Chemical composition of bottom waters and interstitial waters from sediments and deposits within and outside the Haakon Mosby submarine mud volcano in the Norwegian Sea

On the base of data of Cruise 40 of R/V Akademik Keldysh features of formation of saline composition of interstitial waters from sediments containing free hydrocarbons (methane) and gas hydrates (CH4 x 6H2O) were considered. Chemical composition of the interstitial waters is presented for three zones of sediments from the Haakon Mosby submarine mud volcano: (1) zone of kettles containing free hydrocarbons, (2) gas hydrate sediments, and (3) periphery of the volcano. Abnormally high concentrations of bromine and especially iodine characteristic of the interstitial and particularly of the oil-field waters were found. Because of a great interest in natural gas hydrates found in marine sediments, we obtained a possibility to supplement scarce of available published data with some new information.

Chlorophyll and true-color maps of sediments from the intertidal zones in Winyah Bay, South Carolina, USA and List, Sylt, Germany

We used hyperspectral imaging to study short-term effects of bioturbation by lugworms (Arenicola marina) on the surficial biomass of microphytobenthos (MPB) in permeable marine sediments. Within days to weeks after the addition of a lugworm to a homogenized and recomposed sediment, the average surficial MPB biomass and its spatial heterogeneity were, respectively, 150 - 250% and 280% higher than in sediments without lugworms. The surficial sediment area impacted by a single medium-sized lugworm (~4 g wet weight) over this time-scale was at least 340 cm**2. While sediment reworking was the primary cause of the increased spatial heterogeneity, experiments with lugworm-mimics together with modeling showed that bioadvective porewater transport from depth to the sediment surface, as induced by the lugworm ventilating its burrow, was the main cause of the increased surficial MPB biomass. Although direct measurements of nutrient fluxes are lacking, our present data show that enhanced advective supply of nutrients from deeper sediment layers induced by faunal ventilation is an important mechanism that fuels high primary productivity at the surface of permeable sediments even though these systems are generally characterized by low standing stocks of nutrients and organic material.

Palynology of marine sediment cores from the West African coast

Seven sediment cores from the cruises of the "Meteor" and "Valdivia" were examined palynologically. The cores were retrieved from the lower continental slope in the area of between 33.5° N and 8° N, off the West African coast. Most of the cores contain sediments from the last Glacial and Interglacial period. In some cases, the Holocene sediments are missing. Some individual cores contain sediments also from earlier Glacial and Interglacial periods. The main reason for making this palynological study was to find out the differences between the vegetation of Glacial and Interglacial periods in those parts of West Africa which at present belong to the Mediterranean zone, the Sahara and the zones of the savannas and tropical forests. In today's Mediterranean vegetation zone at core 33.5° N, forests and deciduous forests in particular, are missing during Glacial conditions. Semi-deserts are found instead of these. In the early isotope stage 1, there is a very significant development of forests which contain evergreen oaks; this is the Mediterranean type of vegestation development. The Sahara type of vegetation development is shown in four cores from between 27° N and 19° N. The differences between Glacial and Interglacial periods are very small. It must be assumed therefore that in this latitudes, both Glacial and Interglacial conditions gave rise to desert generally. The results are in favour of a slightly more arid climate during Glacial and more humid one during Interglacial periods. The southern boundary of the Sahara and the adjacent savannas with grassland and tropical woods were situated more to the south during the Glacial periods than they were during the Interglacial ones. In front of today's savanna belt, it can be seen from the palynological results that there are considerable differences between the vegetation of Glacial and Interglacial periods. The woods are more important in Interglacial periods. During the Glacial periods these are replaced from north to south decreasingly by grassland (savanna and rainforest type of vegetation development). The southern limit of the Sahara during stage 2 was somewhat between 12° N and 8° N which is between 1.5 and 5 degrees in latitude further south than it i s today. Not only do these differences in climate and vegetation apply to the maximum of the last Glacial and for the Holocene, but they apparently apply also to the older Glacial and Interglacial periods, where they have been found in the profiles. The North African deset belt can be said to have expanded during Glacial times both towards the north and towards the south. All the available evidence of this study indicates that the grass land or the semi-desert of the Southern Europe cam einto connection with those of the N Africa; there could not have been any forest zone between them. The present study was also a good opportunity for investigating some of the basic marine palynological problems. The very well known overrepresentation of pollen grains of the genus Pinus in marine sediments can be traced as fa as 21° N. The present southern limit for the genus Pinus is on the Canaries and on the African continent as approximately 31° N. Highest values of Ephedra pollen grains even occur south of the main area of the present distribution of that genus. These does not seem to be any satisfactory explanation for this. In general, it would appear that the transport of pollen grains from the north is more important than transport from the south. The results so far, indicate strongly that further palynological studies are necessary. These should concentrate particularly on cores from between 33° N and 27° N as well as between 17° N and 10° N. It would also be useful to have a more detailed examination of sediments from the last Intergalcial period (substage 5 e). Absolute pollen counts and more general examination of surface samples would be desirable. Surface samples should be taken from the shelf down to the bottom of the continental slope in different latitudes.

Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Geochemistry of ODP Site 202-1233 and river sediments

Bulk sediment chemistry from three Chilean continental margin Ocean Drilling Program sites constrains regional continental erosion over the past 30,000 years. Sediments from thirteen rivers that drain the (mostly igneous) Andes and the (mostly metamorphic) Coast Range, along with existing rock chemistry datasets, define terrestrial provenance for the continental margin sediments. Andean river sediments have high Mg/Al relative to Coast-Range river sediments. Near 36°S, marine sediments have high-Mg/Al (i.e. more Andean) sources during the last glacial period, and lower-Mg/Al (less Andean) sources during the Holocene. Near 41°S a Ti-rich source, likely from coast-range igneous intrusions, is prevalent during Holocene time, whereas high-Mg/Al Andean sources are more prevalent during the last glacial period. We infer that there is a dominant ice-sheet control of sediment sources. At 36°S, Andean-sourced sediment decreased as Andean mountain glaciers retreated after ~17.6 ka, coincident with local oceanic warming and southward retreat of the Patagonian Forest and, by inference, westerly winds. At 41°S Andean sediment dominance peaks and then rapidly declines at ~19 ka, coincident with local oceanic warming and the earliest deglacial sea-level rise. We hypothesize that this decreased flux of Andean material in the south is related to rapid retreat of the marine-based portion of the Patagonian Ice Sheet in response to global sea-level rise, as the resulting flooding of the southern portion of the Central Valley created a sink for Andean sediments in this region. Reversal of the decreasing deglacial Mg/Al trend at 41°S from 14.5 to 13.0 ka is consistent with a brief re-advance of the Patagonian ice sheet coincident with the Antarctic Cold Reversal.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Pb concentrations, Pb isotopic composition, and amount of metalliferous components in pelagic sediments from the Pacific Ocean

The amount of lead annually transferred from oceanic crust to metalliferous sediments was estimated in order to test the hypothesis that a non-magmatic flux of lead causes the Pb surplus in the continental crust. A Pb surplus has been inferred from global crust-mantle lead mass balances derived from lead concentration correlations with other trace elements and from lead isotope systematics in oceanic basalts. DSDP/ODP data on the amount of metalliferous sediments in the Pacific Ocean and along a South Atlantic traverse are used to calculate the mean worldwide thickness of 3 (+/-1) m for purely metalliferous sediment componens. Lead isotope ratios of 39 metalliferous sediments from the Pacific define mixing lines between continent-derived (seawater) and mantle-derived (basaltic) lead, with the most metal-rich sediments usually having the most mantle-like Pb isotope composition. We used this isotope correlation and the Pb content of the 39 metalliferous sediments to derive an estimate of 130 (+/-70) µg/g for the concentration of mantle-derived lead in the purely metalliferous end-member. Mass balance calculations show that at least 12 (+/-8)% of the lead, annually transferred from upper mantle to oceanic crust at the ocean ridges, is leached out by hydrothermal processes and re-deposited in marine sediments. If all of the metalliferous lead is ultimately transferred to the continental crust during subduction, the annual flux of this lead from mantle to continental crust is 2.6 (+/-2.0) * 10**6 kg. Assuming this transfer rate to be proportional to the rate of oceanic plate production, one can fit the lead transfer to models of plate production rate variations through time. Integrating over 4 Ga, hydrothermal lead transfer to the continental crust accounts for a significant portion of the Pb surplus in the continental crust. It therefore appears to be one of the main reasons for the anomalous behavior of lead in the global crust-mantle system.

