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.

Annotated record and illustrations of Mn nodules retrieved during cruise KH-73-4 of the R/V Hakuho Maru and cruises GH76-1 and GH77-1 of the R/V Hakurei Maru

Deep sea manganese nodules from the Central Pacific Basin are mainly composed of 10Å manganite and d-MnO2 Two zones equivalent to the minerals are evidently distinguishable according to their optical properties. Microscopic and microprobe analyses revealed quite different chemical compositions and textnral characteristics of the two zones. These different feature of the two zones of nodules suggest the different conditions under which they were formed. Concentrations of 11 metal elements in the zones and inter-element relationships show that the 10Å manganite zone is a monomineralic oxide phase containing a large amount of manganese and minor amounts of useful metals, and that the d-MnO2 zone which is apparently homogeneous under the microscope is a mixture of three or more different minerals. The chemical characteristics of the two zones can explain the variation of bulk composition of deep sea manganese nodules and inter-element relationships previously reported, suggesting that the bulk compositions are attributable to the mixing of the 10Å manganite and d-MnO2 zones in various ratios. Characteristic morphology and surface structure of some types of nodules and their relationships to chemistry are also attribut able to the textural and chemical features of the above mentioned two phases. Synthesis of hydrated manganese oxides was carried out in terms of the formation of manganese minerals in the ocean. The primary product which is an equivalent to d-MnO2 was precipitated from Mn 2+ -bearing alkaline solution under oxigenated condition by air bubbling at one atmospheric pressure and room temperature. The primary product was converted to a l0Å manganite equivalent by contact with Ni 2+, Cu 2++ or CO2+ chloride solutions. This reaction caused the decrease of Ni2+, Cu2+ or CO2+ concentrations and the increase of Na+ concentration in the solution. The reaction also proceeded even in diluted solutions of nickel chloride and resulted in a complete removal of Ni2+ from the solution. Reaction products were exclusively 10Å manganite equivalents and their chemical compositions were very similar to those of 10Å manganite in manganese nodules. The maximum value of(Cu+Ni+Co)/Mn ratio of 10Å manganite zones in manganese nodules is 0.16, and the Ni/Mn ratio of synthetic 10Å manganite ranges from 0.15 to 0.18 with the average of 0.167.

(Table 1, Page 94) Elemental abundances in ferromanganese nodules and crusts from the Pernambuco Plateau and guyots off northeast Brazil

Ferromanganese deposits, mostly manganese crusts, are common in elevations along the northeastern Brazilian continental margin. Association of the deposits with more or less altered basaltic rock can be observed. On the Pernambuco Plateau and Ceara Guyot, ferromanganese deposits occur associated with phosphatic material and nodules. The mineralogical composition of the ferromanganese deposits indicates a predominance of the manganese oxide phase dMnO2. Low contents of Mn and Cu are characteristic of their chemical composition. Fe and Mn in the deposits probably precipitated from the sea water.

(Table 1, page 376), Composition of manganese deposits from the Gulf of Aden and the Carlsberg Ridge

Iron-manganese nodules from the ocean floor have been extensively studied. But, because of the fine grain size of the particles of the nodules, structural identification by X-ray and electron diffraction techniques is difficult and the mineralogy of the iron oxide phase has not been well characterized. The observation of the Mössbauer spectrum-in which each nucleus absorbs gamma-rays independently-is not limited by particle size in the same way as is the observation of Bragg peaks in diffraction measurements, in which radiation must be scattered coherently from a large number of atoms. The magnetic hyperfine splitting in the Mössbauer spectrum of magnetic materials is affected, however, when the particles are so small that they become superparamagnetic. We describe here an investigation using the 57Fe Mössbauer effect of two iron-manganese nodules in which the iron oxide phase could not be detected by X-ray or electron diffraction.

Mineralogy and major element oxide composition of sediments from ODP Hole 172-1063D

