Clay mineral analysis of sediments from the Amundsen Sea

The Amundsen Sea embayment is a probable site for the initiation of a future collapse of the West Antarctic Ice Sheet. This paper contributes to a better understanding of the transport pathways of subglacial sediments into this embayment at present and during the last glacial period. It discusses the clay mineral composition of sediment samples taken from the seafloor surface and marine cores in order to decipher spatial and temporal changes in the sediment provenance. The most striking feature in the presentday clay mineral distribution is the high concentration of kaolinite, which is mainly supplied by the Thwaites Glacier system and indicates the presence of hitherto unknown kaolinite-bearing sedimentary strata in the hinterland, probably in the Byrd Subglacial Basin. The main illite input is via the Pine Island Glacier. Smectite originates from the erosion of volcanic rocks in Ellsworth Land and western Marie Byrd Land. The clay mineral assemblages in diamictons deposited during the last glacial period are distinctly different from those in corresponding surface sediments. This relationship indicates that glacial sediment sources were different from modern ones, which could reflect changes in the catchment areas of the glaciers and ice streams.

(Table 1) Shell mass and chemistry of Globigerinoides sacculifer

Using bathymetric transects of surface sediments underlying similar sea surface temperatures but exposed to increasing dissolution, we examined the processes which affect the relationship between foraminiferal Mg/Ca and d18O. We found that Globigerinoides saccculifer calcifies over a relatively large range of water depth and that this is apparent in their Mg content. On the seafloor, foraminiferal Mg/Ca is substantially altered by dissolution with the degree of alteration increasing with water depth. Selective dissolution of the chamber calcite, formed in surface waters, shifts the shell's bulk Mg/Ca and d18O toward the chemistries of the secondary crust acquired in colder thermocline waters. The magnitude of this shift depends on both the range of temperatures over which the shell calcified and the degree to which it is subsequently dissolved. In spite of this shift the initial relationship between Mg/Ca and d18O, determined by their temperature dependence, is maintained. We conclude that paired measurements of d18O and Mg/Ca can be used for reconstructing d18Owater, though care must be taken to determine where in the water column the reconstruction applies.

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.

Relative abundance of prokaryotes in sediments of the Håkon Mosby mud volcano (Z1-Z3, all habitats)

CARD-FISH was performed as previously described in Ruff et al., (2013; doi:10.1371/journal.pone.0072627) with the following modifications. 4-6 µl of 25-fold diluted sediment were used for filtration. Archaeal cell walls were permeabilized with 0.1M HCl for 2 min to detect ANME-3 cells, or Proteinase K solution (15 µg ml-1 (Merck, Darmstadt, Germany) in 0.05 M EDTA (pH 8), 0.1 M Tris-HCl (pH 8), 0.5 M NaCl) for 2-4 min at room temperature for all other archaea. Bacterial cell walls were permeabilized with lysozyme solution (1000kU/ml) for 60 min at 37°. Cells were stained with DAPI (1µg/ml), embedded in mounting medium and counted in 40-60 independent microscopic fields using an Axiophot II epifluorescence microscope (Carl Zeiss, Jena, Germany).

(Table 2) Zn/Si ratios for sponge spicules from sediment core samples

The zinc concentration of siliceous sponge spicules was determined from spicules recovered from four sediment cores spanning the last 160 kyr, from the Campbell Plateau region southeast of New Zealand. Zinc/Si results showed little difference between Holocene and glacial aged spicules. An increase in Zn/Si was observed for core Y14, where Zn/Si peaked at about 0.6 ?mol/mol during marine isotope stages 5a-5b. To better understand the role carbon export has on sponge Zn/Si, we explored the strong relationship observed between surficial sediment particulate organic carbon (POC) and the Zn/Si of sponge silica and related this to sediment trap POC flux estimates. Conversion of the Zn/Si records to benthic POC fluxes suggests that there has been little change in the amount of POC reaching Campbell Plateau sediments over the past 30 kyr. These results suggest that surface productivity over the Campbell Plateau has remained relatively low over the past 160 kyr and suggests that glacial productivity was not significantly higher than the present day. Finally, this work reveals that living marine sponges appear to act as the biological equivalents of moored sediment traps, recording the flux of POC to the seafloor by archiving zinc associated with sinking POC in the growing silica skeleton.

LAPMv2 - software for underwater large-area photo-mosaicking

LAPMv2 is a research software solution specifically developed to allow marine scientists to produce geo-referenced visual maps of the seafloor, known as mosaics, from a set of underwater images and navigation data. LAPMv2 has a graphical user interface that guides the user through the different steps of the mosaicking workflow. LAPMv2 runs on 64-bit Windows, MacOS X and Linux operating systems. There are two versions for each operating system: (1) the WEB-installers (lightweight but require an internet connection during the installation) and (2) the MCR installers (large files but can be installed on computer without internet-connection). The user manual explains how to install and start the program on the different operating systems. Go to http://www.lapm.eu.com for further information about the latest versions of LAPMv2.

