Rare earth and other chemical element contents and partitions in bottom sediments, micronodules, and nodules from the bioproductive zone of the Pacific Ocean

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.

Major and rare earth element contents and their speciations in ferruginous nodules and host sediments from the Barents Sea

Contents of Fe, Mn, Al, P, and rare earth elements (REE) in ferruginous nodules and host sediments of the eastern Barents Sea were studied. A direct Fe-P correlation in reactive components of the sediments and nodules was found. The nodules were shown to be formed through Fe(II) oxidation in the surface layer of sediments and cementation of terrigenous fraction of sediments by Fe(III) oxyhydroxides. The latter accumulate phosphorus due to processes of sorption - co-precipitation, by forming Fe(III) hydrophosphates. REE composition in the sediments and nodules normalized to NASC contents is characterized by increased proportion of light REE that may be caused by regional features of their sources. Due to significant share of terrigenous matter in the Fe nodules (up to 65% for Nd), REE composition of bulk samples is similar to that of host sediments. A negative cerium anomaly in composition of reactive REE may result from REE sorption from seawater. REE bulk composition of a ferruginous crust is closer to that of seawater than one of the ferruginous nodules from the sediments because of essentially lower content of diluent terrigenous matter.

Chemical composition and fluxes of deep sea suspended matter within and over the 9°50'N hydrothermal field, EPR

Results of geochemical studies of suspended matter from the water mass over the hydrothermal field at 9°50'N on the East Pacific Rise are reported. The suspended matter was sampled in background waters, in the buoyant plume, and in the near-bottom waters. Contents of Si, Al, P, Corg, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the elements in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters trace elements are associated with Fe, Zn, and Cu (probably, with their sulfides formed during mixing of hydrothermal fluids with seawater). Chemical composition of sediment matter precipitated in a sediment trap was similar to the near-bottom suspended matter.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Lithologic correlation of ODP Leg 115 holes

Whole-core (WC) measurements of low-field magnetic susceptibility (MS) provide an extremely simple, rapid, and nondestructive technique for high-resolution core logging and lithostratigraphic correlation between subsidiary holes at Ocean Drilling Program (ODP) sites. This is particularly useful for reconstructing composite, stratigraphically continuous sequences for individual ODP sites by splicing the uninterrupted records obtained from subsections of offset cores recovered from adjacent holes. Correlation between the WCMS profiles of holes drilled at different sites is also possible in some instances, especially when lithologic variations at each site are controlled by regional paleoceanographic or global (i.e., orbitally forced) paleoclimatic changes. In such circumstances, WCMS may also be used as a proxy paleoclimatic indicator, duly assisting climatostratigraphic zonation of the recovered sequence by more conventional microfossil and isotopic techniques. High-resolution WCMS profiles are also useful in detecting intervals of the recovered sequence affected by drilling disturbance, in the form of contamination by pipe rust or similar metallic artifacts as well as discontinuities related to repenetration of the corer or loss of material between successively cored intervals. Stratigraphic intervals that have been affected by early (suboxic) diagenesis resulting from a high initial organic matter content of the sediment are also readily identified by WCMS logging. The MS signal of horizons affected by suboxic diagensis is typically degraded in proportion to the duration and intensity (related to initial Corg concentration) of organic matter remineralization. The lowering of MS values during suboxic diagenesis results from "dissolution" (bacterially mediated ionic dissociation) of magnetic iron and manganese oxides and oxyhydroxides in the sediment. It is to be hoped that, on future ODP (or similar) cruises, WCMS logging will cease to be regarded as a mere adjunct to paleomagnetic measurements, but rather as a simple, yet powerful, lithostratigraphic tool, directly analogous to downhole geophysical logging tools, and complimentary to shipboard techniques for whole-core measurements of physical properties (e.g., P-wave logging, GRAPE, etc.).

