Chemical composition of manganese nodules from the Southern Pacific

Deep sea manganese nodules from the Southern Ocean have been studied using chemical analysis, X-ray diffraction, optical mineragraphic and electron probe microanalysis techniques. The nodules were lower in manganese, iron and associated elements than the average grade of manganese nodules from other localities. A number of chemical relationships have been observed. Nickel, copper, cobalt, barium, zinc, molybdenum, strontium, sulphur and phosphorus are associated with the manganese rich phases and titanium with the iron rich phases. X-ray diffraction analysis and electron probe microanalysis results indicate that the manganese phases are similar to the disordered delta-MnO2 and "manganite" phases reported by other workers.

Analyses of Manganese nodules off Izu Island

Manganese nodules have been found by the author in the shallow waters of the Hyotan-se bank west of Shikime-jima, an island of the Izu archipelago in the Sea of Japan. The slopes around the bank are steep and rocks are exposed; gravels and coarse material cover the broad and flat plain on its top; andesite and basalt, which are very common in the bedrock, are found mingled with liparite gravels together with a number of manganese concretions from the bank.

Analysis of Mn-nodules from Breitgrund, Baltic Sea

The usually high concentrations of Zn, Pb, Cd, and Cu in the most recently accreted portions of ferromanganese nodules from the western Baltic Sea are thought to reflect increased metal input due to anthropogenic mobilization. If so, the point of increase represents a time horizon within the structure of the nodule. Similar trace metal distributions of radiometrically dated sediments from the same area suggest that the ferromanganese nodules have grown in thickness between 0.02 and 0.16 mm yr-1. From this growth rate anthropogenic Zn flux to the nodule surface was calculated to be 80 mg m-2 yr-1.

(Table 1, page 146) Iron, manganese and nickel contents of 21 ferromanganese nodules from Combe D'Izame and Mont Peyroux, Montagne Noire

Ferromanganese nodules (equivalent to Recent manganese nodules) are described from the Upper Devonian griotte (red pelagic limestone) of the Montagne Noire (S. France) and the Cephalopodenkalk of the Rheinisches Schiefergebirge, West Germany. They occur as encrustations, commonly exhibiting colloform structures, around skeletal material and limestone clasts. The nodules are associated with encrusting foraminifera and a development in the sublittoral environment is envisaged. Chemically, the ferromanganese nodules are depleted in manganese relative to iron, compared with Recent nodules, a loss which is attributed to diagenetic migration of manganese. Electron probe studies show that manganese covaries positively with calcium, but negatively with iron and silicon. Diagenetic enrichment of hematite occurs in the griotte at hardground horizons where two periods of mineralization can be established. The Devonian ferromanganese nodules show that solution of nodules has not occurred on burial.

Analyses of ferromanganese micronodules from the central Arctic Ocean

In order to determine geochemical compositions of Late Cenozoic Arctic seawater, oxide fractions were chemically separated from 15 samples of hand-picked ferromanganese micronodules (50-300 mu m). The success of the chemical separation is indicated by the fact that >97% of the Sr in the oxide fraction is seawater-derived. Rare-earth element (REE) abundances of the Arctic micronodule oxide fractions are much lower than those of bulk Fe-Mn nodules from other ocean basins of the world (e.g., 33 vs. 145 ppm Nd), but the Arctic oxides are enriched in Ce relative to Nd (Ce-N/Nd-N=2.2+/-0.5) and have convex-upward, shale-normalized REE patterns (Nd-N/Gd-N=0.61+/-0.06, Gd-N/Yb-N = 1.5+/-0.2, Nd-N/Yb-N = 0.9+/-0.2), typical of other hydrogenous and diagenetic marine Fe-Mn-oxides. Bulk sediment samples from the central Arctic Ocean have REE abundances and patterns that are characteristic of those of post-Archean shale. Non-detrital fractions (calcite + oxide coatings) of Recent Arctic foraminifera have REE abundances and patterns similar to those of Recent foraminifera from the Atlantic Ocean. Electron microprobe analyses (n=178) of transition elements in 29 Arctic Fe-Mn micronodules from five different stratigraphic intervals of Late Cenozoic sediment indicate that oxide accretion occurred as a result of hydrogenetic and diagenetic processes close to the sediment-seawater interface. Transition element ratios suggest that no oxide accretion occurred during transitions from oxic to suboxic diagenetic conditions. Only K is correlated with Si and Al, and ratios of these elements suggest that they are associated with illite or phillipsite. Ca and Mg are correlated with Mn, which indicates variable substitution of these elements from seawater into the manganate phase. The geochemical characteristics of Arctic Fe-Mn micronodules indicate that the REEs of the oxide fractions were ultimately derived from seawater. However, because of minute contributions of Sr from siliciclastic detritus during diagenesis or during the chemical leaching procedure, Sr isotope compositions of the oxide fractions cannot be used to trace temporal changes in the Sr-87/Sr-86 ratio of Arctic seawater or to improve the chronostratigraphy.

