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.

The hydrographic conditions at depth below 1000 m water depth in the region of the Romanche Fracture Zones

During the "Atlantic Expedition" in1965 (IQSY) a comprehensive bathymetric survey and a few hydrographic stations were made by R.V. "Meteor" in the equatorial region of the Mid-Atlantic Ridge. The survey results are shown in a bythymetric chart covering the western parts of the Romanche- and Chain Fracture Zones. West of the original Romanche Trench another deep trench with a medium depth of 6000 m was discovered. The maximum sounding obtained was 7028 m. Both trenches apparently belong to the same fracture zone, but are distinctly separated from each other. The estern boundary of the trench against the Brasil Basin is formed by a sill rising to a depth of about 4400 m. The serial hydrographic observations give some indications of the flow of the cold Westatlantic deep water in the fracture zone area and its influence on the hydrographic conditions in the East-Atlantic Basin. The upper limit of the nearly homogenious Westatlantic bottom water with an Antarctic components lies about 4400 m. The water mass entering the system of trenches of the Romanche Fracture Zone over the western sill originates from the lower part of the discontinuity layer lying above the bottom water. Potential temperatures of 0.6°C were the lowest observed by "Meteor" in the western trench. There seems to be a remarkable tongue of relatively high salinity and a minimum of oxygen in the deep water of this trench. At present we can only speculate upon the origin of this highly saline deep water tongue underneath the eastward moving relatively thin layer of less saline Westatlantic deep water. In the range of the sill separating both trenches a lee wave is indicated by the distribution of salinity and oxygen, which implies a vertical transport of water masses. Caused by this transport it is assumed that relatively cold water may be lifted temporarily to a depth, where it can pass the northbounding ridge, thus getting directly into the Sierra Leone Basin. In the original Romanche Trench the cold Westatlantic deep water seems to fill the whole trough, but its extension remains limited to the trench itself. The water masses found east of the sill separating the trench from the East-Atlantic Basin originate from the lower part of the discontinuity layer. With potential temperatures of about 1.3°C they are much warmer than those observed in the Romanche Trench bottom water.

Stable isotopes of foraminifers, mineralogy and ages of sediment core GeoB1523-1

Today the western tropical Atlantic is the most important passage for cross-equatorial transfer of heat in the form of warm surface water flowing from the South into the North Atlantic. Circulation changes north of South America may thus have influenced the global thermohaline circulation system and high northern latitude climate. Here we reconstruct late Quaternary variations of western equatorial Atlantic surface circulation and Amazon lowland climate obtained from a multiproxy sediment record from Ceará Rise. Variations in the illite/smectite ratio suggest drier climatic conditions in the Amazon Basin during glacials relative to interglacials. The 230Thex-normalized fluxes and the 13C/12C record of organic carbon indicate that sea level fluctuations, shelf topography, and changes of the surface circulation pattern controlled variations and amplitude of terrigenous sediment supply to the Ceará Rise. We attribute variations in thermocline depth, reconstructed from vertical planktic foraminiferal oxygen isotope gradients and abundances of the phytoplankton species Florisphaera profunda, to changes in southeast trade wind intensity. Strong trade winds during ice volume maxima are associated with a deep western tropical Atlantic thermocline, strengthening of the North Brazil Current retroflection, and more vigorous eastward flow of surface waters.

Middle Miocene to recent sedimentological record of ODP sites 177-1088 and 177-1092

