Geochemistry of volcanic glass from ODP holes 129-801C and 185-801C in the western Pacific

Major element chemistry of basalt from the southern East Pacific Rise (EPR) is different from that of the EPR at the time of the formation of the Pacific Plate at 170 Ma.Glass recovered from Jurassic age (170 Ma) Pacific ocean crust (Bartolini and Larson, 2001, doi:10.1130/0091-7613(2001)029<0735:PMATPS>2.0.CO;2) at Ocean Drilling Program Hole 801C records higher Fe8 (10.77 wt%) and marginally lower Na8 (2.21 wt%) compared to the modern EPR, suggesting deeper melting and a temperature of initial melting that was 60°C hotter than today.Trace element ratios such as La/Sm and Zr/Y, on the other hand, show remarkable similarities to the modern southern EPR, indicating that Site 801 was not generated on a hotspot-influenced ridge and that mantle composition has changed little in the Pacific over the past 170 Ma. Our results are consistent with the observation that mid-ocean ridge basalts (MORBs) older than 80 Ma were derived by higher temperature melting than are modern MORBs (Humler et al., 1999, doi:10.1016/S0012-821X(99)00218-6), which may have been a consequence of the Cretaceous superplume event in the Pacific.Site 801 predates the formation of Pacific oceanic plateaus and 801C basalt chemistry indicates that higher temperatures of mantle melting beneath Pacific ridges preceded the initiation of the superplume.

Geochemistry of bulk samples and various minerals of sediment core CRP-1 from the Ross Sea, Antarctica

Thirty-nine medium and fine grained sandstones from between 19,26 and 147,23 mbsf in the Cape Roberts-l core (CRP-1) were analysed for 10 major and 16 trace elements. Using whole-lock compositions, 9 samples were selected for analyses of mineral and glass grains by energy dispersive electron microscope. Laser-Ablation Mass-Spectrometry was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to examine their contribution to the bulk rock chemistry. Geochemical data reveal the major contribution played by the Granite Harbour Intrusives to the whole rock composition, even if a significant input is supplied by McMurdo volcanics and Ferrar dolerite pyroxenes McMurdo volcanics were studied in detail; they appeal to derive from a variety of litologies, and a dominant role of wind transpoitation from exposures of volcanic rocks may be inferred from the contemporary occurrence of different compositions at all depths. Only at 116.55 mbsf was a thin layer of tephra found, linked to an explosive eruption McMurdo volcanic rocks exhibit larger abundances at depths above 62 mbsf, in correspondence with the onset of volcanic activity in the McMurdo Sound area. From 62 mbsf to the bottom of the core, McMurdo volcanics are less abundant and probably issued from some centres in the McMurdo Sound region. However, available data do not allow the exclusion of wind transport from some eruptive centres active in north Victoria Land at the beginning of the Miocene Epoch.

Geochemistry of minerals in CRP sediment cores from the Ross Sea, Antarctica

Sixty-four volcanic chists, sandstones and tephras between 5.95 and 618.19 meters below sea floor (mbsf) in the Cape Roberts Project cores 2 and 2A cores (CRP-2/2A) were examined for Cenozoic and Mesozoic volcanic components, using optical and Scanning Electron Microscopy. Minerals and glass shards in a selection of samples were analysed by electron microprobe fined with an EDAX detector. Laser-Ablation ICP-Mass-Spectrometry (ICP-MS) was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to pin-point the onset of McMurdo Volcanic Group (MVG) activity in the stratigraphic column. Pumices in tephra layers of peralkaline phonolite composition in Unit 7.2 -between 108 and 114 mbsf - were also analysed for trace elements by ICP-MS. This tephra unit is not reworked and its isotopic age (21.44 ± 0.05 Ma) is the age of deposition. The height of the eruptive column responsible for the deposition of the tephra was probably less than 8 km; the source was local, probably within 30 km from the drill site. Phonolite of unit 7.2 of CRP-2/2A has no direct petrogenetic relation with the peralkaline trachyte in the tephra-enriched layer of CRP-1 at 116.55 mbsf. Volcanic clasts and sand grains (glass shards, aegirine-augite, anorthoclase) related to Cenozoic activity of MVG were observed only starting from Unit 9.8, where they are dated at 24.22 ± 0.06 Ma at c. 280 mbsf. In this unit the lowest- occurring basaltic glass shard is found at 297.54 mbsf. Sampled McMurdo volcanics are generally vesicular and vary in composition from alkali basalt to trachyte and peralkaline phonolite. By contrast, below 320 mbsf, aphyric or slightly-porphyritic volcanic clasts become more abundant but they are all non-vesiculated, pigeconite and ilmenite-bearing basalts and dolerite of tholeiitic affinity. These rocks are considered to be related to lava flows and associated intrusions of Jurassic age (Kirkpatrick basalts and Ferrar dolerite). As in CRP-1, McMurdo volcanics appear to derive from a variety of lithologics. Besides glaciers, a dominant role of wind transportation from exposed volcanic rocks may be inferred from the contemporary occurrence of glass shards of different compositions at depths above 297.54 mbsf. These data confirm that the onset of magmatic activity in southern Victoria Land is considerably delayed (by about 24 Ma) with respect to northern Victoria Land.

