Pore-water concentration of chloride in sediment cores and equilibrium temperatures and gas bubble analysis at ROV stations from the Vodyanitskii mud volcano

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to 650 mmol L**-1 at 150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at 60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (dD-CH4 = -170.8 per mil (SMOW), d13C-CH4 = -61.0 per mil (V-PDB), d13C-C2H6 = -44.0 per mil (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 x 10**6 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.

Multivariate statistical analysis on the kaolinite/chlorite ratios from 20 South Atlantic sediment cores

Multivariate statistical analysis on the kaolinite/chlorite ratios from 20 South Atlantic sediment cores allowed for the extraction of two processes controlling the fluctuations of the kaolinite/chlorite ratio during the last 130,000 yrs, (1) the relative strength of North Atlantic Deep Water (NADW) inflow into the South Atlantic Ocean and (2) the influx of aeolian sediments from the south African continent. The NADW fluctuation can be traced in the entire deep South Atlantic while the dust signal is restricted to the vicinity of South Africa. Our data indicate that NADW formation underwent significant changes in response to glacial/interglacial climate changes with enhanced export to the Southern Hemisphere during interglacials. The most pronounced phases with Enhanced South African Dust Export (ESADE) occurred during cold Marine Isotope Stage (MIS) 5d and across the Late Glacial/Holocene transition from 16 ka to 4 ka (MIS 2 to 1). This particular pattern is attributed to the interaction of Antarctic Sea Ice extent, the position of the westerlies and the South African monsoon system.

(Table 1) Age determination of sediment cores OCE205-2-100GGGC and KNR166-2-31

Benthic foraminiferal Cd/Ca from a Florida Current sediment core documents the history of the northward penetration of southern source waters within the surface return flow of the Atlantic meridional overturning circulation (AMOC). Cd seawater estimates (CdW) indicate that intermediate-depth southern source waters crossed the equator and contributed to the Florida Current during the Bølling-Allerød warm period of the last deglaciation, consistent with evidence of only a modest AMOC reduction compared to today. The CdW estimates also provide the first paleoceanographic evidence of a reduction in the influence of intermediate-depth southern source waters within the Florida Current during the Younger Dryas, a deglacial cold event characterized by a weak North Atlantic AMOC. Our results reveal a close correspondence between the northward penetration of intermediate-depth southern source waters and the influence of North Atlantic Deep Water, suggesting a possible link between intermediate-depth southern source waters and the strength of the Atlantic AMOC.

Pollen profile and age determination for sediment core M72/5_619-1 (22-GC3)

Sediments from the Black Sea, a region historically dominated by forests and steppe landscapes, are a valuable source of detailed information on the changes in regional terrestrial and aquatic environments at decadal to millennial scales. Here we present multi-proxy environmental records (pollen, dinoflagellate cysts, Ca, Ti and oxygen isotope data) from the uppermost 305 cm of the core 22-GC3 (42°13.53' N, 36°29.55' E) collected from a water depth of 838 m in the southern part of the Black Sea in 2007. The records span the last ~ 18 kyr (all ages are given in cal kyr BP). The pollen data reveal the dominance of the Artemisia-steppe in the region, suggesting rather dry/cold environments ~ 18-14.5 kyr BP. Warming/humidity increase during melt-water pulses (~ 16.1-14.5 kyr BP), indicated by d18O records from the 22-GC3 core sediment and from the Sofular Cave stalagmite, is expressed in more negative d13C values from the Sofular Cave, usually interpreted as the spreading of C3 plants. The records representing the interstadial complex (~ 14.5-12.9 kyr BP) show an increase in temperature and moisture, indicated by forest development, increased primary productivity and reduced surface run-off, whereas the switch from primary terrigenous to primary authigenic Ca origin occurs ~ 500 yr later. The Younger Dryas cooling is clearly demonstrated by more negative d13C values from the Sofular Cave and a reduction of pines. The early Holocene (11.7-8.5 kyr BP) interval reveals relatively dry conditions compared to the mostly moist and warm middle Holocene (8.5-5 kyr BP), which is characterized by the establishment of the species-rich warm mixed and temperate deciduous forests in the low elevation belt, temperate deciduous beech-hornbeam forests in the middle and cool conifer forest in upper mountain belt. The border between the early and middle Holocene in the vegetation records coincides with the opening of the Mediterranean corridor at ~ 8.3 kyr BP, as indicated by a marked change in the dinocyst assemblages and in the sediment lithology. Changes in the pollen assemblages indicate a reduction in forest cover after ~ 5 kyr BP, which was likely caused by increased anthropogenic pressure on the regional vegetation.

