Beschreibung: The relative abundance of the C32 1,15 long-chain alkyl diol (LCD) is an emerging proxy for the input of riverine aquatic particulate organic carbon (POC) into coastal oceans. This compound has the potential to complement other established proxies reflecting riverine terrestrial POC input and allows for a more nuanced assessment of riverine POC export to coastal seas. The current understanding of this proxy is, however, limited. In this study, we compare different indices for riverine sediment input to coastal marine waters (i.e. C32 1,15-LCD, BIT index and Fe/Ca ratio) in a source-to-sink assessment in the Amazon River drainage system and the northeast South American continental margin, and we test their down-core applicability in a marine gravity core containing late Pleistocene fluvial Amazonian sediments. We show that the relative abundance of the C32 1,15-LCD is highest in water bodies with low flow velocity and low turbidity such as the downstream portion of lowland tributaries and floodplain lakes. Relative C32 1,15-LCD abundance is lowest in Andean white water tributaries where autotrophic productivity is hindered by high turbidity and high flow velocity. We also find that suspended particulate matter from all major tributaries during the extreme 2015 dry season has a similar LCD distribution to that of floodplain lakes. This indicates that the chemical composition of the tributaries is less relevant for the LCD distribution than their physical properties such as flow velocity and turbidity. Results from marine surface sediments offshore the Amazon River estuary show significant positive correlations between all three studied proxies. In contrast, we find that the relative C32 1,15-LCD abundance in the down-core record is anti-correlated to the BIT index and Fe/Ca ratio. While BIT index and Fe/Ca ratio show high (low) values during Heinrich stadials (Dansgaard-Oeschger interstadials), the C32 1,15-LCD proxy shows the opposite signal. BIT values are also higher during Marine Isotope Stage (MIS) 2 than during MIS 3, in contrast to trends in the C32 1,15-LCD proxy. We posit that this pattern arises from a reduction in relative C32 1,15-LCD abundance and total LCD productivity in the Amazon River during MIS 2 when less-humid conditions and lower sea level led to reduced area of floodplains. During Heinrich stadials, Andean sediment input increased and led to higher turbidity that resulted in lower C32 1,15-LCD production. Our study shows that major changes in water discharge, sediment transport and river morphology can lead to discrepancies between the BIT index and the relative abundance of the C32 1,15-LCD. Thus, we suggest that Amazonian aquatic and terrestrial POC pools had contrasting responses to changes related to both climate (e.g. increased Andean precipitation) and river morphology (e.g. steeper along-channel slope due to falling and low stand sea level).

Beschreibung: Abundant hydroclimatic evidence from western Amazonia and the adjacent Andes documents wet conditions during Heinrich Stadial 1 (HS1, 18–15 ka), a cold period in the high latitudes of the North Atlantic. This precipitation anomaly was attributed to a strengthening of the South American summer monsoon due to a change in the Atlantic interhemispheric sea surface temperature (SST) gradient. However, the physical viability of this mechanism has never been rigorously tested. We address this issue by combining a thorough compilation of tropical South American paleorecords and a set of atmosphere model sensitivity experiments. Our results show that the Atlantic SST variations alone, although leading to dry conditions in northern South America and wet conditions in northeastern Brazil, cannot produce increased precipitation over western Amazonia and the adjacent Andes during HS1. Instead, an eastern equatorial Pacific SST increase (i.e., 0.5–1.5 °C), in response to the slowdown of the Atlantic Meridional Overturning Circulation during HS1, is crucial to generate the wet conditions in these regions. The mechanism works via anomalous low sea level pressure over the eastern equatorial Pacific, which promotes a regional easterly low-level wind anomaly and moisture recycling from central Amazonia towards the Andes.

