Early diagenesis of organic matter in Peru continental margin sediments: Phosphorite precipitation

Pore water chemistry (total dissolved CO₂, NH₄, NO₃, NO₂, PO₄, Si(OH)₄, Ca, Mg, Fe, Mn, SO₄, H₂S and F, and titration alkalinity), solid phase chemistry (C_org, P_org, C_TOT, N_TOT, F, Si_OPAL and S_II), and sediment characteristics (porosity, dry bulk density and formation factors) were determined on a centimeter-scale spacing in the upper 20–40 cm of sediments under intense upwelling areas on the Peru continental shelf. These data demonstrate that carbonate fluorapatite (CFA) is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content (up to 20% C_org), very high porosity ( > 0.96 ml cm⁻³) and very low dry bulk density (< 0.1 g cm⁻³). Dissolved phosphate concentrations at the sediment-water interface range from 20 to 100 μM, orders of magnitude higher than bottom-water concentrations, and much higher than predicted from regeneration of organic matter. The mechanism of this interfacial phosphate release is unclear, but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments. Fluoride is incorporated into CFA by diffusion from the overlying seawater, and carbonate ions are provided from pore-water alkalinity. Magnesium concentrations in this reaction zone are not significantly different from those of seawater, suggesting that magnesium depletion is not a necessary prerequisite for CFA precipitation.

The environment of precipitation is interface-linked rather than driven by organic diagenesis of phosphorus deeper in the sediment. Most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region, but almost all show the precipitation signature near the interface. This interface-linked early diagenetic porewater environment for the precipitation of CFA explains many of the geochemical characteristics of phosphorites and provides a “testable” model to compare the modern phosphogenic analog with ancient phosphorite deposits. Two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites.     

Petrology and major element geochemistry of Peru margin phosphorites and associated diagenetic minerals: Authigenesis in modern organic-rich sediments

New petrographic and major element geochemical data from modern Peru margin upper slope-outer shelf phosphorites are presented, which provide insight into their origin and paragenetic relationship with other authigenic minerals (glauconite, pyrite and dolomite) occurring in organic-rich sediments. Glauconites are precipitated relatively early following the partial reduction of ferric iron and, following this process, phosphate, pyrite, and then dolomite precipitation take place at progressively deeper levels in the sediment in association with microbial reduction of sulfate. As in many ancient economic phosphorite deposits, the phosphatic facies here consist of nodules, crusts, coatings and strata composed of phosphatic pelletal grains (ooids, structureless grains, intraclasts, clumps and biogenic grains) in association with organic-rich biosiliceous sediments. All are considered to have formed within a few centimeters or within a few tens of centimeters below the sediment-water interface. Important factors that influence which morphology will tend to develop include the amount of available pore space, the presence of suitable nucleation sites, the amount and size of siliciclastic detritus incorporated as inclusions and the relative solution chemistries of the precipitating solutions. Bacterial mediation may play an important, but as yet unspecified role in the precipitation process. Textural data and factor analysis of chemical data suggest that structureless pellets are relatively inclusion-free Na-F-Mg-CO₃-substituted pore-water precipitates whereas ooids are inclusion-rich pore-water precipitates poor in lattice-substituted components. Variations in nodular cement birefringence and crystallinity are suggested to have been produced by similar lattice substitutions that directly reflect pore-water carbonate ion concentrations and thus relative degrees of organic-matter degradation. Phosphate and dolomite are intimately mixed, yet mineralogically distinct phases in phosphatized dolomicrites.

Depth-stratified threshold carbonate ion concentrations may control the lower limit at which phosphatic minerals may precipitate. Below depths of a few centimeters, excessive carbonate ion concentrations and diminished reactive iron and sulfate concentrations favor the development of dolomite while precluding further development of phosphatic minerals and pyrite. Periodic sediment reorganization (bioturbation, current winnowing and erosion, mass wasting, etc.) plays an important role in both concentrating pelletal grains and maintaining nodules and crusts at critical depth levels in the sediment, as well as mixing ordered mineral parageneses into complicated sequences.     

