Description: The Kryos Basin is a deep-sea hypersaline anoxic basin (DHAB) located in the Eastern Mediterranean Sea (34.98°N 22.04°E). It is filled with brine of re-dissolved Messinian evaporites and is nearly saturated with MgCl2-equivalents, which makes this habitat extremely challenging for life. The strong density difference between the anoxic brine and the overlying oxic Mediterranean seawater impedes mixing, giving rise to a narrow chemocline. Here, we investigate the microbial community structure and activities across the seawater–brine interface using a combined biogeochemical, next-generation sequencing, and lipid biomarker approach. Within the interface, we detected fatty acids that were distinctly 13C-enriched when compared to other fatty acids. These likely originated from sulfide-oxidizing bacteria that fix carbon via the reverse tricarboxylic acid cycle. In the lower part of the interface, we also measured elevated rates of methane oxidation, probably mediated by aerobic methanotrophs under micro-oxic conditions. Sulfate reduction rates increased across the interface and were highest within the brine, providing first evidence that sulfate reducers (likely Desulfovermiculus and Desulfobacula) thrive in the Kryos Basin at a water activity of only ~0.4 Aw. Our results demonstrate that a highly specialized microbial community in the Kryos Basin has adapted to the poly-extreme conditions of a DHAB with nearly saturated MgCl2 brine, extending the known environmental range where microbial life can persist.

Description: The Cretaceous period (similar to 145-65 m.y. ago) was characterized by intervals of enhanced organic carbon burial associated with increased primary production under greenhouse conditions. The global consequences of these perturbations, oceanic anoxic events (OAEs), lasted up to 1 m.y., but short-term nutrient and climatic controls on widespread anoxia are poorly understood. Here, we present a high-resolution reconstruction of oceanic redox and nutrient cycling as recorded in subtropical shelf sediments from Tarfaya, Morocco, spanning the initiation of OAE2. Iron-sulfur systematics and biomarker evidence demonstrate previously undescribed redox cyclicity on orbital time scales, from sulfidic to anoxic ferruginous (Fe-rich) water-column conditions. Bulk geochemical data and sulfur isotope modeling suggest that ferruginous conditions were not a consequence of nutrient or sulfate limitation, despite overall low sulfate concentrations in the proto-North Atlantic. Instead, fluctuations in the weathering influxes of sulfur and reactive iron, linked to a dynamic hydrological cycle, likely drove the redox cyclicity. Despite the potential for elevated phosphorus burial in association with Fe oxides under ferruginous conditions on the Tarfaya shelf, porewater sulfide generation drove extensive phosphorus recycling back to the water column, thus maintaining widespread open-ocean anoxia.

Description: Investigating past interglacial climates not only help to understand how the climate system operates in general, it also forms a vital basis for climate predictions. We reconstructed vertical stratification changes in temperature and salinity in the North Atlantic for a period some 400 ka ago (MIS11), an interglacial time analogue of a future climate. As inferred from a unique set of biogeochemical, geochemical, and faunal data, the internal upper ocean stratification across MIS 11 shows distinct depth-dependent dynamical changes related to vertical as well as lateral shifts in the upper Atlantic meridional circulation system. Importantly, transient cold events are recognized near the end of the long phase of postglacial warming at surface, subsurface, mid, and deeper water layers. These data demonstrate that MIS 11 coolings over the North Atlantic were initially triggered by freshwater input at the surface and expansion of cold polar waters into the Subpolar Gyre. The cooling signal was then transmitted downwards into mid-water depths. Since the cold events occurred after the main deglacial phase we suggest that their cause might be related to continuous melting of the Greenland ice sheet, a mechanism that might also be relevant for the present and upcoming climate.

Description: Long-chain diols (LCDs) occur widespread in marine environments and also in lakes and rivers. Transport of LCDs from rivers may impact the distribution of LCDs in coastal environments, however relatively little is known about the distribution and biological sources of LCDs in river systems. In this study, we investigated the distribution of LCDs in suspended particulate matter (SPM) of three river systems (Godavari, Danube, and Rhine) in relation with precipitation, temperature, and source catchments. The dominant long-chain diol is the C32 1,15-diol followed by the C30 1,15-diol in all studied river systems. In regions influenced by marine waters, such as delta systems, the fractional abundance of the C30 1,15-diol is substantially higher than in the river itself, suggesting different LCD producers in marine and freshwater environments. A change in the LCD distribution along the downstream transects of the rivers studied was not observed. However, an effect of river flow is observed; i.e., the concentration of the C32 1,15-diol is higher in stagnant waters such as reservoirs and during seasons with river low stands. A seasonal change in the LCD distribution was observed in the Rhine, likely due to a change in the producers. Eukaryotic diversity analysis by 18S rRNA gene sequencing of SPM from the Rhine showed extremely low abundances of sequences (i.e., 〈0.32% of total reads) related to known algal LCD producers. Furthermore, incubation of the river water with 13C-labeled bicarbonate did not result in 13C incorporation into LCDs. This indicates that the LCDs present are mainly of fossil origin in the fast-flowing part of the Rhine. Overall, our results suggest that the LCD producers in rivers predominantly reside in lakes or side ponds that are part of the river system.

