Studies in diffusion,II. Oxygen in phlogopite mica

Self-diffusion of oxygen in a natural phlogopite mica (annite 4%) has been measured under hydrothermal conditions at 2000 bars pressure and from 500 to 800°C using water enriched in¹⁸O. Diffusional transport is dominantly parallel to the c crystallographic axis. A linear Arrhenius plot was obtained with a pre-exponential term = (1.03 ± 0.38) × 10^?9cm²sec^?1 a and an activation energy of 29 ± 2kcal/g-atom O. The difference in transport rate between oxygens in the OH groups and those in tetrahedral sites is small to non-existent unless the OH oxygens diffuse much more slowly than the other oxygens, which we consider unlikely. A typical phlogopite crystal, 0.2 mm thick by 1 mm across will lose radiogenic argon faster than it will exchange oxygen at temperatures above 435°C, but the reverse holds at lower temperatures if the diffusion mechanism can be extrapolated to temperatures below 500°C. Such a crystal will lose only 5% of its argon if held at 380°C for 1 m.y., but could exchange 27% of its oxygen in that time. The rate at which phlogopite will undergo deformation by diffusional creep does not appear to be controlled by oxygen diffusion.     

Pressure dependence of diffusion in ionic solids

A continuum model of point defects in ionic solids is developed and applied to the estimation of the pressure dependence of diffusion (in alkali halides). Activation enthalpies are expressed using macroscopic physical constants (lattice energy, elastic constants, dielectric constants, etc.) by introducing empirical parameters related to the microscopic nature of defects. Systematic relations are found between these parameters and other physical properties (ionic radius, volume fraction of anions in crystals, etc.). The nature of parameters for anions is shown to be significantly different from that for cations, probably due to the difference in “softness” between anions and cations. Such relations make it possible to estimate activation energy and volume of diffusion from the lattice energy, ionic radius, elastic constants, dielectric constants and their pressure derivatives. The calculated activation volumes agree well with experimental data. The effect of phase transition is also examined by comparing NaCl and CsCl structures. It is suggested that by phase transition from a less dense (NaCl) structure to a denser one (CsCl), the anion diffusion constant may not decrease as much as expected from the associated change in other physical properties. The validity of the models of van Liempt and of Keyes is examined. It is shown that van Liempt's model works well except for the migration process (especially anions), and that Keyes' model does not work so well for all processes.     

Emerald dating through Ar/Ar step-heating and laser spot analysis of syngenetic phlogopite

Emerald, occurring in K-metasomatic rocks developed at the contact of the Carnaíba leucogranite with serpentinite (Bahia State, Brazil), has been dated using an original ⁴⁰Ar/³⁹Ar procedure. It combines step heating and spot fusion experiments on two types of phlogopite crystals: (1) bulk samples and individual grains extracted from the enclosing K-metasomatic host rocks; and (2) syngenetic solid inclusions precipitated along growing zones of the emerald host crystals. The second procedure uses in situ laser probe experiments on rock sections. In spite of the huge amounts of excess ⁴⁰Ar detected in adjacent emerald, we could measure reliable ages of 1951 ± 8 Ma and 1934 ± 8 Ma for the Trecho Velho and Braulia occurrences, respectively. Spot fusion data had higher discrepancy than the step heating data, but minute crystals of phlogopite included in emeralds bearing excess argon do not reveal excess argon. A muscovite belonging to the same granite hydrothermal complex gave a plateau age of 1976 ± 8 Ma, which may correspond to a higher closure temperature of the KAr system during the cooling of the whole pluton and associated hydrothermal halo.

These accurate measurements lead to the following conclusions: (1) direct emerald dating is possible; (2) in spite of a polyphase history during the Transamazonian orogenesis (2 Ga), combined step heating and spot fusion experiments give a better precision for granite-related emerald mineralization than the scattered ages obtained by Rb-Sr and K-Ar methods; (3) the late-Transamazonian tectonothermal retrograde event which probably caused the dispersion of previous Rb-Sr and K-Ar data is not revealed by our procedure; (4) the emerald mineralization and K-metamorphism appear to be linked with the thermal history of the leucogranite; (5) in addition to its use in polyphase crustal domains, accurate ⁴⁰Ar/³⁹Ar dating is of major interest in the field of metallogenic models, even, for instance, for mineralizations characterized by disturbed isotopic systems, which record effects as excess argon.     

