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The doubly labeled water (DLW) technique is used to assess metabolic rate (MR) in free-living conditions. We investigated whether differences in the nutritional and body adiposity status affect validity of the assessment of CO2production (rCO2) by the DLW technique. To serve this purpose, we compared calculated rCO2by the DLW method to actual CO2production concomitantly measured in an indirect calorimetry setup over a 3-day period in mice fed with a low-fat (LF) diet or an obesogenic high-fat/high-sucrose (HF) diet. To uncover a potential effect of body composition on DLW accuracy, the HF-fed group was further subdivided in a diet-induced obesity-prone (DIO) and diet-induced obesity-resistant (DR) group. Furthermore, we assessed the influence of different sampling protocols, duration, and methodology of calculation. An excellent match was found between rCO2assessed by the two methods in the LF-fed mice (least discrepancy −0.5 ± 1.1%). In contrast, there was a consistent overestimation of rCO2by the DLW technique in the HF-fed animals compared with actual CO2production independent from body mass gain (least discrepancy DR +15.9 ± 2.2%, DIO +18.5 ± 3.2%). The least discrepancies were found when two-pool model equations and the intercept method were used to calculate the body water pool. Furthermore, the HF group presented different equilibration kinetics of2H and18O and a lower dilution space ratio between the two. We recommend particular caution when using the DLW method for MR assessment in HF-fed animals and potentially humans because of the overestimation of rCO2.

The stable isotope ratios of atmospheric CO(2) ((18)O/(16)O and (13)C/(12)C) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere-atmosphere exchange fluxes affect the different atomic masses in a measurable way. Interpreting the (18)O/(16)O variability has proved difficult, however, because oxygen isotopes in CO(2) are influenced by both the carbon cycle and the water cycle. Previous attention focused on the decreasing (18)O/(16)O ratio in the 1990s, observed by the global Cooperative Air Sampling Network of the US National Oceanic and Atmospheric Administration Earth System Research Laboratory. This decrease was attributed variously to a number of processes including an increase in Northern Hemisphere soil respiration; a global increase in C(4) crops at the expense of C(3) forests; and environmental conditions, such as atmospheric turbulence and solar radiation, that affect CO(2) exchange between leaves and the atmosphere. Here we present 30 years' worth of data on (18)O/(16)O in CO(2) from the Scripps Institution of Oceanography global flask network and show that the interannual variability is strongly related to the El Niño/Southern Oscillation. We suggest that the redistribution of moisture and rainfall in the tropics during an El Niño increases the (18)O/(16)O ratio of precipitation and plant water, and that this signal is then passed on to atmospheric CO(2) by biosphere-atmosphere gas exchange. We show how the decay time of the El Niño anomaly in this data set can be useful in constraining global gross primary production. Our analysis shows a rapid recovery from El Niño events, implying a shorter cycling time of CO(2) with respect to the terrestrial biosphere and oceans than previously estimated. Our analysis suggests that current estimates of global gross primary production, of 120 petagrams of carbon per year, may be too low, and that a best guess of 150-175 petagrams of carbon per year better reflects the observed rapid cycling of CO(2). Although still tentative, such a revision would present a new benchmark by which to evaluate global biospheric carbon cycling models.

Combined oxygen (O) and nitrogen (N) stable isotope analyses are commonly used in the source determination of nitrate . The source and fate of are studied based on distinct O and N isotopic signatures (d18O and d15N) of various sources and isotopic effects during transformation processes, which differ between sources like fertilizer, atmospheric deposition, and microbial production (nitrification). Isotopic fractionation during production and consumption of further affects the d18O and d15N signal. Regarding the d18O in particular, biochemical O exchange between O from and H2O is implicitly assumed not to affect the d18O signature of . This study aimed to test this assumption in soil-based systems. In a short (24 h) incubation experiment, soils were treated with artificially 18O and 15N enriched . Production of from nitrification during the incubation would affect both the 18O and the 15N enrichment. Oxygen exchange could therefore be studied by examining the change in 18O relative to the 15N. In two out of the three soils, we found that the imposed 18O enrichment of the declined relatively more than the imposed enrichment. This implies that O exchange indeed affected the O isotopic signature of , which has important implications for source determination studies. We suggest that O exchange between and H2O should be taken into consideration when interpreting the O isotopic signature to study the origin and fate of in ecosystems. Highlights ¿ The oxygen isotopic signature of nitrate is commonly used to study its source and fate in ecosystems. ¿ The effect of oxygen exchange is in such studies generally not taken into account. ¿ We used a novel ‘enrichment ratio’ approach to evaluate changes the isotopic signature of NO3. ¿ Our study shows that oxygen exchange can affect the oxygen isotopic signature of nitrate in soils.

