Constraints on the U-Pb isotopic systematics of Mars inferred from a combined U-Pb, Rb-Sr, and Sm-Nd isotopic study of the Martian meteorite Zagami

Uranium-lead, Rb-Sr, and Sm-Nd isotopic analyses have been performed on the same whole-rock, mineral, and leachate fractions of the basaltic martian meteorite Zagami to better constrain the U-Pb isotopic systematics of martian materials. Although the Rb-Sr and Sm-Nd systems define concordant crystallization ages of 166 ± 6 Ma and 166 ± 12 Ma, respectively, the U-Pb isotopic system is disturbed. Nevertheless, an age of 156 ± 6 Ma is derived from the ²³⁸U-²⁰⁶Pb isotopic system from the purest mineral fractions (maskelynite and pyroxene). The concordance of these three ages suggest that the ²³⁸U-²⁰⁶Pb systematics of the purest Zagami mineral fractions have been minimally disturbed by alteration and impact processes, and can therefore be used to constrain the behavior of U and Pb in the Zagami source region. The μ value of the Zagami source region can be estimated, with some confidence from the ²³⁸U-²⁰⁶Pb isochron, to be 3.96 ± 0.02. Disturbance of the U-Pb isotopic systems means that this represents a minimum value. The μ value of the Zagami source is significantly lower than the μ values estimated for most basaltic magma sources from Earth and the Moon. This is surprising given the high initial ⁸⁷Sr/⁸⁶Sr ratio (0.721566 ± 82) and low initial ε_Nd value (−7.23 ± 0.17) determined for Zagami that indicate that this sample is derived from one of the most highly fractionated reservoirs from any known planetary body. This suggests that Mars is characterized by a low bulk planet U/Pb ratio, a feature that is consistent with its relatively volatile-rich nature.The leachates contain terrestrial common Pb that was probably added to the meteorite during handling, curation, or sawing. The mineral fractions, particularly those with significant amounts of impact melt glass, contain a second contaminant. The presence of this contaminant results in Pb-Pb ages that are older than the crystallization age of Zagami, indicating that the contaminant is characterized by a high ²⁰⁷Pb/²⁰⁶Pb ratio. Such a contaminant could be produced by removal of single-stage Pb from a relatively high μ martian reservoir before ∼1.8 Ga, and therefore could be an ancient manifestation of hydrous alteration of martian surface material.     

The age of Dar al Gani 476 and the differentiation history of the martian meteorites inferred from their radiogenic isotopic systematics

Samarium-neodymium isotopic analysis of the martian meteorite Dar al Gani 476 yields a crystallization age of 474 ± 11 Ma and an initial ε_Nd¹⁴³ value of +36.6 ± 0.8. Although the Rb-Sr isotopic system has been disturbed by terrestrial weathering, and therefore yields no age information, an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.701249 ± 33 has been estimated using the Rb-Sr isotopic composition of the maskelynite mineral fraction and the Sm-Nd age. The Sr and Nd isotopic systematics of Dar al Gani 476, like those of the basaltic shergottite QUE94201, are consistent with derivation from a source region that was strongly depleted in incompatible elements early in the history of the solar system. Nevertheless, Dar al Gani 476 is derived from a source region that has a slightly greater incompatible enrichment than the QUE94201 source region. This is not consistent with the fact that the parental magma of Dar al Gani 476 is significantly more mafic than the parental magma of QUE94201, and underscores a decoupling between the major element and trace element-isotopic systematics observed in the martian meteorite suite.Combining the ε_Nd¹⁴²-ε_Nd¹⁴³ isotopic systematics of the martian meteorites yields a model age for planetary differentiation of 4.513_+0.033^−0.027 Ga. Using this age, the parent/daughter ratios of martian mantle sources are calculated assuming a two-stage evolutionary history. The calculated sources have very large ranges of parent/daughter ratios (⁸⁷Rb/⁸⁶Sr = 0.037-0.374; ¹⁴⁷Sm/¹⁴⁴Nd = 0.182-0.285; ¹⁷⁶Lu/¹⁷⁷Hf = 0.028-0.048). These ranges exceed the ranges estimated for terrestrial basalt source regions, but are very similar to those estimated for the sources of lunar mare basalts. In fact, the range of parent/daughter ratios calculated for the martian meteorite sources can be produced by mixing between end-members with compositions similar to lunar mare basalt sources. Two of the sources have compositions that are similar to olivine and pyroxene-rich mafic cumulates with variable proportions of a Rb-enriched phase, such as amphibole, whereas the third source has the composition of liquid trapped in the cumulate pile (i.e. similar to KREEP) after ∼99% crystallization. Correlation between the proportion of trapped liquid in the meteorite source regions and estimates of f_O2, suggest that the KREEP-like component may be hydrous. The success of these models in reproducing the martian meteorite source compositions suggests that the variations in trace element and isotopic compositions observed in the martian meteorites primarily reflect melting of the crystallization products of an ancient magma ocean, and that assimilation of evolved crust by mantle derived magmas is not required. Furthermore, the decoupling of major element and trace element-isotopic systematics in the martian meteorite suite may reflect the fact that trace element and isotopic systematics are inherited from the magma source regions, whereas the major element abundances are limited by eutectic melting processes at the time of magma formation. Differences in major element abundances of parental magma, therefore, result primarily from fractional crystallization after leaving their source regions.     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

