Shock implantation of Martian atmospheric argon in four basaltic shergottites: A laser probe Ar/Ar investigation

Spatially resolved argon isotope measurements have been performed on neutron-irradiated samples of two Martian basalts (Los Angeles and Zagami) and two Martian olivine-phyric basalts (Dar al Gani (DaG) 476 and North West Africa (NWA) 1068). With a ∼50 μm diameter focused infrared laser beam, it has been possible to distinguish between argon isotopic signatures from host rock (matrix) minerals and localized shock melt products (pockets and veins). The concentrations of argon in analyzed phases from all four meteorites have been quantified using the measured J values, ⁴⁰Ar/³⁹Ar ratios and K₂O wt% in each phase. Melt pockets contain, on average, 10 times more gas (7-24 ppb ⁴⁰Ar) than shock veins and matrix minerals (0.3-3 ppb ⁴⁰Ar). The ⁴⁰Ar/³⁶Ar ratio of the Martian atmosphere, estimated from melt pocket argon extractions corrected for cosmogenic ³⁶Ar, is: Los Angeles (∼1852), Zagami (∼1744) and NWA 1068 (∼1403). In addition, Los Angeles shows evidence for variable mixing of two distinct trapped noble gas reservoirs: (1) Martian atmosphere in melt pockets, and (2) a trapped component, possibly Martian interior (⁴⁰Ar/³⁶Ar: 480-490) in matrix minerals. Average apparent ⁴⁰Ar/³⁹Ar ages determined for matrix minerals in the four analyzed meteorites are 1290 Ma (Los Angeles), 692 Ma (Zagami), 515 Ma (NWA 1068) and 1427 Ma (DaG 476). These ⁴⁰Ar/³⁹Ar apparent ages are substantially older than the ∼170-474 Ma radiometric ages given by other isotope dating techniques and reveal the presence of trapped ⁴⁰Ar. Cosmic ray exposure (CRE) ages were measured using spallogenic ³⁶Ar and ³⁸Ar production. Los Angeles (3.1 ± 0.2 Ma), Zagami (2.9 ± 0.4 Ma) and NWA 1068 (2.0 ± 0.5 Ma) yielded ages within the range of previous determinations. DaG 476, however, yielded a young CRE age (0.7 ± 0.25 Ma), attributed to terrestrial alteration. The high spatial variation of argon indicates that the incorporation of Martian atmospheric argon into near-surface rocks is controlled by localized glass-bearing melts produced by shock processes. In particular, the larger (mm-size) melt pockets contain near end-member Martian atmospheric argon. Based on petrography, composition and argon isotopic data we conclude that the investigated melt pockets formed by localized in situ shock melting associated with ejection. Three processes may have led to atmosphere incorporation: (1) argon implantation due to atmospheric shock front collision with the Martian surface, (2) transformation of an atmosphere-filled cavity into a localized melt zone, and (3) shock implantation of atmosphere trapped in cracks, pores and fissures.     

