No abstract

The largest organic carbon (OC) reservoir on Earth is in the geosphere, mainly comprising insoluble organic matter (IOM). IOM formation, therefore, plays an important role in the short and long-term carbon cycle, carbon bioavailability and formation of source rocks. To explore the mechanism of insolubilization of organic matter (OM), we have analysed soluble and IOM fractions of continental shelf marine sediments. We have applied sequential solvent-extractions followed by a selective chemical degradation of the post-extraction residue, specifically targeting prokaryotic membrane lipids (branched fatty acids -FAs, hopanoids, archaeol and glycerol dialkyl glycerol tetraethers -GDGTs). Up to 80% of prokaryotic membrane lipids are not solvent-extractable, and we observe compound-specific differences in partitioning between soluble and IOM fractions. Based on these observations, we propose a variety of mechanisms for the incorporation of prokaryotic lipids into IOM in marine sediments: First, OM association with authigenic carbonates; second, cross-linking via esterification reactions with time, which could be particularly relevant for FAs; third, competition between reactivity and loss of polar head groups, the latter rendering the OM less susceptible to incorporation; and finally, inherent solvent-insolubility of some lipids associated with prokaryotic cells.

Abstract. Cryospheric changes in northern high latitudes are linked to significant greenhouse gas flux to the atmosphere, for example, methane that originates from organic matter decomposition in thermokarst lakes. The set of pathways that link methane production in sediments, via oxidation in the lake system, to the flux of residual methane to the atmosphere is complex and exhibits temporal and spatial variation. The isotopic signal of bacterial biomarkers (hopanoids, e.g. diploptene) in sediments has been used to identify contemporary ocean-floor methane seeps and, in the geological record, periods of enhanced methane production (e.g. the PETM). The biomarker approach could potentially be used to assess temporal changes in lake emissions through the Holocene via the sedimentary biomarker record. However, there are no data on the consistency of the signal of isotopic depletion in relation to source or on the amount of noise (unexplained variation) in biomarker values from modern lake sediments. We assessed methane oxidation as represented by the isotopic signal of biomarkers from methane oxidising bacteria (MOB) in multiple surface sediment samples in three distinct areas known to emit varying levels of methane in two shallow Alaskan thermokarst lakes. Diploptene was present and had δ13C values lower than −38 ‰ in all sediments analysed, suggesting methane oxidation was widespread. However, there was considerable variation in δ13C values within each area. The most 13C-depleted diploptene was found in an area of high methane ebullition in Ace Lake (diploptene δ13C values between −68.2 and −50.1 ‰). In contrast, significantly higher diploptene δ13C values (between −42.9 and −38.8 ‰) were found in an area of methane ebullition in Smith Lake. δ13C values of diploptene between −56.8 and −46.9 ‰ were found in the centre of Smith Lake, where ebullition rates are low but diffusive methane efflux occurs. The small-scale heterogeneity of the samples may reflect patchy distribution of substrate and/or MOB within the sediments. The two ebullition areas differ in age and type of organic carbon substrate, which may affect methane production, transport, and subsequent oxidation. Given the high amount of variation in surface samples, a more extensive calibration of modern sediment properties, within and among lakes, is required before down-core records of hopanoid isotopic signatures are developed.

Abstract. Cryospheric changes in northern high latitudes are linked to significant greenhouse gas flux to the atmosphere, including methane release that originates from organic matter decomposition in thermokarst lakes. The connections between methane production in sediments, transport pathways and oxidation are not well understood and this has implications for any attempts to reconstruct methane production from sedimentary archives. We assessed methane oxidation as represented by methane oxidising bacteria across the surface sediments of two interior Alaska thermokarst lakes in relation to methane emissions via ebullition (bubbling). The bacterial biomarker diploptene was present and had low δ13C values (lower than −38 ‰) in all sediments analysed, suggesting methane oxidation was widespread. The most δ13C-depleted diploptene was found in the area of highest methane ebullition emissions in Ace Lake (δ13C diplotene values between −68.2 and −50.1 ‰), suggesting a positive link between methane production, oxidation, and emission in this area. In contrast, significantly less depleted diploptene δ13C values (between −42.9 and −38.8 ‰) were found in the area of highest methane ebullition emissions in Smith Lake. Lower δ13C values of diploptene were found in the central area of Smith Lake (between −56.8 and −46.9 ‰), where methane ebullition rates are low but methane diffusion appears high. Using δ13C-diplotene as a proxy for methane oxidation activity, we suggest the observed differences in methane oxidation levels among sites within the two lakes could be linked to differences in source area of methane production (e.g. age and type of organic carbon) and bathymetry as it relates to varying oxycline depths and changing pressure gradients. As a result, methane oxidation is highly lake-dependent. The diploptene δ13C values also highlight strong within-lake variability, implying that single-value, down-core records of hopanoid isotopic signatures are not secure indicators of changing methane flux at the whole-lake scale.

Most organic matter (OM) on Earth occurs as kerogen‐like materials, that is naturally formed macromolecules insoluble with standard organic solvents. The formation of this insoluble organic matter (IOM) is a topic of much interest, especially when it limits the detection of compounds of geomicrobiological interest. For example, studies that search for biomarker evidence of life on early Earth or other planets usually use solvent‐based extractions. This leaves behind a pool of OM as unexplored post‐extraction residues, potentially containing diagnostic biomarkers. Since the IOM has an enhanced potential for preservation compared to soluble OM, analysing IOM‐released biomarkers can also provide even deeper insights into the ecology of ancient settings, with implications for early Earth and Astrobiology investigations. Here, we analyse the prokaryotic lipid biosignature within soluble and IOM of the Taupo Volcanic Zone (TVZ) silica sinters, which are key analogues in the search for life. We apply sequential solvent extractions and a selective chemical degradation upon the post‐solvent extraction residue. Moreover, we compare the IOM from TVZ sinters to analogous studies on peat and marine sediments to assess patterns in OM insolubilisation across the geosphere. Consistent with previous work, we find significant but variable proportions—1%–45% of the total prokaryotic lipids recovered—associated with IOM fractions. This occurs even in recently formed silica sinters, likely indicating inherent cell insolubility. Moreover, archaeal lipids seem more prone to insolubilisation as compared to the bacterial analogues, which might enhance their preservation and also bias overall biomarkers interpretation. These observations are similar to those observed in other settings, confirming that even in a setting where the OM derives predominantly from prokaryotic sources, patterns of IOM formation/occurrence are conserved. Differences with other settings, however, such as the occurrence of archaeol in IOM fractions, could be indicative of different mechanisms for IOM formation that merit further exploration.