The stable carbon isotopic composition of n-alkane biomarkers is a commonly used proxy for studying plant community change and palaeohydrology in the geologic record. However, interpretations of n-alkane δ13C tend to assume that all variation is due to changes in bulk plant δ13C, reflecting a signal of fractionation due to photosynthesis, and that the biosynthetic fractionations which occur after photosynthesis (εn-alkane) are constant. However, this untested assumption may overlook environmental influences on εn-alkane which can offer alternative explanations for n-alkane δ13C trends, thereby allowing for the reconstruction of plant biochemistry in geological records. In this study, we use the Free Air CO2 Environment experiment at the Birmingham Institute of Forest Research to investigate the impact of elevated CO2 concentrations on the response of εn-alkane. We measured the δ13C levels of bulk and n-alkanes in two plant species, Acer pseudoplatanus (European sycamore) and Corylus avellana (common hazel), over four years. Our findings indicate that the εn-alkane levels in both species increased under elevated CO2 compared to ambient levels. However, the seasonal variation in εn-alkane suggests that this increase is due to separate mechanisms. In A. pseudoplatanus, this increase occurs consistently throughout the growth season, suggesting that changes in carbon allocation to different tissue types within the plant is responsible. Conversely, in C. avellana, the effect becomes more pronounced as the growth season progresses, indicating that altered timing of n-alkane synthesis under elevated CO2 may influence εn-alkane. Collectively, this suggests that εn-alkane should not be assumed constant in the geologic record, and highlights that biosynthetic processes should be considered when interpreting compound-specific isotopes of carbon.
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