Sulphur geochemistry of interstitial waters and squeeze cake samples of ODP Leg 181 sites

Seventy-nine interstitial water samples from six sites (Ocean Drilling Program Sites 1119-1124) from the southwestern Pacific Ocean have been analyzed for stable isotopes of dissolved sulfate (34S), along with major and minor ions. Sulfate from the interstitial fluids (34S values between +20.7 and +57.5 vs. the Vienna-Canyon Diablo troilite standard) was enriched in 34S with respect to modern seawater (34S +20.6), indicating that differing amounts of microbial sulfate reduction took place at all investigated sites. Microbial sulfate reduction was found at all sites, the intensity depending on the availability of organic matter, which is controlled by paleosedimentation conditions (e.g., sedimentation rate and presence of turbidites). In addition, total reduced inorganic sulfur (essentially pyrite) as a product of microbial sulfate reduction was quantified in selected sediments from Site 1119.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Recent distribution and accumulation of organic carbon on the continental margin west off Spitsbergen

The study compiles the controlling factors for organic matter sedimentation patterns from a suite of organogeochemical parameters in surface sediments off Spitsbergen and direct seabed observations using a Remotely Operated Vehicle (ROV). In addition we assess its storage rates as well as the potential of carbon sinks on the northwestern margin of the Barents Sea with short sediment cores from a selected fjord environment (Storfjord). While sedimentation in the fjords is mainly controlled by river/meltwater discharge and coastal erosion by sea ice/glaciers resulting in high supply of terrigenous organic matter, Atlantic water inflow, and thus enhanced marine organic matter supply, characterizes the environment on the outer shelf and slope. Local deviations from this pattern, particularly on the shelf, are due to erosion and out washing of fine-grained material by bottom currents. Spots dominated by marine productivity close to the island have been found at the outer Isfjord and west off Prins Karls Forland as well as off the Kongsfjord/Krossfjord area and probably reflect local upwelling of nutrient-rich Atlantic water-derived water masses. Accumulation rates of marine organic carbon as well as reconstructed primary productivities decreased since the middle of the last century. Negative correlation of the Isfjord temperature record with reconstructed productivities in the Storfjord could be explained by a reduced annual duration of the marginal ice zone in the area due to global warming. Extremely high accumulation rates of marine organic carbon between 5.4 and 17.2 g/m**2/yr mark the Storfjord area, and probably high-latitude fjord environments in general, as a sink for carbon dioxide.

Chemical composition of bottom sediments from the northern part of the Deryugin Trough, Sea of Okhotsk

Distribution trace element contents in the upper (up to 5 m) Holocene-Upper Pleistocene sediment layer along the northern and southern sublatitudinal profiles in the northern part of the Deryugin Trough is discussed. Mathematical processing of chemical analysis data has been made. On the basis of the cluster analysis 16 elements have been combined into 5 geochemical groups. Two of them (1 - Ag-Mo group and 2 - Mn-Ba-Ni-Sr group) were considered in detail. Analysis of Ag and Mo distributions in the sediments and findings of molybdenite permitted to conclude that enrichment of the sediments by these elements resulted from edaphic washing of magmatic rocks containing Ag-Mo mineralization and probably located on the northwestern slope of the Deryugin trough. The second geochemical group is most likely connected with hydrothermal barite mineralization found in the northeastern part of the Deryugin trough. Considering Mn distribution in bottom sediment cores supply of Mn was pulsating. This allows concluding that during Holocene - Late Pleistocene three cycles of hydrothermal activity occurred in the Deryugin Trough, and the most intensive one was in Holocene.

Seal census raw data during POLARSTERN expedition ANT-XV/3 (PS48)

The density, species composition, and possible change in the status of pack ice seals within the Weddell Sea were investigated during the 1997/1998 summer cruise of the RV "Polarstern" (ANT-XV/3, PS48). Comparisons were made with previous surveys in the Weddell Sea where it was assumed that all seals were counted in a narrow strip on either side oft he ship or aircraft. A total of 15 aerial censuses were flown during the period 23 January - 7 March 1998 in the area bounded by 07°08' and 45°33' West longitude. The censused area in the eastern Weddell Sea was largely devoid of pack ice while a well circumscribed pack ice field remained in the western Weddell Sea. A total of 3,636 (95.4 %) crabeater seals, 21 (0.5 %) Ross seals, 45 (1.2 %) leopard seals and 111 (2.9 %) Weddell seals were observed on the pack ice during a total of 1,356.57 linear nautical miles (244.2 nm) of transect line censused. At a mean density of 21.16 1/nm**2 over an area of 244.2 nm, it is the highest densities on record for crabeater seals, density of up to 411.7 1/nm**2 being found in small areas. The overall high densities of seals (30.18 1/nm**2) recorded for the eastern Weddell Sea (27.46 1/nm**2, 0.27 1/nm**2, and 0.66 1/nm**2 for crabeater, leopard and Weddell seals respectively) is a consequence of the drastically reduced ice cover and the inverse relationship that exists between cover and seal densities. Ross seal densities (0.08 1/nm**2) were the lowest on record fort the area. It is suggested that seals largely remain within the confines of the pack ice despite seasonal and annual changes in its distribution. Indications are that in 1998 the El Niño has manifested itself in the Weddell Sea, markedly influencing the density and distribution of pack ice seals.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Nutrients and oxygen concentrations measured in water samples from the North Atlantic during the James Cook cruise JC087 in March 2013

