Argon, krypton, and xenon in the bulk solar wind as collected by the Genesis mission

We present bulk solar wind isotopic and elemental ratios for Ar, Kr, and Xe averaged from up to 14 individual analyses on silicon targets exposed to the solar wind for ∼2.3 years during NASA’s Genesis mission. All averages are given with 1σ standard errors of the means and include the uncertainties of our absolute calibrations. The isotopic ratios ⁸⁶Kr/⁸⁴Kr and ¹²⁹Xe/¹³²Xe are 0.303 ± 0.001 and 1.06 ± 0.01, respectively. The elemental ratios ³⁶Ar/⁸⁴Kr and ⁸⁴Kr/¹³²Xe are 2390 ± 120 and 9.9 ± 0.3, respectively. Average fluxes of ⁸⁴Kr and ¹³²Xe in the bulk solar wind in atoms/(cm² s) are 0.166 ± 0.009 and 0.017 ± 0.001, respectively. The flux uncertainties also include a 2% uncertainty for the determination of the extracted areas. The bulk solar wind ³⁶Ar/³⁸Ar ratio of 5.50 ± 0.01 and the ³⁶Ar flux of 397 ± 11 atoms/(cm² s) determined from silicon targets agree well with the ³⁶Ar/³⁸Ar ratio and the ³⁶Ar flux determined earlier on a different type of target by Heber et al. (2009). A comparison of the solar wind noble gas/oxygen abundance ratios with those in the solar photosphere revealed a slight enrichment of Xe and, within uncertainties a roughly uniform depletion of Kr-He in the solar wind, possibly related to the first ionization potentials of the studied elements. Thus, the solar wind elemental abundances He-Kr display within uncertainties roughly photospheric compositions relative to each other. A comparison of the Genesis data with solar wind heavy noble gas data deduced from lunar regolith samples irradiated with solar wind at different times in the past reveals uniform ³⁶Ar/⁸⁴Kr ratios over the last 1-2 Ga but an increase of the ⁸⁴Kr/¹³²Xe ratio of about a factor of 2 during the same time span. The reason for this change in the solar wind composition remains unknown.     

The distribution of mantle and atmospheric argon in oceanic basalt glasses

Argon analyses by both high-resolution stepheating and stepcrushing of MORB and Loihi basalt glasses were performed to separate pristine mantle-derived Ar and contaminating atmospheric Ar. In high-vesicularity glasses (> 0.8% vesicles), most of the mantle argon resides in vesicles, from which it is released by crushing or stepheating between 600 and 900 °C. By contrast, in low vesicularity glasses (< permil vesicularity), most mantle argon is dissolved in the glass matrix, as inferred from the correlation with neutron-induced, glass-dissolved argon isotopes (³⁹Ar, ³⁷Ar, ³⁸Ar from K, Ca, Cl). The distribution of mantle Ar between vesicles and glass matrix is well explained by melt-gas equilibrium partitioning at eruption according to Henry’s law, which is compatible with previously determined Henry constants of ∼(5-10) × 10⁻⁵ccSTP ⁴⁰Ar _mantle/g bar. Atmospheric Ar is heterogeneously distributed in all samples. Only a very minor part is dissolved in the glass matrix; a significant part correlates with vesicularity and is released by crushing, most probably from a rather small fraction of vesicles or microcracks that equilibrated with unfractionated air. Other carriers of atmospheric argon are pyroxene microlites and minor phases decomposing at intermediate temperatures that were probably contaminated upon eruption by fractionated atmospheric rare gases. Our high-resolution stepheating and stepcrushing analyses of low vesicularity samples with extraordinary high solar-like ²⁰Ne/²²Ne indicate successful discrimination of unfractionated air as a contamination source and suggest an upper mantle ⁴⁰Ar/³⁶Ar of 32,000 ± 4000 and a Hawaiian mantle plume source ⁴⁰Ar/³⁶Ar ratio close to 8000.     

