The U-Pb systematics of angrite Sahara 99555

Angrite Sahara 99555 (hereafter SAH), precisely dated by Baker et al. (Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131), has been proposed as a new reference point for the early Solar System timescale and for calculation of the revised minimum age of our Solar System. The Pb-Pb age of SAH of 4566.18 ± 0.14 Ma, reported by Baker et al., differs from the Pb-Pb age of D’Orbigny, another basaltic angrite, of 4564.42 ± 0.12 Ma (Amelin Y. (2008) U-Pb ages of angrites. Geochim. Cosmochim. Acta72, 221-232), despite the fact that the relative ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W ages of these meteorites are identical. Here I report U-Pb data for 21 whole rock and pyroxene fractions from SAH, analyzed using the same approach as D’Orbigny (Amelin, 2008). These fractions contain between 1.3 and 8.9 pg of total common Pb, slightly more than analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios are between 625 and 2817 for D’Orbigny, blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios are between 1173 and 6675. Eight acid-washed whole rock fractions yielded an isochron age of 4564.86 ± 0.38 Ma, MSWD = 1.5. Data for pyroxene fractions plot mostly above the whole rock isochron, and do not form a linear array in ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁴Pb/²⁰⁶Pb isochron coordinates. The ²⁰⁷Pb^∗/²⁰⁶Pb^∗ model dates of the pyroxene fractions vary from 4563.8 ± 0.3 to 4567.1 ± 0.5 Ma. The difference between whole rock and pyroxene U-Pb systematics may be a result of re-distribution of radiogenic Pb at a mineral grain scale several million years after crystallization. Complexities of Sm-Nd, Lu-Hf, and possibly ²⁶Al-²⁶Mg mineral systematics of SAH, described previously, may be related to the same process that caused the re-distribution of radiogenic Pb. Disturbance of isotopic chronometers renders SAH an imperfect anchor for the early Solar System timescale. The problems with age determination revealed by the studies of SAH call for greater attention in Pb-isotopic dating of angrites and other achondrites.     

Al-Mg systematics in D’Orbigny and Sahara 99555 angrites: Implications for high-resolution chronology using extinct chronometers

We report on an investigation of the ²⁶Al-²⁶Mg isotope systematics in the D’Orbigny and Sahara 99555 angrites. High precision Mg isotope compositions and Al/Mg ratios were measured in mineral separates and whole rock samples from D’Orbigny and Sahara 99555 using multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Plagioclase separates from both angrites have resolvable excesses in ²⁶Mg (Δ²⁶Mg) that correlate with their respective Al/Mg ratios. ²⁶Al-²⁶Mg systematics in the mineral separates and whole rocks define precise isochrons that correspond to ²⁶Al/²⁷Al ratios of (5.06 ± 0.92) × 10⁻⁷ and (5.13 ± 1.90) × 10⁻⁷ and initial Δ²⁶Mg values of −0.006 ± 0.040‰ and −0.016 ± 0.047‰ for D’Orbigny and Sahara 99555, respectively. The slopes and initial Δ²⁶Mg values are identical for these two meteorites within errors and the data for both angrites considered together define an isochron corresponding to a ²⁶Al/²⁷Al ratio of (5.10 ± 0.55) × 10⁻⁷ and initial Δ²⁶Mg value of −0.012 ± 0.019. Relative to the Efremovka E60 CAI, the ²⁶Al/²⁷Al values reported here for these angrites imply ²⁶Al-²⁶Mg ages of 4562.42 ± 0.29 Ma and 4562.43 ± 0.53 Ma for D’Orbigny and Sahara 99555, respectively. These ²⁶Al-²⁶Mg ages are concordant with model ages determined using other extinct radionuclide chronometers (e.g., ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W), but are ∼2 Myr younger than the absolute ²⁰⁷Pb-²⁰⁶Pb ages that have been reported recently for these angrites. The reason for this discrepancy is not presently known, but may imply disturbance of one or more of the isotope systems under consideration or a possible bias in the ²⁰⁷Pb-²⁰⁶Pb ages of the angrites resulting from natural or analytical causes.     

