Geochemistry and radiogenic isotope ratios of the volcanic sequences from Izu-Bonin Arc, Japan

New radiogenic isotope and trace element data are presented for the volcanic sequences along 600 km of the active Izu-Bonin arc, the Oligocene Izu arc, and their associated rift basins. As with many intra-oceanic island arcs, the Pliocene-Recent Izu-Bonin frontal-arc lavas are highly depleted in Zr, Nb and the rare-earth elements relative to typical mid-ocean ridge basalt (MORB), indicating that the mantle wedge source has undergone a previous episode of melting. Ratios between these elements (such as Nb/Zr and La/Sm), as well as 143Nd/144Nd, do not vary significantly along the length of the frontal-arc. These parameters suggest that each of the arc volcanoes is derived from similar melt fractions of the mantle wedge. However, Ba/Zr, Ba/Rb and 87Sr/86Sr increase along the frontal-arc to the north. This leads us to propose that a variable enrichment in Ba and radiogenic Sr is superimposed on the mantle wedge. Sr-Nd and Pb-Nd isotope variation indicate that both Sr and Pb become more radiogenic after fluid addition. However, Pb isotope ratios do not correlate with increases in Pb concentration or ratios such as Ba/Zr and Nb/Pb. In other words, the Pb isotopic composition of the arc lavas appears to be independent of the amount of Pb introduced by subduction fluids into the mantle source. This buffering of Pb isotopes along the frontal-arc means that the isotopic composition of the lavas is indistinguishable from that of the fluid. Isotopic mixing models presented for the arc are only illustrative of the many plausible combinations of components and quantities. Despite this, we are able to determine that the mantle wedge has isotopic characteristics similar to Indian Ocean MORB, and that the subduction-fluid solute is primarily derived from subducted oceanic basalt with a <2% contribution from subducted sediment. Lavas in the Oligocene Izu arc and fore-arc basin were derived from a mantle wedge of similar composition to the active arc. Despite levels of Pb enrichment comparable to those of the modern arc, the Pb isotopes of the Oligocene volcanics indicate a lower sediment input into the melting region.

