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1. Quantification of biological nitrogen fixation by Mo-independent complementary nitrogenases in environmental samples with low nitrogen fixation activity

   https://doi.org/10.1038/s41598-022-24860-9  

   Haynes, Shannon J. ; Darnajoux, Romain ; Han, Eunah ; Oleynik, Sergey ; Zimble, Ezra ; Zhang, Xinning ( December 2022 , Scientific Reports)

   Biological nitrogen fixation (BNF) by canonical molybdenum and complementary vanadium and iron-only nitrogenase isoforms is the primary natural source of newly fixed nitrogen. Understanding controls on global nitrogen cycling requires knowledge of the isoform responsible for environmental BNF. The isotopic acetylene reduction assay (ISARA), which measures carbon stable isotope (¹³C/¹²C) fractionation between ethylene and acetylene in acetylene reduction assays, is one of the few methods that can quantify isoform-specific BNF fluxes. Application of classical ISARA has been challenging because environmental BNF activity is often too low to generate sufficient ethylene for isotopic analyses. Here we describe a high sensitivity method to measure ethylene δ¹³C by in-line coupling of ethylene preconcentration to gas chromatography-combustion-isotope ratio mass spectrometry (EPCon-GC-C-IRMS). Ethylene requirements in samples with 10% v/v acetylene are reduced from > 500 to ~ 20 ppmv (~ 2 ppmv with prior offline acetylene removal). To increase robustness by reducing calibration error, single nitrogenase-isoformAzotobacter vinelandiimutants and environmental sample assays rely on a common acetylene source for ethylene production. Application of the Low BNF activity ISARA (LISARA) method to low nitrogen-fixing activity soils, leaf litter, decayed wood, cryptogams, and termites indicates complementary BNF in most sample types, calling for additional studies of isoform-specific BNF.
2. Isotopic fractionation accompanying CO2 hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA

   https://doi.org/doi.org/10.1016/j.gca.2021.01.003  

   Christensen, J. ( January 2021 , Geochimica)

   Teagle, Damon A (Ed.)

   The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with ‘‘floes” forming at the atmosphere-water interface, ‘‘snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO3 precipitation occurring in waters with low Mg/Ca (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection. The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in d13C (
   9 to
   28‰ VPDB) and d18O (0 to
   20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO2 hydroxylation but the controls on the d13C-d18O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (0.5 km2) and the limited range of water sources and temperatures, combined with our sampling strategy, allow usmore »to place tight constraints on the processes involved in generating the systematic C and O isotope variations. We develop an isotopic reaction–diffusion model and an isotopic box model for a CO2-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO3. The box model includes four sources or sinks of DIC (atmospheric CO2, high pH spring water, fresh creek water, and CaCO3 precipitation). Model parameters are informed by new floe D44Ca data (
   0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8  10
   7 mol/m2/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO2 and the kinetic isotope fractionation factor (KFF (‰) = (a
   1)  1000) accompanying CO2 hydroxylation, estimated here to be
   17.1 ± 0.8‰ (vs. CO2(aq)) for carbon and
   7.1 ± 1.1‰ (vs. ‘CO2(aq)+H2O’) for oxygen at 17.4 ± 1.0
   C. Combining our results with revised CO2 hydroxylation KFF values based on previous work suggests consistent KFF values of
   17.0 ± 0.3‰ (vs. CO2(aq)) for carbon and
   6.8 ± 0.8‰ for oxygen (vs. ‘CO2(aq)+H2O’) over the 17–28
   C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly HCO- 3, pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate d13C and d18O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water d18O and atmospheric d13C values. There is evidence that older travertine at The Cedars recorded atmospheric d13C that predates large-scale combustion of fossil fuels.« less
3. Methane efflux from an American bison herd

   https://doi.org/10.5194/bg-18-961-2021  

   Stoy, Paul C. ; Cook, Adam A. ; Dore, John E. ; Kljun, Natascha ; Kleindl, William ; Brookshire, E. N. ; Gerken, Tobias ( January 2021 , Biogeosciences)

   null (Ed.)

   Abstract. American bison (Bison bison L.) have recovered from the brink ofextinction over the past century. Bison reintroduction creates multipleenvironmental benefits, but impacts on greenhouse gas emissions are poorlyunderstood. Bison are thought to have produced some 2 Tg yr−1 of theestimated 9–15 Tg yr−1 of pre-industrial enteric methane emissions,but few measurements have been made due to their mobile grazing habits andsafety issues associated with measuring non-domesticated animals. Here, wemeasure methane and carbon dioxide fluxes from a bison herd on an enclosedpasture during daytime periods in winter using eddy covariance. Methaneemissions from the study area were negligible in the absence of bison(mean ± standard deviation = −0.0009 ± 0.008 µmol m−2 s−1) and were significantly greater than zero,0.048 ± 0.082 µmol m−2 s−1, with a positively skeweddistribution, when bison were present. We coupled bison location estimatesfrom automated camera images with two independent flux footprint models tocalculate a mean per-animal methane efflux of 58.5 µmol s−1 per bison, similar to eddy covariance measurements ofmethane efflux from a cattle feedlot during winter. When we sum theobservations over time with conservative uncertainty estimates we arrive at81 g CH4 per bison d−1 with 95 % confidence intervalsbetween 54 and 109 g CH4 per bison d−1. Uncertainty wasdominated by bison location estimates (46 % of the total uncertainty),then the flux footprint model (33 %) and the eddy covariance measurements(21 %), suggesting that making higher-resolution animal location estimatesis a logical starting point formore »decreasing total uncertainty. Annualmeasurements are ultimately necessary to determine the full greenhouse gasburden of bison grazing systems. Our observations highlight the need tocompare greenhouse gas emissions from different ruminant grazing systems anddemonstrate the potential for using eddy covariance to measure methaneefflux from non-domesticated animals.« less
4. Nutrient-Colimited Trichodesmium as a Nitrogen Source or Sink in a Future Ocean

   https://doi.org/10.1128/AEM.02137-17  

   Walworth, Nathan G. ; Fu, Fei-Xue ; Lee, Michael D. ; Cai, Xiaoni ; Saito, Mak A. ; Webb, Eric A. ; Hutchins, David A. ; Liu, Shuang-Jiang ( February 2018 , Applied and Environmental Microbiology)

