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.     

Ar-Ar ages of martian nakhlites

We report ³⁹Ar-⁴⁰Ar ages of whole rock (WR) and plagioclase and pyroxene mineral separates of nakhlites MIL 03346 and Y-000593, and of WR samples of nakhlites NWA 998 and Nakhla. All age spectra are complex and indicate variable degrees of ³⁹Ar recoil and variable amounts of trapped ⁴⁰Ar in the samples. Thus, we examine possible Ar-Ar ages in several ways. From consideration of both limited plateau ages and isochron ages, we prefer Ar-Ar ages of NWA 998 = 1334 ± 11 Ma, MIL 03346 = 1368 ± 83 Ma (mesostasis) and 1334 ± 54 Ma (pyroxene), Y-000593 = 1367 ± 7 Ma, and Nakhla = 1357 ± 11 Ma, (2σ errors). For NWA 998 and MIL 03346 the Ar-Ar ages are within uncertainties of preliminary Rb-Sr isochron ages reported in the literature. These Ar-Ar ages for Y-000593 and Nakhla are several Ma older than Sm-Nd ages reported in the literature. We conclude that the major factor in producing Ar-Ar ages slightly too old is the presence of small amounts of trapped martian or terrestrial ⁴⁰Ar on weathered grain surfaces that was degassed along with the first several percent of ³⁹Ar. A total K-⁴⁰Ar isochron for WR and mineral data from five nakhlites analyzed by us, plus Lafayette data in the literature, gives an isochron age of 1325 ± 18 Ma (2σ). We emphasize the precision of this isochron over the value of the isochron age. Our Ar-Ar data are consistent with a common formation age for nakhlites. The cosmic-ray exposure (CRE) age for NWA 998 of ∼12 Ma is also similar to CRE ages for other nakhlites.     

K–Ar ages of meteorites: Clues to parent-body thermal histories

Whereas most radiometric chronometers give formation ages of individual meteorites >4.5 Ga ago, the K–Ar chronometer rarely gives times of meteorite formation. Instead, K–Ar ages obtained by the ³⁹Ar–⁴⁰Ar technique span the entire age of the solar system and typically measure the diverse thermal histories of meteorites or their parent objects, as produced by internal parent body metamorphism or impact heating. This paper briefly explains the Ar–Ar dating technique. It then reviews Ar–Ar ages of several different types of meteorites, representing at least 16 different parent bodies, and discusses the likely thermal histories these ages represent. Ar–Ar ages of ordinary (H, L, and LL) chondrites, R chondrites, and enstatite meteorites yield cooling times following internal parent body metamorphism extending over ∼200 Ma after parent body formation, consistent with parent bodies of ∼100 km diameter. For a suite of H-chondrites, Ar–Ar and U–Pb ages anti-correlate with the degree of metamorphism, consistent with increasing metamorphic temperatures and longer cooling times at greater depths within the parent body. In contrast, acapulcoites–lodranites, although metamorphosed to higher temperatures than chondrites, give Ar–Ar ages which cluster tightly at ∼4.51 Ga. Ar–Ar ages of silicate from IAB iron meteorites give a continual distribution across ∼4.53–4.32 Ga, whereas silicate from IIE iron meteorites give Ar–Ar ages of either ∼4.5 Ga or ∼3.7 Ga. Both of these parent bodies suffered early, intense collisional heating and mixing. Comparison of Ar–Ar and I–Xe ages for silicate from three other iron meteorites also suggests very early collisional heating and mixing. Most mesosiderites show Ar–Ar ages of ∼3.9 Ga, and their significantly sloped age spectra and Ar diffusion properties, as well as Ni diffusion profiles in metal, indicate very deep burial after collisional mixing and cooling at a very slow rate of ∼0.2 °C/Ma. Ar–Ar ages of a large number of brecciated eucrites range over ∼3.4–4.1 Ga, similar to ages of many lunar highland rocks. These ages on both bodies were reset by large impact heating events, possibly initiated by movements of the giant planets. Many impact-heated chondrites show impact-reset Ar–Ar ages of either >3.5 Ga or <1.0 Ga, and generally only chondrites show these younger ages. The younger ages may represent orbital evolution times in the asteroid belt prior to ejection into Earth-crossing orbits. Among martian meteorites, Ar–Ar ages of nakhlites are similar to ages obtained from other radiometric chronometers, but apparent Ar–Ar ages of younger shergottites are almost always older than igneous crystallization ages, because of the presence of excess (parentless) ⁴⁰Ar. This excess ⁴⁰Ar derives from shock-implanted martian atmosphere or from radiogenic ⁴⁰Ar inherited from the melt. Differences between meteorite ages obtained from other chronometers (e.g., I–Xe and U–Pb) and the oldest measured Ar–Ar ages are consistent with previous suggestions that the ⁴⁰K decay parameters in common use are incorrect and that the K–Ar age of a 4500 Ma meteorite should be possibly increased, but by no more than ∼20 Ma.     

