Sedimentology and geochemistry of the sand fraction in surface sediments off West Africa

Surface sediments from 5 profiles between 30 and 3000 m water depth off W Africa (12-19° N) have been studied for their sand fraction composition and their total calcium carbonate and organic matter contents to evaluate the effect of climatic and hydrographic factors on actual sedimentation. On the shelf and upper slope (< 500 m), currents prevent the deposition of significant amounts of fine-grained material. The sediments forming here are characterized by high sand contents (> 60 %; in most samples > 89 %), low organic carbon contents (in most samples < 0.8 %), high median diameters of the sand fraction (120-500 µm), and by a predominance of quartz and biogenic relict shells (most abundant: molluscs and bryozoans) in the sand fraction. Median diameters of total sand fraction and of major biogenic sand fraction components (biogenic relict material, benthonic molluscs, benthonic and planktonic foraminifers) co-vary to some extent and show maximum values in 100-300 m water depth, reflectingthe sorting effect of currents (perhaps the northward flowing undercurrent). In this water depth, biogenic relict material is considerably enriched relative to wuartz, the second dominating sand fraction component on the shelf and upper slope, resulting in distinct calcium carbonate maxima of the bulk sediments. The influence of the undercurrent is also reflected in a northward transport of fine grained river load and perhaps in the distribution of the red stained, coarse silt and sand-size clay aggregates, which show maxima in 300-500 m water depth. They probably originate from tropical soils. Abundant coarse red-stained quartz on the shelf off Cape Roxo (12-130° N) suggests a southward extension of last glacial dune fields to this latitude. Below about 500 m water depth, current influence becomes negligible - as indicated by a strong decrease in sand content, a concomitant increase in sedimentary organic carbon contents (up to 2.5-3.5 %), and the occurence of high mica/quartz ratios in the sand fraction. Downslope transport, presumably due to the bioturbation mechanism, is indicated by the presence of coarse shelf-borne particles (glauconite, relict shells) down to about 1000 m water depth. The fine/coarse ratio (clay + silt/sand) of the sediments from water deoth > 500 m never exceed a value of 11 in northern latitudes (19° - 26° N), but shows distinct maxima, ranging from 50 to 120, at latitudes 18°, 17° 15°30', and 14° N in about 2000 m water depth. This distribution is attributed to the deposition of fine-grained river load at the continental slope between 18° and 14° N, brought into the sea by the Senegal and souther rivers and transported northward ny the undercurrent. Strong calcium carbonate dissolution is indicated by the complete disappearance of pteropodes (aragonite) and high fragmentation of the planktoic foraminifers (calcite) in sediments from water depth > 300-600 m. Fragmentation ratios of planktonic foraminifers were found to depend on the organic carbon/carbonate ratios of the sediment suggesting that calcite dissolution at the sea bottom may also be significant in shelf and continental slope water depths if the organic matter/carbonate ratio of the surface sediment is high and the test remain long enough within the oxidizing layer on the top of the sulfate reduction zone. The fact that in the region under study intensity and anual duration of upwelling decrease from north to south is neither reflected in the composition on the sand fraction (i.e. radiolarian and fish debris contents, radiolarian/planktonic foraminiferal ratios, benthos/plankton ratios of foraminifers), nor in the sedimentary organic carbon distribution. On the contrary, these parameters even show in comparable water depths a tendency for highest values in the south, partly because primary production rates remain high in the whole region, particularly on the shelf, due to the nutrient input by rivers in the south. In addition, several hydrographic, sedimentological and climatic factors severely affect their distribution - for example currents, dissolution, grain size composition, deposition of river load, and bulk sedimentation rats.

Calcareous microfossil isotopes and Miocene datum events of ODP Holes 189-1170A and 189-1172A

Downcore oxygen and carbon stable isotope records of planktonic and benthic foraminifers and fine-fraction carbonate from the southern high latitudes provide critical paleohydrographic constraints on the evolution of the Southern Ocean climate. In particular, the potential effects of an intensified Antarctic Circumpolar Current on the thermal isolation and cooling of the southern high latitudes, production of cold deep waters, and, ultimately, accumulation of continental ice on Antarctica in the middle Miocene are matters of interest. Using sediment materials from Ocean Drilling Program Leg 189 Sites 1170 and 1172 off Tasmania, Ennyu and Arthur (2004, doi:10.1029/151GM13) established the surface- and deepwater stable isotope records in the Southern Ocean across the middle Miocene event of the east Antarctic ice sheet expansion and discussed the paleoclimate proxy records in terms of the thermal evolution of the southern high latitudes and its effect on deepwater circulation. This report provides data tables and other supporting information relevant to discussions presented in Ennyu and Arthur (2004, doi:10.1029/151GM13). Items included in this report are (1) the oxygen and carbon stable isotope data measured on the Miocene bulk fine-fraction (i.e., <63 µm, primarily polyspecific nannofossil assemblage) carbonate and planktonic and benthic foraminifers from Holes 1170A and 1172A and (2) the Miocene depth-age models for the two sites.