Lithostatigraphy of the CESAR cores

Sixteen piston cores and twelve gravity cores were successfully recovered from northern and southern crests of the eastern Alpha Ridge andfrom the Alpha Ridge graben. All but one core contain late Cenozoic muds with variable amounts of sand- to pebble-sized clastic material that probably reflects transport by ice during the past 4-5 Ma. Sixteen Cenozoic-Holocene lithostratigraphic units have been delimited on the basis of sediment texture, structure, colour, detrital carbonate and authigenicferromanganese content. The composition of the upper 13 units in the CESAR cores is similar to the Fletcher's Ice Island cores; hence most units can be broadly correlated over most of the Central Arctic Ocean. Three new lithostratigraphic units (A1-A3) occur at the base of CESAR cores from the northern Alpha Ridge crest. Paleomagnetic and palynological data indicate a Late Miocene-Early Pliocene age for unit A3, which confirms previous reports of a slow sedimentation rate during the Cenozoic. CESAR core 6 was obtained from an erosional surface on top of a fault block at the north edge of the Alpha Ridge graben. This core contains ca. 2m of laminated diatom ooze of Campanian-Maastrichtian age and two ?Paleogene volcanic ash units below a brown mud unit which probably corresponds to units A2 and A3. The biosiliceous ooze contains no foraminifera or silicoflagellates and only few dinoflagellates. There is little difference in biogenic or clastic sediment content between light and dark laminae and the rhythmites do not appear to be annual varves produced in an upwelling environment. The microstructure and fluctuating mineral composition of the laminae most closely resemble those of lami- nated chert beds in the Triassic forearc basins of Japan.

Description and chemical composition of ferromanganese deposits from Oneida Lake, New York

Saucer-shaped iron-manganese crusts occur adjacent to gravel shoal areas in Oneida lake in central New York. The crusts usually have a crude concentric banding owing to an alternation of orange, iron-rich layers and black, iron-poor layers. Materials from both types of layers are x-ray amorphous. The Oneida lake crusts, like most other freshwater manganese nodules, contain about the same Mn concentration as marine manganese nodules, but are usually higher in Fe and lower in trace metals than their marine equivalents. Although Fe and Mn may be precipitating directly from the lake water, it is more likely that the oxidate crusts are the result of precipitation of Fe and Mn when reduced sediment pore water comes in contact with well oxygenated bottom waters. Organisms, particularly bacteria, may play a role in the formation of the crusts, but to date no evidence of this has been found.

