Contamination of the Bushveld Complex (South Africa) magmas by basinal brines: Stable isotopes in phlogopite from the UG2 chromitite

There is abundant evidence for significant H2O in evolved melts from the platinum-rich UG2 chromitite and the Merensky Reef of the Bushveld Complex (South Africa), but there is no consensus about the source of H2O. We report triple-oxygen and hydrogen isotope ratios of interstitial, late-magmatic phlogopite from three localities of the UG2 layer. The phlogopite yielded δD values of –43‰ to –23‰, which is >30‰ higher than previously known from Bushveld rocks and far above the mantle values of ~–75‰. The phlogopite triple-oxygen isotope ratios are the first to be reported for Bushveld rocks, with values of Δ′17O0.5305 (17O excess relative to the reference line 0.5305) from –0.069‰ to –0.044‰ (δ18O 5.2‰–6.2‰). The oxygen data support existing models of as much as 30%–40% contamination of mantlederived magmas in the lower to middle crust. However, the high δ values require a second step of contamination, which we attribute to brines from the marine sediments in the Transvaal Basin at the emplacement level.

Improving temperature reconstructions from ice-core water-isotope records

Oxygen and hydrogen isotope ratios in polar precipitation are widely used as proxies for local temperature. Used in combination, oxygen and hydrogen isotope ratios also provide information on sea surface temperature at the oceanic moisture source locations where polar precipitation originates. Temperature reconstructions obtained from ice core records generally rely on linear approximations of the relationships among local temperature, source temperature and water-isotope values. However, there are important nonlinearities that significantly affect such reconstructions, particularly for source-region temperatures. Here, we describe a temperature reconstruction method that accounts for these nonlinearities. We provide new reconstructions of absolute surface temperature, condensation temperature, and source-region evaporation temperature for all long Antarctic ice-core records for which the necessary data are available. We also provide thorough uncertainty estimates on all temperature histories. Our reconstructions constrain the pattern and magnitude of polar amplification in the past and reveal asymmetries in the temperature histories of East and West Antarctica.

Continuous-Flow Analysis of δ17O, δ18O, and δD of H2O on an Ice Core from the South Pole

The δD and δ18O values of water are key measurements in polar ice-core research, owing to their strong and well-understood relationship with local temperature. Deuterium excess, d, the deviation from the average linear relationship between δD and δ18O, is also commonly used to provide information about the oceanic moisture sources where polar precipitation originates. Measurements of δ17O and “17O excess” (Δ17O) are also of interest because of their potential to provide information complementary to d. Such measurements are challenging because of the greater precision required, particularly for Δ17O. Here, high-precision measurements are reported for δ17O, δ18O, and δD on a new ice core from the South Pole, using a continuous-flow measurement system coupled to two cavity ring-down laser spectroscopy instruments. Replicate measurements show that at 0.5 cm resolution, external precision is ∼0.2‰ for δ17O and δ18O, and ∼1‰ for δD. For Δ17O, achieving external precision of <0.01‰ requires depth averages of ∼50 cm. The resulting ∼54,000-year record of the complete oxygen and hydrogen isotope ratios from the South Pole ice core is discussed. The time series of Δ17O variations from the South Pole shows significant millennial-scale variability, and is correlated with the logarithmic formulation of deuterium excess (dln), but not the traditional linear formulation (d).

Evidence of hydrogen trapping at second phase particles in zirconium alloys

Zirconium alloys are used in safety–critical roles in the nuclear industry and their degradation due to ingress of hydrogen in service is a concern. In this work experimental evidence, supported by density functional theory modelling, shows that the α-Zr matrix surrounding second phase particles acts as a trapping site for hydrogen, which has not been previously reported in zirconium. This is unaccounted for in current models of hydrogen behaviour in Zr alloys and as such could impact development of these models. Zircaloy-2 and Zircaloy-4 samples were corroded at 350 °C in simulated pressurised water reactor coolant before being isotopically spiked with 2H2O in a second autoclave step. The distribution of 2H, Fe and Cr was characterised using nanoscale secondary ion mass spectrometry (NanoSIMS) and high-resolution energy dispersive X-ray spectroscopy. 2H− was found to be concentrated around second phase particles in the α-Zr lattice with peak hydrogen isotope ratios of 2H/1H = 0.018–0.082. DFT modelling confirms that the hydrogen thermodynamically favours sitting in the surrounding zirconium matrix rather than within the second phase particles. Knowledge of this trapping mechanism will inform the development of current understanding of zirconium alloy degradation through-life.

The Development and Use of Isoscapes to Determine the Geographical Origin of Quercus spp. in the United States

The stable isotope ratios of oxygen, hydrogen, carbon and sulfur from extracted wood of 87 samples of oaks from the United States were analysed. Relationships with climate variables and the stable isotope ratios of the 69 training dataset samples were investigated to a monthly resolution using long-term monthly mean climate data from NASA and the University of East Anglia’s Climate Research Unit, in conjunction with forecast data for hydrogen and oxygen isotope ratios in precipitation. These relationships were used to construct model isoscapes for oxygen, hydrogen, carbon and sulfur for US oak with the aim of using them to forecast isotopic patterns in areas that were not sampled and predict values in samples not used to construct the models. The leading predictors for isoscape generation were oxygen isotope ratios in January precipitation for oak oxygen isotope ratios, hydrogen isotope ratios in July precipitation for oak hydrogen isotope ratios, water vapour in April for carbon isotope ratios, and reflected shortwave radiation in March in combination with sulfate concentration in May for oak sulfur isotopes. The generated isoscapes can be used to show regions an unknown sample may have originated from with a resolution dependent on the rarity of the stable isotope signature within the United States. The models were assessed using the data of 18 samples of georeferenced oak. The assessment found that 100% of oxygen, 94% of hydrogen, 78% of carbon, and 94% of sulfur isotope ratios in the 18 test dataset samples fell within two standard deviations of the isoscape models. Using the results of the isoscapes in combination found that there were 4/18 test samples which did not fall within two standard deviations of the four models, this is largely attributed to the lower predictive power of the carbon isoscape model in conjunction with high local variability in carbon isotope ratios in both the test and training data. The method by which this geographic origin method has been developed will be useful to combat illegal logging and to validate legal supply chains for the purpose of good practice due diligence.