The results from the field replications indicate that the homogeneity of topsoils with regard to 未18Ohemicellulose is very high for most of the 20 sampling sites. Standard deviations for the field replications are 1.5鈥? 2.2鈥?and 1.7鈥? for arabinose, fucose and xylose, respectively. Furthermore, all three hemicellulose biomarkers reveal systematic and similar trends along the climate gradient. However, the 未18Ohemicellulose values (mean of the three sugars) do not correlate positively with 未18Oprec (r = 鈭?.54, p < 0.014, n = 20). By using a P茅clet-modified Craig-Gordon (PMCG) model it can be shown that the 未18Ohemicellulose values correlate highly significantly with modeled 未18Oleaf water values (r = 0.81, p < 0.001, n = 20). This finding suggests that hemicellulose biomarkers in (paleo-)soils do not simply reflect 未18Oprec but rather 未18Oprec altered by evaporative 18O enrichment of leaf water due to evapotranspiration. According to the modeling results, evaporative 18O enrichment of leaf water is relatively low (鈭?0鈥? in the humid northern part of the Argentinian transect and much higher (up to 19鈥? in the arid middle and southern part of the transect. Model sensitivity tests corroborate that changes in relative air humidity exert a dominant control on evaporative 18O enrichment of leaf water and thus 未18Ohemicellulose, whereas the effect of temperature changes is of minor importance. While oxygen exchange and degradation effects seem to be negligible, further factors needing consideration when interpreting 未18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the evaporative 18O enrichment of leaf water.
Overall, our results prove that compound-specific 未18O analyses of hemicellulose biomarkers in soils and sediments are a promising tool for paleoclimate research. However, disentangling the two major factors influencing 未18Ohemicellulose, namely 未18Oprec and relative air humidity controlled evaporative 18O enrichment of leaf water, is challenging based on 未18O analyses alone.