The age of the martian meteorite Northwest Africa 1195 and the differentiation history of the shergottites

Samarium-neodymium isotopic analyses of unleached and acid-leached mineral fractions from the recently identified olivine-bearing shergottite Northwest Africa 1195 yield a crystallization age of 347 ± 13 Ma and an value of +40.1 ± 0.9. Maskelynite fractions do not lie on the Sm-Nd isochron and appear to contain a martian surface component with low ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios that was added during shock. The Rb-Sr system is disturbed and does not yield an isochron. Terrestrial Sr appears to have affected all of the mineral fractions, although a maximum initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7016 is estimated by passing a 347 Ma reference line through the maskelynite fraction that is least affected by contamination. The high initial value and the low initial ⁸⁷Sr/⁸⁶Sr ratio, combined with the geologically young crystallization age, indicate that Northwest Africa 1195 is derived from a source region characterized by a long-term incompatible-element depletion.The age and initial Sr and Nd isotopic compositions of Northwest Africa 1195 are very similar to those of Queen Alexandra Range 94201, indicating these samples were derived from source regions with similar Sr-Nd isotopic systematics. These similarities suggest that these two meteorites share a close petrogenetic relationship and might have been erupted from a common volcano. The meteorites Yamato 980459, Dar al Gani 476, Sayh al Uhaymir 005/008, and Dhofar 019 also have relatively old ages between 474 and 575 Ma and trace element and/or isotopic systematics that are indicative of derivation from incompatible-element-depleted sources. This suggests that the oldest group of meteorites is more closely related to one another than they are to the younger meteorites that are derived from less incompatible-element-depleted sources. Closed-system fractional crystallization of this suite of meteorites is modeled with the MELTS algorithm using the bulk composition of Yamato 980459 as a parent. These models reproduce many of the major element and mineralogical variations observed in the suite. In addition, the rare earth element systematics of these meteorites are reproduced by fractional crystallization using the proportions of phases and extents of crystallization that are calculated by MELTS. Other shergottites that demonstrate enrichments in incompatible-elements and have evolved Sr and Nd isotopic systematics have some geochemical systematics that are similar to those observed in the depleted group. Most notably, although they exhibit a very limited range of incompatible trace element and isotopic compositions, they have highly variable major element compositions. This is also consistent with evolution from a common mantle source region by variable amounts of fractional crystallization. If this scenario is correct, it suggests that the combined effects of source composition and fractional crystallization are likely to account for the major element, trace element, and isotopic diversity of all shergottites.     

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.     

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.     

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.     

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.     

A Rb-Sr and Sm-Nd isotope geochronology and trace element study of lunar meteorite LaPaz Icefield 02205

Rubidium-strontium and samarium-neodymium isotopes of lunar meteorite LaPaz Icefield (LAP) 02205 are consistent with derivation of the parent magma from a source region similar to that which produced the Apollo 12 low-Ti olivine basalts followed by mixing of the magma with small amounts (1-2 wt%) of trace element-enriched material similar to lunar KREEP-rich sample SaU 169. The crystallization age of LAP 02205 is most precisely dated by an internal Rb-Sr isochron of 2991 ± 14 Ma, with an initial ⁸⁷Sr/⁸⁸Sr at the time of crystallization of 0.699836 ± 0.000010. Leachable REE-rich phosphate phases of LAP 02205 do not plot on a Sm-Nd mineral isochron, indicating contamination or open system behavior of the phosphates. Excluding anomalous phases from the calculation of a Sm-Nd isochron yields a crystallization age of 2992 ± 85 (initial ε¹⁴³Nd = +2.9 ± 0.8) that is within error of the Rb-Sr age, and in agreement with other independent age determinations for LAP 02205 from Ar-Ar and U-Pb methods. The calculated ¹⁴⁷Sm/¹⁴⁴Nd source ratios for LAP 02205, various Apollo 12 and 15 basalts, and samples with strong affinities to KREEP (SaU 169, NWA 773, 15386) are uncorrelated with their crystallization ages. This finding does not support the involvement of a common KREEP component as a heat source for lunar melting events that occurred after crystallization of the lunar magma ocean.     

