Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Investigation of Manganese nodules in the southern Baltic Sea

Die Genese von Mangan-Eisen-Akkumulaten der Kieler Bucht wurde durch In-situ-Experimente vor allem in Tauchgängen unter Berücksichtigung der hydrographischen und sedimentologischen Gegebenheiten sowie natürlicher Akkumulatvorkommen und Krusten auf künstlichen Substraten untersucht. An den diagenetisch gebildeten Akkumulaten wurden chemische Zusammensetzung, Mineralogie, physikalische Parameter, Morphologie und Internstrukturen untersucht. Wichtige Faktoren für die Entstehung der Mangan-Eisen-Akkumulate sind geringe Sedimentationsraten am Entstehungsort, das Vorhandensein geeigneter Anlagerungskerne sowie ausreichende Zufuhr von gelöstem Mangan und anderen Metallen durch Diffusion aus dem Sediment und durch lateralen Transport im freien Wasser vor allem im Sommer und Frühherbst infolge absinkender Sauerstoffgehalte im Bodenwasser der Rinnen. Die Experimente ergaben eine saisonale Abscheidungscharakteristik der Mangan-Eisen-Oxide in Abhängigkeit von der hydrographischen Jahresentwicklung mit niedrigen Zuwachsraten im Winter und Frühjahr und hohen Werten im Sommer und Herbst. Die 1981 experimentell ermittelte Wachstumsrate liegt im Bereich der südlichen Kieler Bucht (Boknis Eck) bei ca. 20 mm/1000 a. Für das Vorkommen vor Schleimünde wurden in Anlehnung an SUESS & DJAFARI (1977) 30-50 mm/1000 a berechnet. Unter reduzierenden Bedingungen infolge Sedimentüberdeckung können Mangan-Eisen-Akkumulate partiell oder vollständig wieder aufgelöst werden. Für den Verbleib der Akkumulate an der Sedimentoberfläche wird die Bedeutung der Seenelke Metridium senile nachgewiesen.

Geochemical investigation of ODP Leg 113 sites

Dissolved organic carbon (DOC) was determined in pore water extracted from pelagic and hemipelagic sediments recovered during Leg 113. DOC concentration varied between 1.82 and 13.6 mg C/L which is one to two orders of magnitude less than previously reported for hemipelagic sediments. It is argued that this difference is related to differences in the intensity of degradation of organic matter. As a first approximation it is found that in reducing sediments, the level of DOC is proportional to the intensity of sulfate reduction. It is suggested that DOC is formed by different mechanisms in oxic and reducing environments.

Interstitial-water chemistry of ODP Leg 113 sites

Variations in the distribution of major elements and stable oxygen isotopes in ODP Leg 113 pore water are not related to lithology and thus appear to be controlled by minor constituents. Petrographic observations and geochemical considerations indicate that alteration of calc-alkalic volcanic material dispersed in the sediment is an important process. A diagenetic reaction is constructed that involves transformation of volcanic glass into smectite, zeolite (represented by phillipsite), chert, and iron sulfide. Mass balance calculations reveal that alteration of less than 10% (volume) of volcanogenic material may account for the observed depletion of magnesium, potassium, and 18O and enrichment of calcium. Alteration of this amount of volcanic glass produces less than 4% (volume) of smectite and zeolite. Hence, mass balance is obtained without having to invoke unreasonable large amounts of volcanic matter or interactions between seawater and basement.

Geochemistry on manganese deposit from the Median Valley of the Mid-Atlantic Ridge

A manganese oxide crust from an extensive deposit in the median valley of the Mid-Atlantic Ridge was found to be unusually high in manganese (up to 39.4% Mn), low in Fe (as low as 0.01% Fe), low in trace metals and deficient in Th230 and Pa231 with respect to the parent uranium isotopes in the sample. The accumulation rate is 100 mm to 200 mm/10 million year, or 2 orders of magnitude faster than the typical rate for deep-sea ferromanganese deposits. The rapid growth rate and unusual chemistry are consistent with a hydrothermal origin or with a diagenetic origin by manganese remobilized from reduced sediments. Because of the association with an active ridge, geophysical evidence indicative of hydrothermal activity, and a scarcity of sediment in the sampling area, we suggest that a submarine hot spring has created the deposit.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Manganese contents and accumulation rates in reduced bottom sediments of the Sea of Okhotsk

Manganese contents in reduced sediments and accumulation rates were investigated. Their values in sediments of most of cores are background (0.03-0.07 %).Anomalous concentrations (up to 2.5 %) and accumulation rates (up to 60 mg/cm**2/ka) occur near the known region of hydrothermal barite mineralization in the Derugin Basin. High accumulation rates of Mn (>10 mg/cm**2/ka) also occur in Holocene sediments to south-east from the Derugin Basin. It can be assumed that high Mn contents and accumulation rates occur there due to transportation of Mn-rich water from the Derugin Basin in the near-bottom layer under the lower border of the Sea of Okhotsk Intermediate Water. Intensive Mn accumulation is also typical for the South Okhotsk Basin near the Bussol Strait. Mn accumulation rates of glacial sediments of the second oxygen isotope stage are less significant, which is presumed to be caused by paleoceanological reasons.

Composition of surface layer bottom sediments from the Kem' River estuary, White Sea

Based on grain-size, mineralogical and chemical analyses of samples collected in cruises of R/V Ekolog (Institute of Northern Water Problems, Karelian Research Centre of RAS, Petrozavodsk) in 2001 and 2003 regularities of chemical element distribution in surface layer bottom sediments of the Kem' River Estuary in the White Sea were studied. For some toxic elements labile and refractory forms were determined. Correlation analysis was carried out and ratios Me/Al were calculated as proxies of terrigenous contribution. Distribution of such elements as Fe, Mn, Zn, Cr, Ti was revealed to be influenced by natural factors, mainly by grain size composition of bottom sediments. These metals have a tendency for accumulation in fine-grained sediments with elevated organic carbon contents. Distribution of Ni is different from one of Fe, Mn, Zn, Cr, Ti. An assumption was made that these distinctions were caused by anthropogenic influence.

Concentration and composition of aerosols over the North Atlantic in August 1995

Data on composition of aerosols are considered. Investigations include electron microscopy, grain size, mineralogical and chemical analyses. Samples of aerosols were collected Cruise 37 of R/V Akademik Mstislav Keldysh along a transatlantic section along 40°-50°N. Variability of concentrations and composition of aerosols with distance from continents is shown: concentrations of aerosols decrease by factor of ten and more. Significant portion of mineral components in aerosols collected over the continent is replaced by organic matter due to mechanical differentiation during transportation. Such anthropogenic components as soot, ash, and combustion spheres were detected in all samples. North African dust was found in one sample in the western part of the section.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Chemical composition of hydrothermal deposits and vulcanites from the Menez Gwen vent field, Mid-Atlantic Ridge

Surface hydrothermal deposits of the shallow-water Menez Gwen vent field located in the rift zone of the Mid-Atlantic Ridge are mostly composed of nonmetalliferous minerals in contrast to sulfide deposits of deep-water fields. Here sulfide minerals occur only in dispersed form. High-temperature sulfide deposits strongly enriched in copper and zinc occur only immediately below the surface of the bottom. This is related to subsurface boiling and phase separation of initial high-temperature hydrothermal ore-bearing solution that ascends from the interior to the floor surface.

Chemical composition of bottom sediments and interstitial waters from DSDP Sites 252, 285, 315, 317, 336, and 386

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.