Geochemistry and minerals at DSDP Legs 68-70 Holes

The compositions of natural glasses and phenocrysts in basalts from Deep Sea Drilling Project Sites 501, 504, and 505, near the Costa Rica Rift, constitute evidence for the existence of a periodically replenished axial magma chamber that repeatedly erupted lavas of remarkably uniform composition. Magma compositions were affected by three general components: (1) injected magmas carrying (in decreasing order of abundance) Plagioclase, olivine, and chrome-spinel phenocrysts (spinel assemblage); (2) injected magmas carrying Plagioclase, clinopyroxene, and olivine phenocrysts, but no spinel (clinopyroxene assemblage); and (3) moderately evolved hybrids in the magma chamber itself. The compositions of the injected phenocrysts and minerals in glomerocrysts are as follows: Plagioclase - An85-94; olivine - Fo87-89; clinopyroxene - high Cr2O3 (0.7-1.1%), endiopside (Wo42En51Fs7), and aluminous chromian spinel (Cr/Cr + Al = 0.3). These minerals resemble those thought to occur in upper mantle sources (9 kbars and less) of ocean-ridge basalts and to crystallize in magmas near those sources. In the magma chamber, more sodic Plagioclase (An79-85), less magnesian olivine (Fo81-86) and low-Cr2O3 (0.1-0.4%) clinopyroxene formed rims on these crystals, grew as other phenocrysts, and formed cumulus segregations on the walls and floors of the magma chamber. In the spinel-assemblage magmas, magnesiochromite (Cr/Cr + Al = 0.4-0.5) also formed. Some cumulus segregations were later entrained in lavas as xenoliths. The glass compositions define 16 internally homogeneous eruptive units, 13 of which are in stratigraphic order in a single hole, Hole 504B, which was drilled 561.5 meters into the ocean crust. These units are defined as differing from each other by more than analytical uncertainty in one or more oxides. However, many of the glass groups in Hole 504B show virtually no differences in TiO2 contents, Mg/Mg + Fe2+, or normative An/An + Ab, all of which are sensitive indicators of crystallization differentiation. The differences are so small that they are only apparent in the glass compositions; they are almost completely obscured in whole-rock samples by the presence of phenocrysts and the effects of alteration. Moreover, several of the glass units at different depths in Hole 504B are compositionally identical, with all oxides falling within the range of analytical uncertainty, with only small variations in the rest of the suite. The repetition of identical chemical types requires (1) very regular injection of magmas into the magma chamber, (2) extreme similarity of injected magmas, and (3) displacement of very nearly the same proportion of the magmas in the chamber at each injection. Numerical modeling and thermal considerations have led some workers to propose the existence of such conditions at certain types of spreading centers, but the lava and glass compositions at Hole 504B represent the first direct evidence revealed by drilling of the existence of a compositionally nearly steady-state magma chamber, and this chapter examines the processes acting in it in some detail. The glass groups that are most similar are from clinopyroxene-assemblage lavas, which have a range of Mg/Mg + Fe2"1" of 0.59 to 0.65. Spinel-assemblage basalts are less evolved, with Mg/Mg + Fe2+ of 0.65 to 0.69, but both types have nearly identical normative An/An + Ab (0.65-0.66). However, the two lava types contain megacrysts (olivine, Plagioclase, clinopyroxene) that crystallized from melts with Mg/Mg + Fe2+ values of 0.70 to 0.72. Projection of glass compositions into ternary normative systems suggests that spinel-assemblage magmas originated deeper in the mantle than clinopyroxene-assemblage magmas, and mineral data indicate that the two types followed different fractionation paths before reaching the magma chamber. The two magma types therefore represent neither a low- nor a high-pressure fractionation sequence. Some of the spinel-assemblage magmas may have had picritic parents, but were coprecipitating all of the spinel-assemblage phenocrysts before reaching the magma chamber. Clinopyroxene-assemblage magmas did not have picritic parents, but the compositions of phenocrysts suggest that they originated at about 9 kbars, near the transition between plagioclase peridotite and spinel peridotite in the mantle. Two glass groups have higher contents of alkalis, TiO2, and P2O5 than the others, evidently as a result of the compositions of mantle sources. Eruption of these lavas implies that conduits and chambers containing magmas from dissimilar sources were not completely interconnected on the Costa Rica Rift. The data are used to draw comparisons with the East Pacific Rise and to consider the mechanisms that may have prevented the eruption of ferrobasalts at these sites.

Geochemical composition of sulfide and oxide minerals from ODP Sites 193-1188 and 193-1189, PACMANUS field

Ocean Drilling Program (ODP) Leg 193 recovered core from the active PACMANUS hydrothermal field (eastern Manus Basin, Papua New Guinea) that provided an excellent opportunity to study mineralization related to a seafloor hydrothermal system hosted by felsic volcanic rocks. The purpose of this work is to provide a data set of mineral chemistry of the sulfide-oxide mineralization and associated gold occurrence in samples drilled at Sites 1188 and 1189. PACMANUS consists of five active vent sites, namely Rogers Ruins, Roman Ruins, Satanic Mills, Tsukushi, and Snowcap. In this work two sites were studied: Snowcap and Roman Ruins. Snowcap is situated in a water depth of 1670 meters below sea level [mbsl], covers a knoll of dacite-rhyodacite lava, and is characterized by low-temperature diffuse venting. Roman Ruin lies in a water depth of 1693-1710 mbsl, is 150 m across, and contains numerous large, active and inactive, columnar chimneys. Sulfide mineralogy at the Roman Ruins site is dominated by pyrite with lesser amounts of chalcopyrite, sphalerite, pyrrhotite, marcasite, and galena. Sulfide minerals are relatively rare at Snow Cap. These are dominated by pyrite with minor chalcopyrite and sphalerite and traces of pyrrhotite. Native gold has been found in a single sample from Hole 1189B (Roman Ruins). Oxide minerals are represented by Ti magnetite, magnetite, ilmenite, hercynite (Fe spinel), and less abundant Al-Mg rich chromite (average = 10.6 wt% Al2O3 and 5.8 wt% MgO), Fe-Ti oxides, and a single occurrence of pyrophanite (Mn Ti O3). Oxide mineralization is more developed at Snowcap, whereas sulfide minerals are more extensive and show better development at Roman Ruins. The mineralogy was obtained mainly by a detailed optical microscopy study. Oxide mineral identifications were confirmed by X-ray diffraction, and mineral chemistry was determined by electron probe microanalyses.

