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Stromatolites may be Earth's oldest macroscopic fossils; however, it remains controversial what, if any, biological processes are recorded in their morphology. Although the biological interpretation of many stromatolite morphologies is confounded by the influence of sedimentation, conical stromatolites form in the absence of sedimentation and are, therefore, considered to be the most robust records of biophysical processes. A qualitative similarity between conical stromatolites and some modern microbial mats suggests a photosynthetic origin for ancient stromatolites. To better understand and interpret ancient fossils, we seek a quantitative relationship between the geometry of conical stromatolites and the biophysical processes that control their growth. We note that all modern conical stromatolites and many that formed in the last 2.8 billion years display a characteristic centimeter-scale spacing between neighboring structures. To understand this prominent - but hitherto uninterpreted -organization, we consider the role of diffusion in mediating competition between stromatolites. Having confirmed this model through laboratory experiments and field observation, we find that organization of a field of stromatolites is set by a diffusive time scale over which individual structures compete for nutrients, thus linking form to physiology. The centimeter-scale spacing between modern and ancient stromatolites corresponds to a rhythmically fluctuating metabolism with a period of approximately 20 hr. The correspondence between the observed spacing and the day length provides quantitative support for the photosynthetic origin of conical stromatolites throughout geologic time. Keywords: geobiology; photosynthesis; cyanobacteria; microbialite, United States. National Aeronautics and Space Administration (Grant NNA08CN84A), National Science Foundation (U.S.) (Grant EAR–0420592)

High amplitude positive carbon isotope excursions in the Late Devonian, the punctata and Kellwasser events, reflect major perturbations in the global carbon cycle that have been attributed to increased continental weathering and subsequent ocean eutrophication. Despite the comparable carbon isotope anomalies, however, a major extinction has been reported only for the Kellwasser Events, while the punctata Event is marked by low extinction intensity. This study presents multiple sulfur isotope records of carbonate-associated sulfate (CAS) and pyrite from Late Devonian sections in the Great Basin, USA, in order to document changes in the coupled (or decoupled) geochemical cycles of carbon and sulfur during the punctata and Upper Kellwasser events. A positive sulfur isotope shift in both CAS and pyrite accompanies the onset of the punctata Event, but to a larger extent in the latter. As a result, the sulfur isotope offset between CAS and pyrite (Δ[superscript 34]S[subscript CAS-py]) dropped to less than 10‰. In the middle of the punctata Event, a sharp negative δ[superscript 34]S[subscript CAS] excursion and negative Δ[superscript 34]S[subscript CAS-py] values coincide with the Alamo impact. Unlike the rapid δ[superscript 34]S[subscript py] and δ[superscript 34]S[subscript CAS] oscillations associated with the punctata Event, the Upper Kellwasser was a period of relative stability, except for a brief δ[superscript 34]S[subscript CAS] drop before the event. Paired sulfur isotope data, aided by a simple box model, suggest that the geochemical cycle of sulfur may have been partly responsible for the contrasting biological responses that define these events. High stratigraphic δ[superscript 34]S[subscript py] and δ[superscript 34]S[subscript CAS] variability, coupled with strong reservoir effect, demonstrates a relatively small oceanic sulfate pool existed during the punctata Event. Further, the Alamo impact likely triggered the rapid oxidation of microbially-produced sulfi

In PNAS, Wing and Halevy present a new model that quantitatively describes the magnitude of sulfur isotope fractionation produced by dissimilatory microbial sulfate reduction (MSR). MSR is a major player in the global biogeochemical cycles and is responsible for the respiration of up to 30% of organic matter in marine sediments. This metabolism produces large isotope effects, in which the product, sulfide, is depleted in the heavy isotopes ([superscript 33]S, [superscript 34]S, and [superscript 36]S) relative to the most abundant isotope [superscript 32]S (3), enriching modern seawater sulfate in [superscript 34]S by about 21‰ (parts per thousand) compared with mantle sulfur. Sedimentary sulfur minerals preserve a record of this effect and are used to track changes in the sulfur isotope composition of seawater and the biogeochemical sulfur, carbon, and oxygen cycles through geologic time (4). Such reconstructions require an understanding of factors that control the magnitude of sulfur isotope effects and dictate the fractionation of sulfur isotopes by sulfate reducers under a range of growth conditions.

