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

Abstract

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).

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Source-reported bounding extent: 68.2042121888185° to 71.48308562053703° latitude; -166.728515625° to -141.0205078125° longitude. This indicates report coverage, not an exact sampling location. View area on OpenStreetMap.

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BibTeXRIS

Lindsey L. Vansomeren, Perry S. Barboza, David D. Gustine, M. Syndonia Bret-Harte. 2017-04-04. Variation in δ15N and δ13C values of forages for Arctic caribou: Effects of location, phenology and simulated digestion. https://doi.org/10.1002/rcm.7849

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Reaffirming the consistency of the original stock of NBS 19 limestone and its byproduct with finer grain size for δ13C and δ18O calibrations—Both distributed internationally

Rationale Approximately 3–4 kg of NBS 19 limestone, prepared in 1982 by the U.S. Geological Survey (USGS), serves as a primary reference for the carbon isotope scales VPDB and VPDB-LSVEC and the oxygen isotope scale VPDB. Its consensus values are +1.95‰ for δ 13 C and −2.2‰ for δ 18 O measurements. After more than three decades of distribution, the number of units labeled “NBS 19” shrunk substantially, and the remaining material was quarantined, with a small fraction retained at the USGS and a larger fraction entrusted to the International Atomic Energy Agency (IAEA) for secure storage. Given the critical role of NBS 19, verifying the integrity of its δ 13 C and δ 18 O values across these storage locations is essential. Method Samples from IAEA and USGS stock materials were selected to ensure traceability of carbon and oxygen isotopes to NBS 19 distribution units from various storage locations. To achieve this, distribution units labeled as NBS 19 from both the IAEA and the National Institute of Standards and Technology (NIST) were included. During evaluation, two distinct grain sizes were identified within these units. Grain size was assessed using sieves on five selected samples. The δ 13 C and δ 18 O values of finer and coarser fractions (both labeled NBS 19) were measured at USGS using continuous-flow isotope-ratio mass spectrometry on 100- and 200-μg samples. Results Expanded 95% measurement uncertainties ( k = 2) for δ 13 C and δ 18 O determinations are 0.027‰ and 0.038‰ or better, respectively, for quarantined NBS 19 stocks and finer byproduct calcite, which we term “NBS-19 byproduct,” regardless of storage location. Between the 1990s and circa 2011, NBS-19 byproduct labeled “NBS 19,” distributed by NIST and the IAEA, shows these findings. Conclusions NBS 19 primary isotopic reference material should be used for calibration of new isotopic reference materials rather than NBS-19 byproduct secondary isotopic reference material.

Rapid Communications in Mass Spectrometry

Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements

Rationale Isotope ratio mass spectrometry (IRMS) and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy are independent techniques for determining the isotope ratio R ( 13 C/ 12 C) in organic compounds. However, the lack of suitable reference materials has limited intercalibration of results from these methods. Methods Three high-purity calcium formate isotopic reference materials were developed, each ideal for accurate isotope ratio measurements by both 1 H NMR and isotope-ratio mass spectrometry (IRMS). For each material, R ( 13 C/ 12 C) was determined by 1 H NMR, and the relative isotope abundance ( δ 13 C VPDB-LSVEC ) by IRMS. The combined IRMS and NMR results were used to determine the R ( 13 C/ 12 C) value of Vienna Peedee belemnite (VPDB). Results The combined datasets yield a value for R ( 13 C/ 12 C) of 0.0111050 ± 0.0000047 ( k = 2) for VPDB, which is 6.7‰ lower than the commonly cited value of 0.011180, but similar to other recent determinations. These three calcium formate reference materials exhibit high accuracy across both analytical methods and provide robust tools for instrument calibration, method validation, and inter-laboratory comparison in carbon stable isotope ratio analysis. Conclusions An accurate R ( 13 C/ 12 C) value for VPDB strengthens the link between relative ( δ 13 C VPDB-LSVEC ) values from IRMS and R ( 13 C/ 12 C) isotope ratios from NMR and other techniques. These three calcium formate isotopic reference materials (USGS106, USGS107, and USGS108) are available from the US Geological Survey and provide reference materials for calibration, method validation, and inter-laboratory comparison in carbon isotope ratio analysis.

Rapid Communications in Mass Spectrometry

Correction to “Stable isotope reference materials and scale definitions – outcomes of the 2024 IAEA experts meeting”

This article corrects the following: Camin, F., Besic, D., Brewer, P., Allison, C., Coplen, T., Dunn, P., Gehre, M., Gröning, M., Meijer, H.-A.-J, Hélie, J.-F., Iacumin, P., Kraft, R., Krajnc, B., Kümmel, S., Lee, S., Meija, J., Mester, Z., Mohn, J., Moossen, H., Qi, H., Skrzypek, G., Sperlich, P., Viallon, J., Wassenaar, L. and Wielgosz, R. (2025). Stable Isotope Reference Materials and Scale Definitions—Outcomes of the 2024 IAEA Experts Meeting. Rapid Commun Mass Spectrom, 39: e10018, https://doi.org/10.1002/rcm.10018. In the above article, the text of note 3 in Section 4.2 is incorrect. The correct text is shown below: 3. Whilst limited amounts of the original VSMOW and SLAP scale-defining reference materials may still be available, to enable continuous wide distribution of RMs for VSMOW-SLAP scale realization (normalization, calibration) the scale-maintaining reference materials VSMOW2 and SLAP2 are available. VSMOW2 and SLAP2 have δ(18O) values identical to VSMOW and SLAP, respectively, but with an uncertainty with respect to VSMOW and SLAP. We apologize for this error. The CIAAW-IUPAC endorsed all isotope delta scale definitions appearing in Camin et al. (2025) and agreed to publish the current and all future updates and corrections to these definitions on its website (www.ciaaw.org).

Rapid Communications in Mass Spectrometry