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1. The Role of Tunneling in the Spectra of H ₅ ⁺ and D ₅ ⁺ up to 7300 cm ^-1

   https://doi.org/10.1021/acs.jpca.0c02299  

   Boyer, Mark A.; Chiu, Chloe S.; McDonald, David C.; Wagner, J. Philipp; Colley, Jason E.; Orr, Dylan S.; Duncan, Michael A.; McCoy, Anne B. (May 2020, The Journal of Physical Chemistry A)

   The spectra for H5+ and D5+ are extended to cover the region between 4830 and 7300 cm−1. These spectra are obtained using mass-selected photodissociation spectroscopy. To understand the nature of the states that are accessed by the transitions in this and prior studies, we develop a four-dimensional model Hamiltonian. This Hamiltonian is expressed in terms of the two outer H2 stretches, the displacement of the shared proton from the center of mass of these two H2 groups, and the distance between the H2 groups. This choice is motivated by the large oscillator strength associated with the shared proton stretch and the fact that the spectral regions that have been probed correspond to zero, one, and two quanta of excitation in the H2 stretches. This model is analyzed using an adiabatic separation of the H2 stretches from the other two vibrations and includes the non-adiabatic couplings between H2 stretch states with the same number of quanta of excitation in the H2 stretches. Based on the analysis of the energies and wave functions obtained from this model, we find that when there are one or more quanta of excitation in the H2 stretches the states come in pairs that reflect tunneling doublets. The states accessed by the transitions in the spectrum with the largest intensity are assigned to the members of the doublets with requisite symmetry that are localized on the lowest-energy adiabat for a given level of H2 excitation. 

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2. 2019. Hydrogen isotopes in high 3He/4He submarine basalts: Primordial vs. recycled water and the veil of mantle enrichment. , 508, .

   Loewen, Matthew W. (February 2019, Earth and planetary science letters)

   The hydrogen isotope value (δD) of water indigenous to the mantle is masked by the early degassing and recycling of surface water through Earth's history. High 3He/4He ratios in some ocean island basalts, however, provide a clear geochemical signature of deep, primordial mantle that has been isolated within the Earth's interior from melting, degassing, and convective mixing with the upper mantle. Hydrogen isotopes were measured in high 3He/4He submarine basalt glasses from the Southeast Indian Ridge (SEIR) at the Amsterdam–St. Paul (ASP) Plateau (δD = −51 to −90‰, 3He/4He = 7.6 to 14.1 RA) and in submarine glasses from Loihi seamount south of the island of Hawaii (δD = −70 to −90‰, 3He/4He = 22.5 to 27.8 RA). These results highlight two contrasting patterns of δD for high 3He/4He lavas: one trend toward high δD of approximately −50‰, and another converging at δD = −75‰. These same patterns are evident in a global compilation of previously reported δD and 3He/4He results. We suggest that the high δD values result from water recycled during subduction that is carried into the source region of mantle plumes at the core–mantle boundary where it is mixed with primordial mantle, resulting in high δD and moderately high 3He/4He. Conversely, lower δD values of −75‰, in basalts from Loihi seamount and also trace element depleted mid-ocean ridge basalts, imply a primordial Earth hydrogen isotopic value of −75‰ or lower. δD values down to −100‰ also occur in the most trace element-depleted mid-ocean ridge basalts, typically in association with 87Sr/86Sr ratios near 0.703. These lower δD values may be a result of multi-stage melting history of the upper mantle where minor D/H fractionation could be associated with hydrogen retention in nominally anhydrous residual minerals. Collectively, the predominance of δD around −75‰ in the majority of mid-ocean ridge basalts and in high 3He/4He Loihi basalts is consistent with an origin of water on Earth that was dominated by accretion of chondritic material. 

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3. Hydrogen isotopes in high 3He/4He submarine basalts: Primordial vs. recycled water and the veil of mantle enrichment

   Loewen, Matthew W. (January 2019, Earth and planetary science letters)

