Global Cooling During the Eocene-Oligocene www.sciencemag.org (this information is current as of February 27, 2009 ):The following resources related to this article are available online at

An ammonia-oxidizing, carbon-fixing archaeon, Candidatus ''Nitrosopumilus maritimus,'' recently was isolated from a salt-water aquarium, definitively confirming that chemoautotrophy exists among the marine archaea. However, in other incubation studies, pelagic archaea also were capable of using organic carbon. It has remained unknown what fraction of the total marine archaeal community is autotrophic in situ. If archaea live primarily as autotrophs in the natural environment, a large ammonia-oxidizing population would play a significant role in marine nitrification. Here we use the natural distribution of radiocarbon in archaeal membrane lipids to quantify the bulk carbon metabolism of archaea at two depths in the subtropical North Pacific gyre. Our compound-specific radiocarbon data show that the archaea in surface waters incorporate modern carbon into their membrane lipids, and archaea at 670 m incorporate carbon that is slightly more isotopically enriched than inorganic carbon at the same depth. An isotopic mass balance model shows that the dominant metabolism at depth indeed is autotrophy (83%), whereas heterotrophic consumption of modern organic carbon accounts for the remainder of archaeal biomass. These results reflect the in situ production of the total community that produces tetraether lipids and are not subject to biases associated with incubation and͞or culture experiments. The data suggest either that the marine archaeal community includes both autotrophs and heterotrophs or is a single population with a uniformly mixotrophic metabolism. The metabolic and phylogenetic diversity of the marine archaea warrants further exploration; these organisms may play a major role in the marine cycles of nitrogen and carbon.biomarkers ͉ carbon isotopes ͉ microbial ecology ͉ nitrogen cycle ͉ oceanography N onthermophilic archaea represent up to 40% of the free-living prokaryotic community in the water column of the world's oceans (1-6), but until recently there has been limited information about the sources of carbon and energy that fuel these organisms (7-11). The characteristic membrane lipids of planktonic archaea include glycerol dialkyl glycerol tetraethers (GDGTs) (12). These compounds are ubiquitous in marine sediments and ocean water (12-15). The relative abundance of individual GDGTs recovered from sediments is used to reconstruct sea-surface temperatures (16)(17)(18). This distribution, known as TEX 86 , has been shown through experimental manipulation of surface-water mesocosm experiments to respond to changes in incubation temperature (18). In addition, the ␦ 13 C values of GDGTs display a remarkably constant offset from ␦ 13 C values of dissolved inorganic carbon (DIC) over a range of settings and geologic time (13,(19)(20)(21). The collective metabolic activities of the numerous archaea in the ocean are likely to play a significant role in the cycling of organic carbon (OC) and nutrients, and their membrane lipids show significant utility for paleoceanography. However, neither the metabolic requiremen...

An active microbial assemblage cycles sulfur in a sulfate-rich, ancient marine brine beneath Taylor Glacier, an outlet glacier of the East Antarctic Ice Sheet, with Fe(III) serving as the terminal electron acceptor. Isotopic measurements of sulfate, water, carbonate, and ferrous iron and functional gene analyses of adenosine 5'-phosphosulfate reductase imply that a microbial consortium facilitates a catalytic sulfur cycle. These metabolic pathways result from a limited organic carbon supply because of the absence of contemporary photosynthesis, yielding a subglacial ferrous brine that is anoxic but not sulfidic. Coupled biogeochemical processes below the glacier enable subglacial microbes to grow in extended isolation, demonstrating how analogous organic-starved systems, such as Neoproterozoic oceans, accumulated Fe(II) despite the presence of an active sulfur cycle.

Anaerobic oxidation of methane (AOM) by sulfate has been recognized as a critical process to maintain this greenhouse gas stability by limiting methane flux to the atmosphere. We show geochemical evidence for AOM in deep lake sediments and demonstrate that AOM is likely driven by iron (Fe) reduction. Pore-water profiles from Lake Kinneret (Sea of Galilee, Israel) show that this sink for methane is located below the 20-cm depth in the sediment, which is well below the depths at which nitrate and sulfate are completely exhausted, as well as below the zone of methanogenesis. Iron-dependant AOM was verified by Fe(III)-amended mesocosm studies using intact sediment cores, and native iron oxides were detectable throughout the sediments. Because anaerobic Fe(III) respiration is thermodynamically more favorable than both sulfate-dependent methanotrophy and methanogenesis, its occurrence below the zone of methane production supports the idea that reduction of sedimentary iron oxides is kinetically or biologically limited. Similar conditions are likely to prevail in other incompletely pyritized aquatic sediments, indicating that AOM with Fe(III) is an important global sink for methane.

