40Ar/39Ar geochronology using a quadrupole mass spectrometer

Magnetic sector mass spectrometers dominate the field of ⁴⁰Ar/³⁹Ar geochronology. Recent advances in quadrupole mass spectrometer technology, especially improvements in resolution, have increased the performance of these instruments to the extent that they can be used for isotopic determinations. We describe a triple filter quadrupole mass spectrometer (Hiden HAL 3F Series Pulse Ion Counting Triple Filter QMS) linked to an automated furnace extraction and cleaning system dedicated to ⁴⁰Ar/³⁹Ar incremental heating experiments.The instrument produces peaks with broad flat tops and a width of 0.9 amu at 10 cps height and 0.84 amu at 500,000 cps height on a 1 million cps high peak (peak width at 0.01‰ and 50% peak height respectively). This allows measurement of ratios of the main Ar peaks in the 1‰ range. Measurements of 1.6 × 10^?12 mole of air reference gas over two years yields ⁴⁰Ar/³⁶Ar = 257.9 ± 1.3 (1σ, n = 34). The ability of the instrument to produce ⁴⁰Ar/³⁹Ar ages from rocks/minerals of a wide age range, reaching into the late Quaternary, are demonstrated by a series of tests and comparison with geochronological data from other studies and an in-house MAP 215-50 magnetic sector mass spectrometer. We demonstrate that high-end quadrupole systems can be used for routine ⁴⁰Ar/³⁹Ar dating purposes.     

40Ar/39Ar temporal framework for the Alleret maar lacustrine sequence (French Massif-Central): Volcanological and paleoclimatic implications

The Alleret maar (Massif Central, France) is part of the few Western European early middle Pleistocene lacustrine sequences. In the AL3 core several new ash layers were recovered in the 10 first meters of the sedimentary filling. We obtained three ⁴⁰Ar/³⁹Ar ages, which range from 683 ± 5 ka (MSWD: 1.2, n = 17) to 722 ± 6 ka (MSWD: 3.2, n = 18). All the studied ash layers belong to the Super-Besse eruptive cycle of the Sancy volcano. Based on the chronostratigraphy that we have derived we estimate that the age of the main eruption could correspond to the Sancy volcano caldera formation at 725 ka close to the end of MIS 18 and that the Super-Besse explosive episode duration lasted only about 40 ka. The time framework we build evidences that the Alleret lacustrine sequence represents a time interval of probably 180 ka spanning from MIS 18 to MIS 14. This sequence offers the first well constrained comparison between terrestrial environmental history and that preserved in marine sediments during the Mid-Pleistocene Revolution.     

High-precision 40Ar/39Ar age of the Jänisjärvi impact structure (Russia)

The ～ 14 km diameter Jänisjärvi impact structure is located in Svecofennian Proterozoic terrain in the southeastern part of the Baltic shield, Karelia, Russia. Previous radioisotopic dating attempts gave K/Ar and ⁴⁰Ar/³⁹Ar ages of 700 ± 5 Ma and 698 ± 22 Ma, respectively, with both results being difficult to interpret. Recent paleomagnetic results have challenged these ages and proposed instead ages of either 500 Ma or 850–900 Ma. In order to better constrain the age of the Jänisjärvi impact structure, we present new ⁴⁰Ar/³⁹Ar data for the Jänisjärvi impact melt rock. We obtained five concordant isochron ages that yield a combined isochron age of 682 ± 4 Ma (2σ) with a MSWD of 1.2, P = 0.14, and ⁴⁰Ar/³⁶Ar intercept of 475 ± 3. We suggest that this date indicates the age of the impact and therefore can be used in conjunction with existing paleomagnetic results to define the position of the Baltica paleocontinent at that time. Argon isotopic results imply that melt homogenization was achieved at the hundred-micrometer scale certainly, because of the low-silica content of the molten target rock that allows fast ⁴⁰Ar^? diffusion in the melt. However, the large range of F(⁴⁰Ar^?_inherited) (4.1% to 11.0%) observed for seven grains shows that complete isotopic homogenization was not reached at the centimeter and perhaps the millimeter scale. The F(⁴⁰Ar^?_inherited) results are also in good agreement with previous Rb and Sr isotopic data.     

