(Table 1) Thermal conductivities of lithified core samples from ODP Leg 166 sites

The geothermal regime of the western margin of the Great Bahama Bank was examined using the bottom hole temperature and thermal conductivity measurements obtained during and after Ocean Drilling Program (ODP) Leg 166. This study focuses on the data from the drilling transect of Sites 1003 through 1007. These data reveal two important observational characteristics. First, temperature vs. cumulative thermal resistance profiles from all the drill sites show significant curvature in the depth range of 40 to 100 mbsf. They tend to be of concave-upward shape. Second, the conductive background heat-flow values for these five drill sites, determined from deep, linear parts of the geothermal profiles, show a systematic variation along the drilling transect. Heat flow is 43-45 mW/m**2 on the seafloor away from the bank and decreases upslope to ~35 mW/m**2. We examine three mechanisms as potential causes for the curved geothermal profiles. They are: (1) a recent increase in sedimentation rate, (2) influx of seawater into shallow sediments, and (3) temporal fluctuation of the bottom water temperature (BWT). Our analysis shows that the first mechanism is negligible. The second mechanism may explain the data from Sites 1004 and 1005. The temperature profile of Site 1006 is most easily explained by the third mechanism. We reconstruct the history of BWT at this site by solving the inverse heat conduction problem. The inversion result indicates gradual warming throughout this century by ~1°C and is agreeable to other hydrographic and climatic data from the western subtropic Atlantic. However, data from Sites 1003 and 1007 do not seem to show such trends. Therefore, none of the three mechanisms tested here explain the observations from all the drill sites. As for the lateral variation of the background heat flow along the drill transect, we believe that much of it is caused by the thermal effect of the topographic variation. We model this effect by obtaining a two-dimensional analytical solution. The model suggests that the background heat flow of this area is ~43 mW/m**2, a value similar to the background heat flow determined for the Gulf of Mexico in the opposite side of the Florida carbonate platform.

Carbon and nitrogen content of marine pore waters

We have developed sampling methods and an analytical system to determine the concentration of dissolved organic C (DOC) in marine pore waters. Our analytical approach is a modification of recently developed high-temperature, Pt-catalyzed oxidation methods; it uses Chromatographic trapping of the DOC-derived CO2 followed by reduction to CH4 and flame ionization detection. Sampling experiments with nearshore sediments indicate that pore-water separation by whole-core squeezing causes artificially elevated DOC concentrations, while pore-water recovery by sectioning and centrifugation does not appear to introduce DOC artifacts. Results from a set of northwestern Atlantic continental slope cores suggest that net DOC production accounts for >50% of the organic C that is recycled at the sediment-water interface.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Heat flow determinations of ODP Hole 111-504B

Hole 504B in the eastern equatorial Pacific has been the focus of five scientific drilling expeditions since it was first drilled in 1979. During these five legs, a series of temperature logs has been obtained over a time span of almost 8 yr, documenting the geothermal and hydrologic state of the oceanic crust in this region. Immediately following reentry at the onset of ODP Leg 111 operations, a high-resolution temperature probe was lowered into the borehole and a precise record of temperature vs. depth in Hole 504B was recorded down to 1300 mbsf. As was observed during previous legs, the temperature gradient in the upper 400 m was reduced, indicating that downhole flow of cool ocean waters through the casing continued, though at a diminished rate. As subhydrostatic pressures in the upper basement have gradually diminished, the volume of flow has decayed from an estimated 6000-7000 L/hr in late 1979 to about 80 L/hr during Leg 111. At depths below 480 mbsf, a predominantly conductive heat transfer environment enabled the temperature gradient log to be analyzed with respect to lithology on both fine and broad scales. Anomalies in the gradient log in the cased section through the sedimentary column were found to correspond to biostratigraphic age markers and/or sharp changes in sediment composition and texture. Broad variations in temperature gradient within the basement correlated with large-scale porosity trends. Conductive heatflow estimates depict a systematic reduction with depth, ranging from approximately 196 mW/m**2 in the sediments to 120 ± 17 mW/m**2 at 1300 mbsf. Possible causes for this observation were examined from several perspectives, but none was suitably convincing. A fluid instability analysis indicated the likely existence of convection cells within the borehole and substantiated the hypothesis of mixing within the borehole postulated from isotopic and chemical studies of borehole waters. However, such mixing of borehole fluids does not provide an adequate explanation for the heatflow variations, and the disparity between surficial and deep values of heat flow remains unresolved.