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Geochemistry, mineralogy and isotopes at DSDP Hole 62-464

The relationships between mineralogical and geochemical data on the three successive sedimentary facies at Deep Sea Drilling Project Site 464 are studied. The evolution of siliceous biogenic sediments is derived from the analyses of one Fe-Ti smectite concretion, and of siliceous aggregates occurring in the pelagic "brown clays." Along the sedimentary section, the trace elements enriching the authigenic silicates and the Fe-Mn oxyhydroxides vary, depending on the marine environment. The proportion of clays and carbonates into the siliceous deposits controls the diagenetic evolution of silica making up the quartz aggregates from the "brown clay" or the cristobalite cherts.

Composition of phosphorites from continental margins, seamounts, and islands

Behavior of molybdenum and manganese is studied in phosphorite samples from shelves, seamounts, and islands of the ocean. In shelf phosphorites molybdenum and manganese contents are 2-128 and 12-1915 ppm, respectively, while the Mo/Mn ratio varies from 0.004 to 4.5. Phosphorites from ocean seamounts impregnated with ferromanganese oxyhydroxides contain 0.84-14.5 ppm Mo and 0.1-17% Mn. The Mo/Mn ratio varies within 0.0008-0.004. Phosphate bearing ferromanganese crusts overlying seamount phosphorites contain 54-798 ppm Mo and 10-20% Mn; the Mo/Mn ratio varies within 0.002-0.005. Corresponding values for most island phosphorites are 0.44-11.2 ppm, 27-287 ppm, and 0.008-0.20. Phosphorites from reduced environment are characterized by relative enrichment in Mo and depletion in Mn, whereas the Mo/Mn ratio reaches maximum values. The ratio decreases with transition to suboxic and oxic conditions. Molybdenum content in recent shelf sediments is commonly higher than that in authigenic phosphorites from these sediments. Recent phosphorite nodules from the Namibian shelf become depleted in Mo and Mn during their lithification, but Pliocene-Pleistocene nodules of similar composition and origin from the same region are enriched in Mo and characterized by variable Mn content. Higher Mo contents in phosphate bearing ferromanganese crusts result from coprecipitation of Mo and Mn from seawater. Unweathered phosphorites on continents and phosphorites from ocean shelves are largely enriched in Mo with the Mo/Mn ratio varying from 0.01 to 1.0. This is an evidence of their formation in reduced conditions.

Composition and age of bottom sediments from the Southern Ocean

Geomorphology, geology, stratigraphy, lithology and geochemistry of bottom sediments in the South Ocean are under consideration. Regularities of distribution of iron-manganese nodules, features of occurrence of ore components in the nodules, nodule abundance in bottom sediments have been studied.

Ferromanganese nodules and micro-hardgrounds associated with the Cadiz Contourite Channel (NE Atlantic): Palaeoenvironmental records of fluid venting and bottom currents

