Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Near real time surface ocean velocity, Tyrrhenian Sea and Ligurian Sea in September 2016

The data set consists of maps of total velocity of the surface current in the North-Western Tyrrhenian Sea and Ligurian Sea averaged over a time interval of 1 hour around the cardinal hour. Surface ocean velocities estimated by HF Radar are representative of the upper 0.3-2.5 meters of the ocean. Total velocities are derived using least square fit that maps radial velocities measured from individual sites onto a cartesian grid. The final product is a map of the horizontal components of the ocean currents on a regular grid in the area of overlap of two or more radar stations.

Sea surface temperatures, alkenones and sedimentation rate from ODP Hole 161-977A

A continuous high-resolution Western Mediterranean sea surface temperature (SST) alkenone record spanning the past 250,000 years shows that abrupt changes were more common at warming than at cooling. During marine isotope stage (MIS) 6, SST oscillated following a stadial-interstadial pattern but at lower intensities and rates of change than in the Dansgaard/Oeschger events of MIS 3. Some of the most prominent events occurred over MISs 5 and 7, after prolonged warm periods of high stability. Climate during the whole period was predominantly maintained in interglacial-interstadial conditions, whereas the duration of stadials was much shorter.

Stable isotopes, radionuclides, and calculated sea surface temperature of two sediment cores in the Sicily Channel

The Eastern Mediterranean Transient (EMT) occurred in the Aegean Sea from 1988 to 1995 and is the most significant intermediate-to-deep Mediterranean overturning perturbation reported by instrumental records. The EMT was likely caused by accumulation of high salinity waters in the Levantine and enhanced heat loss in the Aegean Sea, coupled with surface water freshening in the Sicily Channel. It is still unknown whether similar transients occurred in the past and, if so, what their forcing processes were. In this study, sediments from the Sicily Channel document surface water freshening (SCFR) at 1910±12, 1812±18, 1725±25 and 1580±30 CE. A regional ocean hindcast links SCFR to enhanced deep-water production and in turn to strengthened Mediterranean thermohaline circulation. Independent evidence collected in the Aegean Sea supports this reconstruction, showing that enhanced bottom water ventilation in the Eastern Mediterranean was associated with each SCFR event. Comparison between the records and multi-decadal atmospheric circulation patterns and climatic external forcings indicates that Mediterranean circulation destabilisation occurs during positive North Atlantic Oscillation (NAO) and negative Atlantic Multidecadal Oscillation (AMO) phases, reduced solar activity and strong tropical volcanic eruptions. They may have recurrently produced favourable deep-water formation conditions, both increasing salinity and reducing temperature on multi-decadal time scales.

Sea Surface Temperature (SST) Mg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides

We generated a high-resolution SSTMg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides from the core MD99-2346 collected in the Gulf of Lion, and compared it to that obtained using modern analogue techniques applied to fossil foraminiferal assemblages (SSTMAT). The two temperature records display similar patterns during the last 28,000 years but the SSTMg/Ca estimates are several degrees warmer (~+4 °C) than SSTMAT. The temperature shift between SSTMg/Ca and SSTMAT remained relatively constant over time. This seems to exclude a bias on the Mg/Ca record associated with salinity or secondary Mg-rich calcite encrustation on the foraminiferal tests during early diagenesis. Therefore, anomalously high Mg/Ca suggests either: (1) the empirical equation for G. bulloides of Elderfield and Ganssen (2000) is incorrect; or (2) there is a specific Mediterranean genotypes of G. bulloides for which a specific Mg/Ca-temperature calibration is needed.

Seawater carbonate chemistry and egg production, hatching and metabolic rates of a Mediterranean copepod species (Acartia clausi) in a laboratory experiment

This study includes the first information on the combined effect of low pH and raised temperature on egg production rate (EP), hatching success (HS), excretion and respiration of the Mediterranean copepod Acartia clausi. Adult individuals of A. clausi and fresh surface seawater were collected at a coastal station in Saronikos Gulf during April 2012. Four different conditions were applied: two different pH levels (present: 8.09 and future: 7.83) at two temperature values (present: 16°C and present+4 °C= 20°C). EP and HS success decreased significantly over the duration of exposure at future pH at both temperature conditions. However, the analysis of the combined effect of pH, T, chlorophyll a and the duration of the experiments on EP and HS revealed that ocean acidification had no discernible effect, whereas warming; food and the duration of exposure were more significant for the reproductive output of A. clausi. Temperature appeared to have a positive effect on respiration and excretion. Acidification had no clear effect on respiration, but a negative effect on the A. clausi excretion was observed. Acidification and warming resulted in the increase of the excretion rate and the increase was higher than that observed by warming only. Our findings showed that a direct effect of ocean acidification on copepod's vital rates was not obvious, except maybe in the case of excretion. Therefore, the combination of acidification with the ambient oligotrophic conditions and the warming could result in species being less able to allocate resources for coping with multiple stressors.

