten isotope homogeneity in the Moon ................ 144 Duration of magma ocean solidification ...................... 146 4.2.2 Samples and analytical methods.................................................. 139

182

Conclusions...... 148

References 148

4.3

Early differentiation of the Earth and the Moon....151 4.3.1 4.3.2 Introduction ................................................................................. 153 New constraints on the age of the Moon and termination of Earth accretion......................................................................... 154 4.3.2.1 New 182W data and chronological implications............ 154 4.3.2.1.1 4.3.2.1.2 4.3.2.1.3 4.3.2.2 New 182W data and lunar mantle evolution ... 157 Exploring scenarios for Moon-Earth equilibration following the giant impact.. ..... 160 Isotope equilibration of Earth and Moon after the Giant impact ................................... 163

Chronology of terrestrial accretion and astronomical implications. ........................................................... 166 The Age of Early Earth differentiation......................... 168 The Nd isotope composition of terrestrial planets........ 171

4.3.3 Constraints on the early differentiation of the Earth ... 168 4.3.3.1 4.3.3.2 4.3.4

Conclusions ................................................................................. 178

References ............................................................................................... 179

Chapitre 5

Conclusions et perspectives - Conclusions and outlooks...185

Appendice 1 Systmatiques Hf-W des eucrites cumulats et la chronologie du corps parent des eucrites Hf- W systematics of cumulate eucrites and the chronology of the eucrite parent body....195 A1.1 Introduction .......................................................................................... 197 A1.2 Samples and analytical methods........................................................... 197 A1.3 Results .................................................................................................. 197 A1.4 Discussion............................................................................................. 198 A1.4.1 Evidence of W contamination in eucrites and chronological implications ................................................................................. 198 A1.4.2 Chronology of the eucrite parent body ........................................ 198 A1.4.3 Origin of cumulate eucrites ......................................................... 198 A1.5 Conclusions .......................................................................................... 198 References ..................................................................................................... 198

Appendice 2 Chronomtrie Hf-W: Accrtion et volution prcoce des astrodes et des plantes telluriques Hf-W chronometry and accretion and evolution of asteroids and terrestrial planets...........199 Abstract . 201 A2.1 Introduction .......................................................................................... 203 A2.2 The 182Hf-182W chronometer ................................................................ 204 A2.2.1 Hf-W fractionation during planetary differentiation and in meteorites .................................................................................... 204 A2.2.2 Notation and Hf-W isotope systematics ...................................... 206 A2.2.3 Reference parameters for Hf-W chronology ............................... 208 A2.2.3.1 A2.2.3.2 A2.2.3.3 Hf-W systematics of chondrites ................................... 208 Initial 182Hf/180Hf and 182W/184W of CAIs.................... 209 Calibration of the 182Hf-182W chronometer and conversion to absolute ages............................................................. 211

A2.2.4 Closure temperature of the Hf-W system .................................... 212 A2.3 Timescales for the accretion and early evolution of planetesimals ...... 213 A2.3.1 Iron meteorites - remnants of the first planetesimals .................. 213 A2.3.2 Chronology of IAB-IIICD iron meteorites.................................. 216 A2.3.3 Chronology of the eucrite parent body ........................................ 218 A2.3.3.1 A2.3.3.2 Accretion and primordial differentiation...................... 218 Magmatism and thermal metamorphism ...................... 219

A2.3.4 Timing of magmatism on the angrite and mesosiderite parent bodies........................................................................................... 221 A2.3.5 Chronology of the H chondrite parent body................................ 222 A2.3.6 Planetesimal accretion and evolution - the dominant role of 26Al heating ........................................................................................ 224 A2.4 Timescales for core formation and early mantle differentiation in Mars A2.4.1 182W-142Nd systematics of the Martian mantle ............................ 226 A2.4.2 Age of the Martian core............................................................... 228 A2.4.3 Early mantle differentiation in Mars ........................................... 229 A2.5 Hf-W chronometry of the Moon........................................................... 230 A2.5.1 Cosmogenic vs. radiogenic 182W in lunar samples...................... 231 A2.5.2 Lifetime of the lunar magma ocean............................................. 233

A2.6 Timescales for accretion and differentiation of Earth .......................... 235 A2.6.1 Models of core formation and metal-silicate equilibration ......... 235 A2.6.2 Hf-W systematics in continuous core formation models............. 239 A2.6.3 Tungsten model age for the Moon-forming impact..................... 243 A2.6.4 Early mantle differentiation and implications of a non-chondritic bulk Earth .................................................................................... 244 A2.7 Conclusions .......................................................................................... 246 References ..................................................................................................... 248 Figure captions .............................................................................................. 257 Tables..261 Figures ........................................................................................................... 267 Remerciements - Acknowledgments.... 289

10

RESUME Le chronomtre courte priode

182

Hf-182W (T1/2 = 8,9 Ma) est un instrument

puissant dinvestigation de lvolution du systme solaire primitif. Hf et W sont des lments rfractaires et sont supposs tre prsents en abondances chondritiques dans les objets du systme solaire. Toutefois, le W est un lment modrment sidrophile et trs incompatible tandis que lHf est strictement lithophile et galement incompatible mais un degr moindre puisquil est prfrentiellement incorpor dans lilmnite et le clinopyroxene. Ces diffrences de proprits gochimiques permettent une application varie de ce chronomtre, notamment pour contraindre les chelles de temps de laccrtion, du mtamorphisme thermique et de la differentiation des plantes et des plantsimaux. Les isochrones internes ralises sur les acapulcoites, les lodranites et les chondrites H5 et H6 conduisent des ges Hf-W de 5,1 0,9, 5,6 1,0, 5,9 0,9 Ma et 9,6 1,0 Ma aprs la formation des CAI respectivement. Des simulations numriques de la diffusion du W montrent que les tempratures de fermeture du systme Hf-W dans ces diffrentes mtorites sont proches des tempratures maximales atteintes lors du pic thermique du mtamorphisme affectant leurs corps parents. La connaissance de lvolution thermique haute temprature de ces plantsimaux, en conjonction avec un modle thermique de refroidissement dobjets chauffs par la dsintgration de l26Al, permet de dfinir avec plus de prcision leur ge daccrtion. La squence chronologique ainsi obtenue rvle que laccrtion du corps parent des chondrites H (entre 2 et 4 Ma aprs la formation du systme solaire) est plus rcente que celle du corps parent des acapulcoites et des lodranites (entre 1,5 et 2 Ma aprs la formation du systme solaire), elle-mme postrieure laccrtion des plantsimaux diffrencis (moins d1 Ma la formation du systme solaire). Elle suggre que le degr de diffrenciation des plantsimaux est essentiellement contrl par labondance de
26

Al incorpor lors

laccrtion donc par leur temps daccrtion et que le chauffage par impacts na jou quun rle secondaire. Nos rsultats montrent galement que les corps parents des chondrites H et des acapulcoites-lodranites ont des rapports Hf/W similaires (0,63 0,20) mais significativement infrieurs au rapport Hf/W des chondrites carbones (1,21 0,06). 11

Cette diffrence, inattendue pour des lments rfractaires, rvle un fractionnement HfW au cours des deux premiers Ma du systme solaire qui pourrait tre produit lors de processus au sein de la nbuleuse avant ou durant laccrtion des plantsimaux. Contrairement aux rsultats des tudes prcdentes, nos nouvelles donnes isotopiques du W obtenues pour une srie de mtaux lunaires et deux anorthosites lunaires montrent que les produits de la cristallisation de locan magmatique lunaire ont tous une composition isotopique identique, dont la valeur est similaire celle du manteau terrestre. Nous avons montr que les anomalies de
182

W rapportes prcdmment sont

182

dorigine cosmognique, et sont gnres par la production de

W partir de

181

Ta par

capture neutronique, lie lintense exposition de la surface lunaire aux rayonnements cosmiques. En revanche, les compositions isotopiques dtermines dans notre tude sont dpourvues de composant cosmognique : les fractions de mtaux lunaires obtenues sont suffisamment pures et ne contiennent pas de tantale; les anorthosites slectionnes ont des ges dexposition trs jeunes (< 2 Ma) et des fractions pures de plagioclases en ont t extraites. La mise en vidence de signatures isotopiques identiques dans les produits de locan magmatique lunaire en dpit de leurs rapports Hf/W diffrents conduit une rvision importante de lge Hf-W de diffrenciation de la Lune : prdemment estim ~30Ma (Kleine et al., 2005), celle-ci est en ralit intervenue plus de 60Ma aprs la formation du systme solaire. De plus, la similarit des compositions isotopiques des manteaux terrestre et lunaire indiquent que la formation de la Lune a d avoir lieu le plus
10 vraisemblablement 62+ 90 Ma aprs la formation du systme solaire et suggre une

rquilibration des isotopes du tungstne entre locan magmatique terrestre et le disque proto-lunaire. Limpact gant son origine tant le dernier vnement majeur de laccrtion terrestre, cet ge correspond lge de la fin de laccrtion de la Terre. En accord avec les prdictions des modles dynamiques, il constitue, lheure actuelle, la meilleure estimation du temps qui a t ncessaire pour voluer dun disque de poussires et de gaz un systme plantaire. Mots cls :
182 182

Hf,

W, radioactivit teinte, chronometrie, systme solaire primitif,

plantsimal, plante, Lune, mtorite, accrtion, diffrenciation, impact gant, ocan de magma, quilibration isotopique, ge de la Terre.

12

ABSTRACT
182

The short lived

Hf-182W chronometer (T1/2 = 8.9 Ma) is a powerful tool for

investigating the evolution of the early solar system. Hf and W are refractory elements and are supposed to be present in chondritic abundances in the solar system objects. However, W is a moderately siderophile and very incompatible, while Hf is strictly lithophile and also incompatible but to a lesser degree than W, because it is preferentially incorporated in ilmenite and clinopyroxene. These differences in geochemical properties allow to widely apply Hf-W chronometry, in particular to constrain the timescales of accretion, thermal metamorphism and differentiation of planets and planetesimals. The internal isochrons for acapulcoites, lodranites and H5 and H6 chondrites lead to Hf-W ages of 5.1 0.9, 5.6 1.0, 5.9 0.9 Ma and 9.6 1.0 Ma after the formation of CAI respectively. Numerical simulations of the diffusion of W show that the closure temperatures of the Hf-W system in these meteorites are close to the maximum temperatures reached during the peak of thermal metamorphism, affecting their parent bodies. The knowledge of thermal evolution at high temperature for those planetesimals, in conjunction with a thermal model of cooling objects, initially heated by the decay of
26

Al, allows a more precise determination the accretion ages of these bodies. The

obtained chronological sequence shows that the accretion of the H chondrite parent body (between 2 and 4 Ma after the formation of the solar system) is more recent than that of the acapulcoite-lodranite parent body (between 1.5 and 2 Ma after solar system formation), which occurred after the accretion of differentiated planetesimals (less than 1 Ma after solar system formation). This sequence of events suggests that the degree of differentiation of planetesimals is mainly controlled by the abundance of
26

Al

incorporated during accretion and, therefore, by their accretion time and that impact heating has played a secondary role. Our results also show that the H chondrite and acapulcoite-lodranite parent bodies have similar Hf/W ratio (0.63 0.20), which is 13

significantly lower than the Hf/W ratio of carbonaceous chondrites (1.21 0.06). This difference, unexpected for refractory elements, reveals an early Hf-W fractionation during the first two million years of solar system, which could be produced during solar nebula processes before or during the accretion of planetesimals. Our new W isotope data obtained for a series of lunar metals and two lunar anorthosites show that the products of lunar magma ocean crystallization all have an identical W isotopic composition, which is similar to the composition of the Earth's mantle, in contrast with what has been reported in earlier studies. We have shown that previously reported production of
182 182

W anomalies have a cosmogenic origin and are generated by the

W from 181Ta via neutron capture due to the intense exposure to cosmic

rays at the lunar surface. In contrast, the W isotope compositions determined in this study do not contain any cosmogenic component: the lunar metals obtained here are sufficiently pure and contain no tantalum, the selected anorthosites have very young exposure ages (<2 Ma) and the extracted plagioclase fractions are pure. The identification of identical isotopic signatures among the products of the lunar magma ocean in spite of different Hf/W ratios yields a significant revision of lunar differentiation Hf-W ages from ~30 Ma to more than ~60Ma after the formation of the solar system. In addition, the similarity of W isotope compositions of lunar and terrestrial mantles indicates that the formation of the
10 Moon most likely occured 62+ 90 Ma after the formation of the solar system and suggests

an equilibration of W isotopes between the terrestrial magma ocean and the proto-lunar disk in the aftermath of the giant impact. The giant impact being the last major event of terrestrial accretion, its age is the age of the termination of the Earths accretion. Consistently with the predictions of dynamic models, this age is, at present, the best estimate of the time necessary for the solar system to evolve from a disk of dust and gas to a planetary system. Keywords :
182 182

Hf,

W, extinct radionuclide, chronometry, early solar system,

planetesimal, planet, Moon, meteorite, accretion, differentiation, giant impact, magma ocean, isotope equilibration, age of the Earth.

14

Chapitre 1

Introduction

15

16

1.1 Introduction Les mtorites, fragments dastrodes, et les chantillons disponibles de Mars, de la Lune et de la Terre constituent des tmoins uniques de lvolution du sytme solaire primitif. Les tudes isotopiques entreprises sur ces objets permettent de prciser notre connaissance des processus rgissant lvolution du systme solaire primitif, en conjonction avec les observations astronomiques et les simulations thoriques. Plus particulirement, ltude des isotopes radiogniques, dont labondance relative volue ou a volu avec le temps du fait de leur production par dsintgration radioactive, fournissent les contraintes les plus robustes sur les chelles de temps et la chronologie de ces processus. Elles ont notamment permis lidentification des objets les plus vieux du systme solaire, les inclusions rfractaires riches en calcium et en aluminium (CAI) parmi les composants des mtorites. Ces condensats de haute temprature constituent les premiers solides forms lors du refroidissement du gaz nbulaire aprs que la contraction de la nbuleuse pr-solaire, initiallement froide, ait entran son chauffement et la formation du soleil en son centre. Bien que leur ge exact fasse toujours dbat, les datations par les isotopes du Pb conduisent des ges absolus de 4568,50,5 Ma (Bouvier et al., 2005) et 4567,110,16 Ma (Amelin et al., 2002; Amelin et al., 2006) et constituent lheure actuelle la meilleure estimation de lge minimum du systme solaire. Except pour les mtorites lunaires et martiennes, les mtorites sont des fragments dastrodes jects lors de collisions au sein de la ceinture dastrodes situe entre les orbites de Mars et Jupiter. Elles chantillonnent de petits corps parents appels plantsimaux qui sont des objets de taille kilomtrique, et sont donc des intermdiaires volutifs de laccrtion des plantes. Forme partir daggrgats de poussires milli centimtriques, ces plantsimaux se sont collisionns et accrts par attraction gravitationnelle pour donner des embryons plantaires. Ce processus de croissance est appell runaway growth. Selon les simulations dynamiques, ces embryons plantaires et donc les plantsimaux, doivent apparatre rapidement, entre 0,01 et 1 Ma aprs la formation des CAI (Chambers et al., 2004). On distingue deux types principaux de mtorites. Les mtorites non diffrencies ou chondrites sont des fragments de plantsimaux qui nont jamais atteint la temprature de fusion. Par opposition, les 17

mtorites diffrencies sont issues de plantsimaux qui ont t fondus et se sont diffrencis en un noyau mtallique, un manteau silicat et parfois une crote igne. Mtamorphises ou altres diffrents degrs, les chondrites se composent de proportions variables de chondres, de CAI, de grains pr-solaires et dune matrice. La prsence de ces composants primitifs ont longtemps laiss penser que les corps parents des chondrites staient forms avant ceux des mtorites diffrencies. Cependant, les datations isotopiques des mtorites de fer (<1 Ma aprs la formation des CAI, Halliday, 2003, Markowski et al., 2006), qui sont des fragments de noyau de plantsimal, et des chondres (~2 Ma aprs la formation des CAI, Bizzarro et al., 2005), dont la formation doit prcder laccrtion des corps parents des chondrites, rvle une squence inverse, o laccrtion des plantsimaux diffrencis est antrieure laccrtion des plantsimaux non diffrencis. Cette squence suggre que le degr de diffrenciation des plantsimaux est essentiellemnent dtermin par labondance d26Al prsent et dcrot donc avec le temps daccrtion et que, au contraire, les impacts nont jou quun rle marginal dans le chauffage de ces objets. Elle est cependant encore prciser, notamment en contraignant au mieux les ges daccrtion des corps parents des chondrites, dautres mtorites diffrencis, tels que les eucrites, ou dachondrites primitives, comme les acapulcotes et les lodranites, qui sont des intermdiaires entre mtorites diffrencies et non diffrencis. Les embryons plantaires, qui sont des objets pouvant atteindre la taille de Mars, entrent leur tour en collision par attraction gravitationnelle pour former les plantes telluriques (Wetherill et al., 1986 ; Agnor et Asphaug, 2004 ; Asphaug et al., 2006). Beaucoup plus nergtiques que les collisions de plantsimaux, car elles mettent en jeu des corps plus massifs, les collisions dembryons plantaires obissent une physique diffrente. En effet, lnergie relche lors de ces impacts gants produit la fusion totale ou partielle des plantes en formation engendrant une diffrenciation globale et la formation docans de magma. Les simulations dynamiques prdisent que laccrtion de plantes partir des collisions dembryons plantaires doit prendre fin dans les cent premiers millions dannes du systme solaire (Chambers, 2004). La Lune est le meilleur tmoin de cette tape volutive. Sa formation, lors dun impact gant entre la proto-Terre et un impacteur de la taille de Mars (Canup et Asphaug, 2001) partir des dbris ejects 18

qui ont constitu un disque proto-lunaire saccrtant rapidement (10 100 ans, Thompson and Stevenson, 1988, Canup et Ward, 2000), correspond au dernier vnement majeur de laccrtion terrestre. Initiallement totalement ou au moins partiellement fondue (Pritchard et Stevenson, 2000), lvolution prcoce de la Lune est caractrise par la cristallisation dun ocan magmatique (voir Warren, 1985). Si les donnes isotopiques nont pas encore permis de dterminer lge exact de formation de la Lune, les chronomtries et
146 182

Hf-182W

Sm-142Nd sur les chantillons lunaires permettent la datation de la cristallisation de

locan magmatique lunaire qui correspond lge le plus jeune auquel la Lune a pu se former. Les ges obtenus par ces deux chronomtres, respectivement ~40 Ma (Kleine et al., 2005) et ~200 Ma (Nyquist et al., 1995 ; Rankenburg et al., 2006 ; Boyet et al., 2007) sont apparemment en dsaccord. La prsente thse est focalise sur lapplication du chronomtre isotopique Hf-W dans lobjectif de contraindre plus prcisment les chelles de temps de laccrtion des plantsimaux et des plantes. Ce systme isotopique est bas sur la courte dure de vie de l182Hf (9 Ma), aujourdhui teint, mais dont la prsence dans les premires dizaines de Ma du systme solaire peut tre dtecte par le biais du produit de sa dsintgration radioactive, le
182 182

W, car elle se traduit par de petites variations des rapports

W/184W.

Deux axes principaux de recherche ont t choisis: la prcision de la squence daccrtion des plantsimaux, grce ltude des acapulcoites, des lodranites et des chondrites H, et la prcision des ges Hf-W de formation et de diffrenciation de Lune, grce ltude dchantillons lunaires. 1.2 Le chronomtre 182Hf-182W Depuis sa premire application par Harper et al. (1991) sur la mtorite ferreuse Toluca, le radiochronomtre 182Hf-182W sest avr un instrument puissant dinvestigation des chelles de temps des processus gochimiques dans le systme solaire primitif. Ces quinze dernires annes, ce systme isotopique a t utilis extensivement sur des matriels varis, car il possde plusieurs caractristiques particulires: (1) L182Hf se dsintgre en 182W avec une priode de demi-vie courte de 8.9 0,09 Ma (Vockenhuber et al., 2004), ce qui est du mme ordre de grandeur que les temps daccrtion et de diffrenciation des plantsimaux et des plantes. 19

(2)

Hafnium et tungstne sont deux lments rfractaires et par consquent sont supposs avoir une abondance relative identique celle des chondrites dans les objets plantaires totaux (Lee and Halliday, 1996).

(3)

Lhafnium est strictement lithophile tandis que le tungstne est modrment sidrophile, si bien que ces lments fractionnent fortement lors de sgrgation mtal-silicate (Walter and Thibault, 1995, Walker et al., 2000).

(4)

Lhafnium et le tungstne sont deux lments gnralement incompatibles mais certains minraux tels que lilmnite et le clinopyroxene incorporent

prfrentiellement lhafnium (Righter and Shearer, 2003). Des fractionnements HfW entre silicates peuvent donc aussi tre produits par cristallisation ou fusion partielle. Ces diffrences de caractres gochimiques permettent une application du systme Hf-W dune part la datation de mtorites individuelles par la mthode disochrone interne et dautre part la datation de la sgrgation du noyau et de la diffrenciation du manteau silicat des plantsimaux diffrencis et des plantes.

1.2.1

Notations Les variations des rapports 182W/184W tant trs petites, on exprime en gnral les

donnes isotopiques du W en units 182W. Le 182W correspond la dviation du rapport

182

W/184W dun chantillon par rapport sa valeur pour le standard terrestre en part pour 182W 184 W chantillon 182W = 182 1 10 4 W 184W s tan dard

10000.

1.2.2

Ages Hf-W des mtorites Isochrone interne et ge relatif

1.2.2.1

Au sein des chantillons mtoritiques, on retrouve des phases minrales avec des rapports Hf/W trs contrasts : le mtal qui ne contient virtuellement aucun Hf a un rapport Hf/W de ~0. Au contraire, lilmnite et le clinopyroxne, enrichis en Hf 20

relativement au W, ont des rapports Hf/W levs. Quant aux autres phases, telles que lolivine ou le plagioclase par exemple, elles ne fractionnent pas significativement Hf et W et ont donc des rapports Hf/W intermdiaires entre les deux ples prcdents. Si le fractionnement Hf-W entre ces diffrentes phases a eu lieu alors que le
182

Hf tait W/184W

toujours prsent (<60 Ma aprs la formation des CAI) et que le systme est rest ferm jusqu aujourdhui, on observe alors des variations systmatiques du rapport
182

corrles avec le rapport lmentaire Hf/W. Ceci est illustr dans la figure 1.1 et peut tre dmontr partir de la loi classique de la dsintgration radioactive : 182W 184 W = t
182

W 184 W

182 Hf + 184 t 0 W

1 e t t 0

t est le temps (t = 0 au moment de la formation des CAI), t0 est le temps auquel le systme sest clos, c'est--dire le temps au-del duquel la diffusion du W entre les diffrences phases a cess. est la constante de dsintgration du (t=4568,5 0,5 Ma, Bouvier et al., 2007), lensemble du dsintgr en 182W et on obtient : 182W 184 W 182W = 184 mesur W 182W = 184 W 182 Hf + 184 t 0 W 182 Hf + 180 t 0 Hf 182W = 184 t 0 W 182 Hf + 180 t 0 Hf 180 Hf 184 t 0 W
182 182

Hf. Aujourdhui

Hf prsent initialement sest

Hf 1.18 W t 0

Les rapports isotopiques initiaux du W et de lHf sont identiques dans les diffrentes phases minrales si ces dernires sont bien cogntiques, et sont rests imperturbes depuis leur formation et lquilibration des isotopes du W entre les diffrentes phases a bien t atteinte avant le fermeture du systme. En revanche, elles peuvent avoir des rapports Hf/W diffrents, ce qui produit aujourdhui des diffrences de signature isotopique . La pente de la corrlation obtenue dans le diagramme isochrone permet ainsi de dterminer le rapport 182Hf/180Hf au temps t0.

21

Figure 1.1: Schma de diagramme isochrone pour trois fractions minrales avec des rapports Hf/W diffrents.

La comparaison entre les pentes obtenues pour deux objets distincts (A et B) conduit ensuite au calcul dun ge relatif ( t A B ), puisque les processus gochimiques ne fractionnent pas significativement les isotopes lourds donc que le rapport nvolue quavec la dsintgration du 182Hf. 182 Hf 180 Hf 182 Hf = 180 t0A Hf
A B e ( t0 t0 ) t 0B

182

Hf/180Hf

do

t A B

1 = t 0A t 0B = ln

182 180 182 180

Hf Hf Hf Hf

t t

A 0

B 0

1.2.2.2

Calibration sur une chelle de temps absolu

La conversion des ges Hf-W relatifs en ges absolus prcis, afin de faciliter lintercomparaison avec les autres chronomtres, requiert un ancrage du systme sur une chelle de temps absolu. Une bonne rfrence chronomtrique doit remplir deux principaux critres. Le premier est de disposer dun ge absolu suffisamment prcis du matriel. On se concentrera sur le chronomtre Pb-Pb qui fournit les ges absolus les plus prcis pour des objets vieux de 4.5 Ga tels que les mtorites, notamment pour celles 22

dont les rapports U/Pb sont levs. Le second est que la mtorite date doit avoir refroidi suffisament rapidement si bien que la diffrence de temprature de fermeture des deux systmes isotopiques, courte et longue priode, ne rsulte pas en une diffrence dge significative. Les CAI et les angrites remplissent toutes deux ce deuxime critre. Au contraire des CAI (Amelin et al.,, Bouvier et al., 2007), les angrites prsentent lavantage davoir des ges Pb-Pb varis (Lugmair and Galer, 1992; Amelin, 2008) qui stalent sur une priode de 7 Ma. Ceci permet une valuation de la cohrence des deux chronomtres. Le choix des angrites pour lancrage permet galement de contourner le dbat sur les ges Pb-Pb conflictuels des CAIs (Amelin et al., Bouvier et al., 2007). Dans un diagramme ln (182Hf/180Hf) en fonction des ges Pb-Pb (Fig. 1.2), les donnes obtenues pour une srie dangrites dfinissent une droite dont la pente, correspondant la constante de dsintgration du
182

Hf, conduit une valeur de 0,0758 0,0068 Ma-1

(Kleine et al., 2008), en parfait accord avec la valeur exprimentale dtermine par Vockenhuber et al. (2004). Par consquent, lancrage sur les angrites assure la cohrence des ges Hf-W et Pb-Pb et peut tre utilis pour convertir les ges Hf-W relatifs en ges absolus. On choisira prfrentiellement les angrites DOrbigny et Sahara 99555 dont les ges Hf-W sont les plus prcis. Ces deux angrites ont des ges Pb-Pb identiques (Amelin, 2008, Connelly et al., 2008) qui, combins donnent un ge Pb-Pb de 4564,50 0,23 Ma. Markowski et al. (2007) ont obtenu des isochrones internes Hf-W identiques pour ces deux angrites conduisant un rapport initial 182Hf/180Hf de (7,31 0,16) 10-5. Lge HfW absolu de tout chantillon A ancr sur les angrites dOrbigny et Sahara 99555,

(t )

A 0 D' Orb / Sah

, peut maintenant tre dtermin partir de son rapport initial

182

Hf/180Hf

comme suit :

(t )

A 0 D' Orb / Sah

= Pb PbD'Orb/Sah

182 Hf A 180 Hf A t0 1 + ln D' Orb / Sah 182 Hf 180 Hf t D' Orb / Sah 0

23

Figure 1.2: ln(182Hf/180Hf) initial en fonction de lge Pb-Pb pour les angrites (daprs Kleine et al., 2008). Les ges Hf-W pour les angrites sont tirs de Markowski et al. (2007) et Kleine et al. (2008), les ges PbPb de Amelin and Irving (2007) and Amelin (2008).

1.2.2.3

Temprature de fermeture du systme

Les ges Hf-W drivs des isochrones internes datent la dernire quilibration du W entre les phases constitutives dune roche. Celle-ci intervient lorsque la roche a refroidi au dessous de la temprature de fermeture du systme, qui correspond la temprature en dessous de laquelle les changes diffusifs du W cessent entre les diffrents minraux prsents (Dodson, 1973; Ganguly and Tirone, 2001). La comparaison des ges Hf-W aux rsultats obtenus par dautres chronomtres ncessite la connaissance de cette temprature de fermeture. Ceci est dune importance particulire dans le cas des mtorites refroidissement lent, car les diffrences de temprature de fermeture vont sy traduire par des diffrences dge significatives, ce qui permet de retracer leur histoire thermique (voir chapitre 3). La temprature de fermeture du systme Hf-W reflte le comportement diffusif du W entre mtal, principal hte du 182W non radiognique, et silicates/oxydes, en particulier clinopyroxne et ilmnite qui sont les htes principaux du 24
182

W radiognique. La

diffusion du W est quelques ordres de grandeur plus rapide dans le mtal que dans les silicates et les oxides, si bien que la temprature de fermeture Hf-W est essentiellement contrle par la vitesse de diffusion dans le clinopyroxne et lilmnite. Malgr labsence de donnes exprimentales, la temprature de fermeture du systme Hf-W peut tre estime en simulant numriquement la production et la diffusion simultanes du W radiognique entre clinopyroxne et mtal (Van Orman et al., 2001, 2008, Kleine et al., 2008, Touboul et al., soumis). Un exemple des rsultats obtenus par ces simulations pour une temprature initiale et des tailles de grain appropries pour des mtorites trs mtamorphiss est prsent sur la figure 1.3. Pour une large gamme de vitesses de refroidissement et de taille des clinopyroxnes, la temprature de fermeture du systme Hf-W est leve (800-1100C) et proche de la temprature initiale choisie. Elle est suprieure aux tempratures de fermeture du Pb dans les pyroxnes ou les phosphates (Cherniak et al., 1991; Cherniak, 1998) et du Mg dans les anorthites (LaTourrette and Wasserburg, 1998). Par consquent, dans le cadre dun refroidissement, le systme Hf-W se ferme avant les autres chronomtres et cela se traduit pour les chantillons refroidissement suffisamment lent par des ges Hf-W plus anciens que les ges Pb-Pb et Al-Mg (Kleine et al, 2008, Touboul et al, soumis). Ainsi, le chronomtre Hf-W date des processus associs avec lvolution la plus prcoce des corps parents des mtorites.

Figure 1.3: Temprature de fermeture du systme Hf-W en fonction du diamtre des clinopyroxnes et de la vitesse de refroidissement. La temprature initiale a t fixe 1100-1200C (daprs Touboul et al., 2008)

25

1.2.3

Datation de la differenciation plantaire

1.2.3.1

Systmatique 182Hf-182W des chondrites et des objets plantaires totaux

Hafnium et tungstne sont deux lments rfractaires et sont donc supposs avoir une abondance chondritique dans la plupart des objets plantaires. La systmatique des chondrites fournit donc une estimation de la composition des objets plantaires totaux et sert de rfrence pour le calcul des ges Hf-W de formation du noyau. La dtermination de lvolution de la composition isotopique du W dans le rservoir chondritique requiert la connaissance de son rapport
182 182

W/184W actuel et de ses rapports initiaux

182

W/184W et

Hf/180Hf. Les premires donnes obtenues sur les chondrites (Lee and Halliday, 1995; Lee
182

and Halliday, 1996) semblaient montrer quelles avaient un rapport

W/184W identique

au manteau terrestre. Cependant, les travaux ultrieurs (Kleine et al., 2002; Schoenberg et al., 2002a; Yin et al., 2002) ont mis en vidence que les chondrites carbones prsentent une anomalie ngative en
182

W denviron -2 par rapport au manteau terrestre.

Actuellement, la dtermination la plus prcise du rapport pour les chondrites carbones est base sur 14 chantillons dont la moyenne conduit un 182W de -1,9 0,1 (Kleine et al., 2004). La meilleure mthode de dtermination des rapports initiaux
182 182

Hf/180Hf et

W/184W du systme solaire est lutilisation disochrone interne pour les CAI, car ce

sont les objets les plus vieux du systme solaire (Amelin, 2008, Bouvier et al., 2007). Burkhardt et al. (2008) ont obtenu une isochrone interne unique pour des fractions minrales provenant de 8 CAI des chondrites CV3 Allende et NWA 2364. La pente de cette isochrone correspond un rapport
182

Hf/180Hf initial de (9,70 0,40)10-5 et son

intersection avec laxe des ordonnes donne un initial 182W de -3,30 0,12. Le systme Hf-W nest pas affect par le mtamorphisme thermique de basse temprature et laltration aqueuse du fait de la haute temprature de fermeture de ce systme. Par consquent, lisochrone interne Hf-W pour les CAI conduit bien aux rapports initiaux
182

Hf/180Hf and

182

W/184W au moment de leur formation des CAI, c'est--dire il y a

4568,5 Ma.
La composition isotopique du rservoir chondritique a ainsi volu depuis -3,3 lors de la formation des CAI jusqu la valeur actuelle plus radiognique de -1,9 , sous 26

leffet de la dsintgration du

182

Hf dont labondance relative initiale est donne par le

rapport initial des CAI. Cette volution correspond un rservoir ayant un rapport Hf/W de 1.21, ce qui est cohrent avec les rapports mesurs dans les chondrites carbones (de 1.1 1.6, Kleine et al., 2004, Burkhardt et al., 2008).

Figure 1.5: Evolution du 182W avec le temps dans les rservoirs rsultant de la formation du noyau, suppos instantane, au sein dun objet plantaire caractris par une volution chondritique. CHUR = rservoir chondritique uniforme.

1.2.3.2

Ages Hf-W de formation du noyau

Lors de la formation du noyau, lHf, qui est strictement lithophile, saccumule entirement dans le manteau tandis que le W, sidrophile, est incorpor

prfrentiellement dans le noyau mtallique. Dpourvu dhafnium, le noyau conserve un rapport 182W/184W correspondant la composition isotopique du W de la plante totale au moment de la sgrgation du noyau (Fig.1.5). Connaissant lvolution de la composition isotopique du rservoir chondritique, le rapport
182

W/184W de tout chantillon driv de

noyau plantaire permet donc de dterminer un ge de formation du noyau. Par exemple, Markowski et al. (2007) ont montr que les mtorites de fer ont des 182W (corrigs des 27

effets cosmogniques) proches du 182W initial des CAI, indiquant que la sgrgation du noyau au sein du corps parent est intervenu au cours du premier million dannes du systme solaire. Au contraire du noyau, le manteau a hrit dun rapport Hf/W superchondritique. Le coefficient de partage mtal-silicate du W dpend entre autres de la fugacit en oxygne du manteau, de la pression, de la temprature et de la composition du liquide silicat (Walter and Thibault, 1995; Walter et al., 2000). Ainsi, selon les conditions qui prvalent la formation du noyau, lappauvrissement du manteau en W peut varier dun objet plantaire un autre mais aussi au sein dun mme objet au cours de ce processus. Le modle le plus simple permettant de calculer un ge fait lhypothse que la formation du noyau est un vnement discret ayant lieu un instant prcis. Depuis une valeur initialement chondritique cet instant, le rapport
182

W/184W du manteau volue avec le

temps vers des valeurs dautant plus radiogniques que son rapport Hf/W est lev (Fig. 1.5). La calcul dun ge modle deux stades pour la formation du noyau partir du

182W mantellique requiert donc lestimation du rapport Hf/W caractristique du manteau

total. Cependant, ce dernier ne peut tre mesur directement dans la plupart des cas, car des fractionnements Hf-W significatifs ont pu avoir lieu lors de processus ignes ultrieurs au sein du manteau (Righter and Shearer, 2003). Les rapports Hf/W mantelliques doivent donc tre estims en utilisant labondance relative dun lment strictement rfractaire lithophile dont lincompatibilit est identique au W. Deux lments rfractaires lithophiles, Th and U, ont des comportements incompatibles similaires au W (Palme and Rammensee, 1981b; Newsom et al., 1996). Par consquent, les rapports Hf/W des manteaux plantaires totaux peuvent tre dtermins partir des rapports Th/W et U/W dchantillons dorigine mantellique combins aux rapports Hf/Th et Hf/U des chondrites. En utilisant la diffrence de ~2 entre le manteau terrestre et les chondrites en combinaison avec le rapport Hf/W du manteau terrestre ainsi dtermin (~17), on obtient un ge modle deux stades de formation du noyau terrestre de ~30 Ma. Les meilleures estimations actuelles de ces paramtres dans le manteau martien donnent quant eux des ges de formation du noyau martien compris entre 0 et 8 Ma. Cependant, lhypothse de formation instantane du noyau nest pas raliste, notamment dans le cas dobjets 28

plantaires larges comme la Terre et Mars o cette diffrenciation a probablement t continue au cours de laccrtion et largement affecte par les impacts gants marquant la fin de laccrtion. Cette hypothse se traduit par une sous-estimation de lge rel de formation du noyau. Ces ges modle deux stades fournissent cependant des contraintes temporelles importantes puisquils correspondent aux ges les plus vieux auxquels les noyaux terrestre et martien ont pu tre forms (Halliday et al., 1996; Kleine et al., 2004b, Jacobsen et al., 2005, Nimmo et Kleine, 2007).

1.2.3.3

Ages Hf-W de diffrenciation mantellique

Des fractionnements additionnels ceux intervenant lors de la formation du noyau peuvent avoir lieu au sein de la partie silicate des objets diffrencis. Ils rsultent de la plus grande incompatibilit du W par rapport lHf, qui est prfrentiellement incorpor dans certains minraux silicats et oxydes tels que les pyroxnes riches en Ca et les ilmnites. Ces fractionnements, parfois plus importants que ceux produit lors de la formation du noyau, crent des rservoirs mantelliques et crustaux dont les rapports Hf/W diffrent entre eux et bien souvent du rapport Hf/W du manteau total, ce qui complique et parfois empche la dtermination dun ge de formation du noyau. Cependant, si ces fractionnements interviennent alors que le
182

Hf nest pas totalement teint (dans les 60

premiers Ma du systme solaire), les diffrences de rapport Hf/W vont produire des diffrences de 182W entre les rservoirs mantelliques, ce qui fournit des contraintes chronologiques importantes sur la diffrenciation mantellique. Par exemple, la cristallisation de locan magmatique lunaire conduit des rservoirs mantelliques avec des rapports Hf/W diffrents. Les basaltes de mer pauvres en Ti chantillonnent les premiers cumulats qui cristallisent dans locan de magma et qui ont constitu une source mantellique essentiellement compose dolivines et dorthopyroxnes, donc non fractionne par rapport locan magmatique total (Hf/W~26). Les basaltes de mer riches en Ti chantillonnent une source mantellique rapport Hf/W lev (~100) du fait de la prsence dilmnites et de clinopyroxnes. En revanche, les KREEP (chantillons enrichi en Potassium, en Terre-rares et en Phosphore), qui correspondent au liquide rsiduel de la cristallisation de locan magmatique lunaire et sont donc hautement enrichis en lments incompatibles dont le W, ont hrit dun rapport Hf/W bas (~20). 29

Kleine et al. (2005) ont obtenu des variations systmatiques du 182W en fonction des rapports Hf/W entre les KREEP et les sources mantelliques des basaltes de mer pauvres et riches en Ti. Ces variations isotopiques au sein du manteau lunaire indiqueraient que la cristallisation de locan magmatique lunaire sest acheve entre 30-50 Ma aprs la formation des CAI, comme lillustre la figure 1.6.

Figure 1.6: Diagramme isochrone 182W vs. (180Hf/184W)source pour les basaltes lunaires de mer pauvres et riches en Ti et pour les KREEP (daprs Kleine et al., 2005)

1.3 Contenu de la thse Cette thse est consacre ltude de lvolution prcoce des plantsimaux et des plantes grce au systme isotopique
182

Hf-182W. Son objectif principal est

ltablissement dune chronologie prcise de laccrtion, du mtamorphisme thermique ou de la diffrenciation de ces objets mais les rsultats obtenus apportent galement des contraintes importantes sur la nature des processus mis en jeu. Le Chapitre 2 sattache dcrire les techniques analytiques employes, en particulier les procdures chimiques permettant la sparation de lHf et du W, adapte pour le propos de cette tude partir de la mthode dveloppe par Kleine et al. (2004). 30

Les rendements et les blancs de la procdure ont ainsi t amliors permettant de travailler sur de faibles quantits de W. La mthode de mesure par spectromtrie de masse source plasma est galement dcrite. La sensibilit de linstrument est le facteur limitant pour les quantits minimum de W requises : au moins 8 ng de W sont ncessaires pour atteindre une reproductibilit externe suprieure ou gale 0,4 . Le chapitre 3 illustre lutilisation du systme isotopique Hf-W en tant que thermochronomtre, afin de contraindre lhistoire thermique des corps parents des mtorites. Il comporte deux articles. Le premier, en prparation pour tre soumis Geochimica et Cosmochimica Acta, concerne les acapulcotes et les lodranites qui appartiennent au groupe des achondrites primitives et drivent dun corps parent commun. En terme de temprature atteinte lors du pic thermique, les acapulcotes et les lodranites sont des intermdiaires entre mtorites diffrencies et non diffrencies. Les acapulcoites et les lodranites ont fondu partiellement mais la fusion limite na pas permis la migration efficace des liquides, si bien quelles ne se sont pas diffrencies. Nous prsentons des isochrones Hf-W pour une srie dacapulcotes et de lodranites, permettant de dater le refroidissement de ces mtorites au dessous de la temprature de fermeture du systme Hf-W. En collaboration avec James Van Orman, cette temprature de fermeture a pu tre estime par modlisation numrique de la diffusion du W entre mtaux et silicates. La contrainte thermochronomtrique ainsi fournie par le systme HfW est ensuite compare aux contraintes apportes par les autres chronomtres (ex : PbPb, Ar-Ar), ce qui rvle lhistoire thermique du corps parent des acapulcoites et des lodranites et permet de contraindre lge daccrtion de leur corps parent. Le second article a t crit par Thorsten Kleine et publi dans Earth and Planetary Science Letters. Il sagit dune tude parallle laquelle jai collabor et dans laquelle la thermochronomtrie Hf-W est applique aux chondrites ordinaires H selon une approche similaire. Le chapitre 4 se concentre sur la dtermination des ges de formation et de differentiation de la Lune et rassemble trois articles. Le premier, publi dans Nature, prsente les nouvelles donnes Hf-W obtenues sur des mtaux lunaires drivs de KREEP et de basaltes de mer pauvres et riches en Ti. Dans les roches lunaires, la production de
182

W par capture neutronique par le 181Ta, due lintense irradiation de la 31

surface lunaire par les rayonnements cosmiques, masque leur composition isotopique endogne (originelle). Les mtaux prsentent lavantage de ne pas contenir de Ta et leur composition isotopique nest donc pas affecte par cet effet cosmognique. Ils ont donc prserv la signature isotopique originelle des KREEP et des sources mantelliques des basaltes de mer dont ils sont extraits. Les rapports
182

W/184W de ces rservoirs, dont les

rapports Hf/W diffrent, sont utiliss afin de dterminer un ge de diffrenciation mantellique et destimer une composition isotopique du manteau lunaire total. En combinaison avec les rapports Hf/W des manteaux lunaire et terrestre, cette dernire permet de calculer un ge de formation de la Lune. Dans la continuit de ce premier article, le second, accept par Icarus, prsente nos donnes Hf-W obtenues pour deux anorthosites ferreuses lunaires. Faiblement exposes aux rayonnements cosmiques, leur
182

W est galement dpourvue de tout composant cosmogenique significatif. La

182

motivation de cette tude rsidait dans la prsence danomalies du

W obtenues

prcdemment sur ce type dchantillon lunaire (Lee et., 1997), ce qui est en dsaccord avec une formation tardive de Lune (> 60 Ma aprs la formation des CAI) dduite des rsultats obtenus sur les mtaux lunaires. Enfin le troisime article, crit par Bernard Bourdon et publi dans Philosophical Transactions of the Royal Society A, auquel jai collabor, explore plus en dtail le lien entre degr dquilibration entre impacteur et la proto-Terre et lge de formation de la Lune, la lumire des nouvelles donnes Hf-W prsentes dans les deux articles prcdents. Il met galement en parallle les donnes Sm-Nd lunaires et martiennes afin destimer la composition isotopique initiale du Nd. Enfin, le chapitre 5 est consacr aux conclusions principales ainsi qu quelques perspectives de recherche future quouvrent les nouveaux rsultats obtenus au cours de cette thse. Lappendice comprend tout dabord une courte discussion des donnes prliminaires obtenues, pour la premire fois, pour une srie consquente deucrites cumulats. Ces donnes Hf-W sont utilises pour contraindre la formation du noyau et la diffrenciation mantellique du corps parent des eucrites. La seconde partie de lappendice est constitue dun article de Thorsten Kleine auquel jai collabor. Ce dernier est consacr au passage en revue de lensemble des contraintes sur lvolution prcoce des

32

plantsimaux et des plantes, qua apportes la chronomtrie aujourdhui.

182

Hf-182W jusqu

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Solar System, LPI Contribution No. 1374, 20-21.

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on the accretion and cooling history of the H chondrite parent body. Earth Planet.

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Kleine, T., Palme, H., Mezger, K., and Halliday, A. N., 2005. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674. Kleine, T., Mezger, K., Mnker, C., Palme, H., and Bischoff, A., 2004.
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isotope systematics of chondrites, eucrites, and Martian meteorites: Chronology of core formation and mantle differentiation in Vesta and Mars. Geochim. Cosmochim.

Acta 68, 2935-2946.

Kleine, T., Mezger, K., Palme, H., Scherer, E., and Mnker, C., 2004. The W isotope evolution of the bulk silicate Earth: constraints on the timing and mechanisms of core formation and accretion. Earth Planet. Sci. Lett. 228, 109-123. Kleine, T., Mnker, C., Mezger, K., and Palme, H., 2002. Rapid accretion and early core formation on asteroids and the terrestrial planets from Hf-W chronometry. Nature 418, 952-955. Kleine, T., Bourdon, B., Burkhardt, C., and Irving, A. J., 2008. Hf-W chronometry of angrites: constraints on the absolute age of CAIs and planetesimals accretion timescales. Lunar Planet. Sci. Conf. XXXIX, 2367.pdf. LaTourrette, T. and Wasserburg, G. J., 1998. Mg diffusion in anorthite: implications for the formation of early solar system planetesimals. Earth Planet. Sci. Lett. 158, 91108. Lee, D. C. and Halliday, A. N., 1995. Hafnium-tungsten chronometry and the timing of terrestrial core formation. Nature 378, 771-774. Lee, D. C. and Halliday, A. N., 1996. Hf-W isotopic evidence for rapid accretion and differentiation in the early solar system. Science 274, 1876-1879. Lee, D. C., Halliday, A. N., Snyder, G. A., and Taylor, L. A., 1997. Age and origin of the moon. Science 278, 1098-1103. Lugmair, G. W. and Galer, S. J. G., 1992. Age and isotopic relationships among the angrites Lewis Cliff 86010 and Angra dos Reis. Geochim. Cosmochim. Acta 56, 1673-1694.

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Markowski, A., Quitt, G., Halliday, A. N., and Kleine, T., 2006. Tungsten isotopic compositions of iron meteorites: chronological constraints vs. cosmogenic effects.

Earth Planet. Sci. Lett. 242, 1-15.

Markowski, A., Quitt, G., Kleine, T., Halliday, A., Bizzarro, M., and Irving, A. J., 2007. Hf-W chronometry of angrites and the earliest evolution of planetary bodies. Earth

Planet. Sci. Lett. 262, 214-229.

Newsom, H. E., Sims, K. W. W., Noll, P., Jaeger, W., Maehr, S., and Beserra, T., 1996. The depletion of W in the bulk silicate Earth: constraints on core formation.

Geochim. Cosmochim. Acta 60, 1155-1169.

Nimmo, F. and Kleine, T., 2007. How rapidly did Mars accrete? Uncertainties in the HfW timing of core formation. Icarus 191, 497-504. Nyquist, L. E., Wiesmann, H., Bansal, B., Shih, C. Y., Keith, J. E., and Harper, C. L., 1995. Sm-146-Nd-142 Formation Interval for the Lunar Mantle. Geochim.

Cosmochim. Acta 59, 2817-2837.

Pritchard M.E, Stevenson D.J., 2000. Thermal implications of a lunar origin by giant impact. In: Origin of the Earth and Moon. University Arizona Press (d. Canup R.M., Righter K) , 179-196. Rankenburg, K., Brandon, A. D., and Neal, C. R., 2006. Neodymium isotope evidence for a chondritic composition of the Moon. Science 312, 1369-1372. Righter, K. and Shearer, C. K., 2003. Magmatic fractionation of Hf and W: Constraints on the timing of core formation and differentiation in the Moon and Mars. Geochim.

Cosmochim. Acta 67, 2497-2507.

Schoenberg R., Kamber B. S., Collerson K. D. ,Eugster O., 2002. New W-isotope evidence for rapid terrestrial accretion and very early core formation. Geochim.

Cosmochim. Acta 66, 3151-3160.

Thompson C., Stevenson D.J., 1988. Gravitational instability of two phase disks and the origin of the Moon. Atrophys. J. 333, 452-481. Touboul M., Kleine T., Bourdon B., Van Orman J. A., Maden C., Irving A. J., Zipfel J., Bunch T.E., Accretion and thermal history of the acapulcoite-lodranite parent body inferred from Hf-W thermochronometry, submitted

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Van Orman, J. A., Grove, T. L., and Shimizu, N., 2001. Rare earth element diffusion in diopside: Influence of temperature, pressure and ionic radius, and an elastic model for diffusion in silicates. Contrib. Mineral. Petrol. 141, 687-703. Van Orman, J. A., Saal, A. E., Bourdon, B., and Hauri, E. H., 2006. Diffusive fractionation of U-series radionuclides during mantle melting and shallow level melt-cumulate interaction. Geochim. Cosmochim. Acta 70, 4797-4812. Vockenhuber, C., Oberli, F., Bichler, M., Ahmad, I., Quitt, G., Meier, M., Halliday, A. N., Lee, D. C., Kutschera, W., Steier, P., Gehrke, R. J., and Helmer, R. G., 2004. New half-life measurement of
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Earth and Planetary Science, 13, 201-240.

Wetherill G.W., 1986. Accumulation of terrestrial planets and implcations concerning the lunar origin. In: Origin of the Moon (d. Hartmann W.K., Phillips R.J., Taylor J.G.). Lunar and planetary institute, 519-551. Yin, Q. Z., Jacobsen, S. B., Yamashita, K., Blichert-Toft, J., Tlouk, P., and Albarde, F., 2002. A short timescale for terrestrial planet formation from Hf-W chronometry of meteorites. Nature 418, 949-952.

37

38

Chapitre 2

Techniques analytiques
Analytical techniques

39

40

2.1 Introduction Ces quinze dernires annes, durant lesquelles les mesures de la composition isotopique du W ont suscit un intrt croissant et se sont popularises, deux techniques de mesure ont t communment utilises. Les premires donnes (par exemple Harper et al., 1991, Harper et Jacobsen, 1996) ont t produites par spectromtrie de masse thermo-ionisation (N-TIMS) qui permet datteindre une prcision de lordre de 1 sur le rapport
182

W/184W. Malgr le potentiel dionisation lev du W, cette technique permet

danalyser de petites quantits de W ( partir de 400 pg). Depuis lavnement des nouvelles gnrations de spectromtre de masse source plasma (MC-ICPMS) partir des annes 2000, la plupart des donnes isotopiques du W sont produites sur ce type dinstrument (par exemple, Yin et al., 2002, Kleine et al, 2004, 2005, Markowski et al,, 2006) . Bien que moins sensible que la thermo-ionisation (quelques dizaines de ng de W sont ncessaires), la prcision atteinte est environ 5 fois meilleure (~0.2 sur le rapport
182

W/184W). Un autre avantage des sources plasma est que la prparation des chantillons

se trouve simplifie, la phase de dpt sur filament dionisation ntant pas ncessaire. Les chantillons sont repris dans une solution dintroduction qui, pompe au moyen dun cathter, est injecte dans la chambre de nbulisation. Le spray obtenu passe dans la torche du plasma pour y tre atomis et ionis. Les ions produits pntrent dans la partie spectromtre de masse de linstrument, o, de manire classique, ils sont acclrs dans un champs lectrique puis dvis dans un champs magntique selon une trajectoire qui dpend de leur masse. Les isotopes sont ainsi collects sparment dans les cages de Faraday. Afin dviter les problmes dinterfrences et les effets de matrice pouvant perturber lionisation de lchantillon et le faisceau dions au cours des mesures isotopiques, il est fondamental de purifier llment dintrt (W) par sparation chimique. Dans ce chapitre, les techniques utilises pour la prparation des chantillons, permettant dobtenir des fractions pures de mtaux et de silicates, sont tout dabord prsentes. Les mthodes de purification du W par chromatographie ionique sont ensuite dcrites. Initialement adapte partir de celle dveloppe par Kleine et al.(2004), la technique de sparation chimique a t progressivement amliore et modifie pour le

41

propos de cette thse, afin de permettre de travailler sur des chantillons trs pauvres en W, comme les anorthosites lunaires. Enfin, nous exposons le protocole de mesure des compositions isotopiques du W sur le MC-ICPMS Nu Plasma.

2.2 Prparation des chantillons Avant toute opration ultrieure, les surfaces des chantillons sont abrases avec du papier de verre puis laves avec du HNO3 0,05 M, de leau dionise et enfin de lthanol ultrapur distill dans un bain ultrasonique afin dliminer toute contamination ventuelle, introduite au cours du dcoupage de lchantillon massif.

2.2.1

Roches totales Les poudres de roches totales sont obtenues en gnral par broyage dun morceau

de mtorite de 0,5 1 g dans un mortier en agathe. Dans le cas des eucrites basaltiques disponibles en large quantit, nous avons broy ~7 g afin de minimiser les effets lis lhtrognit des chantillons. Tout dabord rduits grossirement en poudre dans un mortier en agathe, les chantillons eucritiques sont ensuite transfrs dans une meule automatique permettant lobtention dune poudre trs fine et homogne.

2.2.2

Sparation magntique Cette mthode de sparation laide dun aimant a t utilise afin dobtenir des

fractions de mtal de haute puret partir des chantillons lunaires (~1 g pour les KREEP, ~4 g pour les basaltes de mer) et des fractions rapports Hf/W contrasts (mtaux et silicates) partir des chantillons dacapulcoites et de lodranites (~2 4 g). Lchantillon est tout dabord dlicatement broy dans un mortier en agathe et spar en utilisant un tamis en nylon en fractions de moins de 40 m et de 40 150 m. Dans le cas des chantillons lunaires o seuls les grains de mtaux nous intressent, la roche est directement broye trs finement. Les grains de mtal sont rcuprs en utilisant un aimant. Les poussires silicates attaches ainsi que les silicates intimement inclus dans les grains de mtal sont ensuite limins en rptant le broyage et la sparation magntique dans lthanol. Cette tape a t ralise avec un soin particulier dans le cas des mtaux lunaires, pour lesquels elle est rpte plusieurs fois afin de sassurer de leur 42

puret. Les fractions de 40 150 m sont toujours un peu magntiques, probablement du fait de la prsence de petites inclusions mtalliques dans les grains de silicates et doxydes. Elles sont spares en utilisant un aimant en fractions faiblement magntiques et non-magntiques. Elles sont ensuite elles-mmes spares en plusieurs fractions faiblement magntiques (WM) et non-magntiques (NM). Inspectes la loupe binoculaire, les fractions NM rvlent un enrichissement en ilmnites/clinopyroxenes et les fractions WM et un enrichissement en olivine/orthopyroxenes/plagioclases. Toutes les fractions (de 150 300 mg) sont ensuite pulvrises dans un mortier en agathe et les ventuels grains de mtal restants sont nouveau spars en utilisant laimant.

2.2.3

Sparation des plagioclases danorthosites lunaires Les plagioclases des anorthosites ferreuses lunaires sont supposs stre forms

par cristallisation dans locan de magma lunaire et stre accumuls la surface par flottation pour former la crote primitive de la Lune. Au sein des anorthosites, ces plagioclases ont t associs des minraux basiques tels que des olivines et des orthopyroxnes (quelques %) et ncessitent donc dtre spars. Lanorthosite (~5 g) est tout dabord broye dlicatement dans un mortier en agathe jusqu ce que lensemble de lchantillon ait une taille de grain infrieure 500 m. La fraction infrieure 40 m, trop fine pour les liqueurs denses, est limine. Une fraction de plagioclases pure est obtenue partir de la fraction de 40 500 m par sparation laide de liqueur dense (iodure de mthyle) puis purifie par prlvement manuel sous une loupe binoculaire et par limination des ventuels grains ou dinclusions de mtal laide dun aimant. La fraction pure de plagioclases est ensuite lave thanol distill dans un bain ultrasons, sche puis pulvrise dans un mortier en agathe.

2.3 Procdures chimiques Afin dviter les problmes dinterfrences au cours des mesures isotopiques aux spectromtres de masse, il est fondamental de purifier les lments dintrt (W, Hf) par sparation chimique de la solution de roche obtenue par attaque acide. La procdure chimique est essentiellement base sur la capacit du W tre complex par lHF et lH2O2. Toute la procdure chimique est effectue en salle blanche sous hte de classe 10 43

en utilisant des ractifs purifis. On utilise, entre autres, du peroxyde dhydrogne 31% Ultrapur, de leau milliQ et des acides nitrique, chlorhydrique et actique Pro Analysis, qui sont distills laide des boilers en quartz, tout comme lthanol. Une purification plus pousse est ncessaire concernant lacide fluorhydrique, qui est distill 2 3 fois pour atteindre des blancs de W satisfaisants. Les blancs mesurs pour tous ces ractifs sont infrieurs 1 ou 2 pg/ml.

2.3.1

Procdure sur les mtaux Les fractions de mtaux sont entirement dissoutes dans des bchers en tflon

Savillex de 15ml sur plaques chauffantes 120C en utilisant une solution de HCl 6M et HF 0,06M. A ce stade, un aliquot de 1 10% est prlev et spik avec un traceur mlang enrichi en 180Hf et 183W afin de dterminer les concentrations en Hf et en W par dilution isotopique. La mthode de sparation du W par chromatographie changeuse dions utilise pour les mtaux (Table 2.1) est similaire celle dcrite par Kleine et al. (2004). Aprs digestion, les chantillons sont vapors, redissous en HF 1M-HNO3 0,1M et chargs sur une colonne changeuse danions (colonne Biorad de 2 ml , 2 ml de rsine AG1X8, 200-400 mesh) prlave (voir ltape de prlavage expos dans la Table 2.1). La matrice est limine de la colonne en utilisant 10 volumes de rsine de HF 1M-HNO3 0,1M puis le W est lu avec du HNO3 6M-HF 0,2M. Aprs vaporation, les fractions lues sont nouveau dissoutes laide dun mlange HNO3 1M-HF 0,1M et charges sur une colonne changeuse danions prlave (colonne Biorad de 2 ml , 1 ml de rsine AG1X8, 200400 mesh) pour purification. La matrice est rince avec du HF 1M-HNO3 0,1M nouveau puis avec du HCl 6M-HF 0,01M qui permet llimination des traces dHf. Le W est ensuite lu en HCl 6M-HF 1M. Le rendement de cet procdure est proche de 100%.

44

Table 2.1: Procdure de sparation chromatographique du W destin aux mesures de composition isotopique dans le cas des mtaux. nb. volumes de solution dlution rsine Chimie sur colonne anionique (Biorad AG1X8, 200-400 mesh, 2ml) conditionnement 2x5 HNO3 1M-HF 0,1M chargement 5 HNO3 1M-HF 0,1M rinage de la matrice 2x5 HNO3 1M-HF 0,1M lution du W 5 HNO3 6M-HF 0,2M prlavage 5 HNO3 3 M 5 HNO3 6M-HF 0,2M 2x1 HCl 0,5mM-HF 0,5mM 5 HCl 6M-HF 1M 5 HCl 0,5M-HF 0,5M 2x1 HCl 0,5mM-HF 0,5mM Chimie de purification sur colonne anionique (Biorad AG1X8, 1ml) quilibration 2x5 HNO3 1M-HF 0,1M chargement 5 HNO3 1M-HF 0,1M rinage de la matrice 10 HNO3 1M-HF 0,1M rinage du HNO3 2x1 HCl 0,5mM HF 0,5mM lution du W 6 HCl 6M HF 1M prlavage 2x1 HCl 0,5mM-HF 0,5mM 2x5 HNO3 3 M 2x5 HNO3 6M-HF 0,2M 2x1 HCl 0,5mM-HF 0,5mM 2x5 HCl 6M-HF 1M 2x5 HCl 0,5M-HF 0,5M 2x1 HCl 0,5mM-HF 0,5mM *HFSE= high field strengh elements. tapes

2.3.2

Procdure sur les fractions silicates et les roches totales Cette procdure (Table 2.2) a t adapte partir de la mthode dcrite par Kleine

et al. (2004). Les fractions silicates et les roches totales sont attaques dans des bchers Savillex de 60 ml sur plaque chauffante 180C avec un mlange HF-HNO3 concentrs (7:3). Aprs digestion les chantillons sont vapors et dissous en HNO3 14M accompagn de quelques gouttes de H2O2 (30%) afin de digrer les composs organiques. Aprs vaporation, les chantillons sont repris en HCl 6M-HF 0,06M. A ce stade, la dissolution des chantillons est complte et une aliquote de 1 10% est prleve pour la dilution isotopique. Aprs aliquotage, les 90 99% de solution restante sont vapors puis sont redissous en HF 4M. Les solutions sont ensuite centrifuges et les rsidus lavs plusieurs fois avec du HF 4M afin dassurer un lessivage quantitatif du W partir des prcipits fluors.

