ALBERT

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: The bulk chemical compositions of ferromanganese nodules recovered from 14 of 38 sediment cores collected from a 230 km2 area of abyssal hill topography in the northern equatorial Pacific (8° 20'N, 153° 0'W; regional depth 5000 m) vary nonrandomly between fairly wide limits. The nodules have Mn/Fe ratios ranging from 2.60 to 5.38 and all samples contain todorokite and delta-MnO2 . The variation in the Mn/Fe ratio is governed by the total Fe contents of the nodules; Mn varies to a much smaller extent. Cu and Ni contents average about 1% and vary independently of the Mn contents. The compositional variation in the nodules is related to two features of the associated sediments, which are siliceous pelagic clays. The total Fe contents correlate positively with the oxalate-soluble Fe contents of the surface (0-2 cm) sediments; and their Mn/Fe ratios correlate negatively with the accumulation rates of the sediments. It is suspected that the composition of the nodules is influenced to a considerable extent by diagenetic reactions in the sediments, the clearest manifestation of this being the transformation of oxyhydroxide Fe into an insoluble form, possibly by the formation of smectite. This in turn leads to the formation of relatively Fe-poor ferromanganese nodules. Such nodules occur on slowly accumulating sediments where relatively more diagenetic reaction in the sediments has taken place.

Description: Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151°W, 9° 15'N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochloride-acetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co/Mn ratio of 300. The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have Delta-MnO2 as the dominant manganese mineral. The ratios of Ni/Mn, Cu/Mn, and Fe/Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the Delta-MnO2 nodules.

Description: 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.