Sterenes in surface sediments from the southwest African shelf and slope

Surface sediment samples collected from the southwest African (Namibian) shelf and slope have been analyzed for their hydrocarbon content. In the surface samples a class of olefinic isoprenoid hydrocarbons, the Sterenes, have been found to represent 20–40% of the total hydrocarbons. To the best of our knowledge Sterenes have not been reported in surface marine sediments in such high concentrations.Cholest-2-ene, cholestadiene, cholestatriene, 24-methylcholest-2-ene, 24-methylcholestadiene, 24-ethylcholest-2-ene and 24-ethylcholestadiene were found in the sediments and identified by high resolution glass capillary gas chromatography-mass spectrometry.The formation of Sterenes from sterols via microbiological processes or chemical auto-oxidation, followed by subsequent dehydration mechanisms and double bond isomerizations. is postulated.It appears that there are highly unique environments in the upwelled area off southwest Africa providing the microbiological and chemical conditions for rapid diagenesis of the sterols within a time scale of 100 yr or less.     

Comparative study of sterols in shelf and slope sediments off northeastern Taiwan

Bottom sediments and suspended matter from the shelf and slope areas off northeastern Taiwan were analyzed for sterol, n-alkanol and n-alkane compositions. The Σ(algal sterols/cholesterol) ratios (mean±1σ) were 1.00±0.31 (n=7) for the shelf sediments, 3.29±0.61 (n=7) for the slope sediments, and 1.54±0.19 (n=3) for the suspended matter. The much higher proportion of cholesterol in the shelf sediments is most likely derived from mollusks in the relict sediments. An additional sterol source for the shelf sediments probably is suspended matter in the water column although the shelf has no apparent sedimentation. Results from phytol and n-alkanols suggest recent inputs of lipids from the water column to the shelf. The stanol/stenol ratios are lower for the older shelf sediments than for the younger slope sediments.     

Geochemistry of recent TOC-rich sediments from the Gulf of California and the Black Sea

Major and minor elements (incl. Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V, Zn) have been determined in recent sediments from the Gulf of California upwelling area and Black Sea sapropels in order to reinterpret their chemical composition in view of reliable seawater and plankton data. The chemistry of the Gulf of California sediments reflects regeneration processes which occur in the water column; i.e. only a small fraction (<10%) of elements like Cd, which in seawater are coupled to the »labile« nutrients (C, N, P), is buried in the sedimentary column. In contrast, elements like the more resistant nutrients (Si) undergo a deeper regeneration cycle (Ba). Several trace metals which are present in comparatively higher concentrations in seawater (As, Mo, U, V) and at the same time are reactive under reducing conditions and/or are able to form stable Sulfides, are fixed in the sediments during early diagenesis. The early diagenetic behavior of Ba is closely related to bacterial sulfate reduction. The formation of barite concretions is discussed.Anoxic conditions in the water column act as ideal traps for a number of redox sensitive and/or stable sulfide forming elements. A simple trace metal balance calculation shows that the chemical composition of Black Sea sapropels is controlled by fluvial and Mediterranean seawater element input and the accumulation rate of terrigenous detrital material.

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Zusammenfassung An rezenten Sedimentproben des Auftriebsgebietes des Golfs von Kalifornien sowie Sapropelen des Schwarzen Meeres wurden sowohl Hauptelement-, als auch Spurenmetall-Gehalte (Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V, Zn, u. a.) ermittelt und mit neueren Spurenmetall-Daten von Meerwasser und marinem Plankton in Beziehung gesetzt. Im Chemismus der Sedimente des Golfs von Kalifornien spiegeln sich die in der Wassersäule ablaufenden Regenerationsprozesse wider. Elemente (z. B. Cd), die sich im Meerwasser wie die »labilen« Nährstoffe (C, N, P) verhalten, gelangen nur in geringem Ausmaß (<10%) in die Sedimentsäule, im Vergleich zu solchen Elementen (z. B. Ba), deren Verhalten im Meerwasser eher dem von »resistenteren« Nährstoff-Elementen (Si) entspricht. Eine Reihe von Spurenmetallen, die vergleichsweise hohe Konzentrationen im Meerwasser aufweisen (As, Mo, U, V) und redox-sensibel sind und/oder stabile Sulfide zu bilden vermögen, werden frühdiagenetisch im Sediment fixiert. Das frühdiagenetische Verhalten von Ba ist eng mit der bakteriellen Sulfat-Reduktion verknüpft. Die Bildung von Baryt-Konretionen wird diskutiert.Anoxische Bedingungen in der Wassersäule wirken als ideale »Fallen« für viele redox-sensible und/oder stabile Sulfide bildende Elemente. Mit Hilfe von Element-Bilanzen kann nachgewiesen werden, daß der Chemismus der Sapropele des Schwarzen Meeres von der Element-Zufuhr durch Fluß- und Mittelmeerwasser sowie die Sedimentationsrate gesteuert wird.

