Supporting Information

Holst et al. 10.1073/pnas.1300383110 SI Materials and Methods background were 30 s. Minerals with known chemical compo- Identification of FUN Inclusions. An ∼3 kg fragment of the Allende sitions were used as standards. Matrix effects were corrected CV meteorite (carbonaceous chondrite of the Vigarano type) using procedures described in Pouchou and Pichoir (2). was cut into numerous 3-mm–thick sections using a 250-μm diamond-coated wire saw that was operated dry to expose the fresh Petrology, Mineralogy, and Mineral Chemistry of the STP-1 FUN CAI. surface of the meteorite. High-resolution photographic images STP-1 is a coarse-grained igneous CAI composed of pure an- were produced for each section and these were characterized vi- orthite, gehlenitic melilite (Åk6−28), and igneously zoned Al,Ti- = − = − sually to identify all igneous calcium–aluminum-rich (CAI)-like diopside (Al2O3 17.7 28.5 wt %, TiO2 0.03 8.7 wt %), all inclusions. Igneous CAI-like inclusions greater than 2 mm in di- poikilitically enclosing euhedral compositionally pure spinel – ameter and present on at least two sections were sampled grains (Table S1). Lath-shaped hibonite grains and spinel using a Micromill sampling device fittedwith300-μm–di- hibonite intergrowths occur in the outermost portion of the in- − ameter diamond-coated microdrills. The sampled material clusion. The hibonite grains have low contents of MgO (0.2 1.7 − was transferred to Savillex beakers and digested using HF– wt %) and TiO2 (0.09 3.2 wt %). The Ti-poor compositions observed in some rare pyroxene grains are found in crystals lo- HNO3 acid mixtures on a hotplate at 130 °C for 48 h. After complete dissolution, a 5% aliquot of the sample was taken for cated at the boundary between melilite and anorthite (dmis- Al/Mg ratio determination to 5% accuracy using the Thermo- teinbergite) and appears to have crystallized at the eutectic point Fisher X-Series II inductively coupled plasma source mass spec- between these minerals from the last portion of melt. This prob- trometer (ICPMS) at the Centre for Star and Planet Formation in ably explains the low Ti abundances in these pyroxenes. No mul- Copenhagen, to discard inclusions with low Al/Mg ratios such as tilayered Wark–Lovering rim sequence is observed around STP-1 chondrules and amoeboid olivine aggregates. All samples with Al/ (Figs. S2 and S5). The inclusion experienced only a small degree of Mg ratio higher than 1.5 were classified as potential CAIs, which secondary alteration resulting in formation of nepheline, sodalite, constitute about 50% of the sampled inclusions. For these sam- and Fe-bearing Al-rich, Ti-poor pyroxene (FeO, 2.5−6.3 wt %, − − ples, we purified the magnesium by ion-exchange chromatogra- Al2O3,5.1 16.2 wt %, TiO2,0.10 0.27 wt %), and enrichment of phy and analyzed its isotopic composition using a ThermoFisher spinel in FeO (up to 19.5 wt %) in its peripheral portion (Table S1, Neptune multiple collector inductively coupled plasma source Figs. S1–S5). In addition, melilite crystals are cross-cut by thin mass spectrometer following protocols outlined in Bizzarro et al. veins of grossular, Al-rich, Ti-poor diopside, and Na-bearing pla- − (1). Out of ∼220 bona fide CAIs analyzed, only one inclusion was gioclase (0.35 0.89 wt % Na2O). Primary coarse anorthite crystals typified by a resolvable deficit in 26Mg* of ∼300 ppm as well as show no evidence for replacement by secondary minerals, but astableMg–isotope composition enriched in the heavy isotopes by display cleavage planes, occasionally filled by grossular (Fig. S5D). ∼1%/amu, which is characteristic of many known fractionation and unidentified nuclear effects (FUN) inclusions. Based on this Bulk Trace Elements Determination (Rare-Earth Element and Uranium). observation, this inclusion, named STP-1, was classified as a FUN Rare-earth element (REE) abundances were determined on the ∼ CAI and selected for further analysis. Present on the surfaces of Thermo X-Series II ICPMS from a separate 5.5-mg bulk aliquot μ two 3-mm–thick sections, the STP-1 FUN CAI is a spherical in- of STP-1, of which 0.5% of the total solution, dissolved in 400 L clusion of ∼10 mm diameter. It was liberated from the Allende 2% HNO3, was used for the analysis. The sample was bracketed matrix using a variable-speed Dremel fitted with either cone-shaped by analyses of a synthetic REE standard solution with a concen- diamond-coated cutting tools or dental drill bits. Once the in- tration of 1 ppb, and the data were reduced in Iolite (3) using the “ clusion was liberated, the easily identified dark matrix was carefully TraceElements data reduction scheme with the semi-quantita- ” removed from all surfaces using the Dremel. A ∼200-μm–thick tive setting. Based on measurements under similar conditions of section was made from the extracted material for petrographic the BCR-2 (Basalt, Columbia River) and BHVO-2 (Basalt, Ha- characterization and in situ 26Al–26Mg and O–isotope work. waiian Volcanic Observatory) rock standards, we estimate the accuracy of our REE results to be 23% (2 SD), apart for Eu, Gd, X-Ray Elemental Mapping and Electron Probe Microanalysis. STP-1 Tb, Dy, and Ho for which we estimate the relative accuracy to be was exposed in three sequential polished sections (1–3), which 45% (2 SD) because of the low count rates obtained for these were studied in reflected light using optical microscopy. Part of elements. The REE data of a bulk rock aliquot of STP-1, reported the central portion of the CAI was possibly lost during cutting. in absolute concentration as well as normalized to the CI chon- Each section was mapped in Mg, Ca, Al, Si, Ti, Na, K, Cl, and Fe drite data of Palme and Jones (4), are presented in Table S2. Kα X-rays with a resolution of 5 μm/pixel using the University of The uranium content of an object of known age can be cal- Hawaii (UH) field-emission electron microprobe JEOL JXA- culated from the amount of radiogenic 206Pb present today, 8500F operating at 15-kV accelerating voltage, 100-nA beam which, in turn, is determined from the total amount of Pb, its Pb current and 3-μm beam size, and studied in backscattered elec- isotopic composition, and the initial Pb isotopic composition at trons with 25-nA beam current and fully focused beam. To in- the time of formation. In a companion study, we analyzed the Pb vestigate the distribution of primary and secondary minerals in isotopic compositions of a number of fractions of the STP-1 STP-1, (i) Mg, Ca, and Al, (ii) Cl, Na, and Mg, and (iii) Ti, Ca, FUN CAI spiked with an equal atom 202Pb–205Pb tracer of and Al X-ray maps were combined using a red-green-blue color known concentration following a stepwise cleaning and dissolu- scheme. These elements and color scheme allow one to distin- tion procedure of a 23.0-mg fragment of this object. Eight of the guish spinel, hibonite, melilite, Al,Ti-diopside, anorthite, neph- 14 fractions analyzed defined a linear array in 204Pb/206Pb vs. eline, and sodalite (Figs. S1, S3, and S4). Electron microprobe 207Pb/206Pb space, with the remaining 6 fractions plotting slightly analyses of individual minerals were performed with the JEOL below the line. The line regresses through the isotopic compo- JXA-8500F operated at 15-kV accelerating voltage, 15-nA beam sition of the Solar System as estimated by Tatsumoto et al. (5). current, and fully focused beam using five wavelength spec- Points falling below the line are attributed to a small amount trometers. For each element, counting times on both peak and of terrestrial Pb contamination in these fractions that was not

