Biogenic silica and silicic acid benthic fluxes of a North-eastern Atlantic Abyssal Locality

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 µM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment-water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment-water interface and the annual DSi efflux was close to 0.057 mol Si/m**2/yr. Biogenic silica accumulation was close to 0.008 mol Si/m**2/yr and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si/m**2/yr. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si/m**2/yr). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.

Stable oxygen isotope record and Calcium concentrations of sediment core GeoB3910-2

There is increasing evidence that the preceding Holocene climate was as unstable as the last glacial period, although variations occurred at much lower amplitudes. However, low-latitude climate records that confirm this variability are sparse. Here we present a radiocarbon-dated Holocene marine record from the tropical western Atlantic. Aragonite dissolution derived from the degree of preservation of the pteropod Limacina inflata records changes in the corrosiveness of the bottom water at the core site due to the changing influence of northern versus southern water masses. The delta18O difference between the shallow-living planktonic foraminifera Globigerinoides sacculifer and the deep-living Globorotalia tumida is used as proxy for changes in the vertical stratification of the surface water, hence the trade wind strength at this latitude. We compared our data to high-latitude records of the North Atlantic region. A good agreement is found between the aragonite dissolution and the strength in the Island-Scotland Overflow Water, which contributes significantly to the North Atlantic Deep Water. This suggests that large-scale variations in the Atlantic thermohaline circulation occurred throughout the Holocene. Concurrently, the comparison of our Delta delta18O with the GISP2 glaciochemical records points to global Holocene atmospheric reorganizations seen in both the tropics and high northern latitudes.

Low-temperature experiments of sediment core GeoB6229-6 at the South American continental margin off the Rio de la Plata estuary

With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

(Table 2) Taxonomic composition of diatoms in dredged samples from the island-side slope of the Kuril-Kamchatka Trench

Studies of diatoms from dredge samples collected on the island slope of the Kuril-Kamchatka Trench have allowed to recognize well-preserved marine diatom assemblages corresponding to assemblages of the followed Oligocene zones: Rhizosolenia oligocaenica (subzone ''a'', 33.6-31 Ma), Cavitatus rectus (29.6-28.2 Ma), and Rocella gelida (28.2-24.0 Ma) as identified in the North Pacific zonal scale. Description of these assemblages and their complete taxonomic composition are presented. Diversity of species together with abundance and degree of preservation of diatoms and accompanying siliceous microorganisms suggests their autochtonous origin and favorable conditions of their development. Assemblages of the Early Oligocene zones Rhizosolenia oligocaenica and Cavitatus rectus recognized in sediments of the outer zone of the Lesser Kuril Ridge (submarine slope of the Shikotan Island) and on the Vityaz' submarine ridge were most probably formed under conditions of a vast shelf, while assemblage of the Late Oligocene zone Rocella gelida encountered only in the region of the Lesser Kuril Ridge formed under more deep-water conditions, presumably, over an island slope. Deepening of the basin in the region of the outer zone of the Lesser Kuril Ridge in Late Oligocene probably reflects one of stages of evolution of the Kuril-Kamchatka Trench.

Benthic foraminifers in Mesozoic and Cenozoic sediments of the southwestern Atlantic

