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At least 163 records · Page 9

Investigating preservation of stable isotope ratios in subfossil deep-sea proteinaceous coral skeletons as paleo-recorders of biogeochemical information over multimillennial timescales

Paleoproxy records in deep-sea proteinaceous coral skeletons can reconstruct past ocean conditions on centennial to millennial time scales. Commonly recovered subfossil specimens could potentially extend these archives through the Holocene. However, protein matrix stability and integrity of stable isotope proxies over multi-millennial timescales in such specimens have never been examined. Here we compare amino acid (AA) composition together with bulk and AA compound-specific carbon (δ 13 C) and nitrogen (δ 15 N) isotopes in live-collected and subfossil (~9.6–11.6 kyrs BP) Kulamanamana haumeaae deep-sea coral specimens from the central Pacific to understand the effects of long-duration benthic oxic exposure on primary coral chemistry. We find large coupled shifts in bulk δ 15 N (~7‰) and δ 13 C (~2‰) in the outermost portion (0–10 mm) of the subfossil coral, coincident with extensive alteration of the protein matrix. Microstructural changes in skeletal texture coincide with higher C/N ratios (+0.8) and isotope-based amino acid degradation parameters (e.g. ΣV ≥ 3), indicating extensive degradation of seawater-exposed gorgonin. However, interior gorgonin (>10 mm) retained amino acid molecular compositions (with exception of major Glycine loss) and bulk and amino acid-specific isotopic values that were similar to live-collected specimens. These results indicate that compound-specific isotope analysis of amino acids can reconstruct paleo-oceanographic biogeochemical and ecosystem information in subfossil corals beyond a clear diagenetic horizon, which is easily identifiable from an evaluation of C/N ratios together with the ΣV degradation proxy.

58 GEOSCIENCES↗

Accuracy and precision of ESI-Orbitrap-IRMS observations of hours to tens of hours via reservoir injection

Here, orbitrap isotope ratio mass spectrometry (Orbitrap-IRMS) has recently been applied to high-precision, natural-abundance isotope ratio measurements of a diverse range of compounds, including amino acids, oxyanions, fatty acids, and metals. These measurements can characterize many isotope ratios simultaneously at high (≈1.0‰) precision. In a successful experiment, observed precision will track the shot-noise limit and be limited by experimental time. Some isotope ratios, for example those involving 17 O in organic compounds or multiply-substituted (‘clumped’) isotopologues, require experimental times of hours to tens of hours to achieve desired precision, while current sample introduction techniques focus on observations on the order of seconds to tens of minutes. In this study, we characterize Orbitrap-IRMS performance for three long duration measurements (individual acquisitions ≥1 h and as long as 24 h) using an automated reservoir injection system coupled to a Q Exactive HF Orbitrap with an electrospray ionization (ESI) source. First, we characterize long-term intra-measurement stability through a 24-h long measurement of acetone. We report the following isotope ratios and precisions (as acquisition errors, errors on the observed ratio within this measurement (σ AE )): 13 C/ 12 C (σ AE = 0.07‰), 17 O/ 16 O (σ AE = 1.1‰), 18 O/ 16 O (σ AE = 0.3‰), and 13 C 13 C/ 12 C (σ AE = 0.65‰). The σ AE of each tracks the shot noise limit throughout and is limited by the challenging conditions (high resolution and low numbers of ions per scan) required for 17 O/ 16 O measurement in the presence of 13 C via Orbitrap. Second, we characterize inter-measurement stability via a sequence of seven 75-min analyses of perchlorate. We observe the following ratios and acquisition errors: 37 Cl/ 35 Cl (σ AE = 0.09‰); 17 O/ 16 O (σ AE = 1.6‰); 18 O/ 16 O (σ AE = 0.7‰), 37 Cl 17 O/ 35 Cl 16 O (σ AE = 2.7‰), and 37 Cl 18 O/ 35 Cl 16 O (σ AE = 1.2‰). However, we find that inter-measurement drift between acquisitions limits our accuracy and precision for standardized measurements (i.e., error on reported δ values) to ≈1‰ for the 37 Cl/ 35 Cl measurement. Hence, the benefits of low σ AE may not be fully realized. Third, we demonstrate accuracy via sample/standard comparisons of a methionine sample with 13 C enrichment of ≈20‰ relative to a known standard. Using a sequence of seven 60-min analyses, we recover the following isotope ratios and standardized precisions (i.e., error on reported δ values, denoted propagated acquisition errors, σ PAE ): 33 S/ 32 S (σ PAE = 1.0‰), 34 S/ 32 S (σ PAE = 0.7‰), 15 N/ 14 N (σ PAE = 2.1‰), 2 H/ 1 H (σ PAE = 3.2‰), 13 C/ 12 C (σ PAE = 0.4‰), 18 O/ 16 O (σ PAE = 1.6‰), & 13 C 13 C/ 12 C (σ PAE = 2.8‰) with confirmation of accurate results for the known 13 C/ 12 C and 13 C 13 C/ 12 C enrichments. Together, our results demonstrate the viability of Orbitrap-IRMS for long duration measurements of diverse sample types via an automated reservoir injection system. Inter-measurement stability remains a challenge; we expect our methods to be most applicable to extended measurements of hard-to-observe properties, such as 17 O in organics and clumped isotopologues.