45

La solution contenant lchantillon en HF 4M est ensuite charge sur une colonne de rsine changeuse danions (3,5 ml de rsine AG1X8, 100-200 mesh) pralablement prlave (Table 2.2). La matrice est limine laide de 6 volumes de colonne dHF 4M et le W est lu en HNO3 6M-HF 0,2M. Aprs vaporation, les fractions de W sont reprises en HCl 1M-HF 0,5M et charges sur une colonne de rsine changeuse danions prlave (3 ml de rsine AG1X8, 100-200 mesh) pour purification. La matrice est limine laide de 2 volumes de rsine de HCl 0,5M-HF 0,5M. Le titane est ensuite lu grce 120ml dun mlange dacide actique (HAc), dHNO3 et dH2O2. Le Zr, Hf et le Nb ainsi que les traces rsiduelles de Cr sont limines par 5 volumes de rsine de HCl 6M-HF 0,01M puis le W est lu avec 15 ml dHCl 6M-HF 1M. Les blancs de cette procdure varient entre 100 et 300 pg et proviennent pour lessentiel de mobilisation de W partir des bchers lors de la premire attaque des chantillons (de lordre de centaines de pg au total) et dans une moindre part de lacide actique et fluorhydrique (de lordre de dizaines de pg au total). Ceci est ngligeable except pour les chantillons les plus pauvres en W comme certaines fractions NM, o les blancs reprsentent jusqu 10% du W prsent. Le rendement de cette procdure, gnralement compris entre 70 et 90%, est variable dun chantillon un autre. Les pertes de W sont probablement lies la prsence de W rsiduel dans les prcipits fluors.

46

Table 2.2 : Procdure de sparation chromatographique du W destin aux mesures de composition isotopique dans le cas des fractions silicates et des roches totales. Volume de Solution dlution rsine Chimie sur colonne anionique (Biorad AG1X8, 100-200 mesh, 3,5ml) conditionnement 2x 5 HF 4M chargement 1 HF 4M rinage de la matrice 2 HF 4M lution du W 5 HNO3 6M-HF 0,2M prlavage 2x5 HNO3 3 M 2x5 HNO3 6M-HF 0,2M 2x 1 HCl 0,5mM-HF 0,5mM 2x5 HCl 6M-HF 1M 2x5 HCl 0,5M-HF 0,5M 2x 1 HCl 0,5mM-HF 0,5mM Chimie de purification sur colonne anionique (Biorad AG1X8, 100-200 mesh, 3ml) quilibration 2x 5 HCl 0,5M-HF 0,5M chargement 1 HCl 1M-HF 0,5M rinage de la matrice 2 HCl 0,5M-HF 0,5M rinage de lHF 3x 1 HCl 0,5mM-HF 0,5mM lution du Ti ~40 Hac 3,6M-HNO3 8mM-H2O2 2% rinage du Ti 3x 1 HAc 9 M lution des HFSE* dont Hf 4 HCl 6M-HF 0,01M lution du W 5 HCl 6M-HF 1M prlavage 2x5 HNO3 3 M 2x5 HNO3 6M-HF 0,2M 2x 1 HCl 0,5mM-HF 0,5mM 2x5 HCl 6M-HF 1M 2x5 HCl 0,5M-HF 0,5M 2x 1 HCl 0,5mM-HF 0,5mM *HFSE= high field strengh elements. tapes

2.3.3

Procdure particulire dveloppe pour les plagioclases danorthosites lunaires Du fait de la trs faible concentration en W des anorthosites (~2-4 ppb W), une

grande quantit dchantillon (~4g) est ncessaire pour obtenir des donnes isotopiques suffisamment prcises. Les blancs doivent tre suffisamment bas (<100 pg), afin que les corrections de blanc de la composition isotopique mesure soient ngligeables, et les rendements doivent tre amliors. De plus, la concentration leve des chantillons en calcium requiert une limination efficace de la matrice avant toute purification plus pousse du W par la technique utilisant des mlanges contenant de lHF, dcrite dans la section prcdente pour les fractions silicates et les roches totales. Les 4 g dchantillon sont attaqus avec 40 ml dHF 29M et HNO3 14M dans des bchers Savillex de 60ml sur plaque chauffante pendant trois jours 120C. Bien que 47

ncessitant une dure plus importante, cette attaque temprature relativement basse permet de limiter le relargage de W par le tflon des bchers. Aprs vaporation, les chantillons sont repris plusieurs fois en HNO3-H2O2 pour liminer les composs organiques et dtruire les prcipits fluors forms lors de la digestion. Les chantillons sont alors redissous en HCl 6M-HF 0,06M. 50 ml de cette solution sont ajouts, lensemble est homognis par ultrasonification puis centrifug. Cette opration est rpte jusqu dissolution complte des rsidus, qui est atteinte dans environ 450 ml dHCl 6M-HF 0,06M, qui sont transfrs dans un bcher Savillex de 500 ml. Une aliquote de 5% est alors prleve et spike pour la dilution isotopique. Le reste est vapor puis dissous dans 30ml dHCl 1M-HF 0,1M. Cette solution est centrifuge, dcante et le rsidu est rinc deux fois avec 10 ml dHCl 1M-HF 0,1M pour assurer la mobilisation complte du W contenu dans les prcipits fluors. La procdure permettant llimination de lessentiel de la matrice (Table 2.3) seffectue sur rsine changeuse de cations et est adapte de la mthode dveloppe par Tatsumoto et Patchett (1980). Les 50 ml de solution dchantillon en HCl 1M-HF 0,1M sont chargs sur 10 colonnes changeuses de cations prlaves (15 ml de rsine BioRad AG50WX8, 200-400 mesh). Le W (ainsi que les autres HFSE) est lu directement puis rinc avec 15 nouveaux ml dHCl 1M-HF 0,1M, tandis que les autres lments de la matrice, notamment lAl et le Ca, restent adsorbs sur la rsine. Les fractions de W sont ensuite vapores, redissoutes dans 10 ml de HCl 0,5 M-HF 0,5M puis charges sur une colonne changeuse danions prlave (3 ml de rsine Biorad AG1X8, 100-200 mesh) pour purification. La procdure suit alors le protocole de la chimie de purification dcrite dans la section prcdente pour les fractions silicates et les roches totales (table 2.2) cela prs quelle est rpte une fois afin dliminer efficacement lensemble du titane. Le rendement de cette nouvelle procdure est toujours suprieur 95%, bien meilleur que celui de la procdure prcdente, car la diminution de la quantit de prcipits fluors avant le chargement sur colonne permet de limiter les pertes de W rsiduel. Les blancs de procdure ont t diminus 50 pg et sont devenus beaucoup plus reproductibles (2 SD = 20 pg). Cette amlioration des blancs a t ralise grce lemploi de temprature plus basse lors de la premire attaque acide, de bchers lavs plusieurs semaines en HF concentr distill, dont les blancs sont toujours vrifis avant 48

usage, et dacide actique distill deux fois. Une fois dveloppe, cette mthode a donc t conserve ensuite, notamment pour la prparation des eucrites parmi lesquels les eucrites cumulats sont galement caractrises par de faible teneur en W.

Table 2.3 : Procdure de sparation chromatographique du W dveloppe pour le cas des anorthosites lunaires. volume de solution dlution rsine Chimie sur colonne cationique (Biorad AG50WX8, 200-400 mesh, 15 ml) quilibration 2x 5 HCl 1M-HF 0,1M Chargement (lution du W) 0,75 HCl 1M-HF 0,1M rinage du W 1 HCl 1M-HF 0,1M prlavage 2 HF 4M 2 HCl 6M 2 HF 4M 2 HCl 6M 2x 1 HCl 0,5mM-HF 0,5mM Chimie de purification sur colonne anionique (Biorad AG1X8, 100-200 mesh, 3ml) quilibration 2x 5 HCl 0,5M-HF 0,5M chargement 1 HCl 1M-HF 0,5M rinage de la matrice 2 HCl 0,5M-HF 0,5M rinage de lHF 3x 1 HCl 0,5mM-HF 0,5mM lution du Ti ~40 Hac 3,6M-HNO3 8mM-H2O2 2% rinage du Ti 3x 1 HAc 9 M lution des HFSE* dont Hf 4 HCl 6M-HF 0,01M lution du W 5 HCl 6M-HF 1M prlavage 2x5 HNO3 3 M 2x5 HNO3 6M-HF 0,2M 2x 1 HCl 0,5mM-HF 0,5mM 2x5 HCl 6M-HF 1M 2x5 HCl 0,5M-HF 0,5M 2x 1 HCl 0,5mM-HF 0,5mM *HFSE= high field strengh elements. tapes

2.4 Spectromtrie de masse Toutes les mesures isotopiques ont t ralises sur un instrument Nu Plasma MC-ICP-MS lETH Zrich, quip dun dsolvateur Cetac Aridus et dun nbuliseur en teflon de type PFA (dbit ~ 80 l.min-1). Avant la mesure, les chantillons sont redissous chaud et vapors plusieurs fois en HNO3-H2O2 afin de dtruire les composs organiques et dliminer lOs qui forme des oxides volatiles. Lchantillon est ensuite repris en HNO3 0,56M-HF 0,24M (0,2 0,5ml) pour la mesure.

49

2.4.1

Protocole de mesure des compositions isotopiques du W Les compositions isotopiques sont typiquement mesures avec un faisceau dune
182

intensit de ~2 V la masse du

W, ce qui correspond une solution de W ~20 ppb.

182

La configuration des cages de Faraday employe, pour laquelle le

W est collect au

niveau de la cage L1, est dcrite dans la table 2.4. Chaque mesure comprend 60 cycles (temps dintgration de 5 s) spars en 3 blocs conduisant une prcision interne de lordre de 0,2 . Une ligne de base lectronique (bruit de fond-5 mV) est mesure pendant 30 s par dflection du faisceau et un centrage de pic sur le
182

W effectu avant

chaque bloc. Pour les chantillons les plus pauvres en W (certaines des fractions NM des acapulcoites et des lodranites, les plagioclases danorthosites lunaires et certaines eucrites cumulats), les compositions isotopiques ont t mesures en 1 ou 2 blocs de 20 cycles avec une intensit de signal de 0,2 1,5 V sur le 182W, rsultant en une prcision interne de ~0,4 ~1,5 . La ligne de base nest alors mesure quune seule fois juste avant lintroduction de lchantillon pendant 120 s avec un temps dintgration de 0,2 s. On utilise la mthode dite de bracketing, consistant intercaler lchantillon entre deux mesures isotopiques du standard ALFA AESAR, ce qui permet de calculer les variations relatives de la composition isotopique du W de lchantillon par rapport la composition terrestre. Les compositions isotopiques des chantillons sont ainsi exprimes en units

18iW qui correspondent la dviation du rapport

18i

W/184W par rapport la valeur du

standard terrestre en parts par 10.000. Entre chaque mesure, le lavage du systme dintroduction ncessite le passage dHNO3 0,56M-HF 0,24M pendant ~5 minutes (juquau retour du signal de
182

W moins de 0.1-0.2 mV de la ligne de base

lectronique). Les gains des collecteurs de Faraday tendent se stabiliser aprs une journe de fonctionnement (qui nest donc utilise qu loptimisation du signal) et ne ncessitent ensuite dtre talonns quune fois par jour en dbut de session. La reproductibilit externe et la justesse des mesures effectues peuvent tre estimes notamment par des mesures rptes du standard ALFA AESAR et de solutions dchantillon de composition isotopique connue (voir section 2.4.3).

50

Table 2.4 : Configuration de cage pour les mesures de composition isotopique du tungstne (W IC) et les dilutions isotopiques pour le W (W ID), pour lhafnium (Hf ID) et pur le tantale (Ta ID) N cage W IC W ID Hf ID Ta ID
188 188

H6 Os Os
-

H5 -

186 186

H4 W W
-

H3 182

H2 181

184 184 180

H1 W W

Axiale 183 W
183 179

182 182 178

L1 W W

L2 177

L3 176 179

Ta

Hf

Hf W

Hf Ta

Hf Ta

Hf Hf

182

181

180

2.4.2

Discrimination de masse instrumentale et interfrences En spectromtrie de masse, les rapports isotopiques mesurs sont diffrents des

rapports isotopiques de lchantillon, car ils sont affects par la prsence dinterfrences isobares et par la discrimination de masse instrumentale. Ce dernier facteur en spectromtrie source plasma est li une meilleure extraction des isotopes lourds par rapport aux plus lgers, qui sont prfrentiellement dvis de leur trajectoire lors de collisions entre ions au sein du faisceau. On notera que la discrimination de masse induite par les spectromtres source plasma rsulte en un effet oppos celui du fractionnement de masse soprant dans les spectromtres thermo-ionisation, qui favorise lvaporation des isotopes les plus lgers. La discrimination de masse thorique suit une loi exponentielle (Fig. 2.1) :
M iW iW j = j i W W ech mes M j avec i et j = 182, 183, 184,186, M=masse atomique,

= facteur de discrimination de masse

Les rapports isotopiques mesurs peuvent tre ainsi corrigs de la discrimination de masse en utilisant un rapport isotopique pralablement connu tel que les rapports disotopes stables. A cet effet, le W prsente lavantage de possder quatre isotopes stables (180W,
183 184 186

W,

W,

W). Peu abondant et prsentant une infrence importante W/184W : laide des rapports
186

avec le 180Hf, le 180W nest pas utilis. Le tungstne nous offre donc deux possibilits de normalisation des rapports
186 182

W/183W (=1.9859) ou

W/184W (=0,92767) ainsi quune possibilit de vrifier la justesse des rapports corrigs

grce au troisime rapport disotopes stables (183W/184W) :

51

 182W 184 W

= ech

182

W 184 W

mes

M 182 M 184

M 184 M 186

ln

186 184

W W ech

186 W 184 W mes

182W 184 W

182W = 184 ech W

M 182 mes M 184

M 183 M ln 186

186 183

W W ech

186 W 183 W mes

183W 184 W

183W = 184 ech W

M 183 mes M 184

M 183 M 186

ln

186 183

W W ech

186 W 183 W mes

Un autre biais vient perturber les mesures isotopiques. Bien que la plupart des lments autres que le W ait t limin par la sparation chimique, certains isobares rsiduels sur les masses des isotopes du W peuvent tre lorigine dinterfrences. Cest le cas notamment de lOs crant de petites interfrences isobares aux masses 184 et 186. Celles-ci peuvent tre corriges en contrlant le de lordre de quelques ppt sur le rapport
182 188

Os mais ces corrections sont toujours

W/

184

W et sont donc ngligeables.

Figure 2.1: Ln (183W/184W) mesur versus ln(182W/184W) mesur pour le standard ALFA AESAR au cours de cette tude. Les donnes sont en parfait accord avec la discrimination de masse thorique. La loi exponentielle permet donc une correction approprie du fractionnement instrumental.

52

2.4.3

Reproductibilit externe et justesse des mesures La reproductibilit externe peut tre estime par des mesures rptes du standard

de W ALFA AESAR (fig 2.2 et Table 2.5) ou par des mesures rptes de solutions dchantillon de mtaux ou de silicates (voir tables de rsultats des chapitres 3 et 4). Les deux mthodes conduisent des rsultats similaires, indiquant que les effets de matrice naltrent pas la reproductibilit externe des mesures. Pour une solution de 20 ppb mesure pendant 60 cycles, la reproductibilit externe est typiquement de ~30 ppm (2 SD) pour le rapport
183 182

W/184W normalis au

186

W/183W, de ~60 ppm (2 SD) pour le

186

rapport 182W/184W normalis au rapport 186W/184W et de ~40 ppm (2 SD) pour le rapport W/184W. La reproductibilit externe avec une normalisation
186

W/183W tant meilleure

186

que celle obtenue avec une normalisation au

W/184W, on utilisera prfrentiellement W/183W. Pour

les compositions isotopiques calcules en utilisant la normalisation au et 80 ppm respectivement sur le rapport 182W/184W normalis au
186

des solutions de 2 10 ppb mesure pendant un bloc, elle se dtriore pour atteindre 200 W/183W.

Figure 2.2: reproductibilit externe sur le 182W/184W normalis au 186W/183W pour dix mesures du standard ALFA AESAR en fonction de sa concentration et de la dure dune mesure. Les courbes pointilles correspondent une extropolation exponentielle des donnes pour des mesures isotopiques comportant 20 ou 60 cycles.

53

Table 2.5 : Reproductibilit externe sur les rapports 182W/184W normalis au 186W/183W, 182W/184W normalis au 186W/184W et 183W/184W normalis au 186W/183W pour dix mesures (de 60 cycles chacune) du standard ALFA AESAR pour diffrentes concentrations. Concentration en W de la solution 2.5 ppb 10 ppb 20 ppb 40 ppb Reproductibilit externe (2SD, n=10, 60 cycles) 182 183 W/184W W/184W W/184W 186 184 186 183 norm. au W/ W norm. au W/ W norm. au 186W/183W 164 ppm 96 ppm 94 ppm 91 ppm 55 ppm 46 ppm 61 ppm 31 ppm 38 ppm 50 ppm 21 ppm 30 ppm
182

La justesse des mesures peut tre vrifie de trois faons diffrentes. Premirement, en vrifiant laccord des rapports isotopiques obtenus avec les deux normalisations. Deuximement en vrifiant que la valeur obtenue pour le rapport
183

W/184W est identique dans la marge derreur la valeur du standard terrestre (voir

tables de rsultats des chapitres 3, 4 et 5). Troisimement, en mesurant un chantillon de composition isotopique connue. Les mesures rptes au cours de cette tude dune poudre de roche dAllende conduisent une valeur en accord avec la composition isotopique des chondrites carbones rapporte prcdemment (182W = -1,9 0,1, Kleine et al., 2004).

2.5 Mesure de concentrations par dilution isotopique Pour obtenir une isochrone, il est ncessaire de dterminer les rapports Hf/W des chantillons et donc de mesurer leur concentration en Hf et en W. Celles-ci sont obtenues par la mthode dite de dilution isotopique, base sur la dtermination de la composition isotopique dun mlange dune quantit connue de spike et dune quantit inconnue dun lment de composition isotopique naturelle. Un spike est une solution contenant une concentration connue dun lment dont la composition isotopique a t enrichie par un ou plusieurs de ses isotopes et est connue. Dans cette tude, nous avons employ un spike enrichi en
180 183 180 233 229

Hf,

W,

Ta,

U et

Th (Table 2.6). Celui-ci est ajout aux

aliquotes dchantillon prleves lorsque la dissolution est complte (voir sections 2.3.1 et 2.3.2). La matrice des mlanges spike-chantillon (contenant galement lU et le Th) ainsi que lHf, le W et le Ta (du fait des interfrences entre 180Hf, 180Ta et 180W) doivent tre spars avant la mesure des compositions isotopiques, qui seffectuent donc

54

sparment pour chacun des lments. La procdure de sparation simplifie sur colonne changeuse danions est celle dcrite par Kleine et al. (2004) et est prsente dans la table 2.7. Les blancs de la procdure pour la dilution isotopique sont gnralement compris entre 10 et 20 pg de W et entre 1 et 2 pg dHf et de Ta.

Table 2.6: Compositions isotopiques et concentrations en W, Hf, Mo, Ta, U et Th pour le spike Mo-W I. Les abondances isotopiques naturelles sont galement indiques pour comparaison. Elements / Isotopes [W] [Hf] Concentration (ppb) [Ta] [Th] [U] Ab 183W Ab 184W Ab 186W Ab 180Hf Ab 179Hf Ab 177Hf Abondance isotopique Ab 180Ta Ab 181Ta Ab 229Th Ab 232Th Ab 233U Ab 238U Spike Mo-W I 97,7 454,8 8,62 0,456 567,9 0,9627 0,0158 0,0001 0,9827 0,0073 0,0026 0,0546 0,9454 0,9955 0,0045 0,9928 0,0071 0,1431 0,3064 0,2843 0,3509 0,1362 0,1860 0,0001 0,9999 0 ~100 0 0,9927 composition naturelle

Afin de dduire les concentrations en W et en Hf de lchantillon partir des compositions isotopiques mesures, un calcul itratif est ncessaire, car les rapports devant tre utiliss pour dterminer la discrimination de masse (186W/184W et 55
179

Hf/177Hf

respectivement) nont pas leur valeur naturelle dans le mlange spike-chantillon, du fait de la composition isotopique anormale du spike. Ce calcul est initi en utilisant directement les rapports
183

W/184W et

180

Hf/177Hf mesurs (non corrige de la

discrimination de masse) et finit par converger aprs quelques itrations. Ce calcul des concentrations en Hf et en W de lchantillon ncessite galement la connaissance de leur concentration, de leur composition isotopique dans le spike et des quantits relatives dchantillon et de spike dans le mlange.

Table 2.7 : Procdure de sparation chromatographique de lHf, du W, du Ta pour les aliquots spiks destins la dilution isotopique. Luranium et le thorium sont rcuprs avec la matrice et seront ensuite purifi selon la procdure dcrite par Vigier (2000) volume de solution dlution rsine Chimie sur colonne anionique (1 ml de rsine Biorad AGX8, 200-400 mesh) quilibration 2x 5 HCl 0,5M-HF 0,5M chargement 1,5 HCl 1M-HF 0,5M rinage de la matrice (+ U + Th) 1 HCl 0,5M-HF 0,5M 5 HF 1M 3x 1 HCl 0,5mM-HF 0,5mM lution de lHf 3 HCl 6M-HF 0,01M lution du W 4 HCl 6M-HF 1M rinage HCl 3x 1 HCl 0,5mM-HF 0,5mM rinage Mo 5 HNO3 6M-HF 0,2M Elution Ta 5 HNO3 6M-HF 0,2M-H2O2 1% prlavage 2x5 HNO3 3M 2x5 HNO3 6M-HF 0,2M 2x 1 HCl 0,5mM-HF 0,5mM 2x5 HCl 6M-HF 1M 2x5 HCl 0,5M-HF 0,5M 2x 1 HCl 0,5mM-HF 0,5mM tapes

2.6 Conclusions Nous avons donc dvelopp une mthode de sparation magntique efficace, capable dassurer la puret des fractions de mtaux obtenues, ce qui est critique dans le cas des chantillons lunaires, mais permet galement dobtenir des fractions silicates minralogie contraste. Ceci savre tre un moyen efficace de sparation de fractions rapport Hf/W vari, ce qui facilite grandement la ralisation disochrones internes. La ncessit de mesures isotopiques sur de faibles quantits de W (6-8 ng) provenant de quantits importantes dchantillon (4 g), dans le cadre de notre tude des anorthosites

56

lunaires, nous a conduit adapter la procdure initiale de sparation du W. En vitant la formation de prcipits fluors massifs par lemploi dune colonne changeuse de cations, qui permet llimination de la plus grande partie de la matrice de lchantillon, les rendements de procdure sont passs de 70% >90%. De plus, les blancs de W et leur reproductibili ont t amliors significativement (de 250 150 50 20 pg), essentiellement grce aux lavages intensifs en HF distill des bchers Savillex et une temprature dattaque maintenue volontairement relativement basse (120C contre 180C auparavant) mais galement, bien que dans une moindre mesure, une distillation plus pousse des acides actique et fluorhydrique.

Rfrences Markowski, A., Quitt, G., Halliday, A. N., and Kleine, T., 2006. Tungsten isotopic compositions of iron meteorites: chronological constraints vs. cosmogenic effects.

Earth Planet. Sci. Lett. 242, 1-15.

Harper, C. L., Vlkening, J., Heumann, K. G., Shih, C. Y., and Wiesmann, H., 1991.
182

Hf-182W: New cosmochronometric constraints on terrestrial accretion, core

formation, the astrophysical site of the r-process, and the origin of the solar system.

Lunar Planet. Sci. Conf. XXII, 515-516.

Harper C.H.J., Jacobsen S.B., 1996. Evidence for
182

Hf in the early solar system and

constraints on the timescale of terrestrial accretion and core formation. Geochim.

Cosmochim. Acta 60, 1131-1153.

Kleine T., Mezger K., Mnker C., Palme H., and Bischoff A. (2004)
182

Hf-182W isotope

systematics of chondrites, eucrites, and Martian meteorites: Chronology of core formation and mantle differentiation in Vesta and Mars. Geochim. Cosmochim.

Acta 68, 2935-2946.

Kleine, T., Palme, H., Mezger, K., and Halliday, A. N., 2005. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674. Patchett P.J., Tatsumoto, M., 1980. A routine high precision method for Lu-Hf geochemistry and chronology. Contribution to Minerlogy and petrology 75(3), 263267.

57

Vigier N., 2000. Apport des sries de lUranium sur les temps caractristiques des processus drosion, thse IPGP. Yin, Q. Z., Jacobsen, S. B., Yamashita, K., Blichert-Toft, J., Tlouk, P., and Albarde, F., 2002. A short timescale for terrestrial planet formation from Hf-W chronometry of meteorites. Nature 418, 949-952.

58

Chapitre 3

Thermochronomtrie Hf-W des mtorites : Contraintes sur laccrtion et lvolution thermique des corps parents

Hf-W thermochronmetry of meteorites: Constraints on the accretion and thermal evolution of parent bodies

59

60

Section 3.1

Accretion and thermal history of the acapulcoitelodranite parent body inferred from Hf-W thermochronometry*

M. Touboul1, T. Kleine1, B. Bourdon1, J. A. Van Orman2, C. Maden1, A. J. Irving3, J. Zipfel4, T.E. Bunch5

Institute for Isotope Geochemistry and Mineral Resources, ETH Zurich, Clausiusstrasse 25, 8092 Zurich, Switzerland Department of Geological Sciences, Case Western Reserve University, Cleveland, OH, USA. Forschungsinstitut und Naturmuseum Senckenberg, Frankfurt am Main, Germany. Departement of Earth & Space Sciences, University of Washington, Seattle, WA, USA. Department of Geology, Northern Arizona University, Flagstaff, AZ, USA

2 3 4 5

* En prparation pour Geochimica et Cosmochimica Acta

61

62

Abstract We obtained Hf-W metal-silicate isochrons for several acapulcoites and lodranites to constrain the accretion timescale and thermal history of their parent body. The high
180

Hf/184W (up to ~60) and radiogenic

182

W/184W ratios (up to ~40 182W) in some silicate

separates combined with low 180Hf/184W and unradiogenic 182W/184W ratios (182W ~-3) in the metals make it possible to obtain precise Hf-W ages with uncertainties of less than 1 Ma. The Hf-W age for the acapulcoites Dhofar 125 and NWA 2775 is tCAI=5.10.9 Ma, which corresponds to an absolute age of 4563.50.7 Ma. The Hf-W age for lodranite NWA 2627 is tCAI=5.61.0 Ma, corresponds to an absolute age of 4563.00.9 Ma, and is indistinguishable from the Hf-W age for acapulcoites. Closure temperatures for the Hf-W system in acapulcoites and lodranites were estimated from numerical simulations of W diffusion in high-Ca pyroxene, the major host of radiogenic 182W, and are 97550 C for acapulcoites and 102550 C for lodranites. These closure temperatures are only ~200 C lower than the peak temperatures, such that the Hf-W ages provide information on the earliest high-temperature evolution of the acapulcoite-lodranite parent body. The peak temperature of acapulcoites and lodranites in conjunction with their Hf-W ages require that the acapulcoite-lodranite parent body accreted later than ~1.5 Ma but before ~2 Ma after CAI formation. Thermal modeling indicates that acapulcoites and lodranites reached their thermal peak ~3 Ma after CAI formation and that decay of 26Al has been an important heat source in their thermal evolution. Cooling rates for acapulcoites decreased from ~120C/Ma just below the thermal peak to ~50C/Ma at ~600 C. Over the same temperature interval the cooling rate for lodranites decreased from ~100C/Ma to ~40 C/Ma. These thermal histories may reflect cooling in the uppermost 10-20 km of a parent body with a radius of 50-100 km. The acapulcoites and lodranites analyzed for this study evolved with carbonaceous chondrites. The low
180 180

Hf/184W ratios of 0.34 and 1.88, which are

indistinguishable from those of H chondrites but significantly lower than 180Hf/184W ~1.24 for Hf/184W ratios of acapulcoites and lodranites were established before ~2 Ma and, hence, prior to partial melting in the parent body at ~3 Ma and thus must reflect Hf-W fractionation of the precursor material by processes in the solar nebula. Combined with Hf-W ages of tCAI<1 Ma for differentiation of the parent bodies of magmatic iron meteorites and an Hf-W age of tCAI~2.5 Ma for the accretion of the H chondrite parent body, the Hf-W results for acapulcoites and lodranites reveal an inverse 63

correlation between accretion age of asteroids and peak temperature in their interiors. This indicates that the different thermal histories of meteorite parent bodies primarily reflect variations in their initial 26Al abundance, which is determined by their accretion time.

3.1.1 Introduction Determining the accretion timescale and early thermal history of meteorite parent bodies is key for understanding the formation of planetesimals and for constraining the parameters that controlled their subsequent evolution. Such information can be obtained by applying short- and long-lived chronometers to meteorites (or preferably a suite of meteorites derived from a single parent body) but also requires knowledge of the closure temperature (Tc) for diffusive exchange of parent and daughter elements among the different minerals in a meteorite (Dodson, 1973; Ganguly and Tirone, 2001). Most chronometers such as the U-Pb, Al-Mg or Ar-Ar systems closed at temperatures much lower than the peak temperatures reached in most meteorite parent bodies and as such provide constraints on the mid- to lowtemperature evolution of meteorite parent bodies (Gpel et al., 1994; LaTourrette and Wasserburg, 1998; Trieloff et al., 2003). As a consequence, their applicability for determining the high-temperature thermal history is limited, except to bodies with very fast cooling rates, but such information is of special interest because it can provide constraints on the accretion timescale and the heat source(s) responsible for parent body heating. In contrast, the Hf-W system (t1/2~9 Ma) has a relatively high closure temperature, which for H chondrites is almost as high as their peak metamorphic temperatures (Kleine et al., 2008b). Thus, the Hf-W system appears ideally suited for determining the accretion timescale and high-temperature evolution of meteorite parent bodies. Recent advances in the chronology of meteorites reveal that the accretion of the parent bodies of most if not all differentiated meteorites occurred within the first Ma after formation of Ca-Al-rich inclusions (CAIs) (Bizzarro et al., 2005; Kleine et al., 2005; Markowski et al., 2006; Schrsten et al., 2006; Burkhardt et al., 2008). In contrast, accretion of chondrite parent bodies occurred later, more than ~2 Ma after CAI formation (Kita et al., 2000; Kunihiro et al., 2004). These results indicate that the early evolution of asteroids was determined by their initial
26

Al content, which was sufficiently abundant in the early-formed planetesimals to

cause global melting and differentiation but had decayed to levels insufficient to trigger melting in the late-formed chondrite parent bodies (Bizzarro et al., 2005; Kleine et al., 2005; Schrsten et al., 2006). Acapulcoites and lodranites are a group of meteorites with properties 64

that place them intermediate between the unmelted chondrites and the differentiated meteorites (Palme et al., 1981; Zipfel et al., 1995; McCoy et al., 1996; McCoy et al., 1997a) and as such are of special interest for understanding the differentiation of asteroids as well as the role of heating by
26

Al decay in the thermal history of asteroids. Acapulcoites and

lodranites have mineral and bulk compositions similar to those of ordinary chondrites but they have non-chondritic textures. These result from recrystallization during high-temperature metamorphism and from partial melting. The acapulcoites show evidence for partial melting at the FeS-FeNi cotectic and in some cases silicate melts may have formed (Palme et al., 1981; Zipfel et al., 1995). The lodranites were heated to higher temperatures than the acapulcoites and are partial melting residues depleted in troilite and plagioclase (McCoy et al., 1997a). Several lines of evidence indicate that acapulcoites and lodranites, despite their different thermal histories, were derived from a common parent body: the occurrence of meteorites that are transitional between acapulcoites and lodranites (McCoy et al., 1997a); similar O isotope compositions (Clayton and Mayeda, 1996); similar mineral compositions (McCoy et al., 1997b); and indistinguishable cosmic ray exposure ages (Eugster and Lorenzetti, 2005). To constrain the accretion timescale and high-temperature thermal history of the acapulcoite-lodranite parent body, we applied the Hf-W chronometer to several acapulcoites and lodranites. The closure temperatures of the Hf-W system in these meteorites were estimated numerically using the model of Van Orman et al. (2001, 2006). The Hf-W ages and Tc estimates are then used in conjunction with previously published ages for acapulcoites and lodranites and thermal modeling to constrain the accretion timescale and thermal history of the acapulcoite-lodranite parent body. Finally, these results are compared to the thermal history of other meteorite parent bodies.

3.1.2 Samples and analytical techniques 3.1.2.1 Samples Four acapulcoites (NWA 2656, NWA 2775, Dhofar 125) and 2 lodranites (NWA 2627, NWA 4663) were selected for determining internal Hf-W isochrons. In addition, Hf-W data for a ~700 mg whole-rock of the lodranite Gibson were obtained. In Fig. 3.1.1, backscattered electron images for some of these samples are shown. Acapulcoites and lodranites are predominantly composed of low-Ca pyroxene and olivines and also contain high-Ca pyroxene, sodic plagioclases, troilite, metal and traces of apatite and chromite. They show 65

characteristic recrystallization texture with abundant 120 triple junctions and exhibit only minor shock effect (S1-S2) (McCoy et al., 1997a, Mittelfehldt et al., 1996, Palme et al., 1981). Detailed descriptions of the acapulcoites and lodranites investigated for this study can be found elsewhere (Greshake et al., 2001, Connelly et al., 2008, Irving et al., 2007). NWA 2775 and 2656 have an average grain size within the typical range of acapulcoites (150-230 m), whereas Dhofar 125 is somewhat finer grained (100m). The high-Ca pyroxenes in NWA 2656 have an average grain size of 11512m, calculating by averaging long and short axes, and a modal content of 13 vol.-%. The high-Ca pyroxene in NWA 2775 is larger (19012m) but less abundant (10 vol.-%). The average grain sizes in NWA 2627 and 4663 are larger than in acapulcoites and within the range of lodranites. Note that NWA 2627 has initially been classified as an acapulcoite but its average grain size clearly indicates that it is a lodranite. The high-Ca pyroxenes in NWA 2627 and NWA 4663 have average grain sizes of 43025m (modal content of 8 vol.-%) and 37318 m (modal content of 7 vol.-%). In addition there are tiny high-Ca pyroxene grains that occur as inclusions in olivine and probably represent trapped liquid within the crystallizing olivine. All acapulcoites and lodranites analyzed here show minimal to moderate degree of alteration (W1 and W2, or W3 in the case of NWA 2627), resulting in the some oxidation of metals.

66

metal plag cpx opx + ol

metal

opx + ol plag

metal cpx cpx metal

NWA 2775

plag cpx plag metal metal opx + ol cpx cpx metal ol cpx opx ol ol opx ph opx plag ol opx cpx metal plag opx NWA 4663 metal cpx plag opx + ol

NWA 2656

metal

Figure 3.1.1: Back-scattered electron (BSE) images for acapulcoites NWA 2775 and NWA 2627, and lodranite NWA 4663. False colors used for NWA 2775 and NWA 2627 are dark grey for FeNi metal and oxide, white for clinopyroxene (cpx), grey for olivine and orthopyroxene (ol+opx) and light grey for plagioclase (plag). False colors used for NWA 4663 are dark grey for FeNi metal and oxide, white for clinopyroxene, grey for orthopyroxene, light grey for plagioclase and phosphate (ph), and very light grey for olivine.

67

3.1.2.2 Analytical techniques Pieces of meteorite (with a total weight of ~3-5 g for each sample) were cleaned with abrasive paper and with 0.05 M HNO3, de-ionized H2O and ethanol in an ultrasonic bath to remove any contamination introduced during cutting from larger samples. Whole-rock powders were obtained by crushing a 0.5-1 g piece of each sample in an agate mortar. The remaining material (~2-4 g) was gently crushed in an agate mortar and separated into <40 m and 40-150 m fractions using nylon sieves. During crushing metal grains were removed using a hand-magnet and silicate dust attached to or silicate grains intergrown with the metal grains were removed by repeated crushing of the magnetic fraction under ethanol. Between 15 and 100 mg of pure metal separates were obtained for most samples, except NWA 2656 for which no pure metal grains could be obtained. Although all visible metal grains were removed, the 40-150 m fractions were still slightly magnetic, most likely reflecting the presence of tiny metal inclusions in the silicate and oxide grains. The 40-150 m fractions were further separated using a hand-magnet into a "weakly-magnetic" and "non-magnetic" fraction. These were then further separated in several weakly- and non-magnetic fractions that were labeled WM-n and NM-n, n=1, 2, 3, where n=1 always denotes the least magnetic fraction among the weakly- and non-magnetic fraction for each sample. All WM and NM fractions were inspected under the binocular microscope and they consist mainly of olivine and pyroxene but most fractions also contain some feldspar. All the WM and NM fractions were cleaned with ethanol in an ultrasonic bath and powdered in an agate mortar. Remaining metal grains were then removed from these powders using a hand-magnet and the resulting fractions weighted between 150 and 300 mg. The metal separates were dissolved in 15 ml Savillex vials at ~120C on a hotplate using 6 M HCl-0.06 M HF. In some cases, a few drops of concentrated HNO3 were added. The NM fractions were dissolved in 60 ml Savillex vials at ~180C on a hotplate using HFHNO3 (7:3). After digestion, the samples were dried down and re-dissolved in HNO3-H2O2 to destroy organic compounds. Then the samples were completely dissolved in 6 M HCl-0.06 M HF and depending on the W contents a 1-10% aliquot was spiked with a mixed tracer that was calibrated against pure Hf and W metals (Kleine et al., 2004). The methods for the separation of Hf and W from the sample matrix were similar to those outlined in Kleine et al. (2008). The metal separates were dried, re-dissolved in 1 M HF-0.1 M HNO3 and loaded onto pre-cleaned anion exchange columns (2 ml BioRad AG1X8, 200-400 mesh). The matrix was washed from the column using 1 M HF-0.1 M HNO3 and W was eluted in 6 M HNO3-0.2 M HF. After drying down, the W cut was re68
180

Hf-183W

dissolved in 1 M HF-0.1 M HNO3 and loaded onto a pre-cleaned anion exchange column (1 ml BioRad AG1X8, 200-400 mesh). Again, the matrix was washed from the column using 1 M HF-0.1 M HNO3, followed by 6 M HCl-0.01 M HF. Tungsten was then eluted in 6 M HCl1 M HF. After aliquoting, the WM and NM fractions were dried and re-dissolved in 4 M HF, the solution centrifuged and decanted and the residue washed several times with 4 M HF. The solution was ultrasonicated several times to ensure optimal release of W from the fluoride residue and was loaded onto pre-cleaned anion exchange columns (3.5 ml BioRad AG1X8, 100-200 mesh). The matrix was washed from the column using ~6 column volumes of 4 M HF and W eluted using 6 M HNO3-0.2 M HF. After drying, this cut was re-dissolved in 1 M HCl-0.5 M HF and loaded onto pre-cleaned anion exchange columns (3 ml BioRad AG1X8, 100-200 mesh), where W was purified following the procedure of Kleine et al. (2004). Titanium was washed from the column using a HAc-HNO3-H2O2 mixture, Zr, Hf, and Nb were rinsed off in 6 M HCl-0.01 M HF and W was finally eluted in 6 M HCl-1 M HF. Total procedural blanks ranged from ~100 to ~300 pg for the W isotope composition measurements and ~10 to 30 pg W and ~10 pg Hf for the isotope dilution measurements. For most samples, blanks are negligible but for some of the most W-depleted fractions blank corrections on the measured 182W/184W ratios were as high as 10% (Table 3.1.1). All isotope measurements were performed using a Nu Plasma MC-ICP-MS at ETH Zurich, equipped with a Cetac Aridus desolvating nebuliser. The measurement protocol was identical to that described in Kleine et al. (2008). Prior to measurement, the samples were redissolved and dried several times in few drops of 14M HNO3 and 30% H2O2 to remove organic compounds and, in the case of metal-rich samples, volatile Os oxides and then taken up in a 0.56 M HNO3-0.24 M HF mixture. Tungsten isotope compositions of metals and whole-rocks were typically measured with a signal intensity of ~2 V on
182

W, which was

obtained for a ~20 ppb W solution. For these samples, 60 ratios (3 blocks of 20 ratios) were measured resulting in within-run statistics of the order of 0.2 units (2). Owing to the low W contents in some NM fractions, their W isotope compositions were measured in 1 or 2 blocks of 20 ratios each with signal intensities of ~0.2 to 1 V on bias was corrected relative to negligible. 69
186 182

W. The within-run

statistics of these measurements were typically between 0.5 and 1.5 units. Instrumental mass W/183W=1.9859 using the exponential law. Small isobaric
188

interferences of Os on masses 184 and 186 were corrected by monitoring

Os and were

The of the
18i

182

W/184W and

183

W/184W ratios of all samples were determined relative to two

standard runs bracketing the sample run and are reported in 18iW units, which is the deviation W/184W ratio from the terrestrial standard value in parts per 10,000. The
182

reproducibility of the ~20 ppb standard during one measurement day is typically equal to or better than ~0.3 units (2 SD) for the
183

W/184W ratio and ~0.2 units (2 SD) for the

183

W/184W ratio. The external reproducibility of the W isotope measurements typically is 0.3182

0.4 units (2 SD) for the

W/184W ratio and 0.2-0.3 units (2 SD) for the

W/184W ratio

(Kleine et al. 2008). The uncertainties for the W isotope measurements of the W-poor NM-1 and -2 fractions of Dhofar 125 and NWA 2775 were assessed by repeated measurement (1 block of 20 ratios each) of ~2 and ~10 ppb W standard solutions that yielded external reproducibilities of ~2 and ~0.8 182W (2 SD). This is similar to the within-run statistics obtained for the measurements of the W-poor NM fractions (Table 3.1.1). Note that the major source of uncertainty in the (3.1. 1). The accuracy of the measurements was monitored by analyzing several carbonaceous chondrites, which all yielded the previously determined value of -1.90.1 182W (Kleine et al., 2004a). Furthermore, 183W/184W ratios were used as a monitor for accurate measurements and agree for most samples to within 0.2 units with the terrestrial value (Table 3.1.1). Elevated
183 182

W/184W of the W-poor NM fractions is the blank correction

W/184W ratios for some fractions from the NWA 2775 acapulcoite and the NWA 4663 and

NWA 2627 lodranites are attributed to an organic interference on mass 183 that was successfully removed for all other samples by treatment with HNO3-H2O2. Elevated measured
183

W/184W ratios have been observed before during W isotope measurements of some W/184W ratio normalized to
186

eucrites, carbonaceous chondrites, CAIs and H chondrites and for these samples the
182

W/184W=0.92767 agrees with

182

W/184W ratios for other

samples of these groups (Kleine et al., 2002; Kleine et al., 2004; Burkhardt et al., 2008; Kleine et al., 2008b). This indicates that only 183W is affected, such that for the fractions with elevated measured
183

W/184W the reported 182W values were calculated from the

182

W/184W

ratio normalized to 186W/184W.

3.1.3 Results The Hf and W concentrations and the W isotope compositions of metals, whole-rocks and non-magnetic fractions analyzed for this study are given in Table 3.1.1 and shown in Fig. 3.1.2 to Fig. 3.1.4. The acapulcoite and lodranite metals have W concentrations ranging from 70

~850 to 1400 ppb and have indistinguishable 182W values of ~-3.0. All metal separates have low
180

Hf/184W ratios of less than ~0.05, indicating that pure metal separates were obtained.

The acapulcoite and lodranite whole-rocks have 180Hf/184W ratios ranging from ~0.3 to ~2 and 182W values ranging from ~-2.4 to ~-1.5 but no systematic difference between acapulcoites and lodranites is apparent. The WM fractions have W contents and 182W between those of the whole-rocks and metals in most cases, most likely reflecting a higher abundance of metal in the WM fractions. The NM fractions have variable Hf and W contents ranging from ~90 to ~660 ppb Hf and from ~4 to ~124 ppb W, respectively. Their ~3 and ~60, resulting in elevated
182 180

Hf/184W ratios are between

W/184W ratios ranging from ~0 to ~40 182W. Owing to

the low W contents and radiogenic 182W/184W of some of the NM fractions, blank corrections were significant and typically ranged from <1 to ~4 182W (Table 3.1.1). As shown in Figs. 3.1.2 and 3.1.3, the 180Hf/184W ratios and 182W values correlate for the acapulcoites Dhofar 125 and NWA 2775, and for the lodranite NWA 2627, such that precise regression could be obtained for these samples (MSWD<1). The uncertainties on the slopes of these regressions are better than ~7%, resulting in uncertainties for the ages of better than 1 Ma, if these regressions are interpreted as isochrons. In contrast, no regression could be obtained for NWA 2656 and NWA 4663 and this most likely reflects disturbance of the Hf-W systematics due to terrestrial weathering. In spite of their different 180Hf/184W ratios, the NM fractions of NWA 2656 have a terrestrial W isotope composition, suggesting that this sample has been contaminated with terrestrial W during weathering in the desert. These effects are less pronounced in the metal and whole-rock fractions because these have much higher W contents. Note that for NWA 2656 no metal grain could be separated from the specimen investigated for this study, indicating substantial oxidation of the metals during terrestrial weathering. Similarly, in spite of very high
180 180

Hf/184W ratios the NM fractions of

NWA 4663 have much lower 182W values compared to fractions from other acapulcoites and lodranites with similar Hf/184W. A plot of 182W vs. 1/W reveals that the NM fractions of NWA 4663 plot on a mixing line with terrestrial W, suggesting that their low 182W values are due to addition of terrestrial W.

71

Figure 3.1.2: 182W versus 180Hf/184W for acapulcoites Dhofar 125, NWA 2656, NWA 2775. m = initial 182 Hf/180Hf, i = initial 182W. Regressions are calculated using the model 1 fit of Isoplot (Ludwig, 1991). tCAI is the formation age relative to CAIs; the absolute age t is calculated relative to the angrite D'Orbigny. Linear regressions of the Hf-W data for Dhofar 125 and NWA 2775 yield identical slopes and intercepts and the regression of the combined data for these two acapulcoites provides the best estimate for the initial 182Hf/180Hf and 182W at the time of the last Hf-W equilibration in acapulcoites. No correlation between 182W and 180 Hf/184W is observed for NWA 2656, indicating that the Hf-W system in this sample is disturbed.

Figure 3.1.3: 182W versus 180Hf/184W for lodranites NWA 2627 and NWA 4663. m = initial 182Hf/180Hf, i = initial 182W. Regressions are calculated using the model 1 fit of Isoplot (Ludwig, 1991). tCAI is the formation age relative to CAIs; the absolute age t is calculated relative to the angrite D'Orbigny. Linear regressions of the Hf-W data for NWA 2627 yield a precise isochron but no correlation between 182W and 180Hf/184W is observed for NWA 4663, indicating that the Hf-W system in this sample is disturbed.

72

3.1.4 Discussion 3.1.4.1 Hf-W isochron ages for acapulcoites and lodranites To define an isochron the minerals of a sample must once have been in W isotope equilibrium, i.e., they must have had the same W isotope composition initially. Given that the acapulcoite and lodranite fractions were obtained mainly based on their magnetic susceptibility, the correlation of 182W with
180

Hf/184W could potentially represent a mixing

182

line between W-rich metal and virtually W-free silicates. Such a mixing line would have no chronological significance if the two endmembers had different initial W/184W ratios. However, as shown in Fig. 3.1.4, the variations in 180Hf/184W ratios among the fractions of the analyzed acapulcoites and lodranites require the presence of at least three independent components for Hf and W among the coexisting phases. The major host of W is metal and the major host of Hf is high-Ca pyroxene. The third component includes olivine and low-Ca pyroxene and is characterized by low Hf and W contents. These two minerals are considered here as one component because no pure olivine and low-Ca pyroxene separates were obtained. Both olivine and low-Ca pyroxene are not capable of incorporating significant amounts of either Hf or W (Righter and Shearer, 2003), such that their presence mainly causes dilution of the high Hf content of high-Ca pyroxene. Therefore, the variability in the Hf contents of the various NM fractions of one sample most likely results from different proportions of high-Ca pyroxene. The presence of at least three independent components with regard to Hf and W among the coexisting phases of acapulcoites and lodranites reveals that the correlation between 182W and
180

Hf/184W observed for the fractions of each of the acapulcoites and

lodranites cannot reflect simple binary mixing between W-rich metal and virtually W-free silicates. This is also apparent from plots of 182W vs. 1/W, in which binary mixtures should form straight lines. This is not the case for any of those samples that exhibit linear correlations in the 182W vs.
180

Hf/184W plots. Each of the fractions, therefore, evolved to

180

radiogenic 182W according to their significance.

Hf/184W. Hence, the Hf-W data for the separates of

acapulcoites and lodranites define isochrons and can be interpreted to have chronological

73

Figure 3.1.4: Hf versus W contents for the different fractions of the analyzed acapulcoites and lodranites. The Hf and W concentrations in the coexisting phases of these acapulcoites and lodranites are not collinear, indicating the presence of at three independent components for Hf and W among the coexisting phases. These components are high-Ca pyroxene, olivine + low-Ca pyroxene, and metal.

Relative Hf-W ages (or formation intervals), tCAI, are calculated from the initial
182

Hf/180Hf ratios obtained from the slopes of the isochrons relative to an initial 182Hf/180Hf =

(9.70.4)10-5 for CAIs (Burkhardt et al., 2008) and refer to the time of Hf-W closure in a sample elapsed since crystallization of type B CAIs. Acapulcoites Dhofar 125 and NWA 2775 have indistinguishable initial isochron with an initial
182 182

Hf/180Hf ratios of (6.70.4)10-5 and (6.50.5)10-5,

respectively (Fig. 3.1.2). All data from these two acapulcoites combined define a single Hf/180Hf of (6.50.3)10-5, corresponding to an age of tCAI =
182

5.10.9 Ma. The initial 5.61.0 Ma (Fig. 3.1.3).

Hf/180Hf of lodranite NWA 2627 of (6.20.4)10-5 is

indistinguishable from the value for the acapulcoites and corresponds to an age of tCAI = The comparison of relative Hf-W ages to absolute ages (e.g., Pb-Pb ages) requires conversion of Hf-W formation intervals to an absolute timescale, which in turn requires knowledge of the initial 182Hf/180Hf and the absolute age of Hf-W closure in a sample. Due to differences in closure temperatures of different chronometers, the ideal samples to obtain such information are angrites because (i) they cooled rapidly, such that differences in closure 74

temperatures do not result in resolvable age differences, and (ii) they exhibit high U/Pb ratios, such that precise Pb-Pb ages are available (Lugmair and Galer, 1992; Amelin, 2008; Connelly et al., 2008). Precise initial
182

Hf/180Hf ratios (Kleine et al., 2008a) and Pb-Pb ages are

182

available for several angrites and all of these can be used to calculate absolute Hf-W ages. Using the Pb-Pb age of 4564.420.12 Ma (Amelin, 2008) and initial Hf/180Hf = (7.20.2)10-5 for the angrite D'Orbigny (Markowski et al., 2007; Kleine et al., 2008a) results in an absolute Hf-W age of 4563.50.7 Ma for the acapulcoites Dhofar 125 and NWA 2775, and 4563.00.9 Ma for lodranite NWA 2627. Identical results are obtained if absolute ages are calculated relative to the angrites Sahara 99555, NWA 4590, or NWA 4801. 3.1.4.2 Closure temperature for the Hf-W system in acapulcoites and lodranites To evaluate the significance of the Hf-W ages for constraining the thermal evolution of the acapulcoite-lodranite parent body, it is necessary to know the closure temperature, Tc, for W diffusion in the appropriate silicate-metal mixture. Here we use the approach employed by Kleine et al. (2008b) to calculate Tc as a function of grain size and cooling rate for H chondrites. This approach is based on the models of Van Orman et al. (2001; 2006) to estimate the diffusion parameters of W in high-Ca pyroxene, the major host of Hf and hence radiogenic
182

W in acapulcoites and lodranites, and to numerically simulate the diffusion

behavior of W in a high-Ca pyroxene-metal system. Details regarding this model are given in Kleine et al. (2008b) and Van Orman et al. (2006). Calculation of Tc as a function of cooling rate requires knowledge of the peak temperature, the grain size of high-Ca pyroxene, and the high-Ca pyroxene/metal ratio. Acapulcoites show evidence for melting at the FeNi-FeS eutectic, indicating that peak temperatures must have been higher than ~1000 C. There is also evidence for limited melting of silicates (Zipfel et al., 1995; Mittlefehldt et al., 1996), such that ~1150C is a reasonable assumption for the peak temperature of acapulcoites. Lodranites exhibit depletions in troilite and plagioclase, suggesting mobility of FeNi-FeS and basaltic melts. This requires temperatures of up to ~1300 C (Mittlefehldt et al., 1996; McCoy et al., 1997a), which was chosen here as the peak temperature for lodranites. The grain size of high-Ca pyroxene and the high-Ca pyroxene/metal ratios in the acapulcoites and lodranites investigated here were determined using the BSE images shown in Fig. 3.1.1 and results are summarized in the caption of Fig. 3.1.1.

75

Figure 3.1.5: Closure temperature of the Hf-W system as a function of grain size and cooling rate. The assumed initial temperature is 1150C for grain sizes of 10-200 m and 1300C for larger grain sizes. Note that cooling rates for acapulcoites and lodranites at 900-1100 C are on the order of ~100 C/Ma (for details see text).

Fig. 3.1.5 shows closure temperatures calculated as a function of cooling rate. For grain sizes of high-Ca pyroxenes from ~100 m to ~200 m, typical for the acapulcoites investigated here (Fig. 3.1.5), the assumed initial temperature is 1150 C. For grain sizes from ~350 m to ~450 m, the assumed initial temperature is 1300 C, as appropriate for lodranites. Fig. 3.1.5 reveals that Tc for the Hf-W system in acapulcoites ranges from ~900 C for slow cooling (dT/dt ~10C/Ma) to ~1050 C for fast cooling (dT/dt ~1000C/Ma). Due to their larger grain sizes the Hf-W closure temperature for lodranites are slightly higher and range from ~975 C for slow cooling (dT/dt ~10C/Ma) to ~1100 C for fast cooling (dT/dt ~1000C/Ma). As we shall see below, the cooling rate of acapulcoites and lodranites at high temperature is on the order of ~100 C/Ma, and for this cooling rate Hf-W closure temperatures for acapulcoites and lodranites are 97550 C and 102550 C. Note that these estimates are not very sensitive to variations in the cooling rate unless cooling is one order of magnitude slower or faster.

76

The comparison of the Hf-W ages to other radiometric ages provides a test for the validity of the Tc estimates for the Hf-W system. Although age information for acapulcoites and lodranites is sparse and the samples investigated here have not been studied with other high precision chronometers, the Hf-W ages for the acapulcoites Dhofar 125 and NWA 2775 can be compared with a Pb-Pb age for Acapulco phosphates (Gpel et al., 1992). The Hf-W age for acapulcoites of 4563.50.7 Ma is ~5 Ma older than the 45572 Ma Pb-Pb age for phosphates from Acapulco. The closure temperature of Pb diffusion in apatite (grain sizes from 100 to 300 m) range from ~490 C for slow cooling (dT/dt ~10C/Ma) to ~655 C for fast cooling (dT/dt ~1000C/Ma) (Cherniak et al., 1991). Hence, Tc for the Pb-Pb system in Acapulco phosphates is always lower than Tc for high-Ca pyroxene in acapulcoites, consistent with the observation that the Hf-W age for Dhofar 125 and NWA 2775 is older than the PbPb age for Acapulco phosphates. 3.1.4.3 Accretion and cooling history of the acapulcoite-lodranite parent body The Hf-W ages and Tc estimates for acapulcoites and lodranites in conjunction with thermochronological information from other chronometers and petrological constraints on peak temperatures can be used to constrain the accretion age and cooling history of the acapulcoite-lodranite parent body. Temperature profiles for spherical asteroids heated by energy released from
26

Al decay (Carslaw and Jaeger, 1959; Miyamoto et al., 1981) were

calculated and the parameters used are identical to those in Kleine et al. (2008b). We assume instantaneous accretion and do neither include the insulating effects of a regolith (Akridge et al., 1998) nor temporal and local variations in physical and thermal parameters (e.g., changes in thermal conductivity due to a decrease in porosity) (Bennett and McSween, 1996). For instance, if accretion had taken place over a timescale similar to the 26Al half-life, then a body would have started retaining the heat produced by
26

Al decay before reaching its terminal

mass and peak temperatures would have been reached earlier than estimated when assuming instantaneous accretion (Merk et al., 2002; Ghosh et al., 2003). A thick insulating regolith would have resulted in slower cooling rates and hence higher temperatures in the interior, compared to the model used here (Akridge et al., 1998). Nevertheless, in spite of these simplifications, the model used here is useful for calculation cooling curves for acapulcoites and lodranites and for obtaining some information on the accretion time, size and internal structure of the acapulcoite-lodranite parent body. In Fig. 3.1.6, calculated temperature profiles for different depths in spherical asteroids with radii of 30, 50, and 100 km are shown for accretion ages of 1.5, 1.7, and 2 Ma after CAI 77

formation. In these models the acapulcoite-lodranite parent body must have had a radius of more than ~35 km because for smaller radii cooling is faster than indicated by the differences in Hf-W and Pb-Pb closure temperatures and ages for acapulcoites. In the thermal model used here, the best fit to the Hf-W and Pb-Pb constraints is obtained for the uppermost 10 to 20 km of a body with radius of 50 to 100 km. However, if the acapulcoite-lodranite parent body had a thick insulating regolith, then cooling at a given depth would have been slower, such that the thermochronological data might also be consistent with a parent body radius of less than ~35 km. The thermal models also reveal that for accretion at ~2 Ma the peak temperatures of the lodranites of ~1300 C are only reached near the center of the parent body but these areas would have cooled below ~1025 C (i.e., Tc of the Hf-W system in lodranites) later than ~10 Ma after CAI formation, which is inconsistent with the ~5.6 Ma Hf-W age for lodranites. This conclusion holds true even if the acapulcoite-lodranite parent body had a thick regolith because in this case cooling at a given depth would have been even slower (Akridge et al., 1998). Conversely, for accretion as early as ~1.5 Ma, peak temperatures for lodranites and acapulcoites are ~1400 C and ~1200 C, respectively, which is somewhat too high. These observations suggest that the acapulcoite-lodranite parent body accreted later than ~1.5 Ma but before ~2 Ma. The thermochronometric data are consistent with a parent body of ~100 km radius that accreted at 1.7 Ma after CAI formation (Fig. 3.1.6). In this model, acapulcoites would have formed ~7 km below the surface and lodranites originate from a layer that is up to ~1.5 km deeper. Peak temperatures in the acapulcoite and lodranite regions were reached at ~3.5 Ma after CAI formation and were ~1150 C and ~1280C, respectively, consistent with petrologic constraints. If this model is correct, then large parts of the acapulcoite-lodranite parent body (i.e., the innermost ~90 km) must be differentiated into a metal core and silicate mantle because this area must have maintained temperatures in excess of ~1300 C for several millions of years. If any of these materials were delivered to Earth, it has yet not been identified in the meteorite collections.

78

Figure 3.1.6: Cooling curves for acapulcoites and lodranites. Solid lines indicate calculated temperature profiles for different depths in spherical bodies with radii of 35, 50, and 100 km. Numbers indicate distance in km from the center. Parameters are identical to those used in Kleine et al. (2008b) and are: thermal conductivity K = 1.0 W m-1 K-1; thermal diffusivity = 5.0 10-7 m2 s-1; density = 3.2 103 kg m-3; heat generation A = 11.67 (26Al/27Al) W m-3; emissivity h = 1.0 m-1. The assumed ambient temperature is T0 = 300 K and the initial 26 Al/27Al ratios are 1.38, 1.14, 0.85 and 0.52 10-5, corresponding to accretion at 1.5, 1.7, 2 and 2.5 Ma after CAIs. Hf-W ages and closure temperatures are from this study, all other ages are from the literature and are summarized in Table 3.1.2. Ar-Ar ages are shifted by ~30 Ma due to the proposed revision in the 40K decay constant (Renne, 2000; Trieloff et al., 2001). The best fit to the thermochronometric data is obtained for a 100 km body that accreted 1.7 Ma after CAI formation.

79

Cooling rates for acapulcoites and lodranites can be obtained from the slope of the cooling curves and for acapulcoites cooling rates decrease from ~120 C/Ma at ~1000 C (i.e., just below their peak temperature) to ~50 C/Ma at ~600 C. Over the same temperature range the cooling rate of lodranites decreased from ~110 C/Ma to ~40 C/Ma (Fig. 3.1.7). This thermal history is different from those of H5 and H6 chondrites, which cooled at a much slower rate (Fig. 3.1. 7). This could reflect a deeper burial depth of H5 and H6 chondrites compared to acapulcoites and lodranites. The thermal history at lower temperatures is less well constrained. Fig. 3.1.6 reveals that the thermal model presented here is consistent with Ar-Ar ages for acapulcoites and lodranites (McCoy et al., 1996; Mittlefehldt et al., 1996; McCoy et al., 1997a; Pellas et al., 1997; Renne, 2000) as well as U-Th-He ages for Acapulco phosphates (Min et al., 2003). However, the uncertainties on the Ar-Ar and U-Th-He ages are large and would be consistent with relatively slow cooling of <20 C/Ma for temperatures below ~400 C (as would be the case for the thermal model shown in Fig. 3.1.7) as well as with almost immediate cooling from ~550 C to ambient temperature. Evidence for very slow cooling at low temperatures comes from the determination of
244

Pu fission track densities in

orthopyroxene, withlockite and apatite, which indicate a cooling rate of 1.7 C/Ma in the temperature range of 280-90 C (Pellas et al., 1997). This is somewhat lower than the cooling rates obtained from the model presented here, which decrease from ~7 C/Ma at ~280 C to ~1 C/Ma at ~100 C. Based on the (U-Th)/He age of 453832 Ma, Min et al. (2003) argued that cooling below ~120 C must have been rapid, inconsistent with the slow cooling rates obtained from the
244

Pu fission track data. These authors suggest that

244

track annealing by later thermal disturbance resulted in spuriously young

Pu fission

track ages. Metallographic cooling rates for acapulcoites and lodranites (McCoy et al., 1996; McCoy et al., 1997a; McCoy et al., 1997b)and estimates based on Ca zonation in Acapulco olivines (Zipfel et al., 1995) indeed suggest relatively fast cooling of >1000 C/Ma for temperatures below ~600 C. The shift from initially moderate cooling at ~50100 C/Ma (from peak temperatures down to ~600 C) to rapid cooling at >1000 C/Ma (at temperatures below ~600 C) might be related to excavation of acapulcoites and lodranites, possibly caused by impacts on their parent body (McCoy et al., 1996; McCoy

80

et al., 1997a; McCoy et al., 1997b). Alternatively, it is possible also that one method for determining cooling rates is not entirely reliable.