(Table 2) Major and trace elements in black smoker particulates

We present geochemical data of black smoker particulates filtered from hydrothermal fluids with seawater-dilutions ranging from 0-99%. Results indicate the dominance of sulphide minerals (Fe, Cu, and Zn sulphides) in all samples taken at different hydrothermal sites on the Mid-Atlantic Ridge. Pronounced differences in the geochemistry of the particles between Logatchev I and 5°S hydrothermal fields could be attributed to differences in fluid chemistry. Lower metal/sulphur ratios (Me/H2S < 1) compared to Logatchev I result in a larger amount of particles precipitated per liter fluid and the occurrence of elemental sulphur at 5°S, while at Logatchev I Fe oxides occur in larger amounts. Systematic trends with dilution degree of the fluid include the precipitation of large amounts of Cu sulphides at a low dilution and a pronounced drop with increasing dilution. Moreover, Fe (sulphides or oxides) precipitation increases with dilution of the vent fluid by seawater. Geochemical reaction path modeling of hydrothermal fluid-seawater mixing and conductive cooling indicates that Cu sulphide formation at Logatchev I and 5°S mainly occurs at high temperatures and low dilution of the hydrothermal fluid by seawater. Iron precipitation is enhanced at higher fluid dilution, and the different amounts of minerals forming at 5°S and Logatchev I are thermodynamically controlled. Larger total amounts of minerals and larger amounts of sulphide precipitate during the mixing path when compared to the cooling path. Differences between model and field observations do occur and are attributable to closed system modeling, to kinetic influences and possibly to organic constituents of the hydrothermal fluids not accounted for by the model.

Microbialites and lipid biomarker from coral reefs off the volcanic islands Tahiti and Vanuatu and from the nonvolcanic sites Belize and the Maldives

The occurrence of microbialites in post-glacial coral reefs has been interpreted to reflect an ecosystem response to environmental change. The greater thickness of microbialites in reefs with a volcanic hinterland compared to thinner microbial crusts in reefs with a non-volcanic hinterland led to the suggestion that fertilization of the reefal environment by chemical weathering of volcanic rocks stimulated primary productivity and microbialite formation. Using a molecular and isotopic approach on reef-microbialites from Tahiti (Pacific Ocean), it was recently shown that sulfate-reducing bacteria favored the formation of microbial carbonates. To test if similar mechanisms induced microbialite formation in other reefs as well, the Tahitian microbialites are compared with similar microbialites from coral reefs off Vanuatu (Pacific Ocean), Belize (Caribbean Sea, Atlantic Ocean), and the Maldives (Indian Ocean) in this study. The selected study sites cover a wide range of geological settings, reflecting variable input and composition of detritus. The new lipid biomarker data and stable sulfur isotope results confirm that sulfate-reducing bacteria played an intrinsic role in the precipitation of microbial carbonate at all study sites, irrespective of the geological setting. Abundant biomarkers indicative of sulfate reducers include a variety of terminally-branched and mid chain-branched fatty acids as well as mono-O-alkyl glycerol ethers. Isotope evidence for bacterial sulfate reduction is represented by low d34S values of pyrite (-43 to -42 per mill) enclosed in the microbialites and, compared to seawater sulfate, slightly elevated d34S and d18O values of carbonate-associated sulfate (21.9 to 22.2 per mill and 11.3 to 12.4 per mill, respectively). Microbialite formation took place in anoxic micro-environments, which presumably developed through the fertilization of the reef environment and the resultant accumulation of organic matter including bacterial extracellular polymeric substances (EPS), coral mucus, and marine snow in cavities within the coral framework. ToF-SIMS analysis reveals that the dark layers of laminated microbialites are enriched in carbohydrates, which are common constituents of EPS and coral mucus. These results support the hypothesis that bacterial degradation of EPS and coral mucus within microbial mats favored carbonate precipitation. Because reefal microbialites formed by similar processes in very different geological settings, this comparative study suggests that a volcanic hinterland is not required for microbialite growth. Yet, detrital input derived from the weathering of volcanic rocks appears to be a natural fertilizer, being conductive for the growth of microbial mats, which fosters the development of particularly abundant and thick microbial crusts.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

Helium and oxygen isotope ratios of ODP Sites 193-1188 and 193-1189

Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/4He ratios from fluid inclusions within pyrite and anhydrite and the d18O signature of anhydrite. Depressed 3He/4He ratios of 0.2-6.91RA appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. d18O anhydrite ratios are 6.5 per mil to 11 per mil for Snowcap and 6.4 per mil to 11.9 per mil for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing d18O equilibration. By comparing new d18O values for anhydrite with corresponding published 87Sr/86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.

(Table 1) Heat flow measurements in the Central Pacific during Cruise 48 of R/V Vityaz

Eight measurements of heat flow in the Pacific floor were made during Cruise 48 of R/V Vityaz; four on the Manihiki Plateau, three - on the Marcus-Necker Rise, and one - in the Hawaiian Trough. Higher than average heat flows, up to 3.2 HFU, were recorded on submarine uplifts.