Holst et al. www.pnas.org/cgi/content/short/1300383110 1of12 removed during the precleaning steps. Subtracting sufficient standards including Burma spinel, Madagascar hibonite, Miya- terrestrial Pb from these 6 fractions to transpose them onto the kejima anorthite, synthetic melilite glass, and synthetic Al,Ti- linear array in 204Pb/206Pb vs. 207Pb/206Pb space defined by the 8 diopside glass. Excess or deficit of radiogenic 26Mg (δ26Mg*) was fractions results in Pb isotopic compositions for all 14 fractions calculated using an exponential law with a mass fractionation that represent binary mixtures of initial Pb and radiogenic Pb. exponent of 0.511. The reported uncertainties include both the An estimate of 5.36 pg of radiogenic 206Pb in the fragment an- internal precision of an individual analysis and the external re- alyzed is calculated by arithmetically combining the Pb in all 14 producibility for standard measurements during a given analytical fractions and subtracting the initial Pb component (based on the session. The relative sensitivity factors for aluminum and mag- + + 204Pb/206Pb ratio of the Solar System initial). This corresponds to nesium were determined from the 27Al /24Mg ratios measured an average concentration of 0.38 ppb of U in STP-1. This con- by SIMS and the Al/Mg ratios measured previously by electron centration is 91–140 times lower than the U contents of three microprobe for each standard mineral. The 27Al/24Mg and Mg recently analyzed canonical CAIs from the chondrite Efremovka isotope data are reported in Table S4 in the δ-notation, which (6). Given the limited amount of material available for STP-1, reflect permil deviations from the terrestrial composition. this concentration is well below the minimum required for a sufficiently precise U isotopic measurement to calculate Analytical Protocols for Tungsten Isotope Measurements. Following a meaningful absolute Pb–Pb age. removal from the Allende slab and cleaning, the bulk STP-1 inclusion was gently crushed in an agate mortar under distilled Analytical Protocols for in Situ Oxygen Isotope Measurements. Oxy- ethanol, and minerals were handpicked under binocular micro- gen–isotope compositions of primary minerals in STP-1 were scopes in both plain and back lighting. Minerals were identified measured in situ by secondary ionization mass spectrometry based on their optical properties, mainly surface relief and color. (SIMS) with the UH Cameca ims-1280 ion microprobe. An ∼1nA The crushing and handpicking were done repeatedly, at each turn + Cs primary ion beam was focused to a diameter of ∼7−10 μmand increasing the mineral purity of the separates. After each crushing rastered over 7 × 7mm2 area on the sample for data collection. cycle, a Nd hand magnet was passed over the separates but in no – – – Secondary ions of 16O , 17O ,and18O were measured simulta- case were any magnetic grains detected. Fines were filtered out of neously in multicollection mode with the magnetic field controlled each mineral separate using a nylon sieve paper with 53-μm mesh. – – by an NMR probe. 16O and 18O were measured by multicollector The crushed and handpicked mineral fractions were then suc- Faraday cups (FCs) with low mass-resolving power (MRP ∼2,000), cessively rinsed in distilled ethanol followed by 0.02 M HNO3 in – whereas 17O was measured using the axial monocollector electron an ultrasonic bath for 15 min. At this point, the samples were multiplier (EM) with MRP ∼5,600, sufficient to separate the in- dried and weighed in 1.5-mL centrifuge tubes of known weight. − terfering 16OH signal. To correct for instrumental mass-frac- The anorthite, melilite, and Al,Ti-diopside fractions weighed tionation effects, Burma spinel, Miyakejima anorthite, terrestrial 45.1, 21.2, and 10.8 mg, respectively. The samples were dissolved diopside, and San Carlos olivine were used as standards. Reported in a 5:4:1 mixture of concentrated HF:HNO3:H2O2 for 2 d on uncertainties include both the internal precision of an individual a hotplate at 150 °C. After drying at no more than 100 °C, they analysis and the external reproducibility for standard measure- were oxidized in 4:1 HNO3:H2O2 to remove organic material ments during a