Description and chemical composition of ferromanganese encrustations and deposits in the Atlantic Ocean from R/V Atlantis II cruises 20, 42, 60, 85; R/V Chain cruise 35; R/V Knorr cruise 61 and RRS Shackleton cruise 75/1 stations

Chemical and mineralogical compositions of ferromanganese oxide coatings on rocks dredged from the New England Seamounts, the Sierra Leone Rise and the Mid-Atlantic Ridge near the Equator have been determined in an investigation of regional differences in Atlantic ferromanganese deposits. Most encrustations are clearly of hydrogenous origin, consisting mainly of todorokite and delta MnO2, but several recovered from the equatorial fracture zones may be hydrothermal accumulations. Differences in the chemistry of the water column and in growth rates of the ferromanganese coatings may be important in producing this regional contrast in composition. Fine-scale changes in element abundances within the encrustations indicate that the nature of the substrate has little influence on compositional variations.

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.

(Table 1, page 129) Chemical composition of ferromanganese coating on glacial erratics from Lydonia Canyon

Ferromanganese coatings have been found on glacial erratics in Lydonia Canyon, off the United States northeastern coast. The coatings, which are about 17 µm thick, consist of an outer manganese-rich layer which covers the top of the erratic, a middle transitional layer, and an internal iron-rich layer that encircles the entire surface of the erratic. Chemical analyses of the coatings, when compared with similar data on abyssal marine ferromanganese deposits, reveal comparable Mn/Fe ratios, higher P and Ti concentrations, and an order of magnitude less of Co, Ni, Cu, and most other metals. A comparison of the Lydonia Canyon coatings with desert varnishes reveals obvious chemical, mineralogical, and morphological differences.

Geochemistry of manganese nodules from a British Columbia fjord

Concretions of iron and manganese oxides and hydrous oxidesóobjects commonly called manganese nodulesóare widely distributed not only on the deep-sea floor but also in shallow marine environments1. Such concretions were not known to occur north of Cape Mendocino in the shallow water zones bordering the North-East Pacific Ocean until the summer of 1966 when they were recovered by one of us (J. W. M.) in dredge samples from Jervis Inlet, a fjord approximately 50 miles north-west of Vancouver, British Columbia.

The amount of water loss was determined by drying at 110°C

Deep-sea deposits, which resemble in nearly every respect the deep-sea oozes have been observed in many islands of the East-Indian Archipelago, notably the islands of Borneo, Rotti and Timor. Manganese nodules are found in equivalents of deeep-sea red clays on Timor and Rotti island. In this paper, those relative to red clay deposits dating from a Cretaceous ocean are analysed in detail in the vicinity of the town of Niki Niki in Western Timor.

Benthic and planktic foraminiferal stable isotope records combined with Nd isotope ratios of ODP Hole 198-1210B

The Pacific Ocean is the largest water body on Earth, and circulation in the Pacific contributed significantly to climate evolution in the latest Cretaceous, the culmination of a period of long-term cooling. Here, we present new high-resolution late Campanian to Maastrichtian benthic and planktic foraminiferal stable isotope data and a neodymium (Nd) isotope record obtained from sedimentary ferromanganese oxide coatings of Ocean Drilling Program Hole 1210B from the tropical Pacific Ocean (Shatsky Rise). These new records resolve 13 million years in the latest Cretaceous, providing insights into changes in surface and bottom water temperatures and source regions of deep to intermediate waters covering the carbon isotope excursions of the Campanian-Maastrichtian Boundary Event (CMBE) and the Mid-Maastrichtian event (MME). Our new benthic foraminiferal d18O and Nd isotope records together with published Nd isotope data show markedly parallel trends across the studied interval over a broad range of bathyal to abyssal water depths interpreted to reflect changes in the intensity of deep-ocean circulation in the tropical Pacific. In particular, we observe a three-million-year-long period of cooler conditions in the early Maastrichtian (72.5 to 69.5 Ma) when a concomitant change toward less radiogenic seawater Nd isotope signatures probably marks a period of enhanced admixture and northward flow of deep waters with Southern Ocean provenance. We suggest this change to have been triggered by intensified formation and convection of deep waters in the high southern latitudes, a process that weakened during the MME (69.5 to 68.5 Ma). The early Maastrichtian cold interval is closely related to the negative and positive carbon isotope trends of the CMBE and MME. The millions-of-years long duration of these carbon cycle perturbations suggests a tectonic forcing of climatic cooling, possibly related to changes in ocean basin geometry and bathymetry.

Analysis of Mn-nodules from the Indian Ocean

This report studies the principal paramters governing the distribution of iron-manganese concretions on the sea floor of the Indian Ocean, as well as their petrography and mineralogy. The results are mainly based on the recoveries made during voyages 31, 33 and 35 of the "Vityaz"' (1959-1962) and partly during voyages 36 and 41 (1964-1966). During these voyages samples of Mn concretions and Mn crust were collected (by bottom grabs, cores, trawlings, and dredgings) at 39 stations. The following account is devoted to the problems concerning the geochemistry of these concretions.

Documentation of manganese nodules form the northwest Indian Ocean

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.

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.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Manganese nodules mesozoic deep-sea deposits off some Indonesian Islands

Concretions of manganese have been discovered by the geological expedition to the islands of the Timor group in 1910-1912 in triassic and jurassic deep-sea deposits, on the Island of Timor, and also well developed in similar jurassic deposits on the island of Rotti, and previously, in 1894, the author noticed them in abysmal deposits of the pre-cretaceous probably jurassic Danau formation, occurring in West and East Borneo. On the island of Rotti nodules of manganese were found in several localities in siliceous limestones, marls, siliceous and calcareous clayshales along with concretions and nodules of chert of jurassic age, full of tests of radiolaria.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.

REE and elemental contents and isotopic compositions in foraminifera from DSDP Hole 39-357

An evaluation has been made of the method of establishing the REE contents and patterns and Nd isotopic compositions of sea water over Cenozoic time from their record in the FeMn-oxide coatings of foraminiferal calcite. Using 0-60 Ma samples from the Rio Grande Rise (DSDP Site 357) it has been established that the REE contents of the coatings are generally similar to those of Recent samples. However, in the Cenozoic samples the surface coatings have been diagenetically modified under suboxic conditions resulting in a distinctly different REE pattern although the original 143Nd/144Nd ratios appear to have been preserved. The Nd isotopic curve for Cenozoic sea water in the S. Atlantic shows clear temporal trends, although these are not so extreme as to show 143Nd/144Nd ratios outside the range observed in modem sea water. With the principal exception of the oldest samples there is an approximate inverse relationship between the Nd and Sr isotopic compositions of the foraminifera. It is suggested that the changes reflect both global changes in the relative proportions of Nd and Sr derived from continental input and from the weathering of volcanic debris together with short term and local variations to which the Sr curve is insensitive, reflecting the different response times of the two elements to changes in oceanic input functions. The Nd isotope curve appears to be a potentially useful tracer of ocean palaeochemistry.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.