Composition of ferromanganese crusts from the Atlantic, Pacific and Indian Oceans

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples. The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10-50) are related to their layer-to-layer variations within a given ore field. The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Chemical and isotopic compositions of rocks, ores, and hydrothermal minerals from the Rainbow and Logachev-2 hydrothermal fields

The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.

Geochemical composition of sediments from ODP Site 164-997, Blake Ridge

Twenty-two trace elements in 355 sediment samples from Site 997 on the Blake Ridge were examined by inductively coupled plasma-optical emission spectrometry and inductively coupled plasma-mass spectrometry, for respective fractions of acid-soluble and insoluble compositions. Downhole profiles of these elements exhibit complicated fluctuations throughout late Miocene to Pleistocene, principally due to the variations in the acid-soluble fraction. Noncarbonate composition is given from the acid-insoluble residues, which permits us to recognize secular feature of selected element variance for four intervals. These intervals (I: 0-183 mbsf; II: 183- 440 mbsf; III: 440-618 mbsf; and IV: 618-750 mbsf) are interpreted to have originated from changes in the suite of sediments of particular sources and chemical composition, sedimentation rate, dilution of biogenic carbonate abundance, and possibly the current system that controlled deposition and reworking of the terrigenous materials.

Zooplankton and seston in the White Sea and its chemical composition

A technique of zooplankton net sampling at night in the Kandalaksha and Dvinskii Bays and during the full tide in the Onezhskii Bay of the White Sea allowed us to obtain "clean" samples without considerable admixtures of terrigenous particulates. Absence of elements-indicators of the terrigenous particulates (Al, Ti, and Zr) in the EDX spectra allows to conclude that ash composition of tested samples is defined by constitutional elements comprising organic matter and integument (chitin, shells) of plankton organisms. A quantitative assessment of accumulation of ca. 40 chemical elements by zooplankton based on a complex of modern physical methods of analysis is presented. Values of the coefficient of the biological accumulation of the elements (Kb) calculated for organic matter and the enrichment factors (EF) relative to Clarke concentrations in shale are in general determined by mobility of the chemical elements in aqueous solution, which is confirmed by calculated chemical speciation of the elements in the inorganic subsystem of surface waters of Onezhskii Bay.

Composition and age of rocks from the King's Trough and Palmer Ridge

This paper presents results of studies of rocks sampled during Cruise 19 of R/V Akademik Mstislav Keldysh with the Mir submersibles in the Atlantic Ocean (slopes of the King's Trough and Palmer Ridge). Based on these materials and published data two stages of magmatism and evolution in the region are distinguished: 1) formation of a mid-ocean ridge in the rift zone (68-32 Ma); 2) development of intraplate volcanism during movement of the plate over a "hot spot" (32-0 Ma).

Chemical composition of mineral phases of serpentinized and steatized peridotite from the Mid Atlantic Ridge (15°20'N Fracture Zone, ODP Leg209)

Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H2,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H2O.We have compiled and evaluated thermodynamic data for Fe-Ni-Co-O-S phases and computed phase relations in fO2,g-fS2,g and aH2,aq-aH2S,aq diagrams for temperatures between 150 and 400°C at 50MPa.We use the relations and compositions of Fe-Ni-Co-O-S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15°20'N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awaruite- magnetite-pentlandite and heazlewoodite-magnetite-pentlandite assemblages forming in the early stages of serpentinization to millerite-pyrite-polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite-vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO2,g-fS2,g in the system follows an isopotential of H2S,aq, indicating that H2S in vent fluids is buffered. In contrast, H2 in vent fluids is not buffered by Fe-Ni-Co-O-S phases, which merely monitor the evolution of H2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite- awaruite-magnetite indicates H2,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

