Chemistry of igneous rocks from, the Celebes Sea basement

Major and trace elements, mineral chemistry, and Sr-Nd isotope ratios are reported for representative igneous rocks of Ocean Drilling Program Sites 767 and 770. The basaltic basement underlying middle Eocene radiolarianbearing red clays was reached at 786.7 mbsf and about 421 mbsf at Sites 767 and 770, respectively. At Site 770 the basement was drilled for about 106 m. Eight basaltic units were identified on the basis of mineralogical, petrographical, and geochemical data. They mainly consist of pillow lavas and pillow breccias (Units A, B, D, and H), intercalated with massive amygdaloidal lavas (Units Cl and C2) or relatively thin massive flows (Unit E). Two dolerite sills were also recognized (Units F and G). All the rocks studied show the effect of low-temperature seafloor alteration, causing almost total replacement of olivine and glass. Calcite, clays, and Fe-hydroxides are the most abundant secondary phases. Chemical mobilization due to the alteration processes has been evaluated by comparing elements that are widely considered mobile during halmyrolysis (such as low-field strength elements) with those insensitive to seafloor alteration (such as Nb). In general, MgO is removed and P2O5 occasionally enriched during the alteration of pillow lavas. Ti, Cs, Li, Rb, and K, which are the most sensitive indicators of rock/seawater interaction, are generally enriched. The most crystalline samples appear the least affected by chemical changes. Plagioclase and olivine are continuously present as phenocrysts, and clinopyroxene is confined in the groundmass. Textural and mineralogical features as well as crystallization sequences of Site 770 rocks are, in all, analogous to typical mid-ocean-ridge basalts (MORBs). Relatively high content of compatible trace elements, such as Ni and Cr, indicate that these rocks represent nearly primitive or weakly fractionated MORBs. All the studied rocks are geochemically within the spectrum of normal MORB compositional variation. Their Sr/Nd isotopic ratios plot on the mantle array (87Sr/87Sr 0.70324-0.70348 with 143Nd/144Nd 0.51298-0.51291) outside the field of Atlantic and Pacific MORBs. However, Sr and Nd isotopes are typical of both Indian Ocean MORBs and of some back-arc basalts, such as those of Lau Basin. The mantle source of Celebes basement basalts does not show a detectable influence of a subduction-related component. The geochemical and isotopic data so far obtained on the Celebes basement rocks do not allow a clear discrimination between mid-ocean ridge and back-arc settings.

Interstitial water chemistry of ODP Leg 103 sites

Interstitial waters were squeezed from strata recovered at Sites 637-641 of ODP Leg 103 on the Galicia margin, along the northwestern Iberian continental margin in the northeast Atlantic. Chemical profiles of Site 638 show the most complexity, which appears to be related to an unconformity in the strata between Cretaceous and Neogene sediments and to rapid deposition of Cretaceous syn-rift sediments upon pre-rift strata. Analyses of waters from all of the Leg 103 sites show generally antithetical trends for calcium and magnesium; calcium increases with depth as magnesium decreases. No calcium-magnesium 'crossover' profiles are observed in these data. Data from Site 637 show an unusual pattern; calcium increases with increasing depth, but magnesium remains relatively constant. Sulfate is either stable or shows an overall decrease with depth, and boron profiles show some structure. At all but one site (Site 638), strontium profiles do not show marked depth structure. The structure of alkalinity and silica profiles is highly site dependent. Bromide profiles are, in general, constant. In nearly every case, observed bromide concentrations are near average seawater values. Relatively low concentrations of iron and manganese are common within the upper 10 m of the sediment sequence and typically are near detection limits at deeper depths

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Chemistry of orthopyroxenes, clinopyroxenes, and spinels of ODP Hole 103-637A peridotites

