Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

Fe-Mn nodules and host sediments from the Gulf of Finland

Distributions of major and trace elements in ferromanganese nodules, which are buried or exposed on the sea floor and in host sediments, were studied in ten concretion/sediment pairs by various physical and chemical methods. It was established that, in addition to Fe and Mn, a limited number of major and trace elements (P, Ca, Sr, Ba, Mo, Co, Zn, Ni, As, Pb, Sb, Tl, U, W, Y, and Ga) is accumulated with variable degree of intensity (relative to sediments) in the nodules. The maximal content of Mn in the nodules is 100 times higher than in the host sediments, whereas for all other elements listed above these ratios vary from more than one to 10-20. Manganese and, to a lesser extent, Ba and Sr are concentrated in the buried concretions. Other elements are primarily concentrated in concretions exposed on the sea floor. The occurrence mode of the concretions and compositional data on interstitial water suggest that metals in the concretions derive from seawater and suspended particulates, in addition to sediments. Burial of concretions in the sediment pile is accompanied by alteration of their composition, accumulation of Mn (relative to Fe), and loss of several associated metals.

Mineral and chemical compositions of hydrothermal ores and sediments from the Menez Gwen Hydrothermal Field, Mid-Atlantic Ridge

Mineralogy and geochemistry of sulfide-bearing rocks and ores discovered within the Menez Gwen Hydrothermal Field are studied. Samples were taken during Cruise 49 of R/V Akademik Mstislav Keldysh of the p.p. Shirshov Institute of Oceanology. Mineral composition of rocks and ores were studied by traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by laser ablation inductively coupled plasma - mass spectrometry (LA-ICP-MS). Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in volcanomictic layered gritstones and/or barite slabs. Mineral composition, zonality and association of trace elements in ore are typical of black smokers formed at the basalt base near the Azores Triple Junction in the MAR. Obtained results make it possible to reconstruct formation history of the Menez Gwen Hydrothermal Field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO2 association) stages.

Composition of rocks, minerals, water, and gases from uplift areas of the Central Atlantic

Original geological, geophysical, lithological, mineralogical data on uplifts of the Central Atlantic are given in the book based on materials of Cruise 1 of the R/V Akademik Nikolaj Strakhov. Geological and geophysical studies include description of the obtained material and analysis of structural and morphological elements of the ocean floor. Results of lithological, petrochemical and geochemical studies were extremely innovative and develop a conceptual model. The latter include studies of petrochemical evolution of tholeiitic alkaline plate volcanism, large-scale hydrothermal transformation of basement rocks - palygorskitization, phosphatization and ferromanganese mineralization. Showing imposition Superposition of hydrogenic alteration on hydrothermally altered rocks and its role in Cenozoic history of sedimentation is shown.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Chemical composition of bottom sediments from the Baltic Sea

According to geochemical analyses carbonaceous sediments from deep basins of the Baltic Sea containing 3-5% of organic carbon are enriched in some metals such as Cu, Mo, Ni, Pb, Zn, V, and U relative to shallow-water facies of the Bay of Finland. These metals also enrich (relative to background values in clayey rocks) ancient carbonaceous shales, where the average Cu and V contents are slightly higher and that of Mo, Pb, and Zn lower than in deep-sea carbonaceous sediments of the Baltic Sea. In addition, the deep-sea carbonaceous sediments of the Baltic Sea are enriched (but less notably than ancient shales) in Ag, As, Bi, and Cd. These data confirm previous assumptions that carbonaceous sediments accumulating now in seas and oceans can be considered as recent analogs of ancient metalliferous shales.

Salinity and SO4 and Br enrichment of seawater and frost flowers near Barrow, Alaska

Frost flowers have been proposed to be the major source of sea-salt aerosol to the atmosphere during polar winter and a source of reactive bromine during polar springtime. However little is known about their bulk chemical composition or microstructure, two important factors that may affect their ability to produce aerosols and provide chemically reactive surfaces for exchange with the atmosphere. Therefore, we chemically analyzed 28 samples of frost flowers and parts of frost flowers collected from sea ice off of northern Alaska. Our results support the proposed mechanism for frost flower growth that suggests water vapor deposition forms an ice skeleton that wicks brine present on newly grown sea ice. We measured a high variability in sulfate enrichment factors (with respect to chloride) in frost flowers and seawater from the vicinity of freezing sea ice. The variability in sulfate indicates that mirabilite precipitation (Na2SO4 x 10 H2O) occurs during frost flower growth. Brine wicked up by frost flowers is typically sulfate depleted, in agreement with the theory that frost flowers are related to sulfate-depleted aerosol observed in Antarctica. The bromide enrichment factors we measured in frost flowers are within error of seawater composition, constraining the direct reactive losses of bromide from frost flowers. We combined the chemical composition measurements with temperature observations to create a conceptual model of possible scenarios for frost flower microstructure development.