given analytical session. Regions sputtered during and Os. Keeping the temperature low during sample drying was O–isotope measurements were photographed before and after found to be critical to obtain high W yields, as a fraction of the measurements. Oxygen–isotope compositions of minerals analyzed W forms a volatile fluoride complex during sample digestion. are listed in Table S3 and shown in Fig. 2 of the main paper. Be- The oxidation step was followed by total dissolution in 6 M HCl + cause only melilite and several analyses of Al,Ti-diopside in STP-1 0.06 M HF and samples were centrifuged to confirm full disso- deviate from the mass-dependent fractionation line defined by lution. At this step, a 15% aliquot of each sample was extracted spinel, hibonite, anorthite, and most analyses of Al,Ti-diopside, all and spiked with a mixed 180Hf/186W tracer for elemental abun- SIMS spots in melilite and Al,Ti-diopside are shown in Figs. S6–S8. dance determinations. After drying down, samples were converted to nitrate form and dissolved in 0.25 M HNO3 + 0.1 M 26 –26 Analytical Protocols for in Situ Al Mg Measurements. Magne- HF + 0.1% H2O2. This solution was fluxed on a hotplate for 1 d sium- and aluminum–isotope compositions of the primary minerals at 100 °C to enable thorough oxidation of Cr. Subsequent puri- in STP-1 were measured in situ with the UH Cameca ims-1280 ion fication of W was achieved on cation and anion exchange resins − microprobe using primary 16O ion beam. Two analytical proce- using a recipe modified from Fritz et al. (7) and Strelow et al. (8). dures were used to measure 26Al−26Mg systematics. Minerals with The solution was loaded on a 2–4-mL AG50W-X8, 200–400 high Al/Mg ratios (anorthite and hibonite) were analyzed by mag- mesh column and W along with Al, Hf, Ti, Zr, and Mo was netic field switching using EM and FC detectors for magnesium eluted with 1–2 column volumes (c.v.) of 0.25 M HNO + 0.1 M + + 3 isotopes and 27Al , respectively. 27Al was measured simulta- HF + 0.1% H O followed by 2.5 c.v. of 0.1 M HF. Adsorbed + 2 2 neously with 25Mg . Primary beam currents of 300 and 60 pA were matrix elements (e.g., Mg, Cr, Ni) were eluted in 6 M HCl for used for anorthite and hibonite, respectively. A spot size was ∼5−10 future analyses. A clean-up column with 1-mL AG1-X4, 200–400 + μm. The MRPs for Mg–isotopes and 27Al were ∼3,800 and ∼2,300, mesh was used to purify W and the samples were loaded in 1 M respectively, sufficient to separate interfering ions. Automated HF. Al was eluted with 5 c.v. of 1 M HF and Ti, Hf, and Zr with 5 fi centering of the secondary beam in the eld aperture of the mass c.v. 2 M HCl + 0.1% H2O2. Residual Hf and Zr were eluted with 2 spectrometer, high-voltage offset control, and mass-peak center- c.v. of 6 M HCl + 0.01 M HF. Finally, W was collected with 4 c.v. ing were applied before each measurement. Minerals with low Al/ of 6 M HCl + 1 M HF. In addition, Mo was unloaded in 1 M HCl. Mg ratios (spinel, melilite, and Al,Ti-diopside) were measured The second column step was repeated twice to obtain sufficiently with multicollection mode using four FC detectors. The primary pure W separates. After drying, the W cuts were oxidized six times ∼ beam currents were set to 5, 8, and 12 nA for spinel, Al,Ti-di- in 4:1 HNO3:H2O2 and dried at 100 °C to remove any remaining opside, and melilite, respectively. A spot size was ∼20−30 μm. The Os and to break down organic material from the resin that may magnetic field was controlled by the NMR probe. The MRP was otherwise produce interferences on W isotope measurements. The set to ∼2,300. Automated centering of secondary beam in the field total W procedural blank of our method and its associated un- aperture and high-voltage offset control were applied before each certainty were determined from a number of replicate blank measurement. Instrumental mass fractionation was corrected by analyses during the course of this study. Based on these meas- standard-sample bracketing by comparing each measurement urements, we estimate the total procedural blank to be 79 ± 40 pg. with the isotope ratios measured in the appropriate terrestrial A blank correction was applied to all samples, which was negli-

