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)

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

Hydrogen isotopic composition (δ2H) of diatom-derived C20 highly branched isoprenoids from lake sediments tracks lake water δ2H

The hydrogen isotopic composition of lake water (δ2Hlw) reflects hydrological processes, which can yield information about evaporation and precipitation changes through time when preserved in lake sediment archives. Unfortunately, few proxies exist that record only δ2Hlw. Instead, most δ2Hlw records represent a mix of aquatic and terrestrial material. Highly branched isoprenoids (HBIs), known to be produced by diatoms in marine and lacustrine settings, may be used as a lake water proxy to directly reconstruct hydroclimate, if the hydrogen isotopic composition of HBIs (δ2HHBI) reflects the δ2Hlw. We test this hypothesis by analyzing 78 sediment samples from 12 lakes in the Adirondack Mountains in New York, for HBI concentrations and δ2H. δ2HHBI was compared to δ2Hlw, which showed an average fractionation (εHBI/lw) of −127.3 ± 15.0‰ (1σ) for all samples in all lakes. Consistency in εHBI/lw between samples implies that δ2HHBI may be used to reconstruct δ2Hlw through time, to help assess how lake systems have changed in the past. Sediment samples collected from deeper (>4 m) zones within the lake had smaller variability in εHBI/lw (±11.9‰, 1σ) than samples from shallower zones, suggesting that εHBI/lw may be sensitive to other factors, such as light availability, which may be related to differences in diatom growth habit (e.g., benthic, planktonic). Similarly, the carbon isotopes of HBIs (δ13CHBI) were higher for sediment samples collected in deeper zones in the lake, suggesting that δ13CHBI can be used to further understand differences in HBI synthesis in diatom communities living in different growth habitats

Highly branched isoprenoid hydrogen and carbon isotope data from lake sediment samples collected from the Adirondack region

Concentrations, hydrogen (δ2H) and carbon isotopes (δ13C) of highly branched isoprenoids (HBIs) from surface sediment samples from 12 lakes in the Adirondack region in New York. To understand the relationship between HBIs and source water, we measured the δ2H of lake water in addition to the δ2H of HBIs. HBIs were isolated using column chromatography, and were identified and quantified using an Agilent 7890A gas chromatograph (GC) coupled with an Agilent 5975C quadrupole mass selective detector (MSD). Compound specific carbon and hydrogen isotopes of the HBIs were measured using a Thermo Trace GC Ultra coupled to an Isolink pyrolysis reactor and interfaced to a Thermo Electron Delta V Advantage IRMS. Water isotopes were measured on either a Picarro L2130-i cavity ring-down spectrometer water isotope analyzer or GasBench-IRMS