Figure 3.1.7: Cooling rates for acapulcoites and lodranites as calculated from the slope of the cooling curves shown in Fig. 3.1.6. Cooling rates for H chondrites are shown for comparison and are from Kleine et al. (2008b).

In the thermal models discussed above it is assumed that

26

Al decay is the sole

heat source for melting and metamorphism of acapulcoites and lodranites. However, it has recently been suggested that impact heating could have been the dominant heat source (Rubin, 2007). While impact heating of asteroids is difficult to exclude as a heat source, the data presented here suggest that energy release by 26Al decay must have been important in the thermal evolution of the acapulcoite-lodranite parent body. This is because the Hf-W age of 5.10.9 Ma for acapulcoites refers to the time of cooling below ~975 C, such that for reasonable cooling rates, which are on the order of 100 C/Ma as constrained by the difference between the Hf-W and Pb-Pb ages, acapulcoites must have reached their thermal peak of ~1150 C at ~3-4 Ma after CAI formation. Obviously, their parent body must have accreted before this time and thermal modeling indicates that in bodies accreted that early 26Al decay was an important heat source. In other words, 26Al decay could only not have been an important heat source if accretion, heating, partial 81

melting, and cooling below ~975 C occurred within less than ~1 Ma. This seems highly unlikely and is also difficult to reconcile with the ~5 Ma difference between the Hf-W and Pb-Pb ages of acapulcoites that require cooling on the order of ~100 C/Ma. 3.1.4.4 Bulk Hf-W systematics of the acapulcoite-lodranite parent body nebular vs. parent body processes The
180

Hf/184W ratios and 182W values of the acapulcoite and lodranite whole-

rocks reported in this study show wide variations and are most likely distinct from the composition of carbonaceous chondrites (Table 3.1.1). This may reflect real differences in the Hf-W systematics caused by Hf/W fractionation related to melting and segregation of metals in the acapulcoite-lodranite parent body. However, the variations in the measured
180

Hf/184W ratios among the different whole-rocks may in part also be due to

sample heterogeneities. This seems likely given that in acapulcoites and lodranites almost all the W is located in the metal, such that small variations in the metal abundance in the analyzed aliquots will lead to variations in the 180Hf/184W ratio. The initial
182 180

Hf/184W ratios of bulk acapulcoites and lodranites are more reliably

determined by their time-integrated W isotope evolution. In a plot of initial 182W vs. Hf/180Hf, the acapulcoites and lodranites analyzed for this study plot below the evolution line for carbonaceous chondrites, indicating that they evolved with a 180Hf/184W ratio lower than that of carbonaceous chondrites (Fig. 8). The latest possible time at which this low
180 180

Hf/184W ratio could have been established is obtained by assuming

Hf/184W~0 for acapulcoites and lodranites. In this case, acapulcoites and lodranites
180

departed from the carbonaceous chondrite evolution line at ~2.5 Ma. However, the acapulcoites-lodranites must have Hf/184W>0, indicating that the Hf-W fractionation event must have taken place well before this time. Given that metal melting in the acapulcoites and lodranites most likely occurred at ~3 Ma after CAI formation (see above and Fig. 6), their low
180

Hf/184W ratios cannot reflect Hf-W fractionation during metal

segregation in the parent body but rather reflect processes prior to parent body accretion. Remarkably, acapulcoites and lodranites plot on the same W isotope evolution line as H chondrites (Kleine et al., 2008b). This is consistent with other compositional similarities between H chondrites and acapulcoites-lodranites (Palme et al., 1981) and suggests that 82

the precursor materials of their parent bodies had similar chemical compositions that were established by fractionation and/or mixing processes in the solar nebula. The similarity in time-integrated
180

Hf/184W ratios of the acapulcoites and

lodranites implies that the FeS-FeNi melts in lodranite NWA 2627 did not migrate, such that the chemical composition of this sample remained unaffected by the partial melting processes that are typical for lodranites (McCoy et al., 1997b). Whether this also applies to other lodranites remains to be determined by future Hf-W studies on a more comprehensive set of lodranites.

Figure 3.1.8: W isotope evolution diagram for acapulcoites and lodranites. The evolution line for carbonaceous chondrites is defined by their present-day 182W of -1.90.1 (Kleine et al., 2004) as well as the initial 182Hf/180Hf = (9.70.4)10-5 and initial 182W=-3.280.12 of Allende CAIs (Burkhardt et al., 2008). These values indicate that carbonaceous chondrites evolved with 180Hf/184W=1.230.15, consistent with 180Hf/184W=1.250.08 measured for carbonaceous chondrites (Kleine et al., 2004; Kleine et al., 2008a). The analyzed acapulcoites and lodranites depart from the evolution line for carbonaceous chondrites but are consistent with the W isotope evolution of H chondrites. The low 180Hf/184W of acapulcoites-lodranites has been established before ~2 Ma after CAI formation and thus must reflect Hf/W fractionation in the solar nebula.

83

3.1.5 Conclusions The Hf-W ages for acapulcoites and lodranites presented here are 5.10.9 Ma and 5.61.0 Ma after CAI formation and are the most ancient ages yet reported for this group of meteorites. This confirms the high closure temperature of the Hf-W system in these meteorites, which for both acapulcoites and lodranites is less than ~200 C below their peak temperatures. The Hf-W ages, therefore, provide constraints on the hightemperature thermal history of the acapulcoite-lodranite parent body, information that is not obtainable from other chronometers due to their much lower closure temperatures. The results presented here indicate that the acapulcoite-lodranite parent body accreted later than ~1.5 Ma but before ~2 Ma after CAI formation and that 26Al was an important heat source in its thermal history. Cooling rates for both acapulcoites and lodranites were ~100-120 C/Ma just below their thermal peak and decreased to ~40-50C/Ma at 600 C. Thus, cooling of acapulcoites and lodranites was roughly one order of magnitude faster than it was for the most metamorphosed H chondrites (i.e., H6 chondrites most of which cooled at ~10 C/Ma in the temperature interval from ~900 to ~200 C). This difference results from a deeper burial depth of H6 chondrites compared to acapulcoites-lodranites. For instance, acapulcoites and lodranites could have been located ~7 and ~9 km below the surface of a parent body with a radius of ~100 km that accreted at ~1.7 Ma after CAI formation, whereas H6 chondrites were located ~40-60 km below the surface of an asteroid with a radius of ~100 km that accreted ~2.5 Ma after CAI formation (Kleine et al., 2008b). Constraining the thermal evolution of asteroids does not only provide information on parent body size and burial depths of a suite of samples but also is key for constraining the parameters that controlled the evolution of meteorite parent bodies. The Hf-W ages in conjunction with petrologic constraints on the peak temperatures of acapulcoites and lodranites indicate that the acapulcoite-lodranite parent body accreted between 1.5 and 2 Ma after CAI formation and, hence, later than the parent bodies of magmatic iron meteorites (Kleine et al., 2005) but earlier than most (or all) chondrite parent bodies (Kita et al., 2000; Kunihiro et al., 2004; Rudraswami and Goswami, 2007; Kleine et al., 2008b). Thus, the accretion age of asteroids is inversely correlated with the peak temperatures reached in their interiors. Differentiated asteroids (i.e., the parent bodies of 84

magmatic iron meteorites) accreted within the first ~1 Ma after CAI formation, partially differentiated bodies - such as the acapulcoite-lodranite parent body - formed between 1.5 and 2 Ma, and undifferentiated asteroids (i.e., the chondrite parent bodies) accreted later than ~2 Ma after CAIs. This provides further evidence for earlier conclusions that the different thermal histories of meteorite parent bodies primarily reflect variations in their initial
26

Al abundance, which, owing to the short

26

Al half-life, is determined by the

accretion time (Bizzarro et al., 2005; Kleine et al., 2005; Schrsten et al., 2006).
Table 3.1.1 : Hf-W data for acapulcoites and lodranites Sample W (ppb) Hf (ppb) 190.3 189.0 0.4
180

Hf/184W 2

82W 2 meas. -1.79 0.28 -1.54 0.18 -2.97 0.21 -3.33 0.24 -3.15 0.36 -2.90 0.21 -2.77 0.17 -1.25 0.19 -1.28 0.18 13.2 0.8 4.01 0.78 4.78 0.52 1.92 0.33

82W 2 corr.

83W 2

Dhofar 125 (acapulcoite) WR-1 109.9 WR-2 118.6 M 901.1 mean (2 SE) fines-1 fines-2 WM-1 WM-2 NM-1 NM-2 NM-3 NM-4

2.042 0.020 1.881 0.019 0.0005 0.0001

373.9 375.1 91.3 105.9 14.3 25.9 30.0 29.4

133.1 131.8 171.8 173.1 257.9 237.4 270.9 174.2

0.415 0.004 0.420 0.004 2.22 0.02 1.92 0.02 21.3 0.4 10.8 0.2 10.6 0.2 6.99 0.07

13.5 1.2 4.11 1.30 4.87 1.20 2.01 0.50

-0.01 0.26 0.01 0.15 0.11 0.17 -0.20 0.18 -0.04 0.31 -0.08 0.11 0.26 0.13 -0.17 0.21 -0.18 0.13 -0.30 0.56 -0.11 0.48 -0.14 0.36 -0.12 0.27

NWA 2775 (acapulcoite) WR 174.4 mean (2 SE) M WM-1

179.8

1.21 0.01

1380.6 329.0

6.2 121.7

0.0053 0.0001 0.436 0.004

mean (2 SE) WM-2

416.6

122.8

0.348 0.003

mean (2 SE)

-2.30 0.21 -2.22 0.32 -2.26 0.09 -3.15 0.37 -2.29 0.23 -2.72 0.14 -2.92 0.18 -2.64 0.37 -2.64 0.19 -2.74 0.19 -2.75 0.14 -2.71 0.07

-0.47 0.17 -0.44 0.21 -0.46 0.04 -0.26 0.18 -0.25 0.13 -0.04 0.12 -0.09 0.11 -0.13 0.13 -0.15 0.13 -0.04 0.13 -0.17 0.11 -0.12 0.08

85

fines

213.4

159.7

0.883 0.009

mean (2 SE) NM-1 NM-2 NM-3

3.8 5.1 27.0

189.9 165.4 180.2

58.2 5.7 38.1 2.9 7.63 0.15

-2.28 0.18 -2.14 0.18 -1.94 0.26 -2.12 0.20 35.4 1.5 24.2 1.6 2.41 0.37

39.7 2.9 26.8 2.3 2.47 1.20

-0.20 0.15 -0.28 0.14 -0.27 0.19 -0.25 0.05 2.21 0.69 1.76 1.10 -0.25 0.55

NWA 2656 (acapulcoite) WR 371.1 mean (2 SE) WM fines mean (2 SE) NM-1 NM-2 NM-3

106.2

0.337 0.003

622.7 461.4

26.3 285.1

0.0499 0.0005 0.729 0.007

123.9 111.3 58.6

657.3 294.5 194.3

6.26 0.06 3.12 0.02 3.92 0.04

-2.41 0.16 -2.29 0.17 -2.35 0.11 -2.23 0.18 -1.06 0.17 -0.93 0.16 -1.00 0.13 -0.43 0.44 -0.47 0.26 -0.01 1.10

-0.06 0.11 -0.09 0.13 -0.07 0.03 -0.04 0.13 -0.08 0.13 -0.10 0.12 -0.09 0.01 -0.27 0.26 -0.31 0.16 0.63 1.45

NWA 2627 (lodranite) WR 168.6 M-1 1163.4 M-2 841.7 mean (2 SE) WM fines NM-1 NM-2

95.7 18.3 36.4

0.670 0.007 0.0185 0.0002 0.051 0.001

58.5 38.4 8.8 12.7

66.8 125.2 126.5 92.7

1.346 0.013 3.85 0.04 17.0 0.6 8.59 0.22

-2.42 0.16 -2.85 0.27 -2.89 0.30 -3.01 0.22 -2.95 0.28 -2.15 0.37 -0.42 0.41 7.77 0.39 3.24 0.35

-2.24 0.60 -0.38 0.60 9.04 0.94 3.58 0.62

-0.09 0.23 0.22 0.27 -0.08 0.27 0.14 0.27 0.03 0.28 1.74 0.23 -0.30 0.36 1.74 0.31 0.31 0.23

NWA 4663 (lodranite) M 1162.8

7.6

0.0077 0.0001

mean (2 SE) WM-2 WM-3 NM-1 NM-2 Gibson (lodranite) WR

224.7 664.0 28.5 23.7

308.9 135.7 651.1 344.9

1.62 0.02 0.241 0.002 26.9 0.4 17.2 0.4

-3.12 0.28 -2.65 0.14 -2.74 0.13 -2.72 0.16 -0.56 0.21 -2.72 0.14 3.24 0.30 4.09 0.33

3.39 0.31 4.38 0.36

0.04 0.15 0.05 0.09 0.02 0.12 0.09 0.11 0.21 0.19 -0.04 0.12 0.91 0.53 0.72 0.15

153.5

154.8

1.19 0.01

-1.78 0.24

-0.03 0.15

86

M = metal fraction, WM = weackly magnetic fraction, NM = non magnetic fraction, WR = whole rock. The quoted 2 uncertainties for measured 82W and 183W are analytical errors. Uncertainties on blank corrected 82W are calculated by propagating the external reproductibility of isotope measurements and a 50% uncertainty on the blank correction. Regression calculation though data assume an external reproductibility of 0.3-0.4 except for the W poor fractions (Dhofar 125 NM-1, 2 and 3, NWA 2656 NM1 and 2, and NWA 2627 NM-1). Table 3.1.2. Radiochronometric ages and closure temperatures for acapulcoites and lodranites Samples Acapulcoites NWA 2775 Dhofar 125 Acapulco Acapulco Acapulco Acapulco Lodranites NWA 2627 Gibson System
182 206 36 244

Minerals metal-silicate phosphates whole rock, plagioclases whitlokites apatites

Age 4563.5 0.7 4557 2 4514 22 4440 26 4538 32

Closure temperature 975 50 550 100 277 50 117 50 120 50

reference This study (1) (2) (2) (3)

Hf-182W

Pb-207Pb Ar-40Ar

Pu tracks U-Th/He

metal-silicate 4563.0 0.9 1025 50 whole rock, 4520 40 277 50 plagioclases (1) Gpel et al. (1992). (2) Pellas et al. (1997). (3) Min et al. (2003). (4) McCoy et al. (1997)
36

182

Hf-182W Ar-40Ar

This study (4)

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Section 3.2

HfW thermochronometry: Closure temperature and constraints on the accretion and cooling history of the H chondrite parent body

Thorsten Kleine 1, Mathieu Touboul 1, James A. Van Orman 2, Bernard Bourdon 1, Colin Maden 1, Klaus Mezger 3, Alex N. Halliday 4

Institute for Isotope Geochemistry and Mineral Resources, Department of Earth Sciences, ETH Zurich, Clausiusstrasse 25, 8092 Zurich, Switzerland
2

Department of Geological Sciences, Case Western Reserve University, 10900 Euclid Ave, Cleveland, Ohio 44106-7216, United States
3

Institut fr Mineralogie, Universitt Mnster, Corrensstrasse 24, 48149 Mnster, Germany

4

Department of Earth Sciences, University of Oxford, Parks Road, OX1 3PR, United Kingdom

Publi dans Earth and Planetary Science Letters, 2008, 270, p.106-118

93

94

Earth and Planetary Science Letters 270 (2008) 106118

Contents lists available at ScienceDirect

Earth and Planetary Science Letters

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e p s l

HfW thermochronometry: Closure temperature and constraints on the accretion and cooling history of the H chondrite parent body
Thorsten Kleine a,, Mathieu Touboul a, James A. Van Orman b, Bernard Bourdon a, Colin Maden a, Klaus Mezger c, Alex N. Halliday d
a

Institute for Isotope Geochemistry and Mineral Resources, Department of Earth Sciences, ETH Zurich, Clausiusstrasse 25, 8092 Zurich, Switzerland Department of Geological Sciences, Case Western Reserve University, 10900 Euclid Ave, Cleveland, Ohio 44106-7216, United States Institut fr Mineralogie, Universitt Mnster, Corrensstrasse 24, 48149 Mnster, Germany d Department of Earth Sciences, University of Oxford, Parks Road, OX1 3PR, United Kingdom
b c

A R T I C L E

I N F O

A B S T R A C T
We obtained HfW metal-silicate isochrons for several H chondrites of petrologic types 4, 5, and 6 to constrain the accretion and high-temperature thermal history of the H chondrite parent body. The silicate fractions have 180Hf/184W ratios up to 51 and 182W/184W ratios up to 33 units higher than the wholerock. These high 180Hf/184W and radiogenic W isotope ratios result in highly precise HfW ages. The HfW ages of the H chondrites become younger with increasing metamorphic grade and range from tCAI = 1.7 0.7 Ma for the H4 chondrite Ste. Marguerite to tCAI = 9.6 1.0 Ma for the H6 chondrites Kernouv and Estacado. Closure temperatures for the HfW system in H chondrites were estimated from numerical simulations of W diffusion in high-Ca pyroxene, the major host of radiogenic 182W in H chondrites, and range from 800 50 C for H4 chondrites to 875 75 C for H6 chondrites. Owing to these high closure temperatures, the HfW system closed early and dates processes associated with the earliest evolution of the H chondrite parent body. Consequently, the high-temperature interval of 8 Ma as dened by the HfW ages is much shorter than intervals obtained from RbSr and PbPb dating. For H4 chondrites, heating on the parent body probably was insufcient to cause W diffusion in high-Ca pyroxene, such that the HfW age of tCAI = 1.7 0.7 Ma for Ste. Marguerite was not reset and most likely dates chondrule formation. This is consistent with AlMg ages of 2 Ma for L and LL chondrules and indicates that chondrules from all ordinary chondrites formed contemporaneously. The HfW ages for H5 and H6 chondrites of tCAI = 5.9 0.9 Ma and tCAI = 9.6 1.0 Ma correspond closely to the time of the thermal peak within the H chondrite parent body. Combined with previously published chronological data the HfW ages reveal an inverse correlation of cooling rate and metamorphic grade: shortly after their thermal peak H6 chondrites cooled at 10 C/Ma, H5 chondrites at 30 C/Ma and H4 chondrites at 55 C/Ma. These HfW age constraints are most consistent with an onion-shell structure of the H chondrite parent body that was heated internally by energy released from 26Al decay. Parent body accretion started after chondrule formation at 1.7 0.7 Ma and probably ended before 5.9 0.9 Ma, when parts of the H chondrite parent body already had cooled from their thermal peak. The well-preserved cooling curves for the H chondrites studied here indicate that these samples derive from a part of the H chondrite parent body that remained largely unaffected by impact disruption and reassembly but such processes might have been important in other areas. The H chondrite parent body has a 180Hf/184W ratio of 0.63 0.20, distinctly lower than the 180Hf/184W = 1.21 0.06 of carbonaceous chondrite parent bodies. This difference reects HfW fractionation within the rst 2 Ma of the solar system, presumably related to processes in the solar nebula. 2008 Elsevier B.V. All rights reserved.

Article history: Received 19 December 2007 Received in revised form 3 March 2008 Accepted 4 March 2008 Available online 15 March 2008 Editor: R.W. Carlson Keywords: W isotopes closure temperature H chondrites thermochronometry chondrules Editor: R.W. Carlson

1. Introduction Hafniumtungsten chronometry has been applied widely to determine the timescales of differentiation of asteroids and terrestrial

Corresponding author. E-mail address: kleine@erdw.ethz.ch (T. Kleine). 0012-821X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.epsl.2008.03.013

planets (Harper and Jacobsen, 1996; Schoenberg et al., 2002; Yin et al., 2002; Halliday, 2004; Kleine et al., 2004b; Jacobsen, 2005; Nimmo and Agnor, 2006; Nimmo and Kleine, 2007) but its potential for dating chondrites and constraining the thermal evolution of their parent bodies has yet to be explored. To utilize HfW chronometry of meteorites meaningfully it is necessary to know the closure temperature (Tc) for diffusive exchange of parent and daughter elements among the different minerals in a rock (Dodson, 1973; Ganguly and

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Tirone, 2001). Knowledge of Tc is essential for evaluating whether an age dates the time of mineral growth or some time along the cooling path. Such information is critical for the interpretation of HfW ages in comparison to results from other chronometers and within the framework of models for the thermal evolution of asteroids. Closure temperatures can be calculated from diffusion rates of the element of interest in the appropriate minerals. Such data are not available for W but here we determine closure temperatures from numerical simulations of W diffusion in silicates using the model of Van Orman et al. (2001, 2006). These results are compared to values of Tc estimated by age comparison. Ideal samples for this (i) should be well dated with different chronometers (i.e., have a well-dened cooling history), (ii) should exhibit protracted cooling, such that differences in closure temperatures result in well-resolved age differences, and (iii) should contain components having substantially different Hf/W ratios, such that precise HfW isochrons can be determined. These criteria are met by ordinary chondrites. First, the thermal evolution and structure of their parent bodies has already been studied with several chronometers (Wasserburg et al., 1969; Podosek and Brannon, 1991; Gpel et al., 1994; Trieloff et al., 2003; Amelin et al., 2005; Bouvier et al., 2007). Second, ordinary chondrites exhibit a wide range of metamorphic conditions from type 3 (unequilibrated) to type 6 (highly equilibrated), reecting widely different cooling histories (Dodd, 1969). Third, ordinary chondrites contain abundant metal, which makes them ideal for HfW chronometry. Metals are virtually Hffree but are enriched in W, resulting in 180Hf/ 184 W 0 in metals and elevated 180Hf/184W ratios in the corresponding silicates. For instance, Kleine et al. (2002) reported 180Hf/184W 14 coupled with radiogenic 182W/184W for a silicate fraction from the H4 chondrite Ste. Marguerite. Such high 180Hf/184W and radiogenic 182 W/184W ratios make it possible to obtain high-precision HfW ages. We present HfW isochrons for several equilibrated H chondrites. Most of the samples investigated here were previously dated with other chronometers, including the 207Pb206Pb system (Gpel et al., 1994; Amelin et al., 2005; Bouvier et al., 2007). The diffusivity of Pb in the relevant minerals is relatively well constrained (Cherniak et al., 1991; Cherniak, 1998), facilitating estimates of closure temperatures by age comparison. These estimates are compared to results from numerical simulations of W diffusion in a metal-silicate assemblage, which, in conjunction with the HfW ages, are used to assess the signicance of the HfW ages and to constrain the thermal evolution of the H chondrite parent asteroid. 2. Analytical methods Pieces of meteorite were cleaned with abrasive paper and with 0.05 M HNO3, de-ionized H2O and ethanol in an ultrasonic bath to remove any contamination introduced during cutting from larger samples. Each fragment was crushed in an agate mortar and separated into b 40 m and 40150 m fractions using nylon sieves. During crushing metal grains were removed using a hand-magnet and separated into two fractions using a 40 m nylon sieve. Where sufcient material was available, the coarser fraction was further separated into several fractions, depending on the size of the metal grains. Silicate dust attached to or intergrown with the metal grains was removed by repeated crushing of the magnetic fraction under ethanol. Although all visible metal grains were removed, the 40150 m fractions were still slightly magnetic, most likely reecting the presence of tiny metal inclusions in the silicate and oxide grains. The 40150 m fractions were further separated using a hand-magnet to obtain several non-magnetic fractions. These were labeled NM-n, n = 1, 2, 3, NM-1 always denoting the least magnetic fraction for each chondrite. The NM-1 fractions are non- magnetic (i.e., with the handmagnet used here) and might be entirely metal-free, the NM-2 fractions are slightly more magnetic, and the NM-3 fractions again are slightly more magnetic than the NM-2 fractions.

All NM fractions were inspected under the binocular microscope. They consist mainly of olivine and pyroxene but most fractions also contain some ilmenite, feldspar and phosphates. All NM fractions were cleaned with ethanol in an ultrasonic bath and powdered in an agate mortar. Remaining metal grains were removed from these powders using a hand-magnet. The metal separates were dissolved in 15 mL Savillex vials at 120 C on a hotplate using 6 M HCl0.06 M HF. In some cases, a few drops of concentrated HNO3 were added. The NM fractions were dissolved in 60 mL Savillex vials at 180 C on a hotplate using HF HNO3HClO4 (5:4:1). After digestion, the samples were dried and redissolved in HNO3H2O2 to remove organic compounds. Then the samples were completely dissolved in 6 M HCl0.06 M HF and a 10% aliquot was spiked with a mixed 180Hf183W tracer that was calibrated against pure Hf and W metals (Kleine et al., 2004a). The methods for the separation of Hf and W from the sample matrix were slightly modied from those outlined in Kleine et al. (2004a). The metal separates were dried, re-dissolved in 1 M HF0.1 M HNO3 and loaded onto pre-cleaned anion exchange columns (2 mL BioRad AG1X8, 200400 mesh). The matrix was washed from the column using 5 resin volumes 1 M HF0.1 M HNO3 and W together with other high eld strength elements and Mo was eluted in 6 M HNO30.2 M HF (Mnker et al., 2001; Weyer et al., 2002; Kleine et al., 2004a). After drying down, the W cut was re-dissolved in 1 M HF 0.1 M HNO3 and loaded onto a pre-cleaned anion exchange column (1 mL BioRad AG1X8, 200400 mesh). Again, the matrix was washed from the column using 5 resin volumes 1 M HF0.1 M HNO3 but high eld strength elements (Hf, Zr, Nb, Ti) were rst removed in 6 M HCl0.01 M HF before W was eluted in 6 M HCl1 M HF. In this acid mixture, Mo is strongly adsorbed on the anion resin (Kleine et al., 2004a). The rst part of the ion exchange procedure employed for the NM fractions is similar to the rst step in the Hf chemistry of Salters and Hart (Salters and Hart, 1991). After aliquoting, the NM fractions were dried and re-dissolved in 4 M HF. The solution was centrifuged and decanted and the residue washed several times with 4 M HF. The solution was ultrasonicated several times to ensure optimal release of W from the uoride residue and was loaded onto pre-cleaned anion exchange columns (3.5 mL BioRad AG1X8, 100200 mesh). The matrix was washed from the column using 6 resin volumes of 4 M HF and W together with Zr, Hf, Ti, Nb, Mo was eluted using 6 M HNO30.2 M HF. After drying, this cut was re-dissolved in 1 M HCl0.5 M HF and loaded onto pre-cleaned anion exchange columns (3 mL BioRad AG1X8, 100 200 mesh), where W was puried following the procedure of Kleine et al. (2004a). Titanium was washed from the column using HAcHNO3 H2O2, Zr, Hf, and Nb were rinsed off in 6 M HCl0.01 M HF and W was eluted in 6 M HCl1 M HF. Total procedural blanks ranged from 50 to 350 pg for the W isotope composition measurements and 12 to 50 pg W and 10 pg Hf for the isotope dilution measurements. The variable W blanks are caused by the use of different batches of acetic acid. All isotope measurements were performed using a Nu Plasma MCICP-MS at ETH Zrich, equipped with a Cetac Aridus desolvating nebuliser. Prior to measurement, the samples were re-dissolved and dried several times in HNO3H2O2 to remove organic compounds and, in the case of metal-rich samples, volatile Os oxides and then taken up in a 0.56 M HNO30.24 M HF mixture. Tungsten isotope compositions of metals and whole-rocks were typically measured with a signal intensity of 2 V on 182W, which was obtained for a 20 ppb W solution. For these samples, 60 ratios (3 blocks of 20 ratios) were measured resulting in within-run statistics of the order of 0.2 units (2). Owing to the low W contents in the NM fractions, their W isotope compositions were measured in 1 or 2 blocks of 20 ratios each with signal intensities of 0.5 to 1 V on 182W. The within-run statistics of these measurements were typically between 0.5 and 1 unit. Instrumental mass bias was corrected relative to 186W/183W = 1.9859

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using the exponential law. Small isobaric interferences of Os on masses 184 and 186 were corrected by monitoring 188Os and were negligible. The 182W/184W and 183W/184W ratios of all samples were determined relative to two standard runs bracketing the sample run and are reported in 18iW units, which is the deviation of the 18iW/ 184 W ratio from the terrestrial standard value in parts per 10,000. The reproducibility of the 20 ppb standard during one measurement day is typically equal to or better than 0.3 units (2 SD) for the 182W/ 184 W ratio and 0.2 units (2 SD) for the 183W/184W ratio. The external reproducibility of the W isotope measurements typically is 0.30.4
Table 1 HfW data for metals, whole-rocks and non-magnetic fractions Sample Ste. Marguerite (H4) Metal Hf (ppb) 1.81 W (ppb) 823.0
180

183

units (2 SD) for the 182W/184W ratio and 0.20.3 units (2 SD) for the W/184W ratio and was estimated by repeated analysis of a wholerock powder of the Kernouv H6 chondrite and several H chondrite metals (Table 1). The external reproducibility of the isotope measurements of these samples is similar to those obtained for the W standard during one measurement session, indicating that matrix effects are minor to absent. The uncertainties for the W isotope measurements of the W-poor NM fractions (i.e., most of the NM-1 and -2 fractions) were assessed by repeated measurement (1 block of 20 ratios each) of a 10 ppb W standard solutions that yielded an external reproducibility of

Hf/184W

182W 2 meas.

182W 2 corr.

183W 2

0.00251 2

Mean NM Richardton (H5) A-metal (N150 m)

223.0 30.34

16.31 660.9

15.6 1 0.0523 4

3.20 0.25 3.19 0.18 3.13 0.19 3.18 0.07 12.8 0.3 3.47 0.19 3.32 0.19 3.27 0.20 3.06 0.18 3.28 0.35 6.9 0.4 5.9 0.5 4.1 0.5 2.1 0.3 1.8 0.6 3.57 0.16 3.18 0.19 3.7 0.7 2.79 0.26 2.82 0.19 3.20 0.26 3.01 0.53 3.14 0.20 3.18 0.18 3.20 0.17 2.85 0.15 3.08 0.39 25.3 0.7 9.6 0.8 4.3 0.5 2.98 0.21 2.98 0.16 3.03 0.16 2.82 0.19 2.72 0.15 2.90 0.26 4.8 1.0 1.1 0.5 2.86 0.19 3.04 0.24 2.95 0.26 3.04 0.20 2.72 0.18 2.85 0.21 2.87 0.32 23.1 0.7 2.7 0.8 2.66 0.22 2.41 0.20 2.53 0.15 2.53 0.26

0.05 0.15 0.21 0.12 0.02 0.14 0.05 0.29 2.9 0.2 0.05 0.11 0.06 0.13 0.03 0.12 0.17 0.16 0.04 0.20 0.03 0.19 0.97 0.52 0.00 0.21 2.63 0.22 0.69 0.29 0.04 0.08 0.12 0.15 0.55 0.48 0.14 0.18 0.10 0.15 0.13 0.18 0.12 0.06 0.05 0.13 0.07 0.13 0.01 0.10 0.22 0.13 0.10 0.21 0.41 0.55 0.16 0.47 0.39 0.48 0.13 0.12 0.08 0.12 0.12 0.11 0.02 0.12 0.02 0.10 0.07 0.10 1.15 0.48 2.44 0.34 0.17 0.16 0.12 0.14 0.15 0.07 0.13 0.14 0.02 0.14 0.03 0.15 0.04 0.16 0.10 0.30 0.84 0.55 0.14 0.14 0.16 0.17 0.01 0.10 0.10 0.16

Mean A-NM-1 Repl. A-NM-2 A-NM-3 A-NM-4 B-metal ( N 230 m) B-metal (40230 m) B-NM C-WR ALH84069 (H5) Metal (40150 m) Mean Metal (N 150 m)

212.9 212.1 174.9 166.9 162.3 15.2 8.11 183.0 143.6 13.9

18.31 18.23 18.28 26.29 26.31 744.6 740.9 18.86 198.9 687.0

13.3 2 13.3 1 10.9 3 7.2 1 7.0 3 0.0233 2 0.0125 1 11.06 8 0.827 1 0.0231 2

7.4 0.8 6.9 1.4 4.5 0.9 2.2 0.6 2.0 0.9

4.0 1.1

17.4

697.8

0.0284 2

Mean NM-1 NM-2 NM-3 Estacado (H6) Metal (N 150 m)

239.2 151.6 139.3 9.64

5.35 7.48 11.58 826.1

47.4 3 20.8 2 12.0 1 0.01331 9

32.5 6.1 12.6 3.1 5.4 1.3

Mean NM-1 NM-2 Kernouv (H6) Metal (40500 m) Mean Metal ( N 500 m)

148.5 134.3 1.94

10.5 21.1 926

16.2 1 7.27 5 0.00238 2

5.1 1.1 1.6 0.5

0.31

857

0.000415 3

Mean NM-1 NM-2 Whole-rock

175.9 125.7 141.3

3.9 13.3 183.4

51.0 4 10.8 1 0.878 7

25.7 2.3 2.9 1.1

Mean

NM = non-magnetic fraction. The quoted 2 uncertainties for 180Hf/184W refer to the last signicant digits. The quoted 2 uncertainties for the measured 182W and 183W are standard errors of the individual mass spectrometric runs and those for the corrected 182W were calculated by propagating the external reproducibility of the isotope measurements and a 50% uncertainty on the blank correction. The meteorites are from the following collections: Ste. Marguerite (MNHN); Richardton-A (USNM); Richardton-B (MNHN); Richardton-C (Senckenbergmuseum Frankfurt); ALH 84069 (NASA); Kernouv (ETH); Estacado (BM).

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0.8 182W (2 SD). This is similar to the within-run statistics obtained for the measurements of the W-poor NM fractions (Table 1), which for these samples is used as the uncertainty for the measured 182W/184W. Note that the major source of uncertainty in the 182W/184W of the W-poor NM fractions is the blank correction (see below and Table 1). The accuracy of the measurements was monitored by analyzing several carbonaceous chondrites, which all yielded the previously determined value of 1.9 0.1 182W (Kleine et al., 2004a). Furthermore, 183 W/184W ratios were used as a monitor for accurate measurements and agree for most samples to within 0.2 units with the terrestrial value (Table 1). Elevated 183W/184W ratios for two NM fractions of the Richardton meteorite are attributed to an organic interference on mass 183 that was successfully removed for all other samples by treatment with HNO3H2O2. Elevated measured 183W/184W ratios have been observed before for W isotope measurements of some eucrites and carbonaceous chondrites and for these samples the 182W/184W ratio normalized to 186W/184W = 0.96727 agrees with 182W/184W ratios for other eucrites and carbonaceous chondrites, respectively (Kleine et al., 2004a). This indicates that only 183W is affected, such that for the two NM fractions from Richardton with elevated measured 183W/184W the reported 182W values were calculated from the 182W/184W ratio normalized to 186W/184W. Note, that the 182W values thus obtained are consistent with the HfW data for the other fractions of Richardton and also with HfW data for the other H5 chondrite ALH84069 (i.e., all fractions plot on one well-dened isochron). 3. Results The Hf and W concentrations and the W isotope composition of metals, whole-rocks and non-magnetic fractions analyzed for this study are given in Table 1. The H chondrite metals have W concentrations ranging from 660 to 926 ppb, consistent with previously published results (Rambaldi, 1976; Kong and Ebihara, 1996; Humayun and Campbell, 2002). These W concentrations are substantially higher than those reported for metals from unequilibrated H chondrites (Rambaldi, 1976; Kong and Ebihara, 1996; Humayun and Campbell, 2002). The 182W/184W ratios of the H chondrite metals are indistinguishable from each other but appear to increase slightly with metamorphic grade from 3.2 for H4 chondrites to 2.9 182W for H6 chondrites. Some of the Richardton metals do not follow this trend and have 182W values as low as 3.57 0.16. Note that given an external reproducibility of 0.30.4 units for the W isotope measurements, the 182W/184W of this sample is not distinguishable from those of the other H chondrite metals. The various NM fractions have low W
Fig. 2. 182W versus 180Hf/184W for H5 chondrites Richardton and ALH84069. m = initial 182 Hf/180Hf, i = initial 182W. Regressions are calculated using the model 1 t of IsoPlot (Ludwig, 1991). Details regarding the calculation of ages are given in the text. Data shown as lled grey symbols (Richardton whole-rock and coarse-grained metal fractions) were not included in the regression and are not shown in the isochron plot for the combined H5 chondrites. tCAI is the formation interval relative to CAIs; the absolute age t is calculated relative to the angrites D'Orbigny and Sahara 99555 (see text).

Fig. 1. 182W versus 180Hf/184W for Ste. Marguerite. Data shown with open symbols are from Kleine et al. (2002), those with lled symbols from this study. m = initial 182Hf/ 180 Hf, i = initial 182W. Regressions are calculated using the model 1 t of IsoPlot (Ludwig, 1991). Details regarding the calculation of ages are given in the text. tCAI is the formation interval relative to CAIs; the absolute age t is calculated relative to the angrites D'Orbigny and Sahara 99555 (see text).

contents between 4 and 26 ppb and Hf contents ranging from 125 to 239 ppb, resulting in high 180Hf/184W ratios from 7 to 51 and elevated 182W/184W ratios from 2 to 33 182W (Table 1). Owing to the low W contents and radiogenic 182W/184W of the NM fractions, the major source of uncertainty in the ages is the blank correction, which is signicant for some of the NM fractions. Typically the blank corrections ranged from b1 to 3 182W. The NM-1 fraction of ALH 84069 required a larger correction of 7 182W, reecting a higher W blank, which was caused by the use of insufciently clean acetic acid (Table 1). In spite of this large correction the HfW data for the NM-1 fraction from ALH 84069 are consistent with the HfW data for its other fractions that did not require such large corrections. As shown in Figs. 13, the 180Hf/184W ratios and 182W values correlate for each of the analyzed H chondrites, such that precise

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isochron. Compared to the coarse-grained metal, the ne-grained Richardton metal has a slightly higher 182W value, which is identical to the 182W/184W of the ALH84069 metal and also consistent with the trend of slightly increasing 182W values dened by the other H chondrite metals (see Section 4.5). The model age of the ne-grained Richardton metal is 3 5 Ma, consistent with the isochron age of 5.6 1.1 Ma. This indicates that the 182W/184W ratio of the coarse-grained Richardton metal has been displaced to too low values and yields spurious ages. This has probably also affected the measured 182W/ 184 W of the Richardton whole-rock, which is slightly displaced to lower 182W values compared to the Kernouv whole-rock (Table 1) and other H chondrite whole-rocks (Kleine et al., 2007). The origin of these low 182W values remains enigmatic but could be related to the incorporation of irradiated metals with low 182W values, as has been observed for many iron meteorites (Kleine et al., 2005a). However, to our knowledge there is no other evidence for the presence of such metal in Richardton. Note that this has no effect on the interpretation of the HfW age for Richardton, which is obtained from the slope of the isochron. This remains unchanged regardless of whether the two metal fractions with low 182W and the whole-rock were included in the isochron regressions. Excluding these fractions from the regression yields a well-dened isochron (MSWD = 1.5) with an initial 182 Hf/180Hf of (6.47 0.44) 10 5 and initial 182W = 3.23 0.38 (Fig. 2). 4. Discussion 4.1. HfW isochron ages for H chondrites To dene an isochron the minerals of an H chondrite must once have been in W isotope equilibrium, i.e., they must have had the same W isotope composition initially. Given that the H chondrite fractions were obtained mainly based on their magnetic susceptibility, the correlation of 182W with 180Hf/184W could potentially represent a mixing line between W-rich metal and virtually W-free silicates. Such a mixing line would have no chronological signicance if the two

Fig. 3. 182W versus 180Hf/184W for H6 chondrites Kernouv and Estacado. m = initial 182 Hf/180Hf, i = initial 182W. Regressions are calculated using the model 1 t of IsoPlot (Ludwig, 1991). Details regarding the calculation of ages are given in the text. tCAI is the formation interval relative to CAIs; the absolute age t is calculated relative to the angrites D'Orbigny and Sahara 99555 (see text).

isochrons could be obtained (MSWD b 1 in most cases). The uncertainties on the slopes of the isochrons are better than 7% in most cases, resulting in uncertainties for the ages on the order of 1 Ma. Only for Estacado the isochron has a higher uncertainty of 12%, resulting in an uncertainty of 1.7 Ma. For Richardton the scatter on the isochron is slightly larger compared to the other H chondrites, indicating a slight disturbance of the HfW system. A regression including all the Richardton data yields a precise isochron (MSWD = 1.2) corresponding to an initial 182Hf/180Hf of (6.60 0.35) 10 5 and an initial 182W of 3.39 0.17. This initial 182W is indistinguishable from the initial 182W of Allende CAIs of 3.30 0.12 (Burkhardt et al., submitted for publication) and corresponds to a W model age of 2 4 Ma (using the W isotope composition of Kernouv as a reference), inconsistent with the age obtained from the initial 182Hf/180Hf of the Richardton

Fig. 4. Hf versus W contents for the different fractions of the analyzed H chondrites. Data for some of the NM (non-magnetic) fractions from Ste. Marguerite are from Kleine et al. (2002). The Hf and W concentrations in the coexisting phases of these H chondrites are not colinear, indicating that presence of at least three independent components for Hf and W among the coexisting phases. These components are high-Ca pyroxene + ilmenite, olivine + low-Ca pyroxene, and metal.

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endmembers had different initial 182W/184W ratios. However, as shown in Fig. 4, the variations in 180Hf/184W ratios among the analyzed H chondrite fractions require the presence of at least three independent components for Hf and W among the coexisting phases. The major host of W is metal, which constitutes one component. The major hosts of Hf are high-Ca pyroxene and ilmenite (Righter and Shearer, 2003) and since no pure high-Ca pyroxene and ilmenite separates could be obtained these two phases are considered together as one component. The third component encompasses olivine and low-Ca pyroxene and is characterized by low Hf and W contents. These two minerals are considered as one component because no pure olivine and low-Ca pyroxene separates were obtained. Both olivine and low-Ca pyroxene are not capable of incorporating signicant amounts of either Hf or W (Righter and Shearer, 2003), such that their presence mainly causes dilution of the high Hf content of high-Ca pyroxene and ilmenite. Given that high-Ca pyroxene, ilmenite, olivine, and low-Ca pyroxene have similar and low W contents, the slightly higher W contents of the NM-3 and -4 fractions compared to the NM1 and -2 fractions of the same meteorite most likely reect the presence of some metal in the NM-3 and -4 fractions. The presence of at least three independent components with regard to Hf and W among the coexisting phases of H chondrites reveals that the correlation between 182W and 180Hf/184W observed for the fractions of each of the H chondrites cannot reect simple binary mixing between W-rich metal and virtually W-free silicates. This is also apparent from plots of 182W vs. 1/W, in which binary mixtures form straight lines. This is not the case for any of the meteorites investigated here, such that the linear correlations in the 182W vs. 180Hf/184W plots cannot be mixing lines (for the H6 chondrites the data seem to plot on straight lines but in the case of Kernouv the MSWD of this 182W vs. 1/W line is 4.5 instead of 0.28 for the isochron). Each of the fractions, therefore, evolved to radiogenic 182W according to their 180Hf/184W. Hence, the HfW data for the H chondrite fractions dene isochrons and can be interpreted to have chronological signicance. Relative HfW ages (or formation intervals), tCAI, are calculated from the initial 182Hf/180Hf ratios obtained from the slopes of the isochrons relative to an initial 182Hf/180Hf = (1.003 0.045) 10 4 for CAIs and refer to the time of HfW closure in a sample elapsed since crystallization of type B CAIs (Burkhardt et al., submitted for publication). With increasing metamorphic grade, the HfW ages of the H chondrites become increasingly younger and range from tCAI = 1.7 0.7 Ma for the H4 chondrite Ste. Marguerite to tCAI = 9.6 1.0 Ma for the H6 chondrites Kernouv and Estacado. The HfW ages for the H5 chondrites Richardton and ALH 84069 are intermediate between the ages for the H4 and H6 chondrites and are tCAI = 5.9 0.9 Ma. The comparison of relative HfW ages and absolute PbPb ages requires conversion of HfW formation intervals to absolute ages, which in turn requires knowledge of the initial 182Hf/180Hf and the absolute age of HfW closure in a sample. Due to differences in closure temperatures of different chronometers, the ideal samples to obtain such information are angrites because (i) they cooled rapidly, such that differences in closure temperatures do not result in resolvable age differences, and (ii) they exhibit high U/Pb ratios, such that precise Pb Pb ages are available (Lugmair and Galer,1992; Amelin, 2008). The most precise PbPb age for the angrites D'Orbigny is 4564.42 0.12 Ma (Amelin, 2008). For the angrite Sahara 99555, the earlier reported Pb Pb age of 4566.18 0.14 Ma (Baker et al., 2005) has now been revised and two identical ages of 4564.58 0.14 and 4564.86 0.38 Ma, obtained using different techniques for the removal of Pb contamination, were reported (Connelly et al., 2008). Mineral separates from D'Orbigny and Sahara 99555 plot on one well-dened HfW isochron (MSWD = 1.4) yielding an initial 182Hf/180Hf of (7.31 0.16) 10 5 [recalculated from the HfW data reported in Markowski et al. (2007) and using the model 1 t of IsoPlot], consistent with identical PbPb

ages for these two angrites. Here we calculate absolute HfW ages relative to an initial 182Hf/180Hf = (7.31 0.16) 10 5 at 4564.50 0.23 Ma (i.e., the average of the aforementioned PbPb ages for D'Orbigny and the more precise age for Sahara 99555). Identical results are obtained if absolute HfW ages were calculated relative to D'Orbigny only or Sahara 99555 only. This approach for calculating absolute HfW ages is based on the assumption that the PbPb ages for D'Orbigny and Sahara 99555 accurately date the crystallization of these rocks. Several PbPb studies on angrites, however, reported PbPb ages for the same angrite that are distinct outside of the reported age uncertainties (Baker et al., 2005; Amelin, 2008; Connelly et al., 2008). Nevertheless, given that two groups obtained identical high-precision PbPb ages for the angrites D'Orbigny and Sahara 99555 (Amelin, 2008; Connelly et al., 2008), these ages appear reliable and their use as reference ages for HfW chronometry justied. Moreover, HfW ages for two other angrites (Kleine et al., 2008) are consistent with their PbPb ages (Amelin and Irving, 2007), indicating that the intercalibration of HfW and PbPb ages provides reliable results. 4.2. Closure temperature for the HfW system in equilibrated H chondrites To evaluate the signicance of the HfW ages for constraining the thermal evolution of meteorite parent bodies, it is necessary to know the closure temperature for W diffusion in the appropriate silicatemetal mixture. In H chondrites, the major hosts of radiogenic 182W are high-Ca pyroxene and ilmenite and each of these minerals might have its distinct HfW closure temperature. In slowly cooled metamorphic rocks such as H chondrites, one of these two minerals may have stayed open while the other had already closed. This would result in scatter on the isochron but this is not observed for the data presented here. This indicates that there are no signicant differences in the HfW closure temperatures of high-Ca pyroxene and ilmenite in H chondrites, given that the variable Hf contents in the different NM fractions most likely reect different proportions of ilmenite and highCa pyroxene in these fractions. There are no experimental data available for diffusion of W in highCa pyroxene or ilmenite that would allow calculation of the closure temperature as a function of effective grain size and cooling rate. Based on the comparison of HfW ages for eucrite metals with PbPb ages for the host eucrites, Kleine et al. (2005b) estimated the closure temperature of the HfW system in basaltic eucrites to be at least 600 C. Here we estimate the closure temperature of the HfW system by modeling the diffusion behavior of W in high-Ca pyroxenes and test these results by comparison to PbPb ages for chondrites. The diffusion behavior of W in high-Ca pyroxene was evaluated by (i) using the model presented by Van Orman et al. (2001) to estimate the diffusion parameters for W in high-Ca pyroxene and by (ii) modeling the diffusion behavior of W in a high-Ca pyroxene-metal system. Tungsten is assumed to have a charge of +4, an ionic radius of 0.066 nm (Shannon, 1976) and is assumed to reside on the 6-fold coordinated M1 site in high-Ca pyroxene, which has an ideal radius of 0.072 nm and metaloxygen bond length of 0.22 nm. Assuming that the Van Orman et al. (2001) model applies to cations that occupy the M1 site which appears reasonable since the model predicts diffusion coefcients for Fe2+ on the M1 site that are in good agreement with experimental data (Azough and Freer, 2000) gives an activation energy estimate of 453 kJ/mol and a pre-exponential factor of 9.53 10 5 m2/s. Simultaneous production and diffusive exchange of radiogenic W between high-Ca pyroxene and metal was simulated numerically using the model of Van Orman et al. (2006). We chose to use this numerical model rather than the analytical models for closure temperature presented by Dodson (1973) and Ganguly and Tirone (2001) because the analytical models make several assumptions that do not necessarily apply to the cases considered here. For example, the

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Dodson (1973) and Ganguly and Tirone (2001) models assume (i) an innite sink for radiogenic daughters (which is a valid assumption in the case of H chondrites); (ii) a decay time that is very long compared to the cooling time (which might not be valid for short-lived chronometers); and (iii) that heating at peak metamorphic conditions was sufcient to homogenize the high-Ca pyroxene. The numerical model used here does not rely on these assumptions, and is thus a more realistic model for the production and exchange of radiogenic daughters in short-lived isotope systems. As will be shown below, the assumption that peak metamorphic conditions were sufcient to reset the HfW system is not valid in the case of the H4 chondrites. Assessing the effects that metamorphism had on the HfW system in H4 chondrites therefore requires a model that can simulate the prograde path, such as the one used here. In the model, exchange of radiogenic W is controlled by diffusion within spherical high-Ca pyroxene grains, which maintain partitioning equilibrium with metal at their surfaces. Because diffusion in Fe Ni alloys is many orders of magnitude more rapid than in high-Ca pyroxene (Watson and Watson, 2003), the metal is assumed to remain homogeneous throughout the simulation. In most simulations, 182W is assumed to be distributed in chemical and isotopic equilibrium between the high-Ca pyroxene and metal at the peak temperature. However, we also performed simulations, described below as applied to H4 and H5 chondrites, in which the sample had experienced a cold pre-history, during which radiogenic W was not transferred from the high-Ca pyroxene to the metal. The system is assumed to cool linearly with time from the peak temperature, and the nal age is calculated based on the integrated concentrations of 182W in the high-Ca pyroxene and the metal resulting from the decay of 182Hf. This age corresponds to a particular temperature along the cooling path, which is by denition the closure temperature of the system. The cooling time from peak temperatures to temperatures at which diffusive exchange becomes negligible is 10 Ma, which is similar to the 182Hf half-life. In the cases considered here, diffusive exchange ceased before 182Hf had completely decayed, such that while the system remains open to exchange, the decay of 182 Hf is signicant. The closure temperature estimates shown in Fig. 5 assume an initial temperature of 1000 C. This temperature provides an upper limit for the peak temperature of H6 chondrites because at 1000 C melting in the FeNiFeS system begins but the texture of H6 chondrites reveals that such melting did not occur. Assuming an

Fig. 5. Closure temperature of the HfW system as function of grain diameter and cooling rate. The assumed starting temperature is 1000 C. Details regarding the calculations are given in the text. The dashed areas indicate two-pyroxene and olivine spinel temperatures for H chondrites. The grey boxes indicate typical cooling rates and grain sizes of high-Ca pyroxene for each of the petrologic types of H chondrites.

initial temperature of 1000 C appears reasonable because temperature estimates for H6 chondrites using the two-pyroxene thermometer (Lindsley, 1983) yield a temperature range of 865 926 C (Slater-Reynolds and McSween, 2005), only slightly below 1000 C. The peak metamorphic temperatures for H45 chondrites are less well constrained, mainly because in these rocks the pyroxenes are not completely equilibrated, such that two-pyroxene thermometry cannot be applied. Based on temperature estimates for type 3 (obtained from Ni proles in taenite) and type 6 chondrites, Dodd (1981) estimated the peak temperatures for type 4 and type 5 chondrites to 600700 C and 700750 C, respectively. In more recent studies olivinespinel thermometry was used to determine temperatures for type 46 chondrites and the results for H46 chondrites tightly cluster between 675 and 750 C (Wlotzka, 2005; Kessel et al., 2007). These temperatures provide a lower limit for the peak temperatures and the tight cluster of olivinespinel temperatures suggest that peak temperatures for H46 chondrites were not very different (Wlotzka, 2005; Kessel et al., 2007). Fig. 5 shows closure temperatures calculated as a function of cooling rate, for an initial temperature of 1000 C and four different high-Ca pyroxene grain diameters between 1 and 150 m. The high-Ca pyroxene/metal ratio in these simulations is 0.5 and the high-Ca pyroxene/metal partition coefcient for W is 0.01 (Walter and Thibault, 1995), but the results are not sensitive to variations in these parameters unless the high-Ca pyroxene/metal ratio and/or partition coefcient become much larger. Fig. 5 reveals that the closure temperature of the HfW system in H chondrites is strongly dependent on the grain size of the high-Ca pyroxenes, particularly for grain sizes below 20 m. As a consequence, Tc increases from H4 to H6 chondrites because the grain sizes of high-Ca pyroxenes increase. In H6 chondrites, the high-Ca pyroxenes are 530 m in diameter, whereas in H5 chondrites they are 25 m but can also be larger (Huss et al., 2006). In H4 chondrites, high-Ca pyroxene microcrystallites may have diameters of less than 1 m but high-Ca pyroxenes also occur as euhedral grains of less than 10 m in the mesostasis and form rims around olivine and low-Ca pyroxene that are 1020 m across (Huss et al., 2006; C. Alexander and J. Grossmann, pers. comm. 2007). Using these grain sizes the following values for Tc are obtained (Fig. 5): 800875 C (H6); 750 850 C (H5); 725850 C (H4). However, these temperature estimates assume that high-Ca pyroxene and metal are always in direct contact but given that high-Ca pyroxene is only a minor constituent in H chondrites this will probably not be the case. A more realistic approach is to assume that the high-Ca pyroxene grains are surrounded and sometimes even enclosed by large olivine and low-Ca pyroxene grains (with grain diameters between 20 and 200 m). These grains would constitute a barrier for W diffusion from the highCa pyroxene to the metal and the estimates for Tc presented above are then lower limits. A higher limit for Tc is given by the peak temperature of H6 chondrites that must have been below 1000 C and above the twopyroxene temperature of 900 C (see above). It therefore is reasonable to assume that the higher limit of Tc in H6 chondrites is 950 C. For H5 chondrites the peak temperature probably was somewhat lower and here we assume 900 C. Combined with the lower limits for Tc obtained from Fig. 5 and based on the grain sizes of the high-Ca pyroxenes the following values for Tc are obtained: 875 75 C for H6 chondrites and 825 75 C for H5 chondrites. The HfW closure temperature for H4 chondrites is more difcult to estimate than those for H5 and H6 chondrites because the peak temperature in H4 chondrites as well as the host phase(s) of radiogenic 182W and its grain size(s) in H3 chondrites are less well constrained. In type 3 chondrites, Hf is enriched in the mesostasis (and high-Ca pyroxenes therein) of chondrules and in high-Ca rims on olivine and low-Ca pyroxene grains in chondrules (Alexander, 1994). Tungsten most likely is concentrated in metal grains outside

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chondrules and in the matrix (see below). The rate of diffusive transport of radiogenic 182W from the chondrules into metal outside the chondrules is difcult to model and critically depends on the exact location of W in the chondrules and, as is evident from Fig. 5, on the high-Ca pyroxene grain size. The range in grain sizes of b 1 m to 10 m corresponds to a range in Tc of 100 C (Fig. 5). In addition, the rate of W diffusion depends on the grain sizes of olivine and low-Ca pyroxene inside the chondrules, which control how many grain boundary paths there are between the high-Ca pyroxenes and the metals. A lower limit for Tc may be obtained by assuming that radiogenic 182W is located inside 0.1 m high-Ca pyroxene microcrystallites, which are in direct contact to metals outside the chondrules. In this model, a closure temperature of 700 C is calculated. The true value for Tc will be signicantly higher because larger highCa pyroxenes are present and the high-Ca pyroxenes inside the chondrules and metal grains outside the chondrules will mostly not be in direct contact. A higher limit for Tc may be obtained by assuming that all high-Ca pyroxenes have grain sizes of 10 m, in which case the closure temperature will be 850 C (Fig. 5). Given that many of the high-Ca pyroxene grains in H4 chondrites have sizes larger than 1 m, Tc will probably be higher than 750 C (Fig. 5) and the best estimate for Tc in H4 chondrites then is 80050 C. The comparison of the HfW ages and other ages provides a test for the validity of the above closure temperature estimates. For Ste. Marguerite, Kernouv and Estacado the HfW ages are the oldest radioisotopic ages reported for these meteorites so far, for Richardton the HfW and PbPb chondrule ages are indistinguishable (Table 2). The most reliable approach for estimating closure temperatures by age comparison uses slowly cooled samples because then differences in closure temperatures among different isotope systems and minerals will result in resolvable age differences. The HfW age for Kernouv is 23 Ma older than PbPb whole-rock and pyroxene ages (Gpel et al., 1994; Bouvier et al., 2007) for this meteorite and the HfW age for Estacado is 30 Ma older than a PbPb chondrule age (Blinova et al., 2007) (Table 2). This indicates that the HfW closure temperature must be well above the closure temperature for Pb diffusion in pyroxenes (Cherniak, 1998; Amelin et al., 2005), consistent with the observation that HfW ages for eucrite metals are older than PbPb ages for their host eucrites (Kleine et al., 2005b). The closure temperature for Pb diffusion in pyroxenes in H6 chondrites was estimated to be 780 100 C for grain sizes of 20200 m (Amelin et al., 2005), which is indistinguishable from but appears to be slightly lower than our estimate for the HfW closure temperature in H6 chondrites of

875 75 C. This indicates that the closure temperature estimates for the HfW system presented here are reasonable. It is important to note that the Pb closure temperature for pyroxenes in H chondrites might be lower than 780 100 C because in these samples the grain sizes of the high-Ca pyroxene (Huss et al., 2006) are smaller than the 20200 m range used in the calculation by Amelin et al. (2005). HighCa pyroxenes are probably an important host of U among the silicate minerals of H chondrites because U ts much better into the M2 (i.e., Ca) site of pyroxenes and should therefore be enriched in high-Ca relative to low-Ca pyroxene. For grain sizes of 530 m the closure temperature for Pb diffusion ranges from 650 C to 780 C and decreases to temperatures as low as 550 C for grain sizes of 1 m. As for the HfW system these closure temperature estimates probably are lower limits because they do not take into account the effects of large olivine and low-Ca pyroxenes (e.g., as barriers for Pb diffusion). However, these calculations reveal that the HfW closure temperature in H6 chondrites is distinctly higher than the UPb closure temperature in pyroxenes, consistent with the well-resolved differences in HfW and PbPb ages for Kernouv and Estacado. 4.3. Signicance of the HfW ages To utilize HfW ages for H chondrites for constraining the timescales of parent body accretion, heating and cooling it is essential to identify which events are being dated. In the case of metamorphic rocks such as H chondrites, these could be (i) cooling from peak metamorphic temperatures below Tc, (ii) mineral growth during metamorphism (this could take place below Tc), or (iii) a premetamorphic event (in the case that metamorphism was not capable of resetting the HfW system). The interpretation of the HfW ages critically depends on (i) whether heating above Tc was achieved, and (ii) how efciently any initial W isotope heterogeneity, produced by the decay of 182Hf in phases having different Hf/W, has been erased by the thermal metamorphism. 4.3.1. HfW age of the H4 chondrite Ste. Marguerite: timing of chondrule formation The lower limit of the HfW closure temperature for H4 chondrites overlaps with the upper limit of 750 C of olivinespinel temperatures determined for this chondrite group (Wlotzka, 2005; Kessel et al., 2007). Peak temperatures of H4 chondrites may be higher than the olivinespinel temperatures but to what extent is unknown. It is therefore difcult to estimate if H4 chondrites were heated above Tc but it appears that for complete resetting of the HfW system heating to 800850 C would be required. This is only slightly below the peak temperatures of H6 chondrites and it seems unlikely that this has been achieved. Moreover, the high olivinespinel temperature for H4 chondrites may in part reect an earlier high-temperature event (such as chondrule formation), in which case the peak temperatures of the H4 chondrites could be below 700 C, consistent with temperature estimates by Dodd (1981). To evaluate whether the HfW age for Ste. Marguerite reects parent body metamorphism, we numerically simulated the diffusional exchange of W between clinopyroxene and metal using the model of Van Orman et al. (see above). In the simulation, we led a clinopyroxene-metal system evolve for 1 Ma at low temperatures, such that no diffusional exchange between clinopyroxene and metal could occur, then instantaneously heated to 800 C and led the system cool at 200/Ma. The simulations indicate that such a scenario is not capable of erasing the previously accumulated radiogenic W isotope signature of the clinopyroxene. In this particular scenario, the age of the system would only shift by 0.07 Ma, i.e., if 2.7 Ma would be the time of heating, the HfW age would still be 1.77 Ma and, hence, almost entirely reect the earlier event. Two lines of evidence further suggest that the HfW age for Ste. Marguerite has not been reset by parent body metamorphism. First,

Table 2 Compilation of radiometric ages for selected H chondrites (in Ma) Sample Minerals Age (Ma) 2 Tc (C) System
182

References

Ste. Marguerite metal-silicate 4566.9 0.5 800 50 whole-rock, 4564.4 3.4 650 100 chondrules phosphates 4562.7 0.6 477 100 Richardton metal-silicate 4563.0 0.9 825 75 chondrules 4562.7 1.7 725 100 phosphates 4550.7 2.6 477 100 Estacado metal-silicate 4558.6 1.6 875 75 chondrules 4527.6 6.3 777 100 phosphates 4492 15 477 100 Kernouv metal-silicate 4559.2 1.0 875 75 whole-rock; 4536 7 777 100 pyroxene-olivine phosphates 4522.5 1.5 477 100

207

Hf182W this study Pb206Pb (3,4) (4) this study (1) (1,4) this study (2) (2) this study (3,4)

207 182

Pb206Pb Hf182W 207 Pb206Pb 207 Pb206Pb 182 Hf182W 207 Pb206Pb 207 Pb206Pb 182 Hf182W 207 Pb206Pb
207

Pb206Pb (4)

The PbPb ages for whole-rocks and silicates from Ste. Marguerite and Kernouv are averages of the ages reported in the literature. The uncertainties are calculated as standard deviations (2) of these ages. For estimates of the closure temperatures see text. (1) Amelin et al. (2005); (2) Blinova et al. (2007); (3) Bouvier et al. (2007); (4) Gpel et al. (1994).