Geochemistry of basement basaltic rocks of ODP Hole 131-808C

Major- and trace-element analyses, mineral chemistry, and Sr-Nd isotopic determinations were obtained on representative igneous rocks drilled from the Nankai accretionary complex (Site 808) during Ocean Drilling Program Leg 131. For the first time, the oceanic basement of the subducting plate below an accretionary prism has been reached. The Nankai Trough basement was encountered at a depth of 1289.9 mbsf and a total of 37.1 m of igneous rocks, middle Miocene (15.6 Ma) in age, was penetrated. Two main lithological units have been distinguished from the top downward; sill-like rocks (Unit I: Cores 105, 106, 107) and pillow lavas (Unit II: Core 108). Basalts are predominantly nonvesicular, hypocrystalline, aphyric to slightly phyric with intersertal to intergranular textures. Alteration is generally slight to moderate. All the basaltic rocks are cut by ramifying veins of varying widths. Secondary mineral assemblages (including vein fillings) are typical of submarine alteration and zeolite to low greenschist facies metamorphism. The order of crystallization of primary minerals is: olivine, plagioclase, clinopyroxene. This, together with mineral chemistry, characterized by forsteritic olivine (Fo 84-85), highly anorthitic Plagioclase (up to An 90), and in particular the composition of clinopyroxene, are typical of normal mid-ocean ridge basalts (MORB). In terms of Zr/Y (2.9-3.8) and Zr/Nb (21-58), all the analyzed samples plot in the normal MORB field. The chondrite-normalized REE patterns confirm the close affinity with normal MORB type (LaN/SmN: 0.6-0.8). Note that such magmatism does not reveal any evidence of subduction-related geochemical components. The 87Sr/86Sr isotopic ratios range from 0.70339 in pillow lavas to 0.70317 in the least-altered basalts of sill units (ratios reduced to 0.70265-0.70271 by HC1 2.5 N hot leaching), whereas 143Nd/144Nd ratios are 0.51314-0.51326. These values conform with those of normal MORB. Stratigraphy, petrography, and geochemistry of the basaltic rocks recovered at Site 808 appear very similar to those from the Shikoku Basin basement (particularly Sites 442 and 443, DSDP Leg 58), analogously identified as normal MORB.

High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev

Geochemistry in the mid Atlantic Ocean ridge basalts

The main objective of Leg 82 of the Glomar Challenger was to document mantle heterogeneity in the vicinity of, and away from, a so-called hot spot: the Azores Triple Junction. One of the geochemical tools that permits, at least in part, the recognition of mantle heterogeneities uses hygromagmaphile elements, those elements that have an affinity for the liquid. This tool is presented in terms of an extended Coryell-Masuda plot, which incorporates within the rare earth elements the hygromagmaphile transition elements Th, Ta, Zr, Hf, Ti, Y, and V. The extended Coryell-Masuda plot is used to summarize our knowledge of mantle heterogeneity along the ridge axis at zero-age. It is also used by choosing those hygromagmaphile elements that can be analyzed on board by X-ray fluorescence spectrometry to give preliminary information on the enriched or depleted character of recovered samples. Shore-based results, which include analyses of most of the hygromagmaphile elements measured either by X-ray spectrometry or neutron activation analysis, confirm the shipboard data. From the point of view of comparative geochemistry, the variety of basalts recovered during Leg 82 provides a good opportunity to test and verify the classification of the hygromagmaphile elements. Analyses from Leg 82 provide new data about the relationship between extended rare earth patterns (enriched or depleted) that can be estimated either by La/Sm ratio or Nb/Zr (or Ta/Hf) ratios: samples from Hole 556 are depleted (low Nb/Zr ratio) but have a high 206Pb/ 204Pb (19.5) ratio; in Hole 558 a moderately enriched basalt unit with a La/Sm (= Nb/Zr) ratio (chondrite normalized) of 2 has a high 206Pb/204Pb (20) ratio. One of the most interesting results of Leg 82 lies in the crossing patterns of extended Coryell-Masuda plots for basalts from the same hole. This result enhances the notion of local mantle heterogeneity versus regional mantle heterogeneity and is confirmed by isotope data; it also favors a model of short-lived, discrete magma chambers. The data tend to confirm the Hayes Fracture Zone as a southern limit for the influence of Azores-type mantle. Nevertheless, north of the Hayes Fracture Zone, the influence of a plumelike mantle source is not simple and probably requires an explanation more complex than a contribution from a single fixed hot spot.