Age and origin of anorthosites,charnockites, and granulites in the Central Virginia Blue Ridge: Nd and Sr isotopic evidence

Rb-Sr isotopic data for anorthosites, charnockites, ferrodioritic to quartz monzonitic plutons, and high-grade gneisses of the Blue Ridge of central Virginia show evidence of post-emplacement metamorphism, but in some cases retain Grenville ages. The Pedlar River Charnockite Suite yields an isochron age of 1021 +/-36 Ma, (initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7047 +/-6), which agrees with published U-Pb zircon ages. Five samples of that unit which contain Paleozoic mylonitic fabrics define a regression line of 683 Ma, interpreted as a mixing line with no age significance. Samples of the Roseland Anorthosite Complex show excessive scatter on a Rb-Sr evolution diagram probably due to Paleozoic (475 m.y.) metamorphism. Data from the ferrodioritic to quartz monzonitic plutons of the area yield an age of 1009 +/-26 Ma (inital ratio=0.7058 +/-4), which is in the range of the U-Pb zircon ages of 1000–1100 Ma. The Stage Road Layered Gneiss yields an age of 1147 +/-34 Ma (initial ratio of 0.7047 +/- 5).Sm-Nd data for the Pedlar River Charnockite Suite reflect a pre-Grenville age of 1489 +/-118 Ma ( _Nd=+6.7 +/-1.2). Data for the Roseland Anorthosite Complex and the ferrodioritic to quartz monzonitic plutons yield Grenville isochron ages of 1045 +/44 Ma ( _Nd=+1.0 +/-0.3) and 1027 +/-101 Ma ( _Nd=+1.4 +/-1.0), respectively. Two Roseland Anorthosite samples plot far above the isochron, demonstrating the effects of post-emplacement disturbance of Sm-Nd systematics, while mylonitized Pedlar River Charnockite Suite samples show no evidence of Sm-Nd redistribution.The disparity of the Sm-Nd age and other isotopic ages for the Pedlar River Charnockite Suite probably reflects a Sm-Nd source age, suggesting the presence of an older crust within this portion of the ca. 1 Ga old basement.     

Evidence for shock heating and constraints on Martian surface temperatures revealed by Ar/Ar thermochronometry of Martian meteorites

The thermal histories of Martian meteorite are important for the interpretation of petrologic, geochemical, geochronological, and paleomagnetic constraints that they provide on the evolution of Mars. In this paper, we quantify ⁴⁰Ar/³⁹Ar ages and Ar diffusion kinetics of Martian meteorites Allan Hills (ALH) 84001, Nakhla, and Miller Range (MIL) 03346. We constrain the thermal history of each meteorite and discuss the resulting implications for their petrology, paleomagnetism, and geochronology. Maskelynite in ALH 84001 yields a ⁴⁰Ar/³⁹Ar isochron age of 4163 ± 35 Ma, which is indistinguishable from recent Pb-Pb (Bouvier et al., 2009a) and Lu-Hf ages (Lapen et al., 2010). The high precision of this result arises from clear resolution of a reproducible trapped ⁴⁰Ar/³⁶Ar component in maskelynite in ALH 84001 (⁴⁰Ar/³⁶Ar = 632 ± 90). The maskelynite ⁴⁰Ar/³⁹Ar age predates the Late Heavy Bombardment and likely represents the time at which the original natural remanent magnetization (NRM) component observed in ALH 84001 was acquired. Nakhla and MIL 03346 yield ⁴⁰Ar/³⁹Ar isochron ages of 1332 ± 24 and 1339 ± 8 Ma, respectively, which we interpret to date crystallization. Multi-phase, multi-domain diffusion models constrained by the observed Ar diffusion kinetics and ⁴⁰Ar/³⁹Ar age spectra suggest that localized regions within both ALH 84001 and Nakhla were intensely heated for brief durations during shock events at 1158 ± 110 and 913 ± 9 Ma, respectively. These ages may date the marginal melting of pyroxene in each rock, mobilization of carbonates and maskelynite in ALH 84001, and NRM overprints observed in ALH 84001. The inferred peak temperatures of the shock heating events (>1400 °C) are sufficient to mobilize Ar, Sr, and Pb in constituent minerals, which may explain some of the dispersion observed in ⁴⁰Ar/³⁹Ar, Rb-Sr, and U-Th-Pb data toward ages younger than ∼4.1 Ga. The data also place conservative upper bounds on the long-duration residence temperatures of the ALH 84001 and Nakhla protolith to be  °C and  °C over the last ∼4.16 Ga and ∼1.35 Ga, respectively. MIL 03346 has apparently not experienced significant shock-heating since it crystallized, consistent with the fact that various chronometers yield concordant ages.     

