(Table 1, pages 283), Elemental concentrations of ferromanganese crusts from Lake Biwa, Japan

Ferromanganese crusts were sampled from the surface of a stone collected at a depth of 20 m in the northern part of Lake Biwa, Japan. These samples were analysed for 37 elements by neutron activation, X-ray fluorescence, and ICP-AE. The crusts were found to be enriched with Ba, P, B, As, and sometimes with Co, Ni, Cu and Sb. The elements were classified into 4 groups based on the varieties of host minerals (Fe-oxides, Mn-oxides or allochthonous materials) in which they were incorporated : elements mainly associated with 1) Mn-oxides : Ba, Ni, Cs, Sr and Co ; 2) Fe-oxides : P, B and As; 3) allochthonous materials : Na, K, Rb, Al, Ti, Sc, Hf and Th ; and 4) Mn-oxides plus allochthonous materials : rare earth elements and major heavy metals. The elemental compositions in the Lake Biwa concretions, including the crusts and Mn-deposits studied previously by these authors, were compared with those in other freshwater and oceanic concretions. As a result, the concentrations of rare earth elements and major heavy metals were found to be much lower, whereas those of B, P and As were higher in the Lake Biwa than in the oceanic concretions. These differences could be well explained in terms of the effects of sea salt, growth rates of the concretions, and pH of the formation environment.

(Table 1, page 400) Metal content of different manganese nodules from cruise VA-04 (R/V Valdivia) in the Pacific Ocean

Deep sea manganese nodules are considered as important natural resources for the future because of their Ni, Cu and Co contents. Their different shapes cannot be correlated clearly with their chemical composition. Surface constitution, however, can be associated with the metal contents. A classification of the nodules is suggested on the basis of these results. The iron content of the nodules strikingly shows relations to the physical properties (e.g. density and porosity). The method of density-measurement is the reason for this covariance. The investigation of freeze-dried nodular substance does not give this result. The Fe-rich nodules lose more hydration water than the Fe-poor ones during heat drying. The reason for this effect is the different crystallinity, respectively the particle size. The mean particle size is calculated on the basis of geometrical models. The X-ray-diffraction analysis proves the variation of crystallinity in connection with the Fe-content, too. The internal nodular textures also show characteristic distinctions.

(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

(Table 1, page 754) Estimated concentrations of various elements in nineteen manganese nodules

Using spectrochemical techniques Fe, Si, Mg, Co, Ni, Cu, V, Mo, Ti and Tl have been estimated in nineteen manganese nodules, eight from the Atlantic ocean, seven from the Pacific ocean and four from the Indian ocean. Though data on more samples are required before firm and detailed conclusions can be made about the distribution of elements in manganese nodules, several distinct features appear when the data on the nineteen samples are examined. Certain elements appear to enrich more strongly than others. For example, relative to igneous rocks Mo is much more strongly enriched than V. For several elements (Ni, Cu and particularly Co and Tl) the degree of enrichment in two Fe-low nodules is far smaller than in the other nodules. The magnitude of dispersion of concentration appears to vary considerably for different elements; thus, whereas variation of concentration of V is relatively small, that of Ni, Cu, Co and Tl is far larger. The statistical nature of the distribution of Fe in manganese nodules appears to be characteristic and different from that of the other elements studied so far. Of the possible inter-element relationships examined that of Ni-Cu appears to be the most strongly developed.

(Table 2, page 2172) Chemical analytical data on thirty-two manganese nodules and crusts

Mn, Fe, Ca, Co, Ni, Cu, Zn, Cd, Sn, Tl, Pb and Bi have been estimated in thirty-two nodules from the Pacific, Atlantic and Indian oceans. Various features about the composition of manganese nodules are discussed: element abundances, degrees of enrichment, inter-element relationships (notably between Ni and Cu, and between Zn and Cd), regional variations and some aspects of statistical distribution.

