A New Multi-Mineral Age Reference Material for 40Ar/39Ar, (U-Th)/He and Fission Track Dating Methods: The Limberg t3 Tuff

The phonolitic Limberg t3 tephra (Kaiserstuhl Volcanic Complex, Germany) was previously dated by the conventional K/Ar method yielding inconsistent results. We have re-dated this tephra layer with three independent methods. Fission Track (FT) external detector analyses on single apatite crystals (16.8 ± 1.3 Ma, 2s) and (U-Th)/He measurements on titanite and apatite (16.5 ± 1.0 Ma, 2s and 16.8 ± 1.0 Ma, 2s, respectively) are in close agreement with laser Ar/Ar dates on incrementally heated single crystals of sanidine (16.3 ± 0.4 Ma, 2s). Due to very rapid cooling, the He, FT and Ar thermochronometers provide one single age representing the eruption event. The different minerals are characterised by favourable properties with respect to their chemical composition, grain size and shape. In particular for the t3 sanidine, homogeneity has been demonstrated by electron microprobe analysis and on a grain-to-grain and grain-internal scale by single crystal incremental laser heating. Based on the agreement between independent methods and the mineral yield of this unit, the Limberg t3 tephra is proposed as multi-method age reference material for single grain laser Ar/Ar, FT and (U-Th)/He dating.     

MK‐1 Apatite: A New Potential Reference Material for (U‐Th)/He Dating

The (U‐Th)/He dating technique has been widely used for several decades to constrain the timing of low temperature geological processes. Recent research has shown that the commonly used reference material (the Durango apatite) often yields dispersed fragment dates that are beyond analytical uncertainties. Here, we report a new apatite (U‐Th)/He dating reference material, MK‐1, which was collected from the Mogok metamorphic belt in Burma. Electron probe microanalysis and backscattered electron images of two randomly selected fragments indicate that this apatite is chemically and structurally homogeneous. We performed single‐grain (U‐Th)/He dating on thirty randomly selected fragments of this material. (U‐Th)/He dating results from multiple laboratories show that fragments of the MK‐1 apatite megacryst yielded reproducible results, with a mean date of 18.0 ± 0.2 Ma. The Th/U ratio of this apatite is homogeneous. Nine randomly selected fragments registered a narrow range of effective uranium (eU) mass fractions (326–354 μg g^?1), with a mean value of 336.6 ± 10.3 μg g^?1. Twenty‐four in situ (U‐Th)/He dates yielded a mean value of 18.0 ± 0.2 Ma (MSWD = 0.41), indistinguishable from the results obtained by the conventional method. All the results suggest that this apatite has the potential to become a new reference material for (U‐Th)/He geochronology.     

矿物中4He同位素提取和含量测定研究

(U-Th)/He定年是一种有效的低温热年代学定年技术,现已被广泛应用于地质研究的各个领域,而矿物中4He同位素的有效提取和含量准确测定是该技术的关键。磷灰石和锆石是(U-Th)/He定年最常用的矿物,其4He提取条件及铀钍含量测定方法都较为成熟;而其他矿物(如磁铁矿、橄榄石、针铁矿、石榴子石等)的研究则相对较少。文章介绍了当前国内外(U-Th)/He研究中采用的4He同位素提取方法———真空炉加热法和激光加热法,激光加热法因具有低4He背景值和耗时短的优点而成为主要的提取方法。以磷灰石样品测试为例,介绍了成都地质矿产研究所建立的采用激光加热法和四极杆质谱提取4He同位素及其含量测量过程、含量计算和校正方法。指出未来(U-Th)/He测试技术除继续改进现有分析方法外,应加强对更多不同矿物的测试研究。     

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.     

