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Abstract. The hydrogen isotopic composition (δ2H) of leaf waxes, especially of n-alkanes (δ2Hn-alkanes), is increasingly used for paleohydrological and paleoclimate reconstructions. However, it is challenging to disentangle past changes in the isotopic composition of precipitation and changes in evapotranspirative enrichment of leaf water, which are both recorded in leaf wax δ2H values. In order to overcome this limitation, Zech M. et al. (2013) proposed a coupled δ2Hn-alkanes–δ18Osugar biomarker approach. This coupled approach allows for calculating (i) biomarker-based "reconstructed" δ2Hδ18O values of leaf water (δ2Hδ18Oleaf water), (ii) biomarker-based reconstructed deuterium excess (d-excess) of leaf water, which mainly reflects evapotranspirative enrichment and which can be used to reconstruct relative air humidity (RH) and (iii) biomarker-based reconstructed δ2Hδ18Oprecipitation values. Here we present a climate transect validation study by coupling new results from δ2H analyses of n-alkanes and fatty acids in topsoils along a climate transect in Argentina with previously measured δ18O results obtained for plant-derived sugars. Accordingly, both the reconstructed RH and δ2Hδ18Oprecipitation values correlate highly significantly with actual RH and δ2Hδ18Oprecipitation values. We conclude that compared to single δ2Hn-alkane or δ18Osugar records, the proposed coupled δ2Hn-alkane–δ18Osugar biomarker approach will allow more robust δ2Hδ18Oprecipitation reconstructions in future paleoclimate research. Additionally, the proposed coupled δ2Hn-alkane–δ18Osugar biomarker approach allows for the establishment of a "paleohygrometer", more specifically, the reconstruction of mean summer daytime RH changes/history.

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Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ(18)O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS δ(18)O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS δ(18)O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with (18)O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS δ(18)O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ(18)Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1-40.1 ‰) than the δ(18)Obulk/ VSMOW values (24.6-27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that δ(18)Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative (18)O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ(18)Osucrose analysis for plant physiology and paleoclimate studies.