Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Geochemical parameters of bottom sediments from the Tajura Rift, Gulf of Aden

Results of a geochemical study of bottom sediments from the Tadjura rift zone are reported. The sediments were analyzed for CaCO3, Si, Al, Ti, Fe, Mn, Cu, Zn, Ni, Co, Cr, V, Zr, Ga, Yb and Y. It was found that formation of chemical composition of the sediments was controlled by factors being appropriate for a near-continental area of the arid climatic zone (aeolian supply of terrigenous material and high biological productivity), as well as by hydrothermal activity in the rift valley. It was shown that high Mn contents were typical for the sediments in study while maximal contents of Fe were found near supposed hydrothermal sources. Total flux of Mn into sediments was been calculated. Diagenetic redistribution gives the main contribution of Mn in surface layer sediments. Speciations of Fe, Mn, Cu, Zn, Ni, Co, and Al were studied. In the surface layer sediments iron and manganese were in hydroxides. Model calculations of contents of chemical elements in sediments of the area in study are given.

Geochemistry of Fe-Mn crusts at seamounts in the Northwest Pacific

Hydrogenetic ferromanganese crusts were dredged from four seamounts in the western Pacific, OSM7, OSM2, Lomilik, and Lemkein, aligned in a NW-SE direction parallel to Pacific Plate movement. The crusts consist of four well-defined layers with distinct textural and geochemical properties. The topmost layer 1 is relatively enriched in Mn, Co, Ni, and Mo compared to the underlying layer 2, which is relatively enriched in Al, Ti, K, and Rb and Cu, Zn, and excess Ba. Textural and geochemical properties of layer 2 suggest growth conditions under high biogenic and detrital flux. Such conditions are met in the equatorial Pacific (i.e., between the Intertropical Convergence Zone (ITCZ) and equatorial high-productivity zone). Layer 2 likely formed when each seamount was beneath the equatorial Pacific along its back track path. On the other hand, layer 1 probably started to grow after seamounts moved northwest from the ITCZ. This interpretation is consistent with the thickness of layer 1 across the four crusts, which increases to the northwest. Ages of the layer 1-layer 2 boundary in each crust, a potential proxy for northern margin of the ITCZ, also increase to the northwest at 17, 11, 8, and 5 Ma for OSM7, OSM2, Lomilik, and Lemkein, respectively. Assuming Pacific Plate motion of 0.3°/Myr, the seamounts were located at 12°N, 11°N, 9°N, and 8°N at the time of boundary formation. This result suggests that the north edge of the ITCZ has shifted south since the middle Miocene in the western Pacific, which agrees with information from the eastern Pacific.

(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.

(Table 2, page 2172) Chemical analytical data on thirty-two manganese nodules and crusts

Mn, Fe, Ca, Co, Ni, Cu, Zn, Cd, Sn, Tl, Pb and Bi have been estimated in thirty-two nodules from the Pacific, Atlantic and Indian oceans. Various features about the composition of manganese nodules are discussed: element abundances, degrees of enrichment, inter-element relationships (notably between Ni and Cu, and between Zn and Cd), regional variations and some aspects of statistical distribution.

(Table 2) Concentration of heavy metals and organic carbon, and 210Pb activity of sediments near Büsum, eastern Wadden Sea

A 3.38 m long sediment core raised from the tidal flat sediments of the 'Blauortsand' in the Wadden Sea northwest of Büsum (Schleswig-Holstein, Germany) was analysed in order to investigate long term changes in sediment pollution with Pb, Cu, Zn and Cd. Comparison with the topographic maps since 1952 and 210Pb activity allowed a general dating of the sediment succession in the core. The heavy metal concentrations including 210Pb of the < 20 µm grain-size fraction in thick sediment slices below 1.30 m indicated background niveaus. Their values increased and reached modern levels in the upper sediment layers of the core above 1 m. The increments for Pb, Cu, Zn was 1 to 3 fold and Cd up to 11 fold since the second half of the 19th century. More investigations are needed to quantify the geographical extent and history of the contaminations shown in this pilot study.

Geochemistry of surface sediment cores (Table 4)

The mineralogy and geochemistry of a suite of nine manganese nodules from the South Atlantic have been determined. The Ce/La ratios of the nodules were investigated to see if they could be used as redox indicators to trace the oxygen content of the ambient water mass and the flow path of the Antarctic Bottom Water as has previously been successfully carried out in the Pacific Ocean. The Ce/La ratios of the nodules decrease in the sequence Lazarev Sea, Weddell Sea (10.4 and 9.7)>East Georgia Basin (6.5 and 7.1)>Argentine Basin (5.0), but then increase in the Brazil Basin (6.2) and Angola Basin (9.8 and 15.1). A further decrease was observed in the Cape Basin (7.6). An extremely high Ce/La ratio of 24.4 had already been determined for nodules sampled north of the Nares Abyssal Plain in the western North Atlantic. These data reflect the more complicated pattern of bottom water flow in the South Atlantic than in the South Pacific. The penetration of more oxygenated North Atlantic Deep Water into the South Atlantic accounts for the higher Ce/La ratios in the nodules from the Angola and Brazil basins. Based on this study, the flow path of the Antarctic Bottom Water could only be traced as far north as the Argentine Basin. The unique geochemistry of nodules from the central Angola Basin (high Mn/Fe and Ce/La ratios, high contents of Ni, Cu, Zn and Mo) appears to be a function of the nature of the overlying water mass and of the multiple diagenetic sources of metals to the nodules.

