Stable isotope analyses of Cretaceous sediment samples

We report the sulfur and oxygen isotope composition of sulfate (d34SSO4 and d18OSO4, respectively) in coexisting barite and carbonate-associated sulfate (CAS), which we use to explore temporal variability in the marine sulfur cycle through the middle Cretaceous. The d34SSO4 of marine barite tracks previously reported sulfur isotope data from the tropical Pacific. The d18OSO4 of marine barite exhibits more rapid and larger isotopic excursions than the d34SSO4 of marine barite; these excursions temporally coincide with Ocean Anoxic Events (OAEs). Neither the d34SSO4 nor the d18OSO4 measured in marine barite resembles the d34SSO4 or the d18OSO4 measured in coexisting CAS. Culling our data set for elemental parameters suggestive of carbonate recrystallization (low [Sr] and high Mn/Sr) improves our record of d18OSO4 in CAS in the Cretaceous. This suggests that the CAS proxy can be impacted by carbonate recrystallization in some marine sediments. A box model is used to explore the response of the d34SSO4 and d18OSO4 to different perturbations in the marine biogeochemical sulfur cycle. We conclude that the d34SSO4 in the middle Cretaceous is likely responding to a change in the isotopic composition of pyrite being buried, coupled possibly with a change in riverine input. On the other hand, the d18OSO4 is likely responding to rapid changes in the reoxidation pathway of sulfide, which we suggest may be due to anoxic versus euxinic conditions during different OAEs.

Age and oxygen isotope data for bulk carbonate from DSDP Sites 41-366 and 72-516 and ODP Sites 111-677A and 130-807

A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured d18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal d18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and d18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal d18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured d18O values of Eocene bulk carbonates are more than 2? lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate d180 values particularly sensitive to diagenetic effects; most of the observed variations in measured d18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.

Mineralogy and interstitial-water chemistry of ODP Leg 101 sites

Concentrations of dissolved Ca2+, Sr2+, Mg2+, SO4[2-], and alkalinity were measured in pore waters squeezed from sediments taken from ODP Holes 626C and 626D in the Florida Straits; Holes 627A and 627B, 628A, and 630A and 630C north of Little Bahama Bank; Holes 631 A, 632A and 632B, and 633A in Exuma Sound; and Holes 634A and 635A and 635B in Northeast Providence Channel. These data are compared with the mineralogy and strontium content of the sediments from which the waters were squeezed. Contrasts in the geochemical profiles suggest that significantly different processes govern pore-water signatures at each group of sites. In Little Bahama Bank, strong positive Ca2+ gradients are correlated with weak negative Mg2+ profiles. These trends are analogous to those seen at DSDP sites where carbonate deposits immediately overlie mafic basement, but as the depth to basement may be in excess of 5000 m, we suggest that diffusion gradients are initiated by an underlying sedimentary unit. In contrast, Ca2+ and Mg2+ gradients in Exuma Sound are not developed to any appreciable extent over similar thicknesses of sediment. We suggest that the pore-water chemistry in these deposits is principally controlled by diagenetic reactions occurring within each sequence. The location and extent of carbonate diagenesis can be estimated from dissolved Sr2+ profiles. In Little Bahama Bank and Exuma Sound, Sr2+ concentrations reach a maximum value of between 700 and 1000 µmol/L. Although the depths at which these concentrations are achieved are different for the two areas, the corresponding age of the sediment at the dissolved Sr2+ maximum is similar. Consequently, the diffusive flux of Sr2+ and the calculated rates of recrystallization in the two areas are likewise of a similar magnitude. The rates of recrystallization we calculate are lower than those found in some DSDP pelagic sites. As the waters throughout most of the holes are saturated with respect to SrSO4, celestite precipitation may cause erroneously low Sr2+ production rates and, consequently, low calculated rates of recrystallization. We therefore encourage only the discriminate use of Sr2+ profiles in the quantification of diagenetic processes.

Grain sizes and mineral composition of the basement of ODP Site 206-1256

Hole 1256C was cored 88.5 m into basement, and Hole 1256D, the deep reentry hole, was cored 502 m into basement during Ocean Drilling Program Leg 206. Hole 1256D is located ~30 m south of Hole 1256C (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). A thick massive flow drilled in both holes, Units 1256C-18 and 1256D-1, consists of a single cooling unit of cryptocrystalline to fine-grained basalt, interpreted as a ponded lava, 32 m and at least 74.2 m thick, respectively. This ponded flow gives us a unique opportunity to examine textural variations from the glassy, folded crust of the lava pond recovered from the top of Unit 1256C-18 through the coarse-grained, thick massive lava body to the unusually recrystallized and deformed base cored in Unit 1256C-18. Some detailed descriptions of the textures and grain size variations through the lava pond (Units 1256C-18 and 1256D-1), with special reference to the recrystallization of the base of Unit 1256C-18, are presented here.

Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Radionuclide concentrations, ratios, and derived ages of massive sulfides from ODP Leg 139 and Leg 169 sites

Massive sulfide samples from the Bent Hill area were analyzed for 230Th/234U and 231Pa/235U disequilibria. Apparent ages calculated from these ratios are between 8.2 and >300 ka. Concordant ages were found for only three samples that originate near the surface from the clastic sulfide zone and suggest "true" ages of between 8.5 and 16.0 ka (mean of 230Th and 231Pa ages). The uranium vs. depth distribution in the Bent Hill Massive Sulfide deposit suggests an open system for uranium for the deeper part of the deposit, which was probably caused by extensive recrystallization processes inhibiting true age determinations.