Annotated record and spectrochemical analyses of Mn nodules from Georgia Strait, British Columbia obtained during CNAV Laymore in 1970

A study of the distribution, dispersal and composition of surficial sediments in the Strait of Georgia, B.C., has resulted in the understanding of basic sedimentologic conditions within this area. The Strait of Georgia is: a long, narrow, semi-enclosed basin with a restricted circulation and a single, main, sediment source. The Fraser. River supplies practically all the sediment now being deposited in the Strait of Georgia, the bulk of it during the spring and summer freshet. This river is building a delta into the Strait from the east side near the south end. Ridges of Pleistocene deposits within the Strait and Pleistocene material around the margins, like bedrock exposures, provide local sources of sediment of only minor importance. Rivers and streams other than the Fraser contribute insignificant quantities of sediment to the Strait. Sandy sediments are concentrated in the vicinity of the delta, and in the area to the south and southeast. Mean grain size decreases from the delta toward the northwest along the axis of the Strait, and basinwards from the margins. Silts and clays are deposited in deep water west and north of the delta front, and in deep basins northwest of the delta. Poorly sorted sediments containing a gravel component are located near tidal passes, on the Vancouver Island shelf area, on ridge tops within the Strait, and with sandy sediments at the southeastern end of the study area. The Pleistocene ridges are areas of non-deposition, having at most a thin veneer of modern mud on their crests and upper flanks. The southeastern end of the study area contains a thick wedge of shandy sediment which appears to be part of an earlier delta of the Fraser River. Evidence suggests that it is now a site of active submarine erosion. Sediments throughout the Strait are compositionally extremely similar, with-Pleistocene deposits of the Fraser River drainage basin providing the principal, heterogeneous source. Gravels and coarse sands are composed primarily of lithic fragments, dominantly of dioritic to granodloritlc composition. Sand fractions exhibit increasing simplicity of mineralogy with decreasing grain-size. Quartz, felspar, amphibole and fine-grained lithic fragments are the dominant constituents of the finer sand grades. Coarse and medium silt fractions have compositions similar to the fine sands. Fine silts show an increase in abundance of phyllosilicate material, a feature even more evident in the clay-size fractions on Montmorillonite, illite, chlorite, quartz and feldspar are the main minerals in the coarse clay fraction, with minor mixed-layer clays and kaolinite. The fine clay fraction is dominated by montmorillonite, with lesser amounts of illite and chlorite. The sediments have high base-exchange capacities, related to a considerable content of montmorillonite. Magnesium is present in exchange positions in greater quantity in Georgia Strait sediments than in sediments from the Fraser River, indicating a preferential uptake of this element in the marine environment. Manganese nodules collected from two localities in the Strait imply slow sediment accumulation rates at these sites. Sedimentation rates on and close to the delta, and in the deep basins to the northwest, are high.

Sm-Nd isotope and Mn/Ca ratios for cleaned Neogloboquadrina pachyderma from ODP Hole 105-647A (Table 1)

The neodymium (Nd) isotope composition of ancient seawater is a potentially useful tracer of changes in continental inputs and ocean circulation on timescales of a few ka. Here we present the first Nd isotope record for seawater using sedimentary foraminifera cleaned using standard oxidative-reductive techniques. The data, along with Mn/Ca ratios, suggest that cleaned foraminifera provide a reliable record of Nd in seawater and hold out the prospect of using Nd in foraminifera to examine changes in seawater that accompany glacial-interglacial climatic cycles. The principal potential problem to be overcome with the use of forams as records of trace elements in ancient seawater is their diagenetic Fe-Mn coatings. These contain large amounts of Nd and other trace elements but can be cleaned off using highly reducing reagents. Mn(Ca ratios for the majority of the cleaned sedimentary foraminifera analysed here lie within the range (10-100 µmol/mol) that has yielded success in studies of transition elements in forams. Mass-balance modelling suggests that for residual Mn/Ca ratios <100 µmol/mol, Nd added to the foram in the coating will never shift the measured Nd isotope composition significantly away from the seawater value acquired by the foram test in the water column. Additionally, Nd concentrations measured in cleaned sedimentary foraminifera are comparable with those for a modern sample that has never encountered diagenetic fluids. Finally, core-top planktonic foraminifera for two sites have Nd isotope compositions that are identical to local surface seawater. The data we present here for Labrador Sea forams over the past 2.5 m.y. are interpreted in terms of changes in the seawater isotopic composition. The data show a pronounced shift from epsilon-Nd values of ~-12 to ~-19 in the period 2.5-1.5 Ma. This change is interpreted to result from the initiation of Northern Hemisphere glaciation and the increased derivation of Labrador Sea Nd via ice-rafting from Archaean terranes in central Canada. In combination with stable isotope and foraminiferal relative species abundance data, the new Nd data are consistent with the surface hydrography of the Labrador Sea being dominated by a fluctuating balance between cold, polar waters containing unradiogenic Nd and warm, subtropical waters containing more radiogenic Nd. The major change in Labrador Sea Nd that is observed in the past 2.5 Ma can, on its own, account for the change in the Nd isotope composition of North Atlantic Deep Water over the same time period.