58 GEOSCIENCES↗

Ecosystem–scale biogeochemical fluxes from three bioenergy crop candidates: How energy sorghum compares to maize and miscanthus

Perennial crops have been the focus of bioenergy research and development for their sustainability benefits associated with high soil carbon (C) and reduced nitrogen (N) requirements. However, perennial crops mature over several years and their sustainability benefits can be negated through land reversion. A photoperiod–sensitive energy sorghum (Sorghum bicolor) may provide an annual crop alternative more ecologically sustainable than maize (Zea mays) that can more easily integrate into crop rotations than perennials, such as miscanthus (Miscanthus × giganteus). This study presents an ecosystem–scale comparison of C, N, water and energy fluxes from energy sorghum, maize and miscanthus during a typical growing season in the Midwest United States. Gross primary productivity (GPP) was highest for maize during the peak growing season at 21.83 g C m –2 day –1 , followed by energy sorghum (17.04 g C m –2 day –1 ) and miscanthus (15.57 g C m –2 day –1 ). Maize also had the highest peak growing season evapotranspiration at 5.39 mm day –1 , with energy sorghum and miscanthus at 3.81 and 3.61 mm day –1 , respectively. Energy sorghum was the most efficient water user (WUE), while maize and miscanthus were comparatively similar (3.04, 1.75 and 1.89 g C mm –1 H 2 O, respectively). Maize albedo was lower than energy sorghum and miscanthus (0.19, 0.26 and 0.24, respectively), but energy sorghum had a Bowen ratio closer to maize than miscanthus (0.12, 0.13 and 0.21, respectively). Nitrous oxide (N 2 O) flux was higher from maize and energy sorghum (8.86 and 12.04 kg N ha –1 , respectively) compared with miscanthus (0.51 kg N ha –1 ), indicative of their different agronomic management. Furthermore, these results are an important first look at how energy sorghum compares to maize and miscanthus grown in the Midwest United States. This quantitative assessment is a critical component for calibrating biogeochemical and ecological models used to forecast bioenergy crop growth, productivity and sustainability.