Beschreibung: The temporal succession of changes in Amazonian hydroclimate during Heinrich Stadial 1 (HS1) (ca. 18–14.7 cal ka BP) is currently poorly resolved. Here we present HS1 records based on isotope, inorganic and organic geochemistry from a marine sediment core influenced by the Amazon River discharge. Our records offer a detailed reconstruction of the changes in Amazonian hydroclimate during HS1, integrated over the basin. We reconstructed surface water hydrography using stable oxygen isotopes (δ18O) and Mg/Ca-derived paleotemperatures from the planktonic foraminifera Globigerinoides ruber, as well as salinity changes based on stable hydrogen isotope (δD) of palmitic acid. We also analyzed branched and isoprenoid tetraether concentrations, and compared them to existing bulk sediment ln(Fe/Ca) data and vegetation reconstruction based on stable carbon isotopes from n-alkanes, in order to understand the relationship between continental precipitation, vegetation and sediment production. Our results indicate a two-phased HS1 (HS1a and HS1b). During HS1a (18–16.9 cal ka BP), a first sudden increase of sea surface temperatures (SST) in the western equatorial Atlantic correlated with the slowdown of the Atlantic Meridional Overturning Circulation (AMOC) and the associated southern hemisphere warming phase of the bipolar seesaw. This phase was also characterized by an increased delivery of terrestrial material. During HS1b (16.9–14.8 cal ka BP), a decrease in terrestrial input was, however, associated with a marked decline of seawater δ18O and palmitic acid δD. Both isotopic proxies independently indicate a drop in sea surface salinity (SSS). A number of records under the influence of the North Brazil Current, in contrast, indicate increases in SST and SSS resulting from a weakened AMOC during HS1. Our records thus suggest that the expected increase in SSS due to the AMOC slowdown was overridden by a two-phased positive precipitation anomaly in Amazonian hydroclimate.

Beschreibung: 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‰) in most samples, indicating a modern forest source for most of the samples. Enriched values (-31 to -33‰) 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‰), while n-alkanes from the lowland tributaries, the Negro, Xingu and Tocantins Rivers (-142 to -154‰), 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.

Beschreibung: 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 (δ13CTOC/, 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 δ13CTOC values (-26.1 to -29.9 ‰) 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 the marine sediments, the distribution of δ13CTOC and 38 (sum of eight lignin phenols in organic carbon (OC), expressed as mg/100 mg 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 δ13CTOC 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.

Beschreibung: Bulk organic parameters and stable and radiocarbon isotope compositions of organic carbon (δ13COC and Δ14COC) as well as various biomarkers (lignin phenols, plant waxes etc.) have been used to investigate the biogeochemical characteristics of organic carbon in the Amazon River system. However, the source, concentration and distribution pattern of lignin on the Amazon shelf and fan has not been assessed so far. In particular, the compound-specific stable carbon isotope compositions (δ13C) of lignin phenols have not been characterized in the Amazon River system. In order to study the distribution of lignin in the lower Amazon basin and its dispersal on the shelf and fan, we used riverbed sediments from the Amazon mainstream and its main tributaries and marine surface sediments on the Amazon shelf and fan. The samples were analyzed for particulate organic carbon content (POC), δ13COC, lignin phenol compositions and compound-specific δ13C of individual lignin phenols. The concentrations of aluminium and silicon (Al/Si) were used as a proxy for grain size[1]. The POC content in the main tributaries ranged from 0.13 to 3.99 wt-% and increased with Al/Si ratio in each tributary. δ13COC varied from -26.1‰ to -29.9‰ VPDB in riverbed sediments. Lignin content (represented by Λ8, sum of eight lignin phenols in OC, expressed as mg/100mg OC) ranged from 0.73 to 6.91 and is positively related with Al/Si ratio in the main tributaries except for the Xingu River, in which Λ8 decreased with Al/Si. Ratios of syringyl to vanillyl (S/V) and cinnamyl to vanillyl (C/V) varied from 0.70 to 1.51 and 0.08 to 0.47, respectively, suggesting that the dominant source of lignin is non-woody angiosperm tissue. The ratios of vanillic acid to vanillin (Ad/Al)v (0.26-0.71) and syringic acid to syringaldehyde (Ad/Al)s (0.15-0.57) indicated relatively fresh, non-degraded lignin. In marine sediments, the δ13COC ranged from -18.6‰ to -26.7‰ and is correlated with the Λ8 value (0.04-2.01). The decreasing Λ8 value along the coast from the Amazon River mouth towards the northwest implies that lignin is distributed by the North Brazil Current. A main plant source of non-woody angiosperm tissue was indicated by the S/V (0.59-1.62) and C/V (0.10-0.43) ratios on the marine samples. The agreement between riverbed and marine sediments suggests that processing of POC during transport from the basin to offshore does not change the plant source information of lignin. Highly degraded lignin on the Amazon fan and the southeast shelf is indicated by (Ad/Al)v (0.49-0.99). δ13C of lignin phenols of 9 marine sediments ranged from -28.6‰ to -33.3‰ and were consistently lower than δ13COC (-19.7‰ to -26.7‰). Depleted δ13C of lignin phenols indicate that the POC produced by the terrestrial biosphere is mainly derived from higher plants using C3 photosynthesis. References Bouchez, J., Galy, V., Hilton, R.G., Gaillardet, J., Moreira-Turcq, P., Pérez, M.A., France-Lanord, C., Maurice, L., 2014. Source, transport and fluxes of Amazon River particulate organic carbon: Insights from river sediment depth-profiles. Geochemica et Cosmochimica Acta 133, 280-298

