Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Geochemistry at DSDP Hole 57-439

Acidic to intermediate volcanic rocks were obtained as boulders, pebbles, and clasts with intercalated matrix sediments near the Japan Trench. A 47.5-meter conglomerate bed unconformably overlies acoustic basement consisting of Upper Cretaceous siltstone and is overlain in turn by massive coarse-sandstone and siltstone beds with many fossil mollusks. The volcanic cobbles and boulders in the conglomerate show pronounced porphyritic texture. Their phenocrysts are plagioclase, hornblende, and biotite; the groundmass consists of plagioclase, K-feldspar, quartz, iron oxide, and altered interstitial glass. The Plagioclase content of these volcanic rocks is very high, whereas iron oxide minerals are rare. The chemical composition of these volcanic rocks was analyzed to determine the rock series. Matrix sediments were also analyzed chemically, and their chemical composition was found to be similar to that of volcanic rocks, except for a lower CaO content. SiO2 content of the volcanic rocks ranges from 60.23 to 73.90, corresponding to that of andesite to rhyolite. All the samples show extremely high Al2O3 content, which reflects the high amounts of modal plagioclase. These volcanic rocks belong to both the calc-alkalic and tholeiitic rock series, and the differentiation trend is controlled by fractional crystallization, mainly of plagioclase, K-feldspar, and hornblende. The assemblage of calc-alkalic and tholeiitic rock series is frequently observed in island arcs and active continental margins. These volcanic rocks are derived from the Oyashio ancient landmass, which is a slightly matured island arc.

Sulfide petrology of basalts at DSDP Holes 69-504B and 69-505B

Primary sulfide mineralization in basalts of the Costa Rica Rift occurs mainly in chrome-spinel-bearing olivine tholeiites. Primary sulfides form both globules, consisting of quenched single-phase solid solutions, and irregular polymineralic segregations of pyrrhotite, chalcopyrite, cubanite, and pentlandite. Two types of sulfide solid solutions - iron-nickel (Mss) and iron-copper (Iss) - were found among sulfide globules. These types appear to have formed because of sulfide-sulfide liquid immiscibility in the host magmas; as proved by the presence of globules with a distinct phase boundary between Mss and Iss. Such two-phase globules are associated with large olivine phenocrysts. Inhomogeneties among the globule composition likewise are caused by sulfide-sulfide immiscibility. Secondary sulfides form irregular segregations and veins consisting of pyrite, marcasite, and chalcopyrite.

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 at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Minerals and geochemistry of DSDP Hole 81-552A

The acid insoluble coarse fractions of the glacial-interglacial sequence of Hole 552A in the NE Atlantic are made up of varying amounts of terrigenous detritus, biogenic silica, and pyroclastic material, principally volcanic glass. Volcanic ash content varies significantly over the entire interval, and the three North Atlantic ash horizons of Ruddiman and Glover (1972) can be recognized satisfactorily. The terrigenous detritus is of mixed metamorphic-basaltic type and probably originated on the Greenland landmass

