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Johnston, David

Detailed iron, sulfur and carbon chemistry through the > 742 million year old ChuarGroup reveals a marine basin dominated by anoxic and ferrous iron-rich (ferruginous) bottom waters punctuated, late in the basin's development, by an intrusion of sulfide-rich (euxinic) conditions. The observation that anoxia occurred frequently in even the shallowest of Chuar environments (10s of meters or less) suggests that global atmospheric oxygen levels were significantly lower than today. In contrast, the transition from ferruginous to euxinic subsurface water is interpreted to reflect basinal control—specifically, increased export of organic carbon from surface waters. Low fluxes of organic carbon into subsurface water masses should have been insufficient to deplete oxygen via aerobic respiration, resulting in an oxic oxygen minimum zone (OMZ). Where iron was available, larger organic carbon fluxes should have depleted oxygen and facilitated anaerobic respiration using ferric iron as the oxidant, with iron carbonate as the expected mineralogical signature in basinal shale. Even higher organic fluxes would, in turn, have depleted ferric iron and up-regulated anaerobic respiration by sulfate reduction, reflected in high pyrite abundances. Observations from the ChuarGroup are consistent with these hypotheses, and gain further support from pyrite and sulfate sulfur isotope abundances. In general, Chuar data support the hypothesis that ferruginous subsurface waters returned to the oceans, replacing euxinia, well before the Ediacaran emergence of persistently oxygenated conditions, and even predating the Sturtian glaciation. Moreover, our data suggest that the reprise of ferruginous water masses may relate to widespread rifting during the break-up of Rodinia. This environmental transition, in turn, correlates with both microfossil and biomarker evidence for an expanding eukaryotic presence in the oceans, suggesting a physiologically mediated link among tectonics, environmental chemistry and life in the dynamic Neoproterozoic Earth system.

The Neoproterozoic was an era of great environmental and biological change, but a paucity of direct and precise age constraints on strata from this time has prevented the complete integration of these records. We present four high-precision U-Pb ages for Neoproterozoic rocks in northwestern Canada that constrain large perturbations in the carbon cycle, a major diversification and depletion in the microfossil record, and the onset of the Sturtian glaciation. A volcanic tuff interbedded with Sturtian glacial deposits, dated at 716.5 million years ago, is synchronous with the age of the Franklin large igneous province and paleomagnetic poles that pin Laurentia to an equatorial position. Ice was therefore grounded below sea level at very low paleolatitudes, which implies that the Sturtian glaciation was global in extent.

Mineralogical, petrographic and sedimentological observations document early diagenetic talc in carbonate-dominated successions deposited on two early Neoproterozoic (~ 800–700 million years old) platform margins. In the Akademikerbreen Group, Svalbard, talc occurs as nodules that pre-date microspar cements that fill molar tooth structures and primary porosity in stromatolitic carbonates. In the upper Fifteenmile Group of the Ogilvie Mountains, NW Canada, the talc is present as nodules, coated grains, rip-up clasts and massive beds that are several meters thick. To gain insight into the chemistry required to form early diagenetic talc, we conducted precipitation experiments at 25 °C with low-SO4 synthetic seawater solutions at varying pH, Mg2+ and SiO2(aq). Our experiments reveal a sharp and reproducible pH boundary (at ~ 8.7) only above which does poorly crystalline Mg-silicate precipitate; increasing Mg2+ and/or SiO2(aq) alone is insufficient to produce the material. The strong pH control can be explained by Mg-silica complexing activated by the deprotonation of silicic acid above ~ 8.6–8.7. FT-IR, TEM and XRD of the synthetic precipitates reveal a talc-like 2:1 trioctahedral structure with short-range stacking order. Hydrothermal experiments simulating burial diagenesis show that dehydration of the precipitate drives a transition to kerolite (hydrated talc) and eventually to talc. This formation pathway imparts extensive layer stacking disorder to the synthetic talc end-product that is identical to Neoproterozoic occurrences. Early diagenetic talc in Neoproterozoic carbonate platform successions appears to reflect a unique combination of low Al concentrations (and, by inference, low siliciclastic input), near modern marine salinity and Mg2+, elevated SiO2(aq), and pH > ~ 8.7. Because the talc occurs in close association with microbially influenced sediments, we suggest that soluble species requirements were most easily met through microbial influences on pore water chemistry, specifically pH and alkalinity increases driven by anaerobic Fe respiration.

