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41 records · Page 3Linked to original sources
USGS2015

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H 2 ) has been suspected as a possible cause of incomplete H 2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H 2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H 2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ 2 H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H 2 and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H 2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H 2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H 2 being substantially shifted to more negative δ 2 H values. The reaction can be understood as an initial disproportionation leading to H 2 and HCN with the HCN-hydrogen systematically enriched in 2 H by more than 50 ‰. In the reaction of HCN with chromium, H 2 and chromium-containing solid residues are formed quantitatively.

Rapid Communications in Mass Spectrometry↗
USGS2016

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

Rationale Perchlorate (ClO 4 − ) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO 4 − source attribution and natural attenuation studies: δ 37 Cl, δ 18 O, and δ 17 O (or Δ 17 O or 17 Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies. Methods Three large batches of KClO 4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O 2 , and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO 4 − to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O 2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O 2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO 4 was reprecipitated as AgCl and converted into CH 3 Cl for DIIRMS. Results KClO 4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO 4 − depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO 4 2 − , NO 3 − , ReO 4 2 − , and C-bearing contaminants include isotope mixing and fractionation effects on CO and O 2 , plus direct interference from CO 2 in the mass spectrometer. The results highlight the importance of effective purification of ClO 4 − from environmental samples. Conclusions KClO 4 reference materials are available for testing methods and calibrating isotopic data for ClO 4 − and other substances with widely varying Cl or O isotopic compositions. Current ClO 4 − extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO 4 − , permitting isotopic evaluation of environmental ClO 4 − sources and natural attenuation.

Rapid Communications in Mass Spectrometry↗
USGS2017

Variation in δ15N and δ13C values of forages for Arctic caribou: Effects of location, phenology and simulated digestion

Rationale The use of stable isotopes for dietary estimates of wildlife assumes that there are consistent differences in isotopic ratios among diet items, and that the differences in these ratios between the diet item and the animal tissues (i.e., fractionation) are predictable. However, variation in isotopic ratios and fractionation of δ 13 C and δ 15 N values among locations, seasons, and forages are poorly described for arctic herbivores especially migratory species such as caribou ( Rangifer tarandus ). Methods We measured the δ 13 C and δ 15 N values of seven species of forage growing along a 200-km transect through the range of the Central Arctic caribou herd on the North Slope of Alaska over 2 years. We compared forages available at the beginning (May; n = 175) and the end ( n = 157) of the growing season (September). Purified enzymes were used to measure N digestibility and to assess isotopic fractionation in response to nutrient digestibility during simulated digestion. Results Values for δ 13 C declined by 1.38 ‰ with increasing latitude across the transect, and increased by 0.44 ‰ from the beginning to the end of the season. The range of values for δ 15 N was greater than that for δ 13 C (13.29 vs 5.60 ‰). Differences in values for δ 13 C between graminoids ( Eriophorum and Carex spp.) and shrubs ( Betula and Salix spp.) were small but δ 15 N values distinguished graminoids (1.87 ± 1.02 ‰) from shrubs (−2.87 ± 2.93 ‰) consistently across season and latitude. However, undigested residues of forages were enriched in 15 N when the digestibility of N was less than 0.67. Conclusions Although δ 15 N values can distinguish plant groups in the diet of arctic herbivores, variation in the digestibility of dietary items may need to be considered in applying fractionation values for 15 N to caribou and other herbivores that select highly digestible items (e.g. forbs) as well as heavily defended plants (e.g. woody browse).

Alaska↗
USGS2018

Effect of heat and singeing on stable hydrogen isotope ratios of bird feathers and implications for their use in determining geographic origin

Rationale Stable hydrogen isotope ( δ 2 H) ratios of animal tissues are useful for assessing movement and geographic origin of mobile organisms. However, it is uncertain whether heat and singeing affects feather δ 2 H values and thus subsequent geographic assignments. This is relevant for birds of conservation interest that are burned and killed at concentrating solar‐energy facilities that reflect sunlight to a receiving tower and generate a solar flux field. Methods We used a controlled experiment to test the effect of known heat loads (exposure to 200, 250 or 300°C for 1 min) on the morphology and δ 2 H values of feathers from two songbird species. Subsequently, we examined the effects of singeing on δ 2 H values of feathers from three other songbird species that were found dead in the field at a concentrating solar‐energy facility. Results Relative to control samples, heating caused visual morphological changes to feathers, including shriveling at 250°C and charring at 300°C. The δ 2 H values significantly declined by a mean of 27.8‰ in experimental samples exposed to 300°C. There was no statistically detectable difference between δ 2 H values of the singed and unsinged portions of field‐collected feathers from the same bird. Conclusions Limited singeing that did not dramatically alter the feather morphology did not substantially affect δ 2 H values of feathers from these songbirds. However, higher temperatures induced charring and reduced δ 2 H values. Therefore, severely charred feathers should be avoided when selecting feathers for δ 2 H‐based assessment of geographic origin.

Rapid Communications in Mass Spectrometry↗