Accumulation of organic and inorganic carbon in Pliocene–Pleistocene sediments along the SW African margin

The Ocean Drilling Program Leg 175 recovered a unique series of stratigraphically continuous sedimentary sections along the SW African margin, an area which is presently affected by active coastal upwelling. The accumulation rates of organic and inorganic carbon are a major component of this record. Four Leg 175 sites (1082, 1084, 1085, 1087) are chosen as part of a latitudinal transect from the present northern to southern boundaries of the Benguela Current upwelling system, to decipher the Pliocene–Pleistocene history of biogenic production and its relationship with global and local changes in oceanic circulation and climate. The pattern of CaCO₃ and C_org mass accumulation rates (MARs) over 0.25-Myr intervals indicates that the evolution of carbon burial is highly variable between the northern and the southern Benguela regions, as well as between sites that have similar hydrological conditions. This, as well as the presence over most locations of high-amplitude, rapid changes of carbon burial, reflect the partitioning of biogenic production and patterns of sedimentation into local compartments over the Benguela margin. The combined mapping of CaCO₃ and C_org MARs at the study locations suggests four distinct evolutionary periods, which are essentially linked with major steps in global climate change: the early Pliocene, the mid-Pliocene warm event, a late Pliocene intensification of northern hemisphere glaciation and the Pleistocene. The early Pliocene spatially heterogeneous patterns of carbon burial are thought to reflect the occurrence of mass-gravitational movements over the Benguela slope which resulted in disruption of the recorded biogenic production. This was followed (3.5–3 Ma) by an episode of peak carbonate accumulation over the whole margin and, subsequently, by the onset of Benguela provincialism into a northern and a southern sedimentary regime near 2 Ma. This mid and late Pliocene evolution is interpreted as a direct response to changes in the ventilation of bottom and intermediate waters, as well as to dynamics of the subtropical gyral circulation and associated wind stress.     

Types of mixing and heterogeneities in siliciclastic-carbonate sediments

Mixed siliciclastic-carbonate deposits consist of a suite of different types of mixing between the two components, from bed (core-plug) to stratigraphic (seismic) scales, producing a high vertical and lateral lithological variability. Mixed deposits results from the interaction of siliciclastic input and coeval carbonate production controlled by temporal and/or spatial factors. Although mixed deposits are very diffuse in the geological record, studies about these deposits are scrappy and not well encoded. Accordingly, mixed deposits represent a labyrinth for researchers who want to investigate them for the first time.In this paper, different types of mixing (compositional versus strata) controlled by different allocyclic (e.g. sea-level, climate) and/or autocyclic (e.g. depositional processes) factors that operate at different scale are documented. Mixing is recognized and described at three main scales of observation: bed/core-plug scale; lithofacies/well-log scale; and stratigraphic/seismic scale. (i) Compositional mixing reflects the contemporaneous accumulation of the two heterolithic fraction in space and time. This type of mixing is observable at lamina to bed scale, locally producing depositional structures diagnostic for particular depositional environments. (ii) Strata mixing results from the alternation of the two heterolithic fraction in time. This type of mixing is observable at lithofacies to stratigraphic scale and can be related to depositional processes, climatic variations and/or relative sea-level changes.A correct identification of these different types of mixing and the scale of their occurrence is crucial in revealing (i) physical processes that control the sedimentation, (ii) environmental factors that influence the carbonate factory related to the siliciclastic dispersal mechanisms, and (iii) internal heterogeneity of the resulting sedimentary deposit. Furthermore, the petroleum industry is interested to unravel new insights about internal properties of mixed siliciclastic-carbonate systems (e.g., porosity, permeability) and to reconstruct predictive 3D models for the related reservoirs. The correct prediction of internal heterogeneity and the recognition of lateral and vertical compartmentalization have an important impact on hydrocarbon exploration and exploitation.     

