Lead 210 concentrations in sediments of the Arabian Sea

In order to evaluate bioturbation in abyssal Arabian-Sea sediments of the Indus fan profiles of 210Pb (half-life: 22.3 yr) and 234Th (half-life: 24.1 d) were measured in cores collected during September and October 1995 and April 1997, respectively. The density and composition of epibenthic megafauna and lebensspuren were determined in vertical seafloor photographs during April 1997. Mean eddy-diffusive mixing coefficients according to the distribution of excess 210Pb ( 210Pb-DB) were 0.072±0.028, 0.068±0.055, 0.373±0.119, 0.037±0.009 and 0.079±0.119 cm**2 yr**-1 in the northern, western, central, eastern and southern abyssal Arabian sea, respectively. Mean eddy-diffusive mixing coefficients according to the distribution of excess 234Th (234Th-DB) were 0.53, 1.64 and 0.47 cm**2 yr**-1 in the northern, western and central abyssal Arabian Sea, respectively. Mobile epibenthic megafauna at the western, northern, central and southern study sites were dominated by ophiuroids, holothurians, ophiuroids and natant decapods (the respective densities were 100, 82, 29 and 6 individuals 1000 m**-2). The northern study site was characterized by a high abundance of spoke traces and fecal casts. The central site showed spoke traces and many tracks. The southern site displayed the highest abundance of spoke traces, whereas at the western site hardly any lebensspuren were observed. There is evidence for at least two functional endmember communities in the Arabian Sea. In the northwestern Arabian Sea (WAST) vertical particle displacement seems to be dominated by macrofauna and primarily eddy-diffusive. In the southern Arabian Sea (SAST) non-local and 'incidental' mixing due to spoke-trace producers might become more important and superimpose reduced eddy-diffusive mixing. With respect to biological data CAST is an intermediate location. Given the biological data, average 210Pb-DB is higher and decimeter-scale variability of 210Pb-DB smaller at CAST than expected. These findings indicate that in a mixture of both endmember communities the organisms may interact in way that increases values of biodiffusivity, as reflected by 210Pb-DB, and reduces decimeter-scale 210Pb-DB heterogeneity in comparison to the simple sum of the isolated effects of the endmembers. For time scales <100 years there was no evidence for a relationship between food supply (POC flux) and bioturbation intensity, as reflected by 210Pb-DB and 234Th-DB. Bioturbation intensity should be controlled primarily by the composition of the benthic fauna, its specific adaptation to the environmental setting, and the abundance of each species of the benthic community. Food supply can have only an indirect influence on bioturbation intensity. In certain parts of the ocean the a priori overall positive relationship between POC flux and biodiffusivity might include restricted intervals displaying no or even negative relations.

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.

Turbidite layers in sediments of the Dakar Canyon

The relationship of sea-level changes and short-term climatic changes with turbidite deposition is poorly documented, although the mechanisms of gravity-driven sediment transport in submarine canyons during sea-level changes have been reported from many regions. This study focuses on the activity of the Dakar Canyon off southern Senegal in response to major glacial/interglacial sea-level shifts and variability in the NW-African continental climate. The sedimentary record from the canyon allows us to determine the timing of turbidite events and, on the basis of XRF-scanning element data, we have identified the climate signal at a sub-millennial time scale from the surrounding hemipelagic sediments. Over the late Quaternary the highest frequency in turbidite activity in the Dakar Canyon is confined to major climatic terminations when remobilisation of sediments from the shelf was triggered by the eustatic sea-level rise. However, episodic turbidite events coincide with the timing of Heinrich events in the North Atlantic. During these times continental climate has changed rapidly, with evidence for higher dust supply over NW Africa which has fed turbidity currents. Increased aridity and enhanced wind strength in the southern Saharan-Sahelian zone may have provided a source for this dust.

Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

Bromine and iodine concentrations in sediments and pore fluids of ODP Leg 112

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl- concentrations. The slope pore fluids are characterized by low Cl- concentrations, but elevated Br- and I- concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl- and Br- concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br-, I-, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I- concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br- concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I- and the I- enrichments relative to NH4+ and Br- correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I-/Br- ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl- concentrations. Other possible sources for low Cl- water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl- fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment I/Br ratios. Comparison of Na+/Cl- and Br-/Cl- molar ratios in the pore fluids shows that the shelf high-Cl- fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.

Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Stable oxygen isotope record and abundances of Globorotalia menardii in sediments from the tropical Atlantic Ocean

Eight box cores from the tropical Atlantic were studied in detail with regard to foraminiferal oxygen isotopes, radiocarbon, and Globorotalia menardii abundance. A standard Atlantic oxygen-isotope signal was reconstructed for the last 20,000 yr. It is quite similar to the west-equatorial Pacific signal published previously. Deglaciation is seen to occur in two steps which are separated by a pause. Onset of deglaciation is after 15,000 yr B.P. The pause is centered between 11,000 and 12,000 yr B.P., but may be correlative with the Younger Dryas (10,500 yr B.P.) if allowance is made for a scale shift due to mixing processes on the sea floor. Step 2 is centered near 10,000 yr B.P. and is followed by a brief excursion toward light oxygen values. This excursion (the M event) may correlate with the Gulf of Mexico meltwater spike.

Amino acids and carbohydrates in sediments and interstitial waters of ODP Site 112-681

Total organic carbon (TOC), dissolved organic carbon (DOC), total hydrolyzable amino acids (THAA), amino sugars (THAS), and carbohydrates (THCHO) were measured in sediments and interstitial waters from Site 681 (ODP Leg 112). TOC concentrations vary between 0.75% and 8.2% by weight of dry sediment and exhibit a general decrease with depth. DOC concentrations range from 6.1 to 49.5 mg/L, but do not correlate with TOC concentrations in the sediment. Amino compounds (AA and AS) and sugars account for 0.5% to 8% and 0.5% to 3% of TOC, respectively, while amino compounds make up between 2% and 27% of total nitrogen. Dissolved hydrolyzable amino acids (free and combined) and amino sugars were found in concentrations from 3.7 to 150 µM and from 0.1 to 3.7 µM, respectively, and together account for an average of 8.5% of DOC. Dissolved hydrolyzable carbohydrates are in the range of 6 to 49 µM. Amino acid spectra are dominated by glycine, alanine, leucine, and phenylalanine; nonproteinaceous amino acids (gamma-amino butyric acid, beta-alanine, and ornithine) are enriched in the deeper part of the section, gamma-amino butyric acid and beta-alanine are thought to be indicators of continued microbial degradation of TOC. Glycine, serine, glutamic acid, alanine, aspartic acid, and ornithine are the dominating amino compounds in the pore waters. Spectra of carbohydrates in sediments are dominated by glucose, galactose, and mannose, while dissolved sugars are dominated by glucose and fructose. In contrast to the lack of correlation between abundances of bulk TOC and DOC in corresponding interstitial waters, amino compounds and sugars do show some correlation between sediments and pore waters: A depth increase of aspartic acid, serine, glycine, and glutamic acid in the pore waters is reflected in a decrease in the sediment, while an enrichment in valine, iso-leucine, leucine, and phenylalanine in the sediment is mirrored by a decrease in the interstitial waters. The distribution of individual hexoseamines appears to be related to zones of bacterial decomposition of organic matter. Low glucoseamine to galactoseamine ratios coincide with zones of sulfate depletion in the interstitial waters.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.

Biostratigraphic and paleomagnetic datum levels in sediments from DSDP Site 85-575

Data on the composition of benthic foraminiferal faunas at Deep Sea Drilling Project Site 575 in the eastern equatorial Pacific Ocean were combined with benthic and planktonic carbon- and oxygen-isotope records and CaCO3 data. Changes in the composition of the benthic foraminiferal faunas at Site 575 predated the middle Miocene period of growth of the Antarctic ice cap and cooling of the deep ocean waters by about 2 m.y., and thus were not caused by this cooling (as has been proposed). The benthic faunal changes may have been caused by increased variability in corrosivity of the bottom waters, possibly resulting from enhanced productivity in the surface waters.