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Résumé Des dosages d'éléments majeurs et en trace (notamment: Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V, Zn) ont été effectués dans des sédiments récents provenant des régions à courants ascendants (upwelling) du Golfe de Californie, ainsi que dans des sapropèles de la Mer Noire, dans le but de rechercher les relations entre leur composition chimique, et celles de l'eau de mer et du plancton. Le chimisme des sédiments du Golfe de Californie reflète les processus de régénération qui se déroulent dans la colonne d'eau. En l'occurrence, les éléments (tels le Cd) qui, dans l'eau de mer, sont associés aux nutrients «labiles» (C, N, P) ne passent qu'en faible quantité (<10%) dans la colonne sédimentaire. L'inverse se présente pour les éléments (Ba, p.ex.) dont le comportement dans l'eau correspond à celui des nutrients «résistants» (Si). Certains métaux en trace, qui existent en proportion relativement élevée dans l'eau de mer (As, Mo, U, V) et qui en même temps sont sensibles au potentiel redox et/ou peuvent former des sulfures stables, sont fixés dans les sédiments au début de la diagenèse. Le comportement diagénétique hatif du Ba est étroitement lié à la réduction du sulfate bactérien. L'auteur discute la formation de concrétions de baryte.Des conditions anoxiques dans la colonne d'eau agissent comme des pièges idéaux pour un certain nombre d'éléments qui sont sensibles au potentiel redox et/ou qui forment des sulfures stables. Un calcul simple du bilan des éléments en trace montre que la composition chimique des sapropèles de la Mer Noire est régie par l'apport des fleuves et de la Méditerrannée ainsi que par le taux d'accumulation des matériaux détritiques terrigènes.

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Free,esterified and residual bound sterols in Black Sea Unit I sediments

Detailed compositional data for the sterols isolated from a surface, Unit I, sediment from the Black Sea are reported. A procedure based on digitonin precipitation has been used to separate the more abundant free sterols from those occurring in esterified forms. Saponification of the solvent extracted sediment residue liberated only a small quantity of residual bound sterols in contrast to studies of other sediments. 4-Methylsterols are much more abundant than 4-desmethylsterols in both the free and esterified sterol fractions which we attribute to a major dinoflagellate input, as in deeper Unit II sediment. The desmethylsterol fraction appears to derive from a variety of sources including dinoflagellates, coccolithophores, diatoms, terrigenous detritus and perhaps invertebrates. 5α(H)-Stanols are particularly abundant in the free sterol fraction. An analysis of the stanol/stenol ratios suggests that the 4-desmethyl-5α(H)-stanols are the result of specific microbial reductions of Δ⁵-sterols and/or the reflection of a contribution of stanol containing source organisms.     

Geochemistry of Jizan shelf sediments, southern Red Sea coast of Saudi Arabia

Surface sediments from the Jizan shelf, southern Red Sea, were analysed for grain size and mineralogical and elemental composition in order to establish their geochemical characteristics. Texturally, sediments are classified into sand and mud; the latter dominates the shelf. Grain size variability and mineralogical assemblages present in the sediments largely control the abundance and distribution of CaCO₃, organic carbon content (OC) and the major and trace elements. Sand sediments are composed of carbonate material of marine origin and contain high concentrations of Ca, Mg and Sr. Mud sediments are relatively rich in OC and are characterised by high concentrations of Al, Fe, Ti, Mn, Cu, Cr, Co, Ni, V and Ba. Unlike the sand, Mg concentration in the mud sediments seems to be controlled by stronger contribution from non-carbonate material. Factor analysis is applied to identify the variables accounting for most of the variance in the mud sediment samples. Three factors are found to describe about 78% of the variance. The first factor which accounts for 41% of the total variance is the Fe and Mn oxides that reach the area through episodic flooding. The second and third factors are the mud (22%) and the mineralogy (15%) of the sediments, respectively.     

