Validation of a coupled <i>δ</i>²H_{<i>n</i>-alkane}–<i>δ</i>¹⁸O_sugar paleohygrometer approach based on a climate chamber experiment

Abstract

The hydrogen isotope composition of leaf-wax-derived biomarkers, e.g., long-chain n-alkanes (δ2Hn-alkane), is widely applied in paleoclimate. However, a direct reconstruction of the isotope composition of source water based on δ2Hn-alkane alone is challenging due to the enrichment of heavy isotopes during evaporation. The coupling of δ2Hn-alkane with δ18O of hemicellulose-derived sugars (δ18Osugar) has the potential to disentangle this limitation and additionally to allow relative humidity reconstructions. Here, we present δ2Hn-alkane as well as δ18Osugar results obtained from leaves of Eucalyptus globulus, Vicia faba, and Brassica oleracea, which grew under controlled conditions. We addressed the questions of (i) whether δ2Hn-alkane and δ18Osugar values allow reconstructions of leaf water isotope composition, (ii) how accurately the reconstructed leaf water isotope composition enables relative humidity (RH) reconstruction, and (iii) whether the coupling of δ2Hn-alkane and δ18Osugar enables a robust source water calculation. For all investigated species, the n-alkane n-C29 was most abundant and therefore used for compound-specific δ2H measurements. For Vicia faba, additionally the δ2H values of n-C31 could be evaluated robustly. Regarding hemicellulose-derived monosaccharides, arabinose and xylose were most abundant, and their δ18O values were therefore used to calculate weighted mean leaf δ18Osugar values. Both δ2Hn-alkane and δ18Osugar yielded significant correlations with δ2Hleaf water and δ18Oleaf water, respectively (r2=0.45 and 0.85, respectively; p<0.001, n=24). Mean fractionation factors between biomarkers and leaf water were found to be −156 ‰ (ranging from −133 ‰ to −192 ‰) for εn-alkane/leaf water and +27.3 ‰ (ranging from +23.0 ‰ to 32.3 ‰) for εsugar/leaf water, respectively. Modeled RHair values from a Craig–Gordon model using measured Tair, δ2Hleaf water and δ18Oleaf water as input correlate highly significantly with modeled RHair values (R2=0.84, p<0.001, RMSE = 6 %). When coupling δ2Hn-alkane and δ18Osugar values, the correlation of modeled RHair values with measured RHair values is weaker but still highly significant, with R2=0.54 (p<0.001, RMSE = 10 %). Finally, the reconstructed source water isotope composition (δ2Hs and δ18Os) as calculated from our coupled approach matches the source water in the climate chamber experiment (δ2Htank water and δ18Otank water). This highlights the great potential of the coupled δ2Hn-alkane–δ18Osugar paleohygrometer approach for paleoclimate and relative humidity reconstructions.