Development and evaluation of a suite of isotope reference gases for methane in air

Measurements from multiple laboratories have to be related to unifying and traceable reference material in order to be comparable. However, such fundamental reference materials are not available for isotope ratios in atmospheric methane, which led to misinterpretations of combined data sets in the past. We developed a method to produce a suite of synthetic CH4-in-air standard gases that can be used to unify methane isotope ratio measurements of laboratories in the atmospheric monitoring community. Therefore, we calibrated a suite of pure methane gases of different methanogenic origin against international referencing materials that define the VSMOW (Vienna Standard Mean Ocean Water) and VPDB (Vienna Pee Dee Belemnite) isotope scales. The isotope ratios of our pure methane gases range between -320 and +40% for delta H-2-CH4 and between -70 and -40% for delta C-13-CH4, enveloping the isotope ratios of tropospheric methane (about -85 and -47% for delta H-2-CH4 and delta C-13-CH4 respectively). Estimated uncertainties, including the full traceability chain, are</p

New Biotite and Muscovite Isotopic Reference Materials, USGS57 and USGS58, for δ2H Measurements–A Replacement for NBS 30

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ2H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ2H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ2H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ2HVSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of −65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ2H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are: USGS57 (biotite) δ2HVSMOW-SLAP = −91.5 ± 2.4 mUr (n =24) Mass fraction hydrogen = 0.416 ± 0.002% (n=4) Mass fraction water = 3.74 ± 0.02% (n=4) USGS58 (muscovite) δ2HVSMOW-SLAP = −28.4 ± 1.6 mUr (n =24) Mass fraction hydrogen = 0.448 ± 0.002% (n=4) Mass fraction water = 4.03 ± 0.02% (n =4). These δ2HVSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration

USGS44, a new high purity calcium carbonate reference material for δ13 C measurements

RATIONALE: The stable carbon isotopic (δ13 C) reference material (RM) LSVEC Li2 CO3 has been found to be unsuitable for δ13 C standardization work because its δ13 C value increases with exposure to atmospheric CO2 . A new CaCO3 RM, USGS44, has been prepared to alleviate this situation. METHODS: USGS44 was prepared from 8 kg of Merck high purity CaCO3 . Two sets of δ13 C values of USGS44 were determined. The first set of values was determined by on-line combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO3 (δ13 CVPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1 ‰), and LSVEC Li2 CO3 (δ13 CVPDB = -46.6 mUr exactly), and normalized to the two-anchor δ13 CVPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI) IRMS of CO2 evolved by reaction of H3 PO4 with carbonates, corrected for cross contamination, and normalized to the single anchor δ13 CVPDB scale. RESULTS: USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr. Single-anchor δ13 CVPDB values of -42.08 ± 0.01 and -41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. CONCLUSIONS: The new high-purity, well homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr for both EA-IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope-delta measurements to the δ13 CVPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ18 O reference material. A δ13 CVPDB-LSVEC value of -29.99 ± 0.05 mUr was determined for NBS 22 oil

Neighbourhood species richness and drought-tolerance traits modulate tree growth and δ13C responses to drought

Mixed-species forests are promoted as a forest management strategy for climate change mitigation and adaptation because they are more productive and can be more resistant and resilient than monospecific forests under drought stress. However, the trait-based mechanisms driving these properties remain elusive, making it difficult to predict which functional identities of species best improve tree growth and decrease tree physiological water stress under drought. We investigated tree growth and physiological stress responses (i.e. increase in wood carbon isotopic ratio; δ13C) to changes in climate-induced water availability (wet-to-dry years) along gradients in neighbourhood tree species richness and drought-tolerance traits. Using tree cores from a large-scale biodiversity experiment, we tested the overarching hypothesis that neighbourhood species richness increases growth and decreases δ13C. We further hypothesized that the abiotic (i.e. climatic conditions) and the biotic context modulate these biodiversity-ecosystem functioning relationships. We characterized the biotic context using drought-tolerance traits of focal trees and their neighbours. These traits are related to cavitation resistance vs. resource acquisition and stomatal control. We found that tree growth increased with neighbourhood species richness. However, we did not observe a universal relief of water stress in species-rich neighbourhoods, nor an increase in the strength of the relationship between richness and growth and between richness and δ13C from wet-to-dry years. Instead, these relationships depended on both the traits of the focal trees and their neighbours. At either end of each drought-tolerance gradient, species responded in opposing directions during drought and non-drought years. Synthesis. We report that the biotic context can determine the strength and nature of biodiversity-ecosystem functioning relationships in experimental tree communities. We derive two key conclusions: (1) drought-tolerance traits of focal trees and their neighbours can explain divergent tree responses to drought and diversity, and (2) contrasting, trait-driven responses of tree species to wet vs dry climatic conditions can promote forest community stability. Mixing tree species with a range of drought-tolerance traits may therefore increase forest productivity and stability

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ^2H_(VSMOW-SLAP) values from −210.8 to +397.0 mUr or ‰, for δ^(13)C_(VPDB-LSVEC) from −40.81 to +0.49 mUr and for δ^(15)N_(Air) from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C_(16) n-alkanes, n-C_(20)-fatty acid methyl esters (FAMEs), glycines, and L-valines, together with polyethylene powder and string, one n-C_(17)-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a ^2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain ^(13)C and carbon-bound organic ^2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies