Annotated record of the detailed examination of Mn micronodules from stations over George Bank, Atlantic Ocean

Ferromanganese micronodules have been found on Georges Bank, off the U.S. northeast coast, distributed throughout the surficial sediments within an area about 125 km long and at least 12 km wide. These coarse, sand-sized concretions have precipitated from metal-rich interstitial waters and contain many of the textural and structural features common to other neritic nodules. Most of the nodules have accreted around detrital grains, and X-ray powder diffraction analyses indicate the presence of geothite and vernadite ( delta -MnO sub(2)) in the ferromanganese layers. Chemical analyses of the micronodules, when compared with similar data on deep-sea manganese nodules, reveal lower Mn/Fe ratios, significantly higher concentrations of V and As, comparable values of Mo, and an order of magnitude less of Co, Ni, Ce and most other, metals.

Annotated record of the detailed examination of Mn deposits recovered by the Geological Survey of Japan (GSJ) during the 1971-1974 period in the Pacific Ocean

In 1974, the Geological Survey of Japan began its systematic investigation of manganese nodules in the Central Pacific Basin on the new geological research vessel Hakurei Maru. The first cruise (GH 74-5) was carried out over an eastern part area of the Basin (6°-10°30'N, 164°30'-171°30'W), and the authors report here the preliminary results on the occurrence of manganese nodule deposits, paying particular consideration to their relationship to submarine topography and surficial and sub-bottom sedimentary facies. The surveyed area comprises a deep-sea basin at 5,000-5,400 m, defined to the north and east by the chain of seamounts and guyots of the Christmas Ridge. The deep-sea basin is divided roughly into 2 contrasting topographic features. The eastern part is characterised by flattened topography resulting from continuous deposition of turbidities; the meridian and western parts are characterised by gently rolling topography and the existence of a large number of deep-sea hills. Manganese nodules are almost lacking in the former flattened eastern area, whereas they are widely distributed in the latter rolling meridian and western parts. The population density of nodules varies from less than 1 Kg/m² to 26 kg/m² and the higher density is found in the siliceous-calcareous ooze zone of rather small, flat basins surrounded by deep-sea hills. The density is closely related to the thickness of the transparent layer obtained by 3.5 kHz PDR profiling over the whole area. Considering the various data of grab sampling, 3.5 kHz PDR profiling and to a lesser extent of deep-sea television and camera observations, the most promising manganese field in the present area seems to be confined to the north of the western sector of the area.

Annotated record of the detailed examination of Mn deposits from the Snellius II - Cruise 4 stations in the vicinity of the island of Misool, Eastern Indonesia

The chemical analyses of ferromanganese encrustations found on the seabed west of Misool, eastern Indonesia, indicate that these deposits formed in a way different from that of world-wide occurring manganese nodules. Ferromanganese coated pebbles and fragments that were found in the deeper parts of the study area probably originate from nearby ridges. The ferromanganese crust on the upper part of a dolomite fragment of ?30 kg is likely to be formed by hydrogenous processes, whereas that from the lower part seems to be formed by diagenetic processes mainly. These assumptions are supported by pore-water data from two box cores taken in the same area. The manganese and iron profiles versus depth in these cores indicate a high flux of these metals to the uppermost sediment layer, and possibly into the overlying bottom water. Factor analysis for the principal components of the microprobe analytical results of the mainly hydrogenous ferromanganese crust demonstrates a strong correlation of manganese with the trace metals, of iron with phosphorus and an antipathetic relationship between iron and manganese. Similar results have also been reported for abyssal manganese nodules in the world oceans. Factor analysis for the principal components of the analytical data obtained for the diagenetic ferromanganese crust results in a clear dolomite (Ca/Mg) dilution factor only.

Annotated record of the detailed examination of Mn deposits from the CLIMAX II (SCAN) Expedition stations aboard R/V Argo in the central North Pacific

A 0.25 m US Naval Electronics Lab box corer was used to take replicate samples from an oligotrophic bottom under the North Pacific Central Water Mass (approx. 28 degrees N, 155 degrees W). The bottom is a red clay with manganese nodules at a depth of 5500-5800 m. Macrofaunal density ranges from 84 to 160 individuals per m super(2) and is therefore much the same as in Northwest Atlantic Gyre waters. Of the macrofaunal taxa, polychaetes dominate (55 per cent), followed by tanaids (18 per cent), bivalves (7 per cent), and isopods (6 per cent). Meiofaunal taxa were only partially retained by the 297 micrometer screen used in washing. Even then, they are 1.5-3.9 times as abundant as the microfaunal taxa, with nematodes being numerically dominant by far. Foraminifera seem to comprise an important portion of the community, but could not be assessed accurately because of the inability to discriminate living and dead tests. Remains of what are probably xenophyophoridans are also very important, but offer the same problem. Faunal diversity is extremely high, with deposit feeders comprising the overwhelming majority. Most spp are rare, being encountered only once. The distributions of only 3 spp show any significant deviation from randomness. The polychaete fauna from box cores collected from 90 m to the north was not significantly different from that of the principal study locality. Concordance appeared at several taxonomic levels, from spp through microfaunal/ meiofaunal relationships. As a result, the variation in total animal abundance shows aggregation among cores. The authors discuss Sokolova's concept of a deep-sea oligotrophic zone dominated by suspension feeders, and reconcile it with our present findings. The high diversity of the fauna combined with the low food level contradict theories that relate diversity directly with productivity.

Chemical composition of oxide-phosphorite pavement from the Blake Plateau under various preparation treatment

Sample preparation technique is critical for valid chemical analyses. A main source of error comes from the fact that the great specific surface area of crusts or nodules enhances their tendency to retain or attract hygroscopic moisture. Variable treatment of this moisture can in extreme cases lead to analytical value differences as great as 40-50 %. In order to quantify these influences, samples of ferromanganese oxide-phosphorite pavement from the Blake Plateau have been subjected to various drying techniques before analysis using X-ray fluorescence.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

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.

(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.

Chemical composition of Fe-Mn nodule from Station PL70-9

During June-August 1970 geologic investigations were carried out to the west of the Cape Verde Islands. One result of these investigations was a discovery of a new region of distribution of iron-manganese nodules. Data on chemical analysis of the nodules and their morphometric characteristics are presented in this paper. The report is illustrated by bottom-relief profiles, underwater photographs, and tables.

Annotated record of the detailed examination of Mn deposits from the H.M.S. Penguin expedition to the Coral Sea

The analyses of the samples from the Balfour Shoal show that these deposits contain a very large quantity of carbonate of lime, ranging from 88.7 per cent, on the summit to 71.9 per cent, in the deeper water at the base of the cone. The decrease in the quantity of carbonate of lime with increase of depth is not quite regular; still, a general fall in the percentage of lime is clearly indicated from shallower to deeper water. As might be expected in such a circumscribed area, there is a great uniformity both in the chemical composition and relative abundance of the organic and inorganic constituents of the deposits. In all cases the carbonate of lime is almost wholly made up of the dead shells which have fallen from the surface waters - belonging to Plankton organisms such as Pteropods, Heteropods, pelagic Foraminifera and coccoliths. The calcareous shells were in very many cases discoloured brown or black by depositions of the peroxide of manganese. On the north-east steep side of the Balfour Shoal there were indications that depositions of manganese peroxide were more abundant than elsewhere. In 1645 fathoms, there was an angular fragment of a mottled yellowish jasper coated with manganese peroxide, and in 1570 fathoms there were three characteristic spherical black manganese nodules from one-half to three-fourths of an inch in diameter, quite similar to those procured by the Challenger in many areas of the Pacific and Atlantic. In one of these nodules the nucleus was a sub-angular fragment of a light-coloured augite-granophyre.

(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.

Annotated record of the detailed examination of Mn deposits from R/V Hakuho Maru Cruise KH-74-4 stations

Using scanning electron microscopy (SEM) the authors have examined the microtexture of Mn nodules. Previous researches using SEM observation on marine Mn nodules have revealed many characteristic features which may relate to their formation. They report the discovery of in situ calcareous nannoplankton fossils in a Mn nodule collected during the RV Hakuho-Maru Cruise KH-74-4, and present a preliminary calculation of the growth rate, using a biostratigraphic method. They also discuss the potential value of Mn nodule biostratigraphy in terms of deep sea palaeoenvironments.