Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Biogenic silica in ODP Hole 105-647A

Eocene to Holocene sediments from Ocean Drilling Program (ODP) Site 647 (Leg 105) in the southern Labrador Sea, approximately 200 km south of the Gloria Drift deposits, were investigated for their biogenic silica composition. Three sections of different diagenetic alteration products of primary siliceous components could be distinguished: (1) opal-A was recorded in the Miocene and the early Oligocene time intervals with strongly corroded siliceous skeletons in the Miocene and mostly well preserved biogenic opal in the early Oligocene; (2) opal-CT precipitation occurs between 250-440 meters below seafloor (mbsf) (earliest Oligocene to late Eocene); (3) between 620-650 mbsf (early/middle Eocene), biogenic opal was transformed to clay minerals by authigenesis of smectites. Using accumulation rates of biogenic opal, paleoproductivity was estimated for the early Oligocene to late Eocene interval. A maximum productivity of biogenic silica probably occurred between 35.5 and 34.5 Ma (early Oligocene). No evidence for opal sedimentation during most of middle Eocene was found. However, at the early/middle Eocene boundary (around 52 Ma), increased opal fluxes were documented by diagenetic alteration products of siliceous skeletons.

Secondary minerals and geochemistry at DSDP Legs 68 and 69

Basalt samples recovered during DSDP Legs 68, 69, and 70 from a 550-meter-thick section in two holes near the Costa Rica Rift (Holes 501 and 504B) were found to contain the following secondary minerals: trioctahedral and dioctahedral smectite, chlorite, mixed-layer clays, talc, hematite, pyrite, foujasite, phillipsite, analcime, natrolite, thomsonite, gyrolite, aragonite, calcite, anhydrite, chalcocite, Fe-hydrosilicate, okenite, apophyllite, actinolite, cristobalite, quartz, and magnesite. A less positive identification of bismutite was made. A mineral rich in Mn and minerals with strong reflections at 12.9 Å and 3.20 Å remain unidentified. Trioctahedral smectite replaces glass and olivine in the basalt groundmass. The other secondary minerals occur in veins. The distribution of the secondary minerals in the basalt section shows both hydrothermal and oxidizing-nonoxidizing zonation. Most of the secondary minerals formed under alkaline, nonoxidizing conditions at temperatures up to 120° C. An acidic regime probably existed in the lowest portion of basalt. Oxidative diagenesis followed nonoxidative diagenesis in the upper part of the section. Oxidative diagenesis is characterized by the absence of celadonite, rare occurrences of dioctahedral smectite, and widespread hematite and phillipsite.

Cenozoic clay mineralogy of DSDP Sites 93-604 and 93-605

Examination of the clay mineralogy of Cenozoic sediment samples from Deep Sea Drilling Project Sites 604 and 605 on the upper continental rise off New Jersey indicates that sediment deposition of two different clay mineral facies has occurred. These sites are marked by Paleogene deposition of illite with subordinate kaolinite and smectite covarying in inverse proportion, and by Neogene deposition dominated by illite with subordinate kaolinite and chlorite. Leg 93 results agree with the clay mineral facies proposed by Hathaway (1972), which defined a "Northern facies" consisting of illite and chlorite, with feldspar and hornblende, from erosion of rocks north of Cape Hatteras, and a "Southern facies" composed of smectite, kaolinite, and mixed-layer illite-smectites. Neogene and Quaternary sediments at Sites 604 and 605 contain the "Northern facies," and Paleogene sediments contain the "Southern facies" minerals. Feldspar is exclusively found in Neogene-Quaternary sediments, as is the majority of the amphibole found in these samples. Widespread Paleogene volcanic source materials are suggested by the presence of smectite throughout the early Paleocenemiddle Eocene sediments recovered at Site 605. The clay mineral stratigraphy at Leg 93 sites is comparable to the record at nearby DSDP sites on the lower continental rise and abyssal plain of the northwestern Atlantic (DSDP Sites 388, 105, and 106), and also with the sediments recovered by drilling on the Mazagan Plateau off northwestern Morocco (DSDP Sites 544-547) in the eastern North Atlantic.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Geochemistry and diatom abundances in sediment trap samples of Effingham Inlet, Canada

