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Abstract: Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900±70years to 4400±170years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers. [Copyright &y& Elsevier]

Abstract: Despite its location on sediment-free basalt, vent fluids from the Main Endeavour Field (MEF) contain chemical species that indicate fluids have interacted with sediments during circulation. We report on the distribution and isotopic abundances of organic compounds (C 1–C 3 alkanes and alkenes, benzene and toluene) in fluids collected from the Main Endeavour Field (MEF) in July, 2000, to understand the processes that regulate their abundances and characterize fluid sources. Aqueous organic compounds are derived from the thermal alteration of sedimentary organic matter and subsequently undergo further oxidation reactions during fluid flow. Fluid:sediment mass ratios calculated using ΣNH4 concentrations indicate that the sediments are distal to the MEF, resulting in a common reservoir of fluids for all of the vents. Following the generation from sediment alteration, aqueous organic compounds undergo secondary alteration reactions via a stepwise oxidation reaction mechanism. Alkane distributions and isotopic compositions indicate that organic compounds in MEF fluids have undergone a greater extent of alteration as compared to Middle Valley fluids, either due to differences in subsurface redox conditions or the residence time of fluids at subsurface conditions. The distributions of the aromatic compounds benzene and toluene are qualitatively consistent with the subsurface conditions indicated by equilibration of aqueous alkanes and alkanes. However, benzene and toluene do not achieve chemical equilibrium in the subsurface. Methane and CO2 also do not equilibrate chemically or isotopically at reaction zone temperatures, a likely result of an insufficient reaction time after addition of CO2 from magmatic sources during upflow. The organic geochemistry supports the assumption that the sediments with which MEF fluids interact has the same composition as sediments present in Middle Valley itself, and highlight differences in subsurface reaction zone conditions and fluid flow pathways at these two sites. [Copyright &y& Elsevier]