High resolution geochemical analyses of ODP Leg 119 samples

Higher resolution pore-water samples were recovered at intervals of 0.3 to 3 m from selected cores during Leg 119 in order to identify zones where active geochemical reactions were occurring. In addition to shipboard measurements, solid- and dissolved-phase samples were analyzed at my shore-based laboratory. Solid-phase samples were analyzed for redox conditions, carbon, total metals, and leachable metals. Pore-water samples were analyzed for ammonia, silica, sulfate, and major cations. Data are presented in tables for 400 samples from Site 739 in Prydz Bay, East Antarctica, and Sites 736, 737, 738, 744, 745, and 746 at the Kerguelen Ridge, South Indian Ocean.

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

Distribution of calcareous nannofossils in upper Cretaceous and Cenozoic sediments of the Kerguelen Plateau

ODP Leg 119 drilled 11 sites on the Kerguelen Plateau (southern Indian Ocean) and Prydz Bay (East Antarctica). Upper Pliocene through Quaternary sediments were recovered at Site 736 on the northern Kerguelen Plateau; calcareous nannofossils occurred in only a few samples. Over 700 m of middle Eocene through Quaternary sediments was cored at Site 737 on the northern Kerguelen Plateau, and calcareous nannofossils are abundant in the middle Eocene through the middle Miocene sediments. Nearly 500 m of sediments ranging from the lower Turanian to the Quaternary was recovered at Site 738 on the southern Kerguelen Plateau; calcareous nannofossils are abundant from the Miocene downward. Calcareous nannofossils are also abundant in the upper Eocene through Miocene section from Site 744 on the southern Kerguelen Plateau. Except for Core 119-746A-13H, the Neogene sequences drilled at deep-water Sites 745 and 746 off the southern Kerguelen Plateau are devoid of calcareous nannofossils. Occurrences of calcareous nannofossils were generally rare and sporadic at Sites 739 and 742 in Prydz Bay and suggest that the diamictite sequences recovered is as old as middle Eocene-early Oligocene age. Other sites drilled in Prydz Bay (Sites 740, 741, and 743) did not yield calcareous nannofossils. Species diversity of calcareous nannofossils was low (about a dozen) in the southern Indian Ocean in the Late Cretaceous. High-latitude nanno floral characteristics are apparent after the Cretaceous/Tertiary boundary extinctions. Cold climatic conditions limited Oligocene calcareous nannofossil assemblages to fewer than a dozen species, and extinctions of species generally were not compensated by originations of new species. Only a few species of calcareous nannofossils were found in the Miocene sequences, in which Coccolithuspelagicus and one or two species of Reticulofenestra exhibit extreme (0%-100%) fluctuations in assemblage dominance, and these fluctuations may reflect rapid fluctuations in the surface-water temperatures. Further deterioration of climate in the late Neogene essentially excluded calcareous nannoplankton from the Southern Ocean. Significantly warmer water conditions during part of the early-middle Pleistocene were inferred by a few lower-middle Pleistocene calcareous nannofossil species found on the Kerguelen Plateau. The calcareous nannofossil zonation of Roth (1978 doi:10.2973/dsdp.proc.44.134.1978) can be applied to the Upper Cretaceous section recovered at Site 738, and the zonation of Okada and Bukry (1980 doi:10.1016/0377-8398(80)90016-X) can be applied without much difficulty to the Paleocene to middle Eocene sequences from the Kerguelen Plateau. However, some conventional upper Paleogene markers are not useful for southern high latitudes, whereas a few nonconventional species events are useful for subdividing the upper Paleogene sequences. The latter species events include the first occurrence (FO) of Reticulofenestra reticulata, the FO and last occurrence (LO) of Reticulofenestra oamaruensis, the LO of Isthmolithus recurvus, and the LO of Chiasmolithus altus. As the Neogene sequences from the southern Indian Ocean contain only a few long-ranging, cold-water species, or are devoid of coccoliths, calcareous nannofossil zonations remain virtually unworkable for the Neogene in the high-latitude southern Indian Ocean as in other sectors of the Southern Ocean.