During Leg 177 of the Ocean Drilling Program (ODP), well-preserved Middle Miocene to Pleistocene carbonate-rich sediment records were recovered on a north-south transect through the south-eastern Atlantic sector of the Southern Ocean at Site 1088 on the Agulhas Ridge and Site 1092 on Meteor Rise. Both sites were dominated by the deposition of calcareous nannofossil oozes through the Miocene, indicating low biological productivity in warm to temperate surface waters. A continuous increase in the proportions of foraminifera since the latest Miocene (6.5 Ma) points to enhanced nutrient supply, possibly related to the global 'biogenic bloom' event across the Miocene-Pliocene boundary. Since the Late Pliocene, different styles of biological productivity developed between the sites. Enhanced deposition of biosiliceous constituents at the southern Site 1092, particularly in the Early Pleistocene, is consistent with the formation of the Circum-Antarctic Opal Belt since 2.5 Ma in a setting near the Polar Front, whereas carbonate deposition still prevailed at the northern Site 1088 situated near the Subtropical Front. Clay-mineral tracers of water-mass advection together with the pattern of sedimentation rates and hiatuses reflect distinct pulses in the development of regional ocean circulation between 14 and 12 Ma, around 8 Ma and since 2.8 Ma. These pulses can be related to Antarctic ice-sheet extension that mediates the production and flow of southern source water, and stepwise increases in North Atlantic Deep Water production that drives global conveyor circulation. At Site 1088, illite chemistry and silt/clay ratios of the terrigenous sediment fraction reflect the history of terrestrial climate in southern Africa, with humid conditions prior to the Early Late Miocene (9.7 Ma), followed by a dry episode until 7.7 Ma. The latest Miocene and Early Pliocene were characterized by a humid episode until modern aridity was established in the Late Pliocene between 4.0 and 2.8 Ma. These climate changes were related to the latitudinal migration of climate belts in response to tectonically caused reorganizations in atmospheric and ocean circulation.

Mineralogy and geochemistry of ODP Hole 176-735B minerals

We present a synthesis of some 20,504 mineral analyses of ~500 Hole 735B gabbros, including 10,236 new analyses conducted for this paper. These are used to construct a mineral stratigraphy for 1.5-km-deep Hole 735B, the only long section of the lower crust drilled in situ in the oceans. At long wavelengths, generally >200 m, there is a good chemical correlation among the principal silicate phases, consistent with the in situ crystallization of three or four distinct olivine gabbro bodies, representing at least two major cycles of intrusion. Initial cooling and crystallization of these bodies must have been fairly rapid to form a crystal mush, followed by subsequent compaction and migration of late iron-titanium-rich liquids into shear zones and fractures through which they were emplaced to higher levels in the lower crust where they crystallized and reacted with the olivine gabbro host rock to form a wide variety of ferrogabbros. At the wave lengths of the individual intrusions, as represented by the several olivine gabbro sequences, there is a general upward trend of iron and sodium enrichment but a poor correlation between the compositions of the major silicate phases. This, together with a wide range in minor incompatible and compatible element concentrations in olivine and pyroxene at a given Mg#, is consistent with widespread permeable flow of late melt through these intrusions, in contrast to what has been documented for a 600-m section of reputedly fast-spreading ocean crust in the Oman Ophiolite. This unexpected finding could be related to enhanced compaction and deformation-controlled late-stage melt migration at the scale of intrusion at a slow-spreading ocean ridge, compared to the relatively static environment in the lower crust at fast-spreading ridges.

Strontium chemistry of anhydrite from DSDP/ODP Hole 504B

A unique record of the chemical evolution of seawater during hydrothermal recharge into oceanic crust is preserved by anhydrite from the volcanic sequences and sheeted dike complex in ODP Hole 504B. Chemical and isotopic analyses 87Sr/86Sr, delta18O, delta34S of anhydrite constrain the changing composition of fluids due to reaction with basalt. There is a general trend of decreasing 87Sr/86Sr of anhydrite, corresponding to the minor incorporation of basaltic strontium with depth in the volcanic rocks. 87Sr/86Sr ratios decrease rapidly with depth in the dikes to values identical to host basalt (0.7029). Sr/Ca ratios (<0.1 mmol/mol) suggest that recharge fluids have very low Sr concentrations and fluids evolve by first precipitating Sr-bearing phases before extensive exchange of Sr with the host basalt. There is a background trend of decreasing sulfate delta18O with depth from +12-13? in the lower volcanics to +7? in the lower sheeted dikes recording an increase in recharge fluid temperature from c. 150° to c. 250°C, and confirming the presence of sulfate in hydrothermal fluids at elevated temperatures. From the amount of anhydrite recovered from Hole 504B and the amount of seawater sulfur that has been reduced to sulfide, a minimum seawater recharge flux can be calculated. This value is 4-25 times lower than estimates of high-temperature fluid fluxes based on either thermal constraints or global chemical budgets and suggests that there is significant deficit of seawater-derived sulfur in the oceanic crust. Only a minor proportion of the seawater that percolates into the crust near the axis is heated to high temperatures and exits as black smoker-type fluids. A significant proportion of the axial heat loss must be advected at 200-250°C by sulfate-bearing hydrothermal solutions that egress diffusely from the crust. These fluids penetrate into the dikes and exchange both heat and chemical tracers without the extensive clogging of porosity by anhydrite precipitation, which would halt hydrothermal circulation for any reasonable fluid flux. The heating of the major proportion of hydrothermal fluids to only moderate temperatures (c. 250°C) reconciles estimates of hydrothermal fluxes derived from thermal models and global geochemical budgets. The flux of hydrothermal sulfate would be of a magnitude similar to the riverine input, and oxygen-isotopic exchange at 200-250°C between dissolved sulfate and recharge fluids during hydrothermal circulation provides a mechanism to continuously buffer seawater sulfate oxygen to the light isotopic composition observed.

