Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.

Description and chemical composition of manganese nodules sampled during the R/V "Vityaz" Expedition Vityaz-35

This paper presents data on the chemical composition of iron-manganese nodules and associated sediments collected during the 35th voyage of the R/V "Vityaz" in 1962. The samples were made available to the author by Prof, P. L. Bezrukov. Data on the general distribution of manganese nodules at the bottom of the Indian Ocean were already given by P. L. Bezrukov (1962, 1963). Here the author analyzed the geochemistry of nodules samples from seven stations and four samples from the associated sediments. The analysis separates the outer layer of nodules from their apparent internal core.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.

Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.

Mineral chemistry of primary and secondary phases in basaltic rocks

Primary magmatic phases (spinel, olivine, plagioclase, clinopyroxene, amphibole, and biotite) and secondary phyllosilicates (smectite, chlorite-smectite, and celadonite) were analyzed by electron microprobe in alkalic and tholeiitic dolerites and basalts from Ocean Drilling Program Sites 800, 801, and 802. Aphyric alkalic dolerite sills (Hole 800A) and basalt flows (Holes 801B and 801C) share common mineralogical features: matrix feldspars are strongly zoned from labradorite cores to discrete sodic rims of alkali feldspar with a high Or component, which overlaps that of quench microlites in glassy mesostasis; little fractionated clinopyroxenes are Ti-rich diopsides and augites (with marked aegirine-augite rims at Site 801); rare, brown, Fe**3+-rich amphibole is winchite; and late biotites exhibit variable Ti contents. Alkalic rims to feldspars probably developed at the same time as quenched mesostasis feldspars and late-stage magmatic biotite, and represent the buildup of K-rich hydrous fluids during crystallization. Phenocryst phases in primitive mid-ocean ridge tholeiites from Hole 801C (Mg numbers about 70) have extreme compositions with chrome spinel (Cr/Cr + Al ratios about 0.2-0.4), Ni-rich olivine (Fo90), and highly calcic plagioclase (An90). Later glomerophyric clumps of plagioclase (An75-80) and clinopyroxene (diopside-augite) are strongly zoned and probably reflect rapidly changing melt conditions during upward transport, prior to seafloor quenching. In contrast, phenocryst phases (olivine, plagioclase, and clinopyroxene) in the Hole 802A tholeiites show limited variation and do not have such primitive compositions, reflecting the uniform and different chemical composition of all the bulk rocks. Replacive phyllosilicates in both alkalic and tholeiitic basalts include various colored smectites (Fe-, Mg-, and Al-saponites), chlorite-smectite and celadonite. Smectite compositions typically reflect the replaced host composition; glass is replaced by brown Fe-saponites (variable Fe/Mg ratios) and olivine by greenish Mg-saponites (or Al-rich chlorite-smectite).

Geochemistry and mineralogy of ODP Leg 107 basalts

During ODP Leg 107, the basement of the Tyrrhenian Sea was drilled at Site 650, located in the Marsili basin, and at Sites 651 and 655, both located in the Vavilov basin. In addition, a lava flow was drilled at Site 654 on the Sardinia rifted margin. Mineral and whole rock major and trace element chemistry, including rare earth element (REE) and Sr and Nd isotopic ratios, were determined in samples of these rocks. Site 654 lava was sampled within uppermost Pliocene postrift sediments. This lava is a basaltic andesite of intraplate affinity, and is analogous to some Plio-Pleistocene tholeiitic lavas from Sardinia. Site 650 basalts, drilled beneath 1.7-1.9-Ma-old basal sediment, are strongly altered and vesicular suggesting a rapid subsidence of the Marsili basin. Based on incompatible trace elements, these basalts show calc-alkaline affinity like some products of the Marsili Seamount and the Eolian arc. The basement of the two sites drilled within Vavilov basin shows contrasting petrologies. Site 655, located along the Gortani ridge in the western part of the basin, drilled a 116-m-thick sequence of basalt flows beneath 3.4-3.6-Ma-old basal sediments. These basalts are chemically relatively homogeneous and show affinity to transitional MORB. Four units consisting of slightly differentiated basaltic lavas, have been identified. Site 655 basalts are geochemically similar to the high Ti lavas from DSDP Leg 42, Site 373 (Vavilov Basin). The basement at Site 651, overlain by 40 m of metalliferous dolostone covered by fossiliferous sediments with an age of 2 Ma, consists of two basalt units separated by a dolerite-albitite intrusive body; serpentinized harzburgites were drilled for 30 m at the base of the hole. The two basalt units of Site 651 are distinct petrochemically, though both show incompatible elements affinity with high-K calc-alkaline/calc-alkaline magmas from Eolian arc. The cpx chemistry and high K/Na ratio of the lower unit lavas suggest a weak alkaline tendency of potassic lineage. Leg 107 basement rock data, together with data from DSDP Site 373 and from dredged samples, indicate that the deepest basins of the central Tyrrhenian Sea are underlain by a complex back-arc basin crust produced by magmas with incompatible element affinities to transitional MORB (Site 655 and DSDP Site 373), and to calc-alkaline and high-K calc-alkaline converging plate margin basalts (Sites 650 and 651). This petrogenetic complexity is in accordance with the back-arc setting of the Vavilov and Marsili basins. Other back-arc basin basalts, particularly those from ensialic basins such as the Bransfield Strait (Antarctica), show a comparable petrogenetic complexity (cf., Sounders and Tarney, 1984).

