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.     

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.     

西昆仑库地韧性剪切带的40Ar/39Ar年龄

西昆仑库地以南有一套变质变形较强的岩系,前人依照区域对比关系将其划为前寒武的古老基底。对西昆仑早期构造演化的论述均基于该观点,但没有提供确凿的同位素年代学证据。笔者通过野外观察、室内研究,确认库地以南的变质变形岩系是大型韧性推覆剪切作用的产物。通过对新生变质矿物角闪石和黑云母单矿物的⁴⁰Ar/³⁹Ar年龄分析,确定剪切变质年龄为426-451Ma,说明库地的变质变形岩系是形成于早古生代晚期的一条大型韧性剪切带,这对于解释西昆仑的早期构造演化具有重要意义。     

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     

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.     

Argon retentivity of hornblendes: A field experiment in a slowly cooled metamorphic terrane

Hornblende from samples of amphibolite and granitic gneiss, collected within a single outcrop in the central Adirondacks, yield significantly different ⁴⁰Ar*/³⁹Ar_k dates of 948 ± 5 and 907 ± 5 Ma. Assuming that this terrane cooled slowly following high-grade metamorphism and that the samples have experienced the same thermal history, the difference in dates apparently reflects a corresponding difference in blocking temperature for diffusion of radiogenic argon in these hornblende samples.The Fe/(Fe + Mg + Mn) of the hornblende samples are 0.8 and 0.6, the higher ratio corresponding to the younger ⁴⁰Ar*/³⁹Ar_k date. Transmission electron microscopy observations indicate that both hornblende samples are homogeneous and devoid of any exsolution, but contain zones of fibrous phyllosilicates ~0.1 to 2 μm wide parallelling (100) and (110). These alteration zones probably formed during post-metamorphic cooling as a result of the migration of fluids through the hornblendes, and are obvious pathways for argon escape from hornblende. As these features are more abundant in the hornblende sample with the younger⁴⁰Ar*/³⁹Ar_k date and higher Fe/(Fe + Mg + Mn), they may influence the argon blocking temperature by effectively partitioning the hornblende grains into diffusion domains of varying size.Biotite from the granitic gneiss yields an ⁴⁰Ar*/³⁹Ar_k date of 853 ± 2 Ma, with a mildly discordant stepheating spectrum that in part reflects the degassing of submicroscopic inclusions precipitated during alteration of the host biotite. Plagioclase from the amphibolite yields a ⁴⁰Ar*/³⁹Ar_k integrated date of 734 ± 3 Ma. All the ⁴⁰Ar*/³⁹Ar_k data are consistent with postmetamorphic cooling rates of 1° to 5°C/Ma.     

Limited mobility of argon in a metamorphic terrain

Excess ⁴⁰Ar in biotite from some relatively anhydrous charnockitic rocks in the Appalachian Piedmont indicates limited mobility of argon. Biotite from the Arden pluton of the granulite-facies Wilmington Complex apparently formed as a retrograde product at the expense of pyroxene and K-feldspar. Rb-Sr ages of biotite from all rocks are approximately 365 Myr. The same micas have apparent K-Ar ages which range from about 365–590 Myr, six of which clearly exceed the Sr isotope whole-rock date of 500 Myr. They contain variable amounts of excess⁴⁰Ar incorporated during crystallization or recrystallization of biotite at about 365 Myr ago. None of the other minerals appears to contain significant amounts of excess argon. The K-Ar apparent ages show strong, positive correlation with whole-rock K concentrations. These relations yield a correlation between excess argon in the biotite phase and rock potassium. This suggests that excess ⁴⁰Ar in biotite is of local derivation and is due to an imprint of the local argon activity. If the amount incorporated is roughly proportional to the prevailing argon partial pressure then substantial differences in p_Ar existed. Argon did not have a uniform chemical potential over large rock volumes. Analysis of closely spaced samples suggests different argon activity over the scale of less than 10m. This implies restricted transport of Ar and is probably due to very low effective permeability of the anhydrous assemblages.     

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.     

Recognition of extraneous argon components through incremental-release 40Ar39Ar analysis of biotite and hornblende across the Grenvillian metamorphic gradient in southwestern Labrador

