ALBERT

Description: 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.

Description: The major and some of the minor constituents and the rate of accumulation of manganese nodules in the western North Pacific were determined. Manganese concentration in the nodules ranged from 20 to 30 per cent in the acid soluble fraction. As to the rare earth concentration, enrichment of cerium was observed in the manganese nodule as compared with that in shales or sea water. Thorium to uranium ratio in the nodule ranged from 9.4 to 14.3, which was very much higher than that in sea water. From the distribution of excess ionium, excess protactinium and Io/Th ratio, a rate of accumulation of 7 mm per million years was obtained with the surface layer of several mm in thickness of the JEDS-4-E4 nodule.

Description: Manganese oxide crusts similar to those reported from the Mid-Atlantic Ridge rift valley by Scott et al., 1974 (https://doi.pangaea.de/10.1594/PANGAEA.848726) were dredged at two sites near the Galapagos spreading axis on ocean floor estimated from magnetic anomalies to be 2.4 and 0.3 m.y. old. Compared to the typical ocean-floor manganese deposits attributed to precipitation from seawater, the 2-6 cm thick manganese crusts reported here exhibit very low Fe/Mn and low 232Th/238U ratios, as well as lower transition metal and higher manganese concentrations. The manganese crusts were deposited several orders of magnitude faster than the more common hydrogenous nodules; this fact together with other geochemical characteristics and the geophysical environment suggests the manganese deposits reported here are of hydrothermal origin.

Description: The major and minor element compositions of a suite of abyssal sea-floor ferromanganese nodules and associated sediments from the eastern central Pacific have been used to examine inter-element relationships and the mineralogy of the nodules, the relationship between the composition of nodules, and their associated sediments and regional variations in composition with respect to likely modes for formation of such deposits. Apart from Mn and Fe, significant proportions of the total Ti, Ca, Mg, K, Ba, Sr, Th and Y and almost all the P, As, Ce, Co, Cu, Mo, Ni, Pb, Zn and Zr are present in the oxide fractions of the nodules. The Mg, Ba, Cu, Mo, Ni and Zn contents are significantly correlated with the total Fe content. Nodules from the northeastern tropical Pacific have Mn/Fe ratios highter than those in the oxide fractions of their associated sediments, todorokite as the principal Mn phase and relatively high concns of minor elements associated with Mn. Nodules from the south central Pacific have Mn/Fe ratios similar to those in the oxide fractions of the associated sediments, {delta}-MnO Sub(2) as the only Mn-phase, and relatively high concns of minor elements associated with Fe. There appears to be a smooth gradation in composition in the tropical Pacific between these 2 end members. The retional compositional variation is interpreted as a reflection of different sources of metals for, and different growth mechanisms of, sea-floor nodules. The oxide precipitate from sea water consists of {delta}-MnO Sub(2), has a relatively low Mn/Fe ratio and minor element contents related to the total Fe and Mn({delta}-MnO Sub(2)) content. The oxide precipitate forming in areas of very low sedimentation as a result of diagenetic remobilisation in the surface sediment consists of todorokite, and has a high Mn/Fe ratio and enhanced metal content in the Mn-(todorokite) phase. Available information on the morphology and compositional variation of individual nodules from the tropical Pacific corroborates these contrasting metal sources and suggests that they can be resolved on the scale of an individual oxide concretion.

Description: Bulk composition of ferromanganese nodules from the pelagic environment of the Pacific Ocean is apparently related to nodule-growth rate, sediment-accumulation rate, and biologic productivity in the overlying seawater. Nodules with a high Mn/Fe ratio and high Ni and Cu concns tend to occur in areas where primary productivity in the surface layer of the ocean is high and the sediment accumulation rate low. They may have a Mn/Fe ratio as low as one and accrete at rates as low as 1 mm/10 M yrs. Nodules with a larger Mn/Fe ratio apparently have growth rates that are greater by as much as a factor of 10.