Description and iron and manganese content of ferromanganese nodules from Oneida Lake, NY

Ferromanganese nodules in the deep-sea and in freshwater lakes usually accrete layers rich in manganese oxides alternating with layers rich in iron oxides. The mechanism producing these alternating layers is unknown; indeed, the mechanism producing the nodules themselves is unknown. In Oneida Lake, New York, precipitants from the lake water and the surfaces of nodules at the sediment-water interface are enriched in Mn, whereas nodules buried in lake sediments have surface layers enriched in Fe. It is hypothesized here, using field and laboratory evidence, that reduction and mobilization of Mn from the nodule surface during periods of anoxic sediment cover produce the high Fe layers observed in the nodules.

Chemical composition and description of a ferromanganese crust, sample 89D, obtained during R/V Capricorne cruise ARCANTE 1

A manganese oxide encrustation (2.5 kg) was dredged, in an island arc setting, downslope of Bertrand bank, a seamount culminating at 70-m depth and located NNE of Grande-Terre, Guadeloupe, and SE of Antigua, West Indies. A thorough texturai analysis indicated a rhythmic precipitation and growth polarity as well as mineralogical ( 10 A tektomanganate) and geochemical (low concentrations of Ni, Cu, Co, Zn, Pb and REE) criteria, point to a submarine hydrothermal origin for most of the sample. The crust was coated with a fine ferromanganese oxide cortex deposited iii a "normal" oceanic environment; it also included micritic fillings, a main pyroclastic zone near the top of the crust, and a Mg-Al sulphate deposit. Planktonic foraminifera coeval with the precipitation of the manganese oxide indicate an age of ca. 3 m. y. (upper Pliocene); i.e., more than 20 m. y. after the cessation of the volcanic activity of the Lesser Antilles outer arc that was responsible for the buildup of the Bertrand seamount. Furthermore, the genesis of the crust is not linked to the activity of the contemporaneous inner arc (Miocene to Present), particularly of its nearmost segment (Basse Terre, Guadeloupe-Montserrat) located about 50 km to the West. The authors suggest that the manganese oxide is the result of convective circulation of sea water through a faulted system occurring in an area of intense seismic activity. The remobilization of chemical elements (Mn, S, etc.) within the seamount volcanic core bas probably affected a substratum that was still hydrothermally altered during the previous volcanic activity of the outer arc. The authors insist on the interest in using texturai analysis for Fe/Mn oxide investigations.

Geochemistry of some manganese nodules

The manganese nodules occur in greater or less quantity all over the ocean-bed, and most abundantly in the Pacific. They occur in all sizes, from minute grains to masses of a pound weight, and even greater, and form nodular concretions of concentric shells, round a nucleus, which is very frequently a piece of pumice or a shark's tooth. Their outside has a peculiar and very characteristic mammillated surface, which enables them to be identified at a glance. When freshly brought up they are very soft, being easily scraped to powder with a knife. They gradually get harder on exposure to the air. The powder, heated in a closed tube, gives out water which re-acts alkaline, and has an empyreumatic odour. Heated with strong hydrochloric acid, it liberates abundance of chlorine, and the residue which remains is white, consisting of silica, clay, and sand, the sand being the same as is found in the bottom mud from the same locality. Their composition varies greatly, different nodules containing different quantities of mechanically admixed mud, and the number of different elements found in them is very large. Copper, iron, cobalt, nickel, manganese, alumina, lime, magnesia, silica, and phosphoric acid have been detected in a large number; but I have not as yet been able to make a complete analysis of any of them. I have, however, made a few determinations of the most important component substances. For this purpose the outside and densest layers of the nodules were selected, and portions of them were pulverised and dried for ten or twelve hours at 140° C. The amount of chlorine liberated on treatment with hydrochloric acid was determined by Bunsen's method, and the iron was determined by titration with stannous chloride. The samples analysed were from four different localities.

