(Table S1, S4) Campanian-Maastrichtian benthic foraminifera from ODP Hole 113-690C

During the latest Cretaceous cooling phase, a positive shift in benthic foraminiferal d18O values lasting about 1.5 Myr (71.5-70 Ma) can be observed at a global scale (Campanian-Maastrichtian Boundary Event, CMBE). This d18O excursion is interpreted as being influenced by a change in intermediate- to deep-water circulation or by temporal build-up of Antarctic ice sheets. Here we test whether benthic foraminiferal assemblages from a southern high-latitudinal site near Antarctica (ODP Site 690) are influenced by the CMBE. If the d18O transition reflects a change in intermediate- to deep-water circulation from low-latitude to high-latitude water masses, then this change would result in cooler temperatures, higher oxygen concentration, and possibly lower organic-matter flux at the seafloor, resulting in a major benthic foraminiferal assemblage change. If, however, the d18O transition was mainly triggered by ice formation, no considerable compositional difference in benthic foraminiferal assemblages would be expected. Our data show a separation of the studied succession into two parts with distinctly different benthic foraminiferal assemblages. Species dominating the older part (73.0-70.5 Ma) tolerate less bottom water oxygenation and are typical components of low-latitude assemblages. In contrast, the younger part (70.0-68.0 Ma) is characterized by species that indicate well-oxygenated bottom waters and species common in high-latitude assemblages. We interpret the observed change in benthic foraminiferal assemblages toward a well-oxygenated environment to reflect the onset of a shift from low-latitude toward high-latitude dominated intermediate- to deep-water sources. This implies that a change in oceanic circulation was at least a major component of the CMBE.

Stable oxygen and carbon isotope data for planktic and benthic foraminifera from southern Atlantic of DSDP Hole 74-525A and ODP Hole 113-690C

Published stable isotope records in marine carbonate are characterized by a positive d18O excursion associated with a negative d13C shift during the early Maastrichtian. However, the cause and even the precise timing of these excursions remain uncertain. We have generated high-resolution foraminiferal stable isotope and gray-scale records for the latest Campanian to early Maastrichtian (73-68 Ma) at two Ocean Drilling Program sites, 525 (Walvis Ridge) and 690 (Weddell Sea). We demonstrate that the negative d13C excursion is decoupled from the d18O increase with a lag of about 600 ka. Our d13C records (both planktic and benthic) show an amplitude for the negative excursion of 0.7 per mill that falls between about 72.1 and 70.7 Ma. Our planktic d18O records indicate an overall increase of 1.2 per mill from 73 to 68 Ma at Site 690, whereas at Site 525 they record a slightly smaller increase (1 per mill) that peaks around 70.1 Ma with decreasing values thereafter. Our benthic d18O data indicate an increase of 1.5 per mill at Site 525 and 0.7 per mill at Site 690 between about 71.4 and 69.9 Ma. Benthic d18O values show different baseline values at the two sites before and after the excursion, but the larger increase at Site 525 means that the values attained at the peak of the excursion are similar at the two sites. We interpret this observation in terms of water mass changes. The excursion is interpreted to reflect a cooling of bottom waters in response to the strengthening contribution of intermediate- to deep-water production in the high southern latitudes rather than increased ice volume. The associated carbon cycle perturbations that we observe are interpreted to reflect a weakening of surface water stratification and increased productivity, as supported by our gray value data.

Stable carbon and oxygen isotope ratios of calcareous dinoflagellate cysts and planktic foraminifera from the Campanian/Maastrichtian section of ODP Hole 113-690C in the Weddell Sea (Table 1)

Delta18O and delta13C values for the calcareous dinoflagellate species Orthopithonella? globosa (Fütterer 1984) Lentin and Williams 1985 and Pirumella krasheninnikovii (Bolli 1974) Lentin and Williams 1993 from lates Campanian and earliest Maastrichtian of ODP Hole 690C (Weddell Sea, Antarctic Ocean) have been studied in order to evaluate the species' depth habitat in the water column and their applicability in paleoceanographic studies. The calcareous dinoflagellates show isotopic values comparable to probably shallow-dwelling planktic foraminifera from the same sample in delta18O, but have an offset of about -5 ? to -7? in delta13C. This suggests that calcareous dinoflagellate oxygen isotopes may provide information for paleoceanographic reconstructions of sea-surface water temperatures, whereas their extremely light carbon isotope values are probably due to photosynthetic processes.

