(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.

(Table 1) Minor and trace element concentrations in interstitial waters from ODP Leg 166 sites

Concentrations of minor and trace elements (Li, Rb, Sr, Ba, Fe, and Mn) in interstitial water (IW) were found in samples collected during Ocean Drilling Program (ODP) Leg 166 from Sites 1005, 1006, and 1007 on the western flank of the Great Bahama Bank (GBB). Concentrations of Li range from near-seawater values immediately below the sediment/water interface to a maximum of 250 µM deep in Site 1007. Concentrations determined during shore-based studies are substantially lower than the shipboard data presented in the Leg 166 Initial Reports volume (range of 28-439 µM) because of broad-band interferences from high dissolved Sr concentrations in the shipboard analyses. Rubidium concentrations of 1.3-1.7 µM were measured in IW from Site 1006 when salinity was less than 40 psu. A maximum of 2.5 µM is reached downhole at a salinity of 50 psu. Shipboard and shore-based concentrations of Sr2+ are in excellent agreement and vary from 0.15 mM near the sediment water interface to 6.8 mM at depth. The latter represent the highest dissolved Sr2+ concentrations observed to date in sediments cored during the Deep Sea Drilling Project (DSDP) or ODP. Concentrations of Ba2+ span three orders of magnitude (0.1-227µM). Concentrations of Fe (<0.1-14 µM) and Mn (0.1-2 µM) exhibit substantially greater fluctuations than other constituents. The concentrations of minor and trace metals in pore fluids from the GBB transect sites are mediated principally by changes in pore-water properties resulting from early diagenesis of carbonates associated with microbial degradation of organic matter, and by the abundance of detrital materials that serve as a source of these elements. Downcore variations in the abundance of detrital matter reflect differences in carbonate production during various sea-level stands and are more evident at the more proximal Site 1005 than at the more pelagic Site 1006. The more continuous delivery of detrital matter deep in Site 1007 and throughout all of Site 1006 is reflected in a greater propensity to provide trace elements to solution. Concentrations of dissolved Li+ derive principally from (1) release during dissolution of biogenic carbonates and subsequent exclusion during recrystallization and (2) release from partial dissolution of Li-bearing detrital phases, especially ion-exchange reactions with clay minerals. A third but potentially less important source of Li+ is a high-salinity brine hypothesized to exist in Jurassic age (unsampled) sediments underlying those sampled during Leg 166. The source of dissolved Sr2+ is almost exclusively biogenic carbonate, particularly aragonite. Concentrations of dissolved Sr2+ and Ba2+ are mediated by the solubility of their sulfates. Barite and detrital minerals appear to be the more important source of dissolved Ba2+. Concentrations of Fe and Mn2+ in anoxic pore fluids are mediated by the relative insolubility of pyrite and incorporation into diagenetic carbonates. The principal sources of these elements are easily reduced Fe-Mn-rich phases including Fe-rich clays found in lateritic soils and aoelian dust.

Mineralogic, elemental, and stable isotopic composition of bulk carbonate sediments from ODP Leg 166 sites

An intensive mineralogic and geochemical investigation was conducted on sediments recovered during Ocean Drilling Program Leg 166 from the western Great Bahama Bank at Sites 1006, 1008, and 1009. Pleistocene through middle Miocene sediments recovered from Site 1006, the distal location on the Leg 166 transect, are a mixture of bank-derived and pelagic carbonates with lesser and varying amounts of siliciclastic clays. A thick sequence of Pleistocene periplatform carbonates was recovered near the platform edge at Sites 1008 and 1009. Detailed bulk mineralogic, elemental (Ca, Mg, Sr, and Na), and stable isotopic (d18O and d13C) analyses of sediments are presented from a total of 317 samples from all three sites.

Whole rock geochemistry and stable isotopes of rocks, fragments and foraminifers from two ODP Leg 166 holes

Total carbon and carbonate contents, quantitative carbonate mineralogy, trace metal concentrations, and stable isotope compositions were determined on a suite of samples from the Miocene sections at Sites 1006 and 1007. The Miocene section at Site 1007, located at the toe-of-slope, contains a relatively high proportion of bank-derived components and becomes fully lithified at a depth of ~300 meters below seafloor (mbsf). By contrast, Miocene sediments at Site 1006, situated in Neogene drift deposits in the Straits of Florida and composed primarily of pelagic carbonates, do not become fully lithified until a depth of ~675 mbsf. Diagenetic and compositional contrasts between Sites 1006 and 1007 are reflected in geochemical data derived from sediment samples from each site.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.