Ferromanganese nodule fields and hardgrounds have recently been discovered in the Cadiz Contourite Channel in the Gulf of Cadiz (850–1000 m). This channel is part of a large contourite depositional system generated by the Mediterranean Outflow Water. Ferromanganese deposits linked to contourites are interesting tools for palaeoenviromental studies and show an increasing economic interest as potential mineral resources for base and strategic metals. We present a complete characterisation of these deposits based on submarine photographs and geophysical, petrographic, mineralogical and geochemical data. The genesis and growth of ferromanganese deposits, strongly enriched in Fe vs. Mn (av. 39% vs. 6%) in this contourite depositional system result from the combination of hydrogenetic and diagenetic processes. The interaction of the Mediterranean Outflow Water with the continental margin has led to the formation of Late Pleistocene–Holocene ferromanganese mineral deposits, in parallel to the evolution of the contourite depositional system triggered by climatic and tectonic events. The diagenetic growth was fuelled by the anaerobic oxidation of thermogenic hydrocarbons (δ13CPDB=−20 to −37‰) and organic matter within the channel floor sediments, promoting the formation of Fe–Mn carbonate nodules. High 87Sr/86Sr isotopic values (up to 0.70993±0.00025) observed in the inner parts of nodules are related to the influence of radiogenic fluids fuelled by deep-seated fluid venting across the fault systems in the diapirs below the Cadiz Contourite Channel. Erosive action of the Mediterranean Outflow Water undercurrent could have exhumed the Fe–Mn carbonate nodules, especially in the glacial periods, when the lower core of the undercurrent was more active in the study area. The growth rate determined by 230Thexcess/232Th was 113±11 mm/Ma, supporting the hypothesis that the growth of the nodules records palaeoenvironmental changes during the last 70 ka. Ca-rich layers in the nodules could point to the interaction between the Mediterranean Outflow Water and the North Atlantic Deep Water during the Heinrich events. Siderite–rhodochrosite nodules exposed to the oxidising seabottom waters were replaced by Fe–Mn oxyhydroxides. Slow hydrogenetic growth of goethite from the seawaters is observed in the outermost parts of the exhumed nodules and hardgrounds, which show imprints of the Mediterranean Outflow Water with low 87Sr/86Sr isotopic values (down to 0.70693±0.00081). We propose a new genetic and evolutionary model for ferromanganese oxide nodules derived from ferromanganese carbonate nodules formed on continental margins above the carbonate compensation depth and dominated by hydrocarbon seepage structures and strong erosive action of bottom currents. We also compare and discuss the generation of ferromanganese deposits in the Cadiz Contourite Channel with that in other locations and suggest that our model can be applied to ferromanganiferous deposits in other contouritic systems affected by fluid venting.

Mineralogy and geochemistry of contrasting hydrothermal systems on the Arctic Mid Ocean Ridge (AMOR) : the Jan Mayen and Loki’s Castle vent fields

Tese de doutoramento, Ciências do Mar, Universidade de Lisboa, Faculdade de Ciências, 2016

Chemical compositions of rocks and minerals from an underwater volcano of the Kuril deep-sea basin

Mineralogy and geochemistry of low-temperature hydrothermal manifestations occurring on the surface of basalts and in their cracks within a submarine volcano in the north-eastern part of the Kuril deep-sea basin have been studied. The following order of isolation of mineral phases has been found out: Fe-rich sulphides (pyrite) - Fe-rich layered silicates (hydromica of celadonite-nontronite type) - amorphous silica (opal) - Fe-oxyhydroxides (goethite) - Mn-oxyhydroxides (vernadite). Sulphide mineralization is of the phenocryst-stockwork type. Finding of pure barite fragments does not exclude presence of hydrothermal exhalations (smokers) on this volcanic structure.

Oxygen microprofiles and porewater chemistry in sediments of the Skagerrak

Sediment porewater oxygen profiles were measured with micro and needle electrodes in sediment cores of 27 stations in the Skagerrak (northeastern North Sea). Oxygen penetration depth ranged from 3 to 20 mm depth. Fluxes estimated from the oxygen gradients varied from 3 to 18 mmol m**-2 d**-1. Oxygen penetration and flux depend on water depth, but possibly more on the hydrological conditions, related to the import of fresh organic matter by primary production in the water column. Oxygen fluxes were not related to the total organic carbon (TOC) content of the sediments. Stations in the eastern part of the Skagerrak showed high burial rates of TOC. At 6 stations porewater chemistry of Fe, Mn and NO3- was strongly associated with the oxygen distribution. The average relative contribution of terminal electron acceptors to carbon mineralisation was estimated at 85% for O2, 0.5% for Mn, 4.5% for [NO3]3-, 1% for Fe and 9% for [SO4]2-. At one station the occurrence of exceptionally high solid manganese oxyhydroxides was probably related to an active internal manganese cycle.

