Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Geochemistry of phosphatic crusts from the shelf off Peru

Authigenic phosphorite crusts from the shelf off Peru (9°40°S to 13°30°S) consist of a facies with phosphatic coated grains covered by younger phosphatic laminite. The crusts are composed of carbonate fluorapatite, which probably formed via an amorphous precursor close to the sediment water interface as indicated by low F/P2O5 ratios, Sr and Ca isotopes, as well as rare earth element patterns agreeing with seawater-dominated fluids. Small negative Ce anomalies and U enrichment in the laminite suggest suboxic conditions close to the sediment-water interface during its formation. Increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and, consequently, point to episodical development of anoxic conditions during phosphogenesis. The Peruvian phosphorites formed episodically over an extended period of time lasting from Middle Miocene to Pleistocene. Individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide-rich phosphatic layers. Coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions. Episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer. Phosphatic coated grains were later transported to the place of crust formation, where subsequent laminite formation was favored under lower energy conditions. A similar succession of phosphatic layers with varying contents of organic matter and sulfide-rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains.

Acid-soluble sulfides in upper layer bottom sediments from the Tsemess and Gelendzhik bays and adjacent shelf area of the Black Sea

Contents of labile (acid-soluble) sulfides were determined in the upper layer of bottom sediments at 80 stations on the Caucasian shelf of the Black Sea. Maximum values of this parameter occurred in black mud accumulated in zones of intense pollution in the Gelendzhik and Tsemess bays and in shelf areas adjacent to large health resort objects and to seaports. Contents of acid-soluble sulfides in sediments varied from 400 to 900 mg S/dm**3 of wet mud. In zones of moderate pollution they varied from 200 to 400 mg S/dm**3. Rate of sulfate reduction was 10-40 mg S/dm**3 of wet sediment per day. Obtained data show that accumulation of labile sulfides in the upper layer of shelf bottom sediments is directly related to anthropogenic pollution and is one of the most hazardous environmental aftereffects.

Fauna composition of benthos communities in bottom sediments from the edge and the central part of the shelf in the California upwelling zone

Two shelf communities from the central part off the California Peninsula are described. The community of Amphiodia urtica - Nephtys ferruginea develops in the central part of the shelf within the depth range 95-105 m. The community of Nephtys ferruginea - Amphiura acrystata develops on the shelf edge at depth 110 m. Biomasses of both communities are very low (about 10 g/m**2). Species richness of the shelf community is high; more than 60 species occur in samples (43-51 species per a community). Various echinoderms and some other groups are abundant on the Californian shelf; these groups are absent in shelf areas of Peruvian and Benguela upwellings. Species structures of the communities were analyzed; the communities were shown to consist of coexisting, but not interacting guilds; this indicates that the communities are undersaturated with individuals. At the same time values of ABC-indices indicate that the communities are stable. We suggest that in this case adaptation to unfavorable but stable environment is observed (selection of species-stressolarents). An explanation seems to lie in the penetrating type of the upwelling in the Californian upwelling zone. Low biomass values seem to result from mass development of necto-benthic carnivorous crustaceans-galateids Pleuroncodes planiceps.

(Table 1) Abundance of radiolarians in the surface layer of bottom sediments from the Peru-Chile trench and shelf

Two radiolarian assemblages are distinguished: an equatorial sub-assemblage of the tropical assemblage in the East Pacific Ocean, which differs somewhat from association of radiolarians in the western part of the ocean, and an assemblage close to transitional one between the tropical and the boreal. The latter is characterized by presence of considerable number of species typical for cold-water regions. Some criteria are presented for distinguishing radiolarian associations in nearshore regions from similar associations in regions of the open ocean.

Pteropod preservation on the Pakistan shelf and continental slope

Fifteen surface sediment samples from the Pakistan shelf and upper continental slope and a Late Quaternary high-sedimentation rate core (573 m water depth, Pakistan continental margin) have been analysed to improve the understanding of the factors influencing pteropod preservation. The aragonite compensation depth (ACD) is located at 250-400 m water depth, which corroborates previous observations of a very shallow ACD in the northern Arabian Sea. With the exception of the Hab transect off Karachi, the ACD coincides with the upper boundary of the OMZ located at 250 m water depth. The shell preservation index of the pteropod Limacina inflata (LDX) was applied on six surface sediment samples showing good to very good preservation (LDX: 2.2 to 1.3). The 30 000 yr long record of sediment core SO90 137KA is characterized by alternations between bioturbated and laminated sediments. Bioturbated sediments occurring in the Early Holocene, Younger Dryas and time-equivalents of Heinrich events contain well to perfectly preserved tests of L. inflata (LDX: 2.1-0.2), whereas only traces of pteropods are found in laminated intervals. The close linkage of pteropod preservation in the surface sediments and in core 137KA to well-oxygenated conditions can be explained by repetitive intermediate water formation in the Arabian Sea down to at least 600 m water depth in times of enhanced NE monsoons during stadials and H-equivalents. Low amounts of pteropods in laminated sediments (interstadials, Late Holocene) and in the present-day oxygen minimum zone (OMZ) indicate a weak NE monsoon, stable OMZ and shallow ACD.