Chemical and isotopic compositions of sediments from DSDP Hole 21-204

The highly depleted intra-oceanic Tonga-Kermadec island arc forms an endmember of arc systems and a unique location in which to isolate the effects of the slab flux. High precision TIMS uranium, thorium, strontium, neodymium, and lead isotopes, along with complete major and trace element data, have been obtained on an extensive sample set comprising fifty-eight lavas along the arc as well as nineteen samples of the subducting sediments at DSDP site 204 just to the east of the Tonga-Kermadec trench. Ca/Ti and Al/Ti ratios extend from values appropriate to an N-MORB source in the southern Kermadecs to very high ratios in Tonga interpreted to reflect increasing degrees of depletion of the mantle wedge due to backarc basalt extraction. The isotope data emphasize the need for four components in the petrogenesis of the lavas: (1) the mantle wedge; (2) a component with elevated 207Pb/204Pb towards which the Kermadec and southern Tongan lavas extend; (3) a component characterised by high 206Pb/204Pb, Ta/Nd, and low 143Nd/144Nd observed only in the northernmost Tongan islands of Tafahi and Niuatoputapu; (4) a fluid component characterised by strong enrichments of Rb, Ba, U, K, Ph, and Sr, relative to Th, Zr, and the REE and producing large 238U excesses ((230Th/238U) = 0.8-0.5) in the more depleted lavas. The mantle wedge (Component 1) is isotopically similar to the source of the Lau BABB. Component 2 is average pelagic sediment on the downgoing Pacific plate as observed at DSDP sites 595/596 and in the upper sections of the sediment pile at DSDP site 204. Mass balance calculations indicate that less than 0.5% is recycled into the arc lavas; essentially all the subducted sediment is returned to the upper mantle (~0.03 km**3/yr). Exceptionally low concentrations of Ta and Nb relative to Th and the LREE requires that this sediment component is added as a partial melt which was in equilibrium with residual rutile or ilmenite. Component 3 is identified as volcaniclastics from the Louisville Ridge which comprise the lower 44 m of the sediment section intersected at DSDP site 204. These volcaniclastics are spatially restricted to the vicinity of the Louisville Ridge and provide a unique sediment tracer which can be used to show that it takes 4 Myr from the time of subduction to its first appearance in the arc lava signature. Component 4, the fluid contribution to the lava source is inferred to contribute ~1 ppm Rb, 10 ppm Ba, 0.02 ppm U, 600 ppm K, 0.2 ppm Ph, and 30 ppm Sr. It has 87Sr/86Sr = 0.7035 and 206Pb/204Pb = 18.5 and thus it is inferred to have been derived from dehydration of the subducting altered oceanic crust. U-Th isotope disequilibria reflect the time since fluid release from the subducting slab and a reference line through the lowest (230Th/232Th) lavas constrains this to be 30000-50000 yr. The U-Th and Th-Ra isotope systematics are decoupled, and it is suggested that Th-Ra isotope disequilibria record the time since partial melting and thus indicate rapid channelled magma ascent. Olivine gabbro xenoliths from Raoul are interpreted as cumulates to their host lavas with which they form zero age U-Th isochrons indicating that minimal time was spent in magma chambers. The subduction signature is not observed in lavas from the backarc island of Niuafo'ou. These were derived from partial melting of fertile peridotite at 130-160 km depth with melt rates around 0.0002 kg/m**3/yr.

Geochemistry at DSDP Leg 62 Holes

A total of 191 samples was collected for inorganic geochemical analyses from DSDP Holes 463, 464, 465, 465A, and 466. These samples were collected with two main goals. First, at least one sample was collected from each core, whenever possible, to document the general geochemical variability within lithologic units. Unfortunately, several lithologic units were inadequately sampled because of poor recovery, mostly due to the presence of chert. The least-sampled units are Units III in Hole 464 and Units IB and II in Hole 466. The second goal was to look for geochemical differences between contrasting lithologies within main lithologic units, particularly between cyclic interbeds of red and green limestone in Lithologic Unit II, Hole 463, and between olive, laminated limestone and gray, massive limestone in Lithologic Unit II, Hole 465A.

Composition of ocean suspended matter

Compositions of different types of ocean suspended matter are under consideration.