Description: Analyses of small samples extracted from different parts of a single manganese nodule have been reported by several investigators, clearly documenting the belief that a nodule is not homogeneous chemically, as a rule. The same sort of evidence has been gathered by use of the X-ray macroprobe and electron microprobe analyses. The X-ray probe work has shown clearly that chemical variations within a nodule can be correlated with optically recognizable mineral,and therefore optical study can tell much about chemical variations and obviate much probe analysis. As we have reported many times, optically anisotropic crystalline todorokite and birnessite contain the bulk of the Mn, Ni, and Cu in any nodule whereas optically isotropic and X-ray amorphous oxides contain most of the Fe and Co in the same nodule.

Description: Manganese nodules and associated sediment from the equatorial North Pacific have been examined to ascertain relations between nodule abundance, texture, and composition, and sediment composition, lithology and acoustic stratigraphy. Nodules are most abundant in areas where the uppermost acoustically transparent layer of sediment is less than approximately 15 m thick. Abundance drops off sharply in areas where this acoustic unit is thicker than 20 m. Nodules have average Zn/Mn and Co/Mn ratios which are approximately the same as these ratios for the component of sediment soluble in hydroxylamine hydrochloride-acetic acid. The relations between Cu and Mn and Ni and Mn in the sediment are also approximately the same as in nodules, but only for those nodules which have a smooth surface texture. Granular nodules have relatively more Ni and Cu. Antimony in nodules, similar to Ni, Cu, and Zn, is strongly correlated with Mn, whereas Co, Hf, Th, and U are strongly correlated with Fe. The insoluble component of sediment has a uniform composition which is similar to the composition of terrigenous shale. This similarity holds for the major oxides as well as for Co, Cr, Zn, Hf, Sb, Th, U, Sc, Cs, Rb, and Ta.

Description: Atlantic manganese nodules and encrustations are most abundant in areas of slow sedimentation beneath the carbonate compensation depth or where currents inhibit sediment accumulation. They principally contain the minerals todorokite and ?MnO2, which are selectively concentrated into nodules and encrustations, respectively, and which show an environmental differentiation thought to be related to redox potentials. Excluding the continental margins, todorokite is most abundant in deepwater deposits. Mineralogical differences between nodules influence their chemical compositions, Ni and Cu being most abundant in samples rich in todorokite and Co in those rich in ?MnO2. Chemically, the deposits differ from those in other major oceans principally in their higher Fe and lower Ni and Cu contents, which may be due to higher rates of supply of Fe to the deposits than those in the other oceans. Regional variations occur in the concentrations of several elements, Mn, Ni, and Cu being enriched in deepwater deposits from areas of slow sedimentation between the Mid-Atlantic Ridge and the continental margins and Co being enriched in some deposits from elevated localities. These variations are thought to be due to variation in the sources of the elements concerned and in the depositional environment.

Description: Manganese nodules from the Scotia Sea and Pacific Ocean sectors of the Southern Ocean display regional differences in chemical and mineralogical composition. Mn/Fe and todorokite/delta-MnO2 ratios decrease southeasterly from the Southwestern Pacific Basin to the Drake passage-Scotia Sea. Relative to Mn, the greatest enrichments of Co, Ti, V, Zn, Mo and Sn occur in Drake Passage-Scotia Sea nodules, while Ni and Cu are most enriched in the Southwestern Pacific Basin. Manganese mineralogy is directly related to the Mn/Fe ratio, so that todorokite rather than delta-MnO2 predominates when high manganese vs iron contents are found. Trace metal contents are also related to mineralogy, with high values of Ni, Cu, Zn and Sn, and low values of Co, Ti, V and Mo associated with high todorokite contents. Nodules having indistinct zeolitits/vesiculite nuclei tend to have Mn/Fe and todorokite/delta-MnO2 ratios significantly higher than average for the region in which they are found, whereas ferromanganese oxide fragments dredged from submarine rock surfaces usually have Mn/Fe and todorokite/delta-MnO2 ratios lower than regional average.