Argon and nitrogen isotopes of trapped air in the GISP2 ice core during the Holocene epoch (0-11,500 B.P.): Methodology and implications for gas loss processes

Argon and nitrogen isotopes of air in polar ice cores provide constraints on past temperature and firn thickness, with relevance to past climate. We developed a method to simultaneously measure nitrogen and argon isotopes in trapped air from the same sample of polar ice. This method reduces the time required for analysis, allowing large numbers of measurements. We applied this method to the entire Holocene sequence of the GISP2 ice core (82.37-1692.22 m) with a 10-20 year sampling interval (670 depths). δ⁴⁰Ar and δ¹⁵N show elevated values in the oldest part of the dataset, consistent with a thicker firn layer and increased temperature gradient in the firn due to the legacy of the abrupt warming at the end of the Younger Dryas interval and the gradual warming during the Preboreal interval (11.5-10.0 ka). The Preboreal Oscillation and the 8.2k event are clearly recorded. The data show remarkable stability after the 8.2k event.Available data suggests that post-coring gas loss involves two distinct types of fractionation. First, smaller molecules with less than a certain threshold size leak through the ice lattice with little isotopic fractionation. Second, gas composition changes via gas loss through microcracks, which induces isotopic fractionation. These two gas loss processes can explain most trends in our data and in other ice core records.     

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.     

Ice-rafted detritus evidence from 40Ar/39Ar ages of individual hornblende grains for evolution of the eastern margin of the Laurentide ice sheet since 43 14C ky

During the last glacial interval, the North Atlantic ice sheets expanded and contracted in approximate synchronicity with orbitally forced global climate change. Variation in ice rafted detritus content in North Atlantic marine sediment cores record the waxing and waning of glaciers, as well as the abrupt temperature changes at millennial time scales. The background variations of ice rafting are punctuated by Heinrich layers, which appear to record the catastrophic collapse of the Laurentide ice sheet through the Hudson Strait. The objective of this paper is to document the evolution of glaciation on Laurentia during the last 43 ¹⁴C kyr. We present a provenance study based on ⁴⁰Ar/³⁹Ar dates of individual hornblende grains from 57 samples taken at 2 cm spacing between 4 and 134 cm from core V23-14 (43.4°N, 45.25°W, 3177 m). Sedimentation rates outside of the Heinrich layers are very low in this core, but the Heinrich layers are easily identified. Laurentide glaciation did not extend into the ocean south of 55°N until about 26 ¹⁴C kyr, and retreated to the coastline or beyond by 14 ¹⁴C kyr. Documenting the history of this major ice sheet has significant implications for understanding ice rafting sources in more distal locations where mixing among different ice sheets is likely.     

Noble gases in ureilites: cosmogenic, radiogenic, and trapped components

Abundances and isotopic compositions of Ne (in bulk samples only), Ar, Kr, and Xe have been investigated in 6 monomict, 3 polymict, and the diamond-free ureilite ALH78019 and their acid-resistant, C-rich residues. Isotopic ratios of Kr and Xe are very uniform and agree with data for ureilites from the literature. The measured ratio ³⁸Ar/³⁶Ar showed large variations due to an experimental artifact. This is shown to be connected to the pressure dependence of the instrumental mass discrimination, which for ureilites with their low abundance of ⁴⁰Ar is different from that of the usual air standard. This observation necessitates a reassessment for the recently reported ³⁶Ar excesses due to possible decay of extinct ³⁶Cl in the Efremovka meteorite.Trapped ²²Ne in the range of (1.4-2.5) × 10⁻⁸ cc STP/g is present in bulk ureilites. A Ne three-isotope plot for polymict ureilites indicates the presence of solar Ne. ²¹Ne-based cosmic ray exposure ages for the 10 ureilites studied range from 0.1 Ma (for ALH78019) to 46.8 Ma (for EET83309)All ureilites may have started with nearly the same initial elemental ratio (¹³²Xe/³⁶Ar)₀, established in the nebula during gas trapping into their carbon carrier phases (diamond, amorphous C) by ion implantation. Whereas diamonds are highly retentive, amorphous C has suffered gas loss due to parent body metamorphism. The correlation of the elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar along the mass fractionation line could be understood as a two-component mixture of the unaffected diamond gases and the fractionated (to varying degrees) gases from amorphous C. In this view, the initial ratio (¹³²Xe/³⁶Ar)₀ is a measure of the plasma temperature in the nebula at the formation location of the carbon phases. Its lack of correlation with Δ¹⁷O (a signature of the silicate formation location) indicates that carbon phases and silicates formed independently in the nebula, and not from a carbon-rich magmaThe elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar in carbon-rich acid residues show a decreasing trend with depth (inferred from carbon consumption during combustion), which can be interpreted as a consequence of the ion implantation mechanism of gas trapping that leads to greater depth of implantation for lighter mass ionThe similarity between trapped gases in phase Q in primitive chondrites and the C phases in ureilites—for both elemental and isotopic compositions—strongly suggests that phase Q might also have received its noble gases by ion implantation from the nebula. The slight differences in the elemental ratios can be explained by a plasma temperature at the location of phase Q gas loading that was about 2000 K lower than for ureilite C phases. This inference is also consistent with the finding that the trapped ratio ¹²⁹Xe/¹³²Xe (1.042 ± 0.002) in phase Q is slightly higher, compared to that of ureilite C phases (1.035 ± 0.002), as a consequence of in situ decay of ¹²⁹I, and becomes observable due to higher value of I/Xe in phase Q as a result of ion implantation at about 2000 K lower plasma temperature.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