${}^{40}\text{Ar}{}^{39}\text{Ar}$ incremental-release ages have been determined for 15 hornblende and 20 biotite concentrates separated from rocks collected across the garnet and kyanite zones of Grenvillian metamorphism in southwestern Labrador. Most hornblende spectra from the kyanite zone are slightly discordant, with low-temperature increments yielding ages older than the ca 1000 Ma date suggested for culmination of Grenvillian metamorphism in the area. However, all the hornblende concentrates record well-defined plateau ages. These range from 968 to 905 Ma across the kyanite zone and date times of diachronous post-metamorphic cooling. The discordant spectra are interpreted to result from low-temperature liberation of excess ⁴⁰Ar components from grain margins. Two hornblende concentrates from the garnet zone display very discordant spectra (total-gas ages of 2100 and 3017 Ma) in which incremental dates systematically decrease during analysis. This pattern of discordance suggests that excess argon components are inhomogeneously distributed throughout these hornblende grains.Most biotites from the garnet and kyanite zones record total-gas or plateau ages in excess of 1000 Ma (2066-857 Ma), reflecting the widespread presence of excess argon components. Because most of the ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectra are internally concordant, the ratios of excess ⁴⁰Ar relative to radiogenic ⁴⁰Ar must have been uniform in the various gas fractions liberated from each sample. This is also reflected in the inability of isotope correlation diagrams to differentiate between excess, radiogenic, and atmospheric argon components. The biotite total-gas or plateau dates show marked local variation. This is interpreted to indicate that the biotite grains were in contact with a post-metamorphic intergranular vapor phase that was characterized by large and variable ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratios. Such ratios most likely resulted from widespread diffusion of the argon liberated from adjacent Archean basement gneisses during the Grenvillian metamorphic overprint.     

Part II. Evaluation of Ar-Ar quartz ages: Implications for fluid inclusion retentivity and determination of initial Ar/Ar values in Proterozoic samples

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of <1 and the ages obtained represent the maximum ages for mineralization. In contrast, the Railway Fault samples that include accidentally trapped mica have K/Cl values of ?1. Excess ⁴⁰Ar_E plus Cl hosted by fluid inclusions, and radiogenic ⁴⁰Ar_R plus K, are strongly correlated in these samples and define a plane in 3D ⁴⁰Ar-³⁶Ar-K-Cl space. In this case, the plane yields an ‘excess ⁴⁰Ar_E’ corrected age of ∼1030 Ma that is 100’s of Ma younger than nearby Cu-mineralization at Mt Isa. The age is interpreted to reflect ⁴⁰Ar-loss from the accidentally trapped mica into the surrounding fluid inclusions, and is not related to the samples’ age of formation. The initial ⁴⁰Ar/³⁶Ar value of fluid inclusions is widely used to provide information on fluid origin. For the IOCG samples that host K in fluid inclusions only, the initial ⁴⁰Ar/³⁶Ar values are close to the measured values at every temperature of stepped heating experiments. For samples that include accidentally trapped mica, the correction for post-entrapment radiogenic ⁴⁰Ar_R production is significant. Furthermore, because ³⁹Ar_K present in accidentally trapped mica crystals is released at different temperatures to radiogenic ⁴⁰Ar_R lost to the surrounding fluid inclusions, intra-sample ⁴⁰Ar/³⁶Ar variation cannot be reliably documented. The results demonstrate that noble gas analysis is readily applicable to Proterozoic, or older, samples but that if K-mineral impurities are present within quartz the abundance of K must be determined before calculation of mean ⁴⁰Ar/³⁶Ar values that are representative of the samples’ initial composition.     

北大别黄土岭麻粒岩中黑云母过剩Ar的成因解释和Ar同位素热年代学研究启示

应用阶段加热脱气技术测定了北大别黄土岭麻粒岩的黑云母和共存花岗岩岩体中斜长角闪岩包体角闪石的Ar-Ar年龄。角闪石给出的坪年龄为(124.9±4.6） Ma,与区域上早白垩世120~130 Ma的变质-岩浆事件年龄相一致。黑云母给出的坪年龄为(176.9±0.8) Ma,年龄大于Ar封闭温度较高的角闪石的年龄,这表明黄土岭麻粒岩黑云母中含有过剩Ar。较低温度和富流体环境生长的晚世代黑云母是过剩Ar的主要载体。因此,在应用Ar-Ar热年代计重塑多成因同类含钾矿物的岩石地质体的冷却速率时,应用激光探针对代表峰期世代矿物进行原位测定应是正确的选择。     

In-situ UV-laser <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronology of a micaceous mylonite : an example of defect-enhanced argon loss

Muscovite and biotite from a crustal-scale mylonite zone (Pogallo Shear Zone, southern Alps) were investigated using furnace step-heating and in-situ UV-laser ablation ⁴⁰Ar/³⁹Ar geochronology. Undeformed muscovite porphyroclasts yield ⁴⁰Ar/³⁹Ar plateau ages of 182.0ǃ.6 Ma, whereas in-situ UV-laser ablation ⁴⁰Ar/³⁹Ar dating and furnace step-heating of strongly deformed muscovite and biotite grains display a range of apparent ages that are systematically younger. The range of ⁴⁰Ar/³⁹Ar ages measured in the deformed muscovite and biotite is consistent with protracted cooling through argon closure in minerals that exhibit variably developed segmentation on the intra-grain scale. These microstructurally controlled segments are bound by either first-order lattice discontinuities, sub-microscopic structural defects and/or zones of high defect density, which create variable length-scales for intragranular argon diffusion. The observed deformational microstructures within muscovite and biotite acted as intra-grain fast diffusion pathways in the slowly cooled mylonitic rocks. Therefore, the high-spatial resolution ⁴⁰Ar/³⁹Ar data record the initial and final closure to argon diffusion over a time span of about 60 Ma.     

