Description: Seepage of methane (CH4) on land and in the sea may significantly affect Earth's biogeochemical cycles. However processes of CH4 generation and consumption, both abiotic and microbial, are not always clear. We provide new geochemical and isotope data to evaluate if a recently discovered CH4 seepage from the shallow seafloor close to the Island of Elba (Tuscany) and two small islands nearby are derived from abiogenic or biogenic sources and whether carbonate encrusted vents are the result of microbial or abiotic processes. Emission of gas bubbles (predominantly CH4) from unlithified sands was observed at seven spots in an area of 100 m(2) at Pomonte (Island of Elba), with a total rate of 234 ml m(-2) d(-1). The measured carbon isotope values of CH4 of around -18 parts per thousand (VPDB) in combination with the measured delta H-2 value of -120 parts per thousand (VSMOW) and the inverse correlation of delta C-13-value with carbon number of hydrocarbon gases are characteristic for sites of CH4 formation through abiogenic processes, specifically abiogenic formation of CH4 via reduction of CO2 by H-2. The H-2 for methanogenesis likely derives from ophiolitic host rock within the Ligurian accretionary prism. The lack of hydrothermal activity allows CH4 gas to become decoupled from the stagnant aqueous phase. Hence no hyperalkaline fluid is currently released at the vent sites. Within the seep area a decrease in porewater sulphate concentrations by ca. 5 mmol/l relative to seawater and a concomitant increase in sulphide and dissolved inorganic carbon (DIC) indicate substantial activity of sulphate-dependent anaerobic oxidation of methane (AOM). In absence of any other dissimilatory pathway, the delta C-13-values between -17 and -5 parts per thousand in dissolved inorganic carbon and aragonite cements suggest that the inorganic carbon is largely derived from CH4. The formation of seep carbonates is thus microbially induced via anaerobic oxidation of abiotic CH4.

Description: Highlights • Naturally enriched AOM biomass was studied in high-pressure continuous incubation. • We report the first S- and O-isotope fractionation values by sulfate reduction coupled to AOM from culture studies. • There is a tight link between methane concentration and S- and O-isotope fractionation. • S- and O-isotope fractionation values indicate reversibility of energy limited microbial processes. • The wide range of environmental S- and O-isotope signatures can be explained. Abstract Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments − thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM1.4±0.6 mM up to 58.8±10.5 mM58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (View the MathML sourceεS34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (θOθO), as well as sulfate reduction rates (SRR). Smallest View the MathML sourceεS34 (21.9±1.9‰21.9±1.9‰) and θOθO (0.5±0.20.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest View the MathML sourceεS34 (67.3±26.1‰67.3±26.1‰) and θOθO (2.5±1.52.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that View the MathML sourceεS34, θOθO and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate–methane transition zones, AOM-SR is likely to induce very large sulfur isotope fractionation between sulfate and sulfide (i.e. 〉60‰〉60‰) and will drive the oxygen isotope composition of sulfate towards the sulfate–water oxygen isotope equilibrium value. Sulfur isotope fractionation by AOM-SR at gas seeps, where methane fluxes are high, will be much smaller (i.e. 20 to 40‰).

Description: Marine sedimentary ikaite is the parent mineral to glendonite, stellate pseudomorphs found throughout the geological record which are most usually composed of calcite. Ikaite is known to be metastable at earth surface temperatures and pressures, readily breaking down to more stable carbonate polymorphs when exposed to warm (ambient) conditions. Yet the process of transformation of ikaite to calcite is not well understood, and there is an ongoing debate as to the palaeoclimatic significance of glendonites in the geological record. This study uses a combination of techniques to examine the breakdown of ikaite to calcite, outside of the ikaite growth medium, and to assess the palaeoclimatic and palaeoenvironmental significance of stable and clumped isotope compositions of ikaite-derived calcite. Powder X-ray diffraction shows that ikaite undergoes a quasi- solid-state transformation to calcite during heating of samples in air, yet when ikaite transforms under a high temperature differential, minor dissolution-recrystallisation may also occur with the ikaite structural waters. No significant isotopic equilibration to transformation temperature is observed in the resulting calcite. Therefore, in cases of transformation of ikaite in air, clumped and stable isotope thermometry can be used to reconstruct ikaite growth temperatures. In the case of ancient glendonites, where transformation of the ikaite occurred in contact with the interstitial waters of the host sediments over unknown timescales, it is uncertain whether the reconstructed clumped isotope temperatures reflect ikaite crystallisation or its transformation temperatures. Yet clumped and stable isotope thermometry may still be used conservatively to estimate an upper limit for bottom water temperatures. Furthermore, stable isotope along with element/Ca ratios shed light on the chemical environment of ikaite growth. Our data indicate that a range of (bio)geochemical processes may act to promote ikaite formation at different marine sedimentary sites, including bacterial sulphate reduction and anaerobic oxidation of methane. The colours of the ikaites, from light brown to dark brown, indicate a high organic matter content, favouring high rates of bacterial sulphate reduction as the main driver of ikaite precipitation. Highest Mg/Ca ratios are found in the most unstable ikaites, indicating that Mg acts to destabilise ikaite structure.