Pressure dependence of melting of metals

A relationship between the melting temperature of a metal and its surface energy is used to predict, in a semi-empirical way, the variation of the melting temperature with pressure for sodium. The agreement of the predicted results with the experiments is very good.     

Ar/Ar geochronology of Neogene phreatomagmatic volcanism in the western Pannonian Basin,Hungary

Neogene alkaline basaltic volcanic fields in the western Pannonian Basin, Hungary, including the Bakony–Balaton Highland and the Little Hungarian Plain volcanic fields are the erosional remnants of clusters of small-volume, possibly monogenetic volcanoes. Moderately to strongly eroded maars, tuff rings, scoria cones, and associated lava flows span an age range of ca. 6 Myr as previously determined by the K/Ar method. High resolution ⁴⁰Ar/³⁹Ar plateau ages on 18 samples have been obtained to determine the age range for the western Pannonian Basin Neogene intracontinental volcanic province. The new ⁴⁰Ar/³⁹Ar age determinations confirm the previously obtained K/Ar ages in the sense that no systematic biases were found between the two data sets. However, our study also serves to illustrate the inherent advantages of the ⁴⁰Ar/³⁹Ar technique: greater analytical precision, and internal tests for reliability of the obtained results provide more stringent constraints on reconstructions of the magmatic evolution of the volcanic field. Periods of increased activity with multiple eruptions occurred at ca. 7.95 Ma, 4.10 Ma, 3.80 Ma and 3.00 Ma.     

Ar,Kr, and Xe in terrestrial materials

³⁶Ar, ⁸⁴Kr, and ¹³²Xe abundances along with Kr and Xe isotopic compositions are reported for two African shales and samples of chert from the Gunflint Formation in Canada. It is observed that these data and similar abundance data from other terrestrial materials show correlations between ³⁶Ar-⁸⁴Kr and between ⁸⁴Kr-¹³²Xe. The elemental ratios defined by all the above data differ significantly from and show greater variations than those measured in carbonaceous chondrites, a well-investigated class of extraterrestrial material. Physical absorption and equilibrium solubility acting on the atmosphere are investigated as explanations for the observations. The Kr and Xe isotopic spectra are also consistent with a mass-dependent incorporation process acting on a reservoir of atmospheric composition.     

40Ar/39Ar Ages and stratigraphy of the Latera caldera,Italy

The Latera caldera is a well-exposed volcano where more than 8 km³ of mafic silica-undersaturated potassic lavas, scoria and felsic ignimbrites were emplaced between 380 and 150 ka. Isotopic ages obtained by ⁴⁰Ar/³⁹Ar analysis of single sanidine crystals indicate at least four periods of explosive eruptions from the caldera. The initial period of caldera eruptions began at 232 ka with emplacement of trachytic pumice fallout and ignimbrite. They were closely followed by eruption of evolved phonolitic magma. After roughly 25 ky, several phonolitic ignimbrites were deposited, and they were followed by phreatomagmatic eruptions that produced trachytic ignimbrites and several smaller ash-flow units at 191 ka. Compositionally zoned magma then erupted from the northern caldera rim to produce widespread phonolitic tuffs, tephriphonolitic spatter, and scoria-bearing ignimbrites. After 40 ky of mafic surge deposit and scoria cone development around the caldera rim, a compositionally zoned pumice sequence was emplaced around a vent immediately northwest of the Latera caldera. This activity marks the end of large-scale explosive eruptions from the Latera volcano at 156 ka.     