Geochemistry of interstitial waters of Lau Backarc Basin sediment samples

Interstitial water samples from Sites 834 through 839, drilled during Ocean Drilling Program Leg 135 in the backarc Lau basin (Southwestern Pacific), have been analyzed for major elements, manganese, copper, strontium, barium, vanadium, and 87Sr/86Sr isotopic composition values. The concentration-depth profiles of the major chemical components show almost straight concentration gradients at all sites, and seem to reflect slight alteration of volcanic material. However, in the lower part of the sedimentary cover, where volcanogenic material is abundant and where diagenetic minerals occur, systematic decreases in calcium, strontium, manganese, copper, and vanadium concentrations are observed. A downwelling flow of bottom seawater, which affected the diagenetic chemical signature of the interstitial water, is probably responsible for the recorded chemical features. This hypothesis is supported by strontium isotope data obtained from interstitial water samples at Site 835. It is also in accordance with data from heat flow and physical properties.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

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 of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

Benthic foraminiferal assemblages of the Barents Sea

Foraminiferal assemblages were studied in northern Barents Sea core ASV 880 along with oxygen and carbon isotope measurements in planktonic (N. pachyderma sin.) and benthic (E. clavatum) species. AMS C-14 measurements performed on molluscs Yoldiella spp. show that this core provides a detailed and undisturbed record of Holocene climatic changes over the last 10000 calendar years. Surface and deep waters were very cold (<0°C) at the beginning of the Holocene. C. reniforme dominated the highly diverse benthic foraminiferal assemblage. From 10 to 7.8 cal. ka BP, a warming trend culminated in a temperature optimum, which developed between 7.8 and 6.8 cal. ka BP. During this optimum, the input of Atlantic water to the Barents Sea reached its maximum. The Atlantic water mass invaded the whole Franz Victoria Trough and was present from subsurface to the bottom. No bottom water, which would form through rejection of brine during winter, was present at the core depth (388 m). The water stratification was therefore greatly reduced as compared to the present. An increase in percentage of I. helenae/norcrossi points to long seasonal ice-free conditions. The temperature optimum ended rather abruptly, with the return of cold polar waters into the trough within a few centuries. This was accompanied by a dramatic reduction of the abundance of C. reniforme. During the upper Holocene, the more opportunistic species E. clavatum became progressively dominant and the water column was more stratified. Deep water in Franz Victoria Trough contained a significant amount of cold Barents Sea bottom water as it does today, while subsurface water warmed progressively until about 3.7 cal. ka BP and reached temperatures similar to those of today. These long-term climatic changes were cut by several cold events of short duration, in particular one in the middle of the temperature optimum and another, which coincides most probably with the 8.2 ka BP cold event. Both long- and short-term climatic changes in the Barents Sea are associated with changes in the flow of Atlantic waters and the oceanic conveyor belt.

Age determination and median grain size of sediment core EN31-PC2

Hemipelagic muds deposited during the past 5.3 cal kyr in the northern Gulf of Mexico (Orca Basin) contain seven intervals punctuated by relatively coarse siliciclastic grain-size peaks, planktonic faunal turnovers, and negative d13C excursions. We believe these episodes represent megaflood deposits reflecting historically unprecedented outfall of North American floodwater and terrigenous mud plumes into the gulf, resulting in collapse of the open-ocean pelagic ecosystem. The deposits record multidecadal episodes of high continental precipitation and large Mississippi River floods at ~4.7, 3.5, 3.0, 2.5, 2.0, 1.2, and 0.3 cal ka (500-1200-year recurrence interval). Variations in tropical plankton frequencies define submillenial warming intervals that culminate in these fluvial episodes. Strengthened tropical currents in the gulf at these times appear to have increased sea surface temperatures and associated flow of moist gulf air to the midwest. Terrestrial paleohydrologic records support the marine evidence for millennial-scale changes in recurrence of large midwest flood episodes.

