(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Geochemistry of Fe-Mn oxyhydroxide samples of ODP Hole 172-1060A

The strength of the North Atlantic Meridional Overturning Circulation during climatically highly variable Marine Isotope Stage (MIS) 3 has attracted much attention in recent years. Here we present high-resolution Nd isotope compositions of past seawater derived from authigenic Fe-Mn oxyhydroxides recovered from drift sediments on the Blake Ridge in the deep western North Atlantic (ODP Leg 172, Site 1060, 3481 m water depth). The data cover the period from 45 to 35 ka BP, tracing circulation changes during major Heinrich iceberg discharge event 4 (H4, ~40-39 ka BP). The Nd isotope record suggests that there was no northern-source water (NSW) mass like modern NADW at the deeper part of Blake Ridge at any time between 45 and 35 ka. This is fundamentally different from the hydrographic situation during the Holocene where NADW extends below 4500 m at this location. The epsilon-Nd of past deep water recorded in the Blake Ridge sediments was least radiogenic during Dansgaard/Oeschger (D/O) Interstadial (IS) 8 (epsilon-Nd = -11.3) and most radiogenic immediately preceding IS 9 (epsilon-Nd = -9.8). More radiogenic compositions were also recorded during H4 (-10.2 <= epsilon-Nd <= -9.9). The Nd isotope variability in MIS 3 matches that of a physical bottom current strength reconstruction from the same location. Neither record follows the pattern of Northern Hemisphere D/O climatic cycles. In our record, reduced mixing with northern source waters started in stadial 12 and lasted until after H4 in stadial 9, followed by a rapid increase in NSW contribution thereafter. This major change in the Nd isotope record predates the iceberg discharge event Heinrich 4 by more than 3 ka indicating a shallowing of the water mass boundary between Glacial North Atlantic Intermediate Water and Southern Source Water beneath. This early change in bottom water properties at the deep Blake Ridge suggests that North Atlantic deep water advection may already have decreased several thousand years before the actual iceberg discharge event and associated freshening of the surface waters in the North Atlantic. The change can thus not be attributed to climatic events in the North Atlantic but may be related to changes in flux of deep water from the South.

(Table 3) Barium barite and excess comparison, accumulation rates and productivity from surface sediments

Since Dymond et al. (1992, doi:10.1029/92PA00181) proposed the paleoproductivity algorithm based on "Bio-Ba", which relies on a strong correlation between Ba and organic carbon fluxes in sediment traps, this proxy has been applied in many paleoproductivity studies. Barite, the main carrier of particulate barium in the water column and the phase associated with carbon export, has also been suggested as a reliable paleoproductivity proxy in some locations. We demonstrate that Ba(excess) (total barium minus the fraction associated with terrigenous material) frequently overestimates Ba(barite) (barium associated with the mineral barite), most likely due to the inclusion of barium from phases other than barite and terrigenous silicates (e.g., carbonate, organic matter, opal, Fe-Mn oxides, and hydroxides). A comparison between overlying oceanic carbon export and carbon export derived from Ba(excess) shows that the Dymond et al. (1992) algorithm frequently underestimates carbon export but is still a useful carbon export indicator if all caveats are considered before the algorithm is applied. Ba(barite) accumulation rates from a wide range of core top sediments from different oceanic settings are highly correlated to surface ocean 14C and Chlorophyll a measurements of primary production. This relationship varies by ocean basin, but with the application of the appropriate f ratio to 14C and Chlorophyll a primary production estimates, the plot of Ba(barite) accumulation and carbon export for the equatorial Pacific, Atlantic, and Southern Ocean converges to a global relationship that can be used to reconstruct paleo carbon export.

Radionuclides measured on 27 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

As part of the GEOTRACES Polarstern expedition ANT XXIV/3 (ZERO and DRAKE) we have measured the vertical distribution of 234Th on sections through the Antarctic Circumpolar Current along the zero meridian and in Drake Passage and on an EW section through the Weddell Sea. Steady state export fluxes of 234Th from the upper 100m, derived from the depletion of 234Th with respect to its parent 238U, ranged from 621±105 dpm/m**2/d to 1773±90 dpm/m**2/d. This 234Th flux was converted into an export flux of organic carbon ranging from 3.1-13.2 mmolC/m**2/d (2.1-9.0 mmolC/m**2/d) using POC/234Th ratio of bulk (respectively >50 µm) suspended particles at the export depth (100 m). Non-steady state fluxes assuming zero flux under ice cover were up to 23% higher. In addition, particulate and dissolved 234Th were measured underway in high resolution in the surface water with a semi-automated procedure. Particulate 234Th in surface waters is inversely correlated with light transmission and pCO2 and positively with fluorescence and optical backscatter and is interpreted as a proxy for algal biomass. High resolution underway mapping of particulate and dissolved 234Th in surface water shows clearly where trace elements are absorbed by plankton and where they are exported to depth. Quantitative determination of the export flux requires the full 234Th profile since surface depletion and export flux become decoupled through changes in wind mixed layer depth and in contribution to export from subsurface layers. In a zone of very low algal abundance (54-58 °S at the zero meridian), confirmed by satellite Chl-a data, the lowest carbon export of the ACC was observed, allowing Fe and Mn to maintain their highest surface concentrations (Klunder et al., this issue, Middag et al., this issue). An ice-edge bloom that had developed in Dec/Jan in the zone 60-65 °S as studied during the previous leg (Strass et al., in prep) had caused a high export flux at 64.5 °S when we visited the area two months later (Feb/March). The ice-edge bloom had then shifted south to 65-69 °S evident from uptake of CO2 and dissolved Fe, Mn and 234Th, without causing export yet. In this way, the parallel analysis of 234Th can help to explain the scavenging behaviour of other trace elements.