Organic Geochemistry of Black Sea cores

Six Black Sea bottom sediments samples were analyzed for their organic content (chloroform extract and humic compounds) by elemental analysis, liquid and gas chromatography, various chemical methods and especially infra-red spectroscopy. Four of these samples came from an euxinic facies (“unit 2”) and two from a normally oxygenated facies below (“unit 3”).Even though important differences exist between the two sets of samples, the origin of the organic matter was found to be the same for both facies; this origin is mixed, with the marine contribution slightly predominant over the terrestrial one.Consequently, the compositional differences originate in the different environmental conditions in the sedimentary basin. More precisely, the euxinic facies appears to “preserve” the organic matter, on both quantitative and qualitative grounds. This effect is due more to the anoxic and toxic nature of the environment than to the reducing conditions.The sulfur incorporation in relatively small molecules does not proceed by a rapid biochemical pathway, but by slow and abiotic reactions.     

Wave and tidal current sorting of shelf sediments southwest of England

The relative roles of waves and tidal currents in transporting bottom sediment on the continental shelf off Lands End, southwest England, are evaluated by study of (a) sediment grain size in relation to boundary layer measurements in tidal currents, (b) regional variation in sediment parameters in relation to peak tidal and wave-induced currents, and (c) visual observation of bedforms. (a) The sediments are mainly zoogenic sands. The average hydraulic equivalent median diameter is Mdφ=1.40φ (medium grade sand), and two-thirds of the median grain sizes fall between 0.97φ and 1.83φ. The linear bottom current which will just move this range of sizes is exceeded only slightly by the highest tidal drag velocities ū* measured in the area. Thus, sediment movement by tidal currents alone is restricted to areas of high bed roughness and strong peak tidal flows. In contrast, wave-induced oscillatory currents at 100 m depth (typical of the area) attain sufficient speed to disturb the same particle sizes over 3% of the time. This includes storm periods when much greater velocities occur. (b) The average Mdφ of the sediment decreases southwest and northeast from south of the Lizard. This correlates well with the pattern of maximum tidal current speeds, suggesting that tidal currents control the areal distribution of sediment median grain size. Most sediments are well sorted (mean σ_i=0.48φ). Sorting improves at shallower depths but does not improve in areas of faster tidal currents, suggesting that wave-induced currents exert the major control on sorting. Silt and clay proportions increase west of the Scilly Isles and are influenced by both wave and tidal currents. (c) Photographs and television pictures show that symmetrical bedforms due to wave action are dominant north and west of the western Channel. Asymmetric bedforms are more common in the western Channel itself, where tidal currents and bed roughness are both high. Results are used to construct a sediment transport model for the study area. Since medium grade well sorted sands occur in depths of over 100 m, many ancient, extensive, well sorted sand sheets may have been deposited at depths greater than previously suspected.     

Origin of friable sediments of the Barents Sea shelf

The origin of friable sediments blanketing the Barents Sea shelf is considered. It is shown that their characteristic seismoacoustic record patterns reflect low degree of diagenetic transformations and indicates continuous sedimentation. According to traditional views, this single sedimentary complex also includes diamicton, and the section is interpreted as a three-unit structure: diamicton, which is considered a till; the overlying friable sediments accumulated under different conditions of deglaciation in glaciomarine settings; and the postglacial marine sediments. It is demonstrated that such views are inconsistent with geomorphologic features (datings by physical methods included) indicating a prolonged hiatus that separates epochs of the diamicton accumulation and formation of friable sediments. The analysis revealed that the composition, vertical succession, and lateral distribution of different lithological types of friable sediments are related to the regular spatiotemporal replacements of different facies settings in the transgressing Arctic sea rather than by the glacial process. This inference is confirmed by the composition of foraminiferal assemblages.     

Mollusks from the lower quaternary Chauda sediments of the Black Sea

The analysis of paleontological remains in many samples from the Lower Quaternary Chauda sediments drilled and cored on the Bulgarian shelf of the Black Sea revealed widespread mollusks of the genera Didacna and Dreissena (Didacna tschaudae guriana, D. tschaudae, D. pleistopleura, D. crassa guriensis, Dreissena rostriformis tschaudae, D. rostriformis abchasica) accompanied by reworked Neogene representatives of the genus Digressodacna. In numerous places of a continental slope and an adjacent deep-sea depressions near Crimea and Caucasus the similar mollusc assemblage is described in the redeposited state for the first time. The composition of palynological spectra and diatom assemblages in shelf sediments indicates climate changes during the Chaudan period. The Chaudan mollusk fauna from the Black Sea sediments, which is lacking Caspian Bakuan species characteristic of the Chauda stratotype, is compositionally close to the mollusk assemblage from basal layers of the Chauda Horizon in the Guriya area of Georgia (“Gurian” Chauda). These data imply repeated changes in the level of the Chaudan basin between present-day isobaths of −30...−50 to −140 m.     

