Here we use an array of major and trace element data to constrain the redox conditions in the water column and extent of basinal restriction during deposition of the ZF. We also present new selenium (Se) abundance and isotopic data to provide firmer constraints on fluctuations across high redox potentials, which might be critical for phosphogenesis. We find that Se isotope ratios shift over a range of ~3‰ in the ZF, with the earliest stratigraphically-resolved negative Se isotope excursion in the geologic record, implying at least temporarily suboxic waters in the basin. Furthermore, we find that redox-sensitive element (RSE) enrichments coincide with episodes of P enrichment, thereby implicating a common set of environmental controls on these processes. Together, our dataset implies deposition under a predominantly anoxic water column with periodic fluctuations to more oxidizing conditions because of connections to a large oxic reservoir containing Se oxyanions (and other RSE’s, as well as sulfate) in the open ocean
We attempted to use vesicle sizes in lavas erupted near sea-level from the ~2.9 Ga Pongola Supergroup from Mahlangatsha and Mooihoek, eSwatini (formerly Swaziland) and the White Mfolozi River gorge of KwaZulu-Natal, South Africa to provide further Archean paleobarometric data. However, reliable results were unobtainable due to small and scarce amygdales, irregular vesicle morphologies and metamorphic mineralogical homogenization preventing the use of X-ray Computed Tomography for accurate vesicle size determination. Researchers attempting paleobarometric analysis using lava vesicle sizes should henceforth avoid these areas of the Pongola Supergroup and instead look at other subaerially emplaced lava flows. With this being only the second time this method has been used on Precambrian rocks, we provide a list of guidelines informed by this study to aid future attempts at vesicular paleobarometry.
University of Washington graduate student and VPL collaborator Owen Lehmer, was the lead author of a new paper recently published…
Earths atmospheric composition during the Archean eon of 4 to 2.5 billion years ago has few constraints. However, the geochemistry of recently discovered iron-rich micrometeorites from 2.7 billionyearold limestones could serve as a proxy for ancient gas concentrations. When micrometeorites entered the atmosphere, they melted and preserved a record of atmospheric interaction. We model the motion, evaporation, and kinetic oxidation by CO2 of micrometeorites entering a CO2-rich atmosphere. We consider a CO2-rich rather than an O2-rich atmosphere, as considered previously, because this better represents likely atmospheric conditions in the anoxic Archean. Our model reproduces the observed oxidation state of micrometeorites at 2.7 Ga for an estimated atmospheric CO2 concentration of >70% by volume. Even if the early atmosphere was thinner than today, the elevated CO2 level indicated by our model result would help resolve how the Late Archean Earth remained warm when the young Sun was ~20% fainter.
We examined standard biogeochemical proxies, including organic carbon and nitrogen isotopes, iron speciation, metal abundances and carbonate-associated sulfate. Much of the primary information has been lost because the rocks of the Callanna Group have experienced extensive metamorphism up to amphibolite facies and are altered by modern weathering. However, relics of these proxies, combined with sedimentological features, preserve evidence of redox stratification within this basin. Furthermore, our observations, in particular weakly fractionated nitrogen isotopes and abundant gypsum pseudomorphs, are incompatible with the interpretation of high alkalinity. The high salt content and occurrences of tidal indicators are most parsimoniously explained by frequent incursions of seawater. Thus, the Callanna Group cannot speak straightforwardly to environmental conditions in non-marine habitats at this time. Lastly, the absence of a large carbon isotope anomaly indicates that these rocks do not correlate with the Bitter Springs Formation.
We find that in the Late Pennsylvanian units, an estuarine nutrient trap on the Midcontinent Shelf enabled vigorous selenium recycling, leading to very high concentrations in sediments and enrichment of heavy isotopes in the aqueous selenium reservoir. In contrast, we find that among the Late Devonian units, differences in local basinal hydrography led to a gradient in selenium abundance and isotopic fractionation, with the more restricted basins depleting their selenium reservoirs and causing enrichment of heavy isotopes in the residual aqueous reservoir. In both of these case studies, the additional context provided by complementary paleo-environmental proxies was critical for distinguishing between possible drivers of selenium isotopic variability. When extending such studies to other paleo-environmental settings, we suggest that the continued use of complementary datasets will enable the most robust use of the selenium paleo-redox proxy. Moreover, further development of techniques for high-precision and phase-specific selenium isotope measurements will greatly improve the ability to deduce subtle redox fluctuations with this proxy.