Compositions of Ni-rich magnesiowüstite and coexisting magnesioferrite spinel from sediments of DSDP Holes 86-577 and 91-596

We have found trace inclusions of Ni-rich magnesiowüstite within grains of magnesioferrite spinel recovered from Cretaceous/Tertiary boundary sediments from DSDP Site 596, South Pacific (23°51.20'S, 169°39.27'W) and DSDP Site 577, North Pacific (3°6.51'N, 157°43.40'E). Measured compositions of these inclusions range from (Mg_0.85Ni_0.74Fe_0.17)O to (Mg_0.74Ni_0.09Fe_0.17)O. Coexisting magnesioferrite and magnesiowüstite can only crystallize from ultramafic, refractory, Mg-rich liquids with Mg/Si > 2 (atom ratio). Such liquid compositions cannot form as a result of fractional crystallization and are unknown to occur as a result of terrestrial igneous processes or meteoroid ablation. We infer that these minerals crystallized from liquid droplets that equilibrated with silicate vapor at high temperatures (probably >2300°C), resulting in fractionation of volatile SiO2 from more refractory MgO. The most plausible source of this high-temperature vapor is in the fireball of the major impact event that terminated the Cretaceous.

Major element concentrations in spinel, olivine and pyroxene from peridotites of ODP Hole 210-1277 of the Newfoundland margin

Serpentinized spinel peridotites of the Newfoundland margin drilled during ODP Leg 210 at Site 1277 have preserved, relic mineral compositions similar to the most depleted abyssal peridotites worldwide and different from those of the conjugate Iberian margin. The samples are derived from mass flows containing clasts of peridotite and gabbro and from in-situ basement, and are mostly mylonitic cpx-poor spinel harzburgites with Cr-rich spinels (Cr#0.35-0.66). Melting of the Newfoundland mantle occurred in the spinel peridotite field and probably exceeded the cpx-out phase boundary for some samples. Using proposed spinel peridotite melting models and experimentally derived phase diagrams, the Newfoundland harzburgites can be modeled as a residue after extraction of 14 to 20-25% melting. Basalts that are interleaved with mass flow deposits on top of the peridotite basement resemble normal to transitional mid-ocean ridge basalt. This, together with the unusually high Cr# of some spinel harzburgites suggest that the formation of basalts and partial melting of the underlying peridotite are not cogenetic. Among mantle samples some of the Newfoundland harzburgites approach mineral compositions of the Bay of island ophiolite and ophiolites from Japan that represent peridotites formed in an arc-setting. Thus, the peridotites drilled at Site 1277 may represent inherited (Caledonian or older) subarc mantle that was exhumed close to the ocean floor during the rifting evolution of the Atlantic. Compared to the spinel harzburgites from Newfoundland, the peridotites from the conjugate Iberian margin are, on average, less depleted and provide evidence for local equilibration in the plagioclase stability field. This can either be explained by an inherited, primary, Ca-richer composition of the Iberia peridotite, or, alternatively, by local melt impregnation and stagnation during continental rifting, and thus refertilizing previously depleted (arc-related) peridotite.

Petrology and geochemistry of peridotites from IODP Site 304-U1309

Peridotite samples recovered from IODP Site U1309 at the Atlantis Massif in the Mid-Atlantic Ridge were examined to understand magmatic processes for the oceanic core complex formation. Original peridotite was fragmented, and the limited short peridotite intervals are now surrounded by a huge gabbro body probably formed by late-stage melt injections. Each peridotite interval has various petrographical and geochemical features. A spinel harzburgite in contact with gabbro shows evidence of limited melt penetrations causing gradual compositional change, in terms of trace-element compositions of pyroxenes, as well as modal change near the boundary. Geochemistry of clinopyroxenes with least melt effects indicates that the harzburgite is originally mantle residue formed by partial melting under polybaric conditions, and that such a depleted peridotite is one of the components of the oceanic core complex. Some of plagioclase-bearing peridotites, on the other hand, have more complicated origin. Although their original features were partly overprinted by the injected melt, the original peridotites, both residual and non-residual materials, were possibly derived from the upper mantle. This suggests that the melt injected around an upper mantle region or into mantle material fragments. The injected melt was possibly generated at the ridge-segment center and, then, moved and evolved toward the segment end beneath the oceanic core complex.

