Manganese fluxes from Mississippi Delta sediments

Massive sediment deposition on the Mississippi River Delta establishes reducing conditions sufficient to bring about Mn dissolution in the top millimeters of sediment. As a result, significant fluxes of dissolved Mn pass from the Delta sediments to the overlying water column. This process is examined by study of chemical partitioning of Mn in river particulates and Delta sediments and from interstitial water chemistry. Remobilized Mn is actively transported away from the Delta area with aluminosilicate detritus thereby providing “excess” Mn to the deep Gulf of Mexico at the expense of the Delta sediments.     

Geochemistry of continental margin sediments from northwest Africa

The geochemistry of the non-carbonate fraction of sediments from the continental shelf and slope off northwest Africa has been investigated using R-mode factor analysis. The geochemistry is governed by a small number of factors controlled quantiatively by glauconite, phosphorite, quartz, clay minerals and secondary iron oxides. The distributions of the factors and of their controls are governed by mineral provenance and by depositional processes. Clay mineral factors predominate in fine grained sediments. Phosphorite, glauconite and oxide factors and quartz predominate in sands. Provenance controls the relative abundances of the minerals of the sand fraction all of which, except a proportion of the glauconite which is clearly recent, are relict and detrital. The recent glauconite is concentrated in poorly oxidised sediments off the southern Sahara. Provenance differences are detected between Saharan and Moroccan clays, and also exist between the clays of north and south Morocco.     

Ordination of sediments from the Cape Hatteras continental margin

Ordination is a multivariate technique developed by plant ecologists which has proven effective in the interpretation of paleoenvironments. It allows gradational relationships among samples to be depicted in contrast to other quantitative techniques which classify samples into discrete groups. In this study, ordination is used to interpret textural data for 62 bottom samples taken from the Cape Hatteras, North Carolina, continental margin. The ordination suggests the existence of six sedimentary facies that are similar to those obtained by cluster analysis using a dendrograph display. The facies represented are: littoral sands and outer-shelf shelly sands; inner-shelf sands; outer-shelf sands and silts; outer-shelf slope silts; and two highly biogenic, deep-water silt and clayey silt facies with similar characteristics. The facies are related in a qualitative manner to the environmental processes operating off Cape Hatteras. Chicago Bridge Technical Paper No. 5139.     

Pore water fluoride in Peru continental margin sediments: Uptake from seawater

Fluoride analyses display downward decreasing pore water gradients in Peru shelf phosphatic muds that require diffusion from the overlying seawater into the sediment column and removal by reaction within the upper few tens of centimeters, presumably by incorporation into carbonate fluorapatite. The profiles can be modeled as first-order F-removal with rate constants of ~3 yr^?1 and asymptotic F-concentrations deep in the cores of 35–45 μM, almost one-half the seawater value. The integrated flux of fluoride from seawater into organic-rich shelf sediments in coastal-upwelling zones (phosphatic muds) yields a contemporaneous global F-burial of 0.54 × 10¹⁰ mol-F yr^?1, about one-fifth the burial in other sinks (mostly carbonates and opal). The associated burial flux of phosphorus in shelf phosphorites is about 1.6 × 10¹⁰ mol-P yr^?1, comparable to P-burial in the deep sea with organic matter (~1.4 × 10¹⁰ mol yr^?1) and biogenic carbonates (~1.4 × 10¹⁰ mol yr^?1). Thus phosphorite formation on the Peru shelf is a significant contemporaneous process.     

Phosphate regeneration from sediments of the Peru continental margin by dissolution of fish debris

Generally, oxidative regeneration of phosphate from anoxic sediments is by microbially mediated sulfate reduction processes. Stoichiometric modelling of such reactions takes into consideration varying proportions of ‘decomposable’ organically bound P to account for the ratios among nutrients in depth-concentration profiles of near-surface sediments. New results of interstitial water composition from sediments underlying the water masses influenced by coastal upwelling of the eastern boundary current system off Peru indicate that dissolution of phosphatic fish debris represents a mechanism for remineralization of phosphate comparable to or larger in magnitude than that by oxidative regeneration of organically bound P.Dissolved interstitial phosphate from fish debris is revealed by an excess amount of phosphate over that predicted from a simple stoichiometric oxidative regeneration model and by anomalously high dissolved interstitial fluoride concentrations. Phosphate flux estimates based on diffusion from the sediment suggest that this mechanism may generate up to 10% of the nutrient pool in the waters of the Peru undercurrent. Partitioning of P among the two sources reveals further that fish debris phosphate is about four times more important than organically bound P in nutrient generation from sediments of the Peru continental margin. Not only does this mechanism of regeneration affect the nutrient cycling but may also control widespread phosphorite formation in this area.     