Holst et al. www.pnas.org/cgi/content/short/1300383110 2of12 gible for the melilite and anorthite fractions (less than 1 ppm). 184W/183W ratios were corrected for mass fractionation using the The blank correction applied on the Al,Ti-diopside fraction cor- 186W/183W = 1.98594 (9) and (ii) the 182W/184W and 183W/184W responds to ∼30 ppm and, although within the final uncertainty of ratios were corrected for mass fractionation using the 186W/184W = the isotope measurement, is not negligible. Final uncertainties of 0.92767 (9). Samples were analyzed only once, and the ratios are the isotope measurements presented in Table 1 of the main paper reported as relative deviations from the mass-bias-corrected NIST include the uncertainty of the blank correction. 3163 tungsten reference material in the μ-notation (106 deviations). Tungsten isotope data were acquired using the ThermoFisher The accuracy and external reproducibility (2 SD) of the W– Neptune MC-ICPMS located at the Centre for Star and Planet isotope measurements acquired using our protocol was evalu- Formation, Natural History Museum of Denmark, University of ated by repeated analysis of a number of distinct aliquots of Copenhagen. Following tungsten purification, samples were con- column-processed BCR-2 rock standard and the Allende car- verted to nitrate form, dissolved in a 2% HNO3 solution con- bonaceous chondrite using a quantity of W comparable to that taining traces of HF, and introduced into the plasma source by present in mineral fractions of the STP-1 FUN CAI. For this means of an Aridus II desolvating nebulizer (dry plasma). The experiment, a single batch of the BCR-2 and Allende samples typical sample aspiration rate with this introduction system was was digested according to our sample digestion procedure. Once ∼0.05 mL/min. Isotope data were acquired in static mode using in solution, five aliquots estimated to contain 5 ng and five ali- 183 five Faraday collectors set up as follows: W in the axial col- quots estimated to contain 1.5 ng of W were extracted from each lector and 182W in the low-1 collector on the low mass side of the 184 186 188 of the BCR-2 and Allende digestions, processed individually for axial Faraday, and W, W, and Os in the high-1, high-2, W purification and analyzed in the same fashion as the un- and high-3 collectors on the high mass side of the axial Faraday. knowns. Results from this experiment are presented in Table S5. 188 fi 12 Ω The Os collector was connected to an ampli er with a 10 - The W–isotope composition of the various aliquots of the BCR-2 feedback resistor, whereas the remainder of the collectors was rock standard returned values that are identical to the compo- connected to amplifiers with 1011-Ω feedback resistors. The 184 186 sition of the NIST 3163 terrestrial W standard within the un- isobaric interferences from Os and Os on the W mass array – 188 certainties of the measurements. The W isotope compositions of were corrected by monitoring the Os signal intensity, but this the various aliquots of the Allende carbonaceous chondrite are correction was in all cases less than 5 ppm and, thus, negligible. identical to that reported by earlier studies (10–13). In both The sensitivity of the instrument in low-resolution mode was cases, the 186W/183W corrected data returned a superior external ∼1,200 V/ppm. Samples and standards were analyzed with 186 184 ∼ – 183 reproducibility compared with the W/ W corrected data a signal intensity of 300 500 mV on mass W and ensuring and, therefore, the 186W/183W normalization is our preferred that the signal intensity of the sample and standard were normalization scheme and was used to correct the STP-1 data. matched to within 2%. Each analysis comprised a total of 1,259 s Based on these experiments, we infer that the external re- of baseline measurements obtained on-peak (in the same 2% producibility of the 182W/183W ratio is 15 and 21 ppm when HNO solution containing traces of HF used to dissolve samples 3 analyzing 5 and 1.5 ng of W, respectively. and standards) and 839 s of data acquisition (100 scans in- tegrated over 8.39 s). Sample analyses were interspaced with 180 184 Analytical Protocols for Hf/W Ratio Determination. The Hf/ W analyses of the National Institute of Standards and Technology ratios were determined using the Thermo X-Series quadrupole (NIST) 3163 standard as follows: standard1, standard2, sample1, ICPMS at the Centre for Star and Planet Formation in Co- standard3, standard4, sample2... A wash time of 30 min was penhagen. A 15% aliquot of each mineral separate was removed applied after each sample and standard analyses. The typical after dissolution, spiked with a 180Hf-186W mixed-tracer solution, total amount of tungsten consumed per analysis using this ap- then dried down and converted to nitrate form. Each aliquot was proach was ∼10 ng. The total amount of W available for analysis then dissolved in 400-μL0.5MHNO + 0.02 M HF in preparation for the melilite, anorthite and Al,Ti-diospide fractions was 7, 6, 3 for mass spectrometry. To deconvolve both instrumental mass bias and 1.5 ng, respectively. Therefore, the length of the data ac- ∼ and the spike-to-sample ratio of Hf, three isotopes were measured quisition sequence was reduced to 500 s for the melilite and 178 179 180 178 179 anorthite fractions and ∼300 s for the Al,Ti-diospide fraction, ( Hf, Hf, and Hf). The Hf/ Hf ratio was used to correct for mass bias using a ratio of 2.00296, and the fraction of spike but not for the bracketing standards. 180 All data reduction was conducted off-line using the freely on Hf was then determined using the equation available Iolite data reduction software that runs within Igor Pro. . . . 178 180 178 180 The data reduction modules used for W isotope ratio calculations F½spike = Hf Hf½sample − Hf Hf½true are freely available and can be obtained from the authors . . 178 180 178 180 on request. Background intensities were interpolated using a Hf Hf½spike Hf Hf½true smoothed cubic spline, as were changes in mass bias with time. Iolite’s Smooth spline auto choice was used in all cases, which 178 180 where Hf/ Hf[sample] is the measured ratio after correction for determines a theoretically optimal degree of smoothing based on 178 180 instrumental mass bias, Hf/ Hf[true] is the natural ratio of variability in the reference standard throughout an analytical 178 180 0.77765, and Hf/ Hf[spike] is the spike ratio of 0.00706. Simi- session. For each analysis, the mean and SE of the measured larly, the fraction of spike on 186W was calculated using the ratios were calculated using a 2 SD threshold to reject outliers. 183W/186W ratio after correction for mass bias using 184W/183W = Although a 2 SD outlier rejection scheme is frowned upon by 183 186 2.14117, together with values of W/ W[true] = 0.50354 and some, we submit that this approach is fully justified in the current 183 186 W/ W[spike] = 0.00010. The above results were then combined study given the limited amounts of W available for study. Sam- to calculate the sample 180Hf/184W ratio using the equation < μ ples were dissolved in small acid volumes ( 400 L) to maximize . . . signal intensities and, thus, were entirely consumed during 180 184 180 186 180 Hf W½sample = Hf W½spike F½spike Hf analysis. This leads to increased uptake rates in the last portion . of the analyses and, as such, increased signal intensities that may × 186 × 186 184 not match that of the bracketing standard. The use of the 2 SD F½spike W W W½true outlier rejection scheme provides an effective and objective 180 186 means of filtering out potentially spurious data imparted by this where F[spike] Hf and F[spike] W are the results of the above 186 184 mismatch. Mass fractionation was corrected using the exponen- calculations, and W/ W[true] is the natural ratio of 0.927670. tial law and two different approaches: (i) The 182W/183W and All calculations were performed on a timeslice-by-timeslice basis