Geochemistry, clay mineralogy and grain size distribution in various sediment cores drilled during ODP Leg 119 on the Antarctic continental shelf off Prydz Bay

Drilling was undertaken at five sites (739-743) on ODP Leg 119 on a transect across the continental shelf of Prydz Bay, East Antarctica, to elucidate the long-term glacial history of the area and to examine the importance of the area with respect to the development of the East Antarctic ice sheet as a whole. In addition to providing a record of glaciation spanning 36 m.y. or more, Leg 119 has provided information concerning the development of a continental margin under the prolonged influence of a major ice sheet. This has allowed the development of a sedimentary model that may be applicable not only to other parts of the Antarctic continental margin, but also to northern high-latitude continental shelves. The cored glacial sedimentary record in Prydz Bay consists of three major sequences, dominated by diamictite: 1. An upper flat-lying sequence that ranges in thickness from a few meters in inner and western Prydz Bay to nearly 250 m in the outer or eastern parts of the bay. The uppermost few meters consist of Holocene diatom ooze and diatomaceous mud with a minor ice-rafted component overlying diamicton and diamictite of late Miocene to Quaternary age. The diamictite is mainly massive, but stratified varieties and minor mudstone and diatomite also occur. 2. An upper prograding sequence cored at Sites 739 and 743, unconformly below the flat-lying sequence. This consists of a relatively steep (4° inclination) prograding wedge with a number of discrete sedimentary packages. At Sites 739 and 743 the sequence is dominated by massive and stratified diamictite, some of which shows evidence of slumping and minor debris flowage. 3. A lower, more gently inclined, prograding sequence lies unconformably below the flat-lying sequence at Site 742 and the upper prograding sequence at Site 739. This extends to the base of both sites, to 316 and 487 mbsf, respectively. It is dominated by massive, relatively clast-poor diamictite which is kaolinite-rich, light in color, and contains sporadic carbonate-cemented layers. The lower part of Site 742 includes well-stratified diamictites and very poorly sorted mudstones. The base of this site has indications of large-scale soft-sediment deformation and probably represents proximity to the base of the glacial sequence. Facies analysis of the Prydz Bay glacial sequence indicates a range of depositional environments. Massive diamictite is interpreted largely as waterlain till, deposited close to the grounding line of a floating glacier margin, although basal till and debris flow facies are also present. Weakly stratified diamictite is interpreted as having formed close to or under the floating ice margin and influenced by the input of marine diatomaceous sediment (proximal glaciomarine setting). Well-stratified diamictite has a stronger marine input, being more diatom-rich, and probably represents a proximal-distal glaciomarine sediment with the glaciogenic component being supplied by icebergs. Other facies include a variety of mudstones and diatom-rich sediments of marine origin, in which an ice-rafted component is still significant. None of the recovered sediments are devoid of a glacial influence. The overall depositional setting of the prograding sequence is one in which the grounded ice margin is situated close to the shelf edge. Progradation was achieved primarily by deposition of waterlain till. The flat-lying sequence illustrates a complex sequence of advances and retreats across the outer part of the shelf, with intermittent phases of ice loading and erosion. The glacial chronology is based largely on diatom stratigraphy, which has limited resolution. It appears that ice reached the paleoshelf break by earliest Oligocene, suggesting full-scale development of the East Antarctic ice sheet by that time. The ice sheet probably dominated the continental margin for much of Oligocene to middle Miocene time. Retreat, but not total withdrawal of the ice sheet, took place in late Miocene to mid-Pliocene time. The late Pliocene to Pleistocene was characterized by further advances across, and progradation of, the continental shelf. Holocene time has been characterized by reduced glacial conditions and a limited influence of glacial processes on sedimentation.

Siliceous fossils in sediments of the Ibero-Moroccan shelf and adjacent deep sea plains