Ar and Ar recoil loss during neutron irradiation of sanidine and plagioclase

The ⁴⁰Ar/³⁹Ar dating technique requires the activation of ³⁹Ar via neutron irradiation. The energy produced by the reaction is transferred to the daughter atom as kinetic energy and triggers its displacement, known as the recoil effect. Significant amounts of ³⁹Ar and ³⁷Ar can be lost from minerals leading to spurious ages and biased age spectra. Through two experiments, we present direct measurement of the recoil-induced ³⁹Ar and ³⁷Ar losses on Fish Canyon sanidine and plagioclase. We use multi-grain populations with discrete sizes ranging from 210 to <5 μm. One population consists of a mixture between sanidine and plagioclase, and the other includes pure sanidine.We show that ³⁹Ar loss (depletion factor) for sanidine is ∼3% for the smallest fraction. Age spectra of fractions smaller than ∼50 μm show slight departure from flat plateau-age spectrum usually observed for large sanidine. This departure is roughly proportional to the size of the grain but does not show typical ³⁹Ar loss age spectra. The calculated thickness of the total depletion layer d₀(sanidine) is 0.035 ± 0.012 (2σ). This is equivalent to a mean depth of the partial depletion layer (x₀) of 0.070 ± 0.024 μm. The latter value is indistinguishable from previous values of ∼0.07-0.09 μm obtained by argon implantation experiments and simulation results.We show that it is possible to adequately correct ages from ³⁹Ar ejection loss provided that the d₀-value and the size range of the minerals are sufficiently constrained. As exemplified by similar calculations performed on results obtained in a similar study of GA1550 biotite [Paine J. H., Nomade S., and Renne P. R. (2006) Quantification of ³⁹Ar recoil ejection from GA1550 biotite during neutron irradiation as a function of grain dimensions. Geochim. Cosmochim. Acta70, 1507-1517.], the d₀(biotite) is 0.46 ± 0.06 μm. The significant difference between empirical results on biotite and sanidine, along with different simulation results, suggests that for biotite, crystal structures and lattice defects of the stopping medium and possibly subsequent thermal degassing (due to ∼150-200 °C temperature in the reactor or extraction line bake out) must play an important role in ³⁹Ar loss.The second experiment suggests that ³⁷Ar recoil can substantially affect the age via the interference corrections with results that suggest up to ∼98% of ³⁷Ar can be ejected from the ∼5 μm grain dimension.Further investigation of silicates of various compositions and structures are required to better understand (and correct) the recoil and recoil-induced effects on both ³⁹Ar and ³⁷Ar and their influences on ⁴⁰Ar/³⁹Ar dating.     

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.     

Testing the apatite-magnetite geochronometer: U-Pb and Ar/Ar geochronology of plutonic rocks, massive magnetite-apatite tabular bodies, and IOCG mineralization in Northern Chile

Detailed zircon and apatite U-Pb dating and ⁴⁰Ar/³⁹Ar dating of actinolite have been carried out on the Carmen-Sierra Aspera Kiruna type magnetite-apatite and iron oxide Cu-Au (IOCG) district in the Coastal Cordillera of northern Chile (∼26°S). They define a precise succession of magmatic and hydrothermal events associated with early Cretaceous Andean magmatism. Apatite and magnetite from a magnetite-apatite tabular body with intergrowth texture in the Carmen deposit yield a total Pb-U isochron age of 131.0 ± 1.0 Ma. This result is the first direct dating of magnetite-apatite mineralization in an early Andean deposit, and the age coincides with zircon ages of a quartz diorite stock that partially hosts mineralization (130.6 ± 0.3 Ma). Magnetite from the studied tabular body contains only small amounts of radiogenic Pb and serves to constrain the initial common Pb isotopic composition. The high degree of correlation suggests that both minerals closed for Pb diffusion at essentially the same time and at a relatively high temperature (close to that of zircon), making the apatite-magnetite pair a reliable geochronometer for igneous or hydrothermal crystallization. Zircon from the Sierra Aspera composite pluton yields ages between 131.3 ± 0.3 Ma and 127.4 ± 0.1 Ma, clearly resolving the timing of intrusion of discrete intrusive phases. Actinolite ⁴⁰Ar/³⁹Ar ages partially overlap the ages of plutonic phases of the Sierra Aspera pluton, but are younger than the magnetite-apatite tabular body. The initial Pb isotopic composition of the melts and/or fluids from which the magnetite-apatite tabular bodies crystallized is very similar to the primitive Pb isotopic composition of granitic magmas associated with early Cretaceous plutons measured in K-feldspar. The Pb isotopic correspondence, combined with the temporal and spatial association between magnetite-apatite mineralization and the dioritic-quartz dioritic magmatism, strongly suggests a genetic relationship between early Cretaceous continental arc magmatism, massive magnetite-apatite deposits, and IOCG mineralization.     

