Radiocarbon dating of alpine ice cores with the dissolved organic carbon (DOC) fraction

High-alpine glaciers are valuable archives of past climatic and environmental conditions. The interpretation of the preserved signal requires a precise chronology. Radiocarbon (14C) dating of the water-insoluble organic carbon (WIOC) fraction has become an important dating tool to constrain the age of ice cores from mid-latitude and low-latitude glaciers. However, in some cases this method is restricted by the low WIOC concentration in the ice. In this work, we report first 14C dating results using the dissolved organic carbon (DOC) fraction, which is present at concentrations of at least a factor of 2 higher than the WIOC fraction. We evaluated this new approach by comparison to the established WIO14C dating based on parallel ice core sample sections from four different Eurasian glaciers covering an age range of several hundred to around 20 000 years; 14C dating of the two fractions yielded comparable ages, with WIO14C revealing a slight, barely significant, systematic offset towards older ages comparable in magnitude with the analytical uncertainty. We attribute this offset to two effects of about equal size but opposite in direction: (i) in-situ-produced 14C contributing to the DOC resulting in a bias towards younger ages and (ii) incompletely removed carbonates from particulate mineral dust (14C-depleted) contributing to the WIOC fraction with a bias towards older ages. The estimated amount of in-situ-produced 14C in the DOC fraction is smaller than the analytical uncertainty for most samples. Nevertheless, under extreme conditions, such as very high altitude and/or low snow accumulation rates, DO14C dating results need to be interpreted cautiously. While during DOC extraction the removal of inorganic carbon is monitored for completeness, the removal for WIOC samples was so far only assumed to be quantitative, at least for ice samples containing average levels of mineral dust. Here we estimated an average removal efficiency of 98±2 %, resulting in a small offset of the order of the current analytical uncertainty. Future optimization of the removal procedure has the potential to improve the accuracy and precision of WIO14C dating. With this study we demonstrate that using the DOC fraction for 14C dating not only is a valuable alternative to the use of WIOC but also benefits from a reduced required ice mass of typically ∼250 g to achieve comparable precision of around ±200 years. This approach thus has the potential of pushing radiocarbon dating of ice f