Geochemical composition and atomic formulas of saponites, celadonites and carbonates from ODP Leg 168 sites

With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).

Mineral chemistry of basalts at DSDP Leg 55 Holes

Microprobe mineral compositions of olivine, plagioclase, clinopyroxene, chrome spinel, ilmenite, and titanomagnetite are presented for 7 samples from 4 flows of hawaiite and one flow of tholeiitic basalt from Hole 430A at Ojin Seamount, 4 samples from 3 flows of alkalic basalt from Hole 432A at Nintoku Seamount, and 29 samples from 2 flows of alkalic basalt and 24 flows of tholeiitic basalt from Holes 433A, 433B, and 433C at Suiko Seamount. The four hawaiite flows from Hole 430A on Ojin Seamount have nearly identical mineralogy. The plagioclase phenocrysts and calculated equilibrium olivine appear to have crystallized at about 1175°C; the groundmass plagioclase crystallized from about 1135° to 1010°C; and the Fe-Ti oxides equilibrated at temperatures from 1000°C to 720°C under oxygen fugacities of 10**-11 to 10**-17. The single tholeiitic flow contains glomerocrysts of plagioclase (An80 to An65) and clinopyroxene (Wo43En46Fsn to Wo42En45Fs13). The plagioclase phenocrysts give calculated temperatures as high as 1400°C, indicating that they were not equilibrated with a magma having the bulk rock composition. The plagioclase groundmass crystallized at 1120° to 1070°C, and the Fe-Ti oxides equilibrated at 1070° to 930°C under oxygen fugacities of 10**-10 to 10**-12. Using mineral compositions of Hawaiian basalts as a guide, we infer that the hawaiite flows were erupted during the post-caldera alkalic eruptive stage and the tholeiite was erupted during the shield-building or caldera collapse stage. The three alkalic basalt flows from Hole 432A on Nintoku Seamount have similar mineralogy, although Flow Units 1 and 2 contain much more abundant plagioclase phenocrysts. The groundmass plagioclase crystallized at temperatures between 1175° and 1000°C. The olivine and plagioclase phenocrysts do not appear to be in equilibrium with the enclosing magmas. The mineral compositions suggest that these samples are intermediate between alkalic basalt and hawaiite; they probably erupted during the post-caldera alkalic stage of eruption. The two analyzed alkalic basalt flows are the two youngest flows recovered at Holes 433A, 433B, and 433C. Flow Unit 1 contains abundant sector-zoned clinopyroxene, and Flow Unit 2 contains rare kink-banded olivine xenocrysts. The plagioclase phenocrysts yield calculated temperatures of 1440° to 1250°C, indicating that they are probably not cognate. Calculated-equilibrium olivine indicates crystallization of olivine at about 1170°C. The Fe-Ti oxides equilibrated at temperatures of 1140° to 870°C under oxygen fugacities of 10**-9 to 10**-14. The groundmass plagioclase crystallized at temperatures of 1178° to 1035 °C. The mineral compositions indicate that these alkalic basalts erupted during the post-caldera alkalic eruptive stage. The 24 analyzed tholeiitic basalts are subdivided on the basis of phenocryst abundances into olivine tholeiites, plagioclase tholeiites, and tholeiites. The crystallization sequence appears to have been chrome spinel, olivine, plagioclase, and clinopyroxene as phenocryst phases, followed by and overlapping with groundmass crystallization of plagioclase (1180° to 920°C), clinopyroxene, and Fe-Ti oxides (1140° to 670°C). At least three flows contain pigeonite. The mineral compositions indicate that all the samples from Flow Unit 4 downward are tholeiitic basalts, although Flow Unit 64 has mineral compositions transitional to those in alkalic basalts.

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.