Holst et al. www.pnas.org/cgi/content/short/1300383110 3of12 in Iolite (3), using a data reduction scheme that is freely avail- We note that the concentration of W in bulk and mineral able from the authors on request. To assess the accuracy of the separates of STP-1 is ∼150 ppb, i.e., depleted by a factor of ∼8 approach, a synthetic Hf–W solution of known composition (Hf/ relative to bulk canonical CAIs. In addition, Hf ranges from 140 W = 4.02) was measured after being doped with varying propor- to 890 ppb, which is ∼4–8 times depleted compared with fassaite tions of the major elements found in CAI material (Ca, Al, Mg, and melilite-rich separates from canonical CAIs (14). Thus, Fe, Ti, and Zr), up to the concentrations present in the mineral hafnium and tungsten in STP-1 are roughly equally depleted separates. Based on these tests we estimate the external repro- relative to canonical CAIs, resulting in comparable Hf/W ratios ducibility of the sample Hf/W ratios to be ± 6% (2 SD). of the two types of inclusions.

1. Bizzarro M, et al. (2011) High-precision Mg-isotope measurements of terrestrial 8. Strelow FWE, Weinert CHSW, Eloff C (1972) Distribution coefﬁcients and anion and extraterrestrial material by HR-MC-ICPMS – implications for the relative and exchange behavior of elements in oxalic acid – hydrochloric acid mixtures. Anal Chem absolute Mg-isotope composition of the bulk silicate earth. JAnalAtSpectrom 44:2352–2356. 26:565–577. 9. Völkening J, Köppe M, Heumann KG (1991) Tungsten isotope ratio determinations by 2. Pouchou JL, Pichoir F (1984) Un nouveau modèle de calcul pour la microanalyse negative thermal ionization mass spectrometry. Int J Mass Spectrom Ion Process quantitative par spectrométrie de rayons X - Partie I: Application à l’analyse 107:361–368. d’échantillons homogènes. La Recherche Aérospatiale 3:167–192. 10. Kleine T, Münker C, Mezger K, Palme H (2002) Rapid accretion and early core 3. Paton C, Hellstrom JC, Paul BT, Woodhead JD, Hergt JM (2011) Iolite: Freeware for the formation on asteroids and the terrestrial planets from Hf-W chronometry. Nature visualisation and processing of mass spectrometric data. J Anal At Spectrom 26: 418(6901):952–955. 2508–2518. 11. Kleine T, Mezger K, Münker C, Palme H, Bischoff A (2004) 182Hf-182W systematics of 4. Palme H, Jones A (2003) Treatise on Geochemistry, ed Davis AM (Elsevier, chondrites, eucrites and martian meteorites: Chronology of core formation and early Amsterdam), Vol 1, pp 41–61. mantle differentiation in Vesta and Mars. Geochim Cosmochim Acta 68:2935–2946. 5. Tatsumoto M, Knight RJ, Allègre CJ (1973) Time differences in the formation of 12. Scherstén A, Elliott T, Hawkesworth C, Norman M (2004) Tungsten isotope evidence that meteorites as determined from the ratio of lead-207 to lead-206. Science 180(4092): mantle plumes contain no contribution from the Earth’score.Nature 427(6971):234–237. 1279–1283. 13. Irisawa K, Yin Q-Z, Hirata T (2009) Discovery of non-radiogenic tungsten isotopic 6. Connelly JN, et al. (2012) The absolute chronology and thermal processing of solids in anomalies in the Allende CV3 chondrite. Geochem J 43:395–402. the solar protoplanetary disk. Science 338(6107):651–655. 14. Burkhardt C, et al. (2008) Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the 7. Fritz JS, Garralda BB, Karraker SK (1961) Cation exchange separation of metal ions by solar system and the timing of core formation in planetesimals. Geochim Cosmochim elution with hydroﬂuoric acid. Anal Chem 33:882–886. Acta 72:6177–6197.

Mg::Ca Al hib

sp mel px

a b 0.5 mm Ti::Ca Al Cl::Na Mg

sod px nph

c d

Fig. S1. Backscattered electron image (A) and combined X-ray elemental maps in (B) Mg (red), Ca (green), and Al (blue), (C) Ti (red), Ca (green), and Al (blue), and (D) Cl (red), Na (green), and Mg (blue) of the coarse-grained Type B2 FUN CAI STP-1 (section 1) from the CV carbonaceous chondrite Allende. Region outlined in B is shown in detail in Fig. S2. The CAI consists of gehlenitic melilite (mel) and igneously zoned Al,Ti-diopside (px) poikilitically enclosing euhedral spinel grains (sp). A bottom part of the CAI contains abundant hibonite (hib) grains (blue in B). Euhedral lath-shaped hibonite grains and spinel–hibonite intergrowths occur also around the CAI periphery. Melilite grains are cross-cut by grossular–anorthite (grs-an) veins; in the CAI periphery, melilite is partially replaced by nepheline (nph, green in D) and sodalite (sod, yellow in D). A part of the CAI (appearing as a black hole) was drilled out for bulk Al–Mg isotope measurement.

Holst et al. www.pnas.org/cgi/content/short/1300383110 4of12 sec px

andr sec an

hib grs nph

fa sod mel

sp a b

and hib grs an and

sod hib sec an mel sp sp

c d mel grs

hib

e f

Fig. S2. Backscattered electron images of the Allende FUN CAI STP-1 section 1 (A–F). Regions outlined in A and E are shown in detail in B and F, respectively. The section mainly consists of gehlenitic melilite (mel) poikilitically enclosing euhedral spinel grains (sp). Lath-shaped hibonite (hib) grains and spinel–hibonite intergrowths occur in the outermost portion of the inclusion; no Wark–Lovering rim layers are present outside the hibonite-rich zone. Melilite grains are cross- cut by grossular–anorthite veins and in the outermost portion of the CAI are partially replaced by sodalite (sod), secondary Fe-bearing Al-rich pyroxene (sec px), andradite (andr), ferroan olivine (fa), grossular (grs), and secondary Na-bearing plagioclase (sec an).

