Solid phase phosphorus geochemistry in surface sediments of sediment cores GeoB3718-4, GeoB3702-2 and GeoB3707-4

In this study we investigate benthic phosphorus cycling in recent continental margin sediments at three sites off the Namibian coastal upwelling area. Examination of the sediments reveals that organic and biogenic phosphorus are the major P-containing phases preserved. High Corg/Porg ratios just at the sediment surface suggest that the preferential regeneration of phosphorus relative to that of organic carbon has either already occurred on the suspension load or that the organic matter deposited at these sites is already rather refractory. Release of phosphate in the course of benthic microbial organic matter degradation cannot be identified as the dominating process within the observed internal benthic phosphorus cycle. Dissolved phosphate and iron in the pore water are closely coupled, showing high concentrations below the oxygenated surface layer of the sediments and low concentrations at the sediment-water interface. The abundant presence of Fe(III)-bound phosphorus in the sediments document the co-precipitation of both constituents as P-containing iron (oxyhydr)oxides. However, highly dissolved phosphate concentrations in pore waters cannot be explained, neither by simple mass balance calculations nor by the application of an established computer model. Under the assumption of steady state conditions, phosphate release rates are too high as to be balanced with a solid phase reservoir. This discrepancy points to an apparent lack of solid phase phosphorus at sediment depth were suboxic conditions prevail. We assume that the known, active, fast and episodic particle mixing by burrowing macrobenthic organisms could repeatedly provide the microbially catalyzed processes of iron reduction with authigenic iron (oxyhydro)oxides from the oxic surface sediments. Accordingly, a multiple internal cycling of phosphate and iron would result before both elements are buried below the iron reduction zone.

Water chemistry of lakes from the Antarctic

This paper reviews Japanese limnological studies mainly in the McMurdo and Syowa oases, with special emphasis on the nutrient distribution. Generally, the chemical composition of the major ionic components in the coastal lakes and ponds is similar to that in seawater, while that in inland Dry Valley lakes and ponds of the McMurdo Oasis is abundant in calcium, magnesium and sulfate ions. The former can be explained by the direct influences of sea salts, while the latter is mainly attributable to the accumulation of atmospheric salts. Most saline lakes are meromictic. Dissolved oxygen concentrations in the upper layers are saturated or supersaturated, but the bottom layers are anoxic and often hydrogen sulfide occurs. The concentrations of nutrients vary largely not only among the lakes but also with depth. Silicate-Si, which is generally abundant in all freshwater and saline lakes, may be due to erosions of soils and rocks. Nitrite-N concentrations in both freshwater and saline lakes are generally low. Nitrate-N concentrations in the oxic layers of the inland saline lakes in the McMurdo Oasis arc often high, but not high in the coastal saline lakes of the Syowa and Vestfold oases. The abundance of phosphate-P and ammonium-N in the bottom stagnant layers of saline lakes can be explained by the accumulation of microbially released nutrients due to the decomposition of organic substances. Nutrients are supplied mainly from meltstreams in the catchment areas, and are proved to play an important role in primary production.

Concentrations of organic carbon, nitrogen and phosphorus on vertical profiles in waters of the tropical North Atlantic in March 2002

In the literature, an inconsistency exists between estimates of biotically-effected carbon export inferred from large-scale geochemical studies (Jenkins 1982; 47 gC m-2 a-1) and local measurements of turbulent nutrient supply (Lewis et al. 1986; 4 gC m-2 a-1) in the eastern subtropical North Atlantic. Nutrient supply to the upper ocean by turbulent mixing is reexamined using local standard oceanographic measurements and high-resolution vertical profiles of nutrients averaged over a large region directly comparable to that investigated by Jenkins (1982). Turbulent fluxes induced by internal waves and salt fingering, respectively, are separated according to Gregg (1989) and Zhang et al. (1998). Nutrient transport into the nutrient-consuming surface layer by salt fingering is more than fivefold higher than transport due to internal-wave induced turbulence. Still, this cannot resolve the above- mentioned apparent inconsistency, even if additional physical transport mechanisms such as eddy pumping, advection and horizontal diffusion are accounted for. Estimated nitrate fluxes due to vertical turbulent diffusion are 0.05-0.15 mol m-2 a-1, corresponding to 4-11 gC m-2 a-1. Observed NO3/PO4 turbulent flux ratios of up to 23 are interpreted as the imprint of N2 fixation.