Bulk mineralogy of Cretaceous to Quaternary sediments from the Kerguelen Plateau

Carbonate-free portions of Upper Cretaceous to Holocene sediment samples from the Kerguelen Plateau in the southern Indian Ocean were investigated by X-ray diffraction. Downhole variations in the content of opal-A, opal-CT, quartz, feldspar, barite, and clinoptilolite were studied at Site 737 on the northern Kerguelen Plateau and at Sites 744 and 738 on the southern Kerguelen Plateau. The variation of these components reflects temporal changes in the depositional history of the Kerguelen Plateau as well as major differences in the sedimentary evolution between the northern plateau and the southern plateau. Carbonate is the dominant component in the pelagic sediments on the Kerguelen Plateau. In addition, biogenic opal sedimentation plays an important role throughout most of the sequence. A major increase in opal accumulation is documented at all sites in late Miocene time, which is in accordance with the well-known increase in silica productivity probably caused by a major cooling step. Because of its position near the Polar Frontal Zone, sediments from Site 737 show a more extensive opal deposition than at Sites 744 and 738. An earlier productivity pulse is documented at Site 744 on the southern plateau within the early Oligocene, following the initial phase of intense East Antarctic glaciation. This cooling event resulted in higher amounts of ice-rafted terrigenous quartz and, to a lesser extent, feldspar. With the exception of the Site 744 sediments, opal deposition in Paleogene and older sediments can be reconstructed only from the diagenetic transformation products of opal-CT and probably clinoptilolite. In contrast to the southern sequence, on the northern Kerguelen Plateau higher amounts of clinoptilolite and no opal-CT were found. These major differences in the diagenetic environments may be due to extensive volcanism in the northern area. The volcanic influence at Site 737 is well recorded by the higher feldspar content and higher amounts of volcanic glass shards.

Geochemistry of marin ash layers and epiclastic rocks from the Kerguelen Plateau

Epiclastic volcanogenic rocks recovered from the Kerguelen Plateau during Ocean Drilling Program Legs 119 and 120 comprise (pre-)Cenomanian(?) claystones (52 m thick, Site 750); a Turonian(?) basaltic pebble conglomerate (1.2 m thick, Site 748; Danian mass flows (45 m thick, Site 747); and volcanogenic debris flows of Quaternary age at Site 736 (clastic apron of Kerguelen Island). Pyroclastic rocks comprise numerous Oligocene to Quaternary marine ash layers. The epiclastic sediments with transitional mid-ocean-ridge basalt (T-MORB) origin indicate weathering (Site 750) and erosion (Site 747) of Early Cretaceous T-MORB from a then-emergent Kerguelen Plateau, connected to Late Cretaceous tectonic events. The basal pebble conglomerate of Site 748 has an oceanic-island basalt (OIB) composition and denotes erosion and reworking of seamount to oceanic-island-type volcanic sources. The vitric- to crystal-rich marine ash layers are a few centimeters thick, have rather uniform grain sizes around 60 ± 40 µm, and are a result of Plinian eruptions. Crystal-poor silicic vitric ashes may also represent co-ignimbrite ashes. The ash layers have bimodal, basaltic, and silicic compositions with a few intermediate shards. The basaltic ashes are evolved high-titanium T-MORB; a few grains in a silicic pumice lapilli layer have a low-titanium basaltic composition. The silicic ashes comprise trachytic and rhyolitic glass shards belonging to a high-K series, except for a few low-K glasses admixed to a basaltic ash layer. Feldspar and clinopyroxene compositions fit the glass chemistry: high-Ti tholeiite-basaltic glasses have Plagioclase of An40-80 and pigeonite to augite clinopyroxene compositions. Silicic ashes have K-rich anorthoclase and minor Plagioclase around An20 and ferriaugitic to hedenbergitic clinopyroxene compositions. The line of magmatic evolution for the glass shards is not compatible with simple two-end member (high-Ti T-MORB and high-K rhyolite) mixing, but favors successive Ca-Mg-Fe pyroxene, Ti magnetite, and apatite fractionation, and K-rich alkali feldspar fractionation in trachytic magmas to yield rhyolitic compositions. Plagioclase fractionation occurs throughout. This qualitative model is in basic accordance with the observed mineral assemblage. However, as the time span for explosive volcanism spans >30 m.y., this basic model cannot comply with fractional crystallization in a single magma reservoir. The ash layers resulted from highly explosive eruptions on Kerguelen and, with less probability, Heard islands since the Oligocene. The explosive history starts with widespread Oligocene basaltic ash layers that indicate sea-level or subaerial volcanism on the Northern Kerguelen Plateau. After a hiatus of 24 m.y.(?), explosive magmatic activity was vigorously renewed in the late Miocene with more silicic eruptions. A peak in explosive activity is inferred for the Pliocene-Pleistocene. The composition and evolution of Kerguelen Plateau ash layers resemble those from other hotspot-induced, oceanic-island realms such as Iceland and Jan Mayen in the North Atlantic, and the Canary Islands archipelago in the Central Atlantic.

