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At least 343 records · Page 19

Impacts of Biopolymer Structural and Chemical Attributes on the Products Distributions of Pyrolyzed Loblolly Pine

This presentation evaluates the impact that biopolymer structural and chemical attributes of pyrolyzed loblolly pine has on product distributions, with a focus on how how the anatomical fractions lead to chemical variability, and then how this variability impacts conversion. As an example, bark and needles represent extreme compositional fractions, and these result in differences in pyrolysis yield.

biomass↗

Rewiring metabolism of Clostridium thermocellum for consolidated bioprocessing of lignocellulosic biomass poplar to produce short-chain esters

Consolidated bioprocessing (CBP) of lignocellulosic biomass uses cellulolytic microorganisms to enable enzyme production, saccharification, and fermentation to produce biofuels, biochemicals, and biomaterials in a single step. However, understanding and redirecting metabolisms of these microorganisms compatible with CBP are limited. Here, a cellulolytic thermophile Clostridium thermocellum was engineered and demonstrated to be compatible with CBP integrated with a Co-solvent Enhanced Lignocellulosic Fractionation (CELF) pretreatment for conversion of hardwood poplar into short-chain esters with industrial use as solvents, flavors, fragrances, and biofuels. The recombinant C. thermocellum engineered with deletion of carbohydrate esterases and stable overexpression of alcohol acetyltransferases improved ester production without compromised deacetylation activities. These esterases were discovered to exhibit promiscuous thioesterase activities and their deletion enhanced ester production by rerouting the electron and carbon metabolism. Ester production was further improved up to 80-fold and ester composition could be modulated by deleting lactate biosynthesis and using poplar with different pretreatment severity.

59 BASIC BIOLOGICAL SCIENCES↗

An Exploratory Approach Using Regression and Machine Learning in the Analysis of Mass Absorption Cross Section of Black Carbon Aerosols: Model Development and Evaluation

Mass absorption cross-section of black carbon (MAC BC ) describes the absorptive cross-section per unit mass of black carbon, and is, thus, an essential parameter to estimate the radiative forcing of black carbon. Many studies have sought to estimate MAC BC from a theoretical perspective, but these studies require the knowledge of a set of aerosol properties, which are difficult and/or labor-intensive to measure. We therefore investigate the ability of seven data analytical approaches (including different multivariate regressions, support vector machine, and neural networks) in predicting MAC BC for both ambient and biomass burning measurements. Our model utilizes multi-wavelength light absorption and scattering as well as the aerosol size distributions as input variables to predict MAC BC across different wavelengths. We assessed the applicability of the proposed approaches in estimating MAC BC using different statistical metrics (such as coefficient of determination (R 2 ), mean square error (MSE), fractional error, and fractional bias). Overall, the approaches used in this study can estimate MAC BC appropriately, but the prediction performance varies across approaches and atmospheric environments. Based on an uncertainty evaluation of our models and the empirical and theoretical approaches to predict MAC BC , we preliminarily put forth support vector machine (SVM) as a recommended data analytical technique for use. We provide an operational tool built with the approaches presented in this paper to facilitate this procedure for future users.

54 ENVIRONMENTAL SCIENCES↗

Using the Black Carbon Particle Mixing State to Characterize the Lifecycle of Biomass Burning Aerosols

The lifecycle of black carbon (BC)-containing particles from biomass burns is examined using aircraft and surface observations of BC mixing state for plume ages from ~15 minutes to 10 days. Because BC is non-volatile and chemically inert, changes in the mixing state of BC-containing particles are driven solely by changes in particle coating, which is mainly secondary organic aerosol (SOA). The coating mass initially increases rapidly (k = 0.84 hr-1), then remains growth relatively constant for 1 to 2 days as plume dilution no longer supports further growth, then decreases slowly until only ~30 % of the maximum coating mass remains after 10 days, (kloss = 0.011 hr-1). The mass ratio of coating-to-core for a BC-containing particle with a 100 nm mass- equivalent diameter BC core reaches a maximum of ~20 after a few hours and drops to ~5 after 10 days of aging. The initial increase in coating mass can be used to determine SOA formation rates. The slow loss of coating material, not captured in global models, comprises the dominant fraction of the lifecycle of these particles. Coating-to-core mass ratios of BC particles in the stratosphere are much greater than those in the free troposphere indicating a different lifecycle.

54 ENVIRONMENTAL SCIENCES↗

An attribution of the low single-scattering albedo of biomass burning aerosol over the southeastern Atlantic