Holst et al. www.pnas.org/cgi/content/short/1300383110 5of12 Mg::Ca Al Ti::Ca Al

an hib

mel

a 1 mm b Si Na

grs-an veins

c d

Fig. S3. Combined X-ray elemental maps in (A) Mg (red), Ca (green), and Al (blue) and (B) Ti (red), Ca (green), and Al (blue), and elemental maps in Si (C)and Na Ka (D) of the coarse-grained Type B2 FUN CAI STP-1 (section 2) from the CV carbonaceous chondrite Allende. The CAI consists of gehlenitic melilite (mel), anorthite (an), and igneously zoned Al,Ti-diopside (px) all poikilitically enclosing euhedral spinel grains (sp). Euhedral lath-shaped hibonite (hib) grains and spinel–hibonite intergrowths are rare and occur in the outermost portion of the inclusion. Melilite grains are cross-cut by grossular–anorthite (grs-an) veins; in the CAI periphery, melilite is partially replaced by secondary Na-rich minerals (nepheline and sodalite). Part of the central portion of the CAI was possibly lost during cutting.

Holst et al. www.pnas.org/cgi/content/short/1300383110 6of12 STP-1 Mg::Ca Al Ti hib sp

an px px mel

a 1 mm b Si Cl::Na Al sod

nph grs-an veins c d

Fig. S4. Combined X-ray elemental maps (A and D)in(A) Mg (red), Ca (green), and Al (blue) and (D) Cl (red), Na (green), and Al (blue), and elemental maps in

Ti (B) and Si Ka (C) of the coarse-grained Type B2 FUN CAI STP-1 (section 3) from the CV carbonaceous chondrite Allende. Region outlined in A is shown in Fig. S5A. The CAI consists of gehlenitic melilite (mel), anorthite (an), and Al,Ti-diopside (px) all poikilitically enclosing euhedral spinel grains (sp). Euhedral lath- shaped hibonite (hib) grains and spinel-hibonite intergrowths occur in the outermost portion of the inclusion. Melilite grains are crosscut by grossular- anorthite (grs-an) veins and partially replaced by nepheline (nph), sodalite (sod), and secondary anorthite. Part of the central portion of the CAI was possibly lost during cutting.

Holst et al. www.pnas.org/cgi/content/short/1300383110 7of12 sod px sec px sp mel andr sec an hib sp mel grs

a b

mel sp an grs grs

hib

mel sp px sec an sod c d

Fig. S5. Backscattered electron images of regions in section 3 (A−C) and 2 (D) of the Allende FUN CAI STP-1. Region outlined in A is shown in detail in B.The CAI consists of gehlenitic melilite (mel), anorthite (an), and Al,Ti-diopside (px) all poikilitically enclosing euhedral spinel grains (sp). Euhedral lath-shaped hibonite (hib) grains and spinel-hibonite intergrowths are rare and occur in the outermost portion of the inclusion. The CAI lacks Wark-Lovering rim layers commonly observed around non-FUN coarse-grained CAIs. Melilite grains are cross-cut by grossular-anorthite (grs-an) veins and in the outermost portion of the CAI are partially replaced by sodalite (sod), secondary Fe-bearing Al-rich pyroxene (sec px), andradite (andr), and secondary Na-bearing plagioclase (Table S1). Regions indicated by red and yellow lines in D correspond to spots sputtered during measurements of oxygen- and aluminum-magnesium isotope compositions, respectively, by the UH Cameca ims-1280 ion microprobe.

Mg::Ca Al BSE hib sec ol px#4,17 O =– 21.8‰ px#3,17 O =– 22.5‰ sec an px

px#5,17 O =– 23.8‰ sec px sod px#6,17 O =– 23.1‰ grs+an mel#2,17 O =– 17.3‰ 17 – veins mel#3, 17O =– 9.9‰ mel#4, O = 15.9‰ mel#5, 17O =– 15.9‰ mel#1, 17O =– 10.9‰

mel mel#7, 17O =– 11.4‰

mel#6, 17O =– 4.1‰ sp px a b Si Ti

c d

Fig. S6. (A) Combined X-ray elemental map in Mg (red), Ca (green), and Al (blue) and (B) backscattered electron image, and elemental maps in Si (C) and Ti Ka (D) X-rays of a region in section 2. The locations of SIMS spots in melilite (mel) and Al,Ti-diopside (px) and their Δ17O values are indicated in B. Two spots in the outer portion of an Al,Ti-diopside grain (highlighted in yellow) are slightly depleted in 16O compared with two other analyses (highlighted in red) closer to the CAI core. Both 16O-depleted spots are in the Ti-depleted part of the pyroxene. Compositions of melilite are 16O-depleted to different degrees relative to those of Al,Ti-diopside. There is no obvious correlation between the degree of 16O depletion and spot location within melilite.

Holst et al. www.pnas.org/cgi/content/short/1300383110 8of12 px#1,17 O =– 24.0‰ px#2,17 O =– 24.0‰

a b

px#10,17 O =– 24.2‰

px#11,17 O =– 23.8‰

px#7,17 O =– 24.4‰

px#9,17 O =– 23.8‰

px#13,17 O =– 24.3‰ px#8,17 O =– 21.1‰ 17 – px#12, O = 16.8‰ px#14,17 O =– 20.7‰ px#15,17 O =– 21.9‰ c d

Fig. S7. Backscattered electron images of regions in section 2 (A–C) and section 1 (D) of STP-1 showing the locations of SIMS spots in Al,Ti-diopside (px) and their Δ17O values. Several spots in Al,Ti-diopside in the section 1 (highlighted in yellow in D) are slightly depleted in 16O(Δ17O range from −16.8 to −21.9‰) compared with the other analyses (Δ 17O < −23‰; highlighted in red) closer to the CAI core. The 16O-depleted spots appear to be closer to the peripheral portion of the CAI and grossular–anorthite veins than the 16O-rich spots.

mel#11, 17O =– 5.0‰ mel#9, 17O =– 5.5‰ an#3, 17O =– 24.2‰ mel#10, 17O =– 5.1‰

mel#8, 17O =– 7.0‰ an#4, 17O =– 24.6‰

an#5, 17O =– 24.6‰

a b

an#6, 17O =– 24.8‰

an#1, 17O =– 25.3‰

an#2, 17O =– 24.3‰

c d

Fig. S8. Backscattered electron images of regions in section 2 (A–D) of STP-1 showing the locations of SIMS spots in melilite (mel) and anorthite (an) and their Δ 17O values. All spots in anorthite have similar 16O-rich compositions (Δ 17O < −24‰), whereas all analyses of melilite are signiﬁcantly 16Odepleted(Δ 17O > −7‰).