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.     

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.     

Isotopic and petrographic evidence for young Martian basalts

Radiometric age data for shergottites yield ages of 4.0 Ga and 180-575 Ma; the interpretation of these ages has been, and remains, a subject of debate. Here, we present new ³⁹Ar-⁴⁰Ar laser probe data on lherzolitic shergottites Allan Hills (ALH) 77005 and Northwest Africa (NWA) 1950. These two meteorites are genetically related, but display very different degrees of shock damage. On a plot of ⁴⁰Ar/³⁶Ar versus ³⁹Ar/³⁶Ar, the more strongly shocked ALH 77005 (45-55 GPa) does not yield an array of values indicating an isochron, but the data are highly scattered with the shock melts yielding ⁴⁰Ar/³⁶Ar ratios of 1600-2026. Apparent ages calculated from these extractions range from 374-8183 Ma, with 50% of the data, particularly from the shock melts, yielding impossibly old ages (>4.567 Ga). On the same plot, extractions from igneous minerals in the less shocked NWA 1950 (30-44 GPa) yield a fitted age of 382 ± 36 Ma. Argon extractions from the shock melts are well distinguished from minerals, with the melts exhibiting the highest ⁴⁰Ar/³⁶Ar ratios (1260-1488) and the oldest apparent ages. Laser step heating was also performed on maskelynite separates from NWA 1950 yielding ages of 1000 Ma at the lowest release temperatures, and ages of 360 and 362 Ma at higher temperature steps. Stepped heating data from previous studies have yielded ages of 500 and 700 Ma to 1.7 Ga for ALH 77005 maskelynite separates. If the ages obtained from igneous minerals represent undegassed argon from an ancient (4.0 Ga) rock, then the ages are expected to anticorrelate with the degree of shock heating. The data do not support this inference. Our data support young crystallization ages for minerals and Martian atmosphere as the origin of excess ⁴⁰Ar in the shock melts.The shock features of shergottites are also reviewed in the context of what is known of the geologic history of the Martian surface through remote observation. The oldest, most heavily cratered surfaces of Mars are thought to be ?4.0 Ga; we contend that ancient rocks from Mars (Noachian >3.5 Ga) are likely to record multiple impact events reflecting megaregolith formation and the cumulative effects of erosion and aqueous alteration occurring during or since that era. Young rocks (Late Amazonian, <0.6 Ga) should record a relatively simple history of emplacement and ejection from the near surface. We show that although shergottites are strongly shocked, they are relatively pristine crystalline igneous rocks and not pervasively altered breccias. The petrography of shergottites is at odds with an ancient age interpretation. A model in which young coherent rocks are preferentially sampled by hypervelocity impact because of material strength is considered highly plausible.     

Thermodynamic constraints on the formation conditions of winonaites and silicate-bearing IAB irons

Silicate inclusions in IAB irons and related winonaite meteorites have textures, mineralogies and mineral chemistries that indicate a complex formation history of heating, followed by brecciation and metamorphism. Using olivine-orthopyroxene-chromite assemblages in five IAB iron silicate inclusions (Caddo County, Campo del Cielo, Copiapo, Lueders, and Udei Station) and one winonaite (Winona), we calculated closure temperatures and oxygen fugacities for these meteorites. Calculated olivine-chromite Fe-Mg exchange temperatures are compared to two-pyroxene temperatures. Olivine-chromite closure temperatures range from ∼590°C to ∼700°C, while two-pyroxene temperatures range from ∼900°C to ∼1200°C. Oxygen fugacities of these meteorites, determined for the first time in this study, range from 2.3 to 3.2 log units below the Fe-FeO buffer and define a line between the Fe-FeO and Cr-Cr₂O₃ buffers. Highly variable temperatures were experienced by these rocks on the hand sample, and sometimes even the thin section, scale consistent with the idea that the winonaite-IAB iron parent body experienced collisional fragmentation and reassembly after peak temperatures were reached. Although modest reduction likely occurred during cooling, the oxygen fugacities and mineral compositions recorded at peak metamorphic temperatures suggest that the chondritic precursor for this parent body was initially more reduced than ordinary chondrites.     