Illustrations of manganese nodules dredged from the Upper Jarvis Inlet

Manganese-iron oxide concretions are presently forming on Patrick Sill in upper Jervis Inlet. The marine geology of Patrick Sill and the adjoining basins (Queen's Reach and Princess Royal Reach) was studied to define the environment in which the concretions form. The river at the inlet head is the principal source of sediment to the upper basin. The average grain size of surficial bottom sediments within this basin decreases uniformly with distance from the source. Patrick Sill separates the upper from the lower basin. The sediment distribution pattern within the lower basin differs markedly from the upper basin as there is no dominant source of material but rather many localized sources. Abundant shallow marine faunal remains recovered in deep water sediment samples indicate that sediments deposited as deltas off river and stream mouths periodically slump to the basin floors. Geologic and optical turbidity information for the upper basin can best be explained by slumping from the delta at the inlet head with the initiation of turbidity or density currents. Patrick Sill appears to create a downstream barrier to this flow. The mineralogy of the bottom sediments indicates derivation from a granitic terrain. If this is so, the sediments presently being deposited in both basins are reworked glacial materials initially derived by glacial action outside the present watershed. Upper Jervis Inlet is mapped as lying within a roof pendant of pre-batholithic rocks, principally slates. Patrick Sill is thought to be a bedrock feature mantled with Pleistocene glacial material. The accumulation rate of recent sediments on the sill is low especially in the V-notch or medial depression. The manganese-iron oxide concretions are forming within the depression and apparently nowhere else in the study area. Also forming within the depression are crusts of iron oxide and what are tentatively identified as glauconite-montmorillonoid pellets. The concretions are thought to form by precipitation of manganese-iron oxides on pebbles and cobbles lying at the sediment water interface. The oxide materials are mobile in the reducing environment of the underlying clayey-sand sediment but precipitate on contact with the oxygenating environment of the surficial sediments. The iron crusts are thought to be forming on extensive rocky surfaces above the sediment water interface. The overall appearance and evidence of rapid formation of the crusts suggests they formed from a gel in sea water. Reserves of manganese-iron concretions on Patrick Sill were estimated to be 117 metric tons. Other deposits of concretions have recently been found in other inlets and in the Strait of Georgia but, to date, the extent of these has not been determined.

Analysis of Manganese nodules from the Challenger Expedition

Manganese nodules from Stations 252 and 281 of the Challenger Expedition, collected in 1875, have recently been discovered in the Redpath Museum. The nodules have been found to be quite typical specimens of two areas in the Central Pacific Ocean except for dehydration and other changes that have taken place during storage. The principal resolvable manganese mineral in nodules from Station 252 proved to be 10 A manganite; there was a very thin surface coating of birnessite. Delta manganite was the only manganese mineral found in nodules from Station 281. Through electron microprobe studies, findings from chemical, optical and x-ray crystallographic work were correlated with the detailed picture of the occurrence and quantities of the different elements within the nodules. In all cases it was found that the iron and manganese had an antithetical relationship, and that nickel and copper were associated with the manganese. Special study was given to a 300-micron-square area in a nodule from Station 252 which included a segregation of 49.39% Mn, 5.31 % Ni, and 1.64% Cu. Crystallization of the manganese phases is thought to have provided a mech¨anism for formation of segregations which were further enriched through chemical scavenger action as long as ocean floor conditions permitted.

Annotated record of the detailed examination of Mn deposits from SESAM cruise stations

The cores and dredges described at this site were taken on the SESAM cruise from 30 April until 10 June 1976 by the Muséum National d'Histoire Naturelle from the R/V Marion Dufresne. A total of 55 cores, dredges and camera stations were recovered and are available at MNHN for sampling and study.

(page 43), Geochemical composition of a phosphatic manganese nodule from Blake Plateau

Mr. John Murray, to whom the specimens of bottom deposits collected by the "Blake" were sent for examination, looked over the whole and selected some typical specimens. These have been described in detail, and he has added some general notes on the specimens characteristic, 1. of the Coast between the Gulf of Maine and Cape Hatteras; 2. of thee coast between Cape Hatteras and Lat. 31? 48' N.; 3. of the coasts around the greater and lesser Antilles ; and, finally, of the Gulf of Mexico and Straits of Florida.