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At least 37 records · Page 2

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modfications on the chemical model of Wirstrom et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of > 2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗

An in-silico NMR laboratory for nuclear magnetic shieldings computed via finite fields: Exploring nucleus-specific renormalizations of MP2 and MP3

Here we developed and implemented a method-independent, fully numerical, finite difference approach to calculating nuclear magnetic resonance shieldings, using gauge-including atomic orbitals. The resulting capability can be used to explore non-standard methods, given only the energy as a function of finite-applied magnetic fields and nuclear spins. For example, standard second-order Møller-Plesset theory (MP2) has well-known efficacy for 1H and 13C shieldings and known limitations for other nuclei such as 15N and 17O. It is, therefore, interesting to seek methods that offer good accuracy for 15N and 17O shieldings without greatly increased compute costs, as well as exploring whether such methods can further improve 1H and 13C shieldings. Using a small molecule test set of 28 species, we assessed two alternatives: κ regularized MP2 (κ-MP2), which provides energy-dependent damping of large amplitudes, and MP2.X, which includes a variable fraction, X, of third-order correlation (MP3). The aug-cc-pVTZ basis was used, and coupled cluster with singles and doubles and perturbative triples [CCSD(T)] results were taken as reference values. Our κ-MP2 results reveal significant improvements over MP2 for 13C and 15N, with the optimal κ value being element-specific. κ-MP2 with κ = 2 offers a 30% rms error reduction over MP2. For 15N, κ-MP2 with κ = 1.1 provides a 90% error reduction vs MP2 and a 60% error reduction vs CCSD. On the other hand, MP2.X with a scaling factor of 0.6 outperformed CCSD for all heavy nuclei. These results can be understood as providing renormalization of doubles amplitudes to partially account for neglected triple and higher substitutions and offer promising opportunities for future applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

NASA Discipline Exobiology↗

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Non-NASA Center↗

Efficient 15 N hyperpolarization of [ 15 N 3 ]metronidazole antibiotic via spin-relayed pulsed SABRE-SHEATH

Signal Amplification by Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) is an NMR hyperpolarization technique that relies of the simultaneous exchange of parahydrogen and a to-be-hyperpolarized molecule on the metal center of a polarization-transfer catalyst in a microtesla magnetic field. Until recently, this method has been understood to perform hyperpolarization by establishing level anti-crossings between the nuclear spins of the parahydrogen derived hydrides (acting as a source of hyperpolarization) and those of the substrate. Recently, the application of highly non-intuitive pulse sequences (comprising pulses of microtesla DC fields) was predicted to hyperpolarize nuclear spins more efficiently than the canonical (static-field) SABRE-SHEATH approach. Here we show that by employing a basic “on-off” pulse sequence of rectangular microtesla pulses, it is possible to improve the hyperpolarization efficiency for SABRE-SHEATH of [ 15 N 3 ]metronidazole, an FDA-approved antibiotic (in non-enriched and non-hyperpolarized form) and potential hypoxia sensing molecule. Specifically, we demonstrate that 15N polarization of 18.5 % can be obtained in 80 s of parahydrogen bubbling parahydrogen through a solution containing 20 mM [ 15 N 3 ]metronidazole. In practice, (1.32 ± 0.14)-fold improvements in P 15N was obtained with the pulsed method described here compared to static field technique variant. These results show that pulsed SABRE-SHEATH was successfully applied to 15 N-labeled biologically relevant molecule. Moreover, we also demonstrate that although the pulsed SABRE-SHEATH sequence was designed for polarization transfer from parahydrogen derived hydrides to the metronidazole’s 15 N catalyst-binding site, all three 15 N sites of [ 15 N 3 ]metronidazole attained the hyperpolarized state. This spin-relayed polarization transfer becomes possible due to the 15 N relay network established by their spin-spin J-couplings. The feasibility of the spin-relayed polarization transfer is demonstrated here for the first time for pulsed SABRE-SHEATH (as opposed to the static-field SABRE-SHEATH reported previously) and it paves the way to broad applicability of the technique.

