Description: Atmospheric transport is an understudied mechanism for leaf wax hydrogen isotope applications that contributes to mobilizing and depositing these compounds on the surface of the Earth. While previous efforts have identified the importance of atmospheric leaf wax deposition in remote marine locations, the processes are not well constrained on land in temperate latitudes where lakes are common and sedimentary leaf wax hydrogen isotope values are an attractive tool for understanding past precipitation changes. This work presents results from a field study that was conducted in 2010 and 2011 at Hainich National Park, Germany in order to evaluate the quantity and sources of leaf waxes in the atmosphere. Aerosols were sam- pled at approximately weekly intervals inside the forest canopy, and n-alkane distributions and hydrogen isotope values were compared with those from major tree species surrounding the sampling site. Despite sampling in what was expected to be a major production center, the distribution and hydrogen isotope values of atmospheric n-alkanes bore little resemblance to those of the local vegetation. Comparison with local meteorological data and to 10-day and 36-h back air mass trajectories indicated shifting effects of winds and temperature, and that mesoscale transport processes were more important than long- range mechanisms. Back trajectories also highlighted source effects, with easterly winds coinciding with relatively lower leaf wax hydrogen isotope values from more continental regions. These results suggest that leaf wax aerosols average over spatial scales that exceed typical surface catchment areas for small lake systems, even in forested areas, yet that the area over which these compounds are derived is still relatively regional. Depositional fluxes were also estimated in order to assess the potential importance of atmospheric transport to sedimentary archives. Although difficult to constrain, these estimates suggest that atmospheric deposition may be non-negligible for lake systems in cases where inputs from rivers or surface runoff are limited. Together, these observations provide new insights on how leaf waxes from different sources are integrated during aeolian transport and the spatial scales over which these processes occur.

Description: Paleoenvironmental studies based on terrigenous biomarker proxies from sediment cores collected close to the mouth of large river systems rely on a proper understanding of the processes controlling origin, transport and deposition of biomarkers. Here, we contribute to the understanding of these processes by analyzing long-chain n-alkanes from the Amazon River system. We use the dD composition of long-chain n-alkanes from river bed sediments from the Amazon River and its major tributaries, as well as marine core-top samples collected off northeastern South America as tracers for different source areas. The d13C composition of the same compounds is used to differentiate between long-chain n-alkanes from modern forest vegetation and petrogenic organic matter. Our d13C results show depleted d13C values (-33 to -36 per mil) in most samples, indicating a modern forest source for most of the samples. Enriched values (-31 to -33 per mil) are only found in a few samples poor in organic carbon indicating minor contributions from a fossil petrogenic source. Long-chain n-alkane dD analyses show more depleted values for the western tributaries, the Madeira and Solimões Rivers (-152 to -168 per mil), while n-alkanes from the lowland tributaries, the Negro, Xingu and Tocantins Rivers (-142 to -154 per mil), yield more enriched values. The n-alkane dD values thus reflect the mean annual isotopic composition of precipitation, which is most deuterium-depleted in the western Amazon Basin and more enriched in the eastern sector of the basin. Samples from the Amazon estuary show a mixed long-chain n-alkane dD signal from both eastern lowland and western tributaries. Marine core-top samples underlying the Amazon freshwater plume yield dD values similar to those from the Amazon estuary, while core-top samples from outside the plume showed more enriched values. Although the variability in the river bed data precludes quantitative assessment of relative contributions, our results indicate that long-chain n-alkanes from the Amazon estuary and plume represent an integrated signal of different regions of the onshore basin. Our results also imply that n-alkanes are not extensively remineralized during transport and that the signal at the Amazon estuary and plume includes refractory compounds derived from the western sector of the Basin. These findings will aid in the interpretation of plant wax-based records of marine sediment cores collected from the adjacent ocean.

