Absolute Carbon Stable Isotope Ratio in the Vienna Peedee Belemnite Isotope Reference Determined by ¹H NMR...

The Vienna Peedee Belemnite (VPDB) isotope reference defines the zero point of the carbon stable isotope scale that is used to describe the relative abundance of ¹³C and ¹²C. An accurate and precise characterization of this isotope reference is valuable for interlaboratory comparisons and conducting robust carbon stable isotope analyses in a vast array of fields, such as chemical forensics, (bio)geochemistry, ecology, or (astro)biology. Here, we report an absolute ¹³C/¹²C ratio for VPDB that has been obtained, for the first time, using proton nuclear magnetic resonance spectroscopy (¹H NMR). Four different NMR instruments were used to determine ¹³C/¹²C ratios in a set of glycine reference materials from the US Geological Survey (USGS64, USGS65, and USGS66) and a set of formate samples that were characterized by isotope ratios mass spectrometry (IRMS). Intercalibration of the NMR-derived ¹³C/¹²C ratios with relative abundance (δ¹³C_VPDB) measurements from IRMS yields a value of 0.011100 for the absolute ¹³C/¹²C ratio in VPDB, with an expanded uncertainty of ±0.000026 (2σ, n = 114). This is significantly different from the value of 0.011180 that is commonly used but falls within the range of values recently revised using IRMS and infrared absorption measurements. ¹H NMR was found to be an effective method for measuring absolute ¹³C/¹²C ratios due to its ability to simultaneously detect signals associated with ¹²C and ¹³C. Results provide a new and independent measure of the carbon isotope composition of VPDB, improving our understanding of this important isotope reference.