Bulk components and ice rafted debris of five sediment cores of the Sophia Basin, Arctic Ocean

Periods of enhanced terrigenous input to the ocean's basins of the North Atlantic have been reported for the last glacial period. We present a set of new sediment cores recovered from the Sophia Basin north of Svalbard which exhibit wide spread IRD layers reflecting enhanced terrigenous input throughout the last ~200 kyr. BP. Their consistent stratigraphic position, sedimentological character, high sedimentation rate and geochemical characteristic point to synchronously deposited layers which we name terrigenous input events (TIEs). Due to their higher densities, they generate excellent reflectors for sediment penetrating acoustic devices and prominent acoustic layers in the imagery of sedimentary structures. Therefore TIEs can be used for regional acoustic stratigraphy. Each of the events can be linked to major glacial activity on Svalbard. However, the Early Weichselian glaciation is not recorded as a TIE and, in agreement with other work, might not have occurred on Svalbard as a major glacial advance to the shelf break. Non-synchronous timing of western and northern sources on Svalbard points against sea-level induced iceberg discharge events.

(Table 1) Age determination of Barents Sea sediment cores

he separate roles of oceanic heat advection and orbital forcing on influencing early Holocene temperature variability in the eastern Nordic Seas is investigated. The effect of changing orbital forcing on the ocean temperatures is tested using the 1DICE model, and the 1DICE results are compared with new and previously published temperature reconstructions from a transect of five cores located underneath the pathway of Atlantic water, from the Faroe-Shetland Channel in the south to the Barents Sea in the north. The stronger early Holocene summer insolation at high northern latitudes increased the summer mixed layer temperatures, however, ocean temperatures underneath the summer mixed layer did not increase significantly. The absolute maximum in summer mixed layer temperatures occurred between 9 and 6 ka BP, representing the Holocene Thermal Maximum in the eastern Nordic Seas. In contrast, maximum in northward oceanic heat transport through the Norwegian Atlantic Current occurred approximately 10 ka BP. The maximum in oceanic heat transport at 10 ka BP occurred due to a major reorganization of the Atlantic Ocean circulation, entailing strong and deep rejuvenation of the Atlantic Meridional Overturning Circulation, combined with changes in the North Atlantic gyre dynamic causing enhanced transport of heat and salt into the Nordic Seas.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

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.

Palaeoenvironment records of six sediment cores collected in the Gulf of Carpentaria

The Gulf of Carpentaria is an epicontinental sea (maximum depth 70 m) between Australia and New Guinea, bordered to the east by Torres Strait (currently 12 m deep) and to the west by the Arafura Sill (53 m below present sea level). Throughout the Quaternary, during times of low sea-level, the Gulf was separated from the open waters of the Indian and Pacific Oceans, forming Lake Carpentaria, an isolation basin, perched above contemporaneous sea-level with outlet channels to the Arafura Sea. A preliminary interpretation is presented of the palaeoenvironments recorded in six sediment cores collected by the IMAGES program in the Gulf of Carpentaria. The longest core (approx. 15 m) spans the past 130 ka and includes a record of sea-level/lake-level changes, with particular complexity between 80 and 40 ka when sea-level repeatedly breached and withdrew from Gulf/Lake Carpentaria. Evidence from biotic remains (foraminifers, ostracods, pollen), sedimentology and geochemistry clearly identifies a final marine transgression at about 9.7 ka (radiocarbon years). Before this transgression, Lake Carpentaria was surrounded by grassland, was near full, and may have had a surface area approaching 600 km-300 km and a depth of about 15 m. The earlier rise in sea-level which accompanied the Marine Isotopic Stage 6/5 transgression at about 130 ka is constrained by sedimentological and biotic evidence and dated by optical- and thermoluminescence and amino acid racemisation methods.