Geochemistry of ODP Hole 135-839B lavas

Four petrographic lava types occur, ranging from aphyric to moderately phyric clinopyroxene-olivine tholeiitic basalts (Unit 1); olivine-clinopyroxene picritic basalts, sparsely to strongly olivine-phyric (Unit 3-type); olivine-clinopyroxene basalts (clinopyroxene dominant) (Unit 4); and moderately to strongly phyric two-pyroxene-plagioclase basaltic andesites (Unit 9-type). The olivine phyric lavas contain forsteritic olivines (extending to Fo92), and very magnesian Cr-rich spinels similar to those occurring in boninitic lavas. The basaltic andesites are mineralogically and petrographically indistinguishable from the modern Tofua Arc basaltic andesites, one notable feature being the highly calcic cores in plagioclase phenocrysts (up to An95). The forsteritic olivines, the Cr-spinels, and the calcic plagioclases are unlikely to have been precipitated in the lava compositions in which they occur, and are thought to have been incorporated from highly primitive melts by way of mixing processes (as advocated by Allan, this volume). Notwithstanding the evidence for mixing, the major element chemistries of the Unit 1- and Unit 9-type lavas are shown to be consistent with the derivation of the Unit 9-type basaltic andesites by means of fractional crystallization, through magmas of similar chemistry to Unit 1. Some trace element discrepancies in the modeling, and the relative volcanic stratigraphy of Site 839, however, preclude a direct liquid line of descent between the actual recovered units. Trace element data as well as TiO2 and Na2O data clearly illustrate the arc-like affinities of the magmas, with strong highfield-strength element depletion and large-ion-lithophile element enrichment. The abundance patterns are very close to those of the Tofua and Kermadec arc magmas, and also Valu Fa. Pb-, Sr-, and Nd-isotopic compositions indicate closest affinities with a "Pacific" MORB source, apparently characteristic of the western, older part of the Lau Basin. A subduction-related isotopic contribution is, however, inferred. The sources of the Site 839 magmas are thus inferred to be similar to, but less depleted geochemically, than those of the modern Tofua Arc magmas. The Site 839 sequence is interpreted as an older remnant of a volcanic construct of the "proto-Tofua arc", originally developed adjacent to the Tonga Ridge. Opening of the eastern Lau Basin, because of southward migrating propagators, has split and isolated the sequence, leaving it stranded within the modern Lau Basin.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Geochemistry of ODP Site 135-834 basalts

New major, trace element, and isotope data (Pb, Sr, and Nd) reveal an impressive compositional variation in the basalts recovered from Site 834. Major element compositions span almost the entire range observed in basalts from the modern axial systems of the Lau Basin, and variations are consistent with low-pressure fractionation of a mid-ocean-ridge-basalt (MORB)-like parent, in which plagioclase crystallization has been somewhat suppressed. Trace element compositions deviate from MORB in all but one unit (Unit 7) and show enrichments in large-ion-lithophile elements (LILEs) relative to high-field-strength elements (HFSEs) more typically associated with island-arc magmas. The Pb-isotope ratios define linear trends that extend from the field of Pacific MORB to highly radiogenic values similar to those observed in rocks from the northernmost islands of the Tofua Arc. The Sr-isotope compositions also show significant variation, and these too project from radiogenic values back into the field for Pacific MORB. The variations in key trace element and isotopic features are consistent with magma mixing between two relatively mafic melts: one represented by Pacific MORB, and the other by a magma similar to those erupted on 'Eua when it was part of the original Tongan arc, or perhaps members of the Lau Volcanic Group (LVG). Based on our model, the most radiogenic compositions (Units 2 and 8) represent approximately 50:50 mixtures of these MORB and arc end-members. Magma mixing requires that both components are simultaneously available, and implies that melts have not shown a compositional progression from arc-like to MORB-like with extension at this locality. Rather, it is apparent that essentially pristine MORB can erupt as one of the earliest products of backarc initiation. Indeed, repetition of isotopic and trace element signatures with depth suggests that eruptions have been triggered by periodic injections of fresh MORB melts into the source regions of these magmas. The slow and almost amagmatic extension of the original arc complex envisaged to explain the observed chemistry is also consistent with the horst-and-graben topography of the western side of the Lau Basin. Given the similarities between basalts erupted at the modern Lau Basin spreading centers and MORB from the Indian Ocean, the overwhelming evidence for involvement of mantle similar to Pacific MORB in the petrogenesis of basalts from Site 834 is a new and important observation. It indicates that the original arc was underlain by asthenospheric material derived from the Pacific mantle convection cell, and that this has somehow been replaced by Indian Ocean MORB during the last ~5.5 Ma.