Ancient relative and absolute ages for a basaltic meteorite: Implications for timescales of planetesimal accretion and differentiation

Asuka 881394 is a unique basaltic meteorite that originated in the crust of a differentiated planetesimal in the early Solar System. We present high precision Pb, Mg, and Cr isotopic compositions of bulk samples and mineral separates from this achondrite. A ²⁰⁷Pb-²⁰⁶Pb internal isochron obtained from the radiogenic pyroxene and whole-rock fractions of Asuka 881394 yields an absolute age of 4566.5 ± 0.2 Ma, which we consider to be the best estimate for the crystallization age of this basaltic achondrite. The ²⁶Al-²⁶Mg systematics show some evidence of disturbance, but 5 of the 6 analyzed whole-rock and mineral fractions define an isochron corresponding to a ²⁷Al/²⁶Al ratio of (1.28 ± 0.07) × 10⁻⁶. Comparison with the ²⁶Al-²⁶Mg and Pb-Pb systematics in the D’Orbigny achondrite translates to a ²⁶Al-²⁶Mg age of 4565.4 ± 0.2 Ma for Asuka 881394. The ⁵³Mn-⁵³Cr systematics in whole-rock, silicate and chromite fractions correspond to a ⁵³Mn/⁵⁵Mn ratio of (3.85 ± 0.23) × 10⁻⁶. Compared to the most precise ⁵³Mn-⁵³Cr and Pb-Pb systematics available for the D’Orbigny angrite, this translates to a ⁵³Mn-⁵³Cr age of 4565.3 ± 0.4 Ma; similarly, a comparison with the NWA 4801 angrite yields a ⁵³Mn-⁵³Cr age of 4565.5 ± 0.4 Ma, in agreement with the age obtained relative to D’Orbigny. While the ²⁶Al-²⁶Mg and ⁵³Mn-⁵³Cr ages appear to be concordant in Asuka 881394, these ages are ∼1 Ma younger than its ²⁰⁷Pb-²⁰⁶Pb age. This discordance might have been caused by one or more of several reasons, including differences in the closure temperatures for Pb versus Cr and Mg diffusion in their host minerals combined with slow cooling of the parent body as well as differential resetting of isotopic systems by a process other than volume diffusion, e.g., shock metamorphism. The ancient age of Asuka 881394 suggests that basaltic volcanism on its parent planetesimal occurred within ∼3 Ma of the formation of earliest solids in the Solar System, essentially contemporaneously with chondrule formation. This requires that the Asuka 881394 parent body was fully accreted within ∼500,000 yrs of Solar System formation.     

Noble gases in D’Orbigny, Sahara 99555 and D’Orbigny glass—Evidence for early planetary processing on the angrite parent body

We analyzed the spallogenic, trapped, fissiogenic and radiogenic noble gas components in various bulk samples of the angrites D’Orbigny and Sahara 99555 as well as in glass separates of D’Orbigny. The D’Orbigny glass samples show hints of solar-like noble gases, as deduced from the trapped elemental and Ne isotopic compositions; the bulk samples do not contain detectable amounts of trapped gases. These observations indicate that D’Orbigny experienced a complex history shortly after its formation 4.56 Ga ago. The glass of D’Orbigny most likely represents magma that rose from the interior of the angrite parent body (APB) and was quenched near the surface. Hence, the APB may contain—similar to the interior of Earth and Mars—solar noble gases. This would call into question the suggested trapping mechanism for solar noble gases in the Earth and Mars, which involves the solution of early atmospheres into magma oceans, due to the APB’s inability to retain a primordial atmosphere. The first detection of—possibly parentless—radiogenic excess ¹²⁹Xe and solar noble gases in the glass of D’Orbigny indicates that the interior of APB degassed to a lesser degree than the outer regions. Therefore primordially trapped, fossil ¹²⁹I was kept. The APB was not completely devolatilized. Sahara 99555 yields a cosmic-ray exposure age of 6.8 ± 0.3 Ma, while D’Orbigny was exposed to cosmic rays for 11.9 ± 1.2 Ma. Both ages are different than those found in the other angrites. Hence, the angrites analyzed so far sampled surface material from the APB that was ejected in at least five events. In contrast to the bulk sample, the D’Orbigny glass separates yield concordant ages of only 3.0 ± 1.1 Ma, apparently suggesting a pre-exposure of the host material. However, such a scenario is unlikely, due to very similar Mn-Cr ages found in the bulk and glass of D’Orbigny. Most likely, this discrepancy is the result of additional, secondary gas-free glass. Such glass might have been formed during the meteorite’s entry into the Earth’s atmosphere. Isotopically anomalous Xe due to the decay of ²⁴⁷Cm has not been found. The presence of ²⁴⁷Cm in glass of D’Orbigny has been suggested based on Pb isotope constraints.     

