Application of 13C Quantitative NMR Spectroscopy to Isotopic Analyses for Vanillin Authentication Source

The carbon stable isotope ratio (δ13C) is a valuable chemical parameter in the investigation of the geographic origin, quality, and authenticity of foods. The aim of this study is the evaluation of the feasibility of 13C-NMR (Nuclear Magnetic Resonance) spectroscopy to determine the carbon stable isotope ratio, at natural abundance, of small organic molecules, such as vanillin, without the use of IRMS (Isotope Ratio Mass Spectrometry). The determination of vanillin origin is an active task of research, and differentiating between its natural and artificial forms is important to guarantee the quality of food products. To reach our goal, nine vanillin samples were analyzed using both 13C quantitative NMR spectroscopy (under optimized experimental conditions) and IRMS, and the obtained δ13C values were compared using statistical analysis (linear regression, Bland–Altman plot, and ANOVA (analysis of variance)). The results of our study show that 13C-NMR spectroscopy can be used as a valuable alternative methodology to determine the bulk carbon isotope ratio and to identify the origin of vanillin. This makes it attractive for the analysis in the same experiment of site-specific and total isotope effects for testing authenticity, quality, and typicality of food samples. Moreover, the improvement of NMR spectroscopy makes it possible to avoid the influence of additives on carbon stable isotope ratio analysis and to clearly identify fraud and falsification in commercial samples.

Carbon stable isotope ratio as a revealer of incomplete decarbonation for particulate organic carbon measurement in river plumes

The characterization of particles in suspension in river plumes contributes to the assessment of net particulate organic carbon (POC) fluxes and to a better understanding of the anthropogenic and climatic impact on blue carbon. Prior to POC analysis in natural waters, inorganic carbon (in the form of carbonates) must be removed. This step is generally carried out by acid leaching. However, the presence of mineral matrices (in turbid waters) may hinder total decarbonation, which may result in biased measurements. This work checks the quality of decarbonation through the analysis of carbon stable isotope ratio (δ13C), considering suspended particles discharged by three rivers into coastal waters under flooding conditions. Carbonates were removed by adding variable volumes of 2N hydrochloric acid (HCl) to filters. Carbon concentrations and stable isotopic ratios were analyzed. Values of δ13Corg (stable isotope ratio of organic carbon) allow the identification of incompletely decarbonated samples. If a small amount of detrital carbonates resists the usual decarbonation treatment, δ13Corg can be significantly shifted towards less negative values, suggesting the need of more efficient decarbonation methods in order to improve the accuracy of organic carbon measurements. Even in the case of a high Corg/Ctotal ratio, the impact of remaining carbonates on the δ13Corg value is strong because δ13Cinorg is significantly different. The sensitivity of δ13Corg measurement might therefore be used to validate POC measurements in estuarine and coastal waters.