Nitrogen is an essential nutrient for all life on Earth and it acts as a major control on biological productivity in the modern ocean. Accurate reconstructions of the evolution of life over the ...course of the last four billion years therefore demand a better understanding of nitrogen bioavailability and speciation through time. The biogeochemical nitrogen cycle has evidently been closely tied to the redox state of the ocean and atmosphere. Multiple lines of evidence indicate that the Earth's surface has passed in a non-linear fashion from an anoxic state in the Hadean to an oxic state in the later Phanerozoic. It is therefore likely that the nitrogen cycle has changed markedly over time, with potentially severe implications for the productivity and evolution of the biosphere. Here we compile nitrogen isotope data from the literature and review our current understanding of the evolution of the nitrogen cycle, with particular emphasis on the Precambrian. Combined with recent work on redox conditions, trace metal availability, sulfur and iron cycling on the early Earth, we then use the nitrogen isotope record as a platform to test existing and new hypotheses about biogeochemical pathways that may have controlled nitrogen availability through time. Among other things, we conclude that (a) abiotic nitrogen sources were likely insufficient to sustain a large biosphere, thus favoring an early origin of biological N2 fixation, (b) evidence of nitrate in the Neoarchean and Paleoproterozoic confirm current views of increasing surface oxygen levels at those times, (c) abundant ferrous iron and sulfide in the mid-Precambrian ocean may have affected the speciation and size of the fixed nitrogen reservoir, and (d) nitrate availability alone was not a major driver of eukaryotic evolution.
Nitrogen limitation caused by trace metal scarcity under euxinic ocean conditions has been proposed as an explanation for the delayed radiation of eukaryotes until at least the late Mesoproterozoic. ...However, evidence for how the nitrogen cycle was operating during the middle Precambrian is, so far, rare. More specifically, it is unknown which steps in the biogeochemical nitrogen cycle, e.g. nitrogen fixation, nitrification or ammonification, were rate-limiting and thus controlling microbial community structures. The Mesoproterozoic Belt Supergroup in western Montana hosts a variety of facies ranging from shallow to deep water and thus offers the opportunity to address this issue. Bulk δ15N values show a clear trend from −1‰ in the deepest part of the basin to +5‰ along basin margins, which suggests that coastal areas were sufficiently oxygenated for aerobic nitrogen cycling. The total fractionation of carbon isotopes between carbonate and organic carbon (Δ13C) increases from 20‰ to 32‰ in the same direction, possibly indicating an ecological response to redox stratification and nitrogen speciation. Evidence from the Belt Supergroup is thus consistent with the idea that nutrient availability may have restricted early eukaryotic organisms to a narrow range of habitats, which thus prevented a global rise to ecological dominance until concentrations of fixed nitrogen increased in the global open ocean.
Nitrogen is an essential nutrient for all organisms that must have been available since the origin of life. Abiotic processes including hydrothermal reduction, photochemical reactions, or lightning ...discharge could have converted atmospheric N2 into assimilable NH4(+), HCN, or NOx species, collectively termed fixed nitrogen. But these sources may have been small on the early Earth, severely limiting the size of the primordial biosphere. The evolution of the nitrogen-fixing enzyme nitrogenase, which reduces atmospheric N2 to organic NH4(+), thus represented a major breakthrough in the radiation of life, but its timing is uncertain. 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.
