The frequency, v, for O-D stretching in D2O films between the superimposed layers of different micas and montmorillonites was measured at several film thicknesses and temperatures of 2° and 25°C by infrared spectroscopy. The molar absorptivity, ε, for O-D stretching in HDO films between the montmorillonite layers was also measured at different film thicknesses and 25°C. It was found that v is related to mw/mm, the mass ratio of D2O to mica or montmorillonite, by the equation v = v0 exp β/(mwmm where v0 is the O-D stretching frequency in pure D2O and ß is a constant. Since mw/mm is proportional to a, the area under the absorption peak, mw/mm can be replaced by a in this equation. It was also found that ε decreased dramatically as the thickness of the water film between the montmorillonite layers decreased. These results were interpreted to mean that the structure of the interlayer water is perturbed by the interlayer cations and/or silicate surfaces.

The crystal structure of a deuterated synthetic boehmite powder, γ-AIOOD, has been determined by time-of-flight neutron diffraction and Rietveld profile refinement in space group Cmcm to a weighted profile R of 3.71%. Cell dimensions are a = 2.868(1), b = 12.2336(4), and C = 3.6923(1) Å. Alternate space groups for the boehmite structure suggested in the recent literature were found to be unacceptable. Atom positions, bond distances, and angles, with the exception of those involving hydrogen, were nearly identical to those determined by R. J. Hill in 1981 who studied a single crystal of boehmite by X-ray diffraction. All atoms were refined with anisotropic thermal parameters. The b value is 0.013 Å larger, and the thermal ellipsoids of oxygen are slightly more anisotropic than those reported by Hill and may reflect the different samples studied.

The Eastern Chukotka is considered a unique permafrost region where massive ice bodies are widespread. However, the origin and age of these ice formations are often discussed. The age of the massive ice of Chukotka was established for the first time using AMS 14C dating. It was revealed that three massive ice bodies on the coast of Mechigmen Bay were formed at the end of the Late Pleistocene: a) near the Akkani site, 21,612 to 22,147 cal BP; b) near the Lavrentiya settlement, 27,553 cal BP; and c) near the Lavrentiya settlement, 22,193 cal BP. Stable isotope values in the studied massive ice vary in a rather wide range by about 10‰ for δ18O values (from –14.8‰ to –24.5‰) and about 75‰ for the δ2H values (from –116‰ to –191‰). The studied massive ice bodies are of intrasedimental genesis and formed epigenetically during the final stage of MIS2 (22–27 cal ka BP).

Zirconium alloys are common fuel claddings in nuclear fission reactors and are susceptible to the effects of hydrogen embrittlement. There is a need to be able to detect and image hydrogen at the atomic scale to gain the experimental evidence necessary to fully understand hydrogen embrittlement. Through the use of deuterium tracers, atom probe tomography (APT) is able to detect and spatially locate hydrogen at the atomic scale. Previous works have highlighted issues with quantifying deuterium concentrations using APT due to complex peak overlaps in the mass-to-charge-state ratio spectrum between molecular hydrogen and deuterium (H2 and D). In this work, we use new methods to analyze historic and simulated atom probe data, by applying currently available data analysis tools, to optimize solving peak overlaps to improve the quantification of deuterium. This method has been applied to literature data to quantify the deuterium concentrations in a concentration line profile across an α-Zr/deuteride interface.

We investigated a new method for estimating specimen hydrogen content in atom probe tomography (APT) in experiments where molecular hydrogen ions (${\rm H}_2^ +$) originating from the measurement environment can overlap with deuterium (D+) in the mass-to-charge-state spectrum, thus preventing the direct application of isotopic marking for unambiguous hydrogen analysis. First, we applied an existing method for hydrogen content estimation, using ${\rm H}^ + {/}{\rm H}_2^ +$ ratios obtained from paired deuterated/nondeuterated experiments. These measurements demonstrated sufficient residual uncertainty to motivate exploring an alternative method to accurately estimate hydrogen content. By varying the time between evaporation events, it is then shown that a highly correlated relationship between field evaporation rate and hydrogen content exists and can also be used to predict hydrogen content. This leads to a new method for measuring hydrogen content within the specimen. We combine this extrapolation technique with continuous cycling of the evaporation rate or pulse frequency during an APT experiment. This could enable spatially resolved imaging of hydrogen concentrations despite the presence of a contaminant background hydrogen signal, without the need for deuteration.

Analysis and understanding of the role of hydrogen in metals is a significant challenge for the future of materials science, and this is a clear objective of recent work in the atom probe tomography (APT) community. Isotopic marking by deuteration has often been proposed as the preferred route to enable quantification of hydrogen by APT. Zircaloy-4 was charged electrochemically with hydrogen and deuterium under the same conditions to form large hydrides and deuterides. Our results from a Zr hydride and a Zr deuteride highlight the challenges associated with accurate quantification of hydrogen and deuterium, in particular associated with the overlap of peaks at a low mass-to-charge ratio and of hydrogen/deuterium containing molecular ions. We discuss possible ways to ensure that appropriate information is extracted from APT analysis of hydrogen in zirconium alloy systems that are important for nuclear power applications.

In this work, we demonstrate a new system for the examination of gas interactions with surfaces via atom probe tomography. This system provides capability of examining the surface and subsurface interactions of gases with a wide range of specimens, as well as a selection of input gas types. This system has been primarily developed to aid the investigation of hydrogen interactions with metallurgical samples, to better understand the phenomenon of hydrogen embrittlement. In its current form, it is able to operate at pressures from 10−6 to 1000 mbar (abs), can use a variety of gasses, and is equipped with heating and cryogenic quenching capabilities. We use this system to examine the interaction of hydrogen with Pd, as well as the interaction of water vapor and oxygen in Mg samples.