(Table, Appendix C) Metal content of nodules at Sea Scope stations based upon XRF analyses at the Ore Microscopy Laboratory, Washington State Unicersity, USA

New information on possible resource value of sea floor manganese nodule deposits in the eastern north Pacific has been obtained by a study of records and collections of the 1972 Sea Scope Expedition. Nodule abundance (percent of sea floor covered) varies greatly, according to photographs from eight stations and data from other sources. All estimates considered reliable are plotted on a map of the region. Similar maps show the average content of Ni, Cu, Mn and Co at 89 stations from which three or more nodules were analyzed. Variations in nodule metal content at each station are shown graphically in an appendix, where data on nodule sizes are also given. Results of new analyses of 420 nodules from 93 stations for mn, fe, ni, cu, CO, and zn are listed in another appendix. Relatively high Ni + Cu content is restricted chiefly to four groups of stations in the equatorial region, where group averages are 1.86, 1.99, 2.47, and 2.55 weight-percent. Prepared for United States Department of the Interior, Bureau of Mines. Grant no. GO284008-02-MAS. - NTIS PB82-142571.

Geochemistry of surface sediment cores (Table 4)

The mineralogy and geochemistry of a suite of nine manganese nodules from the South Atlantic have been determined. The Ce/La ratios of the nodules were investigated to see if they could be used as redox indicators to trace the oxygen content of the ambient water mass and the flow path of the Antarctic Bottom Water as has previously been successfully carried out in the Pacific Ocean. The Ce/La ratios of the nodules decrease in the sequence Lazarev Sea, Weddell Sea (10.4 and 9.7)>East Georgia Basin (6.5 and 7.1)>Argentine Basin (5.0), but then increase in the Brazil Basin (6.2) and Angola Basin (9.8 and 15.1). A further decrease was observed in the Cape Basin (7.6). An extremely high Ce/La ratio of 24.4 had already been determined for nodules sampled north of the Nares Abyssal Plain in the western North Atlantic. These data reflect the more complicated pattern of bottom water flow in the South Atlantic than in the South Pacific. The penetration of more oxygenated North Atlantic Deep Water into the South Atlantic accounts for the higher Ce/La ratios in the nodules from the Angola and Brazil basins. Based on this study, the flow path of the Antarctic Bottom Water could only be traced as far north as the Argentine Basin. The unique geochemistry of nodules from the central Angola Basin (high Mn/Fe and Ce/La ratios, high contents of Ni, Cu, Zn and Mo) appears to be a function of the nature of the overlying water mass and of the multiple diagenetic sources of metals to the nodules.

Chemical composition of manganese micronodules from expedition VA-05/1 in the Pacific Ocean

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel "Valdivia" during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn K alpha X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source. The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise. Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.

Geochemical composition of calcite and aragonite, and characteristics of hydrothermal fluids of ODP Leg 168 sites

During Leg 168 a transect was drilled across the eastern flank of the Juan de Fuca Ridge in an area where the volcanic basement is covered by sediments of variable thickness. Samples of basement volcanic rocks were recovered from nine locations along the transect, where the basement sediment interface is presently heated to temperatures varying from 15° to 64°C. Altered rocks with secondary calcium carbonate were common at four of the sites, where present-day temperatures range from 38° to 64°C. Fluid inclusions in aragonite suggest that the mineral precipitated from an aqueous fluid of seawater salinity at temperatures well below 100°C. The chemical compositions of secondary calcite and aragonite were determined with both an electron microprobe and a laser-ablation inductively coupled plasma-mass spectroscopy (LA-ICP-MS) microprobe. These two techniques yielded consistent analyses of the same minor elements (Mg and Sr) in the same specimens. The combined results show that secondary aragonites contain very little Mg, Mn, Fe, Co, Ni, Cu, Zn, Rb, La, Ce, Pb, or U, yet they contain significant Sr. In contrast, secondary calcites contain significant Mg, Mn, Fe, Ni, Cu, Zn, and Pb, yet very little Co, Rb, Sr, La, Ce, or U. Secondary calcium carbonates provide subseafloor reservoirs for some minor and trace elements. Replacement of aragonite by calcite should result in a release of Sr, Rb, and Zn to solution, and it provides a sink for Mg, Mn, Ni, Cu, Zn, and Pb.

Mineral and chemical compositions of a ferromanganese nodule from Station DM41-3911-76

Processes of authigenic manganese ore formation in sediments of the North Equatorial Pacific are considered on the basis of a study of the surface layer (<2 mm) of a ferromanganese nodule and four micronodule size fractions from associated surface sediment (0-7 cm). Inhomogeneity of nodule composition is shown. Mn/Fe ratio is maximal in samples from lateral sectors of the nodule at the water-sediment interface. Compositional differences of nodules are related to preferential accumulation of trace elements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenic component trapped during nodule growth (Ga, Rb, Ba, and Cs). Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by minimal Mn/Fe values. A compositional comparison of manganese micronodules and surface layers of the nodule demonstrates that micronodule material was subjected to more intense reworking during diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe, but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are the least mobile elements during diagenesis. Differences in chemical composition of the micronodules and nodules are related not only to additional input of Mn in the process of diagenesis, but also to transformation of iron oxyhydroxides after removal of Mn from the close association with Fe formed in suspended matter during sedimentation.