A combined Sm-Nd, Rb-Sr, and U-Pb isotopic study of Mg-suite norite 78238: Further evidence for early differentiation of the Moon

Lunar Mg-suite norite 78238 was dated using the Sm-Nd, Rb-Sr, and U-Pb isotopic systems in order to constrain the age of lunar magma ocean solidification and the beginning of Mg-suite magmatism, as well as to provide a direct comparison between the three isotopic systems. The Sm-Nd isotopic system yields a crystallization age for 78238 of 4334 ± 37 Ma and an initial value of −0.27 ± 0.74. The age-initial (T-I) systematics of a variety of KREEP-rich samples, including 78238 and other Mg-suite rocks, KREEP basalts, and olivine cumulate NWA 773, suggest that lunar differentiation was completed by 4492 ± 61 Ma assuming a Chondritic Uniform Reservoir bulk composition for the Moon. The Rb-Sr isotopic systematics of 78238 were disturbed by post-crystallization processes. Nevertheless, selected data points yield two Rb-Sr isochrons. One is concordant with the Sm-Nd crystallization age, 4366 ± 53 Ma. The other is 4003 ± 95 Ma and is concordant with an Ar-Ar age for 78236. The ²⁰⁷Pb-²⁰⁶Pb age of 4333 ± 59 Ma is concordant with the Sm-Nd age. The U-Pb isotopic systematics of 78238 yield linear arrays equivalent to younger ages than the Pb-Pb system, and may reflect fractionation of U and Pb during sample handling. Despite the disturbed nature of the U-Pb systems, a time-averaged μ (²³⁸U/²⁰⁴Pb) value of the source can be estimated at 27 ± 30 from the Pb-Pb isotopic systematics. Because KREEP-rich samples are likely to be derived from source regions with the highest U/Pb ratios, the relatively low μ value calculated for the 78238 source suggests the bulk Moon does not have an exceedingly high μ value.     