09 BIOMASS FUELS↗

Toward sustainable production of N-containing products via nonthermal plasma-enhanced conversion of natural gas resources

Nonthermal plasmas can directly activate and cleave the strong chemical bonds in molecular nitrogen and methane to facilitate the transformation of these inherently stable molecules through the application of electrical energy. Here, we report a low temperature, atmospheric pressure, nonthermal plasma for the “one-pot” synthesis of olefins, alkynes, higher molecular weight hydrocarbons, ammonia, and nitrogen-containing liquids from a representative shale gas feed enriched with nitrogen. Furthermore, we reproducibly observe a wide range of valuable and synthetically challenging gas-phase and liquid-phase products containing C-N, C-C, and N-H bonding by controlling the N 2 concentration in the inlet feed stream. In nitrogen-lean regimes, hydrocarbon products dominate (e.g., ethylene, acetylene, etc.), while nitrogen-rich regimes promote incorporation of nitrogen into the products, leading to the formation of ammonia and liquid products containing a variety of functionalities (e.g., nitriles, amines, heterocycles). High resolution electrospray ionization mass spectrometry was used to measure molecular weights and identify the chemical formulas of the liquid products. Van Krevelen diagrams were created and showed many products with compositions around H/C = 2 and N/C = 0.5, indicating the potential importance of intermediate species with these ratios for liquid formation (e.g., CH 3 CN + H).

03 NATURAL GAS↗

Evaluating the Persistence of Soil Carbon After a 30-Year Nitrogen Fertilization Experiment at the Fernow Experimental Forest, WV

We sampled soils in a previously nitrogen (N)-fertilized watershed (Watershed 3), which received 35 kg N per hectare annually for 30 years, and a reference watershed (Watershed 7), 4 years after the end of a 30-year N fertilization experiment at the Fernow Experimental Forest in West Virginia. As N deposition has reduced soil pH and plant carbon (C) investments into the rhizosphere, we compared the extent to which removing these potential limitations to microbial decomposition by increasing soil pH, adding artificial root exudates, or elevating soil temperature would increase microbial decomposition (and soil C losses) in soils that have and have not received excess N inputs. As such, we incubated soils with and without the addition of artificial root exudates and dolomitic lime (2 amendment treatments and 1 untreated control), at three different temperatures (15, 20, and 25 C) to simulate warming. We measured soil respiration, enzyme activity (acid phosphatase, N -acetyl-β-glucosaminidase, beta-glucosidase, phenol oxidase, and peroxidase), and microbial biomass carbon in a 15-week microcosm experiment. All of the datasheets include the metadata for all of the treatment combinations from this incubation experiment (ID, incubation temperature, treatment, watershed).The "Soil_Chemistry_Data.csv" data includes (1) the ratio of dry soil weight (g) by wet (or fresh) soil weight (g) after 72 hours at 65 C, (2) the wet (or fresh) weight of the soil samples used to determine soil pH, and (3) soil pH, which was measured in CaCl2. Detailed methods for the measurements of soil pH are described in the datasheet itself.The "Respiration_Data.csv" data includes (1) respiration day for the measurement, and (2) cumulative CO2 respiration (mmol) measured in the microcosms on specific days.The "Microbial_Biomass_Data.csv" data includes (1) mmol microbial biomass carbon per g (dry weight) of soil in each microcosm.The "Enzyme_Data.csv" data includes (1) all extracellular soil enzyme activity (N-acetyl-glucosaminidase (NAG), acid phosphatase (AP), β-glucosidase (BG), phenol oxidase and peroxidase) that we measured in our microcosms.