Chemical composition of Fe-Mn nodules, micronodules, and host bottom sediments of the Northeast Pacific

A set of methods has been used for studying composition, structure and distribution of Fe-Mn-micronodules in bottom sediments of the Northeast Pacific. It has been shown that there are two types of Fe-Mn micronodules differing in size, external shape, internal structure and composition of constituent manganese minerals.

(Table 2) Chemical composition of Fe-Mn nodules and volcanic glass in sediments of the Atlantic Ocean

Distribution pattern of titanium in Quaternary sediments of the Atlantic Ocean are examined on the base of 750 Ti and Fe determinations, and several dozen of complete chemical analyses. Analyses of surface sediment samples and sediment cores up to 6 m long were made. Stratigraphic levels from Middle Pleistocene to Holocene were identified from planktonic foraminifera. Distributions of Ti in recent and Pleistocene deposits were mapped. High titanium contents were found in sediments containing products of basalt vulcanism and in iron-manganese nodules. To determine origin of titanium concentrations in sediments, Ti/Fe ratios were calculated. Maximal values of this ratio were found in areas of basaltic volcanism and of intensive terrigenous sedimentation.

(Table 1) Major and trace element composition of sediment core PS 70/306-3, Gakkel Ridge

The paper presents data on the chemical composition of Late Pleistocene-Holocene sediments in the Gakkel Ridge according to data on sediment core PS 70/306-3, offers a hypothetical litho-stratigraphic model, and provides data on chemo-stratigraphic horizons distinguished based on the distribution of carbonates, organic carbon, metals (Fe, Mn, Cu, Zn, Co, Ni, V, Pb), As, and P in the core. Chemical transformations of sediments at the redox barrier are discussed, along with relations between the composition of the sediments and the facies sedimentation conditions.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Influence of the sputtering flow regime on the structural properties and magnetic behavior of Fe-Ga thin films (Ga ∼ 30 at.%)

In this paper we analyze the structure of Fe-Ga layers with a Ga content of ∼30 at.% deposited by the sputtering technique under two different regimes. We also studied the correlation between the structure and magnetic behavior of the samples. Keeping the Ar pressure fixed, we modified the flow regime from ballistic to diffusive by increasing the distance between the target and the substrate. X-ray diffraction measurements have shown a lower structural quality when growing in the diffusive flow. We investigated the impact of the growth regime by means of x-ray absorption fine structure (XAFS) measurements and obtained signs of its influence on the local atomic order. Full multiple scattering and finite difference calculations based on XAFS measurements point to a more relevant presence of a disordered A2 phase and of orthorhombic Ga clusters on the Fe-Ga alloy deposited under a diffusive regime; however, in the ballistic sample, a higher presence of D0_3/B2 phases is evidenced. Structural characteristics, from local to long range, seem to determine the magnetic behavior of the layers. Whereas a clear in-plane magnetic anisotropy is observed in the film deposited under ballistic flow, the diffusive sample is magnetically isotropic. Therefore, our experimental results provide evidence of a correlation between flow regime and structural properties and its impact on the magnetic behavior of a rather unexplored compositional region of Fe-Ga compounds.

Chemical analysis of water samples of station M1_1207, Red Sea (Table 1-3)

Two water samples and two sediment samples taken in 1965 by the R. V. "Meteor" in the area of the hot salt brine of the Atlantis II-Deep were chemically investigated, and in addition the sediment samples were subjected to X-ray and optical analysis. The investigation of the sulfur-isotope-ratios showed the same values for all water samples. This information combined with the Ca-sulfate solubility data leads us to conclude that, for the most part, the sulfate content of the salt brine resulted from mixing along the boundary with the normal seawater. In this boundary area gypsum or anhydrite is formed which sinks down to the deeper layers of the salt brine where it is redisolved when the water becomes undersaturated. In the laboratory, formation of CaS04 precipitate resulted from both the reheating of the water sample from the uppermost zone of the salt brine to the in-situ-temperature as well as by the mixing of the water sample with normal Red Sea water. The iron and manganese delivered by the hot spring is separated within the area of the salt brine by their different redox-potentials. Iron is sedimented to a high amount within the salt brine, while, as evidenced by its small amounts in all sediment samples, the more easily reducible manganese is apparently carried out of the area before sedimentation can take place. The very good layering of the salt brine may be the result of the rough bottom topography with its several progressively higher levels allowing step-like enlargements of the surface areas of each successive layer. Each enlargement results in larger boundary areas along which more effective heat transfer and mixing with the next layer is possible. In the sediment samples up to 37.18% Fe is found, mostly bound as very poorly crystallized iron hydroxide. Pyrite is present in only very small amounts. We assume that the copper is bound mostly as sulfide, while the zinc is most likely present in an other form. The sulfur-isotope-investigations indicate that the sulfur in the sediment, bound as pyrite and sulfides, is not a result of bacterical sulfate-reduction in the iron-rich mud of the Atlantis II-Deep, but must have been brought up with the hot brine.