U-Pb ages of angrites

Precise U-Pb ages, determined with double spike (²⁰²Pb-²⁰⁵Pb) thermal ionization m1ass spectrometry, are reported for angrites Angra dos Reis (AdoR), Lewis Cliff 86010 (LEW), and D’Orbigny. Nineteen of 23 acid-washed pyroxene fractions from these meteorites and whole rock fractions from D’Orbigny contain between 0.5 and 1.3 pg of total common Pb, indistinguishable from analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios in these fractions are between 6300 and 14,100 for AdoR, 1160-4500 for LEW, and 608-8500 for D’Orbigny. Blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios for all three meteorites vary from 2160 to over 100,000. These fractions yielded precise and reproducible ²⁰⁷Pb^∗/²⁰⁶Pb^∗ dates with the average values of 4557.65 ± 0.13 Ma for AdoR, 4558.55 ± 0.15 Ma for LEW, and 4564.42 ± 0.12 Ma for D’Orbigny. Pb-Pb isochrons including data with slightly elevated common Pb, and U-Pb upper concordia intercepts, yield similar dates. The implications of these new Pb-isotopic ages of angrites are threefold. First, they demonstrate that AdoR and LEW are not coeval, and the group of “slowly cooled” angrites is therefore genetically diverse. Second, the new age of LEW suggests an upward revision of ⁵³Mn-⁵³Cr “absolute” ages by 0.7 Ma. Third, a precise age of D’Orbigny allows consistent linking of the ⁵³Mn-⁵³Cr and ²⁶Al-²⁶Mg extinct nuclide chronometers to the absolute lime scale.     

Large thallium isotopic variations in iron meteorites and evidence for lead-205 in the early solar system

Lead-205 decays to ²⁰⁵Tl with a half-life of 15 Myr and should have been present in the early solar system according to astrophysical models. However, despite numerous attempts, Tl isotopic measurements of meteorites have been unable to demonstrate convincingly its former presence. Here, we report large (∼5‰) variations in Tl isotope composition in metal and troilite fragments from a range of iron meteorites that were determined at high precision using multiple collector inductively coupled plasma mass spectrometry. The Tl isotopic compositions of seven metal samples of the IAB iron meteorites Toluca and Canyon Diablo define a correlation with ²⁰⁴Pb/²⁰³Tl. When interpreted as an isochron, this corresponds to an initial ²⁰⁵Pb/²⁰⁴Pb ratio of (7.4 ± 1.0) × 10⁻⁵. Alternative explanations for the correlation, such as mixing of variably mass-fractionated meteorite components or terrestrial contamination are harder to reconcile with independent constraints. However, troilite nodules from Toluca and Canyon Diablo contain Tl that is significantly less radiogenic than co-existing metal with isotope compositions that are variable and decoupled from ²⁰⁴Pb/²⁰³Tl. These effects are similar to those recently reported by others for Fe and Ni isotopes in iron meteorite sulfides and appear to be the result of kinetic stable isotope fractionation during diffusion. Though it cannot conclusively be shown that the metal fragments are unaffected by the secondary processes that disturbed the troilites, mass balance modeling indicates that the alteration of the troilites is unlikely to have significantly affected the Tl isotope compositions of the co-existing metals. It is therefore reasonable to conclude that the IAB metal isochron is a product of the in situ decay of ²⁰⁵Pb. If the I-Xe ages of IAB silicate inclusions record the same event as the ²⁰⁵Pb-²⁰⁵Tl chronometer then crystallization of the IAB metal was probably completed between 10 and 20 Myr after the condensation of the first solids. This implies an initial solar system ²⁰⁵Pb/²⁰⁴Pb of (1.0-2.1) × 10⁻⁴, which is in excellent agreement with recently published astrophysical predictions. Similar calculations yield an initial solar system Tl isotope composition of ε²⁰⁵Tl = −2.8 ± 1.7. The Tl isotopic composition and concentration of the silicate Earth depends critically on the timing and mechanism of core formation and Earth’s volatile element depletion history. Modeling of the Earth’s accretion and core formation using the calculated initial solar system Tl isotope composition and ²⁰⁵Pb/²⁰⁴Pb, however, does not yield reasonable results for the silicate Earth unless either the Earth lost Tl and Pb late in its accretion history or the core contains much higher concentrations of Pb and Tl than are found in iron meteorites.     

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.     

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.     

