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 21Ne exposure dating of young basaltic lava flows from the Newer Volcanic Province,western Victoria,Australia

Cosmogenic ²¹Ne was utilised to determine exposure ages of young subaerial basaltic lava flows from the Newer Volcanic Province, western Victoria, Australia. The ages (36–53 ka) determined from co-existing cosmogenic ²¹Ne and ³He in olivines separated from basalts are consistent within analytical uncertainties with ages previously determined by cosmogenic ³⁶Cl exposure dating. This paper illustrates the potential of cosmogenic neon exposure ages in studying the eruption, surface morphology, and erosion history of young volcanic rocks, which are difficult to date using other conventional methods, such as K-Ar or ⁴⁰Ar/³⁹Ar dating. The present study demonstrates that combined cosmogenic ³He and ²¹Ne dating, specifically measured cosmogenic ³He/²¹Ne ratios, on the same samples, is powerful for evaluating the validity of calculated cosmogenic ³He and ²¹Ne surface exposure ages.     

Anomalous cosmogenic 3He production and elevation scaling in the high Himalaya

The production rate of cosmogenic ³He in apatite, zircon, kyanite and garnet was obtained by cross-calibration against ¹⁰Be in co-existing quartz in glacial moraine boulders from the Nepalese Himalaya. The boulders have ¹⁰Be ages between 6 and 16 kyr and span elevations from 3200 to 4800 m. In all of these minerals ³He correlates with ¹⁰Be and is dominantly cosmogenic in origin. After modest correction for non-cosmogenic components, ³He/¹⁰Be systematics imply apparent sea-level high-latitude (SLHL) apparent production rates for ³He of 226 atoms g^? 1 yr^? 1 in zircon, 254 atoms g^? 1 yr^? 1 in apatite, 177 atoms g^? 1 yr^? 1 in kyanite, and 153 atoms g^? 1 yr^? 1 in garnet. These production rates are unexpectedly high compared with rates measured elsewhere in the world, and also compared with proposed element-specific production rates. For apatite and zircon, the data are sufficient to conclude that the ³He/¹⁰Be ratio increases with elevation. If this reflects different altitudinal scaling between production rates for the two isotopes then the SLHL production rates estimated by our approach are overestimates. We consider several hypotheses to explain these observations, including production of ³He via thermal neutron capture on ⁶Li, altitudinal variations in the energy spectrum of cosmic-ray neutrons, and the effects of snow cover. Because all of these effects are small, we conclude that the altitudinal variations in production rates of cosmogenic ³He and ¹⁰Be are distinct from each other at least at this location over the last ～ 10 kyr. This conclusion calls into question commonly adopted geographic scaling laws for at least some cosmogenic nuclides. If confirmed, this distinction may provide a mechanism by which to obtain paleoelevation estimates.     

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.     

Cosmogenic neon in ultramafic nodules from Asia and in quartzite from Antarctica

We have performed systematic analyses of both cosmogenic ³He (³He_c) and cosmogenic ²¹Ne (²¹Ne_c) in ultramafic xenoliths from Central Asia and in a quartz sample from Antarctica. Five xenoliths, which show no or insignificant ²¹Ne_c excesses, were used to estimate the initial ⁴He/³He ratio of 90,470 in the subcontinental lithospheric mantle under the Baikal extension zone. Seven xenoliths show large ²¹Ne/²²Ne anomalies ranging up to 0.204 and ⁴He/³He down to 31,000, due to the presence of cosmogenic ²¹Ne and ³He. The (³He/²¹Ne)_c ratio is 1.41 ± 0.22 in the xenoliths and 2.76 in the quartzite. This difference is due to the dependence of the ²¹Ne_c production rate on the elemental composition of the target material. We estimated the ³He_c and ²¹Ne_c production rates at different locations worldwide and calculated the ³He_c and ²¹Ne_c exposure ages. These ages range between 7100 and 28,000 years for the xenoliths, and we determined their relative positions within the volcanic tuff layer. The mean ³He_c and ²¹Ne_c exposure ages of the quartz sample are 1.35 ± 0.07 and 2.21 ± 0.12 Ma, respectively. This difference is most probably related to ³He_c diffusive losses from the quartz mineral grains, even at low temperatures, due to the relatively high diffusion coefficient for cosmogenic ³He.     