U and Th zonation in apatite observed by laser ablation ICPMS, and implications for the (U-Th)/He system

A laser-ablation inductively-coupled plasma mass spectrometry technique was developed to measure U, Th, and Ce zonation in polished sections of apatite for assessing the consequences of parent zonation for (U-Th)/He thermochronometry. The technique produces concentration maps with an averaging length-scale of ∼20 μm, comparable to the α-stopping distance, and a precision of ∼5% down to few ppm concentration levels. A model was developed to transform the measured concentration distribution into a simplified representation for use in spherical-geometry He production-diffusion models. To illustrate these methods, 30 sections of apatite from a single granite (GC863) were mapped. Every analyzed apatite from GC863 is zoned, with most grains having variable thickness rims and terminations that are enriched in U and Th by about a factor of three over the grain cores.Parent zonation has three independent effects on (U-Th)/He He ages: it influences the α ejection correction, the ⁴He concentration profile which governs diffusive loss, and, via radiation damage trap accumulation, spatial variability of diffusivity within the crystal. If the observed zonation is typical of the apatite population in GC863, use of the standard homogenous α ejection correction would cause He ages to be on average 3% too young, and with a large amount of grain-to-grain variability (9% too young in the most rim-enriched case to 6% too old in a core-enriched case). Independent of the ejection correction, the concentration profile modifies the effective closure temperature of the apatites by placing more (or less) ⁴He near the grain edge. The parent zonation in GC863 apatites causes closure temperatures to range from four degrees lower (rim-enriched case) to two degrees higher (core-enriched case) than applies in the homogenous case. Alpha ejection and concentration profile effects on He age are additive and of the same sense. In the case of typical grains in GC863 cooled between 1 and 10 °C/Ma, the two effects are roughly equal in magnitude. The effects of intracrystalline variations in radiation damage trap accumulation become apparent at slow cooling rates (1 °C/Ma). For example, in rim-enriched GC863 grains cooled at 1 °C/Ma, preferential accumulation of radiation damage traps near the grain rim almost compensates for the higher loss rate expected of ⁴He also located preferentially near the rim. Under some circumstances strong rim-enrichment may actually increase the effective closure temperature of an apatite. Zonation at the level observed in GC863 modifies the ⁴He/³He spectra substantially from that expected from a uniform distribution. Measured ⁴He/³He spectra are strikingly similar to predictions based on the mapped eU distributions of the very same crystals, supporting the overall validity of the analytical and interpretive approach presented here.The magnitude and style of U, Th zonation documented in GC863 is one possible source of frequently observed over-dispersion of apatite (U-Th)/He ages as well as anomalous ⁴He/³He spectra.     

α-Emitting mineral inclusions in apatite, their effect on (U-Th)/He ages, and how to reduce it

U-Th rich mineral inclusions in apatite are often held responsible for erroneously old (U-Th)/He ages, because they produce “parentless” He. Three aspects associated with this problem are discussed here. First, simple dimensional considerations indicate that for small mineral inclusions, the parentless helium problem might not be as serious as generally thought. For example, a mineral inclusion that is 10% the length, width and height of its host apatite needs to be a thousand times more concentrated in U and Th to produce an equal amount of He. Therefore, single isolated inclusions smaller than a few μm are unlikely to contribute significant helium. For larger or more abundant inclusions, the parentless helium problem can be solved by dissolution of the apatite and its inclusions in hot HF. Second, besides creating parentless helium, inclusions also complicate α-ejection corrections. Mathematical exploration of this latter problem for spherical geometries reveals that for randomly distributed inclusions, the probability distribution of single-grain ages is predicted to have a sharp mode at the mean age, with tails towards younger and older ages. Multiple-grain measurements will yield accurate and precise age estimates if 10 or more randomly distributed α-emitting mineral inclusions are present in a sample. Third, thermal modeling indicates that mineral inclusions have a non-trivial but minor (<5 °C) effect on the closure temperature. These predictions were tested on apatites from rapidly cooled migmatites of Naxos (Greece) which contain abundant U-rich zircon inclusions. Thirty-seven samples were subjected to two kinds of treatment. The “pooled” age (i.e., the synthetic multi-grain age computed from a number of single-grain analyses) of four inclusion-free samples (13 apatites), prepared in HNO₃ is 10.9 Ma, close to apatite and zircon fission-track ages from the same rock. (U-Th)/He ages of 14 inclusion-bearing samples dissolved in HNO₃ range between 9 and 45 Ma, with a pooled age of 22.6 Ma. The ages of 19 HF-treated samples range between 5 and 16 Ma, with 10 of 14 single-grain samples between 9 and 13 Ma and a pooled age of 10.9 Ma. These observations agree with the theoretical predictions and support the addition of HF-treated apatite (U-Th)/He dating to the thermochronological toolbox.     