Mineral compositions of the plagioclase-bearing ultramafic tectonites dredged and cored seaward of the continental slope of the Galicia margin (Leg 103, Site 637) were compared to mineral compositions from onshore low-pressure ultramafic bodies (southeastern Ronda, western Pyrenees, and Lizard Point), on the basis of standardized (30-s counting time) probe analyses. The comparison was extended to some plagioclase-free harzburgites related to ophiolites (Santa Elena in Costa Rica, north Oman, and the Humboldt body in New Caledonia) on the basis of new analytical data and data from the literature. The behavior of Cr, Na, Al, Mg, Fe, Ni, and Ti in olivine, pyroxenes, and spinel was examined in order to distinguish between the effects of partial melting and mineral facies change, from the spinel to plagioclase stability fields. The peridotite from the Galicia margin appears slightly depleted in major incompatible elements and experienced a minor partial melting. However, it experienced large scale but heterogeneous recrystallization in the plagioclase field. These features are very similar to those observed in Ronda, whereas in the western Pyrenees the minerals exemplify a very minor partial-melting event (or none at all) and have retained compositions corresponding to those of the relatively high-pressure Seiland sub facies. The minerals from the Lizard Point peridotite have characteristics (low Mg/(Mg + Fe) ratio; high Cr/(Cr + Al) ratio in spinel) more related to cumulate from a differentiated tholeiitic melt than related to ophiolitic tectonite. Diffusion profiles of Al and Cr across pyroxenes and spinel show that recrystallization features occurred at different speeds or temperatures in the different bodies. The pyroxenes from Ronda would have experienced recrystallization about 14 times faster than the peridotite from the Galicia margin. The western Pyrenean lherzolites also experienced rapid recrystallization; nevertheless, because they are of a different mineral facies, the data are not directly comparable to that from Ronda and Galicia. The harzburgite at Santa Elena as well as a xenolith from alkali basalt exemplify rapid cooling characterized by very weak re-equilibration. Recrystallization speed is related to emplacement speed in the present geological environment. The slow-rising Galicia margin peridotite was emplaced by thinning of the lithospheric subcontinental mantle near an incipient mid-oceanic ridge. The fast-rising peridotites from Ronda and the western Pyrenees were hot diapirs emplaced from the asthenosphere along transcurrent faults, possibly related to the opening of the Atlantic Ocean.

(Table 1) Color, Fe-C-S chemistry and carbonate content from ODP Sites 172-1062 and 172-1063

Reflectance spectra collected during ODP Leg 172 were used in concert with solid phase iron chemistry, carbonate content, and organic carbon content measurements to evaluate the agents responsible for setting the color in sediments. Factor analysis has proved a valuable and rapid technique to detect the local and regional primary factors that influence sediment color. On the western North Atlantic drifts, sediment color is the result of primary mineralogy as well as diagenetic changes. Sediment lightness is controlled by the carbonate content while the hue is primarily due to the presence of hematite and Fe2+/Fe3+ changes in clay minerals. Hematite, most likely derived from the Permo-Carboniferous red beds of the Canadian Maritimes, is differentially preserved at various sites due to differences in reductive diagenesis and dilution by other sedimentary components. Various intensities for diagenesis result from changes in organic carbon content, sedimentation rates, and H2S production via anaerobic methane oxidation. Iron monosulfides occur extensively at all high sedimentation sites especially in glacial periods suggesting increased high terrigenous flux and/or increased reactive iron flux in glacials.

Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Carbon and Lead chemistry of sediments from the Middle Atlantic Bight

A mass budget was constructed for organic carbon on the upper slope of the Middle Atlantic Bight, a region thought to serve as a depocenter for fine-grained material exported from the adjacent shelf. Various components of the budget are internally consistent, and observed differences can be attributed to natural spatial variability or to the different time scales over which measurements were made. The flux of organic carbon to the sediments in the core of the depocenter zone, at a water depth of 1000 m, was measured with sediment traps to be 65 mg C m**-2 day**-1, of which 6-24 mg C m**-2 day**-1 is buried. Oxygen fluxes into the sediments, measured with incubation chambers attached to a free vehicle lander, correspond to total carbon remineralization rates of 49-70 mg C m**-2 day**-1. Carbon remineralization rates estimated from gradients of Corg within the mixed layer, and from gradients of dissolved ammonia and phosphate in pore waters, sum to only 4-6 mg C m**-2 day**-1. Most of the Corg remineralization in slope sediments is mediated by bacteria and takes place within a few mm of the sediment-water interface. Most of the Corg deposited on the upper slope sediments is supplied by lateral transport from other regions, but even if all of this material were derived from the adjacent shelf, it represents <2% of the mean annual shelf productivity. This value is further lowered by recognizing that as much as half of the Corg deposited on the slope is refractory, having originated by reworking from older deposits. Refractory Corg arrives at the sea bed with an average 14C age 600-900 years older than the pre-bomb 14C age of DIC in seawater, and has a mean life in the sediments with respect to biological remineralization of at least 1000 years. Labile carbon supplied to the slope, on the other hand, is rapidly and (virtually) completely remineralized, with a mean life of < 1 year. Carbon-14 ages of fine-grained carbonate and organic carbon present within the interstices of shelf sands are consistent with this material acting as a source for the old carbon supplied to the slope. Winnowing and export of reworked carbon may contribute to the often-described relationship between organic carbon preservation and accumulation rate of marine sediments.