The present day formation of apatite in Mexican continental margin sediments

Results of pore water and sediment analyses from the western Mexican continental margin strongly suggest the present day formation of apatite. The interstitial water phosphate and fluoride profiles indicate chemical removal at a depth which corresponds to a large maximum in the phosphorus content of the sediments. Apatite is identified within this maximum via X-ray diffraction but is elsewhere undetectable in the core. Radioisotopic thorium, uranium, and radium data support the conclusion that this deposit is modern. The present day depositional environment is consistent with those reported by other workers for phosphorite formation with the exception that pore water magnesium is not depleted below its seawater value.     

Benthic fluxes and porewater concentration profiles of dissolved organic carbon in sediments from the North Carolina continental slope

Numerous studies of marine environments show that dissolved organic carbon (DOC) concentrations in sediments are typically tenfold higher than in the overlying water. Large concentration gradients near the sediment–water interface suggest that there may be a significant flux of organic carbon from sediments to the water column. Furthermore, accumulation of DOC in the porewater may influence the burial and preservation of organic matter by promoting geopolymerization and/or adsorption reactions. We measured DOC concentration profiles (for porewater collected by centrifugation and “sipping”) and benthic fluxes (with in situ and shipboard chambers) at two sites on the North Carolina continental slope to better understand the controls on porewater DOC concentrations and quantify sediment–water exchange rates. We also measured a suite of sediment properties (e.g., sediment accumulation and bioturbation rates, organic carbon content, and mineral surface area) that allow us to examine the relationship between porewater DOC concentrations and organic carbon preservation. Sediment depth-distributions of DOC from a downslope transect (300–1000 m water depth) follow a trend consistent with other porewater constituents (ΣCO₂ and SO₄²⁻) and a tracer of modern, fine-grained sediment (fallout Pu), suggesting that DOC levels are regulated by organic matter remineralization. However, remineralization rates appear to be relatively uniform across the sediment transect. A simple diagenetic model illustrates that variations in DOC profiles at this site may be due to differences in the depth of the active remineralization zone, which in turn is largely controlled by the intensity of bioturbation. Comparison of porewater DOC concentrations, organic carbon burial efficiency, and organic matter sorption suggest that DOC levels are not a major factor in promoting organic matter preservation or loading on grain surfaces. The DOC benthic fluxes are difficult to detect, but suggest that only 2% of the dissolved organic carbon escapes remineralization in the sediments by transport across the sediment-water interface.     

Comparative geochemistry of cadmium, rhenium, uranium, and molybdenum in continental margin sediments

The concentrations of authigenic phases of Cd, Re, U, and Mo increase with depth in four 45-cm-long sediment box cores collected along the axis of the Laurentian Trough, Gulf of St. Lawrence. Average authigenic accumulation rates, estimated from element inventories, are similar to rates in other continental margin environments. Strong regional variations in sediment accumulation rate and sulfide concentration have little influence on the accumulation rates of Cd and Re. This suggests that slow precipitation kinetics controls the accumulation of Cd and Re in these sediments. The accumulation rate of authigenic U is more variable; it may be tied to the kinetics of microbially mediated U reduction and be controlled by the availability of reactive organic matter. Authigenic Mo is distinguished by a sharp subsurface concentration minimum, above which Mo cycles with manganese. Mo released to pore water upon reduction of Mn oxides diffuses downward and enriches the subsurface sediment. Mo accumulates most rapidly in the sediment with the highest sulfide content. Slow conversion of molybdate to thiomolybdate may explain the much slower Mo accumulation rate in the less sulfidic sediments. A component of authigenic Mo accumulates with pyrite in an approximately constant Mo:Fe ratio. The accumulation rate of pyrite and associated Mo is insensitive to AVS abundance. Pyrite formation may be limited by the reactivity of iron oxide minerals.     