U-Pb garnet chronometry in high-grade rocks—case studies from the central Damara orogen (Namibia) and implications for the interpretation of Sm-Nd garnet ages and the role of high U-Th inclusions

Garnets from different migmatites and granites from the Damara orogen (Namibia) were dated with the U-Pb technique after bulk dissolution of the material. Measured ²⁰⁶Pb/²⁰⁴Pb ratios are highly variable and range from ca. 21 to 613. Variations in isotope (²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb) and trace element (Th/U, U/Nd, Sm/Nd) ratios of the different garnets show that some garnets contain significant amounts of monazite and zircon inclusions. Due to their very low ²⁰⁶Pb/²⁰⁴Pb ratios, garnets from pelitic migmatites from the Khan area yield Pb-Pb ages with large errors precluding a detailed evaluation. However, the ²⁰⁷Pb/²⁰⁶Pb ages (ca. 550–500 Ma) appear to be similar to or older than U-Pb monazite ages (530±1–517±1 Ma) and Sm-Nd garnet ages (523±4–512±3 Ma) from the same sample. It is reasonable to assume that the Pb-Pb garnet ages define growth ages because previous studies are consistent with a higher closure temperature for the U-Pb system in garnet relative to the U-Pb system in monazite and the Sm-Nd system in garnet. For igneous migmatites from Oetmoed, Pb-Pb garnet ages (483±15–492±16 Ma) and one Sm-Nd garnet whole rock age (487±8 Ma) are similar whereas the monazite from the same sample is ca. 30–40 Ma older (528±1 Ma). These monazite ages are, however, similar to monazite ages from nearby unmigmatized granite samples and constrain precisely the intrusion of the precursor granite in this area. Although there is a notable difference in closure temperature for the U-Pb and Sm-Nd system in garnet, the similarity of both ages indicate that both garnet ages record garnet growth in a migmatitic environment. Restitic garnet from an unmigmatized granite from Omaruru yields similar U-Pb (493±30–506±30 Ma) and Sm-Nd (493±6–488±7 Ma) garnet ages whereas the monazite from this rock is ca. 15–25 Ma older (516±1–514±1 Ma). Whereas the monazite ages define probably the peak of regional metamorphism in the source of the granite, the garnet ages may indicate the time of melt extraction. For igneous garnets from granites at Oetmoed, the similarity between Pb-Pb (483±34–474±17 Ma) and Sm-Nd (492±5–484±13 Ma) garnet ages is consistent with fast cooling rates of granitic dykes in the lower crust. Differences between garnet and monazite U-Pb ages can be explained by different reactions that produced these minerals at different times and by the empirical observation that monazite seems resistant to later thermal re-equilibration in the temperature range between 750 and 900 °C (e.g. Braun et al. 1998). For garnet analyses that have low ²⁰⁶Pb/²⁰⁴Pb ratios, the influence of high- inclusions is small. However, the relatively large errors preclude a detailed evaluation of the relationship between the different chronometers. For garnet with higher ²⁰⁶Pb/²⁰⁴Pb ratios, the overall similarity between the Pb-Pb and Sm-Nd garnet ages implies that the inclusions are not significantly older than the garnet and therefore do not induce a premetamorphic Pb signature upon the garnet. The results presented here show that garnet with low ²³⁸U/²⁰⁴Pb ratios together with Sm-Nd garnet data and U-Pb monazite ages from the same rock can be used to extract geologically meaningful ages that can help to better understand tectonometamorphic processes in high-grade terranes.Editorial responsibility: J. Hoefs     

The problem of inherited Ar* in dating impact glass by the Ar/Ar method: Evidence from the Tswaing impact crater (South Africa)