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the HfW age for Ste. Marguerite of 1.7 0.7 Ma is identical to AlMg ages for chondrules from L and LL chondrites (Russell et al., 1996; Kita et al., 2000; Rudraswami and Goswami, 2007). Although no ages for chondrules from H chondrites are available it seems likely that H chondrules formed at the same time as L and LL chondrules, given that both L and LL chondrules have identical average AlMg ages of 2 Ma (Russell et al., 1996; Kita et al., 2000; Rudraswami and Goswami, 2007). Hence, H chondrules probably formed at 2 Ma, which is the time given by the HfW age for Ste. Marguerite. Second, since chondrules formed before the assembly of their host parent body, chondrule ages provide the earliest time at which assembly of and hence heating inside the parent body can have started. Thermal modeling of spherical asteroids heated by 26Al decay indicate that a temperature increase to 700 C is unlikely to have been achieved earlier than 1 Ma after accretion. This suggests that the 1.7 0.7 Ma HfW age for Ste. Marguerite could only date parent body processes if the H chondrite parent body formed much earlier than the L and LL chondrite parent bodies. However, this would imply that due to 26Al heating signicant parts of the H chondrite parent body would have melted and differentiated. However, ordinary chondrite parent bodies appear to be well sampled by breccias but these do not contain any differentiated material (Scott, 2006), which would be expected if the H chondrite parent body had been partially differentiated. Based on the similar 17O values of H chondrites and silicate inclusions from IIE iron meteorites it was suggested that IIE metal might represent the core of the H chondrite parent body (Clayton and Mayeda, 1996). However, similarity in 17O values does not require identical parent bodies, as is evident from meteorites that derive from distinct parent bodies but have identical 17O values (e.g., enstatite chondrites, aubrites, terrestrial and lunar rocks; IVA irons and LL chondrites). These arguments suggest that in Ste. Marguerite metamorphism on the parent body did not result in signicant diffusion of radiogenic W out of high-Ca pyroxene. However, elemental diffusion of W into metals clearly occurred. This is evident from the substantially higher W contents of metals from type 4 chondrites compared to metals from type 3 chondrites (Rambaldi, 1976; Kong and Ebihara, 1996; Humayun and Campbell, 2002). Evaluating whether this elemental transfer of W could have caused resetting of the HfW age critically depends on identifying the original host of the W that diffused into the metals during metamorphism of H4 chondrites. H chondrites contain 180 ppb W (Table 1) and metals in H3 chondrites have 300 ppb W, i.e., only 30% of the entire W resides in the metal (assuming a metal mass fraction of 20%). In contrast, metals in H4 chondrites Ste. Marguerite have 800 ppb W, indicating that almost all W (90%) is located in the metals. Consequently, during metamorphism 60% of the entire W in H chondrites must have diffused into the metals. None of the major silicate minerals in H chondrites (i.e., olivine, low-Ca pyroxene, high-Ca pyroxene) is capable of incorporating such high amounts of W (Righter and Shearer, 2003), as a consequence these minerals cannot be the original host of the W that has been mobilized during metamorphism and incorporated into the metals. Nonmagnetic fractions from ordinary chondrites have Ir contents that are too high to reect equilibrium distribution between metal and silicates (Palme et al., 1981). This suggests that ordinary chondrites contain a component with appreciable amounts of siderophile elements (including W) that cannot be separated from silicates with a hand-magnet. This phase could be tiny metal grains (that are too small to be separated with a hand-magnet) or small refractory inclusions that reside in the matrix. It is conceivable that W from these phase(s) became easily mobilized during metamorphism and diffused, probably along grain boundaries, into the metals. This W probably was not radiogenic because the Hf/W ratios in its host metal grains or refractory inclusions likely were low. For instance, the 182W/184W in a reservoir with 180Hf/184W 1.7 (i.e., a value typical for CAIs) only changes by 0.12 /Ma, such that the W that diffused into the metals

of H4 chondrites most likely had a W isotope composition very similar to the 182W/184W of the H3 metal. The elemental diffusion of W from the matrix into the metals therefore most likely had no measurable effect on the 182W/184W of the H4 chondrite metal and hence did not affect the slope of the metal-high-Ca pyroxene isochron. 4.3.2. HfW ages for H5 and H6 chondrites: timing of the thermal peak The HfW isochrons for the H5 and H6 chondrites investigated here are shallower than those of Ste. Marguerite, indicating that diffusion of radiogenic W from high Hf/W phases occurred in these samples. The interpretation of the HfW ages for the H5 and H6 chondrites critically depends on whether this diffusion completely erased any preexisting W isotope heterogeneity. To evaluate this we performed simulations similar to those for H4 chondrites. We let a high-Ca pyroxene-metal system evolve for 1 Ma at low temperatures, such that no diffusional exchange between high-Ca pyroxene and metal could occur, then instantaneously heated to 950 C and let the system cool at 34 C/Ma (see below). Using a 4 m effective grain size for the high-Ca pyroxenes the system homogenizes almost as soon as cooling begins, suggesting that any initial W isotopic heterogeneity in Richardton has been largely erased by the thermal metamorphism. This is consistent with the observation that the HfW age for Richardton is identical to the PbPb age for its chondrules. Owing to the slower diffusivity of W compared to Pb, incomplete resetting would be more pronounced for the HfW system than for the PbPb system, such that in the case of incomplete resetting the apparent Hf W age would be older than the apparent PbPb age. The difference should increase with a decreasing degree of resetting. However, the HfW and PbPb ages for Richardton of 4563.0 0.9 and 4562.7 1.7 Ma (Amelin et al., 2005), respectively, are identical, such that the effects of incomplete resetting seem to be minor or absent and both ages should date cooling from peak metamorphic temperatures. Given that H6 chondrites were heated to higher (or at least similar) peak temperatures and cooled at a slower rate, this implies that the HfW ages for H6 chondrites also reect cooling below the HfW closure temperature. The difference in HfW ages between H4 and H6 chondrites is only 8 Ma and much shorter than intervals of 74 Ma based on the elevated initial 87Sr/86Sr of phosphates from the H6 chondrite Guarea (Wasserburg et al., 1969) and 40 Ma based on the differences in Pb Pb ages of phosphates from Ste. Marguerite (H4) and Kernouv (H6) (Gpel et al., 1994). Humayun and Campbell (2002) argued that the abundance and isotope composition of W in metals from ordinary chondrites of type 4, 5, and 6 was set at the same time during the prograde path, whereas other ages were interpreted as postmetamorphic cooling ages. This conclusion was based on the observation that metals from type 4, 5, and 6 have constant W/Ir ratios that are distinct from the variable W/Ir ratios observed for metals from type 3 ordinary chondrites (Humayun and Campbell, 2002). According to Humayun and Campbell (2002) this reects termination of W diffusion (both elemental and isotopic) from silicates into metal at metamorphic conditions characteristic for type 4 chondrites. These authors further argue that the transfer of W from silicates to metal is facilitated by W reduction in the presence of C and that the major Cbearing phases in ordinary chondrites are decomposed in the earliest stages of metamorphism. As a consequence, reduction of W and its transfer from silicates into metal would no longer be possible in type 5 and 6 ordinary chondrites and HfW ages for type 4, 5, and 6 chondrites should be identical. However, the HfW ages and closure temperature estimates presented here reveal that this is not the case and that continued diffusional exchange of W occurred in the type 5 and 6 chondrites. The much shorter HfW interval compared to the RbSr and PbPb intervals rather highlights the fact that the HfW system closed early and, hence, dates processes associated with the earliest evolution of the H chondrite parent body.

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4.4. Constraints on the accretion and cooling history The HfW ages for the H chondrites can be used to constrain the cooling history and structure of the H chondrite parent body. Temperature proles for spherical asteroids heated by energy released from 26Al decay (Carslaw and Jaeger, 1959) were calculated using parameters similar to those of Miyamoto et al. (1981) and results similar to those of Trieloff et al. (2003) were obtained (details are given in the caption of Fig. 6). The model used here is an oversimplication because it assumes instantaneous accretion and does neither include the insulating effects of a regolith (Akridge et al., 1998) nor temporal and local variations in physical and thermal parameters (e.g., changes in thermal conductivity due to a decrease in porosity) (Bennett and McSween, 1996). If accretion took place over a timescale similar to the 26Al half-life, then a body starts retaining the heat produced by 26Al decay before reaching its terminal mass and peak temperatures are reached earlier than estimated when assuming instantaneous accretion (Merk et al., 2002; Ghosh et al., 2003). A thick insulating regolith results in a more uniform temperature distribution in the interior, such that peak temperatures can be reached at shallower levels compared to the model used here (Akridge et al., 1998). Nevertheless, to a rst order, the thermal model presented here is useful for calculating cooling curves for individual samples that are consistent with the chronological data and for constraining the structure and thermal history of the H chondrite parent body. The calculated temperature proles for different depth in a spherical body with a 100 km radius are shown in Fig. 6 and reveal that all chronological data combined are consistent with the simple thermal model used here: the high-temperature (N 500 C) cooling history constrained by the HfW ages is consistent with the low-temperature (b 500 C) cooling history as constrained earlier (Trieloff et al., 2003). For each of the samples well-dened cooling curves are obtained, suggesting that these samples cooled more or less undisturbed from their peak temperatures to less than 100 C. This provides evidence

Fig. 7. Cooling rate versus petrologic type for H chondrites from this study. For both high and low temperatures there is an inverse correlation of cooling rates with petrologic type, consistent with an onion-shell structure of the H chondrite parent body. The lack of such a correlation between metallographic cooling rates and petrologic type for some H chondrites (Taylor et al., 1987) probably reects impact-related disturbance of parts of the H chondrite parent body during the low-temperature interval (b 500 C).

Fig. 6. Cooling curves for H chondrites. Solid lines indicate calculated temperature proles for different depth in a spherical body with a 100 km radius. Numbers indicate distance in km from the center. We used the following parameters adapted from Miyamoto et al. (Miyamoto et al., 1981): thermal conductivity K = 1.0 W m 1 1; thermal K diffusivity = 5.0 10 7 m2 s 1 ; density r = 3.2 10 3 kg m 3 ; heat generation 26 27 3 1 A = 11.67 ( Al/ Al) W m ; emissivity h = 1.0 m . The assumed ambient temperature is T0 = 300 K and the initial 26Al/27Al is 4.5 10 6, corresponding to accretion at 2.7 Ma after CAIs. HfW ages and closure temperatures are from this study, all other ages are from the literature (references are given in Table 2). wr = whole-rock, ch = chondrules, ph = phosphates, fsp = feldspar, mrl = merrilite. ArAr and 244Pu ages are shifted by 30 Ma due to the proposed revision in the 40K decay constant (Trieloff et al., 2001; Min et al., 2003; Trieloff et al., 2003).

that at least parts of the H chondrite parent body stayed intact and were not disrupted and reassembled. Cooling rates for H chondrites can be obtained from the slope of the cooling curves. This reveals a marked decrease in cooling rates from H4 to H6 chondrites (Fig. 7). For instance, at 700 C the H6 chondrites Kernouv and Estacado cooled at 10/Ma, whereas the H5 chondrite Richardton cooled at 30 C/Ma; at 400 C the H6 chondrites cooled at 5 C/Ma, Richardton at 12 C/Ma and the H4 chondrite Ste. Marguerite at 50 C/Ma. This inverse correlation of cooling rate with petrologic type is most consistent with an onionshell structure of the H chondrite parent body. However, the lack of such a correlation between metallographic cooling rates and petrologic type for some other H chondrites suggests that in some parts of the H chondrite parent body cooling from 500 to 300 C did not take place in a body with onion-shell structure (Taylor et al., 1987). The low temperature cooling history of these parts of the H chondrite parent body therefore is most readily explained by impact-related disturbance of parts of the parent body. Although the HfW data do not provide direct age constraints on the timescales of accretion of the H chondrite parent body because none of the HfW ages directly relates to the process of accretion they can nevertheless be used to obtain minimum and maximum ages for accretion. Accretion could not have started before chondrule formation at 1.7 0.7 Ma, as given by the HfW age for Ste. Marguerite. The end of accretion is less well constrained but the HfW age for H5 chondrites of tCAI = 5.9 0.9 Ma as well as the 4562.7 0.6 Ma PbPb age for phosphates from Ste. Marguerite (H4) indicate that H4 and H5 chondrites had already reached their thermal peak and cooled below 800 C (H5) and 450 C (H4), respectively, as early as 6 Ma after CAI formation. It therefore is unlikely that signicant accretion occurred later than 6 Ma. Additional constraints on the duration of accretion are provided by the distinct sizes and chemical properties of chondrules from each chondrite group. In a turbulent solar nebula, chondrules would be efciently mixed on short timescales (Cuzzi et al., 2005), such that a characteristic population of chondrules with its distinct size distribution and chemical composition could only be preserved, if this chondrule population is accreted into larger bodies soon after chondrule formation. This was quantied by Alexander (2005), who estimated that material in a 1 AU wide area could be mixed within less than 0.5 Ma. Since asteroid feeding zones probably were smaller, these mixing times become even shorter. If these estimates are correct, chondrite accretion must have occurred almost instantaneously after chondrule formation (Alexander, 2005). This

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does not necessarily imply that the entire H chondrite parent body was accreted at 1.7 0.7 Ma (or soon after). It might also be possible that several smaller objects formed at that time and were combined later to the H chondrite parent body. However, as argued above, this process was largely complete by 6 Ma after CAI formation at the latest. There are two endmember interpretations for the HfW age of H6 chondrites. First, this age could reect cooling from the thermal peak of 950 C below Tc = 875 75 C for H6 chondrites. In this case, the HfW age would almost reect the time when cooling from the thermal peak started. Alternatively, temperatures inside the H chondrite parent body remained at their peak for longer but Tc increased due to grain coarsening and the HfW system closed although cooling had not yet started. In this case, metamorphic temperatures could have remained above Tc for longer than 10 Ma. The thermal modeling shown in Fig. 6 reveals that this might be the case, at least for Estacado. All chronological data for Estacado plot on the 40 km cooling curve but at that depth, cooling from peak temperatures might have started as late as 2030 Ma, signicantly later than the HfW age of 10 Ma. Therefore, in Estacado the HfW system might have closed before cooling started. Note, however, that both peak temperature and HfW closure temperature are not known precisely enough to clearly distinguish between these two endmember interpretations. Owing to the similarity of peak metamorphic and HfW closure temperature, both processes (i.e., cooling and increase in Tc due to grain coarsening) were probably important for H6 chondrites. In any case, the HfW age for H6 chondrites corresponds closely to the time of the thermal peak. The HfW results appear to be most consistent with some of the models for the H chondrite parent body presented by Ghosh et al. (2003). In their models 3 and 4, accretion of the H chondrite parent body started at 2 Ma and ended 23.5 Ma later. Peak metamorphic temperatures in the centre are reached at 56 Ma and although Ghosh et al. (2003) do not provide information on how long peak temperatures are maintained in their models 3 and 4, other thermal models indicate that in a body with 100 km radius temperatures can be as high as 900 C at 10 Ma (Miyamoto et al., 1981; Bouvier et al., 2007) (see also Fig. 6). Amelin et al. (2005) also found that the PbPb dating results for Richardton are most consistent with the model 3 of Ghosh et al. (2003). 4.5. HfW fractionation among chondrite parent materials in the solar nebula The initial 182W and initial 182Hf/180Hf obtained from the H chondrite isochrons can be used to constrain the time-integrated W isotope evolution, and hence 180Hf/184W ratio, of the H chondrite asteroid in comparison to average carbonaceous chondrites. The W isotope evolution of carbonaceous chondrites is given by the initial 182W and 182Hf/180Hf determined from internal CAI isochrons [182W = 3.30 0.12; 182Hf/180Hf = (1.003 0.045) 10 4 (Burkhardt et al., submitted for publication)] and the precisely dened presentday 182W = 1.9 0.1 (Kleine et al., 2002; Schoenberg et al., 2002; Yin et al., 2002; Kleine et al., 2004a). These data indicate that carbonaceous chondrites evolved with 180Hf/184W = 1.21, in excellent agreement with 180Hf/184W = 1.210 0.075 (2) measured for 14 carbonaceous chondrites by isotope dilution (Kleine et al., 2004a). In the W isotope evolution diagram (Fig. 8), the analyzed H chondrites dene a trend that is different from the evolution path of the carbonaceous chondrites, indicating that the H chondrite asteroid has 180Hf/184W = 0.63 0.20. With this low 180Hf/184W the radiogenic ingrowth in H chondrite whole-rocks is small ( 0.35 182W in the rst 10 Ma), consistent with the very limited range in 182W of the H chondrite metals. Compositional variations among the chondrite groups are commonly attributed to different proportions of several distinct compo-

Fig. 8. W isotope evolution diagram for H chondrites. The carbonaceous chondrite evolution line is dened by their present-day 182W and the initial 182W of Allende CAIs. The analyzed H chondrites depart from the evolution line of carbonaceous chondrites, indicating evolution in a reservoir with a Hf/W ratio lower than that of carbonaceous chondrites.

nents present in chondritic meteorites (Palme, 2001). Among these, CAIs [180Hf/184W 1.7, (Burkhardt et al., submitted for publication)] and metallic Fe (180Hf/184W 0) have Hf/W ratios different from those of average carbonaceous chondrites, such that different mixing proportions of CAIs and metal potentially can cause variations in Hf/ W ratios among chondrite groups. Fig. 8 shows that the different Hf/W ratios must have been established in the rst 2 Ma of the solar system. Once more high-precision HfW isochrons for other chondrites (in particular LL chondrites with their probably high Hf/W ratios) are available, it should be possible to date the chemical fractionation among chondrites more precisely. 5. Conclusions Key issues regarding the accretion and early evolution of chondrite parent bodies include the timescales of chondrule formation and peak metamorphism. The relatively high closure temperature of the HfW system in high-Ca pyroxene makes internal HfW isochrons involving high-Ca pyroxene a powerful tool for obtaining such age constraints. Although it is more or less well established that most chondrules formed 23 Ma later than CAIs (Russell et al., 1996; Kita et al., 2000; Kunihiro et al., 2004; Rudraswami and Goswami, 2007), this information is mainly based on AlMg ages for chondrules from only a few primitive chondrites. Most chondrites, however, are metamorphosed to some degree and even mild parent body metamorphism might reset the AlMg system. For instance, Kita et al. (2000) showed that AlMg ages for chondrules from chondrites of petrologic types higher than 3.4 are already partially reset. In contrast, HfW ages are more robust and less easily affected by thermal metamorphism and even for chondrites of petrologic type 4 appear to date chondrule formation. The capability of HfW chronometry for dating chondrule formation, however, will need to be assessed with more HfW ages for type 4 chondrites, by investigating the HfW systematics of type 3 chondrites and those ordinary chondrite groups for which AlMg chondrule ages are available. The closure temperature of the HfW system in type 5 and 6 chondrites is essentially identical to their peak metamorphic temperatures, such that HfW ages for type 5 and 6 chondrites correspond closely to the time of the thermal peak. As we have shown here for the H chondrite parent body, such information is essential for constraining models for the thermal evolution of meteorite parent bodies, which is directly related to their accretion rate and terminal size. Formation intervals determined by HfW chronometry are much shorter than those obtained from PbPb or RbSr chronology because the HfW system closed early and hence preserved a record of the

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117

earliest (i.e., high-temperature) evolution of chondrite parent bodies. Therefore, unlike other chronometers that have been used so far to constrain the (low-temperature) cooling history of chondrite parent bodies such as the PbPb, RbSr and ArAr systems the HfW system is less easily disturbed by later events and hence appears most suitable for determining the initial thermal structure and metamorphic history of chondrite parent bodies. Hafniumtungsten ages for chondrites should therefore permit the determination and direct comparison of accretion rate, terminal size, and thermal structure of chondrite parent bodies. Acknowledgements We thank Rainer Wieler for the comments and discussion. Conel Alexander and Jeff Grossmann are thanked for providing insights into chondrule mineralogy, especially regarding occurrence and grain sizes of high-Ca pyroxenes. Yuri Amelin is thanked for providing preprints of his unpublished work. We thank the Museum National d' Historie Naturelle (Paris), The National Museum of Natural History (Washington DC), The Natural History Museum (London), the Senckenbergmuseum (Frankfurt), and NASA for generously providing the samples for this study. Comments and suggestion from an anonymous reviewer and Mario Trieloff signicantly improved the manuscript. Mario Trieloff pointed out the possibility that the ages for H6 chondrite may reect early closure due to grain coarsening. We thank Rick Carlson for his comments and the efcient editorial handling of our manuscript. This study was supported by a Marie Curie post-doctoral fellowship to Thorsten Kleine. References
Akridge, G., Benoit, P.H., Sears, D.W.G., 1998. Regolith and megaregolith formation of Hchondrites: thermal constraints on the parent body. Icarus 132, 185195. Alexander, C.M.D., 1994. Trace element microdistribution within ordinary chondrite chondrules: implications for chondrule formation conditions and precursors. Geochim. Cosmochim. Acta 58, 34513467. Alexander, C.M.D., 2005. From supernovae to planets: the view from meteorites and interplanetary dust particles. In: Krot, A.N., Scott, E.R.D., Reipurth, B. (Eds.), Chondrites and the Protoplanetary Disk, Astronomical Society of the Pacic Conference Series 341. Amelin, Y., 2008. UPb ages of angrites. Geochim. Cosmochim. Acta 72, 221232. Amelin, Y., Irving, A.J., 2007. Seven million years of evolution on the angrite parent body from Pb-isotopic data, Workshop on the chronology of meteorites and the early solar system, LPI Contribution No. 1374, pp. 13201321. Amelin, Y., Ghosh, A., Rotenberg, E., 2005. Unraveling the evolution of chondrite parent asteroids by precise UPb dating and thermal modeling. Geochim. Cosmochim. Acta 69, 505518. Azough, F., Freer, R., 2000. Iron diffusion in single-crystal diopside. Phys. Chem. Miner. 27, 732740. Baker, J.A., Bizzarro, M., Wittig, N., Connelly, J., Haack, H., 2005. Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature 436, 11271131. Bennett, M.E., McSween, H.Y., 1996. Revised model calculations for the thermal histories of ordinary chondrite parent bodies. Meteorit. Planet. Sci. 31, 783792. Blinova, A., Amelin, Y., Samson, C., 2007. Constraints on the cooling history of the Hchondrite parent body from phosphate and chondrule Pb-isotopic dates from Estacado. Meteorit. Planet. Sci. 42, 13371350. Bouvier, A., Blichert-Toft, J., Moynier, F., Vervoort, J.D., Albarde, F., 2007. PbPb dating constraints on the accretion and cooling history of chondrites. Geochim. Cosmochim. Acta 71, 15831604. Burkhardt, C., Kleine, T., Palme, H., Bourdon, B., Zipfel, J., Friedrich, J., Ebel, D., submitted for publication. HfW isochrons for CAIs and timescales for planetesimal accretion Geochim. Cosmochim. Acta. Carslaw, H.S., Jaeger, J.C., 1959. Conduction of heat in solids. Oxford University Press. Cherniak, D.J., 1998. Pb diffusion in clinopyroxene. Chem. Geol. 150, 105117. Cherniak, D.J., Lanford, W., Ryerson, F.J., 1991. Lead diffusion in apatite and zircon using ion implantation and Rutherford backscattering techniques. Geochim. Cosmochim. Acta 55, 16631673. Clayton, R.N., Mayeda, T.K., 1996. Oxygen isotope studies of achondrites. Geochim. Cosmochim. Acta 60, 19992017. Connelly, J., Amelin, Y., Bizzarro, M., Thrane, K., Baker, J.A., 2008. The PbPb age of angrite Sah99555 revisited. Lunar Planet. Sci. Conf. XXXIX, 2386.pdf. Cuzzi, J.N., Ciesla, F.J., Petaev, M.I., Krot, A.N., Scott, E.R.D., Weidenschilling, S.J., 2005. Nebular evolution of thermally processed solids: reconciling models and meteorites. In: Krot, A.N., Scott, E.R.D., Reipurth, B. (Eds.), Chondrites and the Protoplanetary Disk, Astronomical Society of the Pacic Conference Series 341, pp. 732773.

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Chapitre 4

Chronomtrie Hf-W de la Lune: Contraintes sur limpact gant et la cristallisation de locan magmatique lunaire

Hf-W chronometry of the Moon: constraints on the giant impact and the crytallization of the lunar magma ocean

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Section 4.1

Late formation and prolonged differentiation of the Moon inferred from W isotopes in lunar metals*

M. Touboul1, T. Kleine1, B. Bourdon1, H. Palme2, R. Wieler1

Institute for Isotope Geochemistry and Mineral Resources, ETH Zurich, Clausiusstrasse 25, Switzerland.

Institut fr Geologie und Mineralogie, Universitt zu Kln, Zlpicherstrasse 49b, 50674 Kln, Germany.

*Publi dans Nature, 2007, vol. 450, p. 1206-1209

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Abstract The Moon probably formed from debris ejected by a giant impact with the early Earth1. Owing to the high energies involved, the Moon melted to form a magma ocean. The timescales for formation and solidification of the Moon can be quantified using
182

Hf-182W and

146

Sm-142Nd chronometry2-4 but these methods yielded contradicting

results. In earlier studies3,5-7, 182W anomalies in lunar rocks were attributed to 182Hf-decay within the lunar mantle and used to infer that the Moon solidified within the first ~60 Myr of the solar system. The dominant
182

W component in most lunar rocks, however,

181

reflects cosmogenic production mainly by neutron capture of

182

Ta during cosmic-ray

exposure of the lunar surface3,7, compromising a reliable interpretation in terms of 182HfW chronometry. Here we present W isotope data for lunar metals that do not contain any measurable Ta-derived 182W. All metals have identical 182W/184W, indicating that the lunar magma ocean did not crystallize within the first ~60 Myr of the solar system. This is no longer inconsistent with Sm-Nd chronometry8-11. Our new data reveal that the lunar and terrestrial mantles have identical
182

W/184W. This, in conjunction with

147

Sm-143Nd

90 ages for the oldest lunar rocks8-11, constrains the age of the Moon and Earth to 62 -+10 Myr

after solar system formation. The identical 182W/184W of the lunar and terrestrial mantles require either that the Moon is mainly derived from terrestrial material or that W isotopes in the Moon and Earth's mantle equilibrated in the aftermath of the giant impact, as has been proposed to account for identical O isotope compositions of the Earth and Moon12.

4.1.1 Main text We obtained W isotope data for metals from 2 KREEP-rich samples, 4 low- and 5 high-Ti mare basalts (Table 4.1.1, Fig. 4.1.1). We processed 4-5 times more material compared to an earlier study3 and monitored the purity of our metal separates by determining their Hf/W ratios. These indicate that for the analyses reported here any possible contamination from silicate and oxide grains has no measurable effect on
182

W/184W. Most of the samples investigated here have relatively short exposure times

and require corrections of less than 0.1 units (=0.01%) for burnout of W isotopes13,14 and only for samples 15556 and 70017 (exposure ages ~220 and ~500 Ma) corrections were larger (~0.4 and ~0.2 units). Details regarding the corrections are given in the 113

supplement. All samples analyzed here have identical

182

W/184W ratios within 0.32

units (2 standard deviation (SD)) and agree with previously reported data for metals from KREEP-rich samples3. These data combined average at 182W=0.090.10 (2 standard error (SE), n=15; 182W defined in Table 4.1.1).

Table 4.1.1: Hf-W data for lunar metals from KREEP-rich samples, low-Ti and high-Ti mare basalts W Hf Hf/W 183W 2 182Wmeas 2 182Wcorr 2 Sample (ppm) (ppm) KREEP-rich samples 68115 23.9 0.407 0.02 0.000.10 0.330.14 0.330.14 -0.010.10 0.180.12 0.180.12 0.010.09 0.180.12 0.180.12 0.000.11 0.140.15 0.140.15 mean (2 SD) 0.000.02 0.210.17 0.210.17 68815 27.5 0.725 0.03 0.040.11 0.020.18 0.020.18 -0.020.10 0.260.18 0.260.18 0.030.13 0.250.15 0.250.15 -0.010.13 0.220.17 0.220.17 mean (2 SD) 0.010.06 0.180.23 0.190.23 weighted average* (2,n=6) 0.000.03 0.110.21 0.110.21 Low-Ti mare basalts 12004 15058 15499 15556 weighted average (2,n=4) High-Ti mare basalts 70017 70035 74255 74275 75035 weighted average (2,n=5) Bulk lunar mantle* (2 SE, n=15) 11.6 10.1 1.32 8.92 4.65 2.18 5.09 1.30 2.24 25.1 0.19 0.50 1.0 0.25 5.4 -0.130.14 0.080.13 -0.110.14 -0.160.18 0.070.15 -0.040.14 0.000.02 0.200.14 0.050.18 0.090.17 -0.250.25 0.220.18 0.110.19 0.020.09 0.380.16 0.140.18 0.110.16 -0.240.25 0.180.18 0.160.24 0.090.10 48.7 11.3 7.64 21.6 0.539 0.113 0.911 0.477 0.11 0.01 0.12 0.02 0.040.21 -0.100.15 0.030.22 0.020.21 -0.020.09 0.000.36 -0.110.19 0.060.31 -0.140.29 -0.070.13 0.050.36 0.010.20 0.160.31 0.300.36 0.090.14

18iW={(18iW/184W)sample/(18iW/184W)standard-1} 104. Replicates for KREEP-rich samples are repeated measurements of the same solution. Mean values are weighted averages calculated using Isoplot (n=number of samples). * Averages are calculated including data for KREEP-rich samples from ref. 3.

114

Figure 4.1.1: 182W of lunar metals analyzed in this study (closed symbols) compared to previously reported data from Kleine et al.5 (open symbols) and Lee et al.3 (crossed symbols). Some of the previous data (shown with black dots inside the symbols) were corrected for cosmogenic 182W (see text for details). Error bars indicate 2 external reproducibilities. The hatched area indicates the average 182W=0.090.10 (2 SE, n=15) of lunar metals from this study combined with previously reported data for metals from KREEP-rich samples5 (KREEP stands for enrichment in potassium (K) and Rare Earth Elements). The dashed lines indicate the 2 standard deviation of 0.32 182W of these data.

115

In contrast to earlier studies3,5,6, we do not find

182

W/184W variations within the

lunar mantle. Lee et al.5 reported 182W~1.4 for low-Ti mare basalt 15555 but the exposure age of this sample combined with its Sm isotopic composition and Ta/W ratio indicates that this anomaly might entirely be due to cosmogenic
182

W. Kleine et al.3

reported elevated 182W~2 for a magnetic separate from high-Ti mare basalt 79155 but we determined Hf/W=7.5 for an aliquot from the same magnetic separate, most likely indicating the presence of some ilmenite and hence cosmogenic 182W in this separate. The calculated cosmogenic
182

W component is ~1.7 units, hence the elevated

182

182 182

W/184W

reported for 79155 presumably is mainly due to cosmogenic

W. Enhanced
182

W/184W

in high-Ti mare basalts 72155 (ref. 3) and 75075 (ref. 5) also are not well-resolved from 182W=0.090.10. Details regarding the quantification of cosmogenic W are given in the supplement. We conclude that in light of the identical 182W/184W we obtained for pure metal separates from 9 mare basalts (average 182W=0.120.12, 2 SE, n=9), elevated
182 182 182

W/184W ratios in mare basalts reported earlier likely reflect production of cosmogenic W. This production is difficult to quantify, demonstrating that the purely radiogenic W/184W is difficult to determine precisely if cosmogenic 182W is present. We conclude
182

that there are no

Hf-induced W isotope variations among KREEP and the mare basalt

sources. Given that low- and high-Ti mare basalts sample the majority of cumulates from the lunar magma ocean (LMO)15 and that KREEP contains a significant part of the incompatible element inventory of the lunar mantle16, the average 182W=0.090.10 (2 SE) of these lithologies most likely represents the average 182W of the lunar mantle. Although some ferroan anorthosites have elevated 182W up to ~3 (ref. 6), these data are relatively imprecise and their weighted average 182W=1.91.7 (2) is not resolvable from 182W=0.090.10. Moreover, the analyzed anorthosites might also contain cosmogenic 182W.

116

Figure 4.1.2: 182W vs. source 180Hf/184W. Assumed Hf/W ratios are 1010 for KREEP, 26.51.1 for the low-Ti mare basalt source, and >40 for the high-Ti mare basalt source (for details see supplement). 182W values shown for the low-Ti and high-Ti mare basalt sources are weighted averages of the data obtained in this study, the average 182W of KREEP was calculated including data from Kleine et al.3 Error bars indicate the standard errors (2) of these data. Reference isochrons corresponding to 30, 40, 50, 60 and 70 Myr after the start of the solar system are shown. It is assumed that the Hf/W ratio of the bulk lunar mantle is similar to that of the low-Ti mare basalt source. The latter consists mainly of olivine and orthopyroxene, which are not capable of fractionating Hf and W18. he identical 182W values for KREEP and the low- and high-Ti mare basalt sources require that equilibration of W isotopes within the LMO occurred later than ~60 Myr after the start of the solar system. Note that this conclusion depends on neither the choice of Hf/W ratios of the sources nor on using the Hf/W ratio of the low-Ti mare basalt source as representative of the Hf/W ratio of the bulk lunar mantle.

These new constraints have far reaching implications regarding the lifetime of the LMO as well as the age and formation of the Moon. The homogeneous 182W/184W ratios of all lunar samples in spite of strongly fractionated Hf/W ratios in their source areas17,18 indicate that the last equilibration of W isotopes within the LMO occurred later than ~60 Myr (here, Myr refers to time after formation of the first solids in the solar system) (Fig. 4.1.2). Isotopic equilibration among the products of the LMO is possible up to a critical crystal fraction of ~60% until which convection prevents crystal settling19. Although our new results only provide the earliest time (>~60 Myr) for ~60% LMO crystallization, this new age is no longer in conflict with other constraints regarding the lifespan of the LMO. 117

The rapid crystallization of the LMO required by the earlier W isotope data3,5,6 implied that some
147

Sm-143Nd ages for ferroan anorthosites8-11 and the

146

Sm-142Nd model age2,4

of the lunar mantle reflect post-LMO events3,17. With the revised Hf-W time constraint this is no longer required and the aforementioned Sm-Nd ages could possibly date processes associated with the LMO. This suggests that the LMO could have solidified to ~60% as late as ~215 Myr, as given by its 146Sm-142Nd model age2,4. Our data do not only constrain the lifespan of the LMO but also the timing of the giant impact. This utilizes the virtually identical 182W/184W of the bulk silicate Moon and Earth in conjunction with their different Hf/W ratios. The latter can be inferred from U/W and Th/W ratios because U, Th and W have similar incompatibilities during mantle melting20,21. The lunar mantle has U/W=1.930.08 (2)21, distinctly higher than U/W=1.30.4 (2) for the bulk silicate Earth [obtained from Th/W=5.51.6 (2)20 and Th/U=4.20.1 (2)22]. If refractory lithophile elements occur in chondritic proportions in planetary mantles, then Hf/U=13.7 for chondrites23 can be used to calculate Hf/W=26.51.1 (2) and Hf/W=18.05.2 (2) for the bulk silicate Moon and Earth. It is conceivable however that the Moon and Earth have non-chondritic ratios of refractory lithophile elements (e.g., Th/U22,23) and in this case the Hf/W ratios of the bulk silicate Moon and Earth might be different from those calculated above. However, this would only have a small effect on the calculated ages (Fig. 4.1.3). For instance, using a ~15% higher Hf/U ratio only changes the ages by ~2 Myr. A first-order estimate for core formation in the Moon (or the impactor) is obtained using a two-stage model. This assumes a chondritic initial started off with slightly different
182 182 182

W/184W of the Moon and

results in an age of ~37 Myr. This model implies that the bulk silicate Earth and Moon W/184W (~0.5 units difference at most; see supplemental information Fig. 4.1.4) and fortuitously evolved to identical present-day W/184W. However, as the Moon predominantly consists of mantle material with high Hf/W and hence most likely radiogenic 182W/184W, this two-stage model is not valid. The initial 182W/184W of the Moon most likely was higher than chondritic, resulting in an age younger than ~37 Myr and implying that the bulk silicate Moon and Earth must have had indistinguishable initial 182W/184W (supplemental information Fig. 4.1.4).

118

A more reliable age constraint for core formation is obtained from the identical
182

W/184W of the bulk silicate Moon and Earth in conjunction with their distinct Hf/W and

by assuming identical initial 182W/184W for the bulk silicate Moon and Earth. As shown in Fig. 4.1.3, core formation in the Moon must have occurred later than ~50 Myr, otherwise the lunar mantle would have a
182

W excess relative to the terrestrial mantle. This new

constraint provides the earliest time the giant impact could have occurred because the segregation of the lunar core probably occurred briefly after formation of the Moon. This also holds true if the Hf-W systematics of the Moon would largely reflect core formation in the impactor because this must predate the giant impact. Owing to the identical
182

W/184W of the bulk silicate Moon and Earth, our data

only provide the earliest time the Moon could have formed but the latest time is given by the age of the oldest lunar rocks. Combined with the 4.4560.040 Ga 147Sm-143Nd age of
90 the lunar crust10 we obtain an age of 62 -+10 Myr for the formation of the Moon (Fig. 3).

Given that Earth's accretion cannot have terminated before the giant impact, this also provides an age for the accretion of Earth. This is inconsistent with termination of Earth's accretion at ~30 Myr (e.g., ref. 24) and also difficult to reconcile with the <30 Myr
146

Sm-142Nd model age for differentiation of Earth's mantle25. Our new age constraint,

however, is consistent with most U-Pb model ages for the Earth26.

119

Figure 4.1.3: 182W difference between bulk silicate Moon and Earth as a function of time of core formation. The grey shaded area indicates 182W=0.090.10 (2 SE) for the lunar mantle as determined in this study. Assuming that the lunar and terrestrial mantles had identical initial 182W/184W the time at which these two reservoirs separated can be calculated using 182 W 10 - 4 1.14 (Hf U )CHUR (U W )BSE (U W )BSM 182 W 184 W BSE 1 where t = ln , 182 Hf 180 Hf 0 CHUR= chondritic uniform reservoir, BSE=bulk silicate Earth, BSM=bulk silicate Moon, and Hf Hf (182Hf/180Hf)0=1.0710-4 (ref. 14). f Hf/W = 1 . Note that the lower uncertainty on W BSM W BSE the age is calculated by propagating the uncertainties on 182W and 180Hf/184W and hence does not coincide with the intersection of the f=0.1 curve with the grey shaded bar.

]}

The identical

182

W/184W ratios of the lunar and terrestrial mantles provide a key

182

constraint regarding the formation of the Moon. The

W/184W of any planetary mantle

reflects the timescale of accretion and core formation, the degree of W depletion, and the extent of re-equilibration of W isotopes during core formation24,27,28. Hence, it is unlikely that the mantles of the proto-Earth and the impactor evolved to identical 182W/184W ratios. Successful simulations of the giant impact predict that ~80% of the Moon is derived from 120

impactor material1, such that small pre-existing W isotopic differences between protoEarth and impactor should be reflected in the composition of the Moon. This is not observed however in the Hf-W systematics. Similarly, the identical O isotopic compositions of the Earth and Moon in spite of widespread O isotopic heterogeneity among inner solar system objects are unexpected. These have been interpreted to reflect accretion of the Earth and Moon from a similar mix of components formed at the same heliocentric distance29. As explained above, such a scenario cannot account for the identical W isotope compositions of the lunar and terrestrial mantles. Hence, either the Moon almost entirely derived from Earth's mantle (which is contrary to results from numerical simulations of the giant impact) or lunar and terrestrial materials equilibrated in the aftermath of the giant impact. Diffusive exchange between the silicate vapour atmosphere of the proto-Earth and the lunar magma disk might be possible for elements that became vaporized during formation of the lunar magma disk. It has been shown that this is possible for O isotopes12 but the efficiency to which W became vaporized and hence could have been equilibrated isotopically remains to be investigated.
4.1.2 Methods summary

Samples were crushed in an agate mortar and magnetic fractions were obtained using a hand-magnet. The magnetic separates were purified by repeated grinding, magnetic separation and ultrasonication in distilled ethanol. After dissolution a ~5% was spiked with a mixed 180Hf-183W tracer for determination of Hf and W concentrations that are used to monitor the purity of the metal separates. From the remaining ~95% W was extracted using anion exchange techniques, slightly modified from Kleine et al.3,30. All measurements were performed using a Nu Plasma MC-ICPMS at ETH Zrich. Tungsten isotope measurements were normalized to
186

W/183W=1.9859 and

186

W/184W=0.92767

using the exponential law. Results obtained using these two normalization procedures agree for all samples. Tungsten isotope compositions of the samples were determined relative to the
182

W/184W obtained for two bracketing measurements of the ALFA

188

AESEAR W standard solution. Isobaric Os interferences on masses 186 and 184 were monitored by measuring Os but corrections were insignificant for all samples (< 0.01 p.p.m.). The accuracy of the measurements was monitored using the 183W/184W ratio and 121

all samples have

183

W/184W identical to the standard value to within 0.2 units. The

external reproducibility of the W isotope measurements was evaluated by repeated measurements of metals from the two KREEP-rich samples and is 0.17 (2, n=4) and 0.23 (2, n=4) (Table 4.1.1). For the low-Ti mare basalts, the reproducibility is ~0.5 units or better, and for the high-Ti mare basalts, it is 0.3-0.4 units.

4.1.3 Acknowledgements

We are grateful to the Curation and Analysis Planning Team for Extraterrestrial Materials (CAPTEM), NASA curatorial staff, and G. Lofgren for supplying the Apollo lunar samples. We thank L. Borg and A. Brandon for their thoughtful reviews and F. Nimmo and J. Van Orman for discussions. This research was supported by a EU Marie Curie postdoctoral fellowship to T. Kleine.

Supplementary Information accompanies the paper on www.nature.com/nature and after references in section 4.1.5

4.1.4 References

1.

Canup, R. M. & Asphaug, E. Origin of the Moon in a giant impact near the end of the Earth's formation. Nature 412, 708-712 (2001).

2.

Nyquist, L. E. et al. Sm-146-Nd-142 Formation Interval for the Lunar Mantle. Geochim. Cosmochim. Acta 59, 2817-2837 (1995).

3.

Kleine, T., Palme, H., Mezger, K. & Halliday, A. N. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674 (2005).

4.

Rankenburg, K., Brandon, A. D. & Neal, C. R. Neodymium isotope evidence for a chondritic composition of the Moon. Science 312, 1369-1372 (2006).

122

5.

Lee, D. C., Halliday, A. N., Leya, I., Wieler, R. & Wiechert, U. Cosmogenic tungsten and the origin and earliest differentiation of the Moon. Earth Planet. Sci. Lett. 198, 267-274 (2002).

6.

Lee, D. C., Halliday, A. N., Snyder, G. A. & Taylor, L. A. Age and origin of the moon. Science 278, 1098-1103 (1997).

7.

Leya, I., Wieler, R. & Halliday, A. N. Cosmic-ray production of tungsten isotopes in lunar samples and meteorites and its implications for Hf-W cosmochemistry. Earth Planet. Sci. Lett. 175, 1-12 (2000).

8.

Borg, L. E. et al. Isotopic studies of ferroan anorthosite 62236: A young lunar crustal rock from a light rare-earth-element-depleted source. Geochim. Cosmochim. Acta 63, 2679-2691 (1999).

9.

Carlson, R. W. & Lugmair, G. W. The age of ferroan anorthosite 60025: oldest crust on a young Moon? Earth Planet. Sci. Lett. 90, 119-130 (1988).

10. Norman, M. D., Borg, L. E., Nyquist, L. E. & Bogard, D. D. Chronology, geochemistry, and petrology of a ferroan noritic anorthosite clast from Descartes breccia 67215: Clues to the age, origin, structure, and impact history of the lunar crust. Meteorit. Planet. Sci. 38, 645-661 (2003). 11. Nyquist, L. et al. Feldspathic clasts in Yamato-86032: Remnants of the lunar crust with implications for its formation and impact history. Geochim. Cosmochim. Acta 70, 5990-6015 (2006). 12. Palhevan, K. & Stevenson, D. J. Possible Origin of the geochemical similarity of the Earth and Moon. Earth Planet. Sci. Lett., in press (2007). 13. Leya, I., Wieler, R. & Halliday, A. N. The influence of cosmic-ray production on extinct nuclide systems. Geochim. Cosmochim. Acta 67, 529-541 (2003). 14. Kleine, T., Mezger, K., Palme, H., Scherer, E. & Mnker, C. Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from 182Hf-182W in CAIs, metal-rich chondrites and iron meteorites. Geochim. Cosmochim. Acta 69, 5805-5818 (2005).

123

15. Shearer, C. K. & Papike, J. J. Magmatic evolution of the Moon. Am. Mineral. 84, 1469-1494 (1999). 16. Palme, H. & Wnke, H. A unified trace-element model for the evolution of the lunar crust and mantle. Proc. Lunar Sci. Conf. 6th, 1179-1202 (1975). 17. Shearer, C. K. & Newsom, H. E. W-Hf isotope abundances and the early origin and evolution of the Earth-Moon system. Geochim. Cosmochim. Acta 64, 3599-3613 (2000). 18. Righter, K. & Shearer, C. K. Magmatic fractionation of Hf and W: Constraints on the timing of core formation and differentiation in the Moon and Mars. Geochim. Cosmochim. Acta 67, 2497-2507 (2003). 19. Solomatov, V. S. in Origin of the Earth and Moon (eds. Canup, R. M. & Righter, K.) 323-338 (Lunar and Planetary Institute, Houston, 2000). 20. Newsom, H. E. et al. The depletion of W in the bulk silicate Earth: constraints on core formation. Geochim. Cosmochim. Acta 60, 1155-1169 (1996). 21. Palme, H. & Rammensee, W. The significance of W in planetary differentiation processes: Evidence from new data on eucrites. Proc. 12th Lunar Planet. Sci. Conf., 949-964 (1981). 22. Allegre, C. J., Dupre, B. & Lewin, E. Thorium Uranium Ratio of the Earth. Chem. Geol. 56, 219-227 (1986). 23. Rocholl, A. & Jochum, K. P. Th, U and other trace elements in carbonaceous chondrites: Implications for the terrestrial and solar-system Th/U ratios. Earth Planet. Sci. Lett. 117, 265-278 (1993). 24. Jacobsen, S. B. The Hf-W isotopic system and the origin of the Earth and Moon. Ann. Rev. Earth Planet. Sci. 33, 531-570 (2005). 25. Boyet, M. & Carlson, R. W. 142Nd evidence for early (>4.53 Ga) global differentiation of the silicate Earth. Science 309, 576-581 (2005). 26. Allegre, C. J., Manhes, G. & Gopel, C. The age of the Earth. Geochim. Cosmochim. Acta 59, 1445-1456 (1995). 124

27. Kleine, T., Mezger, K., Palme, H., Scherer, E. & Mnker, C. The W isotope evolution of the bulk silicate Earth: constraints on the timing and mechanisms of core formation and accretion. Earth Planet. Sci. Lett. 228, 109-123 (2004). 28. Nimmo, F. & Agnor, C. B. Isotopic outcomes of N-body accretion simulations: Constraints on equilibration processes during large impacts from Hf/W observations. Earth Planet. Sci. Lett. 243, 26-43 (2006). 29. Wiechert, U. et al. Oxygen isotopes and the moon-forming giant impact. Science 294, 345-348 (2001). 30. Kleine, T., Mezger, K., Palme, H., Scherer, E. & Mnker, C. The W isotope composition of eucrites metal: Constraints on the timing and cause of the thermal metamorphism of basaltic eucrites. Earth Planet. Sci. Lett. 231, 41-52 (2005).

125

4.1.5 Supplementary information

4.1.5.1

Lunar metals Metal grains occur in almost all lunar rocks1. Relatively high Ni and Ir contents in

metals from highland samples indicate that these are meteoritic metals added to the lunar surface by impacts2. Unlike meteoritic metals, the metals from KREEPrich highland rocks have extremely high W contents [24-28 ppm, Table 4.1.1 and ref. 2], reflecting the strong enrichment of KREEP in W. The high W/Ir ratios in lunar metals confine the contribution of meteoritic W to less than ~1% (ref. 2,3), precluding any measurable effect on the
182

W/184W of KREEP. Partitioning of W from KREEP into these metals occurred

by impactinduced melting and brecciation during redistribution of KREEP at the lunar surface2. Metals in mare basalts consist of native Fe and probably formed by crystallization from a silicate melt under reducing conditions1. The composition of these metals (namely low Ni contents) distinguishes them from meteoritic metal added to the lunar surface by impacts1,3. 4.1.5.2 Analytical methods Mare basalts (~4 g) and KREEP-rich samples (~1 g) were crushed in an agate mortar and separated into several size fractions using nylon sieves. Magnetic fractions from each of them were separated using a hand-magnet and further purified by repeated grinding, magnetic separation and ultrasonication in distilled ethanol. The purity of the metal separates was checked under the binocular and the final separates (1-6 mg) in most cases did not contain any visible silicate or oxide grains. In some cases ilmenite grains were still present and could not be removed without loosing too many of the metal grains. The presence of these impurities in some of the magnetic separates however has no measurable effect on
182

W/184W (see below). The analytical procedure has slightly been

modified from Kleine et al.4-6. The metal separates were dissolved in 6 M HCl-0.06 M HF in Savillex vials at 120 C on a hotplate. In this acid mixture most of the potentially present silicate and oxide impurities should not dissolve. After metal dissolution, a ~5% aliquot of the sample was spiked with a mixed 180Hf-183W tracer for determination of Hf and W concentrations. The remaining ~95% solution was dried and redissolved in HNO3H2O2, dried and redissolved in 1M HF-0.1 M HNO3. This solution was loaded onto pre126

cleaned anion exchange columns (BioRad AG1X8, 200-400 mesh) and the sample matrix eluted using 1 M HF-0.1 M HNO3. Tungsten was then collected using 6 M HCl-1 M HF. Total procedural blanks were ~20 pg for W isotope composition measurements and therefore negligible. Total procedural blanks for the concentration measurements are ~2 pg W and ~1 pg Hf, resulting in blank corrections of <4% on the measured Hf concentrations. All measurements were performed using a Nu Plasma MC-ICPMS at ETH Zurich. Tungsten isotope measurements were normalized to
186 186

W/183W=1.9859 and

W/184W=0.92767 using the exponential law. Results obtained using these two
182

normalization procedures agree for all samples. Tungsten isotope compositions of the samples were determined relative to the W/184W obtained for two bracketing
188

measurements of the ALFA AESEAR W standard solution. Isobaric Os interferences on masses 186 and 184 were monitored by measuring monitored using the
183

Os but corrections were W/184W identical to the

insignificant for all samples (< 0.01 p.p.m.). The accuracy of the measurements was W/184W ratio and all samples have
183

standard value to within 0.2 units. The external reproducibility of the W isotope measurements was evaluated by repeated measurements of metals from the two KREEPrich samples and is 0.17 (2, n=4) and 0.23 (2, n=4) (Table 4.1.1). This is similar to the reproducibility of the W standard measured at the same beam intensity as was obtained for the KREEP metals. For metals from low- and high-Ti mare basalts less W was available for analyses and the reproducibility was estimated by repeated measurement of the W standard using identical beam intensities than those obtained for the sample runs. For the low-Ti mare basalts, the reproducibility is ~0.5 units or better, and for the high-Ti mare basalts, it is 0.3-0.4 units. 4.1.5.3 Cosmogenic effects on W isotope ratios in lunar samples
4.1.5.3.1 Correction for W isotope data obtained in this study

Elevated

182

W/184W of lunar whole-rocks largely reflect production of

182

cosmogenic 182W by neutron capture of 181Ta and subsequent decay of 182Ta to 182W (ref. 6-8). Metals do not contain any Ta and their cosmogenic
182

W/184W should not be affected by

W production6 but contamination with silicate or oxide grains may result 127

in elevated measured

182

W/184W. The purity of the metal separates can be monitored by

determining their Hf/W ratios because contamination with silicates or oxides would result in high concentrations of lithophile elements. The Hf/W ratios of all metal separates from KREEP-rich samples and low-Ti mare basalts investigated here are below ~0.1. Metal separates from the high-Ti mare basalts have Hf/W ratios between 0.2 and 5.4. Using typical Ta/Hf ratios for the whole-rocks (~0.14 for low-Ti mare basalts, ~0.16 for high-Ti mare basalts, ~0.11 for KREEP9) the Ta/W ratios of the metal separates can be calculated because the dominant contaminant in the metal separates probably is ilmenite which has similar Ta/Hf than the whole-rocks (DHf/DTa ~1 in ilmenite, ref. 10). All calculated Ta/W ratios for metal separates from the KREEP-rich samples and low-Ti mare basalts investigated here are lower than ~0.02, corresponding to a maximum
181

Ta-derived 182W

component of ~0.0003 W (Supplementary Table 4.1.2). The calculated Ta/W ratios for metal separates from the high-Ti mare basalts investigated here are higher and range from 0.03 to 0.86 but the
181

Ta-derived

182

W component in these samples is lower than ~0.02

182W for all samples expect for sample 75035, where this component is ~0.1 182W.

Hence, contamination of the metal separates investigated here with silicates/oxides has no measurable effect on the 182W/184W ratios. The W isotope ratios of metal can also be modified by burnout of W isotopes, as has been observed for iron meteorites with long exposure times11-13. For this reason, most of the samples selected for this study have exposure ages younger than ~135 Ma, such that the downward shift of 182W/184W in the metals of these samples is <0.1 units. Only two of the samples investigated here have older exposure ages and W burnout could have lowered their
182

W/184W by ~0.2 (sample 70017) and ~0.4 (sample 15556) units

182

(Supplementary Table 4.1.2). The combined effects of burnout of W isotopes and production by neutron capture of
181

Ta for all samples analyzed here are summarized in

the Supplementary Table 4.1.2. The corrections for most samples are much smaller than ~0.1 182W and hence well below our analytical precision. For the metal separates from samples 70017 and 15556 (i.e., the two samples with the oldest exposure ages among the investigated samples) the corrections are similar to or slightly higher than the precision of our measurements. The uncertainties of these corrections are difficult to assess and a 50%

128

uncertainty on the correction is conservatively assumed here. This is a factor of 2 higher than given in Leya et al.7,14.
Table 4.1.2: Cosmogenic effects on 182W Sample KREEP 68115 68815 Exposure age (Ma) 2 2 Ta/W 0.002 0.003 182WGCR, burnout -0.002 -0.002 182WGCR,capture 0.00001 0.00002 182WGCR -0.0020.001 -0.0020.001

Low Ti basalts 12004 60 15058 135 15499 114 15556 500 High Ti basalts 70017 220 70035 120 74255 25 74275 32 75035 72

0.015 0.001 0.017 0.003

-0.05 -0.12 -0.10 -0.44

0.001 0.0002 0.003 0.003

-0.050.025 -0.120.06 -0.100.05 -0.440.22

0.03 0.08 0.04 0.16 0.86

-0.19 -0.11 -0.02 -0.03 -0.06

0.01 0.02 0.01 0.01 0.11

-0.180.09 -0.10.05 -0.010.005 -0.020.01 0.040.02

182WGCR, burnout is the effect on 182W/184W caused by burnout of W isotopes; 182WGCR,capture is the cosmogenic production of 182W by neutron-capture of 181Ta; 182WGCR is the overall cosmogenic effect, 182WGCR=182WGCR, burnout+182WGCR,capture

4.1.5.3.2

Correction of W isotope data obtained in earlier studies

We determined Hf/W~7.5 for an aliquot of the magnetic separate from sample 79155 analyzed earlier by Kleine et al.5 for its W isotope composition. Using Ta/Hf~0.18 determined for the 79155 whole-rock results in Ta/W~1.4. Using this Ta/W ratio, an exposure age of 575 Ma and correction equations14, a cosmogenic
182

W component of

~0.85 units is calculated for the magnetic separate from sample 79155. The 79155 whole-rock has 182W~38 and Ta/W~20 (ref. 6) but using the correction equations from Leya et al.14 only results in cosmogenic 182W of ~19 units. This could indicate that this correction procedure might underestimate the production of cosmogenic 182W by a factor of ~2, such that the cosmogenic 182W in the magnetic separate of 79155 might be as high as ~1.7. This is similar to 182W=2.30.9 measured for the 79155 magnetic separate, indicating that the elevated 182W of 79155 most likely reflects contamination with 129

silicate and oxide grains that carry cosmogenic hence cosmogenic the
182 182

182

W. It is plausible that the magnetic

separate from 72155 analyzed earlier by Kleine et al.5 also contains some ilmenite and W. However, the situation for this sample remains unclear because W/
184

W of its whole-rock is not elevated compared to its magnetic separate, no

Hf/W ratio is available for the latter, and the exposure history of 72155 is not well constrained. Lee et al.8 reported 182W=4.73.0 for high-Ti mare basalt 75075, based on a regression of Ta/W and The Ta contents and
182 182

W/184W obtained for one pyroxene and one feldspar separate.

W/184W ratios for the feldspar separate however were not

obtained for the same aliquot and the W contents for the two feldspar separates differ by a factor of almost 4. Hence, the Ta/W ratio of the feldspar separate also analyzed for W isotopes is not well constrained, rendering it unclear whether this sample has radiogenic
182W that is well resolved from 182W=0.090.10.

Lee et al.8 argued that the average 182W=1.40.4 of low-Ti mare basalt 15555 reflects 182Hf decay and that this sample contains no significant cosmogenic 182W because it exhibits no correlation between the
182

W/184W of mineral separates having variable

Ta/W. However, using the 149Sm/150Sm ratio of sample 15555 (ref. 15,16), its Ta/W ratio of 4.14 (ref. 8) and correction equations14 reveals that this sample may contain a cosmogenic component of ~0.7 182W. Although the presence of cosmogenic 182W should result in systematic variations of anticipated cosmogenic
182 182

W/184W with Ta/W, the entire spread in Ta/W ratios

among the investigated mineral fractions of 15555 is less than ~3, such that the W/184W variations are similar to the analytical uncertainty of
182

the W isotope measurements. After correction for cosmogenic

W, the 15555 whole-

rock (measured W=1.130.36) has 182W=0.450.50 (assuming a 50% uncertainty on the correction), indistinguishable from the 182W values determined here for metals from other low-Ti mare basalts. As outlined above, the correction procedure used here possibly underestimates the true cosmogenic
182 182

W by a factor of ~2, such that the cosmogenic

W/184W of the 15555 whole-rock might be as high as ~1.4 182W, identical to the 182W It is important to note that the possible underestimation of the cosmogenic
182

reported for this sample8. W production by neutron capture of

181

Ta by a factor of ~2 has no significant influence on

the correction of the samples investigated here because the highest correction required 130

here is only ~0.1 unit (Supplementary Table 4.1.2). In case of the correction for burnout of W isotopes it is unlikely that the correction procedure underestimates the effects significantly because the burnout effects observed in iron meteorites are similar to those that are predicted by the correction method used here11. 4.1.5.4 Hf/W fractionation in the crystallizing lunar magma ocean The first rocks to crystallize from the LMO consisted mainly of olivine and pyroxene and were followed by plagioclase-rich cumulates that floated to the surface and formed the earliest lunar crust14. The late stages of magma ocean crystallization involved the precipitation of ilmenite and clinopyroxene until solidification of the last few percents of the magma ocean14. This residual liquid is termed KREEP for its strong enrichment in incompatible elements including K, Rare Earth Elements and Phosphorus17. Subsequent melting and mixing among these primary rocks produced the variety observed in the lunar sample suite. Mare basalts formed by remelting of early mafic cumulates which in the case of high-Ti mare basalts included assimilation of ilmenite and clinopyroxene. Impacts on the lunar surface resulted in the redistribution of KREEP, making KREEP the major carrier of incompatible elements in lunar highland rocks. Hafnium-tungsten fractionations in the LMO resulted from the compatibility of Hf in clinopyroxeneilmenite and the high incompatibility of W18,19. These led to high Hf/W in the high-Ti mare basalt source and correspondingly low Hf/W in KREEP. Based on mineral-melt partition coefficients for the relevant minerals in the crystallizing LMO, Righter and Shearer18 estimated Hf/W=40-80 in the source of high-Ti mare basalts. Measured Hf/W ratios of high-Ti mare basalts are even higher (up to ~110), such that it is safe to assume Hf/W>40 for the high-Ti mare basalt source. This is consistent with estimates for the Hf/W ratio in the low-Ti mare basalt source. This consists of olivine and orthopyroxene, which are not capable of fractionating Hf and W18, such that the Hf/W ratio of the low-Ti mare basalt source should be similar to that of the bulk lunar mantle6. The latter has Hf/W=26.51.1, similar to Hf/W ratios measured for low-Ti mare basalts. This ratio is lower than the Hf/W ratio estimated above for the highTi mare basalt source, consistent with the presence of ilmenite and clinopyroxene. Estimates for the Hf/W ratio of KREEP range from 12 to 19 (ref. 17,20) and hence are 131

lower than the Hf/W ratio of the low-Ti mare basalt source, as expected from the high incompatibility of W.

