Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

Composition of Fe-Mn nodules and crusts from the Cape Basin

Facies zonation of the Cape basin with respect to Fe-Mn nodules based on data from Cruise 43 of R/V Akademik Kurchatov and published data is presented. Three facies regions are distinguished: the southern end of the Walvis Ridge and seamounts, the continental slope of the Southwest Africa and the deep-water Cape Basin. Iron-manganese nodules in the first of these areas are predominantly sedimentary, those in the second area are diagenetic and those in the third are sedimentary-diagenetic. Chemical characteristics and type of metallogenic specialization for each of the regions are identified.

(Table 2) Comparative growth rates of upper and lower parts of Fe-Mn nodules from the Pacific Ocean

Dates and growth rates of iron-manganese nodules obtained by various direct and indirect methods, including radiometric, micropaleontological, geological and experimental, are discussed. Validity of assumptions, on which the radiometric dating of nodules is based and reliability of results are discussed. The problem of "buoyancy" of slow-growing nodules resting on the surface of faster-accumulating sediments is considered: It may be caused by action of deep-water fauna, bottom currents, or plastic properties of sediments.

(Table 1) Color, Fe-C-S chemistry and carbonate content from ODP Sites 172-1062 and 172-1063

Reflectance spectra collected during ODP Leg 172 were used in concert with solid phase iron chemistry, carbonate content, and organic carbon content measurements to evaluate the agents responsible for setting the color in sediments. Factor analysis has proved a valuable and rapid technique to detect the local and regional primary factors that influence sediment color. On the western North Atlantic drifts, sediment color is the result of primary mineralogy as well as diagenetic changes. Sediment lightness is controlled by the carbonate content while the hue is primarily due to the presence of hematite and Fe2+/Fe3+ changes in clay minerals. Hematite, most likely derived from the Permo-Carboniferous red beds of the Canadian Maritimes, is differentially preserved at various sites due to differences in reductive diagenesis and dilution by other sedimentary components. Various intensities for diagenesis result from changes in organic carbon content, sedimentation rates, and H2S production via anaerobic methane oxidation. Iron monosulfides occur extensively at all high sedimentation sites especially in glacial periods suggesting increased high terrigenous flux and/or increased reactive iron flux in glacials.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Dissolved iron and Fe(II) in an iron induced Southern Ocean phytoplankton bloom measured during TANGAROA cruise SOIREE

During the 13 day Southern Ocean Iron RE-lease Experiment (SOIREE), dissolved iron concentrations decreased rapidly following each of three iron-enrichments, but remained high (>1 nM, up to 80% as FeII) after the fourth and final enrichment on day 8. The former trend was mainly due to dilution (spreading of iron-fertilized waters) and particle scavenging. The latter may only be explained by a joint production-maintenance mechanism; photoreduction is the only candidate process able to produce sufficiently high FeII, but as such levels persisted overnight (8 hr dark period) -ten times the half-life for this species- a maintenance mechanism (complexation of FeII) is required, and is supported by evidence of increased ligand concentrations on day 12. The source of these ligands and their affinity for FeII is not known. This retention of iron probably permitted the longevity of this bloom raising fundamental questions about iron cycling in HNLC (High Nitrate Low Chlorophyll) Polar waters.