Reconciling discrepant chronologies for the geomagnetic excursion in the Mono Basin,California: Insights from new 40Ar/39Ar dating experiments and a revised relative paleointensity correlation

Lacustrine sediments of the Wilson Creek Formation in the Mono Basin, California, record a paleomagnetic field excursion constrained by ¹⁴C and ⁴⁰Ar/³⁹Ar geochronology to have occurred within the last 50 ka. However, ¹⁴C and ⁴⁰Ar/³⁹Ar ages are discordant, making it difficult to distinguish which of two possible excursions during this period, the Mono Lake or Laschamp, is recorded in the Mono Basin. New ⁴⁰Ar/³⁹Ar age determinations from sanidine, as well as the first biotite and obsidian ages, for three of the nineteen rhyolitic ashes intercalated with these sediments are presented and compared to previous ¹⁴C and ⁴⁰Ar/³⁹Ar data sets. Although the sanidine ages of the three ashes are stratigraphically consistent with each other and previously determined ⁴⁰Ar/³⁹Ar ages for other ashes in the Wilson Creek Formation, each is significantly older than ¹⁴C ages obtained from stratigraphically equivalent beds, relative paleointensity field correlations, oxygen isotope records, and glacial histories. These data indicate an absence of juvenile, eruptive crystals and most likely reflect the incorporation of crystals from older volcanic centers or underlying sediment. We examine the strengths and weaknesses of all available geochronologic data for the section exposed at Wilson Creek to arrive at an internally consistent set of age constraints. Using these constraints we propose two new relative paleointensity correlations for the section, both of which indicate that the excursion recorded in the Mono Basin occurred at ～30–34 ka on the Greenland Ice Sheet Project 2 (GISP2) ice core time scale.     

The timing and extent of the eruption of the Siberian Traps large igneous province: Implications for the end-Permian environmental crisis

We present new high-precision ⁴⁰Ar/³⁹Ar ages on feldspar and biotite separates to establish the age, duration and extent of the larger Siberian Traps volcanic province. Samples include basalts and gabbros from Noril'sk, the Lower Tunguska area on the Siberian craton, the Taimyr Peninsula, the Kuznetsk Basin, Vorkuta in the Polar Urals, and from Chelyabinsk in the southern Urals. Most of the ages, except for those from Chelyabinsk, are indistinguishable from those found at Noril'sk. Cessation of activity at Noril'sk is constrained by a ⁴⁰Ar/³⁹Ar age of 250.3 ± 1.1 Ma for the uppermost Kumginsky Suite.The new ⁴⁰Ar/³⁹Ar data confirm that the bulk of Siberian volcanism occurred at 250 Ma during a period of less than 2 Ma, extending over an area of up to 5 million km². The resolution of the data allows us to confidently conclude that the main stage of volcanism either immediately predates, or is synchronous with, the end-Permian mass extinction, further strengthening an association between volcanism and the end-Permian crisis. A sanidine age of 249.25 ± 0.14 Ma from Bed 28 tuff at the global section and stratotype at Meishan, China, allows us to bracket the P–Tr boundary to 0.58 ± 0.21 myr, and enables a direct comparison between the ⁴⁰Ar/³⁹Ar age of the Traps and the Permo–Triassic boundary section.Younger ages (243 Ma) obtained for basalts from Chelyabinsk indicate that volcanism in at least the southern part of the province continued into the Triassic.     

Dating Holocene lavas on Stromboli,Italy using cosmogenic He

In-situ cosmogenic ³He exposure ages of pyroxene phenocrysts from basalts from the Upper Neostromboli formation in southwest Stromboli date its eruption at 7.0 ± 0.3 ka (1σ, n = 3, Ginostra site) and 6.8 ± 0.2 ka (1σ, n = 10, Timpone del Fuoco site) respectively. Correlation of our new data to previous K/Ar and palaeomagnetic ages from the northwestern Neostromboli phase suggests that it erupted within a confined period between roughly 6 and 14 ka. The low uncertainty on the ³He_cos ages as well as on individual exposure ages (4.4–8.7%) demonstrates that ³He_cos exposure dating is a viable tool for dating Holocene basalt lavas. The ages compare favourably to uncertainties obtained for radiocarbon dating of similar rocks.     