Hyperpolarization↗

A Study of the Conformational Isomerism of n-Propyl Nitrate by Microwave Spectroscopy

The rotational spectrum of n-propyl nitrate was measured in the frequency range between 6 to 18 GHz using a Balle-Flygare Fourier transform microwave jet/cavity spectrometer. Parent, 13C and 15N isotopologue transitions for the lower-energy anti-gauche (AG) conformer were found using this instrument. The search for spectra from other conformers was performed using a broadband chirped-pulse jet spectrometer. Transitions from the anti-anti (AA) conformer were observed in this manner. Parent, 13C and 15N isotopologue transitions for the AA conformer were rescanned using the cavity instrument to improve resolution and the signal-to-noise ratio. Rotational, centrifugal distortion, and nuclear electric quadrupole coupling constants for all conformers/isotopologues were fit using Pickett’s SPFIT program. The structure of n-propyl nitrate is discussed considering these results.

Orellana, Will D.↗

Experimentally-validated correlation analysis reveals new anaerobic methane oxidation partnerships with consortium-level heterogeneity in diazotrophy

Abstract Archaeal anaerobic methanotrophs (“ANME”) and sulfate-reducing Deltaproteobacteria (“SRB”) form symbiotic multicellular consortia capable of anaerobic methane oxidation (AOM), and in so doing modulate methane flux from marine sediments. The specificity with which ANME associate with particular SRB partners in situ, however, is poorly understood. To characterize partnership specificity in ANME-SRB consortia, we applied the correlation inference technique SparCC to 310 16S rRNA amplicon libraries prepared from Costa Rica seep sediment samples, uncovering a strong positive correlation between ANME-2b and members of a clade of Deltaproteobacteria we termed SEEP-SRB1g. We confirmed this association by examining 16S rRNA diversity in individual ANME-SRB consortia sorted using flow cytometry and by imaging ANME-SRB consortia with fluorescence in situ hybridization (FISH) microscopy using newly-designed probes targeting the SEEP-SRB1g clade. Analysis of genome bins belonging to SEEP-SRB1g revealed the presence of a complete nifHDK operon required for diazotrophy, unusual in published genomes of ANME-associated SRB. Active expression of nifH in SEEP-SRB1g within ANME-2b—SEEP-SRB1g consortia was then demonstrated by microscopy using hybridization chain reaction (HCR-) FISH targeting nifH transcripts and diazotrophic activity was documented by FISH-nanoSIMS experiments. NanoSIMS analysis of ANME-2b—SEEP-SRB1g consortia incubated with a headspace containing CH4 and 15N2 revealed differences in cellular 15N-enrichment between the two partners that varied between individual consortia, with SEEP-SRB1g cells enriched in 15N relative to ANME-2b in one consortium and the opposite pattern observed in others, indicating both ANME-2b and SEEP-SRB1g are capable of nitrogen fixation, but with consortium-specific variation in whether the archaea or bacterial partner is the dominant diazotroph.

58 GEOSCIENCES↗

Community RNA-Seq: multi-kingdom responses to living versus decaying roots in soil

Abstract Roots are a primary source of organic carbon input in most soils. The consumption of living and detrital root inputs involves multi-trophic processes and multiple kingdoms of microbial life, but typical microbial ecology studies focus on only one or two major lineages. We used Illumina shotgun RNA sequencing to conduct PCR-independent SSU rRNA community analysis (“community RNA-Seq”) and simultaneously assess the bacteria, archaea, fungi, and microfauna surrounding both living and decomposing roots of the annual grass, Avena fatua. Plants were grown in 13CO2-labeled microcosms amended with 15N-root litter to identify the preferences of rhizosphere organisms for root exudates (13C) versus decaying root biomass (15N) using NanoSIMS microarray imaging (Chip-SIP). When litter was available, rhizosphere and bulk soil had significantly more Amoebozoa, which are potentially important yet often overlooked top-down drivers of detritusphere community dynamics and nutrient cycling. Bulk soil containing litter was depleted in Actinobacteria but had significantly more Bacteroidetes and Proteobacteria. While Actinobacteria were abundant in the rhizosphere, Chip-SIP showed Actinobacteria preferentially incorporated litter relative to root exudates, indicating this group’s more prominent role in detritus elemental cycling in the rhizosphere. Our results emphasize that decomposition is a multi-trophic process involving complex interactions, and our methodology can be used to track the trajectory of carbon through multi-kingdom soil food webs.

Nuccio, Erin E. (ORCID:000000030189183X)↗

Interactions among rooting traits for deep water and nitrogen uptake in upland and lowland ecotypes of switchgrass ( Panicum virgatum L.)

