Contrasting sensitivity of lake sediment n-alkanoic acids and n-alkanes to basin-scale vegetation and regional-scale precipitation δ2H in the Adirondack Mountains, NY (USA)

Abstract

The hydrogen isotope values of plant waxes (δ2Hwax) primarily reflect plant source water. δ2Hwax preserved in lake sediments has therefore been widely used to investigate past hydroclimate. The processes by which plant waxes are integrated at regional and catchment scales are poorly understood and may affect the δ2Hwax values recorded in sediments. Here, we assess the variability of sedimentary δ2Hwax for two plant wax compound classes (n-alkanes and n-alkanoic acids) across 12 lakes in the Adirondack Mountains that receive similar regional precipitation δ2H but vary at the catchment-scale in terms of vegetation structure and basin morphology. Total long-chain (n-C27 to n-C35) alkane concentrations were similar across all sites (191 ± 53 µg/g TOC) while total long-chain (n-C28 and n-C30) alkanoic acid concentrations were more variable (117 ± 116 µg/g TOC) and may reflect shoreline vegetation composition. Lakes with shorelines dominated by evergreen gymnosperm plants had significantly higher concentrations of long-chain n-alkanoic acids relative to n-alkanes, consistent with our observations that deciduous angiosperms produced more long-chain n-alkanes than evergreen gymnosperms (471 and 33 µg/g TOC, respectively). In sediments, the most abundant chain lengths in each compound class were n-C29 alkane and n-C28 alkanoic acid, which had mean δ2H values of −188 ± 6‰ and −164 ± 9‰, respectively. Across sites, the range in sedimentary n-C29 alkane (22‰) and n-C28 alkanoic acid δ2H (35‰) was larger than expected based on the total range in modeled mean annual precipitation δ2H (4‰). We observed larger mean εapp (based on absolute values) for n-alkanes (−123‰) than for n-alkanoic acids (−97‰). Across sites, the δ2H offset between n-C29 alkane and the biosynthetic precursor n-C30 alkanoic acid (εC29-C30) ranged from −8 to −58‰, which was more variable than expected based on observations in temperate trees (−20 to −30‰). Sediments with greater aquatic organic matter contributions (lower C/N ratios) had significantly larger (absolute) εC29-C30 values, which may reflect long-chain n-alkanoic acids from aquatic sources. Concentration and δ2Hwax data in Adirondack lakes suggest that long-chain n-alkanes are more sensitive to regional-scale precipitation signals, while n-alkanoic acids are more sensitive to basin-scale differences in catchment vegetation and wax sourcing.