40Ar / 39Ar geochronology constraints on late miocene weathering rates in Minas Gerais,Brazil

⁴⁰Ar / ³⁹Ar incremental heating ages for twenty one grains of cryptomelane, collected at 0, 42, 45, and 60 m depths in the Cachoeira Mine weathering profile, Minas Gerais, permit calculating long-term (10 Ma time scale) weathering rate (saprolitization rate) in SE Brazil. Pure well-crystallized cryptomelane grains with high K contents (3–5 wt.%) yield reliable geochronological results. The ⁴⁰Ar / ³⁹Ar plateau ages obtained decrease from the top to the bottom of the profile (12.7 ± 0.1 to 7.6 ± 0.1 Ma at surface; 7.6  ± 0.2 to 6.1 ± 0.2 Ma at 42 m; and 7.1 ± 0.2 to 5.9 ± 0.1 Ma at 45 m; 6.6 ± 0.1 to 5.2 ± 0.1 Ma at 60 m), yielding a weathering front propagation rate of 8.9 ± 1.1 m/m.y. From the geochronological results and the mineral transformations implicit by the current mineralogy in the weathering profiles, it is possible to calculate the saprolitization rate for the Cachoeira Mine lithologies and for adjacent weathering profiles developed on granodiorites and schists. The measured weathering front propagation rate yields a saprolitization rate of 24.9 ± 3.1 t/km²/yr. This average long-term (> 10 Ma) saprolitization rate is consistent with mass balance calculations results for present saprolitization rates in weathering watersheds. These results are also consistent with long-term saprolitization rates estimated by combining cosmogenic isotope denudation rates with mass balance calculations.     

A volcanological and geochemical investigation of Boa Vista,Cape Verde Islands; 40Ar/39Ar geochronology and field constraints

Boa Vista, the easternmost island in the Cape Verde archipelago, consists of volcanic products, minor intrusions and a thin partial sedimentary cover. The first 15 age results from ⁴⁰Ar/³⁹Ar incremental heating analysis of groundmass separates from volcanic and plutonic rocks from Boa Vista are presented. The combination of age results and field observations demonstrates that the volcanic activity that formed the island occurred in three main stages: (1) > 16 Ma, (2) 15–12.5 Ma and (3) 9.5–4.5 Ma. The first stage, restricted to the north eastern part of the island, is dominated by ankaramitic lavas. The second stage, consisting of evolved lavas of phonolitic–trachytic compositions and nepheline syenites, makes up large central parts of the island. The large volume of evolved rocks and the extended eruption period of several Ma make stage 2 in Boa Vista unique to Cape Verde. Mainly basanites and nephelinites were erupted during the third stage, initially dominated by eruption of subaerial mafic lavas around 9 Ma. Pillow lavas are erupted around 7 Ma whereupon dominantly subaerial mafic lavas were erupted. Stage 3 saw volcanism in many centres distributed mainly along the present coastline and with activity partly overlapping in time. The volcanic evolution of Boa Vista constrains the initiation of volcanic activity in the Cape Verde archipelago to the eastern islands. Major and trace element geochemistry of 160 volcanic and plutonic rocks representing the entire exposed chronological sequence on Boa Vista is presented, revealing an extremely well developed Daly Gap. Only a little was modified from the mafic magmas that rose in small batches from the mantle. Compositional variation distinguishes each volcanic complex and was to a large extent present in the mantle melts. The highly evolved stage 2 phonolites and trachytes are related through the fractional crystallization of three compositionally distinct magmas. Two of these may have been derived by crystal fractionation of primitive Boa Vista melts, whereas the third was not.     

An age for the Korath Range,Ethiopia and the viability of 40Ar/39Ar dating of kaersutite in Late Pleistocene volcanics

The Korath Range is the northernmost of five Quaternary volcanic fields along the axis of the Turkana rift of northern Kenya and southern Ethiopia. It is located within the Omo River valley of Ethiopia, a culturally diverse region that contains abundant Plio-Pleistocene human remains, which have been essential to refining our understanding of hominid evolution. Yet, very little geochronologic information is available for the Korath Range. We have undertaken ⁴⁰Ar/³⁹Ar incremental heating experiments, using two techniques, on kaersutite phenocrysts from a pyroclastic flow and obtained a weighted mean age of 91 ± 15 ka (2σ). The results, although imprecise, suggest that ⁴⁰Ar/³⁹Ar geochronology of these Ti-rich amphiboles can yield useful age information.     