(Table 1) Sample levels of diatom and silicoflagellate datums at DSDP Holes 69-504 and 69-505

A standard biostratigraphic system, based upon diatom datum levels previously correlated to the paleomagnetic record, was applied to Deep Sea Drilling Project Sites 501/504 and 505. Sedimentation appears to have been constant at the three sites, averaging 50 m/m.y. at Sites 501/504 and 60 m/m.y. at Site 505. Calcium carbonate is rather poorly preserved at both sites, because of depth of water and, at Sites 501/504, alteration by diagenesis. Siliceous microfossils are common and moderately well preserved at the three sites; at Sites 501/504, diatoms disappear abruptly below the first occurrence of chert. The uppermost Miocene diatom assemblage occurs just above chert and is characterized by a strong dominance of Thalassionema and Thalassiothrix, which implies very high silica production during the latest Miocene; the chert probably is derived from a similar assemblage. In the earliest Pliocene, silica production appears to have decreased sharply; about 3 Ma, preservation of calcium carbonate also diminished, suggesting a shoaling of the CCD. At 2 Ma, there occurred a short interval of low production of both calcium carbonate and silica, which lasted into the earliest Pleistocene.

(Table 1) Gypsum, pyrite and glauconite at DSDP Hole 36-329

Authigenic gypsum, pyrite, and glauconite are disseminated throughout an unusually long (346 m) Miocene section of mixed biogenic carbonate and diatomaceous ooze drilled on the Falkland Plateau at DSDP Site 329 (water depth, 1519 m). The present organic carbon content of the sediment is low, ranging between 0.1 and 0.7%. Gypsum occurs as euhedral single or twinned crystals of selenite up to 5 mm in diameter, sometimes in the form of gypsum rosettes. These crystals are intact and unabraded, comprising up to 4% of the washed sample. The authigenic nature of the gypsum is demonstrated by the presence of diatoms and radiolarians embedded within the gypsum crystals. The gypsum co-occurs with pyrite and glauconite in these samples. The pyrite occurs as framboids, foraminiferal infillings, rods, and granular sheetlike masses composed of pyrite octahedra. The glauconite occurs as foraminiferal infillings and as free grains. The gypsum and pyrite were identified by energy-dispersive X-ray analysis and scanning electron micrographs. Some of the gypsum has grown on pyrite, indicating that it precipitated after the pyrite, perhaps in response to a change in pH conditions. The formation of the mineral suite can be explained by current models of in situ sulfide and sulfate precipitation coincident with diagenesis and oxidation of much of the original organic carbon.

Age model and sediment description of DSDP Hole 90-594, Chatham Ridge east of New Zealand

Detailed sedimentological investigations were performed on sediments from DSDP-Site 594 (Chatham Rise, east of New Zealand) in order to reconstruct the evolution of paleoclimate and paleoceanographic conditions in the Southwest Pacific during the last 6 million years. The results can be summarized as follows: (1) High accumulation rates of biogenic opal and carbonate and the dominance of smectites in the clay fraction suggest increased oceanic productivity and an equable dominantly humid climate during the late Miocene. (2) During Pliocene times, decreasing contents of smectites and increasing feldspar/quartz ratios point to an aridification in the source area of the terrigenous sediments, culmunating near 2.5 Ma. At that time, accumulation rates of terrigenous components distinctly increased probably caused by increased sediment supply due to intensified atmospheric and oceanic circulation, lowered sea level, and decreased vegetation cover. (3) A hiatus (1.45 to 0.73 Ma) suggests intensified intermediate-water circulation. (4) Major glacial/interglacial cycles characterize the upper 0.73 Ma. During glacial times, oceanic productivity and terrigenous sediment supply was distinctly increased because of intensified atmospheric and oceanic circulations and lowered sea level, whereas during interglacials productivity and terrigenous sediment supply were reduced. (5) An increased content of amphibols in the sediments of Site 594 indicates increased volcanic activities during the last 4.25 Ma.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Stable isotopic record of late Pliocene and Pleistocene foraminifera of ODP Site 114-704