Al-Mg dating of asteroidal magmatism in the young Solar System

We present high-precision Mg isotope data for most classes of basaltic meteorites including eucrites, mesosiderite silicate clasts, angrites and the ungrouped Northwest Africa (NWA) 2976 measured by pseudo-high-resolution multiple-collector inductively coupled plasma mass spectrometry and utilising improved techniques for chemical purification of Mg. With the exception of the angrites Angra dos Reis, Lewis Cliff (LEW) 86010, NWA 1296 and NWA 2999 and the diogenite Bilanga, which have either been shown to have young ages by other dating techniques or have low Al/Mg ratios, all bulk samples of basaltic meteorites have ²⁶Mg excesses (δ²⁶Mg^∗=+0.0135 to +0.0392‰). The ²⁶Mg excesses cannot be explained by analytical artefacts, cosmogenic effects or heterogeneity of initial ²⁶Al/²⁷Al, Al/Mg ratios or Mg isotopes in asteroidal parent bodies as compared to Earth or chondrites. The ²⁶Mg excesses record asteroidal melting and formation of basaltic magmas with super-chondritic Al/Mg and confirm that radioactive decay of short-lived ²⁶Al was the primary heat source that melted planetesimals. Model ²⁶Al-²⁶Mg ages for magmatism on the eucrite/mesosiderite, angrite and NWA 2976 parent bodies are 2.6-3.2, 3.9-4.1 and 3.5 Myr, respectively, after formation of calcium-aluminium-rich inclusions (CAIs). However, the validity of these model ages depends on whether the elevated Al/Mg ratios of basaltic meteorites result from magma ocean evolution on asteroids through fractional crystallisation or directly during partial melting. Mineral isochrons for the angrites Sahara (Sah) 99555 and D’Orbigny, and NWA 2976, yield ages of and , respectively, after CAI formation. Both isochrons have elevated initial δ²⁶Mg^∗ values. Given the brecciated and equilibrated texture of NWA 2976 it is probable that its isochron age and elevated initial δ²⁶Mg^∗(+0.0175±0.0034‰) reflects thermal resetting during an impact event and slow cooling on its parent body. However, in the case of the angrites the marginally elevated initial δ²⁶Mg^∗(+0.0068±0.0058‰) may reflect either δ²⁶Mg^∗ ingrowth in a magma ocean prior to eruption and crystallisation or in an older igneous protolith with super-chondritic Al/Mg prior to impact melting and crystallisation of these angrites, or partial internal re-equilibration of Mg isotopes after crystallisation. ²⁶Al-²⁶Mg model ages and an olivine + pyroxene + whole rock isochron for the angrites Sah 99555 and D’Orbigny are in good agreement with age constraints from ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W short-lived chronometers, suggesting that the ²⁶Al-²⁶Mg feldspar-controlled isochron ages for these angrites may be compromised by the partial resetting of feldspar Mg isotope systematics. Even when age constraints from the ²⁶Al-²⁶Mg angrite model ages or the mafic mineral + whole rock isochron are considered, the relative time difference between Sah 99555/D’Orbigny crystallisation and CAI formation cannot be reconciled with Pb-Pb ages for Sah 99555/D’Orbigny and CAIs, which are ca. 1.0 Myr too old (angrites) or too young (CAIs) for reasons that are not clear. This discrepancy might indicate that ²⁶Al was markedly lower (ca. 40%) in the planetesimal- and planet-forming regions of the proto-planetary disc as compared to CAIs, or that CAI Pb-Pb ages may not accurately date CAI formation, which might be better dated by the ¹⁸²Hf-¹⁸²W and ²⁶Al-²⁶Mg chronometers as 4568.3±0.7 (Burkhardt et al., 2008) and (herein), respectively, when mapped onto an absolute timescale using Pb-Pb ages for angrites.     

The distribution of short-lived radioisotopes in the early solar system and the chronology of asteroid accretion, differentiation, and secondary mineralization