Abstract The response of plant growth and development to nutrient and water availability is an important adaptation for abiotic stress tolerance. Roots need to intercept both passing nutrients and water while foraging into new soil layers for further resources. Substantial amounts of nitrate can be lost in the field when leaching into groundwater, yet very little is known about how deep rooting affects this process. Here, we phenotyped root system traits and deep 15N nitrate capture across 1.5 m vertical profiles of solid media using tall mesocosms in switchgrass (Panicum virgatum L.), a promising cellulosic bioenergy feedstock. Root and shoot biomass traits, photosynthesis and respiration measures, and nutrient uptake and accumulation traits were quantified in response to a water and nitrate stress factorial experiment for switchgrass upland (VS16) and lowland (AP13) ecotypes. The two switchgrass ecotypes shared common plastic abiotic responses to nitrogen (N) and water availability, and yet had substantial genotypic variation for root and shoot traits. A significant interaction between N and water stress combination treatments for axial and lateral root traits represents a complex and shared root development strategy for stress mitigation. Deep root growth and 15N capture were found to be closely linked to aboveground growth. Together, these results represent the wide genetic pool of switchgrass and show that deep rooting promotes nitrate capture, plant productivity, and sustainability.

59 BASIC BIOLOGICAL SCIENCES↗

Plant-Nitrifier Interactions in Topsoil and Subsoil

Plants can influence soil microbes through resource acquisition and interference competition, with consequences for ecosystem function such as nitrification. However, how plants alter soil conditions to influence nitrifiers and nitrification rates remains poorly understood, especially in the subsoil. Here, coupling the 15N isotopic pool dilution technique, high throughput sequencing and in situ soil O2 monitoring, we investigated how a deep-rooted perennial grass, miscanthus, versus an adjacent shallow-rooted turfgrass reference shapes nitrifier assembly and function along 1 m soil profiles. In topsoil, the suppression of ammonia (NH3) oxidizing archaea (AOA) and gross nitrification rates in miscanthus relative to the reference likely resulted from nitrifiers being outcompeted by plant roots and heterotrophic bacteria for ammonium (NH4+). The stronger tripartite competition under miscanthus may have been caused in part by the lower soil organic matter (SOM) content, which supported lower gross nitrogen (N) mineralization, the major soil process that produces NH4+. In contrast, below 10 cm soil depth, significantly greater gross nitrification rates were observed in miscanthus compared to the reference. This was likely driven by the significantly lower oxygen (O2) in miscanthus than reference subsoil, which selected against aerobic heterotrophic bacteria but in favor of AOA. Overall, we found that plants can regulate AOA community structure and function through different mechanisms in topsoil and subsoil, with suppression of nitrification in topsoil and enhancement of nitrification in subsoil.

Field Data↗

Nitrogen recycling during phenylpropanoid metabolism in sweet potato tubers

In the first step of the phenylpropanoid metabolic pathway, L-phenylalanine (L-Phe) is deaminated to form E-cinnamate, in a conversion catalyzed by phenylalanine ammonia-lyase (PAL; EC 4.3.1.5). The metabolic fate of the ammonium ion (NH4+) produced in this reaction was investigated in sweet potato (Ipomoea batatas) tuber discs. [15N]-Labeled substrates including L-Phe, in the presence or absence of specific enzyme inhibitors, were administered to sweet potato discs in light under aseptic conditions. 15N-Nuclear magnetic resonance spectroscopic analyses revealed that the 15NH4+ liberated during the PAL reaction is first incorporated into the amide nitrogen of L-glutamine (L-Gln) and then into L-glutamate (L-Glu). These results extend our previous observations in pine and potato that PAL-generated NH4+ is assimilated by the glutamine synthetase (GS; EC 6.3.1.2)/glutamate synthase (GOGAT; EC 1.4.1.13) pathway, with the NH4+ so formed ultimately being recycled back to L-Phe via L-Glu as aminoreceptor and donor.