Evaluation of cosmogenic 3He and 21Ne production rates in olivine and pyroxene from two Pleistocene basalt flows,western Grand Canyon,AZ, USA

Combining cosmogenic ³He and ²¹Ne (³He_c and ²¹Ne_c) measurements on both pyroxene and olivine from the Pleistocene Bar Ten flows (85–107 ka) greatly increases our ability to evaluate the accuracy of ³He_c and ²¹Ne_c production rates and, therefore, ³He_c and ²¹Ne_c surface exposure ages. Comparison of ³He_c and ²¹Ne_c age-pairs yielded by experimentally determined production rates and composition-based model calculations indicates that the former give more accurate surface exposure ages than the latter in this study. However, experimental production rates should be adjusted to the composition of the minerals being analyzed to obtain the best agreement between ³He_c and ²¹Ne_c ages for any given sample. ²¹Ne_c/³He_c values are 0.400 ± 0.029 and 0.204 ± 0.014 for olivine and pyroxene, respectively, in Bar Ten lava flows, in agreement with previously published values, and indicate that ²¹Ne_c/³He_c in olivine and pyroxene is not affected by erosion and remains constant with latitude, elevation, and time (up to 10 Myr). Samples with ²¹Ne_c/³He_c that do not agree with these values may indicate the presence of non-cosmogenic helium and/or neon. The neon three-isotope diagram can also indicate whether or not all excess neon in mineral separates comes from cosmogenic sources. An error-weighted regression for olivine defines a spallation line [y = (1.033 ± 0.031)x + (0.09876 ± 0.00033)], which is indistinguishable from that for pyroxene (Schäfer et al., 1999). We have derived a production rate of 25 ± 8 at/g/yr for ²¹Ne_c in clinopyroxene (En_43–44) based on the ⁴⁰Ar/³⁹Ar age of the upper Bar Ten flow. Our study indicates that the production rate of ²¹Ne_c in olivine may be slightly higher than previously determined. Cosmogenic ³He and ²¹Ne remain extremely useful, particularly when paired, in determining accurate eruption ages of young olivine- and pyroxene-rich basaltic lava flows.     

Cosmogenic 3He exposure dating of the Quaternary basalts from Fogo,Cape Verdes: Implications for rift zone and magmatic reorganisation

We have used cosmogenic ³He to date pre- and post-collapse lava flows from southwestern Fogo, Cape Verdes, in order to date rift zone magmatic reorganisation following the lateral collapse of the flank of the Monte Amarelo volcano. The post-collapse flows have exposure ages ranging from 62 to 11 ka. The analysis of multiple flow tops on each lava flows, often at different elevations, provides an internal check for age consistency and the exposures ages conform with stratigraphic level. The exposure ages suggest that volcanic activity along the western branch of the triple-armed rift zone was more or less continuous from before 62 ka to approximately 11 ka. The absence of magmatic activity for the last 11 kyr reflects a structural reconfiguration of the volcano and may be related to renewed flank instability. This volcanic hiatus is similar in duration to that observed in the Canary Islands. Replicate ³He exposure ages of a pre-collapse flow (123.0 ± 5.2 ka) brackets the time of the Monte Amarelo collapse between 62 ka and 123 ka. Reproducible cosmogenic ³He exposure ages of less than 123 ka from flows away from major erosion features demonstrates that the technique is a viable alternative to the radiocarbon, K/Ar and ⁴⁰Ar/³⁹Ar chronometers for dating recent volcanism in arid climate zones.     

Glacial–interglacial sediment transport to the Meiji Drift,northwest Pacific Ocean: Evidence for timing of Beringian outwashing

A large sediment deposit known as the Meiji Drift, located in the northwestern Pacific Ocean, is thought to have formed from deep water exiting the Bering Sea, although no notable deep water forms there presently. We determine the terrigenous sources since 140 ka to the drift using bulk sediment ⁴⁰Ar–³⁹Ar and Nd isotopic analyses on the silt-sized (20–63 μm) terrigenous fraction from Ocean Drilling Program (ODP) Site 884 to reconstruct paleo-circulation patterns. There are large changes in both isotopic tracers, varying on glacial–interglacial cycles. During glacial intervals, bulk sediment ⁴⁰Ar–³⁹Ar ages range between 40 and 80 Ma, while Nd isotopic values range from ε_Nd = ? 1 to + 2. During interglacial intervals, sediments become much younger and more radiogenic, with bulk sediment ages falling to 2–15 Ma and Nd isotopic values ranging between ε_Nd = + 5 and + 9. These data and quantitative comparison to potential source rocks indicate that the young Kamchatkan and Aleutian Arcs, lying NW and NE of the Meiji Drift, contribute the majority of sediment during interglacials. Conversely, older source rocks, such as those drained by the Yukon River and northeast Russia are the dominant origin of sediments during glacials. Mixing model calculations suggest that as much as 35–45% of the sediment deposited in the Meiji Drift during glacials is from the Bering Sea. It remains unclear whether thermohaline-type circulation or focussing of Bering Sea flow lead to the glacial–interglacial sediment source changes observed here.     