Analysis for micro-molar concentrations of nitrate and nitrite, nitrite, phosphate, silicate and ammonia was undertaken on a SEAL Analytical UK Ltd, AA3 segmented flow autoanalyser following methods described by Kirkwood (1996). Samples were drawn from Niskin bottles on the CTD into 15ml polycarbonate centrifuge tubes and kept refrigerated at approximately 4oC until analysis, which generally commenced within 30 minutes. Overall 23 runs with 597 samples were analysed. This is a total of 502 CTD samples, 69 underway samples and 26 from other sources. An artificial seawater matrix (ASW) of 40g/litre sodium chloride was used as the inter-sample wash and standard matrix. The nutrient free status of this solution was checked by running Ocean Scientific International (OSI) low nutrient seawater (LNS) on every run. A single set of mixed standards were made up by diluting 5mM solutions made from weighed dried salts in 1litre of ASW into plastic 250ml volumetric flasks that had been cleaned by washing in MilliQ water (MQ). Data processing was undertaken using SEAL Analytical UK Ltd proprietary software (AACE 6.07) and was performed within a few hours of the run being finished. The sample time was 60 seconds and the wash time was 30 seconds. The lines were washed daily with wash solutions specific for each chemistry, but comprised of MQ, MQ and SDS, MQ and Triton-X, or MQ and Brij-35. Three times during the cruise the phosphate and silicate channels were washed with a weak sodium hypochlorite solution.

Percentage of cultured cell-populations that stained positively and/or negatively for apoptotic markers cleaved caspase-3 and cleaved PARP, following DNA damage treatments induced by doxorubicin and TNF-alpha co-treatments

The present dataset contains the source data for Figure 2B of Tentner et al. (2012). The data shows the percentage of cultured cell-populations that stained positively and/or negatively for apoptotic markers cleaved caspase-3 and cleaved PARP, following DNA damage treatments induced by various doses of doxorubicin (0, 2 and 10 µmole/L) in the presence (100 ng/mL) or absence (0 ng/mL) of TNF-alpha co-treatment. For the six treatment conditions investigated, cell counts were made by flow cytometry at times 6, 12, 24, and 48 h following treatment; CULTURE DETAILS: U2OS cells were obtained from ATCC were maintained at 21% oxygen and 5% CO2 in Dulbecco's modified Eagle medium supplemented with 10% fetal bovine serum, penicillin, streptomycin, 2mM L-glutamine, and used within 15-20 passages. The first thymidine block was released by washing the plates three times with PBS, and incubating them in fresh thymidine-free media for 12 h. A second thymidine block was then performed by re-addition of thymidine to 2.5 mM followed by incubation for an additional 18 h. Media was aspirated, plates were washed 3 with PBS, and replaced with fresh media in the presence or absence of 10 mM aphidicolin; ANALYSIS DETAILS: See supplementary journal publication; RESULT: The authors of the supplementary journal publication conclude that TNF enhances dose-dependent cell death following doxorubicin-induced DNA damage with minimal affect on dose-dependent cell-cycle arrest.

Niche differentiation among mat-forming, sulfide-oxidizing bacteria in chemosynthetic ecosystems of the Nile Deep Sea Fan (Eastern Mediterranean Sea)

Sulfidic muds of cold seeps on the Nile Deep Sea Fan are populated by different types of mat-forming sulfide-oxidizing bacteria. The predominant sulfide oxidizers of three different mats were identified by microscopic and phylogenetic analyses as (i) Arcobacter species producing cotton-ball-like sulfur precipitates, (ii) large filamentous sulfur bacteria including Beggiatoa species, or (iii) single, spherical cells resembling Thiomargarita species. High resolution in situ microprofiles revealed different geochemical settings selecting for different mat types. Arcobacter mats occurred where oxygen and sulfide overlapped at the bottom water interface. Filamentous sulfide oxidizers were associated with non-overlapping, steep gradients of oxygen and sulfide. A dense population of Thiomargarita was favored by temporarily changing supplies of oxygen and sulfide. These results indicate that the decisive factors in selecting for different mat-forming bacteria within one deep-sea province are spatial or temporal variations in energy supply. Furthermore, the occurrence of Arcobacter spp.-related 16S rRNA genes in the sediments below all three types of mats, as well as on top of brine lakes of the Nile Deep Sea Fan, indicates that this group of sulfide oxidizers can switch between different life modes depending on the geobiochemical habitat setting.