The Tswaing meteorite impact crater is a 1.13 km diameter structure located in the 2.05 Ga Nebo granite of the Bushveld Complex. The impact age had previously been determined by fission track dating to 220 ± 104 ka. ⁴⁰Ar/³⁹Ar step-heating and total fusion experiments performed on single- and multi-grain impact glass aliquots gave apparent ages ranging from 1.0 ± 0.3 Ma to 204 ± 6 Ma. These “ages” indicate that the radiogenic Ar derived from the target rocks has not been completely degassed as a result of the impact process, despite fusion of the target material. Results of step-heating experiments imply that the trapped within the glass is located in two distinct reservoirs thought to be the glass matrix and fluid/vapor inclusions (or un-melted residual clasts). Calculations assuming an age of 0.2 ± 0.1 Ma for Tswaing (fission track data) reveal that the amount of inherited ⁴⁰Ar*() relative to the pre-impact concentration varies from 0.015% to 4.15%. The spread defined by likely reflects the various quench rates experienced by the glass, most certainly due to the pre-impact position of the sample relative to the center of the crater. We compare the influence of on the apparent ⁴⁰Ar/³⁹Ar age determination of five impact structures. Our calculations show that the main characteristic controlling the age offset (for a given proportion of ) is the age difference between the impact and the target rocks (i.e., the ⁴⁰Ar* concentration in the target rock). The buffer effect for a given crater structure can be predicted knowing the age of the basement and having a rough estimation of the age of the crater structure itself. The occurrence of is likely influenced by (1) the degree of polymerization (i.e., silicate structure complexity) of the target rock and presumably related to the diffusivity of Ar in the melt and glass, (2) the Ar partial pressure at the grain boundary, (3) the quantity of energy involved in the impact, and (4) the porosity of the target rocks. For glass that inevitably suffers inherited and/or excess ⁴⁰Ar*, the use of the inverse isochron technique can be appropriate but should be applied with careful statistical treatment.     

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.     

Sm−Nd and Pb isotopic study of mafic rocks associated with early Proterozoic continental rifting: the Peröpohja schist belt in northern Finland

The Peräpohja schist belt in northern Finland rests unconformably on Archaean granitoids, and marks the early stages of Proterozoic crustal evolution in the Fennoscandian (Baltic) shield. 2440 Ma old layered mafic intrusions predate the supracrustal , and ca. 2200 Ma old sills of the gabbro-wehrlite association intrude the lowest quartzites and volcanics (Runkaus) of the sequence. The Sm-Nd mineral isochron of the Penikat layered intrusion gives an age of 2410±64 Ma. The initial _Nd-values of the Penikat intrusion (_Nd(2440) = –1.6) and the Runkausvaara sill (_Nd(2200) 0) suggest that these mafic magmas were contaminated by older crustal material. The Sm-Nd and Pb isotopic results on the 2.44–2.2 Ga old Runkaus volcanics indicate mobility of Pb, fractionation of Sm/Nd during late greenschist facies metamorphism, and crustal contamination. The Pb-Pb data provide an age of 1972±80 Ma with a high initial ²⁰⁷Pb/²⁰⁴Pb ratio (₁ = 8.49), while scattered Sm-Nd data result in an imprecise age of 2330±180 Ma, with an initial _Nd-value of about zero. Secondary titanite gives an U-Pb age of ca. 2250 Ma. The Jouttiaapa basalts, in contrast, ascended from the mantle without interaction with older crust. These LREE depleted tholeiites mark a break in continental sedimentation, and yield a Sm-Nd age of 2090±70 Ma. Their initial _Nd = + 4.2 ±0.5 implies that the subcontinental early Proterozoic mantle had been depleted in LREE for a long period of time. The first lava flows are strongly depleted in LREE, suggesting that their source was significantly more depleted than the source of mid-ocean ridge basalts today.     