We evaluate initial (²⁶Al/²⁷Al)_I, (⁵³Mn/⁵⁵Mn)_I, and (¹⁸²Hf/¹⁸⁰Hf)_I ratios, together with ²⁰⁷Pb/²⁰⁶Pb ages for igneous differentiated meteorites and chondrules from ordinary chondrites for consistency with radioactive decay of the parent nuclides within a common, closed isotopic system, i.e., the early solar nebula. The relative initial isotopic abundances of ²⁶Al, ⁵³Mn, and ¹⁸²Hf in differentiated meteorites and chondrules are consistent with decay from common solar system initial values, here denoted by I(Al)_SS, I(Mn)_SS, and I(Hf)_SS, respectively. I(Mn)_SS and I(Hf)_SS = 9.1 ± 1.7 × 10⁻⁶ and 1.07 ± 0.08 × 10⁻⁴, respectively, correspond to “canonical” I(Al)_SS = 5.1 × 10⁻⁵. I(Hf)_SS so determined is consistent with I(Hf)_SS = 9.72 ± 0.44 × 10⁻⁵ directly determined from an internal Hf-W isochron for CAI minerals. I(Mn)_SS is within error of the lowest value directly measured for CAIs. We suggest that erratically higher values measured for CAIs in carbonaceous chondrites may reflect proton irradiation of unaccreted CAIs by the early Sun after other asteroids destined for melting by ²⁶Al decay had already accreted. The ⁵³Mn incorporated within such asteroids would have been shielded from further “local” spallogenic contributions from within the solar system. The relative initial isotopic abundances of the short-lived nuclides are less consistent with the ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding materials than with one another. The best consistency of short- and long-lived chronometers is obtained for (¹⁸²Hf/¹⁸⁰Hf)_I and the ²⁰⁷Pb/²⁰⁶Pb ages of angrites. (¹⁸²Hf/¹⁸⁰Hf)_I decreases with decreasing ²⁰⁷Pb/²⁰⁶Pb ages at the rate expected from the 8.90 ± 0.09 Ma half-life of ¹⁸²Hf. The model solar system age thus determined is T_SS,Hf-W = 4568.3 ± 0.7 Ma. (²⁶Al/²⁷Al)_I and (⁵³Mn/⁵⁵Mn)_I are less consistent with ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding meteorites, but yield T_SS,Mn-Cr = 4568.2 ± 0.5 Ma relative to I(Al)_SS = 5.1 × 10⁻⁵ and a ²⁰⁷Pb/²⁰⁶Pb age of 4558.55 ± 0.15 Ma for the LEW86010 angrite. The Mn-Cr method with I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶ is useful for dating accretion (if identified with chondrule formation), primary igneous events, and secondary mineralization on asteroid parent bodies. All of these events appear to have occurred approximately contemporaneously on different asteroid parent bodies. For I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶, parent body differentiation is found to extend at least to ∼5 Ma post-T_SS, i.e., until differentiation of the angrite parent body ∼4563.5 Ma ago, or ∼4564.5 Ma ago using the directly measured ²⁰⁷Pb/²⁰⁶Pb ages of the D’Orbigny-clan angrites. The ∼1 Ma difference is characteristic of a remaining inconsistency for the D’Orbigny-clan between the Al-Mg and Mn-Cr chronometers on one hand, and the ²⁰⁷Pb/²⁰⁶Pb chronometer on the other. Differentiation of the IIIAB iron meteorite and ureilite parent bodies probably occurred slightly later than for the angrite parent body, and at nearly the same time as one another as shown by the Mn-Cr ages of IIIAB irons and ureilites, respectively. The latest recorded episodes of secondary mineralization are for carbonates on the CI carbonaceous chondrite parent body and fayalites on the CV carbonaceous chondrite parent body, both extending to ∼10 Ma post-T_SS.     

The Pb-Pb age of Angrite SAH99555 revisited

Representing a suite of well-preserved basaltic meteorites with reported ages from 4566.18 ± 0.14 Ma to 4557.65 ± 0.13 Ma, angrites have been recurring targets for cross-calibrating extinct and absolute chronometers. However, inconsistencies exist in the available chronological data set, including a 4566.18 ± 0.14 Ma Pb-Pb age reported by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] for Sahara 99555 (herein SAH99555) that is significantly older than a Pb-Pb age for D’Orbigny, despite the two meteorites yielding indistinguishable Hf-W and Mn-Cr ages. We re-evaluate the Pb-Pb age of SAH99555 using a stepwise dissolution procedure on a whole rock fragment and a pyroxene separate. The combined data set yields a linear array that reflects a mixture of radiogenic Pb and terrestrial contamination and corresponds to an age of 4564.58 ± 0.14 Ma, which is 1.60 ± 0.20 Ma younger than that reported by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131]. Our conclusion that SAH99555 crystallized at 4564.58 ± 0.14 Ma requires that all initial Pb was removed in the first progressive dissolution steps, an assertion supported by linearity of data generated by stepwise dissolution of a single fragment and the removal of an obvious highly-radiogenic component early in the dissolution process. We infer that the linear array defined by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] and their older age reflects a ternary mixture of Pb with constant relative proportions of highly-radiogenic initial Pb and radiogenic Pb with varying amounts of a terrestrial contamination. This requires that the phase harboring the initial Pb is insoluble in 2 M HCl, the only acid applied to the samples by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] prior to dissolution.     

New constraints on early Solar System chronology from Al-Mg and U-Pb isotope systematics in the unique basaltic achondrite Northwest Africa 2976

