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.

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.

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.

Age, 232Th, 230Th, 238U, CaCO3, organic carbon, lithogenic fraction and opal concentrations of 4 sediment cores from the southwest Pacific, with calculated 230Th-normalized mass flux

No clear scenario has yet been able to explain the full carbon drawdown that occurred during the Last Glacial Maximum (LGM); however, increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron (Fe) fertilisation has been proposed to have provided a key mechanism affecting the air-sea partitioning of carbon. We chronicle changes in marine EP based on four sediment cores in Subtropical Waters (STW) and SAZ around New Zealand since the LGM. For the first time in this region, we present 230-Thorium normalised fluxes of biogenic opal, carbonate (CaCO3), excess Barium (xsBa), and organic Carbon (Corg). In STW and SAZ, these flux variations show that EP did not change markedly since the LGM. The only exception was a site in the SAZ close to the STF, where we suggest the STF shifted over the core site, driving increased EP. To understand why EP was mostly low and constant we investigated dust deposition changes by measuring lithogenic fluxes at the four sites. These data are coherent with an increased dust deposition in the southwest Pacific during the LGM. Additionally, we infer an increased lithogenic material discharge from erosion and glacier melts during the deglaciation, limited to the Campbell Plateau. Therefore, we propose that even though increased glacial dust deposition may have relieved Fe limitation within the SAZ, the availability of silicic acid (Si(OH)4) limited any resultant increase in carbon export during the LGM. Consequently, we infer low Si(OH)4 concentrations in the SAZ that have not significantly changed since the LGM. This result suggests that both Si(OH)4 and Fe co-limit EP in the SAZ around New Zealand, which would be consistent with modern process studies.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

The permafrost carbon inventory on the Tibetan Plateau : a new evaluation using deep sediment cores

Acknowledgements We are grateful for Dr. Jens Strauss and the other two anonymous reviewers for their insightful comments on an earlier version of this MS, and appreciate members of the IBCAS Sampling Campaign Teams for their assistance in field investigation. This work was supported by the National Basic Research Program of China on Global Change (2014CB954001 and 2015CB954201), National Natural Science Foundation of China (31322011 and 41371213), and the Thousand Young Talents Program.

Clay mineralogy of sediment cores from the South-East Atlantic off Namibia

Independent proxies were assessed in two Late Quaternary sediment cores from the eastern South Atlantic to compare deep-water changes during the last 400 kyr. Two cores were recovered from beneath North Atlantic Deep Water (NADW) at approximately 3 000 m depth. Late Quaternary presence of NADW is indicated by the Cibicidoides wuellerstorfi assemblage on the Walvis Ridge (Core GeoB 1214) and the Bulimina alazanensis assemblage on the Namibian continental slope (Core GeoB 1710). The propagation of NADW is exclusively observed during interglacials, with maximum factor loadings in Stages 1, 5, 7, 9 and 11. These maxima are consistent with peaks in kaolinite/chlorite ratios and maxima of poorly crystalline smectite in the clay-mineral record. Kaolinite and poorly crystalline smectite are products of intense chemical weathering. They are injected into the NADW at low latitudes, north of the study area, and advected south. Chlorite, which is stable under cold weathering regimes, is a characteristic mineral of water masses of southern origin. During glacial stages, it is advected north with Southern Component Water (SCW). Above the NADW/SCW depths, kaolinite/chlorite ratios vary only slightly without a significant glacial-interglacial pattern, as measured in a core (GeoB 1712) from 1 000 m deep on the same profile of the Namibian continental slope off Walvis Bay.

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.