Apatite (U-Th)/He thermochronometry using a radiation damage accumulation and annealing model

Helium diffusion from apatite is a sensitive function of the volume fraction of radiation damage to the crystal, a quantity that varies over the lifetime of the apatite. Using recently published laboratory data we develop and investigate a new kinetic model, the radiation damage accumulation and annealing model (RDAAM), that adopts the effective fission-track density as a proxy for accumulated radiation damage. This proxy incorporates creation of crystal damage proportional to α-production from U and Th decay, and the elimination of that damage governed by the kinetics of fission-track annealing. The RDAAM is a version of the helium trapping model (HeTM; Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249, 148-161), calibrated by helium diffusion data in natural and partially annealed apatites. The chief limitation of the HeTM, now addressed by RDAAM, is its use of He concentration as the radiation damage proxy for circumstances in which radiation damage and He are not accumulated and lost proportionately from the crystal.By incorporating the RDAAM into the HeFTy computer program, we explore its implications for apatite (U-Th)/He thermochronometry. We show how (U-Th)/He dates predicted from the model are sensitive to both effective U concentration (eU) and details of the temperature history. The RDAAM predicts an effective He closure temperature of 62 °C for a 28 ppm eU apatite of 60 μm radius that experienced a 10 °C/Ma monotonic cooling rate; this is 8 °C lower than the 70 °C effective closure temperature predicted using commonly assumed Durango diffusion kinetics. Use of the RDAAM is most important for accurate interpretation of (U-Th)/He data for apatite suites that experienced moderate to slow monotonic cooling (1-0.1 °C/Ma), prolonged residence in the helium partial retention zone, or a duration at temperatures appropriate for radiation damage accumulation followed by reheating and partial helium loss. Under common circumstances the RDAAM predicts (U-Th)/He dates that are older, sometimes much older, than corresponding fission-track dates. Nonlinear positive correlations between apatite (U-Th)/He date and eU in apatites subjected to the same temperature history are a diagnostic signature of the RDAAM for many but not all thermal histories.Observed date-eU correlations in four different localities can be explained with the RDAAM using geologically reasonable thermal histories consistent with independent fission-track datasets. The existence of date-eU correlations not only supports a radiation damage based kinetic model, but can significantly limit the range of acceptable time-temperature paths that account for the data. In contrast, these datasets are inexplicable using the Durango diffusion model. The RDAAM helps reconcile enigmatic data in which apatite (U-Th)/He dates are older than expected using the Durango model when compared with thermal histories based on apatite fission-track data or other geological constraints. It also has the potential to explain at least some cases in which (U-Th)/He dates are actually older than the corresponding fission-track dates.     

Duluth Complex FC1 Apatite and Zircon: Reference Materials for (U-Th)/He Dating?

The accuracy and validation of geo- and thermochronological dating hinges on the availability of well-characterised age reference materials. The Mesoproterozoic gabbroic anorthosite FC1 from the Duluth Complex, Minnesota is a reference material for zircon U-Pb and a suggested reference material for apatite fission-track dating. We evaluate FC1 as (U-Th)/He reference material, and determine its apatite U-Pb, and zircon and apatite (U-Th)/He age. Our dating results constrain the thermal history of FC1, showing that fast cooling occurred between ~ 1099 and 1040 Ma from ≥ 600 °C to ~ 200 °C. The zircon (U-Th)/He data from air-abraded grains give a robust isochron age of 1037 ± 25 Ma (2s) without overdispersion. The within-grain homogeneity of U and Th, the availability of FC1 zircon, and the absence of radiation-damage effects on the (U-Th)/He age support its use as reference material. Unabraded zircon grains give lower and more dispersed ages, highlighting the usefulness of air abrasion to control for α-ejection in (U-Th)/He dating. Our apatite (U-Th-Sm)/He single-grain ages vary between 180 and 300 Ma. Their wide dispersion argues against the use of FC1 apatite as (U-Th-Sm)/He reference material and makes the interpretation of their low-temperature thermal history complicated.     

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.     