Pressure dependence of nickel partitioning between forsterite and aluminous silicate melts

Nickel partitioning between forsterite and aluminosilicate melt of fixed bulk composition has been determined at 1300°C to 20 kbar pressure. The value of the forsterite-liquid nickel partition coefficient is lowered from >20 at pressures equal to or less than 15 kbar to <10 at pressures above 15 kbar.Published data indicate that melts on the join Na₂O-Al₂O₃-SiO₂ become depolymerized in the pressure range 10–20 kbar as a result of Al shifting from four-coordination at low pressure to higher coordination as the pressure is increased. This coordination shift results in a decreasing number of bridging oxygens in the melt. It is suggested that the activity coefficient of nickel decreases with this decrease in the number of bridging oxygens. As a result, the nickel partition coefficient for olivine and liquid is lowered.Magma genesis in the upper mantle occurs in the pressure range where the suggested change in aluminum coordination occurs in silicate melts. It is suggested, therefore, that data on nickel partitioning obtained at low pressure are not applicable to calculation of the nickel distribution between crystals and melts during partial melting in the upper mantle. Application of high-pressure experimental data determined here for Al-rich melts to the partial melting process indicates that the melts would contain about twice as much nickel as indicated by the data for the low-pressure experiments. If, as suggested here, the polymerization with pressure is related to the Al content of the melt, the difference in the crystal-liquid partition coefficient for nickel at low and high pressure is reduced with decreasing Al content of the melt. Consequently, the change ofD_Ni^{ol-andesite melt} is greater than that ofD_Ni^{ol-basalt melt}, for example.     

(40)~Ar/(39)~Ar chronology and geochemistry of high-K volcanic rocks in the Mangkang basin, Tibet

Our two newly obtained high-quality 40Ar/39Ar ages suggest that the high-K volcanic rocks of the Lawuxiang Formation in the Mangkang basin, Tibet were formed at 33.5±0.2 Ma. The tracing of elemental and Pb-Sr-Nd isotopic geochemistry indicates that they were derived from an EM2 enriched mantle in continental subduction caused by transpression. Their evidently negative anomalies in HFSEs such as Nb and Ta make clear that there is an input of continental material into the mantle source. The high-K rocks at 33.5±0.2 Ma in the Mangkang basin may temporally, spatially and compositionally compare with the early one of two-pulse high-K rocks in eastern Tibet distinguished by Wang J. H. et al., implying that they were formed in the same tectonic setting.     

Ar/Ar ages and paleomagnetism of São Miguel lavas, Azores

We present new ⁴⁰Ar/³⁹Ar ages and paleomagnetic data for São Miguel island, Azores. Paleomagnetic samples were obtained for 34 flows and one dike; successful mean paleomagnetic directions were obtained for 28 of these 35 sites. ⁴⁰Ar/³⁹Ar age determinations on 12 flows from the Nordeste complex were attempted successfully: ages obtained are between 0.78 Ma and 0.88 Ma, in contrast to published K–Ar ages of 1 Ma to 4 Ma. Our radiometric ages are consistent with the reverse polarity paleomagnetic field directions, and indicate that the entire exposed part of the Nordeste complex is of a late Matuyama age. The duration of volcanism across São Miguel is significantly less than previously believed, which has important implications for regional melt generation processes, and temporal sampling of the geomagnetic field. Observed stable isotope and trace element trends across the island can be explained, at least in part, by communication between different magma source regions at depth. The ⁴⁰Ar/³⁹Ar ages indicate that our normal polarity paleomagnetic data sample at least 0.1 Myr (0–0.1 Ma) and up to 0.78 Myr (0–0.78 Ma) of paleosecular variation and our reverse polarity data sample approximately 0.1 Myr (0.78–0.88 Ma) of paleosecular variation. Our results demonstrate that precise radiometric dating of numerous flows sampled is essential to accurate inferences of long-term geomagnetic field behavior. Negative inclination anomalies are observed for both the normal and reverse polarity time-averaged field. Within the data uncertainties, normal and reverse polarity field directions are antipodal, but the reverse polarity field shows a significant deviation from a geocentric axial dipole direction.     

The interpretation of inverse isochron diagrams in Ar/Ar geochronology

The concepts involved in the construction and interpretation of inverse isochron diagrams used in ⁴⁰Ar/³⁹Ar geochronology are reviewed. The diagrams can be useful as a means of recognising atmospheric argon and excess ⁴⁰Ar, incorporated in the mineral lattice, which cannot be recognised from ⁴⁰Ar/³⁹Ar spectra. The age established using an inverse isochron plot, unlike that yielded by a spectrum, is not affected by trapped argon ⁴⁰Ar/³⁶Ar ratios that are different from the atmospheric argon ratio (e.g. due to excess ⁴⁰Ar), and may contribute to a better age interpretation. However, a heterogeneous distribution of excess ⁴⁰Ar or heterogeneous argon loss can cause ‘false’ isochrons, with axial intercepts indicating an incorrect age and an incorrect trapped argon composition. Inconsistency between the ages from a spectrum and from the associated inverse isochron plot may indicate the degree of inaccuracy of isochrons. However, it is possible that both the spectrum and inverse isochron yield the same incorrect age. The importance of considering all possible interpretations before assigning an age to a specimen is stressed.     