54 ENVIRONMENTAL SCIENCES↗

Strangeness-correlations on the pseudocritical line in ( 2 + 1 )-flavor QCD

We present some lattice QCD results on first ( χ 1 i ) and second ( χ 2 i ) cumulants of and correlations ( χ 11 i j ) among net baryon-number ( B ), strangeness ( S ) and electric charge ( Q ) along the pseudocritical line [ T p c ( μ B ) ] in the temperature ( T )–baryon chemical potential ( μ B ) phase diagram of ( 2 + 1 )-flavor QCD. We point out that violations of sum rules among second order cumulants, which hold in the isospin symmetric limit of vanishing electric charge chemical potential, are small along the T p c ( μ B ) for the entire range of μ B covered in the RHIC beam energy scan. For the strangeness neutral matter produced in heavy-ion collisions this leads to a close relation between χ 11 B S and χ 11 Q S . We compare lattice QCD results for χ 11 B S / χ 2 S along the T p c ( μ B ) line with preliminary experimental measurements of χ 11 B S / χ 2 S for collision energies 7.7 GeV ≤ s N N ≤ 62.4 GeV . While we find good agreements for s N N ≥ 39 GeV , differences are sizeable at smaller values of s N N . Moreover, we compare lattice QCD results for the ratio of the strangeness ( μ S ) to baryon ( μ B ) chemical potentials, which define a strangeness neutral system with fixed electric charge to baryon number density, with experimental results obtained by the STAR collaboration for μ S / μ B using strange baryon yields on the freeze-out line. Finally, we determine the baryon chemical potential at the freeze-out ( μ B f ) by comparing χ 1 B / χ 2 B along the T p c ( μ B ) with the experimentally measured net-proton cumulants χ 1 p / χ 2 p . We find that { μ B f , T p c ( μ B f ) } are consistent with the freeze-out parameters of the statistical-model fits to experimentally measured hadron yields for s N N ≥ 11.5 GeV . Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Bottom‐Up Synthesized Nanoporous Graphene Transistors

Abstract Nanoporous graphene (NPG) can exhibit a uniform electronic band gap and rationally‐engineered emergent electronic properties, promising for electronic devices such as field‐effect transistors (FETs), when synthesized with atomic precision. Bottom‐up, on‐surface synthetic approaches developed for graphene nanoribbons (GNRs) now provide the necessary atomic precision in NPG formation to access these desirable properties. However, the potential of bottom‐up synthesized NPG for electronic devices has remained largely unexplored to date. Here, FETs based on bottom‐up synthesized chevron‐type NPG (C‐NPG), consisting of ordered arrays of nanopores defined by laterally connected chevron GNRs, are demonstrated. C‐NPG FETs show excellent switching performance with on–off ratios exceeding 10 4 , which are tightly linked to the structural quality of C‐NPG. The devices operate as p‐type transistors in the air, while n‐type transport is observed when measured under vacuum, which is associated with reversible adsorption of gases or moisture. Theoretical analysis of charge transport in C‐NPG is also performed through electronic structure and transport calculations, which reveal strong conductance anisotropy effects in C‐NPG. The present study provides important insights into the design of high‐performance graphene‐based electronic devices where ballistic conductance and conduction anisotropy are achieved, which could be used in logic applications, and ultra‐sensitive sensors for chemical or biological detection.

Mutlu, Zafer↗

Detailed chemistry modeling of rotating detonations with dilute n -heptane sprays and preheated air

Utilization of liquid fuels is crucial to enabling commercialization of rotating detonation engines (RDE) in the near future. In this study, Eulerian-Lagrangian simulations are conducted for rotating detonative combustion with dilute n-heptane sprays and preheated air. Two-dimensional flattened configuration is used and a skeletal chemical mechanism with 44 species and 112 elementary reactions for n-heptane combustion is adopted. The flow structure, droplet distribution, and thermochemical parameters in the refill zone are first analyzed. It is shown that the mixture in the refill zone is heterogeneous, including evaporating droplets, vapor, and air. When the total temperature is below 950 K, the average equivalence ratio increases with the total temperature. When it is higher than 950 K, the average equivalence ratio is almost constant. Subsequently, the chemical explosive mode analysis is applied to identify the controlling reactions and dominant combustion modes in the fuel refill zone and reaction fronts. Results demonstrate that the initiation reaction (R104: n-C 7 H 16 + O 2 2-C 7 H 15 + HO 2 ) and low-temperature reaction (R107: RO 2 R'O 2 H) are dominant in the upstream and downstream of the refill zone, respectively. The intermediate species from low-temperature chemistry, R'O 2 H, is found to be important for the chemical explosive mode in the undetonated mixture. The influence of species diffusion and dispersed droplets is further analyzed. Results show that vapor autoignition facilitated by droplet evaporation occurs in the refill zone. Finally, the effects of the air total temperature on the detonation propagation speed and RDE propulsion performance are investigated. Further, it is found that the detonation propagation speed and specific impulse increase with air total temperature. The total pressure ratio first increases and then decreases as the air total temperature increases. Moreover, when the total temperature of the preheated air is above 1,300 K, the effects of low-temperature chemistry are negligible.