（U-Th）/He定年——低温热年代学研究的一种新技术

近年来（U-Th）/He定年方法在技术和低温热年代学应用上的优势吸引人们以此开展构造、地形地貌演化等的研究；与裂变径迹、K Ar、Ar Ar等定年方法的比较，该方法是有效的；人们研究了温度及矿物粒径对He扩散的影响，确定了校正方法。（U-Th）/He的封闭温度低于其它体系（磷灰石的仅为75℃±）；有质谱仪只需数十毫克样品就能获得 U、Th、He含量；有较裂变径迹法快速、省样、省力的优点；该技术虽还有待完善，但仍不失为开展低温热年代学和低温热演化研究的潜在有效方法。     

A Potential (U‐Th)/He Zircon Reference Material from Penglai Zircon Megacrysts

In this study (U‐Th)/He dating of the Penglai zircons, which occur as abundant megacrysts in Neogene alkaline basalts in northern Hainan Province, south‐eastern China, was undertaken. A weighted mean age of 4.06 ± 0.35 Ma (2s) with a mean square weighted deviation (MSWD) of 1.79 was obtained from eighteen fragments of four zircon megacrysts using single‐crystal laser fusion He determinations and the U‐Th isotope dilution (ID) method. The (U‐Th)/He ages are consistent, homogeneous and systematically slightly younger than the preferred ²⁰⁶Pb/²³⁸U age of 4.4 ± 0.1 Ma (95% confidence interval) determined by ID‐TIMS and subsequently published U‐Pb results. The U‐Pb isotopic system in zircon has a high closure temperature of ~ 900 °C, and the preferred U‐Pb age may record both the time since eruption and the zircon residence time in the magma chamber. In contrast, the closure temperature of the zircon (U‐Th)/He system is ~ 190 °C and the zircon megacrysts were brought quickly to the surface by the host basaltic magma. Thus, the (U‐Th)/He age represents the timing of the eruption. Based on the unlimited quantity, large grain size, mostly weak broad zoning, rapid cooling and homogenous (U‐Th)/He ages, we consider the Penglai zircons suitable for use as a reference material in (U‐Th)/He isotope geochronology.     

Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar/Ar dating

(U-Th)/He chronometry of zircon has a wide range of potential applications including thermochronometry, provided the temperature sensitivity (e.g., closure temperature) of the system be accurately constrained. We have examined the characteristics of He loss from zircon in a series of step-heating diffusion experiments, and compared zircon (U-Th)/He ages with other thermochronometric constraints from plutonic rocks. Diffusion experiments on zircons with varying ages and U-Th contents yield Arrhenius relationships which, after about 5% He release, indicate E_a = 163-173 kJ/mol (39-41 kcal/mol), and D₀ = 0.09-1.5 cm²/s, with an average E_a of 169 ± 3.8 kJ/mol (40.4 ± 0.9 kcal/mol) and average D₀ of 0.46^+0.87_−0.30 cm²/s. The experiments also suggest a correspondence between diffusion domain size and grain size. For effective grain radius of 60 μm and cooling rate of 10°C/myr, the diffusion data yield closure temperatures, T_c, of 171-196°C, with an average of 183°C. The early stages of step heating experiments show complications in the form of decreasing apparent diffusivity with successive heating steps, but these are essentially absent in later stages, after about 5-10% He release. These effects are independent of radiation dosage and are also unlikely to be due to intracrystalline He zonation. Regardless of the physical origin, this non-Arrhenius behavior is similar to predictions based on degassing of multiple diffusion domains, with only a small proportion (<2-4%) of gas residing in domains with a lower diffusivity than the bulk zircon crystal. Thus the features of zircon responsible for these non-Arrhenius trends in the early stages of diffusion experiments would have a negligible effect on the bulk thermal sensitivity and closure temperature of a zircon crystal.We have also measured single-grain zircon (U-Th)/He ages and obtained ⁴⁰Ar/³⁹Ar ages for several minerals, including K-feldspar, for a suite of slowly cooled samples with other thermochronologic constraints. Zircon He ages from most samples have 1 σ reproducibilities of about 1-5%, and agree well with K-feldspar ⁴⁰Ar/³⁹Ar multidomain cooling models for sample-specific closure temperatures (170-189°C). One sample has a relatively poor reproducibility of ∼24%, however, and a mean that falls to older ages than predicted by the K-feldspar model. Microimaging shows that trace element zonation of a variety of styles is most pronounced in this sample, which probably leads to poor reproducibility via inaccurate α-ejection corrections. We present preliminary results of a new method for characterizing U-Th zonation in dated grains by laser-ablation, which significantly improves zircon He age accuracy.In summary, the zircon (U-Th)/He thermochronometer has a closure temperature of 170-190°C for typical plutonic cooling rates and crystal sizes, it is not significantly affected by radiation damage except in relatively rare cases of high radiation dosage with long-term low-temperature histories, and most ages agree well with constraints provided by K-spar ⁴⁰Ar/³⁹Ar cooling models. In some cases, intracrystalline U-Th zonation can result in inaccurate ages, but depth-profiling characterization of zonation in dated grains can significantly improve accuracy and precision of single-grain ages.     