Ar/Ar illite dating of Late Caledonian (Acadian) metamorphism and cooling of K-bentonites and slates from the Welsh Basin, U.K.

The vacuum-encapsulation laser ⁴⁰Ar³⁹Ar technique allows extremely small (10⁻⁶ g) samples of fine-grained materials such as diagenetic clays to be dated. Here we show that the method can be extended to higher-grade clay minerals. The integration of transmission electron microscopic (TEM) characterization with ⁴⁰Ar³⁹Ar dating of vacuum encapsulated samples permits the resolution of the timing of metamorphic growth/cooling from the time of diagenesis. We have applied this technique to well characterized Lower Paleozoic slates and K-bentonites from the Welsh Basin, which span the transition from anchizonal to epizonal grade, which had been previously studied using RbSr and SmNd dating.

TEM observations of epizonal K-bentonites and slate showed that illite in these samples is of 2M₁ polytype, of muscovite-like composition, and oriented parallel to cleavage, suggesting that they are of metamorphic origin. Total gas ages (equivalent to conventional KAr ages) for encapsulated epizonal K-bentonites and slate (340–408 Ma) are considerably variable. The Ar retention ages (calculated from ³⁹Ar and ⁴⁰Ar atoms retained in the sample after irradiation) are more consistent (383–411 Ma). The ³⁹Ar recoil losses are minor for illites from whole rock samples of epizonal K-bentonites but very significant for clay separates of epizonal slate. Plateaus in age spectra were observed in epizonal K-bentonites and slate. The plateau ages (414–421 Ma) and retention ages (383–411 Ma) can be correlated with the onset of Acadian metamorphism and culmination of uplift and inversion of the Welsh Basin, respectively. These ages are significantly younger than the 450 Ma ages previously reported for diagenetic clays using the same method, suggesting that diagenetic history has been lost in these epizonal K-bentonites and slate.

TEM observations of anchizonal slates showed that there are two modes of illite. The first mode is similar to that observed in epizonal samples, suggesting a metamorphic origin. The second mode consists of the 1M_d polytype, has typical diagenetic illite composition, and is oriented parallel to bedding, suggesting a diagenetic origin. Total gas ages for encapsulated anchizonal slates vary considerably (361–422 Ma). The retention ages are more consistent (413–432 Ma) than the total gas ages. The ³⁹Ar recoil losses are more significant than those for epizonal K-bentonites and slate. Plateaus in age spectra are generally not observed. However, the consistent retention ages for the anchizonal slates correspond to the plateau ages for the epizonal samples, and are inferred to represent the onset of Acadian metamorphism.

These data, when combined with our previously published results for diagenetic shales, suggest that thermal conditions near the boundary of anchizonal and epizonal grades are necessary to completely reset Ar systems in shales and slates.     

High-precision 40Ar/39Ar sanidine geochronology of ignimbrites in the Mogollon-Datil volcanic field,southwestern New Mexico