Chemistry and age determination of basement fluids from Juan de Fuca Ridge

The geochemical implications of thermally driven flow of seawater through oceanic crust on the mid-ocean ridge flank have been examined on a well-studied 80 km transect across the eastern flank of the Juan de Fuca Ridge at 48°N, using porewater and basement fluid samples obtained on ODP Leg 168. Fluid flow is recognised by near-basement reversals in porewater concentration gradients from altered values in the sediment section to seawater-like values in basaltic basement. In general, the basement fluids become more geochemically evolved with distance from the ridge and broadly follow basement temperature which ranges from not, vert, similar16° to 63°C. Although thermal effects of advective heat exchange are only seen within 20 km east of where basement is exposed near the ridge crest, chemical reactivity extends to all sites. Seawater passing through oceanic crust has reacted with basement rocks leading to increases in Ca2+ and decreases in alkalinity, Mg2+, Na+, K+, SO42- and delta18O. Sr isotope exchange between seawater and oceanic crust off axis is unequivocally demonstrated with endmember 87Sr/86Sr ~ 0.707. Evidence of more evolved fluids is seen at sites where rapid upwelling of fluids through sediments occurs. Chlorinities of the basement fluids are consistent with post-glacial seawater and thus a short residence time in the crust. Rates of lateral flow have been by estimated by modelling porewater sulphate gradients, using Cl as a glacial chronometer, and from radiocarbon dating of basal fluids. All three methods reveal fluid flow with 14C ages less than 10,000 yr and particle velocities of ~1-5 m/yr, in agreement with thermally constrained volumetric flow rates through a ~600 m thick permeable layer of ~10% porosity. Delta(element)/Delta(heat) extraction ratios are similar to values for ridge-crest hydrothermal systems.

Chemistry of upper Eocene microtektites

Late Eocene microtektites and crystal-bearing microkrystites extracted from DSDP and ODP cores from the Atlantic, Pacific, and Indian oceans have been analyzed to address their provenance. A new analysis of Nd and Sr isotopic compositions confirms previous work and the assignment of the uppermost microtektite layer to the North American tektites, which are associated with the 35.5 Ma, 85 km diameter Chesapeake impact structure of Virginia, USA. Extensive major element and Nd and Sr isotopic analyses of the microkrystites from the lowermost layer were obtained. The melanocratic microkrystites from Sites 216 and 462 in the Indian and Pacific oceans possess major element chemistries, Sr and Nd isotopic signatures and Sm-Nd, T CHUR, model ages similar to those of tagamite melt rocks in the Popigai impact structure. They also possess Rb-Sr, T UR, model ages that are younger than the tagamite TCHUR ages by up to ~1 Ga, which require a process, as yet undefined, of Rb/Sr enrichment. These melanocratic microkrystites are consistent with a provenance from the 35.7 Ma, 100 km diameter Popigai impact structure of Siberia, Russia, while ruling out other contemporaneous structures as a source. Melanocratic microkrystites from other sites and leucocratic microkrystites from all sites possess a wide range of isotopic compositions (epsilon (143Nd) values of -16 to -27.7 and epsilon (87Sr) values of 4.1-354.0), making the association with Popigai tagamites less clear. These microkrystites may have been derived by the melting of target rocks of mixed composition, which were ejected without homogenization. Dark glass and felsic inclusions extracted from Popigai tagamites possess epsilon (143Nd) and epsilon (87Sr) values of -26.7 to -27.8 and 374.7 and 432.4, respectively, and T CHUR and T UR model ages of 1640-1870 Ma and 240-1830 Ma, respectively, which require the preservation of initially present heterogeneity in the source materials. The leucocratic microkrystites possess diverse isotopic compositions that may reflect the melting of supra-basement sedimentary rocks from Popigai, or early basement melts that were ejected prior to homogenization of the Popigai tagamites. The ejection of melt rocks with chemistries consistent with a basement provenance, rather than the surface ~1 km of sedimentary cover rocks, atypically indicates a non-surficial source to some of the ejecta. Microkrystites from two adjacent biozones possess statistically indistinguishable major element compositions, suggesting they have a single source. The occurrence of microkrystites derived from a single impact event, but in different biozones, can be explained by: (1) diachronous biozone boundaries; (2) post-accumulation sedimentary reworking; or (3) erroneous biozonation.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Stable isotope organic chemistry of ODP Leg 105 sites

Stable carbon and nitrogen isotopic compositions as well as organic carbon and total nitrogen contents are reported for Site 645 in Baffin Bay and Sites 646 and 647 in the Labrador Sea. Both low-resolution analyses (1 sample/section) and high-resolution results (up to 7 samples/section) are presented. These records indicate that large-scale changes in productivity since the middle Miocene have occurred in Baffin Bay. Such changes are not evident in samples from the Labrador Sea. Isotopic records of all the sites are influenced strongly by rapidly changing influxes that combine terrigenous debris with planktonic production. In parts of the cores, relationships to other phenomena, such as ice stages, are present. However, these correlations are not common and indicate that these events were masked by the dynamic changes in sources of organic matter occurring in this complex system.