If the process of microbial N2 fixation records the δ15N value of atmospheric N2 in cycad foliage, the fossil record of cycads may provide an archive of atmospheric δ15N values. To explore this potential proxy, we conducted a survey of wild cycads growing in a range of modern environments to determine whether cycad foliage reliably records the isotopic composition of atmospheric N2. We find that neither biological nor environmental factors significantly influence the δ15N values of cycad foliage, suggesting that they provide a reasonably robust record of the δ15N of atmospheric N2. Application of this proxy to the record of carbonaceous cycad fossils may not only help to constrain changes in atmospheric nitrogen isotope ratios since the late Paleozoic, but also could shed light on the antiquity of the N2‐fixing symbiosis between cycads and cyanobacteria.
Current evidence for oxygenated environments in the Mesoarchean is limited to the shallowest marine and fluvio-lacustrine settings. It is not until the Neoarchean that signs of oxygenated surface waters above outer shelf and basinal depositional environments become evident. In order to further explore the Mesoarchean redox landscape for signs of basinward surface water oxygenation, we present nitrogen and carbon isotope ratios from the turbiditic Mosquito Creek Formation of the Nullagine Group (?2.9?Ga). The ?15N and ?13Corg values are invariant around ?1.8 and ?32 respectively throughout a 70?m section of drill-core, suggesting an ecosystem dominated by nitrogen fixers (anaerobic nitrogen cycling) and CO2 fixation by the Calvin Cycle. When compared with other Archean isotopic data, these results (i) provide further evidence that the Mosquito Creek Formation was deposited in a marine basin, and (ii) contain ?15N values that highlight the prevalence of nitrogen fixation by Mo-nitrogenase and the dearth of aerobic nitrogen metabolisms in the Mesoarchean.
Here, we calculate absolute Archaean barometric pressure using the size distribution of gas bubbles in basaltic lava flows that solidified at sea level ∼2.7 Gyr in the Pilbara Craton, Australia. Our data indicate a surprisingly low surface atmospheric pressure of Patm = 0.23 ± 0.23 (2σ) bar, and combined with previous studies suggests ∼0.5 bar as an upper limit to late Archaean Patm. The result implies that the thin atmosphere was rich in auxiliary greenhouse gases and that Patm fluctuated over geologic time to a previously unrecognized extent.
Ashes of ancient meteors recovered from a 2.7-billion-year-old lake bed imply that the upper atmosphere was rich in oxygen at a time when all other evidence implies that the atmosphere was oxygen-free
Our data show a small positive excursion in δ82/78Se prior to the extinction, consistent with local euxinia. However, this is followed by a significant negative excursion with a minimum of −1.8‰ (relative to NIST SRM 3149), immediately preceding the principal extinction horizon. A net fractionation of this magnitude likely resulted from partial reduction of Se oxyanions dissolved in the water column. Due to their low abundance, Se oxyanions are rapidly scavenged in anoxic basins or regions of high biological productivity with little net isotopic fractionation. We therefore interpret the uniquely negative fractionations in this section as an indicator for relatively oxygenated conditions in this marine basin at the time when biological productivity declined.
Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2 Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth’s history and all are mass-dependent within error. In the Archean, especially after 2.7 Gyr, we find an isotopic enrichment in marine (+0.37 ± 0.27‰) relative to non-marine samples (−0.28 ± 0.67‰), paired with increasing Se abundances.
Our results show that the ∼3350 Ma Euro Basalt preserves a shallow magnetic inclination that appears to have formed as a result of early seafloor hydrothermal alteration, suggesting that the evaporitic carbonate platform of the conformably underlying Strelley Pool Formation was deposited in a near-equatorial location. This is consistent with (although does not require) late Paleoarchean climatic zoning, low orbital obliquity, and a geocentric axial dipole (GAD) field geometry similar to that of the Phanerozoic. The Euro Basalt paleopole overlaps with previously published Paleoarchean poles from the East Pilbara craton and with time-equivalent poles reported from the Barberton Greenstone Belt of the Kaapvaal craton, supporting the existence of a Paleoarchean Vaalbara continental aggregation.