33 ADVANCED PROPULSION SYSTEMS↗

Observation of N-rich solid-electrolyte interphase by ToF-SIMS.

Formation of a stable solid electrolyte interphase (SEI) between lithium electrodes and electrolyte upon multiple charge/discharge cycles is crucial to a long-term lithium-ion battery performance. Addition of LiNO3 to lithium bis (fluorosulfonyl) imide/poly(ethylene oxide) (LiFSI/PEO) electrolyte leads to a durable SEI that is electrically insulating yet highly conductive to Li ions, chemically and electrochemically stable, physically uniform, and mechanically robust. ToF-SIMS was used here in combination with sputtering by a gaseous cluster ion beam (GCIB) to examine how the addition of a small proportion of LiNO3 to the LiFSI/PEO electrolyte affects the SEI composition. Negative ion ToF-SIMS spectra of the cycled samples display an intense m/z 26 peak associated with the SEI. Exact mass assignments and isotopic ratios indicate that this peak should be assigned as (CN-)-C-12, with little to no negative secondary ion signal arising from (LiF-)-Li-7. This CN- signal appears to arise from an N-rich portion of the SEI adjacent to the Li electrode that is depleted in LiF relative to the bulk electrolyte. The dearth of LiF- (and LiF+ from the positive ion spectra) is unexpected because LiF has been identified in the SEI in similar samples. Finally, GCIB sputtering indicates that the SEI adheres more strongly to the Li electrode than to the LiFSI/PEO electrolyte.

Shavandi, Seyedeh Reyhaneh↗

Crystal structures of polymerized lithium chloride and dimethyl sulfoxide in the form of {2LiCl·3DMSO} n and {LiCl·DMSO} n

Two novel LiCl·DMSO polymer structures were created by combining dry LiCl salt with dimethyl sulfoxide (DMSO), namely, catena-poly[[chlorido­lithium(I)]-μ-(dimethyl sulfoxide)-κ 2 O:O-[chlorido­lithium(I)]-di-μ-(dimethyl sulfoxide)-κ 4 O:O], [Li 2 Cl 2 (C 2 H 6 OS) 3 ]n, and catena-poly[lithium(I)-μ-chlorido-μ-(dimethyl sulfoxide)-κ 2 O:O], [LiCl(C 2 H 6 OS)]n. The initial synthesized phase had very small block-shaped crystals (<0.08 mm) with monoclinic symmetry and a 2 LiCl: 3 DMSO ratio. As the solution evaporated, a second phase formed with a plate-shaped crystal morphology. After about 20 minutes, large (>0.20 mm) octa­hedron-shaped crystals formed. The plate crystals and the octa­hedron crystals are the same tetra­gonal structure with a 1 LiCl: 1 DMSO ratio. These structures are reported and compared to other known LiCl·solvent compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of climate and disturbance on nutrient fluxes and stoichiometry in mixed-conifer forests

Elucidating climatic impacts on stream nutrient export and stoichiometry will improve the understanding of forest carbon (C) storage in a warmer world. We constructed C, nitrogen (N), and phosphorus (P) budgets in four watersheds within a rain-snow transition site and another four within a higher-elevation, snow-dominated site, in California’s mixed-conifer zone. We used these two sites in a space-for-time substitution to assess the potential effects of warming on nutrient cycles in currently snow-dominated areas that will become more rain-dominated. During a non-drought period (water year (WY) 2004 – 2011), mean annual stream exports of C and N in particulate forms at the transition site were double that at the snow-dominated site, suggesting that sediment-associated nutrient losses may increase with warming. The transition site had 12% lower N but double the P content in mineral horizons, lower N:P mass ratios in organic horizons, and lower stream export of dissolved inorganic N than the snow-dominated site. Furthermore, these differences suggest that montane forests may receive lower supply of N relative to P with warming. In addition, given strong interests in forest thinning to increase drought resiliency, we examined changes in stream nutrient export after thinning and during a major drought period (WY 2013 – 2015). Stream exports of C, N, and P were similar between unthinned and thinned watersheds during drought, suggesting negligible thinning impacts on stream nutrient export during excessively dry periods. Taken together, our results suggest that as the climate warms, California’s montane forests may lose more nutrients through erosion and receive less N input than P.