Holst et al. www.pnas.org/cgi/content/short/1300383110 9of12 Table S1. Representative electron microprobe analyses of primary and secondary minerals in the Allende FUN CAI STP-1

Mineral SiO2 TiO2 Al2O3 Cr2O3 FeO MnO MgO CaO Na2OK2O Total Ak, mol %

Primary minerals Anorthite 42.6 n.d. 36.9 n.d. 0.03 n.d. 0.05 20.2 n.d. n.d. 99.8 –– Al,Ti-diopside 41.0 0.03 24.5 0.17 0.07 n.d. 9.2 25.4 n.d. n.d. 100.4 –– Al,Ti-diopside 37.7 8.7 22.0 0.10 0.03 n.d. 8.1 24.9 n.d. n.d. 101.6 –– Hibonite 0.22 0.52 89.0 n.d. 0.37 n.d. 0.27 8.7 n.d. n.d. 99.0 –– Hibonite 0.15 3.2 84.4 n.d. 0.31 n.d. 1.6 8.4 0.04 n.d. 98.0 –– Melilite 23.2 0.04 35.3 n.d. 0.10 n.d. 1.1 40.8 n.d. n.d. 100.4 6.3 Melilite 28.5 n.d. 27.2 n.d. n.d. n.d. 4.0 40.3 0.30 n.d. 100.2 28.1 Spinel 0.29 0.43 70.7 0.36 0.16 n.d. 28.2 0.68 n.d. n.d. 100.9 –– Spinel 0.30 0.29 65.4 0.12 19.5 0.05 14.8 0.29 0.04 n.d. 100.8 –– Secondary minerals Al-rich pyroxene 47.6 0.10 10.8 n.d. 5.1 n.d. 12.3 24.7 0.29 n.d. 100.7 –– Andradite 36.1 n.d. 0.59 n.d. 26.9 0.06 0.31 32.7 n.d. n.d. 96.6 –– Ferroan olivine 37.0 0.07 0.62 n.d. 26.0 0.12 34.9 0.46 0.04 n.d. 99.2 –– Grossular 38.1 n.d. 23.6 n.d. 0.64 0.10 1.2 35.0 n.d. n.d. 98.6 –– Nepheline 43.7 0.11 36.9 n.d. 1.1 n.d. 0.46 5.2 9.9 1.4 98.9 –– Anorthite 43.5 n.d. 37.1 n.d. 0.29 0.03 0.29 18.3 0.89 n.d. 100.4 ––

n.d., not detected.

Table S2. REE concentrations of a bulk aliquot of the STP-1 FUN CAI REE Concentration, ppm 2 SD CI normalized

La 1.795 0.413 7.326 Ce 3.274 0.753 5.131 Pr 0.641 0.147 6.648 Nd 3.212 0.739 6.775 Sm 0.903 0.208 5.861 Eu 0.255 0.115 4.404 Gd 0.604 0.272 2.959 Tb 0.093 0.042 2.476 Dy 0.457 0.206 1.798 Ho 0.038 0.017 0.662 Er 0.090 0.021 0.542 Tm 0.121 0.028 4.716 Yb 0.474 0.109 2.871 Lu 0.017 0.004 0.679

CI normalized represents the absolute concentration normalized to the CI chondrite reference values reported by Palme and Jones (4). The quoted uncertainty reﬂects the accuracy of our measurements and is typically 23% (2 SD) for most REE apart from Eu, Gd, Tb, Dy, and Ho, which have an uncertainty of 45%.

Holst et al. www.pnas.org/cgi/content/short/1300383110 10 of 12 Table S3. Oxygen–isotope compositions of individual minerals in the Allende STP-1 FUN CAI Mineral δ17O2σδ18O2σΔ17O2σ