Irradiation records in regolith materials, II: Solar wind and solar energetic particle components in helium, neon, and argon extracted from single lunar mineral grains and from the Kapoeta howardite by stepwise pulse heating

High-resolution stepped heating has been used to extract light noble gases implanted in a suite of 13 individual lunar ilmenite and iron grains and in the Kapoeta howardite by solar wind (SW) and solar energetic particle (SEP) irradiation. Isotopic analyses of gases evolved at low temperatures from the lunar grains confirm the neon and argon compositions obtained by Pepin et al. (Pepin R. O., Becker R. H., and Schlutter D. J., “Irradiation records in regolith materials, I: Isotopic compositions of solar-wind neon and argon in single lunar regolith grains”, Geochim. Cosmochim. Acta63, 2145-2162, 1999) in an initial study of 11 regolith grains, primarily ilmenites. Combination of the data sets from both investigations yields ²⁰Ne/²²Ne = 13.85 ± 0.04, ²¹Ne/²²Ne = 0.0334 ± 0.0003, and ³⁶Ar/³⁸Ar = 5.80 ± 0.06 for the lunar samples; the corresponding ³⁶Ar/³⁸Ar ratio in Kapoeta is 5.74 ± 0.06. The neon ratios agree well with those measured by Benkert et al. (Benkert J.-P., Baur H., Signer P., and Wieler R., “He, Ne, and Ar from the solar wind and solar energetic particles in lunar ilmenites and pyroxenes”, J. Geophys. Res. (Planets)98, 13147-13162, 1993) in gases extracted from bulk lunar ilmenite samples by stepped acid etching and attributed by them to the SW. The ³⁶Ar/³⁸Ar ratios, however, are significantly above both Benkert et al.’s (1993) proposed SW value of 5.48 ± 0.05 and a later estimate of 5.58 ± 0.03 from an acid-etch analysis of Kapoeta (Becker R. H., Schlutter D. J., Rider P. E., and Pepin R. O., “An acid-etch study of the Kapoeta achondrite: Implications for the argon-36/argon-38 ratio in the solar wind”, Meteorit. Planet. Sci.33, 109-113, 1998). We believe, for reasons discussed here and in our earlier report, that 5.80 ± 0.06 ratio most nearly represents the wind composition. The ³He/⁴He ratio in low-temperature gas releases, not measured in the first particle suite, is found in several grains to be indistinguishable from Benkert et al.’s (1993) SW estimate. Elemental ratios of He, Ne, and Ar initially released from grain-surface SW implantation zones are solar-like, as found earlier by Pepin et al. (1999). Gases evolved from these reservoirs at higher temperatures show evidence for perturbations from solar elemental compositions by prior He loss, thermal mobilization of excess Ne from fractionated SW components, or both.Attention in this second investigation was focused on estimating the isotopic compositions of both the SW and the more deeply sited SEP components in regolith grains. Several high-temperature “isotopic plateaus”—approximately constant isotopic ratios in gas fractions released over a number of consecutive heating steps—were observed in the close vicinities of the SEP ratios for He, Ne, and Ar reported by Benkert et al. (1993). Arguments presented in the text suggest that these plateaus are relatively free of interferences from multicomponent mixing artifacts that can mimic pure component signatures. Average SEP compositions derived from the stepped-heating plateau measurements are in remarkable agreement with the Zürich acid-etch values for all three gases.     