54 ENVIRONMENTAL SCIENCES↗

Biogeochemical Fluxes for Three Bioenergy Crops

Perennial crops have been the focus of bioenergy research and development for their sustainability benefits associated with high soil carbon (C) and reduced nitrogen (N) requirements. However, perennial crops mature over several years and their sustainability benefits can be negated through land reversion. A photoperiod‐sensitive energy sorghum (Sorghum bicolor) may provide an annual crop alternative more ecologically sustainable than maize (Zea mays) that can more easily integrate into crop rotations than perennials, such as miscanthus (Miscanthus × giganteus). This study presents an ecosystem‐scale comparison of C, N, water and energy fluxes from energy sorghum, maize and miscanthus during a typical growing season in the Midwest United States. Gross primary productivity (GPP) was highest for maize during the peak growing season at 21.83 g C m−2 day−1, followed by energy sorghum (17.04 g C m−2 day−1) and miscanthus (15.57 g C m−2 day−1). Maize also had the highest peak growing season evapotranspiration at 5.39 mm day−1, with energy sorghum and miscanthus at 3.81 and 3.61 mm day−1, respectively. Energy sorghum was the most efficient water user (WUE), while maize and miscanthus were comparatively similar (3.04, 1.75 and 1.89 g C mm−1 H2O, respectively). Maize albedo was lower than energy sorghum and miscanthus (0.19, 0.26 and 0.24, respectively), but energy sorghum had a Bowen ratio closer to maize than miscanthus (0.12, 0.13 and 0.21, respectively). Nitrous oxide (N2O) flux was higher from maize and energy sorghum (8.86 and 12.04 kg N ha−1, respectively) compared with miscanthus (0.51 kg N ha−1), indicative of their different agronomic management. These results are an important first look at how energy sorghum compares to maize and miscanthus grown in the Midwest United States. This quantitative assessment is a critical component for calibrating biogeochemical and ecological models used to forecast bioenergy crop growth, productivity and sustainability.

Field Data↗

Continuous liquid-phase synthesis of nickel phosphide nanoparticles in a helically coiled tube reactor

The continuous liquid phase synthesis of nickel phosphide (Ni 2 P) nanoparticles was studied in a helically coiled tube (HCT) reactor both in single-phase and two-phase slug flows. The reactants were nickel acetylacetonate and tri-n-octylphosphine (TOP) in a 1-octadecane solvent. For the single-phase mode, various parameters such as reaction temperature, residence time, TOP concentration, and P/Ni ratio were studied. It was found that lower temperatures of 320 and 340 °C resulted in the formation of mixed Ni 12 P 5 and Ni 2 P phases, while a higher temperature of 360 °C gave mostly Ni 2 P, with particle sizes increasing from 28 to 42 nm. Upon varying the contact time between 88 and 340 s at 360 °C, a likely sequence of reaction involved an amorphous phase that was transformed in parallel to Ni, Ni 12 P 5 , and Ni 2 P. When the flow in the HCT was changed to a two-phase slug flow by using N 2 to split the continuous liquid phase into small liquid columns, the product was nearly 100% Ni 2 P and the particle size was as small as 3–4 nm. This was attributed to the enhanced mass transfer in the small liquid columns of the slug flow that led to higher reaction rates. Finally, it is highlighted that the HCT operated in a slug flow is an efficient and continuous method for the fabrication of nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global meta-analyses show that conservation tillage practices promote soil fungal and bacterial biomass