Tracing the exhumation of the Eclogite Zone (Tauern Window,Eastern Alps) by <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of white mica in eclogites

New radiometric ages from the Subpenninic nappes (Eclogite Zone and Rote Wand – Modereck Nappe, Tauern Window) show that phengites formed under eclogite-facies metamorphic conditions retain their initial isotopic signature, even when associated lithologies were overprinted by greenschist- to amphibolite-facies metamorphism. Different stages of the eclogite-facies evolution can be dated provided ⁴⁰Ar/³⁹Ar dating is combined with micro-structural analyses. An age of 39 Ma from the Rote Wand – Modereck Nappe is interpreted to be close to the burial age of this unit. Eclogite deformation within the Eclogite Zone started at the pressure peak along distinct shear zones, and prevailed along the exhumation path. An age of ca. 38 Ma is only observed for eclogites not affected by subsequent deformation and is interpreted as maximum age due to the possible influence of homogenously distributed excess argon. During exhumation deformation was localised along distinct mylonitic shear zones. This stage is mainly characterised by the formation of dynamically recrystallized omphacite2 and phengite. Deformation resulted in the resetting of the Ar isotopic system within the recrystallized white mica. Flat argon release spectra showing ages of 32 Ma within mylonites record the timing of cooling along the exhumation path, and the emplacement onto the Venediger Nappe. Ar-release patterns and ³⁶Ar/⁴⁰Ar vs.³⁹Ar/⁴⁰Ar isotope correlation analyses indicate no significant ⁴⁰Ar-loss after initial closure, and only a negligible incorporation of excess argon. From the pressure peak onwards, eclogitic conditions prevailed for almost 8–10 Ma.     

Effects of progressive mylonitization on Ar retention in biotites from the Santa Rosa mylonite zone,California, and thermochronologic implications

The Santa Rosa mylonite zone developed predominantly from a granodiorite protolith in the eastern margin of the Peninsular Ranges batholith. A wide variation in K−Ar biotite dates within the zone is shown to reflect the times of cooling through closure temperatures whose variability is chiefly a result of deformation-induced reduction in grain size. We suggest that such variation generally may be exploited to place constraints on the timing of deformation episodes. Previous workers have shown that deformation in the Santa Rosa mylonite zone involved the formation of mylonites and an imbricate series of low-angle faults which divide the area into structural units. Field work, petrographic studies, and TEM analysis of deformation mechanisms in biotite show that the granodiorite mylonite, the lowermost structural unit, formed below the granodiorite solidus. The granodiorite mylonite varies from protomylonite to ultramylonite, with regions of high strain distributed heterogeneously within the zone. Previously reported biotite and hornblende K−Ar dates from the granodiorite protolith below (82–89 Ma) and the Asbestos Mountain granodiorite above (61–68 Ma) the mylonite zone indicate dramatically dissimilar thermal histories for the lowermost and uppermost structural units. Other workers' fission track dates on sphene, zircon, and apatite from the granodiorite mylonite and the Asbestos Mountain granodiorite suggest thermal homogenization and rapid cooling to ∼100° C by ca 60 Ma. Within and adjacent to the mylonite zone, K−Ar dates on 5 samples of biotite from variably deformed granodiorite range from 62–76 Ma; dates are not correlated with structural depth but clearly decrease with degree of deformation and concomitant grain size reduction. ⁴⁰Ar/³⁹Ar incremental heating analyses of biotite from the granodiorite protolith reveals no evidence of excess argon and produces a relatively flat age spectrum. ⁴⁰Ar/³⁹Ar incremental heating analysis of biotite from the granodiorite mylonite discloses discordance consistent with ³⁹Ar recoil loss. K analysis of samples, allowing K−Ar dates to be calculated, is therefore recommended as an adjunct to ⁴⁰Ar/³⁹Ar step heating analysis in rocks that have experienced similar deformation. During mylonitization, biotite grain size reduction through intracrystalline cataclasis results in estimated grain dimensions as small as 0.05 μm locally within porphyroclasts as large as 1 mm. Because biotite compositions are relatively Uniform (Fe/[Fe+Mg+Mn+Ti+Al^VI]=0.47–0.52) and show no systematic variation with grain size, compositional dependence of activation energy and diffusivity can be eliminated as sources of variation in Ar retention. Ar closure temperatures, calculated with appropriate diffusion parameters for the observed grain sizes, are in the range ∼220–280° C and define a cooling curve consistent with a thermal history intermediate between those of the granodiorite protolith below and the Asbestos Mountain granodiorite above the mylonite zone. Changes in the slope of the cooling curve indicate that the main deformation episode initiated at or above ca 330° C (∼80 Ma), above the closure temperature for thermally activated diffusion of argon in biotite, and continued to a minimum of ca 220–260° C (∼62 Ma).     