(Tables 1-3) Silicon dioxide, Corg and trace element concentrations in sediments of the outer Eckernfoerder Bay, Western Baltic Sea

The main question, posed in the work scheme before laboratory analysis was started, was expressed as follows: Do marked seasonal fluctuations occur in trace element content of the sediment surface, and what are the probable influences of factors such as changing hydrographical parameters, plankton sequence etc. ? Special attention was paid to elements known as pollutants, for example mercury. Within this framework samples have been analysed for their contents of manganese, iron, zinc, lead, and mercury. The amounts of silica and organically-bound carbon serve in most cases as reference values for the trace element content. On sand temporary conditions of increased C org content raise the concentrations of all determined elements. Especially the values reached for mercury in July are worth nothing. It is concluded that Zn, Pb, and Hg tend to enrich with respect to C org as the decomposition of organic matter progresses. On mud-sand flocculation and precipitation of Mn/Fe-hydroxides probably represent an additional concentrating factor for the other elements as the relationship of the results for zinc and manganese shows. Manganese may indicate a seasonally related concentrating cycle at the sediment surface.

(Table 1, page 126) Concentration of elements in Fe and Mn rich pisoliths (nodules) from Lake Storsjoen, South Norway

A detailed description of the ores of Lake Storsjoen was given by Vogt J. H. L., 1915 who pointed out that the ores may be divided into two principal types; first, iron ore with 2% or less of manganese (ex: Ertemalm), and, second, ores with manganese contents of up to 30% (ex: Korinter). The iron-rich ore sometimes occurs as a conglomerate embedded in manganese-rich ores, clearly demonstrating that two distinctly different precipitates are involved. In the iron-rich ore, a concentric structure is common of which light brown layers of loose, almost dusty material alternate with hard and brittle black layers, the thickness of each being 0.5 mm or less. The analyses presented in this paper seem to demonstrate that the composition of the sedimentary ores of Lake Storsjden could result from fluctuations in the composition of ground waters feeding the lake.

Chemical composition of Fe-Mn nodule from Station PL70-9

During June-August 1970 geologic investigations were carried out to the west of the Cape Verde Islands. One result of these investigations was a discovery of a new region of distribution of iron-manganese nodules. Data on chemical analysis of the nodules and their morphometric characteristics are presented in this paper. The report is illustrated by bottom-relief profiles, underwater photographs, and tables.

(Table 1) Mn, Fe, TOC and CaCO3 concentrations in bottom sediments and silt waters of Kandalaksha Bay, White Sea

The redox stratification of bottom sediments in Kandalaksha Bay, White Sea, is characterized by elevated concentrations of Mn (3-5%) and Fe (7.5%) in the uppermost layer, which is two orders of magnitude and one and a half times, respectively, higher than the average concentrations of these elements in the Earth's crust. The high concentrations of organic matter (Corg = 1-2%) in these sediments cannot maintain (because of its low reaction activity) the sulfate-reducing process (the concentration of sulfide Fe is no higher than 0.6%). The clearest manifestation of diagenesis is the extremely high Mn2+ concentration in the silt water (>500 µM), which causes its flux into the bottom water, oxidation in contact with oxygen, and the synthesis of MnO2 oxy-hydroxide enriching the surface layer of the sediments. Such migrations are much less typical of Fe. Upon oxygen exhaustion in the uppermost layer of the sediments, the synthesized oxyhydroxides (MnO2 and FeOOH) serve as oxidizers of organic matter during anaerobic diagenesis. The calculated diffusion-driven Mn flux from the sediments (280 µM/m**2 day) and corresponding amount of forming Mn oxyhydrate as compared to opposite oxygen flux to sediments (1-10 mM/m**2 day) indicates that >10% organic matter in the surface layer of the sediments can be oxidized with the participation of MnO2. The roles of other oxidizers of organic matter (FeOOH and SO4**2-) becomes discernible at deeper levels of the sediments. The detailed calculation of the balance of reducing processes testifies to the higher consumption of organic matter during the diagenesis of surface sediments than it follows from the direct determination of Corg. The most active diagenetic redox processes terminate at depths of 25-50 cm. Layers enriched in Mn at deeper levels are metastable relicts of its surface accumulation and are prone to gradual dissemination.