Geochemistry of ferromanganese deposits from the Wombat Plateau

Ferromanganese crusts, nodules, and ferromanganese-rich sediments were recovered on the Wombat Plateau, northwest Australian continental margin, by dredging during Bureau of Mineral Resources cruise 56 of Rig Seismic and by drilling during ODP Leg 122 of JOWES Resolution. We report here the chemistry and mineralogy of the ferromanganese crusts, nodules, and associated ferromanganese-rich sediments. The ferromanganese deposits from the ODP sites are up to 40 cm thick and probably formed in Late Cretaceous to Eocene times. Those from outcrops usually formed in several phases, and their age is unconstrained except that the substrates are Mesozoic. The samples were recovered from present-day water depths of 2000-4600 m, on the Wombat Plateau adjacent to the Argo Abyssal Plain. Both the nodules and crusts are primarily vernadite (delta-MnO2) and are chemically and mineralogically similar, and not dissimilar from ferromanganese deposits found elsewhere on Australian and other marginal plateaus. They are markedly different from most deep-sea deposits. The only crystalline iron phase identified within the ferromanganese deposits is goethite. Concentrations of metals of potential economic interest are generally low compared to those from vernadite-rich seamount crusts and nodules and from abyssal nodules from areas of high resource potential in the Pacific Ocean. Maximum metal values reach 0.55% Co, 0.58% Ni, and 0.20% Cu in deposits containing 4.8% to 30.9% Fe and 4.4% to 21.1% Mn.

(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.

Chemical composition of Fe-Mn manifestations from the Laptev Sea

In sediments of the Laptev Sea unknown earlier ferromanganese manifestations have been found. On the basis of structural-textural external signs they have been divided to five groups: 1) tube- and spindle-shaped pseudomorphs after and within invertebrates; 2) nuclear and non-nuclear nodules; 3) flagellum- and tube-like skeletons of polychaetes; 4) flat and flattened crustate nodules and crusts; 5) micronodules. All types of ferromanganese manifestations have been sorted in three main genetic series: eigenferrous formations of autochthonous (polychaetes, goethite micronodules) and allochthonous (nuclear nodules) nature; ferromanganese nodules formed under mild hydro-geodynamic conditions at the sediment-seawater geochemical barrier; and ferromanganese manifestations formed under conditions of the variable physico-chemical environment. Ferromanganese manifestations of allochthonous type have signs of littoral zones. They contain both ferrous and ferric iron and have low oxidation degree of manganese in comparison with the autochthonous type manifestations. Manganese minerals with moderate oxidation degree are represented by vernadite and buserite. Such features of iron and manganese indicate different conditions of their formation and occurrence. The main distinctive feature of ferromanganese mineralisation in the Laptev Sea is the redox barrier: the oxidized water layer enriched in oxygen and reduced sediments. This barrier provides favorable conditions for bacterial formation of ferromanganese ores. Understanding of the genesis of ferromanganese manifestations should be found in a study of organic matter reworking by bacteria.

Composition of recent pelagic sediments from the South Pacific

Lithologic, grain size, chemical and mineral compositions of recent bottom sediments from the South Pacific are reported in the paper.

Rock magnetic, element, and color data of three sediment cores along the Senegalese continental margin

We present a suite of new high-resolution records (0-135 ka) representing pulses of aeolian, fluvial, and biogenic sedimentation along the Senegalese continental margin. A multiproxy approach based on rock magnetic, element, and color data was applied on three cores enclosing the present-day northern limit of the ITCZ. A strong episodic aeolian contribution driven by stronger winds and dry conditions and characterized by high hematite and goethite input was revealed north of 13°N. These millennial-scale dust fluxes are synchronous with North Atlantic Heinrich stadials. Fluvial clay input driven by the West African monsoon predominates at 12°N and varies at Dansgaard-Oeschger time scales while marine productivity is strongly enhanced during the African humid periods and marine isotope stage 5. From latitudinal signal variations, we deduce that the last glacial ITCZ summer position was located between core positions at 12°26' and 13°40'N. Furthermore, this work also shows that submillennial periods of aridity over northwest Africa occurred more frequently and farther south than previously thought.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Magnetic and mineralogical analyses of Ganzi and Luochuan sections

We present a first combined environmental magnetic and geochemical investigation of a loess-paleosol sequence (<55 ka) from the Chuanxi Plateau on the eastern margin of the Tibetan Plateau. Detailed comparison between the Ganzi section and the Luochuan section from the Chinese Loess Plateau (CLP) allows quantification of the effects of provenance and climate on pedogenic magnetic enhancement in Chinese loess. Rare earth element patterns and clay mineral compositions indicate that the Ganzi loess originates from the interior of the Tibetan Plateau. The different Ganzi and CLP loess provenances add complexity to interpretation of magnetic parameters in terms of the concentration and grain size of eolian magnetic minerals. Enhanced paleosol magnetism via pedogenic formation of ferrimagnetic nanoparticles is observed in both sections, but weaker ferrimagnetic contributions, finer superparamagnetic (SP) particles and stronger chemical weathering are found in the Ganzi loess, which indicates the action of multiple pedogenic processes that are dominated by the combined effects of mean annual precipitation (MAP), potential evapotranspiration (PET), organic matter and aluminium content. Under relatively high MAP and low PET conditions, high soil moisture favours transformation of ferrimagnetic minerals to hematite, which results in a relatively higher concentration of hematite but weaker ferrimagnetism of Ganzi loess. Initial growth of superparamagnetic (SP) particles is also documented in the incipient loess at Ganzi, which directly reflects the dynamic formation of nano-sized pedogenic ferrimagnets. A humid pedogenic environment with more organic matter and higher Al content also helps to form finer SP particles. We therefore propose that soil water balance, rather than solely rainfall, dominates the type, concentration and grain size of secondary ferrimagnetic minerals produced by pedogenesis.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.