Mechanisms for incompatible-element enrichment on the Moon deduced from the lunar basaltic meteorite Northwest Africa 032

The lunar meteorite Northwest Africa (NWA) 032 is a low-Ti basalt that has incompatible-element abundances and Th/Sm ratios characteristic of the involvement of late stage magma ocean crystallization products (urKREEP) in its petrogenesis. This sample is very fine-grained and contains terrestrial weather products. A progressive leaching procedure was therefore developed and applied to magnetic separates and whole rock fractions to obtain Rb-Sr and Sm-Nd ages. Although many of the leachates, as well as the unleached mineral and whole rock fractions contain terrestrial alteration products, selected residue fractions yield concordant Rb-Sr and Sm-Nd ages. Rubidium-Sr isotopic analyses yield an age of 2947 ± 16 Ma with an initial ⁸⁷Sr/⁸⁶Sr of 0.700057 ± 17. These characteristics indicate NWA 032 is derived from a source region with an ⁸⁷Rb/⁸⁶Sr ratio of 0.044 ± 0.001. This value is higher than all but those determined for KREEP basalts, and suggests that NWA 032 is derived from a source region that has higher incompatible-element abundances than other low-Ti basalts. Samarium-neodymium isotopic analysis yield a concordant age of 2931 ± 92 Ma and an initial ε_Nd of +9.71 ± 0.74 corresponding to a source region with ¹⁴⁷Sm/¹⁴⁴Nd ratio of 0.246 ± 0.004. The initial Nd isotopic composition stands in contrast to the initial Sr isotopic composition by requiring NWA 032 to be derived from a source with lower incompatible-element abundances than most low-Ti basalts. The source of NWA 032 is therefore unlike those of other lunar basalts.Modeling of magma ocean cumulate formation demonstrates that unlike other low-Ti basalt source regions the NWA 032 source is a mixture of olivine, pigeonite, and clinopyroxene bearing cumulates and only a small amount of urKREEP. Furthermore, unlike other mare basalt sources, the NWA 032 source does not contain appreciable quantities of plagioclase. Partial melting models demonstrate that the incompatible-element characteristics of the NWA 032 result from formation by smaller degrees of partial melting than other mare basalts. Thus, the incompatible-element geochemical signature that is observed in NWA 032 appears to reflect the combined effects of generation from an unusual plagioclase-free incompatible-element-depleted source region by very small degrees of partial melting. This study demonstrates that both the presence of urKREEP in the source region and small degrees of partial melting generate magmas with similar, but not identical, incompatible-element characteristics. In addition, it underscores the fact that there is significantly more geochemical diversity on the Moon than is represented by samples collected by the American and Soviet lunar missions.     

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.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).     

Genesis of basalt-hosted massive sulphide deposits from the Trondheim and Sulitjelma districts,Norway: ore lead isotopic considerations

Lead isotopic ratios of bulk sulphides from eleven stratigraphically equivalent deposits from the Köli Nappe sequence in the Trondheim district, and eleven from the Köli sequence at Sulitjelma Norway, have been determined. When plotted on ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagrams, the data define a linear trend extending from the mantle to the upper crustal model growth curves of Doe and Zartman (1979). Moreover, the data from both districts lie on the same trend. This isotopic trend is interpreted as resulting from the mixing of lead from a mantle source (probably the host basalts) with that of an upper-crustal end member (either sialic basement or the terrigenous sediments surrounding the host basalts). It is also concluded that the deposits in both camps formed more or less contemporaneously. The isotopic mixing line is comparable with that obtained from Besshi ore pyrites in Japan, for which an aulacogenic depositional environment, similar to that found today in the Gulf of California, has been proposed (Fox 1984). It is concluded that a similar depositional environment was responsible for the Trondheim and Sulitjelma ores, although an ensialic back-arc basin, or other possible environments, cannot be entirely ruled out.     