Benthic organic carbon flux and oxygen penetration depth in the Southern Ocean

For the investigation of organic carbon fluxes reaching the seafloor, oxygen microprofiles were measured at 145 sites in different sub-regions of the Southern Ocean. At eleven sites, an in situ oxygen microprofiler was deployed for the measurement of oxygen profiles and the calculation of organic carbon fluxes. At four sites, both in situ and ex situ data were determined for high latitudes. Based on this dataset as well as on previous published data, a relationship was established for the estimation of fluxes derived by ex situ measured O2 profiles. The fluxes of labile organic matter range from 0.5 to 37.1 mgC m**2/day. The high values determined by in situ measurements were observed in the Polar Front region (water depth of more than 4290 m) and are comparable to organic matter fluxes observed for high-productivity, upwelling areas like off West Africa. The oxygen penetration depth, which reflects the long-term organic matter flux to the sediment, was correlated with assemblages of key diatom species. In the Scotia Sea (~3000 m water depth), oxygen penetration depths of less than 15 cm were observed, indicating high benthic organic carbon fluxes. In contrast, the oxic zone extends down to several decimeters in abyssal sediments of the Weddell Sea and the southeastern South Atlantic. The regional pattern of organic carbon fluxes derived from micro-sensor data suggest that episodic and seasonal sedimentation pulses are important for the carbon supply to the seafloor of the deep Southern Ocean.

(Table 2) Concentrations and D/L values for three amino acids in bulk foraminifera from ODP Sites 182-1126 and 182-1127

A number of studies have shown that methanogens are active in the presence of sulfate under some conditions. This phenomenon is especially exemplified in carbonate sediments of the southern Australian continental margin. Three sites cored during Ocean Drilling Program (ODP) Leg 182 in the Great Australian Bight have high concentrations of microbially-generated methane and hydrogen sulfide throughout almost 500 m of sediments. In these cores, the sulfate-reducing and methanogenic zones overlap completely; that is, the usual sulfate-methane transition zone is absent. Amino acid racemization data show that the gassy sediments consist of younger carbonates than the low-gas sites. High concentrations of the reduced gases also occur in two ODP sites on the margin of the Bahamas platform, both of which have similar sedimentary conditions to those of the high-gas sites of Leg 182. Co-generation of these reduced gases results from an unusual combination of conditions, including: (1) a thick Quaternary sequence of iron-poor carbonate sediments, (2) a sub-seafloor brine, and (3) moderate amounts of organic carbon. The probable explanation for the co-generation of hydrogen sulfide and methane in all these sites, as well as in other reported environments, is that methanogens are utilizing non-competitive substrates to produce methane within the sulfate-reducing zone. Taken together, these results form the basis of a new model for sulfate reduction and methanogenesis in marine sediments. The biogeochemical end-members of the model are: (1) minimal sulfate reduction, (2) complete sulfate reduction followed by methanogenesis, and (3) overlapping sulfate reduction and methanogenesis with no transition zone.

(Table 1) Determined and theoretical chemical composition of thaumasite of ODP Hole 135-841B

Hole 841B was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The hole penetrated a roughly 500-m-thick series of Miocene volcanic sediments with a number of basaltic to andesitic units (sills?) varying in thickness between 7 cm and 17 m. The volcanics are slightly to moderately altered and contain analcite, chabazite, natrolite-thompsonite, heulandite (?), prehnite, and quartz as secondary phases. In addition, thaumasite [Ca3Si(OH)6 * 12H2O](SO4)(CO3) was identified in the altered sequence. Sulfur isotope data of two thaumasite separates (+23.5 per mil and +21.1 per mil d34S) indicate a seawater origin of the sulfate sulfur. It is suggested that thaumasite is a product of low-temperature (<60 °C), seawater-derived CaCl2-rich fluids that were almost identical in composition to those presently circulating in the sub-seafloor.