Organic and inorganic carbon isotope records reflect the burial of organic carbon over geological timescales. Permanent burial of organic carbon in the crust or mantle oxidizes the surface environment (atmosphere, ocean and biosphere) by removing reduced carbon. It has been claimed that both organic and inorganic carbon isotope ratios have remained approximately constant throughout Earth’s history, thereby implying that the flux of organic carbon burial relative to the total carbon input has remained fixed and cannot be invoked to explain the rise of atmospheric oxygen (Schidlowski, 1988; Catling and others, 2001; Holland, 2002; Holland, 2009; Kump and others, 2009; Rothman, 2015). However, the opposite conclusion has been drawn from the same carbon isotope record (Des Marais and others, 1992; Bjerrum and Canfield, 2004). To test these opposing claims, we compiled an updated carbon isotope database and applied both parametric and non-parametric statistical models to the data to quantify trends and mean-level changes in fractional organic carbon burial with associated uncertainties and confidence levels.
The advent of oxygenic photosynthesis set the stage for the evolution of complex life on an oxygenated planet, but it is unknown when this transformative biochemistry emerged. The existing hydrocarbon biomarker record requires that oxygenic photosynthesis and eukaryotes emerged more than 300 million years before the Great Oxidation Event [∼2.4 billion years ago (Ga)]. We report that hopane and sterane concentrations measured in new ultraclean Archean drill cores from Australia are comparable to blank concentrations, yet their concentrations in the exteriors of conventionally collected cores of stratigraphic equivalence exceed blank concentrations by more than an order of magnitude due to surficial contamination. Consequently, previous hydrocarbon biomarker reports no longer provide valid evidence for the advent of oxygenic photosynthesis and eukaryotes by ∼2.7 Ga.
We test this idea with Se data from the 2.5 Ga Mount McRae Shale (Hamersley Basin, Australia), which records temporary enrichments in abundances and isotopes of other redox-sensitive elements indicating a “whiff of oxygen” in Earth’s atmosphere before the Great Oxidation Event. Se isotopic ratios expressed as δ82/78Se and abundances relative to crustal background show significant positive excursions of up to 1.1‰ and an enrichment 13 times above background, respectively, overlapping with excursions in Mo and N isotopes and abundances. Because Se has a relatively high redox potential and photosynthetic oxidation pathways are unknown, our data thus suggest that Se was mobilized by free O2 during this interval. The isotopic fractionation likely occurred during transport of Se oxyanions from the site of weathering to the outer shelf.
Here we propose that NH3 volatilization is largely responsible for δ15N values of up to +50% at high C/N ratios in the late Archean Tumbiana Formation. This sequence of sedimentary rocks represents a system of lakes that formed on subaerial flood basalts and were partly filled by basaltic volcanic ash. Aqueous alteration of volcanic glass followed by evaporative concentration of ions should have led to the development of high alkalinity with a pH of 9 or higher, as in modern analogues. In this sedimentologically unusual setting, nitrogen isotope ratios thus provide indirect evidence for the oldest alkaline lake system in the rock record. These very heavy lacustrine δ15N values contrast markedly with those of Archean marine sedimentary rocks, making a Precambrian “soda ocean” unlikely. Today, alkaline lakes are among the most productive ecosystems on Earth. Some nutrients, in particular molybdenum, are more soluble at high pH, and certain prebiotic reactions would likely have been favored under alkaline conditions in similar settings earlier in Earth’s history. Hence alkaline lakes in the Archean could have been significant for the origin and early evolution of life.
Here we present nitrogen isotope ratios with a mean of 0.0 ± 1.2‰ from marine and fluvial sedimentary rocks of prehnite-pumpellyite to greenschist metamorphic grade between 3.2 and 2.75 billion years ago. These data cannot readily be explained by abiotic processes and therefore suggest biological nitrogen fixation, most probably using molybdenum-based nitrogenase as opposed to other variants that impart significant negative fractionations. Our data place a minimum age constraint of 3.2 billion years on the origin of biological nitrogen fixation and suggest that molybdenum was bioavailable in the mid-Archaean ocean long before the Great Oxidation Event.