U-Pb SHRIMP geochronology of Th-poor, hydrothermal monazite: An example from the Llallagua tin-porphyry deposit, Bolivia

In situ U-Pb SHRIMP analysis of hydrothermal monazite virtually free of Th and poor in U (<0.2 ppm Th, 40-103 ppm U) from the world-class Llallagua tin porphyry deposit in Bolivia defines a mineralization age of 23.4 ± 2.2 Ma (MSWD 0.48) confirming earlier K-Ar sericite alteration age data. These ages are, however, in contrast with a weighted mean single crystal ²⁰⁷Pb/²⁰⁶Pb evaporation age of 39.3 ± 6.0 Ma, and a related Pb-Pb inverse isochron age of 42.4 ± 4.0 Ma (MSWD 0.66) on zircon from a post-porphyry dike, as well as with an earlier single crystal Sm-Nd apatite isochron age.Our data points to a significant time gap between emplacement of the ore-hosting porphyry intrusion (magmatism) and its hydrothermal overprint (tin mineralization), suggesting long-lived magmatic-hydrothermal activity in this part of the Andean back-arc crust. The decoupling of porphyry magmatism and hydrothermal activity may explain the unusual occurrence of relatively little fractionated felsic rocks together with extensive tin mineralization.Our study demonstrates the usefulness of the application of the U-Pb SHRIMP method to direct age determination of ore mineralization using Th-poor hydrothermal monazite even when dealing with geological young events. The common assumption of synchronous magmatism and hydrothermal ore formation in porphyry systems may not always be warranted.     

U-Pb zircon dating of mafic dykes and its application to the Proterozoic geological history of the Vestfold Hills,East Antarctica

The Vestfold Hills, one of several Archaean cratonic blocks within the East Antarctic Shield, comprises a high-grade metamorphic basement complex intruded by at least nine generations of Early to Middle Proterozoic mafic dykes. Extensive U-Pb ion microprobe (SHRIMP) analyses of zircons, derived predominantly from late-stage felsic differentiates of the mafic dykes, provide precise crystallisation ages for several dyke generations. These new ages enable constraints to be placed on both the history of mafic magmatism in the Vestfold Hills and the timing of the various interspersed Proterozoic deformation events. In addition to demonstrating the utility of zircons derived from felsic late-stage differentiates for the dating of co-genetic mafic dykes, this study also places doubt on previous wholerock Rb-Sr dating of mafic dyke suites in this and other areas of East Antarctica. The ²⁰⁷Pb/²⁰⁶Pb zircon ages of 2241±4 Ma and 2238±7 Ma for the Homogeneous and Mottled Norites, respectively, provide a younger emplacement age for associated group 2 High-Mg tholeiite dykes than the whole-rock Rb-Sr date (2424±72 Ma) originally interpreted as the age of all high-Mg intrusives in the Vestfold Hills. Zircon ages of 1754±16 Ma and 1832±72 Ma confirm the previously defined Rb-Sr age of the group 2 Fe-rich tholeiites. Two later dyke generations, the group 3 and 4 Fe-rich tholeiites, are distinguished on the basis of field orientations and cross-cutting relationships, and yield zircon emplacement ages of 1380±7 Ma and 1241±5 Ma which also define minimum ages for two suites of lamprophyre dykes. Xenocrystic zircons within both felsic segregations and mafic dykes yield zircon ages of 2478±5 Ma to 2740 Ma, indicating the presence of Archaean crustal source rocks of this antiquity beneath the Vestfold Hills.     

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.     

The Hadean upper mantle conundrum: evidence for source depletion and enrichment from Sm-Nd, Re-Os, and Pb isotopic compositions in 3.71 Gy boninite-like metabasalts from the Isua Supracrustal Belt, Greenland