Benthic foraminiferal assemblages in Mesozoic and Cenozoic sediments were studied at Sites 511, 512, 513, and 514 drilled during Leg 71 in the southwestern Atlantic on the Maurice Ewing Bank and in the Argentine Basin. Benthic foraminifers in almost all stratigraphic subdivisions of Sites 511 and 512 reflect the gradual subsidence of the Falkland Plateau from shelf depths in the Barremian-Albian, when a semiclosed basin with restricted circulation of water masses and anaerobic conditions existed, to lower bathyal depths in the Late Cretaceous and Cenozoic, with an abrupt acceleration at the boundary of Lower and Upper Cretaceous. The composition, distribution, and preservation of Late Cretaceous assemblages of benthic foraminifers suggest considerable fluctuations of the foraminiferal lysocline and the CCD. This is evidenced by dissolution facies and foraminiferal assemblages in which agglutinated and resistant calcareous forms predominated during high stands of the CCD and by calcareous facies in which rich assemblages of calcareous species predominated during low stands. The highest position of the CCD on the Plateau (less than 1500-2000 m) was in the late Cenomanian, Turonian, and Coniacian. In the Santonian and Campanian the CCD was at depths below 1500-2000 meters. At the end of the Campanian the CCD shifted again to depths comparable with those of Cenomanian and Turonian time. In the latest Campanian and the Maestrichtian the CCD was low and nanno-foraminiferal oozes with a rich assemblage of benthic foraminifers accumulated. Foraminiferal assemblages at Sites 513 and 514 in the Argentine Basin also testify to oceanic subsidence from lower bathyal depths in the Oligocene to abyssal ones at present. This process was complicated by the influence of geographical migrations of the Polar Front caused by extensions of the ice sheet in the Antarctic after the opening of the Drake Passage during the Oligocene. In Mesozoic and Cenozoic deposits of the Falkland Plateau and the Argentine Basin seven assemblages of benthic foraminifers were distinguished by age: early-middle Albian, middle-late Albian, Late Cretaceous (including four groups), middle Eocene, late Eocene-early Miocene, middle-late Miocene, and Pliocene-Quaternary. The Albian assemblages contain many species common to the foraminiferal fauna of the Austral Biogeographical Province. The Late Cretaceous assemblage contains, along with Austral species, species common to foraminifers of North America, Western Europe, the Russian platform, and the south of the U.S.S.R. Deep-sea cosmopolitan species prevail in Cenozoic assemblages.

Abundances of dinoflagellate cysts in sediment trap MST-9 (Appendix 1)

To study the ecology of calcareous dinoflagellates we examined the impact of the SW and NE monsoons on cyst formation using sediment trap material, collected at 1032 m water depth, off Somalia from June 1992 to February 1993. The results do not confirm the relationship between cyst production and lower nutrient concentrations, as highest cyst fluxes were recorded during late SW monsoon under the relatively nutrient-rich and less agitated conditions of mature upwelled water. Lowest cyst fluxes were found under strongly stratified, nutrient-depleted surface waters during the inter-monsoon. Although all of the studied species seem to prefer a stratified water column, an elevated concentration of nutrients appears to be necessary to maintain high cyst production. Comparison of the mean cyst flux to the sediment trap with that into the underlying surface sediments reveals a loss of 81-96%, which can be attributed to calcite dissolution. The relatively small spheres of Thoracosphaera heimii are affected more than the cysts of the other species.

Planktonic foraminifera stratigraphy and datums of ODP Site 184-1143 and Hole 184-1146A, South China Sea

The biostratigraphy of Miocene-age sediment samples recovered from Ocean Drilling Program Sites 1143 and 1146, South China Sea, is presented. The preservation of the planktonic foraminifers recovered from both sites varies widely, from poor to very good. The volume of biogenic sediment in the >63-µm size fraction also varies considerably, with many samples being dominated by mud. In comparison to shipboard biostratigraphy, based on core catcher analyses with a depth resolution of ~10 m, we analyzed samples from the two stratigraphic columns every 2-3 m (~45- to 93-k.y. resolution). The placement of planktonic foraminifer zonal boundaries was made at a resolution of ~1.5 m at Site 1146 and ~3.0 m at Site 1143. The higher resolution has resulted in significant changes in biostratigraphic zonal boundary locations compared to shipboard results. For the time interval of 5.54-10.49 Ma, the changes in zonation reveal similar age-depth models at both sites, with three segments of changing sedimentation rate through the upper Miocene, though the differences in sedimentation rates at Site 1146 are subtler than those at Site 1143. The boundary between lithologic Units II and III at Site 1146 corresponds to a sharp change in sedimentation rate (58 to 21 m/m.y.) at 15.1 Ma (the first occurrence of Orbulina suturalis). At this site, the interval from 16.4 to 15.1 Ma is characterized by very high mass accumulation rates in the noncarbonate fraction. Above this interval the carbonate fraction becomes increasingly important in the sediment flux to the South China Sea. At Site 1143, sedimentation rates increase from 8 to 99 m/m.y. at 8.6 Ma. This corresponds to a dramatic increase in both carbonate and noncarbonate mass accumulation rates at the site, but no change in lithology.

