Optical Measurement of Radiocarbon below Unity Fraction Modern by Linear Absorption Spectroscopy

High-precision measurements of radiocarbon (14C) near or below a fraction modern 14C of 1 (F14C ≤ 1) are challenging and costly. An accurate, ultrasensitive linear absorption approach to detecting 14C would provide a simple and robust benchtop alternative to off-site accelerator mass spectrometry facilities. Here we report the quantitative measurement of 14C in gas-phase samples of CO2 with F14C < 1 using cavity ring-down spectroscopy in the linear absorption regime. Repeated analysis of CO2 derived from the combustion of either biogenic or petrogenic sources revealed a robust ability to differentiate samples with F14C < 1. With a combined uncertainty of 14C/12C = 130 fmol/mol (F14C = 0.11), initial performance of the calibration-free instrument is sufficient to investigate a variety of applications in radiocarbon measurement science including the study of biofuels and bioplastics, illicitly traded specimens, bomb dating, and atmospheric transport.