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC)a in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125 per thousand, an artificially enriched reference water (delta(18)O of +78.91 per thousand) and two barium sulfates (one depleted and one enriched in (18)O) were prepared and calibrated relative to VSMOW2b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material delta(18)O and estimated combined uncertainty IAEA-602 benzoic acid+71.28 +/- 0.36 per thousand USGS 35 sodium nitrate+56.81 +/- 0.31 per thousand IAEA-NO-3 potassium nitrate+25.32 +/- 0.29 per thousand IAEA-601 benzoic acid+23.14 +/- 0.19 per thousand IAEA-SO-5 barium sulfate+12.13 +/- 0.33 per thousand NBS 127 barium sulfate+8.59 +/- 0.26 per thousand VSMOW2 water 0 per thousand IAEA-600 caffeine-3.48 +/- 0.53 per thousand IAEA-SO-6 barium sulfate-11.35 +/- 0.31 per thousand USGS 34 potassium nitrate-27.78 +/- 0.37 per thousand SLAP water-55.5 per thousand The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for delta(18)O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (delta(18)O) of nitrates, sulfates, or organic material should explicitly state in their reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(2)H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

ispartof: Rapid communications in mass spectrometry vol:21 issue:8 pages:1475-1478 ispartof: location:England status: published

International audience; Due to its resistance to oxidation, TaSiN is a promising candidate as an electrically conductive barrier layer for integration of high permittivity oxides in advanced memory devices. In this study we report on the properties of TaSiN thin films deposited by reactive magnetron sputtering of a TaSi2 target in an Ar/N-2 atmosphere. We especially focus on the influence of deposition parameters (pressure and power density) on TaSiN film properties. To study oxidation resistance, films are processed by rapid thermal annealing in O-18(2) at 650 degrees C. The concentration depth profiles of O-18 were measured via the narrow resonance of O-18(p,alpha)N-15 at 151 keV (FWHM = 100 eV). Whatever the power density, films deposited above 2 Pa are porous and exhibit high resistivity. Ta26Si47N27 deposited at 0.5 Pa with a power density of 2.65 W/cm(2) exhibits high density, low resistivity, and good oxidation resistance. (c) 2006 Elsevier B.V. All rights reserved.

The highest oxygen isotope ratios ever measured in the Galaxy have been recorded in silica-rich grains from the Murchison meteorite. The excess oxygen-18 and oxygen-17 could be the result of nucleosynthesis in a single exotic star in the early Solar System or evidence of irradiation by highly accelerated particles produced during an active early phase of the Sun. The origins of the building blocks of the Solar System can be studied using the isotopic composition of early planetary and meteoritic material. Oxygen isotopes in planetary materials show variations at the per cent level that are not related to the mass of the isotopes1,2; rather, they result from the mixture of components having different nucleosynthetic or chemical origins1,2,3. Isotopic variations reaching orders of magnitude in minute meteoritic grains are usually attributed to stellar nucleosynthesis before the birth of the Solar System, whereby different grains were contributed by different stars4,5. Here we report the discovery of abundant silica-rich grains embedded in meteoritic organic matter, having the most extreme 18O/16O and 17O/16O ratios observed (both ∼10-1) together with a solar silicon isotopic composition. Both O and Si isotopes indicate a single nucleosynthetic process. These compositions can be accounted for by one of two processes: a single exotic evolved star seeding the young Solar System6, or irradiation of the circumsolar gas by high energy particles accelerated during an active phase of the young Sun. We favour the latter interpretation, because the observed compositions are usually not expected from nucleosynthetic processes in evolved stars, whereas they are predicted by the selective trapping of irradiation products.

D2O and H218O are often used as tracers for the determination of total body water (TBW). For newborn infants, the commonly used noninvasive method has not been validated. In this study TBW was calculated from D2O concentrations in blood and compared with TBW calculated from D2O concentrations in urine. TBW calculated from all urine portions voided at least 6 h after D2O administration on average was 1.0% lower. TBW calculated from only three urine portions voided 6, 12, and 24 h after D2O administration was 0.6% (mean) lower compared to TBW calculated from D2O concentrations in blood. This study indicates that the noninvasive method to measure TBW can be considered a reliable method when used in newborn infants.