ALBERT

Description: 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.

Description: The main objective of the project was to develop a geochemical method for exploration of ores associated with granitic rocks. Fe and Mn oxidates were sampled in streambeds and lakes from 129 localities in Southeastern Norway. 65 of these localities are situated in the northern Oslo Graben. The samples were examined mineralogically and chemically by a variety of methods. Geochemical maps of the element content in oxidates show regional distribution patterns for several elements. Sampling and analysis of oxidates can be used in exploration for mineralizations such as the Skrukkelia Mo-deposit in the northern Oslo Graben. New anomalies (especially for Zn and W) have been detected. Appendix I contains a description of samples, chemical and mineralogical determinations performed on the samples, backscattered electron image-, X-ray image- and scanning electron image pictures of the oxidate preparates. Appendix II contains spectral plots, point analysis with the microprobe, X-ray diffractograms, analytical results, correlation coefficient matrix, scatterplots, frequency distributions and information on data storage. Appendix III containS maps of the element content in oxidates.

Description: Manganese nodules have been analysed at the Scripps Institution of Oceanography after having been ground to to a diameter less than 74 microns. Some analysises were performed on pellets by X-ray Emission Spectroscopy for 1000 Seconds. All concentrations have been corrected to 110 degrees Celsius drying conditions (see: https://doi.pangaea.de/10.1594/PANGAEA.854202).

Description: Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

Description: The Tuamotu Archipelago in French Polynesia is a Co-rich ferromanganese crust province. The NODCO I survey (1986) provided detailed data on Co-rich crusts in this environment through the exploration of a restricted zone in the vicinity of Niau Island on the southern flank of the archipelago. This flat zone is a fossil atoll which, under the action of subsidence and tectonic movements, has collapsed to a water depth of 1000 m. The plateau is partially filled with coralline sediments. Outcrops of ferromanganese crusts, associated with rare nodules and slabs, are located on the inner side of the coral reef which bounds the ancient lagoon. The successive episodes of plateau history have been recorded in the different growth periods of the ferromanganese crusts. The crusts, nodules and slabs belong to the same morphological, mineralogical and geochemical family. Cobalt contents vary from 0.7 to 1.3%. The highest values belong to the thinnest ferromanganese crusts which are located on the flanks of the plateau. Average Ni contents are about 0.5% and Cu contents about 0.1%; Pt contents vary from 0.2 to 1.3 ppm. Platinum and Co are enriched in the outermost oxide zone of the crusts. Poorly crystallized -MnO2 is the dominant mineralogical phase. Cobalt enrichment seems to be related to -MnO2 particle size. The greatest contents are located in the finest material where the particle size is less than 0.1 m. Cobalt-rich crusts of the Niau Zone have the same characteristics as the Co-rich crusts from the Equatorial North Pacific. They differ in original setting: the reefal environment in the Niau Zone is superficial, overlying a volcanic substrate.

Description: Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (〉 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition.

Description: Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151°W, 9° 15'N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochloride-acetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co/Mn ratio of 300. The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have Delta-MnO2 as the dominant manganese mineral. The ratios of Ni/Mn, Cu/Mn, and Fe/Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the Delta-MnO2 nodules.

Description: Manganese nodules from 36 stations in the Cape Leeuwin field were analyzed for Mn, Fe, Ni, Cu and Co and the results were combined with earlier work to demonstrate quantitative and geographic variations. Nodules in this field are moderately enriched in Ni, moderately depleted in Cu, and contain intermediate values of Co. The sum of Ni + Cu vs. Mn/Fe plots along a hyperbolic regression line derived from nodules of the southeastern Pacific, suggesting that this relationship has general applicability. Regional variations in nodule grade (Ni + Cu + Co) assist in defining pathways of Antarctic Bottom Water between the Southeast Indian Ridge and the Wharton basin.