Organic carbon stable isotope ratios of continental margin sediments

Stable isotope ratios (δ¹³C) of total organic carbon were measured in surface sediments from the continental margins of the northern and western Gulf of Mexico, the north coast of Alaska and the Niger Delta. Gulf of Mexico outer-shelf isotope ratios were in the same range as has been reported for Atlantic coastal shelf sediments, ?21.5 to ?20‰. Off large rivers including the Mississippi, Niger and Atchafalaya (Louisiana), δ¹³C values increased from terrigenous-influenced (around ?24‰) to typically marine ($\text{～?20‰}$) within a few tens of kilometers from shore. This change was accompanied by a decrease in the amount of woody terrigenous plant remains in the sediment. Alaskan continental margin samples from the cold Beaufort Sea had isotopically more negative carbon (?25.5 to ?22.6‰) than did warmer-water sediments. The data indicate that the bulk of organic carbon in Recent sediments from nearshore to outer continental shelves is marine derived.     

Fish scales in sediments from off Callao,central Peru

We study fish scales as a proxy of fish abundance and preservation biases together with phosphorus from fish remains (P_fish) in a sediment core retrieved off Callao, Peru (12°1′S, 77°42′W; water depth=179 m; core length=52 cm). We interpret our results as a function of changing redox conditions based on ratios of redox-sensitive trace elements (Cu/Al, Mo/Al, Ni/Al, Zn/Al, V/Al), terrigenous indicators (Fe in clays, Ti, Al), and biogenic proxies (CaCO₃, biogenic opal, total nitrogen, organic carbon, barite Ba). The core covers roughly 700 years of deposition, based on ²¹⁰Pb activities extrapolated downcore and ¹⁴C dating at selected intervals. Our fish-scale record is dominated by anchovy (Engraulis ringens) scales followed by hake (Merluccius gayii) scales.The core presented an abrupt lithological change at 17 cm (corresponding to the early 19th century). Above that depth, it was laminated and was more organic-rich (10–15% organic carbon) than below, where the core was partly laminated and less organic-rich (<10%). The lithological shift coincides with abrupt changes in dry bulk density and in the contents of terrigenous and redox-sensitive trace elements, biogenic proxies, and fish scales. The remarkable increase in redox-sensitive trace elements in the upper 17 cm of the core suggests more reducing conditions when compared with deeper and older horizons, and is interpreted as an intensification of the oxygen minimum zone off Peru beginning in the early 19th century. Higher fish-scale contents and higher P_fish/P_total ratios were also observed within the upper 17 cm of the core. The behavior of biogenic proxies and redox-sensitive trace elements was similar; more reduced conditions corresponded to higher contents of CaCO₃, C_org, total nitrogen and fish scales, suggesting that these proxies might convey an important preservation signal.     