Siliceous skeletons were investigated in two core profiles (9 cores), one off Cap de Sines, Portugal and the other off Cap de Mazagan, Morocco. Total number of skeletons was determined per gram of dried sediment at different core depths of the fraction >21 µ. Results are compared with a core profile from the Arabian Sea. Diatoms are of four groups: (A) marine-planktonic, B) marine-benthic, (C) freshwater and (D) Tertiary species (Trinacria e.g.). Species from groups (B), (C) and (D) are redeposited in all cores taken at a water depth of greater than 100 m. Small numbers of Silicoflagellates and Radiolarians were found throughout the cores from the Ibero-Moroccan shelf. In the Arabian Sea core, Radiolarians were concentrated in distinct horizons in which Tertiary material was redeposited (40-50, 140-150, 250-260 cm). The number of siliceous skeletons per gram of dried sediment decreases more or less rapidly with increasing depth in all cores. Whereas about 2500 skeletons were found in sediments close to the surface, approximately 100 skeletons only were found in deeper (>40 cm) layers. Deeper horizons with more than 100 specimens were interpreted as redeposited material. This sediment contained robust skeletons, resistant against dissolution, as well as benthic and Tertiary material. The decrease of siliceous skeletons relative to core depth depends upon the sedimentation rate. Where the sedimentation rate is high, the opal dissolution zone extends down to 30-60 cm, where the sedimentation rate is low, it is located at 10-30 cm. Below these depths opals disappears. These zones also have approximately the same age (4000 years) everywhere. Siliceous skeletons dissolve differentially, first the Silicoflagellates disappear, second the Diatoms, third the Radiolarians, and fourth the Sponge Spicules. Surface structure of skeletons from near the opal dissolution zones are similar to those of skeletons treated with NaOH. Tertiary diatoms (Trinacria e. g.) and benthic diatoms (Campylodiscus e.g.) dissolve less rapidly than skeletons of modern planktonic diatoms (Coscinodiscus e.g.). The time control of the opal dissolution zones appeared rather independent of various oceanic influences. No evidence was found for effects from upwelling either off Portugal or off Morocco. No difference in dissolution rates was recorded between the abyssal plains lying off these two areas. Likewise, there was no change in solution rates from Pleistocene to Holocene within either one of the abyssal plains. The Mediterranean outflow, which is enriched in dissolved silica, apparently had no effect on dissolution rates of siliceous skeletons in the sediment.

Heterocyst glycolipids in surface sediments and water samples of the Amazon shelf

Marine endosymbiotic heterocystous cyanobacteria make unique heterocyst glycolipids (HGs) containing pentose (C5) moieties. Functionally similar HGs with hexose (C6) moieties found in free-living cyanobacteria occur in the sedimentary record, but C5 HGs have not been documented in the natural environment. Here we developed a high performance liquid chromatography multiple reaction monitoring (MRM) mass spectrometry (HPLC-MS2) method specific for trace analysis of long chain C5HGs and applied it to cultures of Rhizosolenia clevei Ostenfeld and its symbiont Richelia intracellularis which were found to contain C5 HGs and no C6 HGs. The method was then applied to suspended particulate matter (SPM) and surface sediment from the Amazon plume region known to harbor marine diatoms carrying heterocystous cyanobacteria as endosymbionts. C5 HGs were detected in both marine SPM and surface sediments, but not in SPM or surface sediment from freshwater settings in the Amazon basin. Rather, the latter contained C6 HGs, established biomarkers for free-living heterocystous cyanobacteria. Our results indicate that the C5 HGs may be potential biomarkers for marine endosymbiotic heterocystous cyanobacteria.

Sedimentology of the Vietnam shelf

On the Vietnam Shelf more than 1000 miles of shallow high-resolution seismics were analyzed to unravel post-glacial evolution in a tropical, siliciclastic environment together with 25 sediment cores from water depths between 21 and 169 m to determine stratigraphy, distribution and style of sedimentation. Fourty-seven samples were dated with the AMS-14C technique. The shelf was grouped into three regions: a southern part, a central part, and a northern part. On the broad Southern Shelf, sedimentation is influenced by the Mekong River, which drains into the SCS in this area. Here, incised valley fills are abundant that were cut into the late Pleistocene land surface by the Paleo-Mekong River during times of sea level lowstand. Those valleys are filled with transgressive deposits. The Holocene sedimentation rate in this low gradient accommodation-dominated depositional system is in the range of 5-10 and 25-40 cm/ky at locations sheltered from currents. The Central Shelf is narrow and the sedimentary strata are conformable. Here, numerous small mountainous rivers reach the SCS and transport large amounts of detrital sediment onto the shelf. Therefore, the Holocene sedimentation rate is high with values of 50-100 cm/ky in this supply-dominated depositional system. The broad Northern Shelf in the vicinity of the Red River Delta shows, as on the Southern Shelf, incised valleys cut into the Pleistocene land surface by paleo river channels. In this accommodation-dominated shelf area, the sedimentation rate is low with values of 5-10 cm/ky. Where applicable, we assigned the sampled deposits to different paleo-facies. The latter are related to certain intervals of water depths at their time of deposition. Comparison with the sea-level curve of (Hanebuth et al., 2000, doi:10.1126/science.288.5468.1033) indicates subsidence on the Central Shelf, which is in agreement with the high sedimentation rates in this area. In contrast, data from the Northern Shelf suggest tectonic uplift that might be related to recent tectonic movements along the Ailao Shan-Red River Fault zone. Data from the Southern Shelf are generally in agreement with the sea-level curve mentioned above.