Characterization of diagenetic fluids at ODP Site 103-639

Site 639, drilled during Leg 103 of the Ocean Drilling Program, penetrated an Upper Jurassic to Lower Cretaceous carbonate platform on a tilted fault block along the Galicia margin off the northwest Iberian Peninsula. The carbonate platform is composed primarily of a sequence of dolomite overlying limestone. Samples were analyzed for mineral chemistry, stable isotope geochemistry, fluid inclusion microthermometry, and volatile contents and by dolomite pyrolysis mass spectrometry for trace sulfate minerals. The dolomite recovered from the Galicia margin at Site 639 formed during shallow burial from sulfate-bearing, hypersaline brines at slightly elevated temperatures. The light oxygen isotopic signatures of the dolomite are interpreted as the result of the evaporative loop and slightly elevated temperatures during dolomite formation or from reequilibration at higher temperatures during deeper burial. The hypersalinity is interpreted to be associated with a nearby, shallow restricted basin that formed during rifting of the Iberian margin from Newfoundland. The dolomitization of the platform is therefore a by-product of the rifting.

Microthermometry and Raman analysis of fluid inclusions in different generations of quartz veins of the Athabasca Basin

The Athabasca Basin (Canada) contains the highest grade unconformity-type uranium deposits in the world. Underlying the Athabasca Group sedimentary rocks of the Dufferin Lake zone are variably graphitic pelitic schists (VGPS), altered to chlorite and hematite (Red/Green Zone: RGZ), and locally bleached near the unconformity during paleoweathering and/or later fluid interaction, leading to a loss of graphite near the unconformity. Fluid inclusions were examined in different generations of quartz veins, using microthermometry and Raman analysis, to characterize and compare the different fluids that interacted with the RGZ and the VGPS. In the VGPS, CH4-, N2- and CO2-rich fluids circulated. CH4- and N2-rich fluids could be the result of the breakdown of graphite to CH4/CO2, whereas N2-rich fluid is interpreted to be the result of breakdown of feldspars/micas to NH4+/N2. In the RGZ, highly saline fluids interpreted to be basinally derived have been recorded. The circulation of the two types of fluids (carbonic and brines) occurred at two different distinct events: 1) during the retrograde metamorphism of the basement rocks before the deposition of the Athabasca Basin for the carbonic fluids, and 2) after the deposition of the Athabasca Basin for the brines. Thus, in addition to possibly be related to graphite depletion in the RGZ, the brines can be linked to uranium mineralization.

Chemistry of upper Eocene microtektites

Late Eocene microtektites and crystal-bearing microkrystites extracted from DSDP and ODP cores from the Atlantic, Pacific, and Indian oceans have been analyzed to address their provenance. A new analysis of Nd and Sr isotopic compositions confirms previous work and the assignment of the uppermost microtektite layer to the North American tektites, which are associated with the 35.5 Ma, 85 km diameter Chesapeake impact structure of Virginia, USA. Extensive major element and Nd and Sr isotopic analyses of the microkrystites from the lowermost layer were obtained. The melanocratic microkrystites from Sites 216 and 462 in the Indian and Pacific oceans possess major element chemistries, Sr and Nd isotopic signatures and Sm-Nd, T CHUR, model ages similar to those of tagamite melt rocks in the Popigai impact structure. They also possess Rb-Sr, T UR, model ages that are younger than the tagamite TCHUR ages by up to ~1 Ga, which require a process, as yet undefined, of Rb/Sr enrichment. These melanocratic microkrystites are consistent with a provenance from the 35.7 Ma, 100 km diameter Popigai impact structure of Siberia, Russia, while ruling out other contemporaneous structures as a source. Melanocratic microkrystites from other sites and leucocratic microkrystites from all sites possess a wide range of isotopic compositions (epsilon (143Nd) values of -16 to -27.7 and epsilon (87Sr) values of 4.1-354.0), making the association with Popigai tagamites less clear. These microkrystites may have been derived by the melting of target rocks of mixed composition, which were ejected without homogenization. Dark glass and felsic inclusions extracted from Popigai tagamites possess epsilon (143Nd) and epsilon (87Sr) values of -26.7 to -27.8 and 374.7 and 432.4, respectively, and T CHUR and T UR model ages of 1640-1870 Ma and 240-1830 Ma, respectively, which require the preservation of initially present heterogeneity in the source materials. The leucocratic microkrystites possess diverse isotopic compositions that may reflect the melting of supra-basement sedimentary rocks from Popigai, or early basement melts that were ejected prior to homogenization of the Popigai tagamites. The ejection of melt rocks with chemistries consistent with a basement provenance, rather than the surface ~1 km of sedimentary cover rocks, atypically indicates a non-surficial source to some of the ejecta. Microkrystites from two adjacent biozones possess statistically indistinguishable major element compositions, suggesting they have a single source. The occurrence of microkrystites derived from a single impact event, but in different biozones, can be explained by: (1) diachronous biozone boundaries; (2) post-accumulation sedimentary reworking; or (3) erroneous biozonation.