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin

Methylmercury (MeHg) concentration and production rates were studied in bottom sediments along the mainstem of Chesapeake Bay and on the adjoining continental shelf and slope. Our objectives were to 1) observe spatial and temporal changes in total mercury (HgT) and MeHg concentrations in the mid-Atlantic coastal region, 2) investigate biogeochemical factors that affect MeHg production, and 3) examine the potential of these sediments as sources of MeHg to coastal and open waters. Estuarine, shelf and slope sediments contained on average 0.5 to 1.5% Hg as MeHg (% MeHg), which increased significantly with salinity across our study site, with weak seasonal trends. Methylation rate constants (k_meth), estimated using enriched stable mercury isotope spikes to intact cores, showed a similar, but weaker, salinity trend, but strong seasonality, and was highly correlated with % MeHg. Together, these patterns suggest that some fraction of MeHg is preserved thru seasons, as found by others [Orihel, D.M., Paterson, M.J., Blanchfield, P.J., Bodaly, R.A., Gilmour, C.C., Hintelmann, H., 2008. Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem. Environmental Pollution 154, 77] Similar to other ecosystems, methylation was most favored in sediment depth horizons where sulfate was available, but sulfide concentrations were low (between 0.1 and 10 μM). MeHg production was maximal at the sediment surface in the organic sediments of the upper and mid Bay where oxygen penetration was small, but was found at increasingly deeper depths, and across a wider vertical range, as salinity increased, where oxygen penetration was deeper. Vertical trends in MeHg production mirrored the deeper, vertically expanded redox boundary layers in these offshore sediments. The organic content of the sediments had a strong impact on the sediment:water partitioning of Hg, and therefore, on methylation rates. However, the HgT distribution coefficient (K_D) normalized to organic matter varied by more than an order of magnitude across the study area, suggesting an important role of organic matter quality in Hg sequestration. We hypothesize that the lower sulfur content organic matter of shelf and slope sediments has a lower binding capacity for Hg resulting in higher MeHg production, relative to sediments in the estuary. Substantially higher MeHg concentrations in pore water relative to the water column indicate all sites are sources of MeHg to the water column throughout the seasons studied. Calculated diffusional fluxes for MeHg averaged  1 pmol m^− 2 day^− 1. It is likely that the total MeHg flux in sediments of the lower Bay and continental margin are significantly higher than their estimated diffusive fluxes due to enhanced MeHg mobilization by biological and/or physical processes. Our flux estimates across the full salinity gradient of Chesapeake Bay and its adjacent slope and shelf strongly suggest that the flux from coastal sediments is of the same order as other sources and contributes substantially to the coastal MeHg budget.     

Accumulation rate and heavy metal pollution in Osaka Bay sediments

The accumulation rates of sediment cores in Osaka Bay have been determined by using²¹⁰Pb dating technique. In the upper 10 cm²¹⁰Pb_ex contents show a constant value with depth. The accumulation rates below the homogeneous layer of sediments ranging from 0.12 to 0.61cm y^–1 (0.067–0.34 g cm^–2 y^–1) were obtained. The higher contents of Zn, Cu, Pb and Cr were observed in the upper 10 to 30 cm of sediments. Assuming that the increment of heavy metal content in sediments is due to anthropogenic origin, the amount of anthropogenic input of heavy metals into sediments were estimated to be 1,300–2,700g cm^–2 for Zn, 150 – 480 for Cu, 360 – 410 for Pb and 320 – 480 for Cr. The increment appears to start about 100 years ago. In surfical sediments most of heavy metal contents exceeded the background content, and then most part of Osaka Bay is polluted by heavy metals.     

Meiofaunal distributions on the Peru margin:: relationship to oxygen and organic matter availability

A quantitative study of metazoan meiofauna was carried out on bathyal sediments (305, 562, 830 and 1210 m) along a transect within and beneath the oxygen minimum zone (OMZ) in the southeastern Pacific off Callao, Peru (12°S). Meiobenthos densities ranged from 1517 (upper slope, middle of OMZ) to 440–548 ind. 10 cm⁻² (lower slope stations, beneath the OMZ). Nematodes were the numerically dominant meiofaunal taxon at every station, followed by copepods and nauplii. Increasing bottom-water oxygen concentration and decreasing organic matter availability downslope were correlated with observed changes in meiofaunal abundance. The 300-m site, located in the middle of the OMZ, differed significantly in meiofaunal abundance, dominance, and in vertical distribution pattern from the deeper sites. At 305 m, nematodes amounted to over 99% of total meiofauna; about 70% of nematodes were found in the 2–5 cm interval. At the deeper sites, about 50% were restricted to the top 1 cm. The importance of copepods and nauplii increased consistently with depth, reaching ∼12% of the total meiofauna at the deepest site. The observation of high nematode abundances at oxygen concentrations <0.02 ml l⁻¹ supports the hypothesis that densities are enhanced by an indirect positive effect of low oxygen involving (a) reduction of predators and competitors and (b) preservation of organic matter leading to high food availability and quality. Food input and quality, represented here by chloroplastic pigment equivalents (CPE) and sedimentary labile organic compounds (protein, carbohydrates and lipids), were strongly, positively correlated with nematode abundance. By way of contrast, oxygen exhibited a strong negative correlation, overriding food availability, with abundance of other meiofauna such as copepods and nauplii. These taxa were absent at the 300-m site. The high correlation of labile organic matter (C-LOM, sum of carbon contents in lipids, proteins and carbohydrates) with CPE (Pearson's r=0.99, p<0.01) suggests that most of the sedimentary organic material sampled was of phytodetrital origin. The fraction of sediment organic carbon potentially available to benthic heterotrophs, measured as C-LOM/Total organic carbon, was on average 17% at all stations. Thus, a residual, refractory fraction, constitutes the major portion of organic matter at the studied bathyal sites.     