Geochemistry of mafic clasts of ODP Holes 125-778A and 125-779A

Clasts of metamorphosed mafic igneous rock of diverse composition were recovered in two drill sites on a serpentine mud volcano in the outer Mariana forearc during Ocean Drilling Program Leg 125. These clasts are xenolithic fragments that have been entrained in the rising serpentine mud, and make up less that 9% of the total rock recovered at Sites 778 and 779. Most samples are metabasalt or metadiabase, although one clast of possible boninite and one cumulate gabbro were recovered. On the basis of trace element signatures, samples are interpreted to represent both arc-derived and mid-ocean ridge-derived compositions. Rocks with extremely low TiO2 (<0.3 wt%) and Zr (<30 ppm) are similar to boninite series rocks. Samples with low TiO2 (<0.9 wt%) and Zr (<50 ppm) and extreme potassium enrichment (K2O/Na2O >3.9) may represent island arc rocks similar to shoshonites. However, the K2O/Na2O ratios are much higher than those reported for shoshonites from modem or ancient arcs and may be the result of metamorphism. Samples with moderate TiO2 (1.4 to 1.5 wt%) and Zr (72 to 85 ppm) are similar to rocks from mid-ocean ridges. A few samples have TiO2 and Zr intermediate between island arc and mid-ocean ridge basalt-like rocks. Two samples have high iron (Fe2O3* = >12.8 to 18.5 wt%) (Fe2O3* = total iron calculated as Fe2O3) and TiO2 (>2.3 wt%) and resemble FeTi basalt recovered from mid-ocean ridges. Metamorphism in most samples ranges from low-temperature zeolite, typical of ocean floor weathering, to prehnite-pumpellyite facies and perhaps lower greenschist. Blue amphibole and lawsonite minerals are present in several samples. One diabase clast (Sample 9) exhibits Ca enrichment, similar to rodingite metamorphism, typical of mafic blocks in serpentinized masses. The presence of both low-grade (clays and zeolites) and higher grade (lawsonite) metamorphism indicates retrograde processes in these clasts. These clasts are fragments of the forearc crust and possibly of the subducting plate that have been entrained in the rising serpentine and may represent the deepest mafic rocks ever recovered from the Mariana forearc. The variable compositions and degree of metamorphism of these clasts requires at least two tectonic origins. The recovery of clasts with mid-ocean ridge and arc chemical affinities in a single drill hole requires these clasts to have been "mixed" on a small scale either (1) in the forearc crustal sequence, or (2) after inclusion in the rising serpentine mud. The source of the MORB-like samples and an explanation for the presence of both MORB-like and arc-like rocks in close proximity is critical to any model of the evolution of the Mariana forearc. The source of the MORB-like samples likely will be one (or more) of the following: (1) accretion of Pacific plate lithosphere, (2) remnants of original forearc crust (trapped plate), (3) volcanism in the supra-subduction zone (arc or forearc) environment, or (4) derivation from the subducting slab by faulting along the dÈcollement.

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.

Geochemistry and petrology of ODP Site 136-843 basalts

About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

Geochemistry of the volcanic basement of ODP Hole 134-831B

The basement of Bougainville Guyot drilled at Site 831 consists of andesitic hyalobreccias derived from a submarine arc volcano. The volcanic sequence has been dated by K/Ar at approximately 37 Ma. The 121 m of andesitic hyalobreccias drilled in Hole 831B have been divided into five subunits of two types: one appears to be primary, and the other contains evidence of reworking and a subaerial clastic input. Variations are attributed to fluctuations in water depth. The distinctive hyalobreccias consist of andesitic blebs with chilled margins and peripheral fractures set in a chaotic greenish matrix that is mainly altered glass, with crystals similar to those in the blebs or clasts. Their formation is attributed to violent reaction of andesitic magma discharged into seawater, in perhaps the submarine equivalent of fire-fountaining. There was limited reworking by currents and debris flows on the flanks of the submarine volcano. The andesite shows no significant compositional variation in phenocryst phases throughout the drilled sequence and contains phenocrysts of plagioclase (An88-43), clinopyroxene (Ca44Mg46Fe10-Ca41Mg40Fe19), orthopyroxene (Ca4Mg79Fe17-Ca3Mg58Fe39), and titanomagnetite. There is a systematic change in volcanic composition with height in the section, from more mafic andesites at the base, to overlying more acid andesites, and strong evidence exists that magma mixing may have played a significant role in the genesis of these lavas. The andesites have affinities with the low-K arc tholeiite series. Trace element and isotopic systematics for these rocks indicate very minor involvement of a LILE- and 87Sr-enriched slab-derived fluid in their petrogenesis. This accords with the previous suggestion that Bougainville Guyot forms part of an Eocene proto-island arc developed along the southern side of the d'Entrecasteaux Zone, above a southward-dipping subduction zone.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Geochemistry of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

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.

Petrology and geochemistry of basalts at DSDP Hole 86-581

Approximately 5 m of aphyric to sparsely phyric basalt was recovered from Hole 581, the only hole on Leg 86 where basement was cored. The occurrence of samples with altered glassy rinds indicates that at least three cooling units (pillows or thin flows) were sampled. The samples were moderately to intensely altered; groundmass crystals are generally fresh, but all glass is altered. Alteration is greatest in vesicular samples, but most of the samples have fractures filled with iron oxyhydroxide, clay, and/or calcite. All 13 samples analyzed are moderately fractionated aluminous N-type mid-ocean ridge basalts. The samples can be divided into two groups based on TiO2 and FeO contents. The least-evolved group may be derived from a more primitive mid-ocean ridge basalt by the crystallization of 18% plagioclase, 24% clinopyroxene, and 3% olivine. The more evolved group may be derived from the first group by the fractionation of 18% plagioclase, 11% clinopyroxene, and 3% olivine. However, higher Ce/Yb ratios in the more evolved group cannot be produced by fractionation and thus we must invoke a more complex process such as dynamic melting to relate the two groups to a common source.

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.