Search

The repeated association during the late Neoproterozoic Era of large carbon-isotopic excursions, continental glaciation, and stratigraphically anomalous carbonate precipitation provides a framework for interpreting the reprise of these conditions on the Late Permian Earth. A paleoceanographic model that was developed to explain these stratigraphically linked phenomena suggests that the overturn of anoxic deep oceans during the Late Permian introduced high concentrations of carbon dioxide into surficial environments. The predicted physiological and climatic consequences for marine and terrestrial organisms are in good accord with the observed timing and selectivity of Late Permian mass extinction.

The evolution of non-photosynthetic sulphide-oxidizing bacteria was contemporaneous with a large shift in the isotopic composition of biogenic sedimentary sulphides between 0.64 and 1.05 billion years ago. Both events were probably driven by a rise in atmospheric oxygen concentrations to greater than 5-18% of present levels--a change that may also have triggered the evolution of animals.

Bacteria that disproportionate elemental sulfur fractionate sulfur isotopes such that sulfate is enriched in sulfur-34 by 12.6 to 15.3 per mil and sulfide is depleted in sulfur-34 by 7.3 to 8.6 per mil. Through a repeated cycle of sulfide oxidation to S0 and subsequent disproportionation, these bacteria can deplete sedimentary sulfides in sulfur-34. A prediction, borne out by observation, is that more extensive sulfide oxidation will lead to sulfides that are more depleted in sulfur-34. Thus, the oxidative part of the sulfur cycle creates circumstances by which sulfides become more depleted in sulfur-34 than would be possible with sulfate-reducing bacteria alone.

Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

Stromatolites offer an unparalleled geologic record of early life, because they constitute the oldest and most abundant recognizable remains of microbial ecosystems. Microbial mats are living homologs of stromatolites; thus, the physiology of the microbiota as well as the processes which create those features of mats (e.g., biomarker organic compounds, elemental and stable isotopic compositions) which are preserved in the ancient record. Observations of the carbon isotopic composition (delta C-13) of stromatolites and microbial mats were made and are consistent with the hypothesis that atmospheric CO2 concentrations have declined by at least one to two orders of magnitude during the past 2.5 Ga. Whereas delta C-13 values of carbonate carbon average about 0 permil during both the early and mid-Proterozoic, the delta C-13 values of stromatolitic organic matter increase from an average of -35 between 2.0 and 2.6 Ga ago to an average of about -28 about 1.0 Ga ago. Modern microbial mats in hypersaline environments have delta C-13 values typically in the range of -5 to -9, relative to an inorganic bicarbonate source at 0 permil. Both microbial mats and pur cultures of cyanobacteria grown in waters in near equilibrium with current atmospheric CO2 levels exhibit minimal discrimination against C-13. In contrast, hot spring cyanobacterial mats or cyanobacterial cultures grown under higher CO2 levels exhibit substantially greater discrimination. If care is taken to compare modern mats with stromatolites from comparable environments, it might be possible to estimate ancient levels of atmospheric CO2. In modern microbial mats, a tight coupling exists between photosynthetic organic carbon production and subsequent carbon oxidation, mostly by sulfate reduction. The rate of one process fuels a high rate of the other, with much of the sulfate reduction occurring within the same depth interval as oxygenic photosynthesis. Other aspects of this study are presented.

Sulfate reduction rates calculated from about 200 DSDP pore water sulfate profiles have been contoured and plotted on a map covering most areas of the world ocean. Rates show a remarkable spatial consistency, with high rates observed near the continental margins, becoming progressively lower toward the central ocean basins. Relatively elevated rates are also found in the eastern equatorial Pacific, a site of upwelling and correspondingly high rates of primary organic production. Overall, the distribution of sulfate reduction in pelagic sediments looks very similar to the distribution of primary organic carbon production. When rates are directly compared, however, the correlation between sulfate reduction and primary production is only moderately strong. Perhaps the most important influence on sulfate reduction is sediment deposition rate and the control this has over the fraction of the sedimentary organic carbon flux that becomes available for sulfate reduction. The slower the rate of sediment deposition the more time for oxic respiration and the less organic carbon that escapes to the zone of sulfate reduction. To predict most accurately sulfate reduction rates, however, the variables of primary production, water depth, and sediment deposition rate must all be integrated.

Data are reported for Mn, Fe, Co, Ni, Cu and Cd in the Onyx River, and for Mn, Co, Ni, Cu and Cd in Lake Vanda, a closed-basin Antarctic lake. Oxic water concentrations for Co, Ni, Cu and Cd were quite low and approximate pelagic ocean values. Scavenging of these metals by sinking particles is strongly indicated. Deep-lake profiles reveal a sharp peak in the concentrations of Mn, Fe and Co at the oxic-anoxic boundary at 60 m. Maxima for Ni, Cu and Cd occur higher in the water column, in the vicinity of a Mn submaximum, suggesting early release of these metals from sinking manganese oxide-coated particles. A rough steady-state model leads to the conclusion that there is a large downward flux of Mn into the deep lake and that this flux is sufficient to explain the annual loss of Co, Ni, Cu and Cd. A pronounced geochemical separation between Fe and Mn apparently occurs in this system--Fe being best lost in near-shore environments and Mn being lost in deeper waters. Comparison of metal residence times in Lake Vanda with those in the oceans shows that in both systems Mn, Fe and Co are much more reactive than Ni, Cu and Cd. Energetically favorable inclusion of the more highly charged metals, Mn(IV), Fe(III) and Co(III), into oxide-based lattices is a plausible explanation.

Compilations have been made of sulfate reduction rates and oxic respiration rates over the entire range of marine sedimentation rates, and sedimentary environments, including several euxinic sites. These data show, consistent with the findings of Jorgensen (1982, Nature, 296, 643-645), that sulfate reduction and oxic respiration oxidize equal amounts of organic carbon in nearshore sediments. As sedimentation rates decrease, oxic respiration, becomes progressively more important, and in deep-sea sediments 100-1000 times more organic carbon is oxidized by oxic respiration than by sulfate reduction. By contrast, nearly as much organic carbon is oxidized by sulfate reduction in euxinic sediments as is oxidized by the sum of sulfate reduction and oxic respiration in normal marine sediments of similar deposition rate. This observation appears at odds with the enhanced preservation of organic carbon observed in euxinic sediments. However, only small reductions in (depth-integrated) organic carbon decomposition rates (compared to normal marine) are required to give both high organic carbon concentrations and enhanced carbon preservation in euxinic sediments. Lower rates of organic carbon decomposition (if only by subtle amounts) are explained by the diminished ability of anaerobic bacteria to oxidize the full suite of sedimentary organic compounds.