Range charts of stratigraphically important radiolarian species in sediments of ODP Leg 165 sites

The Paleogene sequences from three sites in the Caribbean were examined for radiolarians. In general, samples are highly lithified, requiring lengthy and repetitive cleaning procedures, and the assemblages are usually fragmented and/or partially dissolved. Both abundances and preservation of the assemblages vary considerably from site to site and within a single site; even within a single sample more than one degree of preservation was observed. It was possible, however, to construct at least partial stratigraphies for each of the three sites. Because the abundance of radiolarians is high even in extremely poorly preserved assemblages, we conclude that the differences in biogenic silica preservation are the result of postdepositional processes and not productivity. In both Sites 999 and 1001, near the Paleocene/Eocene boundary (Bekoma bidartensis Zone [RP7]), there is a short interval in which the abundance and preservation state of the radiolarians improves relative to overlying and underlying assemblages. In each case the intervals corresponds to the level, identified by calcareous microfossils, as representing changes in paleoceanographic conditions associated with the late Paleocene thermal maximum.

Isotopic survey of diagenetic carbonates, at DSDP Leg 63 Holes

Authigenic carbonates, principally calcium-rich dolomites, with extremely variable isotopic compositions were recovered in organic-rich marine sediments during Leg 63 drilling off southern California and Baja California. These carbonates occur as thin layers in fine-grained, diatomaceous sediments and siliceous rocks, mostly deposited during the Neogene. A combination of textural, geochemical, and isotopic evidence indicates these dolomites formed as cements and precipitates in shallow subsurface zones of high alkalinity spawned by abundant CO2 and methane production during progressive microbial decay of organic matter. Depths and approximate temperatures of formation estimated from oxygen isotopes are 87 to 658 meters and 10°C to 50°C, respectively. Within any sedimentary section, dolomites may form simultaneously at several depths or at different times within the same interval. Highly variable carbon isotopes (-30 to +16 per mil) reflect the isotopic reservoir in which the carbonates formed. Oxidation of organic matter through microbial reduction of sulfate at shallow depths favors light-carbon carbonates such as those at Sites 468 and 471; heavy-carbon carbonates at Site 467 most likely formed below this zone where HC**12O3**- is preferentially removed by reduction of CO2 to methane during methanogenesis. An important controlling factor is the sedimentation rate, which dictates both the preservation of organic matter on the sea floor and depth distribution of subsurface zones of organic-matter decay.

Occurrence and estimated abundance of planktonic foraminifers at DSDP Leg 85 holes

Tropical planktonic foraminifers occur throughout the sequences at all sites of Leg 85, and the standard planktonic foraminiferal zonation of Blow (1969) is applicable to most of the recovered sequences. However, the abundance and state of preservation of foraminifers decline markedly in certain intervals because of the effects of dissolution. Although siliceous microfossils studied on this leg indicate recovery of nearly complete records for the Pleistocene to Oligocene interval, the planktonic foraminiferal biostratigraphy is interrupted by strongly dissolved sections at all sites. Particularly, faunas assignable to Zone N7 (early Miocene) and Zone N15-16 (early late Miocene) are almost totally unrecognizable throughout the eastern equatorial Pacific. Well-preserved and diverse planktonic foraminifers occur in the lower middle Miocene, where the evolutionary developments of Orbulina universa d'Orbigny and Globorotalia fohsi Cushman and Ellisor are well represented. The Orbulina first appearance datum is observed to be nearly coincident with the last occurrence level of the diatom Annellus californicus Tempère, thus .establishing an age of 15 Ma for this datum by using the paleomagnetic calibration of the diatom datum. Moderately well-preserved late Eocene planktonic foraminifers occur in the carbonate sediments immediately overlying the basalt basement at Sites 573 and 574. The Eocene-Oligocene faunal transition, however, is masked at both sites by an intercalation of metalliferous layers containing no planktonic foraminifers.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Magnetostratigraphic synthesis of ODP Leg 123 sites