(Table 2) Radiocarbon content and 14C AMS ages of planktonic foraminifera from sediment cores Louis_1900 and Louis_2023

North American freshwater runoff records have been used to support the case that climate flickers were caused by shutdowns of the ocean thermohaline circulation (THC) resulting from reversals of meltwater discharges. Inconsistencies in the documentation of these meltwater switches, however, continue to fuel the debate on the cause/s of the oscillatory nature of the deglacial climate. New oxygen and carbon isotope records from the northern Gulf of Mexico depict in exceptional detail the succession of meltwater floods and pauses through the southern routing during the interval 16 to 8.9 ka (14C years BP; ka, kiloannum). The records underscore the bimodal role played by the Gulf of Mexico as a destination of meltwater discharges from the receding Laurentide Ice Sheet. The evidence indicates that the Gulf of Mexico acted as the principal source of superfloods at 13.4, 12.6, and 11.9 ka that reached the North Atlantic and contributed significantly to density stratification, disruption of ocean ventilation, and cold reversals. Gulf of Mexico lapsed into a "relief valve" position in post-Younger Dryas time, when meltwater discharges were rerouted south at 9.9, 9.7, 9.4, and 9.1 ka, thus temporarily interrupting North Atlantic-bound freshwater discharges from Lake Agassiz. The history of meltwater events in the Gulf of Mexico contradicts the model that meltwater flow via the eastern outlets into the North Atlantic disrupted the ocean THC, causing cooling, while diversions to the Gulf of Mexico via the Mississippi River enhanced THC and warming.

Iridium concentrations and abundances of meteoritic ejecta from the Eltanin impact in sediment cores from POLARSTERN cruise ANT-XII/4

The abundances of meteoritic ejecta from the Eltanin asteroid impact have been examined in seven sediment cores recovered by the FS Polarstern during expedition ANT XII/4 using elemental concentrations of iridium and weights of coarse (>500 ?m) ejecta debris. Three cores with well-preserved impact deposits, PS2704-1, PS2708-1, and PS2709-1, each contain Ir and ejecta fluences similar to those found previously in USNS Eltanin core E13-4. Small Ir anomalies and traces of ejecta were found in cores PS2706-1 and PS2710-1, but since these cores lack well-defined deposits, these are considered to be reworked and not representative of the fallout. No evidence of ejecta was found in cores PS2702-1 and PS2705-1. These results confirm earlier speculation that the Eltanin impact resulted in deposits of ejecta with up to 1 g/cm**2 of debris over a wide area of the ocean floor. However, there are still large uncertainties over the actual regional or global extent of this unique sediment deposit.

(Table 1) Helium isotope ratios of sediment core TT013_114

We present a helium isotope record for core TT013-114PC from the central equatorial Pacific (140°W, 4°N, 4432 m water depth) spanning a period of 1 million years. We focus on the time interval from 560 to 800 kyr, largely coinciding with the mid-Pleistocene climate transition (MPT) when the dominant period of the Earth's climate variability shifted from 41 kyr to 100 kyr. The terrigenous 4He concentrations from our study correlate very well with published titanium concentrations in this core strongly supporting the use of terrigenous 4He as a monitor of continental dust. Normalizing titanium and terrigenous 4He concentrations to 3He suggests that the dust supply during the MPT was approximately 30% lower compared to the subsequent period (560-100 kyr). The 3He-normalized barium, aluminum and phosphorus concentrations, trace elements with a predominantly biogenic source in these sediments, are relatively constant. This is in contrast to previous studies that reported an apparent rise of titanium-normalized productivity proxies. Rather than a significant increase in productivity during the MPT, we conclude that the dust flux to the central equatorial Pacific was reduced and that the export productivity was approximately constant during this period of climate reorganization.