Middle Eocene Fe and Ca counts, Ca/Fe ratios, revised splices and astronomical age models form different Sites of IODP Exp342

Accurate age models are a tool of utmost important in paleoclimatology. Constraining the rate and pace of past climate change are at the core of paleoclimate research, as such knowledge is crucial to our understanding of the climate system. Indeed, it allows for the disentanglement of the various drivers of climate change. The scarcity of highly resolved sedimentary records from the middle Eocene (Bartonian - Lutetian Stages; 47.8 - 37.8 Ma) has led to the existence of the "Eocene astronomical time scale gap" and hindered the establishment of a comprehensive astronomical time scale (ATS) for the entire Cenozoic. Sediments from the Newfoundland Ridge drilled during Integrated Ocean Drilling Program (IODP) Expedition 342 span the Eocene gap at an unprecedented stratigraphic resolution with carbonate bearing sediments. Moreover, these sediments exhibit cyclic lithological changes that allow for an astronomical calibration of geologic time. In this study, we use the dominant obliquity imprint in XRF-derived calcium-iron ratio series (Ca/Fe) from three sites drilled during IODP Expedition 342 (U1408, U1409, U1410) to construct a floating astrochronology. We then anchor this chronology to numerical geological time by tuning 173-kyr cycles in the amplitude modulation pattern of obliquity to an astronomical solution. This study is one of the first to use the 173-kyr obliquity amplitude cycle for astrochronologic purposes, as previous studies primarily use the 405-kyr long eccentricity cycle as a tuning target to calibrate the Paleogene geologic time scale. We demonstrate that the 173-kyr cycles in obliquity's amplitude are stable between 40 and 50 Ma, which means that one can use the 173-kyr cycle for astrochronologic calibration in the Eocene. Our tuning provides new age estimates for magnetochron reversals C18n.1n - C21r and a stratigraphic framework for key sites from Expedition 342 for the Eocene. Some disagreements emerge when we compare our tuning for the interval between C19r and C20r with previous tuning attempts from the South Atlantic. We therefore present a revision of the original astronomical interpretations for the latter records, so that the various astrochronologic age models for the middle Eocene in the North- and South-Atlantic are consistent.

Benthic foraminifera of the Red Sea

The distribution of living (Rose Bengal-stained), dead and fossil benthic foraminifera was investigated in six short cores (multicores, 30-32 cm total length) recovered from the central Red Sea. The ecological preferences as well as the relationship between the live and dead/fossil assemblages (preserved down-core) were examined. The sites, located along a W-E profile and between the depth of 366 and 1782 m, extend from the center of the oxygen minimum zone (OMZ, ~200-650 m), through its margin at ~600 m, and down to the well-aerated deep-water environment. Live (Rose-Bengal stained) and coexisting dead foraminifera were studied in the upper 5 cm of each of the sites, and the fossil record was studied down to ~32 cm. Q-mode Principal Component Analysis was used and four distinct foraminiferal fossil assemblages were determined. These assemblages follow different water mass properties. In the center of the OMZ, where the organic carbon content is highest and the oxygen concentration is lowest (<=0.5 ml O2/l), the Bolivina persiensis-Bulimina marginata-Discorbinella rhodiensis assemblage dominates. The slightly more aerated and lower organic-carbon-content seafloor, at the margin of the OMZ, is characterized by the Neouvigerina porrecta-Gyroidinoides cf. G. soldanii assemblage. The transitional environment, between 900-1200 m, with its well-aerated and oligotrophic seafloor, is dominated by the Neouvigerina ampullacea-Cibicides mabahethi assemblage. The deeper water (>1500 m), characterized by the most oxygenated and oligotrophic seafloor conditions, is associated with the Astrononion sp. A-Hanzawaia sp. A assemblage. Throughout the Red Sea extremely high values of temperature and salinity are constant below ~200 m depth, but the flux of organic matter to the sea floor varies considerably with bathymetry and appears to be the main controlling factor governing the distribution pattern of the benthic foraminifera. Comparison between live and the dead/fossil assemblages reveals a large difference between the two. Processes that may control this difference include species-specific high turnover rates, and preferential predation and loss of fragile taxa (either by chemical or microbial processes). Significant variations in the degree of loss of the organic-cemented agglutinants were observed down core. This group is preserved down to 5-10 cm at the shallow OMZ sites and down to greater depths at well-aerated and oligotrophic sites. The lower rate of disintegration of these forms, in the deeper locations of the Red Sea, may be related to low microbial activity. This results in the preservation of increasing numbers of organic-cemented shells down-core.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

(Table 1) Stable nitrogen isotopes of ammonium in interstitial waters from ODP Site 164-997