   The hydrogen isotope value (δD) of water indigenous to the mantle is masked by the early degassing and recycling of surface water through Earth’s history. High 3He/4He ratios in some ocean island basalts, however, provide a clear geochemical signature of deep, primordial mantle that has been isolated within the Earth’s interior from melting, degassing, and convective mixing with the upper mantle. Hydrogen isotopes were measured in high 3He/4He submarine basalt glasses from the Southeast Indian Ridge (SEIR) at the Amsterdam–St. Paul (ASP) Plateau (δD =−51 to −90, 3He/4He =7.6 to 14.1 RA) and in submarine glasses from Loihi seamount south of the island of Hawaii (δD =−70 to −90, 3He/4He =22.5 to 27.8 RA). These results highlight two contrasting patterns of δD for high 3He/4He lavas: one trend toward high δD of approximately −50, and another converging at δD =−75. These same patterns are evident in a global compilation of previously reported δD and 3He/4He results. We suggest that the high δD values result from water recycled during subduction that is carried into the source region of mantle plumes at the core–mantle boundary where it is mixed with primordial mantle, resulting in high δD and moderately high 3He/4He. Conversely, lower δD values of −75, in basalts from Loihi seamount and also trace element depleted mid-ocean ridge basalts, imply a primordial Earth hydrogen isotopic value of −75or lower. δD values down to −100also occur in the most trace element-depleted mid-ocean ridge basalts, typically in association with 87Sr/86Sr ratios near 0.703. These lower δD values may be a result of multi-stage melting history of the upper mantle where minor D/H fractionation could be associated with hydrogen retention in nominally anhydrous residual minerals. Collectively, the predominance of δD around −75in the majority of mid-ocean ridge basalts and in high 3He/4He Loihi basalts is consistent with an origin of water on Earth that was dominated by accretion of chondritic material. 

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4. Heterogeneous mantle-derived helium isotopes in the Canary Islands and other ocean islands

   https://doi.org/10.1130/G47676.1  

   Day, James MD; Hilton, David R (September 2020, Geology)

   Abstract Consistent 3He/4He ratios have been measured for >25 years in geothermal fluids and gases from Cumbre Vieja, La Palma (9.4 ± 0.1RA, where RA is the 3He/4He of air), and Teide, Tenerife (6.8 ± 0.3RA), Canary Islands. Both locations are characterized by similar CO2/3He (∼2 to 4 × 109), mantle-like δ13C (−3.3‰ to −4.4‰) and CO2 output (0.1–0.2 × 1010 mol yr–1). Helium isotopic differences between the islands cannot be explained by differential aging and 4He ingrowth in their mantle sources. Instead, distinct He reservoirs exist, with a high-μ (HIMU)–type mantle source for La Palma and a more enriched mantle, with possible lithospheric mantle influence, for Tenerife. Geothermal samples from the Canary Islands record a present-day He distribution distinct from higher 3He/4He in olivine from older eastern Canary Island lavas, indicating temporal variability in sources. Comparison of geothermal sample data versus olivine, pyroxene, and glass He isotope data for the Canary Islands, Azores, Cape Verde, Hawaiian islands, and Iceland reveals generally good correspondence, even across >1 m.y. of stratigraphy. However, in addition to the Canary Islands, there are examples of inter-island heterogeneity for He isotopes at Hawaii, the Azores, and within Iceland, preserved in hydrothermal samples, minerals, and glasses. In particular, in northwest Iceland, olivine separates from older lavas preserve higher 3He/4He than present-day geothermal samples from the same region. This difference likely reflects a reduced mantle-derived 3He input to Icelandic magmatism since the Miocene. Temporal variability in 3He/4He, assessed using geothermal and geological materials in conjunction, offers a powerful tool for examining heterogeneity and temporal evolution of mantle sources at intraplate volcanoes. 

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5. The 3-Helium Problem

   Balser, D.; Bania, T. (January 2020, American Astronomical Society meeting #235)

   The light element 3He is produced in copious amounts during the first three minutes after the Big Bang. The 3He abundance is then modified primarily by nucleosynthesis in stars, whereby low-mass stars (< 2 solar masses) are expected to produce 3He due to the astration of deuterium. The higher temperatues in more massive stars fuse 3He completely into 4He thus destroying 3He. Measurements of 3He are made via observations of the hyperfine transition of 3He+ at 3.46 cm. Observations of 3He+ in HII regions located throughout the Milky Way disk reveal very little variation in the 3He/H abundance ratio — the "3He Plateau", indicating that the net effect of 3He production in stars is negligible. This is in contrast to much higher 3He/H abundance ratios found in some planetary nebula (PNe). This discrepancy is known as the "3He Problem." One solution to this problem is that thermohaline mixing occurs just above the hydrogen-burning shell to process 3-Helium: 3He(3He, 2p)4He. Thermohaline mixing is a double-diffusive instability that occurs in oceans and is also called thermohaline convection. We discuss how more accurate observations of the 3He/H abundance ratio can constrain stellar evolution models that include thermohaline mixing. 

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