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200–500 kPa (2–5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide–metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

X-ray powder diffraction data for ErH2−xDx formed by hydrogen (i.e., protium)–deuterium loading of Er metal are reported. Lattice parameters for the varying hydrogen–deuterium compositions followed Vergard’s law behavior. The cubic lattice parameter at room temperature for ErH2−xDx obeys a linear relationship according to the formula a=5.1287−1.1120×10−4⋅x, where a is the lattice parameter of the fluorite-type structure and x is the mole percent of deuterium. Microstrain measurements suggest a possible ordering of hydrogen and deuterium in the composition ErH1D1.

The application of stable-hydrogen isotope (δD) measurements to the study of animal movement, resource use and physiology depends on understanding factors driving variation in δD in animal tissues. The source of micro-scale variation in δD is poorly known, yet understanding micro-scale patterns of δD could shed light on important ecological processes and improve our abilities to track animal movements. Using linear and additive models, we explored the influence of micro-scale habitat use, moisture and diet on tissue δD values of Nicaraguan cloud-forest birds. Using mist nets, we captured 211 individuals of 22 resident Neotropical species at 500–1390 m asl and collected feather and claw samples. Based on three years of data from year-round sampling, our results suggest that microhabitat, seasonal shifts in moisture δD, and diet all influence bird tissue δD values. Our model results reveal a previously undescribed microgeographical effect on δD, where foraging level (understorey versus overstorey) and foraging location (forest interior versus adjacent coffee plantation) were significant predictors of δD values in bird claws and feathers. Mean claw and feather δD values among species varied from −83‰ to −19‰. Top models for claws and feathers explained 57% and 52% of variation in δD respectively. Direct comparisons of understorey (mean ± SD of −30‰ ± 15‰) versus overstorey (−50‰ ± 15‰) claw values suggest that δD may be useful in tracking vertical, micro-scale movement. Higher δD values in forest understorey birds reveal a heavy reliance upon recycled, fog moisture. Fragmentation and climate change may result in increasingly desiccated cloud forest that may exert a more negative influence on the food webs of understorey species that seem to be supported by recycled sources of moisture in the dry season.

Evaluations of the energy requirements of working animals have been confounded by the constraints of indirect calorimetric techniques (Cal). This study sought to investigate a non-restrictive methodology, the doubly labelled water (DLW; 2H218O) technique, for the measurement of energy expenditure in free ranging equids. Six pony geldings were intravenously injected with DLW in two sequential studies that permitted first, isotope equilibration and half-lives to be determined and then second, heat production (HP) to be measured simultaneously by DLW and traditional (Cal) techniques.

In study 1, three animals were injected with DLW, three animals were untreated controls. Blood samples were collected every 30 min for 12 h and thereafter at 24 h intervals for 14 days. Isotopes equilibrated throughout the body water pool within 300 (2H) and 240 (18O) min and half-lives were 6.3 ± 0.6 days (2H) and 5.6 ± 0.4 days (18O).

In study 2, HP was simultaneously determined by Cal and DLW over a 4-day period. Animals (no. = 6) were assigned to pairs and in successive weeks two ponies were injected with DLW and confined to metabolism chambers 12 h later. Cal HP was 0.51 ± 0.02 MJ/kg M0.75 per day compared with 0.48 ± 0.29 MJ/kg M0.75 per day estimated by DLW. Maintenance metabolizable energy intake was 0.53 ± 0.01 MJ/kg M0.75 per day (Cal) and 0.50 ± 0.01 MJ/kg M0.75 per day (DLW). Validation of the DLW technique may empower essential, systematic appraisal of energy requirements in unrestrained working horses.

The purpose of the present study was to estimate whole-body fatty acid and cholesterol synthesis in weight-stable adults and to determine the likely effect on the doubly-labelled water (DLW) method for measuring energy expenditure. Synthesis was measured by 2H incorporation over 14 d in six adult males in approximate energy balance following noradrenaline infusion to maximize mobilization of free fatty acid from adipose tissue. The inter-individual variation in synthesis rates was large and in one subject the proportion of free fatty acid synthesized was ten times that of the mean of the rest of the group; the fasting concentration of esterified fatty acid in this subject was five times that of the rest of the group indicating likely violation of the assumptions underlying the calculation of whole-body synthesis. After 14 d of labelling in the other five subjects, 0·9 (SEM 0·3) % OF THE CIRCULATING FREE FATTY ACID, 9·3 (sem 3·0) % of the esterified fatty acid, 14·6 (sem 2·4) % of the free cholesterol and 28·3 (sem 3·7) % of esterified cholesterol had been synthesized de novo. A high rate of synthesis correlated with a low pre-dose 2H abundance both within and between lipid classes suggesting that natural 2H abundance variations in some lipid classes may be used to determine their metabolic origin. Whole-body synthetic rates were 8 g/d for fatty acid and 0·3–0·5 g/d for cholesterol. These values correspond to very small errors on DLW-derived estimates of CO2 production; -2·5 litres/d for fatty acid and -0·1 to -0·2 litres/d for cholesterol. These results, obtained in subjects typically consuming a diet with a lower fat and cholesterol content that the typical Western diet, suggest that the DLW method is unlikely to be affected by fatty acid and cholesterol synthesis in subjects in energy balance consuming a typical Western diet.