We studied the stable isotopic and carbonate stratigraphy of ODP Hole 704A to reconstruct the paleoceanographic evolution of the eastern subantarctic sector of the South Atlantic Ocean. Site 704 is well positioned with respect to latitude (46°52.8'S, 7°25.3'E) and bathymetry (2532 m) to monitor past migrations in the position of Polar Front Zone (PFZ) and changes in deep-water circulation during the late Pliocene-Pleistocene. Several important changes occurred in proxy paleoceanographic indicators across the Gauss/Matuyama boundary at 2.47 Ma: (1) accumulation rates of biogenic sedimentary components increased by an order of magnitude (Froelich et al., this volume); (2) planktonic d1 8O values increased by an average of 0.5 per mil; (3) the amplitude of the benthic d18O signal increased; (4) the accumulation rate of ice-rafted detritus increased several fold (Warnke and Allen, this volume); and (5) carbon isotopic ratios of benthic foraminifers decreased by 0.5 per mil, as did the d13C of the fine-fraction carbonate by 1.5 per mil (Mead et al., 1991, doi:10.2973/odp.proc.sr.114.152.1991), but no change occurred in planktonic foraminiferal d13C values. Most of these changes are consistent with more frequent expansions and contractions of the PFZ over Site 704 after 2.47 Ma, bringing cold, nutrient-rich waters to 47°S that stimulated both carbonate and siliceous productivity. The synchronous increase in d18O values and ice-rafted detritus accumulation in Hole 704A indicates that the 2.4 Ma paleoceanographic event included ice volume growth on both Antarctica and Northern Hemisphere continents. The decrease in benthic d13C values indicates that the ventilation rate of Southern Ocean deep water decreased and the nutrient content increased during glacial events after 2.5 Ma. At the Gauss/Matuyama boundary, benthic d13C values of the Southern Ocean shifted toward those of the Pacific end member, indicating a decrease in the relative mixing ratio of Northern Component Water and Circumpolar Deep Water. During the early Matuyama (~2.3 to 1.7 Ma), the PFZ generally occupied a southerly position with respect to Site 704 and carbonate productivity prevailed. Exceptions to these general conditions occurred during strong glacial events of the early Matuyama (e.g., isotopic stages 82, 78, 74, and 70), when the PFZ migrated to the north and opal sedimentation predominated at Site 704. At 1.7 Ma, the PFZ migrated toward the equator and occupied a more northerly position for a prolonged interval between ~1.7 and 1.5 Ma. Beginning at ~1.5-1.4 Ma, surface and bottom water parameters (d18O, d13C, %CaCO3, and %opal) in the subantarctic South Atlantic became highly correlated such that glacial events (d18O maxima) corresponded to d13C and carbonate minima and opal maxima. This pattern is typical of the correlation found during the latest Pleistocene in the Southern Ocean (Charles and Fairbanks, in press). This event coincided with increased suppression of Northern Component Water during glacial events after 1.5 Ma (Raymo et al., 1990, doi:10.1016/0012-821X(90)90051-X), which may have influenced the climatology of the Southern Hemisphere by altering the flux of heat and salt to the Southern Ocean).

Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

Sedimentology and Th, Pa, U, and N isotopic composition of core MD84-527

High-resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high-sedimentation rate core (MD84-527: 43°50'S; 51°19'E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point-by-point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment delta15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate-induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa-231/Th-230 ratios, suggesting increased scavenging from the water column. Sediment delta15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

Planktonic foraminiferal abundance and flux in the Porcupine Seabight, Northeast Atlantic

Modern planktonic foraminifera collected with a sediment trap and subfossil assemblages from surface sediments from Galway Mound in the Porcupine Seabight off southwestern Ireland, northeastern Atlantic, were studied to show recent assemblage variations. The sediment trap operated from April to August 2004 and covers the spring bloom and early summer conditions with sampling intervals of 8 days. Eleven different species were recorded. Glorotalia hirsuta, Turborotalita quinqueloba and Globigerinita glutinata appeared predominately in spring. Neogloboquadrina incompta, Globigerina bulloides and Globorotalia inflata were abundant in spring and summer. The highest foraminiferal tests flux occured in June. The faunal composition was similar to subfossil assemblages from surface sediments, but the species proportions were different. This was mainly affected by the subtropical G. hirsuta, which was frequent in 2004 and rare in surface sediment samples and in earlier plankton collections from the southern Porcupine Seabight that were performed during the 1990s. The weight of deposited foraminifera is mainly influenced by spring bloom as indicated by sea-surface chlorophyll-a data. The top three-ranked species, G. hirsuta, N. incompta and G. bulloides contributed 87 % to the foraminiferal carbonate flux at Galway Mound. Foraminiferal carbonate and shell flux as well as the shell size revealed variations, which are related to lunar periodicity. The data infer a lunar pacing of reproduction for the main species as well as for G. glutinata and G. inflata, which was not recorded before.