Intercalibration of the Hb3gr Ar/Ar dating standard

The ⁴⁰Ar/³⁹Ar dating technique is based on the knowledge of the age of neutron fluence monitors (standards). Recent investigations have improved the accuracy and precision of the ages of most of the Phanerozoic-aged standards (e.g. Fish Canyon Tuff sanidine (FCs), Alder Creek sanidine, GA1550 biotite and LP-6 biotite); however, no specific study has been undertaken on the older standards (i.e. Hb3gr hornblende and NL-25 hornblende) generally used to date Precambrian, high Ca/K, and/or meteoritic rocks.In this study, we show that Hb3gr hornblende is relatively homogenous in age, composition (Ca/K) and atmospheric contamination at the single grain level. The mean standard deviation of the ⁴⁰Ar^?/³⁹Ar_K (F-value) derived from this study is 0.49%, comparable to the most homogeneous standards. The intercalibration factor (which allows direct comparison between standards) between Hb3gr and FCs is R_FCs^Hb3gr = 51.945 ± 0.167. Using an age of 28.02 Ma for FCs, the age of Hb3gr derived from the R-value is 1073.6 ± 5.3 Ma (1σ; internal error only) and ± 8.8 Ma (including all sources of error). This age is indistinguishable within uncertainty from the K/Ar age previously reported at 1072 ± 11 Ma [Turner G., Huneke, J.C., Podosek, F.A., Wasserburg, G.J., 1971. ⁴⁰Ar-³⁹Ar ages and cosmic ray exposure ages of Apollo 14 samples. Earth Planet. Sci. Lett. 12, 19-35].The R-value determined in this study can also be used to intercalibrate FCs if we consider the K/Ar date of 1072 Ma as a reference age for Hb3gr. We derive an age of 27.95 ± 0.19 Ma (1σ; internal error only) for FCs which is in agreement with the previous determinations. Altogether, this shows that Hb3gr is a suitable standard for ⁴⁰Ar/³⁹Ar geochronology.     

Concordant Rb-Sr, Sm-Nd, and Ar-Ar ages for Northwest Africa 1460: A 346 Ma old basaltic shergottite related to “lherzolitic” shergottites

Multiple lines of evidence show that the Rb-Sr, Sm-Nd, and Ar-Ar isotopic systems individually give robust crystallization ages for basaltic (or diabasic) shergottite Northwest Africa (NWA) 1460. In contrast to other shergottites, NWA 1460 exhibits minimal evidence of excess ⁴⁰Ar, thus allowing an unambiguous determination of its Ar-Ar age. The concordant Rb-Sr, Sm-Nd, and Ar-Ar results for NWA 1460 define its crystallization age to be 346 ± 17 Ma (2σ). In combination with petrographic and trace element data for this specimen and paired meteorite NWA 480, these results strongly refute the suggestion by others that the shergottites are ∼4.1 Ga old. Current crystallization and cosmic-ray exposure (CRE) age data permit identification of a maximum of nine ejection events for Martian meteorites (numbering more than 50 unpaired specimens as of 2008) and plausibly as few as five such events. Although recent high resolution imaging of the Martian surface has identified limited areas of sparsely cratered terrains, the meteorite data suggest that either these areas are representative of larger areas from which the meteorites might come, or that the cratering chronology needs recalibration. Time-averaged ⁸⁷Rb/⁸⁶Sr = 0.16 for the mantle source of the parent magma of NWA 1460/480 over the ∼4.56 Ga age of the planet is consistent with previously estimated values for bulk silicate Mars in the range 0.13-0.16, and similar to values of ∼0.18 for the “lherzolitic” shergottites. Initial ε_Nd for NWA 1460/480 at 350 ± 16 Ma ago was +10.6 ± 0.5, which implies a time-averaged ¹⁴⁷Sm/¹⁴⁴Nd of 0.217 in the Martian mantle prior to mafic melt extraction, similar to values of 0.211-0.216 for the “lherzolitic” shergottites. These time-averaged values do not imply a simple two-stage mantle/melt evolution, but must result from multiple episodes of melt extractions from the source regions. Much higher “late-stage” ε_Nd values for the depleted shergottites imply similar processes carried to a greater degree. Thus, NWA 1460/480, the “lherzolitic” shergottites and perhaps EET 79001 give the best (albeit imperfect) estimate of the Sr- and Nd-isotopic characteristics of bulk silicate Mars.     

Imbrium provenance for the Apollo 16 Descartes terrain: Argon ages and geochemistry of lunar breccias 67016 and 67455