It has been proposed that an “oxygen overshoot” occurred during the early Paleoproterozoic Great Oxidation Event (GOE) in association with the extreme positive carbon isotopic excursion known as the ...Lomagundi Event. Moreover, it has also been suggested that environmental oxygen levels then crashed to very low levels during the subsequent extremely negative Shunga–Francevillian carbon isotopic anomaly. These redox fluctuations could have profoundly influenced the course of eukaryotic evolution, as eukaryotes have several metabolic processes that are obligately aerobic. Here we investigate the magnitude of these proposed oxygen perturbations using selenium (Se) geochemistry, which is sensitive to redox transitions across suboxic conditions. We find that δ82/78Se values in offshore shales show a positive excursion from 2.32 Ga until 2.1 Ga (mean +1.03 ± 0.67‰). Selenium abundances and Se/TOC (total organic carbon) ratios similarly show a peak during this interval. Together these data suggest that during the GOE there was pervasive suboxia in near-shore environments, allowing nonquantitative Se reduction to drive the residual Se oxyanions isotopically heavy. This implies O₂ levels of >0.4 μM in these settings. Unlike in the late Neoproterozoic and Phanerozoic, when negative δ82/78Se values are observed in offshore environments, only a single formation, evidently the shallowest, shows evidence of negative δ82/78Se. This suggests that there was no upwelling of Se oxyanions from an oxic deep-ocean reservoir, which is consistent with previous estimates that the deep ocean remained anoxic throughout the GOE. The abrupt decline in δ82/78Se and Se/TOC values during the subsequent Shunga–Francevillian anomaly indicates a widespread decrease in surface oxygenation.
Phosphorus plays a crucial role in controlling biological productivity, but geological estimates of phosphate concentrations in the Precambrian ocean, during life's origin and early evolution, vary ...over several orders of magnitude. While reduced phosphorus species may have served as alternative substrates to phosphate, their bioavailability on the early Earth remains unknown. Here, we reconstruct the phylogenomic record of life on Earth and find that phosphate transporting genes (pnas) evolved in the Paleoarchean (ca. 3.6-3.2 Ga) and are consistent with phosphate concentrations above modern levels ( > 3 µM). The first gene optimized for low phosphate levels (pstS; <1 µM) appeared around the same time or in the Mesoarchean depending on the reconstruction method. Most enzymatic pathways for metabolising reduced phosphorus emerged and expanded across the tree of life later. This includes phosphonate-catabolising CP-lyases, phosphite-oxidising pathways and hypophosphite-oxidising pathways. CP-lyases are particularly abundant in dissolved phosphate concentrations below 0.1 µM. Our results thus indicate at least local regions of declining phosphate levels through the Archean, possibly linked to phosphate-scavenging Fe(III), which may have limited productivity. However, reduced phosphorus species did not become widely used until after the Paleoproterozoic Great Oxidation Event (2.3 Ga), possibly linked to expansion of the biosphere at that time.
During the Marinoan Ice Age (ca. 654-635 Ma), one of the 'Snowball Earth' events in the Cryogenian Period, continental icesheets reached the tropical oceans. Oceanic refugia must have existed for ...aerobic marine eukaryotes to survive this event, as evidenced by benthic phototrophic macroalgae of the Songluo Biota preserved in black shales interbedded with glacial diamictites of the late Cryogenian Nantuo Formation in South China. However, the environmental conditions that allowed these organisms to thrive are poorly known. Here, we report carbon-nitrogen-iron geochemical data from the fossiliferous black shales and adjacent diamictites of the Nantuo Formation. Iron-speciation data document dysoxic-anoxic conditions in bottom waters, whereas nitrogen isotopes record aerobic nitrogen cycling perhaps in surface waters. These findings indicate that habitable open-ocean conditions were more extensive than previously thought, extending into mid-latitude coastal oceans and providing refugia for eukaryotic organisms during the waning stage of the Marinoan Ice Age.
Rationale
Ion chromatography (IC) combined with inductively coupled plasma mass spectrometry (ICPMS) is an ideal tool for measuring low concentrations of anionic species such as phosphite; however, ...the high concentration of chloride and other anions in natural solutions may negatively impact chromatographic separation and data quality.
Method
We developed an on‐line mechanism of removing chloride from a sample within an ion chromatograph, using an additional valve and a separation column that transfers chloride to waste while phosphite and most other anions are retained. We installed this system in a coupled IC/ICPMS system (ICS6000 and Element 2 in medium‐resolution mode) and determined linearity and detection limits. In addition, we measured phosphorus species by NMR for comparison as an alternative method for phosphite determination.
Results
Chloride was fully removed from the samples while phosphite was retained and could be analysed by IC/ICPMS. Concentrations could be measured down to 0.003 μmol/L and possibly less with good linearity over the explored range (up to 1.615 μmol/L; r2 = 0.999). In contrast, the detection limit by NMR was 6.46 μmol/L.