Geochemical investigation of ODP Leg 113 sites

Dissolved organic carbon (DOC) was determined in pore water extracted from pelagic and hemipelagic sediments recovered during Leg 113. DOC concentration varied between 1.82 and 13.6 mg C/L which is one to two orders of magnitude less than previously reported for hemipelagic sediments. It is argued that this difference is related to differences in the intensity of degradation of organic matter. As a first approximation it is found that in reducing sediments, the level of DOC is proportional to the intensity of sulfate reduction. It is suggested that DOC is formed by different mechanisms in oxic and reducing environments.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

Interstitial-water chemistry of ODP Leg 113 sites

Variations in the distribution of major elements and stable oxygen isotopes in ODP Leg 113 pore water are not related to lithology and thus appear to be controlled by minor constituents. Petrographic observations and geochemical considerations indicate that alteration of calc-alkalic volcanic material dispersed in the sediment is an important process. A diagenetic reaction is constructed that involves transformation of volcanic glass into smectite, zeolite (represented by phillipsite), chert, and iron sulfide. Mass balance calculations reveal that alteration of less than 10% (volume) of volcanogenic material may account for the observed depletion of magnesium, potassium, and 18O and enrichment of calcium. Alteration of this amount of volcanic glass produces less than 4% (volume) of smectite and zeolite. Hence, mass balance is obtained without having to invoke unreasonable large amounts of volcanic matter or interactions between seawater and basement.

Strontium isotope geochemistry of ODP Leg 113 sites

The concentration of dissolved Sr and the distribution of 87Sr/86Sr isotope ratios in Leg 113 interstitial waters may be interpreted in terms of mixing of Sr from four different reservoirs: indigenous seawater, marine carbonate minerals, and basaltic and siliceous detrital material. The input to the pore water from these reservoirs is determined by the reactivity of the reservoir rather than its size. The presence of strontium derived from siliceous detrital material is unequivocally demonstrated in the pore waters of the hemipelagic deposits, and is also significant in the calcareous Maud Rise sediments due to the unusually low degree of carbonate recrystallization. Also, alteration of basic volcanic material is important at several sites.

Amino acid concentrations in interstitial waters from ODP Sites 113-689 and 113-690

Biogenic calcareous and siliceous sediments were drilled at ODP Sites 689 and 690 on the Maud Rise, Antarctic Ocean. We analyzed dissolved combined amino acids (DCAA) and dissolved free amino acids (DFAA) in interstitial waters in order to characterize the amino acids in dissolved organic matter. The DFAA was predominant over the DCAA in interstitial waters at Sites 689 and 690, which contradicted the previous results from interstitial water and seawater studies. The DCAA in the interstitial waters probably originated from calcareous biogenic debris with less amounts of siliceous debris. Although glutamic acid constituted 41% of the total concentration of DCAA, it accounted for only 1% of the total concentration of DFAA due to the adsorption and/or reaction with biogenic carbonate. Ornithine, a nonprotein amino acid, is a decomposed product of arginine and made up 17 mol% of the total DFAA and. The total hydrolyzable amino acids (=DCAA + DFAA) accounted for 5 to 28% of the dissolved organic carbon (DOC) concentration, which implied that high molecular weight organic matter was a major contributor for the DOM (dissolved organic matter) in interstitial waters. Fairly positive correlation between the dissolved manganese and the total DCAA values suggested that the redox condition plays a significant role in controlling the total DCAA content. A small decrease in the sulfate concentration in the interstitial waters from both sites suggested fairly low microbial activity by sulfate-reducing bacteria.

Consolidation tests of ODP Leg 113 samples

Examination of the geotechnical characteristics of Weddell Sea, Maud Rise, and South Orkney microcontinental margin sediments recovered during ODP Leg 113 reveals that the reduction in porosity (consolidation) of the siliciclastic, calcareous, and diatomaceous sediments is primarily a process governed by vertical stresses created by overburden. The initial porosity of the sediments in these areas is governed by the amount of diatoms present. The more diatoms, the higher the porosity. Surficial diatom-rich sediments are everywhere overconsolidated. This is attributed to the strong microfabric created by the diatoms, calcareous and clay particles. The deeper diatom-free sediments of Maud Rise range from slightly underconsolidated to normally consolidated. The silty clays and clays of the Weddell Sea and South Orkney margin are underconsolidated. The degree of underconsolidation of these sediments is similar to that determined in a number of different locations throughout the world's oceans. The very low permeability of the Weddell Sea and South Orkney margin sediments appears to account for this underconsolidation.

Upper Cretaceous-Paleogene stratigraphy of ODP Sites 113-689 and 113-690

This contribution summarizes the biostratigraphy of planktonic foraminifers, calcareous nannofossils, and benthic foraminifers, in combination with the magnetostratigraphy, carbon and oxygen isotope stratigraphy of benthic foraminifers, and CaCO3 stratigraphy for the Maestrichtian through Paleogene calcareous sequences recovered at Sites 689 and 690 on Maud Rise (at about 65°S, eastern Weddell Sea, Antarctica). These data represent the southernmost calciumcarbonate record available for that interval, and thus extend the biostratigraphic and isotopic database to higher latitudes. Sites 689 and 690 form the southernmost anchor of a north-south transect through the Atlantic Ocean for Paleogene biostratigraphy and chemostratigraphy.