Description and chemical composition of manganese deposits during the deep-sea expedition of the streamer Valdivia in 1898-1899

This monograph forms the fourth part of the tenth volume of the scientific results of the voyage of the German exploring ship Valdivia in the Atlantic and Indian Oceans, made during the years 1898-1899. These volumes are published under the editorship of Prof. Chun, the zoologist of Leipzig, who was leader of the expedition ; and Prof. E. Philippi with the cooperation of Sir John Murray. The nature of the materials brought up at various points during the voyage is well illustrated by a series of plates, similar to those accompanying the Challenger volumes. Among the concretions from the Agulhas Bank were found phosphatic nodules containing 33 per cent, of calcium carbonate, 28 of calcium phosphate, 14.6 of calcium sulphate, and 4.8 of magnesium carbonate, with some ferric oxide, alumina, and silica. These nodules were dredged at a depth of 155 metres. Off the coast of Namibia, a large quantity of manganese nodules were also dredged. Their chemical analysis performed at the Mineralogical Institute of the University Jena show similar composition as the nodules recovered by the "Challenger" at station 253 in the Pacific Ocean.

(Table 3) Chemical analyses from DSDP Holes 22-214, 22-215 and 22-216 in the Indian Ocean

The basalts and oceanic andesites from the aseismic Ninetyeast Ridge display trachytic, vesicular and amygdaloidal textures suggesting a subaerial volcanic environment. The normative composition of the Ninetyeast Ridge ranges from olivine picriteto nepheline-normative alkaline basalt, suggesting a wide range of differentiation. This is further supported by the fractionation-differentiation trends displayed by transition metal trace elements (Ni, Cr, V and Cu). The Ninetyeast Ridge rocks are enriched in rare earth (RE) and large ion lithophile (LIL) elements and Sr isotopes (0.7043-0.7049), similar to alkali basalts and tholeiites from seamounts and islands, but different from LIL-element-depleted tholeiitic volcanic rocks of the recent seismic mid-Indian oceanic ridge. The constancy of 87Sr/86Sr ratios for basalts and andesites is compatible with a model involving fractional crystallization of mafic magma. The variation of 87Sr/86Sr ratios between 0.97 and 2.79 may possibly be explained in terms of a primordial hot mantle and/or chemically contrasting heterogeneous mantle source layers relatively undepleted in LIL elements at different periods in the geologic past. In general, the Sr isotopic data for rocks from different tectonic environments are consistent with a "zoning-depletion model" with systematically arranged alternate alkali-poor and alkali-rich layers in the mantle beneath the Indian Ocean.

Manganese nodules recovered by R/V Vityaz expedition

Uranium, radium, thorium and ionium were determined directly on seven concretions from three stations in the Indian Ocean, and on two concretions and a manganese-rich crust from two stations in the Pacific Ocean. The uranium content averages 3 to 5 gamma/g and the thorium content varies only slightly, but the Th/U ratio in the concretions is typically 2 to 5 in the Indian Ocean and 5 to 15.5 in the Pacific. The ionium content ranges from 1.0 x 10-9 to 3.6 10**-9 g/g in concretions from both oceans. Radium is more abundant in specimens from the Pacific Ocean (Ra = 3 - 12.7 x 10**-11 g/g) than from the Indian Ocean (1.5 - 5.2 x 10**-11 g/g). Analyses for Ca, Mn, Fe, Si, Ni, P, and ignition loss are also given. Radioactive equilibria between uranium, ionium, and radium are strongly disturbed throughout the concretions, and the RA/U and lo/U ratios generally exceed equilibrium ratios. Migration of radium from interior layers was established, so that neither determination of the ages of the concretions nor of their rates of growth can be considered reliable. The age of the concretions cannot exceed 800,000 years, and all grew within relatively short periods of time; there may have been "dormant" periods during growth. Estimates of growth rates are calculated from the radium and ionium contents; they show marked discordance.