Description: The Amazon River transports large amounts of terrestrial organic carbon (OCterr) from the Andean and Amazon neotropical forests to the Atlantic Ocean. In order to compare the biogeochemical characteristics of OCterr in the fluvial sediments from the Amazon drainage basin and in the adjacent marine sediments, we analysed riverbed sediments from the Amazon mainstream and its main tributaries as well as marine surface sediments from the Amazon shelf and fan for total organic carbon (TOC) content, organic carbon isotopic composition (d13CTOC) and lignin phenol compositions. TOC and lignin content exhibit positive correlations with Al/Si ratios (indicative of the sediment grain size) implying that the grain size of sediment discharged by the Amazon River plays an important role in the preservation of TOC and leads to preferential preservation of lignin phenols in fine particles. Depleted d13CTOC values (-26.1 per mil to -29.9 per mil) in the main tributaries consistently correspond with the dominance of C3 vegetation. Ratios of syringyl to vanillyl (S/V) and cinnamyl to vanillyl (C/V) lignin phenols suggest that non-woody angiosperm tissues are the dominant source of lignin in the Amazon basin. Although the Amazon basin hosts a rich diversity of vascular plant types, distinct regional lignin compositions are not observed. In marine sediments, the distribution of d13CTOC and Lambda8 (sum of eight lignin phenols in organic carbon (OC), expressed as mg/100mg OC) values implies that OCterr discharged by the Amazon River is transported north-westward by the North Brazil Current and mostly deposited on the inner shelf. The lignin compositions in offshore sediments under the influence of the Amazon plume are consistent with the riverbed samples suggesting that processing of OCterr during offshore transport does not change the encoded source information. Therefore, the lignin compositions preserved in these offshore sediments can reliably reflect the vegetation in the Amazon River catchment. In sediments from the Amazon Fan, low lignin content, relatively depleted d13CTOC values and high (Ad/Al)V ratios indicating highly degraded lignin imply that a significant fraction of the deposited OCterr is derived from petrogenic (sourced from ancient rocks) sources.

Description: Terrestrial signals in marine sediment archives are often used for paleoclimatic reconstructions. It is therefore important to know the origin of the different terrestrial sedimentary components. The proximity to a river mouth is often the key location to determine the source. Especially in regions with strong ocean currents, such an assumption might,however, lead to considerable misinterpretations. To investigate the source of various terrigenous sediment fractions in southeastern Africa, a region with strong sediment redistribution, we have performed an extensive comparison between terrestrial material (pollen, plant lipids, detrital modes and heavy minerals as well as bulk inorganic geochemical composition) from potential source regions and the same components in the adjacent coastal and continental shelf sediments. Onshore the proxy‐indicators reflect small‐scale diversity in sampling locations and associated environments (riverbank sediments, flood deposits, suspension loads and soils). Nevertheless, the overall trends reflect significant environmental gradients along a SW to NE transect. We note a general comparability of the studied parameters between the continental and marine sediments regardless of their specific differences in transport and depositional characteristics. We propose that the influence of the Agulhas Current affects sediment deposition and distribution only seaward of the mid‐shelf and that pockets of sediment remain preserved in the lee of coastal protrusions where they are protected from erosion. This study provides the essential prerequisite to allow the attribution of temporal variations of compositional changes in marine sediment cores to environmental changes in southeastern Africa.

Description: Mg/Ca-based SST and thermocline temperatures with 1Sigma error at different sites, their difference (DeltaT), and the average DeltaT values for different periods with 95% confidence interval (CI). Also shown are hydrogen isotope (dD) values of n-C31 alkanes relative to the standard mean ocean water (per mil SMOW) with the 95% CI (LGM values are corrected for ice-volume), the C31 n-alkane concentrations in nanogram per gram sediment (ng g-1), the Carbon Preference Index (CPI27-33) as a measure of the degree of terrestrial organic matter degradation (higher CPI reflects less degraded plant waxes and vice versa), and their 1Sigma standard deviations (SD).