Origin of lead in the Gulf of California Ecoregion using stable isotope analysis

The magnitude and sources of lead (Pb) pollution in the Gulf of California Ecoregion (GCE) in northwest Mexico were evaluated using various samples collected from urban and rural areas around two typical subtropical coastal ecosystems. Lead concentrations and isotopic compositions (²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb, ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb) were measured using high resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS) and thermal ionization mass spectrometry (TIMS). Urban street dust (157 ± 10.1 μg g^− 1) was heavily enriched with Pb, compared to the Pb enrichment of agricultural soils (29.0 ± 16.0 μg g^− 1) and surface estuary sediments (35.6 ± 15.4 μg g^− 1), all of which contained higher Pb concentrations than found in the natural bedrock (16.0 ± 5.0 μg g^− 1). Pb concentrations in SPM (> 95% of total Pb) were significantly higher in sewage effluent (132 ± 49.9 μg g^− 1) than in agricultural effluents (29.3 ± 5.9 μg g^− 1), and river runoff (7.3 ± 4.2 μg g^− 1). SPM in estuary water column averaged 68.3 ± 48.0 μg g⁻¹. The isotopic composition of Pb (²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb) in rural samples of aerosols (1.181 ± 0.001, 2.444 ± 0.003) and soil runoff (1.181 ± 0.003, 2.441 ± 0.004) was comparable to that of natural Pb-bearing bedrock (1.188 ± 0.005, 2.455 ± 0.008); while urban samples of aerosols, street dust, and sewage (1.190–1.207, 2.452–2.467) showed a significant contribution from automotive emissions from past leaded gasoline combustion (1.201 ± 0.006, 2.475 ± 0.005). The absence of lead from fertilizer (1.387 ± 0.008, 2.892 ± 0.005) suggests that this mixture is not representative of the GCE. A mixing model revealed that the Pb content in the environmental samples is predominantly derived from natural weathering and the past leaded gasoline combustion with the later influence of inputs from a more radiogenic source related with anthropogenic lead of North American origin (1.21 ± 0.02; 2.455 ± 0.02).     

Concentration, isotopic composition, and sources of lead in Southern Ocean air during 1999/2000, measured at the Cape Grim Baseline Air Pollution Station, Tasmania

Southern Ocean aerosols were collected at the Cape Grim Baseline Air Pollution Station from onshore air under baseline conditions between February 1999 and April 2000. Thermal ionization techniques (TIMS) and isotope dilution mass spectrometry (IDMS) were used to measure the isotopic composition and concentration of lead in the air giving concentrations as low as 0.6 ± 0.1 pg · m⁻³. Air collected under baseline conditions for 12 months (May 1999-April 2000) yielded an overall lead concentration of 11.0 ± 0.2 pg · m⁻³ and isotopic composition of ²⁰⁶Pb/²⁰⁷Pb = 1.154, ²⁰⁸Pb/²⁰⁷Pb = 2.387 and ²⁰⁶Pb/²⁰⁴Pb = 17.93. The range in isotopic ratios was consistent with the mixing of lead from major population centers in the Southern Hemisphere in the mid to high latitudes, except for the presence of highly radiogenic lead in some samples. Contributions from radiogenic lead of up to ∼0.8% were observed. Three periods with the highest percentage contribution of radiogenic lead (>0.5%) were investigated in more detail, and 4-d back-trajectories and radon concentrations were used to help identify the sources. The sources are probably associated with the mining and processing of uranium rich ores in southern Africa and possibly South Australia.     

K-Ar ages and Pb,Sr isotopic characteristics of Cenozoic volcanic rocks in Shandong Province,China

28 samples of Cenozoic volcanic rocks collected from Shandong Province have been dated by K-Ar method. They are mainly Neogene with an age range of 4–19 m. y. The basalts from Linqu and Yishui in west Shandong Province are Miocene and those from Penglai and Qixia in east Shandong Province are Miocene and Pliocene in age. The basalts from Wudi in north Shandong Province are Middle-Early Pleistocene in age. In each area the duration of volcanic eruption was estimated at about 2–3 m. y. Pb and Sr isotopic compositions and U, Th, Pb, Rb, Sr, and major elements in most of the samples were determined. The isotopic compositions are:²⁰⁶Pb/²⁰⁴Pb—16.92-18.48,²⁰⁷Pb/²⁰⁴Pb—15.30-15.59,²⁰⁸Pb/²⁰⁴Pb—37.83-38.54, and (⁸⁷Sr/⁸⁶Sr)_i—0.70327-0.70632. There are some positive or negative linear correlations between²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb, Pb isotopes and Pb content, Pb isotopes and Sr isotopes, and Sr isotopes and other elements. The basaltic rocks from east and west Shandong Province have somewhat differences in isotopic composition and element content. The basalts probably are products of multi-stage evolution of the mantle. They have preserved the primary features of the source, although they were influenced, to some extent, by the contamination of crustal materials.     