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.     

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.     

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.     

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.     

K-Ar法地质年龄标准物质ZBJ角闪石的定值结果

为了满足K-Ar定年中K和⁴⁰Ar^*分析的质量监控及Ar-Ar法样品在反应堆照射时中子通量监测的需要,我国氩同位素年代学工作者研制了一个K-Ar法年龄标准物质ZBJ角闪石,它采自北京房山花岗闪长岩体。它的⁴⁰Ar-³⁹Ar阶段加热分析结果表明:⁴⁰Ar^*在矿物晶格中保存均匀稳定,年龄谱平坦,³⁹Ar析出量高达97%。这些证据充分表明该黑云母结晶以后未受过热扰动,40K-⁴⁰Ar^*同位素计时体系封闭良好。坪年龄为133.3±0.6Ma,总气体年龄为134.4±1.4Ma,³⁶Ar/⁴⁰Ar-³⁹Ar/⁴⁰Ar反等时线年龄为133.2±0.8Ma,⁴⁰Ar/³⁶Ar初始值为297.6±4.8,此值与(⁴⁰Ar/³⁶Ar)a大气氩丰度比(295.5±0.5)处于同一范围,表明样品不含过剩氩。这几个年龄值的一致性,说明该样品具有良好的均匀性和稳定性,它作为K-Ar和Ar-Ar法地质年龄标准物质是适合的。ZBJ角闪石均匀性检验结果表明:在0.05显著性水平下经统计学方法检验,证明K和⁴⁰Ar^*的F分布值小于F临界值,说明该样品是均匀的。国内8个实验室参加了ZBJ角闪石K含量和⁴⁰Ar^*含量的定值分析,经统计学方法检验,结果显示全部定值数据都服从正态分布并具等精度。在置信概率为0.95时,⁴⁰Ar*和K含量的相对标准偏差都小于1%。两个特性量值定值分析结果的一致值(认定值)和不确定度分别为:⁴⁰Ar^*=(2.464±0.018)×10^-10mol/g,K=(1.027±0.008)%,K-Ar年龄(标准值)=133.3±1.5Ma(2σ)。此标准物质纯度为98.1%,粒度为0.15～0.30mm,总重量为740g,缩分成最小样品单元共100瓶,每瓶7.4g,可供我国K-Ar和Ar-Ar法同位素年代学实验室使用37年。     

Excess and Radiogenic Argon in High-Pressure Mylonites of the Tan-Lu Fault Zone, Eastern China

Bulk separates of porphyroclastic phengite, neoformed phengite and their mixtures from the Tan-Lu HP mylonites overprinted on the Sulu UHP rocks were analyzed with the 40Ar/39Ar step heating method. Two samples of the neoformed phengite from ultramylonite give 40Ar/39Ar plateau ages of 209.9±1.8 Ma and 214.3±1.8 Ma, which are interpreted as representing cooling times of the TanLu sinistral faulting, and provide geochronological evidence for the syn-orogenic faulting of the Tan-Lu fault zone. The results show that the phengite formed during the retrograde eclogite-facies mylonitization was not contaminated with excess argon and can be used for dating the deformation. Argon closure in previous K-bearing minerals with excess argon under a retrograde HP dry condition is considered to be the reason for lack of excess argon incorporation in the neoformed phengite. Five porphyroclastic phengite samples yield 40Ar/39Ar plateau ages ranging from 666±12 Ma to 307.1±3.3 Ma, which are interpreted as being contaminated with excess argon. Two mixture samples with plateau ages of 239.4±2.1 Ma and 239.3±2.0 Ma show upward-convex age spectra caused by the mixture of older porphyroclastic phengite with excess argon incorporation and younger neoformed phengite without excess argon incorporation. It is demonstrated that excess argon introduced from the previous UHP metamorphism is still preserved in the pre-existing phengite after the Tan-Lu eclogite-facies mylonitization. The intense deformation under HT and HP conditions cannot erase excess argon in the previous phengite totally due to restricted fluid activities. These porphyroclastic phengite previously contaminated with excess argon cannot be used for dating the later HP deformation. This indicates that deformation under a HP dry condition does not play an important role in removing previous 40Are in phengite.