In order to improve our understanding of impact history and surface geology on the Moon, we obtained ⁴⁰Ar-³⁹Ar incremental heating age data and major + trace element compositions of anorthositic and melt breccia clasts from Apollo 16 feldspathic fragmental breccias 67016 and 67455. These breccias represent the Descartes terrain, a regional unit often proposed to be ejecta from the nearby Nectaris basin. The goal of this work is to better constrain the emplacement age and provenance of the Descartes breccias.Four anorthositic clasts from 67016 yielded well-defined ⁴⁰Ar-³⁹Ar plateau ages ranging from 3842 ± 19 to 3875 ± 20 Ma. Replicate analyses of these clasts all agree within measurement error, with only slight evidence for either inheritance or younger disturbance. In contrast, fragment-laden melt breccia clasts from 67016 yielded apparent plateau ages of 4.0-4.2 Ga with indications of even older material (to 4.5 Ga) in the high-T fractions. Argon release spectra of the 67455 clasts are more variable with evidence for reheating at 2.0-2.5 Ga. We obtained plateau ages of 3801 ± 29 to 4012 ± 21 Ma for three anorthositic clasts, and 3987 ± 21 Ma for one melt breccia clast. The anorthositic clasts from these breccias and fragments extracted from North Ray crater regolith (Maurer et al., 1978) define a combined age of 3866 ± 9 Ma, which we interpret as the assembly age of the feldspathic fragmental breccia unit sampled at North Ray crater. Systematic variations in diagnostic trace element ratios (Sr/Ba, Ti/Sm, Sc/Sm) with incompatible element abundances show that ferroan anorthositic rocks and KREEP-bearing lithologies contributed to the clast population.The Descartes breccias likely were deposited as a coherent lithologic unit in a single event. Their regional distribution suggests emplacement as basin ejecta. An assembly age of 3866 ± 9 Ma would be identical with the accepted age of the Imbrium basin, and trace element compositions are consistent with a provenance in the Procellarum-KREEP Terrane. The combination of age and provenance constraints points toward deposition of the Descartes breccias as ejecta from the Imbrium basin rather than Nectaris. Diffusion modeling shows that the older apparent plateau ages of the melt brecia clasts plausibly result from incomplete degassing of ancient crust during emplacement of the Descartes breccias. Heating steps in the melt breccia clasts that approach the primary crystallization ages of lunar anorthosites show that earlier impact events did not completely outgas the upper crust.     

Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing

The ⁴⁰Ar/³⁹Ar stepwise crushing technique is applied for the first time to date garnet from ultra-high-pressure metamorphic (UHPM) eclogites. Three garnet samples from the Bixiling eclogites analyzed by ⁴⁰Ar/³⁹Ar stepwise crushing yield regular, predictable age spectra, and a clear separation between excess ⁴⁰Ar and concordant plateau and isochron ages. All three age spectra begin with high apparent ages followed by step by step decreasing ages, and finally age plateaux with apparent ages in the range from 427 ± 20 to 444 ± 10 Ma. The data points constituting the age plateaux yield excellent isochrons with radiogenic intercept ages ranging from 448 ± 34 to 459 ± 58 Ma, corresponding to initial ⁴⁰Ar/³⁶Ar ratios from 292.1 ± 4.5 to 294.5 ± 6.7, statistically indistinguishable from the modern air. The high initial ages are interpreted to derive from secondary fluid inclusions containing excess ⁴⁰Ar, whereas the plateau ages are attributed to gas from small primary fluid inclusions without significant excess ⁴⁰Ar. The plateau ages are interpreted to approximate the time of garnet growth during initial UHPM metamorphism. Phengite analyzed by laser stepwise heating yielded a complicated two-saddle age spectrum with a scattered isochron corresponding to age of 463 ± 116 Ma and initial ⁴⁰Ar/³⁶Ar ratio of 1843 ± 1740 indicative of the presence of extraneous ⁴⁰Ar within phengite. These concordant isochron ages measured on minerals diagnostic of eclogite grade metamorphism strongly suggest that Dabie UHPM eclogites were first formed in the early Paleozoic, during the same event that caused the Qinling-Northern Qaidam Basin-Altyn Tagh eclogites.     

Silicate inclusions in group IAB irons and a relation to the anomalous stones Winona and Mt Morris (Wis)

Silicates are found in many group IAB irons; in some cases as abundant angular cm-sized inclusions and in other cases as smaller fragments or single grains in troilite or graphite nodules. The mineralogy of the silicates is chondritic—olivine, pyroxene, albitic plagioclase—as is the bulk composition. The degree of oxidation of the olivine and pyroxene is intermediate between E and H chondrites (Fa 1–8, Fs 4–9). IAB inclusions have ages of about 4.5 Gyr, I¹²⁹-Xe¹²⁹ formation intervals in the ranges of chondrites and contain planetary-type rare gases.Samples of San Cristobal, Campo del Cielo, Mundrabilla and Woodbine were examined by microprobe and bulk inclusions from Campo del Cielo, Copiapo, Landes and Woodbine were analyzed by instrumental and radiochemical neutron activation analysis. Nonvolatile lithophilic and siderophih'c elements in Copiapo, Landes and Woodbine have approximately chondritic abundances. The chondritic level of lithophiles indicates the inclusions have not undergone igneous differentiation while the chondritic levels of siderophiles is evidence the metal is native to the inclusions and not matrix metal injected into the silicates. The two Campo del Cielo inclusions analyzed have roughly chondritic abundances of lithophiles but have fractionated rare earth patterns and widely varying amounts and abundances (relative to Ni) of siderophiles. These inclusions appear to have experienced some partial melting. Siderophile ratios for the inclusions have some differences when compared to matrix metal. One Campo del Cielo inclusion contains kamacite (5.5% Ni) with over 1000 μg Ge.Three-isotope O analyses by Clayton and coworkers of parts of the same or neighboring inclusions to those analyzed chemically place the inclusions slightly below the terrestrial fractionation line of clayton et al. (1976) and rule out the possibility of the inclusions being trapped fragments of one of the ordinary chondrite groups.The IAB silicates formed probably in a similar manner as chondrite groups but in a different region of the nebula and they record the O₂ fugacity and O isotopic composition of that location. They later became trapped in the metal-rich matrix probably as the result of collisions producing the breccialike texture. The relationship of the silicates to the kamacite-taenite structure of the metal requires that the metal-silicate mix have been heated to over 1000 K for an extended period.Two anomalous stony meteorites, Winona and Mt. Morris (Wis), are similar to IAB inclusions in mineralogy, bulk composition, $\text{FeO}\text{(FeO + Mg)}$ ratio of the silicates, and chromite composition and are possibly related to the IAB silicates. Winona also has an age of 4.6 Gyr and contains planetary-type rare gases. Microprobe data are reported for the major minerals of these anomalous meteorites. Although attempts to detect IAB levels of Ge in the metal phases were not successful, the weight of the evidence favors a relationship between these meteorites and IAB     

