(Table 2, page 72) Chemical compositin of the two nodule types used in this investigation

Two Pacific Ocean manganese nodules, one from the ocean basin and one from a sea-mount, were examined in transmission electron microscopes at 100 and 650 kV. Of the many specimens examined, ten electron diffraction crystal spot patterns were identified. Sodium birnessite was observed six times and todorokite, Giavanoli's synthetic birnessite, hydrohausmanite and -Fe2O3 one time each. Ferric hydroxide was synthesized in the laboratory and shown to be the same as the primary iron mineral observed in the manganese nodules. The ferric hydroxide had a particle size range from 30 to 450 ?. Manganese oxide particles were frequently embedded in a mass of smaller ferric hydroxide particles.

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.

(Figure 2, page 940) K-T boundary enrichment for cerium and iridium chemical composition of layers inside the ZETES-3D manganese nodule in the Pacific Ocean

Hydrogenous manganese nodules form on the ocean floor by slow authigenic precipitation (1-6 mm/Ma) of the oxyhydroxides of manganese and iron that continuously scavenge trace elements from the marine environment. Consequently, these nodules represent independent marine deposits useful for the study of the chemical signatures of the paleomarine environments. The results presented are a continuation of a study of the Zetes-3D nodule from the Pacific Ocean. It is a large (24x17x10 cm) hydrogenous nodule whose slow growth rate of 1.3 mm/Ma was detremined using 10Be techniques. A positive cerium anomaly is observed throughout the nodule and its Ir content indicates a sharp spike at 54-62 Ma in fair agreement with the K-T event.

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.

Chemical composition of a manganese nodule from the Blake Plateau, Atlantic Ocean

The area surveyed during project AMC-11-67 was the portion of the Blake Plateau between latitude 30°00'N and 33°00'N and between the 100 to 1000 fathom curves. The survey was conducted from 3 October until 18 October 1967. Survey operations included dredgings, camera and multi-sensor lowerings. A collection of manganese and phosphate concretions as well as coral and sediment samples were examined by the ESSA(NOAA) Atlantic Oceanographic Laboratories. Chemical analyses were conducted at the NASA Manned Spacecraft Center, Houston by Richard A. Laidley for X-Ray Fluorescence Analysis and H. Costello for Atomic Absorption Analysis. Later the whole collection of samples was transferred to the Smithsonian National Museum of Natural History were it is available for study (see, http://mineralsciences.si.edu/collections.htm).

(Table 2, page 1376) Chemical analyses of manganese nodules and crusts from the South-western Pacific

Phosphate deposits which apparently formed during the Miocene climatic optimum are widespread on the Chatham Rise and Camp bell Plateau, and on seamounts in the north Tasman Sea. They formed under oxidising conditions by the phosphatisation of older or contemporaneous foraminiferal oozes (Campbell Plateau and Chatham Rise) and coral limestones (Tasman Sea). The phosphorites of the rise and plateau were formed where current activity was sufficiently strong to prevent normal sedimentation, and now form lag deposits. After the Miocene, phosphorite formation ceased and was followed by manganese oxide deposition where conditions were highly oxidising on the eastern Campbell Plateau and north Tasman seamounts, and by glauconite formation in the much less oxidising environments of the western Campbell Plateau and the Chat ham Rise. The manganese deposits are not volcanogenic, as was formerly thought, but formed by slow precipitation from well oxygenated sea water.

(Table 3, page 8) Chemical composition and physical cahracteristics of manganese nodules from the Pacific Ocean

This paper reviews the state of the art in processing and extraction of ocean floor manganese nodules. It briefly reviews the mining sites where the abundant rich nodules occur and also discusses the metal distribution in nodules in view of economical processing and extraction of these metal values. The paper discloses in a detailed manner the physical and chemical characteristics of nodules, including porosity, surface area, water content and the effect of temperature on crystal structure of major constituents of nodules. In the extraction aspect of nodules, the paper reviews two different extraction schemes revealed in the literature, namely hydrometallurgical treatment and pyrometallurgical treatment. The hydrometallurgical treatments include acid leaching, ammonia leaching, leaching with reducing agents and leaching after high temperature pre-treatments such as in sulfating rousting, while the pyrometallurgical processes include smelting, chlorination-vaporization and segregation. The paper also covers metal recovery processes from leach liquor. An economic survey of processing nodules has been made in terms of problems associated with metal-marketing, and impact of metal production from nodules on mineral industries.

(Table 2, Page 270) Average chemical composition of manganese nodules and crust collected at different localities the Pacific Ocean

Considerable regional variations in the chemical composition of manganese nodules from a wide range of the Pacific Ocean have been observed. These variations can be more exactly expressed in terms of inter-element relationships. In particular, Cu-Mn and Cu-Ni associations reveal that Cu content in pelagic nodules increases rapidly in proportion to those of Mn or Ni. In nodules from continental borderland and hemipelagic areas, even if Mn or Ni contents increase, that of Cu increases only slightly. It is suggested that the considerable chemical differences within individual nodules and between nodules from the same site, at a limited pelagic area where there is no marked change in depositional conditions of nodules, are due to the role of hydrolyzable trace elements in the formation of nodules.

Chemical composition of ocean manganese nodules from the Pacific Ocean using different techniques

Mineralogical and chemical analyses performed on 67 ferromanganese nodules from widely varying locations and depths within the marine environment of the Pacific Ocean indicate that the minor element composition is controlled by the mineralogy and that the formation of the mineral phases is depth dependent. The pressure effect upon the thermodynamics or kinetics of mineral formation is suggested as the governing agent in the depth dependence of the mineralogy. The minor elements, Pb and Co, appear concentrated in the dMnO2 phase, whereas Cu and Ni are more or less excluded from this phase. In the manganites, Pb and Co are relatively low in concentration, whereas Cu and Ni are spread over a wide range of values. The oxidation of Pb and Co from divalent forms in sea water to higher states can explain their concentration in the dMnO2 phase.