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.     

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (³He/⁴He = 4-6 Ra, ⁴⁰Ar/³⁶Ar = 20,000-30,000, δ¹³C = −4.5‰ to −6.9‰ and δ¹⁵N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high ³⁶Ar content of the diamonds (>1 × 10⁻⁹ cm³/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the ³⁶Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10⁻¹² cm³/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.     

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.     

Evidence for excess argon during high pressure metamorphism in the dora maira massif (Western Alps,Italy), using an ultra-violet laser ablation microprobe 40Ar-39Ar technique

 Ultra-high pressure eclogite/amphibolite grade metamorphism of the Dora Maira Massif in the western Alps is a well established and intensively studied event. However, the age of peak metamorphism and early cooling remains controversial. The ⁴⁰Ar-³⁹Ar step-heating and laser spot ages from high pressure phengites yield plateau ages as old as 110 Ma which have been interpreted as the time of early cooling after the high pressure event. Recent U/Pb and Sm/Nd results challenge this assertion, indicating a much younger age for the event, around 45 Ma, and hence a radically different timing for the tectonic evolution of the western Alps. In a new approach to the problem, samples from the undeformed Hercynian metagranite, Brossasco, were studied using an ultra-violet laser ablation microprobe technique for ⁴⁰Ar-³⁹Ar dating. The new technique allowed selective in situ analysis, at a spatial resolution of 50 μm, of quartz, phengite, biotite and K-feldspar. The results demonstrate the frequent occurrence of excess argon with high ⁴⁰Ar-³⁶Ar ratios (1000–10000) and a strong relationship between apparent ages and metamorphic textures. The highest excess argon ratios are always associated with high closure temperature minerals or large diffusion domains within single mineral phases. The best interpretation of this relationship seems to be that excess argon was incorporated in all phases during the high pressure event, then mixed with an atmospheric component during rapid cooling and retrogression, producing a wide range of argon concentrations and ⁴⁰Ar/³⁶Ar ratios. Step-heating analysis of minerals with this mixture would produce linear arrays on a ³⁶Ar/⁴⁰Ar versus ³⁹Ar/⁴⁰Ar correlation diagram, leading to geologically meaningless plateau ages, older than the true closure age. In the present case, some ages in the range 60–110 Ma could be explained by the presence of excess argon incorporated around 40–50 Ma ago. Similar results found in other high pressure terrains in the Alps may reconcile the argon geochronometer with other systems such as Rb/Sr, U/Pb or Sm/Nd. This study therefore calls for an increasing use of high resolution in situ sampling techniques to clarify the meaning of ⁴⁰Ar/³⁹Ar ages in many high pressure terrains. Received: 6 January 1994/Accepted: 4 April 1995     

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.     

Evidence for a nitrogen flux directly derived from the European subcontinental mantle in the Western Eger Rift, Central Europe

In the Czech-German border region of the Vogtland and NW Bohemia (western Eger rift, Central Europe), chemical and isotopic compositions (C, N, He, Ar) of free gas from a thermal water escape (fluorite mine, Schönbrunn), two mineral springs (“Eisenquelle,” Bad Brambach; “Sprudel III,” Bad Elster) and a mofette (Bublak) located along an ∼40-km long traverse are reported. The gases of Bublak and Bad Brambach are CO₂-rich (>99 vol.%) and have δ¹³C values of −1.95 and −4.29‰, respectively. With distance from the center of CO₂ degassing (Bublak) the δ¹³C values decrease, most likely due to physico-chemical fractionation of CO₂ between gaseous and aqueous phases rather than to admixture of organic/biogenic CO₂. The δ¹⁵N values range between −3.2 and −0.6‰, compared to an upper mantle value of −4.0 ± 1.0‰. The four locations are characterized by ³He/⁴He ratios decreasing from 5.9 R_a in the center (Bublak) to 0.8 R_a in the periphery (Schönbrunn) and give evidence for mixing of He from a deep-seated magmatic source with a crustal source. The location with the highest ³He/⁴He ratio (5.9 R_a) is accompanied by the highest ⁴⁰Ar/³⁶Ar (550). We argue that the nitrogen of the Bublak mofette gas is a mixture of predominantly atmospheric and mantle-derived components, whereas at the other three locations crustal nitrogen may also be present. The Bublak δ¹⁵N value of ≈−4.5 ± 1.0‰ represents the first free gas δ¹⁵N reference from the European subcontinental mantle (ESCM) and indicates that, in contrast to the ³He/⁴He ratios, the δ¹⁵N values are equal for ESCM and MORB, respectively.     