Ar-Ar laser dating of tektites from the Cheb Basin (Czech Republic): Evidence for coevality with moldavites and influence of the dating standard on the age of the Ries impact

Moldavites (Central European tektites) are genetically related to the impact event that produced the ∼24-km diameter Ries crater in Germany, representing one of the youngest large impact structures on Earth. Although several geochronological studies have been completed, there is still no agreement among ⁴⁰Ar-³⁹Ar ages on both moldavites and glasses from Ries suevites. Even recently published data yielded within-sample mean ages with a nominal spread of more than 0.6 Ma (14.24-14.88 Ma). This age spread, which significantly exceeds current internal errors, must be in part ascribed to geological and/or analytical causes.This study reports the results of a detailed geochronological investigation of moldavites from the Cheb area (Czech Republic), which have never been dated before, and, for comparison, of two samples from type localities, one in southern Bohemia and the other in western Moravia. We used ⁴⁰Ar-³⁹Ar laser step-heating and total fusion techniques in conjunction with microscale petrographic and chemical characterization. In addition, with the purpose of ascertaining the influence of the dating standards on the age of the Ries impact and making data from this study and literature consistent with the now widely used Fish Canyon sanidine (FCs) standard, we performed a direct calibration of multi-grain splits of the Fish Canyon biotite (FCT-3) with FCs. The intercalibration factors (), determined for eight stack positions in one of the three performed irradiations, were indistinguishable within errors and gave an arithmetic mean and a standard deviation of 1.0086 ± 0.0031 (±2σ), in agreement with previous works suggesting that biotite from the Fish Canyon Tuff is somewhat older (∼0.8%) than the coexisting sanidine.Laser total fusion analysis of milligram to sub-milligram splits of five tektite samples from the Cheb area yielded mostly concordant intrasample ⁴⁰Ar-³⁹Ar ages, and within-sample weighted mean ages of 14.66 ± 0.08-14.75 ± 0.12 Ma (±2σ internal errors, ages relative to FCs) that overlap within errors. These ages match those obtained for samples from western Moravia (14.66 ± 0.08 Ma) and southern Bohemia (14.68 ± 0.11 Ma), supporting the genetic link between Cheb Basin tektites and moldavites, and, consequently, between Cheb Basin tektites and the Ries impact. In contrast to samples from the Cheb area and Moravia, ⁴⁰Ar-³⁹Ar ages from total fusion experiments on the Bohemian specimen ranged widely from ∼14.6 to ∼17.0 Ma. Older apparent ages, however, were systematically obtained from fragments characterized by visible surface alteration. Laser step-heating experiments, although displaying slightly disturbed age profiles, were in line with total fusion analyses and yielded well-defined plateau ages of 14.64 ± 0.11-14.71 ± 0.11 Ma (±2σ internal errors, ages relative to FCs).A thorough comparison of our and previous ⁴⁰Ar-³⁹Ar ages on both moldavites and Ries suevite glasses, recalculated relative to the ⁴⁰Ar^∗/⁴⁰K ratio recently determined for FCs using intercalibration factors available in or derivable from the literature, reveals some inconsistencies which may be ascribed to either geological or analytical causes. Based on our data, decay constants in current use in geochronology, and ages calculated relative to FCs, we infer that the age of moldavites is 14.68 ± 0.11 Ma (±2σ, neglecting uncertainties in the ⁴⁰K decay constants).     

