Description: 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 ∑[C1–C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] 〉 1000) and stable isotopic compositions of methane (δ13C = − 53.5‰ V-PDB; D/H around − 175‰ 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.% (∑[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.% ∑(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.

Description: Highlights: • Multiproxy record from S Ethiopia extends knowledge about environment and climate of past 116,000 yrs during human expansion. • Hydroclimate during Marine Isotope Stage (MIS) 5 was much more variable (frequency and amplitude) than during MIS 3 and 4. • Earth system models and model simulations of intermediate complexity emulate corresponding amplitude shifts in hydroclimate. • Environment was arid during MIS 3 and 4, but permanent lake water bodies existed as inferred from our biological proxies. Abstract: Archaeological findings, numerical human dispersal models and genome analyses suggest several time windows in the past 200 kyr (thousands of years ago) when anatomically modern humans (AMH) dispersed out of Africa into the Levant and/or Arabia. From close to the key hominin site of Omo-Kibish, we provide near continuous proxy evidence for environmental changes in lake sediment cores from the Chew Bahir basin, south Ethiopia. The data show highly variable hydroclimate conditions from 116 to 66 kyr BP with rapid shifts from very wet to extreme aridity. The wet phases coincide with the timing of the North African Humid Periods during MIS5, as defined by Nile discharge records from the eastern Mediterranean. The subsequent record at Chew Bahir suggests stable regional hydrological setting between 58 and 32 kyr (MIS4 and 3), which facilitated the development of more habitable ecosystems, albeit in generally dry climatic conditions. This shift, from more to less variable hydroclimate, may help account for the timing of later dispersal events of AMH out of Africa.