Volcanic ash from the Peru continental margin

During Leg 112 off Peru, volcanic material was recorded from middle Eocene to Holocene time. The petrographical and chemical composition of tephra is consistent with an origin from the Andean volcanic arc. The amount and thickness of ash layers provide valuable evidence for explosive volcanic episodicity. The first indication of volcanism was found in mid-Eocene sediments. Three volcanic pulses date from Miocene time. Two intense episodes took place in upper Pliocene and from Pleistocene to Holocene time. Pliocene-Pleistocene tephra are restricted to the southern upper-slope and shelf sites, indicating a removal of the volcanic arc and the extinction of the northern Peru volcanoes. The Cenozoic tectonic phases of the Andean margin may be correlated with the Leg 112 volcanic records. The explosive supply of evolved magmatic products succeeded the Incaic and Quechua tectonic phases. Acidic glasses are related to both andesitic and shoshonitic series. The calc-alkaline factor (CAF) of these glasses exhibited moderate magmatic variations during middle and late Miocene time. A dramatic change occurred during the Pliocene-Pleistocene, reflected in a strong CAF increase and the appearance of potassium-rich evolved shoshonitic glasses. This took place when the Nazca Ridge subduction began. This change in the magma genesis and/or differentiation conditions is probably related to thickening of the upper continental plate and to a new configuration of the Benioff Zone.

Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Pedogeomorphology, geochronology and paleobotany of soil profiles obtained in the Nagqu area, central Tibet

Vast areas on the Tibetan Plateau are covered by alpine sedge mats consisting of different species of the genus Kobresia. These mats have topsoil horizons rich in rhizogenic organic matter which creates turfs. As the turfs have recently been affected by a complex destruction process, knowledge concerning their soil properties, age and pedogenesis are needed. In the core area of Kobresia pygmaea mats around Nagqu (central Tibetan Plateau, ca. 4500 m a.s.l.), four profiles were subjected to pedological, paleobotanical and geochronological analyses concentrating on soil properties, phytogenic composition and dating of the turf. The turf of both dry K. pygmaea sites and wet Kobresia schoenoides sites is characterised by an enrichment of living (dominant portion) and dead root biomass. In terms of humus forms, K. pygmaea turfs can be classified as Rhizomulls mainly developed from Cambisols. Wet-site K. schoenoides turfs, however, can be classified as Rhizo-Hydromors developed from Histic Gleysols. At the dry sites studied, the turnover of soil organic matter is controlled by a non-permafrost cold thermal regime. Below-ground remains from sedges are the most frequent macroremains in the turf. Only a few pollen types of vascular plants occur, predominantly originating from sedges and grasses. Large amounts of microscopic charcoal (indeterminate) are present. Macroremains and pollen extracted from the turfs predominantly have negative AMS 14C ages, giving evidence of a modern turf genesis. Bulk-soil datings from the lowermost part of the turfs have a Late Holocene age comprising the last ca. 2000 years. The development of K. pygmaea turfs was most probably caused by an anthropo(zoo)-genetically initiated growth of sedge mats replacing former grass-dominated vegetation ('steppe'). Thus the turfs result from the transformation of pre-existing topsoils comprising a secondary penetration and accumulation of roots. K. schoenoides turfs, however, are characterised by a combined process of peat formation and penetration/accumulation of roots probably representing a (quasi) natural wetland vegetation.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Chemistry of peridotites from ODP Hole 109-670A

Two types of serpentinized peridotites from Hole 670A of Leg 109 were studied in detail. A small piece of relatively unaltered sample, 109-670A-9R-1, #3 (22-24 cm), is olivine websterite characterized by aluminous chromian spinel with Cr/(Cr + Al) ratio of about 0.2. The other minerals have compositions essentially identical with those in more commonly observed serpentinized harzburgite like 109-670A-9R-01, #12 (94-97 cm). The occurrence of pyroxene-rich peridotite with normal harzburgite suggests that small scale heterogeneity in modal compositions exists in the upper mantle beneath the Mid-Atlantic Ridge. Low Cr/Al ratios of spinel and pyroxenes of those peridotites indicate that they are relatively less refractory among peridotites ever recovered from the oceanic region. Textures and the estimated equilibration temperatures indicate that peridotites recovered from Hole 670A are recrystallized and reequilibrated at subsolidus temperature. The occurrence of serpentinized peridotites from the rift valley of the active mid-oceanic ridge may suggest that they represent direct exposure of upwelling mantle materials rather than serpentine diapirs.

