Pristine helium from the Karoo mantle plume within the shallow asthenosphere beneath Patagonia.

Mantle xenoliths usually represent fragments derived from the depleted and degassed lithospheric mantle with 3He/4He isotope ratios (6 ± 1 RA) lower than those of mid-ocean ridge basalts (8 ± 1 RA). Otherwise, basalts from oceanic islands related to hotspots often have high 3He/4He ratios (>10 RA), suggesting a deep and pristine undegassed mantle source. Here we present a striking high-3He/4He component (up to 27.68 RA) recorded by spinel-facies mantle xenoliths from Patagonia. Remarkably, the highest ratios were found in a long-lived trans-lithospheric suture zone related to the Carboniferous-Permian collision of two continental blocks: the Deseado and the North Patagonian massifs. The mantle xenoliths with notably high-3He/4He ratios are inferred to be fragments of the shallow asthenosphere rising through the eroded and rejuvenated thin lithosphere. The pristine helium component is derived from the western margin of the Karoo mantle plume, related to the initial stages of the Gondwana fragmentation.

Monitoring of magmatic-hydrothermal system by noble gas and carbon isotopic compositions of fumarolic gases.

We repeatedly measured isotopic compositions of noble gases and CO2 in volcanic gases sampled at six fumaroles around the Kusatsu-Shirane volcano (Japan) between 2014 and 2021 to detect variations reflecting recent volcanic activity. The synchronous increases in 3He/4He at some fumaroles suggest an increase in magmatic gas supply since 2018. The increase in magmatic gas supply is also supported by the temporal variations in 3He/CO2 ratios and carbon isotopic ratios of CO2. The 3He/40Ar* ratios (40Ar*: magmatic 40Ar) show significant increases in the period of high 3He/4He ratios. The temporal variation in 3He/40Ar* ratios may reflect changes in magma vesicularity. Therefore, the 3He/40Ar* ratio of fumarolic gases is a useful parameter to monitor the current state of degassing magma, which is essential for understanding the deep process of volcanic unrest and may contribute to identifying precursors of a future eruption. These results provide additional validation for the use of noble gas and carbon isotopic compositions of fumarolic gases for monitoring magmatic-hydrothermal systems.

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.

Instrumentation and Method Development for On-Site Analysis of Helium Isotopes.

Helium isotope determination may be useful in measuring volcanic activity and issuing earlier warnings of possible eruptions. A method is presented for measuring the 3He/4He ratio in a gas sample using a multiturn time-of-flight mass spectrometer "infiTOF". In contrast to conventional waveform averaging, peaks are determined by counting ion pulses from each time-of-flight trigger. Samples were also measured by conventional magnetic-sector mass spectrometry for comparison. Magnetic sector results were used to designate a standard for infiTOF measurement and to calculate a ratio for each sample measured by infiTOF. Mass assignment error for ultrapure 3He+ standard was 4.30 × 10-5 Da. Mass assignment error of 4He2+ and 3He+ for sample cylinders was 3.00 × 10-8 Da and 2.25 × 10-4 Da, respectively. Abundance ratios determined by infiTOF were found to be within 2% of the abundance ratios determined by magnetic-sector mass spectrometry. Mass drift was <50 × 10-6 Da over 10 h. Sample flow rate was not found to affect the results as long as the reference sample was analyzed under the same conditions. Results indicate that the infiTOF system may be a viable tool for measuring helium isotopes, which may eventually lead to earlier warnings of volcanic activity.

Construction of a newly designed small-size mass spectrometer for helium isotope analysis: toward the continuous monitoring of (3)he/(4)he ratios in natural fluids.

The construction of a small-size, magnetic sector, single focusing mass spectrometer (He-MS) for the continuous, on-site monitoring of He isotope ratios ((3)He/(4)He) is described. The instrument is capable of measuring (4)He/(20)Ne ratios dissolved in several different types of natural fluids of geochemical interest, such as groundwater and gas from hot springs, volcanoes and gas well fields. The ion optics of He-MS was designed using an ion trajectory simulation program "TRIO," which permits the simultaneous measurement of (3)He and (4)He with a double collector system under a mass resolution power (M/ΔM) of >700. The presently attained specifications of He-MS are; (1) a mass resolving power of ca. 430, sufficient to separate (3)He(+) from interfering ions, HD(+) and H3 (+), (2) ultra-high vacuum conditions down to 3×10(-8) Pa, and (3) a sufficiently high sensitivity to permit amounts of (3)He to be detected at levels as small as 10(-13) cm(3) STP (3×10(6) atoms). Long term stability for (3)He/(4)He analysis was examined by measuring the (3)He/(4)He standard gas (HESJ) and atmospheric He, resulting in ∼3% reproducibility and ≤5% experimental error for various amounts of atmospheric He from 0.3 to 2.3×10(-6) cm(3) STP introduced into the instrument. A dynamic range of measurable (3)He/(4)He ratios with He-MS is greater than 10(3) which was determined by measuring various types of natural fluid samples from continental gas (with a low (3)He/(4)He ratio down to 2×10(-8)) to volcanic gas (with a high (3)He/(4)He ratio up to 3×10(-5)). The accuracy and precision of (3)He/(4)He and (4)He/(20)Ne ratios were evaluated by comparing the values with those measured using well established noble gas mass spectrometers (modified VG5400/MS-III and -IV) in our laboratory, and were found to be in good agreement within analytical errors. Usefulness of the selective extraction of He from water/gas using a high permeability of He through a silica glass wall at high temperature (700°C) is demonstrated.

Emisión difusa de dióxido de carbono en el volcán Irazú, Costa Rica

El primer estudio sobre desgasificación difusa de CO2 en el volcán Irazú se realizó en el 2001 con el objetivo de evaluar el origen y la distribución espacial del flujo difuso de CO2 así como la tasa de emisión de CO2 a la atmósfera. La mayor parte del área de estudio presentó valores de fondo para el flujo difuso de CO2 inferiores a los 20 g m-2 d-1. El mayor valor medido fue de 316 g m-2 d-1, que es relativamente inferior a los mayores valores medidos en otros sistemas volcánicos asentados en el mismo ambiente volcano-tectónico. Los mayores valores de flujo difuso de CO2 se detectaron en el borde NE del cráter Principal y al N del cráter Diego de La Haya. La firma isotópica del carbono en el CO2 de la atmósfera del suelo presentó un amplio rango de valores ? 13C-CO2, entre -65,3 y -19,8

, que sugiere una importante contribución biogénica para la emisión difusa de CO2 en el Irazú. La tasa de emisión difusa de CO2 para el área de estudio en el Irazú se estimó en 44 t d-1. El estudio de los gases fumarólicos mostró una relación 3He/4He característica de volcanes relacionados con zonas de subducción (6,6 RA), y que el 90

del CO2 emitido procede de la incorporación de sedimentos calcáreos en el proceso de subducción.(AU)