Dissimilatory sulfate reduction serves as a key metabolic carbon remineralization process in anoxic marine environments. Sulfate reducing microorganisms can impart a wide range in mass-dependent sulfur isotopic fractionation. As such, the presence and relative activity of these organisms is identifiable from geological materials. By extension, sulfur isotope records are used to infer the redox balance of marine sedimentary environments, and the oxidation state of Earth's oceans and atmosphere. However, recent work suggests that our understanding of microbial sulfate reduction (MSRs) may be missing complexity associated with the presence and role of key chemical intermediates in the reductive process. This study provides a test of proposed metabolic models of sulfate reduction by growing an axenic culture of the well-studied MSRs, Desulfovibrio alaskensis strain G20, under electron donor limited conditions on the terminal electron acceptors sulfate, sulfite or thiosulfate, and tracking the multiple S isotopic consequences of each condition set. The dissimilatory reduction of thiosulfate and sulfite produce unique minor isotope effects, as compared to the reduction of sulfate. Further, these experiments reveal a complex biochemistry associated with sulfite reduction. That is, under high sulfite concentrations, sulfur is shuttled to an intermediate pool of thiosulfate. Site-specific isotope fractionation (within thiosulfate) is very large (34ε ~ 30‰) while terminal product sulfide carries only a small fractionation from the initial sulfite (34ε < 10‰): a signature similar in magnitude to sulfate and thiosulfate reduction. Together these findings show that microbial sulfate reduction (MSR) is highly sensitive to the concentration of environmentally important sulfur-cycle intermediates (sulfite and thiosulfate), especially when thiosulfate and the large site-specific isotope effects are involved.

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H2S and S0 by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum . Discrimination between 34S and 32S was +1.8 ± 0.5‰ during the oxidation of H2S to S0, and −1.9 ± 0.8‰ during the oxidation of S0 to View the MathML sourceSO42-, consistent with previous studies. The accompanying Δ33S and Δ36S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ33S and 0.9‰ for Δ36S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small δ34S effects associated with S oxidation combined with large δ34S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ33S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record.

Sulfur isotopes in ancient sediments provide a record of past environmental conditions. The long–time-scale variability and apparent asymmetry in the magnitude of minor sulfur isotope fractionation in Archean sediments remain unexplained. Using an integrated biogeochemical model of the Archean sulfur cycle, we find that the preservation of mass-independent sulfur is influenced by a variety of extra-atmospheric mechanisms, including biological activity and continental crust formation. Preservation of atmospherically produced mass-independent sulfur implies limited metabolic sulfur cycling before ~2500 million years ago; the asymmetry in the record indicates that bacterial sulfate reduction was geochemically unimportant at this time. Our results suggest that the large-scale structure of the record reflects variability in the oxidation state of volcanic sulfur volatiles.

Life, as recorded in almost every corner of the oceans and continents, has evolved to take advantage of chemical gradients. Organisms, both big and small, utilize reduction–oxidation (redox) reactions to gain the energy required to live and grow. Although aerobic respiration (using O2) is the most popular form, other modes of respiration use oxygen alternatives and drive additional element cycles (for example, nitrogen, sulfur, and metals such as iron and manganese). These alternative metabolisms, and especially those cycling sulfur, helped shape Earth's long history and much of the world we see today. Sulfur is a fundamental constituent in macroscopic and microscopic worlds alike and is a key oxidant in the anaerobic biosphere. By reconstructing the distribution of sulfur metabolisms throughout the marine realm, we can better understand the role that sulfur plays in marine biogeochemical cycling and Earth-surface processes.