   ABSTRACT Nitrogen-fixing (N 2 ) cyanobacteria provide bioavailable nitrogen to vast ocean regions but are in turn limited by iron (Fe) and/or phosphorus (P), which may force them to employ alternative nitrogen acquisition strategies. The adaptive responses of nitrogen fixers to global-change drivers under nutrient-limited conditions could profoundly alter the current ocean nitrogen and carbon cycles. Here, we show that the globally important N 2 fixer Trichodesmium fundamentally shifts nitrogen metabolism toward organic-nitrogen scavenging following long-term high-CO 2 adaptation under iron and/or phosphorus (co)limitation. Global shifts in transcripts and proteins under high-CO 2 /Fe-limited and/or P-limited conditions include decreases in the N 2 -fixing nitrogenase enzyme, coupled with major increases in enzymes that oxidize trimethylamine (TMA). TMA is an abundant, biogeochemically important organic nitrogen compound that supports rapid Trichodesmium growth while inhibiting N 2 fixation. In a future high-CO 2 ocean, this whole-cell energetic reallocation toward organic nitrogen scavenging and away from N 2 fixation may reduce new-nitrogen inputs by Trichodesmium while simultaneously depleting the scarce fixed-nitrogen supplies of nitrogen-limited open-ocean ecosystems. IMPORTANCE Trichodesmium is among the most biogeochemically significant microorganisms in the ocean, since it supplies up to 50% of the new nitrogen supporting open-ocean food webs. We usedmore »Trichodesmium cultures adapted to high-CO 2 conditions for 7 years, followed by additional exposure to iron and/or phosphorus (co)limitation. We show that “future ocean” conditions of high CO 2 and concurrent nutrient limitation(s) fundamentally shift nitrogen metabolism away from nitrogen fixation and instead toward upregulation of organic nitrogen-scavenging pathways. We show that the responses of Trichodesmium to projected future ocean conditions include decreases in the nitrogen-fixing nitrogenase enzymes coupled with major increases in enzymes that oxidize the abundant organic nitrogen source trimethylamine (TMA). Such a shift toward organic nitrogen uptake and away from nitrogen fixation may substantially reduce new-nitrogen inputs by Trichodesmium to the rest of the microbial community in the future high-CO 2 ocean, with potential global implications for ocean carbon and nitrogen cycling.« less
5. Cold plasma-Metal Organic Framework (MOF)-177 breathable system for atmospheric remediation

   https://doi.org/https://doi.org/10.1016/j.jcou.2021.101642  

   Fnu Gorky ; Apolo Nambo ; Maria L. Carreon ( July 2021 , Journal of CO2 utilization)

   Non-thermal plasma Methane capture Carbon dioxide capture Metal organic framework Methanol synthesis Atmospheric remediation 1. Introduction The stabilization of CO2 and CH4 concentrations in the air to control global warming is accelerating. There are continued efforts to develop and optimize different technologies for capture and sequestration of these greenhouse gases from industrial emission sites. From these gases, CH4 is the most dominant anthropogenic greenhouse gas (after CO2). Methane can react with nitrogen oxides leading to tropospheric ozone pollution and posses a higher global warming potential (GWP) than CO2. It is 84 times more potent than CO2 over the first 20 years after release and ~28 times more potent after a century. Methane concentrations could be restored to preindustrial levels by removing ~3.2 of the 5.3 Gt of CH4 currently in the atmosphere [1]. Rather than capturing and storing the methane, CH4 could be oxidized to CO2, through the ther- modynamically favorable reaction: CH4 + 2O2 → CO2 + 2H2O; ΔHrx = –803 kJ mol–1. With the possible production of valuable condensates such as form- aldehyde and methanol when employing different reaction conditions (i. e., gas ratio, oxidant type, temperature) and rational selected catalysts. The large activation barrier associated with splittingmore »methane’s C– H * Corresponding author. E-mail address: Maria.CarreonGarciduenas@sdsmt.edu (M.L. Carreon). https://doi.org/10.1016/j.jcou.2021.101642 The direct capture of CO2 and CH4 from the atmosphere to stabilize the concentrations in the air to control global warming is accelerating. There are continued efforts to develop and optimize different technologies for capture and sequestration of these greenhouse gases from industrial emission sites. In this work we employed MOF-177 as an efficient CO2 and CH4 adsorbent at standard temperature and pressure conditions. We demonstrated the possibility of desorbing the gases under study when employing gentle plasma pulses of He. Moreover, we per- formed the synthesis of methanol from CH4 using O2 and CO2 as oxidants respectively in the presence of MOF- 177. We observed the highest conversion for the CH4 + O2 system when employing the MOF-177 at (5:1) (CH4: O2) flow ratio of 23.5 % and methanol selectivity of 17.65 %. While the best performance for the CH4 + CO2 system at the same conditions i.e., (5:1) (CH4: O2) flow ratio was 18.4 % for the methane conversion and 11.68 % for the selectivity towards methanol. We expect this preliminary understanding of the adsorption-reaction system under non-thermal plasma environment can lead to future atmospheric remediation technologies.« less