An olivine-melt thermometer based on the partitioning of Ni (DNiOl/liq) was hypothesized by Pu et al. (2017) to have a negligible dependence on dissolved water in the melt (and pressure variations from 0–1 GPa), in marked contrast to thermometers based on DMgOl/liq. In this study, 15 olivine-melt equilibrium experiments were conducted on a basaltic glass starting material (9.6 wt% MgO; 353 ppm Ni) to test this hypothesis by comparing the effect of dissolved H2O in the melt on DMgOl/liq and DNiOl/liq on the same set of experiments. Results are presented for six anhydrous experiments at 1 bar, two anhydrous experiments at 0.5 GPa, and seven hydrous experiments at 0.5 GPa. Analyzed olivine and glass compositions in the quenched run products were used to calculate DMgOl/liq and DNiOl/liq values for each experiment, which in turn permit temperature to be calculated with the Mg- and Ni-thermometers calibrated in Pu et al. (2017) on anhydrous, 1-bar experiments from the literature. The Ni-thermometer recovers the temperatures of all 15 experiments from this study with an average deviation of –3 °C, including those with up to 4.3 wt% H2O dissolved in the melt. In contrast, the Mg-thermometer recovers the anhydrous, 1-bar experimental temperatures within +14 °C on average, but overestimates the hydrous experimental temperatures by +49 to +127 °C, with an average of +83 °C. When the Mg-thermometer of Putirka et al. (2007) is applied, which includes a correction for analyzed H2O (≤4.3 wt%) in the quenched melts of the run products, all experimental temperatures are recovered with an average (±1σ) deviation of +7 °C. The combined results show that DNiOl/liq has a negligible dependence on dissolved water in the melt (≤4.3 wt% H2O), which is in marked contrast to the strong dependence of DMgOl/liq on water in the melt. An understanding of why DNiOl/liq is insensitive to dissolved water, unlike DMgOl/liq, is obtained from spectroscopic evidence in the literature, which shows that Ni2+ (transition metal) and Mg2+ (alkaline earth metal) have distinctly different average coordination numbers (predominantly fourfold and sixfold, respectively) in silicate melts and that fourfold-coordinated Ni2+ is unaffected by the presence of dissolved water in the melt. This difference in coordination number explains why DNiOl/liq and DMgOl/liq each have a different dependence on pressure, anhydrous melt composition, and melt water content. Application of the Ni-thermometer of Pu et al. (2017) to five natural samples from the Mexican arc, for which H2O contents (3.6–6.7 wt%) in olivine-hosted melt inclusions are reported in the literature, leads to temperatures that match those obtained from the Putirka et al. (2007) Mg-thermometer that corrects for analyzed H2O contents. This study demonstrates that a thermometer based on DNiOl/liq can be applied to hydrous basalts at crustal depths without the need to correct for dissolved water content or pressure.
The two most commonly invoked processes for generating plagiogranites in mid-ocean ridge environments are extended fractional crystallization of mid-ocean ridge basalt (MORB) magma and ''hydration melting'' of hot, dry MOR gabbro initiated by the influx of seawater-derived hydrothermal fluids within localized zones of shear. Brophy (Contrib Mineral Petrol 158:99-111, 2009) has proposed on theoretical grounds that, for liquids greater than *62 wt. % SiO 2 , hydration melting should yield, among other features, a negative correlation between rare earth element (REE) abundances and increasing SiO 2 , while fractional crystallization should yield a positive correlation. If correct, the REE-SiO 2 systematics of natural systems might be used to distinguish between the two processes. The Ordovician Fournier oceanic fragment, New Brunswick, Canada, contains MOR gabbro-hosted plagiogranite veins and dikes that are believed to have formed from hydration melting, thus forming an appropriate location for field verification of the proposed REE-SiO 2 systematics for such a process. In addition to a negative correlation between liquid SiO 2 and REE abundance for liquids in excess of *62% SiO 2 , other important model features include the following: (1) relative to a gabbro source rock, the degree of enrichment at liquids of 62 and 75% SiO 2 decreases from the LREE to the HREE; (2) the degree of enrichment at 75% SiO 2 approaches 1 for the HREE; (3) the rate of change of the degree of enrichment with increasing liquid SiO 2 (i.e., the slope) diminishes from the LREE to the HREE. All of these predicted features are observed in the Fournier plagiogranites. Assuming an initial source rock equivalent to the host gabbro, an additional strongly LREE-enriched component must be added prior to melting in order to make the absolute REE abundances agree with the model values. The most likely candidates are the very seawater-derived hydrothermal fluids that triggered hydration melting in the first place.
Corrosion of aluminium alloy clad nuclear fuel, during reactor operation and under subsequent wet storage conditions, promotes the formation of aluminium hydroxide and oxyhydroxide layers. These hydrated mineral phases and the chemisorbed and physisorbed waters on their surfaces are susceptible to radiation-induced processes that yield molecular hydrogen gas (H2), which has the potential to complicate the long-term storage and disposal of aluminium clad nuclear fuel through flammable and explosive gas mixture formation, alloy embrittlement, and pressurization. Here, we present a systematic study of the radiolytic formation of H2 from aluminium alloy 1100 (AA1100) and 6061 (AA6061) coupons in “dry” (~0% relative humidity) and “wet” (50% relative humidity) helium environments. Cobalt-60 gamma irradiation of both aluminium alloy types promoted the formation of H2, which increased linearly up to ~2 MGy, and afforded G-values of 1.1 ± 0.1 and 2.9 ± 0.1 for “dry” and “wet” AA1100, and 2.7 ± 0.1 and 1.7 ± 0.1 for “dry” and “wet” AA6061. The negative correlation of H2 production with relative humidity for AA6061 is in stark contrast to AA1100 and is attributed to differences in the extent of corrosion and varying amounts of adsorbed water in the two alloys, as characterized using optical profilometry, scanning electron microscopy, Raman spectroscopy, and X-ray diffraction techniques.
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