Water chemistry of lakes from the Antarctic

This paper reviews Japanese limnological studies mainly in the McMurdo and Syowa oases, with special emphasis on the nutrient distribution. Generally, the chemical composition of the major ionic components in the coastal lakes and ponds is similar to that in seawater, while that in inland Dry Valley lakes and ponds of the McMurdo Oasis is abundant in calcium, magnesium and sulfate ions. The former can be explained by the direct influences of sea salts, while the latter is mainly attributable to the accumulation of atmospheric salts. Most saline lakes are meromictic. Dissolved oxygen concentrations in the upper layers are saturated or supersaturated, but the bottom layers are anoxic and often hydrogen sulfide occurs. The concentrations of nutrients vary largely not only among the lakes but also with depth. Silicate-Si, which is generally abundant in all freshwater and saline lakes, may be due to erosions of soils and rocks. Nitrite-N concentrations in both freshwater and saline lakes are generally low. Nitrate-N concentrations in the oxic layers of the inland saline lakes in the McMurdo Oasis arc often high, but not high in the coastal saline lakes of the Syowa and Vestfold oases. The abundance of phosphate-P and ammonium-N in the bottom stagnant layers of saline lakes can be explained by the accumulation of microbially released nutrients due to the decomposition of organic substances. Nutrients are supplied mainly from meltstreams in the catchment areas, and are proved to play an important role in primary production.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Chemistry of abyssal and Horman peridotites

The concentrations of the platinum-group elements (PGE) Ir, Ru, Pt and Pd were determined in 11 abyssal peridotites from ODP Sites 895 and 920, as well in six ultramafic rocks from the Horoman peridotite body, Japan, which is generally thought to represent former asthenospheric mantle. Individual oceanic peridotites from ODP drill cores are characterized by variable absolute and relative PGE abundances, but the average PGE concentrations of both ODP suites are very similar. This indicates that the distribution of the noble metals in the mantle is characterized by small-scale heterogeneity and large-scale homogeneity. The mean Ru/Ir and Pt/Ir ratios of all ODP peridotites are within 15% and 3%, respectively, of CI-chondritic values. These results are consistent with models that advocate that a late veneer of chondritic material provided the present PGE budget of the silicate Earth. The data are not reconcilable with the addition of a significant amount of differentiated outer core material to the upper mantle. Furthermore, the results of petrogenetic model calculations indicate that the addition of sulfides derived from percolating magmas may be responsible for the variable and generally suprachondritic Pd/Ir ratios observed in abyssal peridotites. Ultramafic rocks from the Horoman peridotite have PGE signatures distinct from abyssal peridotites: Pt/Ir and Pd/Ir are correlated with lithophile element concentrations such that the most fertile lherzolites are characterized by non-primitive PGE ratios. This indicates that processes more complex than simple in-situ melt extraction are required to produce the geochemical systematics, if the Horoman peridotite formed from asthenospheric mantle with chondritic relative PGE abundances. In this case, the PGE results can be explained by melt depletion accompanied or followed by mixing of depleted residues with sulfides, with or without the addition of basaltic melt.

Chemistry of volcanic ash from Celebes and Sulu Sea Basins

During Leg 124, off the Philippines, volcanic material was recovered in deep-sea sediments dating from the late Oligocene in the Celebes Sea Basin, and from the early Miocene in the Sulu Sea Basin. Chemical and petrological studies of fallout ash deposits are used to characterize volcanic pulses and to determine their possible origin. All of the glass and mineral compositions belong to medium-K and high-K calc-alkaline arc-related magmatic suites including high-Al basalts, pyroxene-hornblende andesites, dacites, and rhyolites. Late Oligocene and early Miocene products may have originated from the Sunda arc or from the Sabah-Zamboanga old Sulu arc. Late early Miocene Sulu Sea tuffs originated from the Cagayan arc, whereas early late Miocene fallout ashes are attributed to the Sulu arc. A complex magmatic production is distinguished in the Plio-Quaternary with three sequences of basic to acidic lava suites. Early Pliocene strata registered an important activity in both Celebes Sea and Sulu Sea areas, from the newly born Sangihe arc (low-alumina andesite series) and from the Sulu, Zamboanga, and Negros arcs (high-alumina basalt series and high-K andesite series). In the late Pliocene and the early Pleistocene, renewal of activity affects the Sangihe-Cotobato arc as well as the Sulu and Negros arcs (same magmatic distinctions). The last volcanic pulse took place in the late Pleistocene with revival of all the present arc systems.