Formation of seep carbonates along the makran convergent margin, northern Arabian sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane

Authigenic carbonate deposits have been sampled with the remotely operated vehicle ‘MARUM-QUEST 4000 m’ from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The δ18Ocarbonate values range from 1.3 to 4.2‰ V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low δ13Ccarbonate values (as low − 54.6‰ V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by δ13Cmethane values ranging from − 70.3 to − 66.7‰ V-PDB, and also by back-calculations considering δ13Cmethane values of carbonate and incorporated lipid biomarkers. These calculations (Δδ13Cmethane–carbonate, Δδ13CANME–methane, Δδ13CMOX–methane) prove to be useful to assess the carbon stable isotope composition of seeping methane if this has not been determined in the first place; such an approach represents a useful tool to reconstruct fluid composition of ancient seeps. AOM is also revealed by lipid biomarkers of anaerobic methane oxidizing archaea such as crocetane, pentamethylicosane (PMI), and sn2-hydroxyarchaeol strongly depleted in 13C (δ13C values as low as − 127‰ V-PDB). Biomarkers of sulphate-reducing bacteria are also abundant, showing slightly less negative δ13C values, but still significantly 13C-depleted (average values as low as − 101‰). Other bacterial biomarkers, such as bacteriohopanepolyols (BHPs), hopanols, and hopanoic acids are detected in most carbonates, but are particularly common in seep carbonates from the non-OMZ sites. The BHP patterns of these carbonates and their low δ13C values resemble patterns of aerobic methanotrophic bacteria. In the shallower OMZ sites, BHPs revealed much lower contents and varying compositions, most likely reflecting other sources than aerobic methanotrophic bacteria. 230Th/U carbonate ages indicate that AOM-induced carbonate precipitation at the deeper non-OMZ seeps occurred mainly during the late Pleistocene-Holocene transition, i.e. between 19 and 15 ka before present, when the global sea level was lower than today.

Characterizing, modelling and understanding the climate variability of the deep water formation in the North-Western Mediterranean Sea

Observing, modelling and understanding the climate-scale variability of the deep water formation (DWF) in the North-Western Mediterranean Sea remains today very challenging. In this study, we first characterize the interannual variability of this phenomenon by a thorough reanalysis of observations in order to establish reference time series. These quantitative indicators include 31 observed years for the yearly maximum mixed layer depth over the period 1980–2013 and a detailed multi-indicator description of the period 2007–2013. Then a 1980–2013 hindcast simulation is performed with a fully-coupled regional climate system model including the high-resolution representation of the regional atmosphere, ocean, land-surface and rivers. The simulation reproduces quantitatively well the mean behaviour and the large interannual variability of the DWF phenomenon. The model shows convection deeper than 1000 m in 2/3 of the modelled winters, a mean DWF rate equal to 0.35 Sv with maximum values of 1.7 (resp. 1.6) Sv in 2013 (resp. 2005). Using the model results, the winter-integrated buoyancy loss over the Gulf of Lions is identified as the primary driving factor of the DWF interannual variability and explains, alone, around 50 % of its variance. It is itself explained by the occurrence of few stormy days during winter. At daily scale, the Atlantic ridge weather regime is identified as favourable to strong buoyancy losses and therefore DWF, whereas the positive phase of the North Atlantic oscillation is unfavourable. The driving role of the vertical stratification in autumn, a measure of the water column inhibition to mixing, has also been analyzed. Combining both driving factors allows to explain more than 70 % of the interannual variance of the phenomenon and in particular the occurrence of the five strongest convective years of the model (1981, 1999, 2005, 2009, 2013). The model simulates qualitatively well the trends in the deep waters (warming, saltening, increase in the dense water volume, increase in the bottom water density) despite an underestimation of the salinity and density trends. These deep trends come from a heat and salt accumulation during the 1980s and the 1990s in the surface and intermediate layers of the Gulf of Lions before being transferred stepwise towards the deep layers when very convective years occur in 1999 and later. The salinity increase in the near Atlantic Ocean surface layers seems to be the external forcing that finally leads to these deep trends. In the future, our results may allow to better understand the behaviour of the DWF phenomenon in Mediterranean Sea simulations in hindcast, forecast, reanalysis or future climate change scenario modes. The robustness of the obtained results must be however confirmed in multi-model studies.