Here we present Sm-Nd, Re-Os, and Pb isotopic data of carefully screened, least altered samples of boninite-like metabasalts from the Isua Supracrustal Belt (ISB, W Greenland)that characterize their mantle source at the time of their formation. The principal observations of this study are that by 3.7-3.8 Ga melt source regions existed in the upper mantle with complicated enrichment/depletion histories. Sm-Nd isotopic data define a correlation line with a slope corresponding to an age of 3.69 ± 0.18 Gy and an initial εNd value of +2.0 ± 4.7. This Sm-Nd age is consistent with indirect (but more precise) U-Pb geochronological estimates for their formation between 3.69-3.71 Ga. Relying on the maximum formation age of 3.71 Gy defined by the external age constraints, we calculate an average εNd [T = 3.71 Ga] value of +2.2 ± 0.9 (n = 18, 1σ) for these samples, which is indicative of a strongly depleted mantle source. This is consistent with the high Os concentrations, falling in the range between 1.9-3.4 ppb, which is similar to the estimated Os concentration for the primitive upper mantle. Re-Os isotopic data (excluding three outliers) yield an isochron defining an age of 3.76 ± 0.09 Gy (with an initial γOs value of 3.9 ± 1.2), within error consistent with the Sm-Nd age and the indirect U-Pb age estimates. An average initial γOs [T = 3.71 Ga] value of + 4.4 ± 1.2 (n = 8; 2σ) is indicative of enrichment of their source region during, or prior to, its melting. Thus, this study provides the first observation of an early Archean upper mantle domain with a distinctly radiogenic Os isotopic signature. This requires a mixing component characterized by time-integrated suprachondritic Re/Os evolution and a Os concentration high enough to strongly affect the Os budget of the mantle source; modern sediments, recycled basaltic crust, or the outer core do not constitute suitable candidates. At this point, the nature of the mantle or crustal component responsible for the radiogenic Os isotopic signature is not known.Compared with the Sm-Nd and Re-Os isotope systems, the Pb isotope systematics show evidence for substantial perturbation by postformational hydrothermal-metasomatic alteration processes accompanying an early Archean metamorphic event at 3510 ± 65 Ma and indicate that the U-Th-Pb system was partially opened to Pb-loss on a whole rock scale. Single stage mantle evolution models fail to provide a solution to the Pb isotopic data, which requires that a high-μ component was mixed with the depleted mantle component before or during the extrusion of the basalts. Relatively high ²⁰⁷Pb/²⁰⁴Pb ratios (compared to contemporaneous mantle), support the hypothesis that erosion products of the ancient terrestrial protocrust existed for several hundred My before recycling into the mantle before ∼3.7 Ga.Our results are broadly consistent with models favoring a time-integrated Hadean history of mantle depletion and with the existence of an early Hadean protocrust, the complement to the Hadean depleted mantle, which after establishment of subduction-like processes was, at least locally, recycled into the upper mantle before 3.7 Ga. Thus, already in the Hadean, the upper mantle seems to be characterized by geochemical heterogeneity on a range of length scales; one property that is shared with the modern upper mantle. However, a simple two component mixing scenario between depleted mantle and an enriched-, crustal component with a modern analogue can not account for the complicated and contradictory geochemical properties of this particular Hadean upper mantle source.     

The partitioning behavior of silver in a vapor-brine-rhyolite melt assemblage

The partitioning of silver in a sulfur-free rhyolite melt-vapor-brine assemblage has been quantified at 800 °C, pressures of 100 and 140 MPa and f_O2≈NNO (nickel-nickel oxide). Silver solubility (±2σ) in rhyolite increases 5-fold from 105 ± 21 to 675 ± 98 μg/g as pressure increases from 100 to 140 MPa. Nernst-type partition coefficients describing the mass transfer of silver at 100 MPa between vapor and melt, brine and melt and vapor and brine are 32 ± 30, 1151 ± 238 and 0.026 ± 0.004, respectively. At 140 MPa, values for for vapor and melt, brine and melt, and vapor and brine are 32 ± 10, 413 ± 172 and 0.06 ± 0.03, respectively. Apparent equilibrium constant values (±2σ) describing the exchange of silver and sodium between vapor and melt, , at 100 and 140 MPa are 105 ± 68 and 14 ± 6. The average values (±2σ) for silver and sodium exchange between brine and melt, , at 100 and 140 MPa are 313 ± 288 and 65 ± 12. These data indicate that the mass transfer of silver from rhyolite melt to an exsolved volatile phase(s) is enhanced at 100 MPa relative to 140 MPa, suggesting that decompression increases the silver ore-generative potential of an evolving silicate magma. Model calculations using the new data suggest that the evolution of low-density, aqueous fluid (i.e., vapor) may be responsible for the the silver tonnage of many porphyry-type and perhaps epithermal-type ore deposits. For example, Halter et al. (Halter W. E., Pettke T. and Heinrich C. A. (2002) The origin of Cu/Au ratios in porphyry-type ore deposits. Science296, 1842-1844) used detailed silicate and sulfide melt inclusion and vapor and brine fluid inclusions analyses to estimate a melt volume on the order of 15 km³ to satisfy the copper budget at the Bajo de la Alumbrera copper-, gold-, silver-ore deposit. Using their melt volume estimate with the data presented here, model calculations for a 15-km³ felsic melt, saturated with pyrrhotite and magnetite, suggest that a low-salinity magmatic vapor may scavenge on the order of 7 × 10¹² g of silver from the melt. This quantity of silver exceeds the discovered 2 × 10⁹ g of Ag at Alumbrera. Calculated tonnages for numerous other deposits yield similar results. The excess silver in the vapor, remaining after porphyry formation, is then available to precipitate at lower PTconditions in the stratigraphically higher epithermal environment. These data suggest that silver, and perhaps other ore metals, in the porphyry-epithermal continuum may be derived solely from the time-integrated flux of dominantly low-salinity vapor exsolved from a series of sequential magma batches.     

