Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Comparisons of z values between fine-grained titanomagnetites within interstitial glass and large-grained titanomaghemtes in older ocean-floor basalts

Transmission electron microscopy observations and rock magnetic measurements reveal that alteration of fine- and large-grained iron-titanium oxides can occur at different rates. Fine-grained titanomagnetite occurs as a crystallization product within interstitial glass that originated as an immiscible liquid within a fully differentiated melt; in several samples with ages to 32 Ma it displays very little or no oxidation (z = ca. 0). In contrast, samples with ages of 10 Ma or older are observed to also contain highly oxidized (z >/= 0.66) large-grained titanomaghemite. These large grains, having originated by direct crystallization from melt, are associated with pore space. Such pore space can serve as a conduit for fluids that promote alteration, whereas fine grains may have been "armored" against alteration by the glass matrix in which they are embedded. Apparently, alteration of oceanic crust is a heterogeneous process on a microscopic scale. The existence of pristine, fine-grained titanomagnetite in the interstitial glass of older ocean-floor basalts that have undergone significant alteration implies that such glassy material is capable of carrying original thermal remanent magnetization and may be suitable for paleointensity determinations.

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.

Chemical composition of glass inclusions of volcanic rocks from the Bonin Arc

The chemical composition of glass inclusions in phenocrystic plagioclase and pyroxene from Sites 792 and 793, drilled during Ocean Drilling Program Leg 126 in the Bonin Arc, is examined. Immiscible liquid, which is preserved as glass inclusions with unmixed textures in plagioclase, is observed in a high-magnesian andesite, which suggests an important role of liquid immiscibility in the fractionation of high-magnesian andesite. In other andesitic rocks (SiO2 = 57-60 wt%), such unmixed textures of glass inclusions in calcic plagioclase with a similar percentage of An (around 80%) is not found. The degree of fractionation and mixing of liquid are inferred from the glass composition in pyroxene.

(Table 1) Geochemistry of upper Paleocene and upper Eocene glass particles at DSDP Hole 80-549

Two ash horizons have been identified in Hole 549, one in the upper Paleocene (basal NP9), the other in the upper Eocene (NP18); both are mixed lithic crystal tuffs of rhyolitic composition. These tuffs are absent in Hole 550 owing to unconformities, but the basal Eocene (NP10) of Hole 550 includes a series of over 50 thin bentonite layers. Intermediate plagioclase associated with these bentonites indicates that the original ash was of basaltic to andesitic composition. The bentonites are absent in Hole 549, probably because of an unconformity, but they have been identified in Hole 401 (Leg 48, Bay of Biscay). Two of the pyroclastic phases can be matched with phases previously reported for the North Sea Basin. The bentonites of Site 550 are probably equivalent to the widespread "ash series" of northwestern Europe, which may therefore be regarded as being lower Eocene in terms of Martini's calcareous nannoplankton zonation.

Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

(Table 1) Geochemistry of glass shards at DSDP Site 87-582 and 87-583

In the Leg 87A holes, 45 ash layers were sampled in Recent to upper Pliocene strata. The main volcanogenic deposits came from single eruptions or subcontemporaneous eruptions of cognate volcanoes. Some of them are mixed ashes produced from multiple eruptions and accumulated in reworked sediments. The petrographic and geochemical patterns indicate rhyolitic and dacitic compositions; andesitic glasses are scarce. We infer a magmatic affinity with calc-alkaline sources and a possible origin from the volcanic arc of southwestern Japan. A few samples may originate from the alkaline volcanism of southwestern Japan or the area south of Korea and the Sea of Japan.

Geochemistry of glass shards in the volcanic ash layers of the Izu-Bonin Arc

To examine the processes and histories of arc volcanism and of volcanism associated with backarc rifting. 130 samples containing igneous glass shards were taken from the Plioccne-Quatemai^ succession on the rift Hank (Site 788) and the Quaternary fill in the basin fill of the Sumisu Rift (Sites 790 and 791). These samples were subsequently analyzed at the University of Illinois at Chicago and Shizuoka University. The oxides determined by electron probe do not account for the total weight of the material; differences between summed oxides and 100% arise from the water contents, probably augmented by minor losses thai result from alkali vaporization during analysis. Weight losses in colorless glasses are up to 9%; those in brown glasses (dacitcs to basalts) arc no more than 4.5%; shards from the rift-flank (possibly caused by prolonged proximity to ihc scafloor) generally have higher values than those from the rift-basin fill How much of the lost water is magmatic, and how much is hydrated is uncertain; however, although the shards absorb potassium, calcium, and magnesium during hydration in the deep sea, they do so only to a minor extent that does not significantly alter their major element compositions. Therefore, the electron-probe results are useful in evaluating the magmatism recorded by the shards. Pre- and syn-rift Izu-Bonin volcanism were overwhelmingly dominated by rhyolile explosions, demonstrating that island arcs may experience significant silicic volcanism in addition to the extensive basaltic and basaltic andestic activity, documented in many arcs since the 1970s, that occurs in conjunction with the andesitic volcanism formerly thought to be dominant. Andesitic eruptions also occurred before rifting, but the andesitic component in our samples is minor. All the pre- and syn-rift rhyolites and andesites belong to the low-alkali island-arc tholeiitic suite, and contrast markedly with the alkali products of Holocene volcanism on the northernmost Mariana Arc that have been attributed to nascent rifting. The Quaternary dacites and andesites atop the rift flank and in the rift-basin fill are more potassic than those of Pliocene age, as a result of assimilation from the upper arc crust, or from variations in degrees of partial melting of the source magmas, or from metasomatic fluids. All the glass layers from the rift-flank samples belong to low-K arc-tholeiitic suites. Half of those in the Pliocene succession are exclusively rhyolitic: the others contain minor admixtures of dacite and andesite, or andesite and either basaltic andesite or basalt. In Contrast, the Quaternary (syn-rift) volcaniclastics atop the rift-flank lack basalt and basaltic andesite shards. These youngest sediments of the rift flank show close compositional affinities with five thick layers of coarse, rhyolitic pumice deposits in the basin fill, the two oldest more silicic than the younger ones. The coarse layers, and most thin ash layers that occur in hemipelagites below and intercalated between them, are low-K rhyolites and therefore probably came from sources in the arc. However, several thin rhyolitic ash beds in the hemipelagites are abnormally enriched in potassium and must have been provided by more distal sources, most likely to the west in Japan. Remarkably, the Pliocene-Pleistocene geochemistry of the volcanic front does not appear to have been influenced by the syn-rift basaltic volcanism only a few kilometers away. Rare, thin layers of basaltic ash near the bases of the rift-basin successions are not derived from the arc. They deviate strongly from trends that the arc-derived glasses display on oxide-oxide plots, and show close affinities to the basalts empted all over the Sumisu Rift during rifting. These basalts, and the basaltic ashes in the basal rift-basin fill, arc compositionally similar to those erupted from mature backarc basins elsewhere.