Chemical and isotopic compositions and age of carbonates from the Lost City hydrothermal field, Mid-Atlantic Ridge

Two genetically different types of authigenic carbonate mounds are studied: (1) from an active hydrothermal field related to serpentinite protrusions in a zone of intersection of a transform fracture zone with the Mid-Atlantic Ridge, (2) from an active field of methane seepings in the Dnieper canyon of the Black sea. General geochemical conditions, under which authigenic carbonate formation occurs within these two fields, were found. They include: presence of reduced H2S, H2, and CH4 gases at absence of free oxygen; high alkalinity of waters participating in carbonate formation; similarity of textural and structural features of authigenic aragonite, which represents the initial carbonate mineral of the mounds; paragenesis of aragonite with sulfide minerals; close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested. It implies their microbial sulfate reduction over hydrogen from fluid in the subsurface mixing zone of hydrothermal solution and adjacent seawater.

Macroturbidites of ODP Hole 103-641C

Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

K-Ar dating of altered deep-sea igneous rocks from DSDP Legs 2, 34, and 35

In an attempt to establish criteria for obtaining reliable K-Ar dates, conventional K-Ar studies of several Deep Sea Drilling Project sites were undertaken. K-Ar dates of these rocks may be subject to inaccuracies as the result of sea-water alteration. Inaccuracies may also result from the presence of excess radiogenic 40Ar trapped in rapidly cooled rocks at the time of their formation. The results obtained for DSDP Leg 34 basalts indicate that lowering of K-Ar dates, which is related to potassium addition by weathering, is a major cause of uncertainty in obtaining reliable K-Ar dates for deep-sea rocks. It could not be determined if the potassium addition to the basalts occurred at the time of formation, t_o, or continuously from t_o to the present. Calculations show that sediment cover is not a significant barrier to the diffusion of potassium into the basalt. 40Ar loss contributes, at least in part, to the lowering of the K-Ar date in rocks that have added potassium. The meaning of the K-Ar results obtained for DSDP Legs 35 and 2 basalts could not be unambiguously established. Because of the problems involved, caution must be used in interpreting the meaning of conventional K-Ar dates for deep-sea rocks.

Iron and carbon geochemistry of sediment core GeoB1401-4

Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative.

Composition of suspended matter and bottom sediments from the North Dvina mouth area

Grain-size, mineral and chemical compositions of suspended particulate matter (SPM) from waters of the Severnaya (North) Dvina River mouth area during the spring flood in May 2004 is studied. Data published on composition of riverine SPM in the White Sea basin are very poor. The spring flood period when more than half of annual runoff is supplied from the river to the sea in during short time is understood more poorly. The paper considers comparison results of the grain size compositions of SPM and bottom sediments. Data of laser and hydraulic techniques of grain size analysis are compared. Short-period variations of SPM concentration and composition representing two diurnal peaks of the tide level are studied. It is found that SPM is mainly transferred during the spring flood as mineral aggregates up to 40 µm diameter. Sandy-silty fraction of riverine SPM settles in delta branches and channels, and bulk of clay-size material is supplied to the sea. Mineral and chemical compositions of SPM from the North Dvina River are determined by supply of material from the drainage basin. This material is subjected to intense mechanic separation during transfer to the sea. Key regularities of formation of mineral composition of SPM during the flood time are revealed. Effect of SPM grain size composition on distribution of minerals and chemical elements in study in the dynamic system of the river mouth area are characterized.

Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.

(Table 1) Lead, thorium and uranium isotopic concentration and ages of zircons from Yenisey Ridge metapelites

Reconstruction of the geologic history of the Yenisey Ridge, which developed as an accretionary collision orogen on the western margin of the Siberian craton is essential to understanding the evolution of mobile belts surrounding older cratons, as well as to resolving the recently much debated problem of whether Siberia was part of the supercontinent Rodinia. Available paleotectonic models suggest that this supercontinent was assembled at the Middle-Late Riphean boundary (1100-900 Ma) as a result of the Grenville orogeny, the first long-lived mountain building event which occurred in geosynclinal areas during the Neogaea. However, the character of crustal evolution at that stage is still speculative due to the lack of reliable and conclusive isotope data. In many current geodynamic models, a common underlying assumption is that the Yenisey Ridge showed very little endogenic activity for 1 Gyr, from the time of Tarak granite emplacement (1900-1840 Ma) to the Middle Neoproterozoic (~750 Ma). On the basis of this assumption, several recent studies suggested the absence of Grenvillian collisional events within the Yenisey Ridge. The results of the SHRIMP II U-Pb analysis of rift-related plagiogranites of the Nemtikha Complex, Yenisey Ridge (1380-1360 Ma) suggest an increase in magmatic activity in the Mesoproterozoic. Interpretation of these results in terms of a supercontinent cycle may help find evidence for possible occurrence of the Grenville orogeny on the western margin of the Siberian craton. With this in mind, we attempted to reconstruct using recent geochronological constraints the evolution of metapelitic rocks from the Teya polymetamorphic complex (TPMC), which is a good example of superimposed zoning of low and medium-pressure facies series. High precision age determinations from rock complexes formed in different geodynamic settings under different thermodynamic conditions and geothermal gradients were used to distinguish several major metamorphic events and unravel their time relations with tectonic and magmatic activity in the region.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.