A microstructural and argon laserprobe study of shear zone development at the western margin of the Nanga Parbat–Haramosh Massif,western Himalaya

A sample of banded amphibolite from the western margin of the Nanga Parbat–Haramosh Massif as Sassi has been studied using microstructural and ⁴⁰Ar/³⁹Ar laserprobe techniques to investigate the relationship between deformation and argon isotope variations in a natural system. Amphibolite-grade deformation occurred during south-directed overthrusting of the Kohistan arc over India along the Main Mantle Thrust and was overprinted by extensional reactivation of the earlier fabric and the formation of biotite-rich shear zones. Subsequent deformation along discrete fine-grained fault zones was characterised by the formation of scapolite, chlorite and K-feldspar, early plastic deformation and later cataclasis. Different minerals developed during this history show a wide range in apparent ⁴⁰Ar/³⁹Ar ages. Biotite, chlorite and scapolite exhibit much lower concentrations of excess argon, indicating their equilibration in a fluid relatively poor in excess argon. A `true' age of ca. 8 Ma from biotite represents a minimum age for deformation associated with formation of the Nanga Parbat Syntaxis and also precludes Pliocene metamorphism in this area of the syntaxis. Both high- and low-closure temperature minerals (amphiboles and feldspars) record apparent ages which are associated with the incorporation of excess argon within the mineral lattice. Although differential thermal resetting of minerals at different closure temperatures is important, variations in the inherited ⁴⁰Ar/³⁶Ar ratio throughout the sample is dominated by deformation and fluid infiltration. Consequently it appears that within deforming metamorphic rocks, areas with significantly different argon isotope compositions may be present and need not be homogenised by diffusion. Received: 6 July 1994 / Accepted: 24 December 1996     

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.     

柴北缘锡铁山榴辉岩退变质成因角闪石40Ar/39Ar年代学研究

采用激光阶段加热⁴⁰Ar/³⁹Ar技术,对柴达木盆地北缘锡铁山榴辉岩退变质作用形成的榴闪岩和斜长角闪岩之角闪石进行了定年分析。09NQ44Amp来自榴闪岩,各阶段表观年龄(以现代空气氩⁴⁰Ar/³⁶Ar比值295.5扣除非放射性成因⁴⁰Ar)构成了单调下降的阶梯状年龄谱。在反等时线图解上,2~4阶段数据点和5~18阶段数据点分别构成了两条等时线,等时年龄分别为427.6±10Ma和425.1±2.6Ma,对应的初始⁴⁰Ar/³⁶Ar比值则分别为435.2±6.1和705.3±13。角闪石09NQ43Amp来自榴辉岩强烈退变质作用形成的斜长角闪岩,⁴⁰Ar/³⁹Ar阶段加热分析也获得单调下降的年龄谱,在反等时线图解上其数据点3~6阶段和7~16阶段分别构成了两条等时线,等时年龄分别为418.9±2.9Ma和418.1±2.1Ma,对应的初始⁴⁰Ar/³⁶Ar比值则分别为493.7±2.8和685.8±34.3。等时线截距值高于现代大气⁴⁰Ar/³⁶Ar比值,表明角闪石中含过剩⁴⁰Ar。同时,由低温和中-高温阶段加热数据点分别构成两条等时年龄基本一致,截距值却明显不同的等时线,表明在角闪石热力学性质不同的源区,存在两期明显不同且未混合的初始捕获Ar组分。等时年龄425~418Ma代表的是锡铁山榴辉岩角闪岩相退变质作用发生的时间。等时线图解法虽然有效的校正了角闪石中的过剩⁴⁰Ar,但仅根据表观年龄图谱和等时线图谱还无法清晰判断过剩⁴⁰Ar在角闪石中的赋存状态,有待进一步探讨。     