⁴⁰Ar/³⁹Ar age spectra have been obtained from 85 sanidine separates from 36 ignimbrites and one rhyolitic lava in the latest Eocene-Oligocene Mogollon-Datil volcanic field of southwestern New Mexico. Of the 97 measured age spectra, 94 yield weighted-mean plateau ages each giving single-spectrum 1 precision of±0.25%–0.4% (±0.07–0.14 Ma). Replicate plateau age determinations for eight different samples show within-sample 1 precisions averaging ±0.25%. Plateau ages from multiple (n=3–8) samples of individual ignimbrites show 1 within-unit precision of ±0.1%–0.4% (±0.04–0.13 Ma). This within-unit precision represents a several-fold improvement over published K-Ar data for the same ignimbrites, and is similar to the range of precisions reported from single-crystal laser fusion studies. A further indication of the high precision of unit-mean ⁴⁰Ar/³⁰Ar ages is their close agreement with independently established stratigraphic order. Two samples failed to meet plateau criteria, apparently due to geologic contamination by older feldspars. Effects of minor contamination are shown by six other samples, which yielded slightly anomalous plateau ages. ⁴⁰Ar/³⁹Ar plateau ages permit resolution of units differing in age by 0.5% (0.15 Ma) or less. This high resolution, combined with paleomagnetic studies, has helped to correlate ignimbrites among isolated ranges and has allowed development of an integrated timestratigraphic framework for the volcanic field. Mogollon-Datil ignimbrites range in age from 36.2 to 24.3 Ma. Ignimbrite activity was strongly episodic, being confined to four brief (<2.6 m.y.) eruptive episodes separated by 1–3 m.y. gaps. Ignimbrite activity generally tended to migrate from the southeast toward the north and west.     

Earliest human remains in Eurasia: New 40Ar/39Ar dating of the Dmanisi hominid-bearing levels,Georgia

Several hominid remains have been discovered in the open-air site of Dmanisi (Georgia), the oldest prehistoric site in Eurasia. Two major arguments prove that this site is close in age to the Plio-Pleistocene boundary: a Villafranchian fauna and the morphological characteristics of hominid remains recently ascribed to Homo georgicus. Direct dating of the lower hominid-bearing level was carried out on volcanic glass and minerals using the ⁴⁰Ar/³⁹Ar method. The concordant results from two different sampled locations allow the determination of the age of the earliest human presence in Eurasia. This radioisotopic result strengthens the argument that the first dispersal of hominids outside Africa occurred at least 1.8 Ma ago.     

The 40Ar/39Ar age of the epithermal gold-silver mineralization of Asachinskoe Deposit, southern Kamchatka

New data on the age of epithermal gold-silver mineralization of Asachinskoe Deposit (southern Kamchatka) are obtained by the ⁴⁰Ar/³⁹Ar method of stage heating involving preirradiation of samples for 48 hours by fast neutron currents in a cadmium-plated reactor channel. Correlation with the earlier data on integral K/Ar dating and a laser variant of the ⁴⁰Ar/³⁹Ar method has been carried out. According to the structural orderliness revealed by high resolution X-ray analysis and infrared spectroscopy, potassic feldspars found in veins have been identified as a continuous series: maximum microcline → intermediate microcline → intermediate orthoclase → extreme orthoclase. The age of quartz-orthoclase vein 1 is 3.2 ± 0.2 Ma (the Piacenzian). A younger age, about 1.1 ± 0.3 Ma (the Early Pleistocene) is determined for a quartz-microcline vein with post-mineralization brecciation and recrystallization related to the basalt dike magmatism of this age.     

Emplacement age for the mafic-ultramafic plutons in the northern Dabie Mts. (Hubei): Zircon U-Pb, Sm-Nd and 40Ar/39Ar dating

The protoliths of mafic-ultramafic plutons in the northern Dabie Mts. (NDM) (Hubei) include pyroxenite and gabbro. The zircon U-Pb dating for a gabbro suggests that emplacement of mafic magma took place in the post-collisional setting at the age of 122.9(0.6 Ma. It is difficult to obtain a reliable Sm-Nd isochron age, due to disequilibrium of the Sm-Nd isotopic system. Two hornblende 40Ar/39Ar ages of 116.1(1.1 Ma and 106.6(0.8 Ma may record cooling of metamorphism in the mafic-ultramafic plutons in Hubei below 500(C. The hornblende 40Ar/39Ar ages for the mafic-ultramafic rocks in Hubei are evidently 15-25 Ma younger than those for the same rocks in Anhui, indicating that there is a diversity of the cooling rates for the mafic-ultramafic rocks in Hubei and Anhui. The difference in their cooling rates may be controlled by the north-dipping normal faults in the NDM. The intense metamorphism occurring in the mafic-ultramafic rocks in Hubei may result from the Yanshanian magmatic reheating and thermal fluid action induced by the Cretaceous migmatization. The geochemical similarity of these mafic-ultramafic rocks wherever in Hubei and Anhui may be attributed to the same tectonic setting via an identical genetic mechanism.     