Paleomagnetic of ODP Hole 197-1203A

On the basis of studies of Holocene samples,submarine basaltic glass (SBG) is thought to be an ideal paleointensity recorder because it contains unaltered single domain magnetic inclusions that yield Thellier paleointensity data of exceptional quality. To be useful as a recorder of the long-term geomagnetic field, older SBG must retain these optimal properties. Here, we examine this issue through rock magnetic and transmission electron microscope (TEM) analyses of Cretaceous SBG recovered at Ocean Drilling Program Site 1203 (northwestern Pacific Ocean). These SBG samples have very low natural remanent magnetization intensities (NRM <50 nAm**2/g) and TEM analyses indicate a correspondingly low concentration of crystalline inclusions. Thellier experiments on samples with the strongest NRM intensity (>5*10**-11 Am**2) show a rapid acquisition of thermoremanent magnetization (TRM) with respect to NRM demagnetization. Taken at face value,this behavior implies magnetization in a very weak (617 WT) ambient field. But monitoring of magnetic hysteresis properties during the Thellier experiments (on subsamples of the SBG samples used for paleointensity determinations) indicates systematic variations in values over the same temperature range where the rapid TRM acquisition is observed. A similar change in properties during heating is observed on monitor SBG specimens using low-temperature data: with progressive heatings the Verwey transition becomes more distinct. We suggest that these experimental data record the partial melting and neocrystallization of magnetic grains in SBG during the thermal treatments required by the Thellier method,resulting in paleointensity values biased to low values. We further propose that this process is pronounced in Cretaceous and Jurassic SBG (relative to Holocene SBG) because devitrification on geologic time scales (i.e., tens of millions of years) lowers the transition temperature at which the neocrystallization can commence. Magnetic hysteresis monitoring may provide a straightforward means of detecting the formation of new magnetic inclusions in SBG during Thellier experiments.

Chemical and isotopic compositions of Archean magmatic and metasedimentary rocks and minerals from the Podolia domain, Ukrainian Shield

Zircons from the oldest magmatic and metasedimentary rocks in the Podolia domain of the Ukrainian shield were studied and dated by the U-Pb method on a NORDSIM secondary-ion mass spectrometer. Age of zircon cores in enderbite gneisses sampled in the Kazachii Yar and Odessa quarries on the opposite banks of the Yuzhnyi Bug River reaches 3790 Ma. Cores of terrigenous zircons in quartzites from the Odessa quarry as well as in garnet gneisses from the Zaval'e graphite quarry have age within 3650-3750 Ma. Zircon rims record two metamorphic events around 2750-2850 Ma and 1900-2000 Ma. Extremely low U content in zircons of the second age group indicates conditions of the granulite facies metamorphism in Paleoproterozoic within the Podolia domain. Measured data on orthorocks (enderbite-gneiss) and metasedimentary rocks unambiguously suggest existence of the ancient Paleoarchean crust in the Podolia (Dniester-Bug) domain of the Ukrainian shield. They contribute in our knowledge of scales of formation and geochemical features of the primordial crust.

K-Ar dating of magmatic rocks from the Urup Island, Kuril Island Chain

An isotope-geochronological study of Neogene-Quaternary igneous rocks from the Urup Island (Greater Kuril Ridge) was carried out. It was established that magmatic activity in the island developed during the last 10 my and it was not interrupted by long inactive periods. K-Ar data obtained along with results of diatomic analysis are in good agreement with the regional stratigraphic scheme of Paleogene and Neogene deposits and the intraregional correlation scheme of magmatic rocks in the Kuril Islands, which are developed for the State Geologic Map, scale 1:200 000 (Second edition). In the present-day territory of the Urup Island, the earliest Late Miocene - Early Pliocene (10.5-4.5 Ma) magmatic stage was associated with formation of the Rybakovsky andesite volcanic complex, which is represented by an effusive series (Rybakovskaya Suite) and subvolcanic rocks. Actually at the same time (6.6-4.7 Ma), but at a great depth, intrusive bodies of the Prasolovsky plagiogranite-diorite plutonic complex were intruded. The Pliocene stage of magmatism in the Urup Island is characterized by formation of rocks of the Kamuysky dacitic volcanic complex (4.0-2.1 Ma). This complex is locally represented only by subvolcanic acidic bodies, and its occurrence in the island is limited. During the Pliocene - Early Neopleistocene stage of magmatism (3.0-0.8 Ma) the Fregatsky andesibasalt volcanic complex was formed in the Urup Island. This complex includes effusive series (Fregatskaya unit) and subvolcanic bodies. Quaternary time in the Urup Island is characterized by eruptive activity in subaerial conditions with formation of effusive-pyroclastic intermediate-basic rocks of the Bogatyrsky Middle Neopleistocene - Holocene complex (<0.5 Ma). Rocks of this complex formed stratovolcano cones. Pyroclastic rocks of the Rokovsky dacitic volcanic complex were erupted simultaneously. The mentioned magmatic complexes of the Urup Island well correlate with the distinguished magmatic complexes within the bounds of contiguous insular blocks of the Greater Kuril Arc and confirm uniform geologic history of magmatic development of the region.