Petrography and mineral compositions of gabbros at DSDP Leg 60 Holes

The compositions, mineralogies, and textures of gabbros recovered in polymict breccias in Hole 453 indicate that they are the cumulus assemblages of calc-alkalic crystal fractional on that occurred beneath the West Mariana Ridge. They are among a class of gabbros known only from other calc-alkalic associations (e.g., the Lesser Antilles and the Peninsular Ranges batholith of Southern California) and differ from gabbros of stratiform complexes, ophiolites, and the ocean crust. Particularly abundant in the Hole 453 breccias are olivine-bearing gabbros with extremely calcic Plagioclase (An94-97) but with fairly iron-rich olivines (Fo76-77). Other gabbros contain biotite and amphibole and occur in breccias with fairly high-grade greenschist facies (amphibole-chlorite-stilpnomelane) metabasalts. One unusual gabbro has experienced almost complete subsolidus recrystallization to an assemblage of aluminous magnesio-hornblende, anorthite, and green hercynitic spinel. This reaction, the extremely calcic Plagioclase, the occurrence of biotite and amphibole, and the association with greenschist facies metamorphic rocks suggest that crystallization of the gabbros occurred at elevated P(H2O). Comparisons with other calc-alkalic gabbro suites suggest pressures in excess of 4 kbar (about 12 km depth). The gabbros were exposed by the early stages of opening of the Mariana Trough and imply that considerable uplift may have attended rifting. They were also subjected to hydrothermal alteration after breccia formation, resulting in formation of chlorite, epidote, actinolite, and prehnite. Temperatures of at least 200°C - and probably 350°C - were reached, and most likely could not have been attained without extrusion or intrusion of magmas nearby, even though no such rocks were cored.

Chemical composition of minerals and rocks from the Sierra Leone segment of the Mid-Atlantic Ridge and from the Markov depression, Central Atlantic

Silicic Fe-Ti-oxide magmatic series was the first recognized in the Sierra Leone axial segment of the Mid-Atlantic Ridge near 6°N. The series consists of intrusive rocks (harzburgites, lherzolites, bronzitites, norites, gabbronorites, hornblende Fe-Ti-oxide gabbronorites and gabbronorite-diorites, quartz diorites, and trondhjemites) and their subvolcanic (ilmenite-hornblende dolerites) and, possibly, volcanic analogues (ilmenite-bearing basalts). Deficit of most incompatible elements in the rocks of the series suggests that parental melts derived from a source that had already been melted. Correspondingly, these melts could not be MORB derivatives. Origin of the series is thought to be related to melting of the hydrated oceanic lithosphere during emplacement of an asthenospheric plume (protuberance on the surface of large asthenospheric lens beneath MAR). Genesis of different melts was supposedly controlled by ascent of a chamber of hot mantle magmas thought this lithosphere in compliance with the zone melting mechanism. Melt acquired fluid components from heated rocks at peripheries of the plume and became enriched in Fe, Ti, Pb, Cu, Zn, and other components mobile in fluids.

Geochemistry of ODP Leg 135 basalts

Cr-spinels in cores drilled during Ocean Drilling Program Leg 135 exhibit wide variations in composition and morphology that reflect complex petrogenetic histories. These Cr-spinels are found within basaltic lava flows that erupted in north-trending sub-basins within the Lau Basin backarc. Cr-spinels from Sites 834 and 836 occur as euhedral groundmass grains and inclusions in plagioclase, and range up to 300 ?m in size. These Cr-spinels are similar in composition, morphology, and mode of occurrence to Cr-spinels found within depleted, N-type mid-ocean-ridge basalts (N-MORB), reflecting similar crystallization conditions and host lava composition to N-MORB. Their compositional range is relatively narrow, with Cr/(Cr + Al + Fe3+) (Cr#) and Mg/(Mg + Fe2+) (Mg#) varying from 0.38 to 0.48 and 0.56 to 0.72, respectively; like Cr-spinels from N-MORB, they contain low amounts of TiO2 (0.37%-1.05%) and Fe3+/(Cr + Al + Fe3+) (Fe3+#; <0.11). In contrast, Cr-spinels from Site 839 have much higher Cr# at a given Mg#, with Cr# varying from 0.52 to 0.76 and Mg# varying from 0.27 to 0.75. These Cr-spinels are similar in composition to those from primitive, boninitic or low-Al2O3 arc basalts, sharing their low TiO2 and Fe3+# (typically below 0.35% and 0.1, respectively for spinel grain interiors). Site 839 Cr-spinels occur as small (to 50 µm) euhedra within strongly zoned olivine or as unusually large (to 3 mm), euhedral to subhedral megacrysts. These megacrysts are strongly zoned in Mg#, but they display little zoning in Cr#, providing evidence of strong compositional disequilibria with the host melt. The magnesian cores of the megacrysts crystallized from primitive, near-primary melts derived from harzburgitic or highly depleted lherzolitic sources, and they provide evidence that the Site 839 spinel-bearing lavas were derived by the mixing of melt with a Mg# of 0.75-0.80 and evolved, Cr-spinel barren melt with a Mg# < 0.6 shortly before eruption.

Geochemical composition and atomic formulas of saponites, celadonites and carbonates from ODP Leg 168 sites

With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).