The study of mixing rates and sedimentation rates in Meizhou Bay sediments

-The applicability of the doubie-layer model for 210Pb chronology in coastal marine environments was discussed,which is successfully used in the study of mixing rates and sedimentation rates in Meizhou Bay. Differences among sedimentation rates deduced from 210Pb, 210Po, and 137Cs were compared. Mixing rates in the sediment surface layer were determined by means of excess 234Th.     

Partitioning of organic matter in continental margin sediments among density fractions

Hydrodynamic processes sort and redistribute organic matter (OM) and minerals on continental margins. Density fractionations were conducted on sediments from diverse margins (Mexico margin, Gulf of Mexico, Mississippi River delta, Eel River margin) to investigate the nature, provenance and age of OM among density fractions. Mass, elemental (C and N), lignin, and surface area distributions, as well as stable carbon and radiocarbon isotopic compositions were measured. The lowest density fractions (< 1.6 g cm^− 3) contained the highest organic carbon (OC) (up to 45%) and lignin concentrations (up to 8 mg g^− 1) due to abundant woody debris, whereas high density fractions (> 2.5 g cm^− 3) were OC-poor (%OC < 0.5) mineral material. Most sediment mass was found in the mesodensity fractions (1.6 to 2.5 g cm^− 3) that contained the highest proportion of OC (up to ~ 75%) for each sediment. Stable carbon isotope compositions (δ¹³C − 25.5‰ to − 22.9‰) show terrigenous OC as a significant component of density isolates from the river-dominated sediments (Gulf of Mexico, Mississippi River, and Eel margin), whereas the Mexico margin, least influenced by riverine input, was dominated by autochthonous marine OC (δ¹³C ~ − 21.5‰). Radiocarbon compositions of density fractions indicate significant pre-aged OC (Δ¹⁴C as low as − 900‰) in river-influenced sediments but not on the Mexico margin (Δ¹⁴C > − 200‰). Ratios of vanillic acid to vanillin (Ad/Al)v among lignin oxidation products increase with increasing particle density suggesting variable lignin sources or selective degradation of lignin among the different density fractions.     

Accumulation of biogenie silica and opal dissolution in upper quaternary skagerrak sediments

In a core from the outer Skagerrak, the content of biogenic opal is higher in Late Pleistocene (Younger Dryas) than in Holocene deposits. In terms of opal accumulation, rates are 1 g/cm²/1,000 y during the Holocene and five to ten times larger during the Younger Dryas. Intensive dissolution has greatly reduced the Holocene opal content and does not allow calculation of paleoproductivity. The intensity of opal dissolution is reflected by dissolution stages of both the diatomParalia sulcata and sponge spicules. The intensity of dissolution is negatively correlated to the sedimentation rate and appears to be controlled by silica-undersaturated environment on the sea floor and the uppermost sediment layer.     