No abstract

Molecular oxygen (O2) began to accumulate in the atmosphere and surface ocean ca. 2,400 million years ago (Ma), but the persistent oxygenation of water masses throughout the oceans developed much later, perhaps beginning as recently as 580 -550 Ma. For much of the intervening interval, moderately oxic surface waters lay above an oxygen minimum zone (OMZ) that tended toward euxinia (anoxic and sulfidic). Here we illustrate how contributions to primary production by anoxygenic photoautotrophs (including physiologically versatile cyanobacteria) influenced biogeochemical cycling during Earth's middle age, helping to perpetuate our planet's intermediate redox state by tempering O 2 production. Specifically, the ability to generate organic matter (OM) using sulfide as an electron donor enabled a positive biogeochemical feedback that sustained euxinia in the OMZ. On a geologic time scale, pyrite precipitation and burial governed a second feedback that moderated sulfide availability and water column oxygenation. Thus, we argue that the proportional contribution of anoxygenic photosynthesis to overall primary production would have influenced oceanic redox and the Proterozoic O 2 budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe 2؉ rich) subsurface waters set in motion Earth's transition from its prokaryote-dominated middle age, removing a physiological barrier to eukaryotic diversification (sulfide) and establishing, for the first time in Earth's history, complete dominance of oxygenic photosynthesis in the oceans. This paved the way for the further oxygenation of the oceans and atmosphere and, ultimately, the evolution of complex multicellular organisms.ocean chemistry ͉ primary production ͉ Proterozoic biosphere

Sterol biosynthesis is viewed primarily as a eukaryotic process, and the frequency of its occurrence in bacteria has long been a subject of controversy. Two enzymes, squalene monooxygenase and oxidosqualene cyclase, are the minimum necessary for initial biosynthesis of sterols from squalene. In this work, 19 protein gene sequences for eukaryotic squalene monooxygenase and 12 protein gene sequences for eukaryotic oxidosqualene cyclase were compared with all available complete and partial prokaryotic genomes. The only unequivocal matches for a sterol biosynthetic pathway were in the proteobacterium, Methylococcus capsulatus, in which sterol biosynthesis is known, and in the planctomycete, Gemmata obscuriglobus. The latter species contains the most abbreviated sterol pathway yet identified in any organism. Analysis shows that the major sterols in Gemmata are lanosterol and its uncommon isomer, parkeol. There are no subsequent modifications of these products. In bacteria, the sterol biosynthesis genes occupy a contiguous coding region and possibly comprise a single operon. Phylogenetic trees constructed for both enzymes show that the sterol pathway in bacteria and eukaryotes has a common ancestry. It is likely that this contiguous reading frame was exchanged between bacteria and early eukaryotes via lateral gene transfer or endosymbiotic events. The primitive sterols produced by Gemmata suggest that this genus could retain the most ancient remnants of the sterol biosynthetic pathway. S terol biosynthesis is nearly ubiquitous among eukaryotes; conversely, it is almost completely absent in prokaryotes (1). As a result, the presence of diverse steranes in ancient rocks is used as evidence for eukaryotic evolution Ͼ2.7 billion years ago (2). However, the occasional presence of sterols in prokaryotes is poorly understood. Sterol production by bacteria previously has been demonstrated only in the Methylococcales (3, 4) and Myxobacteriales (5,6).Understanding the evolution of sterol biosynthesis is of significant interest to biochemistry, evolutionary biology, and the geosciences, because the only known biosynthetic pathway requires molecular oxygen. The first step in this pathway is the epoxidation of the hydrocarbon squalene, in which the addition of 1 ⁄2O 2 is catalyzed by the enzyme squalene monooxygenase (SQMO) (7). Unless there are other unknown enzymes or abiogenic reactions capable of producing squalene epoxide, this would require the prior evolution of oxygenic photosynthesis. For sterol biosynthesis to date to the last common ancestor, a biogenic or abiogenic peroxidation could be a potential mechanism, although this has not yet been demonstrated.Cyclization of squalene epoxide to form the initial sterol proceeds immediately through the action of a second enzyme, oxidosqualene cyclase (OSC). It is believed that OSC evolved from the hopanoid pathway predecessor, bacterial squalenehopene cyclase (SHC) (8, 9). In eukaryotes, the initial sterols lanosterol and cycloartenol are merely biosynthetic intermediates; i.e.,...

Techniques for making precise and accurate radiocarbon accelerator mass spectrometry (AMS) measurements on samples containing less than a few hundred micrograms of carbon are being developed at the NOSAMS facility. A detailed examination of all aspects of the sample preparation and data analysis process shows encouraging results. Small quantities of CO2 are reduced to graphite over cobalt catalyst at an optimal temperature of 605°C. Measured 14C/12C ratios of the resulting targets are affected by machine-induced isotopic fractionation, which appears directly related to the decrease in ion current generated by the smaller sample sizes. It is possible to compensate effectively for this fractionation by measuring samples relative to small standards of identical size. Examination of the various potential sources of background 14C contamination indicates that the sample combustion process is the largest contributor, adding ca. 1 µg of carbon with a less-than-modern 14C concentration. c