Description: An area of about 22,000 km² on the northern Blake Plateau, off the coast of South Carolina, contains an estimated 2 billion metric tons of phosphorite concretions, and about 1.2 billion metric tons of mixed ferromanganese-phosphorite pavement. Other offshore phosphorites occur between the Blake Plateau and known continental deposits, buried under variable thicknesses of sediments. The phosphorite resembles other marine phosphorites in composition, consisting primarily of carbonate-fluorapatite, some calcite, minor quartz and other minerals. The apatite is optically pseudo-isotropic and contains about 6% [CO3]**2- replacing [PO4]**3- in its structure. JOIDES drillings and other evidence show that the phosphorite is a lag deposit derived from Miocene strata correlatable with phosphatic Middle Tertiary sediments on the continent. It has undergone variable cycles of erosion, reworking, partial dissolution and reprecipitation. Its present form varies from phosphatized carbonate debris, loose pellets, and pebbles, to continuous pavements, plates, and conglomeratic boulders weighing hundreds of kilograms. No primary phosphatization is currently taking place on the Blake Plateau. The primary phosphate-depositing environment involved reducing conditions and required at least temporary absence of the powerful Gulf Stream current that now sweeps the bottom of the Blake Plateau and has eroded away the bulk of the Hawthorne-equivalent sediments with which the phosphorites were once associated.

Description: Depth profiles of 10Be and 9Be concentrations have been measured in five manganese nodules from widely varying locations of the Pacific Ocean. Mean accumulation rate of these manganese nodules ranges from 2.7 to 8.0 mm/m.y.. The variation of 10Be and 10Be/9Be with depth or time is found to be less than ±30% for periods from 0.4-1.0 m.y. back to 6 m.y. B.P. Surface 10Be/9Be atomic ratio is found to be (9-13) x 10**-8, that shows authigenic nature of manganese nodule acuumulation by comparison with (12-31) x 10-8 for deep-sea water, (2-7) x 10**-8 for clay sediments and (7-9) x 10**-8 for fossil-rich sediments.

Description: This report describes the results of some two years of effort devoted to archiving the Marine Manganese Nodule Collection in the Geology Department at Washington State University, Pullman, Washington. As proposed to the National Oceanic and Atmospheric Administration in 1984, the Collection was organized, labelled, and indexed so that efficient use by outside investigators would be possible. Since the late 1990s, the collection has been transferred to the Smithsonian National Museum of Natural History, Washington, D. C., U.S.A where it is available for study.

Description: This report presents the results of chemical analyses of pelagic sediment samples and associated ferromanganese nodules collected at DOMES Site A, located in the equatorial North Pacific. The samples examined in this study were taken from 7.5 cm diameter sub-cores of 66 box cores. The box cores were collected on two cruises of the R/V Oceanographer, cruises RP-23-OC77 and RP-1-OC78. Cores containing two types of sediment lithology were recovered cores containing only Quaternary sediment and those containing early Tertiary sediment overlain by 0.5 to 20 cm of Quaternary sediment. The two sediments of different age can be distinguished by their radiolarian assemblage, color, and mineralogy. The sea floor coverage of nodules tended to be lower in cores which contained Tertiary sediment than in those containing only Quaternary sediment.

Description: Methods of estimating manganese nodule grade and concentration were investigated using data from a well-explored east-central Pacific manganese nodule deposit. Bulk chemical analyses of 159 nodules recovered from 21 box cores show that the range in metal values between nodules from a single box core is commonly small but may be greater than the range in mean metal content of nodules from widely separated box cores. The metal exhibiting the greatest variability in the 21 box cores is Zn, followed in decreasing order by Cu, Mn, Co, Ni, and Fe. Approximately half of the box cores required analysis of 11 nodules or more to predict metal content within plus or minus 10 percent of the mean value.