Geochemistry of igneous rocks recovered from a transect across the Mariana Trough, arc, fore-arc, and trench, at DSDP Leg 60 Holes and DM17

Major and trace element analyses are presented for 110 samples from the DSDP Leg 60 basement cores drilled along a transect across the Mariana Trough, arc, fore-arc, and Trench at about 18°N. The igneous rocks forming breccias at Site 453 in the west Mariana Trough include plutonic cumulates and basalts with calc-alkaline affinities. Basalts recovered from Sites 454 and 456 in the Mariana Trough include types with compositions similar to normal MORB and types with calc-alkaline affinities within a single hole. At Site 454 the basalts show a complete compositional transition between normal MORB and calc-alkaline basalts. These basalts may be the result of mixing of the two magma types in small sub-crustal magma reservoirs or assimilation of calc-alkaline, arc-derived vitric tuffs by normal MORB magmas during eruption or intrusion. A basaltic andesite clast in the breccia recovered from Site 457 on the active Mariana arc and samples dredged from a seamount in the Mariana arc are calc-alkaline and similar in composition to the basalts recovered from the Mariana Trough and West Mariana Ridge. Primitive island arc tholeiites were recovered from all four sites (Sites 458-461) drilled on the fore-arc and arc-side wall of the trench. These basalts form a coherent compositional group distinct from the Mariana arc, West Mariana arc, and Mariana Trough calc-alkaline lavas, indicating temporal (and perhaps spatial?) chemical variations in the arc magmas erupted along the transect. Much of the 209 meters of basement cored at Site 458 consists of endiopside- and bronzite-bearing, Mg-rich andesites with compositions related to boninites. These andesites have the very low Ti, Zr, Ti/Zr, P, and rare-earthelement contents characteristic of boninites, although they are slightly light-rare-earth-depleted and have lower MgO, Cr, Ni, and higher CaO and Al2O3 contents than those reported for typical boninites. The large variations in chemistry observed in the lavas recovered from this transect suggest that diverse mantle source compositions and complex petrogenetic process are involved in forming crustal rocks at this intra-oceanic active plate margin.

Petrology of basalts from DSDP Hole 66-487

Basaltic rocks recovered at the Middle America Trench area off Mexico are typical plagioclase-olivine phyric abyssal tholeiites containing less than 0.2 wt.% K2O. Phenocrysts of plagioclase and olivine usually make up the aggregate. Plagioclase phenocrysts are Ca-rich and up to An90. Olivine phenocrysts, which are always attached to plagioclase phenocrysts, are magnesian, Fo88 to Fo89, and contain 0.2 to 0.3 wt. % of NiO. Plagioclase phenocrysts contain numerous glass inclusions with the Mg/Mg+Fe atomic ratio of 0.70 to 0.73, which is distinctly higher than the same ratio of the bulk rock (0.62-0.63). Olivine of Fo88 to Fo89 is equilibrated with the liquid with an Mg/Mg+Fe atomic ratio of about 0.7, assuming the KDMg-Fe between liquid and olivine of 0.3. Small droplets of glass within glass inclusions in plagioclase are more enriched in K2O and volatiles than the host glass. This enrichment may have been caused by the extraction of Al2O3 as plagioclase from the trapped liquid and implies its immiscibility. Aggregates of plagioclase with small amounts of olivine may have been floated from more primitive magma with an Mg/Mg+Fe atomic ratio of about 0.7, judging from the chemical characteristics mentioned above. Flotation must have occurred at relatively high pressure. Large crystals of plagioclase and smaller crystals of olivine are xenocryst rather than phenocryst. Parental magma of Leg 66 basalt was high-MgO olivine tholeiite.

