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Leaf wax n-alkane H-2 values carry important information about environmental and ecophysiological processes in plants. However, the physiological and biochemical drivers that shape leaf wax n-alkane H-2 values are not completely understood. It is particularly unclear why n-alkanes in grasses are typically H-2-depleted compared with plants from other taxonomic groups such as dicotyledonous plants and why C3 grasses are H-2-depleted compared with C4 grasses. To resolve these uncertainties, we quantified the effects of leaf water evaporative H-2-enrichment and biosynthetic hydrogen isotope fractionation on n-alkane H-2 values for a range of C3 and C4 grasses grown in climate-controlled chambers. We found that only a fraction of leaf water evaporative H-2-enrichment is imprinted on the leaf wax n-alkane H-2 values in grasses. This is interesting, as previous studies have shown in dicotyledonous plants a nearly complete transfer of this H-2-enrichment to the n-alkane H-2 values. We thus infer that the typically observed H-2-depletion of n-alkanes in grasses (as opposed to dicots) is because only a fraction of the leaf water evaporative H-2-enrichment is imprinted on the H-2 values. Our experiments also show that differences in n-alkane H-2 values between C3 and C4 grasses are largely the result of systematic differences in biosynthetic fractionation between these two plant groups, which was on average -198 and-159 parts per thousand for C3 and C4 grasses, respectively. We present novel and exciting data on how leaf wax n-alkane 2H values from grasses are affected by plant physiological (leaf water evaporative 2H-enrichment) or biochemical processes (biosynthetic hydrogen isotope fractionation). These results are very interesting because they shed new light on how naturally observed differences between 2H values from C3 and C4 grasses and dicots can be explained by systematic differences in the biosynthesis of n-alkanes between these plant group (i.e. largely driven by NADPH origins).
One of the most significant Late Holocene climate shifts occurred around 2800 years ago, when cooler and wetter climate conditions established in western Europe. This shift coincided with an abrupt change in regional atmospheric circulation between 2760 and 2560 cal years BP, which has been linked to a grand solar minimum with the same duration (the Homeric Minimum). We investigated the temporal sequence of hydroclimatic and vegetation changes across this interval of climatic change (Homeric climate oscillation) by using lipid biomarker stable hydrogen isotope ratios (ED values) and pollen assemblages from the annually-laminated sediment record from lake Meerfelder Maar (Germany). Over the investigated interval (3200-2000 varve years BP), terrestrial lipid biomarker ED showed a gradual trend to more negative values, consistent with the western Europe long-term climate trend of the Late Holocene. At ca. 2640 varve years BP we identified a strong increase in aquatic plants and algal remains, indicating a rapid change in the aquatic ecosystem superimposed on this long-term trend. Interestingly, this aquatic ecosystem change was accompanied by large changes in ED values of aquatic lipid biomarkers, such as nC(21) and nC(23) (by between 22 and 30%(0)). As these variations cannot solely be explained by hydroclimate changes, we suggest that these changes in the Wag value were influenced by changes in n-alkane source organisms. Our results illustrate that if ubiquitous aquatic lipid biomarkers are derived from a limited pool of organisms, changes in lake ecology can be a driving factor for variations on sedimentary lipid MN values, which then could be easily misinterpreted in terms of hydro climatic changes. (C) 2017 Elsevier Ltd. All rights reserved.