Non-NASA Center↗

Stable isotopic biogeochemistry of carbon and nitrogen in a perennially ice-covered Antarctic lake

Lake Hoare (77 degrees 38' S, 162 degrees 53' E) is an amictic, oligotrophic, 34-m-deep, closed-basin lake in Taylor Valley, Antarctica. Its perennial ice cover minimizes wind-generated currents and reduces light penetration, as well as restricts sediment deposition into the lake and the exchange of atmospheric gases between the water column and the atmosphere. The biological community of Lake Hoare consists solely of microorganisms -- both planktonic populations and benthic microbial mats. Lake Hoare is one of several perennially ice-covered lakes in the McMurdo Dry Valleys that represent the end-member conditions of cold desert and saline lakes. The dry valley lakes provide a unique opportunity to examine lacustrine processes that operate at all latitudes, but under an extreme set of environmental conditions. The dry valley lakes may also offer a valuable record of catchment and global changes in the past and present. Furthermore, these lakes are modern-day equivalents of periglacial lakes that are likely to have been common during periods of glacial maxima at temperate latitudes. We have analyzed the dissolved inorganic carbon (DIC) of Lake Hoare for delta 13C and the organic matter of the sediments and sediment-trap material for delta 13C and delta 15N. The delta 13C of the DIC indicates that 12C is differentially removed in the shallow, oxic portions of the lake via photosynthesis. In the anoxic portions of the lake (27-34 m) a net addition of 12C to the DIC pool occurs via organic matter decomposition. The dissolution of CaCO3 at depth also contributes to the DIC pool. Except near the Canada Glacier where a substantial amount of allochthonous organic matter enters the lake, the organic carbon being deposited on the lake bottom at different sites is isotopically similar, suggesting an autochthonous source for the organic carbon. Preliminary inorganic carbon flux calculations suggest that a high percentage of the organic carbon fixed in the water column is remineralized as it falls through the water column. At nearby Lake Fryxell, the substantial (relative to Lake Hoare) glacial meltstream input overprints Fryxell's shallow-water biological delta 13C signal with delta 13C-depleted DIC. In contrast, Lake Hoare is not significantly affected by surface-water input and mixing, and therefore the delta 13C patterns observed arise primarily from biological dynamics within the lake. Organic matter in Lake Hoare is depleted in 15N, which we suggest is partially the result of the addition of relatively light inorganic nitrogen into the lake system from terrestrial sources.

NASA Program Exobiology↗

Evidence for Surprising Heavy Nitrogen Isotopic Enrichment in Comet 46P/Wirtanen's Hydrogen Cyanide

46P/Wirtanen is a Jupiter-family comet, probably originating from the solar system's Kuiper Belt, that now resides on a 5.4 yr elliptical orbit. During its 2018 apparition, comet 46P passed unusually close to the Earth (within 0.08 au), presenting an outstanding opportunity for close-up observations of its inner coma. Here we present observations of HCN, H13CN, and HC15N emission from 46P using the Atacama Compact Array. The data were analyzed using the SUBLIME non-LTE radiative transfer code to derive 12C/13C and 14N/15N ratios. The HCN/H13CN ratio is found to be consistent with a lack of significant 13C fractionation, whereas the HCN/HC15N ratio of 68 ± 27 (using our most conservative 1σ uncertainties), indicates a strong enhancement in 15N compared with the solar and terrestrial values. The observed 14N/15N ratio is also significantly lower than the values of ∼140 found in previous comets, implying a strong 15N enrichment in 46P's HCN. This indicates that the nitrogen in Jupiter-family comets could reach larger isotopic enrichments than previously thought, with implications for the diversity of 14N/15N ratios imprinted into icy bodies at the birth of the solar system.

Short period comets↗

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds Using Isotopic Labeling

Abstract: Surface functionalization of two-dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced here is a mild, surface-specific protocol for the surface functionalization of few-layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational (infrared, Raman), Xray (emission, photoelectron), CPMAS NMR, and UV-vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15N-labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

Walz, Kendall↗

A Thorough Characterization of the Tellurocyanate Anion

Tellurocyanate, [TeCN] − , is the heaviest group 16 congener of the cyanate anion, [OCN] − . Due to the relative instability of the C─Te bond, tellurocyanate chemistry has seen only scarce attention. Here, we present the facile synthesis and thorough characterization of [K@crypt-222][TeCN]. The anion is essentially linear with interatomic distances C─N = 1.150(6)Å and C─Te = 2.051(4)Å, thus approximating a C≡N triple bond and for C─Te a bond order between 1 and 2. Fully 13 C and 15 N labeled [Te 13 C 15 N] − allowed for the extraction of chemical shifts and all possible coupling constants ( 13 C = 77.8 ppm, 15 N = 285.7 ppm, 125 Te = −566 ppm, 1 J 13C-15N = 8 Hz, 1 J 13C-125Te = 748 Hz, 2 J1 5N-125Te = 55 Hz), which were also determined independently by quantum chemical calculations. In the series [ChCN] − (Ch = O─Te), [TeCN] − shows the strongest spin-orbit coupling (SOC) induced heavy-atom effect on the light-atom shielding (SO-HALA-effect). In contrast, 15 N shifts are also well described without considering relativistic effects and/or SOC. Negative-ion photoelectron spectroscopy was used to extract the electron affinity (EA = 3.034 eV) and spin-orbit splitting (3807 cm −1 ) of [TeCN] • . These values continue the trends of falling EA and rising SOC in the series [ChCN] • .