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.

Organic matter composition and sulfate reduction intensity in Oman Margin sediments

Petrographical and geochemical studies of Neogene marine sediments from the Oman Sea (Leg 117, Sites 720, 724, 726 and 730), show a close relationship between the nature and amount of the organic matter, and the degree of degradation of organic matter by sulfate reduction, i.e. pyritization. Petrographically, three major pyritization types were observed: (1) Finely dispersed pyrite framboids in sediments from Oman Margin and Indus Fan, enriched in autochthonous marine organic matter. (2) Infilling of pores by massive pyrite crystals in Oman Margin sediments with a low TOC and a high microfossil content. (3) Pyrite mineralization of lignaceous fragments in organic-depleted sediments from the Indus Fan leading to more massive pyrite. Geochemically, we can define a sulfate reduction index (SRI) as the percentage of initial organic carbon versus that of residual organic carbon. Finely laminated Pliocene-Pleistocene sediments from the Oman Margin exclusively contain organic matter deriving from organic phytoplankton, for which the quantity (TOC) positively correlates with the geochemical quality (Hydrogen Index). We think that the occurrence of this residual organic matter is linked mainly to a high primary paleo-productivity. The intensity of sulfate reduction is constant for sediments with TOC up to 2% and becomes more important when organic input decreases. This degradation process can destroy up to 50% of the initial organic matter, but is not sufficient to explain some of the encountered very low TOC values. It can be seen that sharp increases of certain plankton species (with mineral skeletons) are responsible for a pronounced degradation of organic matter, due to increased sulfate reduction. In that case, the organic matter may be strongly degraded (high SRI), although deposited in an oxygen-depleted environment. Conversely, Miocene-Pliocene sediments contain an autochthonous organic matter that is typical of both low productivity and oxic processes; their very low sulfate reduction index indicates that very little metabolizable organic matter was initially present.

Sediments in Arctic sea ice

Despite the Arctic sea ice cover's recognized sensitivity to environmental change, the role of sediment inclusions in lowering ice albedo and affecting ice ablation is poorly understood. Sea ice sediment inclusions were studied in the central Arctic Ocean during the Arctic 91 expedition and in the Laptev Sea (East Siberian Arctic Region Expedition 1992). Results from these investigations are here combined with previous studies performed in major areas of ice ablation and the southern central Arctic Ocean. This study documents the regional distribution and composition of particle-laden ice, investigates and evaluates processes by which sediment is incorporated into the ice cover, and identifies transport paths and probable depositional centers for the released sediment. In April 1992, sea ice in the Laptev Sea was relatively clean. The sediment occasionally observed was distributed diffusely over the entire ice column, forming turbid ice. Observations indicate that frazil and anchor ice formation occurring in a large coastal polynya provide a main mechanism for sediment entrainment. In the central Arctic Ocean sediments are concentrated in layers within or at the surface of ice floes due to melting and refreezing processes. The surface sediment accumulation in central Arctic multi-year sea ice exceeds by far the amounts observed in first-year ice from the Laptev Sea in April 1992. Sea ice sediments are generally fine grained, although coarse sediments and stones up to 5 cm in diameter are observed. Component analysis indicates that quartz and clay minerals are the main terrigenous sediment particles. The biogenous components, namely shells of pelecypods and benthic foraminiferal tests, point to a shallow, benthic, marine source area. Apparently, sediment inclusions were resuspended from shelf areas before and incorporated into the sea ice by suspension freezing. Clay mineralogy of ice-rafted sediments provides information on potential source areas. A smectite maximum in sea ice sediment samples repeatedly occurred between 81°N and 83°N along the Arctic 91 transect, indicating a rather stable and narrow smectite rich ice drift stream of the Transpolar Drift. The smectite concentrations are comparable to those found in both Laptev Sea shelf sediments and anchor ice sediments, pointing to this sea as a potential source area for sea ice sediments. In the central Arctic Ocean sea ice clay mineralogy is significantly different from deep-sea clay mineral distribution patterns. The contribution of sea ice sediments to the deep sea is apparently diluted by sedimentary material provided by other transport mechanisms.