We report elemental abundances and the isotopic systematics of the short-lived ²⁶Al-²⁶Mg (half-life of ∼0.73 Ma) and long-lived U-Pb radiochronometers in the ungrouped basaltic meteorite Northwest Africa (NWA) 2976. The bulk geochemical composition of NWA 2976 is clearly distinct from that of the eucrites and angrites, but shows broad similarities to that of the paired NWA 001 and 2400 ungrouped achondrites indicating that it is likely to also be paired with these two samples. The major and trace element abundances in NWA 2976 further indicate that it formed by extensive melting and magmatic fractionation processes on its parent body. The Al-Mg and Pb-Pb isotope systematics indicate that this meteorite represents the earliest stages of crust formation on a differentiated parent body in the early Solar System. The absolute Pb-Pb internal isochron age of NWA 2976, obtained from acid leaching residues of three whole-rock samples and two pyroxene separates, is 4562.89 ± 0.59 Ma (MSWD = 0.02). This Pb-Pb age is calculated using the measured ²³⁸U/²³⁵U ratio of a NWA 2976 whole-rock of 137.751 ± 0.018 (2σ) which was determined relative to the recently revised value of 137.840 ± 0.008 for the SRM 950a U isotope standard. The Al-Mg systematics reveal the presence of ²⁶Mg isotopic anomalies produced by the decay of ²⁶Al with an (²⁶Al/²⁷Al)₀ of (3.94 ± 0.16) × 10⁻⁷, and indicate a time of formation of 0.26 ± 0.18 Ma after the D’Orbigny angrite. Using the revised Pb-Pb age of 4563.36 ± 0.34 Ma for the D’Orbigny anchor (corrected for its U isotopic composition), we deduce an Al-Mg model age of 4563.10 ± 0.38 Ma for NWA 2976, which is consistent with its Pb-Pb internal isochron age.The concordance of the Pb-Pb and Al-Mg chronometers, when taking into account the differences in the U isotopic compositions of the D’Orbigny and NWA 2976 achondrites (whose parent bodies likely formed in distinct regions of early Solar System as indicated by their different oxygen isotopic compositions), implies that ²⁶Al was homogeneously distributed in the early Solar System. It also suggests that igneous processes on planetesimals, as represented by the formation of various basaltic meteorite groups that likely originated on distinct parent bodies (e.g., eucrites and angrites, as well as ungrouped achondrites), were widespread throughout the protoplanetary disk within the first ∼5 Ma of the history of the Solar System.     

Mn-Cr systematics of the early Solar System revisited

We have reinvestigated the Mn-Cr systematics in a number of primitive meteorites, differentiated planetesimals and terrestrial planets in order to address the chronology of the early stages of protoplanetary disk evolution and planetary formation. Our analytical procedure is based on the assumption of terrestrial abundances for ⁵⁰Cr and ⁵²Cr only; recognizing that a data reduction scheme based on Earth-like ⁵⁴Cr/⁵²Cr abundances in all meteorites is not tenable. Here we show that initial ε_⁵³Cr compositions of ⁵⁴Cr-rich and ⁵⁴Cr-poor acid leach fractions in the primitive carbonaceous chondrite Orgueil differ by 0.9ε, reflecting primordial mineral-scale heterogeneity. However, asteroidal processing effectively homogenized any ε_⁵³Cr variations on the planetesimal scale, providing a uniform present-day solar ε_⁵³Cr=0.20±0.10. Thus, our ⁵³Mn-⁵³Cr data argue against the previously suggested ⁵³Mn heliocentric gradient. Instead, we suggest that inner Solar System objects possessed an initially homogeneous ⁵³Mn/⁵⁵Mn composition, which determined by two independent means is estimated at (6.28 ± 0.66) × 10⁻⁶. Our revised Mn-Cr age for Ste. Marguerite (SM) metamorphism of 4562.9 ± 1.0 Ma is identical to the Pb-Pb age of SM phosphates. Using this age, we confirm that mantle differentiation of the eucrite parent body occurred 4564.9 ± 1.1 Ma ago, and revise the time interval between this event and CAI formation to 2.2 ± 1.1 Ma. We also constrain metamorphism in carbonaceous chondrites of type 2 and 3 to have occurred between 1 and 6 Ma after CAI formation. The ⁵³Mn-⁵³Cr correlation among chondrites, planetesimals and terrestrial planets (the eucrite parent body, Mars and Earth) provides evidence for Mn/Cr fractionation within the protoplanetary disk recorded by all precursor materials of the terrestrial planets and primitive asteroids. This fractionation appears to have occurred within 2 Ma of CAI formation.     

Direct dating of hydrothermal W mineralization: U-Pb age for hübnerite (MnWO4), Sweet Home Mine, Colorado