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide

The quantification of silicon isotopic fractionation by biotic and abiotic processes contributes to the understanding of the Si continental cycle. In soils, light Si isotopes are selectively taken up by plants, and concentrate in secondary clay-sized minerals. Si can readily be retrieved from soil solution through the specific adsorption of monosilicic acid () by iron oxides. Here, we report on the Si-isotopic fractionation during adsorption on synthesized ferrihydrite and goethite in batch experiment series designed as function of time (0-504 h) and initial concentration (ic) of Si in solution (0.21-1.80 mM), at 20 °C, constant pH (5.5) and ionic strength (1 mM). At various contact times, the δ²⁹Si vs. NBS28 compositions were determined in selected solutions (ic = 0.64 and 1.06 mM Si) by MC-ICP-MS in dry plasma mode with external Mg doping with an average precision of ±0.08‰ (±2σ_SEM). Per oxide mass, ferrihydrite (74-86% of initial Si loading) adsorbed more Si than goethite (37-69%) after 504 h of contact over the range of initial Si concentration 0.42-1.80 mM. Measured against its initial composition (δ²⁹Si = +0.01 ± 0.04‰ (±2σ_SD)), the remaining solution was systematically enriched in ²⁹Si, reaching maximum δ²⁹Si values of +0.70 ± 0.07‰ for ferrihydrite and +0.50 ± 0.08‰ for goethite for ic 1.06 mM. The progressive ²⁹Si enrichment of the solution fitted better a Rayleigh distillation path than a steady state model. The fractionation factor ²⁹ε (±1σ_SD) was estimated at −0.54 ± 0.03‰ for ferrihydrite and −0.81 ± 0.12‰ for goethite. Our data imply that the sorption of onto synthetic iron oxides produced a distinct Si-isotopic fractionation for the two types of oxide but in the same order than that generated by Si uptake by plants and diatoms. They further suggest that the concentration of light Si isotopes in the clay fraction of soils is partly due to sorption onto secondary clay-sized iron oxides.     

U-Pb zircon,monazite and Rb-Sr whole rock systematics of granitic gneiss and psammitic to semi-pelitic host gneiss from Glenfinnan,Northwestern Scotland

New U-Pb zircon data from a segregation pegmatite in the granitic gneiss at Glenfinnan yield discordant points which appear to be aligned along a chord on a concordia diagram with upper and lower intersection ages of 1,517±30 Ma and 556±8 Ma, respectively. The results are similar to published U-Pb zircon data from the granitic gneiss but the lower intersection age does not correspond to concordant ages of 455±3 Ma obtained for monazites from the segregation pegmatite and from paragneiss which hosts the granitic gneiss. The apparent U-Pb zircon chord also gives no indication of a 1,030±50 Ma (large sample) Rb-Sr whole rock isochron age for the granitic gneiss (Brook et al. 1976). A traverse of adjacent 5–8 cm thick slabs in the paragneiss yields a Rb-Sr errochron of 455±60 Ma which also does not agree with the U-Pb zircon lower intersection age. The scale of this Sr whole rock diffusion (ca. 10 cm) is not at variance with existing thermal, temporal and experimental constraints.A two episodic loss model has been applied to the zircon data from the segregation pegmatite, to the previously published zircon data on the granitic gneiss and to new U-Pb zircon data on the host paragneiss. The first lead loss event, if assumed to be in Grenville time, was computed to be strongest in the granitic gneiss and segregation pegmatite. For the three suites of zircon considered, primary ages converge in the 1,700–1,800 Ma range with a final disturbance event at ca. 490 Ma, i.e., close to a plausible prograde stage of Caledonian metamorphism.The zircons in both the granitic gneiss and the paragneiss are believed to have been derived from the ubiquitous early Proterozoic shields bordering the North Atlantic. Furthermore the above model is consistent with the hypothesis that the zircons in the granitic gneiss were largely derived from the paragneiss. However, the U-Pb zircon data are not inconsistent with new Sr-isotopic evidence which suggests an additional, possibly deeper source with lower ⁸⁷Sr/ ⁸⁶Sr ratios.     