During ODP Leg 123, Sites 765 and 766 were drilled to examine the tectonic evolution, sedimentary history, and paleoceanography of the Argo Abyssal Plain and lower Exmouth Plateau. At each site, the quality of magnetostratigraphic and biostratigraphic records varies because of complicating factors, such as the predominance of turbidites, the presence of condensed horizons, or deposition beneath the CCD. Based primarily on the presence of nannofossils, the base of the sedimentary section at Site 765 was dated as Tithonian. A complete Cretaceous sequence was recovered at this site, although the sedimentation rate varies markedly through the section. The Cretaceous/Tertiary boundary is represented by a condensed horizon. The condensed Cenozoic sequence at Site 765 extends from the upper Paleocene to the lower Miocene. A dramatic increase in sedimentation rate was observed in the lower Miocene, and a 480-m-thick Neogene section is present. The Neogene section is continuous, except for a minor hiatus in the lower Pliocene. The base of the sedimentary section at Site 766 is Valanginian, in agreement with the site's position on marine magnetic anomaly Mil. Valanginian to Barremian sediments are terrigenous, with variable preservation of microfossils, and younger sediments are pelagic, with abundant well-preserved microfossils. Sedimentation rate is highest in the Lower Cretaceous and decreases continually upsection. Upper Cenozoic sediments are condensed, with several hiatuses.

Silt grain-size analysis of ODP holes from the western equatorial Atlantic

Grain-size records of the terrigenous and calcareous silt fraction, preservation of planktic foraminifera, and benthic foraminiferal stable-isotope data (delta13C, delta18O values of C. wuellerstorfi) at ODP Site 927 on the Ceará Rise (5°27.7'N, 44°28.8'W), are used to reconstruct variations in the history of bottom current strength, ventilation, and carbonate corrosiveness of deep waters during the time interval from 0.8 to 0.3 Ma. Glacial periods are characterized by generally smaller mean sizes of the terrigenous sortable silt fraction (mean(SS)), lower delta13C values, and poorer preservation of planktic foraminifera compared to interglacials. This indicates lower bottom current speeds, larger nutrient contents and more corrosive deep water. By contrast, larger mean(SS) sizes, higher delta13C values, and well preserved planktic foraminifera indicate strong circulation and a well ventilated deep-water mass during interglacials. The observed changes are most likely related to the weakening and strengthening of circulation of Lower North Atlantic Deep Water (LNADW). Cross-spectral analysis between the mean(SS) and benthic delta18O records reveals that minima in mean(SS) occur about 7.6 k.y. after the maximum in ice volume. This indicates a considerable lag time between ice-shield induced changes in LNADW production and subsequent changes in the velocity of LNADW flow in the western equatorial Atlantic. Striking changes in bottom current speed occur regularly during glacial to interglacial transitions. Extremely fine mean(SS) minima point to an almost complete shutdown of bottom current vigor in response to a cessation of LNADW production caused by an enhanced melt water release during the initial phases of deglaciation. However, each of the fine minima extremes is followed by a rapid shift to very high mean(SS) values that indicate strong bottom currents, and hence, vigorous LNADW flow during the early interglacials. After the onset of glacial Stage 12, generally poorer carbonate preservation and higher variability is registered. This coincides with a global decrease in carbonate preservation during the mid-Brunhes (mid-Brunhes dissolution event). Detailed grain-size analysis of the calcareous fine fraction (<63 µm) revealed a considerable reduction of particles in the fraction from 7 to 63 µm during periods of enhanced dissolution. This indicates a preferential dissolution of larger planktic foraminiferal fragments which leads to an enrichment of coccoliths in the calcareous fine fraction.