Biogeochemical processes involving acetate in sub-seafloor sediments from the Bering Sea shelf break

Biogeochemical processes involving acetate in sub-seafloor sediments from piston core PC23B from the Bering Sea shelf break were inferred by examining the stable carbon isotopic relationships between acetate and other relevant carbon compounds: total organic carbon (TOC) in the sediment solid phase, and dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in pore water. Throughout the core, the isotopic composition of acetate (δ¹³C_acetate), from −31‰ to −29‰, was ¹³C-depleted by ca. 7‰ vs. DOC (δ¹³C_DOC) and its depth profile approximately paralleled that of δ¹³C_DOC, suggesting that the principal process producing acetate was fermentation of dissolved organic compounds. However, the ¹³C depletion in δ¹³C_acetate indicates some contribution of acetogenesis to total acetate production, because acetogenesis results in ¹³C depletion of the acetate produced. The relative contribution of acetogenesis via the H₂/CO₂ reaction, calculated by using a two source isotope mixing model, increased with depth in the sulfate reduction zone from 10% to 15% and was constant at 19% in the methanogenic zone. The acetogenic contribution to acetate production in the methanogenic zone underlying the sulfate reduction zone is consistent with reported observations, whereas the occurrence of acetogenesis in the sulfate reduction zone may be related to the contribution of terrestrial organic matter (OM) to the sedimentary OM in that depth interval, because the terrestrial component likely includes precursors that favor organoautotrophic acetogenesis. The high acetate concentration (up to 81 μM) and TOC content (up to 1.4%) at the same depth (<200 cmbsf) suggest that some relationship exists between acetate production rate and TOC content, or that a temperature increase during core storage at room temperature might stimulate acetate-producing microbial activity in the high TOC sediment.     

Trace metals in sediments from the inner continental shelf of the western Beaufort Sea

Increased development and changing climate have enhanced global interest in the Arctic Ocean and adjacent seas. Using a large, 3-yr data base, we have determined the distribution of trace metals in sediments from the inner shelf of the western Beaufort Sea. Metal concentrations in these sediments reflect pristine conditions, consistent with those for most coastal areas in the Arctic and with predictions based on average continental crust. Geographic variations in metal values are primarily related to sediment grainsize distribution. However, grain-size patterns are a complex function of several variables including source areas, ice and water movement, as well as physical and chemical weathering. Future identification of any metal contamination in Beaufort Sea sediments will be simplified by understanding the predictable natural patterns.     

Stratigraphic and structural characteristics of the Romanian Black Sea shelf

The Western Black Sea basin opened during Cretaceous times by back-arc rifting in association with a north dipping subduction at the rear of the Cretaceous–Early Tertiary Pontide volcanic arc. The sedimentary wedge developed on the shelf of the Romanian Black Sea sector reflects a complex interplay between large scale rifting, uplift of the orogenic flanks, large-scale post-rift subsidence and sea level changes. We examine the detailed structural configuration of this sector for a regional correlation with the adjacent offshore in Ukraine and Bulgaria. The evolution of the western Black Sea basin started in the Albian–Cenomanian times, when two extensional phases with significantly different directions (N–S and subsequently E–W) lead to the formation of a complex interplay between isolated blocks organised in horsts and grabens generally deepening eastwards. Superposition of normal faults footwall blocks from the two extensional episodes generated a deeply subsided area with enhanced accommodation space, i.e., the Histria Depression, and, consequently, recorded a larger thickness of Paleogene sediments in the post-rift stage. (Re)activation of faults and associated folding reflects repeated inversion during the Late Cretaceous–Oligocene times, associated with subsequent periods of non-deposition and/or erosion during moments of basin fill exposure. These periods of inversion recorded in the Black Sea are controlled by coeval orogenic deformations taking place in the Balkans, Pontides and the Crimean thrust belt. Sea level fluctuations during the Neogene and late Alpine tectonics in the neighbouring orogens caused massive sedimentation followed by sediment starvation and/or significant erosion. Large thicknesses of sediments accumulated during the Pontian, presumably associated with an extensional episode deepening the distal parts of the basin and with differential compaction structures. The interpretation of a high-quality seismic dataset combined with published data allowed the correlation of major structural units and lineaments defined onshore towards the Carpathians with the ones deeply buried below the western Black Sea basin sediments. Unit correlations are furthermore used to derive an integrated tectonic image of the western Black Sea area.     