Sediment traps were deployed inside the anoxic inner basin of Effingham Inlet and at the oxygenated mouth of the inlet from May 1999 to September 2000 in a pilot study to determine the annual depositional cycle and impact of the 1999-2000 La Niña event within a western Canadian inlet facing the open Pacific Ocean. Total mass flux, geochemical parameters (carbon, nitrogen, opal, major and minor element contents, and stable isotope ratios) and diatom assemblages were determined and compared with meteorological and oceanographic data. Deposition was seasonal, with coarser grained terrestrial components and benthic diatoms settling in the autumn and winter, coincident with the rainy season. Marine sedimentary components and abundant pelagic diatoms were coincident with coastal upwelling in the spring and summer. Despite the seasonal differences in deposition, the typical temperate-zone Thalassiosira-Skeletonema-Chaetoceros bloom succession was muted. A July 1999 total mass flux peak and an increase in biogenous components coincided with a rare bottom-water oxygen renewal event in the inlet. Likewise, there were cooler-than-average sea surface temperatures (SSTs) just outside the inlet, and unusually high abundances of a previously undescribed cool-water marine diatom (Fragilariopsis pacifica sp. nov.) within the inlet. Each of these occurrences likely reflects a response to the strong La Niña that followed the year after the strongest-ever recorded El Niño event of 1997-1998. By the autumn of 1999, SSTs had returned to average, and F. pacifica had all but disappeared from the remaining trap record, indicating that oceanographic conditions had returned to normal. Oxygenation events were not witnessed in the inlet in the years before or after 1999, suggesting that a rare oceanographic and climatic event was captured by this sediment trap time series. The data from this record can therefore be used as a benchmark for identifying anomalous environmental conditions on this coast.

Chemical and mineral compositions of basalts from the Pacific Ocean, DSDP data

Mineral and chemical alterations of basalts were studied in the upper part of the ocean crust using data of deep-sea drilling from D/S Glomar Challenger in the main structures of the Pacific floor. Extraction of majority of chemical elements (including heavy metals) from basalts results mainly from their interaction with heated sea water. As a result mineralized hydrothermal solutions are formed. On entering the ocean they influence greatly on ocean sedimentation and ore formation.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Composition of hydrothermal manifestations in the World Ocean

The monograph summarizes results of studies of hydrothermal fields on the ocean floor, hydrothermal plumes and metalliferous sediments. Hydrothermal ore manifestations formed in different geodynamic settings, with different character of volcanism in different facial conditions of deposition are described. Causes of non-uniformity of hydrothermal system functioning in different parts of the ocean and therefore variability of hydrothermal deposits are under consideration. On the base of found relationships of these irregularities with geodynamics, volcanism and sedimentation a new classification of hydrothermal processes and genetic models of hydrothermal ore formation in the ocean have been created. Regularities of hydrothermal sedimentary material dispersion in bottom waters are discussed.

210Pb dates, radiocarbon ages and sedimentation and accumulation rates of sediment cores JM99-1198 and MD99-2297

The magnitude of Late Holocene climatic variations are less significant than those that took place during ice ages and deglaciations. However, detailed knowledge about this period is vital in order to understand and model future climate scenarios both as a result of natural climate variation and the effects of global warming. Oceanic heat flux is important for the sensitive climate regime of northern Europe. Our aim is to connect hydrographical changes, reflected by the dinoflagellates cyst (dinocysts) assemblages in the sediments in the Malangen fjord, to local and regional climatic phases. Previous studies have shown that dinocyst assemblages are influenced by temperature, salinity, and the availability of nutrients (e.g. de Vernal et al. 2005, doi:10.1016/j.quascirev.2004.06.014; de Vernal et al. 2001, doi:10.1002/jqs.659; Grosfjeld et al. this volume; Rochon et al. 2008, doi:10.1016/j.marmicro.2008.04.001; Solignac et al. this volume). Dinoflagellates are mostly unicellular organisms that make up one of the main groups of phytoplankton. They are able to regulate their depth within the photic zone and to concentrate along oceanic fronts, which provide nutrient-enriched waters. The dinoflagellate cysts are the hypnozygotes of dinoflagellates naturally produced during the life cycle. Their wall is composed of a highly resistant organic material, which has a high potential to fossilize. Because dinocysts species are linked to particular abiotic and biotic parameters, the dinocyst assemblages provide information about past surface water conditions. Since each fjord has its own hydrographic setting, it is necessary to establish a firm link between the dinocyst composition of the sediment surface samples and the surface water conditions. Indeed the modern dinocyst distribution in subarctic fjords is little known. Thus, in addition to detailing dinocyst results from two shallow cores, several sediment surface samples located along a transect running from the head to the mouth of the fjord, and extending onto the shelf, are also presented.

Biogeochemical processes in anoxic sediment from Lake Plußsee, Germany

In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative d13C values of -62 per mil and -55 per mil, respectively. Labeling with NaH**13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H2**35S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only <10% of the accumulation rates of DMS. Therefore, the major source of the 13C-depleted MT was neither bicarbonate nor methoxylated aromatic compounds. Other possibilities for isotopically depleted MT, such as other organic precursors like methionine, are discussed. This DMS-forming pathway may be relevant for anoxic environments such as hydrothermally influenced sediments and fluids and sulfate-methane transition zones in marine sediments.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Pore water and solid phase sulfur, carbon and iron data from samples collected in the Argentine Basin during expedition M78

Sulfur phases in the Argentine Basin.