Some modern filamentous oxygenic photosynthetic bacteria (cyanobacteria) form macroscopic tufts, laminated cones and ridges that are very similar to some Archean and Proterozoic stromatolites. However, it remains unclear whether microbes that constructed Archean clumps, tufts, cones and ridges also produced oxygen. Here, we address this question by examining the physiology of cyanobacterial clumps, aggregates ~0.5 mm in diameter that initiate the growth of modern mm- and cm-scale cones. Clumps contain more particulate organic carbon in the form of denser, bowed and bent cyanobacterial filaments, abandoned sheaths and non-cyanobacterial cells relative to the surrounding areas. Increasing concentrations of oxygen in the solution enhance the bending of filaments and the persistence of clumps by reducing the lateral migration of filaments away from clumps. Clumped mats in oxic media also release less glycolate, a soluble photorespiration product, and retain a larger pool of carbon in the mat. Clumping thus benefits filamentous mat builders whose incorporation of inorganic carbon is sensitive to oxygen. The morphogenetic sequence of mm-scale clumps, reticulate ridges and conical stromatolites from the 2.7 Ga Tumbiana Formation likely records similar O2-dependent behaviors, preserving currently the oldest morphological signature of oxygenated environments on Early Earth., United States. National Aeronautics and Space Administration (NASA Astrobiology Institute NNA08CN84A), National Science Foundation (U.S.) (EAR-0843358)

Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS) to carbon monoxide (CO) and elemental sulfur (S[superscript 0]). The OCS gas at 3.7 to 501 mbar was irradiated with or without a N₂ bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S[superscript 0] and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF₆ as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8‰ for the ratio [superscript 34]S/[superscript 32]S, where product S[superscript 0] is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5‰ when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS) reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1‰ for [superscript 34]S which gives the photolysis isotope effect as −10.5 to +5.3‰. The observed triple isotope coefficients are ln(δ[superscript 34]S + 1)/ln(δ[superscript 34]S + 1) = 0.534 ± 0.005 and ln(δ[superscript 36]S + 1)/ln(δ[superscript 34]S + 1) = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10‰ for [superscript 34]S/[superscript 32]S, and can be the major source of background stratospheric sulfate aerosol (SSA) during volcanic quiescence., United States. National Aeronautics and Space Administration (Exobiology program, Grant No. NNX10AR85G)

Some modern filamentous oxygenic photosynthetic bacteria (cyanobacteria) form macroscopic tufts, laminated cones and ridges that are very similar to some Archean and Proterozoic stromatolites. However, it remains unclear whether microbes that constructed Archean clumps, tufts, cones and ridges also produced oxygen. Here, we address this question by examining the physiology of cyanobacterial clumps, aggregates ~0.5 mm in diameter that initiate the growth of modern mm- and cm-scale cones. Clumps contain more particulate organic carbon in the form of denser, bowed and bent cyanobacterial filaments, abandoned sheaths and non-cyanobacterial cells relative to the surrounding areas. Increasing concentrations of oxygen in the solution enhance the bending of filaments and the persistence of clumps by reducing the lateral migration of filaments away from clumps. Clumped mats in oxic media also release less glycolate, a soluble photorespiration product, and retain a larger pool of carbon in the mat. Clumping thus benefits filamentous mat builders whose incorporation of inorganic carbon is sensitive to oxygen. The morphogenetic sequence of mm-scale clumps, reticulate ridges and conical stromatolites from the 2.7 Ga Tumbiana Formation likely records similar O2-dependent behaviors, preserving currently the oldest morphological signature of oxygenated environments on Early Earth.

Conical stromatolites are thought to be robust indicators of the presence of photosynthetic and phototactic microbes in aquatic environments as early as 3.5 billion years ago. However, phototaxis alone cannot explain the ubiquity of disrupted, curled, and contorted laminae in the crests of many Mesoproterozoic, Paleoproterozoic, and some Archean conical stromatolites. Here, we demonstrate that cyanobacterial production of oxygen in the tips of modern conical aggregates creates contorted laminae and submillimeter-to-millimeter-scale enmeshed bubbles. Similarly sized fossil bubbles and contorted laminae may be present only in the crestal zones of some conical stromatolites 2.7 billion years old or younger. This implies not only that cyanobacteria built Proterozoic conical stromatolites but also that fossil bubbles may constrain the timing of the evolution of oxygenic photosynthesis.