Geochemistry of surface sediment cores (Table 4)

The mineralogy and geochemistry of a suite of nine manganese nodules from the South Atlantic have been determined. The Ce/La ratios of the nodules were investigated to see if they could be used as redox indicators to trace the oxygen content of the ambient water mass and the flow path of the Antarctic Bottom Water as has previously been successfully carried out in the Pacific Ocean. The Ce/La ratios of the nodules decrease in the sequence Lazarev Sea, Weddell Sea (10.4 and 9.7)>East Georgia Basin (6.5 and 7.1)>Argentine Basin (5.0), but then increase in the Brazil Basin (6.2) and Angola Basin (9.8 and 15.1). A further decrease was observed in the Cape Basin (7.6). An extremely high Ce/La ratio of 24.4 had already been determined for nodules sampled north of the Nares Abyssal Plain in the western North Atlantic. These data reflect the more complicated pattern of bottom water flow in the South Atlantic than in the South Pacific. The penetration of more oxygenated North Atlantic Deep Water into the South Atlantic accounts for the higher Ce/La ratios in the nodules from the Angola and Brazil basins. Based on this study, the flow path of the Antarctic Bottom Water could only be traced as far north as the Argentine Basin. The unique geochemistry of nodules from the central Angola Basin (high Mn/Fe and Ce/La ratios, high contents of Ni, Cu, Zn and Mo) appears to be a function of the nature of the overlying water mass and of the multiple diagenetic sources of metals to the nodules.

Radionuclides in sediment cores from the higher latitudes

In this thesis it is shown that the cosmogenic radionuclide 10Be proved to be a sensitive stratigraphic tool for sediment cores from the Arctic Ocean with low or negligible content of biogenic carbonate, impeding a reliable 0180 stratigraphy. 10Be enables a stratigraphy of Arctic sediments comparable to the d18O stratigraphy Imbrie et al. [1984] in that high concentration of 10Be are related to interglacial stages in contrast to lower values during glacial periods. To use the °Be profile as dating tool it is necessary to investigate the sources and sinks as well as the pathways of this radiotracer. 10Be is produced in the upper atmosphere and transfered to the earth's surface by dry and wet deposition. Besides the atmospheric component there is an important input of 10Be with the rivers to the Arctic Ocean. I determined depositional 10Be fluxes in the shelf area of the Laptev Sea, which is characterized by a huge input of river water, the continental slope of the Laptev Sea, the central Arctic Ocean and the Norwegian- and Greenland Sea. The depositional 10Be fluxes of (20 ± 5) x 10**6 atoms/cm**2/a in the shelf area of the Laptev Sea are by two orders of magnitude higher than the recent atmospheric input (0.2 - 0.5) x 10**6 atoms/cm**2/a in Greenland. while the fluxes in the central Arctic Ocean are in the same range. Further I developed a model to reconstruct the pathways of radionuclides 230Th, 231Pa and 10Be in high northern latitudes. The modelling results were compared with the measured concentrations in the water column and the recent depositional fluxes. These results show that the recent pathways of these nuclides can be rebuild by this model. Thus we can apply this model to earlier oxygen isotope stages to find out which predominate conditions lead to the determined depositional fluxes.

Descriptions of 104 gravity and piston sediment cores from POLARSTERN expedition ARK-VIII/3 to the Arctic Ocean