Geochemistry of recent sediments from the Indian Ocean

During the International Indian Ocean Expedition (1964/65) sediment cores were taken on six profiles off the western coast of the Indian Subcontinent. These profiles run approximately perpendicular to the coast, from the deep-sea over the continental slope to the continental shelf. Additional samples and cores were taken in a dense pattern in front of the delta of the Indus River. This pattern of sampling covered not only marine sediments, but also river and beach sediments in Pakistan. The marine samples were obtained with piston, gravity and box corers and by a Van Veen grab sampler. The longest piston core is about 5 meters long. 1. Distribution of the elements on the sediment surface The area of maximal carbonate values (aprox. 80-100% CaCO3) essentially coincides with the continental shelf. The highest Sr values were observed largely within this area, but only in the vicinity of the Gulf of Cambay. Mainly the aragonitic coprolites are responsible for those high Sr contents. The Mg contents of the carbonates are comparatively low; surprisingly enough the highest Mg concentrations were also measured in the coprolites. The maximum contents of organic matter (Core) were found along the upper part of the continental slope. They coincide with the highest porosity and water content of the sediments. Frequently the decomposition of organic matter by oxydation is responsible for the measured Corg contents. On the other side the quantity of originally deposited organic material is less important in most cases. The enrichment of the "bauxitophile" elements Fe, Ti, Cr and V in the carbonate- and quartz-free portions of the sediments is essentially due to the influence of coarse terrigenous detritus. For the elements Mn, Ni and Cu (in per cent of the carbonateand quartz-free sediment) a strong enrichment was observed in the deep-sea realm. The strong increase in Mn toward the deep-sea is explained by authigenesis of Mn-Fe-concretions. Mn-nodules form only under oxydizing conditions which obviously are possible only at very low rates of deposition. The Mg, B and, probably also Mn contents in the clay minerals increase with increasing distance from the continent. This can be explained by the higher adsorption of those elements from sea water because of increasing duration of the clay mineral transport. The comparison of median contents of some elements in our deep-sea samples with deep-sea sediments described by TUREKIAN & WEDEPOHL (1961) shows that clear differences in concentration exist only in the case of "bauxitophile" elements Cr and Be. The Cr and Be contents show a clear increase in the Indian Ocean deep-sea samples compared to those described by TUREKIAn & WEDEPOHL (1961) which can obviously be attributed to the enrichment in the lateritic and bauxitic parent rocks. The different behaviour of the elements Fe, Ti and Mn during decomposition of the source rocks, transport to the sea and during oxydizing and reducing conditions in the marine environment can be illustrated by Ti02/Fe and MnO/Fe ratios. The different compositions of the sediments off the Indus Delta and those of the remaining part of the area investigated are characterized by a different distribution of the elements Mn and Ti. 2. Chemical inhomogenities in the sediments Most longer cores show 3 intervals defined by chemical and sedimentological differences. The top-most interval is coarse-grained, the intermedial interval is fine grained and the lower one again somewhat coarser. At the same time it is possible to observe differences from interval to interval in the organogenic and detrital constituents. During the formation of the middle interval different conditions of sedimentation from those active during the previous and subsequent periods have obviously prevailed. Looking more closely at the organogenic constituents it is remarkable that during the formation of the finer interval conditions of a more intensive oxydation have prevailed that was the case before and after: Core decreases, whereas P shows a relative increase. This may be explained by slower sedimentation rate or by a vertical migration of the oxygen rich zone of the sea-water. The modifications of the elements from minerals in detrital portion of the sediments support an explanation ascribing this fact to modifications of the conditions of denudation and transportation which can come about through a climatic change or through tectonic causes. The paleontological investigations have shown (ZOBEL, in press) that in some of the cores the middle stratum of fine sedimentation represents optimal conditions for organic life. This fact suggests also oxydizing conditions during the sedimentation of this interval. In addition to the depositional stratification an oxydation zone characterized by Mn-enrichment can be recognized. The thickness of the oxidation zone decreases towards the coast and thins out along the middle part of the continental slope. At those places, where the oxydation zone is extremely thin, enrichment of Mn has its maximum. This phenomenon can probably be attributed to the migration of Mn taking place in its dissociated form within the sediment under reducing conditions. On the other side this Mn-migration in the sediment does not take place in the deep-sea, where oxydizing conditions prevail. 3. Interstitial waters in the sediments Already at very small core depths, the interstitial waters have undergone a distinct modification compared with the overlying sea water. This distinct modification applies both to total salinity and to the individual ions. As to the beginning of diagenesis the following conclusions can be drawn: a) A strong K-increase occurs already at an early stage. It may be attributable to a diffusion barrier or to an exchange of Mg-ions on the clays. Part of this increase may also originate from the decomposition of K-containing silicates (mica and feldspars). A K-decrease owing to the formation of illite (WEAVER 1967), however, occurs only at much greater sediment depth. b) Because of an organic protective coating, the dissolution of carbonate is delayed in recent organogenic carbonates. At the same time some Ca is probably being adsorbed on clay minerals. Consequently the Ca-content of the interstitial water drops below the Ca-content of the sea water. c) Already at an early stage the Mg adsorption on the clays is completed. The adsorbed Mg is later available for diagenetic mineral formations and transformations.