Sources of in-situ 36Cl in basaltic rocks. Implications for calibration of production rates

In-situ cosmogenic ³⁶Cl production rates from spallation of Ca and K determined in several previously published calibration studies differ by up to 50%. In this study we compare whole rock ³⁶Cl exposure ages with ³⁶Cl exposure ages evaluated in Ca-rich plagioclase in the same 10 ± 3 ka lava sample taken from Mt. Etna (Sicily, 38° N). The exposure age of the sample was determined by K–Ar and corroborated by cosmogenic ³He measurements on cogenetic pyroxene phenocrysts. Sequential dissolution experiments showed that high Cl concentrations in plagioclase grains could be reduced from 450 ppm to less than 3 ppm after 16% dissolution. ³⁶Cl exposure ages calculated from the successive dissolution steps of this leached plagioclase sample are in good agreement with K–Ar and ³He age. Stepwise dissolution of whole rock grains, on the other hand, is not as effective in reducing high Cl concentrations as it is for the plagioclase. 330 ppm Cl still remains after 85% dissolution. The ³⁶Cl exposure ages derived are systematically about 30% higher than the ages calculated from the plagioclase. We could exclude contamination by atmospheric ³⁶Cl as an explanation for this overestimate. Magmatic ³⁶Cl was estimated by measuring a totally shielded sample, but was found to account for only an insignificant amount of ³⁶Cl in the case of the 10 ka whole rock sample. We suspect that the overestimate of the whole rock exposure age is due to the difficulty in accurately assessing all the factors which control production of ³⁶Cl by low-energy neutron capture on ³⁵Cl, particularly variable water content and variable snow cover. We conclude that some of the published ³⁶Cl spallation production rates might be overestimated due to high Cl concentrations in the calibration samples. The use of rigorously pretreated mineral separates reduces Cl concentrations, allowing better estimates of the spallation production rates.In the Appendix of this paper we document in detail the equations used. These equations are also incorporated into a ³⁶Cl calculation spreadsheet made available in the supplementary data.     

Luminescence dating of archaeosediments: A comparison of K-feldspar and plagioclase IRSL ages

IRSL single-aliquot dating of three feldspar fractions from a Howieson's Poort (SA) industry site has been investigated. In the case of the plagioclase fraction (ρ > 2.62 g cm^?3) equivalent dose is similar to that of the other fractions (i.e. ρ < 2.58 g cm^?3, high-K-feldspar; and 2.58 < ρ < 2.62 g cm^?3; low-K-feldspar). However, the g values measured for this fraction is such that the fading-corrected age is overestimated. The K content of each fraction was estimated by SEM. The DRC-corrected ages for the two lighter feldspar fractions are consistent with the archaeological interpretation. This study shows that reliable single-aliquot luminescence ages can be obtained using K-feldspar and Na-plagioclase.     

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.     

Large-volume silicic volcanism in Kamchatka: Ar–Ar and U–Pb ages,isotopic, and geochemical characteristics of major pre-Holocene caldera-forming eruptions

