Description: The applicability of two organic geochemical proxies (UK'37 based on alkenones and TEXH86 based on glycerol dialkyl glycerol tetraethers) for ocean temperatures was investigated on a regional scale in the SE Brazilian continental margin (Campos Basin) using 53 core-top sediments. In 71% of the samples for UK'37 and 85% for TEXH86, the estimated annual mean sea surface temperature (SST) is comparable to the climatological annual mean data, with deviations within the calibration error. The surface TEXH86 estimates reflects the surface mixed layer, while the depth-integrated (0–200 m) TEXH86 estimates showed better agreement with temperatures at 100–200 mdepth. In addition, the SST-UK'37 results were more consistent (73% of the samples) using a winter calibration rather than an annual mean calibration. This seasonal effect might be ascribed to an increase in the abundance of haptophytes in the region during the winter. Exceptions to these general trends were observed for both proxies as a strong cold bias in reconstructed temperature in a few samples in the southern portion of the studied region, which may be related to (i) a predominant subsurface habitat of Thaumarchaeota combined with enhanced primary production and flux of particles during upwelling and (ii) alkenones being laterally transported from adjacent colder waters. Effects of river input of terrestrially sourced GDGTs on TEXH 86 are not evident. Overall, our findings show that UK'37 and TEXH86 are suitable temperature proxies for paleoclimate studies at a regional scale in the SE Brazilian continental margin, but on a local scale the effects of upwelling must be taken in consideration.

Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 μg carbon (μgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 μgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.

Description: The radiocarbon analysis laboratory at Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI) is equipped with an accelerator mass spectrometer (AMS) MICADAS (MIni CArbon Dating System). The laboratory provides routine 14C analyses on bulk organic matter, plant fragments, dissolved and particulate organic matter, individual molecular lipids, and carbonate (micro-) fossils with the aim to foster international research efforts in vulnerable high latitudes. The AWI MICADAS allows AMS 14C analysis on graphite targets as well as on CO2 samples via gas injection into the hybrid ion source. The laboratory thus provides reliable datasets even if only small amounts of sample material are available, a problem often encountered in polar research. Here we describe the standard operation procedures and sample preparation methods employed, and demonstrate the instrument performance and data quality based on repeat analysis of international reference materials.

Description: Sedimentary high molecular weight (HMW) n-alkyl lipids derived from the waxes of terrestrial plants are common target compounds in biogeochemical and paleoenvironmental research. These plant waxes derive predominantly from the epicuticular cover of vascular plant leaves and their relative and absolute abundances and stable isotopic composition can be used as proxies to decipher, e.g., continental climate and land-ocean carbon transfer processes. In marine sediments, however, compound-specific radiocarbon analysis has revealed that plant waxes are often not syn-depositional, but instead are substantially 14C-depleted (‘pre-aged’) upon deposition. This 14C-depletion can be caused by various processes that either promote retention of plant waxes during transport from source to sink such as storage in soils or entrainment in deposition-resuspension loops in rivers and on continental shelves or, alternatively, by processes that add HMW n-alkyl lipids from other sources (e.g., petrogenic inputs). Here, we review the intrinsic and extrinsic processes affecting the sedimentary plant wax 14C composition (ranging from chemical processes to continental-scale environmental conditions), how plant wax 14C compositions translate into mean ages, and which processes control plant wax mean ages in marine sediments. Finally, we use a compilation of available and new compound-specific plant wax 14C data to provide a synthesis and evaluate the major controls on plant wax mean ages in marine sediments at the global scale.

Description: 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.

Description: Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by bacteria usually ascribed to soil and peat deposits. The presence of brGDGTs in marine sediments can thus be used to track terrigenous organic matter inputs to the continental margin and to infer the local continental mean annual air temperature (MAT) and soil pH. The proxy rationale is based on the degree methylation and cyclization of the brGDGTs from terrestrial bacteria, but recently evidence was found of river and oceanic production of brGDGTs with similar configuration, indicating the necessity to better constrain the applicability of the soil brGDGTs in the marine realm. Here we considered crenarchaeol and brGDGTs obtained in 46 core-top sediments from cross-margin transects in the Campos Basin in the Southwest Atlantic, with the goal to evaluate the effectiveness of the brGDGT-associated proxies in a region in the southeastern tropical Brazilian continental margin influenced by upwelling events and low terrigenous inputs. The separation of the 5- and 6-methyl brGDGTs proved to be essential for a better evaluation of the sources of brGDGTs in the environment. Direct evidence of input of terrigenous organic matter by the medium-sized Paraíba do Sul River and other small rivers in the region were observed. More importantly, the high proportions of ring-containing brGDGTs—and the consequent increased values of the #ringstetra–in the sediments deposited between 75 and 400 m water depths (mid-shelf to upper slope) were clear evidence of marine in situ production of brGDGTs. In some stations deeper than 1,900 m, an increase in the acyclic 6-methyl hexamethylated compounds can also be ascribed to in situ production. Our results revealed that the initial soil signal is lost during transport and after river discharge in the Campos Basin, which compromise the use of brGDGTs to reconstruct the soil pH and MAT of the nearby land area.

