Abstract The measured carbon isotopic compositions of carbonate sediments (δ13Ccarb) on modern platforms are commonly13C‐enriched compared to predicted values for minerals forming in isotopic equilibrium with the dissolved inorganic carbon (DIC) of modern seawater. This offset undermines the assumption that δ13Ccarbvalues of analogous facies in the rock record are an accurate archive of information about Earth's global carbon cycle. We present a new data set of the diurnal variation in carbonate chemistry and seawater δ13CDICvalues on a modern carbonate platform. These data demonstrate that δ13Ccarbvalues on modern platforms are broadly representative of seawater, but only after accounting for the recent decrease in the δ13C value of atmospheric CO2and shallow seawater DIC due to anthropogenic carbon release, a phenomenon commonly referred to as the13C Suess effect. These findings highlight an important, yet overlooked, aspect of some modern carbonate systems, which must inform their use as ancient analogs.
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Variation in δ 15 N and δ 13 C values of forages for Arctic caribou: effects of location, phenology and simulated digestion: Variation in δ 15 N and δ 13 C values of forages for Arctic caribou
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Abstract In oriented‐sample (OS) solid‐state NMR of membrane proteins, the angular‐dependent dipolar couplings and chemical shifts provide a direct input for structure calculations. However, so far only1H–15N dipolar couplings and15N chemical shifts have been routinely assessed in oriented15N‐labeled samples. The main obstacle for extending this technique to membrane proteins of arbitrary topology has remained in the lack of additional experimental restraints. We have developed a new experimental triple‐resonance NMR technique, which was applied to uniformly doubly (15N,13C)‐labeled Pf1 coat protein in magnetically aligned DMPC/DHPC bicelles. The previously inaccessible1Hα–13Cαdipolar couplings have been measured, which make it possible to determine the torsion angles between the peptide planes without assuming α‐helical structure a priori. The fitting of three angular restraints per peptide plane and filtering by Rosetta scoring functions has yielded a consensus α‐helical transmembrane structure for Pf1 protein.more » « less
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An NMR supersequence is introduced for the rapid acquisition of 15 N-CEST and methyl- 13 C-CEST experiments in the same pulse sequence for applications to proteins. The high sensitivity and accuracy allows the simultaneous quantitative characterization of backbone and side-chain dynamics on the millisecond timescale ideal for routine screening for alternative protein states.more » « less
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Abstract Compound‐specific stable isotope analysis of individual amino acids (CSIA‐AA) has emerged as a transformative approach to estimate consumer trophic positions (TPCSIA) that are internally indexed to primary producer nitrogen isotope baselines. Central to accurate TPCSIAestimation is an understanding of beta (β) values—the differences between trophic and source AA δ15N values in the primary producers at the base of a consumers’ food web. Growing evidence suggests higher taxonomic and tissue‐specificβvalue variability than typically appreciated.This meta‐analysis fulfils a pressing need to comprehensively evaluate relevant sources ofβvalue variability and its contribution to TPCSIAuncertainty. We first synthesized all published primary producer AA δ15N data to investigate ecologically relevant sources of variability (e.g. taxonomy, tissue type, habitat type, mode of photosynthesis). We then reviewed the biogeochemical mechanisms underpinning AA δ15N andβvalue variability. Lastly, we evaluated the sensitivity of TPCSIAestimates to uncertainty in meanβGlx‐Phevalues and Glx‐Phe trophic discrimination factors (TDFGlx‐Phe).We show that variation inβGlx‐Phevalues is two times greater than previously considered, with degree of vascularization, not habitat type (terrestrial vs. aquatic), providing the greatest source of variability (vascular autotroph = −6.6 ± 3.4‰; non‐vascular autotroph = +3.3 ± 1.8‰). Within vascular plants, tissue type secondarily contributed toβGlx‐Phevalue variability, but we found no clear distinction among C3, C4and CAM plantβGlx‐Phevalues. Notably, we found that vascular plantβGlx‐Lysvalues (+2.5 ± 1.6‰) are considerably less variable thanβGlx‐Phevalues, making Lys a useful AA tracer of primary production sources in terrestrial systems. Our multi‐trophic level sensitivity analyses demonstrate that TPCSIAestimates are highly sensitive to changes in bothβGlx‐Pheand TDFGlx‐Phevalues but that the relative influence ofβvalues dissipates at higher trophic levels.Our results highlight that primary producerβvalues are integral to accurate trophic position estimation. We outline four key recommendations for identifying, constraining and accounting forβvalue variability to improve TPCSIAestimation accuracy and precision moving forward. We must ultimately expand libraries of primary producer AA δ15N values to better understand the mechanistic drivers ofβvalue variation.more » « less