Dansgaard-Oeschger (D-O) cycles in sediment at Site 1063 are characterized by distinct fluctuations in physical properties. Stadials are marked by low bulk density and interstadials by high bulk density. Compressional (P-)wave velocity is in phase with bulk density over some but not all depth intervals. Four of the D-O cycles straddling the oxygen isotope Stage 4/5 boundary have been studied in detail to understand the origin of the physical properties changes. Sediment on the Bermuda Rise is comprised of three main components: calcite, aluminosilicate minerals, and biogenic silica. Calcite concentrations vary from 1% to 43% of bulk sediment and are highest during interstadials. Aluminosilicate concentrations vary from 52% to 92% of bulk sediment and are highest during stadials. The major element ratios Al2O3/TiO2 and K2O/Al2O3 show increases across bulk density cycles, suggesting a change in the composition of aluminosilicates. This interpretation is supported by mineralogical analyses, which show a subtle change in clay composition. Biogenic silica concentrations vary from 0% to 23% of bulk sediment and are also highest during stadials. However, the abundance of silica varies significantly from one D-O cycle to another. Silt and fine sand abundance also increase during the first of the four stadials. This coarsening of sediment coincides with the increase in biogenic silica. The low grain density and high porosity associated with biogenic silica result in intervals of low bulk-sediment density. The abundance of biogenic silica closely matches P-wave velocity, suggesting that silica imparts a greater rigidity to the sediment.

(Supplemet S1) Silicon oxide and Potassium + Sodium oxide from the PACManus hydrothermal area

This study presents a systematic analysis and interpretation of autonomous underwater vehicle-based microbathymetry combined with remotely operated vehicle (ROV) video recordings, rock analyses and temperaturemeasurements within the PACManus hydrothermal area located on Pual Ridge in the Bismarck Sea of eastern Manus Basin. The data obtained during research cruise Magellan-06 and So-216 provides a framework for understanding the relationship between the volcanism, tectonismand hydrothermal activity. PACManus is a submarine felsic vocanically-hosted hydrothermal area that hosts multiple vent fields locatedwithin several hundredmeters of one another but with different fluid chemistries, vent temperatures and morphologies. The total area of hydrothermal activity is estimated to be 20,279m**2. Themicrobathymetrymaps combinedwith the ROV video observations allow for precise high-resolution mapping estimates of the areal extents of hydrothermal activity.We find the distribution of hydrothermal fields in the PACManus area is primarily controlled by volcanic features that include lava domes, thick andmassive blocky lava flows, breccias and feeder dykes. Spatial variation in the permeability of local volcanic facies appears to control the distribution of venting within a field.We define a three-stage chronological sequence for the volcanic evolution of the PACManus based on lava flow morphology, sediment cover and lava SiO2 concentration. In Stage-1, sparsely to moderately porphyritic dacite lavas (68-69.8 wt.% SiO2) erupted to form domes or cryptodomes. In Stage-2, aphyric lava with slightly lower SiO2 concentrations (67.2-67.9 wt.% SiO2) formed jumbled and pillowed lava flows. In the most recent phase Stage-3, massive blocky lavaswith 69 to 72.5wt.% SiO2were erupted throughmultiple vents constructing a volcanic ridge identified as the PACManus neovolcanic zone. The transition between these stages may be gradual and related to progressive heating of a silicic magma following a recharge event of hot, mantle-derived melts.

Summary of phase compositions of experimental silicate melt, un-normalised analyses

The solubility of Re and Au in haplobasaltic melt has been investigated at 1673-2573 K, 0.1 MPa-2 GPa and IW-1 to +2.5, in both carbon-saturated and carbon-free systems. Results extend the existing, low pressure and temperature, dataset to more accurately predict the results of metal-silicate equilibrium at the base of a terrestrial magma ocean. Solubilities in run-product glasses were measured by laser ablation ICP-MS, which allows for the explicit assessment of contamination by metal inclusions. The Re and Au content of demonstrably contaminant-free glasses increases with temperature, and shows variation with oxygen fugacity (fO2) similar to previous results, although lower valence states for Re (1+, 2+) are suggested by the data. At 2 GPa, and Delta IW of +1.75 to +2, the metal-silicate partition coefficient for Re (DMet/Sil) is defined by the relation LogD[met/sil][Re] = 0.50(±0.022)*10**4/T(K)+3.73(±0.095) For metal-silicate equilibrium to endow Earth's mantle with the observed time-integrated chondritic Re/Os, (and hence 187Os/188Os), DMet/Sil for both elements must converge to a common value. Combined with previously measured DMet/Sil for Os, the estimated temperature at which this convergence occurs is 4500 (±900) K. At this temperature, however, the Re and Os content of the equilibrated silicate is ~100-fold too low to explain mantle abundances. In the same experiments, much lower Dmet/sil values have been determined for Au, and require the metal-silicate equilibration temperature to be <3200 K, as hotter conditions result in an excess of Au in the mantle. Thus, the large disparity in partitioning between Re or Os, and Au at core-forming temperatures argues against their mantle concentrations set solely by metal-silicate equilibrium at the base of a terrestrial magma ocean.