Spatially correlated anomalous Ar/Ar “age” variations in biotites about a lithologic contact near Simplon Pass, Switzerland: a mechanistic explanation for excess Ar

Forty-four biotite samples collected about a lithologic contact between pelite and amphibolite were analyzed for ⁴⁰Ar/³⁹Ar and demonstrate the importance of bulk Ar diffusivity and system geometry—factors not usually considered in the interpretation and collection of ⁴⁰Ar/³⁹Ar age data. The resulting ⁴⁰Ar/³⁹Ar apparent ages range from 11.30 ± 0.05 Ma to 17.90 ± 0.10 Ma. The ages (and excess argon contents) are spatially and lithologically correlated. The pelite samples all yield ages clustering around ∼12 Ma, the age expected for cooling through biotite closure (∼360°C) in this region of the Alps. Ages in the amphibolite biotites are older, showing a smooth trend between 15 Ma at the contact with the pelite to 18 Ma, 34 cm from the contact. This data shows that characterization of the Ar closure age for biotite in a given system should not rest on a single sample, as otherwise irresolvable differences in age between samples within the same outcrop can exist. A generalized mechanistic model for excess argon is presented. The presence (or absence) of excess Ar depends on an intrinsic system parameter, τ_T, the transmissive timescale, which is the characteristic time for ⁴⁰Ar to escape through the local intergranular transporting medium (ITM) to some sink for argon. To prevent buildup of geochronologically significant excess ⁴⁰Ar, τ_T must be very short relative to the true closure age of the mineral. A FORTRAN code including radiogenic Ar production, diffusive loss of Ar from biotite, and bulk Ar diffusion through the ITM has been developed. Application of numerical modeling suggests that the time-averaged effective bulk diffusivity, D_eff^Ar, in the biotite-amphibolite rock during early retrograde cooling is 2.2 ± 1.0 × 10⁻⁸ m²/yr (assuming steady state conditions) - the first such measurement available. Numerical modeling also provides information about the transmissivity and geologic history specific to the field site, including a drop in D_eff^Ar at 15.5 ± 1.0 Ma. The timing of this drop is related to coincident rheological changes and the onset of rapid exhumation of the nappe stack.     

Development of high precision Rb-Sr phlogopite and biotite geochronology; an alternative to Ar/Ar tri-octahedral mica dating

Potassium-Ar and Rb-Sr dating of minerals was fundamental in early efforts to date magmatic and metamorphic processes and paved the way for geochronology to become an important discipline within the earth sciences. Although K-Ar and, in particular, ⁴⁰Ar/³⁹Ar dating of micas is still widely applied, Rb-Sr dating of micas has declined in use, even though numerous studies demonstrated that tri-octahedral mica yields geologically realistic, and more reliable and reproducible Rb-Sr ages than the K-Ar or ⁴⁰Ar/³⁹Ar system. Moreover, a reduction of uncertainties typically reported for Rb-Sr ages (ca. 1%) can now be achieved by application of multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) rubidium isotope dilution measurements (<0.3%). Replicate Rb-Sr biotite ages from the Oslo rift, Norway, yield an external reproducibility of ±0.3% (n=4) and an analytical error of ±0.8 Ma for individual ages that vary between 276.9 and 275.5 Ma. Conventional thermal ionisation mass spectrometry (TIMS) Rb analysis on the same mineral separates yields ages between 276.1 and 271.7 Ma, three times the spread compared to Rb MC-ICPMS data. Biotite and phlogopite from the central Nagssugtoqidian orogen, West Greenland, yield ⁴⁰Ar/³⁹Ar plateau ages (ca. 1700 Ma) with a spread of ±150 Ma, while Rb-Sr ages on either biotite or phlogopite separates have a much narrower range of ±10 Ma. This comparison of Rb-Sr and ⁴⁰Ar/³⁹Ar ages demonstrates the robustness of the Rb-Sr system in tri-octahedral micas and cautions against the sole use of ⁴⁰Ar/³⁹Ar tri-octahedral mica ages to date geological events. Analytical errors of 16 Ma for these Rb-Sr mica ages determined by TIMS are reduced to <±5 Ma when the Rb concentration is determined by MC-ICPMS. All the TIMS and MC-ICPMS data from the Nagssugtoqidian orogen agree within assigned analytical uncertainties. However, high precision Rb-Sr dating by MC-ICPMS can resolve geological information obscured by TIMS age determinations. TIMS data for seven phlogopite samples form an isochron age of 1645±6 Ma, and thus, no differentiation in age between the different samples can be made. In contrast, MC-ICPMS Rb measurements on the same samples reveal two distinct populations with ages of 1633±3 or 1652±5 Ma.Combining the mica Rb-Sr geochronological data with the well-constrained thermal history of this ancient orogen, we estimate the closure temperature of the Rb-Sr system in 1-2 mm slowly cooled phlogopite crystals, occurring in a matrix of calcite and plagioclase to be ∼435 °C, and at least 50 °C above that of biotite.     