Planktonic foraminifer assemblages and stable oxygen and carbon isotope record of sediment core MD07-3076Q

We report high-resolution planktonic foraminifer census counts and stable oxygen and carbon isotope measurements of the planktonic foraminifera G. bulloides and N. pachyderma s. from sediment core MD07-3076Q for the last deglaciation, the last glacial maximum and Marine Isotope Stage 3. These data provide insights into the marine cycling of carbon and frontal dynamics in the sub-Antarctic Atlantic during the last 68 ka.

Calcareous nannofossil range-distribution and zonation of sediments from three ODP Leg 205 holes

Ocean Drilling Program Leg 205 of the research vessel JOIDES Resolution was a return expedition to the Leg 170 sites located on the Costa Rica subduction zone. Here the entire sediment cover on the incoming Cocos plate, including significantly large sections of calcareous nannofossil ooze and chalk, is underthrust beneath the overriding Caribbean plate. The large amount of subducted carbonate produces characteristic styles of volcanic and seismic activity that differ from those found farther along strike in Nicaragua and elsewhere. An understanding of the fate of subducted carbonate sediment sections is an essential component to our understanding of the global biogeochemical cycling of carbon dioxide. Because Leg 205 drilling operations were performed within meters of the Leg 170 drill sites occupied during October-December 1996, minimal coring was done during Leg 205. Although the biostratigraphy of the Leg 170 sites has since been documented in detail, questions remained regarding the age and nature of a gabbro sill that was only partially penetrated by coring during Leg 170. Coring operations during Leg 205 fully penetrated the gabbro sill, followed by an additional 12 m of sediments below the sill, and then ~160 m of gabbro. Coring halted at 600 meters below seafloor (mbsf). Calcareous nannofossil age dating of the sediments immediately above the igneous sill, as well as the sediment between the sill and the lower igneous unit, indicates a minimum age of 15.6 Ma and a maximum age of 18.2 Ma for the sediments. This implies that the sill was emplaced more recently than 18.2 Ma. The calcareous nannofossil assemblage in baked sediments in contact with the top of the lower igneous unit also suggests that the maximum age for emplacement is 18.2 Ma. At Site 1254, coring was accomplished between 150 and 230 mbsf (prism section), and from 300 to 367.5 mbsf (prism and through the décollement into the underthrust section). In the interval from 150 to 322 mbsf, the biostratigraphic analysis of calcareous nannofossils suggests that the sediments are early Pleistocene age between 150 and 161 mbsf, late Pliocene age from 161 to 219 mbsf, and early Pliocene age from 219 to 222 mbsf (no younger than 3.75 Ma). The lack of marker fossils in the interval of sediments cored from 300 to 350.6 mbsf does not allow for any age determinations; however, sediments from 351.6 to 359.81 mbsf could be age dated and are also early Pliocene age, but no younger than 3.75 Ma.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

(Table 1) Biomass (as energy) of different elements of the planktonic community in the Equatorial Pacific in the 0-150 m layer

An analysis was made of composition and content of nutrients, salts, particulate and dissolved organic matter, and various plankton groups in a series of samples collected by a 140-liter sampling bottle to depth up to 150 m at 4 equatorial stations between 97° and 154°W. Large and small phytoplankton, bacteria (aggregated and dispersed), heterotrophic flagellates, infusorians, radiolarians, foraminifers, fine filter-feeders, small and large, mostly herbivorous copepods, cyclopoids, predatory calanoids, and other predators were investigated separately. Trophic relations between these elements are established from personal and published data, and rate of their metabolism and some other physiological parameters are determined. Such functional characteristics as extent of satisfaction of food requirements of organisms belonging to various trophic groups, intensity of trophic relations, balance between production and consumption by individual elements of the community, ecological efficiency, and net and specific production of the groups distinguished, of individual trophic levels, of total zooplankton, and of the community as a whole are calculated. Variations of these characteristics along the equator with decreasing upwelling intensity are examined and their possible causes and mechanisms are discussed.

Component composition and benthic foraminifera in sediments of ODP Leg 112

Indicators of surface-water productivity and bottom-water oxygenation have been studied for the age interval from the latest Pleistocene to the Holocene at three holes (679D, 680B, and 68IB) located in the center and at the edges of an upwelling cell at approximately 11°S on the Peruvian continental margin. Upwelling activity was maximal at this latitude during d18O Stages 1 (lower part), 3, the upper part of 5, the lower part of 6, and 7, as documented by high diatom abundance. During these time intervals, the bottom water was poorly oxygenated, as documented by low diversity benthic foraminiferal assemblages that are dominated by B. seminuda s.l. Both surface- and bottom-water-circulation patterns appear to have changed rapidly over short time intervals. Due to changes in surface circulation, the intensity of upwelling decreased, thereby decreasing the concentration of nutrients, and reducing the supply of organic matter to the bottom. Radiolarians became more abundant in the surface waters, and the bottom-water environment was less depleted in oxygen, allowing for the establishment of more diverse benthic foraminiferal assemblages. Surface-water productivity was probably minimal during the early part of d18O Stages 5 and 9, as indicated by the increased abundance of planktonic foraminifers and pteropods and their subsequent preservation.

Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.

Relative abundances and microbial numbers of organisms from water sample station GeoB15704-2

Due to sampling difficulties, little is known about microbial communities associated with sinking marine snow in the twilight zone. A drifting sediment trap was equipped with a viscous cryogel and deployed to collect intact marine snow from depths of 100 and 400 m off Cape Blanc (Mauritania). Marine snow aggregates were fixed and washed in situ to prevent changes in microbial community composition and to enable subsequent analysis using catalyzed reporter deposition fluorescence in situ hybridization (CARD-FISH). The attached microbial communities collected at 100 m were similar to the free-living community at the depth of the fluorescence maximum (20 m) but different from those at other depths (150, 400, 550, and 700 m). Therefore, the attached microbial community seemed to be "inherited" from that at the fluorescence maximum. The attached microbial community structure at 400 m differed from that of the attached community at 100 m and from that of any free-living community at the tested depths, except that collected near the sediment at 700 m. The differences between the particle-associated communities at 400 m and 100 m appeared to be due to internal changes in the attached microbial community rather than de novo colonization, detachment, or grazing during the sinking of marine snow. The new sampling method presented here will facilitate future investigations into the mechanisms that shape the bacterial community within sinking marine snow, leading to better understanding of the mechanisms which regulate biogeochemical cycling of settling organic matter.

Analysis of soils from King George Island and Casey station, Antarctica

A comparative study was carried out on soils of the maritime (Arctowski, King George Island) and the continental (Casey, Wilkes Land) Antarctic. Soil sampIes are described for surface layers (0-10 cm) by their in situ temperature profiles as well as by field and laboratory analyses of grain sizes, pH and nutrient contents. Active cryoturbation is a main factor of mixing processes in surfaces with high silt and clay content. In both regions processes of podzolisation were recognized. Microclimatic conditions show the importance of small scale processes which are of special importance for freeze-thaw cycles. The distribution of nutrients and other inorganic components is rather homogeneous in regosols and leptosols. But in soils with organic top layers by lichen and moss cushions (crusts) accumulation occurs as well as displacement of metal ions into deeper layers (>10 cm). Histosols show patterns of brown soils. Special attention is given to the origin of nitrogen compounts and the different ways of import of other components (e.g. chloride) into the Antarctic system are discussed.

Water chemistry and heat budget of the Churchill River estuary region

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April-May. In the Churchill Estuary, conditions varied abruptly throughout winter-spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (~6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter-spring transition, which implies sensitivity to climate change.

Neodymium isotope ratios of fish debris from late Cretaceous black shales

Neodymium isotopes of fish debris from two sites on Demerara Rise, spanning ~4.5 m.y. of deposition from the early Cenomanian to just before ocean anoxic event 2 (OAE2) (Cenomanian-Turonian transition), suggest a circulation-controlled nutrient trap in intermediate waters of the western tropical North Atlantic that could explain continuous deposition of organic-rich black shales for as many as ~15 m.y. (Cenomanian-early Santonian). Unusually low Nd isotopic data (epsilon-Nd(t) ~-11 to ~-16) on Demerara Rise during the Cenomanian are confirmed, but the shallower site generally exhibits higher and more variable values. A scenario in which southwest-flowing Tethyan and/or North Atlantic waters overrode warm, saline Demerara bottom water explains the isotopic differences between sites and could create a dynamic nutrient trap controlled by circulation patterns in the absence of topographic barriers. Nutrient trapping, in turn, would explain the ~15 m.y. deposition of black shales through positive feedbacks between low oxygen and nutrient-rich bottom waters, efficient phosphate recycling, transport of nutrients to the surface, high productivity, and organic carbon export to the seafloor. This nutrient trap and the correlation seen previously between high Nd and organic carbon isotopic values during OAE2 on Demerara Rise suggest that physical oceanographic changes could be components of OAE2, one of the largest perturbations to the global carbon cycle in the past 150 m.y.