Description: Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but have also revealed uncertainty about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors such as sea surface temperature (SST), salinity and nutrient concentration. Previous studies of cultures indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified as the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices for surface sediments showed no relationship with annual mean SST of the overlying water. It remains unknown as to what determines the DSI, although our data suggest that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions from algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15- diols have been applied previously as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

Description: Although commonly reported in marine and freshwater environments, little is known about the biological sources of long chain alkyl 1,13- and 1,15-diols, and factors controlling their distributions. Here we analyzed the occurrence and distribution of these lipids in a comprehensive set of marine surface sediments and compare their distributions with environmental conditions like sea surface temperature (SST), salinity and nutrient concentrations. Fractional abundances of the C28 1,13-, C30 1,13- and C30 1,15-diols show a strong correlation with SST and based on these results, we propose the Long chain Diol Index (LDI), which expresses the C30 1,15-diol abundance relative to those of C28 1,13-, C30 1,13- and C30 1,15-diols. The LDI shows a strong linear correlation with SST (LDI = 0.033 � SST + 0.095; R2 = 0.969, n = 162) over a temperature range of �3 to 27 �C. Long chain diol distributions in sediments from the South Atlantic close to the Congo River outflow (West Africa) provided a 43 kyr LDI SST record. This record reflects several known climatic events and shows similarities with an alkenone- derived SST record obtained using the same suite of sediments, both in trend and in terms of absolute SST. This confirms the potential of the LDI as a proxy for palaeo-SST reconstruction.

Description: Oceanic anoxic events (OAEs) were a frequent occurrence in the Cretaceous greenhouse ocean. Based on a variety of paleoredox indicators, euxinic water column conditions are commonly invoked for these OAEs. However, in a high resolution study of OAE3 deep sea sediments [1], revised paleoredox indicators suggest that euxinic conditions fluctuated with anoxic ferruginous conditions on orbital timescales. Building upon this, we here present new data for a continental shelf setting at Tarfaya, Morocco, that spans a period prior to, and during, the onset of OAE2. We again find strong evidence for orbital transitions from euxinic to ferruginous conditions. The presence of this distinct cyclicity during OAE2 and OAE3 in shallow and deep water settings, coupled with its occurrence on the anoxic shelf prior to the global onset of anoxia, suggests that these fluctuations were a fundamental feature of anoxia in the Cretaceous ocean. The observed redox cyclicity has major implications for the cycling of phosphorus, and hence the maintenance and longevity of OAEs. However, despite this significance, controls on the observed redox cyclicity are essentially unknown. Here, we utilize S isotope measurements (pyrite S and carbonate-associated S) from the deep sea and shelf settings to model oceanic sulphate concentrations across the redox transitions. Perhaps surprisingly, we find no evidence to suggest that ferruginous conditions arose due to extensive drawdown of seawater sulphate (as pyrite-S and organic-S) under euxinic conditions. Instead, S isotope systematics in the deep sea imply increased sulphate concentrations during ferruginous intervals. Based on these observations and other major element data, we infer that the redox cyclicity instead relates to orbitally-paced fluctuations in continental hydrology and weathering, linking the redox state of the global ocean to climate-driven processes on land. [1] März et al (2008) GCA, 72, 3703-3717.

Description: Lipid biomarker records from sinking particles collected by sediment traps can be used to study the seasonality of biomarker production as well as processes of particle formation and settling, ultimately leading to the preservation of the biomarkers in sediments. Here we present records of the biomarker indices based on alkenones and TEX86 based on isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), both used for the reconstruction of sea surface temperatures (SST). These records were obtained from sinking particles collected using a sediment trap moored in the filamentous upwelling zone off Cape Blanc, Mauritania, at approximately 1300 water depth during a four-year time interval between 2003 and 2007, and supplemented by and TEX86 determined on suspended particulate matter collected from surface waters in the study area. Mass and lipid fluxes are highest during peak upwelling periods between October and June. The alkenone and GDGT records both display pronounced seasonal variability. Sinking velocities calculated from the time lag between measured SST maxima and minima and corresponding index maxima and minima in the trap samples are higher for particles containing alkenones (14-59 m d-1) than for GDGTs (9-17 m d-1). It is suggested that GDGTs are predominantly exported from shallow waters by incorporation in opal-rich particles. SST estimates based on the index correspond to the amplitude observed fluctuations in SST during the study period. Temperature estimates based on TEX86 show smaller seasonal amplitudes, which can be explained by either predominant production of GDGTs during the warm season, or a contribution of GDGTs exported from deep waters, which are in this region known to carry GDGTs in a distribution that translates to a high TEX86 signal.