Description: The report is divided into three sections: morphology, mineralogy and elemental composition. The nodule morphology section defines what is considered a nodule for the study, and details the external characteristics and internal structure. Nodule mineralogy is discussed in three sections: manganese minerals, iron oxide minerals, and accessory minerals. The major manganese minerals discussed are todorokite, birnessite, and vernadite. The iron oxide minerals are less well known and include feroxyhyte, goethite, and lepidocrocite. Accessory minerals present include quartz, clays, and other silicates and nonsilicates. A discussion on moisture content is also included. The elemental composition section presents data on 74 elements occurring as cations or anions. Summary data, histograms, and interelement correlation coefficients are presented.

Description: Pelagic clay and Mn nodules from DOMES sites in the North Pacific and a varved glacial lake deposit from Connecticut were analysed for Os concentration and isotopic composition by isotope-dilution secondary ion mass spectrometry after treatment by NiS fusion or oxalic acid leaching. Bulk pelagic clay from DOMES site C has 187Os/186Os = 6.5 and Os = 0.14 ng/g. Oxalic acid leaches of this same sediment and of Mn nodules from DOMES sites A and C have more radiogenic 187Os/186Os ratios which average 8.3. Bulk glacial Lake Hitchcock sediment has 187Os/186Os = 12.5 and Os = 0.06 ng/g. The total Os flux to North Pacific pelagic clay is 7 to 10 ng Os/cm**2/10**6 y. Lake Hitchcock sediment provides an integrated value for the local crustal 187Os/186Os ratio. The oxalic acid leaches are assumed to attack hydrogenous phases selectively. A simple model in which the only sources of Os to the ocean are continental crust with the isotopic composition of Lake Hitchcock (187Os/186Os = 12.5) and extraterrestrial particles with 187Os/186Os = 1.1 results in a cosmic flux of osmium to the sediment of 4.9 ng Os/cm**2/10**6 y of which 20% is hydrogenous. A model in which the sources of Os to the ocean are continental crust with an 187Os/186Os ratio of 30 (from the model of Palmer and Turekian, 1986), oceanic mantle or crust with 187Os/186Os = 1.04 and extraterrestrial particles with 187Os/186Os = 1.1 results in a cosmic flux of Os to the sediment of 5.7 ng Os/cm**2/10**6 y of which none is hydrogenous. These extraterrestrial Os fluxes correspond to maximum C-1 chondrite accretion rates of between 4.9 × 104 and 5.6 × 104 tonnes/y.

Description: A model that predicts the flux of 222Rn out of deep-sea sediment is presented. The radon is ultimately generated by 230Th which is stripped from the overlying water into the sediment. It is shown that the continental contribution of ionium is not significant, and that at low sedimentation rates, biological mixing and erosional processes strongly affect the surface concentration of the ionium. Two cores from areas of slow sediment accumulation, one from a manganese nodule region of the central Pacific and one from the Rio Grande Rise in the Atlantic were analyzed at closely spaced intervals for 230Th, 226Ra, and 210Pb. The Pacific core displayed evidence of biological mixing down to 12 cm and had a sedimentation rate of only 0.04 cm/kyr. The Atlantic core seemed to be mixed to 8 cm and had a sedimentation rate of 0.07 cm/kyr. Both cores had less total excess 230Th than predicted. Radium sediment profiles are generated from the 230Th model. Adsorbed, dissolved, and solid-phase radium is considered. According to the model, diffusional losses of radium are especially important at low sedimentation rates. Any particulate, or excess radium input is ignored in this model. The model fits the two analyzed cores if the fraction of total radium available for adsorption-desorption is about 0.5-0.7, and if K, the distribution coefficient, is about 1000. The flux of radon out of the sediments is derived from the model-generated radium profiles. It is shown that the resulting standing crop of SUP-222 Rn in the overlying water may be considered as an added constraint in budgeting 230Th and 226Ra in deep-sea sediments.

