14C concentrations of algal and archaeal lipids and their associated sea surface temperature proxies in the Black Sea

Understanding the preservation and deposition history of organic molecules is crucial for the understanding of paleoenvironmental information contained in their abundance ratios such as Uk'37 and TEX86 used as proxies for sea surface temperature (SST). Based on their relatively high refractivity, alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) can survive postdepositional processes like lateral transport, potentially causing inferred SSTs to be misleading. Likewise, selective preservation of alkenones and GDGTs may cause biases of the SST proxies themselves and can lead to decoupling of both proxy records. Here we report compound-specific radiocarbon data of marine biomarkers including alkenones, GDGTs, and low molecular weight (LMW) n-fatty acids from Black Sea sediments deposited under different redox regimes to evaluate the potentially differential preservation of both biomarker classes and its effect on the SST indices Uk'37 and TEX86 . The decadal D14C values of alkenones, GDGTs, and LMW n-fatty acids indicate similar preservation under oxic, suboxic, and anoxic redox regimes and no contribution of pre-aged compounds, e.g., by lateral supply. Moreover, similar 14C concentrations of crenarchaeol, alkenones, and LMW n-fatty acids imply that the thaumarchaeotal GDGTs preserved in these sediments are produced in the euphotic zone rather than in subsurface/thermocline waters. However, we observe biomarker-based SSTs that strongly deviate (deltaSST up to 8.4 °C) from in situ measured mean annual SSTs in the Black Sea. This is not due to redox-dependent differential biomarker preservation as implied by their D14C values and spatial SST pattern. Since contributions from different sources can largely be excluded, the deviation of the Uk'37 and TEX86 proxy-derived SSTs from in situ SSTs requires further study of phylogenetic and other yet unknown environmental controls on alkenone and GDGT lipid distributions in the Black Sea.

Gas analysis of sediment cores from the Batumi seep area

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (>99.85 mol.% of Sum[C1-C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (d13C = -53.5 per mill V-PDB; D/H around -175 per mill SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by >0.03 mol.% (Sum[C1-C4, CO2]) relative to the other gas types and the virtual lack of 14C-CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% Sum(C1-C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C-CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.

(Table 1) Organic carbon, hydrogen and oxygen index and hydrocarbons at DSDP Hole 93-603B

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 27 shipboard-sealed, deep-frozen core samples of DSDP Hole 603B off the east coast of North America were determined by a gas-stripping/thermovaporization method. Total yields representing the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediments vary from 22 to 2400 ng/g of dryweight sediment. Highest yields are measured in the two black shale samples of Core 603B-34 (hydrogen index of 360 and 320 mg/g Corg, respectively). In organic-carbon-normalized units these samples have hydrocarbon contents of 12,700 and 21,500 ng/g Corg, respectively, indicating the immaturity of their kerogens. Unusually high organic-carbonnormalized yields are associated with samples that are extremely lean in organic carbon. It is most likely that they are enriched by small amounts of migrated light hydrocarbons. This applies even to those samples with high organic-carbon contents (1.3-2.2%) of Sections 603B-28-4, 603B-29-1, 603B-49-2, and 603B-49-3, because they have an extremely low hydrocarbon potential (hydrogen index between 40 and 60 mg/g Corg). Nearly all samples were found to be contaminated by varying amounts of acetone that is used routinely in large quantities on board ship during core-cutting procedures. Therefore, 48 samples from the original set of 75 collected had to be excluded from the present study.