798 resultados para Doped manganese oxide
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We examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic Cd inventory, thereby decoupling Cd from PO4. We suggest that the precipitation of Cd-sulfide in suboxic sediments is the single largest sink in the oceanic Cd budget and that the accumulation of authigenic Cd and U is tightly coupled to the organic carbon flux into the seafloor. Sediments from the Subantarctic Ocean and the Cape Basin (South Atlantic), where oxic conditions currently prevail, show high accumulation rates of authigenic Cd and U during glacial intervals associated with increased accumulation of organic carbon. These elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon. A third core, overlain by Circumpolar Deep Water (CPDW) as are the other two cores but located south of the Antarctic Polar Front, shows an approximately inverse pattern to the Subantarctic record. The contrasting patterns to the north and south of the Antarctic Polar Front suggest that higher accumulation rates of Cd and U in Subantarctic sediments were driven primarily by increased productivity. This proposal is consistent with the hypothesis of glacial stage northward migration of the Antarctic Polar Front and its associated belt of high siliceous productivity. However, the increase in authigenic Cd and U glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts, suggesting greater partitioning of organic carbon into the sediments during glacial intervals. Lower oxygen content of CPDW and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes. Higher glacial productivity in the Cape Basin record very likely reflects enhanced coastal up-welling in response to increased wind speeds. We suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum. However, our calculations suggest low sensitivity of seawater Cd concentrations to glacial doubling of the extent of reducing sediments. The model suggests that during the last 250 kyr seawater Cd concentrations fluctuated only slightly, between high levels (about 0.66 nmol/kg) on glacial initiations and reaching lowest values (about 0.57 nmol/kg) during glacial maxima. The estimated 5% lower Cd content at the last glacial maximum relative to modern levels (0.60 nmol/kg) cannot explain the discordance between Cd and delta13C, such as observed in the Southern Ocean. This low sensitivity is consistent with foraminiferal data, suggesting minimal change in the glacial Cd mean oceanic content.
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Depth profiles of major element and rare earth element (REE) abundances in sediment samples (mainly siliceous ooze and clay) recovered from Holes 1179B and 1179C at Site 1179, Ocean Drilling Program Leg 191 (41.4°N, 159.6°E) were determined. The oxidation states of Mn and Ce were determined by X-ray absorption near-edge structure. Some geochemical indicators were tested, including the MnO/TiO2 ratios, a bivariate diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), and other discrimination diagrams. The oxidation state of Mn is reduced Mn(II) in the depth profile below 0.60 meters below seafloor (mbsf), which is consistent with relatively low and high abundances of Mn in the sediments and pore waters, respectively. It is possible that the diagenetic effect on the oxidation state and abundance of Mn makes it difficult for the MnO/TiO2 ratio to reflect the depositional environment. The normalized ratio of La and Ce does not change very much with depth, suggesting that the diagenetic effect does not affect the REE signature in the sediments. On the diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), the sediments studied here plot at the boundary of the pelagic and continental margin fields. This suggests that continental material has contributed to the sediment to some degree, even though Site 1179 is in a pelagic region of the northwestern Pacific Ocean, >1600 km from Japan.
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Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.
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Detection of climate response to orbital forcing during Cenozoic long-term global cooling is a key to understanding the behavior of Earth's icehouse climate. Sedimentary rhythm, which is a rhythmic or cyclic variation in the sequence of sediments and sedimentary rocks, is useful for quantitative reconstruction of Earth's evolution during geological time. In this study, we attempt to (1) identify sources of natural gamma ray (NGR) emissions of core recovered during Ocean Drilling Program (ODP) Leg 186 by analyses of physical properties, major element concentrations, diatom abundances, and total organic carbon contents, (2) integrate whole-core NGR intensity of recovered core with wireline logging NGR measurements in order to construct a continuous sedimentary sequence, and (3) discuss changes in the NGR signal in the time domain. This attempt gives us preliminary information to discuss climate stability in relation to orbital forcing thorough geologic time. NGR values are obtained mainly by indirectly measuring the amount of terrigenous minerals including potassium and related elements in the sediments. NGR intensity is also affected by high porosity, which in these sediments was related to the amount of diatom valves. NGR signals might be a proxy of the intensity of the East Asian monsoon off Sanriku. A continuous sedimentary record was constructed by integration of the whole-core NGR intensity measured in sediments obtained from the drilled holes with that measured directly in the borehole by wireline logging, then using a stratigraphic age model to convert to a time series covering 1.3-9.7 Ma with a short break at ~5 Ma. High sedimentation rate (H) stages were identified in the sequence, related to intervals of low-amplitude precession and eccentricity variations. The transition of the dominant periodicities through the four H stages may correlate to major shifts in the climate system, including the onset of major Northern Hemisphere glaciation, the initial stage of the East Asian monsoon intensification, and the onset of the East Asian monsoon with uplift of the Himalayas and the Tibetan Plateau.
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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.