Geochemical composition of calcite and aragonite, and characteristics of hydrothermal fluids of ODP Leg 168 sites

During Leg 168 a transect was drilled across the eastern flank of the Juan de Fuca Ridge in an area where the volcanic basement is covered by sediments of variable thickness. Samples of basement volcanic rocks were recovered from nine locations along the transect, where the basement sediment interface is presently heated to temperatures varying from 15° to 64°C. Altered rocks with secondary calcium carbonate were common at four of the sites, where present-day temperatures range from 38° to 64°C. Fluid inclusions in aragonite suggest that the mineral precipitated from an aqueous fluid of seawater salinity at temperatures well below 100°C. The chemical compositions of secondary calcite and aragonite were determined with both an electron microprobe and a laser-ablation inductively coupled plasma-mass spectroscopy (LA-ICP-MS) microprobe. These two techniques yielded consistent analyses of the same minor elements (Mg and Sr) in the same specimens. The combined results show that secondary aragonites contain very little Mg, Mn, Fe, Co, Ni, Cu, Zn, Rb, La, Ce, Pb, or U, yet they contain significant Sr. In contrast, secondary calcites contain significant Mg, Mn, Fe, Ni, Cu, Zn, and Pb, yet very little Co, Rb, Sr, La, Ce, or U. Secondary calcium carbonates provide subseafloor reservoirs for some minor and trace elements. Replacement of aragonite by calcite should result in a release of Sr, Rb, and Zn to solution, and it provides a sink for Mg, Mn, Ni, Cu, Zn, and Pb.

Mineral and chemical compositions of a ferromanganese nodule from Station DM41-3911-76

Processes of authigenic manganese ore formation in sediments of the North Equatorial Pacific are considered on the basis of a study of the surface layer (<2 mm) of a ferromanganese nodule and four micronodule size fractions from associated surface sediment (0-7 cm). Inhomogeneity of nodule composition is shown. Mn/Fe ratio is maximal in samples from lateral sectors of the nodule at the water-sediment interface. Compositional differences of nodules are related to preferential accumulation of trace elements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenic component trapped during nodule growth (Ga, Rb, Ba, and Cs). Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by minimal Mn/Fe values. A compositional comparison of manganese micronodules and surface layers of the nodule demonstrates that micronodule material was subjected to more intense reworking during diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe, but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are the least mobile elements during diagenesis. Differences in chemical composition of the micronodules and nodules are related not only to additional input of Mn in the process of diagenesis, but also to transformation of iron oxyhydroxides after removal of Mn from the close association with Fe formed in suspended matter during sedimentation.

Geochemical composition of snow samples from Antarctica, Greenland and northeast Canada

In this paper, we present new detailed data on the trace metal content of more than 200 shallow polar snow samples collected at various depths in numerous locations mainly in Antarctica and Greenland. The samples were collected in ultraclean plexiglass or teflon tubes from the walls of hand dug pits, using stringent contamination free techniques controlled by severe blank tests. They were then analysed for Na, Mg, K, Ca, Fe, Al, Mn, Pb, Cd, Cu, Zn and Ag in clean room conditions by flameless atomic absorption, after a preconcentration step (by non boiling evaporation in teflon bulbs) which includes dissolving any solid particles by concentrated nitric and hydrofluoric acids. The overall precision on the measured concentrations is of the order of 10 % for all the metals except Pb (20 %) and Cd (35 %), using 95 % confidence limits. The data obtained are compared with those published previously in the literature. Part of these previous data are shown to be erroneously too high, probably because of con-tamination problems both during field collection and analysis.

(Table 2) Concentrations of dissolved Zn, Cd, Pb, and Cu in waters of the Baltic Sea

A method of determination of low concentrations of zinc, cadmium, lead, and copper dissolved in seawater and interstitial water with use of inversion voltammetry with AC solution conditions is described. The optimum conditions for measurements with accumulation on a mercury-film electrode with a silver substrate are presented. Detection limit is 0.2 ?g/l for zinc and 0.05 ?g/l for cadmium, lead, and copper. Large number of determinations can be carried out during expeditions at natural pH of seawater containing these four metals.