Magnetic properties and chemical composition at DSDP Hole 77-538A

Magnetic properties of doleritic and some metamorphic basement rocks underlying Catoche Knoll are studied. Doleritic rocks show a high saturation magnetic moment (2-5 emu/g) compared to metamorphic rocks (0.1-1 emu/g). Magnetic minerals of rocks from this hole show a high stability when heated in vacuo up to 600°C at a fixed rate of heating. Curie temperatures are distributed close to 550°C. These properties differ markedly from those of common submarine basalts observed before. X-ray microprobe analysis techniques were used to determine internal structures of ferromagnetic minerals; in most of ferromagnetic minerals there exist two different types of magnetic phases (i.e., products of high-temperature and low-temperature oxidations). Interpretations on the coexisting, seemingly contradictory, phases can be made based upon present analyses.

Age and chemical composition of apatites from five DSDP and ODP Sites in the Pacific, Atlantic and Indian Oceans

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ~10° and 70°C over geological time scales of ~15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analyzed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30°C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 µm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30°C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ~30°C. For samples which experienced maximum temperatures between ~30 and 70°C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.

Chemical composition of mineral phases of serpentinized and steatized peridotite from the Mid Atlantic Ridge (15°20'N Fracture Zone, ODP Leg209)

Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H2,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H2O.We have compiled and evaluated thermodynamic data for Fe-Ni-Co-O-S phases and computed phase relations in fO2,g-fS2,g and aH2,aq-aH2S,aq diagrams for temperatures between 150 and 400°C at 50MPa.We use the relations and compositions of Fe-Ni-Co-O-S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15°20'N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awaruite- magnetite-pentlandite and heazlewoodite-magnetite-pentlandite assemblages forming in the early stages of serpentinization to millerite-pyrite-polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite-vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO2,g-fS2,g in the system follows an isopotential of H2S,aq, indicating that H2S in vent fluids is buffered. In contrast, H2 in vent fluids is not buffered by Fe-Ni-Co-O-S phases, which merely monitor the evolution of H2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite- awaruite-magnetite indicates H2,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

Physical, chemical and biological characteristics of disturbed and undisturbed Arctic lakes, Northwest Territories

1. Global warming is predicted to cause changes in permafrost cover and stability in the Arctic. Zones of high ion concentration in regions of ice-rich permafrost are a reservoir of chemicals that can potentially be transferred to fresh waters during thawing. Consequently, input of enriched runoff from the thaw and sediment and vegetation from the landscape could alter lakes by affecting their geochemistry and biological production. 2. Three undisturbed lakes and five lakes disturbed by retrogressive permafrost thaw slumps were sampled during late summer of 2006 to assess the potential effects of thermokarst shoreline slumping on water and sediment chemistry, the underwater light regime, and benthic macrophyte biomass and community structure. 3. Undisturbed lakes had sediments rich in organic material and selected micronutrients, while disturbed lakes had sediments richer in calcium, magnesium and strontium, greater transparency of the water column, and a well-developed submerged macrophyte community. 4. It is postulated that enriched runoff chemistry may alter nutrient availability at the sediment-water interface and also the degradation of organic material, thus affecting lake transparency and submerged macrophytes. The results suggest that retrogressive permafrost slumping can significantly affect food webs in arctic tundra lakes through an increase in macrophyte biomass and development of a more complex benthic habitat.

Mineralogy, geochemistry and selected chemical formulas of sediments from ODP Holes 161-986B and 161-977A

