Investigation of manganese nodules from the Southern Tasman Sea

Two manganese nodules having a high clay content, a low Mn/Fe ratio, and low contents of valuable metals (Ni 0.25%, Cu 0.17%, Co 0.06%) were recovered in a grab sample during a short geological cruise in HMAS Kimbla in the southern Tasman Sea in May 1979. Five stations were occupied. Free-fall grabs recovered sediment or pumice from four stations; nothing was recovered from the fifth. The carbonate compensation depth in the region is about 4500 m. Reddish brown clay, but no manganese nodules, was recovered in the central southern Tasman Sea, from depths of 4900-5100 m. The nodules, together with grey calcareous mud, were obtained from a depth of 4300 m, farther to the northwest, near Gascoyne Seamount (250 n. miles SE of Sydney). The results suggest nodules with high metal values are likely to exist only in the broad and deep depression in the central southern Tasman Sea southeast of Gascoyne Seamount, where sedimentation rates are low and oxidising conditions prevail. Whether nodule fields are present or not will only be resolved by considerably more sampling.

Geochemistry on manganese nodules from Loch Fyne, Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10-15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180-200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5-8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments. The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn. The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice. Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.

(Table 1, page 1124), Chemical composition of Lake Michigan manganese nodules

Manganese nodules containing up to 22 percent manganese oxide were found in Green Bay and the western and northern parts of Lake Michigan. The chemical composition of these nodules resembles that of shallow-water lacustrine and marine nodules. The manganese content of interstitial water is in some places enriched as much as 4000 times over that of lake water.

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Observation of manganese nodules and crusts in the Blake Plateau area

Visual observations of manganese deposits on the Blake plateau from a manned submersible indicate that the occurrence of manganese as nodules, slabs, or pavement may be related to localized environmental conditions. Manganese is concentrated at the crests of sand waves and, in areas of gentle slope, grades locally from nodules to solid pavement.

Manganese concentrations and flux data of sediments from Broken and Ninetyeast Ridge

Decomposition of organic matter combined with density stratification generate a pronounced intermediate water oxygen minimum zone (OMZ) in the northwest Indian Ocean. This zone currently lies between water depths of 200 and 2000 m and extends approximately 5000 km southeast from the Arabian coast. Based upon benthic foraminiferal assemblage changes, it has been suggested that this OMZ was even more extensive during the late Miocene-early Pliocene (6.5-3.0 Ma), with a maximum volume and/or intensity at approximately 5.0 Ma. While this inference may contribute to an understanding of the history of northwest Indian Ocean upwelling, corroborating geochemical evidence for this interpretation has heretofore been lacking. Ocean Drilling Program (ODP) sites 752, 754, and 757 on Broken and Ninetyeast ridges are located within central Indian Ocean intermediate water depths (1086-1650 m) but outside the present lateral dimensions of the Indian Ocean OMZ. High-resolution chemical analyses of sediment from these sites indicate significant reductions in the flux of Mn and normalized Mn concentrations between 6.5 and 3.0 Ma that are most pronounced at approximately 5.0 Ma. Because late Miocene-Pliocene paleodepths for these sites were essentially the same as at present and because extremely low sedimentation rates (0.3-1.3 cm/ky) most likely precluded sedimentary metal oxide diagenesis, we suggest that the observed Mn depletions reflect diminished deposition of reducible Mn oxyhydroxide phases within O2 deficient intermediate waters and that this effect was most intense at approximately 5.0 Ma. This interpretation implies that waters with less than 2.0 mL/L O2 extended at least 1500 km beyond their present limits and is consistent with changes in benthic foraminifera assemblages. We further suggest this expanded Indian Ocean OMZ is related to regionally and/or globally increased biological productivity.

Manganese nodules recovered by R/V Vityaz expedition

Uranium, radium, thorium and ionium were determined directly on seven concretions from three stations in the Indian Ocean, and on two concretions and a manganese-rich crust from two stations in the Pacific Ocean. The uranium content averages 3 to 5 gamma/g and the thorium content varies only slightly, but the Th/U ratio in the concretions is typically 2 to 5 in the Indian Ocean and 5 to 15.5 in the Pacific. The ionium content ranges from 1.0 x 10-9 to 3.6 10**-9 g/g in concretions from both oceans. Radium is more abundant in specimens from the Pacific Ocean (Ra = 3 - 12.7 x 10**-11 g/g) than from the Indian Ocean (1.5 - 5.2 x 10**-11 g/g). Analyses for Ca, Mn, Fe, Si, Ni, P, and ignition loss are also given. Radioactive equilibria between uranium, ionium, and radium are strongly disturbed throughout the concretions, and the RA/U and lo/U ratios generally exceed equilibrium ratios. Migration of radium from interior layers was established, so that neither determination of the ages of the concretions nor of their rates of growth can be considered reliable. The age of the concretions cannot exceed 800,000 years, and all grew within relatively short periods of time; there may have been "dormant" periods during growth. Estimates of growth rates are calculated from the radium and ionium contents; they show marked discordance.

Composition of hydrothermal manganese oxide deposits from Galapagos mounds, DSDP Leg 70, Hole 509B

During DSDP Leg 70, a 1.60 m thick manganese oxide layer was sampled in hole 509B. This deposit is formed of alternating layers of hard plates of pure todorokite, about 2 mm thick, and of a more powdery material deeply impregnated with manganese oxide, about 3 mm thick. A SEM study of the plates and the associated powder shows that the powdery material is a transformation of a pre-existing sediment, while the plates are a direct precipitation from a hydrothermal solution. The uranium series disequilibrium method was used to determine the ages of the plates. They are found to be in good chronological sequence and in accordance with the sedimentation rate of the area (4.9 cm/10^3 years) which implies that they have been formed at the sediment-seawater interface during a pulsed injection of hydrothermal solution. The powder presents systematically an "older age" which is explained by a slowing down of the injection while the normal sediment settles; the older age is due to the 230Th excess of the sediment.