Nitrogen Oxide Concentrations in Natural Waters on Early Earth

A key challenge in origins-of-life studies is estimating the abundances of species relevant to the chemical pathways proposed to have contributed to the emergence of life on early Earth. Dissolved nitrogen oxide anions (NO$_{X}^{-}$), in particular nitrate (NO$_{3}^{-}$) and nitrite (NO$_{2}^{-}$), have been invoked in diverse origins-of-life chemistry, from the oligomerization of RNA to the emergence of protometabolism. Recent work has calculated the supply of NO$_{X}^{-}$ from the prebiotic atmosphere to the ocean, and reported steady-state [NO$_{X}^{-}$] to be high across all plausible parameter space. These findings rest on the assumption that NO$_{X}^{-}$ is stable in natural waters unless processed at a hydrothermal vent. Here, we show that NO$_{X}^{-}$ is unstable in the reducing environment of early Earth. Sinks due to UV photolysis and reactions with reduced iron (Fe$^{2+}$) suppress [NO$_{X}^{-}$] by several orders of magnitude relative to past predictions. For pH$=6.5-8$ and $T=0-50^\circ$C, we find that it is most probable that NO$_{X}^{-}$]$<1~\mu$M in the prebiotic ocean. On the other hand, prebiotic ponds with favorable drainage characteristics may have sustained [NO$_{X}^{-}$]$\geq 1~\mu$M. As on modern Earth, most NO$_{X}^{-}$ on prebiotic Earth should have been present as NO$_{3}^{-}$, due to its much greater stability. These findings inform the kind of prebiotic chemistries that would have been possible on early Earth. We discuss the implications for proposed prebiotic chemistries, and highlight the need for further studies of NO$_{X}^{-}$ kinetics to reduce the considerable uncertainties in predicting [NO$_{X}^{-}$] on early Earth.Comment: In review for publication at Geochemistry, Geophysics, and Geosystems (G-cubed). Comments, questions, and criticism solicited; please contact corresponding author at [email protected]. SI at: https://web-cert.mit.edu/sukrit/Public/nox_si.pdf. GitHub at: https://github.com/sukritranjan/no

"Candidatus Subterrananammoxibiaceae," a New Anammox Bacterial Family in Globally Distributed Marine and Terrestrial Subsurfaces

Bacteria specialized in anaerobic ammonium oxidation (anammox) are widespread in many anoxic habitats and form an important functional guild in the global nitrogen cycle by consuming bio-available nitrogen for energy rather than biomass production. Due to their slow growth rates, cultivation-independent approaches have been used to decipher their diversity across environments. However, their full diversity has not been well recognized. Here, we report a new family of putative anammox bacteria, “Candidatus Subterrananammoxibiaceae,” existing in the globally distributed terrestrial and marine subsurface (groundwater and sediments of estuary, deep-sea, and hadal trenches). We recovered a high-quality metagenome-assembled genome of this family, tentatively named “Candidatus Subterrananammoxibius californiae,” from a California groundwater site. The “Ca. Subterrananammoxibius californiae” genome not only contains genes for all essential components of anammox metabolism (e.g., hydrazine synthase, hydrazine oxidoreductase, nitrite reductase, and nitrite oxidoreductase) but also has the capacity for urea hydrolysis. In an Arctic ridge sediment core where redox zonation is well resolved, “Ca. Subterrananammoxibiaceae” is confined within the nitrate-ammonium transition zone where the anammox rate maximum occurs, providing environmental proof of the anammox activity of this new family. Phylogenetic analysis of nitrite oxidoreductase suggests that a horizontal transfer facilitated the spreading of the nitrite oxidation capacity between anammox bacteria (in the Planctomycetota phylum) and nitrite-oxidizing bacteria from Nitrospirota and Nitrospinota. By recognizing this new anammox family, we propose that all lineages within the “Ca. Brocadiales” order have anammox capacity.publishedVersio

An atlas of depth-gridded and density-gridded interpolated and un-interpolated oxygen deficient zones (ODZs) in the Eastern tropical and subtropical Pacific Ocean

Dataset: Depth-gridded and Density-gridded ODZsThis dataset is made up of four NetCDF files, comprising an atlas of depth-gridded and density-gridded interpolated and un-interpolated Pacific oxygen deficient zones. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/865316Schmidt Ocean Institute (SOI) No Award Number, Simons Foundation (Simons) 62206

Nitrogen substrate–dependent nitrous oxide cycling in salt marsh sediments

Nitrous oxide (N2O) is important to Earth\u27s climate because it is a strong absorber of radiation and an important ozone depletion agent. Increasing anthropogenic nitrogen input into the marine environment, especially to coastal waters, has led to increasing N2O emissions. Identifying the nitrogen compounds that serve as substrates for N2O production in coastal waters reveals important pathways and helps us understand their control by environmental factors. In this study, sediments were collected from a long-term fertilization site in Great Sippewissett Marsh, Falmouth, Massachusetts. The 15N tracer incubation time course experiments were conducted and analyzed for potential N2O production and consumption rates. The two nitrogen substrates of N2O production, ammonium and nitrate, correspond to the two production pathways, nitrification and denitrification, respectively. When measurable nitrate was present, despite ambient high ammonium concentrations, denitrification was the major N2O production pathway. When nitrate was absent, ammonium became the dominant substrate for N2O production, via nitrification and coupled nitrification-denitrification. Net N2O consumption was enhanced under low oxygen and nitrate conditions. N2O production and consumption rates increased with increasing levels of nitrogen fertilization in long-term experimental plots. These results indicate that increasing anthropogenic nitrogen input to salt marshes can stimulate sedimentary N2O production via both nitrification and denitrification, whereas episodic oxygen depletion results in net N2O consumption