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.     

SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ¹⁸O range from +7.9‰ to +27.5‰ and include the highest reported δ¹⁸O values for BIF quartz. Values of δ³⁰Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ³⁰Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ¹⁸O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ³⁰Si up to 3‰, similar to the range in δ³⁰Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ³⁰Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ³⁰Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ³⁰Si < −0.5‰) but silicon from continental weathering (δ³⁰Si ∼ 1‰) was an important source as early as 3.8 Ga.     

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.     

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.     

Joint determination of K decay constants and Ar∗/K for the Fish Canyon sanidine standard, and improved accuracy for Ar/Ar geochronology

⁴⁰Ar/³⁹Ar and K-Ar geochronology have long suffered from large systematic errors arising from imprecise K and Ar isotopic data for standards and imprecisely determined decay constants for the branched decay of ⁴⁰K by electron capture and β⁻ emission. This study presents a statistical optimization approach allowing constraints from ⁴⁰K activity data, K-Ar isotopic data, and pairs of ²³⁸U-²⁰⁶Pb and ⁴⁰Ar/³⁹Ar data for rigorously selected rocks to be used as inputs for estimating the partial decay constants (λ_ε and λ_β) of ⁴⁰K and the ⁴⁰Ar∗/⁴⁰K ratio (κ_FCs) of the widely used Fish Canyon sanidine (FCs) standard. This yields values of κ_FCs = (1.6418 ± 0.0045) × 10⁻³, λ_ε = (0.5755 ± 0.0016) × 10⁻¹⁰ a⁻¹ and λ_β = (4.9737 ± 0.0093) × 10⁻¹⁰ a⁻¹. These results improve uncertainties in the decay constants by a factor of >4 relative to values derived from activity data alone. Uncertainties in these variables determined by our approach are moderately to highly correlated (cov(κ_FCs, λ_ε) = 7.1889 × 10⁻¹⁹, cov(κ_FCs, λ_β) = −7.1390 × 10⁻¹⁹, cov(λ_ε, λ_β) = −3.4497 × 10⁻²⁶) and one must take account of the covariances in error propagation by either linear or Monte Carlo methods. ⁴⁰Ar/³⁹Ar age errors estimated from these results are significantly reduced relative to previous calibrations. Also, age errors are smaller for a comparable level of isotopic measurement precision than those produced by the ²³⁸U/²⁰⁶Pb system, because the ⁴⁰Ar/³⁹Ar system is now jointly calibrated by both the ⁴⁰K and ²³⁸U decay constants, and because λ_ε(⁴⁰K) < λ(²³⁸U). Based on this new calibration, the age of the widely used Fish Canyon sanidine standard is 28.305 ± 0.036 Ma. The increased accuracy of ⁴⁰Ar/³⁹Ar ages is now adequate to provide meaningful validation of high-precision U/Pb or astronomical tuning ages in cases where closed system behavior of K and Ar can be established.     

A redetermination of the isotopic abundances of atmospheric Ar

Atmospheric argon measured on a dynamically operated mass spectrometer with an ion source magnet, indicated systematically larger ⁴⁰Ar/³⁶Ar ratios compared to the generally accepted value of Nier [Nier A.O., 1950. A redetermination of the relative abundances of the isotopes of carbon, nitrogen, oxygen, argon, and potassium. Phys. Rev. 77, 789-793], 295.5 ± 0.5, which has served as the standard for all isotopic measurements in geochemistry and cosmochemistry. Gravimetrically prepared mixtures of highly enriched ³⁶Ar and ⁴⁰Ar were utilized to redetermine the isotopic abundances of atmospheric Ar, using a dynamically operated isotope ratio mass spectrometer with minor modifications and special gas handling techniques to avoid fractionation. A new ratio ⁴⁰Ar/³⁶Ar = 298.56 ± 0.31 was obtained with a precision of 0.1%, approximately 1% higher than the previously accepted value. Combined with the ³⁸Ar/³⁶Ar (0.1885 ± 0.0003) measured with a VG5400 noble gas mass spectrometer in static operation, the percent abundances of ³⁶Ar, ³⁸Ar, and ⁴⁰Ar were determined to be 0.3336 ± 0.0004, 0.0629 ± 0.0001, and 99.6035 ± 0.0004, respectively. We calculate an atomic mass of Ar of 39.9478 ± 0.0002. Accurate Ar isotopic abundances are relevant in numerous applications, as the calibration of the mass spectrometer discrimination.     