Description: The chemical and mineralogical composition of burrowed sediment, recovered in 66 box cores at latitude 9°25'N and longitude 151°15'W in the equatorial Pacific, demonstrates the important role of infauna in determining the geochemistry of pelagic sediment. Haloed burrows, approximately 3 cm across, were present in many of the cores. Within early Tertiary sediment that was covered by less than 5 cm of surface Quaternary sediment in several cores, the burrows in cross-section consist of three units: (1) a dark yellowish-brown central zone of Quaternary sediment surrounded, by (2) a pale yellowish-orange zone (the halo) of Tertiary sediment, which is surrounded by (3) a metal-oxide precipitate; the enclosing Tertiary sediment is dusky brown. Several elements - Mn, Ni, Cu, Co, Zn, Sb and Ce - have been leached from the light-colored halo, whereas Cr, Cs, Hf, Rb, Sc, Ta, Th, U, the rare earth elements exclusive of Ce, and the major oxides have not been leached. The metal-oxide zone, 1-5 mm thick, contains as much as 16% MnO2, as the mineral todorokite. The composition of the todorokite, exclusive of the admixed Tertiary sediment, resembles the composition of the metal deficit of the halo and also the composition of surface ferromanganese nodules that have been interpreted as having a predominantly diagenetic origin. Thus bioturbation contributes not only to the redistribution of metals within pelagic sediment, but also to the accretion of ferromanganese nodules on the sea floor.

Description: Relationships among Th and Ra isotopes in nodule, sediment and water phases at MANOP Site S establish the most likely source for Th in the nodules, the frequency of nodule turning, and the similarity of micro and macro nodules. Manganese nodules and bottom waters have 230Th/232Th activity ratios considerably higher than other phases at this site suggesting that sea water is the likely source of Th for the nodules. Similar 230Th/232Th activity ratios in nodule tops and bottoms and in certain cases departure from expected 226Ra/230Th activity ratios in nodule tops and bottoms indicate that the nodules rotate every one to ten thousand years. The micro nodules have diffusion coefficients of Ra similar to macro nodule bottoms. I suggest that they may act as a carrier phase for transporting metals through oxic sediments to nodules.

Description: 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.

Description: Thirty sediment cores (30-40 cm in length), 47 Ekman dredge sediments, and Mn concretions were collected from Lake Biwa. The concentrations of 36 elements in the samples were determined by instrumental neutron activation, X-ray fluorescence, atomic absorption, and colorimetric analyses. The elements determined included Mn, P, As, Sb, Fe, Ni, Co, Zn, Cu, Pb, Hg, Cr, Ti, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Hf, La, Ce, Sm, Eu, Yb, Lu, U, Th, Au, Ta, Nd, Br and N. Based on statistical considerations and calculation of the concentration factors of the elements, the features of the elemental distribution in Lake Biwa sediment were determined. The main results are summarized as follows : (1) Concentrations of Mn and As were very high in the uppermost oxidized layer of the offshore sediment and Mn concretions. This resulted from the dissolution-deposition cycles of these elements within the sedimentary column and the bottom water. The fixation of As at the sediment surface is mainly attributed to the adsorption of arsenate onto Mn (II) -rich hydrous Mn (IV) oxide. (2) There were high concentrations of Zn, Cu, Pb and Hg in the recent sediments. Although the source of these elements is attributed to human activities, the individual distributions of Zn and Cu in the sediment may result from the deposition of metal-rich planktonic debris and subsequent degradation of the debris. (3) The orders of increasing concentrations of alkali metals and lanthanides in the sediment from the central region compared with the nearshore pediment were identical to the orders of increasing atomic numbers from Na to Cs and from La to Lu, respectively.

Description: This text offers a general introduction to the geological history of the North-Tethys Platform from the Malm to the Lower Eocene periods. It is followed by three parts: a sedimentology development, a geochemical study and a part devoted to the reconstitution of the environment and the sedimentation rates, the subsidence, the depth and the morphology of the seabed and therefore the paleogeography of the Briançonnais domain. The last two chapters deal, one with the evolution of the Briançonnais domain in the context of events affecting Western Tethys and the Central Atlantic, and the other with two sedimentation models deduced from the previous study.