Figure 4.1.4: 182W vs. time for the lunar and terrestrial mantles. The 182W evolution for chondrites (CHUR) is shown for reference. The hatched area marks the combination of 182W and time that is inconsistent with the Hf-W data for the lunar and terrestrial mantles.

4.1.5.5 Supplementary references 1. 2. Reid, A. M., Meyer, C., Harmon, R. S. & Brett, R. Metal grains in Apollo 12 igneous rocks. Earth Planet. Sci. Lett. 9, 1-5 (1970). Palme, H., Spettel, B., Wnke, H., Borchardt, D. & Stffler, D. Can metal segregation remove siderophiles from lunar impact melts? Lunar and Planetary Science XIII, 609-610 (1982). 3. Wnke, H. et al. Apollo 12 samples: Chemical composition and its relation to sample locations and exposure ages, the two component origin of the various soil samples and studies on lunar metallic particles. Proc. Sec. Lunar Planet. Sci. Conf. 2, 1187-1208 (1971).

132

4.

Kleine, T., Mezger, K., Mnker, C., Palme, H. & Bischoff, A.

182

Hf-182W isotope

systematics of chondrites, eucrites, and Martian meteorites: Chronology of core formation and mantle differentiation in Vesta and Mars. Geochim. Cosmochim. Acta 68, 2935-2946 (2004). 5. Kleine, T., Mezger, K., Palme, H., Scherer, E. & Mnker, C. The W isotope composition of eucrites metal: Constraints on the timing and cause of the thermal metamorphism of basaltic eucrites. Earth Planet. Sci. Lett. 231, 41-52 (2005). 6. Kleine, T., Palme, H., Mezger, K. & Halliday, A. N. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674 (2005). 7. Leya, I., Wieler, R. & Halliday, A. N. Cosmic-ray production of tungsten isotopes in lunar samples and meteorites and its implications for Hf-W cosmochemistry. Earth Planet. Sci. Lett. 175, 1-12 (2000). 8. Lee, D. C., Halliday, A. N., Leya, I., Wieler, R. & Wiechert, U. Cosmogenic tungsten and the origin and earliest differentiation of the Moon. Earth Planet. Sci. Lett. 198, 267-274 (2002). 9. Munker, C. et al. Evolution of planetary cores and the earth-moon system from Nb/Ta systematics. Science 301, 84-87 (2003). 10. Klemme, S., Gunther, D., Hametner, K., Prowatke, S. & Zack, T. The partitioning of trace elements between ilmenite, ulvospinel, annalcolite and silicate melts with implications for the early differentiation of the moon. Chem. Geol. 234, 251-263 (2006). 11. Kleine, T., Mezger, K., Palme, H., Scherer, E. & Mnker, C. Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from 182Hf-182W in CAIs, metal-rich chondrites and iron meteorites. Geochim. Cosmochim. Acta 69, 5805-5818 (2005). 12. Schrsten, A., Elliot, T., Hawkesworth, C., Russell, S. S. & Masarik, J. Hf-W evidence for rapid differentiation of iron meteorite parent bodies. Earth Planet. Sci. Lett. 241, 530-542 (2006).

133

13. Markowski, A., Quitt, G., Halliday, A. N. & Kleine, T. Tungsten isotopic compositions of iron meteorites: chronological constraints vs. cosmogenic effects. Earth Planet. Sci. Lett. 242, 1-15 (2006). 14. Leya, I., Wieler, R. & Halliday, A. N. The influence of cosmic-ray production on extinct nuclide systems. Geochim. Cosmochim. Acta 67, 529-541 (2003). 15. Nyquist, L. E. et al. Sm-146-Nd-142 Formation Interval for the Lunar Mantle. Geochim. Cosmochim. Acta 59, 2817-2837 (1995). 16. Rankenburg, K., Brandon, A. D. & Neal, C. R. Neodymium isotope evidence for a chondritic composition of the Moon. Science 312, 1369-1372 (2006). 17. Warren, P. H. & Wasson, J. T. The origin of KREEP. Rev. Geophys. Space Phys. 17, 73-88 (1979). 18. Righter, K. & Shearer, C. K. Magmatic fractionation of Hf and W: Constraints on the timing of core formation and differentiation in the Moon and Mars. Geochim. Cosmochim. Acta 67, 2497-2507 (2003). 19. Shearer, C. K. & Newsom, H. E. W-Hf isotope abundances and the early origin and evolution of the Earth-Moon system. Geochim. Cosmochim. Acta 64, 3599-3613 (2000). 20. Palme, H. & Wnke, H. A unified trace-element model for the evolution of the lunar crust and mantle. Proc. Lunar Sci. Conf. 6th, 1179-1202 (1975).

134

Section 4.2

182

Hf-182W systematics of ferroan anorthosites and the lifetime of the lunar magma ocean*

M. Touboul1, T. Kleine1, B. Bourdon1, H. Palme2, R. Wieler1

Institute for Isotope Geochemistry and Mineral Resources, ETH Zurich, Clausiusstrasse 25, 8092 Zurich, Switzerland

Institut fr Geologie und Mineralogie, Universitt zu Kln, Zlpicherstrasse 49b, 50674 Kln, Germany

*Accept par Icarus

135

136

Abstract

New W isotope data for ferroan anorthosites 60025 and 62255 and low-Ti mare basalt 15555 show that these samples, contrary to previous reports [Lee et al. 1997, Science 278; Lee et al. 2002, Earth Planet Sci. Lett. 198], have a W isotope composition that is indistinguishable from KREEP and other mare basalts. This requires crust extraction on the Moon later than ~60 Ma after CAI formation, consistent with
143 147

Sm-

Nd ages for ferroan anorthosites.

4.2.1 Introduction

The dominant processes in the early evolution of the Moon are the formation and subsequent solidification of a magma ocean. As this lunar magma ocean (LMO) crystallized, dense mafic minerals sank to the bottom and lighter plagioclase floated to the surface, forming an anorthositic crust (Smith et al., 1970; Warren, 1985; Wood et al., 1970). Most petrologic models for the magma ocean predict that olivine and orthopyroxene were the first mafic minerals that crystallized, whereas clinopyroxene and ilmenite formed in the late crystallization stages. The residual liquid of the LMO - termed KREEP for its high contents of potassium (K), rare earth elements (REE) and phosphorus (P) - is a distinct chemical component in the Moon and constitutes the major carrier of incompatible elements in lunar highland rocks (Warren and Wasson, 1979). Later remelting of the mafic LMO cumulates gave rise to the formation of mare basalts and their compositional diversity is thought to reflect melting of different cumulate assemblages: low-Ti mare basalts were derived from olivine and orthopyroxene cumulates, whereas high-Ti mare basalts were derived from cumulate layers containing olivine, pyroxenes and ilmenite (Shearer and Papike, 1999). The timescale for magma ocean solidification can be quantified using 182Hf-182W chronometry (half life~9 Ma) because substantial Hf-W fractionations occurred during crystallization of the LMO (Kleine et al., 2005; Righter and Shearer, 2003; Shearer and Newsom, 2000). These fractionations stem from the high incompatibility of W and the compatibility of Hf in clinopyroxene-ilmenite, leading to low Hf/W in KREEP and complementary high Hf/W in the high-Ti mare basalt sources. Therefore, the presence of 137

182

W variations in lunar rocks would imply fractionation in the lunar interior within the

first ~60 Ma of the solar system because 182Hf became effectively extinct after that time. Although 182W variations were initially reported among lunar whole-rock samples (Lee et al., 1997), Touboul et al. (2007) recently showed that these variations are entirely due to production of cosmogenic Cosmogenic
182 182

W during cosmic-ray exposure of the lunar surface.

181

W is predominantly produced via the reaction

182

Ta(n,)182Ta and

subsequent decay to

W and is significant for lunar whole-rocks that have elevated

182

Ta/W (Kleine et al., 2005). However, Touboul et al. (2007) investigated metals, which contain no Ta and hence no cosmogenic W. The homogeneous
182

W/184W of metals

from KREEP-rich highland rocks, low-Ti and high-Ti mare basalts require that the separation of KREEP and the mafic cumulates in the LMO occurred later than ~60 Ma after CAI formation, otherwise high-Ti mare basalts would carry a resolvable positive
182

W anomaly relative to KREEP (Touboul et al., 2007). In contrast to the homogeneous

182

W/184W of lunar metals, Lee et al. (1997)

reported positive cosmogenic

182

182

W anomalies for some ferroan anorthosites. These cannot reflect

W production at the lunar surface because some of these samples have

young exposure ages of only ~2 Ma (Arvidson et al., 1975). The W isotope data for some ferroan anorthosites, therefore, seem to imply that anorthosites were extracted from the mantle within the first ~60 Ma of the solar system. This, however, is inconsistent with
147

Sm-143Nd ages for ferroan anorthosites that are thought to reflect crystallization of
182

these rocks at 4.460.04 Ga (Norman et al., 2003). This inconsistency and the significance of identifying any present study. We present new W isotope data for pure plagioclase separates from ferroan anorthosites 60025 and 62255. These data are used to assess whether the anorthositic lunar crust has a W isotope composition different from the lunar mantle. In addition, we obtained new W isotope and Ta-Hf-W concentration data for low-Ti mare basalt 15555. For this sample, Lee et al. (2002) did not find any evidence for cosmogenic reported a significantly higher
182 182

Hf-induced

182

W variations among lunar samples for

constraining the timescales of lunar formation and differentiation have inspired the

W and

W/184W compared to metals from low-Ti mare basalts.

182

This is inconsistent with the homogeneous

W/184W of metals from all mare basalt

138

investigated so far and requires a reassessment of the W isotope composition of mare basalt 15555.

4.2.2 Samples and analytical methods

Ferroan anorthosites 60025 and 62255 were selected for this study based on the following criteria: (i) they have young exposure ages of ~2 Ma, such that the amount of cosmogenic
182

W is negligible; (ii) they have low contents of Ni and Ir, indicating that

they are pristine, i.e., any meteoritic contamination is minor to absent (Warren and Wasson 1977); (iii) large amounts of sample are available, which is important because the low W contents of anorthosites require large amounts of sample (~4-5 g) to be processed. Ferroan anorthosite 60025 is a coarse-grained cataclastic rock, consisting mainly of calcic plagioclase. Mafic minerals are mainly olivine and orthopyroxene and are heterogeneously distributed in 60025. The 60025 sample investigated for this study contained only ~1 % of mafic material, which was entirely removed during sample preparation. Ferroan anorthosite 62255 is a breccia of cataclastic anorthosites associated with finely crystalline impact melt. These melt fragments (~5% of our sample) were first removed before further processing of the sample. Both anorthosites were gently crushed in an agate mortar until the entire sample had grain sizes of less than 500 m. Pure plagioclase separates were prepared from a 40-500 m grain size fraction using heavy liquids. They were further purified by hand picking under a binocular until all mafic minerals were removed. Any potentially present metal grains were removed using a hand magnet but the anorthosite samples investigated here did not contain metal. The pure plagioclase fractions (~4 g for 60025; ~2 g for 62255) were then washed by ultrasonication in distilled ethanol, dried and powdered in an agate mortar. Due to the low W contents of anorthosites (~2-4 ppb W), large amounts of sample needed to be processed to obtain sufficiently precise W isotope data. Moreover, the high Ca contents require an effective removal of the sample matrix prior to the purification of W by ion exchange methods that employ HF-containing acid mixtures. Samples were dissolved in 60 ml Savillex vials on a hotplate at 120C for 3 days using 40 ml of 29 M 139

HF and 10 ml 14 M HNO3. After digestion the samples were dried and repeatedly redissolved in HNO3-H2O2 to remove organic compounds and dissolve Ca-fluorides that formed during sample digestion. Then the samples were completely dissolved in 6 M HCl-0.06 M HF and a ~5% aliquot was spiked with a mixed concentration determination by isotope dilution. The remaining ~95% were dried and re-dissolved in 30 ml of 1 M HCl-0.1 M HF, The solution was centrifuged and decanted and the residue washed two times with ~10 ml 1 M HCl-0.1 M HF and ultrasonicated at each step to ensure optimal release of W from the fluoride residue. The solutions were then loaded onto pre-cleaned cation exchange columns (15 ml BioRad AG50WX8, 200-400 mesh) and the ~50 ml solutions from each sample were split over 10 columns. Tungsten (together with other high field strength elements) was eluted using 15 ml of a 1 M HCl- 0.1 M HF mixture, whereas most other matrix elements (most notably Ca and Al) were adsorbed on the resin. This procedure was adapted from the column A of the Hf chemistry described by Tatsumoto and Patchett (1981). The W cuts for each sample were combined, dried and re-dissolved in 10 ml 0.5 M HCl-0.5M HF and loaded onto pre-cleaned anion exchange columns (3 ml AG1X8, 100-200 mesh), where W is separated from remaining matrix elements and especially Zr, Nb, Hf, Ti, Mo, and Ta using our previously described methods (Kleine et al., 2004a; Kleine et al., 2002). Each sample was split over two anion exchange columns and the W cuts combined. These were re-dissolved in 5 ml 0.5 M HCl-0.5 M HF and W further purified by an additional pass through the anion exchange columns. With this procedure we obtained high purity W cuts and >90% of the W originally loaded on the ion exchange columns. A non-magnetic fraction from low-Ti mare basalt 15555 was processed using the same procedure as for the anorthosites, but given its much smaller sample size (~400 mg compared to ~4 g for the anorthosites), the entire sample could be processed on a single cation exchange column, followed by purification on anion exchange resins as described above. Despite the extensive purification procedure, W blanks for the isotope measurements were as low as 5020 pg for the entire procedure. This corresponds to less
180

Hf-183W-180Ta tracer for

140

than 1% of the W present in the samples, such that blanks are negligible. The blanks for the isotope dilution measurements were also insignificant. All isotope measurements were performed using a Nu Plasma MC-ICPMS at ETH Zurich, which is equipped with a Cetac Aridus desolvating nebuliser. Details regarding our measurement protocol are given elsewhere (Kleine et al., 2008). Repeated measurements of the ALFA AESAR W standard during the course of this study yielded
182

W/184W = 0.864843 0.000015 (2 of the mean) and

183

W/184W = 0.467128

0.000006 (2 of the mean).

4.2.3 Results
Table 4.2.1: Hf-W data for lunar anorthosites and low-Ti mare basalt 15555 Sample Anorthosites 60025 plagioclase 62255 plagioclase Low-Ti mare basalt 15555 non-magnetic 58.5 2007 287.5 40.50.4 0.860.10 0.340.07 1.8 2.2 8.0 17.6 0.5 1.8 5.20.4 9.40.4 -0.030.30 -0.570.52 0.680.26 -0.830.43 W (ppb) Hf (ppb) Ta (ppb)
180

Hf/184W 2

182W 2

183W 2

Uncertainties for the 182W and 183W values are the 2 internal errors of the individual mass spectrometric runs.

The W isotope compositions and Hf-W-Ta contents for anorthosites 60025 and 62255 and low-Ti mare basalt 15555 are summarized in Table 4.2.1. The plagioclase separates from both ferroan anorthosites have Hf and W concentrations that are lower than the Hf and W concentrations previously reported for whole-rock analyses of these two anorthosites (Lee et al., 1997). The Hf/W ratios range from ~4 to ~8 and are lower than those of the mare basalts and KREEP (Kleine et al., 2005). The W isotope composition of the plagioclase separates from ferroan anorthosites 60025 and 62255 are indistinguishable from each other and also from the W isotope composition of metals from KREEP-rich samples and low- and high-Ti mare basalts (Fig. 4.2.1). This contrasts with results from an earlier study reporting positive 182W values for some ferroan anorthosites (Lee et al., 1997), including sample 60025. Note that compared to these

141

previously published results for ferroan anorthosites, our new W isotope data are more precise by a factor of ~5.

Figure 4.2.1: W isotope composition of plagioclase separates from ferroan anorthosites 60025 and 62255. Previously published W isotope data for ferroan anorthosites (Lee et al., 1997) are shown for comparison. The average compositions of KREEP (Kleine et al., 2005, Touboul et al. 2007) and the sources of low- and high-Ti mare basalts (Touboul et al. 2007) are also shown for comparison. 182W is the deviation of the 182 W/184W ratio of a sample relative to the terrestrial standard in parts per 10,000. Error bars shown here correspond to the 2 external reproducibility (0.4 and 0.8 for 60025 and 62255, respectively), estimated by repeated measurements of ~15 and ~5 ppb ALFA AESER standard solutions.

142

The non-magnetic fraction of low-Ti mare basalt 15555 has 182W=0.90.3, ~58.5 ppb W and ~287 ppb Ta, corresponding to Ta/W4.9 (Fig. 4.2.2). The 182W is somewhat lower than the average 182W of 1.30.4 previously reported for 15555 by (Lee et al., 2002) and the Ta/W ratio is slightly higher than those reported for several fractions from sample 15555 (Fig. 4.2.2). The higher Ta/W ratio for the non-magnetic fraction most likely is due to the removal of metal from the sample analyzed here. Note that the amount of metal obtained was insufficient for precise W isotope measurements.

Figure 4.2.2: W isotope composition versus Ta/W ratio for mineral separates and whole rocks from low-Ti mare basalt 15555. The predicted cosmogenic 182W production as a function of Ta/W are calculated using equations from Leya et al. (2003) and the Sm isotopic composition of 15555 (solid line, Nyquist et al. 1995) or noble gas exposure ages (dashed lines, York et al., 1972, Podosek et al., 1971; Marti and Lightner, 1971). Dashed curves are labeled with two possible exposure ages for sample 15555. The error bar shown here for the non-magnetic fraction from mare basalt 15555 corresponds to the 2 external reproducibility of 0.3 , as estimated by repeated measurements of a ~20 ppb ALFA AESAR standard solution.

143

4.2.4 Discussion

4.2.4.1 Tungsten isotope homogeneity in the Moon Our W isotope data for plagioclase separates from ferroan anorthosites 60025 and 62255 contrast with results from Lee et al. (1997), who reported positive 182W values for some anorthosites (including 60025). It is unlikely that the higher earlier reflects the presence of cosmogenic
181 182 182

W/184W reported

W because the exposure age of sample

182

60025 is only ~2 Ma; the calculated cosmogenic

W production by neutron capture of

Ta in this case is less than ~0.1 units for Ta/W ratios lower than ~15 (note that the

Ta/W ratio of 60025 whole rock is ~2.2 based on data from Lee et al., 1997 and Mnker et al., 2003). The reason for the discrepancy between our and previously reported W isotope data for ferroan anorthosites is unclear but could be related to the presence of cosmogenic
182

W in the mafic component in the 60025 sample analyzed by Lee et al.

(1997), which is not present in the pure plagioclase separate investigated in the present study. The presence of a mafic component can also account for the higher W contents reported by Lee et al. (1997) for their 60025 sample. However, it is difficult to assess whether this mafic component has cosmogenic 182W, such that the origin of the elevated
182

W reported by Lee et al. (1997) remains unclear. Note that the amount of mafic

material separated from the 60025 investigated here is insufficient to obtain precise W isotope data. Whatever the reason for the elevated 182W reported for ferroan anorthosites in an earlier study, several lines of evidence indicate that the 182W/184W of the lunar highlands is best presented by W isotope data presented here for samples 60025 and 62255. First, the data presented here are a factor of ~5 and do not show the large range of W isotope compositions reported earlier. Second, in the present study W isotope data were obtained on pure plagioclase separates and therefore do not contain components that could have spuriously elevated
182

W/184W. Third, the

182

W/184W ratios obtained here for ferroan

anorthosites are consistent with current models for the chronology of the lunar magma ocean (see below). In contrast, given that anorthosites have low Hf/W ratios, the elevated and variable
182

W/184W reported for anorthosistes earlier would require a complex

petrogenesis involving evolution in a high Hf/W reservoir followed by re-melting of this reservoir to generate the anorthosites. 144

Lee et al. (2002) reported Ta-W data for several mineral separates from low-Ti mare basalt 15555. In spite of their different Ta/W, the
182

W/184W of these mineral

separates are indistinguishable within uncertainty (individual uncertainties range from 0.4 to 1.5 182W). Lee et al. (2002) therefore argued that mare basalt 15555 does not contain any significant cosmogenic decay of
182 182

W and that its elevated 182W of 1.30.4 reflects in-situ

Hf. However, noble gas isotope systematics of mare basalt 15555 indicate a

cosmic-ray exposure at the lunar surface over a period of 70 to 90 Ma (York et al., 1972, Podosek et al., 1971; Marti and Lightner, 1971). Likewise, low 149Sm/150Sm ratios in this sample reflect burnout of
149

Sm by thermal neutrons produced by interaction with the

182

cosmic rays (Nyquist et al., 1995). The noble gas and Sm isotope data provide two distinct approaches for calculating the magnitude of cosmogenically produced W as a function of Ta/W ratio. The approach based on Sm isotopes is more reliable because it provides a direct proxy for the thermal neutron flux, which is the main concern when determining the amount of cosmogenic produced 2003). Fig. 4.2.2 shows the expected 182W variations due to neutron capture of 181Ta as a function of their Ta/W ratios, calculated using the 149Sm/150Sm ratio of mare basalt 15555 (Nyquist et al., 1995) and correction equations given in Leya et al. (2003). Fig. 2 also shows the expected effects using the exposure age of mare basalt 15555 as a proxy for the thermal neutron flux (see Leya et al., 2003). Both methods yield similar results and reveal that for a range in Ta/W from ~0 to ~5 (i.e., the range in Ta/W that has been reported for several fractions of 15555), the
182 182

W in lunar samples (Leya et al.,

W/184W can shift by ~1 182W. This is significant

because this effect is similar to the reported 182W anomaly of mare basalt 15555. Our new data for a non-magnetic fraction of mare basalt 15555, as well as previously reported data for a 15555 whole-rock (Kleine et al., 2005), are remarkably consistent with the predicted cosmogenic effect in this sample (Fig. 4.2.2). After correction for cosmogenic
182

W, the non-magnetic fraction and the whole rock of this

sample have 182W values of 0.10.4 and -0.10.8, respectively. This provides to important conclusions. First, after proper correction for cosmogenic effects, sample 15555 has 182W~0, indistinguishable from the 182W values of metals from other mare basalts (Touboul et al., 2007). Second, both the presence of cosmogenic noble gases as 145

well as the depletion in

182

149

Sm indicate a significant thermal neutron flux in sample

15555, such that mineral separates having different Ta/W ratios should exhibit different W/184W ratios. These variations are small and were not resolvable with the precision obtained by Lee et al. (2002). However, the data for mineral separates of 15555 reported by Lee et al. (2002) plot systematically above the line for the predicted cosmogenic 182W production. The reasons for this are unclear but our new data for sample 15555 in combination with noble gas and Sm isotope data show that this sample contains cosmogenic
182

W and thus is not suited to determine the indigenous

182

W/184W of mare

basalts. Therefore, the indigenous 182W/184W of low-Ti mare basalts is best defined by W isotope for their metals, all of which have 182W~0 (Touboul et al., 2007).

4.2.4.2

Duration of magma ocean solidification The indistinguishable

182

W/184W ratios of metals from low- and high-Ti mare

basalts and KREEP (Touboul et al. 2007) combined with the corrected 182W/184W of mare basalt 15555 indicate that the different Hf/W ratios of the mare basalt sources and KREEP were established after
182

Hf extinction, i.e., later than ~60 Ma after CAI

182

formation. Likewise, ferroan anorthosites have an indigenous

W/184W that is

indistinguishable from that of the mare basalts and KREEP. Given that ferroan anorthosites have Hf/W ratios much lower than KREEP (Hf/W~12-19; Kleine et al. 2005) and the mare basalt sources (Hf/W~26 for low-Ti and Hf/W>40 for high-Ti mare basalts; Kleine et al. 2005), extraction of ferroan anorthosites from the lunar mantle must also have occurred later than ~60 Ma after CAI formation. Most importantly, this revised Hf-W timescale for the formation of the lunar crust is now consistent with
147

Sm143Nd

ages for ferroan anorthosites of 445640 Ma (i.e., 11240 Ma after CAI formation) (Norman et al. 2003). In most models for the solidification of the lunar magma ocean, the lunar crust formed by flotation of plagioclase after substantial (~50-70 %) crystallization of the magma ocean (Snyder et al., 1992). The
182

Hf-182W and

147

Sm-143Nd systematics

therefore indicate that ~50-70 % crystallization of the magma ocean could have been achieved at ~60 Ma at the earliest and at ~150 Ma at the latest. These ages can potentially be used to constrain the duration of magma ocean solidification but this requires an independent estimate for the formation time of the 146

Moon. Based on Hf-W systematics of Earth's mantle and chondritic meteorites it has been argued that the giant Moon-forming impact might have occurred as early as ~30 Ma (e.g., Jacobsen, 2005) but the Hf-W systematics are also consistent with a later formation of the Moon (Halliday, 2004; Kleine et al., 2004b). More recently, Touboul et al. (2007) showed that the Moon most likely formed later than ~60 Ma after CAI formation, provided that the Hf/W ratios of the lunar and terrestrial mantles are different, as seems likely. Therefore, the uncertainties in the age of the Moon and the age of the ferroan anorthosites currently hamper a precise determination of the duration of magma ocean solidification and the available age constraints are consistent with both an almost immediate crystallization and a more protracted timescale of ~100 Ma. Thermal models of magma oceans indicate that cooling might be very rapid initially but may become more protracted as soon as an insulating crust forms (Solomatov, 2000; Tonks and Melosh, 1990). Therefore, if ferroan anorthosites represent the first crust of the Moon, their crystallization age should closely correspond to the age of Moon formation. In this case, the indistinguishable
182

W/184W ratios of ferroan

anorthosites and other lunar rocks (mare basalts and KREEP) require that the Moon formed later than ~60 Ma, consistent with the age estimate from Touboul et al. (2007). It should be noted however that the formation of the ferroan anorthosites might have been far more complex and might have involved remelting of earlier cumulates (Longhi, 2003). In this case, the crystallization age of ferroan anorthosites might not provide a close estimate of the time of Moon formation. Based on
146

Sm-142Nd systematics it has been argued that the final solidification

of the lunar magma ocean might have occurred as late as ~200-250 Ma after CAI formation (Rankenburg et al., 2006). More recently, however, Boyet and Carlson (2007) argued that the
146 142,143

Nd systematics of lunar samples is most consistent with a

differentiation age of ~4.45 Ga (i.e., ~100 Ma after CAI formation), implying that the Sm-142Nd isochron of the lunar mantle does not reflect the timing of differentiation. Likewise, Bourdon et al. (2008) showed that cumulate overturn, magma mixing and melting following magma ocean solidification at 50-100 Ma could produce a linear array in the
146

Sm-142Nd isochron diagram that yields an apparent age of ~200-250 Ma.

Therefore, the most reliable time constraints on magma ocean solidification are currently 147

provided by the Hf-W systematics of lunar rocks and the anorthosites.

147

Sm-143Nd ages of ferroan

4.2.5 Conclusions

We have shown that, contrary to a previous report (Lee et al. 2002), low-Ti mare basalt 15555 contains cosmogenic
182

W and that its indigenous

182

W/184W is

indistinguishable from that of metals from all other mare basalts analyzed for W isotopes so far (Touboul et al., 2007). We have also shown that in contrast to a previous result (Lee et al., 1997), ferroan anorthosites have an indigenous
182

W/184W that is

indistinguishable from that of KREEP and the mare basalts. The homogeneous 182W/184W ratios of all lunar rocks requires differentiation of the Moon later than ~60 Ma after CAI formation, consistent with 147Sm-143Nd ages for ferroan anorthosites.

References

Arvidson, R., et al., 1975. Cosmic ray exposure ages of features and events at the Apollo landing sites. The Moon 13, 259-276. Bourdon, B., Touboul, M., Caro, G., Kleine T., 2008. Early differentiation of the Earth and the Moon. Phil. Trans. Royal Soc., in press. Boyet, M., Carlson, R. W., 2007. A highly depleted moon or a non-magma ocean origin for the lunar crust? Earth Planet Sci. Lett. 262, 505-516. Halliday, A. N., 2004. Mixing, volatile loss and compositional change during impactdriven accretion of the Earth. Nature 427, 505-509. Jacobsen, S. B., 2005. The Hf-W isotopic system and the origin of the Earth and Moon. Ann. Rev. Earth Planet. Sci. 33, 531-570. Kleine, T., et al., 2004a.
182

Hf-182W isotope systematics of chondrites, eucrites, and

Martian meteorites: Chronology of core formation and mantle differentiation in Vesta and Mars. Geochim. Cosmochim. Acta 68, 2935-2946. Kleine, T., et al., 2004b. The W isotope evolution of the bulk silicate Earth: constraints on the timing and mechanisms of core formation and accretion. Earth Planet Sci. Lett. 228, 109-123. 148

Kleine, T., et al., 2002. Rapid accretion and early core formation on asteroids and the terrestrial planets from Hf-W chronometry. Nature 418, 952-955. Kleine, T., et al., 2005. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674. Kleine, T., et al., 2008. Hf-W thermochronometry: closure temperature and constraints on the accretion and cooling history of the H chondrite parent body. Earth Planet Sci. Lett. 270, 106-118. Lee, D. C., et al., 2002. Cosmogenic tungsten and the origin and earliest differentiation of the Moon. Earth Planet Sci. Lett. 198, 267-274. Lee, D. C., et al., 1997. Age and origin of the moon. Science 278, 1098-1103. Leya, I., et al., 2003. The influence of cosmic-ray production on extinct nuclide systems. Geochim. Cosmochim. Acta 67, 529-541. Longhi, J., 2003, A new view of lunar ferroan anorthosites: Postmagma ocean petrogenesis. J. Geophys. Res. 108(E8), 2-1. Marti, K., Lightner, B. D., 1972. Rare gas record in the largest Apollo 15 rock. Science 175, 421 - 422. Norman, M. D., et al., 2003. Chronology, geochemistry, and petrology of a ferroan noritic anorthosite clast from Descartes breccia 67215: Clues to the age, origin, structure, and impact history of the lunar crust. Met. Planet. Sci. 38, 645-661. Nyquist, L. E., et al., 1995.
146

Sm-142Nd Formation interval for the lunar mantle.

Geochim. Cosmochim. Acta 59, 2817-2837. Podosek, F. A., Huneke, J. C., Wasserburg, G. J., Gas-Retention and cosmic-ray exposure ages of lunar rock 15555. Science 175, 423-425. Rankenburg, K., Brandon, A. D., Neal, C. R., 2006. Neodymium isotope evidence for a chondritic composition of the Moon. Science 312, 1369-1372. Righter, K., Shearer, C. K., 2003. Magmatic fractionation of Hf and W: Constraints on the timing of core formation and differentiation in the Moon and Mars. Geochim. Cosmochim. Acta 67, 2497-2507. Shearer, C. K., Newsom, H. E., 2000. W-Hf isotope abundances and the early origin and evolution of the Earth-Moon system. Geochimica et Cosmochimica Acta. 64, 35993613. 149

Shearer, C. K., Papike, J. J., 1999. Magmatic evolution of the Moon. Am. Min. 84, 14691494. Smith, J. V., et al., 1970. Petrologic history of the moon inferred from petrography, mineralogy and petrogenesis of Apollo 11 rocks. Proceedings of the Apollo 11 Lunar Science Conference. 1, 897-925. Snyder, G. A., Taylor, L. A., Neal, C. R., 1992. A chemical model for generating the sources of mare basalts - combined equilibrium and fractional crystallization of the lunar magmasphere. Geochim. Cosmochim. Acta 56, 3809-3823. Solomatov, V. S., 2000. Fluid dynamics of the terrestrial magma ocean. In: Canup, R. M. and Righter, K. (eds) Origin of the Earth and Moon. Univ. Arizona Press, pp. 323338. Touboul, M., et al., 2007. Late formation and prolonged differentiation of the Moon inferred from W isotopes in lunar metals. Nature 450, 1206-1209. Tonks, W. B. and Melosh, H. J., 1990. The physics of crystal settling and suspension in a turbulent magma ocean. In: Newsom, H. E. and Jones, J. H. (eds). Origin of the Earth. Oxford Univ. Press, New York, pp. 151 - 174. Warren, P. H., 1985. The magma ocean concept and lunar evolution. Ann. Rev. Earth Planet. Sci. 13, 201-240. Warren, P. H., Wasson, J. T., 1977. Pristine nonmare rocks and the nature of the lunar crust. Proceedings of the 8th Lunar Science Conference, 2215-2235. Warren, P. H., Wasson, J. T., 1979. The origin of KREEP. Rev. Geophys. Space Phys. 17, 73-88. Wood, J. A., et al., 1970. Lunar anorthosites and a geophysical model of the moon. Proceedings of the Apollo 11 Lunar Science Conference. 1, 965-988. York, D., Kenyon, W. J., Doyle, R. J., 1972, 40Ar-39Ar ages of Apollo 14 and 15 samples. Proceedings of the Lunar Science Conference. 2, 1613-1622.

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Section 4.3

Early differentiation of the Earth and the Moon

Bernard Bourdon1*, Mathieu Touboul1, Guillaume Caro2, Thorsten Kleine1

Institute of Isotope Geochemistry and Mineral Resources, ETH Zurich, Clausiusstrasse 25, Zurich, CH-8092 Switzerland Centre de Recherches Ptrographiques et Gochimiques- CNRS, 15 rue Notre Dame des Pauvres, 54501 Vandoeuvre-les-Nancy, France
2

Publi dans Philosophical Transactions of the Royal Society A doi: 10.1098/rsta.2008.0125

151

152

Abstract

We examine the implications of new 182W and 142Nd data for Mars and the Moon for the early evolution of the Earth. The similarity of
182

W in the terrestrial and lunar

mantles indicates that the Moon-forming giant impact took place most likely >60 Ma after CAI formation (4.568 Gyr) because as a result of equilibration between the lunar magma disk and the Earth's mantle, the lunar and terrestrial mantles must have started off with identical initial 182W/184W ratios. This is not inconsistent with the apparent U-Pb age of the Earth. New 142Nd data for martian meteorites show that Mars probably has a superchondritic Sm/Nd that could coincide with that of the Earth and Moon. If this is interpreted by an early mantle differentiation event, this requires a buried enriched reservoir for the three objects. This is highly unlikely. For the Earth we show, based on new mass balance calculations for Nd isotopes, that the presence of a hidden reservoir is difficult to reconcile with the combined
142

Nd-143Nd systematics of the Earth's mantle.

We argue that a likely possibility is that the missing component was lost during or prior to accretion. Furthermore, 142Nd data for the Moon that was used to argue for a ~200 Myr for the solidification of the magma ocean is reinterpreted. Cumulate overturn, magma mixing and melting following lunar magma ocean crystallization at 50-100 Myr could have yielded the 200 Myr model age.
4.3.1 Introduction

Understanding the formation of planets is proven to be a crucial task for constraining their later evolution. First, this question is inherently linked to the bulk composition of the planet since designing a scenario for planet accretion and differentiation is often necessary to derive their composition (Sun and McDonough, 1995, Allgre et al. 1995). Particularly crucial in this respect are the behaviors of siderophile elements. Namely the incorporation of these elements in the core will be a function of the accretion scenario and oxidation state of the Earth. This will in turn determine the chemical composition of the mantle. Second, as early differentiation events rapidly follow accretion, a description of these processes is essential for determining the initial conditions of the Earths system. The initial energy available upon accretion may 153

allow a wholesale differentiation that may be difficult to erase at a later stage. There are now indications that following magma ocean crystallization, a dense and enriched reservoir could have formed in the lower mantle (Boyet and Carlson 2005; Labrosse et al. 2007) and fluid dynamical constraints on mantle convection have shown that if an initial density stratification existed in the Earth then it is likely that it could have persisted over timescales of several billion years (Davaille et al. 2002). Third, the early evolution of planets will also determine their rate of cooling and this has implications on stirring rates. A large planet is likely to cool slower but this can be strongly compounded by the existence of an insulating lid. Another important parameter is the presence of water. If water is a component in the accreting material (as is the case on Earth), the lithosphere becomes more ductile and plate tectonics is more likely to take place. This will ultimately result in faster cooling rates. In this contribution, we examine recent data we have obtained for the Moon and Mars that pertain to the early evolution of the Earth and Moon and we discuss their implications for the evolution of terrestrial planets. This approach further emphasizes that the study of nearby planetary objects can provide a wealth of information about the history of our own planet.
4.3.2 New constraints on the age of the Moon and termination of Earth accretion

4.3.2.1 New 182W data and chronological implications There are several reasons to argue that the giant impact represents the last significant stage of terrestrial accretion (Canup and Asphaug, 2000; Morbidelli this volume). First, significant accretion following Moon formation could only have involved numerous small impacts because otherwise the angular momentum of the Earth-Moon system would have been substantially altered and the Moon might have been lost. Second, if significant amounts of mass had been accreted after the Giant Impact, there would be a potential problem in accounting for the siderophile elements in both objects. These considerations limit the amount of mass that can have accreted to the Earth after the giant impact to less than 0.05 Earth's masses (Canup and Asphaug, 2000). Third, if significant accretion takes place after the Moon-forming giant impact, then the oxygen isotopes in the Earth and the Moon could have become different. High precision oxygen 154

isotope measurements have shown that within 0.02 this is not the case (Wiechert et al. 2001). If we assume that the later incoming material had a 1 deviation in 18O from the Earth (equivalent to the difference between Mars and Earth), this limits the mass fraction of material accreted by a giant impact to less than 2%. A similar calculation could be made for 17O. Thus, it would seem that the age of the Moon would provide an age of termination for the Earth accretion. Several previous studies have attempted to derive a meaningful age for the formation of the Moon based on
182

Hf-182W chronometry (Lee et al. 1997, Shearer and

Newsom 2000, Righter and Shearer 2003, Lee et al. 2002, Kleine et al. 2005, Touboul et al. 2007). One major difficulty has been to tackle the issue of cosmogenic production of
182

W via the reaction

181

Ta(n,)182Ta followed by - decay to

182

W. This reaction is

obviously enhanced in silicate rocks for which Ta/W ratios are higher than in metals. After an initial report of large variations in the 182W/184W of lunar whole-rocks (Lee et al. 1997) it was realized that the enhanced
182

W/184W ratios in many samples reflects

cosmogenic 182W production (Leya et al. 2000). Attempts to correct for these effects have yielded imprecise results because of the large corrections required. The most direct method to determine the
182

W/184W unaffected by cosmic-ray effects is the W isotope W (Kleine et al. 2005, Touboul et al. 2007). As shown in

analyses of Fe-metal separated from lunar rocks because these metals do not contain any Ta and hence cosmogenic
182

Figure 4.3.1, the new study by Touboul et al. (2007), which used larger sample sizes and focused on the analysis of high-purity metal separates seems to represent the most selfconsistent data set. Remarkably, the W isotopes are constant among all the investigated lunar samples and similar to terrestrial samples. In what follows we examine in more details the implications of these results.

155

Figure 4.3.1: Compilation of W isotope data for the Moon. Data source : Touboul et al. (2007); Lee et al. (2002); Kleine et al. (2005). The data clearly shows that the 182W for the Moon is indistinguishable within error from the terrestrial composition. Circles are for KREEP-rich samples, diamonds are for high Ti-mare basalts and squares for low-Ti mare basalts.

156

4.3.2.1.1 New 182W data and lunar mantle evolution

The new 182W isotope data for the Moon has three major important features. First, the W isotope composition of the Moon is distinct from that of chondrites. Second, the
182

W/184W ratio of the lunar mantle is identical to that of the bulk silicate Earth and third,

despite a significant range in Hf/W in their sources, all lunar samples have identical
182W (defined as (182W/184Wsample/182W/184Wstd-1)104). In what follows, we discuss in

more detail, the implications of these features. This discussion represents an extension of the first report by Touboul et al. (2007). The formation of the Moon by a giant impact implies that its original temperature must have been very high. As a consequence, the initial state of the Moon was so hot that it must have been molten and must have evolved initially as a magma ocean. The magma ocean concept proposed for the Moon is in part based on the existence of complementary Eu anomalies in the lunar crust (anorthosite) and lunar basalts (mare basalts) as well as the existence of the so-called KREEP component assumed to represent the latest stage of magma ocean crystallization. The data of Touboul et al. (2007) provides an important outlook on this question because it can be used to estimate a lower limit for the age of the lunar magma ocean. At face value, the data indicates that the closure of the Hf-W system took place more than 60 Ma after the beginning of the solar system. In the context of a lunar magma ocean, one could assume that the closure of the system took place when the convection in the magma ocean slows down (60% crystal fraction, Solomatov 2000). As
182

Hf is short-lived (t1/2=8.9 Ma), the absence of

182

W differences in the lunar rocks

implies that the various lunar reservoirs have been remixed and isotopically homogenized until after 182Hf became effectively extinct. This corresponds roughly to a time of at least 6010 Myr (Touboul et al. 2007), given the range in Hf/W ratios in the sources of lunar rocks (Shearer and Newsom 2000; Righter and Shearer 2003; Kleine et al. 2005). This timescale now seems to be consistent with the
142

Nd data available for the Moon,

indicating Sm-Nd closure around 200 Ma, if one takes the data at face value. One surprising aspect of the Sm-Nd data for the Moon is that it is much younger than the corresponding Sm-Nd age for Mars and Earth (Caro et al. 2003, Bennett et al. 2007, Boyet and Carlson 2005). This would imply that the Moon in spite of its smaller size had a longer cooling time than Mars and Earth. This would seem rather paradoxical and has 157

been rationalized by Albarde and Blichert-Toft (2007) who argued that the lunar anorthosite crust has formed a lid that insulated the Moon and considerably slowed down the cooling of the Moon (Martin et al. 2006). Such a stable and early lid was not preserved on Earth and thus the cooling time could have been shorter. It is quite clear that conductive cooling through a boundary layer is much slower than if the boundary layer is not stable, which is typically the case when plate tectonics causes the generation of new seafloor. There is, however, a difficulty in the scenario proposed by Martin et al. (2006) as the plagioclase forming the anorthosite crust only appears when the lunar magma ocean has cooled by 500C and the crystal fraction has reached at least 70% (e.g. Longhi 2003). By that time, the temperature in the lunar mantle would be 1250 C and convection should be more sluggish. Above a 60% melt fraction, convection of the crystal-melt assemblage becomes sluggish but the mobility of melts at a planetary scale could allow some chemical reequilibration. Using the scaling of Solomatov (2007) for the case of the Moon, a typical differentiation timescale related to melt percolation would be
3 Ma. Thus, the chemical and isotope equilibration would effectively stop shortly after

the 60% crystal fraction is reached. This simple calculation does not consider the effect of compositionally-driven melt convection that could take place in the magma ocean cumulate pile. Thus, it is not clear how Nd isotopes would effectively equilibrate at a planetary scale to yield a ~200 Myr isochron. There seems to be a contradiction that calls upon a reexamination of this question. One possibility to explain the young have disturbed the original
146 146

Sm-142Nd

apparent age of the Moon is if thermal solid-convection and later differentiation would Sm-142Nd isochron derived from magma ocean crystallization. In what follows, we explore this possibility with a simple box model and its implications for the actual age of lunar differentiation. In this respect, the lunar data could be compared with terrestrial data. For several long-lived isotope systems, we know that, in open and continuously differentiating systems, the slope of isochrons does not directly date a differentiation event (Allgre et al. 1995, Kellogg et al. 2002, Rudge, 2006). Rather, the slope of a mantle isochron is a function of both differentiation and later mixing. Although the history of the Moon does not involve plate tectonics and thorough mixing, magmatic activity in the Moon lasted until ~3 Ga ago. Thus, it is worth

158

exploring models of continuing differentiation that would yield a 200-250 Myr isochron in the 146Sm-142Nd system. To approach this question, we have used a simplified statistical model including melting of the lunar mantle, radioactive decay and mixing. The model runs over a number of steps and at each step the melt is assumed to mix with a randomly chosen component already present in the lunar mantle (or crust). This model attempts to simulate the various processes affecting the lunar mantle: magma ocean crystallization, cumulate overturn, melting and contamination. The essential processes involved are thus fractionation due to melting (or crystallization) and mixing. As shown on Fig. 4.3.2, this statistical model can produce an array in the
142

Nd/144Nd versus

147

Sm/144Nd diagram that mimics the

observations in Sm-Nd data. The slope of this array does not represent the age of fractionation since in this model Sm-Nd fractionation starts at 70 Myr and proceeds until 3.5 Gyr ago. Rather, it is a function of the successive steps of fractionation and mixing. Arguably, there is more dispersion in the model array in Fig. 4.3.2, which indicates that the model does not perfectly match observations. On the other hand, the 142Nd data set for lunar rocks is still limited and more data should enable a better assessment. The basic conclusion of this simplistic modeling is that the apparent 200 Myr age for the Moon does not necessarily represent the age of crystallization of the lunar magma ocean. Rather, it reflects both crystallization of the LMO as well as later processes that both have induced Sm/Nd fractionation and mixing.

159

Figure 4.3.2: 146Sm-142Nd systematics and the age of solidification of the magma ocean. The slope in the 142 Nd versus 147Sm/144Nd diagram has been interpreted as reflecting the solidification of the lunar magma ocean. Our simple statistical model of fractionation/mixing shows that this need not be the case. The model operates with five time steps of 70 Ma and at each step, component are fractionated (or not) and the melt can be then re-mixed with a pre-existing component. The model then runs for 350 Ma. One can obtain an array using the following parameters in a melting model: DSm=0.1 and DNd=0.07, melt fraction 0.05, fraction of mixing=0.05 at each time step. We assume that the Moon forms at 70 Ma followed the giant impact.

4.3.2.1.2

Exploring scenarios for Moon-Earth equilibration following the giant impact

As mentioned above, an important aspect of the 182W isotope in lunar rocks is that the 182W in the lunar and terrestrial mantles are identical while their Hf/W ratios are not identical. Using U/W, Th/W and Th/U of the lunar and terrestrial mantles, Touboul et al. (2007) estimated the following values: Hf/WMoon=26.41.5 Hf/WEarth=185. As explained in Touboul et al. (2007), there are several ways of rationalizing this important observation. However, in order to derive time constraints on the giant impact, one needs to define a scenario for the interaction of the impactor with Earth. One reasonable expectation is that prior to the impact, the impactor was differentiated into a mantle and a 160

core. Thus, upon impact it is possible that the impactors core merged almost entirely with the Earths core. In this case, the equilibration would have involved equilibration between the Earth and the impactors mantle. Alternatively, the impactors core might be entirely or partially mixed with the Earths mantle during the impact, in which case metal-silicate interaction will be the dominant process (Halliday 2004, Kleine et al. 2004, Nimmo et al. 2006). Another important aspect is the age of core differentiation for the impactor and the proto-Earth. As noted by Nimmo et al. (2006), depending on the age of differentiation and the degree of metal-equilibration, the 182W could be either highly radiogenic or simply close to chondritic values. Furthermore, the oxidation state of the impactor and proto-Earth (Halliday 2004) will strongly influence the degree of Hf/W fractionation and hence the 182W of the mantle. A model including all these aspects would have too many unconstrained parameters (Halliday 2004, Kleine et al. 2004, Nimmo et al. 2006). To make this problem more tractable while assessing the implications of the new data of Touboul et al. (2007), we have considered a model for the Giant Impact using only two parameters. First, we consider the W isotope difference between the proto-lunar mantle and the proto-Earth and we use this as the first parameter in the model. The second parameter of this model is the degree of reequilibration (f) between the proto-Earths mantle and the proto-lunar mantle and is defined as:
f = 1 182Wafter impact 182Wbefore impact

With this definition, f=0 means no equilibration while f=1 means full equilibration. Our approach was to consider two-stage models for the evolution of the impactor because we will only focus on the latest event in Earth accretion (i.e., the Giant Impact and Moon formation). As argued by Morbidelli (this volume), it is very likely that the Moon represented the latest giant impact while there could have been a number of preceding giant impacts. It would seem more logical to model the Earth accretion with a multistage model, but in our case, since we are only dealing with the last event, considering only a mean composition for Earth and impactor is sufficient. Our modelling enables to consider only two parameters to represent a large range of possible models including variable degrees and processes of equilibration between proto-Earth and protoMoon, previous history of the impactor and proto-Earth (including variable core sizes, 161

Hf/W ratios, or age of proto-core formation). It considerably extends the number of possibilities considered in Touboul et al. (2007). The results of the modelling are shown in Fig. 4.3.3 and 4.3.4. What this modeling shows is that there is a priori a large range of possibilities that would satisfy the observations. As shown in Fig. 4.3.3, an important feature that the theoretical lower age for the earliest formation of the Moon is ~37 Ma, as obtained from a two-stage model (Touboul et al. 2007), which assumes a chondritic initial
182

W/184W of the Moon.

However, two lines of evidence suggest that this lower limit is highly improbable. First, it is unlikely that the Moon had a chondritic initial W isotope composition because the Moon formed mostly from high Hf/W mantle material. Second, the difference in both Hf/W and initial 182W between the lunar and terrestrial mantles must have been such that the 182W evolved fortuitously to identical present-day values. Another important result of this modelling is that it shows that some degree of equilibration between the proto-lunar mantle and the proto-Earth is very likely. Depending on the Hf/W ratio in the impactor's mantle, the accretion and differentiation history of the impactor, and the degree to which impactor core material was remixed with proto-lunar material, the 182W of the proto-lunar mantle could in principle be either lower or higher than the 182W of the proto-Earth. However, consideration of Fig. 4.3.3a shows that since the present-day Hf/W of the lunar mantle is higher than that of the Earth, the 182W in the lunar mantle had to be lower than the 182W of the Earth, if the giant impact occurred before 62 Myr (Fig. 4.3.4). This is only possible if the impactor's mantle was highly oxidized (and hence had a relatively low Hf/W) or if there has been more silicate-metal equilibration between proto-lunar mantle and impactor core than with the Earths mantle. Given that the numerical simulations of the giant impact suggest that most of the impactor's core directly merges with Earth's core, this seems implausible. This scenario would also seem unlikely because the impactors mantle should have had a highly radiogenic 182W, given that the impactor most likely differentiated early. Consequently, it is probable that the consists of terrestrial material.
182

W similarity of the terrestrial and lunar mantles

reflects equilibration in the aftermath of the giant impact, unless the Moon predominantly

162

4.3.2.1.3

Isotope equilibration of Earth and Moon after the Giant impact

182

The identical

W isotope composition of the lunar and terrestrial mantles

suggests either that the Moon mainly derives from material of the Earth's mantle or that there has been isotope equilibration between the lunar magma disk and the Earth. The first of these options appears inconsistent with results from numerical simulations of the giant impact, all of which indicate that more than ~80% of the Moon is derived from the impactor. For future simulations, it will be essential to determine whether there are scenarios in which the Moon could be formed entirely from terrestrial material. In case of an equilibration between the lunar magma disk and the Earth, one important question is whether the equilibration process that has been proposed for O isotopes by Pahlevan and Stevenson (2007) could also be valid for W. The condition for having isotope equilibration between the Earth and the lunar magma disk is to reach a temperature in the disk that will be high enough to allow volatilization of W. A key factor in this respect will be the oxygen fugacity because, as pointed out by Fegley and Palme (1985), WO3 is far more volatile than the reduced species WO2. If the temperature in the disk reaches 2000 K, then it is quite likely that W will be volatilized and this could ultimately lead to a loss of W as has been argued for Mo by ONeill (1991). Although ONeill (1991) argues that the case for W loss by volatility is difficult to make based on a thermodynamic calculation, the temperature of the lunar magma disk might have been substantially higher than the temperature of 1400 K assumed in the calculation of O'Neill (1991). For a higher temperature a significant fraction of W might have been lost as WO3. Volatilization of W would also facilitate isotope equilibration of W isotopes between Earth and proto-Moon. An additional implication could be that the higher Hf/W of the Moon (26.41.5 as opposed to 181.6) is due to volatile loss of W rather than core formation. In brief, while one cannot fully ascertain that there has been W isotope equilibration between the Moon and the Earth at the time of the giant impact, the mechanism described by Pahlevan and Stevenson (2007) could be plausible. More detailed modelling will be needed to ascertain this process. It will also be essential to evaluate in future dynamical models if the Moon could have been formed largely from terrestrial mantle material.

Figure 4.3.3: Degree of reequilibration as a function of the difference in 182W before impact between the impactor and the proto-Earth for different times of giant impact (black curves). The possibilities of reequilibration scenarios are limited, as indicated by shaded area. First, the Moon obviously must be older than the oldest lunar rocks dated at about 140 Myr after the start of the solar system. Second, the giant impact should have occurred later than 37 Myr after the start of the solar system. Indeed, an earlier formation would required that the Moon initially had a subchondritic 182W (grey area). Note that it is possible (but not required) to have subchondritic 182W impactor above the 37 Ma isochron line. Open squares correspond to reequilibration scenarios exemplified by W isotope evolution diagrams shown in Fig. 4. Assuming Hf/W ratios of 26.51.1 (2) and 185.2 (2 ) for bulk silicate Moon and Earth respectively, their W isotope compositions are strictly identical at 62 Myr, as in the model developed in Touboul et al. (2007). A giant impact at 62 Myr would require that any 182W heterogeneity between impactor materials and the proto-Earth mantle has been entirely erased by equilibration (f=1). If the giant impact occurred later, the impactor mantle should be more radiogenic than the proto-Earth mantle (182W<0 before equilibration) and the W isotope equilibration is partial. Inversely, a giant impact earlier than 62 Myr would require an impactor less radiogenic than the proto-Earth mantle (182W>0 before equilibration). Figure 4.3.4 (on the right): (A) Schematic diagram showing the various pools of W involved in the make up of the lunar and terrestrial mantle. The vertical double arrows show the show 182W before impact (large arrow) and 182W after equilibration is shown with the small arrow. (B-E) Time evolution diagrams of 182W for the bulk silicate Moon and Earth, illustrating reequilibration scenarios as labeled in Fig. 4.3.3. Solid and long-dashed curves show evolutions of lunar and terrestrial mantles respectively, calculated using their present day 182W combined with their Hf/W ratio. Solid vertical lines indicate reequilibration of W isotope at different times of giant impact. Equation (1) together with input parameters is used to set a 182W prior to equilibration. A complete model of impactor and proto-Earth and their equilibration would involve too many unknown parameters. Short-dashed curves give a hypothetical simplistic example of pre-giant impact 182W evolution for impactor and proto-Earth reservoirs. The chondritic evolution (grey curve) is also shown for reference. (B) Unrealistic scenario with a giant impact at 32 Myr involving essentially materials from the impactor core. (C) Earliest possible scenario (37 Myr), which assumes an undifferentiated impactor (or a reequilibration between its core and its mantle) and no reequilibration between Earth and lunar materials in the aftermath of the giant impact. (D) Scenario with a giant impact at 45 Myr, which requires a terrestrial mantle initially slightly more radiogenic than the lunar mantle. This implies that the impactor mantle had a lower 182W than the mantle of the proto-Earth prior partial equilibration. (E) Scenario with a giant impact at 62 Myr that requires complete W isotope re-equilibration between terrestrial mantle and proto-lunar materials to yield identical initial 182W for the bulk silicate Moon and Earth. (F) Scenario with a giant impact at 88 Myr. The terrestrial mantle had to be slightly less radiogenic than the lunar mantle and this scenario therefore requires partial equilibration between the terrestrial mantle and a more radiogenic impactor mantle.

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165

4.3.2.2 Chronology of terrestrial accretion and astronomical implications An important implication of the new W isotope data for the Moon is that the age of the Moon and the last episode of terrestrial accretion are younger than previously thought (30 Myr). The new data of Touboul et al. (2007) indicates that the last stage of Earth accretion occurred later than 50 Ma. As the age of the oldest lunar rocks is approximately 11240 Myr (Carlson and Lugmair 1988, Norman et al. 2003), one can estimate the age of the giant impact and last stage of terrestrial accretion to be between 50 and 150 Myr. This estimate is compatible with earlier estimate for the age of the Earth based on U-Pb but also on I-Xe systematics (Allgre et al. 1995, Ozima and Podosek 1999). It has been argued by Harper and Jacobsen (1996) that the elevated U/Pb ratio of Earth's mantle is due to loss of volatile Pb rather than removal of Pb into the Earth's core. This was based on the comparison of the Pb abundance of Earth's mantle to the depletion of lithophile elements with similar volatility. We have reexamined this question by considering trends in chondrites between Rb and Pb, which have similar condensation temperature in a gas of solar composition (Allgre et al. 2001). Based on Pb and Rb abundances in chondrites, the estimated Earths core, then the
238 238

U/204Pb ratio

ranges between 1 and 1.4 in the bulk Earth (Fig. 4.3.5). If no Pb is segregated into the U/204Pb ratio of the Bulk Silicate Earth (BSE) should be equal to the 238U/204Pb ratio of the bulk Earth (BE). Yet, the BSE has a 238U/204Pb8-9, which indicates that a significant part of the U-Pb fractionation is not only related to volatile depletion but must be also to core segregation. As argued by Jacobsen and Harper (1996), the continuous model age of core formation is almost identical to the two stage model age for U-Pb, such that, if Pb was indeed partitioned into Earth's core, the U-Pb model age of ~70-100 Ma should closely reflect the time of terrestrial core formation. This is consistent with the new constraints on the age of the Giant impact based on W isotopes. Based on the observation that the Hf-W and U-Pb model ages for formation of the Earth's core are different, Wood and Halliday (2005) argued that Pb was removed into Earth's core by late sulfide segregation. The new W isotope data for lunar rocks however reveal that there must have been ongoing core formation until after 50 Ma, such that there is not contradiction between the U-Pb and Hf-W systems.

166

Figure 4.3.5: Derivation of a bulk Earth 238U/204Pb ratio based on Pb-Rb systematics for meteorite data. Meteorite data is from Wasson and Kayllemen (1988). Data from primitive mantle is from Hofmann (1988). The Pb/Rb versus Rb data for meteorite defines a negative trend reflecting the greater volatility of Rb relative to Pb. The Bulk Earth composition is marked as BE. If one assumes that Pb and Rb are not incorporated in the core, the bulk silicate earth composition should lie on the trend (once Rb is corrected for the mass of the core). The observed value of BSE plots well below this trend and that Pb/Rbpredicted/Pb/Rbobserved defines the degree of depletion of Pb due to incorporation of Pb in the core. One can then infer the degree of depletion of Pb due to core formation.

The W results also have important astronomical implications for the dynamics of the solar system. As shown by the models of OBrien et al. (2006), an early termination of terrestrial accretion (<30 Myr) requires an excentric orbit for Jupiter and Saturn (EJS model). However, this is not the preferred model of OBrien et al. (2006) because this initial condition leads to a rather complete clean up of water-rich planetesimals in the region that is supposed to deliver water to the Earth at a late stage. Their preferred model is to have a circular orbit for Jupiter and Saturn (CJS model). Remarkably, this model leads to a later termination for Earth's accretion (> 70 Myr) and allows the delivery of water to the Earth. It is also worth pointing out that an initially circular orbit is easier to justify from a dynamical viewpoint (Morbidelli 2008).