Description: During the last deglaciation (18–8 kyr BP), shelf flooding and warming presumably led to a large-scale decomposition of permafrost soils in the mid-to-high latitudes of the Northern Hemisphere. Microbial degradation of old organic matter released from the decomposing permafrost potentially contributed to the deglacial rise in atmospheric CO2 and also to the declining atmospheric radiocarbon contents (Δ14C). The significance of permafrost for the atmospheric carbon pool is not well understood as the timing of the carbon activation is poorly constrained by proxy data. Here, we trace the mobilization of organic matter from permafrost in the Pacific sector of Beringia over the last 22 kyr using mass-accumulation rates and radiocarbon signatures of terrigenous biomarkers in four sediment cores from the Bering Sea and the Northwest Pacific. We find that pronounced reworking and thus the vulnerability of old organic carbon to remineralization commenced during the early deglaciation (∼16.8 kyr BP) when meltwater runoff in the Yukon River intensified riverbank erosion of permafrost soils and fluvial discharge. Regional deglaciation in Alaska additionally mobilized significant fractions of fossil, petrogenic organic matter at this time. Permafrost decomposition across Beringia’s Pacific sector occurred in two major pulses that match the Bølling-Allerød and Preboreal warm spells and rapidly initiated within centuries. The carbon mobilization likely resulted from massive shelf flooding during meltwater pulses 1A (∼14.6 kyr BP) and 1B (∼11.5 kyr BP) followed by permafrost thaw in the hinterland. Our findings emphasize that coastal erosion was a major control to rapidly mobilize permafrost carbon along Beringia’s Pacific coast at ∼14.6 and ∼11.5 kyr BP implying that shelf flooding in Beringia may partly explain the centennial-scale rises in atmospheric CO2 at these times. Around 16.5 kyr BP, the mobilization of old terrigenous organic matter caused by meltwater-floods may have additionally contributed to increasing CO2 levels.

Description: Detailed organic geochemical and carbon isotopic (δ13C and Δ14C) analyses are performed on permafrost deposits affected by coastal erosion (Herschel Island, Canadian Beaufort Sea) and adjacent marine sediments (Herschel Basin) to understand the fate of organic carbon in Arctic nearshore environments. We use an end‐member model based on the carbon isotopic composition of bulk organic matter to identify sources of organic carbon. Monte Carlo simulations are applied to quantify the contribution of coastal permafrost erosion to the sedimentary carbon budget. The models suggest that ~40% of all carbon released by local coastal permafrost erosion is efficiently trapped and sequestered in the nearshore zone. This highlights the importance of sedimentary traps in environments such as basins, lagoons, troughs, and canyons for the carbon sequestration in previously poorly investigated, nearshore areas.

Description: Tropical and subtropical rivers deliver large quantities of terrestrial organic carbon (OCterr) to the ocean, acting as a crucial part of the global carbon cycle, but little is known about the timescale and efficiency of its transport to and in the adjacent coastal sea. Here we examined source-specific biomarker (fatty acids, FAs) contents and isotope compositions in surface sediments in an alongshore transect southwestward from the Pearl River mouth. The C28+30, rather than other long-chain saturated FAs, were found to be the most representative for OCterr, and a plant wax mean age of 3060 ±90 yr (resulting from protracted storage) was estimated in the Pearl River watershed from the 14C age of C28+30FA in a river mouth sample. A compilation of plant wax mean ages in global (sub)tropical river systems including this study suggests that regional differences in climate and morphology may have a limited impact on plant wax mean ages in (sub)tropical regions. A four-source mixing model based on bulk OC and biomarker isotope compositions demonstrated that surface sediments in the Pearl River-derived mudbelt consist of 0.15–0.36 wt.% marine OC, 0.03–0.13 wt.% riverine primary production-derived OC, 0.18–0.49 wt.% soil OC, and 0.07–0.16 wt.% fossil OC. The mean burial efficiency of fossil and soil OC is ∼85% and 49%, respectively, indicating the refractory nature of fossil OC but a significant loss of soil OC due to remineralization during transport in the marine environment before final burial. Over longer timescales, the OCterrloss experienced during transport may, thus, to some extent reduces the capacity of terrestrial ecosystems (particularly soils) as CO2sinks.