Signatures of the source for the Emeishan flood basalts in the Ertan area： Pb isotope evidence

The Emeishan flood basalts can be divided into high-Ti (HT) basalt (Ti/Y>500) and low-Ti (LT) basalt (Ti/Y<500). Sr, Nd isotopic characteristics of the lavas indicate that the LT- and the HT-type magmas originated from distinct mantle sources and parental magmas. The LT-type magma was derived from a shallower lithospheric mantle, whereas the HT-type magma was derived from a deeper mantle source that may be possibly a mantle plume. However, few studies on the Emeishan flood basalts involved their Pb isotopes, especially the Ertan basalts. In this paper, the authors investigated basalt samples from the Ertan area in terms of Pb isotopes, in order to constrain the source of the Emeishan flood basalts. The ratios of 206Pb/204Pb (18.31–18.41), 207Pb/204Pb (15.55–15.56) and 208Pb/204Pb (38.81–38.94) are significantly higher than those of the depleted mantle, just lying between EM I and EM II. This indicates that the Emeishan HT basalts (in the Ertan area) are the result of mixing of EMI end-member and EMII end-member.     

The isotopic evolution of atmospheric Pb in central Ontario since AD 1800, and its impacts on the soils, waters, and sediments of a forested watershed, Kawagama Lake

A peat core from an ombrotrophic bog documents the isotopic evolution of atmospheric Pb in central Ontario since AD 1804 ± 53 (²¹⁰Pb dating). Despite the introduction of unleaded gasoline in the mid-1970’s, the ratio ²⁰⁶Pb/²⁰⁷Pb in atmospheric deposition has not increased as expected, but rather continues to decline. In fact, snowpack sampling (2005 and 2009) and rainwater samples (2008) show that the isotopic composition of atmospheric Pb today is often far less radiogenic than the gasoline lead that had been used in Canada in the past. The peat, snow, and rainwater data presented here are consistent with the Pb isotope data for aerosols collected in Dorset in 1984 and 1986 which were traced by Sturges and Barrie (1989) to emissions from the Noranda smelter in northern Quèbec, Canada’s largest single source of atmospheric Pb. Understanding atmospheric Pb deposition in central Ontario, therefore, requires not only consideration of natural sources and past contributions from leaded gasoline, but also emissions from metal smelting and refining.Lead in the streams which enter Kawagama Lake today (²⁰⁶Pb/²⁰⁷Pb = 1.16 − 1.19) represents a mixture between the natural values (1.191 − 1.201 estimated using pre-industrial lake sediments) and the values found in the humus layer of the surrounding forest soils (²⁰⁶Pb/²⁰⁷Pb = 1.15 − 1.19). In the lake itself, however, Pb is much less radiogenic (²⁰⁶Pb/²⁰⁷Pb as low as 1.09) than in the streams, with the dissolved fraction less radiogenic than particulate material. The evolution of Pb isotope ratios within the watershed apparently reflects preferential removal by sedimentation of comparatively dense, radiogenic, terrestrial particles (derived from the mineral fraction of soils) from the humus particles with lower ratios of ²⁰⁶Pb/²⁰⁷Pb (because of atmospheric Pb contamination). Despite the contemporary enrichments of Pb in rain and snow, concentrations of dissolved Pb in the lake are extremely low (sometimes below 10 ng/l), with Pb concentrations and Pb/Sc ratios approaching “natural” values because of efficient binding to particles, and their subsequent removal in the watershed.     