167

4.3.3 Constraints on the early differentiation of the Earth

The early differentiation of the Earths mantle is currently a highly debated topic and a recent overview is given in Bourdon and Caro (2007). There is now clear evidence for an early terrestrial mantle differentiation event (Caro et al., 2003) and the remaining questions are related to the exact timing of this differentiation as well as the composition of the bulk Earth. The recent analyses of
142

Nd in meteorites (Boyet and

Carlson, 2005) have revealed that (1) the composition of the Earth is distinct from that of meteorites and (2) that the two main classes of chondrites (ordinary and carbonaceous chondrites) also have a distinct 142Nd isotope composition despite having almost similar Sm/Nd ratios. This latter observation can apparently be rationalized by a difference in the abundance of r- and s-process nuclides (Rasmusen and Sharma 2007, Carlson et al. 2007). If we assume that the bulk silicate Earth has a chondritic composition in Nd isotopes, then the positive 142Nd measured in terrestrial rocks relative to ordinary chondrites can be explained by early segregation of an enriched reservoir (with a low Sm/Nd) that would have led to a higher Sm/Nd in the remaining portion of the mantle. In order to produce a positive 142Nd anomaly, this differentiation would have had to take place early enough in Earths history. In what follows, we examine the consistency of the W isotope constraints on the timing of the formation of the Moon inferred by Touboul et al. (2007) and the hypothesis of an early mantle differentiation of Boyet and Carlson (2005). 4.3.3.1 The Age of Early Earth differentiation As argued by Boyet and Carlson (2005), if the Earth has a chondritic Nd isotope composition, then the difference in 142Nd between Earth and chondrites yields an age for mantle differentiation of less than 30 Myr. The actual age of differentiation given by this system is likely to be significantly less than 30 Myr. Boyet and Carlson (2005) have used the 143Nd in MORBs to estimate the maximum degree of Sm/Nd fractionation in the early Earth. As shown in their Fig. 4.3.3, if the Early depleted mantle (EDM) had formed later than 30 Myr, the mean 143Nd of the observable silicate Earth (=EDM) should be greater than 10.5. We know that this is not the case and this estimate is therefore an upper limit, as clearly stated by Boyet and Carlson (2005). An additional 168

reason why this is an upper limit include that the effects of later continental crust extraction are ignored (as is the OIB reservoir that also has a lower Sm/Nd on average than the MORB reservoir). Here, we attempt to refine this estimate by taking into account the fact that the continental crust has to be be included for estimating the composition of the EDM. A conceptual model for this calculation is illustrated in Fig. 4.3.6a. If one takes into account the Nd in the continental crust (CC), one can calculate a new age for mantle depletion based on the following equations:
143 Nd 143 Nd 147 Sm = 144 + 144 e147Tcc 1 144 Nd EDM Nd EDM Nd EDM
today Tcc today

143 Nd 143 Nd 147 Sm = 144 + 144 144 Nd CC Nd EDM Nd CC

today Tcc

today

Tcc

today

(e (

147Tcc

) ) )

143 Nd 143 Nd 147 Sm = 144 + 144 e147Tcc 1 144 Nd DM Nd EDM Nd DM

TCC TEDM today

today

143 Nd 143 Nd 147 Sm = 144 + 144 e147TEDM e147Tcc 144 Nd EDM Nd EDM Nd EDM

142 Nd 142 Nd 144 Sm 146 Sm T T e 146 ( 0 EDM ) = 144 + 144 144 144 Nd EDM Nd CHUR Nd EDM Sm CHUR

today

TEDM

) )

142 Nd 142 Nd 144 Sm 146 Sm T T 1 e 146 ( 0 EDM ) = 144 + 144 144 Nd CHUR Nd CHUR Nd CHUR 144 Sm CHUR

TEDM

147 Sm 147 Sm 147 Sm = DM 144 + (1 DM ) 144 144 Nd EDM Nd DM Nd CC 143 Nd 143 Nd 143 Nd = DM 144 144 + (1 DM ) 144 Nd EDM Nd DM Nd CC The values of input parameters are given in the caption of Fig. 4.3.6. We assume a chondritic evolution prior to the formation of the EDM reservoir. These eight equations are non-linear and can be solved iteratively for the eight unknowns assuming starting input parameters TEDM and DM, the fraction of Nd in the depleted mantle. This latter parameter is used to calculate the concentration of Nd in the depleted mantle. The main results of this calculation is that given that the concentration of Nd in the depleted mantle should be around 1 ppm at most (Hofmann 1988, Salters and Stracke 2004, Workman and Hart, 2005), the age of early mantle depletion has to be less than 10 Ma

169

after CAI (Fig. 4.3.6b). Essentially, this means that the formation of a hidden reservoir complementary to the EDM has to be formed before the Earth is completely accreted, which is unrealistic. This conclusion is very similar to what is discussed below in section B.2 based on observations of 142Nd in Martian meteorites. A major conclusion is that it is more plausible to have the loss of enriched material at prior to complete accretion rather than due to magma ocean differentiation as argued by Boyet and Carlson (2005). Having an early mantle depletion at 20-30 Myr would require a prohibitively high Nd concentration in the depleted mantle.
Figure 4.3.6: (a) Conceptual model used to calculate the age of terrestrial differentiation based on coupled 147Sm-144Nd and 146Sm-142Nd systematics of the Earth as inferred. EDM is the early depleted mantle. The original estimate of Boyet and Carlson (2005) assuming a chondritic Earth composition ignored the effect of later crustal extraction and obtained a maximum age of differentiation. The age of the formation of an early depleted mantle is TEDM, while the age of crustal extraction is TCC. (b) Age of early mantle depletion based on mass balance equations and evolution of 142 Nd and 143Nd in the bulk silicate Earth, depleted mantle and continental crust. The composition of the EDM was calculated by taking into account the budget of Nd in the continental crust (Nd=16 ppm). The equations are solved iteratively as explained in the main text with the following input parameters: 142NdEDM=+0.2, 143NdDM=+11 and 143NdDM=-20. 147 147 Sm/144Ndchondrite=0.1967, Sm/144NdCC=0.115. We made no assumption about the 147Sm/144Nd of the depleted MORB mantle, as the values given by Salters and Stracke (2004) and Workman and Hart (2005) are based on a chondritic model for the Earth. The grey band indicates plausible values for the Nd concentration in the depleted mantle (1 ppm). We assumed for this calculation the maximum possible mass for the depleted mantle, i.e. the total mass of the mantle. A lower value will push TEDM to older ages. The arrow indicates the determination of Boyet and Carlson (2005) for the early mantle depletion. This solution, which did not take into account the continental crust, is not viable.

170

Even if we ignore this mass balance calculation and take the estimate of Boyet and Carlson (2005) for the differentiation of the early Earth, it is quite clear that this early event (<30 Ma) should have taken place prior to the Moon-forming giant impact (>50 Myr, see above). If that earlier event resulted itself from another giant impact (as is most likely in order to produce large scale mantle differentiation), then the Earth should have remained quite hot just prior to the Moon-forming impact (Tonks and Melosh, 1993). In this case, the calculations of Tonks and Melosh (1993) show quite clearly that the entire Earth must have been molten during the giant impact. It is likely that the giant impact would have violently disturbed an early segregation. First, much of the impactors core most likely has merged with the terrestrial core either as a single event or by Rayleigh-Taylor instabilities, and this must have seriously disrupted any dense layer at the base of the mantle. Second, the heat provided by the segregation of the impactors core is likely to strengthen convection and buoyancy driven instabilities. All this would appear inconsistent with the idea that the preservation of an earlier enriched reservoir stored at the bottom of the lower mantle, unless the viscosity and density contrasts were large enough to avoid remixing of the enriched dense layer. Obviously, this point will need to be explored more thoroughly with dynamical models. Yet the new timing for the formation of the Moon does not lend strong support for the very early storage of an enriched reservoir. In addition, our mass balance calculation on the Sm-Nd budget casts some serious doubts on the plausibility of a hidden reservoir. In what follows, we examine this point further and propose an alternative model. 4.3.3.2 The Nd isotope composition of terrestrial planets In this section, we examine whether one can assume that the bulk composition of planets in Sm-Nd is chondritic on the basis of new Nd isotope data for Martian meteorites (Caro et al. 2008). The new data of Caro et al. (2008) shown in Figure 4.3.7 in a 142Nd versus 147Sm/144Nd diagram clearly shows that the Martian bulk composition is probably not chondritic. It must be noted that enriched shergottites have an 142Nd equal to that of ordinary chondrites but they have lower
147

Sm/144Nd ratios and their

143Nd and 176Hf are both negative (-7 and -13 respectively), which is a typical crustal

171

signature. On this basis, it would seem that 142Nd -20 ppm cannot be representative of a bulk composition for Mars.
Figure 4.3.7: (a) Sm-Nd planetary isochron for Mars, Moon and Earth showing a common composition for all these inner solar system planetary objects. This suggests it could represent the bulk composition of inner solar planets. The figure shows possible scenarios for obtaining planetary isochrons in Mars starting from a chondritic composition. We assume that the bulk Mars composition lies on the planetary isochron formed by shergottites (Caro et al. 2008). If the bulk Sm/Nd of Mars is smaller than the intersect with Earth (line A), then the age of Mars-chondrite fractionation is earlier than the age of the solar system. If the bulk Sm/Nd of Mars is higher than the intersect with Earth then the age of Sm/Nd fractionation is less than 40 Ma. This scenario while being possible would still require a super-chondritic composition for Mars. The common intersect for Mars, Moon and Earth would have to be purely coincidental. (b) Hypothetical scenario for 146Sm-142Nd systematics for the chondritic Moon composition assuming that the 142Nd isotopes equilibrate with the terrestrial composition at the time of the giant impact taken to be 70 Ma. Crystallization of a magma ocean (and later evolution) then produces a fractionation with a model age of 200 Ma. In this scenario that is consistent with W isotopes, the intersection with terrestrial composition should have a much higher Sm/Nd than what is observed. This would also be inconsistent with the data of Rankenburg et al. (2006).

If the intersection of the mantle compositions of Mars, Moon and Earth represents the mean composition of terrestrial planets, one would infer that the composition of these planets is superchondritic in Sm/Nd, unless Mars has also experienced an early episode of mantle differentiation leading to a hidden reservoir with a composition identical to that of the Earth. Caro et al. (2008) have argued that this is an unlikely possibility. To make this case more convincing, we explore more systematically scenarios whereby the common point for terrestrial planets shown on Figure 4.3.7 can be explained by an early differentiation event as argued for the Earth by Boyet and Carlson (2005). Unlike Debaille et al. (2007), we assume that that the bulk

172

composition of Mars lies on the planetary isochron, implying that there is no hidden reservoir on Mars. One question is whether the intersect with the Earth is likely to represent the bulk composition of Mars. If the bulk composition of Mars lies above the intersection with terrestrial composition (Fig. 4.3.7a), then the chondrite-Mars Sm-Nd fractionation event would have to post-date the accretion of Mars dated at 0-10 Myr as shown by Kleine et al. (2002) and Nimmo and Kleine (2007). This putative event would have to pre-date the large scale mantle differentiation event dated at 40 Myr (Caro et al. 2008), which seems unreasonable. If the bulk composition of Mars is below the terrestrial composition, then the fractionation in Sm/Nd must be older than the solar system, which is impossible. Thus, in both cases, it seems likely that the intersect with the terrestrial composition represents the bulk Martian composition (Fig. 4.3.7a). Thus, one may conclude that the observations of Caro et al. (2008) imply that the Sm/Nd fractionation observed in Martian meteorites must have taken place either before accretion or right after accretion. However, if one calls upon the segregation of a hidden reservoir, the Sm/Nd fractionation must have been strikingly identical to that observed in the Earth. Although there has not been a physically plausible scenario proposed by Boyet and Carlson (2005) to explain their hidden reservoir, it is not clear why the hidden reservoir on Earth would lead to identical Sm/Nd in the Martian mantle. A different line of argument has been used by Debaille et al. (2007) who have argued that the linear array formed by shergottites in an 142Nd versus 143Nd diagram cannot be explained by a super-chondritic mantle identical to that of the Earth. For their argument they have assumed that the 143Nd for bulk Mars would be the same as the depleted terrestrial mantle (i.e. 143Nd10.7, which is the value used by Boyet and Carlson (2005). However, the choice of this particular composition for Earth (or Mars) is not justified since we know that both magma ocean crystallization and later crustal extraction has modified the
143

Nd isotope composition while

142

Nd is only affected by

the earlier event. As a consequence the argument of Debaille is not conclusive and an alternative solution is discussed below (see section 4.3.2). The 146Sm-142Nd systematics for lunar rocks are also difficult to reconcile with a hidden reservoir model that would be consistent with both Nd and W observations. A reasonable scenario would be that the Moon formed at 50 Myr (the earliest age possible based on W isotopes) with a bulk chondritic composition and that the Nd isotopes

173

would equilibrate during the proto-Moon stage as has been argued for O, Si and W isotopes (Pahlevan and Stevenson 2007, Georg et al. 2007; Touboul et al. 2007). As shown in Figure 4.3.7b, the intersection of the lunar mantle isochron with the terrestrial Nd isotope composition would fall at a higher Sm/Nd than is observed. Thus, this scenario cannot explain the observations. The only realistic explanation is then to have the Moon formed entirely from the Earths mantle but this scenario would then be in conflict with inferences about the iron abundance in the Moon (ONeill 1991). It would also contradict dynamical models that predicts that the Moon is formed mostly from the impactor (Canup and Asphaug 2001), although more recent models have shown that the mass fraction of proto-Earth in the Moon could be as large as 0.5 (Canup 2004). One may note that there is a substantial uncertainty in the intersection of Mars, Moon and Earth in the Sm-Nd diagram. In principle, the produce a 20 ppm offset in
142 147

Sm/144Nd value required to

Nd between chondrites and planets is 0.21, which is

142

slightly higher than the value given by the intersect. This discrepancy could come from several sources of uncertainties. First, one may note that the chondrites is obtained based on a correction using
148

Nd of carbonaceous

Nd isotope (Carlson et al. 2007),

142

which introduces an additional source of uncertainty. If one considers only the difference between planets and ordinary chondrites then the difference in becomes 17 ppm. Another source of uncertainty is the initial diagram. This slope is slightly steeper if
147 146 146

Nd

Sm/144Sm ratio
146

(=0.0081) used to determine the slope of the 4.568 Ga isochron in the

Sm-142Nd

Sm/144Sm is increased to 0.009 and the

Sm/144Nd needs to be increased to 0.207 to match a difference of 17 ppm in between An important implication is that the Sm/Nd fractionation observed in Mars,

ordinary chondrites and Earth. Earth and the Moon would predate the accretion and the high Sm/Nd would characterize the chemical composition of the inner solar system. As there is no direct meteorite sample from this inner solar system region, it is difficult to test that inference. Because Sm and Nd are both lithophile and refractory, the expectation is that the Sm/Nd ratio of the bulk planets should be identical to that of chondrites. There are reports of REE fractionation under specific nebular conditions. One could consider the following two hypotheses: (1) given that chondrules have systematically higher Sm/Nd than bulk chondrites (Amelin 2004; Krestina et al. 1999), a preferential accumulation of

174

chondrules in the inner solar system region should in principle lead to a higher Sm/Nd in terrestrial planets; (2) as the Earth, Mars and possibly Moon-forming impactor formed from precursory planetesimals, the impact history of these differentiated object could have led to removal of a crust with a low Sm/Nd. The observation that each chondrite group has a characteristic size distribution of chondrules has led to the hypothesis that chondrules have been sorted by a dynamical process (Kuebler et al. 1999). Furthermore, modelling of turbulence in the solar nebula has also shown that the abundances of chondrules themselves could be enhanced by the process of turbulent concentration (Cuzzi et al. 1996, 2001). More importantly, the prediction is that chondrules should be concentrated in the terrestrial planet regions (Cuzzi et al. 1998), while porous aggregates would be concentrated in the outer planet regions. In essence, this is exactly what our inference would be based on the
142 146

Sm-

Nd systematics, suggesting that the offset in Sm/Nd ratio in terrestrial planets could

be due to an accumulation of chondrules with a higher Sm/Nd. In practical terms, the calculated concentration of chondrules can increase by a factor of ten with a high probability, Cuzzi et al. 2001). Using the histogram shown on Figure 4.3.8, this is enough to shift the 147Sm/144Nd from 0.1967 to 0.206. One important question that arises is what process would have caused the Sm/Nd to be greater than chondritic in the first place. This represents a shift of only 4.5% and several processes can a priori be proposed. From a cosmochemical viewpoint, the relative volatility of rare earths has been explored in variable conditions including oxidizing and reducing environment (Boynton 1977, Lodders and Fegley 1993, Pack et al. 2004). In general, there can be an enhancement of Sm or Nd volatility in oxidizing and reducing conditions but the expectation is that other REE will then be far more fractionated (i.e. Eu, Ce or Yb) and this extreme fractionation is not observed in terrestrial mantle peridotites (Jagoutz et al. 1979). Thus, the fractionation due to volatility, although it has been observed in CAIs and special chondrules (Pack et al. 2004) does not seem to be the process to explain the difference between bulk chondrites and chondrules.

175

Figure 4.3.8: Histogram showing the 147Sm/144Nd for bulk chondrites and chondrules (adapted from Caro et al. 2008). The high Sm/Nd found in chondrules could be a result of REE redistribution during the formation of low Sm/Nd phosphate but the Sm/Nd does not correlate with degree of metamorphism. Further investigations of Sm-Nd systematics in chondrites is required to prove that the concentration of chondrules can effectively explain the high Sm/Nd in inner planets. The mean chondrule 147Sm/144Nd is 0.21, while the bulk chondrite 147Sm/144Nd is 0.1967.

There are only few high precision REE data set on chondrules (Krestina et al. 1999, Amelin 2004) and these studies do not reveal the origin of the fractionation. High Sm/Nd ratios are observed in ordinary chondrites that also have a low Sm/Nd phosphate phase. If one assumes that the REE were redistributed during the formation of the phosphate on the parent body, then the high Sm/Nd ratio in the chondrule would not be a primary feature and thus would not be relevant to explaining the high Sm/Nd of planets. It is worth noting, however, that chondrules in carbonaceous chondrites that do not have a phosphate phase also have a high Sm/Nd ratio. Furthermore, as shown in Fig. 8, the chondrules of one of the least metamorphosed ordinary chondrites (Krymka, LL 3.1) also have a high Sm/Nd ratios, such that this observation is not linked to thermal processing. It is worth pointing out, however, that recent studies of type 1 chondrules (Libourel et al. 2007) that include relicts of planetesimal mantles could give clues on the 176

observed Sm/Nd fractionation. Although there are very few of these chondrules, perhaps because many chondrules have been entirely molten, these observations provide important insights about the origin of chondrules. If the chondrules were part of differentiated parent bodies, then it is likely that they experienced melt extraction leading to depletion in Nd relative to Sm. One could speculate that these observations could explain the higher Sm/Nd in chondrules but further documentation will need to be given in the future. Clearly, there are potential difficulties in explaining the high Sm/Nd in Earth, Mars and Moon by accumulation of chondrules and further investigations are needed to test this hypothesis. The second hypothesis involving impact erosion of a differentiated crust was also proposed by Caro et al. (2008) and is discussed at greater length by ONeill in this volume. Numerous models (e.g. Benz and Asphaug 1999, Agnor and Asphaug 2004, Asphaug et al. 2006) have reported that collisions are commonly non-accretionary and lead to erosion of the outer layers of a growing planet. The inference that one might make here is that this process should have taken place at a very early stage (within the first few Ma after the beginning of the solar system) and have led to removal of an early formed crust on planetesimals that ultimately formed Earth, Mars and Moon. One additional constraints brought by the 142Nd data is that the age and composition of the removed crust would have be similar on the precursory material of Earth, Mars and Moon (Fig. 4.3.9). This requirement would seem easier to fulfill at an early stage (when bodies have not grown significantly yet) rather than at a late stage once the planets are formed (see above). Our present state of knowledge does not allow us to conclude on the actual process that would have led to a chemical depletion in the bulk composition of the Earth, Mars and Moon.

177

Figure 4.3.9: Model for the Nd (top) and Hf (bottom) evolution of Western Greenland rocks (Isua). In order to explain the chondritic Hf isotope in Isua at 3.8 Ga, one needs to consider a three-stage model. First, the Earths mantle is depleted which leads to elevated Lu/Hf and Sm/Nd ratios. Then the precursor of Isua rocks is isolated into the crust at an age where 146Sm is almost extinct (e.g. 4.2 Ga), then the Lu/Hf is further fractionated due to intracrustal refinement at 3.8 Ga. The system would have remained closed until today. This scenario is consistent with a scenario proposed by Kamber et al. (2003) to explain the Pb isotope systematics of Isua rocks.

4.3.4 Conclusions

New 182W data for the Moon provide new constraints on the timing of the Moonforming giant impact (later than 50 Myr). Based on this data one can also estimate that the solidification of the magma ocean took place later than 60 Myr. This solves the apparent conflict with
142

Nd age constraints for differentiation of the lunar magma

ocean. However, because the 146Sm-142Nd is sensitive to fractionation until 4.1-4.2 Gyr, the relatively young age given by this system (200-250 Myr) for magma ocean crystallization probably reflects later events including melting, mixing, convection and contamination. A simple model including these processes shows that this hypothesis is perfectly plausible. A wide exploration of models for the giant impact and the subsequent W isotope evolution suggests that there must have been some degree of W isotope equilibration

178

between the Earth and the Moon following the impact. Most likely, part of the core of the impactor partially reequilibrated with the Earth and Moon mantle. We have shown based on Sm-Nd mass balance that the hidden reservoir scenario proposed by Boyet and Carlson (2005) based on the difference in
142

Nd abundance

between the Earth and chondrites needs to be questioned. This Sm/Nd fractionation associated with the formation of a hidden reservoir has to take place prior to the accretion of the Earth to match the Nd isotope observations. Based on new data for Martian meteorites, we further hypothesize that the Sm/Nd composition of terrestrial planets could be higher than that of chondrites. This process could result from enrichment in a chondrule component by sorting or alternatively by impact erosion the outer layers of planetesimals forming the Earth and Mars. Deciding between these alternatives will require deeper investigations of both processes.
Acknowledgements

We would like to thank Stein Jacobsen, Rick Carlson, Hugh ONeill, Charlie Langmuir, Alessandro Morbidelli, Alan Brandon, Dave Stevenson, Claude Allgre for discussions prior to or during the preparation of this manuscript. We also thank one anonymous reviewer for his constructive and insightful remarks as well as the patient editorial handling by Andrew Jephcoate.
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Chapitre 5

Conclusions et perspectives
Conclusions and outlooks

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186

5.1 Conclusions Au cours de cette thse, nous avons appliqu la chronomtrie 182Hf-182W courte priode des objets varis afin de prciser la chronologie et la nature des processus rgissant lvolution du systme solaire primitif. Dans un premier temps, nous nous sommes intresss aux ges daccrtion et lvolution thermique des corps parents de mtorites, tels que les chondrites, les acapulcoites et les lodranites, qui peuvent tre dtermins en employant le systme
182

Hf-182W comme

thermochronomtre. La seconde partie est essentiellement consacre ltude dchantillons lunaires, ramens sur Terre par les misssions Appollo, qui a permis de contraindre les ges de formation et de diffrenciation de la Lune. Les mesures isotopiques ralises sur les anorthosites lunaires, en particulier, ont ncessit le dveloppement de nouvelles procdures chimiques qui ont permis une amlioration des rendements et des blancs de W. Nos tudes des chondrites ordinaires H (Kleine et al., 2008) et des acapulcoites et lodranites (Touboul et al., en prparation) ont permis de prciser les chelles de temps daccrtion et lvolution thermique des plantsimaux dont ces mtorites sont issues et dmontrent les potentialits du systme Hf-W en tant que thermochronomtre. Les isochrones internes conduisent des ges Hf-W de 5,1 0,9 et 5,6 1,0 Ma aprs la formation des CAI, correspondant un ge absolu de 4563,5 0,7 et 4563,0 0,9 Ma pour deux acapulcoites et une lodranite respectivement. Celles ralises sur des chondrites H5 et H6 donnent des ges Hf-W relatifs de 5,9 0,9 Ma et 9,6 1,0 Ma. Les simulations de la diffusion du W entre clinopyroxne et mtal mettent en vidence que les tempratures de fermeture du systme Hf-W dans ces diffrents objets est proche des tempratures maximales atteintes lors de leur mtamorphisme. Ces ges Hf-W sont donc proches de correspondre lge du pic thermique lors du mtamorphisme affectant les corps parents des chondrites H et des acapulcoites-lodranites. Etant donn que la temprature de fermeture de lHf-W est suprieure aux autres systmes chronomtriques comme le Pb-Pb, lAl-Mg et lAr-Ar, les ges Hf-W sont systmatiquement plus jeunes et fournissent des informations sur lvolution aux plus hautes tempratures et par consquent la plus prcoce de ces plantsimaux. Leur volution thermique, ainsi rvle par le biais des donnes thermochromtriques fournies par les diffrents systmes isotopiques, est compatible avec celle de plantsimaux chauffs de faon interne par la dsintgration radioactive de l26Al et qui refroidissent par conduction thermique, suggrant que les impacts nont pas jou un rle majeur en tant que source de chaleur pour les corps parents des chondrites H et des acapulcoites-lodranites. Bien que le diamtre du corps parent ainsi que la 187

localisation en son sein ait une certaine influence, le paramtre, dont dpend de manire critique son volution thermique, est labondance d26Al prsent. Cette abondance est fixe par le moment auquel laccrtion intervient, qui peut donc tre contraint relativement prcisment. Ainsi, les donnes thermochronomtriques et les tempratures des pics thermiques requirent que les corps parents des chondrites H et des acapulcoites-lodranites se soient accrts entre 2 et 4 Ma et entre 1,5 et 2 Ma aprs la formation des CAI respectivement. Elles suggrent donc que laccrtion des plantsimaux non diffrencis (2 4 Ma) est postrieure celle des plantsimaux diffrencis (<1 Ma, Markowski et al., 2007) et que laccrtion du corps parent des acapulcoites-lodranites (1,5 2 Ma), qui sont vus comme des intermdiaires entre mtorites non diffrenci et diffrenci, est intervenue dans un intervalle de temps compris entre laccrtion de leurs corps parents. A la lumire de cette squence chronologique, il apparat donc que le degr de diffrenciation des plantsimaux est essentiellement dtermin par leur ge daccrtion. Une autre implication importante de nos rsultats est que les corps parents des chondrites H et des acapulcoites-lodranites ont des rapports Hf/W similaires (0,63 0,20) mais significativement infrieurs au rapport Hf/W des chondrites carbones (1,21 0,06, Kleine et al., 2004, Burkhardt et al., 2008). Cette diffrence, inattendue pour des lments rfractaires, rvle un fractionnement Hf-W au cours des deux premiers Ma du systme solaire. Ce fractionnement ne peut tre li des processus au sein des corps parents mais pourrait tre produit lors de processus au sein de la nbuleuse avant ou durant laccrtion des plantsimaux. Nos nouvelles donnes isotopiques du W obtenues pour les mtaux lunaires (Touboul et al., 2007) et les anorthosites lunaires faible ge dexposition (Touboul et al., accept) conduisent une rvision importante des ges Hf-W de diffrenciation de la Lune (Kleine et al., 2005) et permettent de contraindre son ge de formation. La chronomtrie Hf-W est bien adapte linvestigation des chelles de temps de la diffrenciation prcoce de la Lune car des fractionnements Hf-W importants ont lieu au cours de la cristallisation de locan magmatique lunaire dont les produits ont donc des rapports Hf/W variables (Shearer et Newsom, 2000, Righter et Shearer, 2003). Lapplication de la chronomtrie Hf-W aux roches lunaires est complique du fait de la production de
182 181

W par capture neutronique par le

Ta durant lexposition aux

rayonnements cosmiques la surface de la Lune, si bien que le composant dominant du 182W dans la plupart des chantillons lunaires est dorigine cosmognique et masque leur signature isotopique originelle (Kleine et al., 2005, Lee et al., 2002, Leya et al., 2003). Afin de contourner cet 188

inconvnient, notre tude sest focalise sur les mtaux extraits de KREEP et de basaltes de mer, car les mtaux ne contiennent pas de Ta, donc de
182 182

W cosmognique, et sur les anorthosites

faiblement exposes (<2 Ma). Les mtaux et les anorthosites lunaires mesures dans cette tude ont tous les mmes rapports W/184W, qui sont identiques la valeur du standard terrestre et nous
182

montrons galement que les anomalies en

W (Kleine et al., 2005, lee et al, 1997, 2002)

182

rapportes prcdemment refltent la prsence de

W cosmognique. Contrairement aux tudes

182

prcdentes, nous navons donc trouv aucune variation systmatique des rapports

W/184W des

chantillons lunaires en dpit de larges diffrences des rapports Hf/W de leurs sources. Ceci indique que la cristallisation de locan magmatique sest prolonge au-del de lextinction du
182

Hf, cest--dire au-del des 60 premiers Ma du systme solaire. Cette nouvelle contrainte Hf-W
146

sur la diffrenciation de la Lune (plus de 60 Ma aprs la formation du systme solaire) nest plus incohrente avec les estimations drives de la chronomtrie Sm-142Nd (200Ma aprs la

formation du systme solaire ; Nyquist et al., 1995 ; Rankenburg et al., 2006 ; Boyet et al., 2007). Une autre implication majeure des nouvelles donnes est quelles indiquent que le manteau lunaire a une composition isotopique du W homogne et apparemment identique celle du manteau terrestre. Cette similarit entre les manteaux lunaire et terrestre pourrait indiquer que la Lune est principalement compose de matriaux drivs du manteau terrestre, mais les contraintes apportes par les simulations dynamiques de limpact gant indiquent, au contraire, que la Lune sest constitue essentiellement partir de matriaux drivs de limpacteur (Canup et Asphaug, 2001) Alternativement, les isotopes du W ont pu se rquilibrer entre locan magmatique terrestre et le disque proto-lunaire, comme cela a t propos pour expliquer la similarit des compositions isotopiques de lO de la Terre et de la Lune (Pahlevan et Stevenson, 2007). Les compositions isotopiques similaires du W des manteaux terrestre et lunaire rvlent galement que limpact a d arriver suffisamment tard afin que leur diffrence de rapports Hf/W ne se traduise pas en une diffrence de rapports
182

W/184W. Lge maximum de formation de la Lune qui peut ainsi tre

dtermin dpend de manire critique du degr de rquilibration entre locan magmatique terrestre et le disque proto-lunaire. Dans larticle de Bernard Bourdon (2008), nous avons explor les diffrents scnarios dquilibration possibles et leur influence sur les ges calculs. Dans le cas le plus probable o cette rquilibration est totale, lge Hf-W maximum driv, en conjonction avec lge Sm-Nd des roches lunaires les plus anciennes, permet de contraindre lge de formation
10 de la Lune 62+ 90 Ma aprs la formation du systme solaire. Dans le cas dune rquilibration

189

partielle, la formation de la Lune peut ventuellement intervenir antrieurement mais en aucune manire avant 37 Ma aprs la formation du systme solaire. Limpact gant constituant le dernier vnement majeur de laccrtion terrestre, cet ge constitue actuellement la meilleure estimation de lge maximal de la fin de laccrtion de la Terre. Ces nouvelles contraintes chronomtriques remettent en cause la datation de la fin de laccrtion terrestre 30 Ma aprs la formation du systme solaire (Jacobsen, 2005) estime partir dun modle deux stades des donnes Hf-W terrestres et lge encore plus ancien obtenu avec un modle continu. Elles sont galement difficiles rconcilier avec une diffrenciation prcoce du manteau terrestre moins de 30 Ma aprs la formation du systme solaire, suggre par Boyet and Carlson (2005) pour expliquer la diffrence de 142Nd de 20 ppm entre les chondrites et la Terre. Cette diffrenciation prcoce requiert la prsence dun rservoir complmentaire cach, isol la base du manteau (Boyet and Carlson 2005; Labrosse et al. 2007), rapport Sm/Nd subchondrititique, qui devrait tre prserv lors de limpact gant. Ceci est extrmement improbable et nous suggrons que ce rservoir est prfrentiellement perdu pendant laccrtion par rosion collisionelle ou que les plantes telluriques totales aient des rapports Sm/Nd superchondritiques, du fait dune accumulation prfrentielle de chondres dans la partie interne du systme solaire, leur zone nouricire.

5.2 Perspectives La ralisation disochrones internes Hf-W sur dautres groupes de chondrites ordinaires tels que les L et LL permettrait de rvler leurs ges et leur composition isotopique initiale. En utilisant ensuite une approche similaire celle applique ici pour les chondrites H et les achondrites primitives, il sera possible de dterminer lge daccretion et le rapport Hf/W de leur corps parent. La combainaison des dterminations de la composition isotopiques du W et de concentrations en U, en Th, en Hf et en W devrait permettre lidentification parmi les eucrites de celles ayant une signature 182W et un rapport Hf/W reprsentatifs de ces paramtres dans le manteau total de leur corps parent. Il devrait ainsi tre possibe de contraindre lge de la formation du noyau et donc de donner un ge minimum daccrtion de ce plantsimal. Ces investigations supplmentaires permettraient donc dobserver si lensemble des plantsimaux obit la squence daccrtion mise en vidence jusqu prsent et a donc t chauff essentiellement par la dsintgration de l26Al ou si, pour certains dautres eux, le chauffage par impacts est requis. De plus, la dtermination des

190

rapports Hf/W dautres corps parents non diffrencis permettrait de prciser lge et la nature des processus gochimiques responsables du fractionnement Hf-W prcoce au sein de la nbuleuse. Comme le montre notre modlisation des nouvelles donnees lunaires, lge de formation de la Lune dpend de manire critique du degr dquilibration choisi. Des tudes exprimentales des changes isotopiques entre phase gazeuse et phase liquide silicates hautes tempratures sont requises afin de prciser le comportement du W dans le contexte de limpact gant et ainsi de mieux contraindre le degr dquilibration atteint entre la proto-Terre et le disque proto-lunaire et donc lge de formation de la Lune. Dautre part, la multiplication des dterminations combines de concentration dHf, de W, dU et de Th dans les chondrites et les chantillons lunaires et terrestres fournirait une meilleure estimation des rapports Hf/W des manteaux lunaire et terrestre. Une meilleure connaissance de ces rapports permettrait damliorer la precision des ges dtermins.

Rfrences : Bourdon, B., Touboul, M., Caro, G., Kleine, T., Early differentiation of the Earth and the Moon, Phil. Trans. Roy. Soc. A. doi: 10.1098/rsta.2008.0125. Boyet, M., and Carlson, R. W., 2007 A highly depleted moon or a non-magma ocean origin for the lunar crust? Earth Planet. Sci. Lett. 262, 505-516. Boyet, M. and Carlson, R. W., 2005. 142Nd evidence for early (>4.53 Ga) global differentiation of the silicate Earth. Science 309, 576-581. Burkhardt, C., Kleine, T., Palme, H., Bourdon, B., Zipfel, J., Friedrich, J., and Ebel, D., 2008. HfW isochrons for CAIs and timescales for planetesimal accretion Geochim. Cosmochim. Acta, submitted. Canup, R. M., and Asphaug, E., 2001. Origin of the Moon in a giant impact near the end of the Earth's formation. Nature 412, 708-712. Jacobsen, S. B., 2005. The Hf-W isotopic system and the origin of the Earth and Moon. Ann. Rev. Earth Planet. Sci. 33, 531-570. Kleine, T., Touboul, M., Van Orman, J. A., Bourdon, B., Maden, C., Mezger, K., and Halliday, A., 2008. Hf-W thermochronometry: closure temperature and constraints on the accretion and cooling history of the H chondrite parent body. Earth Planet. Sci. Lett. 270, 106-118.

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Kleine, T., Mezger, K., Mnker, C., Palme, H., and Bischoff, A., 2004a.

182

Hf-182W isotope

systematics of chondrites, eucrites, and Martian meteorites: Chronology of core formation and mantle differentiation in Vesta and Mars. Geochim. Cosmochim. Acta 68, 2935-2946. Kleine, T., Palme, H., Mezger, K., and Halliday, A. N., 2005c. Hf-W chronometry of lunar metals and the age and early differentiation of the Moon. Science 310, 1671-1674. Lee, D. C., Halliday, A. N., Snyder, G. A., and Taylor, L. A., 1997. Age and origin of the moon. Science 278, 1098-1103. Lee, D. C., Halliday, A. N., Leya, I., Wieler, R., and Wiechert, U., 2002. Cosmogenic tungsten and the origin and earliest differentiation of the Moon. Earth Planet. Sci. Lett. 198, 267-274. Leya, I., Wieler, R., and Halliday, A. N., 2003b. The influence of cosmic-ray production on extinct nuclide systems. Geochim. Cosmochim. Acta 67, 529-541. Markowski, A., Quitt, G., Halliday, A. N., and Kleine, T., 2006b. Tungsten isotopic compositions of iron meteorites: chronological constraints vs. cosmogenic effects. Earth Planet. Sci. Lett. 242, 1-15. Nyquist, L. E., Wiesmann, H., Bansal, B., Shih, C. Y., Keith, J. E., and Harper, C. L., 1995. Sm146-Nd-142 Formation Interval for the Lunar Mantle. Geochim. Cosmochim. Acta 59, 28172837. Pahlevan, K., and Stevenson, D. J., 2007. Possible Origin of the geochemical similarity of the Earth and Moon. Earth Planet. Sci. Lett. 262, 438-449. Rankenburg, K., Brandon, A. D., and Neal, C. R., 2006. Neodymium isotope evidence for a chondritic composition of the Moon. Science 312, 1369-1372. Righter, K. and Shearer, C. K., 2003. Magmatic fractionation of Hf and W: Constraints on the timing of core formation and differentiation in the Moon and Mars. Geochim. Cosmochim. Acta 67, 2497-2507. Shearer, C. K. and Newsom, H. E., 2000. W-Hf isotope abundances and the early origin and evolution of the Earth-Moon system. Geochim. Cosmochim. Acta 64, 3599-3613. Touboul, M., Kleine, T., Bourdon, B., Palme, H., and Wieler, R., 2007. Late formation and prolonged differentiation of the Moon inferred from W isotopes in lunar metals. Nature 450, 1206-1209.

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Touboul, M., Kleine, T., Bourdon, B., Palme, H., and Wieler, R., HfW thermochronometry: Closure temperature and constraints on the accretion and cooling history of the H chondrite parent body. Accepted by Icarus. Touboul M., Kleine T., Bourdon B., Van Orman J. A., Maden C., Irving A. J., Zipfel J., Bunch T.E., Accretion and thermal history of the acapulcoite-lodranite parent body inferred from HfW thermochronometry. In preparation.

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194

Appendice 1 Systmatiques Hf-W des eucrites cumulats et la chronologie du corps parent des eucrites*
Hf-W Systematics of cumulate eucrites and the chronology of the eucrites parent body*

M. Touboul, T. Kleine, B. Bourdon

Institute for Isotope Geochemistry and Mineral Resources, Department of Earth Sciences, ETH Zurich, Clausiusstrasse 25, 8092 Zurich, Switzerland

* 39th Lunar and Planetary Science Conference LPI Contribution No 1391, p. 2336

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196

Hf-W SYSTEMATICS OF CUMULATE EUCRITES AND THE CHRONOLOGY OF THE EUCRITE PARENT BODY. M. Touboul1, T. Kleine1, B. Bourdon1, 1Institute for Isotope Geology and Mineral Resources, ETH Zrich, 8092 Zrich, Switzerland (touboul@erdw.ethz.ch).

Introduction: Key issues regarding the early evolution of planetary bodies are the timescales of accretion, core formation, and silicate differentiation. The extinct 182Hf-182W decay system has proven particularly useful as a chronometer for these early planetary processes because Hf-W fractionations occurred during both core formation and melting processes in the silicate mantle. The latter is mainly related to the presence of clinopyroxene and ilmenite that have very high Hf/W ratios. For instance, the crystallization of these minerals in the lunar magma ocean produced large Hf/W variations in the lunar mantle, such that Hf-W chronometry could provide a precise age for the crystallization of the lunar magma ocean [1]. The combined 147Sm-143Nd and 176Lu-176Hf isotope systematics of cumulate eucrites indicate that ilmenite was present in their source regions [2]. Therefore, cumulate eucrites may exhibit highly variable Hf/W ratios and the formation of their source region can potentially be dated using the Hf-W system. Here we present new Hf-W data for five cumulate eucrites (Serra de Mage, Moore County, Talampaya, Moama, and Binda) and use these data to constrain the chronology of core formation and mantle differentiation in the eucrite parent body. Methods: Samples (~1 g) were finely crushed in an agate mortar and ~400 mg of the whole rock powder were dissolved in Savillex beakers using HFHNO3 at 120C for 72 hours. After drying, the samples are re-dissolved several times in HNO3-H2O2 and finally in 6 M HCl-0.06 M HF. At this stage, complete dissolution is achieved and a ~5% aliquot is spiked with a mixed 180Hf-183W tracer for concentration determination by isotope dilution. The remaining ~95% were first loaded onto cation exchange columns to remove most of the sample matrix. Tungsten together with other high field strength elements (HFSEs) was eluted from this column using 1 M HCl-0.1 M HF. Separation of W from the other HFSEs was achieved using our previously established anion exchange techniques [3]. The anion exchange chemistry was repeated once to ensure complete Ti removal. All measurments were performed using a Nu Plasma MCICPMS at ETH Zurich. Tungsten isotope compositions of the samples were determined relative to the 182 W/184W obtained for two bracketing measurements of the W standard. In each run 40 ratios were measured and, depending on the W content of the samples, the measurements were performed with ~0.6-1.5V for 182 W, resulting in within-run statistics of 0.2-0.4

units. The external reproducibility of these measurements is 0.4-0.8 (2) for the 182W/184W ratio. Results: In spite of largely different 180Hf/184W ratios, Moama, Serra de Mage and Talampaya have similar 182W values of 18.00.8, 17.20.4, 18.20.4, respectively (Fig. 1). Moore County has the highest 180 Hf/184W of the cumulate eucrites investigated here but has slightly lower 182W value of 14.90.4. In contrast to the radiogenic 182W values and low W contents (~4-14 ppb) of these four cumulate eucrites, Binda has much lower 182W=2.60.3 and higher W content (70 ppb). Compared to basaltic eucrites, the range in 180Hf/184W among the cumulate eucrites is much larger and their 182W values are lower. Quitt et al. [4] obtained 182W~0 and ~525 ppb W in their analyses for Serra de Mag, clearly inconsistent with the results presented here.

Figure 1: Hf-W isochron diagram for whole rocks of cumulate and basaltic eucrites. 182W are the deviation of the 182W/184W ratio of a sample relative to the terrestrial standard in part per 10,000.

Discussion: Chronology of the eucrite parent body. Quitt et al. [4] argue that the high W content they obtained for Serra de Mag reflects sample heterogeneity, implying the presence of a component with an extreme enrichment of W. Several lines of evidence indicate that this cannot be the case and that the low 182W and Hf/W obtained for Serra de Mage by Quitte et al. are due to contamination with terrestrial W. First, a linear regression of the Hf-W data presented here and those reported by Quitte et al. [4] yields an initial 182 Hf/180Hf that exceeds the solar system initial by a factor of ~2. Second, Quitte et al. reported an 182W for Serra de Mage that is identical to the terrestrial W isotope composition and a W content that is ~40 times higher than the one obtained here, indicating substantial addition of W having terrestrial isotopic composi-

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tion. Third, in a plot of 182W vs. 1/W, those eucrites that have anomalously high W contents (Serra de Mage and Jonzac [4], Juvinas [5], Binda [this study]) plot on straight lines. This is a characteristic feature of two-component mixtures. Note that the Hf-W data for Binda obtained here plot exactly on the mixing line defined by the Serra de Mage data reported here and by Quitte et al. [4]. Likewise, Jonzac and the Hf-W data point for Juvinas from Yin et al. [5] plot on a straight line defined by the average of basaltic eucrites and terrestrial W. Therefore, the linear array defined by the basaltic eucrites (+ Serra de Mage as reported by Quitte et al. [4]) in the Hf-W isochron diagram does not represent an isochron but is a mixing line between basaltic eucrites and terrestrial W. If those samples that were clearly contaminated with terrestrial W are excluded from the regression, no statistically meaningful isochron is obtained for the basaltic eucrites. This is because the variation in Hf/W ratios among the remaining basaltic eucrites is too small.

Figure 2: W isotope composition versus 1/W for cumulate and basaltic eucrites. Dashed lines show mixing between terrestrial W and W of cumulate and basaltic eucrite endmembers.

The Hf-W data for basaltic eucrite nevertheless provide important age constraints. The combined 147 Sm-143Nd and 176Lu-176Hf isotope systematics of basaltic eucrites indicate that they probably formed as large degree melts from a chondritic source [2]. The lack of substantial variations in 176Hf/177Hf ratios among the basaltic eucrites rules out a significant role of ilmenite in their sources. Therefore, only limited fractionation of Hf and W is expected during formation of the basaltic eucrites. This is consistent with the narrow spread in Hf/W ratio and 182W values among most basaltic eucrites and indicates that the average 182W and Hf/W of basaltic eucrites may provide a good estimate of these parameters in the bulk mantle of the eucrite parent body. If this is correct, these val-

ues can be used to constrain the timing of core formation. Using 180Hf/184W= 28.81.8 and 182W = 24.43.2 for average basaltic eucrites and assuming a chondritic composition for the bulk eucrite parent body, a twostage model age for core formation of 2.51.2 Ma can be calculated. This corresponds to an absolute age of 4566.11.2 Ma (calculated relative to the angrites DOrbigny and Sahara 99555) and is consistent with the timescales for the differentiation of the eucrite parent body deduced from Al-Mg systematics [6], with a Pb-Pb age of 4566.520.33 Ma for cumulate eucrite Asuka 881394 [7], and with the 53Mn-53Cr age of 4566.50.6 Ma obtained from a eucrite whole-rock isochron [8] (recalculated relative to the angrite D'Orbigny). The initial 182W calculated from the chondritemantle isochron of the eucrite parent body is -3.05 0.15, slightly higher than 182W values for magmatic iron meteorites. Therefore, core formation in the eucrite parent body appear to have occurred later as in the parent bodies of magmatic iron meteorites. Origin of cumulate eucrites. One of the key observations of our study is that cumulate eucrites, in spite of widely different 180Hf/184W ratios, have homogeneous W isotope composition. The much lower 182W value of Binda most likely reflects contamination with terrestrial W and the slightly lower 182W ~15 of Moore County compared to the other cumulate eucrites (182W ~18) also is most readily explained by slight terrestrial contamination (Fig. 2). Therefore, cumulate eucrites appear to be characterized by constant 182W values of ~18, indicating that their widely different 180 Hf/184W ratios must have been established after 182 Hf became effectively extinct, i.e., later than ~60 Ma after CAI formation. This is consistent with results from 147Sm-143Nd and 176Lu-177Hf whole-rock isochrons corresponding to an age of ~100 Ma after CAI formation [2]. Note, however, that these age constraints are difficult to reconcile with the ~4566.5 PbPb age for cumulate eucrite Asuka 881394 [7]. Acknowlegment: We thank the teams of the Smithsonian Institution in Washington, the Museum National dhistoire naturelle de Paris and the Museum Victoria in Melbourn for providing the samples. References: [1] Touboul et al., (2007) Nature 450,
1206-1209. [2] Blichert-Toft J. et al. (2002) EPSL 204, 167181. [3] Kleine T. et al. (2004) GCA 68, 2935-2946. [4] Quitt G. et al. (2000) EPSL 184, 83-94. [5] Yin Q. et al. (2002) Nature 450, 949-952. [6] Bizzarro M. et al. (2005) ApJ 632, 41-44. [7] Amelin Y. et al. (2006) LPSC XXXVII, #1970. [8] Shukolyukov A. and Lugmair G.W. (1997) GCA 62, 28632886 [9] Markowski A. et al. (2006) EPSL 242, 115.

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Appendice 2 Chronomtrie Hf-W: Accrtion et volution prcoce des astroides et des plantes telluriques*
Hf-W chronometry and the accretion and early evolution of asteroids and terrestrial planets* T. Kleine1, M. Touboul1, B. Bourdon1, F. Nimmo2, K. Mezger3, H. Palme4, Q.-Z. Yin5, S.B. Jacobsen6, A.N. Halliday7

Institute for Isotope Geochemistry and Mineral Resources, ETH Zurich, NW, Clausiusstrasse 25, 8092 Zurich, Switzerland 2 Department of Earth and Planetary Sciences, University of California Santa Cruz, 1156 High St., Santa Cruz CA 95064, USA 3 Institut fr Mineralogie, Universitt Mnster, Corrensstrasse 24, 48149 Mnster, Germany 4 Institut fr Geologie und Mineralogie, Universitt zu Kln, Zlpicherstrasse 49b, 50674 Kln, Germany 5 Department of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge, MA 02138, USA Department of Geology, University of California Davis, One Shields Avenue, Davis, CA 95616, USA 7 Department of Earth Sciences, University of Oxford, Parks Road, OX1 3PR, United Kingdom
6

* Accept par Geochimica et Cosmochimica Acta

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200

Abstract We review the chronology for the accretion and earliest evolution of asteroids and terrestrial planets as obtained by applying Hf-W chronometry to meteoritic and planetary samples. The Hf-W systematics of meteorites and some of their components lead to the following succession and duration of events. CAI formation at 4568.50.5 Ma was followed by the accretion and differentiation of the parent bodies of magmatic iron meteorites within less than ~1 Ma. Chondrules from H chondrites formed 1.70.7 Ma after CAIs, consistent with 26Al-26Mg ages for L and LL chondrules. Magmatism on the parent bodies of angrites, eucrites, and mesosiderites started at ~3 Ma after CAI formation and might have extended until ~10 Ma. A similar timescale is obtained for the high-temperature metamorphic evolution of the H chondrite parent body. Thermal modeling combined with these age constraints reveals that the different thermal histories of meteorite parent bodies primarily reflect their initial abundance of 26Al, which is determined by their accretion age. Impact-related processes are an important heat source for the subsequent evolution of asteroids but these do not appear to have induced largescale melting. Hafnium-tungsten ages for eucrite metals postdate CAI formation by ~20 Ma and probably reflect impact-triggered thermal metamorphism in the crust of the eucrite parent body. Hafnium-tungsten data for IAB irons appear most consistent with mixing of metals and silicates during reassembly of the IAB parent body following its impact disruption. The timing of this event, however, remains poorly constrained. The strong fractionation of lithophile Hf from siderophile W during core formation makes the Hf-W system an ideal chronometer for this major differentiation event. However, for larger planets such as the terrestrial planets the calculated Hf-W ages are particularly sensitive to the occurrence of large impacts, the degree to which impactor cores re-equilibrated with the target mantle during large collisions, and changes in the metal-silicate partition coefficients of W due to changing fO2 in differentiating planetary bodies. Calculated core formation ages for Mars range from 0-20 Ma after CAI formation and currently cannot distinguish between scenarios where Mars formed by runaway growth and where its formation was more protracted. Tungsten model ages for core formation in Earth range from ~30 Ma to >100 Ma after CAIs and hence do not provide a unique age for the formation of Earth. However, the identical 182W/184W ratios of the lunar and terrestrial mantles suggest that the giant Moon-forming impact and the

201

termination of Earth's core formation occurred after extinction of ~50 Ma after CAIs). The identical
182

182

Hf (i.e., more than

W/

184

W ratios of the lunar and terrestrial mantles

also require that either the Moon consists predominantly of terrestrial material or that W isotopes in the proto-lunar magma disk had equilibrated with the Earth's mantle. Hafnium-tungsten chronometry also provides constraints on the duration of magma ocean solidification in terrestrial planets. Variations in the
182

W/184W ratios of

Martian meteorites reflect solidification of a Martian magma ocean during the effective life-time of 182Hf and are consistent with global differentiation of the Martian mantle at ~40 Ma after CAI formation. In contrast to Mars, no
143 182

W variations exist in the lunar

mantle, indicating magma ocean solidification later than ~60 Ma, consistent with 147SmNd ages for ferroan anorthosites. Differentiation of the bulk silicate Earth, which
146

probably was related to the crystallization of a global magma ocean, most likely occurred after the giant Moon-forming impact. This is consistent with a Sm-142Nd age of 50-200 Ma for the differentiation of Earth's mantle but is difficult to reconcile with the mantle differentiation age of <30 Ma that has been suggested based on different
142

Nd abundances in chondrites and Earth's mantle.

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INTRODUCTION

The formation of asteroids and terrestrial planets began with the accumulation of dust grains to kilometre-sized planetesimals, which is thought to have occurred in less than ~104 years (Chambers, 2004). Gravity and gas drag caused these planetesimals to collide and form increasingly larger bodies in a period of runaway growth, the products of which include numerous Moon- to Mars-sized planetary embryos that are thought to have formed in ~106 years (Weidenschilling et al., 1997). Collisions among these bodies mark the late stages of accretion, culminating in the formation of a few terrestrial planets that sweep up all the other bodies. Numerical simulations suggest that this stage may have taken 107-108 years (Chambers and Wetherill, 1998; Agnor et al., 1999). The Moon probably formed during this period and involves a 'giant impact' of a Mars-sized body with proto-Earth at the very end of Earth's accretion (Canup and Asphaug, 2001). Collisions among the planetary embryos and the decay of short-lived radioactive isotopes (especially 26Al) caused the planetary interiors to heat up and eventually melt and differentiate. As a consequence, all major bodies of the inner solar system and also many smaller bodies are chemically differentiated into a metallic core and a silicate mantle (Walter and Tronnes, 2004). However, some objects such as the parent bodies of chondritic meteorites remained undifferentiated. Determining the timescales for the accretion of asteroids and terrestrial planets is essential for evaluating planetary accretion models and, hence, is key to constraining the nature of the planet formation process. Similarly, determining the timescales for the early, high-temperature evolution of planetary bodies (i.e., chemical differentiation and thermal metamorphism) provides essential information for constraining the initial conditions that controlled the subsequent evolution of planets. Short-lived nuclides have proven particularly useful for obtaining such age constraints and, depending on their half-lives, can provide information on different stages of early planetary accretion and evolution. While the 26Al-26Mg chronometer (t1/2 ~0.73 Ma) is suitable for dating processes in the first ~5 Ma of the solar system to high precision, the 182Hf-182W system, owing to its longer half-life of ~8.9 Ma, can potentially be used to date processes in the first ~60 Ma. This timescale is most relevant to the formation and early differentiation of terrestrial planets, processes that are thought to have been largely complete in the first ~100 Ma of the solar system (Chambers, 2004). In the past ~15 years 182Hf-182W chronometry has successfully been applied to date a variety of processes associated with the formation and earliest evolution of planetary bodies. The main interest in the Hf-W system was initially related to its potential

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for dating core formation (Harper et al., 1991; Lee and Halliday, 1995; Harper and Jacobsen, 1996) but Hf-W fractionations also occur during mantle melting processes (Shearer and Newsom, 2000; Righter and Shearer, 2003). This allows the timescales of early mantle differentiation (e.g., magma ocean crystallization) to be determined. There is also an increasing number of applications that use internal Hf-W isochrons for meteorites to date the timing of Hf-W closure in meteorites and constrain the thermal evolution of their parent bodies (Markowski et al., 2007; Burkhardt et al., 2008; Kleine et al., 2008b). Here we review the chronology of the accretion and earliest evolution of asteroids and terrestrial planets as obtained by applying Hf-W chronometry to meteoritic and planetary samples. THE 182HF-182W CHRONOMETER

Hafnium-182 is produced by both the r- and s-processes and decays to 182W with a half-life of ~8.9 Ma. Given the range in Hf/W ratios in planetary reservoirs and meteorite components, 182Hf was sufficiently abundant to create resolvable 182W differences in the first ~60 Ma of the solar system and Hf-W chronometry can be used to date chemical and physical processes that fractionated Hf and W during this period. This time span is most appropriate for studying the formation and early differentiation of planetary objects in the inner solar system, processes that are generally thought to have been complete within the first ~100 Ma of the solar system (Chambers, 2004). Due to the different geo- and cosmochemical properties of Hf and W, these two elements are fractionated by a variety of processes that occurred during accretion, differentiation and early evolution of planetary bodies. This makes the Hf-W system an extremely useful chronometer for the early solar system. 2.1 Hf-W fractionation during planetary differentiation and in meteorites

Hafnium and W are refractory elements and as such should occur in chondritic relative abundances in most bulk planetary objects. The Hf-W systematics of chondrites therefore provide an estimate for the W isotope composition of a bulk planetary object and serve as a reference for calculating Hf-W ages of core formation. During core formation lithophile Hf is entirely retained in the mantle, whereas siderophile W is preferentially partitioned into the metal core, resulting in Hf/W~0 in the core and correspondingly high Hf/W ratios in the silicate mantle. The metal-silicate partition coefficient of W depends on several parameters including fO2, p, T, and silicate melt composition (Walter and Thibault, 1995; Walter et al., 2000). Therefore, depending on the conditions

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of core formation, the depletion of W in the silicate mantle can vary among different planetary objects but also during core formation within one object. Additional fractionation of Hf from W can occur in the silicate part of differentiated planetary objects and in this case is related to the higher incompatibility of W relative to Hf (Righter and Shearer, 2003). Whereas W is one of the most incompatible elements (similar to Th and U), Hf can be incorporated into some minerals such as highCa pyroxene and ilmenite. Crystallization of these two minerals - e.g. during solidification of a magma ocean or during basalt crystallization - can result in the formation of reservoirs with high Hf/W ratios. In some cases, these fractionations can exceed those induced by core formation. For instance, due to the presence of ilmenite and high-Ca pyroxene in their source, lunar high-Ti mare basalts have Hf/W ratios as high as ~100, whereas KREEP-rich samples have much lower Hf/W ratios of ~20 (Kleine et al., 2005c). Such large fractionations greatly enhance the application of the Hf-W system as a chronometer of mantle differentiation. The Hf/W ratio that is characteristic for the entire mantle of a differentiated planetary body cannot be measured directly in most cases because substantial Hf-W fractionations occurred during igneous processes within the mantle (Righter and Shearer, 2003). The bulk mantle Hf/W ratio must therefore be inferred by comparing the W concentrations in mantle-derived samples with a refractory lithophile element that is as incompatible as W and whose abundance relative to Hf is known. Trace element studies of lunar, terrestrial, and meteoritic basalts indicate that Th, U, and W have similar incompatibilities (Palme and Rammensee, 1981a; Newsom et al., 1996), such that Th/W and U/W ratios in silicate mantles in conjunction with Hf/Th and Hf/U ratios in chondrites can be used to determine the Hf/W ratios in bulk planetary mantles. Table 1 summarizes current best estimates for the Hf/W ratios in the bulk mantles of Mars, the Earth and Moon. Nimmo and Kleine (2007) estimated the Th/W ratio of the Martian mantle to be 0.980.13. Using the Hf/Th = 3.10.1 of carbonaceous chondrites (Kleine et al., 2007) this Th/W translates into Hf/W = 3.00.4. However, ordinary chondrites have higher Hf/Th ratios of 4.00.2 (Kleine et al., 2007), in which case the calculated Hf/W ratio of the Martian mantle would be 3.90.6. As shown below, uncertainties and variations in the Hf/Th ratio of chondrites have a significant effect on the calculated core formation ages for Mars because the Hf/W ratio of the Martian mantle is only slightly higher than the Hf/W ratio of chondrites (Nimmo and Kleine, 2007). The Hf/W ratio of the bulk silicate Earth can be inferred from its Th/W ratio of 5.51.6 (Newsom et al., 1996), which, using Hf/Th = 3.10.1 for carbonaceous chondrites, corresponds to Hf/W = 175. Similarly, the Hf/W ratio of the bulk lunar mantle can be estimated from its U/W ratio of 1.930.08 (Palme and Rammensee, 1981b). Us-

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ing Hf/U = 13.70.7 for chondrites (Rocholl and Jochum, 1993) this corresponds to an Hf/W ratio of the lunar mantle of 262. A slightly lower Hf/W of 252 is obtained if Th/U = 4.20.2 for the Moon and Hf/Th = 3.10.1 for chondrites are used. The differences in these estimates reflect uncertainties and/or variations in the Hf, U and Th concentrations of chondrites as well as uncertainties in the trace element composition of the lunar and terrestrial mantles. Additional uncertainties may arise if planetary bodies have non-chondritic relative abundances of refractory lithophile elements (in this case Hf, Th and U). For instance, Pb isotope data for terrestrial mantle rocks were used to estimate the terrestrial Th/U to 4.20.2 (Allgre et al., 1986), slightly higher than Th/U~3.8 in chondrites (Rocholl and Jochum, 1993). Moreover, Caro et al. (2008) proposed that Earth (+Moon and Mars) have superchondritic Sm/Nd ratios. The fractionation of Hf from W is not restricted to planetary differentiation but also occurs among the constitutive minerals of many meteorites and some of their components. Table 1 summarizes measured Hf/W ratios in mineral separates from various meteorites along with the ratios of mineral-melt partition coefficients for Hf and W (Righter and Shearer, 2003). The high Hf/W ratios in high-Ca pyroxene make it possible to obtain precise internal isochron for meteorites because high-Ca pyroxene is an important constituent of numerous meteorites and their components, such as eucrites, angrites and CAIs. Almost all meteorites contain some metal, which has Hf/W~0 and allows direct measurement of the initial 182W/184W of a sample. Precise Hf-W ages can thus be obtained from Hf-W isochrons involving high-Ca pyroxene and other silicates (e.g., olivine, melilite), such as for CAIs (Burkhardt et al., 2008) and angrites (Markowski et al., 2007; Kleine et al., 2008a), or co-genetic metal and silicate fractions, such as for H chondrites (Kleine et al., 2008b). Table 2 summarizes initial 182Hf/180Hf ratios for meteorites that have been obtained from internal isochrons. 2.2 lows:
182

Notation and Hf-W isotope systematics Tungsten isotope data are commonly expressed in 182W, which is defined as fol W=

( (

182

184 184

182

) W)
W

sample

standard

-1 104

(1)

Note that similarly to other short-lived chronometers such as the 53Mn-53Cr and 26Al26 Mg systems, 182W values are calculated relative to the 182W/184W of the terrestrial standard. However, for modeling purposes some authors (Harper and Jacobsen, 1996; Jacobsen, 2005; Nimmo and Agnor, 2006) also expressed 182W/184W relative to the W isotope composition of the Chondritic Uniform Reservoir (CHUR), as defined by the W

206

isotope evolution of carbonaceous chondrites (section 2.3). To distinguish between these notations W ( t ) for a sample or reservoir j is defined as: 182 W 184 W (t ) j (2) W (t ) = 182 1 104 184 W W (t ) CHUR Thus, by definition, W ( t ) of chondrites is always 0 at any time. The present-day W
j

isotope composition of a sample or reservoir is given by: 182 W 182 W 180 Hf 182 Hf 184 = 184 + 184 180 W 0 W i W 0 Hf i

(3)

where the subscript 0 refers to the present-day and the subscript i to the initial value. Equation (3) reveals that the initial 182Hf/180Hf of a sample or reservoir can be obtained from the slope of an isochron in a plot of 182W/184W vs. 180Hf/184W. Relative ages or formation intervals between any two samples or reservoirs can then be calculated using the following equation: 182 Hf 180 Hf 1 1 t = ln 182 (4) 180 Hf Hf 2

( (

) )

where is the decay constant and has a value of 0.0780.002 Ma-1 (Vockenhuber et al., 2004). In the simplest model of core formation it is assumed that the core formed instantaneously from a bulk planet having chondritic Hf/W. Then the two-stage model age of core formation, tcf, can be calculated from Hf-W data for a mantle or core j as follows (e.g., Lee and Halliday, 1995): 180 Hf 180 Hf 184 184 W j W CHUR 182 Hf 1 (5) tcf = ln 180 182 182 Hf T0 W W 184 184 W j W CHUR where

182

Hf

180

Hf

T0

refers to the initial 182Hf/180Hf of the solar system as determined

from internal Hf-W isochrons for CAIs. An alternative equation for calculation two-stage model ages for core formation was introduced by Harper and Jacobsen (1996) and uses the following notation: 182 Hf (T T ) j W (t ) = Q182W f jHf /W 180 e 0 cf e T0 Hf T0 (6) 182 Hf ( tcf ) = Q182W f jHf /W 180 e Hf T0

207

where Q182W = 10 4

180

Hf/ 182 W

CHUR

= 1.42 104 (see below and Table 3). The Hf/W

fractionation in reservoir j relative to CHUR is defined by ( Hf W ) j f jHf/W = 1 ( Hf W )CHUR

(7)

In practice, to determine the age of core formation of a sample or reservoir, we will rewrite equation (6) as follows: 182 Hf Q182W f jHf /W 180 Hf T0 1 tcf = ln j W (0) (8) Hf /W 1 1.38 f j = ln j W (0) Note that the second equality is derived by assuming a carbonaceous chondritic composition, i.e., Q182W = 10 4 180 Hf/ 182 W = 1.42 104 .