Diatom biostratigraphy of the Kerguelen Plateau and Prydz Bay, Southern Ocean

Samples were examined for diatoms from 22 holes at 11 sites cored by ODP Leg 119 on the Kerguelen Plateau and in Prydz Bay, East Antarctica. Diatoms were observed in Oligocene through Holocene sediments recovered from the Kerguelen Plateau. The diatom flora from the Kerguelen Plateau is characterized by species such as Azpeitia oligocenica, Rocella gelida, Rocella vigilans, and Synedra jouseana in the Oligocene and Crucidenticula nicobarica, Denticulopsis hustedtii, Nitzschia miocenica, and Thalassiosira miocenica in the Miocene. This somewhat cosmopolitan assemblage gives way to a Pliocene and Holocene assemblage characterized by species such as Nitzschia kerguelensis, Thalassiosira inura, and Thalassiosira torokina, which are endemic to the Southern Ocean region. Samples examined from Prydz Bay are generally devoid of diatoms. The exception is Site 739, where diatoms occur sporadically in lower Oligocene and upper Miocene through Quaternary sediments. The Leg 119 diatom biostratigraphic results allow the development of a stratigraphic framework for the Indian sector of the Southern Ocean. This diatom zonation integrates diatom zonations developed previously for other sectors of the Southern Ocean. The zonation proposed here is based on biostratigraphic events of both geographically widespread and endemic species calibrated to the paleomagnetic stratigraphy. As such, this zonation has application throughout the Southern Ocean and allows correlation from the southern high latitudes to the low latitudes.

(Table 1) Porewater analysis with respect to gypsum from different ODP holes

The stability of gypsum in marine sediments has been investigated through the calculation of its saturation index at the sediment in situ temperature and pressure, using the entire ODP/IODP porewater composition database (14416 samples recovered from sediments collected during 95 ODP and IODP Legs). Saturation is reached in sediment porewaters of 26 boreholes drilled at 23 different sites, during 12 ODP/IODP Legs. As ocean bottom seawater is largely undersaturated with respect to gypsum, the porewater Ca content or its SO4 concentration, or both, must increase in order to reach equilibrium. At several sites equilibrium is reached either through the presence of evaporitic gypsum layers found in the sedimentary sequence, and/or through a salinity increase due to the presence of evaporitic brines with high concentrations of Ca and SO4. Saturation can also be reached in porewaters of seawater-like salinity (~ 35 per mil), provided sulfate reduction is limited. In this case, saturation is due to the alteration of volcanogenic material which releases large amounts of Ca to the porewaters, where the Ca concentration can reach 55 times its seawater value as for example at ODP Leg 134 site 833. At a few sites, saturation is reached in hydrothermal environments, or as a consequence of the alteration of the basaltic basement. In addition to the well known influence of brines on the formation of gypsum, these results indicate that the alteration of sediments rich in volcanogenic material is a major process leading to gypsum saturation in marine sediment porewaters. Therefore, the presence of gypsum in ancient and recent marine sediments should not be systematically interpreted as due to hypersaline waters, especially if volcanogenic material is present.