Nitrogen is an essential element to life and exerts a strong control on global biological productivity. The rise and spread of nitrogen-utilizing microbial metabolisms profoundly shaped the biosphere on the early Earth. Here we reconciled gene and species trees to identify birth and horizontal gene transfer events for key nitrogen-cycling genes, dated with a time-calibrated tree of life, in order to examine the timing of the proliferation of these metabolisms across the tree of life. Our results provide new insights into the evolution of the early nitrogen cycle that expand on geochemical reconstructions. We observed widespread horizontal gene transfer of molybdenum-based nitrogenase back to the Archean, minor horizontal transfer of genes for nitrate reduction in the Archean, and an increase in the proliferation of genes metabolizing nitrite around the time of the Mesoproterozoic (∼1.5 Ga).
The origin of life is perhaps the most perplexing unanswered question in science. The main reason for this perplexity is the overlap of four critical components to lifes origin: when and where life emerged, how it formed, and what the earliest life forms looked like. Each of these components has their own set of questions that cross multiple disciplines. For example, insights into the question of when and where life began are predicated on the early Archaean rock record, which is limited due to metamorphism and erosion. With time, continued study of the rock record will reveal more about the…
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.
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.
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.
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.