Geochemistry of ODP Leg 135 igneous rock samples

Ocean Drilling Program Leg 135 provided igneous rock cores from six sites drilled on a transect across the Lau Basin between the Lau Ridge remnant arc and the modem spreading ridges of the Central and Eastern Lau Spreading Centers. The drill cores sampled crust from the earliest stage of backarc extension (latest Miocene time, about 6 Ma), and younger crust (late Pliocene, about 3.8-2 Ma, and middle Pleistocene, about 0.64-0.8 Ma). Nearly all of the igneous samples are from tholeiitic basalt flows; many of them are interbedded with arc-composition volcaniclastic sediments. Rock compositions range from olivine-plagioclase-clinopyroxene basalt, with up to 8% MgO, to oceanic andesites with less than 3.2% MgO and silica contents as high as 56%. The oldest rocks recovered are close in composition to rocks formed at the modern Central and Eastern Lau Spreading Centers and have MORB-like characteristics. Generation of the oldest units was coeval with arc-tholeiitic volcanism on the Lau Ridge less than 100 km to the west. The arc and backarc melts came from different mantle sources. At three sites near the center of the basin, the crust is arc-tholeiitic basalt, two-pyroxene basaltic-andesite, and two-pyroxene andesite. These rocks have many similarities to modem Tofua Arc lavas yet they were drilled within 70 km of the MORB-like Eastern Lau Spreading Center. Estimates of the minimum age for these arc-like rocks indicate that they are late Pliocene (about 2 Ma). These ages overlap the age of the nearby Eastern Lau Spreading Center. The heterogeneous crust of the Lau Basin carries many of the signatures of supra-subduction zone (SSZ) melts but also has a distinct MORB-like component. Mixing between SSZ and MORB mantle sources may explain the variations and the spatial distribution of magma types.

Chemistry of Pliocene-Pleistocene pumice from the Izu-Bonin Arc

Thick pumice deposits were found in the cored sequences of forearc, arc, and backarc sites of Leg 126 in the Izu-Bonin Arc. These deposits, composed of fragmental rhyolite pumice with the chemical composition of low-alkali tholeiites, are products of arc volcanism. Pumice deposits constitute more than half of the thickness of the sediment fill of the Sumisu Rift, a backarc rift of the Izu-Bonin Arc. They comprise five thick pumiceous beds separated by thin hemipelagic units; as such, they record four major episodes or pulses of explosive, rhyolitic volcanism during the last 0.15 Ma, separated by quiescent intervals that each lasted about 30-60 k.y. The thick pumiceous beds were deposited in the rift mainly by sediment gravity flows during and immediately after the eruption of arc volcanos, which were probably submarine. Initiation of rifting was also preceded in the Pliocene by submarine rhyolitic volcanism, as seen in samples from the top of the eastern rift flank. Thick pumice beds correlative with those in the backarc also occur in the forearc basin to the east.

Analysis of manganese nodules in lakes of Scotland

During the "Challenger" Deep-Sea Exploring Expedition a great many peculiar-looking manganese nodules or concretions were dredged from the floor of the ocean at great depths, chiefly in the Red Clay areas of the Pacific. In the present paper we propose to point out the distribution of the oxides of manganese in the geological series of rocks, in fresh and sea water, and in marine deposits, with special reference to our explorations in the lochs of the west of Scotland; to give an account of investigations undertaken to ascertain the source of the manganese present in marine deposits in the form of the higher oxides, and thereafter to discuss the various views that have been advanced to explain the formation and distribution of manganese concretions in marine deposits in general.