Ar loss in experimentally deformed muscovite and biotite with implications for Ar/Ar geochronology of naturally deformed rocks

The effects of deformation on radiogenic argon (⁴⁰Ar^∗) retentivity in mica are described from high pressure experiments performed on rock samples of peraluminous granite containing euhedral muscovite and biotite. Cylindrical cores, ∼15 mm in length and 6.25 mm in diameter, were drilled from granite collected from the South Armorican Massif in northwestern France, loaded into gold capsules, and weld-sealed in the presence of excess water. The samples were deformed at a pressure of 10 kb and a temperature of 600 °C over a period 29 of hours within a solid medium assembly in a Griggs-type triaxial hydraulic deformation apparatus. Overall shortening in the experiments was approximately 10%. Transmitted light and secondary and backscattered electron imaging of the deformed granite samples reveals evidence of induced defects and for significant physical grain size reduction by kinking, cracking, and grain segmentation of the micas.Infrared (IR) laser (CO₂) heating of individual 1.5-2.5 mm diameter grains of muscovite and biotite separated from the undeformed granite yield well-defined ⁴⁰Ar/³⁹Ar plateau ages of 311 ± 2 Ma (2σ). Identical experiments on single grains separated from the experimentally deformed granite yield results indicating ⁴⁰Ar^∗ loss of 0-35% in muscovite and 2-3% ⁴⁰Ar^∗ loss in biotite. Intragrain in situ ultraviolet (UV) laser ablation ⁴⁰Ar/³⁹Ar ages (±4-10%, 1σ) of deformed muscovites range from 309 ± 13 to 264 ± 7 Ma, consistent with 0-16% ⁴⁰Ar^∗ loss relative to the undeformed muscovite. The in situ UV laser ablation ⁴⁰Ar/³⁹Ar ages of deformed biotite vary from 301 to 217 Ma, consistent with up to 32% ⁴⁰Ar^∗ loss. No spatial correlation is observed between in situ⁴⁰Ar/³⁹Ar age and position within individual grains. Using available argon diffusion data for muscovite the observed ⁴⁰Ar^∗ loss in the experimentally treated muscovite can be utilized to predict average ⁴⁰Ar^∗ diffusion dimensions. Maximum ⁴⁰Ar/³⁹Ar ages obtained by UV laser ablation overlap those of the undeformed muscovite, indicating argon loss of <1% and an average effective grain radius for ⁴⁰Ar^∗ diffusion ?700 μm. The UV laser ablation and IR laser incremental ⁴⁰Ar/³⁹Ar ages indicating ⁴⁰Ar^∗ loss of 16% and 35%, respectively, are consistent with an average diffusion radius ?100 μm. These results support a hypothesis of grain-scale ⁴⁰Ar^∗ diffusion distances in undeformed mica and a heterogeneous mechanical reduction in the intragrain effective diffusion length scale for ⁴⁰Ar^∗ in deformed mica. Reduction in the effective diffusion length scale in naturally deformed samples occurs most probably through production of mesoscopic and submicroscopic defects such as, e.g., stacking faults. A network of interconnected defects, continuously forming and annealing during dynamic deformation likely plays an important role in controlling both ⁴⁰Ar^∗ retention and intragrain distribution in deformed mica. Intragrain ⁴⁰Ar/³⁹Ar ages, when combined with estimates of diffusion kinetics and distances, may provide a means of establishing thermochronological histories from individual micas.     

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.     