Epibiotic assemblages on seaweeds in the German Wadden Sea (North Sea)

After detachment from benthic habitats, the epibiont assemblages on floating seaweeds undergo substantial changes, but little is known regarding whether succession varies among different seaweed species. Given that floating algae may represent a limiting habitat in many regions, rafting organisms may be unselective and colonize any available seaweed patch at the sea surface. This process may homogenize rafting assemblages on different seaweed species, which our study examined by comparing the assemblages on benthic and floating individuals of the fucoid seaweeds Fucus vesiculosus and Sargassum muticum in the northern Wadden Sea (North Sea). Species richness was about twice as high on S. muticum as on F. vesiculosus, both on benthic and floating individuals. In both seaweed species benthic samples were more diverse than floating samples. However, the species composition differed significantly only between benthic thalli, but not between floating thalli of the two seaweed species. Separate analyses of sessile and mobile epibionts showed that the homogenization of rafting assemblages was mainly caused by mobile species. Among these, grazing isopods from the genus Idotea reached extraordinarily high densities on the floating samples from the northern Wadden Sea, suggesting that the availability of seaweed rafts was indeed limiting. Enhanced break-up of algal rafts associated with intense feeding by abundant herbivores might force rafters to recolonize benthic habitats. These colonization processes may enhance successful dispersal of rafting organisms and thereby contribute to population connectivity between sink populations in the Wadden Sea and source populations from up-current regions.

Mineralogy of the clay fraction from Cenozoic Strata at DSDP Leg 94

Leg 94 Sites are located in a large geographic area of the northeastern Atlantic. Clay mineral analyses of the sediments recovered on Leg 94 (Eocene to the present), together with results obtained from previous DSDP legs (47B, 48, 80, 81, 82), provide greater insight into the paleoenvironmental evolution of the northeastern Atlantic. The characteristics of Eocene clay sediments are regional, reflecting, in the absence of strong bottom currents, the influence of neighboring petrographic environments: basic volcanic rocks (Sites 403-406, 552, and 608) and acid volcanic rocks (Sites 508 to 510). During the Oligocene, atmospheric circulation patterns left their mineralogical signatures in the southern part of the area investigated (Sites 558 and 608), whereas during the Miocene the intrusion of northern water masses led to the gradual homogenization of the clay sedimentation throughout the North Atlantic. In the late Pliocene, input from glacial sources became widespread.

Chemical composition of clinopyroxenes and melt inclusions in clinopyroxenes from rocks of the Malaita Island, Ontong Java Plateau (Pacific Ocean)

The paper is based on new results of melt inclusion studies in minerals. Physicochemical and geochemical parameters of plateau basalt magmatic systems of the Siberian Platform and Ontong Java Plateau (Pacific Ocean) have been established. The studied melts are enriched in Fe. That differs them from magmatic melts of mid-ocean ridges (MOR). A comparative analysis of data on inclusions has shown a similarity of continental and oceanic plateau basalt magmatic systems. They considerably differ from those of MOR and intraplate oceanic islands. Crystallization of oceanic plateau basalts took place at lower temperatures and pressures as compared with similar rocks of the Siberian Platform. The data on inclusions evidence that the melts of the Siberian Platform and the Malaita Island underwent a serious evolution in contrast to magmas of the Nauru Basin that have more stable geochemical parameters. The most fractionated low-temperature high-Fe magmas with elevated contents of trace and rare-earth elements occur in the Malaita Island (Ontong Java Plateau) magmatic system.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Results of analyses of fluid inclusions from ODP Site 735B, Leg 118 and 176