Geochemistry of ODP Hole 176-735B igneous and hydrothermal veins

During Legs 118 and 176, Ocean Drilling Program Hole 735B, located on Atlantis Bank on the Southwest Indian Ridge, was drilled to a total depth of 1508 meters below seafloor (mbsf) with nearly 87% recovery. The recovered core provides a unique section of oceanic Layer 3 produced at an ultraslow spreading ridge. Metamorphism and alteration are extensive in the section but decrease markedly downward. Both magmatic and hydrothermal veins are present in the core, and these were active conduits for melt and fluid in the crust. We have identified seven major types of veins in the core: felsic and plagioclase rich, plagioclase + amphibole, amphibole, diopside and diopside + plagioclase, smectite ± prehnite ± carbonate, zeolite ± prehnite ± carbonate, and carbonate. A few epidote and chlorite veins are also present but are volumetrically insignificant. Amphibole veins are most abundant in the upper 50 m of the core and disappear entirely below 520 mbsf. Felsic and plagioclase ± amphibole ± diopside veins dominate between ~50 and 800 mbsf, and low-temperature smectite, zeolite, and prehnite veins are present in the lower 500 m of the core. Carbonate veinlets are randomly present throughout the core but are most abundant in the lower portions. The amphibole veins are closely associated with zones of intense crystal plastic deformation formed at the brittle/ductile boundary at temperatures above 700°C. The felsic and plagioclase-rich veins were formed originally by late magmatic fluids at temperatures above 800°C, but nearly all of these have been overprinted by intense hydrothermal alteration at temperatures between 300° and 600°C. The zeolite, prehnite, and smectite veins formed at temperatures <100°C. The chemistry of the felsic veins closely reflects their dominant minerals, chiefly plagioclase and amphibole. The plagioclase is highly zoned with cores of calcic andesine and rims of sodic oligoclase or albite. In the felsic veins the amphibole ranges from magnesio-hornblende to actinolite or ferro-actinolite, whereas in the monomineralic amphibole veins it is largely edenite and magnesio-hornblende. Diopside has a very narrow range of composition but does exhibit some zoning in Fe and Mg. The felsic and plagioclase-rich veins were originally intruded during brittle fracture at the ridge crest. The monomineralic amphibole veins also formed near the ridge axis during detachment faulting at a time of low magmatic activity. The overprinting of the igneous veins and the formation of the hydrothermal veins occurred as the crustal section migrated across the floor of the rift valley over a period of ~500,000 yr. The late-stage, low-temperature veins were deposited as the section migrated out of the rift valley and into the transverse ridge along the margin of the fracture zone.

Chemical composition of tephra from the Greenland-Iceland-Norwegian-Sea

Explosive ocean island volcanism in the Greenland-Iceland-Norwegian Sea (GIN Sea) is indicated by marine tephra layers at 10-300 ka. Peaks of explosive volcanism occurred in oxygen isotope stages 8, 7, 5 and 1. The depositional age of the tephra was estimated using the oxygen isotope stratigraphy and dating of marine records. Geochemical analyses of the tephra layers show that all originate from Iceland. Here we report the characteristics of tephra from these major Icelandic events in 30 deep-sea cores from the GIN Sea. Our findings provide constraints on the distribution of tephra from the eruption source. For the Vedde Ash (oxygen isotope stage 1) we estimate a minimum fallout area of 2*10**5 km**2, stretching from central Greenland in the west and southern Sweden in the east, to 71°N in the GIN Sea. The magnitude of the eruption and the regional wind conditions controlled the extent and concentrations of these ash fallout events. Oceanic circulation and differential settling may have affected the distribution and final deposition of ash particles such as bubble wall shards.

Age determination of seven sediment cores from the South Pacific Ocean

During the last deglaciation, the opposing patterns of atmospheric CO2 and radiocarbon activities (D14C) suggest the release of 14C-depleted CO2 from old carbon reservoirs. Although evidences point to the deep Pacific as a major reservoir of this 14C-depleted carbon, its extent and evolution still need to be constrained. Here we use sediment cores retrieved along a South Pacific transect to reconstruct the spatio-temporal evolution of D14C over the last 30,000 years. In ~2,500-3,600 m water depth, we find 14C-depleted deep waters with a maximum glacial offset to atmospheric 14C (DD14C = -1,000 per mil). Using a box model, we test the hypothesis that these low values might have been caused by an interaction of aging and hydrothermal CO2 influx. We observe a rejuvenation of circumpolar deep waters synchronous and potentially contributing to the initial deglacial rise in atmospheric CO2. These findings constrain parts of the glacial carbon pool to the deep South Pacific.