Primitive neon and helium isotopic compositions of high-MgO basalts from the Kerguelen Archipelago,Indian Ocean

The geochemical characteristics of mildly alkalic basalts (24–25 Ma) erupted in the southeastern Kerguelen Archipelago are considered to represent the best estimate for the composition of the enriched Kerguelen plume end-member. A recent study of picrites and high-MgO basalts from this part of the archipelago highlighted the Pb and Hf isotopic variations and suggested the presence of mantle heterogeneities within the Kerguelen plume itself. We present new helium and neon isotopic compositions for olivines from these picrites and high-MgO basalts (6–17 wt.% MgO) both to constrain the enriched composition of the Kerguelen plume and to determine the origin of isotopic heterogeneities involved in the genesis of Kerguelen plume-related basalts. The olivine phenocrysts have extremely variable ⁴He / ³He compositions between MORB and primitive values observed in OIB (∼90,000 to 40,000; i.e., R / R_a ∼8 to 18) and they show primitive neon isotopic ratios (average ²¹Ne / ²¹Ne_ext ∼0.044). The neon isotopic systematics and the ⁴He / ³He ratios that are lower than MORB values for the Kerguelen basalts clearly suggest that the Kerguelen hotspot belongs to the family of primitive hotspots, such as Iceland and Hawaii. The rare gas signature for the Kerguelen samples, intermediate between MORB and solar, is apparently inconsistent with mixing of a primitive component with a MORB-like source, but may result from sampling a heterogeneous part of the mantle with solar ³He / ²²Ne and with a higher (U, Th) / ³He ratio compared to typically high R / R_a hotspot basalts such as those from Iceland and Hawaii.     

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.     

Radiogenic heat production in the lithosphere of Sulu ultrahigh-pressure metamorphic belt

The Chinese Continental Scientific Drilling (CCSD) project is located at the Sulu ultrahigh-pressure metamorphic (UHPM) belt. It offers a unique opportunity for studying the radiogenic heat production of both shallower and deeper rocks. Based on the concentrations of radiogenic elements U, Th and K on 349 samples from main hole of CCSD (CCSD MH), pilot holes and exposures, we determined radiogenic heat productions of all major rock types in the Sulu UHPM belt. Results show the mean values of orthogneiss and paragneiss are respectively 1.65 ± 0.81 and 1.24 ± 0.61 µW m^? 3. Due to different composition and grade of retrogressive metamorphism, the eclogites display significant scatter in radiogenic heat production, ranging from 0.01 to 2.85 µW m^? 3, with a mean of 0.44 ± 0.55 µW m^? 3. The radiogenic heat production in ultramafic rocks also varies within a large range of 0.02 to 1.76 µW m^? 3, and the average turns out to be 0.18 ± 0.31 µW m^? 3. Based on the measurements and crustal petrologic model, the vertical distribution model of heat production in Sulu crust is established. The resulting mean heat production (0.76 µW m^? 3) contributes 24 mW m^? 2 to the surface heat flow. 1-D thermal model indicates that the temperature at the Moho reaches above 750 °C, and the thermal thickness of the lithosphere is ~ 75 km, in good agreement with the geophysical results. The high teat flow (~ 75 mW m^? 2) together with thin lithosphere presents strong support for the extension events during the late Cretaceous and Cenozoic.     

Selected trace metals (As,Cd and Hg) distribution and contamination in the coastal wetland sediment of the northern Beibu Gulf,South China Sea

Contamination with As, Cd and Hg, their spatial and temporal distribution are reported from the coastal wetland sediments of the northern Beibu Gulf, South China Sea. The content of As, Cd, Hg and TOC in surface sediments is 8.1 ± 5.8 μg g^?1, 0.08 ± 0.14 μg g^?1, 0.034 ± 0.028 μg g^?1 and 0.45 ± 0.39%, respectively. The mean sedimentation rates are 0.93–1.37 cm year^?1 during 1920s to 2008 determined by ²¹⁰Pb and ¹³⁷Cs dating in three cores. The vertical profiles of As, Cd and Hg content in the cores retrieved from Qin and Nanliu River estuaries show increasing trends during 1985–2008 due to anthropogenic impact caused by local economic development. Locally the surface sediments have potential ecological risk of As to benthos according to the NOAA sediment quality guidelines.     