Distribution of benthic and planktic foraminifera in surface sediments of the Indian and Pakistan continental margin, Arabian Sea

During the Indian Ocean Expedition of the German research vessel "Meteor" and the following cruise with the Pakistani fishing vessel "Machhera" in February and March 1965, sediments were sampled from the shelf, continental slope and the Arabian Basin off Pakistan and India. The biostratigraphic studies are based on sedimentary material from 24 sediment cores up to 480 cm long and 100 grab samples. The faunal residues of the > 160 µ fraction (chiefly foraminifera and pteropods) were determined and counted in order to get an idea of the climatic conditions during the Late Quaternary of this region. Biostratigraphic correlations of these Late Quaternary deposits are only possible if the thanatocoenosis of the surface sediments are well known. The analysis of the benthonic foraminiferal populations resulted in the definition of several foraminiferal facies. The following sequence of forarniniferal facies, named after their most characteristic members, can be distinguished from the shelf to the deep-sea: 1. Ammonia-Florilus facies ; 2. Ammonia-Cancris facies; 3. Cassidulina-Cibicides facies; 4. Uvigerina-Cassidulina facies ; 5. Buliminacea facies ; 6. deepwater facies, partly with Bulimina aculeata or with Nonionidae. On the upper continental slope there is a zone extremely poor in benthonic foraminifera. In this water depth the oxygen minimum layer (0.05-0.02 ml/l) of the water column reaches the slope. Almost no connection can be observed between the living and the dead foraminiferal population of the same sample. The regional distribution of the planktonic foraminifera from plankton tows as well as from the surface sediments shows marked differences in the species composition of faunas from different regions within the area of investigation. That depends on oceanographic conditions such as upwelling, dissolution of carbonate at great depths etc. Based on the results of faunal analysis of samples from the recent sea-floor, a biostratigraphic subdivision of the sediments in the cores was established. The following biostratigraphically defined sections could be distinguished from the top of the sediment cores downwards : 1. Relatively cool climatic conditions are reflected by the foraminifera of the uppermost core sections. 2. The next section is characterized by much warmer conditions (Holocene climatic optimum). The C-14 ages of this interval range from 4000 to 10 000 years B.P. according to different authors. C-14 dates on the material investigated do not give reliable clues. 3. Foraminiferal populations adapted to much colder conditions can be observed in the underlying core section. The boundary between the warm climate reflected by the foraminifera of section 2 and the cold climate (section 3) is relatively sharp. It can be correlated from core to core over the whole area investigated. The cold climate sediments of section 3 are underlain by different cool-, warm- and cold-climate sediments which can only be correlated over very short distances. Since it appears certain that the last really cold conditions ended earlier in the Arabian Sea and its vicinity than in Europe it is recommended not to use the European stratigraphic terms for the Quaternary. Because of the lack of reliable absolute sediment ages for the cores no exact sedimentation rates can be given. According to rough estimates, however, the rates are 1-2 cm/1000 years in the deep basin and up to 40 cm/1000 years on the upper continental slope. Sedimentation rates are always larger near the mouth of the Indus-River than off South India at stations of about the same water depth. Planktonic gastropods (mainly pteropods) cannot be used for biostratigraphic purposes in the region under consideration. All of them seem to be displaced from the shelf. Their distribution there is given in.

Description and illustrations of Mn deposits from the John Murray Expedition (R/V Mabahiss)

During the cruise of the" Mabahiss" from Zanzibar to Colombo at Station 133 (1° 25' 54" S. to 1° 19' 42" S. and 66° 34' 12" E. to 66° 35' 18" E.) several small rock fragments were brought up in the Monegasque net; and, since at this position there is no possibility of the material being transferred by floating Ice, these specimens are of some interest as samples of oceanic rock foundations. All the rocks have a black appearance, but in the majority this skin is of negligible thickness. Exceptionally, however, it may attain to 1/3 in. (St. 133, 8), and then the specimens are rounded. The coating is made of dark opaque manganese material. At Station 166 one or two similar specimens of angular basalt were found in the trawl consisting mainly of manganese nodules.

Description and chemical composition of manganese nodules sampled during the R/V "Vityaz" Expedition Vityaz-35

This paper presents data on the chemical composition of iron-manganese nodules and associated sediments collected during the 35th voyage of the R/V "Vityaz" in 1962. The samples were made available to the author by Prof, P. L. Bezrukov. Data on the general distribution of manganese nodules at the bottom of the Indian Ocean were already given by P. L. Bezrukov (1962, 1963). Here the author analyzed the geochemistry of nodules samples from seven stations and four samples from the associated sediments. The analysis separates the outer layer of nodules from their apparent internal core.

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.