Sources and distributions of tetraether lipids in surface sediments across a large river-dominated continental margin

Glycerol dialkyl glycerol tetraether (GDGT)-based proxies are increasingly used in modern carbon cycling and palaeoenvironmental investigations. It is therefore crucial to examine the robustness (sources, transport and degradation) of all GDGT-based proxies in continental margins, where sedimentation rates and extent of carbon cycling are high. We have analyzed the distributions of GDGTs in surface sediments from the Lower Yangtze River and East China Sea (ECS) shelf. The results revealed multiple sources and complex shelf processes that govern the distributions. The isoprenoid GDGT-inferred sea surface temperatures (SSTs) are robust and reflect the satellite-derived annual mean SSTs on the shallow ECS shelf, confirming an origin from surface water column-dwelling crenarchaeota. The input from methanogen-sourced, isoprenoid GDGTs is significant in the river surface sediments but they are almost absent from the ECS shelf. Branched GDGTs are also abundant in the river sediments, but ca. 95% are degraded in the Yangtze estuary, a much greater extent than observed for other terrigenous organic matter (OM) proxies. There is also evidence for production of branched GDGTs in the oxic ECS shelf water column and the anoxic sediments/waters of the Lower Yangtze River. As a result, branched GDGT-based proxies in the lower river and ECS surface sediments do not reflect the catchment environmental conditions. The effective degradation in the estuary and widespread aquatic contributions of branched GDGTs improves our understanding of how to use branched GDGT-based proxies in marginal seas.     

Limestone lithofacies from the South African continental margin

Carbonate sedimentation has played an important part in the Cainozoic history of the South African offshore areas. The Agulhas Bank sector of the continental shelf and upper slope is covered by a patchy veneer of relict and Recent sediment. Under this thin cover of sediment lies a succession of Cainozoic carbonate rocks very different from those exposed onshore. The Agulhas Bank rocks have been divided into the following lithofacies: (1) lagoonal-quartzose lime wackestones; (2) pelagicforaminiferal lime packstones; and (3) infralittoral-skeletal lime packstones. The rocks within each lithofacies are not necessarily time-equivalents; indeed any one lithofacies may have a considerable time range.     

Holocene denudation of the northwest sector of Iceland as determined from accumulation of sediments on the continental margin

Radiocarbon-dated marine cores, measurements of sediment density and seismic surveys were used to estimate the sediment and mass accumulation rates (m/kyr and kg/m²/kyr) in the troughs from the southwest to north-central Iceland shelf (i.e. northwest sector of Iceland). The 3.5-kHz seismic survey showed varying thicknesses of acoustically transparent sediment in the troughs, whereas the inter-trough banks were largely devoid of sediment. The survey showed a pervasive reflector 1 to ≥60 m below the sea floor, which turned out to be Saksunarvatn tephra, dated at 10 180±60 cal. yr BP. The 3.5-kHz analogue data were digitized at 1-min intervals and provided 1645 estimates of maximum sediment thickness and 979 estimates of sediment accumulation over the last 10 200 cal. yr BP. Maximum sediment accumulation occurred in the mid-troughs and not, as expected, in the fjords. The median sediment accumulation rate (SAR) based on the core data was 0.23 m/kyr, but was 0.77 m/kyr based on the seismic data: the difference is attributed to coring limitations. Based on the volume of offshore sediment and the contributing terrestrial drainage area, the Holocene denudation of northern Iceland (c. 50 000 km²) is calculated to have been between 0.02 to 0.05 m/kyr, substantially lower that the 1-3 m/kyr derived from the suspended sediment load of rivers from southern Iceland but in agreement with the rate of accumulation of Holocene glacial lacustrine sediments in central Iceland.     

Terrigenous sedimentation processes along the continental margin off NW Africa: implications from grain-size analysis of seabed sediments

The terrigenous fraction of seabed sediments recovered along the north‐west African continental margin illustrates spatial variability in grain size attributed to different transport mechanisms. Three subpopulations are determined from the grain‐size analyses (n = 78) of the carbonate‐free silt fraction applying an end‐member modelling algorithm (G. J. Weltje, 1997). The two coarsest end‐members are interpreted as representing aeolian dust, and the fine‐grained end‐member is related to fluvial supply. The end‐member model thus allows aeolian fallout to be distinguished from fluvial‐sourced mud in this area. The relative contributions of the end‐members show distinct regional variations that can be related to different transport processes and pathways. Understanding present‐day sediment dispersal and mixing is important for a better understanding of older sedimentary records and palaeoclimate reconstructions in the region.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Granitic and monzonitic rocks dredged from the southeast Australian continental margin

Four Middle Devonian (381 Ma) granodiorite samples have been recovered from two dredge sites approximately 65 km east of Green Cape, New South Wales. The granodiorite samples are similar in age and composition to members of the Moruya Suite and probably form an along‐strike extension of that suite. The location of granodiorite on the southeastern margin requires that a piece of continental lithosphere was located to the present east of the study area in the Devonian. This piece of lithosphere may now be located somewhere on the western Lord Howe Rise.