The Kamchatka Peninsula in far eastern Russia represents the most volcanically active arc in the world in terms of magma production and the number of explosive eruptions. We investigate large-scale silicic volcanism in the past several million years and present new geochronologic results from major ignimbrite sheets exposed in Kamchatka. These ignimbrites are found in the vicinity of morphologically-preserved rims of partially eroded source calderas with diameters from ～ 2 to ～ 30 km and with estimated volumes of eruptions ranging from 10 to several hundred cubic kilometers of magma. We also identify and date two of the largest ignimbrites: Golygin Ignimbrite in southern Kamchatka (0.45 Ma), and Karymshina River Ignimbrites (1.78 Ma) in south-central Kamchatka. We present whole-rock geochemical analyses that can be used to correlate ignimbrites laterally. These large-volume ignimbrites sample a significant proportion of remelted Kamchatkan crust as constrained by the oxygen isotopes. Oxygen isotope analyses of minerals and matrix span a 3‰ range with a significant proportion of moderately low-δ¹⁸O values. This suggests that the source for these ignimbrites involved a hydrothermally-altered shallow crust, while participation of the Cretaceous siliceous basement is also evidenced by moderately elevated δ¹⁸O and Sr isotopes and xenocryst contamination in two volcanoes. The majority of dates obtained for caldera-forming eruptions coincide with glacial stages in accordance with the sediment record in the NW Pacific, suggesting an increase in explosive volcanic activity since the onset of the last glaciation 2.6 Ma. Rapid changes in ice volume during glacial times and the resulting fluctuation of glacial loading/unloading could have caused volatile saturation in shallow magma chambers and, in combination with availability of low-δ¹⁸O glacial meltwaters, increased the proportion of explosive vs effusive eruptions. The presented results provide new constraints on Pliocene–Pleistocene volcanic activity in Kamchatka, and thus constrain an important component of the Pacific Ring of Fire.     

Geochemistry of a new enriched mantle type locality in the northern hemisphere: Implications for the origin of the EM-I source

Late Cretaceous (66.2 ± 0.5 Ma amphibole and 66.7 ± 0.2 Ma phlogopite ⁴⁰Ar/³⁹Ar ages) nephelinitic volcanic rocks from Godzilla Seamount in the eastern North Atlantic (34°N latitude) have trace element and Sr–Nd–Pb–Hf-isotope compositions similar to the Enriched Mantle I (EM-I) endmember, except for their low ²⁰⁷Pb/²⁰⁴Pb relative to ²⁰⁶Pb/²⁰⁴Pb ratios (²⁰⁶Pb/²⁰⁴Pb_in = 17.7, ²⁰⁷Pb/²⁰⁴Pb_in = 15.34) plotting below the Northern Hemisphere Reference Line on the uranogenic Pb isotope diagram. O isotope data on amphibole separates are mantle-like (δ¹⁸O = 5.6–5.8‰). Age and location of the isolated Godzilla Seamount, however, preclude it from being derived from the Madeira or Canary hotspots, making a lower-mantle origin unlikely. Therefore we propose derivation from a shallow (lithospheric/asthenospheric) melting anomaly. As observed in mid-ocean-ridge and ocean-island basalts, there is a systematic decrease of ²⁰⁷Pb/²⁰⁴Pb ratios (and Δ7/4) in the individual EM-I endmember type localities towards northern latitudes with Godzilla lying on the extension of this trend. This trend is mirrored in ultra-potassic volcanic rocks such as lamproites and kimberlites, which reflect the composition of enriched subcontinental lithospheric mantle. Therefore, a global pattern in ²⁰⁷Pb/²⁰⁴Pb ratios and Δ7/4 is suggested. The geochemical composition of EM-I endmember type localities, including Godzilla lavas, and the enriched (DUPAL) anomaly in the southern hemisphere could reflect derivation from ancient, metasomatized subcontinental lithospheric mantle. We propose a two-stage model to explain the trace element and isotopic composition of the EM-I mantle endmember localities worldwide: 1) during the early history of the Earth, subcontinental lithosphere was metasomatized by melts from subducted slabs along convergent margins generating high μ (²³⁸U/²⁰⁴Pb) sources, and 2) as the Earth cooled, hydrous fluids replaced hydrous melts as the main slab component metasomatizing the subcontinental lithospheric mantle (generating EM-I sources with lower μ). In accordance with this model, the global variations in ²⁰⁷Pb/²⁰⁴Pb ratios and Δ7/4 could reflect geographic differences in μ and/or the age at which the transition from stages 1 to 2 took place in the Archaean lithosphere. The model would require a re-definition of the EM-I endmember to low ²⁰⁶Pb/²⁰⁴Pb, high ²⁰⁸Pb/²⁰⁴Pb (positive Δ8/4) but variable ²⁰⁷Pb/²⁰⁴Pb (positive and negative Δ7/4).     