Geochemistry of ash layers from the Bonin Forearc

Many ash-rich layers, varying from a few millimeters to several centimeters thick, were identified in the sedimentary sequences penetrated during Ocean Drilling Program Leg 125 at Sites 782, 784, and 786, located about 400 to 500 km south of Tokyo in the Bonin forearc. The total age range of the ash layers is from Eocene to Pleistocene, although not all sites cover this full span. The ashes consist of vitric, microlite-bearing, and crystal-rich components; the glassy shards are typically highly vesicular, with elongate, flattened bubbles. The dominant crystalline phases are orthopyroxene, clinopyroxene, and plagioclase. The major-element compositions of individual vitric shards collected from selected layers of Holes 782A, 784A, and 786A were determined by electron microprobe analyses; particular care was taken to ensure that the analytical results were not compromised by electron beam damage to the glasses. Compositions range from basalt through andesite and dacite to rhyolite and generally belong to a tholeiitic, low-K suite. There is no indication of any regular secular change during the evolution of the Bonin arc from tholeiitic through calc-alkalic to alkali compositions with time. In Holes 782A and 784A, some high-K rhyolite compositions of late Miocene and Pleistocene age are present. A clear chemical distinction has existed since arc inception between the source(s) of these ashes and the upper mantle source(s) tapped during construction of the igneous basement that formed the forearc.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Chemical composition of manganese nodules from the Southern Pacific

Deep sea manganese nodules from the Southern Ocean have been studied using chemical analysis, X-ray diffraction, optical mineragraphic and electron probe microanalysis techniques. The nodules were lower in manganese, iron and associated elements than the average grade of manganese nodules from other localities. A number of chemical relationships have been observed. Nickel, copper, cobalt, barium, zinc, molybdenum, strontium, sulphur and phosphorus are associated with the manganese rich phases and titanium with the iron rich phases. X-ray diffraction analysis and electron probe microanalysis results indicate that the manganese phases are similar to the disordered delta-MnO2 and "manganite" phases reported by other workers.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Chemical composition of hydrogarnet and celadonite from ODP Hole 206-1256D

Mid-ocean-ridge basalts recovered from Hole 1256D during Ocean Drilling Program Leg 206 exhibit the effects of various low-temperature (<100°C) alteration processes, including the formation of black or dark green alteration halos adjacent to celadonite-bearing veins. In several samples from the deepest basalts, a Ti-rich hydrogarnet occurs. To our knowledge, such a mineral has never been reported in the oceanic crust. This report presents a brief description and microprobe analyses of this hydrogarnet and associated celadonite. More detailed characterizations of this mineral and a description of its relationship to other secondary minerals will be undertaken in a future study, in an attempt to determine the mineral's formation conditions and its place in the general alteration history of the Hole 1256D basalts.

Petrology and relict mineralogy of serpentinites at DSDP Leg 84 Holes

Eleven serpentine samples from DSDP Leg 84 and four serpentinized ultramafic samples from Costa Rica and Guatemala were described and their relict mineral compositions measured by electron microprobe to try to determine the origin of the Leg 84 serpentinites and their relationship to the ultramafic rocks of the onshore ophiolites. The Leg 84 samples comprise more than 90% secondary minerals, principally serpentine, with hematitic and opaque oxides, and minor talc and smectites. Four distinct textural types can be identified according to the distribution of opaque phases and smectite. Remnants of spinel, olivine, orthopyroxene, and clinopyroxene occur variously in the samples; spinal occurs in all the samples. Textural evidence suggests that the serpentinites were originally clinopyroxene-bearing harzburgites. Relict mineral compositions are refractory and relatively uniform: olivine, Fo90.6-90.9; orthopyroxene, En90-91; clinopyroxene, Wo47 En50 Fs3; spinels, Cr/Cr + Al = 0.4-0.6. 567A-29-2, 30-35 cm has slightly more magnesian olivines (Fo92) and orthopyroxene, and more aluminous spinels (Cr/Cr + Al = 0.3). These compositions are similar to those inferred for refractory upper-mantle materials and also fall within the range of compositions for relict minerals in abyssal peridotites. They could be of oceanic origin. The onshore samples include serpentinites, a clinopyroxene-bearing harzburgite, and a clinopyroxenite. They too have magnesium-rich silicate assemblages, but relative to the drilled samples have more iron-rich olivines (Fogo) and more aluminous and sodic pyroxenes; spinels which are clearly relicts are very aluminum-rich (Cr/Cr + Al = 0.1-0.25). These samples are most likely mantle materials, but significantly less depleted. Their relationship to the drilled samples is unclear. Serpentinites were the most common basement materials recovered during Leg 84, and there appears to be a bimodal assemblage (basalt/diabase and serpentine) of igneous rocks sampled from the trench slope. Diapirism of serpentine throughout the trench slope and forearc is suggested as an explanation for this distribution of samples.