Despite a large number of published studies, a consensus has not been reached on how soil fungal and bacterial biomass, the primary regulators for soil organic matter decomposition, respond to conservation tillage, i.e., no or reduced tillage with >30 % residue covers. In this study we conducted a global meta-analysis of 60 studies to investigate the effects of conservation versus conventional tillage on soil fungal and bacterial biomass, fungal-to-bacterial ratios, and their relationship to other soil properties. Our results showed that conservation tillage greatly increased overall soil microbial biomass (37 %), including both fungal (31 %) and bacterial biomass (11 %), especially in top 20-cm soils or no-till agro-ecosystems, but conservation tillage effects were non-significant in sandy soils. Regardless of soil depth and tillage intensity, fungal-to-bacterial ratios did not greatly increase in conservation tillage scenarios, but were significantly affected by soil texture. Conservation tillage was also associated with significant increases in soil total C and N, and reduced soil pH. Increases in soil total C were positively associated with both fungal and bacterial biomass increases. Years under conservation tillage, time between last convention tillage to soil sampling, may indirectly affect fungal and bacterial biomass through soil C accumulation. Finally, our meta-analysis demonstrates that soil fungi and bacteria both respond positively to conservation tillage and are significantly associated with soil C content increase.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of inoculants on the fermentation characteristics and in vitro digestibility of reed canary grass ( Phalaris arundinacea L.) silage on the Qinghai‐Tibetan Plateau

Abstract To effectively use local available grass resources to cover the winter feed shortage on the Qinghai‐Tibetan Plateau, direct‐cut and wilted reed canary grass (RCG) silages were prepared by using a rolled‐bale system, and their ensiling characteristics and in vitro digestibility were studied. Silages were treated without (control) or with inoculants including LP ( Lactobacillus plantarum ), LPLB ( L. plantarum , L. buchneri ), and LPLBc ( L. plantarum , L. buchneri , and cellulase), and were stored at ambient temperature (5.7–14.6°C) for 90 days. Compared with control, the inoculated silages increased ( p < .05) lactic acid and acetic acid contents, and reduced ( p < .05) final pH value and ammonia‐N ratio of total N. The highest WSC content (41.2 g/kg DM) occurred for LPLB‐inoculated silage, whereas LPLBc‐treated silage displayed the lowest contents of NDF (522.9 g/kg DM) and ADF (275.5 g/kg DM). In addition, LPLBc‐inoculated silage had the highest in vitro gas production (51.0 ml/g DM), in vitro DM digestibility (619.3 g/kg DM), and metabolic energy (9.6 kJ/kg DM). These results confirmed that treatments with inoculants at ensiling could improve silage fermentation and in vitro digestibility of RCG, and this could be a potential winter feed for animals on the Qinghai‐Tibetan Plateau.

Chen, Liangyin↗

Natural Abundance Isotope Ratio Measurements of Organic Molecules Using 21 T FTICR MS

Subtle variations in stable isotope ratios at natural abundance are challenging to measure but can yield critical insights into biological, physical, and geochemical processes. Well established methods, particularly multi-collector, gas-source or plasma isotope ratio mass spectrometry (IRMS) are the gold standard for stable isotope measurement but inherent limitations in these approaches make them ill-suited to determining site-specific and multiply substituted isotopic abundances of all but a few compounds, or to characterizing mixtures or larger intact molecules. Additionally, Fourier transform mass spectrometry (FTMS), namely Orbitrap mass spectrometry, has recently demonstrated the ability to measure natural abundance isotope ratios with chemically informative accuracy and precision. Here, we report the first use of Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the accurate (<1‰) and precise (<1‰ standard error) simultaneous determination of $δ$ 13 C and $δ$ 15 N in caffeine isotopologues and provide a discussion of the critical instrumental parameters necessary to make such measurements. Finally, we report the ability to make these measurements with online liquid chromatography, expanding the ability of this technique to explore mixtures in the future.

07 ISOTOPE AND RADIATION SOURCES↗