CHUR

182

Equations (5) and (8) reveal that core formation ages can be calculated from the W/ W and 180Hf/184W ratios of a mantle or core once the Hf-W systematics of chondrites and the 182Hf/180Hf at the time of CAI formation are known. We shall see later that the calculation of realistic core formation ages requires more complex models, at least for Earth-sized bodies.
184

2.3

Reference parameters for Hf-W chronology

2.3.1 Hf-W systematics of chondrites The first W isotope data for chondrites indicated that Earth's mantle and chondrites had identical 182W/184W ratios (Lee and Halliday, 1995; Lee and Halliday, 1996). However, in 2002 it was shown that carbonaceous chondrites have 182W/184W ~2 units lower than Earth's mantle (Kleine et al., 2002; Schoenberg et al., 2002a; Yin et al., 2002). The currently most precise determination of the 182W/184W ratio of carbonaceous chondrites is based on 14 samples that have an average 182W of -1.90.1 (Kleine et al., 2004a). There are no resolvable differences in the 182W/184W among the carbonaceous chondrite groups (Fig. 1), consistent with their limited spread in 180Hf/184W ratios (180Hf/184W = 1.18 Hf/W) from ~1.1 to ~1.6 (Kleine et al., 2004a). Ordinary chondrite groups exhibit a larger range in 180Hf/184W ratios and 182W values (Fig. 1). H chondrites have lower 180Hf/184W ratios (from ~0.6 to ~1.1) and 182W values (from ~-2.5 to ~-2.0), whereas LL chondrites have higher 180Hf/184W ratios (from ~1.6 to ~2.1) and

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182W values (from ~-1.7 to ~-1.5) (Kleine et al., 2007). Likewise, enstatite chondrites have 180Hf/184W ratios and 182W values that are similar to those of the H chondrites (Lee and Halliday, 2000). The different Hf/W ratios among the chondrite groups most likely reflect metalsilicate and refractory element fractionation in the solar nebula. Therefore, bulk planetary objects may have different Hf/W ratios, at least to the extent as present in the different chondrite groups. In most cases, however, the variations of the Hf/W ratios among bulk chondrites are small compared those produced during planetary differentiation (section 2.1). 2.3.2 Initial 182Hf/180Hf and 182W/184W of CAIs Precise knowledge of the 182Hf/180Hf and 182W/184W at the time of CAI formation is essential for making full use of the time constraints provided by Hf-W chronometry. This is because CAIs are the oldest yet dated material formed in the solar system (Gray et al., 1973) and as such are the most suitable reference point for constraining the duration of processes in the early solar system. Moreover, intervals relative to CAIs determined with the Hf-W chronometer can be directly compared to 26Al-26Mg ages that are also commonly expressed as time intervals calculated based on the initial 26Al/27Al of CAIs. Several approaches have been used to determine the initial 182Hf/180Hf and 182 W/184W ratios of the solar system and for this task Hf-W data for meteorites can be utilized in three different ways (Table 4). The first approach is to assume that the lowest 182 W/184W measured in iron meteorites represents the initial W isotope composition of the solar system (Lee and Halliday, 1995; Quitt and Birck, 2004). The difference between this assumed initial value and the present-day 182W/184W of chondrites then represents ingrowth from decay of 182Hf in a reservoir with a chondritic 180Hf/184W ratio. However, the 182W/184W of most iron meteorites have been lowered by the interaction with cosmic rays (Masarik, 1997; Leya et al., 2003) and the lowest 182W/184W reported for iron meteorites does not provide a robust estimate for the initial 182W/184W of the solar system but rather reflects the effects of interaction with thermal neutrons (Masarik, 1997; Leya et al., 2003; Kleine et al., 2005a; Markowski et al., 2006b; Schrsten et al., 2006). Therefore, using the lowest 182W/184W ratio reported for iron meteorites results in estimates for the initial 182Hf/180Hf of the solar system (Quitt and Birck, 2004) that are too high. The second approach uses internal Hf-W isochrons for meteorites with a welldefined absolute age and relies on two assumptions: (i) the absolute age determined for a sample corresponds to the time of Hf-W closure, and (ii) the absolute age of CAIs is

209

known. The first assumption is strictly valid only for rapidly cooled samples such as angrites or CAIs (see below). One problem with this approach is that the absolute age of CAIs is not known with sufficient precision, with Pb-Pb ages ranging from 4567.110.16 Ma (Amelin et al., 2002; Amelin et al., 2006) to 4568.50.5 Ma (Bouvier et al., 2007). This introduces some uncertainty when the 182Hf/180Hf at any point in time is back-calculated to the time of CAI formation. This approach was employed by Kleine et al. (2002) using Hf-W data for the H4 chondrite Ste. Marguerite and an initial 182 Hf/180Hf of (1.090.09)10-4 at the time of CAI formation was calculated (assuming a CAI age of 4566 Ma). The main reason for using this sample was that at that time no precise Hf-W isochrons for rapidly cooled samples were available. Similarly, Yin et al. (2002) used Hf-W data for one CAI and two equilibrated ordinary chondrites to determine an initial 182Hf/180Hf of (1.000.08)10-4 at the time of CAI formation. This approach is based on the assumption that closure of the Hf-W system in those equilibrated ordinary chondrites occurred at the time of CAI formation. The third and most direct approach to determine the initial 182Hf/180Hf of the solar system is to obtain Hf-W data for the first solids that formed in the solar system. Ireland and Bukovanska (2003) reported ionprobe Hf-W data for zircons from the H5 chondrite Simmern. These zircons have an ultrarefractory-enriched trace element pattern, a feature commonly associated with refractory inclusions, and their initial 182Hf/180Hf of (7.24.5)10-5 might be close the initial value of the solar system. The initial 182Hf/180Hf of the solar system is most reliably and directly determined from internal isochrons for CAIs because these are the oldest known objects that formed in the solar system. Hafnium-tungsten data are available for 5 bulk CAIs and these exhibit a narrow range in Hf/W and 182W/184W, which are slightly elevated relative to carbonaceous chondrites (Burkhardt et al., 2008). However, in type B CAIs melilite and fassaite have very different 180Hf/184W ratios, mainly reflecting the compatibility of Hf in fassaites. Their high 180 Hf/184W resulted in radiogenic 182W/184W ratios, which makes it possible to obtain precise internal Hf-W isochrons for CAIs (Burkhardt et al., 2008). Whole-rocks and mineral separates from 8 CAIs from the Allende and NWA 2364 CV3 chondrites plot on a single well-defined isochron corresponding to an initial 182W of -3.280.12 and an initial 182Hf/180Hf of (9.720.44)10-5 (Burkhardt et al., 2008). As discussed in detail by Burkhardt et al. (2008), parent body processes such as aqueous alteration or thermal metamorphism had no detectable effect on the Hf-W systematics of these CAIs, such that the CAI isochron provides the initial 182W/184W and 182Hf/180Hf ratios at the time of CAI formation.

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2.3.3 Calibration of the 182Hf-182W chronometer and conversion to absolute ages The accurate application of Hf-W chronometry to constrain timescales in the early solar system requires that relative Hf-W ages between different early solar system materials are consistent with the differences in their absolute ages. This criterion is strictly applicable only to those samples that cooled rapidly, such that potential differences in closure temperatures did not result in resolvable age differences among various chronometers. This requirement is met by angrites. These exhibit high U/Pb ratios, such that precise Pb-Pb ages are available (Lugmair and Galer, 1992; Amelin, 2008) and the available Pb-Pb ages for angrites reveal an age dispersion of ~7 Ma, which makes it possible to intercalibrate the Hf-W and U-Pb system. In angrites, fassaites have high 180Hf/184W ratios whereas the other constituents olivine, plagioclase and in one case metal - have low 180Hf/184W ratios (see Table 1), resulting in variations in W isotope compositions of up to ~15 182W. This spread makes it possible to obtain precise Hf-W isochrons for angrites (Markowski et al., 2007; Kleine et al., 2008a) and the initial 182Hf/180Hf ratios obtained from the slope of these isochrons are summarized in Table 2. The comparison of Pb-Pb and Hf-W ages can be made for several angrites including D'Orbigny, Sahara 99555 and Northwest Africa 2999, 4590, and 4801. In Fig. 2, the initial 182Hf/180Hf ratios of these angrites are plotted against their Pb-Pb ages. The angrites D'Orbigny and Sahara 99555 as well as Northwest Africa 4590 and 4801 plot on a straight line, whose slope corresponds to 182Hf=0.0750.007 Ma-1, in excellent agreement with the experimental determination that yielded 182Hf=0.0780.002 Ma-1 (Vockenhuber et al., 2004). This provides evidence that the absolute Hf-W ages calculated relative to these angrites are robust and accurate. Northwest Africa 2999 plots slightly below, but within uncertainty of this line, most likely indicating a slight disturbance of the Hf-W system in this sample. This is evident from the Hf-W data for one of the whole-rock and the fines fraction of Northwest Africa 2999, which plot off the isochron (Markowski et al., 2007). The Hf-W and Pb-Pb ages of angrites can also be used to convert relative Hf-W ages to absolute ages, which is essential for facilitating a comparison and combination with results from Pb-Pb chronometry. An important feature of Fig. 2 is that the calibration of the Hf-W system onto an absolute timescale yields consistent results regardless of which of the four angrites, D'Orbigny, Sahara 99555, Northwest Africa 4590 or 4801 are used. Here absolute ages are calculated relative to D'Orbigny [initial 182Hf/180Hf = (7.180.22) 10-5 at 4564.420.12 Ma (Amelin, 2008)] but identical results are obtained if absolute Hf-W ages are calculated relative to any of the other angrites. Fig. 2 reveals that the absolute Hf-W age for CAIs, as calculated relative to angrites, is 4568.50.5 Ma (Burkhardt et al., 2008) and, hence, ~1.5 Ma older than the

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4567.110.16 Ma Pb-Pb age for Efremovka CAIs (Amelin et al., 2002; Amelin et al., 2006). The reasons for this discrepancy are currently unclear but may be related to a partial resetting of the U-Pb system in CAIs. An important observation from Fig. 2 is that if CAIs were used as an age anchor for the Hf-W system, then the Hf-W ages for all angrites would be younger than their Pb-Pb ages, which is highly unlikely.
2.4 Closure temperature of the Hf-W system

The interpretation of Hf-W ages in comparison to results from other chronometers and within the framework of models for the thermal evolution of asteroids requires knowledge of the closure temperature (Tc) for diffusive exchange of Hf and W among the constituent minerals in a rock (Dodson, 1973; Ganguly and Tirone, 2001). Closure temperatures can be calculated from diffusion rates of W in the appropriate minerals but such data are not available yet. Nevertheless, using the model developed by Van Orman et al. (2001), Kleine et al. (2008b) estimated the diffusion parameters of W in high-Ca pyroxene, the major host of radiogenic 182W in most meteorites, and obtained an activation energy of 453 kJ/mol and a pre-exponential factor of 9.53 10-5 m2/s. These parameters can be used to calculate Tc for the Hf-W system as a function of cooling rate and effective grain size. Fig. 3 presents Hf-W closure temperatures as a function of cooling rate, calculated for a 10 m grain size and using the analytical model from Dodson (1973). Also shown are closure temperatures for the U-Pb system in clinopyroxene (Cherniak, 1998) and phosphates (Cherniak et al., 1991) and for the Al-Mg system in anorthite (LaTourrette and Wasserburg, 1998). Fig. 3 reveals that for a wide range of cooling rates (and grain sizes), Tc for the Hf-W system is always higher than closure temperatures of the U-Pb system in high-Ca pyroxene and phosphates and the Al-Mg system in anorthite. Consequently, in slowly cooled samples (e.g., in most metamorphosed meteorites) the Hf-W system will have closed at higher temperatures than other chronometers and Hf-W ages are expected to be older than Pb-Pb and 26Al26 Mg ages. Hence, Hf-W chronometry has the potential to date processes associated with the earliest evolution of meteorite parent bodies and is less susceptible to resetting by later thermal events than any other chronometer commonly used in cosmochronology. The analytical models for closure temperature presented by Dodson (1973) and Ganguly and Tirone (2001) make several assumptions that do not necessarily apply to short-lived chronometers. For example, the Dodson (1973) and Ganguly and Tirone (2001) models assume (i) an infinite sink for radiogenic daughters; (ii) a decay time that is very long compared to the cooling time (which might not be valid for short-lived chronometers); and (iii) that heating at peak metamorphic conditions was sufficient to

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homogenize any pre-existing isotopic heterogeneity. By contrast, the model of Van Orman et al. (2006) does not rely on these assumptions, and is thus a more realistic model for the production and exchange of radiogenic daughters in short-lived isotope systems. This model was applied by Kleine et al. (2008b) to numerically simulate the production and diffusive exchange of radiogenic W between high-Ca pyroxene and metal in H chondrites. These simulations show that for highly metamorphosed rocks, such as the H6 and H5 chondrites peak metamorphic temperatures were sufficiently high to homogenize any pre-existing W isotope heterogeneity. In this case, the calculated closure temperatures are identical to those calculated using the Dodson (1973) model. By contrast, in case of the H4 chondrites, the assumption that peak metamorphic conditions were sufficient to reset the Hf-W system is not valid. Consequently, for such samples the Hf-W closure temperature cannot be calculated using the Dodson (1973) model and assessing the effects of metamorphism on the Hf-W system in H4 chondrites requires a model that can simulate the prograde path, such as the Van Orman et al. (2006).

TIMESCALES FOR THE ACCRETION AND EARLY EVOLUTION OF PLANETESIMALS Iron meteorites - remnants of the first planetesimals

3.1

The first comprehensive investigation of the W isotope composition of iron meteorites was performed by Horan et al. (1998), who showed that iron meteorites have 182W values between ~-5 and ~-3. More recently, the W isotope compositions of a large number of iron meteorites was determined to higher precision than was obtainable during the Horan et al. study and these studies confirmed the range in 182W values obtained by Horan et al. (Kleine et al., 2005a; Markowski et al., 2006b; Schrsten et al., 2006; Qin et al., 2008). With the higher precision obtained in these more recent studies variations within groups of iron meteorites became apparent. Moreover, the nonmagmatic irons appear to have slightly higher 182W values than the magmatic irons. It was observed that the 182W values of iron meteorites become more negative with increasing exposure ages and values lower than ~-4.0 were only reported for samples having exposure ages as old as ~1 Ga (Fig. 4). This decrease in 182W reflects burnout of W isotopes by capture of thermal neutrons produced by cosmic rays (Masarik, 1997; Leya et al., 2003). The production rate of thermal neutrons depends on the pre-atmospheric size of and the location within the meteorite, such that cosmogenic effects on the W isotope composition can vary within a single meteorite. This was demonstrated for the two iron meteorites Grant and Carbo. In both samples, 182W/184W ra-

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tios were lower close to the pre-atmospheric centre compared to those close to the preatmospheric surface (Markowski et al., 2006a). There is currently no direct proxy available for precisely determining the flux of the thermal neutrons relevant to the effects on W isotopes, such that these effects can currently only be estimated from the concentrations of cosmogenic noble gases in particular samples (Markowski et al., 2006a; Qin et al., 2008). However, since this does not provide a direct measure of the production rate of thermal neutrons, the estimated thermal neutron fluxes are model-dependent (Masarik, 1997; Leya et al., 2003). Consequently, there is not yet a reliable method to correct for cosmogenic effects on W isotopes in iron meteorites. Therefore, the currently most reliable age information regarding core formation in iron meteorite parent bodies are provided by the W isotope compositions of magmatic iron meteorites that have not been exposed to thermal neutrons, either because they have young exposure ages or because they were large enough for their interior to have been shielded from thermal neutrons. Among the analyzed iron meteorites, this is only the case for Negrillos (IIAB) and Gibeon (IVA). Negrillos has an exposure age of ~50 Ma (Leya et al., 2000) and several authors have reported W isotope data for the IIAB Negrillos averaging at 182W=-3.420.08 (2) (Kleine et al., 2005a; Lee, 2005; Markowski et al., 2006b). From the exposure age a downward shift of 182W of ~0.03 is calculated (Leya et al., 2003), resulting in a corrected 182W of 3.390.08 (assuming a 50% uncertainty on the correction). Note however that the accuracy of this correction is difficult to assess. The IVA iron meteorite Gibeon has 182W=3.380.05 (Qin et al., 2007) and the low concentrations of cosmogenic noble gases in this meteorite indicate that it is derived from the inner part of a larger body. Gibeon therefore probably was largely shielded from thermal neutrons produced by the cosmic rays. It should be noted, however, that cosmogenic noble gases are produced by primary protons whereas the effects on W isotopes are caused by secondary neutrons, which may reach deeper inside the meteoroid due to the poor capacity of Fe for slowing down neutrons. The estimates based on exposure ages indicate that in iron meteorites the 182 184 W/ W ratio might be lowered by ~0.1 182W per ~100 Ma of cosmic-ray exposure and for an "average" shielding. This decrease in 182W is similar to the radiogenic 182W ingrowth that is achieved during the first Ma in a chondritic reservoir. Therefore, even in iron meteorites that were exposed to very low thermal neutron fluxes the effects of 182 W burnout can be significant but are essentially undetectable with current analytical techniques. It will thus be important to develop a monitor for the thermal neutron flux in the energy range that is relevant for W isotopes.

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The corrected 182W=-3.390.08 for Negrillos and the measured 182W=3.380.05 for Gibeon correspond to W model ages for core formation of -1.01.3 (2) and -0.91.2 (2) Ma after crystallization of type B CAIs. The uncertainties of these ages were calculated by propagating the uncertainties on the 182W values of the iron meteorites, the initial 182W of CAIs, and the present-day 182W of carbonaceous chondrites. A more conservative approach is to calculate the range of ages obtained from the minimum and maximum 182W differences between iron meteorites and CAIs. This approach results in W model ages that range from -2.8 to +0.8 for Negrillos and from -2.5 to +0.6 Ma for Gibeon. Note that the uncertainties of these ages do not include any cosmic-ray effects, which may be present but are essentially undetectable with current analytical techniques. This makes it difficult to exactly determine the time of core formation based on W isotope data. Table 5 summarizes W model ages for different group of magmatic iron meteorites that are based on 182W values that were corrected for cosmic-ray effects using noble gas isotope systematics (Qin et al., 2008). For the IVB iron meteorites negative ages are obtained, implying that the correction procedure did not fully account for the cosmic-ray effects on their 182W/184W ratios. This highlights the fact that noble gas systematics are not a direct proxy for thermal neutrons. Nevertheless, the range of ages obtained from these corrected 182W values is similar to the ages obtained for Negrillos and Gibeon, which have minor to absent cosmic-ray effects. In spite of the presence of cosmogenic effects on W isotopes in iron meteorites and difficulties in reliably quantifying them, it can be stated with confidence that core formation in the parent bodies of magmatic iron meteorites predated the formation of chondrules, most of which have Al-Mg and Pb-Pb ages of ~2-3 Ma after CAI formation (Kita et al., 2000; Amelin et al., 2002; Kunihiro et al., 2004; Rudraswami and Goswami, 2007). For instance, the estimated cosmogenic effect on the W isotope composition of Negrillos is ~-0.03, corresponding to an age correction of ~0.3 Ma. Therefore, the correction would need to be ~10 times larger for the core formation age to be younger than the chondrule ages. However, it seems unlikely that the correction equations (Leya et al., 2003) are incorrect by one order of magnitude because they predict the observed effects to within ~50%. The finding that the parent bodies of magmatic iron meteorites accreted and differentiated before chondrules formed perhaps is the single most significant result of W isotope investigations in meteorites. This result has several far-reaching implications and it is therefore important to consider cases in which the W isotope composition of iron meteorites would not reflect the timing of core formation: (i) iron meteorite parent bodies did not contain 182Hf, such that their 182W/184W never evolved over time; (ii) temperatures during core formation were too low to allow diffusion of radiogenic W

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from silicates into the metal; (iii) there are nucleosynthetic W isotope anomalies in iron meteorites. As discussed in detail by Burkhardt et al. (2008), these scenarios are inconsistent with the Hf-W data for meteorites, such that the most straightforward interpretation of the low 182W/184W ratios of iron meteorites is an early metal segregation in their parent bodies. These results provide two important constraints. First, the assembly of iron meteorites parent bodies prior to chondrule formation is inconsistent with the standard model for asteroid accretion, in which chondrites represent the precursor material from which asteroids accreted and then differentiated. It is important to note that the early formation of iron meteorite parent bodies is consistent with results from numerical simulations, which predict that accretion of planetesimal occurred in less than 1 Ma (Chambers, 2004). Second, the parent bodies of iron meteorites formed so early that heating by decay of 26Al must have been an important heat source. Thermal modeling indicates that for planetesimals that formed within 2 Ma after CAI formation and that are larger than ~20 km in diameter, heating by 26Al decay was sufficient to cause melting and core formation (Hevey and Sanders, 2006). The implications of these results will be discussed in more detail below (section 3.6).
3.2 Chronology of IAB-IIICD iron meteorites

In contrast to the magmatic iron meteorites, the IAB-IIICD irons show little evidence for trace element fractionation and probably do not sample a planetary core (Scott and Wasson, 1975; Wasson and Kallemeyn, 2002). Moreover, metal-silicate separation was less efficient in the IAB-IIICD iron meteorites, as is evident from abundant silicate inclusions. Some authors have suggested that the IAB-IIICD iron meteorites formed in localized impact-melt pools in the megaregolith of a chondritic parent asteroid (Choi et al., 1995; Wasson and Kallemeyn, 2002), whereas others proposed formation of the IAB-IIICD irons by impact disruption of a partially differentiated body (Benedix et al., 2000) or incomplete differentiation of a chondritic planetesimal (Takeda et al., 2000). Horan et al. (1998) were the first to show that most IAB-IIICD iron meteorites have slightly elevated 182W values compared to magmatic irons. This was confirmed by later W isotope investigations of iron meteorites (Kleine et al., 2005a; Markowski et al., 2006b; Schrsten et al., 2006). Whereas most magmatic iron meteorites have 182W values below the initial 182W of CAIs, all the non-magmatic irons have 182W values similar to or slightly higher than the CAI initial (Fig. 5). Both groups of iron meteorites have a similar range in exposure ages, such that the higher 182W of the IAB-IIICD irons compared to the magmatic irons cannot be caused by cosmic-ray effects on W isotopes in magmatic irons (see section 3.1). They rather reflect a later event on the

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IAB-IIICD parent asteroid. Due to the presence of cosmic-ray effects on W isotopes the exact difference in the 182W/184W ratios of non-magmatic and magmatic irons is difficult to assess but can be estimated from samples that were not exposed to substantial thermal neutron fluxes. This is the case for the non-magmatic iron Caddo County, whose 182 W/184W is 0.20.1 units more radiogenic than values for the magmatic irons Gibeon and Negrillos. The W isotope composition of the Caddo County metal can be interpreted in different ways. It may represent the W isotope composition at the time of metal-silicate separation during partial melting of a chondritic source, in which case its two-stage model age of tCAI = 0.92.2 Ma would date this event. An alternative interpretation is that the W isotope composition was partially or completely reset during impacttriggered mixing of metal and silicates. This requires diffusion of radiogenic W from the silicate inclusions into the metal. The metamorphic temperature of IAB silicates is similar to those of H6 chondrites [i.e., ~900 C (Benedix et al., 2000)], which, depending on the grain sizes of the silicates and the cooling rate might be sufficiently high to cause W diffusion (Kleine et al., 2008b). Schulz et al. (2006) reported W isotope data for several bulk IAB silicates that have 182W values ranging from ~6 to ~30. Silicate inclusions and host metals do not define isochrons, indicating that silicates and metals are not in W isotope equilibrium. This may reflect incomplete resetting of the Hf-W system during thermal metamorphism of IAB silicates, consistent with 26Al-26Mg (Liu et al., 2002) and 129I-129Xe ages (Bogard et al., 2005) for silicate inclusions from Caddo County of >7 Ma and ~12 Ma, which postdate the W model age for the Caddo County metal. The W isotope composition of the Caddo County metal nevertheless provides important age information. Partial (or complete) resetting of the Hf-W system during thermal metamorphism results in an increase of the 182W/184W ratio of the metal, such that the two-stage model age is too young. Therefore, metal segregation in the IAB parent body must have occurred earlier than 0.92.2 Ma. At such an early time, 26Al was sufficiently abundant to cause global melting of asteroids, indicating that the partial melting that resulted in the formation of IAB metals was caused by internal heating from 26Al decay. Taken together the Hf-W data for IAB iron meteorites appear most consistent with the model of Benedix et al. (2000). This model invokes an early differentiation of the IAB parent body combined with impact disruption followed by mixing of molten metals with a variety of solid silicates during reassembly. Such processes seem capable of causing the partial resetting observed for the Hf-W system because silicates from different sources and possibly different ages will be mixed together. In such a scenario, sili-

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cates and metals are not co-genetic and hence should not define an isochron, consistent with the observed Hf-W systematics.
3.3 Chronology of the eucrite parent body

3.3.1 Accretion and primordial differentiation The first W isotope data for eucrites were obtained by Lee and Halliday (1996) and Quitt et al. (2000) presented the first comprehensive investigation of the Hf-W systematics of basaltic eucrites. Subsequently, Yin et al. (2002) reported Hf-W data for one Juvinas whole-rock, Kleine et al. (2004a) reported Hf-W data for several additional basaltic eucrites and Kleine et al. (2005b) determined the W isotope composition of eucrite metals. Most recently, the W isotope composition of zircons in eucrites was determined (Srinivasan et al., 2007) and the Hf-W systematics of bulk-rock eucrites reinvestigated (Touboul et al., 2008a). Most basaltic eucrites exhibit high 180Hf/184W and radiogenic 182W/184W ratios (Lee and Halliday, 1996; Quitt et al., 2000; Kleine et al., 2004a). Quitt et al. (2000) reported a large range in 180Hf/184W from ~0.1 to ~46 and 182W values from ~0 to ~39. In contrast, Kleine et al. (2004a) found a much narrower range in 180Hf/184W from ~12 to ~32 and 182W from ~14 to ~26. The Hf-W data for eucrites define a linear trend in a plot of 182W/184W vs. 180Hf/184W, which yields a slope of (7.250.05)10-5 and an initial 182W of -0.50.3. Quitt et al. (2000) initially interpreted the Hf-W data for eucrites as indicating differentiation of the eucrite parent body at ~11 Ma after CAI formation. However, this age was obtained using an initial 182Hf/180Hf of ~2.7510-4 for CAIs but this value was later corrected to ~110-4 (Kleine et al., 2002; Yin et al., 2002). Subsequently, Quitt and Birck (2004) used the Hf-W data for eucrites to infer an age of ~8 Ma for parent body differentiation but this age was obtained using an initial 182Hf/180Hf of ~1.610-4 derived from the 182W/184W of the iron meteorite Tlacotepec. However, the 182 W/184W of this sample has been lowered by the interaction with cosmic rays, such that the age estimate from Quitt and Birck (2004) is too young. Recently, Touboul et al. (2008a) showed that the Hf-W data for basaltic eucrites do not define an isochron. The correlation line is mainly defined by three samples [Serra de Mag and Jonzac (Quitt et al., 2000) and Juvinas (Yin et al., 2002)] that have anomalously high W contents. Using larger samples sizes, Touboul et al. (2008a) were not able to reproduce the Hf-W data for these three samples and obtained much lower W contents and much higher 182W/184W. Moreover, these authors could show that, in a plot of 182W/184W vs. 1/W, the earlier reported W data for these three samples plot on mixing lines between terrestrial W and the W data obtained by Touboul et al. (2008a).

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This relationship sheds doubt on the usefulness of the W data of these three samples to constrain the age of eucrite differentiation. The Hf-W data for basaltic eucrite may nevertheless be used to extract age information on the differentiation of the eucrite parent body. The narrow range in Sm/Nd and Lu/Hf ratios as obtained from the combined 147Sm-143Nd and 176Lu-176Hf isotope systematics of basaltic eucrites indicate that they may have formed as large degree melts from a source having chondritic relative abundances of refractory lithophile elements (Blichert-Toft et al., 2002). The lack of substantial variations in 176Hf/177Hf ratios among the basaltic eucrites rules out a significant role of ilmenite in their sources because this would have resulted in substantial Lu-Hf fractionations. Therefore, only limited fractionation of Hf and W is expected during formation of the basaltic eucrites. This is consistent with the narrow spread in Hf/W ratios and 182W values among basaltic eucrites (Kleine et al., 2004a; Touboul et al., 2008a). If this correct, the 180Hf/184W and 182 W/184W ratios of basaltic eucrites may closely reflect that of their sources and the HfW data can be used to constrain the timing of the earliest differentiation of the eucrite parent body. However, there is substantial variation in the 180Hf/184W and 182W/184W ratios reported for basaltic eucrites, which probably reflects sample heterogeneities and the small sample sizes used for these analyses. Therefore, the average 180Hf/184W ratio and 182W value of basaltic eucrites are rather imprecisely defined and are 180 Hf/184W=278 and 182W=228 [calculated using the data reported in Kleine et al. (2004a; 2005b)]. Using these values a two-stage model age for core formation of tCAI = 36 Ma is calculated. The large uncertainty on this age reflects uncertainties in the Hf/W ratio and W isotope composition of the bulk mantle of the eucrite parent body and highlights the need for Hf-W data for representative bulk rock samples of basaltic eucrites. 3.3.2 Magmatism and thermal metamorphism Basaltic eucrites have magmatic textures similar to those of terrestrial and lunar basalts, indicating formation as lava flows at or near the surface of their parent body, presumably the asteroid Vesta. As a result of rapid cooling near the surface, the pyroxenes in terrestrial and lunar basalts are chemically zoned. In contrast, pyroxenes in most eucrites show no chemical zoning and contain exsolution lamellae, indicating slow cooling and/or a protracted thermal metamorphism after crystallization (Takeda and Graham, 1991). In addition to this thermal overprint, most eucrites are brecciated as a result of impacts on the surface of Vesta. Most basaltic eucrites contain some zircons, which owing to their very high Hf/W ratios (up to ~17'000) can be dated with the Hf-W system (Ireland and Bukovanska,

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2003; Srinivasan et al., 2007). Srinivasan et al. (2007) reported ion probe Hf-W data for zircons and pyroxenes from basaltic eucrites Asuka 881388 and Asuka 881467. The zircon-pyroxene isochrons yield 182Hf/180Hf ratios of ~7.510-5 and ~6.010-5, corresponding to Hf-W ages of tCAI~3 and ~6 Ma and absolute ages of ~4565 Ma and ~4562 Ma, respectively. All eucrites contain at least some metal (typically <0.5%), which formed either during crystallization of the basalts or during later metamorphism (Duke, 1965). The low Ni contents of these metals exclude a meteoritic origin by impacts on the surface of Vesta. The Camel Donga eucrite has the highest metal contents among eucrites and the metal in this meteorite evidently formed by reduction of FeO and FeS during thermal metamorphism (Palme et al., 1988). Metals from five basaltic eucrites (Camel Donga, Juvinas, Bereba, Bouvante, Ibitira) have radiogenic W isotope compositions ranging from ~11 to ~16 182W but only for Camel Donga could a metal-silicate isochron be obtained (Kleine et al., 2005b). This isochron yields an initial 182Hf/180Hf of (1.70.7)10-5, corresponding to an age of tCAI = 225 Ma and an absolute age of 45465 Ma (Kleine et al., 2005b) (Fig. 6). The W model ages for the metals from the other basaltic eucrites, calculated relative to the average 180Hf/184W and 182W/184W of basaltic eucrites, yield similar ages (Kleine et al., 2005b). The major hosts of radiogenic W in basaltic eucrites are high-Ca pyroxene, ilmenite and zircon. Identifying which of these minerals is the source of the radiogenic 182W in the metals requires knowledge of their respective closure temperatures for W diffusion as well as of the peak metamorphic temperatures of eucrites. Based on the diffusion profiles in pyroxenes the metamorphic temperatures of eucrites were ~800-900C (Takeda and Graham, 1991). There are no experimental data available for diffusion of W in high-Ca pyroxene, ilmenite or zircon that could be used to calculate closure temperatures. However, the Hf-W closure temperature in a high-Ca pyroxene-metal system has been estimated using the numerical model of Van Orman et al. (2001) [see section 2.4 and (Kleine et al., 2008b)] and, for an assumed starting temperature of 1000 C, closure temperatures of 750-900 C were obtained for a wide range of grain sizes and cooling rates (Kleine et al., 2008b). It therefore seems likely that post-crystallization heating of basaltic eucrites resulted in W diffusion from high-Ca pyroxenes into metals. In contrast, W diffusion out of zircons probably did not occur because their Hf-W closure temperature is most likely very high. If W diffusion in zircon is slower than Pb diffusion, as is the case in other silicates such as high-Ca pyroxene (Kleine et al., 2008b), then the Hf-W closure temperature in zircons will be higher than the Pb closure temperature of >1000C (Mezger and Krogstad, 1997). This is higher than the crystallization temperature of zircons in

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basaltic melts, indicating that the zircons crystallized below the Hf-W closure temperature but were not reset during later thermal metamorphism. This is consistent with the higher initial 182Hf/180Hf of the zircons compared to the metal (see below) and indicates that the Hf-W zircon ages most likely dates the crystallization of basaltic eucrites. Obtaining an age for crystallization from the Hf-W zircon data, however, requires Hf-W data for another phase that is co-genetic with the zircons and remained a closed system for Hf and W after crystallization. Srinivasan et al. (2007) used their Hf-W data for pyroxenes in the isochron calculations but the Hf-W closure temperature for high-Ca pyroxene in conjunction with temperatures estimates for the thermal metamorphism of basaltic eucrites indicate that high-Ca pyroxene did not remain closed for W diffusion during thermal metamorphism (see above). In this case, the slope of the zircon-pyroxene isochron might be too steep and the apparent age too old. More reliable age information may then be obtained from a zircon-whole-rock isochron, provided that the eucrite whole-rocks remained closed systems with regard to Hf and W. Using the average 180 Hf/184W and 182W/184W of basaltic eucrites in the regression of the zircon data results in Hf-W ages of tCAI = 62 Ma and 95 Ma for the Asuka 881467 and Asuka 881388 zircons, corresponding to absolute ages of 45622 Ma and 45605 Ma (Fig. 6). An important observation is that eucrite metals plot above the regression line defined by the zircon and whole-rock Hf-W data (Fig. 6). This is consistent with a significant time gap between zircon crystallization and the time of metal closure during thermal metamorphism. However, the metal and zircon data were not obtained on the same samples and a comprehensive assessment of the effects that thermal metamorphism had on the Hf-W system in eucrites will require Hf-W data for all major constituents of the same eucrite. The similarity of Hf-W closure temperature in high-Ca pyroxene and metamorphic temperature for basaltic eucrites suggests that the Hf-W metal age corresponds closely to the time of the thermal peak and hence provides an age for the thermal metamorphism. This event occurred ~15 Ma after crystallization of Asuka 881467 zircons, suggesting that the thermal metamorphism is not related to the magmatic activity on the eucrite parent body. Therefore, the thermal metamorphism may be caused either by impact heating or by burial of the basaltic eucrites under hot interior material that was excavated by impacts (Kleine et al., 2005b).
3.4 Timing of magmatism on the angrite and mesosiderite parent bodies

The angrites D'Orbigny and Sahara 99555 formed by rapid cooling of basaltic magmas. Therefore, their Hf-W ages of tCAI=3.90.7 Ma and tCAI=4.30.7 Ma reflects the crystallization age of these basaltic rocks. The angrites NWA 2999, NWA

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4590, and NWA 4801 have significantly younger Hf-W ages ranging from ~8 to ~10 Ma after CAI formation. This may reflect protracted cooling of more deeply buried igneous bodies inside the angrite parent body. Evidence for such a protracted cooling is provided by the annealed textures of NWA 2999 and NWA 4801 and the coarse plutonic texture of NWA 4590 and NWA 4801. The absence of chemical zoning in the pyroxenes of NWA 2999 and NWA 4801 provides evidence for annealing at temperatures above ~700800 C (Takeda and Graham, 1991), consistent with olivine-spinel temperatures of ~870 C for NWA 2999 (Kuehner et al., 2006). The chronological data combined with the petrologic evidence therefore suggest that extrusion of basalts occurred at ~4 Ma and that interior parts of the angrite parent body cooled below ~800 C (i.e., Tc of the Hf-W system) in less than ~10 Ma, as constrained by the Hf-W ages for NWA 4801 and NWA 4590. Schnbchler et al. (2000) reported a Hf-W isochron for a basaltic clast from the mesosiderite Vaca Muerta. The plagioclase-pyroxene isochron corresponds to an age of tCAI = 3.01.5 Ma and an absolute Hf-W age of 4565.31.4 Ma. This age is similar to Hf-W ages for the quenched angrites D'Orbigny and Sahara 99555 as well as to Hf-W zircon ages for basaltic eucrites. These Hf-W ages suggest that extrusion of basaltic melts on the eucrite, angrite and mesosiderite parent bodies occurred in a narrow time interval of ~3-10 Ma after CAI formation. This is an important observation because it is consistent with results from numerical simulations for the thermal evolution of planetesimals heated by decay of 26Al and 60Fe. These simulations show that magmatism on bodies that accreted within the first 2-3 Ma of CAI formation will initiate within the first ~4 Ma after CAI formation and that the last melting will have occurred before 10 Ma after CAI formation (Sahijpal et al., 2007).
3.5 Chronology of the H chondrite parent body

The early formation of the parent bodies of iron meteorites contrasts with the relatively late formation of chondrules. Based on 26Al-26Mg and Pb-Pb ages it is well established that most chondrules formed ~2-3 Ma after CAIs (Kita et al., 2000; Amelin et al., 2002; Kunihiro et al., 2004; Rudraswami and Goswami, 2007; Connelly et al., 2008a; Kurahashi et al., 2008; Rudraswami et al., 2008). Chondrules must have formed prior to the assembly of chondrite parent bodies, such that the formation ages of chondrules provide the earliest possible time of parent body accretion. Furthermore, the distinct physical and chemical characteristics of chondrules from each chondrite group suggest that parent body accretion occurred briefly after chondrule formation. In a turbulent solar nebula, chondrules would be efficiently mixed on short timescales (Cuzzi et al., 2005), such that a characteristic population of chondrules with its distinct size distribu-

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tion and chemical composition could only be preserved, if this chondrule population is accreted into larger bodies soon after chondrule formation. This was quantified by Alexander (2005), who estimated that material in a 1 AU wide area could be mixed within less than ~0.5 Ma. Since asteroid feeding zones probably were smaller, these mixing times become even shorter. If these estimates are correct, chondrite accretion must have occurred almost instantaneously after chondrule formation at ~2-3 Ma after CAI formation (Alexander, 2005). This timescale for the accretion of chondrite parent bodies is also consistent with results from thermal modeling, which suggest that the parent bodies of chondrites accreted more than ~2 Ma after CAIs because otherwise they would have differentiated due to heating from abundant 26Al. The question then arises as to whether this timescale for accretion is consistent with the long-term thermal evolution of chondrite parent bodies. Although the thermal evolution of carbonaceous chondrites is difficult to constrain because except for CK chondrites there are only few metamorphosed samples the thermal evolution of ordinary chondrites can be investigated in detail because these samples exhibit a wide range of metamorphic grades (Dodd, 1969). Many ordinary chondrites are brecciated and shocked, such that a signature of their earliest thermal evolution which is of main interest here might have partly been erased. However, relatively unshocked H chondrites appear to have preserved their earliest cooling history (Trieloff et al., 2003). Kleine et al. (2008b) presented Hf-W ages for such H chondrites and the selected samples cover the range of metamorphic conditions characteristic for H4-H6 chondrites. The Hf-W ages of the H chondrites become younger with increasing metamorphic grade and range from tCAI=1.70.7 Ma for the H4 chondrite Ste. Marguerite to tCAI=9.61.0 Ma for the H6 chondrites Kernouv and Estacado (Fig. 7a). The closure temperature of the Hf-W system in H4 chondrites is 80050 C and thus higher than the peak metamorphic temperature of H4 chondrites. Therefore, parent body metamorphism did not result in significant diffusion of radiogenic W from silicates into metals, such that the Hf-W age for Ste. Marguerite (H4), which is based on a metal-silicate isochron, was not reset. Consequently, the 1.70.7 Ma age for Ste. Marguerite must reflect an earlier high temperature event, and the only viable process in H chondrites is chondrule formation. The 1.70.7 Ma Hf-W age for Ste. Marguerite (H4) is consistent with 26Al-26Mg ages for chondrules from L and LL ordinary chondrites (Kita et al., 2000; Rudraswami and Goswami, 2007). Due to the similarity of peak metamorphic and Hf-W closure temperature in H5 and H6 chondrites, the Hf-W ages for these H chondrites correspond closely to the time of the thermal peak in the respective parts of the H chondrite parent body (Fig. 7b). As a

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consequence, the Hf-W system closed earlier than any other isotope systems and the high temperature interval of ~8 Ma obtained from the Hf-W system is much shorter than intervals obtained from Rb-Sr and Pb-Pb chronometry (Wasserburg et al., 1969; Gpel et al., 1994). Combined with previously published chronological data (Trieloff et al., 2003) the Hf-W ages reveal that shortly after their thermal peak H6 chondrites cooled at ~10C/Ma, H5 chondrites at ~30 C/Ma and H4 chondrites at ~55C/Ma (Kleine et al., 2008b). This inverse correlation of cooling rate and metamorphic grade is most consistent with an onion-shell structure (Miyamoto et al., 1981) of an H chondrite parent body that was internally heated internally by 26Al decay (Kleine et al., 2008b). Therefore, heating by 26Al decay does not only account for the peak temperatures reached inside the H chondrite parent body but is also consistent with its long-term thermal evolution. For planetesimals other than the H chondrite parent body, the thermal evolution is less well constrained and it will be important to investigate whether their thermal evolution is also consistent with the dominant role of heating by 26Al decay.
3.6 Planetesimal accretion and evolution - the dominant role of 26Al heating

Hafnium-tungsten chronometry of meteorites as summarized above indicates that melting and differentiation occurred in bodies that accreted within the first ~1 Ma [parent bodies of the iron meteorites and possibly eucrites and angrites (Bizzarro et al., 2005)] whereas thermal metamorphism with peak temperatures of 900-1000 C is characteristic for the ordinary chondrite parent bodies that formed shortly after ~2 Ma. The thermal histories of these meteorite parent bodies are consistent with heating by decay of 26Al as the dominant heat source. This is illustrated in Fig. 8, where the peak temperature in the centre of an asteroid is plotted against its (instantaneous) accretion age for parent body radii of 10 and 100 km. Also shown are the Hf-W ages for iron meteorites, which provide the latest possible time of accretion of their parent bodies, as well as ages for chondrules from various chondrite parent bodies, which provide the earliest possible time of parent body accretion. Fig. 8 predicts that, if 26Al was the dominant heat source in meteorite parent bodies, then the parent bodies of the weakly metamorphosed carbonaceous chondrites should have accreted more than ~3 Ma after CAI formation. Recent applications of Al-Mg chronometry to chondrules suggest that this indeed is the case. These studies show that chondrules from L and LL chondrites formed in a narrow interval of 1 to 2.5 Ma after CAI formation and that younger ages for L and LL chondrules reflect partial resetting by parent body metamorphism (Rudraswami and Goswami, 2007; Rudraswami et al., 2008). By contrast, chondrules from carbonaceous chondrites show no evidence for resetting by thermal metamorphism but their ages ex-

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tend to more than ~3 Ma after CAI formation. For instance, chondrules from the CO 3.0 chondrite Yamato 81020 have Al-Mg ages ranging from 1.7 to 3.0 Ma (Kunihiro et al., 2004; Kurahashi et al., 2008) and many chondrules from CR chondrites formed more than ~3 Ma after CAIs (Nagashima et al., 2008). If these young chondrule ages do not reflect resetting by low-temperature aqueous alteration on chondrite parent bodies, then the Al-Mg ages for chondrules from carbonaceous chondrites require that their parent bodies accreted more than ~3 Ma after CAI formation and, hence, later than the ordinary chondrite parent bodies. In this case, 26Al had decayed to a level too low to cause significant heating, consistent with the scarcity of highly metamorphosed specimens among the carbonaceous chondrites (Fig. 8). The chronological data summarized above combined with results from thermal modeling (Hevey and Sanders, 2006; Sahijpal et al., 2007) indicate that the abundance of 26Al present at the time of parent body accretion is the essential factor controlling the early evolution of planetesimals: 26Al was sufficiently abundant to melt early-formed planetesimals (<1 Ma), whereas in the late-formed chondrite parent bodies (>2 Ma) too little 26Al remained to raise the temperatures high enough to cause differentiation (Kleine et al., 2005a; Schrsten et al., 2006). Moreover, heating that caused the thermal metamorphism of ordinary chondrites also is consistent with energy release from 26Al decay, as is the scarcity of metamorphosed carbonaceous chondrites, whose parent bodies accreted more than ~3 Ma after CAI formation (Fig. 8). Finally, crystallization ages of meteoritic basalts from the eucrite, angrite and mesosiderite parent bodies are remarkably consistent with the timescale for basaltic magmatism predicted by thermal models for asteroids heated by decay of 26Al (Sahijpal et al., 2007). Different thermal evolutions of meteorite parent bodies therefore largely reflect their initial 26Al abundance, which, due to the rapid decay of 26Al, is controlled by the time of parent body accretion. These observations can be rationalized if the variation of accretion time across the asteroid belt is of the order of several 26Al half-lives (Grimm and McSween, 1993). Due to longer orbital periods and a decrease in surface density, the accretion time increases with increasing distance to the Sun (e.g., Weidenschilling, 1977) and this may account for the heliocentric zoning of the asteroid belt in igneous, metamorphic and unaltered asteroids, with igneous asteroids being located closest to the Sun (Gradie and Tedesco, 1982). Grimm and McSween (1993) considered the variation of accretion time as a function of semimajor axis and calculated the subsequent thermal histories for these planetesimals. The results show that the zonation of the asteroid belt and the thermal histories of meteorite parent bodies can be achieved by heating from 26Al decay. The results of these calculations are remarkably consistent with the chronological constraints

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for asteroid accretion and evolution as summarized above. However, Bottke et al. (2006) proposed that the parent bodies initially accreted within the terrestrial planet region, where the fast accretion rates led to early melting even of small planetesimals, and were later scattered in the main asteroid belt. The Hf-W evidence for early core formation in the parent bodies of magmatic iron meteorites is also consistent with this scenario. It is remarkable that some of the most primitive material that has been preserved in the meteorite record was accreted and processed last. Although this seems somewhat paradoxical at first glance, it reflects the fact that due to the intense heating by 26Al decay only late-formed material could preserve its primitive character. In addition to 26Al heating, impacts may have been an important heat source in the thermal evolution of asteroids but they probably played only a minor role in the early high-temperature evolution of asteroids. This is because the Hf-W ages for hightemperature events such as core formation, magmatism and parent body-wide thermal metamorphism summarized above are entirely consistent with 26Al as the sole heat source. Nevertheless impact-related processes were an important heat source for the subsequent evolution of asteroids. Hafnium-tungsten ages for eucrite metals postdate CAI formation by ~20 Ma and probably reflect impact-triggered thermal metamorphism in the crust of the eucrite parent body. Hafnium-tungsten data for IAB irons appear most consistent with mixing of metals and silicates during reassembly of the IAB parent body following its impact disruption. The timing of this event, however, remains poorly constrained.

TIMESCALES FOR CORE FORMATION AND EARLY MANTLE DIFFERENTIATION IN MARS

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4.1

W-142Nd systematics of the Martian mantle

The first W isotope data for Martian meteorites were presented by Lee and Halliday (1997) and additional analyses were reported by Kleine et al. (2004a) and Foley et al. (2005). The 182W/184W ratios of Martian meteorites mainly fall into two groups (Fig. 9). Basaltic shergottites have 182W~0.3-0.6 and nakhlites and Chassigny (hereafter NC group) have 182W~2-3 (Lee and Halliday, 1997; Kleine et al., 2004a; Foley et al., 2005). The only lherzolitic shergottite that has been analyzed for W isotopes so far is ALHA 77005 and its 182W value of 0.910.32 appears to be slightly higher but is not well resolved from the basaltic shergottites (Foley et al., 2005). Orthopyroxenite ALH 84001 has 182W = 0.490.33, similar to the values for basaltic shergottites (Foley et al., 2005). The W isotope data provide two important constraints. First, all Martian meteor-

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ites have elevated 182W/184W ratios relative to chondrites. This is not surprising because Hf and W can be strongly fractionated by large-scale parent body processes such as core formation and mantle melting. Second, there are 182W variations within the Martian mantle, indicating that, in spite of relatively young crystallization ages for most Martian meteorites (Nyquist et al., 2001), a signature of an early mantle differentiation (i.e., <60 Ma after CAI formation) has been preserved. Application of Hf-W chronometry to date core formation in Mars requires knowledge of the 182W/184W ratio of the bulk Martian mantle. Estimating this value requires distinguishing W isotope variations that are due to early mantle differentiation from those that reflect core formation. This in turn requires independent estimates for the timing of mantle differentiation, which can be obtained from 146,147Sm-142,143Nd isotope systematics of Martian meteorites (Harper et al., 1995; Debaille et al., 2007a; Caro et al., 2008). All samples from the NC group studied so far have relatively constant 142Nd values of ~0.6 (Harper et al., 1995; Caro et al., 2008). In contrast, shergottites show 142Nd ranging from ~-0.3 to ~+0.7 (Fig. 9) (Debaille et al., 2007a; Caro et al., 2008). Whereas the shergottites define a planetary isochron in the 143Nd-142Nd two-stage evolution diagram, the NC group plots outside the two-stage evolutionary field, indicating that their source(s) had a more complex history (Borg et al., 2003; Caro et al., 2008; Debaille et al., 2008). The NC group has 146Sm-142Nd systematics similar to the depleted shergottites, whereas the 147Sm143Nd systematics reveal differences. This could indicate a disturbance of the Sm-Nd system after extinction of 146Sm (Caro et al., 2008; Debaille et al., 2008). The elevated 142Nd and 182W values of the NC group nevertheless provide evidence for an early differentiation event in their source(s). Therefore, the timing of mantle differentiation in Mars is currently best dated by 146,147 the Sm-142,143Nd systematics of shergottites, which were interpreted to indicate differentiation at 4018 Ma (Caro et al., 2008) or, alternatively, differentiation in the interval from ~30 to ~100 Ma after CAI formation (Debaille et al., 2007a). This event could potentially have resulted in W isotope variations, such that the effects of silicate mantle differentiation on W isotopes need to be taken into account in any attempt to derive the 182W/184W of the bulk Martian mantle. Kleine et al. (2004a) and Foley et al. (2005) used the 142Nd/144Nd ratios of shergottites for this task, mainly because the Nd isotope data available at that time suggested that at least some of the shergottites have 142 Nd/144Nd identical to that of the bulk Martian mantle, assumed to be 142Nd=0 (i.e., identical to the terrestrial standard). However, two recent high precision 142Nd data sets for meteorites require a reassessment of this approach. Firstly, it was shown that chondrites, assumed to be representative for the bulk composition of Mars and other terrestrial planets, have 142Nd values ~20 ppm below those for the terrestrial standard (Boyet

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and Carlson, 2005). Secondly, new highly precise 142Nd data for shergottites show that the 142Nd/144Nd ratios of all shergottites deviate from 142Nd=0 (Debaille et al., 2007a; Caro et al., 2008). Although some shergottites have 142Nd values similar to those of ordinary chondrites [142Nd ~ -0.2 (Boyet and Carlson, 2005)], their 143Nd and 176Hf values are negative, indicating that these are crustal samples (Bourdon et al., 2008; Caro et al., 2008). Therefore, the similar 142Nd values of these shergottites and chondrites seem fortuitous. The 142Nd data for chondrites and shergottites show that, as a result of early mantle differentiation, the 142Nd/144Nd ratios of all shergottites deviate from that of the bulk Martian mantle. It is therefore difficult to assess whether the 182W/184W ratio of any of the shergottites is representative for the bulk Martian mantle. However, in spite of their different 142Nd values, basaltic shergottites have very similar 182W values ranging from ~0.3 to ~0.6 (Foley et al., 2005), indicating that the event that caused the 142Nd variations among the shergottites did not result in significant 182W variations. This is consistent with the ~40 Ma 146,147Sm-142,143Nd age, if differentiation in the shergottite source(s) involved only limited Hf/W fractionations. Therefore, it seems reasonable to assume that the bulk Martian mantle has 182W values between ~0.3 and ~0.6.
4.2 Age of the Martian core

The W model ages for the formation of the Martian core reported in the literature range from ~3 to ~12 Ma after CAI formation (Kleine et al., 2004a; Foley et al., 2005; Jacobsen, 2005). This range in ages primarily reflects the use of different Hf/W ratios for the bulk Martian mantle (Nimmo and Kleine, 2007). Based on Hf, Th and W concentration data for Martian meteorites and chondrites the currently best estimate for the Hf/W ratio of the bulk Martian mantle is Hf/W~3-4 (see section 2.1). Using this value and 182W ~0.3-0.6 for the bulk Martian mantle results in two-stage model ages for core formation ranging from ~0 Ma to ~8 Ma after CAI formation (Fig. 10a). As is evident from Fig. 10a, the uncertainty in these model ages is largely due to uncertainty in the Hf/W ratio of the bulk Martian mantle. Fig. 10a also demonstrates that the lowest possible Hf/W ratio of the Martian mantle is ~3 because lower Hf/W ratios would result in negative core formation ages. The Martian mantle likely has a Hf/W ratio that is only slightly higher than this minimum value of ~3, such that the Hf/W ratio must be determined very precisely to yield core formation ages of higher precision. A different approach for determining the age of the Martian core was employed by Halliday and Kleine (2006), who argued that core formation in Mars might have started within the first Ma of CAI formation. These authors observed that the 182W/184W ratios of SNC meteorites are broadly correlated with their Th/W, which they used as a

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proxy for the Hf/W ratio in the sources. If this is correct, then the W isotope heterogeneity in the Martian mantle might be due to different degrees of siderophile element depletion in the shergottite and NC sources. Later work by Nimmo and Kleine (2007), however, could not identify a systematic difference between the Th/W ratios of shergottites and nakhlites (+chassignites). Nimmo and Kleine (2007) showed that in the case of Mars two-stage model ages may underestimate the time Mars reached ~90% of its final mass by a factor of more than 3. For instance, for a two-stage model age of ~6 Ma, which is at the upper end of the age range shown in Fig. 10, Mars might have completed 90% of its accretion as late as ~20 Ma. Therefore, Hf-W chronometry can currently not distinguish between scenarios in which Mars formed within ~1 Ma during the runaway growth stage of planetary accretion (Halliday and Kleine, 2006) and scenarios in which accretion was more protracted (Nimmo and Kleine, 2007)
4.3 Early mantle differentiation in Mars

The range of 182W values observed in Martian meteorites combined with the time constraints provided by their 146,147Sm-142,143Nd systematics can be used to infer the Hf/W ratios of the source areas of the shergottites and nakhlites (Foley et al., 2005). Combined with mineral-melt partition coefficients for Hf and W (Righter and Shearer, 2003) this can then be used to constrain the source mineralogy. This is illustrated in Fig. 10b, which shows a possible (but not unique) scenario for the W isotope evolution of the Martian mantle. In this model it is assumed that the bulk Martian mantle has a present-day 182W~0.4 and 180Hf/184W = 4. This yields 182W~0.2 at ~40 Ma, i.e., at the time of mantle differentiation. The corresponding two-stage model age for core formation is ~4 Ma. The enriched and depleted shergottites might have slightly different W isotope compositions and these could have been produced by Hf-W fractionation during mantle differentiation at ~40 Ma. The inferred 180Hf/184W ratio for the source of the depleted shergottites is ~8, whereas this ratio is ~2 in the source region of the enriched shergottites (Fig. 10b). This is consistent with 176Lu-176Hf constraints on the evolution of shergottites, which were interpreted to indicate the presence of garnet in the source of the enriched shergottites and derivation of the depleted shergottites from an already depleted source (Blichert-Toft et al., 1999). Garnets have DHf/DW~30, such that residual garnet in the source will result in low Hf/W ratios in the melts, as observed for the enriched shergottites. Likewise, elevated 180Hf/184W in the source of the depleted shergottites are consistent with derivation from an already depleted source.

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An important observation is that, if Hf-W fractionation in the NC source occurred at the same time as differentiation in the shergottite source(s), then the NC source must have evolved with very high 180Hf/184W to reach their present-day 182W of ~3 (Fig. 10b). The inferred 180Hf/184W~56 is consistent with 180Hf/184W~57 as calculated for a majorite-rich garnet-bearing deep mantle based on mineral-melt partition coefficients for Hf and W (Righter and Shearer, 2003). Therefore, if the initial differentiation of the NC source occurred as late as ~40 Ma, then the radiogenic W isotope composition of these samples would require a deep mantle source for the NC group. This is consistent with the 147Sm-143Nd and 176Lu-177Hf systematics of nakhlites (Debaille et al., 2007b).

HF-W CHRONOMETRY OF THE MOON

The early evolution of the Moon is characterized by the crystallization of a lunar magma ocean (LMO) in chemically distinct layers (Shearer and Papike, 1999). The first minerals to crystallize from the LMO were mainly olivine and orthopyroxene and were followed by plagioclase that floated to the surface, forming the ferroan anorthosites. Towards the end of the crystallization sequence ilmenite and clinopyroxene precipitated, until the residual liquid of the magma ocean, termed KREEP (for enrichments in K, REE, and P), solidified. Subsequent melting and mixing among these primary rocks produced the variety observed in the lunar sample suite. For example, mare basalts formed by remelting of early mafic cumulates, which in the case of high-Ti mare basalts included assimilation of ilmenite and clinopyroxene. The redistribution of KREEP during impacts on the lunar surface resulted in the contamination of most highland breccias with various amounts of the KREEP-component. The 182Hf-182W chronometer is potentially well-suited for determining the timescale of LMO crystallization because substantial Hf-W fractionation occurred during magma ocean solidification. This results from the high incompatibility of W and the compatibility of Hf in clinopyroxene and ilmenite, leading to low Hf/W in KREEP and complementary high Hf/W in the high-Ti mare basalt source (Shearer and Newsom, 2000; Righter and Shearer, 2003; Kleine et al., 2005c). If these Hf-W fractionations occurred during the effective lifetime of 182Hf, variations in the 182W/184W of lunar mantle reservoirs can be expected. Lee et al. (1997) reported the first W isotope data for lunar whole-rock samples and found variations in 182W/184W ranging from ~0 to ~7 182W. These were interpreted to indicate formation of the Moon ~54 Ma after formation of CAIs (Lee et al., 1997). Later work, however, revealed that elevated 182W/184W ratios in lunar samples largely reflect the presence of cosmogenic 182W. Nevertheless, small 182W variations that were

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attributed to 182Hf decay were thought to be present and implied formation of the Moon within the first ~60 Ma after CAI formation (Leya et al., 2000; Lee et al., 2002; Kleine et al., 2005c). However, Touboul et al. (2007, 2008b) showed that all their measured lunar samples have constant 182W/184W ratios and that elevated 182W/184W ratios in lunar samples entirely reflect cosmogenic 182W production.
5.1 Cosmogenic vs. radiogenic 182W in lunar samples

Lunar samples collected during the Apollo and Luna missions all derive from the surface of the Moon and during their residence at the lunar surface these rocks were exposed to cosmic rays that could have produced 182W via the reaction 181Ta(n,)182Ta followed by - decay to 182W (Leya et al., 2000). Thus, elevated 182W/184W ratios of lunar whole-rock samples can reflect contribution from two sources: decay of 182Hf and cosmogenic production of 182W. Cosmogenic 182W production is significant in lunar samples because of their long exposure times to cosmic rays combined with their high Ta/W ratios, making cosmogenic 182W a dominant component in lunar samples (Fig. 11). Lee et al. (2002) showed that in some high-Ti mare basalts the 182W of mineral separates is correlated with their Ta/W ratios, providing clear evidence for the presence of cosmogenic Ta-derived 182W in these samples (Fig. 11). Lee et al. (2002) regressed their Ta-W data to determine the purely radiogenic 182W/184W at Ta/W=0. Although this approach yielded rather imprecise corrected 182W/184W ratios with uncertainties of ~2-3 units, these corrected 182W/184W ratios revealed variations among the investigated mare basalts that possibly could be as large as ~7 units (Lee et al., 2002). The most direct method to determine the 182W/184W of lunar samples devoid of any cosmogenic 182W is to analyze minerals that do not contain any Ta and hence no Ta-derived cosmogenic 182W. This condition is met by metals, which are found in trace amounts in most lunar samples (Kleine et al., 2005c). Relatively high Ni and Ir contents in metals from highland samples indicate that these are meteoritic metals added to the lunar surface by impacts. Unlike meteoritic metals, however, the metals from KREEP rich highland rocks have extremely high contents of W [~30 ppm (Kleine et al., 2005c)], reflecting the strong enrichment of W in KREEP. Partitioning of W from KREEP into these metals probably occurred by impactinduced melting and brecciation during redistribution of KREEP at the lunar surface. Metals in mare basalt consist of native Fe and probably formed by crystallization from a silicate melt under reducing conditions. The composition of these metals, particularly their low Ni contents, distinguishes them from meteoritic metal added to the lunar surface by impacts. Kleine et al. (2005c) reported the first W isotope data for lunar metals and found small variations in the 182W/184W ratios of metals from high-Ti mare basalts and

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KREEP-rich samples. However, Touboul et al. (2007) recently presented W isotope data for high-purity metal separates from a comprehensive set of lunar mare basalts. These new data reveal that low- and high-Ti mare basalts have identical W isotope compositions that are also identical to the 182W/184W of KREEP. This result is inconsistent with the earlier reported W isotope data for magnetic separates for two high-Ti mare basalts (Kleine et al., 2005c) but Touboul et al. (2007) could show that these magnetic separates probably contained a small fraction of ilmenite with high Ta/W and hence cosmogenic 182W. After correction for cosmogenic 182W, these high-Ti mare basalts have 182W/184W indistinguishable from the metals of all other mare basalts (Touboul et al., 2007). Mineral separates from low-Ti mare basalt 15555, in spite of having variable Ta/W ratios, show no resolvable difference in their 182W values averaging at 1.40.4 (Lee et al., 2002). This elevated 182W/184W appears inconsistent with 182W~0 for all metals from mare basalts but Touboul et al. (2008b) reported a somewhat lower 182W of 0.90.4 and Ta/W~4.6 for sample 15555 (Fig. 11b). Using correction equations (Leya et al., 2000) and the Sm isotope composition of sample 15555 (Nyquist et al., 1995; Rankenburg et al., 2006), the calculated cosmogenic 182W at Ta/W~4.6 is ~0.9, remarkably consistent with the measured W isotope composition as reported by Touboul et al. (2008). This is also consistent with the 182W value and Ta/W ratio reported for a 15555 whole-rock analysis by Kleine et al. (2005) and indicates that the W isotope composition of mare basalt 15555 is indistinguishable from 182W~0 (Fig. 11b). The reason for this systematic offset reported by Lee et al. (2002) for the same sample remains unclear. Similarly, Lee et al. (1997) reported a positive 182W anomaly of 3.11.7 182W in ferroan anorthosite 60025. This sample has an exposure age of ~2 Ma, such that its elevated 182W/184W cannot reflect the presence of cosmogenic 182W. However, more recently Touboul et al. (2008b) obtained new W isotope data for pure plagioclase separates from the two ferroan anorthosites 60025 and 62255 and in contrast to the earlier study by Lee et al. (1997) did not find any resolvable 182W excess in these samples (Fig. 12). The reason for this discrepancy is not known but could potentially reflect the presence of cosmogenic 182W in a mafic component of anorthosite 60025, which is not present in the pure plagioclase separates analyzed by Touboul et al. (2008b). Therefore, the lunar crust and mantle have indistinguishable W isotope compositions that are also indistinguishable from that of the terrestrial mantle (Fig. 12).