Sediment descriptions and lithostratigraphy (chapter 6.4) NANSEN BASIN The upperrnost 20-50 cm of sedirnents in the Nansen Basin norrnally cornprise soft dark brown, brown-grayish and brown clay. Except for the toprnost clay, the four piston cores retrieved, contained quite different lithologies: a rnuddy diarnicton with outsized clasts (PS2157-6), sandy-silt beds alternating with clay beds (PS2159-6), and silty clay beds of brownish and grayish colours (PS2161-3). Core PS2208-3 was retrieved frorn a plateau on a searnount. The plateau was serni-encircled by hills. The upper 250 cm of this core cornprise brown and olive brown clays. Below these are several sandlayers and a 74 cm thick unit of a sandy mud with rnud-clasts up to 20 cm in diameter. GAKKEL RIDGE The uppermost 20-50 cm of sediments on the Gakkel Ridge comprise soft dark brown, brown, grayish brown clay. In most of the cores there are two horizons of brown clay separated by olive brown clay. The upper horizon is darker. The older stratigraphy is rather varied. Core PS2165-1 contains several thin gray sandlsilt layers, probably distal turbidites. The sarne is found in Core PS2167-1. This core also has a thick (approx. 2 rn) coarse grained turbidite containing large rnud clasts and basaltic rock fragrnents. The color of the turbiditic layers is dark gray. There are several horizons of hernipelagic sandylsilty clays with quite a variety in colours; black, gray, olive, brown, yellowish brown and reddish. The colour variation rnay be due to hydrotherrnal activity or provenance or a shift in redox potential. Cores PS2168-2 and PS2169-1 have typical sequences of very dark gray sandy mud with sharp lower boundaries grading upwards into olive brown clay. Below the lower boundary is often a thin (1-2 cm) gray clay layer. AMUNDSEN BASIN The giant box cores (GKG) provided in most cases excellently preserved sedirnent surfaces which consisted in the entire Amundsen Basin of dark brown to dark grayish brown silty clay with few dropstones and common calcareous microfossils (foraminifers and calcareous nannofossils). The brown and grayish brown color of the sediment surface is a result of the oxidizing conditions at the seafloor due to the rapid renewal of the bottom water rnasses. Planktic forarninifers and calcareous nannofossils are relatively frequent and well preserved despite the rernote location of the basin and its water depths of >4000 rn. Srnear slide descriptions have shown that the surface sedirnents consist dorninantly of clays to silty rnuds with clay rninerals and quartz as the rnost important constituents. The coarse fractions contained besides planktic and benthic forarninifers and coarse clastic rnaterials, rare bivalves, dropstones and mud clasts. The Station PS2190 at the North Pole is a particular good exarnple of the type of sedirnents deposited at the sea floor surface of the Arnundsen Basin, with hornogenous dark brown soft clay covering a sedirnent sequence of highly variable cornposition. Nurnerous giant box cores also provide insight into the detailed lithostratigraphy of the upperrnost sedirnent layers. Twelve box cores have been collected frorn the Arnundsen Basin. Below the youngest unit of 5-20 crn thick silty clays deposits of variable stratigraphies have been found, rnostly consisting of clays or silty clays. In a few instances turbidites have been observed. Benthic forarninifers have not been found in the surface sedirnents. Other fossils were extrernely rare. Bioturbation is weakly developed on all stations. Benthic anirnals seern to live only in and on the upperrnost 2 cm of the uppermost sediment layer. They cornprise amphipods (on all stations) and holothurians, bryozoans, polychaetes, and porifers at one station each. LOMONOSOV RIDGE Sediments from the Lomonosov Ridge show a variety of colors and textures. Following smear slide analyses they are composed mostly of clay minerals and quartz with mica and feldspars, especially in the siltier and sandier parts. Volcanic glass, microcrystalline carbonate, opaque minerals and green amphibole are occasional accessories. The sediments from the Lomonosov Ridge show a noticeable difference from sediments collected from the surrounding basins. Lomonosov Ridge sediments are richer in silt and sand than basin sediments. Occasional turbidites occur in ridge sediments but these must be of entirely local origin. The ridge sediments include frequent layers of "cottage cheese" texture made up of what appear to be small, angular mud clasts of a variety of colors.

Detrital layer thickness in 12 varved sediment cores in Lake Mondsee and related flood events AD1976-2005

A succession of 23 sub-millimetre to maximum 12-mm-thick, mostly flood-triggered detrital layers, deposited between 1976 and 2005, was analysed in 12 varved surface sediment cores from meso-scale peri-alpine Lake Mondsee applying microfacies and high-resolution micro X-ray fluorescence analyses. Detailed intrabasin comparison of these layers enabled identification of (i) different source areas of detrital sediments, (ii) flood-triggered sediment flux and local erosion events, and (iii) seasonal differences of suspended flood sediment distribution within the lake basin. Additional calibration of the detrital layer record with river discharge and precipitation data reveals different empirical thresholds for flood layer deposition for different parts of the basin. At proximal locations detrital layer deposition requires floods exceeding a daily discharge of 40 m**3/s, whereas at a location 2 km more distal an hourly discharge of 80 m**3/s and at least 2 days of discharge above 40 m**3/s are necessary. Furthermore, we observe a better correlation between layer thickness and flood amplitude in the depocentre than in distal and proximal areas of the basin. Although our results are partly site-specific, the applied dual calibration approach is suitable to precisely decipher flood layer formation processes and, thereby, improve the interpretation of long flood time series from lake sediments.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.