Sedimentation and mixing rates of radionuclides in Barents Sea sediments off Novaya Zemlya

Radionuclide measurements have been conducted on sediment cores collected in 1992 in the south-eastern region of the Barents Sea, known as the Pechora Sea. Cesium-137 and ^239,24OPu activities in surface sediments are generally less than 30 Bq/kg, with the highest levels being measured in sediments off the southwestern coastline of the island of Novaya Zemlya. High correlations between both ¹³⁷Cs and ^239,24OPu and the concentration of fine (< 63 μm) particles in surface sediments indicate that much of the variance in radionuclide concentrations throughout the Pechora Sea can be explained by particle size fractionation. However, elevated activities of ¹³⁷Cs (138 Bq/kg), ⁶⁰Co (92 Bq/kg), ²⁴¹Am (433 Bq/kg), and especially ^239,24OPu (8.47 × 103 Bq/kg) were measured in one surface sediment sample from the fjord of Chernaya Bay on the southern coast of Novaya Zemlya. The source of radioactive contamination is two underwater nuclear tests conducted in Chernaya Bay in 1955 and 1957.The ²³⁸Pu/^239,240Vu activity ratio of 0.0245 in Chernaya Bay is equivalent to values measured in global fallout. The ²⁴⁰Pu/²³⁹Pu atom ratio (0.0304), measured by mass spectrometry, is much lower than values (0.18) typical of global fallout, but is consistent with ratios measured for fallout from the early (1951–1955) series of weapons tests at the Nevada Test Site. The timing of the Chernaya Bay source term, estimated from the ²⁴¹Am/²⁴¹Pu ratio, is consistent with the timing of the 1955 and 1957 underwater nuclear tests. Relatively low initial yields of ²⁴¹Pu (²⁴¹Pu/²³⁹Pu atom RATIO = 0.00 123) in these tests have resulted in relatively low ²⁴¹Am/^239,240Pu activity ratios (0.05) in recent sediments in Chernaya Bay.Radionuclide tracer profiles in cores from the Pechora Sea can be simulated using a two-layer biodiffusion model with rapid, near-homogeneous mixing in the surface mixed layer and reduced mixing in the deep layer. Lead-210 profiles are consistent with a wide range of sedimentation and mixing rates in the deep sediment layer. However, the ¹³7Cs and ^239,240Pu results further constrain the model parameters and indicate that the downward transport of radionuclides in the sediments is governed primarily by sediment mixing, with sediment burial playing a secondary role.     

Comparison of marine gas hydrates in sediments of an active and passive continental margin

Two sites of the Deep Sea Drilling Project in contrasting geologic settings provide a basis for comparison of the geochemical conditions associated with marine gas hydrates in continental margin sediments. Site 533 is located at 3191 m water depth on a spit-like extension of the continental rise on a passive margin in the Atlantic Ocean. Site 568, at 2031 m water depth, is in upper slope sediment of an active accretionary margin in the Pacific Ocean. Both sites are characterized by high rates of sedimentation, and the organic carbon contents of these sediments generally exceed 0.5%. Anomalous seismic reflections that transgress sedimentary structures and parallel the seafloor, suggested the presence of gas hydrates at both sites, and, during coring, small samples of gas hydrate were recovered at subbottom depths of 238m (Site 533) and 404 m (Site 568). The principal gaseous components of the gas hydrates wer methane, ethane, and CO₂. Residual methane in sediments at both sites usually exceeded 10 mll^?1 of wet sediment. Carbon isotopic compositions of methane, CO₂, and ΣCO₂ followed parallel trends with depth, suggesting that methane formed mainly as a result of biological reduction of oxidized carbon. Salinity of pore waters decreased with depth, a likely result of gas hydrate formation. These geochemical characteristics define some of the conditions associated with the occurrence of gas hydrates formed by in situ processes in continental margin sediments.     