湘中龙山大型金锑矿床成矿时代研究——黄铁矿Re-Os和锆石U-Th/He定年

龙山金锑矿床是湘中锑-金矿集区最重要的矿床之一,因缺少适合传统放射性同位素定年的矿物,其成矿时代以往未得到很好的限定,制约了对矿床成因的认识。由于分析测试技术的进步,Re-Os同位素定年技术得到了发展,可对热液矿床中形成的低Re、Os含量的硫化物进行较准确可靠的年龄测定,从而可为低温热液矿床的形成时代提供有效制约。锆石U-Th/He同位素定年,也是近年发展和成熟起来的定年技术,对低温热事件极其敏感,同样是约束低温成矿年龄的重要手段之一。本文采用矿床中黄铁矿Re-Os同位素和蚀变围岩中受成矿热事件影响的锆石U-Th/He同位素定年技术,对龙山金锑矿床的成矿时代进行了研究。定年结果显示:热液成因黄铁矿的Re-Os等时线年龄为195±36Ma,对应于印支晚期;锆石U-Th/He年龄为51.2~133.3Ma,经Ft校正后,U-Th/He年龄分布于93.78~258.29Ma之间,平均值为160.7±7.3Ma,对应于燕山早期。该矿床可能发生了200Ma和160Ma的两次成矿作用;或者矿床形成于200Ma左右,但是受到了160Ma左右岩浆热事件的改造,黄铁矿Re-Os年龄代表成矿年龄,而锆石U-Th/He年龄则代表第二期热事件发生的时间。无论是200Ma左右一次成矿,还是另有160Ma左右的成矿作用叠加,这两个年龄分别与区内两期岩浆活动的时间相当,这表明岩浆事件对驱动矿床的形成发挥了重要的作用。     

Evidence from zircon dating for existence of approximately 2.1 Ga old crystalline basement in southern Bohemia,Czech Republic

Zircon ages are reported for three Moldanubian amphibolite grade orthogneisses from the southern Bohemian Massif obtained by conventional U/Pb analyses. For two of these orthogneisses, conventional U/Pb data are supported by ion microprobe single zircon ages or single grain evaporation data. The amphibolite grade orthogneisses, occurring in three small tectonic lenses within the Varied Group close to the South Bohemian Main Thrust, are of tonalitic, granodioritic or quartz dioritic composition.Conventional bulk size fraction and ion microprobe analyses of nearly euhedral zircons from a metatonalite, erroneously interpreted as a metagreywacke in a previous study, yielded an upper Concordia intercept age of 2048 ± 12 Ma. The well preserved euhedral grain shapes of the zircons suggest crystallization from a magmatic phase, and the upper Concordia intercept age is now interpreted as reflecting a magmatic event at that time. The age of this rock is compatible with the conventional zircon data and the (²⁰⁷Pb/²⁰⁶Pb)^* single grain evaporation result from two further orthogneisses providing intrusion ages of 2 060 ± 12, 2 104 ± 1 and 2 061 ± 6 Ma, respectively. For one sample a concordant U/Pb age for sphene of 355 ± 2 Ma defines the age of amphibolite facies metamorphism. The upper Concordia intercept ages of three orthogneisses constitute the first direct evidence for the presence of early Proterozoic crust under the supracrustal cover in the southern part of the Bohemian Massif. Correspondence to: J. I. Wendt     

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.     

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.     

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.     

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

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

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.