Geochemistry of ash from Santorin, Greece

Santorin, am südlichsten Punkt des Kykladenbogens gelegen, ist der einzige noch tätige Vulkan in der südlichen Ägäis. Der Vulkanismus begann vor ca. 1.6 Mio. Jahren. Santorin besteht aus 5 Inseln, die nahezu vollständig aus vulkanischen Gesteinen aufgebaut sind, die im Laufe der Vulkangeschichte aus verschiedenen Eruptionszentren gefördert wurden. Abgesehen von den Laven im N der Hauptinsel Thera, wird der Zentral- und Südteil der Insel in der Hauptsache von den pyroklastischen Förderprodukten des sog. Thera-Vulkans aufgebaut. In der vorliegenden Arbeit waren diese pyroklastischen Serien Ziel der Untersuchungen. Die Ergebnisse daraus können folgendermaßen zusammengefaßt werden: - Die Aufnahme von 14 detaillierten Profilen und deren Korrelierung erbrachte die Einteilung der pyroklastischen Schichten in 5 Haupt-Folgen: T5/1 - Untere Bimsstein-Folge (Bu), T5/2-Mittlere Bimsstein-Folge (Bm), - T5/3, Die Obere Bimsstein-Folge (Bo) wurde dabei nicht weiter berücksichtigt, da sie bereits in zahlreichen Arbeiten untersucht worden ist. - Die als T5/1-3 bezeichneten Serien bestehen aus Aschen, Schlacken, wenigen Bimsstein-Horizonten und untergeordnet Ignimbriten, 'pyroclastic' und 'ash flow'-Ablagerungen, sowie Laharen. Umlagerungen und Bodenhorizonte zeigen die Unterbrechung in der vulkanischen Tätigkeit an. - In den Tg-Folgen konnten jeweils einer oder mehrere Leit-Horizonte gefunden werden, die es ermöglichen die drei Tg-Serien zu unterscheiden und zu korrelieren. - Die Untere Bimsstein-Folge (Bu) wurde in sechs Einheiten unterteilt, die eine Wechselfolge von 'pumice fall' und 'pumice flow'-Ablagerungen bilden. - Mineralogische Untersuchungen zeigen für die 5 Haupt-Folgen nur geringe Unterschiede. Die Bimssteine und Schlacken bestehen überwiegend aus Glas und haben nur wenige Phänokristalle (3-12 Vol.*), wobei der Plagioklas (Andesin-Labradorit) überwiegt; Orthopyroxen (Hypersthen) und Klinopyroxen (diops. Augit) stellen ca. 30% der Einsprengunge. An Akzessorien sind vorhanden: Apatit, Magnetit, Hämatit und sehr selten Hornblende. - Ein Versuch zur Unterscheidung der Gesteine in den einzelnen Schicht-Einheiten war die Bestimmung der Lichtbrechung und der Dichte. Es zeigte sich, daß die Dichte weniger geeignet ist, die Lichtbrechung aber eine schwache Differenzierung widerspiegelt und somit für die Bimssteine und Schlacken, aber auch für die Bimssteine innerhalb des Bu unterschiedliche Werte gefunden wurden - Aus den Korngrößen-Analysen des Asche-Leithorizontes der T5/3-Folge ergaben sich die Lage des Eruptionszentrums und die damals vorherrschende Windrichtung. - Die Oberen Ignimbrite (Ign., im Hangenden der T5/3-Folge) konnten erstmals in 5 Einheiten unterteilt werden. - Die Seltenen Erden-Analysen erbrachten für die einzelnen Folgen in etwa die gleichen SEE-Spektren. - Die geochemischen Untersuchungen von ca. 120 Proben sind in verschiedenen Diagrammen dargestellt. Daraus wird deutlich, daß die T5-Folgen die basischsten Glieder sind. Es handelt sich überwiegend um Quarz-Andesite und Quarz-Latiandesite, während die Bimsstein-Serien (Bu u. Bm) eine quarz-latiandesitische bis rhyodacitische Zusammensetzung haben. Es sind aber alles kalkalkaline Gesteine, die in den Bereich der Kontinentalrand-Andesite gehören. - Es wird angenommen, daß die Gesteine des Thera-Vulkans aus einer Magmakammer stammen. Während Zeiten ± kontinuierlicher, explosiver Tätigkeit wurden die Aschen und Schlacken der T5-Serien gefördert, die gegenüber den Bimsstein-Folgen relativ basisch sind. Während längerer Ruheperioden (Bodenhorizonte am Top der Tc-Folgen) differenzierte die Schmelze in der Magmakammer, vorwiegend durch Kristallfraktionierung. In den paroxysmalen Ausbrüchen wurden dann die sauren, gasreichen Bimssteine des Bu, Bm und Bo gefördert. - Anhand der lithologischen und geochemischen Untersuchungen ließen sich die etwaigen Eruptionszentren, die Ausbruchsmechanismen und der Ablagerungstyp der Schichten herleiten und daraus die Vulkangeschichte rekonstruieren, wie sie in vier Tabellen übersichtlich zusammengefaßt sind. - Schließlich sollen paläomorphologische Karten die einzelnen Stadien des Thera-Vulkans veranschaulichen.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.

Mineral chemistry of basalts from DSDP Holes 65-483 and 65-483B

During DSDP Leg 65, a series of holes was drilled into the oceanic basement across the mouth of the Gulf of California to study the composition of the crust and the nature of its construction at a young spreading center. In Holes 483 and 483B, two of the deepest basement holes drilled on this leg, the basement is characterized by an upper sequence of interlayered massive basalts and sediments underlain by a lower sequence of interlayered pillow and massive basalts. Electron microprobe analyses were performed on pyroxene, plagioclase, olivine, spinel, and glass from 14 representative samples of 10 of the 16 major lithologic units. These analyses along with petrographic results can be used to interpret the detailed crystallization history of the basalts. We believe from the results of this study that the basalts were formed by at least a three-stage cooling process, followed by eruption and formation of quench phases. Our data do not support magma mixing.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Composition of volcanic rocks from the Alchan Basin, Northwestern Primorie

Geological, petrochemical, and geochemical data are reported for volcanic rocks of a Cretaceous pull-apart basin in the Tan Lu strike-slip system, Asian continental margin. A comparison of these volcanic rocks with magmatic rocks from typical Cenozoic transform margins in the western North America and rift zones of Korea made it possible to distinguish some indicator features of transform-margin volcanic rocks. Magmatic rocks from strike-slip extension zones bear island-arc, intraplate, and occasionally depleted MORB geochemical signatures. In addition to calc-alkaline rocks there are bimodal volcanic series. The rocks are characterized by high K2O, MgO, and TiO2 contents. They show variable enrichment in LILE relative to HFSE, which is typical of island-arc magmas. At the same time they are rich in compatible transition elements, which is a characteristic of intraplate magmas. Trace element distribution patterns normalized to MORB or primitive mantle usually show a negative Ta-Nb anomaly typical of suprasubduction settings. Their Ta/Nb ratio is lower, whereas Ba/Nb, Ba/La, and La/Yb ratios are higher than those of some MORB and OIB. In terms of trace element systematics, for example, Ta-Th-Hf, Ba/La-(Ba/La)_n, (La/Sm)_n-La/Hf, and others, they fall within the area of mixing of magmas from several sources (island arc, intraplate, and depleted reservoirs). Magmatic rocks of transform settings show a sigmoidal chondrite-normalized REE distribution pattern with a negative slope of LREE, depletion in MREE, and an enriched or flat HREE pattern. Magmas with mixed geochemical characteristics presumably originated in a transform margin setting in local extension zones under influence of mantle diapirs, which caused metasomatism and melting of the lithosphere at different levels, and mixing of melts from different sources in variable proportions.