Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition

Aiming at developing a novel tool for palaeoclimate research, we recently proposed a new method for determining the oxygen isotope composition of monosaccharides (Zech, M., Glaser, B., 2009. Compound-specific δ18O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Communications in Mass Spectrometry 23, 3522–3532). In order to answer the question whether isotope fractionation and oxygen exchange reactions during litter decomposition affect the climatically controlled δ18O values of plant derived sugars, such as for instance xylose and arabinose from hemicelluloses, we studied the compound specific δ18O values of five different litter species having been decomposed in a field litterbag experiment for 27 months. δ18O values of bulk organic matter yielded a systematic 18O depletion of 3.3‰ (pine) to 4.6‰ (spruce) accompanying total cellulose decomposition of 51% (beech) to 86% (ash), δ18O values of individual sugars show no significant trend with time. In addition to the observed absence of isotope fractionation during decomposition, we also rule out 18O exchange reactions affecting the δ18O signature of sugar molecules during diagenetic processes as well as during analytical procedure based on experimental findings and on theoretical biochemical mechanistic considerations. We conclude that our new method may become an analytical tool that elegantly overcomes extraction, purity and hygroscopicity problems of previous 18O cellulose methods. It furthermore has the potential to be applied to a wide range of climate archives such as tree rings, lacustrine sediments and loess palaeosol sequences.