Upper Miocene to Pleistocene hemipelagites and resedimented facies recovered at Holes 976B and 977A (Leg 161) in the Alboran Basin consist mainly of biogenic and detrital components, with a minor contribution of neoformed mineral phases. Diagenetic processes have not obliterated the primary deposition signal, and therefore detrital components (quartz, feldspar, detrital dolomite, rock fragments, and clays) provide information about source rocks and provenances. No major bulk or clay mineralogy differences were recognized between resedimented and hemipelagic facies; in fact, similar mineral assemblages in both types of facies suggest common source rocks. However, mineral abundance fluctuations can be related to climate variations and tectonic factors, as the main controls of sediment fill of this basin. A marked increase in smectites in Messinian sediments suggests an extensive development of soils during that time, probably favored by the alternation of wet and dry climate episodes and the relative aridification of the Mediterranean borderlands. A notable increase in detrital components suggests a sea-level fall and/or tectonic uplift during the late Pliocene. The significant increase in detrital dolomite in the uppermost Pliocene deposits suggests the uplift of dolomite-rich rocks as source areas. Mineral components in Pleistocene sediments indicate increasing tectonic stability, and clay-mineral fluctuations during the Pleistocene can be related not only to tectonic events, but also to alternating cooling and warming periods.

Mineral, chemical and isotopic compositions of altered rocks at ODP Sites 193-1188 and 193-1189

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite+/-illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite+/-mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite+/-illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite+/-chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ~250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite+/-chlorite alteration formed at ~300°C; (2) chlorite+/-illite alteration at 235°C; (3) chlorite+/-illite and mixed layer clay alteration; and (4) chlorite+/-illite alteration at 220°C. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.

Chemical observations in the Red Sea and the inner Gulf of Aden during the International Indian Ocean Expedition 1964/65

The Red Sea has a special place among the adjacent seas of the world. High evaporation, exclusion of its deep water from contact with the Indian Ocean proper and complete absence of continental drainage may result special conditions of the chemistry of the Red Sea. This paper aims to describe and explain the peculiarity of the hydrochemical situation. The influence of the topography, of the inflow and outflow through the straights of Bab el Mandeb, of the evaporation, of the stability of the water layers, and of the circulation will be studied. An attempt is made to estimate the apparent oxygen ultilisation in order to obtain an indication of the biological activity. A further attempt is made toward the quantitative estimation of the circulation of the nutrients and also to obtain some information about transport, dissolution, and precipitation of calcium carbonate. The basis of these investigations are mainly observations of R. V. "Meteor" during the International Indian Ocean Expedition 1964/65. The determination of dissolved oxygen, dissolved inorganic phosphate, nitrate, nitrite, ammonia, pH, alkalinity, silicate as well as salinity and temperature forms the necessary basis for such an investigation of the chemical conditions. In the first chapter the methods and some modifications for the determination of the chemical properties as applied during the I.I.O.E. cruise of R. V. "Meteor" are described. The new methods, as worked out and tested under sea going conditions during several years by the author, are described in more detail. These are the methods for nitrate, silicate, the automatic determination of dissolved inorganic phosphate and silicate, the automated determination of total phosphorus, the in situ recording of the oxygen tension, and the modification for the determination of ammonia, calcium, and dissolved oxygen. With these revised methods more than 18,000 determinations have been carried out during the Indian Ocean cruise. The complete working up of the chemical data of the Indian Ocean Expedition of R. V. "Meteor" is devided into four sections: Contributions 1) to the Chemistry of the Red Sea and the Inner Gulf of Aden, 2) to the Gulf of Aden and the Somali Coast Region, 3) to the Western Indian Coast Region, and 4) to the Persian Gulf and the Straits of Oman. This paper presents the first contribution. The special hydrographical conditions are discussed. It can be shown, that the increase of salinity in the surface waters from the south to the north of the Red Sea is only to about 30 % due to evaporation. The remaining increase is presumed to be due to the admixture of deep water to the surface layers. A special rate for the consumption of oxygen (0.114 ml/ l/a) is derived for the deep water of the Red Sea at 1500 m. Based upon the distribution of the dissolved oxygen along the axii of the Red Sea, a chematic model for the longitudinal circulation of the Red Sea is constructed. This model should be considered as a first approximation and may explain the special distribution of phosphate, nitrate, and silicate. Based upon the evaluation of the residence time of the deep water a dissolution rate for silicate is estimated as 1 mygat/a. It seems possible to calculate residence times of water masses outside the Red Sea from the silicate content. The increase of silicate and the consumption of oxygen lead to residence times of the water below the thermocine of 30 to 48 years. The distribution of oxygen in the Straits of Bab el Mandeb is described and discussed. The rate of consumption of the oxygen in the outflowing Red Sea water is estimated to 8.5 ml/ l/a. This rather high rate is explained with reference to the special conditions in the outflowing water. The Red Sea water is characterized initially by a relative high content of oxygen and a low content of nutrients. The increase in nutrients and the decrease in the oxygen content is a secondary process of the Red Sea water on its way to the Arabian Sea. Based upon the vertical distribution of the dissolved inorganic phosphate vertical exchange coefficients of 1 - 4 g/cm/sec and vertical current speeds of 10**-5 to 10**-4 cm/sec are calculated for some stations in the Red Sea. The distribution of phosphate, silicate, nitrate, nitrite and ammonia for the Red Sea and the Straits of Bab el Mandeb are discussed. The special circulation is evaluated and the balance of the nutrients is estimated by means of the brutto transport. The nutrient deficit is assumed to be balanced by sporadic inflow of intermediate water from the Gulf of Aden. An example for such an inflow has been observed and is demonstrated. The silicate-salinity relationships are a suitable way for characterizing water masses in the Red Sea. Equations for the calculation of the different components from the carbonate system, the ion activities, and the calcium carbonate saturation are evaluated. The influence of temperature and pressure is taken into account. The carbonate saturation is calculated from the determined concentrations of calcium, alkalinity, and the hydrogen ion activity. Saturation values of 320 % are found for the surface layer and of 100% ± 1 for the deep water. The extraordinary equilibrium conditions may explain the constant Ca/Cl ratio and also the sedimentation of undissolved carbonate skelecons even in greater depths. A main sedimentation rate of 2 * 10**-3cm/year is evaluated from a total sedimentation of 10 * 106 to/a of calcium carbonate in the Red Sea. The appendix contains those data, which are not published in the data volume of the I.I.O.E. expedition of R. V. "Meteor".