ESR dating of dental enamel from Middle Palaeolithic levels at Lazaret Cave,France

ESR dating was carried out on Cervus elaphus tooth enamel samples from the depositional sequence of Lazaret Cave, Nice, France. The deposits contain Anteneandertal hominid fossils associated with abundant lithic artefacts and faunal remains. Three samples from the Mousterian occupations in complex CIII (Fouille d'entrée) yielded early uptake (EU) ages between 108 and 125 ka and linear uptake (LU) ages between 133 and 160 ka. Seven samples from the Acheulian levels in the upper part of the complex CII (Fouille d'entrée and Fouille centre) gave EU ages between 113 and 165 ka and LU ages between 147 and 210 ka, with weighted means at 131 ± 7 and 165 ± 9 ka, respectively. The results of six enamel samples from the lower Acheulian levels at Locus VIII, another place in the cave, were discarded because of their decreasing tendency with depth. The US–ESR combination method was also applied and the CSUS–ESR dates were calculated using the ESR-DATA program. Altogether, the data suggest that the Lazaret Acheulian and Mousterian occupations were rapidly formed during OIS 6.     

Assessing the use of U–Th methods to determine the age of cold-water calcareous algae

Calcitic crusts of calcareous red algae could be suitable material for age determination of raised marine deposits and palaeothermometry at annual to sub-annual resolution. We examined the potential of U–Th dating of cold-water calcareous algae by analysing fossil specimens (n=10) from Kapp Ekholm (Svalbard) and recent specimens from Norway (n=3) and Scotland (n=1). After initial measurements using α-spectrometry, thermal ionisation mass spectrometry (TIMS) was used to study the material in more detail. Recent specimens contain 0.19–1.55 μg g⁻¹ U, and the measured (²³⁴U/²³⁸U) activity ratios vary between 1.12 and 1.30. Fossil specimens contain 1–168 μg g⁻¹ U, and display variable and highly elevated initial (²³⁴U/²³⁸U) activity ratios. In general, the TIMS results show increasing (²³⁴U/²³⁸U) activity ratios and concentrations of U and Th with increasing stratigraphic age. From this it is evident that marine calcareous red algae contain U in-vivo and they experience substantial post-mortem uptake of U. We conclude that direct U–Th dating of fossil calcareous algae from raised marine deposits is not viable without further geochemical understanding of the in-vivo uptake and post-depositional pathways of U and Th in such deposits. Despite the convincing open-system behaviour of the material, comparison with previously published chronostratigraphy from the site shows that the calcareous algae generally yield ages that are too old. This is in contrast to the expected result based on simple continuous post-mortem U accumulation and calls for a complex model comprising migration of U and multi-component addition of Th (detrital/colloidal) to explain the observed trends.     

Composite mesoscopic and magnetic fabrics of the Paleo-Proterozoic Wangtu Gneissic Complex,Himachal Himalaya,India: Implications for ductile deformation and superposed folding of the Himalayan basement rocks

The present study demonstrates how the Paleo-Proterozoic Wangtu Gneissic Complex (WGC) of the Lesser Himalayan Crystalline sequence experienced superposed folding and doming prior to its exhumation, with the help of integrated field, microstructural, magnetic fabric anisotropy and geochronological studies. The WGC forms the basement of the Lesser Himalaya and is bounded by Vaikrita Thrust (VT) to the northeast and Munsiari Thrust (MT) to the southwest. The regional structure consists of upright large scale early folds (D1) trending NW–SE. The mesoscopic fabric is related to axial plane foliation of the D1 folds and, to a lesser extent, late D2 folds. The axis of maximum compression for D1 and D2 folds are mutually orthogonal. The D1 folds have formed simultaneously with the major Himalayan thrusts whereas the D2 folds have developed during a later deformation event. The magnetic lineation at the hangingwall of the VT is sub-horizontal indicating stretching along the strike of the thrust. In the interior parts of the WGC, the magnetic fabric is of two types: (i) magnetic lineation demarks the intersection of mesoscopic and magnetic foliation indicating superposed deformation and (ii) scattered distribution of magnetic lineations due to D2 folding on initially curved and non-cylindrical D1 surface. ⁴⁰Ar–³⁹Ar dating of biotite from one site from the core of WGC gives an age of 9.3 ± 0.3 (2σ) Ma. It is inferred that the doming of the WGC took place at ∼9 Ma and, instead of large scale thrusting, it is characterized by superposed folding and strike-parallel stretching along the VT zone. It is suggested that the effect of superposed folding and ductile deformation of the Himalayan basement rocks has to be taken into account before cross-section balancing or any estimation of crustal shortening is attempted.