Bonding analysis↗

Pyrolysis temperature and soil depth interactions determine PyC turnover and induced soil organic carbon priming

Pyrogenic organic carbon (PyC) is a complex, heterogeneous class of thermally altered organic substrates, but its dynamics and how its behavior changes with soil depth remain poorly understood. We conducted a laboratory incubation study to investigate the interactive effects of pyrolysis temperature and soil depth on the turnover of PyC compared to its precursor wood and native SOC (NSOC). We incubated dual-labeled (13C and 15N) jack pine pyrogenic organic matter produced at 300 °C (PyC300), 450 °C (PyC450), and their precursor pine wood in a fine-loamy, mixed-conifer forest soil for 745 days. A mixture of surface (0–10 cm) and subsurface (50–70 cm) forest soils, with and without labeled biomass were incubated in the dark at 55% soil water field capacity and 25 °C. Total 13C from PyC and wood mineralized as 13C-CO2 (as % of C added to soil) declined with an increase in pyrolysis temperature as follows: 54 ± 7.7% for wood, 3.1 ± 0.2% for PyC300, and 0.94 ± 0.08% for PyC450. Furthermore, after 2 years, soil depth interacted with pyrolysis temperature to affect C turnover, with total wood C losses significantly declining from 70.6% in surface soils to 37.5% in subsurface soil, while total losses of PyC300 and PyC450 were unaffected by differences between surface and subsurface soils. Wood induced negative priming (i.e., decreased mineralization rates) in surface soil at days 3 and 60, while PyC300 induced positive priming (i.e., increased mineralization rates) in subsurface soil at day 60. After 2 years, unlabeled NSOC losses increased from 9.2 ± 0.8% of NSOC in unamended treatments to 16.5 ± = 2.6% of NSOC with PyC450 additions. Our results suggest that PyC pyrolyzed at a given temperature can mineralize at similar rates between soil depths, and high amounts of PyC450 in subsurface soils can stimulate NSOC losses. These findings indicate that soil depth imposes critical controls on PyC dynamics belowground.

13C-labeling↗

Trophic interactions shape the spatial organization of medium-chain carboxylic acid producing granular biofilm communities

Abstract Granular biofilms producing medium-chain carboxylic acids (MCCA) from carbohydrate-rich industrial feedstocks harbor highly streamlined communities converting sugars to MCCA either directly or via lactic acid as intermediate. We investigated the spatial organization and growth activity patterns of MCCA producing granular biofilms grown on an industrial side stream to test (i) whether key functional guilds (lactic acid producing Olsenella and MCCA producing Oscillospiraceae) stratified in the biofilm based on substrate usage, and (ii) whether spatial patterns of growth activity shaped the unique, lenticular morphology of these biofilms. First, three novel isolates (one Olsenella and two Oscillospiraceae species) representing over half of the granular biofilm community were obtained and used to develop FISH probes, revealing that key functional guilds were not stratified. Instead, the outer 150–500 µm of the granular biofilm consisted of a well-mixed community of Olsenella and Oscillospiraceae, while deeper layers were made up of other bacteria with lower activities. Second, nanoSIMS analysis of 15N incorporation in biofilms grown in normal and lactic acid amended conditions suggested Oscillospiraceae switched from sugars to lactic acid as substrate. This suggests competitive-cooperative interactions may govern the spatial organization of these biofilms, and suggests that optimizing biofilm size may be a suitable process engineering strategy. Third, growth activities were similar in the polar and equatorial biofilm peripheries, leaving the mechanism behind the lenticular biofilm morphology unexplained. Physical processes (e.g., shear hydrodynamics, biofilm life cycles) may have contributed to lenticular biofilm development. Together, this study develops an ecological framework of MCCA-producing granular biofilms that informs bioprocess development.

09 BIOMASS FUELS↗

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Zhou, Jiahua↗