Annotated record and chemical analyses of a polygenetic manganese nodule (slab) from the Scott Plateau, Indian Ocean (core VA-16-13KD)

A large manganese nodule (manganese slab) was dredged from 2100 m on the Scott Plateau by R.V. Valdivia in 1977. It is an irregular ellipsoid, with a maximum dimension of 28 cm, parallel to the sea floor. Chemical analyses show that Mn and Fe proportions are comparable, and total Ni + Cu + Co content averages 0.7%. The nodule has a complex growth history which started with radial upward growth leading to coalescing into a continuous crust. The crust was coated with horizontal layers. After fracturing and infilling of cracks with calcareous sediment, further layers encased the nodule.

(Table 3, page 280) Chemical composition of micronodules from a series of stations and sediment depths from Areas C, F, G and K in the Pacific Ocean from R/V Sonne Cruise SO06

Compositional data for coexisting manganese nodules, micronodules, sediments and pore waters from five areas in the equatorial and S.W. Pacific have been obtained. This represents the largest study of its type ever undertaken to establish the distribution of elements between the various phases within the sediment column. The composition of manganese nodules, micronodules and sediments (on a carbonate-free basis) shows marked differences between the equatorial high productivity zone and the low productivity region of the S.W. Pacific. In the case of the nodules, th is reflects an increased supply of transition elements (notably Ni, Cu and Zn) to the nodules as a result of the in situ dissolution of siliceous tests within the sediment column in the equatorial Pacific high productivity zone. Micronodules display similar, but somewhat different, compositions to those of the associated nodules in each area. Micronodule composition is therefore influenced by the same basic factors that control nodule composition, but is modified by dissolution of the micronodules in situ within the sediment column. Locally, as in the area immediately south of the Marquesas Fracture Zone, the micronodule population is contaminated by small, angular volcanic rock fragments; this leads to apparently anomalous micronodule compositions. Micronodules appear to be a transient feature in the sediment column, especially in the equatorial Pacific. Dissolution of micronodules in the sediment column therefore represents an important source of elements for the growth of manganese nodules in the equatorial Pacific. Sediment composition is markedly influenced by the carbonate content. On a carbonate-free basis, the sediments from the equatorial high productivity zone are quite distinct in composition from those in the S.W. Pacific. This reflects differences in the lithology of the sediments. In the Aitutaki Passage, the local influence of volcanoclastic material in sediment composition has been established. The major cations and anions in pore waters measured here show no major differences between equatorial and S.W. Pacific sediments. Silica is, however, higher in equatorial Pacific pore waters reflecting the dissolution of siliceous tests in these sediments.

Annotated record of the detailed examination of Mn deposits from R/V Xiang Yang Hong 16 stations (1983) in the Pacific Ocean

Electron microprobe and X-ray diffraction data for north Pacific manganese nodules reveal that the transition metal distributions are controlled by the mineralogy. Microlayers rich in 10Å-manganates generally have high Mn/Fe ratios and positive correlations between Ni, Cu and Mn, and between Co and Fe. Microlayers rich in vernadite, on the other hand, show low Mn/Fe ratios, and Co, Ni and Cu all show positive correlations with Mn. The 10Å-manganates form mainly in porewaters with high Mn/Fe ratios. The Ni2+ and Cu2+ ions are post-depositionally incorporated into the interlayers of the manganates, whereas Co3+ is substituted for Fe3+ in ferric oxyhydroxides. In seawater with a low Mn/Fe ratio, on the other hand, the adsorption of positively charged ferric oxyhydroxides on negatively charged [MnO6] octahedral layers suppresses the growth of 10Å-manganates, enhancing the formation of vernadite. Positively charged hydroxides of Co3+, Ni2+ and Cu2+ are also adsorbed on the [MnO6] layers. These mechanisms of mineral formation and metal uptake are corroborated by data for other oceanic non-hydrothermal manganese nodules and crusts.