We have investigated the potential of hübnerite for U-Pb dating. Hübnerite forms typically at medium to low-temperatures in a wide range of pneumatolytic-hydrothermal mineral deposits, particularly porphyry molybdenum and Sn-specialized granites. Hübnerite from the Sweet Home Mine (Alma, Colorado) formed in a Pb-rich, U-poor environment, but still developed relatively radiogenic Pb isotopic compositions. The low Pb_common contents in hübnerite (0.075 to 0.155 ppm) demonstrate that Pb is efficiently excluded from the crystal lattice. In contrast, U may substitute for Mn. The U-Pb data of hübnerite scatter. Most of the scatter originates from samples with ²⁰⁶Pb/²⁰⁴Pb values below 50, where Pb_blank contributes up to 30% to Pb_total. Using the least radiogenic galena Pb, samples with ²⁰⁶Pb/²⁰⁴Pb values above 70 have overlapping ²⁰⁶Pb∗/²³⁸U and ²⁰⁷Pb∗/²³⁵U values and yield a ²⁰⁶Pb/²³⁸U age of 25.7 ± 0.3 Ma (2σ). Late stage apatite from the Sweet Home Mine yields a ²⁰⁶Pb/²⁰⁴Pb-²³⁸U/²⁰⁴Pb isochron corresponding to an age of 24.8 ± 0.5 Ma (2σ). A comparison of the U-Pb hübnerite ages with literature ⁴⁰Ar/³⁹Ar ages on earlier sericite and the U-Pb age on later apatite suggests that (i) hübnerite yields accurate U-Pb ages and (ii) the evolution of the Sweet Home mineralization from greisen-type mineralization to medium-temperature hydrothermal vein mineralization took place in a few hundred thousand years at most. Aqueous low-N₂-bearing and aqueous inclusions in the dated hübnerite have homogenization temperatures between 325 and 356 °C and moderate salinity (up to 6.7 wt% NaCl equiv.). Thus, hübnerite represents one of the rare examples of a mineral that can be dated accurately and carries petrological information.     

Eoarchean–Paleoproterozoic zircon inheritance in Japanese Permo-Triassic granites (Unazuki area,Hida Metamorphic Complex): Unearthing more old crust and identifying source terrranes

U–Pb zircon geochronology of two Permo-Triassic granites (samples OT-52 and OT-272 with ages of 229 ± 8 Ma and 256 ± 2 Ma, respectively) in the Unazuki area, Hida Metamorphic Belt, southwest Japan, revealed the presence of Eoarchean to Paleoproterozoic inheritance. Inheritance is consistent with both samples showing low zircon saturation temperatures for their bulk compositions. In OT-52, dark in CL, low Th/U zircon domains have a mean ²⁰⁷Pb/²⁰⁶Pb age of 1940 ± 17 Ma, which is consistent with an age of 1937 ± 6 Ma for anatexis in the Precambrian Busan gneiss complex in Korea. Eoarchaean inherited zircons with ²⁰⁷Pb/²⁰⁶Pb ages from ca. 3750 to 3550 Ma are common in OT-272 but are few in OT-52, suggesting a source from rocks with affinities to those in the Anshan area in the northeast China part of the North China Craton. On the other hand, a Hida Metamorphic Belt metasedimentary gneiss into which the granites were intruded contains ca. 1840, 1130, 580, 360, 285 and 250 Ma zircons (Sano et al., 2000). These ages suggest that the Unazuki Mesozoic granites did not originate from proximal Hida Metamorphic Complex rocks, but instead from unrelated rocks obscured at depth. The predominance of Eoarchean to Paleoproterozoic age components, and the marked lack of 900–700 Ma components suggest that the source was the (extended?) fringe of the North China Craton, rather than from Yangtze Craton crust. The Mesozoic evolution of Japan and its linkages to northeast Asia are discussed in the context of these results.     

Ar-Ar and I-Xe ages and thermal histories of three unusual metal-rich meteorites

Portales Valley, Sombrerete, and Northwest Africa (NWA) 176 are three unrelated meteorites, which consist of silicate mixed with substantial amounts of metal and which likely formed at elevated temperatures as a consequence of early impacts on their parent bodies. Measured ³⁹Ar-⁴⁰Ar ages of these meteorites are 4477 ± 11 Ma and 4458 ± 16 Ma (two samples of Portales Valley), 4541 ± 12 Ma, and 4524 ± 13 Ma, respectively (Ma = million years; all one-sigma errors). The Ar-Ar data for Portales Valley show no evidence of later open system behavior suggested by some other chronometers. Measured ¹²⁹I-¹²⁹Xe ages of these three meteorites are 4559.9 ± 0.5 Ma, 4561.9 ± 1.0 Ma, and ∼4544 Ma, respectively (relative to Shallowater = 4562.3 ± 0.4 Ma). From stepwise temperature release data, we determined the diffusion characteristics for Ar and Xe in our samples and calculated approximate closure temperatures for the K-Ar and I-Xe chronometers. Adopting results and interpretations about these meteorites from some previous workers, we evaluated all these data against various thermal cooling models. We conclude that Portales Valley formed 4560 Ma ago, cooled quickly to below the I-Xe closure temperature, then cooled deep within the parent body at a rate of ∼4 °C/Ma through K-Ar closure. We conclude that Sombrerete formed 4562 Ma ago and cooled relatively quickly. NWA 176 likely formed and cooled quickly ∼4544 Ma ago, or later than formation times of most meteorite parent bodies. For all three meteorites, the Ar-Ar ages are in better agreement with I-Xe ages and preferred thermal models if we increase these Ar-Ar ages by ∼20 Ma. Such age corrections would be consistent with probable errors in ⁴⁰K decay parameters in current use, as suggested by others. The role of impact heating and possible disruption and partial reassembly of meteorite parent bodies to form some meteorites likely was an important process in the early solar system.     