Chemical composition of Fe-Mn nodules and crusts from the North Atlantic

In terms of physical and genetic features studied nodules are assigned to the sedimentational manganese-iron type (Canary Basin) and to the iron-containing type (Guyana Basin). They are enriched in Fe, Co and Pb and depleted in Mn, Ni, Cu, and Zn. Cores of the nodules from the Canary Basin consist primarily of peridotite, gabbro, dolerite, and metamorphic rock. Great predominance of peridotite and gabbro indicates that blocks of ocean crust underwent considerable displacement, bringing the third and fourth layers of a crust to the surface.

(Tables 1-2) Composition of red coloured tills from Schobuell, Schleswig-Holstein and Møn Island, Denmark

The stratigraphic position of the glacially transported 'Scholle' (large-size erratic block) at Schobüll near Husum (Schleswig-Holstein) is now considered to be Devonian rather than 'Rotliegendes'. The 'Scholle', consisting of red clay and dolomite, is overlain by red-colored till without any flint but with up to 90% carbonate clasts (containing 15% dolomite), which indicates an eastern Baltic origin. The relationship of the 'Scholle' with the glacial till also points to an eastern Baltic origin for it, with up to 1 000 km transport distance.

Annotated record and illustrations of Mn nodules retrieved during cruise KH-73-4 of the R/V Hakuho Maru and cruises GH76-1 and GH77-1 of the R/V Hakurei Maru

Deep sea manganese nodules from the Central Pacific Basin are mainly composed of 10Å manganite and d-MnO2 Two zones equivalent to the minerals are evidently distinguishable according to their optical properties. Microscopic and microprobe analyses revealed quite different chemical compositions and textnral characteristics of the two zones. These different feature of the two zones of nodules suggest the different conditions under which they were formed. Concentrations of 11 metal elements in the zones and inter-element relationships show that the 10Å manganite zone is a monomineralic oxide phase containing a large amount of manganese and minor amounts of useful metals, and that the d-MnO2 zone which is apparently homogeneous under the microscope is a mixture of three or more different minerals. The chemical characteristics of the two zones can explain the variation of bulk composition of deep sea manganese nodules and inter-element relationships previously reported, suggesting that the bulk compositions are attributable to the mixing of the 10Å manganite and d-MnO2 zones in various ratios. Characteristic morphology and surface structure of some types of nodules and their relationships to chemistry are also attribut able to the textural and chemical features of the above mentioned two phases. Synthesis of hydrated manganese oxides was carried out in terms of the formation of manganese minerals in the ocean. The primary product which is an equivalent to d-MnO2 was precipitated from Mn 2+ -bearing alkaline solution under oxigenated condition by air bubbling at one atmospheric pressure and room temperature. The primary product was converted to a l0Å manganite equivalent by contact with Ni 2+, Cu 2++ or CO2+ chloride solutions. This reaction caused the decrease of Ni2+, Cu2+ or CO2+ concentrations and the increase of Na+ concentration in the solution. The reaction also proceeded even in diluted solutions of nickel chloride and resulted in a complete removal of Ni2+ from the solution. Reaction products were exclusively 10Å manganite equivalents and their chemical compositions were very similar to those of 10Å manganite in manganese nodules. The maximum value of(Cu+Ni+Co)/Mn ratio of 10Å manganite zones in manganese nodules is 0.16, and the Ni/Mn ratio of synthetic 10Å manganite ranges from 0.15 to 0.18 with the average of 0.167.

(Table 2) Chemical composition of Fe-Mn nodules and volcanic glass in sediments of the Atlantic Ocean

Distribution pattern of titanium in Quaternary sediments of the Atlantic Ocean are examined on the base of 750 Ti and Fe determinations, and several dozen of complete chemical analyses. Analyses of surface sediment samples and sediment cores up to 6 m long were made. Stratigraphic levels from Middle Pleistocene to Holocene were identified from planktonic foraminifera. Distributions of Ti in recent and Pleistocene deposits were mapped. High titanium contents were found in sediments containing products of basalt vulcanism and in iron-manganese nodules. To determine origin of titanium concentrations in sediments, Ti/Fe ratios were calculated. Maximal values of this ratio were found in areas of basaltic volcanism and of intensive terrigenous sedimentation.

(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.