Geochemistry and descriptions of manganese nodules and crusts retrieved from the open ocean

The book is a compilation of all available data at the time of publication (1965) on the subject of marine minerals together with the author's original ideas regarding their exploitation. It is one of the most significant publications on ocean resources. It is particularly focused on manganese deposits, their description, sedimentary setting, formation and geochemistry.

Observation of manganese coating and encrustation in different environments of the North-Western Atlantic ocean

The major topographic features, or provinces, beyond the continental slope off the Atlantic coast of the United States are (1) Sohm Plain, (2) Hatteras Plain, (3) Nares Plain, (4) Blake Basin, (5) Blake Plateau-Bahama Banks, and (6) Bermuda Rise. The whole of the described area is commonly referred to as the North American Basin. This basin is bounded on the north by Newfoundland Ridge and on the south by Puerto Rico Trench. Topographic features of note within the basin are the divide and the area of depressions between Sohm and Hatteras Plains, the sharply crested Blake Ridge, and the Puerto Rico Ridge. Recently accumulated data on deep-sea oores has given good evidence that the silt and sand covering the abyssal plains are displaced continental sediments in a virtually quartz-free oceanic environment. These sediments were deposited on a primary volcanic bottom. The primary or volcanic bottom is characterized by abyssal hills and seamounts, and the sediment bottom is characterized by abyssal plains, which extend seaward from the continental margins. On the Blake Plateau, bottom photographs and dredge hauls in the axis of the stream show that locally sediment has been removed and the bottom is paved with crusts and nodules of manganese. Photographs and dredged samples from the outer part of the New England Seamount, Chain and Caryn Peak also indicate extensive encrustations of manganese oxide which acts as a binding agent in areas of ooze or other organic debris and thus helps to stabilize the bottom.

Observation of manganese nodules and encrustations in various lakes of Finland

The limnic ferromanganese ore concretions in some Finnish lakes are described. Their chemical and mineral compositions have been measured as have their natural surroundings - the latter by means of physico-chemical in-situ analysis. The sources of the nodules' contents are discussed, and a theory based on the calculated precipitation fields of the important ore minerals is presented for the ore formation.

(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 2, Page 252) Average chemical composition of 11 manganese nodules and crust from the Pacific Ocean

The ability of the hydrated oxides of manganese and iron to adsorb ions from solution (scavenging) is considered in relation to some problems in marine geology, chemistry, and biology. In the ferruginous sediments of the Pacific Ocean, iron oxides are accompanied by titanium, cobalt, and zirconium in amounts proportional to the iron content. Similarly, copper and nickel are linearly related to the manganese content. These observations are explained on the basis of scavenging. An electrochemical theory for the formation of manganese nodules is presented. Marine sediments are classified on the basis of the geosphere in which the solid phases originate. The distribution of certain ionic species in sea water between the solid and aqueous phases is considered on the basis of scavenging and co-ordination compound theory. The concentration of minor elements by members of the marine biosphere is explained either by the direct uptake of the element or by the uptake of iron or manganese oxides with the accompanying scavenged element.

(Table 5, page 206) The uranium contents of some manganese nodules

The uranium concentrations in marine calcareous material of a biological origin varied between 0.0X and 0.X p.p.m. with the exception of corals which had concentrations of several p.p.m. The aragonitic oolites and aragonite precipitated from sea-water had values similar to those of the corals. A geochronology based on the growth of ionium (thorium-230) from uranium is applicable not only to corals, as previous investigators have pointed out, but also to oolites. Several examples of "oolite ages" are given. The uranium content of ferromanganese minerals from pelagic deposits is of the order of from 4 to 5 p.p.m.

(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, page 351-359) Chemical composition of manganese nodules and crusts from the Pacific and Indian Ocean

Chemical and mineralogical analyses of manganese nodules from a large number of widely spaced localities in the Pacific and Indian Oceans have shown that their mineralogy and chemical composition varies both areally and with depth of formation. This is considered to result from a number of factors, important among which are: (a) their proximity to continental or volcanic sources of elements; (b) the chemical environment of deposition, including the degree of oxygenation; and (c) local factors such as the upward migration of reduced manganese in sediments from certain areas. Sub-surface nodules appear to share the chemical characteristics of their surface counterparts, especially those from volcanic areas where sub-surface sources of elements are probably important.

(Table 1) Chemical composition of Central Pacific manganese micronodules containing birnessite as a major component

Detailed mineralogical characterization of micronodules is given. The main regularities of variations in composition of micronodules from Central Pacific sedimentary rocks of different ages are revealed. New data on structure and structural features of manganese minerals are reported.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

(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.