Shallow impact: Isotopic insights into crustal contributions to the Sudbury impact melt sheet

The largest known terrestrial impact melt sheet occurs within the 1850 Ma Sudbury Structure, Ontario. In order to evaluate the relative contributions of different target lithologies to the melt sheet, we have investigated the Pb isotope compositions of feldspar separates from early-formed quartz diorite magmas within Offset Dykes from around the impact structure. The samples define a linear array on plots of age-corrected ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb. Samples from Offset Dykes hosted by the Huronian Supergroup (South Range) have a range of ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ from 15.424 to 17.255 and ²⁰⁷Pb/²⁰⁴Pb₁₈₅₀ from 15.390 to 15.801, whilst those hosted by Archean gneisses of the Superior Province (North Range) cluster around ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ ≈ 14.8 and ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ ≈ 15.1. These values can be approximated by binary mixing between the two major groups of target lithologies. A mix of 60-70% of Superior Province gneisses with 30-40% of Huronian metasedimentary material closely matches the Pb isotope compositions of North Range Offset Dyke samples, whereas in the South Range the required Huronian component is up to ca. 80%.These mixing proportions are consistent with Sr, Nd and Os isotope and trace element constraints. A third minor component, either locally-exposed Paleoproterozoic mafic rocks or the lower crust is also required. However, the isotopic, trace element and Ni-Cu-platinum group element characteristics of the melt sheet can be accommodated without the involvement of an average lower crustal or meteoritic component.A major contribution of Huronian supracrustal material, which had a pre-impact thickness of up to 12 km, is required to explain the chemical characteristics of the impact melts, which also have a strong upper crustal affinity (e.g. Eu/Sm = 0.22, Rb/Sr = 0.2-0.35). As such, a shallower level of melting is apparent than that predicted by many previous impact models for the Sudbury event. This can be accommodated by considering approach trajectories for the impactor oblique to the Earth’s surface. In addition, the isotopic and trace element variability identified indicates that the melt sheet was heterogeneous at an early stage, and may not have been completely homogenised during crater formation. Our findings have significant implications for the nature of the Sudbury impact event, the evolution of the melt sheet and the crustal sources of metals contained in Sudbury’s world class Ni-Cu-PGE sulphide ores.     

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.     

Sr,Nd and Pb Isotopic Systematics of the Cenozoic Basalts of the Korean Peninsula and Their Implications for the Permo-Triassic Continental Collision Boundary

Sr, Nd and Pb isotopic compositions of the Cenozoic basalts were analyzed from Baengnyeongdo Island, Jeongok, Ganseong, and Jejudo Island of Korea. They reveal relatively enriched Sr and Nd isotopic compositions (⁸⁷Sr/⁸⁶Sr = 0.70330∼0.70555, ¹⁴³Nd/¹⁴⁴Nd = 0.51298∼0.51256) compared with MORB.²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of all the analyzed Korean basalts lie above the Northern Hemisphere Reference Line (NHRL) defined by Hart (1984). Pb isotopic compositions of basalts from Jejudo Islands (²⁰⁶Pb/²⁰⁴Pb = 18.61∼19.12, ²⁰⁷Pb/²⁰⁴Pb = 15.54∼15.69, ²⁰⁸Pb/²⁰⁴Pb = 38.98∼39.72) are significantly more radiogenic than the rest (²⁰⁶Pb/²⁰⁴Pb = 17.72∼18.03, ²⁰⁷Pb/²⁰⁴Pb = 15.44∼15.58, ²⁰⁸Pb/²⁰⁴Pb = 37.77∼38.64). The Cenozoic Korean basalts thus can be divided into two groups based on their Sr, Nd and Pb isotopic compositions. The north group reveals mixing between DMM and EM1 while the south group displays DMM-EM2 mixing. Such a distribution is the same as Chinese Cenozoic basalts and it can be interpreted that the subcontinental lithospheric mantle under Korea represents simple lateral continuation of the South and North China Blocks. We suggest that Korean continental collision zone cross the Korean Peninsula through the region between the north and south basalt groups of Korea.