A sample of Early Cretaceous leuco‐quartz monzodiorite was also recovered from a dredge site approximately 45 km north‐northeast of Dalmeny, New South Wales. It represents a body that was intruded at essentially the same time as, and is inferred to be of similar origin to, the syenite rocks of the nearby Mt Dromedary and Montague Island complexes.     

210Pb activities in and fluxes to sediments of the Washington continental slope and shelf

Surface sediments of the Washington coast have ²¹⁰Pb activites which average 104 ± 48dpm/g for submarine canyon and slope regimes and 18 ± 12dpm/g for the continental shelf regime. ²¹⁰Pb sedimentary fluxes are also higher in canyons, averaging 18 ± 13dpm/cm² per yr, compared to 5.2 ± 3.1 dpm/cm² per yr for slope and 4.8 ± 1.8dpm/cm² per year for shelf regions. These ²¹⁰Pb activities and fluxes are 2–7 times greater than those reported for other coastal regions. Inputs from the atmosphere and the Columbia River are not sufficient to supply the ²¹⁰Pb, but advection of seawater containing dissolved ²¹⁰Pb produced in situ from ²²⁶Ra provides an input several times larger than the sedimentary fluxes. The sedimentary ²¹⁰Pb flux is limited by scavenging reactions rather than by supply of dissolved ²¹⁰Pb.Calculations of maximum biological uptake and fluxes of ²¹⁰Pb and ‘selective’ chemical leaching experiments all show that the primary scavenging processes are due to hydrous Mn and Fe oxides rather than biological phases. The pattern of higher ²¹⁰Pb depositional fluxes in canyons than in nearby open slope areas of comparable water depth is most reasonably explained by enhanced scavenging of dissolved ²¹⁰Pb near the sea floor, rather than by processes operating throughout the water column. Relatively rapid removal of dissolved ²¹⁰Pb from the near bottom nepheloid layer to slope and canyon sediments is shown by its mean residence time of less than two years in this layer.     

Flexure of the lithosphere and continental margin basins

The accumulation of sediments at an Atlantic-type continental margin constitutes a load on the lithosphere which simply sags due to its weight. Studies of the geometry of deformation suggests the lithosphere will respond to these loads either by local loading of an Airy-type crust or flexural loading of a strong rigid crust. Sediment loading models of either type cannot, however, explain the substantial thicknesses of shallow-water sediments observed in commercial boreholes from Atlantic-type margins. Other factors such as thermal contraction, gravitational outflow of crustal material or deep crustal metamorphism may contribute to the subsidence. We have used biostratigraphic data from commercial boreholes from the Gulf of Lion and the East Coast U.S.A. to quantitatively determine the contribution of sediment loading to the subsidence. From these data we determined sea-floor and basement depths for sequential time intervals during margin development. Using the sediment loading models the sediment layers at each margin were progressively “backstripped” and the depth basement would have been without the sediment load calculated. The computed basement depths indicate there is a recognizable component of the subsidence of these margins which is caused by processes other than adjustments to the weight of the sediment. The nature of this subsidence is discussed and comparisons are made with that which would be expected from thermal-contraction models.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

Geological framework of the Brazilian continental margin

Based on distinctive stratigraphic and/or structural characteristics, the Brazilian continental margin can be divided into two main provinces:

1. The southeastern-eastern province, extending from the Pelotas to the Recife-João Pessoa Basin, presents a tensional tectonic style of Late Jurassic-Early Cretaceous age, paralleling the structural alignements of the Precambrian basement, except in the north-eastern segment where the Mesozoic faults of the Recife-João Pessoa Basin cut across the east-west basement directions. The basin-fill, Upper Jurassic through Recent, consists, where complete, of three stratigraphic sequences, each of a distinct depositional environment: (a) a lower clastic non-marine sequence; (b) a middle evaporitic sequence, and (c) an upper clastic paralic and open marine sequence.
2. The northern province, extending from the Potiguar Basin to the Amazon Submarine Basin, displays both tensional and compressional tectonic styles of Upper Jurassic (?) to Upper Cretaceous age either paralleling or cutting transversally the basement alignments. The stratigraphic column differs from the southeastern-eastern province in lacking the Lower Cretaceous evaporitic rocks.

The integration of the stratigraphie and structural data allows one to determine in the eastern Brazilian marginal basins the main evolutionary stages of a typical pull-apart continental margin: a continental pre-rift and rift stage, an evaporitic proto-ocean stage, and a normal marine open ocean stage. In the northern province it is possible to infer a continental rift-valley-stage, a transform stage and an open continental-margin stage. The relationship between the rift-valley and the transform stages is yet not clear.