Microthermometric and isotopic analyses of fluid inclusions in primitive olivine gabbros, oxide gabbros, and evolved granitic material recovered from Ocean Drilling Program Hole 735B at the Southwest Indian Ridge provide new insights into the evolution of C-O-H-NaCl fluids in the plutonic foundation of the oceanic crust. The variably altered and deformed plutonic rocks span a crustal section of over 1500 m and record a remarkably complex magma-hydrothermal history. Magmatic fluids within this suite followed two chemically distinct paths during cooling through the subsolidus regime: the first path included formation of CO2+CH4+H2O+C fluids with up to 43 mole% CH4; the second path produced hypersaline brines that contain up to 50% NaCl equivalent salinities. Subsequent to devolatilization, respeciation of magmatic CO2, attendant graphite precipitation, and cooling from 800°C to 500°C promoted formation of CH4-enriched fluids. These fluids are characterized by average d13C(CH4) values of -27.1+/-4.3 per mil (N=45) with associated d13C(CO2) compositions ranging from -24.9 per mil to -1.9 per mil (N=39), and average dD values of exsolved vapor of -41+/-12 per mil (N=23). In pods, veins, and lenses of highly fractionated residual material, hypersaline brines formed during condensation and by direct exsolution in the absence of a conjugate vapor phase. Entrapped CO2+CH4+H2O-rich fluids within many oxide-bearing rocks and felsic zones are significantly depleted in 13C (with d13C(CO2) values down to about -25 per mil) and contain CO2 concentrations higher than those predicted by equilibrium devolatilization models. We hypothesize that lower effective pressures in high-temperature shear zones promoted infiltration of highly fractionated melts and compositionally evolved volatiles into focused zones of deformation, significantly weakening the rock strength. In felsic-rich zones, volatile build-up may have driven hydraulic fracturing of gabbroic wall rocks resulting in the formation of magmatic breccias. Comparison of isotopic compositions of fluids in plutonic rocks from 735B, the MARK area of the Mid-Atlantic Ridge, and the Mid-Cayman Rise indicate (1) that the carbon isotope composition of the lower oceanic crust may be far more heterogeneous than previously believed and (2) that carbon-bearing species in the oceanic crust and their distribution at depth are highly variable.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

Major and trace element composition of melts from the Gorely volcanic center, southern Kamchatka

Melt inclusions in olivine and plagioclase phenocrysts from rocks (magnesian basalt, basaltic andesite, andesite, ignimbrite, and dacite) of various age from the Gorely volcanic center, southern Kamchatka, were studied by means of their homogenization and by analyzing the glasses in 100 melt inclusions on an electron microprobe and 24 inclusions on an ion probe. The SiO2 concentrations of the melts vary within a broad range of 45-74 wt%, as also are the concentrations of other major components. According to their SiO2, Na2O, K2O, TiO2, and P2O5 concentrations, the melts are classified into seven groups. The mafic melts (45-53 wt% SiO2) comprise the following varieties: potassic (on average 4.2 wt% K2O, 1.7 wt% Na2O, 1.0 wt% TiO2, and 0.20 wt% P2O5), sodic (3.2% Na2O, 1.1% K2O, 1.1% TiO2, and 0.40% P2O5), and titaniferous with high P2O5 concentrations (2.2% TiO2, 1.1% P2O5, 3.8% Na2O, and 3.0% K2O). The melts of intermediate composition (53-64% SiO2) also include potassic (5.6% K2O, 3.4% Na2O, 1.0% TiO2, and 0.4% P2O5) and sodic (4.3% Na2O, 2.8% K2O, 1.3% TiO2, and 0.4% P2O5) varieties. The acid melts (64-74% SiO2) are either potassic (4.5% K2O, 3.6% Na2O, 0.7% TiO2, and 0.15% P2O5) or sodic (4.5% Na2O, 3.1% K2O, 0.7% TiO2, and 0.13% P2O5). A distinctive feature of the Gorely volcanic center is the pervasive occurrence of K-rich compositions throughout the whole compositional range (silicity) of the melts. Melt inclusions of various types were sometimes found not only in a single sample but also in the same phenocrysts. The sodic and potassic types of the melts contain different Cl and F concentrations: the sodic melts are richer in Cl, whereas the potassic melts are enriched in F. We are the first to discover potassic melts with very high F concentrations (up to 2.7 wt%, 1.19 wt% on average, 17 analyses) in the Kuriles and Kamchatka. The average F concentration in the sodic melts is 0.16 wt% (37 analyses). The melts are distinguished for their richness in various groups of trace elements: LILE, REE (particularly HREE), and HFSE (except Nb). All of the melts share certain geochemical features. The concentrations of elements systematically increase from the mafic to acid melts (except only for the Sr and Eu concentrations, because of active plagioclase fractionation, and Ti, an element contained in ore minerals). The paper presents a review of literature data on volcanic rocks in the Kurile-Kamchatka area in which melt inclusions with high K2O concentrations (K2O/Na2O > 1) were found. K-rich melts are proved to be extremely widespread in the area and were found on such volcanoes as Avachinskii, Bezymyannyi, Bol'shoi Semyachek, Dikii Greben', Karymskii, Kekuknaiskii, Kudryavyi, and Shiveluch and in the Valaginskii and Tumrok Ranges.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.

Composition of rocks and minerals from the transition zone of the Reykjanes Ridge

Investigations of petrography, mineralogy, and chemical composition of gases and fluids in tuffs and lavas were carried out on samples dredged in the transition zone from the shelf and slope of Iceland to the Reykjanes Ridge. The samples were collected from the depths of 950-720 m during different expeditions of R/V Akademik Kurchatov and Mikhail Lomonosov. Mantle ultrabasite inclusions were first recognized in the region of Iceland. It can be assumed that they are related to eruptive structures formed on the ocean floor during Pliocene and are associated with the Iceland hot spot.