Age calibration of the Fish Canyon sanidine Ar/Ar dating standard using primary K-Ar standards

The ⁴⁰Ar/³⁹Ar dating technique requires the use of neutron fluence monitors (standards). Precise calibrations of these standards are crucial to decrease the uncertainties associated with ⁴⁰Ar/³⁹Ar dates. Optimal calibration of ⁴⁰Ar/³⁹Ar standards should be based on K/Ar standards having independent isotope dilution measurements of ⁴⁰K and ⁴⁰Ar*, based on independent isotope tracers (spikes) because this offers the possibility to eliminate random interlaboratory errors. In this study, we calibrate the widely used Fish Canyon sanidine (FCs) standard based on four primary K/Ar standards (GA-1550, Hb3gr, NL-25, and GHC-305) on which K and Ar* concentrations have been determined in different labs with independently calibrated tracers. We obtained a mean age of 28.03 ± 0.08 Ma (1σ; neglecting uncertainties of the ⁴⁰K decay constants) for FCs, based on the decay constant recommended by Steiger and Jäger [Steiger R.H., Jäger. E. 1977. Subcommission on geochronology: convention of the use of decay constants in geo- and cosmochronology. Earth Planet. Sci. Lett.36, 359-362.]. This age corresponds to a mean ⁴⁰Ar*/⁴⁰K value of (1.6407 ± 0.0047) × 10⁻³. We also discuss several criteria that prevent the use of previous calibrations of FCs based on other primary standards (LP-6, SB-3 and MMhb-1). The age of FCs obtained in this study is based on the ⁴⁰K decay constants of Steiger and Jäger (1977) but we anticipate the imminent need for revision of the value and precision of the ⁴⁰K decay constants (representing the main source of uncertainties in ⁴⁰Ar/³⁹Ar dating). The ⁴⁰Ar*/⁴⁰K result of FCs obtained in this study allows therefore a rapid calibration of the age of FCs with uncertainties at the 0.29% level but perhaps more importantly this value is independent of any particular value of the ⁴⁰K decay constants and may be used in the future in conjunction with revised decay constants.     

Rb-Sr whole-rock and 40Ar/39Ar mineral ages of the Togus and Hallowell quartz monzonite and Three Mile Pond granodiorite plutons,South-Central Maine: Their bearing on post-Acadian cooling history

Generally synmetamorphic granitic stocks intrude high-grade, Silurian-lowermost Devonian metasedimentary rocks near Augusta, Maine. Rb-Sr whole-rock isochrons (8 points each) define mutually overlapping crystallization ages of 394±8 m.y. (Togus quartz monzonite), 387±11 m.y. (Hallowell quartz monzonite), and 381±14 m.y. (Three Mile Pond biotite granodiorite), thereby providing a narrow chronologic bracket for Acadian tectonothermal activity in the area. Igneous hornblende, muscovite, and biotite display internally concordant ⁴⁰Ar/³⁹Ar age spectra with plateau dates of 350 m.y. (hornblende) and 300-265 m.y. (muscovite and biotite), with an overall southwestward younging trend. The mineral dates are similar to those recorded in adjacent portions of the regional metamorphic terrain and suggest a prolonged postmagmatic cooling which closely followed the diachronous northeast-southwest post-Acadian cooling of the country rocks. No evidence for a distinct Permian thermal overprint of older isotopic systems has been observed.     

Retrograde evolution of eclogites: evidences from microstructures and 40Ar/39Ar white mica dates,Münchberg Massif,northern Bavaria

Phengites from eclogites and pegmatites (3T, 2M₁, coarse-grained and recrystallized) of the Münchberg Massif (Weissenstein and Oberkotzau) have been dated by the ⁴⁰Ar/³⁹Ar method. 3T-micas from the eclogites yielded plateau and isochron ages of 365±7 Ma. 2M₁-micas show disturbed degassing spectra. Micas from pegmatites show a slight excess Ar component, with an isochron age of 353 to 351±3 Ma. An age component of approximately 300 Ma was also detected. In combination with age values from the literature, the cooling history of the Münchberg Massif from eclogite-facies conditions (390 Ma) to cooling below 350°C (350 Ma) is documented. The age component of 300 Ma is attributed to a low-grade stage of mineral growth accompanied by a transitional ductile-brittle deformation. The petrological effects include formation of pumpellyite-prehnite-facies minerals, frequently precipitated in microcraks and cleavage planes of earlier formed minerals. This stage has to be seen in conjunction with the intrusions of the Fichtelgebirge granite.     