Cretaceous seamounts along the continent-ocean transition of the Iberian margin: U-Pb ages and Pb-Sr-Hf isotopes

To elucidate the age and origin of seamounts in the eastern North Atlantic, 54 titanite and 10 zircon fractions were dated by the U-Pb chronometer, and initial Pb, Sr, and Hf isotope ratios were measured in feldspars and zircon, respectively. Rocks analyzed are essentially trachy-andesites and trachytes dredged during the “Tore Madeira” cruise of the Atalante in 2001. The ages reveal different pulses of alkaline magmatism occurring at 104.4 ± 1.4 (2σ) Ma and 102.8 ± 0.7 Ma on the Sponge Bob seamount, at 96.3 ± 1.0 Ma on Ashton seamount, at 92.3 ± 3.8 Ma on the Gago Coutinho seamount, at 89.3 ± 2.3 Ma and 86.5 ± 3.4 Ma on the Jo Sister volcanic complex, and at 88.3 ± 3.3 Ma, 88.2 ± 3.9, and 80.5 ± 0.9 Ma on the Tore locality. No space-time correlation is observed for alkaline volcanism in the northern section of the Tore-Madeira Rise, which occurred 20-30 m.y. after opening of the eastern North Atlantic. Initial isotope signatures are: 19.139-19.620 for ²⁰⁶Pb/²⁰⁴Pb, 15.544-15.828 for ²⁰⁷Pb/²⁰⁴Pb, 38.750-39.936 for ²⁰⁸Pb/²⁰⁴Pb, 0.70231-0.70340 for ⁸⁷Sr/⁸⁶Sr, and +6.9 to +12.9 for initial epsilon Hf. These signatures are different from Atlantic MORB, the Madeira Archipelago and the Azores, but they lie in the field of worldwide OIB. The Cretaceous seamounts therefore seem to be generated by melts from a OIB-type source that interact with continental lithospheric mantle lying formerly beneath Iberia and presently within the ocean-continent transition zone. Inheritance in zircon and high ²⁰⁷Pb of initial Pb substantiate the presence of very minor amounts of continental material in the lithospheric mantle. A long-lived thermal anomaly is the most plausible explanation for alkaline magmatism since 104 Ma and it could well be that the same anomaly is still the driving force for tertiary and quaternary alkaline magmatism in the eastern North Atlantic region. This hypothesis is agreement with the plate-tectonic position of the region since Cretaceous time, including an about 30° anti-clockwise rotation of Iberia.     

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

Uranium-lead ratios (commonly represented as ²³⁸U/²⁰⁴Pb = μ) calculated for the sources of martian basalts preserve a record of petrogenetic processes that were active during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of μ values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range (²⁰⁶Pb/²⁰⁴Pb = 11.16-11.61). In contrast, the Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in ²⁰⁶Pb/²⁰⁴Pb-²⁰⁷Pb/²⁰⁴Pb-²⁰⁸Pb/²⁰⁴Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial Pb. This terrestrial Pb contamination generated a ²⁰⁶Pb-²⁰⁷Pb array in the QUE fractions that appears to represent an ancient age, which contrasts with a much younger crystallization age of 327 ± 10 Ma derived from Rb-Sr and Sm-Nd isochrons (Borg L. E., Nyquist L. E., Taylor L. A., Wiesmann H. and Shih C. -Y. (1997) Constraints on Martian differentiation processes from Rb-Sr and Sm-Nd isotopic analyses of the basaltic shergottite QUE 94201. Geochim. Cosmochim. Acta61, 4915-4931). Despite the contamination, and accepting 327 ± 10 Ma as the crystallization age, we use the U-Pb data to determine the initial ²⁰⁶Pb/²⁰⁴Pb of QUE 94201 to be 11.086 ± 0.008 and to calculate the μ value of its mantle source to be 1.82 ± 0.01. The μ value calculated for the QUE 94201 source is the lowest determined for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that μ values in martian source reservoirs vary by at least a factor of two. Additionally, the range of source μ values indicates that the μ value of bulk silicate Mars is approximately three. The amount of variation in the μ values of the mantle sources (μ ∼ 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate greater extents of U-Pb fractionation during formation of the mantle sources of martian basalts.     