Chemical composition of ODP Leg 138 sediments

A major oceanographic event preserved in the Cocos plate sedimentary column survived subduction and is recorded in the changing composition of Nicaraguan magmas. A uranium increase in these magmas since the latest Miocene (after 7 Ma) resulted from the 'carbonate crash' at 10 Ma and the ensuing high organic carbon burial in the sediments. The response of the arc to this paleoceanographic event requires near steady-state sediment recycling at this margin since 20 Ma. This relative stability in sediment subduction invites one of the first attempts to balance sedimentary input and arc output across a subduction zone. Calculations based on Th indicate that as much as 75% of the sedimentary column was subducted beneath the arc. The Nicaraguan margin is one of the few places to observe such strong links between the oceans and the solid earth.

(Table 1, page 1376) Chemical analyses of manganese nodules and crusts from the Pacific Ocean

A compilation of chemical analyses of Pacific Ocean nodules using an x-ray fluorescence technique. The equipment used was a General Electric XRD-5 with a tungsten tube. Lithium fluoride was used as the diffraction element in assaying for all elements above calcium in the atomic table and EDDT was used in conjunction with a helium path for all elements with an atomic number less than calcium. Flow counters were used in conjunction with a pulse height analyzer to eliminate x-ray lines of different but integral orders in gathering count data. The stability of the equipment was found to be excellent by the author. The equipment was calibrated by the use of standard ores made from pure oxide forms of the elements in the nodules and carefully mixed in proportion to the amounts of these elements generally found in the manganese nodules. Chemically analyzed standards of the nodules themselves were also used. As a final check, a known amount of the element in question was added to selected samples of the nodules and careful counts were taken on these samples before and after the addition of the extra amount of the element. The method involved the determination and subsequent use of absorption and activation factors for the lines of the various elements. All the absorption and activation factors were carefully determined using the standard ores. The chemically analyzed samples of the nodules by these methods yielded an accuracy to at least three significant figures.