Gold and copper partitioning in magmatic-hydrothermal systems at 800 °C and 100 MPa

Porphyry-type ore deposits sometimes contain fluid inclusion compositions consistent with the partitioning of copper and gold into vapor relative to coexisting brine at the depositional stage. However, this has not been reproduced experimentally at magmatic conditions. In an attempt to determine the conditions under which copper and gold may partition preferentially into vapor relative to brine at temperatures above the solidus of granitic magmas, we performed experiments at 800 °C, 100 MPa, oxygen fugacity () buffered by Ni-NiO, and fixed at either 3.5 × 10⁻² by using intermediate solid solution-pyrrhotite, or 1.2 × 10⁻⁴ by using intermediate solid solution-pyrrhotite-bornite. The coexisting vapor (∼3 wt.% NaCl eq.) and brine (∼68 wt.% NaCl eq.) were composed initially of NaCl + KCl + HCl + H₂O, with starting HCl set to <1000 μg/g in the aqueous mixture. Synthetic vapor and brine fluid inclusions were trapped at run conditions and subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Our experiments demonstrate that copper and gold partitioned strongly into the magmatic volatile phase(s) (MVP) (i.e., vapor or brine) relative to a silicate melt over the entire imposed range of . Nernst style partition coefficients between coexisting brine (b) and melt (m), D^b/m (±1σ), range from 3.6(±2.2) × 10¹ to 4(±2) × 10² for copper and from 1.2(±0.6) × 10² to 2.4(±2.4) × 10³ for gold. Partition coefficients between coexisting vapor (v) and melt, D^v/m range from 2.1 ± 0.7 to 18 ± 5 and 7(±3) × 10¹ to 1.6(±1.6) × 10² for copper and gold, respectively. Partition coefficients for all experiments between coexisting brine and vapor, D^b/v (±1σ), range from 7(±2) to 1.0(±0.4) × 10² and 1.7(±0.2) to 15(±2) for copper and gold, respectively. Observed average D^b/v at an of 1.2 × 10⁻⁴ were elevated, 95(±5) and 15 ± 1 for copper and gold, respectively, relative to those at the higher of 3.5 × 10⁻² where D^b/v were 10(±5) for copper and 7(±6) for gold. Thus, there is an inverse relationship between the and the D^b/v for both copper and gold with increasing resulting in a decrease in the D^b/v signifying increased importance of the vapor phase for copper and gold transport. This suggests that copper and gold may complex with volatile S-species as well as Cl-species at magmatic conditions, however, none of the experiments of our study at 800 °C and 100 MPa had a D^b/v ? 1. We did not directly determine speciation, but infer the existence of some metal-sulfur complexes based on the reported data. We suggest that copper and gold partition preferentially into the brine in most instances at or above the wet solidus. However, in most systems, the mass of vapor is greater than the mass of brine, and vapor transport of copper and gold may become more important in the magmatic environment at higher , lower , or near the critical point in a salt-water system. A D^b/v ? 1 at subsolidus hydrothermal conditions may also occur in response to changes in temperature, , , and/or acidity.Additionally, both copper and gold were observed to partition into intermediate solid solution and bornite much more strongly than into vapor, brine or silicate melt. This suggests that, although vapor and brine are both efficient at removing copper and gold from a silicate melt, the presence of Cu-Fe sulfides can sequester a substantial portion of the copper and gold contained within a silicate melt if the Cu-Fe sulfides are abundant.