The thermal history of the Acapulco meteorite and its parent body deduced from U/Pb systematics in mineral separates and bulk rock fragments

U/Pb systematics of the Acapulco meteorite have been determined on phosphate and feldspar separates and on grain size fractions of bulk material. The latter show an enrichment of U and Th with respect to CI chondrites and a low (∼1) Th/U ratio. This is consistent with the model that the majority of U and Th was added early by a low temperature melt to the Acapulco precursor. The feldspar exhibits a Pb isotope composition that is close to the primordial Pb composition. Mineral separates and bulk fractions define a ²⁰⁷Pb/²⁰⁶Pb isochron. The age corresponds to 4555.9 ± 0.6 Ma. This age anchors the thermal evolution of the Acapulco parent body into an absolute time scale. Evaluation of the Hf/W and U/Pb records with the cooling rates deduced from mineralogical investigations confirms the idea that the Acapulco parent body was fragmented during its cooling. The U/Pb system precisely dates this break-up at 4556 ± 1 Ma.     

Ar/Ar thermochronology of the fossil LL6-chondrite from the Morokweng crater, South Africa

Studies of meteorites are based mostly on samples that fell to Earth in the recent past (i.e., a few million years at most). The Morokweng LL-chondrite meteorite is a particularly interesting specimen as its fall is much older (ca. 145 Ma) than most other meteorites and because it is the only macro-meteorite clast (width intersected in drill core: 25 cm) found in a melt sheet of a large impact structure. When applied to the Morokweng meteorite, ⁴⁰Ar/³⁹Ar thermochronology provides an opportunity to study (1) effects associated with pre-impact and post-impact processes and (2) collision events within a potentially distinct and as yet unsampled asteroid population.A single multi-grain aliquot yielded an inverse isochron age of 625 ± 163 Ma. This suggests a major in-space collisional event at this time. We have modeled the diffusion of ⁴⁰Ar^∗ within the meteorite and plagioclase during and after the ∼145 Ma impact on Earth to tentatively explain why pre-terrestrial impact ⁴⁰Ar^∗ has been preserved within the plagioclase grains. The ∼145 Ma terrestrial impact age is recorded in the low-retentivity sites of the meteorite plagioclase grains that yielded a composite inverse isochron age at 141 ± 15 Ma and thus, confirms that age information about major (terrestrial or extraterrestrial) impacts can be recorded in the K-rich mineral phases of a meteorite and measured by the ⁴⁰Ar/³⁹Ar technique. More studies on fossil meteorites need to be carried out to understand if the rough 0.6 Ga age proposed here corresponds to major LL-chondrite asteroid population destructions or, rather, to an isolated collision event.     

Constraints on the petrogenesis of Martian meteorites from the Rb-Sr and Sm-Nd isotopic systematics of the lherzolitic shergottites ALH77005 and LEW88516

Detailed Rb-Sr and Sm-Nd isotopic analyses have been completed on the lherzolitic shergottites ALH77005 and LEW88516. ALH77005 yields a Rb-Sr age of 185 ± 11 Ma and a Sm-Nd age of 173 ± 6 Ma, whereas the Rb-Sr and Sm-Nd ages of LEW88516 are 183 ± 10 and 166 ± 16 Ma, respectively. The initial Sr isotopic composition of ALH77005 is 0.71026 ± 4, and the initial ε_Nd value is +11.1 ± 0.2. These values are distinct from those of LEW88516, which has an initial Sr isotopic composition of 0.71052 ± 4 and an initial ε_Nd value of +8.2 ± 0.6. Several of the mineral and whole rock leachates lie off the Rb-Sr and Sm-Nd isochrons, indicating that the isotopic systematics of the meteorites have been disturbed. The Sm-Nd isotopic compositions of the leachates appear to be mixtures of primary igneous phosphates and an alteration component with a low ¹⁴³Nd/¹⁴⁴Nd ratio that was probably added to the meteorites on Mars. Tie lines between leachate-residue pairs from LEW88516 mineral fractions and whole rocks have nearly identical slopes that correspond to Rb-Sr ages of 90 ± 1 Ma. This age may record a major shock event that fractionated Rb/Sr from lattice sites located on mineral grain boundaries. On the other hand, the leachates could contain secondary alteration products, and the parallel slopes of the tie lines could be coincidental.Nearly identical mineral modes, compositions, and ages suggest that these meteorites are very closely related. Nevertheless, their initial Sr and Nd isotopic compositions differ outside analytical uncertainty, requiring derivation from unique sources. Assimilation-fractional-crystallization models indicate that these two lherzolitic meteorites can only be related to a common parental magma, if the assimilant has a Sr/Nd ratio near 1 and a radiogenic Sr isotopic composition. Further constraints placed on the evolved component by the geochemical and isotopic systematics of the shergottite meteorite suite suggest that it (a) formed at ∼4.5 Ga, (b) has a high La/Yb ratio, (c) is an oxidant, and (d) is basaltic in composition or is strongly enriched in incompatible elements. The composition and isotopic systematics of the evolved component are unlike any evolved lunar or terrestrial igneous rocks. Its unusual geochemical and isotopic characteristics could reflect hydrous alteration of an evolved Martian crustal component or hydrous metasomatism within the Martian mantle.