U-Pb and Lu-Hf isotope record of detrital zircon grains from the Limpopo Belt - Evidence for crustal recycling at the Hadean to early-Archean transition

Detrital zircon grains from Beit Bridge Group quartzite from the Central Zone of the Limpopo Belt near Musina yield mostly ages of 3.35-3.15 Ga, minor 3.15-2.51 Ga components, and numerous older grains grouped at approximately 3.4, 3.5 and 3.6 Ga. Two grains yielded concordant Late Hadean U-Pb ages of 3881 ± 11 Ma and 3909 ± 26 Ma, which are the oldest zircon grains so far found in Africa. The combined U-Pb and Lu-Hf datasets and field relationships provide evidence that the sedimentary protolith of the Beit Bridge Group quartzite was deposited after the emplacement of the Sand River Gneisses (3.35-3.15 Ga), but prior to the Neoarchean magmatic-metamorphic events at 2.65-2.60 Ga. The finding of abundant magmatic zircon detritus with concordant U-Pb ages of 3.35-3.15 Ga, and ¹⁷⁶Hf/¹⁷⁷Hf of 0.28066 ± 0.00004 indicate that the Sand River Gneiss-type rocks were a predominant source. In contrast, detrital zircon grains older than approximately 3.35 Ga were derived from the hinterland of the Limpopo Belt; either from a so far unknown crustal source in southern Africa, possibly from the Zimbabwe Craton and/or a source, which was similar but not necessarily identical to the one that supplied the Hadean zircons to Jack Hills, Western Australia. The Beit Bridge Group zircon population at >3.35 Ga shows a general εHf_t increase with decreasing age from εHf_3.9Ga = −6.3 to εHf_3.3-3.1Ga = −0.2, indicating that Hadean crust older than 4.0 Ga (T_DM = 4.45-4.36 Ga) was rejuvenated during magmatic events between >3.9 and 3.1 Ga, due to a successive mixing of crustal rocks with mantle derived magmas. The existence of a depleted mantle reservoir in the Limpopo’s hinterland is reflected by the ∼3.6 Ga zircon population, which shows εHf_3.6Ga between −4.6 and +3.2. In a global context, our data suggest that a long-lived, mafic Hadean protocrust with some tonalite-trondhjemite-granodiorite constituents was destroyed and partly recycled at the Hadean/Archean transition, perhaps due to the onset of modern-style plate tectonics.     

Combined U-Th/He and Ar/Ar geochronology of post-shield lavas from the Mauna Kea and Kohala volcanoes, Hawaii

Late Quaternary, post-shield lavas from the Mauna Kea and Kohala volcanoes on the Big Island of Hawaii have been dated using the ⁴⁰Ar/³⁹Ar and U-Th/He methods. The objective of the study is to compare the recently demonstrated U-Th/He age method, which uses basaltic olivine phenocrysts, with ⁴⁰Ar/³⁹Ar ages measured on groundmass from the same samples. As a corollary, the age data also increase the precision of the chronology of volcanism on the Big Island. For the U-Th/He ages, U, Th and He concentrations and isotopes were measured to account for U-series disequilibrium and initial He. Single analyses U-Th/He ages for Hamakua lavas from Mauna Kea are 87 ± 40 to 119 ± 23 ka (2σ uncertainties), which are in general equal to or younger than ⁴⁰Ar/³⁹Ar ages. Basalt from the Polulu sequence on Kohala gives a U-Th/He age of 354 ± 54 ka and a ⁴⁰Ar/³⁹Ar age of 450 ± 40 ka. All of the U-Th/He ages, and all but one spurious ⁴⁰Ar/³⁹Ar ages conform to the previously proposed stratigraphy and published ¹⁴C and K-Ar ages. The ages also compare favorably to U-Th whole rock-olivine ages calculated from ²³⁸U-²³⁰Th disequilibria. The U-Th/He and ⁴⁰Ar/³⁹Ar results agree best where there is a relatively large amount of radiogenic ⁴⁰Ar (>10%), and where the ⁴⁰Ar/³⁶Ar intercept calculated from the Ar isochron diagram is close to the atmospheric value. In two cases, it is not clear why U-Th/He and ⁴⁰Ar/³⁹Ar ages do not agree within uncertainty. U-Th/He and ⁴⁰Ar/³⁹Ar results diverge the most on a low-K transitional tholeiitic basalt with abundant olivine. For the most alkalic basalts with negligible olivine phenocrysts, U-Th/He ages were unattainable while ⁴⁰Ar/³⁹Ar results provide good precision even on ages as low as 19 ± 4 ka. Hence, the strengths and weaknesses of the U-Th/He and ⁴⁰Ar/³⁹Ar methods are complimentary for basalts with ages of order 100-500 ka.     

