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.

Organic geochemistry of ODP Leg 135 sediment samples

The average total organic carbon (TOC) content obtained after Rock-Eval/TOC analysis of 156 sediment samples from the eight sites cored during Leg 135 is 0.05%. Hence, the TOC content of Leg 135 sediments is extremely low. The organic matter that is present in these samples is probably mostly reworked and oxidized material. Ten sediment samples were selected for extraction and analysis by gas chromatography and gas chromatography-mass spectrometry. Very low amounts of extractable hydrocarbons were obtained and some aspects of the biomarker distributions suggest that these hydrocarbons are not representative of the organic matter indigenous to the samples. A sample of an oil seep from Pili, Tongatapu was also analyzed. The seep is a biodegraded, mature oil that shows many characteristics in common with previously published analyses of oil seeps from Tongatapu. Biomarker evidence indicates that its source is a mature, marine carbonate of probable Late Cretaceous-Early Tertiary age. The source rock responsible for the Tongatapu oil seeps remains unknown.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

(Table 1) Geochemistry of basalts of Nauru Basin

Leg 61 of the Deep Sea Drilling Project (DSDP) was concerned with drilling a single continuously cored multiple re-entry hole at site 462 in the Central Nauru Basin (Fig. 1). Preliminary results of this drilling, which penetrated more than 1 km beneath the sea floor, were presented earlier. One major result was the discovery of a late Cretaceous off-ridge volcanic/intrusive complex of basaltic composition and great thickness (>500 m). We now present trace element abundance data for these basalts. Results of the drilling provide further support for a relatively long-lived thermal and magmatic event in the late Cretaceous resulting in voluminous and widespread magmatism in the central and western Pacific consistent with earlier suggestions. The trace element data show that most of the rocks produced during this event have trace element characteristics intermediate between those of normal and transitional mid-ocean ridge basalts (N- and T-type MORB) and different from Hawaiian basalts. These results indicate that basalts which are depleted in light rare earth elements (LREE) relative to the heavy REE may, in certain conditions, be erupted as voluminous intra-plate eruptions far from active ridge crests.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.

Geochemistry and petrography of organic matter at DSDP Hole 77-535

Organic geochemical and organic petrographic methods were used to study three Lower to middle Cretaceous sediment samples from Hole 535 in the southeastern Gulf of Mexico for organic matter contents and origin and level of maturation. All three samples contain mixed kerogen Type II/III organic matter with a maturity corresponding to about 0.4% vitrinite reflectance. The marine component increases with stratigraphic age, and microbial reworking of the organic matter is significant in each age. The lower two samples of Hauterivian to Valanginian age appear to be impregnated (or contaminated) with soluble polar organic compounds, but there is only a weak indication for the presence of more mature, nonindigenous hydrocarbons.

Organic geochemistry of sediment samples from Prydz Bay

High molecular weight aliphatic hydrocarbons were extracted from sediments at two sites (741 and 742) drilled during Ocean Drilling Program Leg 119 in Prydz Bay, a major embayment on the continental shelf of East Antarctica. The distributions of n-alkanes and triterpenoid and steroid hydrocarbons suggest that the n-alkanes and steranes are mainly of terrestrial origin and that the hydrocarbons are immature to slightly mature in the Lower Cretaceous sediments and immature to mature in the Tertiary sediments. At Site 741, the Lower Cretaceous depositional sequence, which is generally characterized by immature hydrocarbons, is interrupted by sediment having more mature components, suggesting a change of source during part of Early Cretaceous time. At Site 742, the mature geochemical parameters of a Pliocene sample correlate with results reported elsewhere for Site 739. In all but one of the other Tertiary samples, the geochemical parameters indicate intermediate maturity. The Lower Cretaceous and Pliocene sediments average about 1.9% organic carbon, a value of interest from the point of view of potential sources of petroleum offshore from Antarctica.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Organofacies reconstruction and lipid geochemistry of sediments from the Galicia margin

Samples of Lower to middle Cretaceous rocks from ODP Sites 638, 640, and 641, drilled on the Galicia continental margin in the northeast Atlantic, have been investigated by organic geochemical methods (i.e., organic carbon determination, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry) to define the Organofacies types and the depositional environments of these sediments. The results of this study fit well into the general picture drawn for the depositional history of the organic matter in Cretaceous organic-carbon-rich sediments in the North Atlantic from previous DSDP investigations. During the Valanginian to Albian, terrigenous organic carbon dominated the organic matter deposited on the Galicia continental margin. Cyclic changes in total organic carbon content were probably controlled by climatic-triggered changes in the supply of terrigenous organic matter from the nearby continent. A drastic change in depositional environment must have occurred near the Cenomanian/Turonian boundary. The preservation of large amounts of marine organic carbon in these sediments was probably caused by anoxic deep-water conditions during that time, rather than high productivity. All of the primary organic matter of the sediment samples investigated is thermally immature, as indicated by very low vitrinite reflectance values.