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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. 

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. 

Magma‐water interaction can dramatically influence the explosivity of volcanic eruptions. However, syn‐ and post‐eruptive diffusion of external (non‐magmatic) water into volcanic glass remains poorly constrained and may bias interpretation of water in juvenile products. Hydrogen isotopes in ash from the 2009 eruption of Redoubt Volcano, Alaska, record syn‐eruptive hydration by vaporized glacial meltwater. Both ash aggregation and hydration occurred in the wettest regions of the plume, which resulted in the removal and deposition of the most hydrated ash in proximal areas <50 km from the vent. Diffusion models show that the high temperatures of pyroclast‐water interactions (>400°C) are more important than the cooling rate in facilitating hydration. These observations suggest that syn‐eruptive glass hydration occurred where meltwater was entrained at high temperature, in the plume margins near the vent. Ash in the drier plume interior remained insulated from entrained meltwater until it cooled sufficiently to avoid significant hydration.