Hafnium isotope homogenization during metamorphic zircon growth in amphibolite-facies rocks: Examples from the Shackleton Range (Antarctica)

Hafnium isotope analyses of a large number of metamorphic zircon grains of two garnet-kyanite-staurolite schist samples from the Shackleton Range yielded ¹⁷⁶Hf/¹⁷⁷Hf of 0.28160 ± 0.00003 and 0.28142 ± 0.00003, respectively. The variations of these analyses are less than ±1.2 epsilon units and indicate that all metamorphic zircon grains in the two rocks formed in environments with nearly homogenous Hf isotopic composition. The metamorphic origin of the zircon grains is constrained by textures as well as by their low Th/U (<0.2), ¹⁷⁶Lu/¹⁷⁷Hf (<0.0003), and ¹⁷⁶Yb/¹⁷⁷Hf ratios (<0.009), indicating that they grew in the presence of garnet. Furthermore, the grains yield Pb-Pb ages of c. 1.7 Ga, which is the time of amphibolite-facies metamorphism. In combination with petrological results, it is suggested that the observed ¹⁷⁶Hf/¹⁷⁷Hf homogeneity was caused by a fluid- and deformation-assisted dissolution of detrital zircon grains, followed by new zircon re-precipitation that was accompanied by Hf transport on at least a hand-specimen scale. This interpretation is supported by results obtained from an additional paragneiss sample that contains zoned zircon grains with xenocrystic cores formed at 2.6-1.8 Ga and metamorphic rims with a U-Pb age of 1.7 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf variation of the zircon rims is mostly at ±0.0003, which is much less than that of the magmatic cores (±0.0019). The metamorphic fluid for the dissolution-homogenization-re-precipitation process most likely resulted from prograde reactions among the minerals chlorite-muscovite-biotite-garnet-staurolite-apatite, in agreement with thin section observations and P-T pseudosection calculations.     

LA-MC-ICPMS and SHRIMP U-Pb dating of complex zircons from Quaternary tephras from the French Massif Central: Magma residence time and geochemical implications

Analyses of zircon grains from the Queureuilh Quaternary tephras (pumice) provide new information about their pre-eruptive history. U-Pb dating was performed in situ using two methods: SHRIMP and LA-MC-ICPMS equipped with a multi-ion counting system. Both methods provided reliable ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U ratios as well as U and Th abundances required for U-Pb Concordia intercept age determination, after initial ²³⁰Th disequilibrium correction. The new LA-MC-ICPMS method was validated by dating a reference zircon (61.308B) and zircons from a phonolitic lava dated independently with the two techniques. A time resolution of about 20 kyr for 1 Ma zircon crystals was achieved for both methods.The clear euhedral zircon population from Queureuilh tephras is quite complex from several points of view: (1) some grains are reddish or yellowish while others are colorless; (2) the U and Th composition changes by more than an order of magnitude and Th/U is generally high (∼1-2); (3) there are three discrete ages recorded at 2.35 ± 0.04, 1.017 ± 0.008 and 0.640 ± 0.010 Ma.From the previously determined ⁴⁰Ar/³⁹Ar age at 0.571 ± 0.060 Ma [Duffell H. (1999) Contribution géochronologique à la stratigraphie volcanique du Massif des Monts Dore par la méthode ⁴⁰Ar/³⁹Ar. D.E.A. Univ. Clermont-Ferrand, 56 p.], the discontinuous zircon age populations, the color of the grains and their composition, we favor the following model as explanation: The oldest, less numerous group of reddish zircons represents xenocrystic grains resulting from assimilation of the local material during magma ascent. A primitive magma chamber, perhaps deep in crustal level, was formed at 1.0 Ma. The related magma, previously characterized by high Th/U ratio (2.2 ± 1.1), underwent rejuvenation during ascent to a new chamber at shallow depth and/or during injection of more mafic magmas. During this stage, at 0.64 Ma, the colorless zircon grains of lower Th/U ratio (1.3 ± 0.5) crystallized. This last stage defined the magma residence time of 70 kyr prior to eruption dated by the ⁴⁰Ar/³⁹Ar method. However, if the primitive magma is considered, the magma residence time as a whole from this first stage reached 446 kyr.In the light of the complex history of such magmas, which commonly involves recycling of zircon grains that precipitated tens to hundreds of kyr earlier than eruptions, the use of Zr concentration in geochemical modeling of whole rock compositional data can be problematic.     