Methane fluxes and carbonate deposits at eastern Mediterranean cold seeps

High acoustic seafloor-backscatter signals characterize hundreds of patches of methane-derived authigenic carbonates and chemosynthetic communities associated with hydrocarbon seepage on the Nile Deep Sea Fan (NDSF) in the Eastern Mediterranean Sea. During a high-resolution ship-based multibeam survey covering a ~ 225 km**2 large seafloor area in the Central Province of the NDSF we identified 163 high-backscatter patches at water depths between 1500 and 1800 m, and investigated the source, composition, turnover, flux and fate of emitted hydrocarbons. Systematic Parasound single beam echosounder surveys of the water column showed hydroacoustic anomalies (flares), indicative of gas bubble streams, above 8% of the high-backscatter patches. In echosounder records flares disappeared in the water column close to the upper limit of the gas hydrate stability zone located at about 1350 m water depth due to decomposition of gas hydrate skins and subsequent gas dissolution. Visual inspection of three high-backscatter patches demonstrated that sediment cementation has led to the formation of continuous flat pavements of authigenic carbonates typically 100 to 300 m in diameter. Volume estimates, considering results from high-resolution autonomous underwater vehicle (AUV)-based multibeam mapping, were used to calculate the amount of carbonate-bound carbon stored in these slabs. Additionally, the flux of methane bubbles emitted at one high-backscatter patch was estimated (0.23 to 2.3 × 10**6 mol a**-1) by combined AUV flare mapping with visual observations by remotely operated vehicle (ROV). Another high-backscatter patch characterized by single carbonate pieces, which were widely distributed and interspaced with sediments inhabited by thiotrophic, chemosynthetic organisms, was investigated using in situ measurements with a benthic chamber and ex situ sediment core incubation and allowed for estimates of the methane consumption (0.1 to 1 × 10**6 mol a**-1) and dissolved methane flux (2 to 48 × 10**6 mol a**-1). Our comparison of dissolved and gaseous methane fluxes as well as methane-derived carbonate reservoirs demonstrates the need for quantitative assessment of these different methane escape routes and their interaction with the geo-, bio-, and hydrosphere at cold seeps.

Mediterranean cold-water coral measurements

This study presents aggradation rates supplemented for the first time by carbonate accumulation rates from Mediterranean cold-water coral sites considering three different regional and geomorphological settings: (i) a cold-water coral ridge (eastern Melilla coral province, Alboran Sea), (ii) a cold-water coral rubble talus deposit at the base of a submarine cliff (Urania Bank, Strait of Sicily) and (iii) a cold-water coral deposit rooted on a predefined topographic high overgrown by cold-water corals (Santa Maria di Leuca coral province, Ionian Sea). The mean aggradation rates of the respective cold-water coral deposits vary between 10 and 530 cm kyr?1 and the mean carbonate accumulation rates range between 8 and 396 g cm?2 kyr?1 with a maximum of 503 g cm?2 kyr?1 reached in the eastern Melilla coral province. Compared to other deep-water depositional environments the Mediterranean cold-water coral sites reveal significantly higher carbonate accumulation rates that were even in the range of the highest productive shallow-water Mediterranean carbonate factories (e.g. Cladocora caespitosa coral reefs). Focusing exclusively on cold-water coral occurrences, the carbonate accumulation rates of the Mediterranean cold-water coral sites are in the lower range of those obtained for the prolific Norwegian coral occurrences, but exhibit much higher rates than the cold-water coral mounds off Ireland. This study clearly indicates that cold-water corals have the potential to act as important carbonate factories and regional carbonate sinks within the Mediterranean Sea. Moreover, the data highlight the potential of cold-water corals to store carbonate with rates in the range of tropical shallow-water reefs. In order to evaluate the contribution of the cold-water coral carbonate factory to the regional or global carbonate/carbon cycle, an improved understanding of the temporal and spatial variability in aggradation and carbonate accumulation rates and areal estimates of the respective regions is needed.