Description: During the last glacial termination atmospheric carbon dioxide (CO2atm) rose about 100 ppm and atmospheric radiocarbon activity (Δ14C) concurrently dropped by about ca. 400 ‰. Global warming likely triggered large-scale thawing of permafrost soils in the northern hemisphere resulting in release of 14C-depleted carbon which may have contributed to the changes in CO2atm and Δ14C1. However, the timing and duration of the thawing as well as regional differences regarding these points are poorly understood. In order to unravel the evolution of permafrost decomposition and its role within the glacial-interglacial climate change a profound understanding of the deglacial carbon-turnover and temperature development in subarctic and arctic regions are of great importance. Working with two sediment cores from the continental margin off Kamchatka Peninsula, western Bering Sea (WBS, site SO201-2-114KL) & Northwest Pacific (NW Pacific, site SO201-2-12KL) we establish Glacial to Holocene records in sea surface temperature (SST) and mean air temperature (MAT) using the TEXL86 (SST) and CBT/MBT (MAT) temperature proxies that are based on marine and terrigenous biomarkers (Glycerol dialkyl glycerol tetraethers). The hydrogen isotopic composition (δD) of plant-wax derived lipid biomarkers (long-chain n-alkanes and long-chain n-fatty acids) is another tool for reconstructing air temperature but can also provide information of the provenance of terrigenous organic matter (OM). The radiocarbon activity of the lipid biomarkers is applied to reconstruct changes in terrestrial residence times of terrigenous OM. Our records in SST and CBT/MBT-based MAT are interpreted as summer temperatures. From the Bølling/Allerød interstadial (B/A) to the present they show temperature fluctuations similar to Greenland ice core records including a warming at the onset of the B/A and a cooling during the Younger Dryas (YD) followed by a warming into the Preboreal (PB) suggesting an atmospheric coupling between N-Atlantic and N-Pacific, East Siberian/Kamchatka temperature development. However, during Heinrich Stadial 1 (HS1) where WBS SST and Kamchatka MAT cool down synchronously with Greenland temperatures, the NW-Pacific SST rises gradually and seems to be decoupled from the N-Atlantic. Since the gradual warming trend and the subsequent synchronization with Greenland ice core data during B/A is known from SST records from the Gulf of Alaska2 (GOA) surface conditions in the NW Pacific likely are controlled by the Alaskan Stream overprinting the atmospheric effect and the influence of the East Kamchatka Current. Asynchronous development of our TEXL86 record and the GOA records during the Holocene indicate that the AS weakenes over the deglaciation. For the time-span of the Last Glacial Maximum to the onset of the B/A interstadial, the CBT/MBT temperature proxy may be seasonally biased as it produces improbably high summer temperatures that level Holocene conditions. In contrast to the CBT/MBT-based temperatures the δD of n-fatty acids does not show clear stadial-interstadial fluctuations and remains on a stable level during the deglaciation instead. During the Holocene, δD increases progressively, which may have resulted from a gradual warming trend. Comparing the radiocarbon activity of the n-fatty acids to the Δ14C-signature of the atmosphere at the time of deposition the dimension of the terrestrial residence time prior to the deposition (ΔΔ14C) can be estimated. High ΔΔ14C values during deglaciation indicate that the plat-wax biomarkers are strongly pre-aged which may bias the δD-temperature record. Gradually decreasing ΔΔ14C imply declining terrestrial residence times from late glacial to late Holocene and argue for major changes in the relative contribution of weakly and strongly pre-aged OM. Possible sources for strongly pre-aged OM include permafrost decomposition and the congruent mobilization of 14C-depleted carbon but also the erosion of basal tills from the North-American or Kamchatka ice sheets that bear OM dating back to times prior to the glaciation. The n-C25/n-C25+n-C27 ratio, an indicator for the relative contribution of sphagnum spp.3, is on a stable level over most parts of the deglaciation indicating a constant composition of the vegetation and/or a constant carbon source. Between 16.5-14.6 kaBP the record shows a sharp excursions towards higher values congruent with a sharp increase in the δD of n-alkanes that is not evident in the δD of n-fatty acids. Coevally, lowered CPI-values (carbon preference index) point to a major contribution of fossil carbon at that time. Thus, our sites may be subject to a change in the carbon source. It coincides with melting events of the N-American ice sheets4 which may indicate that large amounts of OM from eastern Beringia accumulated in the WBS/NW Pacific during HS1. 1. S. A. Zimov, E. A. G.Schuur & F. S. Chapin III (2006). Permafrost and the global carbon budget.- Science, 312, p. 1612-1613 2. J. E. Vonk & Ö. Gustaffsson (2009). Calibrating n-alkanes Sphagnum proxies in sub-Arctic Scandinavia.- Organic Geochemistry, 40, p. 1085-1090. 3. S. K. Praetorius & A. C. Mix (2014). Synchronization of North Pacific and Greenland climates preceded abrupt deglacial warming.- Science, 345, p. 444-448. 4. I. L. Hendy & T. Cosma (2009).Vulnerability of the Cordilleran Ice Sheet to iceberg calving during late Quaternary rapid climate change events.- Paleoceanography, 23, p. PA2101

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 (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.

