Person:

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.

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.

The fossilization of organic remains and shell material by calcium phosphate minerals provides an illuminating, but time-bounded, window into Ediacaran–Cambrian animal evolution. For reasons that remain unknown, phosphatic fossil preservation declined significantly through Cambrian Series 2. Here, we investigate the phosphorus (P) sources for phosphatic Cambrian carbonates, presenting sedimentological, petrographic, and geochemical data from the Cambrian Series 2–3 Thorntonia Limestone, Australia, some of the youngest Cambrian strata to display exceptional phosphatic preservation of small shelly fossils. We find that within Thorntonia sediments, phosphate was remobilized by organic decay and bacterial iron reduction, with subsequent reprecipitation largely as apatite within the interiors of small shelly fossils. We discuss the merits of bioclastic-derived, organic matter–bound, or iron-bound P as potential sources to these strata. Petrographic observations suggest that the dissolution of phosphatic skeletal material did not provide the P for fossil preservation. In contrast, high organic carbon contents imply significant organic fluxes of P to Thorntonia sediments. Sedimentology and iron-speciation data indicate that phosphorus enrichment occurred during times of expanded anoxic, ferruginous conditions in subsurface water masses, suggesting that phosphorus adsorption to iron minerals precipitating from the water column provided a second significant P source to Thorntonia sediments. Simple stoichiometric models suggest that, by themselves, neither organic carbon burial nor an iron shuttle can account for the observed phosphorus enrichment. Thus, we infer that both processes were necessary for the observed phosphorus enrichment and subsequent fossil preservation in the Thorntonia Limestone.

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 O2 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 O2 budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe2+ 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.

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1Md illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M1 illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian–Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.

The ca. 1.8 Ga Duck Creek Formation, Western Australia, preserves 1000 m of carbonates and minor iron formation that accumulated along a late Paleoproterozoic ocean margin. Two upward-deepening stratigraphic packages are preserved, each characterized by peritidal precipitates at the base and iron formation and carbonate turbidites in its upper part. Consistent with recent studies of Neoarchean basins, carbon isotope ratios of Duck Creek carbonates show no evidence for a strong isotopic depth gradient, but carbonate minerals in iron formations can be markedly depleted in [super]13C. In contrast, oxygen isotopes covary strongly with depth; δ[super]18O values as positive as 2‰ VPDB in peritidal facies systematically decline to values of −6 to −16‰ in basinal rocks, reflecting, we posit, the timing of diagenetic closure. The Duck Creek Formation contains microfossils similar to those of the Gunflint Formation, Canada; they are restricted to early diagenetic cherts developed in basinal facies, strengthening the hypothesis that such fossils capture communities driven by iron metabolism. Indeed, X-ray diffraction data indicate that the Duck Creek basin was ferruginous throughout its history. The persistence of ferruginous waters and iron formation deposition in Western Australia for at least several tens of millions of years after the transition to sulfidic conditions in Laurentia suggests that the late Paleoproterozoic expansion of sulfidic subsurface waters was globally asynchronous.

Studies of microbial sulfate reduction have suggested that the magnitude of sulfur isotope fractionation varies with sulfate concentration. Small apparent sulfur isotope fractionations preserved in Archean rocks have been interpreted as suggesting Archean sulfate concentrations of <200 μm, while larger fractionations thereafter have been interpreted to require higher concentrations. In this work, we demonstrate that fractionation imposed by sulfate reduction can be a function of concentration over a millimolar range, but that nature of this relationship depends on the organism studied. Two sulfate-reducing bacteria grown in continuous culture with sulfate concentrations ranging from 0.1 to 6 mm showed markedly different relationships between sulfate concentration and isotope fractionation. Desulfovibrio vulgaris str. Hildenborough showed a large and relatively constant isotope fractionation (34εSO4-H2S ≅ 25‰), while fractionation by Desulfovibrio alaskensis G20 strongly correlated with sulfate concentration over the same range. Both data sets can be modeled as Michaelis–Menten (MM)-type relationships but with very different MM constants, suggesting that the fractionations imposed by these organisms are highly dependent on strain-specific factors. These data reveal complexity in the sulfate concentration–fractionation relationship. Fractionation during MSR relates to sulfate concentration but also to strain-specific physiological parameters such as the affinity for sulfate and electron donors. Previous studies have suggested that the sulfate concentration–fractionation relationship is best described with a MM fit. We present a simple model in which the MM fit with sulfate concentration and hyperbolic fit with growth rate emerge from simple physiological assumptions. As both environmental and biological factors influence the fractionation recorded in geological samples, understanding their relationship is critical to interpreting the sulfur isotope record. As the uptake machinery for both sulfate and electrons has been subject to selective pressure over Earth history, its evolution may complicate efforts to uniquely reconstruct ambient sulfate concentrations from a single sulfur isotopic composition.

A substantial body of evidence suggests that subsurface water masses in mid-Proterozoic marine basins were commonly anoxic, either euxinic (sulfidic) or ferruginous (free ferrous iron). To further document redox variations during this interval, a multiproxy geochemical and paleobiological investigation was conducted on the approximately 1000-m-thick Mesoproterozoic (Lower Riphean) Arlan Member of the Kaltasy Formation, central Russia. Iron speciation geochemistry, supported by organic geochemistry, redox-sensitive trace element abundances, and pyrite sulfur isotope values, indicates that basinal calcareous shales of the Arlan Member were deposited beneath an oxygenated water column, and consistent with this interpretation, eukaryotic microfossils are abundant in basinal facies. The Rhenium–Osmium (Re–Os) systematics of the Arlan shales yield depositional ages of 1414 ± 40 and 1427 ± 43 Ma for two horizons near the base of the succession, consistent with previously proposed correlations. The presence of free oxygen in a basinal environment adds an important end member to Proterozoic redox heterogeneity, requiring an explanation in light of previous data from time-equivalent basins. Very low total organic carbon contents in the Arlan Member are perhaps the key—oxic deep waters are more likely (under any level of atmospheric O2) in oligotrophic systems with low export production. Documentation of a full range of redox heterogeneity in subsurface waters and the existence of local redox controls indicate that no single stratigraphic section or basin can adequately capture both the mean redox profile of Proterozoic oceans and its variance at any given point in time.

Small shelly fossils are preserved as apatite steinkerns in the Cambrian Series 2–3 Thorntonia Limestone, Australia. Petrological observations indicate that phosphorus delivered to Thorntonia sediment was remobilized before precipitating in microenvironments defined by the matrix-filled interiors of small, mostly conical skeletons. A previous geochemical study concluded that both organic matter and iron oxides sourced phosphorus to Thorntonia sediments, and that anoxia governed phosphorus remobilization within the sediment column. This contribution asks: What factors allowed for the selective preservation of skeleton interiors, and what biases result from this preservation? We find that small shells physically trapped phosphorus-laden pore waters, creating local conditions where kinetic barriers to apatite precipitation could be overcome. Only a subset of Thorntonia Limestone skeletons is preserved by apatite, showing evidence of selectivity with respect to shell size, shape, and orientation. Both the biological and physical factors that govern phosphorus remineralization and precipitation have changed through time, accounting for the opening and closing of the Ediacaran-Cambrian phosphatization taphonomic window. The opening of this window may have required a global increase in phosphate delivery to the oceans.

Sedimentary rocks deposited across the Proterozoic–Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.