Evaluation of intracavity optogalvanic spectroscopy for radiocarbon measurements

Ever since the first publication of intracavity optogalvanic spectroscopy (ICOGS) in 2008, this novel technique for measuring the (14)C/(12)C ratio in carbon dioxide has rendered considerable attention. As a result, there are currently at least five different research groups pursuing research on ICOGS. With a claimed limit of detection of 10(-15) ((14)C/(12)C), i.e., in the same order as accelerator mass spectroscopy, achieved with a relatively inexpensive and uncomplicated table-top system, ICOGS has major scientific and commercial implications. However, during the past 5 years, no research group has been able to reproduce these results or present additional proof for ICOGS's capability of unambiguous (14)C detection, including the authors of the original publication. Starting in 2010, our group has set up a state-of-the-art ICOGS laboratory and has investigated the basic methodology of ICOGS in general and tried to reproduce the reported experiments in particular. We have not been able to reproduce the reported results concerning the optogalvanic signals dependence on (14)C concentration and wavelength and, ultimately, not seen any evidence of the capability of ICOGS to unambiguously detect (14)C at all. Instead, we have found indications that the reported results can be products of measurement uncertainties and mistakes. Furthermore, our results strongly indicate that the reported limit of detection is likely to be overestimated by at least 2 orders of magnitude, based on the results presented in the original publication. Hence, we conclude that the original reports on ICOGS cannot be confirmed and therefore must be in error.