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.

Chemical composition of bulk sediments from ODP Hole 199-1215A

Elemental concentrations were determined on 21 samples from Hole 1215A to evaluate the influence of hydrothermal sources on bulk sediment composition. Rare earth element (REE) concentrations were also determined on 10 of these samples. Concentration profiles and REE patterns are consistent with a strong hydrothermal influence on sediment composition at the base of Hole 1215A.

(Table 1) Luminescence age determination of sediments from the Arkhangelsk area

The Arkhangelsk area lies in the region that was reached by the northeastern flank of the Scandinavian ice sheet during the last glaciation. Investigations of Late Pleistocene sediments show interglacial terrestrial and marine conditions with sea level up to 52 m above the present level. An unconformity in the stratigraphy suggests a hiatus representing the Early Valdaian (Weichselian) and the beginning of the Middle Valdaian. This unconformity could be related to a low base level and isostatic depression of the area north of Arkhangelsk, either caused by ice masses advancing from the Kara and Barents ice sheets and/or to Scandinavian ice over the Kola Peninsula. During Middle Valdaian, from c. 66 ka BP, until the advance of the Late Valdaian glacier, c. 17-16 ka BP, peat formation, and northward fluvial sedimentation occurred coexisting with permafrost conditions in a later phase. Before the glacier advance, the base level rose and thick vertical accumulations of fluvial sediments were formed. Associated with this glacier advance from the north-northwest, ice damming occurred. Fluvial drainage was opposite to the present drainage pattern and deposition appeared in glaciolacustrine ponds in the area outside the limit of the glaciation. After the deglaciation that started c. 15 ka BP, permafrost conditions and downwasting of buried stagnant glacier ice prevailed until at least 10.7 ka BP.

Biogenic opal content in bulk sediments of ODP Leg 181 sites, southwest Pacific

Biogenic opal concentrations were measured on bulk sediments recovered at Ocean Drilling Program Sites 1123, 1124, and 1125 off North Island of New Zealand in the southwest Pacific. Site 1124 showed opal contents ranging from approximately 2 to 8 wt%, which is relatively high compared to other sites. The subbottom maximum in biogenic opal content located between 1.0 and 1.5 m composite depth can be recognized at each site. Patterns of biogenic opal content in the uppermost parts of the cores appear to reflect the surface ocean settings relating to the migration of the Subtropical Convergence Zone.

Contents of organic compounds in sediments from DSDP Legs 1 and 4

Fifteen sediment samples were studied from five drill sites recovered by the Glomar Challenger on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids. Carbon isotope (dC13) data [values <(-26)?, relative to PDB], long-chain n-alkyl hydrocarbons (>>C27) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized. The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Climatic impact on Al, K, Sc and Ti in marine sediments: Evidence from ODP Site 1144, South China Sea

Al, K, Sc and Ti concentrations of the terrestrial material-dominant sediments from ODP site 1144 were reported. Comparison between the bulk and the acid-leached sediments indicates that about 20~30% of the Al, K and Sc in the bulk sediments are not hosted in terrestrial detritus, rather they are of authigenic origin. However, authigenic Ti is negligible. The results indicate that Ti rather than Al is the best proxy for terrestrial materials. Significant climate controls are displayed in the Al/Ti, K/Ti and Sc/Ti variation patterns both for the bulk and the acid leached sediments. Such variation patterns can be mainly accounted for in terms of climate change in their provenance areas in South China. Elevated Al/Ti, K/Ti and Sc/Ti ratios during interglacial periods indicate that chemical weathering then was stronger than during glacial periods, which might be related to a more humid climate in interglacial periods.

Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,sediments.

Geochemical and isotopic composition of sediments and pore waters from ODP Leg 164 sites

Authigenic carbonates were recovered from several horizons between 0 and 52 mbsf in sediments that overlay the Blake Ridge Diapir on the Carolina Rise (Ocean Drilling Program [ODP] Site 996). Active chemosynthetic communities at this site are apparently fed by fluid conduits extending beneath a bottom-simulating reflector (BSR). Gas hydrates occur at several depth intervals in these near-surface sediments. The carbonate nodules are composed of rounded to subangular intraclasts and carbonate cemented mussel shell fragments. Electron microprobe and X-ray diffraction (XRD) investigations show that aragonite is the dominant authigenic carbonate. Authigenic aragonite occurs both as microcrystalline, interstitial cement, and as cavity-filling radial fibrous crystals. The d13C values of the authigenic aragonite vary between -48.4 per mil and -30.5 per mil (Peedee belemnite [PDB]), indicating that carbon derived from 13C-depleted methane is incorporated into these carbonates. The d13C of pore water sum CO2 values are most negative in the upper 10 mbsf, near the sediment/water interface (-38 per mil ± 5 per mil), but noticeably more positive below 25 mbsf (+5 per mil ± 6 per mil). Because carbonates derive their carbon from HCO3-, dissimilarities between the d13C values of carbonate precipitates recovered from greater than 10 mbsf and d13C values of the associated pore fluids suggests that these carbonates formed near the seafloor. Differences of about 1 per mil in the oxygen isotopic composition of carbonate precipitates from different depths are possibly related to changes in bottom-water conditions during glacial and interglacial time periods. Measurements of the strontium isotopic composition on 13 carbonate samples show 87Sr/86Sr values between 0.709125 and 0.709206 with a mean of 0.709165, consistent with the approximate age of their host sediment. Furthermore, the 87Sr/86Sr values of six pore-water samples from Site 996 vary between 0.709130 and 0.709204. The similarity of these values to seawater (87Sr/86Sr = 0.709175), and to 87Sr/86Sr values of pore water from similar sample depths elsewhere on the Blake Ridge (Sites 994, 995, and 997), indicates a shallow Sr source. The 87Sr/86Sr values of the authigenic carbonates at Site 996 are not consistent with the Sr isotopic values predicted for carbonates precipitated from fluids transported upward along fault conduits extending through the base of the gas hydrate-stability zone. Based on our data, we see no evidence of continuing carbonate diagenesis with depth. Therefore, with the exception of their seafloor expression as carbonate crusts, fossil vent sites will not be preserved. Because these authigenic features apparently form only at the seafloor, their vertical distribution and sediment age imply that seepage has been going on in this area for at least 600,000 yr.