Ammonium (NH4+) concentration profiles in piston-core sediments of the Carolina Rise and Blake Ridge generally have linear concentration profiles within the sulfate reduction zone (Borowski, 1998). Deep Sea Drilling Project (DSDP) Site 533, located on the Blake Ridge, also displayed a linear ammonium concentration profile through the sulfate reduction zone and the profile linearity continues into the upper methanogenic zone to a depth of ~200 meters below seafloor (mbsf), where the first methane gas hydrates probably occur (Jenden and Gieskes, 1983, doi:10.2973/dsdp.proc.76.114.1983; Kvenvolden and Barnard, 1983, doi:10.2973/dsdp.proc.76.106.1983). Sediments from the Ocean Drilling Program (ODP) Leg 164 deep holes (Sites 994, 995, and 997) also exhibit linear ammonium profiles above the top of the gas hydrate zone (~200 mbsf) (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996). We hypothesized that a possible cause of linear ammonium profiles was diffusion of ammonium from a concentrated ammonium source at depth. We further reasoned that if this ammonium were produced by microbial fermentation reactions at depth, that a comparison of the nitrogen isotopic composition of sedimentary organic nitrogen and the nitrogen with pore-water ammonium would test this hypothesis. Convergence with depth of d15N values of the nitrogen source (sedimentary organic matter) and the nitrogen product (dissolved NH4+) would strongly suggest that ammonium was produced within a particular depth zone by microbial fermentation reactions. Here, we report d15N values of pore-water ammonium from selected interstitial water (IW) samples from Site 997, sampled during ODP Leg 164.

Characterization of the defined MDC types and compilation of MDC initiation times (excel-file 19 kB)

Mud accumulates on continental shelves under a variety of environmental conditions and results in a diverse formation of mud depocenters (MDCs). Their three-dimensional architectures have been in the focus of several recent studies. Due to some terminological confusion concerning MDCs, the present study sets out to define eight individual MDC types in terms of surface sediment distribution and internal geometry. Under conditions of substantial sediment supply, prodeltas (distal zones off river deltas; triangular sheets), subaqueous deltas (disconnected from deltas by strong normal-to-shore currents; wedge-like clinoforms), and mud patches (scattered distribution) and mud blankets (widespread covers) are formed. Forced by hydrodynamic conditions, mud belts in the strict sense (detached from source; elongated bodies), and shallow-water contourite drifts (detached from source; growing normal to prevailing current direction; triangular clinoforms) develop. Controlled by local morphology, mud entrapments (in depressions, behind morphological steps) and mud wedges (triangular clinoforms growing in flow direction) are deposited. Shelf mud deposition took place (1) during early outer-shelf drowning (~14 ka), (2) after inner-shelf inundation to maximum flooding (9.5-6.5 ka), and (3) in sub-recent times (<2 ka). Subsequent expansion may be (1) concentric, in cases where the depocenter formed near the fluvial source, (2) uni-directional, extending along advective current transport paths, and (3) progradational, forming clinoforms that grow either parallel or normal to the bottom current direction. Classical mud belts may be initiated around defined nuclei, the remote sites of which are determined by seafloor morphology rather than the location of the source. From a stratigraphic perspective, mud depocenters coincide with sea-level highstand-related, shelf-wide condensed sections. They often show a conformable succession from transgressive to highstand systems tract stages.

Ketones in hydrothermal petroleums and sediments from Guaymas Basin

The polar compound (NSO) fractions of seabed petroleums and sediment extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry. The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolysates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore samples are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds correlated with samples exhibiting a high degree of thermal maturity. Several homologous series of related ketone isomers are enriched in the interiors of the hydrothermal vent samples or in hydrothermally-altered sequences of the downcore sediments (DSDP Holes 477 and 481A). The n-alkanones range in carbon number from C11 to C33 with a Cmax from 14 to 23, distributions that are similar to those of the n-alkanes. The alkan-2-ones are usually in highest concentrations, with lower amounts of 3-, 4-, 5-, 6-, 7- (and higher) alkanones, and they exhibit no carbon number preference (there is an odd carbon number preference of alkanones observed for downcore samples). The alkanones are enriched in the interiors of the hydrothermal vent spires or in downcore hydrothermally-altered sediments, indicating an origin at depth or in the hydrothermal fluids and not from an external biogenic deposition. Minor amounts of C13 and C18 isoprenoid ketones are also present. Simulation of the natural hydrothermal alternation process by laboratory hydrous pyrolysis techniques provided information regarding the mode of alkanone formation. Hydrous pyrolysis of n-C32H66 at 350°C for 72 h with water only or water with inorganic additives has been studied using a stainless steel reaction vessel. In each experiment oxygenated hydrocarbons, including alkanones, were formed from the n-alkane. The product distributions indicate a reaction pathway consisting of n-alkanes and a-olefins as primary cracking products with internal olefins and alkanones as secondary reaction products. Hydrous pyrolyses of Messel shale spiked with molecular probes have been performed under similar time and temperature constraints to produce alkanone distributions like those found in the hydrothermal vent petroleums.