A mechanistic understanding of relationships between global glaciation, a putative second rise in atmospheric oxygen, the Shuram carbon isotope excursion, and the appearance of Ediacaran-type fossil impressions and bioturbation is dependent on the construction of accurate geological records through regional stratigraphic correlations. Here we integrate chemo-, litho-, and sequence-stratigraphy of fossiliferous Ediacaran strata in northwestern Canada. These data demonstrate that the FAD of Ediacara-type fossil impressions in northwestern Canada occur within a lowstand systems tract and above a major sequence boundary in the informally named June beds, not in the early Ediacaran Sheepbed Formation from which they were previously reported. This distinction is substantiated by δ13Ccarb chemostratigraphy of the Sheepbed carbonate, which overlies the Sheepbed Formation, and the Gametrail Formation, which overlies the June beds. The Sheepbed carbonate hosts heavy δ13Ccarb values whereas the Gametrail Formation contains a large δ13Ccarb excursion, which we correlate with the globally recognized Shuram excursion. Stratigraphically above the Gametrail excursion, the first bilaterian burrows are present in the basal Blueflower Formation. Together, these data allow us to construct an age model for Ediacaran strata in northwestern Canada and conclude that a purported shift in Fe speciation in the Sheepbed Formation significantly predates the shift recorded above the ca. 582 Ma Gaskiers glaciation in Newfoundland and the first appearance of Ediacaran biota. The Gametrail excursion shares many characteristics with Shuram negative δ13Ccarb excursion: 1) δ13Ccarb and δ18Ocarb covary; 2) δ13Ccarb and δ13Corg do not covary; 3) the excursion is developed during a transgressive systems tract and recovers in an highstand systems tract; and 4) values in some sections are well below mantle δ13C input values but are variable between sections. We relate regional lateral variability in the magnitude and character of this excursion to condensation and diachronous deposition during the transgression and local authigenic carbonate production. In light of these observations, we explore a variety of models for the genesis of the Shuram excursion and suggest that the location and amount of authigenic carbonate production played a role in the excursion.

Late Neoproterozoic (Ediacaran) strata from northwestern Canada provide a thick and rich sedimentological record, preserving intercalated carbonates and shale extending from the ~ 635 million year old Marinoan glacial deposits up through the ~ 541 million year old Precambrian–Cambrian boundary. This region also holds one of the classic localities for the study of early animal life, with the ensuing suggestion that this temporal interval captures a gross change in the O2 content of the Earth's atmosphere. To test this hypothesis and bring records of northwestern Canada into line with other Ediacaran, fossil-bearing basins, we provide a detailed geochemical reconstruction from the Wernecke Mountains of the Yukon. Where possible, we also extend these records to the Ogilvie Mountains to the west and previously published data from the Mackenzie Mountains to the east. Our work in the Wernecke Mountains is set against a composite δ13C record for carbonate that preserves three distinct Ediacaran isotope excursions, the lowermost of which (preserved in the Gametrail Formation) is a putative Shuram excursion equivalent. What emerges from a multi-proxy (Fe speciation, sulfur isotopes, major and trace element analyses) reconstruction is a picture of a persistently anoxic and ferruginous Ediacaran ocean. Notably absent is geochemical evidence for a prominent oxygenation event, an expectation given the appearance of animals and large swings in δ13C. The new insight gained through these data challenges the idea of an Ediacaran jump in atmospheric oxygen, which in turn muddles the link between animal evolution and local geochemical environments.

The information encoded by the two stable isotope systems in sulfate (δ34SSO4 and δ18OSO4) has been widely applied to aid reconstructions of both modern and ancient environments. Interpretation of δ18OSO4 records has been complicated by rapid oxygen isotope equilibration between sulfoxyanions and water. Specifically, the apparent relationship that develops between δ18OSO4 and δ18Owater during microbial sulfate reduction is thought to result from rapid oxygen isotope equilibrium between intracellular water and aqueous sulfite – a reactive intermediate of the sulfate reduction network that can back-react to produce sulfate. Here, we describe the oxygen equilibrium isotope effect between water and sulfite (referring to all the sum of all S(IV)-oxyanions including sulfite and both isomers and the dimer of bisulfite). Based on experiments conducted over a range of pH (4.5–9.8) and temperature (2–95 °C), where ε = 1000 * (α − 1), we find εSO3–H2O=13.61-0.299∗pH-0.081∗T°C. Thus, at a pH (7.0) and temperature (25 °C) typifying commonly used experimental conditions for sulfate reducing bacterial cultures, sulfite is enriched in 18O by 9.5‰ (±0.8‰) relative to ambient water. We examine the implication of these results in a sulfate reduction network that has been revised to reflect our understanding of the reactions involving oxygen. By evaluating previously published data within this new architecture, our results are consistent with previous suggestions of high reversibility of the sulfate reduction biochemical network. We also demonstrate that intracellular exchange rates between SO32- and water must be on average 1–3 orders of magnitude more rapid than intracellular fluxes of sulfate reduction intermediates and that kinetic isotope effects upstream of SO32- are required to explain previous laboratory and environmental studies of δ18OSO4 resulting as a consequence of sulfate reduction.