Sources, degassing, and contamination of CO2, H2O, He, Ne, and Ar in basaltic glasses from Kolbeinsey Ridge, North Atlantic

New volatile data (CO₂, H₂O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO₂ and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ¹³C values of dissolved CO₂ or coupled CO₂-Ar variations. This suggests that δ¹³C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H₂O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO₂ with δ¹³C of −6‰, 0.1 to 0.35 wt.% H₂O, ³He/⁴He ∼11 R_A, and CO₂/³He of ∼2 × 10⁹. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the ⁴⁰Ar/³⁶Ar may be low. The ³He/⁴He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R_A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of ³He/⁴He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.     

Ar/Ar dating of hydrothermal activity, biota and gold mineralization in the Rhynie hot-spring system, Aberdeenshire, Scotland

This study presents a new high-precision ⁴⁰Ar/³⁹Ar age for the Devonian hot-spring system at Rhynie. Hydrothermal K-feldspar sampled from two veins that represent feeder conduits and a hydrothermally altered andesite wall rock, date the hydrothermal activity, the fossilised biota, and syn - K-feldspar gold mineralization at 403.9 ± 2.1 Ma (2σ). Oxygen isotope data for the parent fluid (−4‰ to 2‰) show that the K-feldspar was precipitated from a dominantly meteoric fluid, which mixed with magmatic fluids from a degassing magma chamber.The ⁴⁰Ar/³⁹Ar age (403.9 ± 2.1 Ma [2σ]) when recalculated (407.1 ± 2.2 Ma [2σ]) with respect to the astronomically tuned age for Fish Canyon sanidine (28.201 ± 0.023 Ma [1σ]), also provides a robust marker for the polygonalis-emsiensis Spore Assemblage Biozone within the Pragian-?earliest Emsian. Furthermore, the age identifies the Devonian pull-apart volcano-sedimentary basins of the British and Irish Caledonides (and their root zones), as specific targets for future gold exploration.     

A K-Ar and 40Ar/39Ar study on white micas from the Brixen Quartzphyllite,Southern Alps

The Brixen Quartzphyllite, basement of the Southern Alps (Italy), consists of metasediments which had suffered progressive deformation and low grade metamorphism (p _max4 kbar, T _max375±25° C) during the Palaeozoic. It has been excavated by pre-Permian erosion, buried again beneath a pile of Permo-mesozoic to Cainozoic sediments (estimated T _max150° C), and is now exposed anew due to late Alpine uplift and erosion. The behavior of the K-Ar system of white micas is investigated, taking advantage of the narrow constraints on their thermal history imposed by the geological/stratigraphic reference systems.The six structurally and petrographically differing samples come from a single outcrop, whose position is roughly two kilometers beneath the Permian land-surface. White mica concentrates from five grain size fractions (<2 , 2–6 , 6–20 , 20–60 , 60–75 ) of each sample have been analyzed by the conventional K-Ar method, four selected concentrates additionally by the ⁴⁰Ar/³⁹Ar stepwise heating technique; furthermore, Ar content and isotopic composition of vein quartz were determined.The conventional ages of the natural grain size fractions (20–60 , 60–75) are in the range 316±8 Ma, which corresponds to the ⁴⁰Ar/³⁹Ar plateau age of 319.0±5.5 Ma within the error limits. The finer grain size fractions yield significantly lower ages, down to 233 Ma for fractions <2 . Likewise low apparent ages (down to 83 Ma) are obtained for the low temperature ⁴⁰Ar/³⁹Ar degassing steps.There is no correlation between microstructural generation of white mica prevailing in the sample and apparent age. This favours an interpretation of the 316±8 Ma values as cooling age; progressive deformation and metamorphism must be respectively older and their timing cannot be resolved by these methods. The data preclude any significant influence of a detrital mica component as well as of excess argon.The lower ages found for the fine grain-size fractions (respectively the low-T degassing steps) correspond to a near-surface period (p-T-minimum); the values are geologically meaningless. The effect is interpreted to result from partial Ar loss due to reheating during Mesozoic-Cainozoic reburial. A model based on diffusion parameters derived from the outgassing experiments and Dodson's (1979) equation yields a closure temperature of 284±40 °C for a cooling rate of 18° C/Ma. Furthermore, this model suggests that the observed argon loss of up to 5% may in fact have been induced by reheating to 150 °C for 50 Ma.