Comment on “Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing” by Qiu and Wijbrans (2006)

Qiu and Wijbrans [Qiu H.-N. and Wijbrans J. R. (2006) Paleozoic ages and excess ⁴⁰Ar in garnets from the Bixiling eclogite in Dabieshan, China: new insights from ⁴⁰Ar/³⁹Ar dating by stepwise crushing. Geochim. Cosmochim. Acta70, 2354-2370] present three Ar-Ar age spectra for fluid inclusions in garnet from eclogite at Bixiling in the Dabie orogen, east-central China. These Paleozoic ages of 427 ± 20 to 444 ± 10 Ma are interpreted to represent the first formation of Dabie ultrahigh-pressure (UHP) eclogite and thus require subduction of Yangtze crust to have started much earlier than previously accepted. However, no petrographic evidence, such as mineral inclusions in the garnet relating to the particular metamorphic conditions, is presented to substantiate the proposed UHP metamorphic event. Because garnet growth is not uniquely responsible for UHP eclogite-facies metamorphism, a distinction between UHP and high-pressure (HP) metamorphic events must be made in the interpretation of geochronological results. Available data from mineral Sm-Nd and zircon U-Pb dating of eclogites from the same area have firmly established that the UHP eclogite-facies metamorphism took place at Triassic. Neither the age of UHP metamorphism nor the timing of continental collision is reliably constrained by their presented data; the fluid inclusions in garnet must contain inherited ⁴⁰Ar from UHP eclogite precursor, without considerable resetting of the Ar-Ar isotopic system during Triassic UHP metamorphism. Therefore, their data are either meaningless, or at best viewed as the age of garnet growth by low-T/HP blueschist/eclogite-facies metamorphism of the UHP eclogite precursor during arc-continent collision in the early Paleozoic. Furthermore, it is critical for metamorphic geochronology to substantiate the timing of UHP metamorphic event by means of zircon U-Pb in situ dating on coesite-bearing domains of metamorphically grown zircon.     

Thermal history of the Ecstall pluton from Ar/Ar geochronology and thermal modeling

New ⁴⁰Ar/³⁹Ar thermochronology results and thermal modeling support the hypothesis of Hollister et al. (2004), that reheating of the mid-Cretaceous Ecstall pluton by intrusion of the Coast Mountains Batholith (CMB) was responsible for spatially variable remagnetization of the Ecstall pluton. ⁴⁰Ar/³⁹Ar ages from hornblende and biotite from 12 locations along the Skeena River across the northern part of the Ecstall pluton decrease with proximity to the Quottoon plutonic complex, the nearest member of the CMB to the Ecstall pluton. The oldest ⁴⁰Ar/³⁹Ar ages are found farthest from the Quottoon plutonic complex, and are 90 ± 3 Ma for hornblende, and 77.9 ± 1.2 Ma for biotite. The youngest ⁴⁰Ar/³⁹Ar ages are found closest to the Quottoon plutonic complex, and are 51.6 ± 1.2 Ma for hornblende, and 45.3 ± 1.7 Ma for biotite. No obvious relationship between grain size and age is seen in the Ecstall pluton biotites. Spatial trends in ⁴⁰Ar/³⁹Ar ages are consistent with model results for reheating by a thermal wall at the location of the Quottoon plutonic complex. Although no unique solution is suggested, our results indicate that the most appropriate thermal history for the Ecstall pluton includes both reheating and northeast side up tilting of the Ecstall pluton associated with intrusion of the Quottoon plutonic complex. Estimates of northward translation from shallow paleomagnetic inclinations in the western part of the Ecstall pluton are reduced to ∼3000 km, consistent with the Baja-BC hypothesis, when northeast side up tilting is accounted for.     

A single asteroidal source for extraterrestrial Ordovician chromite grains from Sweden and China: High-precision oxygen three-isotope SIMS analysis

We examined oxygen three-isotope ratios of 48 extraterrestrial chromite (EC) grains extracted from mid-Ordovician sediments from two different locations in Sweden, and one location in south-central China. The ages of the sediments (∼470 Ma) coincide with the breakup event of the L chondrite parent asteroid. Elemental compositions of the chromite grains are generally consistent with their origin from L or LL chondrite parent bodies. The average Δ¹⁷O (‰-deviation from the terrestrial mass-fractionation line, measured in situ from 15 μm spots by secondary ion mass spectrometry; SIMS) of EC grains extracted from fossil meteorites from Thorsberg and Brunflo are 1.17 ± 0.09‰ (2σ) and 1.25 ± 0.16‰, respectively, and those of fossil micrometeorites from Thorsberg and Puxi River are 1.10 ± 0.09‰, and 1.11 ± 0.12‰, respectively. Within uncertainty these values are all the same and consistent with the L chondrite group average Δ¹⁷O = 1.07 ± 0.18‰, but also with the LL chondrite group average Δ¹⁷O = 1.26 ± 0.24‰ (Clayton et al., 1991). We conclude that the studied EC grains from correlated sediments from Sweden and China are related, and most likely originated in the same event, the L chondrite parent body breakup. We also analyzed chromites of modern H, L and LL chondrites and show that their Δ¹⁷O values coincide with averages of Δ¹⁷O of bulk analyses of H, L and LL chondrites. This study demonstrates that in situ oxygen isotope data measured by SIMS are accurate and precise if carefully standardized, and can be used to classify individual extraterrestrial chromite grains found in sediments.