Argon and halogen geochemistry of hydrothermal fluids in the Loch Ainort granite,Isle of Skye,Scotland

Highly turbid alkali feldspars from the Loch Ainort granite (59 Ma), Isle of Skye, have been analysed using the ⁴⁰Ar-³⁹Ar method to obtain chronological and chemical (K, Cl, Br, I) information concerning their origin and hydrothermal alteration. Three methods of gas extraction have been applied to neutron-irradiated samples: laser probe spot fusion of feldspars, in vacuo crushing of a feldspar/quartz separate, and laser stepped heating of the crushed residue. Apparent ages obtained by laser probe spot fusion are mostly similar to the 59 Ma intrusion age. Analyses of relatively pristine regions give some high apparent ages (>59 Ma) indicating the presence of small amounts of ⁴⁰Ar_E (excess ⁴⁰Ar). Crushing releases significant amounts of ⁴⁰Ar_E, but is dominated by an ⁴⁰Ar_A (atmospheric ⁴⁰Ar) component. ⁸⁴Kr/³⁶Ar values obtained by crushing are higher than air and are consistent with air equilibration with fresh water at low temperature 20°C). Therefore, ⁴⁰Ar_A was most probably introduced as palaeoatmospheric argon dissolved in the circulating hydrothermal fluids that interacted with the granite, thus supporting a meteoric origin for the fluids. Stepped heating gives a flat age spectrum and an age of 56±4 Ma. Crushing and stepped heating both released significant amounts of halogens with high Br/Cl and I/Cl ratios; excess Xe is also present as indicated by the high ¹³²Xe/³⁶Ar values. It seems likely that the halogen (and possibly Xe) enrichments resulted from interaction of the meteoric fluids with Jurassic sedimentary country rocks.     

40Ar39Ar studies of Precambrian cherts; an unsuccessful attempt to measure the time evolution of the atmospheric 40Ar/36Ar ratio

KAr isochron techniques can provide, in principle, an experimental reconstruction of the time evolution of the atmospheric ⁴⁰Ar/³⁶Ar ratio if minerals can be found which contain samples of argon from the ancient atmosphere and which have had a simple geologic history. Authigenic sedimentary minerals with low potassium content appear to be the best candidates. An experimental reconstruction of the evolution of the atmospheric ⁴⁰Ar/³⁶Ar ratio will serve as a test of various models for the chemical and thermal evolution of the Earth.⁴⁰Ar³⁹Ar studies of five chert samples from the Swaziland sequence and the Bulawayan and Gunflint Formations indicate that lower Precambrian cherts do not contain appreciable samples of the ancient atmospheric argon and have experienced complicated geologic histories. The chert sample from the Kromberg Formation contains excess ⁴⁰Ar. The other four samples yield age spectra which are complicated but which are interpretable in terms of geologically reasonable ages.The lack of evidence for argon loss in the chert data suggests that some cherts may prove to be datable sedimentary minerals.     

氩同位素分馏的实验研究

尽管⁴⁰Ar和36Ar之间质量相差达1/10,但是受放射性成因⁴⁰Ar的影响,一般认为难以进行氩同位素分馏研究.本文通过自行设计的一套氩扩散迁移实验分析系统,对比研究了氩在不同的扩散介质条件下扩散迁移前后氩同位素组成变化情况,证实氩在致密的扩散介质条件下以分子流形式从一个储库向另一个储库的迁移过程中,由于36Ar和⁴⁰Ar的迁移速率不同,扩散后的⁴⁰Ar/36Ar值比扩散前的值要小,也即发生了氩同位素分馏.氩同位素分馏的特征表现为最初的一段时间内分馏程度逐步增强,在一定时间后,由于储库之间压力逐渐达到平衡,分馏程度逐步减小.研究自然界中存在的氩同位素分馏,不仅可以判别油气田中油气运移的方向、增强油气远景评价和地球化学勘探,而且对深源岩浆的起源、迁移等研究也可提供新的研究思路和途径.