New constraints on the HIMU mantle from neon and helium isotopic compositions of basalts from the Cook–Austral Islands

High ⁴He/³He ratios of 100 000 to 160 000 found at HIMU ocean islands (“high μ,” where μ is the U/Pb ratio) are usually attributed to the presence of recycled oceanic crust in the HIMU mantle source. However, significantly higher ⁴He/³He ratios are expected in recycled crust after residence in the mantle for periods greater than 1 Ga. In order to better understand the helium isotopic signatures in HIMU basalts, we have measured helium and neon isotopic compositions in a suite of geochemically well-characterized basalts from the Cook–Austral Islands. We observe ⁴He/³He ratios ranging from 56 000 to 141 000, suggesting the involvement of mantle reservoirs both more and less radiogenic than the mantle source for mid-ocean ridge basalts (MORBs). In addition, we find that the neon isotopic compositions of HIMU lavas extend from the MORB range to compositions less nucleogenic than MORBs. The Cook-Austral HIMU He–Ne isotopic compositions, along with Sr, Nd, Pb, and Os isotopic compositions, indicate that in addition to recycled crust, a relatively undegassed mantle end-member (e.g., FOZO) is involved in the genesis of these basalts. The association of relatively undegassed mantle material with recycled crust provides an explanation for the close geographical association between HIMU lavas and EM (enriched mantle)-type lavas from this island chain: EM-type signatures represent a higher mixing proportion of relatively undegassed mantle material. Mixing between recycled material and relatively undegassed mantle material may be a natural result of entrainment processes and convective stirring in deep mantle.     

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.     

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.     

40Ar/39Ar dating of the SP and Bar Ten lava flows AZ,USA: Laying the foundation for the SPICE cosmogenic nuclide production-rate calibration project

Precise ⁴⁰Ar/³⁹Ar age determinations made on basalt groundmass collected from the SP and upper and lower Bar Ten lava flows in the San Francisco and Uinkaret volcanic fields of Arizona, USA, yield ages of 72 ± 4, 97 ± 10, and 123 ± 12 ka (2σ; relative to Renne et al., 2010, 2011, full external precision), respectively. Previous ages of the SP lava flow include a K–Ar age of 70 ± 8 ka and OSL ages of 5.5–6 ka. ⁴⁰Ar/³⁹Ar age constraints, relative to the optimization model of Renne et al. (2010, 2011), of 81 ± 50 and 118 ± 64 ka (2σ; full external precision) were previously reported for the upper and lower Bar Ten lava flows, respectively. The new ⁴⁰Ar/³⁹Ar ages are within uncertainty of previous age constraints, and are more robust, accurate, and precise. Preliminary cosmogenic ³He and ²¹Ne production rates from the Bar Ten flows reported by Fenton et al. (2009) are updated here, to account for the improved quality of the ⁴⁰Ar/³⁹Ar data. The new ⁴⁰Ar/³⁹Ar age for the SP flow yields cosmogenic ³He and ²¹Ne production rates for pyroxene (119 ± 8 and 26.8 ± 1.9 at/g/yr; error-weighted mean, 2σ uncertainty; Dunai (2000) scaling method) that are consistent with production rate values reported throughout the literature. The ⁴⁰Ar/³⁹Ar and cosmogenic ³He and ²¹Ne data support field observations indicating the SP flow has undergone negligible erosion. The SP flow contains co-existing phenocrysts of olivine and pyroxene, as well as xenocrysts of quartz in a fine-grained groundmass facilitating cross-calibration of cosmogenic production rates and production-rate (³He, ¹⁰Be, ¹⁴C, ²¹Ne, ²⁶Al, and ³⁶Cl). Thus, we propose the SP flow is an excellent location for a cosmogenic nuclide production-rate calibration site (SPICE: the SP Flow Production-Rate Inter-Calibration Site for Cosmogenic-Nuclide Evaluations).     