Description: Due to the high sensitivity of southern Africa to climate change, a reliable understanding of its hydrological system is crucial. Recent studies of the regional climatic system have revealed a highly complex interplay of forcing factors on precipitation regimes. This includes the influence of the tropical easterlies, the strength of the southern hemispheric westerlies as well as sea surface temperatures along the coast of the subcontinent. However, very few marine records have been available in order to study the coupling of marine and atmospheric circulation systems. Here we present results from a marine sediment core, recovered in shallow waters off the Gouritz River mouth on the south coast of South Africa. Core GeoB18308-1 allows a closer view of the last ∼4 kyr. Climate sensitive organic proxies, like the distribution and isotopic composition of plant-wax lipids as well as indicators for sea surface temperatures and soil input, give information on oceanographic and hydrologic changes during the recorded time period. Moreover, the micropaleontology, mineralogical and elemental composition of the sediments reflect the variability of the terrigenous input to the core site. The combination of down-core sediment signatures and a catchment-wide provenance study indicate that the Little Ice Age (∼300–650 cal yr BP) was characterized by climatic conditions favorable to torrential flood events. The Medieval Climate Anomaly (∼950–650 cal yr BP) is expressed by lower sea surface temperatures in the Mossel Bay area and humid conditions in the Gouritz River catchment. These new results suggest that the coincidence of humid conditions and cooler sea surface temperatures along the south coast of South Africa resulted from a strengthened and more southerly anticyclonic circulation. Most probably, the transport of moisture from the Indian Ocean by strong subtropical easterlies was coupled with Agulhas Bank upwelling pulses, which were initiated by an increase in Agulhas Current strength.

Description: 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

Description: To achieve a better understanding of the hydrologic evolution of the North-West (NW) African monsoon system during the Holocene, in particular during inferred abrupt climate changes at the end of the African Humid Period (AHP), we investigated terrigenous plant lipids deposited in marine sediments offshore NW Africa. Changes in rainfall amount were estimated by compound-specific hydrogen isotope (δD) analyses. The spatial gradient of rainfall isotopic compositions is reflected in marine surface sediments. δD changes in plant waxes covering the last 100 years confirm the observed decrease in rainfall during the late twentieth century Sahel drought, and thus can be used for a quantitative calibration of δD and pre- cipitation. δD changes in sedimentary plant waxes show no abrupt change at the end of the AHP suggesting a gradual precipitation decline. These results are supported by Holocene climate simulations using a coupled atmosphere-land surface model, which includes an explicit modeling of isotopic fractionation within the hydrological cycle.

Description: © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Chemical Geology 466 (2017): 454-465, doi:10.1016/j.chemgeo.2017.06.034.

Description: We present dissolved organic carbon (DOC) concentrations, particulate organic matter (POM) composition (δ13C, δ15N, ∆14C, N/C), and particulate glycerol dialkyl glycerol tetraether (GDGT) distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model using δ13C and N/C indicates that exported POM is consistently dominated by C3 rainforest soil sources, with increasing contribution from C3 vegetation and decreasing contribution from phytoplankton at high discharge. Large C4 inputs are never observed despite covering ≈ 13 % of the catchment. Low and variable ∆14C values during 2011 [annual mean = (-148 ± 82) ‰], when discharge from left-bank tributaries located in the southern hemisphere reached record lows, likely reflect a bias toward pre-aged POM derived from the Cuvette Congolaise swamp forest. In contrast, ∆14C values were stable near -50 ‰ between January and June 2013, when left-bank discharge was highest. We suggest that headwater POM is replaced and/or diluted by C3 vegetation and pre-aged soils during transit through the Cuvette Congolaise, whereas left-bank tributaries export significantly less pre-aged material. GDGT distributions provide further evidence for seasonal and inter-annual variability in soil provenance. The cyclization of branched tetraethers and the GDGT-0 to crenarchaeol ratio are positively correlated with discharge (r ≥ 0.70; p-value ≤ 4.3×10-5) due to the incorporation of swamp-forest soils when discharge from right-bank tributaries located in the northern hemisphere is high. Both metrics reach record lows during 2013, supporting our interpretation of increased left-bank contribution at this time. We conclude that hydrologic variability is a major control of POM provenance in the Congo River Basin and that tropical wetlands can be a significant POM source despite their small geographic coverage.

Description: J.D.H. was supported by the NSF Graduate Research Fellowship Program under grant number 2012126152; E.S. was supported by the DFG Research Center/Cluster of Excellence “The Ocean in the Earth System” at MARUM – Center for Environmental Sciences; V.V.G. was partly supported by the US National Science Foundation, grants OCE-0851015 and OCE-0928582; R.G.M.S. was partly supported by the US National Science Foundation, grants OCE-0851101, OCE-1333157, and OCE-1464396; and T.I.E. was partly supported by the Swiss National Science Foundation (SNF Grant No. 200021_140850).