Noble gas isotopes reveal degassing-derived eruptions at Deception Island (Antarctica): implications for the current high levels of volcanic activity.

Deception Island is one of the most active volcanoes in Antarctica with more than twenty explosive eruptions in the past two centuries. Any future volcanic eruption(s) is a serious concern for scientists and tourists, will be detrimental to marine ecosystems and could have an impact to global oceanographic processes. Currently, it is not possible to carry-out low and high frequency volcanic gas monitoring at Deception Island because of the arduous climatic conditions and its remote location. Helium, neon and argon isotopes measured in olivine samples of the main eruptive events (pre-, syn- and post caldera) offer insights into the processes governing its volcanic history. Our results show that: (i) ascending primitive magmas outgassed volatiles with a MORB-like helium isotopic signature (3He/4He ratio); and (ii) variations in the He isotope ratio, as well as intensive degassing evidenced by fractionated 4He/40Ar* values, occurred before the beginning of the main eruptive episodes. Our results show how the pre-eruptive noble gas signals of volcanic activity is an important step toward a better understanding of the magmatic dynamics and has the potential to improve eruption forecasting.

Recycled Components in Mantle Plumes Deduced From Variations in Halogens (Cl, Br, and I), Trace Elements, and 3He/4He Along the Hawaiian-Emperor Seamount Chain.

Halogens are primarily located within surface reservoirs of the Earth; as such they have proven to be effective tracers for the identification of subducted volatiles within the mantle. Subducting lithologies exhibit a wide variety of halogen compositions, yet the mantle maintains a fairly uniform signature, suggesting halogens may be homogenized during subduction to the mantle or during eruption. Here we present halogen (Cl, Br, and I), K, noble gas, and major and trace element data on olivines from three seamounts along the Hawaiian-Emperor seamount chain to determine if the deep mantle source has retained evidence of halogen heterogeneities introduced through subduction. High Ni contents indicate that the Hawaiian-Emperor mantle source contains a recycled oceanic crust component in the form of pyroxenite, which increases from the 46% in the oldest (Detroit) to 70% in the younger seamount (Koko). Detroit seamount retains mid-ocean ridge basalts (MORB)-like Br/Cl and I/Cl, while the Br/Cl and I/Cl of Suiko and Koko seamounts are higher than MORB and similar to altered oceanic crust and dehydrated serpentinite. Helium isotopes show a similar evolution, from MORB-like values at Detroit seamount toward higher values at Suiko and Koko seamounts. The correlation between pyroxenite contributions, Br/Cl, I/Cl, and 3He/4He indicates that subducted material has been incorporated into the primordial undegassed Hawaiian mantle plume source. The identification of recycled oceanic crustal signatures in both the trace elements and halogens indicates that subduction and dehydration of altered oceanic crust may exert control on the cycling of volatile elements to the deep mantle.

Halogens in chondritic meteorites and terrestrial accretion.

Volatile element delivery and retention played a fundamental part in Earth's formation and subsequent chemical differentiation. The heavy halogens-chlorine (Cl), bromine (Br) and iodine (I)-are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth's silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth's surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth's dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.

The origin and degassing history of the Earth's atmosphere revealed by Archean xenon.

Xenon (Xe) is an exceptional tracer for investigating the origin and fate of volatile elements on Earth. The initial isotopic composition of atmospheric Xe remains unknown, as do the mechanisms involved in its depletion and isotopic fractionation compared with other reservoirs in the solar system. Here we present high precision analyses of noble gases trapped in fluid inclusions of Archean quartz (Barberton, South Africa) that reveal the isotopic composition of the paleo-atmosphere at ≈3.3 Ga. The Archean atmospheric Xe is mass-dependently fractionated by 12.9±2.4 ‰ u-1 (± 2σ, s.d.) relative to the modern atmosphere. The lower than today 129Xe excess requires a degassing rate of radiogenic Xe from the mantle higher than at present. The primordial Xe component delivered to the Earth's atmosphere is distinct from Solar or Chondritic Xe but similar to a theoretical component called U-Xe. Comets may have brought this component to the Earth's atmosphere during the last stages of terrestrial accretion.

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt.

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth's mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F-Cl-Br-I-H2O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H2O (DClol/melt = 1.6 ± 0.9 × 10-4) to 0.33 (6) wt% H2O (DClol/melt = 2.2 ± 1.1 × 10-4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65-78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F-Cl-Br-I-H2O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with (R2 = 0.99): [Formula: see text]. The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287-295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65-78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth's mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.

Nitrogen isotopic composition and density of the Archean atmosphere.

Understanding the atmosphere's composition during the Archean eon is fundamental to unraveling ancient environmental conditions. We show from the analysis of nitrogen and argon isotopes in fluid inclusions trapped in 3.0- to 3.5-billion-year-old hydrothermal quartz that the partial pressure of N2 of the Archean atmosphere was lower than 1.1 bar, possibly as low as 0.5 bar, and had a nitrogen isotopic composition comparable to the present-day one. These results imply that dinitrogen did not play a significant role in the thermal budget of the ancient Earth and that the Archean partial pressure of CO2 was probably lower than 0.7 bar.

Argon isotopic composition of Archaean atmosphere probes early Earth geodynamics.

Understanding the growth rate of the continental crust through time is a fundamental issue in Earth sciences. The isotopic signatures of noble gases in the silicate Earth (mantle, crust) and in the atmosphere afford exceptional insight into the evolution through time of these geochemical reservoirs. However, no data for the compositions of these reservoirs exists for the distant past, and temporal exchange rates between Earth's interior and its surface are severely under-constrained owing to a lack of samples preserving the original signature of the atmosphere at the time of their formation. Here, we report the analysis of argon in Archaean (3.5-billion-year-old) hydrothermal quartz. Noble gases are hosted in primary fluid inclusions containing a mixture of Archaean freshwater and hydrothermal fluid. Our analysis reveals Archaean atmospheric argon with a (40)Ar/(36)Ar value of 143 ± 24, lower than the present-day value of 298.6 (for which (40)Ar has been produced by the radioactive decay of the potassium isotope (40)K, with a half-life of 1.25 billion years; (36)Ar is primordial in origin). This ratio is consistent with an early development of the felsic crust, which might have had an important role in climate variability during the first half of Earth's history.