Observation of manganese nodules and crusts recovered during the CHAIN 115 cruise from Nov 1973 until June 1974 in the Atlantic Ocean

Investigations of piston cores from the Vema Channel and lower flanks of the Rio Grande Rise suggest the presence of episodic flow of deep and bottom water during the Late Pleistocene. Cores from below the present-day foraminiferal lysocline (at ~4000 m) contain an incomplete depositional record consisting of Mn nodules and encrustations, hemipelagic clay, displaced high-latitude diatoms, and poorly preserved heterogeneous microfossil assemblages. Cores from the depth range between 2900 m and 4000 m contain an essentially complete Late Pleistocene record, and consist of well-defined carbonate dissolution cycles with periodicities of ~100,000 years. Low carbonate content and increased dissolution correspond to glacial episodes, as interpreted by oxygen isotopic analysis of bulk foraminiferal assemblages. The absence of diagnostic high-latitude indicators (Antarctic diatoms) within the dissolution cyclss, however, suggests that AABW may not have extended to significantly shallower elevations on the lower flanks of the Rio Grande Rise during the Late Pleistocene. Therefore episodic AABW flow may not necessarily be the mechanism responsible for producing these cyclic events. This interpretation is also supported by the presence of an apparently complete Brunhes depositional record in the same cores, suggesting current velocities insufficient for significant erosion. Fluctuations in the properties and flow characteristics of another water mass, such as NADW, may be involved. The geologic evidence in core-top samples near the present-day AABW/NADW transition zone is consistent with either of two possible interpretations of the upper limit of AABW on the east flank of the channel. The foraminiferal lysocline, at ~4000 m, is near the top of the benthic thermocline and nepheloid layer, and may therefore correspond to the upper limit of relatively corrosive AABW. On the other hand, the carbonate compensation depth (CDD) at ~4250 m, which corresponds to the maximum gradient in the benthic thermocline, is characterized by rapid deposition of relatively fine-grained sediment. Such a zone of convergence and preferential sediment accumulation would be expected near the level of no motion in the AABW/NADW transition zone as a consequence of Ekman-layer veering of the mean velocity vector in the bottom boundary layer. It is possible that both of these interpretations are in part correct. The "level of no motion'' may in fact correspond to the CCD, while at the same time relatively corrosive water of Antarctic origin may mix with overlying NADW and therefore elevate the foraminifera] lysocline to depths above the level of no motion. Closely spaced observations of the hydrography and flow characteristics within the benthic thermocline will be required in order to use sediment parameters as more precise indicators of paleo-circulation.

(Plate 3) Manganese nodules and deep-sea sediment core from Pacific Ocean

A synoptic review of the studies of well-known occurrences of palagonite tuffs is presented. Included are palagonite tuffs from Iceland, and pillow-lava palagonite complexes from Columbia River basalts and from the central Oregon coast. Additional petrologic and x-ray defraction data for selected samples are presented. Petrologic evidence shows that basaltic glass of aqueous tuffs and breccias consists of sideromelane, which is susceptible to palagonitization. It is shown that palagonitization is a selective alteration process, involving hydration, oxidation and zeolitization. Some of the manganese nodules dredged from the Pacific Ocean floor contain nucleus of palagonite-tuff breccias or of zeolite. A brief megascopic and microscopic description of nodules from the south Pacific, the Mendocino ridge and the 'Horizon' Nodule from the north Pacific is presented. Petrographic studies of palagonite-tuff breccias of manganese nodules and other palagonites suggest that migration and segregation of metallic elements occur during and subsequent to palagonitization. During the palagonitization of sideromelane, nearly 30 percent of sea water is absorbed. The hydration of sideromelane is also accompanied by oxidation of iron and other elements. These oxides may be released either in colloidal form or in true solution and tend to precipitate first from the unstable palagonite.

(Table 1) Iron and manganese speciations in surface layer bottom sediments of the Pacific Ocean

Distribution of iron and manganese speciations in ocean sediments of a section from the coast of Japan to the open Pacific Ocean is under consideration. Determinations of total iron, as well as of reactive iron contents and of total manganese, as well as of Mn4+ contents have been done. Significant increase of total Fe content in sediments from the coast to the pelagic zone occurs without noticeable increase in reactive Fe content. Presence of layers of volcanic and terrigenous coarse clastic material in clayey sediments results to sharp change in iron content. Manganese content increases from near coastal to pelagic sediments more than 10 times; oxidation degree of sediments also increases. There are three types of bottom sediments different by contents of iron and manganese forms: reduced, oxidized (red clay), and transitional. Content of total Fe is almost does not change with depth in sediments, content of reactive Fe increases in reduced sediments, and decreases in oxidized ones. Manganese content in red clay mass increases several times.