We present measurements of three different organic-rich shales of varying ages prepared with eight different sample preparation protocols and identify a method with which high selenium yields are obtained for all three samples while the concentration of germanium is greatly reduced. We further investigate the quantitative importance of isobaric interferences and present new post-analytical data correction protocols. If selenium concentrations in standards and samples are matched to within 5%, the ratios of five isotopes of selenium (74Se, 76Se, 77Se, 78Se and 82Se) can be measured with precisions better than 0.2‰ for δ76/78Se, δ77/78Se and δ82/78Se and 0.5‰ for δ74/78Se, allowing analytical accuracy to be monitored with three-isotope diagrams and thus enabling the detection of any mass-independent isotopic fractionation.
Here, we report the occurrence of phosphite in early Archean marine carbonates at levels indicating that this was an abundant dissolved species in the ocean before 3.5 Ga. Additionally, we show that schreibersite readily reacts with an aqueous solution of glycerol to generate phosphite and the membrane biomolecule glycerol–phosphate under mild thermal conditions, with this synthesis using a mineral source of P. Phosphite derived from schreibersite was, hence, a plausible reagent in the prebiotic synthesis of phosphorylated biomolecules and was also present on the early Earth in quantities large enough to have affected the redox state of P in the ocean. Phosphorylated biomolecules like RNA may, thus, have first formed from the reaction of reduced P species with the prebiotic organic milieu on the early Earth.
We present a new dynamic thresholding method for computationally separating amygdules from their basaltic matrix in X-ray images that is based on a technique used in seismology. The technique is sensitive to the gradient of the gray-scale value, rather than an absolute threshold value often applied to an entire set of X-ray images. Additionally, we present statistical methods for extrapolating the volumetric measurement mean and standard deviation of amygdules in the measured samples to the entire population in the flow. To do so, we create additional amygdule sample sets from the original sample set in the process of ‘bootstrap’ resampling, and use the Central Limit Theorem to calculate the mean and standard deviation of the amygdule population from these sample sets. This suite of methods allows the extension of bubble-size distribution studies typically done on modern flows to the ancient rock record and potentially has many other uses in geosciences where quantitative discrimination between materials with a range of densities is required.
We find that terrestrial oxidation of pyrite by microbes using oxygen has contributed a substantial fraction of the total sulphur weathering flux since at least 2.5 Gyr ago, with probable evidence of such activity 2.7–2.8 Gyr ago. The late Archaean onset of terrestrial sulphur cycling is supported by marine molybdenum abundance data and coincides with a shift to more sulphidic ocean conditions5. We infer that significant microbial land colonization began by 2.7–2.8 Gyr ago. Our identification of pyrite oxidation at this time provides further support for the appearance6 of molecular oxygen several hundred million years before the Great Oxidation Event.
Here we show that raindrop imprints in tuffs of the Ventersdorp Supergroup, South Africa, constrain surface air density 2.7 billion years ago to less than twice modern levels. We interpret the raindrop fossils using experiments in which water droplets of known size fall at terminal velocity into fresh and weathered volcanic ash, thus defining a relationship between imprint size and raindrop impact momentum. Fragmentation following raindrop flattening limits raindrop size to a maximum value independent of air density, whereas raindrop terminal velocity varies as the inverse of the square root of air density. If the Archaean raindrops reached the modern maximum measured size, air density must have been less than 2.3 kg m(-3), compared to today’s 1.2 kg m(-3), but because such drops rarely occur, air density was more probably below 1.3 kg m(-3). The upper estimate for air density renders the pressure broadening explanation possible, but it is improbable under the likely lower estimates. Our results also disallow the extreme CO(2) levels required for hot Archaean climates.
The nitrogen cycle provides essential nutrients to the biosphere, but its antiquity in modern form is unclear. In a drill core though homogeneous organic-rich shale in the 2.5-billion-year-old Mount McRae Shale, Australia, nitrogen isotope values vary from +1.0 to +7.5 per mil (‰) and back to +2.5‰ over ∼30 meters. These changes evidently record a transient departure from a largely anaerobic to an aerobic nitrogen cycle complete with nitrification and denitrification. Complementary molybdenum abundance and sulfur isotopic values suggest that nitrification occurred in response to a small increase in surface-ocean oxygenation. These data imply that nitrifying and denitrifying microbes had already evolved by the late Archean and were present before oxygen first began to accumulate in the atmosphere.