Geochemistry of tephra from Lake Ohrid

Here we present a tephrostratigraphic record (core Co1202) recovered from the northeastern part of Lake Ohrid (Republics of Macedonia and Albania) reaching back to Marine Isotope Stage (MIS) 6. Overall ten horizons (OT0702-1 to OT0702-10) containing volcanic tephra have been recognised throughout the 14.94 m long sediment succession. Four tephra layers were visible at macroscopic inspection (OT0702-4, OT0702-6, OT0702-8 and OT0702-9), while the remaining six are cryptotephras (OT0702-1, OT0702-2, OT0702-3, OT0702-5, OT0702-7 and OT0702-10) identified from peaks in K, Zr and Sr intensities, magnetic susceptibility measurements, and washing and sieving of the sediments. Glass shards of tephra layers and cryptotephras were analysed with respect to their major element composition, and correlated to explosive eruptions of Italian volcanoes. The stratigraphy and the major element composition of tephra layers and cryptotephras allowed the correlation of OT0702-1 to AD 472 or AD 512 eruptions of Somma-Vesuvius, OT0702-2 to the FL eruption of Mount Etna, OT0702-3 to the Mercato from Somma-Vesuvius, OT0702-4 to SMP1-e/Y-3 eruption from the Campi Flegrei caldera, OT0702-5 to the Codola eruption (Somma-Vesuvius or Campi Flegrei), OT0702-6 to the Campanian Ignimbrite/Y-5 from the Campi Flegrei caldera, OT0702-7 to the Green Tuff/Y-6 eruption from Pantelleria Island, OT0702-8 to the X-5 eruption probably originating from the Campi Flegrei caldera, OT0702-9 to the X-6 eruption of generic Campanian origin, and OT0702-10 to the P-11 eruption from Pantelleria Island. The fairly well-known ages of these tephra layers and parent eruptions provide new data on the dispersal and deposition of these tephras and, furthermore, allow the establishment of a chronological framework for core Co1202 for a first interpretation of major sedimentological changes.

Granulometry, mineralogy and geochemistry of ODP Holes 184-1147A and 184-1148A, South China Sea

Green clay layers are reported from the Pliocene-Holocene intervals in five of the six sites drilled in the South China Sea (SCS) during Leg 184. Centimeter-scale discrete, discontinuous, and bioturbated layers, constituted by stiff and porous green clays, were observed, sometimes associated with iron sulfides and pyrite. Detailed mineralogical and geochemical analyses indicate that they differentiate from the host sediments in their higher content of iron, smectite, and mixed-layered clays and lower amounts of calcite, authigenic phosphorus, quartz, and organic matter. Although no glauconite was observed, the mineralogy and geochemistry of green clay layers, along with their geometrical relation to background sediments, suggest that they most likely represent the result of the first steps of glauconitization. Correlation between green layers and volcanic ash layers was suggested for green laminae observed elsewhere in Pacific sediments but was not confirmed at SCS sites. Statistical analysis of the temporal distribution of green layers in the records of the last million years suggests that green clay layers have become more frequent since 600 ka. Only at Site 1148 does the green layer record show a statistically significant cyclicity which may be related to orbital eccentricity. A possible influence of sea level variations, related both to climatic changes and tectonism, is postulated.

Mineralogy, geochemistry and elemental ratios of ODP Core 171B-1049C-8X

Inorganic geochemistry and mineralogy of Core 171B-1049C-8X, containing a Cretaceous/Tertiary boundary section, was investigated by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The ages of samples analyzed stretched from the latest Maastrichtian into the Danian. XRD measurements were made using the peak height method. A reduction in low-magnesium calcite and an increase in quartz were found above the spherule layer. Substantial amounts of dolomite were noted just above the spherule layer. XRF analyses were performed using the RHSMALL program to measure the abundance of major and minor elements. Replicate analyses for each technique were performed to assess the precision of the results. The section above the spherule bed was found to be characterized by peaks in many elements, including Si, Al, Fe, and Mg, as well as the following elemental ratios: Fe/Al, Ni/Al, Zr/Rb, and Rb/Sr'. Above the spherule bed, there were significant reductions in Ca, Sr/Ca, Ti/Al, K/Al, Rb/Al, Cr/Al, Ba/Al, biogenic Ba, and excess P.