40Ar/39Ar constraints on the temporal evolution of Graciosa Island, Azores (Portugal)

Lava flows spanning the eruptive record of Graciosa Island (Azores archipelago) and a gabbro xenolith were dated by ⁴⁰Ar/³⁹Ar in order to constrain the Pleistocene and Holocene volcanic evolution of the island. The results range from 1.05 Ma to 3.9 ka, whereas prior published K–Ar and ¹⁴C ages range from 620 to 2 ka. The formation of the Serra das Fontes shield volcano started at minimum 1.05 Ma, and the magmatic system was active for ca. 600 ky, as suggested by the formation of the gabbro xenolith by magmatic differentiation. Evolved magmas making up the Serra das Fontes–Serra Branca composite volcano were generated at ca. 450 ka. After a period of ca. 110 ky of volcanic inactivity and erosion of volcanic edifices, volcanism was reactivated with the formation of the Vitória Unit NW platform. Later, the development of the Vulcão Central Unit started with the formation of monogenetic cones located to the south of the Serra das Fontes–Serra Branca–Vitória Unit. This volcanism became progressively more evolved and was concentrated in a main eruptive center, forming the Vulcão Central stratovolcano with an age older than 50 ka. The caldera related to this stratovolcano is older than 47 ka and was followed by effusion of basaltic magmas into the caldera, resulting in the formation of a lava lake, which ultimately spilled over the caldera rim at ca. 11 ka. The most recent eruptions on Graciosa formed two small pyroclastic cones within the caldera and the Pico do Timão cone within the Vitória Unit at ca 3.9 ka.     

Paleomagnetism, geochemistry and Ar/Ar dating of the North-eastern Paraná Magmatic Province: tectonic implications

Seventy sites of sills, flows and dikes from Northeastern Paraná Magmatic Province (PMP), were submitted to paleomagnetic, chemical and radiometric analyses. The rocks are high in TiO₂ content, and similar in composition to the rocks from the northern region of PMP. The sills intrude mainly Paleozoic sediments, and can be subdivided into two domains; the northern being characterized by sills showing reversed polarities, and the southern essentially by sills of normal polarities. ⁴⁰Ar/³⁹Ar dating of three distinct sills gave plateau ages (129.9 ± 0.1, 130.3 ± 0.1 and 131.9 ± 0.4 Ma) that are similar to surface-outcropping flows of the Northern Paraná Basin, and the Ponta Grossa dikes. The new paleomagnetic data combined with existing data from the northern PMP allowed the calculation of a paleomagnetic pole at 71.4° E and 83.0° S (N = 92; α₉₅=2.4°; k = 39). This pole is in good agreement with poles for central and southern PMP, which are slightly older than the northern PMP, as well as for the contemporaneous Central Alkaline Province (Paraguay) on the western side of PMP. In contrast, the coeval pole for the Ponta Grossa dikes (eastern border of PMP), however, is slightly displaced from that group of poles, suggesting that dikes in that area may have undergone some tectonic tilting.     

Refinement of the late Quaternary geologic history of Erebus volcano,Antarctica using Ar/Ar and Cl age determinations

Six new ⁴⁰Ar/³⁹Ar and three cosmogenic ³⁶Cl age determinations provide new insight into the late Quaternary eruptive history of Erebus volcano. Anorthoclase from 3 lava flows on the caldera rim have ⁴⁰Ar/³⁹Ar ages of 23 ± 12, 81 ± 3 and 172 ± 10 ka (all uncertainties 2σ). The ages confirm the presence of a second, younger, superimposed caldera near the southwestern margin of the summit plateau and show that eruptive activity has occurred in the summit region for 77 ± 13 ka longer than previously thought. Trachyte from “Ice Station” on the eastern flank is 159 ± 2 ka, similar in age to those at Bomb Peak and Aurora Cliffs. The widespread occurrences of trachyte on the eastern flank of Erebus suggest a major previously unrecognized episode of trachytic volcanism. The trachyte lavas are chemically and isotopically distinct from alkaline lavas erupted contemporaneously in the summit region < 5 km away.