Environmental characteristics and gas composition of Lost Hammer, Canadian Arctic

We report the first microbiological characterization of a terrestrial methane seep in a cryo-environment in the form of an Arctic hypersaline (~24% salinity), subzero (-5 C), perennial spring, arising through thick permafrost in an area with an average annual air temperature of -15 C. Bacterial and archaeal 16S rRNA gene clone libraries indicated a relatively low diversity of phylotypes within the spring sediment (Shannon index values of 1.65 and 1.39, respectively). Bacterial phylotypes were related to microorganisms such as Loktanella, Gillisia, Halomonas and Marinobacter spp. previously recovered from cold, saline habitats. A proportion of the bacterial phylotypes were cultured, including Marinobacter and Halomonas, with all isolates capable of growth at the in situ temperature (-5 C). Archaeal phylotypes were related to signatures from hypersaline deep-sea methane-seep sediments and were dominated by the anaerobic methane group 1a (ANME-1a) clade of anaerobic methane oxidizing archaea. CARD-FISH analyses indicated that cells within the spring sediment consisted of ~84.0% bacterial and 3.8% archaeal cells with ANME-1 cells accounting for most of the archaeal cells. The major gas discharging from the spring was methane (~50%) with the low CH4/C2 + ratio and hydrogen and carbon isotope signatures consistent with a thermogenic origin of the methane. Overall, this hypersaline, subzero environment supports a viable microbial community capable of activity at in situ temperature and where methane may behave as an energy and carbon source for sustaining anaerobic oxidation of methane-based microbial metabolism. This site also provides a model of how a methane seep can form in a cryo-environment as well as a mechanism for the hypothesized Martian methane plumes.

Planktonic foraminifera stratigraphy and datums of ODP Site 184-1143 and Hole 184-1146A, South China Sea

The biostratigraphy of Miocene-age sediment samples recovered from Ocean Drilling Program Sites 1143 and 1146, South China Sea, is presented. The preservation of the planktonic foraminifers recovered from both sites varies widely, from poor to very good. The volume of biogenic sediment in the >63-µm size fraction also varies considerably, with many samples being dominated by mud. In comparison to shipboard biostratigraphy, based on core catcher analyses with a depth resolution of ~10 m, we analyzed samples from the two stratigraphic columns every 2-3 m (~45- to 93-k.y. resolution). The placement of planktonic foraminifer zonal boundaries was made at a resolution of ~1.5 m at Site 1146 and ~3.0 m at Site 1143. The higher resolution has resulted in significant changes in biostratigraphic zonal boundary locations compared to shipboard results. For the time interval of 5.54-10.49 Ma, the changes in zonation reveal similar age-depth models at both sites, with three segments of changing sedimentation rate through the upper Miocene, though the differences in sedimentation rates at Site 1146 are subtler than those at Site 1143. The boundary between lithologic Units II and III at Site 1146 corresponds to a sharp change in sedimentation rate (58 to 21 m/m.y.) at 15.1 Ma (the first occurrence of Orbulina suturalis). At this site, the interval from 16.4 to 15.1 Ma is characterized by very high mass accumulation rates in the noncarbonate fraction. Above this interval the carbonate fraction becomes increasingly important in the sediment flux to the South China Sea. At Site 1143, sedimentation rates increase from 8 to 99 m/m.y. at 8.6 Ma. This corresponds to a dramatic increase in both carbonate and noncarbonate mass accumulation rates at the site, but no change in lithology.

Chemical composition in phosphate materials from the ocean floor

Content, distribution patterns, and speciation of Cl in phosphorites and bone phosphate from the ocean floor, as well as in a set of samples from the land are studied. Total Cl content varies from 0.05 to 4.25% in phosphorites and from 2.48 to 2.75% in recent phosphate-bearing sediments. Recent phosphorites are enriched in Cl relative to ancient ones. Bound Cl content (not extractable by washing), which increases with lithification, varies from 0.17 to 0.60% in ocean and land phosphorites and from 0.02% to 1.30% in bone phosphate. Na content in most samples is higher relative to Na of NaCl due to its incorporation into the crystal lattice of apatite. However, the opposite relationship is observed in some samples indicating partial Cl incorporation into the anion complex of phosphate. Behavior of Cl in phosphorites from the present-day ocean floor is controlled by early diagenetic processes, whereas the role of weathering, catagenesis, and hydrogeological factors may be crucial for phosphorites on continents.