Conclusions
The on‐line removal mechanism works well for simplifying sample matrices. It removes the need for costly pre‐analytical sample treatment with OnGuard columns. We confirm that IC/ICPMS is the most powerful technique for quantifying phosphite in natural solutions. The new chloride‐removal method may also be applicable to analyses of other anions.
Limited oxygen production in the Mesoarchean ocean Ossa, Frantz Ossa; Hofmann, Axel; Spangenberg, Jorge E. ...
Proceedings of the National Academy of Sciences - PNAS,
04/2019, Letnik:
116, Številka:
14
Journal Article
Recenzirano
Odprti dostop
The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to “oxygen oases” well documented for the ...Neoarchean 2.8 to 2.5 billion years ago (Ga), the magnitude, spatial extent, and underlying causes of possible Mesoarchean (3.2 to 2.8 Ga) surface-ocean oxygenation remain controversial. Here, we report δ15N and δ13C values coupled with local seawater redox data for Mesoarchean shales of the Mozaan Group (Pongola Supergroup, South Africa) that were deposited during an episode of enhanced Mn (oxyhydr)oxide precipitation between ∼2.95 and 2.85 Ga. Iron and Mn redox systematics are consistent with an oxygen oasis in the Mesoarchean anoxic ocean, but δ15N data indicate a Mo-based diazotrophic biosphere with no compelling evidence for a significant aerobic nitrogen cycle. We propose that in contrast to the Neoarchean, dissolved O₂ levels were either too low or too limited in extent to develop a large and stable nitrate reservoir in the Mesoarchean ocean. Since biological N₂ fixation was evidently active in this environment, the growth and proliferation of O₂-producing organisms were likely suppressed by nutrients other than nitrogen (e.g., phosphorus), which would have limited the expansion of oxygenated conditions during the Mesoarchean.
Phosphorus sets the pace of marine biological productivity on geological time scales. Recent estimates of Precambrian phosphorus levels suggest a severe deficit of this macronutrient, with the ...depletion attributed to scavenging by iron minerals. We propose that the size of the marine phosphorus reservoir was instead constrained by muted liberation of phosphorus during the remineralization of biomass. In the modern ocean, most biomass-bound phosphorus gets aerobically recycled; but a dearth of oxidizing power in Earth's early oceans would have limited the stoichiometric capacity for remineralization, particularly during the Archean. The resulting low phosphorus concentrations would have substantially hampered primary productivity, contributing to the delayed rise of atmospheric oxygen.
Evolution of a complete nitrogen (N) cycle relies on the onset of ammonia oxidation, which aerobically converts ammonia to nitrogen oxides. However, accurate estimation of the antiquity of ...ammonia-oxidizing bacteria (AOB) remains challenging because AOB-specific fossils are absent and bacterial fossils amenable to calibrate molecular clocks are rare. Leveraging the ancient endosymbiosis of mitochondria and plastid, as well as using state-of-the-art Bayesian sequential dating approach, we obtained a timeline of AOB evolution calibrated largely by eukaryotic fossils. We show that the first AOB evolved in marine Gammaproteobacteria (Gamma-AOB) and emerged between 2.1 and 1.9 billion years ago (Ga), thus postdating the Great Oxidation Event (GOE; 2.4 to 2.32 Ga). To reconcile the sedimentary N isotopic signatures of ammonia oxidation occurring near the GOE, we propose that ammonia oxidation likely occurred at the common ancestor of Gamma-AOB and Gammaproteobacterial methanotrophs, or the actinobacterial/verrucomicrobial methanotrophs which are known to have ammonia oxidation activities. It is also likely that nitrite was transported from the terrestrial habitats where ammonia oxidation by archaea took place. Further, we show that the Gamma-AOB predated the anaerobic ammonia-oxidizing (anammox) bacteria, implying that the emergence of anammox was constrained by the availability of dedicated ammonia oxidizers which produce nitrite to fuel anammox. Our work supports a new hypothesis that N redox cycle involving nitrogen oxides evolved rather late in the ocean.
PDF