The Himalayan foreland basin crust and upper mantle

Modeling of multimode surface wave group velocity dispersion data sampling the eastern and the western Ganga basins, reveals a three layer crust with an average V_s of 3.7 km s^?1, draped by ～2.5 km foreland sediments. The Moho is at a depth of 43 ± 2 km and 41 ± 2 km beneath the eastern and the western Ganga basins respectively. Crustal V_p/V_s shows a felsic upper and middle crust beneath the eastern Ganga basin (1.70) compared to a more mafic western Ganga basin crust (1.77). Due to higher radiogenic heat production in felsic than mafic rocks, a lateral thermal heterogeneity will be present in the foreland basin crust. This heterogeneity had been previously observed in the north Indian Shield immediately south of the foreland basin and must also continue northward below the Himalaya. The high heat producing felsic crust, underthrust below the Himalayas could be an important cause for melting of midcrustal rocks and emplacement of leucogranites. This is a plausible explanation for abundance of leucogranites in the east-central Himalaya compared to the west. The uppermost mantle V_s is also significantly lower beneath the eastern Ganga basin (4.30 km s^?1) compared to the west (4.44 km s^?1).     

The oxidation state of sulfur in magmatic fluids

Sulfur compounds in volcanic gases are responsible for the global cooling after explosive eruptions and they probably controlled the early evolution of the Earth's atmosphere. We have therefore studied the oxidation state of sulfur in aqueous fluids under the pressure and temperature conditions and oxygen fugacities typical for magma chambers (0.5–3 kbar, 650–950 °C, Ni–NiO to Re–ReO₂ buffer conditions). Sulfur speciation was determined by Raman spectroscopy of quenched fluids trapped as inclusions in quartz. Our results show that sulfur in hydrothermal fluids and volcanic gases is much more oxidized than previously thought and in particular, some explosive eruptions may release a significant fraction of sulfur as SO₃ or its hydrated forms. In the pressure range from 500 to 2000 bar, the equilibrium constant K₁ of the reaction 2H₂S + 3O₂ = 2SO₂ + 2H₂O in aqueous fluids can be described by lnK₁ = ?(57.1 ± 7.1) + (173,480 ± 7592)T^? 1, where T is temperature in Kelvin. The equilibrium constant K₂ for the reaction SO₂ + ½O₂ = SO₃ in aqueous fluids, where SO₃ may include hydrated forms, such as H₂SO₄, was found to be strongly pressure dependent, with lnK₂ = ?(5.2 ± 5.7) + (19,243 ± 5993)T^? 1 at 1500 bar; lnK₂ = ?(11.1 ± 1.3) + (25,383 ± 1371)T^? 1 at 2000 bar and lnK₂ = ?(22.1 ± 2.2) + (37,082 ± 2248)T^? 1 at 2500 bar. Our data imply that volcanoes may directly inject hexavalent sulfur in the form of H₂SO₄ into the atmosphere, not only on Earth, but possibly also on Venus and on Mars, when it was still tectonically active. Remote measurements from satellites may have underestimated the sulfur yield of some recent eruptions. Moreover, the mechanisms of the interaction of volcanic gases with the stratosphere need to be reconsidered.     

Helium isotopes in the Izu Peninsula,Japan: Relation of magma and crustal activity

The relation of magma and crustal activity has been studied from spatial distribution of ³He/⁴He ratios of gas and/or water samples over the Izu Peninsula, where significant crustal deformation associated with seismic swarm activities has been observed since 1970s. The air-corrected values of ³He/⁴He ratios ranged from 3.5 to 8.2 R_A, where R_A is the atmospheric ³He/⁴He ratio = 1.4 × 10^? 6, indicating that helium is mostly of magmatic origin. Among the three pressure sources proposed to explain the crustal deformation, two inflation sources beneath the inland of northeast and the mid east coast of the Izu Peninsula locate in the broad distribution of high ³He/⁴He ratios, which supports relation of magma to the crustal uplift. In contrast, the distribution of ³He/⁴He ratios around the tensile fault assumed in the area of seismic swarms appears not to indicate existence of significant amount of magma below the tensile fault. Alternatively, the results suggest magma below a point several kilometers south of the tensile fault. The seismic swarms are explained either by fluid pressurization of thermal water heated by this magma or by intrusion of magma to the tensile fault moved obliquely from the deep magma reservoir.     