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5.2

Lifetime of the lunar magma ocean

The homogeneous W isotope composition of the mare basalt sources, KREEP and the lunar crust in spite of their strongly fractionated Hf/W ratios (Fig. 13) indicates that the last equilibration of W isotopes in the LMO occurred after the effective life-time of 182 Hf (Touboul et al., 2007; Touboul et al., 2008b). At ~60% crystallization and beyond the viscosity of the crystal-melt mixture in a magma ocean increases strongly, such that mixing (and isotopic equilibration) becomes very slow (Solomatov, 2000) The W isotope data could therefore be interpreted to indicate that ~60% crystallization of the LMO was achieved later than ~60 Ma after CAI formation. However, the minerals responsible for Hf-W fractionation in the LMO (i.e., high-Ca pyroxene and ilmenite) form at the very end of the crystallization sequence, most likely after ~80% crystallization (Shearer and Papike, 1999). Therefore, the Hf-W data could also be interpreted to indicate that >80% crystallization was achieved later than at ~60 Ma. In any case, crust formation by plagioclase flotation occurs after ~70% crystallization of the LMO, such that the 147Sm-143Nd ages for ferroan anorthosites (Carlson and Lugmair, 1988; Norman et al., 2003; Nyquist et al., 2006) reveal that ~70% LMO crystallization was achieved at 11240 Ma, entirely consistent with the Hf-W constraints. Although the revised Hf-W chronology of the LMO (Touboul et al., 2007; Touboul et al., 2008a) now appears to be consistent with the ~200 Ma 146Sm-142Nd age of the lunar mantle isochron (Nyquist et al., 1995; Rankenburg et al., 2006), the latter probably does not reflect the timing of magma ocean solidification. Bourdon et al. (2008) recently showed that cumulate overturn, magma mixing and melting following lunar magma ocean crystallization at 50-100 Ma could produce an array in the 142Nd/144Nd147 Sm/144Sm diagram that yields an ~200 Ma model age. Therefore, the crystallization timescale of the LMO appears to be best constrained by the combined Hf-W and 147Sm143 Nd isotope systems that indicate that ~70% crystallization could have been achieved at ~60 Ma at the earliest and at ~150 Ma at the latest (Touboul et al., 2007; Touboul et al., 2008b).

TIMESCALES FOR ACCRETION AND DIFFERENTIATION OF EARTH

The application of the 182Hf-182W system as a chronometer for the formation of Earth's core goes back to the work of Harper et al. (1991) and the first comprehensive investigation of W isotope evolution during core formation in Earth was given by Harper and Jacobsen (1996). At that time, however, important parameters for calculating core formation ages had not been determined yet. These include the 182W/184W ratio of chondrites and the initial 182Hf/180Hf at the time of CAI formation (or another well-

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defined point in time). These parameters were first determined by Lee and Halliday (1995, 1996) but their results were revised in 2002 (Kleine et al., 2002; Schoenberg et al., 2002a; Yin et al., 2002). Since then Hf-W chronometry has been utilized in various accretion and core formation models, which are summarized in Table 4. In the simplest model of core formation it is assumed that the core formed instantaneously and an age for core formation can then be calculated by assuming a two-stage model. Using the 182W excess of Earth's mantle of 182W = +1.90.1 relative to chondrites and a Hf/W ratio of ~17 for the bulk silicate Earth (see section 2.1), results in a two-stage model age for core formation of ~30 Ma (equation 5; section 0). However, at least for bodies as large as the Earth, core formation did not occur as a single event but took place episodically during planetary growth, which probably lasted several tens of millions of years (Halliday et al., 1996; Harper and Jacobsen, 1996; Halliday, 2004; Kleine et al., 2004b; Jacobsen, 2005; Nimmo and Agnor, 2006). Thus, for the Earth the assumption of instantaneous core formation is not justified, and the two-stage model age of ~30 Ma would only date core formation if during this event the entire core was first remixed and homogenized with the entire mantle before segregating again. This seems physically implausible. The two-stage model age nevertheless provides important age constraints. It assumes that Earth's mantle had a chondritic W isotope composition at the time of its formation. This corresponds to the minimum 182W/184W Earth's mantle could have had at any time because core formation in Earth cannot result in a mantle with a subchondritic Hf/W ratio. Therefore, the two-stage model age corresponds to the earliest time core formation could have been complete (Halliday et al., 1996; Kleine et al., 2004b), implying that core formation in the Earth could not have ceased before ~30 Ma after CAI formation. In models of continuous evolution of a reservoir, such as core formation, there is no single "age" for core formation and the reported ages rather correspond to a certain growth stage of the core. In this regard, two different ages have proven to be useful: (i) the mean time of core formation, < tcf >, which corresponds to ~63% of the core (in the case of exponentially decaying rate of accretion) (cf. Harper and Jacobsen, 1996), and (ii) the time of the Moon-forming impact, which most likely determines the termination of the major stage of Earth's accretion and core formation. Obtaining these age constraints requires an understanding of the mechanisms of core formation in Earth because the magnitude of the W isotope effects in the bulk silicate Earth depend on the type of mechanism by which metal is transported to the core and the degree to which isotopic equilibrium is achieved during metal segregation (Harper and Jacobsen, 1996). This has been addressed in several W isotope evolution models for Earth (Halliday, 2004; Kleine

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et al., 2004b; Jacobsen, 2005; Nimmo and Agnor, 2006) but these models yield different apparent timescales for core formation in Earth, which largely reflects different assumptions regarding the degree and processes of metal-silicate re-equilibration during core formation.
6.1 Models of core formation and metal-silicate equilibration

6.1.1 Mechanisms of core formation Two lines of evidence suggest that Earth accreted mostly from planetesimals and planetary embryos already differentiated into mantle and core. First, the Hf-W data for meteorites reveal that differentiation of many planetesimals occurred within the first few Ma of the solar system. Second, current models for the accretion of terrestrial planets suggest that planetary embryos formed within the first Ma of the solar system, in which case they will have differentiated owing to heating from decay of abundant 26Al. Therefore, there are two endmember models for the formation of Earths core during growth from pre-differentiated bodies: either Earth's core formed by merging of metal cores from pre-differentiated objects or the cores of these objects dispersed as small metal droplets in the terrestrial magma ocean prior to sinking to join the existing core. Which of these scenarios is most appropriate for a given collision depends on the relative size of the two colliding bodies. Collisions in which the impactor is much smaller than the target led to vaporization of the impactor, in which case the impactor material can efficiently mix and homogenize within the magma ocean of the target. In this case any information on the differentiation of the impactor is lost, such that the chemical and isotopic consequences for Earths mantle are identical to those for addition of an undifferentiated, chondritic body. What happens in detail during larger collisions, however, is less well understood. Hydrocode simulations of giant impacts (Canup and Asphaug, 2001) show that the cores of target and impactor merge rapidly although more recent simulations indicate that some re-equilibration might occur (Canup, 2004). The problem is that these simulations currently provide a resolution on the order of 100 km, whereas the length-scale on which chemical and isotopic re-equilibration occurs is probably on the order of centimeters (Stevenson, 1990). An alternative approach for constraining the degree of reequilibration is provided by the abundances of siderophile elements in Earth's mantle. The observed depletions of several siderophile elements in Earth's mantle are consistent with metal-silicate equilibration at high temperatures and pressures in a terrestrial magma ocean (cf. Rubie et al., 2003). This equilibration can be achieved only if the metal cores of the impactor emulsified as small metal droplets in a magma ocean (Rubie

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et al., 2003; Hoink et al., 2006). If this is correct, then efficient W isotope reequilibration between impactor core and target mantle can be expected. However, Sasaki and Abe (2007) observed that even in this case re-equilibration might not have been complete because the metal droplets might not have been distributed throughout the entire mantle. Furthermore, full equilibration may have been also limited if the terrestrial magma ocean was not global. The 182W/184W ratio of Earth's mantle at time t2 immediately after accretion of a new object at t1 can be expressed as a mixture of three components as follows: yBSE RBSE ( t1 ) + yImantle RImantle ( t1 ) + k yIcore RIcore ( t1 ) (9) RBSE ( t2 ) = yBSE + yImantle + k yIcore where BSE denotes bulk silicate Earth, Ri is the 182W/184W ratio, yi = mi CW is the amount of W in an object i, and k is the fraction of the impactor's core that first equilibrates with the Earth's mantle before entering Earth's core. Fig. 14 schematically illustrates the W isotope evolution of Earths mantle in the different modes of core formation. In the core-merging model (Fig. 14c), metal-silicate re-equilibration does not occur and the W isotope composition of the targets mantle immediately after the impact results from addition of impactor mantle material to the targets mantle. The resulting 182 W/184W ratio will always be higher than chondritic because no core material (with subchondritic 182W/184W) is involved in these mixing processes. In the case of core merging, no isotopic record of the collision was generated and the W isotope effect in Earths mantle would largely reflect the timing of core formation in the pre-merged objects. By contrast, small metal droplets in a magma ocean could have equilibrated efficiently with the surrounding molten silicates (Fig. 14a,b). If re-equilibration was complete this is equivalent to adding an undifferentiated object to Earths mantle, followed by metal segregation. In this case the resulting W isotope effect reflects the timing of core formation in Earth. 6.1.2 Metal-silicate equilibration in a magma ocean An additional complication is that the process by which re-equilibration occurs is not well understood and two different models have been used to calculate the effects of full equilibration. In the fully equilibrative plumbing model, Harper and Jacobsen (1996) assume that, during a single impact, each infinitesimal parcel of the impactor fully re-equilibrates with the target's mantle before the next parcel arrives (Fig. 14a). By contrast, other models assume that the entire impactor equilibrates with the entire target mantle at one go (Fig. 14b) (Kleine et al., 2004b; Nimmo and Agnor, 2006; see also equation 8). Thus, these two models essentially assume fractional and batch re-

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equilibration, respectively. Here we summarize the important equations governing these two different equilibration scenarios and then evaluate the reduction in W isotope effects that is achieved in both equilibration models during giant impacts. Fractional equilibration model. The fully equilibrative plumbing model of Harper and Jacobsen (1996) was termed magma ocean differentiation model by Jacobsen (2005). In this model the reservoir content (Nj2) of a stable species j in the magma ocean is given by equation 37 of Jacobsen (2005): & & dN j 2 C j1M 2 D m / s M 2 j N j2 = (10) dt 1 1 M 2 Here the subscripts 1, 2, and 3 refer to bulk, mantle, and core, Cj1 is the bulk Earth concentration, Djm/s is the metal/silicate partition coefficent (considered constant), is the core mass fraction (also considered constant), M2 is the mass of the mantle and & M 2 = dM 2 dt . With these simplifying assumptions, the concentration of j in the mantle is

C j2 C j1

1 D m/ s j

1 + 1

(11)

This is equivalent to the expression for static models of trace element partitioning (cf. Righter and Drake, 1997) and is also identical to that for a batch equilibration model (see equ. (3) in Nimmo and Agnor, 2006). Jacobsen (2005) showed that the W isotopic evolution of the magma ocean (equ. 72) can, for a very short interval (i.e., no decay) such as directly after an impact, be simplified to & d W M = (1 + f Hf W ) 2 W (12) dt M2 Thus, the difference between the initial (ti) and final states (tf) after an impact is given by W t f W ( ti )

( )

M (t ) = 2 i M2 t f

( )

1+ f Hf

(13)

Batch equilibration model. Consider a collision between two bodies of mass mA and mB, respectively, where mB<mA. The core mass fraction in each case is and the ratio mB/mA = g. During the collision, it is assumed that the metal + silicates of body B are completely homogenized with the silicates of body A, and that the metallic fraction from body B then separates from this reservoir. During this separation process elements are partitioned according to the metal/silicate partition coefficient, Djm/s = Cmet/Csil, where Cmet and Csil are the concentrations in the metal and silicate fractions, respectively. From
B B B

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mass balance considerations, it can be shown that the final concentration of an element j in the mantle of the resulting object C jf2 is given by C jf2 =

(1 ) C ij 2 + gC j1
1 + g 1 + D m / s 1 j

(14)

where C ij 2 is the initial concentration of the element j in the mantle of body A, and C j1 is the bulk concentration of the element in body B (assumed chondritic). If Djm/s = 1 then equation (14) shows that the final concentration is just the massweighted average of the initial concentrations, as required. In the limit as g 0 the final concentration equals the initial concentration, as required. In the limit as g (i.e., the pre-existing silicate reservoir is vanishingly small), we recover equation (39) of Jacobsen (2005). After some additional algebra, it may be shown that the final 182W anomaly, W t f , immediately after the impact, is given by

( )

(15) D m / s j 1 + g 1 + 1 182 where W ( ti ) is the W anomaly of the silicate portion of body 1 immediately prior to the impact. Recognizing that f = D m / s / (1 ) (Jacobsen 2005; equ. 49) we may rewrite j equation (15) as W t f = W ( ti ) which for g
1 yields

W t f = W ( ti )

( )

( )

1 + g 1 + f Hf /W

(16)

W t f

W ( ti )

( ) 1 g (1 + f Hf /W ) + ...

(17)

Similarly, recognizing that M 2 (ti ) / M 2 (t f ) = 1 (1 + g ) equation (13) (i.e., the reduction of the W isotope effects in the fractional equilibration model) may be written W t f W ( ti )

( ) =

1 1+ g

1+ f Hf /W

1 g (1 + f Hf /W ) + ...

(18)

where the approximation is appropriate for g

1 . Thus, in the limit of small g the two

approaches give the same answer, as required. Fig. 15 compares the reduction in W isotope effects calculated for different impactor to target ratios and using the fractional and batch equilibration models. As expected, for small impactor to target ratios the reduction is small and the effects are es-

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sentially identical for both the fractional and batch equilibration models. For large impactor to target ratios, however, the reduction in the W isotope effects is less pronounced for batch equilibration compared to the fractional equilibration. An important observation is that for fractional equilibration and impactor to target ratios of larger than ~0.2, the W isotope effects is reduced to less than ~0.1, such that very large collisions might reduce the W value of Earth's mantle to almost the chondritic value.
6.2 Hf-W systematics in continuous core formation models

6.2.1 Exponential accretion One may assume that the accretion of Earth took place at an exponentially decaying accretion rate (Jacobsen and Harper, 1996), such that: m (19) (t ) = 1 e t ME where m/ME is the cumulative fractional mass of the Earth at time t and is the time constant of accretion. The mean time of accretion, <t>, is the inverse of the time constant and corresponds to the time taken to achieve ~63% accretion. Fig. 16a shows the growth curve of Earth, calculated by assuming growth at an exponentially decaying rate and mean times of accretion of 8, 11 and 20 Ma. Using these growth curves and equation (9) the 182W/184W evolution of Earth's mantle can be calculated for each value of . Thus, in principle, the accretion rate of Earth can be determined by finding the value that yields the present day 182W/184W ratio of Earth's mantle. This is illustrated in Fig. 16b where the W isotope evolution curves for Earth's mantle are shown for different mean times of accretion. In these calculations it is assumed that the metal cores of newly accreted planetesimals always entirely reequilibrated in the terrestrial magma ocean (by the batch equilibration process described above). This is a reasonable assumption if accretion occurred by the incremental growth of small mass fractions but a more realistic view is that Earth accreted by several distinct large collisions that may have occurred at an exponentially decaying rate. In this case, the degree of metal-silicate equilibration is less well constrained. Fig. 16b reveals that the present-day W of Earth's mantle of +1.9 can be produced if the mean time of accretion is ~11 Ma. This corresponds to ~63% growth at ~11 Ma and ~90% growth at ~25 Ma. Note that in these models the end of accretion is not well defined because there is a small exponential tail of accretion that is technically still continuing today (Harper and Jacobsen, 1996). Effects of incomplete metal-silicate re-equilibration. Fig. 16b also illustrates the effect of incomplete metal-silicate re-equilibration on the W isotope evolution of Earth's man-

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tle. Metal-silicate re-equilibration during core formation results in a decrease of the 182 W excess in Earth's mantle that had previously accumulated due to 182Hf decay. For a given accretion rate, a decreasing degree of metal-silicate re-equilibration (i.e., decreasing k values) will result in an increasingly radiogenic W isotope composition of Earth's mantle. For instance, if 75 % instead of 100 % of the newly accreted core material first equilibrated with Earth's mantle before entering Earth's core, the W value of Earth's mantle would be +2.8 instead of +1.9 (for a given <t> of 11 Ma). Thus, to match the present-day W isotope composition of Earth's mantle, a decreasing degree of metalsilicate re-equilibration must be accompanied by longer accretion timescales. This is illustrated in Fig. 17a, where the calculated age of core formation is plotted as a function of the degree of metal-silicate re-equilibration k. As is evident from this figure, the calculated core formation ages strongly depend on the assumed value for k. Changes in metal-silicate partition coefficient of W. Similar effects are observed if it is assumed that the Hf/W ratios in the mantles of newly accreting planetesimals were different from the value observed in Earths mantle today. This is likely because the metalsilicate distribution coefficient for W (DW) is sensitive to many parameters such as pressure, melt compositions, and particularly oxygen fugacity (see section 2.1). These parameters likely were different in the various objects that accreted to Earth and also probably changed over time, such that considerable variability in the mantle Hf/W ratios is expected (Righter, 2003; Wade and Wood, 2005). Wade and Wood (2005) considered changes in pressure, temperature and oxygen fugacity during accretion. They found the best match to the observed mantle depletions in siderophile elements if the oxygen fugacity of Earth's mantle increased during accretion. In their model, DW started off at values >104 and decreased to ~20 at the end of accretion. This would also be consistent with heterogeneous accretion scenarios that predict that Earth was initially highly reducing and became more oxidized by the late addition of volatile-rich material (Wnke and Dreibus, 1988). However, Halliday (2004) proposed the opposite and suggested that Earth accreted from relatively oxidized planetesimals having low Hf/W ratios, similar to the present-day values observed for the Martian mantle. Such a scenario has important consequences for interpreting the W isotope record of Earth's mantle because a mantle with a relatively low Hf/W ratio will never develop a large 182W excess. Therefore, upon accretion of such objects to Earth, the W isotope composition of Earths mantle can stay at a relatively low value even without significant metal-silicate re-equilibration. Thus, changes in the Hf/W ratios of the mantles of newly accreting objects and different values of k have similar effects on the W isotope evolution of the Earth's mantle. This is illustrated in Fig. 17b, where for a given core formation age (calculated assuming an

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exponentially decaying rate of accretion) the Hf/W ratio in the mantle of the accreting planetesimals is plotted against the degree of metal-silicate re-equilibration k. This plot illustrates that, for a given core formation age (in this case <t>=11 Ma), the present-day 182 W/184W of Earth's mantle can be obtained by assuming several distinct pairs of these two parameters. For instance, assuming k=1 and Hf/W=20 in the mantles of the accreting planetesimals yields the same result as assuming k=0.7 and Hf/W=4 (Fig. 17b). Therefore, W isotope systematics alone cannot distinguish between scenarios involving a high degree of metal-silicate re-equilibration and those involving low Hf/W ratios in early-formed proto-planets. 6.2.2 Tungsten isotope evolution in N-body simulations of planetary accretion In the models discussed above, it is assumed that accretion of the Earth occurred at an exponentially decreasing accretion rate. Dynamical modeling, however, suggests that the final stages of terrestrial planet formation is characterized by multiple and stochastic impacts that bring in large core masses at once (Agnor et al., 1999; Chambers, 2001). Jacobsen (2005) and Nimmo and Agnor (2006) presented a framework for implementing the evolution of W isotopes in N-body simulations of planetary accretion. Nimmo and Agnor (2006) showed that the physical and isotopic characteristics of Earth can be reproduced with the last large impact occurring at ~30 Ma. This result is similar to those of Jacobsen (2005), who showed that the W isotope composition of Earth's mantle is consistent with most of Earth's growth taking place in ~10 Ma and a final giant impact at ~32 Ma. At the time of these studies it was thought that the Moon-forming impact occurred earlier than ~50 Ma (cf. Lee et al., 2002; Kleine et al., 2005) but a more recent study of the Hf-W systematics of the Moon showed that this is not necessarily the case (Touboul et al., 2007). Therefore, we applied the approach of Nimmo and Agnor (2006) to two accretion simulations from Raymond et al. (2006) that were selected mainly on the basis that they are characterized by a relatively late formation of the Moon. In the first of these simulations, a giant impact resembling the Moon-forming collision occurs at ~125 Ma after CAI formation (Fig. 18a), in the second simulation it occurs at ~75 Ma after CAI formation (Fig. 19a). These are near the upper and lower end of the 62+90 Ma age for the giant 10 impact as proposed by Touboul et al. (2007), which is described in more detail below. Another important difference between these two simulations is the history of the impactor, whose collision resulted in the formation of the Moon. In the first simulation the silicate part of the impactor had, at the time of its collision with proto-Earth, a W isotope composition that was less radiogenic than that of proto-Earth's mantle. This results from a relatively late collision of the impactor with another body at ~40 Ma (Fig. 18b).

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In the second simulation the impactor has highly radiogenic 182W at the time it collided with proto-Earth because this impactor was largely accreted and differentiated within the first few Ma (Fig. 19b). In the simulations both a high and low degree of metal-silicate equilibration was assumed (Fig. 18b and Fig. 19b) and in the case of full equilibration the effects of both fractional and batch equilibration were calculated (Fig. 18c and Fig. 19c). These simulations reveal that, if the degree of metal-silicate equilibration was low throughout accretion, Earths mantle should exhibit a much more radiogenic 182W anomaly than observed. This suggests that substantial metal-silicate re-equilibration occurred but at what stage of accretion this occurred is less well constrained. In both simulations, the presentday W of Earth's mantle of +1.9 can be obtained for both a high and low degree of metal-silicate re-equilibration prior to the final, Moon-forming impact (Fig. 18b and Fig. 19b). Thus, the conditions of metal-silicate separation during most of Earths growth are only poorly constrained by the W isotope data and most of this information is erased by the final giant impact. In the two exemplary accretion scenarios considered here, the degree of metal-silicate re-equilibration must have been high during the final impact because otherwise the 182W anomaly of the bulk silicate Earth would be larger than observed. Whether this is a common feature of all accretion simulations that can reproduce the physical properties of Earth is unclear. In the case of full equilibration, fractional equilibration results in a stronger reduction of the W isotope effects (Fig. 18c and Fig. 19c), as expected from the discussion above. In summary, the physical and isotopic characteristics of Earth can be reproduced in a variety of accretion and differentiation scenarios. Therefore, the 182W excess of Earth's mantle relative to chondrites cannot be used to firmly establish an age of core formation and models can be constructed that result in core formation ages as early as ~30 Ma or as late as ~125 Ma, for example. Knowing the degree of metal-silicate reequilibration in particular and the processes by which equilibration occurred (fractional vs. batch) is critical for interpreting the W isotope record of Earths mantle and for distinguishing among different scenarios for Earths accretion. Nevertheless, the Hf-W systematics provide important constraints on the processes of core formation because the present-day physical and isotopic characteristics of the Earth (and Mars) can only be reproduced if the degree of metal-silicate equilibration during core formation was relatively high (Fig. 21). This suggests that core formation largely occurred by the separation and segregation of small metal droplets in a magma ocean.

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6.3

Tungsten model age for the Moon-forming impact

Tungsten isotopes can provide important constraints on the time at which the Moon formed. This is important not only for understanding the formation and early history of the Moon but also provides information on the accretion rate of Earth because most theories for the formation of the Moon suggest that the giant Moon-forming impact was the last major event in Earth's accretion. If, as numerical simulations suggest, the Moon mainly consist of impactor mantle material (Canup, 2004), then its W isotope composition should reflect the accretion and differentiation history of the impactor. Therefore, that two such different objects as the proto-Earth and impactor would evolve to identical W isotope compositions in their mantles seems highly unlikely, given the evidence for widely different W isotope signatures in the meteorite record. This is also exemplified in the two accretion simulations shown in Fig. 18, where, regardless of the degree of re-equilibration and accretion history, impactor and Earth have very different 182 W anomalies at the time of the Moon-forming impact. Therefore, the identical W isotope compositions of the lunar and terrestrial mantles could indicate that the Moon is largely derived from terrestrial mantle material but this is inconsistent with results from numerical simulations, all of which indicate that the Moon predominantly consists of impactor material. If this is correct, then equilibration of W isotopes between the Earth's mantle and proto-lunar material during or after the giant impact seems to be required. Such equilibration processes could involve metal-silicate re-equilibration between the impactor mantle and core, which would reduce a radiogenic W isotope signature in the proto-lunar material (Bourdon et al., 2008) but it is unlikely that this process fortuitously resulted in a 182W/184W that is identical to that of the Earth's mantle. Therefore, the equilibration should have involved the Earth's mantle and could potentially have occurred via a shared silicate vapor atmosphere of the lunar magma disk and the terrestrial magma ocean (Pahlevan and Stevenson, 2007). This requires that W became efficiently vaporized to enter this atmosphere but the efficiency to which this is possible and hence W isotopes could equilibrate remains to be investigated. The two-stage Hf-W model time for separation of the Moon from a chondritic reservoir is ~37 Ma (Touboul et al., 2007). This model age could either date formation of a small lunar core or, if the Moon does not possess a metal core, the isolation of the Moon from the proto-lunar circumterrestrial magma disk. In any case, this model age should correspond closely to the time of the giant impact. Note that this age cannot correspond to the time of core formation in the impactor - which might be expected if the Moon predominantly consists of impactor material - because the identical 182W/184W of the lunar and terrestrial mantles require either formation of the Moon from terrestrial material or Moon-Earth equilibration. Although the formation of the Moon occurred by

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a single event, such that the timing of this event can in principle be calculated using a two-stage model, the initial W isotope composition of the Moon most likely was higher than chondritic. This is because the Moon is predominantly derived from silicate mantle material having high Hf/W and therefore most likely radiogenic 182W/184W ratios (see for instance Fig. 18). Therefore, the Moon probably formed later than given by its twostage model age of ~37 Ma. Fig. 20 shows the difference in 182W/184W between the lunar and terrestrial mantles that would have developed as a function of age and difference in Hf/W. As is evident from this figure, core formation in Earth could have terminated as early as ~30-40 Ma only if the difference in Hf/W between the bulk silicate Moon and Earth is less than ~10 %. The current best estimates for these Hf/W ratios (Table 1) indicate that this difference might be as high as ~50 % (i.e., fHf/W=0.5 in Fig. 20), in which case the Moon would have formed later than ~50 Ma after CAI formation (Touboul et al., 2007). The Hf/W estimates are based on the U/W and Th/W ratios of the lunar and terrestrial mantles and assume that these ratios were not fractionated during melting processes within the mantle. It will important in future studies to assess whether this is correct and to determine the U/W and Th/W ratios of the lunar and terrestrial mantles to high precision. If the Hf/W ratios of the lunar and terrestrial mantles are indeed different, then the Moon formed later than ~50 Ma after CAI formation. Given that the giant impact most likely was the last major event in Earth's accretion (Canup and Asphaug, 2001), this age also provides an age for the termination of Earth's core formation and would be consistent with U-Pb age for the formation of Earth (Allgre et al., 1995; Galer and Goldstein, 1996) and with I-Pu-Xe constraints for the formation of Earth's atmosphere (Podosek and Ozima, 2000; Yokochi and Marty, 2005; Pepin and Porcelli, 2006). In this case, the U-Pb, Hf-W, and I-Pu-Xe chronometers converge to provide identical ages for what might be the major early differentiation of the Earth at ~4.50-4.42 Ga (Allgre et al., 2008).
6.4 Early mantle differentiation and implications of a non-chondritic bulk Earth

Hafnium-tungsten chronometry cannot be directly applied to constrain the timescales of early mantle differentiation in Earth because no 182W variations have yet been detected in terrestrial samples. A possible exception are low 182W/184W ratios in a few Archean metasediments from Greenland but these were attributed to incorporation of meteoritic material into these sediments (Schoenberg et al., 2002b). Traces of an early mantle differentiation have been preserved in some Archean rocks and the slightly elevated 142Nd/144Nd ratios of these rocks reflect differentiation at 50-200 Ma after CAI

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formation (Harper and Jacobsen, 1992; Boyet et al., 2003; Caro et al., 2003; Caro et al., 2006). This differentiation probably occurred too late to have resulted in resolvable W isotope variations because these can only be produced in the first ~60 Ma. This is also consistent with the absence of resolvable 182W variations among lunar samples, which indicate differentiation later than ~60 Ma after CAI formation. However, Boyet and Carlson (2005) observed that the ~20 ppm 142Nd excess of terrestrial samples relative to chondrites could be explained by an early mantle differentiation prior to ~30 Ma. This differentiation generated an early depleted reservoir (EDM) and an early enriched reservoir (EER) that since its formation has remained hidden. In this model the W isotope composition of terrestrial samples would not reflect the composition of the bulk silicate Earth but rather that of the EDR. The Hf/W ratio of the EDR most likely would be elevated relative to that of the bulk silicate Earth because the EDR formed by melt depletion. Thus, in this model the bulk silicate Earth would have a Hf/W ratio and W value lower than those of the EDR (Hf/W~17, W ~1.9). However, as discussed in detail above, the earliest time a reservoir having Hf/W~17 and W ~1.9 could have formed is ~30 Ma after CAI formation. Such a reservoir could only have formed prior to ~30 Ma if its initial W would be negative, i.e., the 182W/184W would have been lower than chondritic at that time. This however cannot be achieved in Earth's mantle which is characterized by elevated Hf/W relative to chondrites. Therefore, mantle differentiation before 30 Ma, as deduced from 146Sm-142Nd systematics does not seem consistent with the Hf-W constraints. The 146Sm-142Nd and 182Hf-182W constraints on the chronology of Earth's early differentiation provide a consistent picture if Earth's mantle is characterized by 142Nd=0, as proposed by Caro et al. (2008), implying that Earth has a non-chondritic Sm/Nd ratio. If this is true, then the Hf/W ratio of bulk Earth most likely also is not chondritic, such that one of the basic assumptions for calculating core formation timescales may not be valid. The magnitude of this effect is difficult to assess and depends on the process(es) that were responsible for generating non-chondritic ratios of refractory elements in bulk Earth. If this is related to impact erosion of an early-formed crust or explosive volcanism, then W, due to its higher incompatibility relative to Hf, would be preferentially lost. Consequently, bulk Earth would be characterized by elevated Hf/W and 182W/184W ratios relative to chondrites and the two-stage model age of core formation would be >30 Ma, that is, younger than that calculated relative to a chondritic composition of bulk Earth. Therefore, uncertainties in the bulk composition of Earth constitute an additional uncertainty in calculating core formation ages but these effects are difficult to quantify. It is important to note that the age of the Earth and Moon estimated using the identical 182W values of the terrestrial and lunar mantles [Touboul et

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al. (2007) and section 6.3] is insensitive to the actual bulk composition of the Earth and thus provides a more reliable estimate for the termination of Earths accretion.

CONCLUSIONS

Hafnium-tungsten chronometry of meteorites provides age constraints on several key events in the early evolution of the solar system and its planetary objects, and has led to the establishment of a new model for the accretion and early evolution of asteroids. Important events that are being dated using the Hf-W chronometer include the formation of CAIs and chondrules as well as core formation, magmatism and thermal metamorphism in meteorite parent bodies (Fig. 22). The chronological data indicate that melting and differentiation was prevalent in planetesimals that accreted within the first ~1 Ma (parent bodies of the iron meteorites and possibly eucrites and angrites), thermal metamorphism is characteristic for bodies formed shortly after ~2 Ma (ordinary chondrite parent bodies), and aqueous alteration is the dominant parent body process in asteroids that formed more than ~3 Ma after CAI formation (some carbonaceous chondrite parent bodies). These accretion ages for asteroids are inversely correlated with the peak temperature reached in their interiors, indicating that the different thermal histories of meteorite parent bodies are determined by their accretion age, which determines their initial 26Al abundance. This is most consistent with a model that involves decreasing accretion rates across the asteroid-forming region that is of the order of several 26Al half-lives. Moreover, thermal models for asteroids heated by energy release from 26Al decay not only reproduce the peak temperatures reached inside the meteorite parent bodies but are also consistent with the timescales of thermal metamorphism and cooling of chondrite parent bodies as well as with the time span of basaltic magmatism on asteroids. For terrestrial planets, the timescales of accretion and primordial differentiation are much longer, and determined by different parameters. This is consistent with dynamical models of planetary accretion that indicate that the final stage of terrestrial planet formation is characterized by multiple large and stochastic impacts. Although the Hf-W timescale for the formation of Mars is currently uncertain and would allow core formation ages ranging from 0-20 Ma, Mars clearly formed much earlier than the Earth and Moon. The Hf-W ages for termination of Earth's accretion and core formation range from ~30 Ma to more than ~100 Ma after CAI formation. This range in ages primarily reflects different assumption regarding the mechanisms of accretion and core formation. Unless their Hf/W ratios differ by less than ~10 %, the identical 182W/184W ratios of the lunar and terrestrial mantles provide an independent age estimate for the Moon-forming

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90 giant impact of 62 +10 Ma. This time constraint is consistent with U-Pb ages for the for

mation of Earth and I-Pu-Xe ages for the formation of Earth's atmosphere, such that these chronometers combine to provide evidence for the formation and major differentiation of the Earth at ~4.50-4.42 Ga. The preservation of different 182W abundances in the Martian mantle contrasts with the constant 182W/184W ratios of lunar and terrestrial rocks and indicates that the global differentiation of the Martian mantle occurred when 182Hf was still extant and any later process was not efficient enough to re-homogenize the Martian mantle. This is consistent with 146,147Sm-142,143Nd systematics of Martian rocks. In contrast solidification of the lunar and terrestrial magma ocean occurred later, after extinction of 182Hf, consistent with the 50-200 Ma 146,147Sm-142,143Nd age for differentiation of Earth's mantle. The Hf-W timescale of planetary accretion is remarkably consistent with predictions from dynamical simulations. That is, the first planetary objects formed within less than 1 Ma, whereas the final assembly of the terrestrial planets may have taken as long as ~100 Ma. Moreover, implementation of Hf-W systematics in N-body simulations of planetary accretion indicates that the physical and isotopic characteristics of Earth can successfully be reproduced in such simulations. Acknowledgements - T. Kleine thanks Sasha Krot and Martin Bizzarro for inviting his participation to the Workshop on the Chronology of Meteorites and the Early Solar System. We thank Sean Raymond for generously providing the data of his planetary accretion simulations, and Rainer Wieler for an informal review of an earlier version of this manuscript. We thank Mary Horan and Maud Boyet for their reviews and Rich Walker for his comments and editorial efforts, which greatly improved our manuscript. We thank the Museum National d' Historie Naturelle (Paris), The National Museum of Natural History (Washington DC), The Natural History Museum (London), the Senckenbergmuseum (Frankfurt), the Institute for Planetology (Mnster), the Naturhistorisches Museum (Wien), and NASA for generously providing the samples for the studies summarized here. F. Nimmo acknowledges funding by NASA-Origins NNG05G039G.

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FIGURE CAPTIONS

Fig. 1: W isotope data for chondrites. Data for carbonaceous chondrites are from Kleine et al. (2002, 2004a), Yin et al. (2002) and Schnberg et al. (2002), for ordinary chondrites from Yin et al. (2002) and Kleine et al. (2007), and for enstatite chondrites from Lee and Halliday (2000). Note that, in contrast to earlier reports (Lee and Halliday, 1995; Lee and Halliday, 1996), all chondrites exhibit a 182W deficit relative to the terrestrial standard. Fig. 2: Initial 182Hf/180Hf ratios vs. Pb-Pb for angrites. Slightly modified from Burkhardt et al. (2008). References are given in Table 2. Solid lines are decay lines calculated using the 182Hf half-life of 0.078 Ma-1. The dashed line is the best fit line of the data for DOrbigny, Sahara 99555, NWA 4590 and 4801 and corresponds to 182Hf = 0.075 0.006 Ma-1. Note that the Hf-W system in NWA 2999 is disturbed and the initial 182 Hf/180Hf plotted here is higher than originally reported in Markowski et al. (2007). This higher value is obtained from excluding the Hf-W data for the whole-rock, fines and leached fractions. Fig. 3: Closure temperature of the Hf-W, U-Pb and Al-Mg systems in various minerals as a function of grain diameter and cooling rate. Fig. 4: 182W vs. exposure ages for magmatic iron meteorites. W isotope data are from Kleine et al. (2005a), Lee (2005), Markowski et al. (2006b), Schrsten et al. (2006), and Qin et al. (2008). For exposure ages see these references. The three lines indicate the calculated 182W burnout using different correction procedures (Leya et al., 2003; Qin et al., 2008), assuming that the pre-exposure 182W of the magmatic irons is identical to the initial 182W of CAIs (Burkhardt et al., 2008). KASKAD and JEF are two different libraries for cross sections of neutron induced reactions that were used by Qin et al. (2008) and for which reasonable agreement between the predicted effects and those measured in Grant and Carbo (Markowski et al., 2006a) were observed. Fig. 5: 182W values for IAB-IIICD iron meteorites in comparison to values the two magmatic irons Gibeon and Negrillos and the initial 182W of CAIs (shown as the hatched area). Data are from Kleine et al. (2005a), Markowski et al. (2006b), and Schrsten et al. (2006). Fig. 6: Hf-W isochron diagram for basaltic eucrites. The value for average basaltic eucrites is based on the Hf-W data for whole-rock samples (Kleine et al., 2004a; Kleine et al., 2005b). The data for metals and Camel Donga separates are from Kleine et al. (2005b). CC = average carbonaceous chondrites (Kleine et al., 2004a). The model age for Asuka 881467 zircons is obtained from the regression of the zircon data (Srinivasan et al., 2007) and average basaltic eucrites.

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Fig. 7: (a) Hf-W isochrons for H chondrites. Data are from Kleine et al. (2008b). (b) Cooling curves for the high-T evolution (>450 C) of H chondrites (from Kleine et al. 2008b). Solid lines indicate calculated temperature profiles for different depth in a spherical body with a 100 km radius. Numbers indicate depth in km from the centre. Calculations assume an initial 26Al/27Al of 5.8510-5 and instantaneous accretion at 2.7 Ma after CAIs. Fig. 8: Peak temperature vs. accretion age for asteroids (R~10-100 km) that were heated internally by decay from 26Al. Hatched areas indicate the accretion age of and peak temperatures reached in the center of asteroids of different size. For iron meteorite parent bodies, the accretion age is derived from the W model ages for iron meteorites, which must postdate accretion. For chondrites, the accretion age is derived from Al-Mg ages for chondrules. Note that parent body accretion must postdate the formation of the youngest chondrule of a given group. Chondrule ages are from the following references: ordinary chondrites (OC) (Kita et al., 2000; Rudraswami and Goswami, 2007; Rudraswami et al., 2008); CO chondrites (Kunihiro et al., 2004; Kurahashi et al., 2008); CR chondrites (Nagashima et al., 2008). Peak temperature estimates are from the following references: OC (Slater-Reynolds and McSween, 2005); CO (Huss et al., 2006); CR (Krot et al., 2002). To facilitate core formation, temperatures inside the iron meteorite parent bodies must have been above the Fe-FeS eutectic but probably were higher because some melting of silicates may also be required for efficient metal-silicate separation. Solid lines indicate calculated temperature profiles for the centre of spherical bodies with radii of 10 and 100 km. Fig. 9: 142Nd vs. 182W for Martian meteorites. Nd isotope data are from Caro et al. (2008) and Debaille et al. (2007a), W isotope data from Lee and Halliday (1997), Kleine et al. (2004a), and Foley et al. (2005). S = Shergotty, LA = Los Angeles, Z = Zagami. Fig. 10: Hf-W chronology of Mars. (a) Two-stage model age for core formation as a function of Hf/W ratio in the bulk Martian mantle. The grey hatched area indicates the best estimate for the Hf/W ratio of bulk silicate Mars. The solid line represents ages calculated using 182W=0.4 for the bulk Martian mantle. The dashed lines indicate ages calculated using 182W values that are 0.2 higher and lower, respectively. (b) Model for the W isotope evolution of Martian mantle reservoirs. In this model it is assumed that bulk silicate Mars has 180Hf/184W~4 (i.e., Hf/W~3.5) and 182W~0.4. If Martian mantle reservoirs were established by a global event at ~40 Ma, the NC source must have evolved with very high 180Hf/184W, which requires the presence of garnet. In contrast, Hf-W fractionations in the shergottite sources were more modest, consistent with the limited range in 182W of shergottites. DS = depleted shergottites, ES = enriched shergottites. Fig. 11: 182W vs. Ta/W for lunar samples. (a) Data for whole-rocks from KREEP-rich samples as well as low- and high-Ti mare basalts (Kleine et al., 2005c; Touboul et al., 2008b). Also shown are data for mineral separates from some high-Ti mare basalts (Lee et al., 2002). Solid lines indicate the variations in 182W that can be produced by interaction with thermal neutrons as a function of exposure age and Ta/W. These lines were

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calculated using equations given in Leya et al. (2000). High-Ti mare basalt 79155 has 182W~38 and Ta/W~20 (Kleine et al., 2005c) and is not shown here. (b) 182W vs. Ta/W for low-Ti mare basalt 15555. The predicted cosmogenic 182W is calculated as a function of Ta/W ratio and using the Sm isotope composition of sample 15555 (Nyquist et al., 1995; Rankenburg et al., 2006). Whereas the data reported by Kleine et al. (2005) and Touboul et al. (2008) are consistent with the calculated cosmogenic 182W, the data reported by Lee et al. (2002) appear to be systematically shifted to higher values. After correction for cosmogenic 182W, this sample has 182W indistinguishable from 0. Fig. 12: W isotope composition of lunar metals and ferroan anorthosites having young exposure ages (Kleine et al., 2005c; Touboul et al., 2007; Touboul et al., 2008b). Fig. 13: Hf-W isochron for the lunar magma ocean (Touboul et al., 2007; Touboul et al., 2008b). The estimated 180Hf/184W ratios of the sources are from Kleine et al. (2005c) and Righter and Shearer (2003). For ferroan anorthosites the measured 180Hf/184W are plotted because these were obtained on pure anorthite separates. Fig. 14: Schematic illustration of different processes of core formation and their effect on the W isotope evolution of the bulk silicate Earth. Fig. 15: Reduction in W isotope effects during collision between two bodies as a function of impactor to target mass ratio. The reduction is calculated using equations (13) and (16) for fractional and batch equilibration. Fig. 16: (a) Growth curves for Earth assuming an exponentially decreasing accretion rate and accretion mean times of 8, 11, and 20 Ma. (b) W isotope evolution for the bulk silicate Earth for the growth curves for Earth from (a) and assuming complete metalsilicate re-equilibration. Also shown is the W isotope evolution for an accretion mean time of 11 Ma but for incomplete metal-silicate re-equilibration (i.e., k=0.75). The present-day W value of Earth's mantle can be reproduced for mean time of accretion of 11 Ma. Fig. 17: (a) Effect of incomplete metal-silicate re-equilibration on calculated core formation ages. (b) Relationship between the degree of re-equilibration k and Hf/W ratios in the mantles of accreting objects. Fig. 18: Growth curves and W isotope evolution for a model Earth and Moon-forming impactor from accretion simulations of Raymond et al. (2006). (a) Growth curves are from run 2b of the N-body accretion simulations of Raymond et al. (2006), which track the evolution of 1054 planetesimals as they orbit and collide. The Moon-forming impact occurs at ~125 Ma and the impactor itself underwent a large impact at ~40 Ma. (b) W isotope evolution of these bodies and considering the two extreme cases of core merging and full metal-silicate re-equilibration (batch equilibration). Silicate mass fraction of bodies is variable; W partition coefficient is fixed at DW=29.4 (i.e., Hf/WBSE~17). Other parameter values and methods are as in Nimmo and Agnor (2006). Note that the iso-

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topic evolution of all planetesimals is tracked in these calculations. (c) As for (b) but both fractional and batch equilibration were considered. Fig. 19: (a) As for Fig. 18a except that run 2a of Raymond et al. (2006) is used. The Moon-forming impact occurs at ~75 Ma and the impactor was largely accreted in the first few Ma. (b) As for Fig. 18b. (c) As for Fig. 18c. Fig. 20: Difference in 182W between bulk silicate Moon (BSM) and Earth (BSE) as a function of time (slightly modified from Touboul et al. 2007). The dotted area indicates the W isotope composition of the lunar mantle. Assuming that BSM and BSE had identical initial 182W/184W ratios, the time of their formation can be calculated from their present-day 182W/184W and Hf/W ratios. The current best estimates for the Hf/W ratios in BSM and BSE indicate a difference of ~50 %. If this is correct, the Moon must have formed more than ~50 Ma after CAI formation. Fig. 21: a) Mass and semi-major axis of planetary bodies after 150 Ma, from the Nbody simulations of Raymond et al. (2006). Solid symbols plot planet in this solar system, open symbols are model results. b) Present-day 182W anomaly (relative to chondrites) for all bodies assuming core merging throughout, and using the methods given in Nimmo and Agnor (2006). c) As for b) but assuming complete metal-silicate (batch) equilibration throughout. Note that in case of core merging the present-day characteristics of Mars and the Earth cannot be reproduced. By contrast, assuming complete metalsilicate equilibration results in the observed physical and isotopic properties of the Earth and Mars. Fig. 22: Timing of events in the first ~100 Ma of the solar system as determined mostly by Hf-W chronometry.

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Table 1. Hf/W ratios in planetary reservoirs and minerals Hf/W Planetary reservoirs Chondrites ~0.6-1.8 Metal core ~0 Basaltic eucrites 278 Bulk silicate Mars 3-4 Bulk silicate Moon 262 Bulk silicate Earth 175 Minerals High-Ca pyroxene 8-18 (DHf/DW ~ 5) Fassaites 6-14 Olivine ~0.5 (DHf/DW ~ 1) Plagioclase ~0.6 Melilites ~0.8 Garnet DHf/DW ~ 30

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Table 2. Summary of initial 182Hf/180Hf and calculated Hf-W ages as obtained from internal isochronsa 207 Sample (182Hf/180Hf)i 105 tCAI (Ma) Pb-206Pb age (Ma) Reference t (Ma) CAIs 9.720.44 =0 4568.50.5 4567.110.16 Burkhardt et al. (2008) Ste. Marguerite (H4) 8.500.23 1.70.7 4566.60.5 Kleine et al. (2008b) Richardton (H5) 6.230.30 5.70.9 4562.60.8 Kleine et al. (2008b) ALH841069 (H5) 6.120.62 5.91.4 4562.41.4 Kleine et al. (2008b) Kernouv (H6) 4.660.34 9.41.1 4558.91.0 Kleine et al. (2008b) Estacado (H6) 4.430.53 10.11.7 4558.21.6 Kleine et al. (2008b) Vaca Muerta clast 7.690.82 3.01.5 4565.31.4 Schnbchler et al. (2001) D'Orbigny 7.180.22 3.90.7 =4564.420.12 4564.420.12 Markowski et al. (2007) Sahara 99555 6.950.22 4.30.7 4564.00.6 4564.580.14 Markowski et al. (2007) NWA 2999 (px-metal) 5.380.48 7.61.3 4560.71.2 4561.790.42 Markowski et al. (2007) NWA 4590 4.650.17 9.50.8 4558.90.6 4558.860.30 Kleine et al. (2008a) NWA 4801 4.340.23 10.30.9 4558.00.8 4558.060.15 Kleine et al. (2008a) Camel Donga 1.70.7 225 45465 Kleine et al. (2005b) a 182 180 all initial Hf/ Hf ratios were re-calculated from Hf-W data given in the original references using the model 1 fit of IsoPlot and 180HF/184W = 1.18Hf/W. The Pb-Pb ages are from the following references: CAIs (Amelin et al., 2002; Amelin et al., 2006); DOrbigny (Amelin, 2008); NWA 2999, 4590, 4801 (Amelin and Irving, 2007); Sahara 99555 (Connelly et al., 2008b).

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Table 3. Reference parameters for Hf-W chronology Parameter Value

( ( (

182

Hf
Hf

180

182

180

182

W
W

184

) Hf ) W)
Hf
0

Remarks Internal isochron for CAIs Internal isochron for DOrbigny

T0
4564.420.12Ma

(9.720.44)10-5 (7.180.22)10-5

T0
BSE

182 184 0.8645790.000014 ( 182W = -3.280.12) Initial W/ W of CAI isochron

( ( (

182

182 180

Q182W

) W W) Hf W) =10 ( Hf
184

0.8648630.000018 ( 182W 0) 0.8646990.000012 ( 182W = -1.90.1) = 1.230.08

182

182

W/184W of terrestrial standard as measured at ETH Zurich

184

CHUR 0

Average 182W/184W of carbonaceous chondrites

184

CHUR

4 180

= 1.42 104

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Table 4. Summary of estimates for the initial 182Hf/180Hf of the solar system Initial 182Hf/180Hf Reference Method -5 ~210 Harper and Jacobsen 1996 Models for 182Hf nucleosynthesis >2.610-4 Lee and Halliday 1995 Hf-W data for chondrites, iron meteorites -4 Lee and Halliday 2000 Isochrons for Ste. Marguerite, Forest Vale (2.750.24)10 Yin et al. 2002 Isochron for Dalgety Downs (L4), Dhurmsala (LL6) (1.000.08)10-4 Kleine et al. 2002 Isochron for Ste. Marguerite (H4) (1.090.09)10-4 Ireland and Bukovanska 2003 Hf-W data for zircons from Simmern (H5) (7.44.5)10-4 Quitt and Birck 2004 Iron meteorites (1.600.25)10-4 Kleine et al. 2005a Isochron for CAIs (1.070.10)10-4 Burkhardt et al. 2008 Mineral isochrons for CAIs (9.720.44)10-5

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Table 5. Summary of 182W values and twostage model ages for magmatic iron meteoritesa tCAI (Ma) Sample 182W Gibeon (IVA) -3.380.05 -2.5 to 0.6 Negrillos (IIAB) -3.390.08 -2.8 to 0.8 IC -3.63 to -3.35 -4.4 to 0.4 IIAB -3.43 to -3.23 -2.7 to 1.4 IID -3.95 to -3.24 -6.7 to 1.4 IIIAB -3.40 to -3.28 -2.4 to 1.0 IIIE -3.41 to -3.33 -2.5 to 0.6 IIIF -3.35 to -3.00 -1.9 to 3.7 IVA -3.43 to -3.28 -2.7 to 1.0 IVB -3.50 to -3.46 -3.3 to -0.5 a Range of 182W values for different groups of magmatic iron meteorites are from Qin et al. (2008) and are corrected for cosmic-ray effects using noble gas systematics. Note for IVB irons the calculated W model ages are negative, suggesting that this correction procedure did not entirely correct the cosmic-ray effects. W model ages, tCAI, are calculated relative to an initial 182W=-3.280.12 for CAIs and include uncertainties on the 182W values of the iron meteorites, CAIs and average carbonaceous chondrites (182W=-1.90.1).

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Table 6. Summary of proposed Hf-W ages for the formation of Earth's corea Age Based on Accretion/core formation model 182 t100% >62 Ma Two-stage WBSE = 0 182 t100% ~30 Ma Two-stage WBSE = +1.9 t63% = 11 Ma t99% ~50-100 Ma tGI ~55 Ma tGI ~50 Ma 182WBSE = +1.9 182WBSE = +1.9 182WBSE = +1.9 Hf/WBSE = 15 Hf/WBSI = 15 182WBSE = +1.9 Hf/WBSE = 15 Hf/WBSI = Hf/WBSE = 5 before the giant impact 182WBSE = +1.9 182WBSE = 182WBSM Hf/WBSE < Hf/WBSM 182WBSE = +1.9 Continuous core formation during exponentially decreasing accretion Continuous core formation during exponentially decreasing accretion Multiple giant impacts that occur at an overall exponentially decreasing rate

Metal-silicate re-equilibration n.a. n.a. 100 % 60-100 %

Reference Lee and Halliday (1995) Kleine et al. (2002); Schnberg et al. (2002); Yin et al. (2002) Yin et al. (2002) Kleine et al. (2004b) Halliday (2004) Halliday (2004)

100 % before the Moon-forming impact; 26 % during the Moonforming impact; batch equ. Multiple giant impacts that occur at an 100 % before the Moon-forming overall exponentially decreasing rate impact; 4 % during the Moonforming impact; batch equ. 100 %; fractional equ. n.a.

t63% ~11 Ma tGI ~32 Ma

90 tGI = 62 +10 Ma

~100 % for the final MoonThis study forming impact tGI ~75 Ma Multiple stochastic giant impacts ~100 % for the final MoonThis study 182WBSE = +1.9 forming impact a BSE = bulk silicate Earth; BSM = bulk silicate Moon; BSI = bulk silicate impactor; GI = giant impact (i.e., the Moon-forming impact) tGI ~125 Ma

Exponentially decreasing accretion, which terminates by the Moonforming impact Independent on the accretion/core formation model Multiple stochastic giant impacts

Jacobsen (2005) Touboul et al. (2007)

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Fig. 1

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271

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272

Fig. 7

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274

Fig. 9

275

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276

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277

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278

Fig. 13

279

Fig. 14

280

Fig. 15

281

Fig. 16

282

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Fig. 18

284

Fig. 19

285

Fig. 20

286

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287

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Remerciements - Acknowledgments

Pour conclure je voudrais remercier tous ceux qui ont contribu la ralisation de cette thse et qui mont soutenu au cours de ces annes passes lIPGP et lETH. Je suis tout particulirement reconnaissant envers Bernard Bourdon et Thorsten Kleine, mes deux superviseurs. Leur encadrement et nos nombreuses et fructueuses discussions mont permis dapprendre beaucoup leur contact et de mpanouir dans mon travail. Bernard ma tout dabord donn lopportunit de dcouvrir la recherche scientifique lors de mon stage de master sur les sries de luranium dans les laves de la Guadeloupe. Il ma ensuite renouvel sa confiance en me prenant en thse lInstitut de Physique du Globe de Paris. Je lui suis sincrement reconnaissant de mavoir propos et conseill de le suivre Zrich lorsquil a t nomm pour prendre la succession dAlex Halliday lETH. Cela ma permis de raliser mon rve, travailler sur la formation du systme solaire, et de mouvrir au monde au contact de lenvironnement international de lensemble du dpartement des Sciences de la Terre. Ce fut une grande chance pour moi de faire la connaissance de Thorsten Kleine et de pouvoir travailler Zrich sous sa direction. Il ma tout appris sur la chronomtrie Hf-W et a toujours t disponible. Merci pour les nombreuses heures passes ensemble en chimie ou devant le spectromtre de masse et pour son aide et ses corrections pour les diffrents articles. Je tenais galement le remercier pour mavoir soutenu lors de mon sjour lhpital. Je voudrais remercier Alex Halliday, Francis Albarde et Jean-Louis Birck davoir accept dtre examinateur de cette thse et de stre dplac Zrich pour sa soutenance. Je tenais exprimer toute ma gratitude envers Rainer Wieler et Herbert Palme, pour leur collaboration lors de ltude des chantillons lunaires, pour les nombreuses discussions scientifiques et pour leur aide dans linterprtation des donnes. Je tenais remercier James Van Orman et Colin Maden pour leur aide sur les modles de diffusion du W et de refroidissement des plantsimaux, indispensables linterprtation des donnes. Je remercie Tony Irving, Juta Zipfel et Ted Bunch pour nous avoir fourni certains des chantillons mtoritiques ainsi que leur caractrisation minralogique. Je suis sincrement reconnaissant envers Amlie Hubert et Monique Pierre pour mavoir initi aux manipulations en salle blanche et aux mesures isotopiques sur Neptune avec laide de Pascal Louvat. Un grand merci galement Guillaume Caro pour mavoir instruit la mthode de sparation du Nd et la mesure de sa composition isotopique sur Triton. Je remercie Agns Markowski et Ghylaine Quitt pour leur soutien et pour leur aide mieux cerner la chronomtrie Hf-W lors de mon arrive Zrich. Merci Irene Ivanov pour mavoir appris la sparation de minraux par liqueurs denses. Merci galement Andreas Stracke, Ben Reynolds et Felix Oberli pour leurs conseils et pour avoir assurer la maintenance des machines et des salles blanches, permettant de travailler dans des conditions optimales.

289

Je tenais remercier lensemble des chercheurs, des tudiants et des techniciens de lIPGP pour leurs conseils et leurs aides au cours de mon anne passe au sein de LIPGP, et plus particulirement Laure Meynadier, Jean Louis Birck, Grard Manhs, Christa Gpel, Manuel Moreira, Grme Gaillardet, Claude Allgre, Benjamin Chetelat, Damien Calmels, Anne-Lise Salom, Joel Dyon, Lydia Zerbib, Sylvie Cangemi. Merci galement Audrey Bouvier, Vinciane Debaille, Anne Trinquier, Morten Anderson, Oliver Nebel, Craig ONeil, Ben Jacobsen, Anders Meibom, Marcus Gutjahr, Ansgar Grimberg, Bastian Georg, Sune Nielsen, Simone de Leuw, Matthias Van Ginneken et Dim Coumou pour les bons moments passs lors des diffrentes confrences et pour les changes dides scientifiques. Durant ces quatre annes, jai tout particulirement apprci lenvironnement de LETH et les nombreuses relations que jy ai noues avec mes collgues. Ils ont normment contribu la russite de ce projet en me soutenant et en me permettant de passer des moments agrables linstitut et lextrieur. Pour cela, je voudrais remercier : - mes collgues de bureau, Ulrik Hans, Gregory de Souza et Janne Koornneef (une vrai dream team), pour lambiance dans le bureau et au labo ainsi que pour les nombreuses soires passes ensemble. - lquipe de la Friday beer, Jessica Langlade, Marion Louvel, Pierre Bouilhol et Maarten Aerts, pour lentretien de cette tradition qui permet de renforcer les liens entre les membres du dpartement. - lensemble des personnes non encore cites avec qui jai partag multes rires, bires et autres: Caroline Fitoussi, Ed Tipper, Sarah Aciego, Manuel Petitat, Antoine Roth, Benjamin Le Bayon, Christoph Burkhardt, Olivier Reubi, Jrg Rickli, Ruth Hindshaw , Paula Ardia, Lucas Carrichi, Estelle Auzanneau, Carmen Sanchez, Etienne Mdard, Sarah Bureau, Matthias Meier, Veronika Heber, Veronika Klemm, Claudia Pudack, Nadia Vgel, Adlie Delacour. Je voudrais remercier pour leur indfectible amiti depuis vingt ans les Malgaches (Benot, Lolo, Paulo, Gg, Papy, la Miche, Alex, Vincent, le Dude, Micool, Toto, Guigui, Pi-oui, David, Tata, Yanno) et les Malgachettes (la Marie, Nono, Valou, Hlne, Caro, Cc, Dodo). Longue vie lassociation Tripcycle! Enfin pour terminer, je voudrais exprimer toute ma gratitude aux membres de ma famille pour leur soutien, leur encouragement et leur patience. Rien naurait t possible sans eux: en tout premier lieu, mes parents Anne Clment et Jean Touboul qui ont su veiller ma curiosit scientifique et mapprendre raisonner ; merci mes frres et surs (Vincent, Ccile, Justine et Marion); merci Thierry et Isabel ; merci mes regretts grands parents (Yvonne, Albert, Monette et Jacques). Je suis sincrement reconnaissant lEtat Franais de mavoir permis de parvenir ici grce lenseignement fourni au cours de ma scolarit et de mes tudes universitaires et au ministre franais de la recherche pour mavoir offert une bourse de recherche pour cette tude.

290