Carbonate removal by acidification causes loss of nitrogenous compounds in continental margin sediments

This study reports on measurements of organic carbon (C_org) and total nitrogen (N_tot) in surface sediments originating from 6 transects along the northwest European continental margin. After elimination of carbonates by an acidification technique using sulphurous acid, both elements were analysed in the same sediment sample using an elemental analyser. C_org and N_tot in the sample were comparatively low, ranging between 1 and 10 mg C and 0.2 to 1 mg N g⁻¹ dry sediment. In a second analysis, the samples were analysed without acid addition, resulting in N_tot concentrations of 0–50% higher compared to their acidified counterparts. As a consequence, molar C/N ratios derived from the analysis of C_org and N_tot in the acidified sample ranged between 6 to 11, while the N_tot separate analysis reduced C/N ratios to 6 to 8. It is suggested that the addition of sulphurous acid to eliminate inorganic carbon volatilises nitrogenous organic matter.     

Surficial sediments on the continental margin off the west coast of South Africa

A combination of climatic and oceanic factors has resulted in slow sedimentation rates on the continental shelf off the west coast of South Africa since Tertiary times. This has enabled a study to be made of the residual Late Tertiary, relict Pleistocene and Holocene sediments.Sediments on the continental shelf form rough belts parallel to the coast. Most of the coarse sediment is confined to the littoral zone and Holocene mud is concentrated at the base of a rocky nearshore platform. A veneer of Quaternary quartzitic sand seawards of the Recent mud belt wedges out onto a Tertiary erosion surface on the mid shelf. Residual glauconite and phosphorite sands derived by erosion during Tertiary sea-level fluctuations cover large parts of the mid shelf in the south. Most of the slope and parts of the outer shelf in the north are draped by Recent foraminiferal and coccolithophorid debris.     

Seismic quality factor observations for gas-hydrate-bearing sediments on the western margin of India

Any propagating wave undergoes attenuation, which is primarily governed by the physical properties of the medium, determined in terms of quality factor (Q). Research into the characteristics of both P- and S-wave Q with reference to gas-hydrates exploration remains in its infancy. Presence of gas-hydrates increases the Q, and this again depends on the nature of distribution and amount of hydrates within the sediments. Thus, estimation of Q provides useful input for both the detection and quantitative assessment of gas-hydrates. Here we propose a simple technique of deriving Q from prestack surface seismic reflection data based on the logarithm of spectral ratio (LSR), and apply the method to marine multi-channel seismic (MCS) data collected on the western margin of India where a bottom simulating reflector (BSR), which is a prime marker for gas-hydrates, has already been identified. The Q (256 ± 11) estimated over the region with a strong BSR is found to be more than double the Q (101 ± 9) derived for the region without any BSR or a weak BSR. The anomalously high Q with respect to the background can be used to detect gas-hydrates in areas where the BSR is not very clearly observed on seismic sections.     

Accumulation of uranium in sediments and phosphorites on the South West African shelf

Organic-rich sediments and coexisting phosphorites from the continental shelf off South West Africa have been analysed for uranium and thiorum by alpha-spectrometry. The uranium concentrations in the sediments range from 10 to 55 ppm, with an isotopic composition close to that of sea-water, indicating that uranium is passing into the sediments at the present time. The phosphorites occur in the sediments as thin unconsolidated laminae and as lithified nodules and pellets, with uranium contents ranging from 79 to 158 ppm. Based on the uranium isotopic composition, only the unconsolidated phosphorite laminae are recent, while the lithified nodules and pellets, with ²³⁴U/²³⁸U and ²³⁰Th/²³⁴U ratios close to radio-active equilibrium, appear to be inherited from a previous period of phosphorite deposition. Deposition of uranium appears to take place predominantly by incorporation into carbonate fluorapatite growing authigenically within the sediment. Uranium accumulation rates, computed from ¹⁴C-dated sections of the sediment cores, and using only uranium values with modern isotopic composition, range from 232 to 765 μg/cm² per 1,000 years. These results stress the importance of organic-rich sediments containing authigenic phosphorite beneath areas of high organic productivity as a major sink for uranium in the ocean.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.