Stratigraphic first occurrence of Emiliania huxleyi in sediments of the Chatham Rise (Table 2)

A quantitative analysis was carried out of planktonic diatoms (biogenic opal) and calcareous nannofossils (biogenic calcite) in late Quaternary sediments (MIS 1-6) from four cores along a N-S transect east of New Zealand from 39°50'S to 50°04'S across the E-W-trending submarine ridge, the Chatham Rise. This was done to trace movements of oceanic fronts and to improve calcareous nannofossil stratigraphy for the last 130 000 yr in the SW Pacific. Sites ODP 1123 and Q 858 are below present day subtropical surface waters north of Chatham Rise. Site DSDP 594 is below present-day mixed temperate-subantarctic surface water south of the rise, and site ODP 1120 is below subantarctic surface water. The more diverse and opportunistic planktonic diatoms provided marker species for subtropical surface waters (Alveus marina, Fragilariopsis doliolus, Rhizosolenia bergonii and Azpeitia nodulifer) and others for subantarctic surface waters (Nitzschia kerguelensis, Thalassiosira lentiginosa). Application of these tracers permits the following conclusions: (1) subtropical conditions persisted north of Chatham Rise throughout the past 130 000 yr, in spite of the cooling of surface waters during colder periods; (2) during warm times (MIS 5 and MIS 3, and in MIS 1), the sporadic occurrence of subtropical species south of Chatham Rise indicates occasional admixture of subtropical surface waters that far south; (3) subantarctic waters extended to the southern slopes of the Chatham Rise during MIS 5b, late MIS 5a to early MIS 4, during the warmer time intervals in early MIS 3, and during latest MIS 3 to early MIS 2; (4) subantarctic frontal conditions existed over southern Chatham Rise during early MIS 4 and late MIS 3 to early MIS 2; and (5) it is probable that during cooler times, MIS 6, MIS 5b, and in MIS 2, intensified particle transport from the Bounty Trough to the northern flank of Chatham Rise occurred by intensified boundary currents. The larger abundance fluctuations in both microfossil groups at the sites south of Chatham Rise than north of Chatham Rise reflect northward shifts of the Circumpolar Subantarctic Water (CSW) and a contemporaneous disappearance of Australasian Subantarctic Water (ASW), implying an elevated temperature gradient between the surface water masses north and south of the Chatham Rise at the times of such northward shifts of CSW. Calcareous nannofossils are less diverse than diatoms, and are less specialised. Some calcareous nannofossil species show abundance shifts at the same time at different latitudes. Two of these abundance shifts can be used for correlation between subtropical and subantarctic sediments in the SW Pacific: (1) reversal in the relative abundance of Calcidiscus leptoporus and Coccolithus pelagicus associated with the MIS 2/1 boundary; and (2) drop in abundance of Gephyrocapsa muellerae or medium-sized Gephyrocapsa at the MIS 4/3 boundary. An additional abundance shift seems to be restricted to subtropical to mixed temperate-subtropical-subantarctic surface waters: (3) increase in abundance of G. muellerae or medium-sized Gephyrocapsa at the beginning of MIS 2 below the Okareka tephra.

The distribution of sulfur in oceanic crust with respect to oxidative diagenesis (Table 1)

A detailed geochemical-petrological examination of layer 2 basalts recovered during Leg 37 of the DSDP has revealed that the original distribution, form and abundance of igneous sulfide have been profoundly altered during low-grade oxidative diagenesis. The net result appears to have been a rather pervasive remobilization of igneous sulfide to form secondary pyrite accompanied by a bulk loss of sulfur equivalent to about 50-60% of the original igneous value, assuming initial saturation. It is suggested that during infiltration of seawater into the massive crystalline rock, igneous sulfide has experienced pervasive oxidation, under conditions of limited oxidation potential, to form a series of unstable, soluble sulfur species, primarily in the form of SO3[2-] and S2O3[2-]. Spontaneous decomposition of these intermediate compounds through disproportionation has resulted in partial reconstitution of the sulfur as secondary pyrite and the generation of SO4[2-] ion, which, due to its kinetic stability, has been lost from the basalt system and ultimately transferred to the ocean. This model not only satisfies the geochemical and petrological observations but also provides a suitable explanation for the highly variable delta34S values which characterize secondary sulfides in deep ocean floor basalts.

Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.