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 altered smectites

In basalts and volcanogenic sediments from the Indian Ocean, the successive stages of submarine alteration of volcanic rocks and glasses give rise to the incorporation or the relative increase of iron in smectite lattices. During the first stage, the Mg-smectites are the most abundant; they are occasionally associated with Al-smectites. Afterwards, they are gradually replaced by iron-rich smectites. The REE distribution follows the same trend as the mineralogical changes. During the f'trst stage of alteration, REE distribution in clay minerals is the same as in the fresh glasses but, when the iron-rich smectites increase, the Ce has a specific behaviour. The Ce shows a positive anomaly in iron-rich smectites formed early in palagonitized glasses, and a negative one in authigenic smectites formed later from solutions in equilibrium with seawater.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Geochemistry at DSDP Leg 60

Eocene to Pleistocene volcanogenic sediments from the Mariana Trough and the Mariana arc-trench system have been studied by X-ray diffraction, X-ray fluorescence, and atomic absorption, and with a scanning electron microscope with an X-ray-energy-dispersive attachment. The mineralogical composition of the volcaniclastic sediments (tuffs) is the same as that of the other associated sediments (mudstones). Diagenetic alterations are significant and seem to result from two processes. The first (low-temperature alteration) develops with age and depth; it consists of the genesis of pure smectite, coupled with zeolites (phillipsite, clinoptilolite). The second is limited to sediments immediately overlying basalts and to the altered basalts themselves. It consists of the massive development of palygorskite, and seems to be linked with hydrothermal activity in the igneous basement.

Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Geochemistry at DSDP Leg 59

Deep Sea Drilling Project Legs 59 and 60 drilled 15 sites along an east-west transect at 18°N from the West Philippine Basin to the Mariana Trench (Fig. 1) in order to study the nature and genesis of the back-arc, marginal basins and the remnant and active arcs of the region. Leg 59 drilled at five sites at the western end of the traverse: Site 447 in the West Philippine Basin; Site 448 on the Palau-Kyushu Ridge; Sites 449 and 450 in the Parece Vela Basin; and Site 451 on the West Mariana Ridge. Penetration into basaltic basement of these sites was 183.5 meters at 447 (8 basalt flows); 623 meters at 448 (46 basalt flows, sills, and dikes and volcaniclastic units); 40.5 meters at 449 (2 basalt flows); 7 meters at 450 (1 basalt intrusion); and 4 meters of basalt breccia at 451 overlain by 861 meters of volcaniclastic sedimentary rocks.

Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Composition and properties of rocks and sediments from the Cape Verde fracture zone

The book presents results of comprehensive geological and geophysical studies, carried out in the Cape Verde fault zone in the 3-rd cruise of R/V Akademik Nikolaj Strakhov (1986). Detailed characterization of bottom relief, thickness and structure of the sedimentary cover, magnetic field, crust structure, lithology and stratigraphy of sediments, petrography and geochemistry of magmatic rocks. Conclusions about tectonic layering of the crust and upper mantle in the fault zone, and about a concurrent structural section of large mantle inhomogeneities have been done. The book is the first monographic description of a major fault structure of the ocean floor.

Age and isotopic and chemical compositions of volcanic rocks from the Japan and Okhotsk Seas

This paper reports results of petrographic and geochemical studies of Miocene-Pleistocene volcanic rocks that accompanied formation of deep-water basins of the Sea of Japan and Sea of Okhotsk. Geochemical types of these rocks, their geodynamic settings, and their derivation from different magmatic sources were determined. Marginal-sea basaltoids from the Sea of Japan are derivatives of fluid-enriched mantle (EMI), while volcanics from the Kuril basin were generated from mantle enriched in continental crust matter (EMU). In spite of different conditions of their genesis, they have some common geochemical features, in particular, their calc-alkaline signatures. These traces of influence of the sialic crust on magma generation confirm development of the basins of both these seas on the continental basement.

Chemical composition of ferromanganese nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied by transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese oxyhydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. Oxyhydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Concentrations of Mn, As, and Mo are 12-18 times higher relative to sediments, while concentrations of Fe, P, Ni, and Co increase 5-7 times during nodule formation.

Geochemistry of clinopyroxene megacrysts, xenocrysts, and phenocrysts in diabase dikes from ODP Hole 140-504B

We report the major, rare earth, and other trace element compositions of clinopyroxenes from two Leg 140, Hole 504B diabase dikes. These pyroxenes reflect a complex history of crystal growth and magma evolution. The large ranges of composition found reflect incorporation of exotic phenocrysts into the melt, the early formation of crystal clots before dike intrusion during an undercooling event, and in-situ fractionation of melt during and following dike emplacement. Some of the pyroxenes occur in coarse two- and three-phase glomerocrysts, which may be ôprotogabbrosö representing early stages of melt crystallization in the lower crust. Large variations in trace element composition are found. These likely reflect heterogeneous nucleation and growth of plagioclase and pyroxene in the melt, as well as complex interface kinetics that may affect partition coefficients during rapid crystal growth expected during undercooling. This can explain the formation of irregular chemical sector zoning in some equant anhedral phenocrysts. Undercooling of magmas in the lower crust most likely reflects input of fresh hot melt into a stagnating melt-storage zone. Dikes intruded upward from an inflated melt-storage zone during such a cycle are likely to be larger than those intruded from the storage zone between such cycles, when it would be deflated, consistent with the greater overall thickness of the phyric dikes in the Leg 140 section of Hole 504B.

Petrology and geochemistry of basalt at DSDP Hole 66-487

Major oxide and trace element determinations of the composition basalts from the bottom of Hole 487, together with microprobe analyses of their minerals (olivine, magnesiochromite, salite, and plagioclase), prove that they are depleted oceanic tholeiites.