Geochemistry and lithology of clayey nannofossil ooze turbidites and hemipelagites at ODP Holes 135-834A and 135-835A

The western Lau Basin, between the Central and Eastern Lau Spreading Centers and the Lau Ridge, contains several small, elongate, fault-bounded, partially sediment-filled sub-basins. Sites 834 and 835 were drilled in the oldest part of the Lau Basin in two of these small extensional basins close to the Lau Ridge, formed on late Miocene to early Pliocene oceanic crust. Both sites show a similar sediment sequence that consists of clayey nannofossil oozes and mixed sediments interbedded with epiclastic vitric sands and silts. The vitric sands and silts are largely restricted to the deeper part of the sediment column (early Pliocene-late Pliocene), and the upper part of the sediment column at both sites consists of a distinctive sequence of brown clayey nannofossil ooze, stained by iron and manganese oxyhydroxides (late Pliocene-Holocene). However, the clayey nannofossil ooze sequence at Site 835 is anomalously thick and contains several medium- to very thick beds of matrix-supported, mud-clast conglomerate (interpreted as muddy debris-flow deposits), together with large amounts of redeposited clayey nannofossil ooze and coherent rafted blocks of older hemipelagic material. Redeposited clayey nannofossil oozes can be distinguished from hemipelagic nannofossil oozes using several sedimentological criteria. These include variation in color hue and chroma, presence or absence of bioturbation, presence or absence of scattered foraminifers, grain-size characteristics, variability in calcium carbonate content, presence or absence of pumice clasts, and micropaleontology. Clayey nannofossil ooze turbidites and hemipelagites are also geochemically distinct, with the turbidites being commonly enriched in Mn, Ni, Pb, Zn, Cr, and P. The sediment sequence at Site 835 is dominated by allochthonous sediments, either muddy debris-flow deposits, coherent rafted blocks, or thick clayey nannofossil ooze turbidites. Since 2.9 Ma, only 25% of the 133 m of sediments deposited represents hemipelagic deposition, with an average sedimentation rate of 1.5 cm/k.y.. Allochthonous sediments were the main sediment type deposited during the Brunhes geomagnetic Epoch and make up 80% of the thickness of sediment deposited during this period. Short intervals of mainly hemipelagic deposition occurred from 0.4 to 0.9 Ma, 1.0 to 1.4 Ma, and 1.7 to 2.1 Ma. However, allochthonous sediments were again the dominant sediment type deposited between 2.1 and 2.5 Ma, with a large slide complex emplaced around 2.5 Ma. We conclude that the adjacent high ground, surrounding the basin in which Site 835 was drilled, was affected by marked instability throughout the late Pliocene and Pleistocene. In contrast, sedimentation at Site 834 during this period has been dominated by hemipelagic deposition, with redeposited sediments making up slightly less than 17% of the total thickness of sediment deposited since 2.3 Ma. However, there was a marked increase in frequency and magnitude of redeposited sediments at around 0.2 Ma at Site 834, which broadly corresponds to the onset of a major episode of turbidite and debris-flow emplacement beginning about 0.4 Ma at Site 835. This episode of instability at both sites may be the effect of the approach and passing of the Central Lau propagator at the latitude of Sites 834 and 835 at about 0.5 Ma.

(Table 1) Calcium carbonate and <2 µm fractions of bulk sample and insoluble residue at DSDP Hole 92-597

Particles of red brown to yellow brown semiopaque oxides (RSO) dominate the insoluble residue fraction of the sediments at Site 597. Unlike the X-ray amorphous particles in the Bauer Deep sediments, these particles are composed of mainly goethite; the amount of X-ray amorphous ferric hydroxide and poorly crystalline ferromanganese oxyhydroxides is generally small relative to the amount of goethite. A qualitative goethite crystallinity index was established. The variations observed in the crystallinity of goethite with increasing depth and changes in lithology suggest that aging and long-term exposure to seawater in a high water/sediment regime influence and increase the rate of recrystallization of the Fe-oxyhydroxides of the RSO particles. The percentage of organic carbon is low in these sediments; it varies primarily between 0.2 and 0.4 wt.%. Phillipsite is present throughout the sediment column and is more concentrated in the youngest clay layer and in the oldest basal sediments.