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg_(fum)^T, plume gaseous elemental Hg_(g)⁰ and plume particulate Hg_(p)^II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg^T/SO₂ in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y^? 1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO₂ at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg_(p)^II increases with distance from the fumarole vent, at the expense of Hg_(g)⁰ and indicates significant in-plume oxidation and condensation of fumarole Hg_(fum)^T.Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ²⁰²Hg_(fum)^T = ? 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg_(fum)^T, δ²⁰²Hg_(g)⁰ = ? 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg_(g)⁰ at the F0 fumarole, and δ²⁰²Hg_(p)^II = ? 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg_(p)^II. The enrichment of Hg_(p)^II in the heavy isotopes and Hg_(g)⁰ in the light isotopes relative to the total condensed fumarolic Hg_(fum)^T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α_cond-gas of 1.00135 ± 0.00058.     

New insights into the origin and evolution of Lake Vida,McMurdo Dry Valleys,Antarctica — A noble gas study in ice and brines

Unlike other lakes in the McMurdo Dry Valleys, Antarctica, Lake Vida has a thick (~ 19 m) ice cover sealing a liquid brine body of unusually high salinity (~ 245 g/L) from the atmosphere. To constrain the conditions under which the atypical Lake Vida ice cover formed and evolved, 19 ice samples were collected down to a depth of ~ 14 m, together with three brine samples trapped in the ice at ~ 16 m for analysis of helium, neon, argon, krypton, and xenon concentrations. The broad pattern of noble gas concentrations for Lake Vida samples is fundamentally different from that of air saturated water (ASW) at 0 °C and an elevation of 340 m for salinities of 0 (ice) and 245 g/L (brine). Overall, ice samples are enriched in He and depleted in Ne with saturation relative to ASW averages of 1.38 and 0.82, respectively, and strongly depleted in Ar, Kr, and Xe with relative saturations of 0.10, 0.06, and 0.05, respectively. By contrast, brine samples are generally depleted in He and Ne (relative saturation averages of 0.33 and 0.27, respectively) but enriched in Ar, Kr, and Xe, with relative saturation averages of 1.45, 3.15, and 8.86, respectively. A three-phase freezing partitioning model generating brine, ice and bubble concentrations for all stable noble gases was tested and compared with our data. Measured brine values are best reproduced for a salinity value of 175 g/L, a pressure of 1.1 atm, and a bubble volume of 20 cm³ kg^?1. Sensitivity tests for ice + bubble samples show an ideal fit for bubble volumes of ~ 1–2 cm³ kg^?1. Our results show that the conditions under which ice and brine formed and evolved at Lake Vida are significantly different from other ice-covered lakes in the area. Our brine data suggest that Lake Vida may be transitioning from a wet to a dry-based lake, while the ice + bubble data suggest at least partial re-equilibration of residual liquid with the atmosphere as ice forms at the top of Lake Vida ice cover.     

Cosmogenic 3He exposure ages and geochemistry of basalts from Ascension Island,Atlantic Ocean

The chronology and origin of volcanism of Ascension Island, South Atlantic Ocean, is poorly resolved. Here we use in situ produced cosmogenic ³He in olivine and pyroxene phenocrysts from well-preserved lava flows to date the main sub-aerial basalt volcanism on the island. Etching olivine separates in HF/HNO₃ appears to remove a significant proportion of the implanted radiogenic ⁴He contribution. Average exposure ages of each flow corrected for radiogenic He range from 328 ka to 186 ka and are used to refine the chronology and stratigraphy of the island. Magmatic ³He/⁴He ratios derived from in vacuo crushing are in the range of 6.3–7.3 R_A. This range is lower than the neighbouring Mid-Atlantic Ridge segment (6–8°S) but slightly higher than measured in regional ocean islands of St. Helena, Tristan da Cunha and Gough. Combining these data with new trace element data and published radiogenic isotope ratios it appears that the Ascension Island magmatism is a mix of HIMU mantle material, typified by basalts from St. Helena, and depleted MORB-source mantle.     

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.