Al,Ti-diopside −38.0 0.9 −32.5 0.9 −21.1 1.1 Al,Ti-diopside −42.6 1.0 −36.2 1.0 −23.8 1.1 Al,Ti-diopside −43.4 1.0 −36.9 1.0 −24.2 1.1 Al,Ti-diopside −42.5 1.0 −36.0 1.0 −23.8 1.1 Al,Ti-diopside −29.3 1.1 −24.1 1.0 −16.8 1.2 Al,Ti-diopside −43.8 1.0 −37.5 1.0 −24.3 1.1 Al,Ti-diopside −36.8 1.0 −30.9 1.0 −20.7 1.1 Al,Ti-diopside −39.0 1.0 −32.9 1.0 −21.9 1.1 Al,Ti-diopside −43.7 0.7 −37.9 0.8 −24.0 0.8 Al,Ti-diopside −43.4 0.7 −37.5 0.7 −24.0 0.8 Al,Ti-diopside −40.5 0.7 −34.6 0.8 −22.5 0.9 Al,Ti-diopside −39.2 0.8 −33.5 0.8 −21.8 0.9 Al,Ti-diopside −42.4 0.8 −35.7 0.8 −23.8 0.9 Al,Ti-diopside −42.3 0.7 −36.9 0.7 −23.1 0.8 Al,Ti-diopside −43.9 0.7 −37.5 0.8 −24.4 0.8 Anorthite −43.5 0.8 −35.1 0.8 −25.3 0.9 Anorthite −42.5 0.8 −35.0 0.8 −24.3 0.9 Anorthite −43.2 0.8 −36.5 0.9 −24.2 0.9 Anorthite −43.4 0.9 −36.0 0.9 −24.6 1.0 Anorthite −43.0 0.8 −35.4 0.8 −24.6 0.9 Anorthite −42.6 0.8 −34.2 0.9 −24.8 1.0 Hibonite −42.8 1.0 −37.8 0.7 −23.1 1.0 Hibonite −42.3 1.1 −34.7 0.7 −24.3 1.1 Hibonite −42.9 1.0 −35.3 0.7 −24.6 1.1 Hibonite −43.8 1.0 −36.4 0.8 −24.8 1.1 Hibonite −40.6 1.0 −33.9 0.7 −23.0 1.1 Hibonite −43.1 1.0 −35.8 0.7 −24.5 1.1 Melilite −17.7 0.8 −13.2 0.6 −10.9 0.8 Melilite −30.6 0.8 −25.6 0.7 −17.3 0.8 Melilite −15.9 0.8 −11.6 0.7 −9.9 0.9 Melilite −27.8 0.8 −22.9 0.6 −15.9 0.8 Melilite −27.5 0.9 −22.3 0.6 −15.9 0.9 Melilite −4.4 0.7 −0.6 0.8 −4.1 0.9 Melilite −17.7 0.8 −12.2 0.6 −11.4 0.9 Melilite −9.8 0.9 −5.5 0.7 −7.0 0.9 Melilite −7.0 0.8 −3.0 0.7 −5.5 0.9 Melilite −5.7 0.7 −1.2 0.7 −5.1 0.8 Melilite −6.3 0.7 −2.6 0.7 −5.0 0.8 Spinel −43.6 1.0 −38.0 0.7 −23.8 1.0 Spinel −46.4 1.1 −42.9 0.7 −24.1 1.1 Spinel −44.4 1.0 −38.2 0.7 −24.6 1.0 Spinel −43.2 1.0 −37.5 0.7 −23.7 1.0 Spinel −41.4 1.0 −33.2 0.7 −24.1 1.1 Spinel −39.5 1.0 −29.0 0.7 −24.5 1.1 Spinel −38.3 1.0 −27.9 0.7 −23.7 1.1 Spinel −39.7 1.0 −30.2 0.7 −24.0 1.1 Spinel −43.3 1.0 −35.7 0.7 −24.7 1.1

Holst et al. www.pnas.org/cgi/content/short/1300383110 11 of 12 Table S4. 27Al/24Mg ratios and Mg isotope compositions of individual minerals in the Allende STP-1 FUN CAI Sample 27Al/24Mg 2σδ26Mg* 2σδ25Mg 2σ

Anorthite 744.5 16.0 14.99 2.41 8.48 1.18 Anorthite 773.5 16.4 14.24 3.06 9.99 1.46 Anorthite 247.3 5.3 5.46 2.36 8.44 1.16 Anorthite 643.4 16.0 13.43 3.21 8.07 1.49 Anorthite 829.0 17.5 16.85 3.22 10.38 1.52 Anorthite 754.0 15.9 15.75 2.91 10.19 1.36 Anorthite 768.7 16.3 16.91 3.12 8.75 1.47 Hibonite 1147.9 23.7 27.46 8.28 27.87 4.11 Hibonite 165.2 3.4 2.93 3.35 13.11 2.37 Hibonite 474.9 10.0 10.60 4.55 23.25 2.79 Hibonite 129.9 2.7 1.83 2.95 4.44 2.21 Spinel 2.5 0.4 −0.31 0.09 10.88 0.15 Spinel 2.5 0.4 −0.29 0.11 10.99 0.15 Spinel 2.5 0.4 −0.33 0.10 10.95 0.15 Spinel 2.5 0.4 −0.33 0.09 10.79 0.15 Spinel 2.5 0.3 −0.34 0.08 10.84 0.15 Melilite 17.1 0.8 0.026 0.564 12.09 0.27 Melilite 12.8 0.7 0.017 0.530 12.24 0.26 Melilite 10.6 0.6 −0.182 0.546 12.05 0.27 Melilite 6.2 0.6 −0.107 0.507 13.20 0.25 Melilite 14.7 1.5 −0.158 0.597 12.43 0.28 Melilite 23.4 1.1 0.068 0.619 12.03 0.29 Melilite 23.6 1.1 −0.145 0.563 12.25 0.27 Fassaite 2.4 0.5 −0.416 0.335 11.14 0.17 Fassaite 2.8 0.6 −0.257 0.300 10.76 0.16 Fassaite 1.8 0.4 −0.415 0.295 10.85 0.15 Fassaite 3.0 0.5 −0.508 0.379 11.23 0.18 Fassaite 3.1 0.6 −0.380 0.326 10.81 0.16 Bulk 3.180 0.06 −0.303 0.010 9.33 0.02

Table S5. W isotope data of multiple column processed aliquots of Allende and BCR-2 rock powders Sample μ182W (6/3) 2 SD μ184W (6/3) 2 SD μ182W (6/4) 2 SD μ183W (6/4) 2 SD N

Allende (5 ng) −227 15 −20 19 −176 19 30 29 5 Allende (1.5 ng) −206 20 −13 18 −184 34 20 27 5 BCR-2 (5 ng) −3.8 8 1.6 10 −319 −2145 BCR-2 (1.5 ng) −17 21 8 17 −22 23 −13 26 5

Uncertainties reﬂect the external reproducibility of the method. N, number of individual column processed aliquots; (6/3), internally normalized to 186W/183W; (6/4), internally normalized to 186W/184W.

Holst et al. www.pnas.org/cgi/content/short/1300383110 12 of 12