Hydrocarbon gas in sediment from the shelf,slope, and basin of the Bering Sea

Hydrocarbon gases (methane, ethane, ethene, propane, propene, isobutane and n-butane) are present in low concentrations in the top two meters of sediment from the shelf, slope and basin of the Bering Sea. Methane is most abundant and its concentration increases with depth in the sediment. Average concentrations of methane recovered from these sediments are between about 4000 and 5000 nl per 1 of interstitial water. Ethane, ethene, propane and propene are present in almost all samples, but the concentrations of these gases are about two orders of magnitude lower than the concentration of methane. The average ratios of ethane to ethene are usually greater than one in shelf sediment, about one in slope sediment, and usually less than one in basin sediments. These hydrocarbon gases are probably derived from low-temperature chemical and biochemical processes operating at or near the sea-floor. At one location on the shelf, hydrocarbon gases suggest the possibility of petroleum at depth.     

Sulfur speciation in the upper Black Sea sediments

We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RS_x), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite – sulfur was the major phase in all cores [200-400 µmol (g dry wt)^- 1] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 µmol (g dry wt)^- 1, respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.     

Biogeochemical processes of carbon and sulfur cycles in sediments of the outer shelf of the Black Sea (Russian Sector)

Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using ³⁵S and ¹⁴C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.     

The sources of metal contents in the shelf sediments from the Marmara Sea, Turkey

The shelf area is the largest morphological unit of the Marmara Sea and is subjected to increasing population, urbanization, and industrial activities. Metal contents (Al, Fe, Mn, Cu, Pb, Zn, Ni, Cr, Co and Hg) of the surface sediments from the shelf areas of the Marmara Sea generally do not indicate shelf-wide pollution. The variability of the metal contents of the shelf sediments is mainly governed by the geochemical differences in the northern and southern hinterlands. Northern shelf sediments contain lower values compared to those of the southern shelf, where higher Ni, Cr, Pb, Cu and Zn are derived from the rock formations and mineralized zones. However, besides from the natural high background in the southern shelf, some anthropogenic influences are evident from EF values of Pb, Zn and Cu, and also from their high mobility in the semi-isolated bay sediments. Anthropogenic influences are found to be limited at the confluence of Istanbul Strait in the northern shelf. However, suspended sediments along the shallow parts of the northern shelf were found to be enriched in Pb and Hg and to a lesser degree in Zn, reflecting anthropogenic inputs from Istanbul Metropolitan and possibly from the Black Sea via the Istanbul Strait.     

Stable carbon and oxygen isotopes distribution in carbonates from the Central Barents Sea shelf sediments

Carbonate macrofaunal remains and diagenetic tubes collected from a number of structures in the Central Barents Sea area during the 18th TTR (Training Through Research) cruise were subdivided into three groups according to the results of stable carbon and oxygen isotopes analysis. The first group includes carbonates that were formed from bicarbonate only from surrounding sea waters. The carbonates of the second group were formed during diagenesis with use of mixed sources of bicarbonate. The fourth group includes methane-derived carbonates that were formed as a result of anaerobic oxidation of methane (AOM).     

Uronic and other organic acids in Baltic Sea and Black Sea sediments

Organic acids were released from marine sediments by acid hydrolysis. Ion-exchange chromatography and GC-MS were used to separate and identify the acids. The major compounds detected were galacturonic, glucuronic, mannuronic, 4-O-methylglucuronic, cellobiouronic, guluronic, glyceric, glycolic, lactic and erythronic acids. Numerous biouronic (sugar-uronic acid compounds) and aldonic acids were also found. The low abundance of uronic acids characteristic of terrigenous plants and the similarity of the biouronic composition to that of marine algae indicate a marine algal source for the acids in the sediment. Results from the Black Sea are compared with those from the Baltic Sea and several diagenetic transformations are discussed.