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57Fe Mössbauer spectra for 26 sediment and 6 carbonate concretion samples from Sites 798 and 799 were recorded at 293 K. Most spectra were deconvolved to two quadrupole doublets without magnetic hyperfine structure. Typical Mössbauer parameters were: isomer shift (I.S.) = 0.34 mm/s and quadrupole splitting (Q.S.) = 0.64 mm/s for the paramagnetic Fe3+ component (partly, pyrite); I.S. = 1.13 mm/s and Q.S. = 2.64 mm/s for the high-spin Fe2+ component derived from iron-bearing aluminosilicates. A few spectra included other high-spin Fe2+ components ascribed to iron-bearing carbonate minerals (e.g., ferroan magnesite), according to the Mössbauer parameters for Fe2+ in the carbonate concretions. We present the distribution of iron among different chemical forms as a function of depth. These data might indicate changes of depositional and diagenetic conditions.
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This report presents all the available major and trace elemental analyses and Sr, Nd, and Pb isotopic compositions of basaltic rocks recovered from Ocean Drilling Program Sites 800, 801, and 802 during Leg 129 (Table 1). Its main purpose is to provide other investigators a complete summary of geochemical data for Leg 129 basement basalts that they can use for later work. Detailed discussions of the data are presented elsewhere in the volume by Floyd and Castillo (Site 801 geochemistry and petrogenesis, dataset: doi:10.1594/PANGAEA.779154) Floyd et al. (Sites 800 and 802 geochemistry and petrography, dataset: doi:10.1594/PANGAEA.779129), Alt et al. (Site 801 alteration, dataset: doi:10.1594/PANGAEA.779207), and Castillo et al. (Sr, Nd, and Pb isotope geochemistry of Leg 129 basalts, dataset: doi:10.1594/PANGAEA.779191).
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Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.
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New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.
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We present a synthesis of some 20,504 mineral analyses of ~500 Hole 735B gabbros, including 10,236 new analyses conducted for this paper. These are used to construct a mineral stratigraphy for 1.5-km-deep Hole 735B, the only long section of the lower crust drilled in situ in the oceans. At long wavelengths, generally >200 m, there is a good chemical correlation among the principal silicate phases, consistent with the in situ crystallization of three or four distinct olivine gabbro bodies, representing at least two major cycles of intrusion. Initial cooling and crystallization of these bodies must have been fairly rapid to form a crystal mush, followed by subsequent compaction and migration of late iron-titanium-rich liquids into shear zones and fractures through which they were emplaced to higher levels in the lower crust where they crystallized and reacted with the olivine gabbro host rock to form a wide variety of ferrogabbros. At the wave lengths of the individual intrusions, as represented by the several olivine gabbro sequences, there is a general upward trend of iron and sodium enrichment but a poor correlation between the compositions of the major silicate phases. This, together with a wide range in minor incompatible and compatible element concentrations in olivine and pyroxene at a given Mg#, is consistent with widespread permeable flow of late melt through these intrusions, in contrast to what has been documented for a 600-m section of reputedly fast-spreading ocean crust in the Oman Ophiolite. This unexpected finding could be related to enhanced compaction and deformation-controlled late-stage melt migration at the scale of intrusion at a slow-spreading ocean ridge, compared to the relatively static environment in the lower crust at fast-spreading ridges.
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During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.
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Distribution trace element contents in the upper (up to 5 m) Holocene-Upper Pleistocene sediment layer along the northern and southern sublatitudinal profiles in the northern part of the Deryugin Trough is discussed. Mathematical processing of chemical analysis data has been made. On the basis of the cluster analysis 16 elements have been combined into 5 geochemical groups. Two of them (1 - Ag-Mo group and 2 - Mn-Ba-Ni-Sr group) were considered in detail. Analysis of Ag and Mo distributions in the sediments and findings of molybdenite permitted to conclude that enrichment of the sediments by these elements resulted from edaphic washing of magmatic rocks containing Ag-Mo mineralization and probably located on the northwestern slope of the Deryugin trough. The second geochemical group is most likely connected with hydrothermal barite mineralization found in the northeastern part of the Deryugin trough. Considering Mn distribution in bottom sediment cores supply of Mn was pulsating. This allows concluding that during Holocene - Late Pleistocene three cycles of hydrothermal activity occurred in the Deryugin Trough, and the most intensive one was in Holocene.
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New data on microstructures and mineral and chemical compositions of ferromanganese crusts sampled from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. Lithic mineral assemblage includes apatite, quartz, epidote, and montmorillonite. According to chemical analysis most of the crusts contain significant part of volcanogenic and hydrothermal material. It is evident from elevated values of Mn/Fe and (Mn+Fe)/Ti ratios, low concentrations of some trace elements, and positive Eu anomaly.
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Research of the ocean floor using the Mir submersibles carried out south of the Hawaiian Archipelago allowed to recover flows of recent picrite basalts. Lava vents are confined to a field of development of open fractures of a gjar type. Basalts represent initial lava flows in the structure of the Hawaiian volcanic archipelago. Considering contents of alkali and rare-earth elements in them, the picrite basalts of the bottom could be assigned to a series of island tholeiites. They are products of high level melting of asthenospheric matter at depth about 75-80 km as a result of decompression near a deep fracture that occurred in the lithosphere and asthenosphere. Similar picrite basalts were found in the base of the youngest volcano of the Hawaiian chain the Loihi Volcano. With respect to contents of alkali metals, these rocks are assigned to the subalkaline series of rocks formed during melting of garnet lherzolites. This could probably be explained by supply of melts from deeper levels of the asthenosphere after partial packing of an initial magma effluent fracture.