(Table 2) Concentrations and D/L values for three amino acids in bulk foraminifera from ODP Sites 182-1126 and 182-1127

A number of studies have shown that methanogens are active in the presence of sulfate under some conditions. This phenomenon is especially exemplified in carbonate sediments of the southern Australian continental margin. Three sites cored during Ocean Drilling Program (ODP) Leg 182 in the Great Australian Bight have high concentrations of microbially-generated methane and hydrogen sulfide throughout almost 500 m of sediments. In these cores, the sulfate-reducing and methanogenic zones overlap completely; that is, the usual sulfate-methane transition zone is absent. Amino acid racemization data show that the gassy sediments consist of younger carbonates than the low-gas sites. High concentrations of the reduced gases also occur in two ODP sites on the margin of the Bahamas platform, both of which have similar sedimentary conditions to those of the high-gas sites of Leg 182. Co-generation of these reduced gases results from an unusual combination of conditions, including: (1) a thick Quaternary sequence of iron-poor carbonate sediments, (2) a sub-seafloor brine, and (3) moderate amounts of organic carbon. The probable explanation for the co-generation of hydrogen sulfide and methane in all these sites, as well as in other reported environments, is that methanogens are utilizing non-competitive substrates to produce methane within the sulfate-reducing zone. Taken together, these results form the basis of a new model for sulfate reduction and methanogenesis in marine sediments. The biogeochemical end-members of the model are: (1) minimal sulfate reduction, (2) complete sulfate reduction followed by methanogenesis, and (3) overlapping sulfate reduction and methanogenesis with no transition zone.

Maxima of interstitial water and gas parameters in ODP Leg 182 sediments

During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106?) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200-400 m) and relative warm bottom water temperatures (11-14°C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant (SO4)2- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

Chert intervals in DSDP and ODP sites (Table 1)

Radiolarian cherts in the Tethyan realm of Jurassic age were recently interpreted as resulting from high biosiliceous productivity along upwelling zones in subequatorial paleolatitudes the locations of which were confirmed by revised paleomagnetic estimates. However, the widespread occurrence of cherts in the Eocene suggests that cherts may not always be reliable proxies of latitude and upwelling zones. In a new survey of the global spatio-temporal distribution of Cenozoic cherts in Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) sediment cores, we found that cherts occur most frequently in the Paleocene and early Eocene, with a peak in occurrences at ~50 Ma that is coincident with the time of highest bottom water temperatures of the early Eocene climatic optimum (EECO) when the global ocean was presumably characterized by reduced upwelling efficiency and biosiliceous productivity. Cherts occur less commonly during the subsequent Eocene global cooling trend. Primary paleoclimatic factors rather than secondary diagenetic processes seem therefore to control chert formation. This timing of peak Eocene chert occurrence, which is supported by detailed stratigraphic correlations, contradicts currently accepted models that involve an initial loading of large amounts of dissolved silica from enhanced weathering and/or volcanism in a supposedly sluggish ocean of the EECO, followed during the subsequent middle Eocene global cooling by more vigorous oceanic circulation and consequent upwelling that made this silica reservoir available for enhanced biosilicification, with the formation of chert as a result of biosilica transformation during diagenesis. Instead, we suggest that basin-basin fractionation by deep-sea circulation could have raised the concentration of EECO dissolved silica especially in the North Atlantic, where an alternative mode of silica burial involving widespread direct precipitation and/or absorption of silica by clay minerals could have been operative in order to maintain balance between silica input and output during the upwelling-deficient conditions of the EECO. Cherts may therefore not always be proxies of biosiliceous productivity associated with latitudinally focused upwelling zones.

Calcium carbonate and trace element composition of ODP Leg 182 sites

An intensive geochemical investigation was conducted on carbonate sediments recovered during Ocean Drilling Program Leg 182. Four trace elements in 635 sediment samples from Sites 1126-1132 on the Great Australian Bight were examined by atomic absorption spectrometry on the acid-soluble fraction. Downhole profiles of these elements exhibit complicated fluctuations throughout the late Eocene to Pleistocene, principally because of the variations in the acid-soluble fraction. The purpose of this study is to present initial results on the geochemical composition of Cenozoic cool-water carbonates as a basis for a future detailed investigation to determine the paleoenvironment of a carbonate-dominated continental margin during the evolution of the Southern Ocean.

Planktonic foraminiferal stratigraphy and datum levels of ODP Leg 182 sites

Planktonic foraminifers from Ocean Drilling Program Leg 182, Holes 1126B and 1126C, 1128B and 1128C, 1130A and 1130B, 1132B, and 1134A and 1134B confirm the neritic record that during the early Miocene the Great Australian Bight region was in a cool-temperate regime with abundant Globoturborotalita woodi. Warm marine environments started to develop in the later part of the early Miocene, and the region became warm temperate to subtropical in the early middle Miocene with abundant Globigerinoides, Orbulina, and Globorotalia, corresponding to global warming at the Miocene climatic optimum. Fluctuations between cool- and warm-temperate conditions prevailed during the late Miocene, as indicated by abundant Globoconella conoidea and Menardella spp. A major change in planktonic foraminiferal assemblages close to the Miocene/Pliocene boundary not only drove many Miocene species into extinction but also brought about such new species as Globorotalia crassaformis and Globoconella puncticulata. Warm-temperate environments continued into the early and mid-Pliocene before being replaced by cooler conditions, supporting numerous Globoconella inflata and Globigerina quinqueloba. Based on data from this study and published results from the Australia-New Zealand region, we established a local planktonic foraminifer zonation scheme for separating the southern Australian Neogene (SAN) into Zones SAN1 to SAN19 characterizing the Miocene and Zones SAN20 to SAN25 characterizing the Pliocene. The Neogene sections from the Great Australian Bight are bounded by hiatuses of ~0.5 to >3 m.y. in duration, although poor core recovery in some holes obscured a proper biostratigraphic resolution. A total of 15 hiatuses, numbered 1 to 15, were identified as synchronous events from the base of the Miocene to the lower part of the Pleistocene. We believe that these are local manifestations of major third-order boundaries at about (1) 23.8, (2) 22.3, (3) 20.5, (4) 18.7, (5) 16.4, (6) 14.8, (7) 13.5, (8) 11.5, (9) 9.3, (10) 7.0, (11) 6.0, (12) 4.5, (13) 3.5, (14) 2.5, and (15) 1.5 Ma, respectively. This hiatus-bounded Neogene succession samples regional transgressions and stages of southern Australia and reveals its stepwise evolutionary history.