Multiple Metabolisms Constrain the Anaerobic Nitrite Budget in the Eastern Tropical South Pacific

The Eastern Tropical South Pacific is one of the three major oxygen deficient zones (ODZs) in the global ocean and is responsible for approximately one third of marine water column nitrogen loss. It is the best studied of the ODZs and, like the others, features a broad nitrite maximum across the low oxygen layer. How the microbial processes that produce and consume nitrite in anoxic waters interact to sustain this feature is unknown. Here we used 15N-tracer experiments to disentangle five of the biologically mediated processes that control the nitrite pool, including a high-resolution profile of nitrogen loss rates. Nitrate reduction to nitrite likely depended on organic matter fluxes, but the organic matter did not drive detectable rates of denitrification to N2. However, multiple lines of evidence show that denitrification is important in shaping the biogeochemistry of this ODZ. Significant rates of anaerobic nitrite oxidation at the ODZ boundaries were also measured. Lodate was a potential oxidant that could support part of this nitrite consumption pathway. We additionally observed N2 production from labeled cyanate and postulate that anammox bacteria have the ability to harness cyanate as another form of reduced nitrogen rather than relying solely on ammonification of complex organic matter. The balance of the five anaerobic rates measured—anammox, denitrification, nitrate reduction, nitrite oxidation, and dissimilatory nitrite reduction to ammonium—is sufficient to reproduce broadly the observed nitrite and nitrate profiles in a simple one-dimensional model but requires an additional source of reduced nitrogen to the deeper ODZ to avoid ammonium overconsumption. ©2017. American Geophysical Union. All Rights Reserved

Ratio of electron donor to acceptor influences metabolic specialization and denitrification dynamics in Pseudomonas aeruginosa in a mixed carbon medium

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Zhang, I. H., Mullen, S., Ciccarese, D., Dumit, D., Martocello, D. E., Toyofuku, M., Nomura, N., Smriga, S., & Babbin, A. R. Ratio of electron donor to acceptor influences metabolic specialization and denitrification dynamics in Pseudomonas aeruginosa in a mixed carbon medium. Frontiers in Microbiology, 12, (2021): 711073, https://doi.org/10.3389/fmicb.2021.711073.Denitrifying microbes sequentially reduce nitrate (NO3–) to nitrite (NO2–), NO, N2O, and N2 through enzymes encoded by nar, nir, nor, and nos. Some denitrifiers maintain the whole four-gene pathway, but others possess partial pathways. Partial denitrifiers may evolve through metabolic specialization whereas complete denitrifiers may adapt toward greater metabolic flexibility in nitrogen oxide (NOx–) utilization. Both exist within natural environments, but we lack an understanding of selective pressures driving the evolution toward each lifestyle. Here we investigate differences in growth rate, growth yield, denitrification dynamics, and the extent of intermediate metabolite accumulation under varying nutrient conditions between the model complete denitrifier Pseudomonas aeruginosa and a community of engineered specialists with deletions in the denitrification genes nar or nir. Our results in a mixed carbon medium indicate a growth rate vs. yield tradeoff between complete and partial denitrifiers, which varies with total nutrient availability and ratios of organic carbon to NOx–. We found that the cultures of both complete and partial denitrifiers accumulated nitrite and that the metabolic lifestyle coupled with nutrient conditions are responsible for the extent of nitrite accumulation.Funding for this work was provided by Simons Foundation award 622065 and an MIT Environmental Solutions Initiative seed grant to AB. Additional support was received by the MIT Ferry Fund

Nitrous oxide production by nitrification and denitrification in the Eastern Tropical South Pacific oxygen minimum zone

The Eastern Tropical South Pacific oxygen minimum zone (ETSP-OMZ) is a site of intense nitrous oxide (N2O) flux to the atmosphere. This flux results from production of N2O by nitrification and denitrification, but the contribution of the two processes is unknown. The rates of these pathways and their distributions were measured directly using 15N tracers. The highest N2O production rates occurred at the depth of peak N2O concentrations at the oxic-anoxic interface above the oxygen deficient zone (ODZ) because slightly oxygenated waters allowed (1) N2O production from both nitrification and denitrification and (2) higher nitrous oxide production yields from nitrification. Within the ODZ proper (i.e., anoxia), the only source of N2O was denitrification (i.e., nitrite and nitrate reduction), the rates of which were reflected in the abundance of nirS genes (encoding nitrite reductase). Overall, denitrification was the dominant pathway contributing the N2O production in the ETSP-OMZ

A link between the ice nucleation activity and the biogeochemistry of seawater

Emissions of ice-nucleating particles (INPs) from sea spray can impact climate and precipitation by changing cloud formation, precipitation, and albedo. However, the relationship between seawater biogeochemistry and the ice nucleation activity of sea spray aerosols remains unclarified. Here, we demonstrate a link between the biological productivity in seawater and the ice nucleation activity of sea spray aerosol under conditions relevant to cirrus and mixed-phase cloud formation. We show for the first time that aerosol particles generated from both subsurface and microlayer seawater from the highly productive eastern tropical North Pacific Ocean are effective INPs in the deposition and immersion freezing modes. Seawater particles of composition similar to subsurface waters of highly productive regions may therefore be an unrealized source of effective INPs. In contrast, the subsurface water from the less productive Florida Straits produced less effective immersion mode INPs and ineffective depositional mode INPs. These results indicate that the regional biogeochemistry of seawater can strongly affect the ice nucleation activity of sea spray aerosol