A novel methodological approach for δ18O analysis of sugars using gas chromatography-pyrolysis-isotope ratio mass spectrometry

Abstract

Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ18O 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 δ18O 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 δ18O 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 18O-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 δ18O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ18Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1–40.1 ‰) than the δ18Obulk/ 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 δ18Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative 18O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ18Osucrose analysis for plant physiology and paleoclimate studies.