Beschreibung: The western tropical Atlantic plays an important role in the interhemispheric redistribution of heat during millennial-scale changes in the strength of the Atlantic Meridional Overturning Circulation (AMOC). The proper evaluation of this role depends on a clear understanding of sea surface temperature (SST) variations during AMOC slowdown periods like Heinrich Stadials (HS) in the western tropical Atlantic. However, published SST records from the western tropical Atlantic between ca. 4°S and 7°N show inconsistencies that are apparently related to the employed temperature proxy (i.e., Mg/Ca versus alkenone unsaturation index ). In general, while Mg/Ca values indicate warming during Heinrich Stadials, values show cooling. To assess this issue, we sampled core GeoB16224-1 retrieved off French Guiana (i.e., 6°39.38′N) and reconstructed water temperatures at high resolution using Mg/Ca on the foraminifera species Globigerinoides ruber, , TEX86 and modern analogue technique (MAT) transfer functions using planktonic foraminifera assemblages calibrated for 50 m water depth. Our results show that Mg/Ca and TEX86 values recorded an increase in SST related to AMOC slowdown. Conversely, and MAT values registered a decrease in temperatures during HS3 and HS1. Our and Mg/Ca results thus confirm the previously reported inconsistency for the period between 48–13 cal ka BP. We suggest that several non-thermal physiological effects probably imparted a negative temperature bias on the temperatures during Heinrich Stadials. However, MAT-based temperatures show similar variability with -based temperatures. Hence, we also suggest that during severe slowdown periods of the AMOC, a steeper meridional temperature gradient together with a southward shift of the Intertropical Convergent Zone produced not only an increase in SST but also a stronger upper water column stratification and a shoaling of the thermocline, decreasing subsurface temperatures. Our new high resolution temperature records allow a better characterization of the thermal response of the upper water column in the tropical western Atlantic to slowdown events of the AMOC, reconciling previously discrepant records.

Beschreibung: We investigate the redistribution of terrigenous materials in the northeastern (NE) South American continental margin during slowdown events of the Atlantic Meridional Overturning Circulation (AMOC). The compilation of stratigraphic data from 108 marine sediment cores collected across the western tropical Atlantic shows an extreme rise in sedimentation rates off the Parnaíba River mouth (about 2◦S) during Heinrich Stadial 1 (HS1, 18–15 ka). Sediment core GeoB16206-1, raised offshore the Parnaíba River mouth, documents relatively constant 143 Nd/144 Nd values (expressed as εNd(0) ) throughout the last 30 ka. Whereas the homogeneous εNd(0) data support the input of fluvial sediments by the Parnaíba River from the same source area directly onshore, the increases in Fe/Ca, Al/Si and Rb/Sr during HS1 indicate a marked intensification of fluvial erosion in the Parnaíba River drainage basin. In contrast, the εNd(0) values from sediment core GeoB16224-1 collected off French Guiana (about 7◦N) suggest Amazon-sourced materials within the last 30 ka. We attribute the extremely high volume of terrigenous sediments deposited offshore the Parnaíba River mouth during HS1 to (i) an enhanced precipitation in the catchment region and (ii) a reduced North Brazil Current, which are both associated with a weakened AMOC.