Abstract. Aerosol over the remote southeastern Atlantic is some of the most sunlight-absorbing aerosol on the planet: the in situ free-tropospheric single-scattering albedo at the 530 nm wavelength (SSA530 nm) ranges from 0.83 to 0.89 within ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) aircraft flights from late August–September. Here we seek to explain the low SSA. The SSA depends strongly on the black carbon (BC) number fraction, which ranges from 0.15 to 0.4. Low organic aerosol (OA)-to-BC mass ratios of 8–14 and modified combustion efficiency values >0.975 point indirectly to the dry, flame-efficient combustion of primarily grass fuels, with back trajectories ending in the miombo woodlands of Angola. The youngest aerosol, aged 4–5 d since emission, occupied the top half of a 5 km thick plume sampled directly west of Angola with a vertically consistent BC:ΔCO (carbon monoxide) ratio, indicating a homogenization of the source emissions. The younger aerosol, transported more quickly off of the continent by stronger winds, overlaid older, slower-moving aerosol with a larger mean particle size and fraction of BC-containing particles. This is consistent with ongoing gas condensation and the coagulation of smaller non-BC particles upon the BC-containing particles. The particle volumes and OA:BC mass ratios of the older aerosol were smaller, attributed primarily to evaporation following fragmentation, instead of dilution or thermodynamics. The CLARIFY (CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017) aircraft campaign sampled aerosols that had traveled further to reach the more remote Ascension Island. CLARIFY reported higher BC number fractions, lower OA:BC mass ratios, and lower SSA yet larger mass absorption coefficients compared to this study's. Values from one ORACLES 2017 flight, held midway to Ascension Island, are intermediate, confirming the long-range changes. Overall the data are most consistent with continuing oxidation through fragmentation releasing aerosols that subsequently enter the gas phase, reducing the OA mass, rather than evaporation through dilution or thermodynamics. The data support the following best fit: SSA530nm=0.801+0055⋅(OA:BC) (r=0.84). The fires of southern Africa emit approximately one-third of the world's carbon; the emitted aerosols are distinct from other regional smoke emissions, and their composition needs to be represented appropriately to realistically depict regional aerosol radiative effects.

54 ENVIRONMENTAL SCIENCES↗

Effect of High-Temperature Stress on Plant Physiological Traits and Mycorrhizal Symbiosis in Maize Plants

Increasing high temperature (HT) has a deleterious effect on plant growth. Earlier works reported the protective role of arbuscular mycorrhizal fungi (AMF) under stress conditions, particularly influencing the physiological parameters. However, the protective role of AMF under high-temperature stress examining physiological parameters with characteristic phospholipid fatty acids (PLFA) of soil microbial communities including AMF has not been studied. This work aims to study how high-temperature stress affects photosynthetic and below-ground traits in maize plants with and without AMF. Photosynthetic parameters like quantum yield of photosystem (PS) II, PSI, electron transport, and fractions of open reaction centers decreased in HT exposed plants, but recovered in AMF + HT plants. AMF + HT plants had significantly higher AM-signature 16:1ω5cis neutral lipid fatty acid (NLFA), spore density in soil, and root colonization with lower lipid peroxidation than non-mycorrhizal HT plants. As a result, enriched plants had more active living biomass, which improved photosynthetic efficiency when exposed to heat. This study provides an understanding of how AM-mediated plants can tolerate high temperatures while maintaining the stability of their photosynthetic apparatus. This is the first study to combine above- and below-ground traits, which could lead to a new understanding of plant and rhizosphere stress.

59 BASIC BIOLOGICAL SCIENCES↗

Building Blocks from Biocrude: High-Value Methoxyphenols (Final Scientific/Technical Report)

Integrating biofuels production with bioproducts presents an opportunity to explore options for recovering high-value chemicals as additional revenue-generating products from biofuel conversion pathways. Thus, the overall objective of this project was to develop a comprehensive separation strategy to economically recover valuable methoxyphenols (MPs) consisting of guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-propylguaiacol, eugenol, and isoeugenol from biocrude as building blocks to demonstrate that bioproducts could enable cost-effective production of biofuels via integrated catalytic pyrolysis and hydroprocessing. The upgradability of the remaining biocrude fraction to biofuel after separation of the products was evaluated by hydrotreating. Finally, techno-economic analysis (TEA) was performed to examine the economic potential of recovering select MPs from biocrude in parallel with biofuels production.

09 BIOMASS FUELS↗

Mechanical and biochemical recovery of landfill waste in an underserved community

Historically in the United States, waste collected for recycling has been sold and shipped to processors in China. In 2013 and 2018, China introduced the Green Fence and National Sword policies which restricts the import of contaminated materials and banned the import of many recyclables. The cost of recycling in the United States has increased following these policy changes, which has led to many communities reducing their recycling programs or halting them altogether. Rural and underserved communities that don’t have resources to afford sophisticated recycling programs have been heavily impacted. Previous work at INL demonstrated that MSW is a potentially viable feedstock for both biochemical and thermochemical conversion. The goal of this project is to assess preprocessing tools that can produce consistent feedstocks that meet conversion specifications, remove problematic contaminants, and reduce the amount of waste that is landfilled. Municipal solid waste was collected from an underserved community in southeast Idaho, contaminants were characterized, and mechanically separated into two discrete fractions. The unit operations identified during mechanical separation trials will be mobilized to on-site with a goal of 50% recovery of paper and plastic waste.

09 - BIOMASS FUELS↗

Production and Catalytic Upgrading of 2,3-Butanediol Fermentation Broth into Sustainable Aviation Fuel Blendstock and Fuel Properties Measurement

With the increasing demand for sustainable supplies of aviation fuel and need to address climate change, new conversion technologies are needed to efficiently process biomass, produce high quality jet fuel blendstock, and meet carbon emission targets. This study demonstrates the synthesis, conditioning, and catalytic upgrading of 2,3-butanediol (BDO) fermentation broth into a jet fuel blendstock candidate. A high-titer 2,3-BDO fermentation broth (i.e., ~90 g/L) was produced at a 100-L scale and pretreated via nanofiltration to decrease the impurities level in the broth from 4.6 to 0.6 wt%. A novel process for catalytic upgrading of aqueous 2,3-BDO into a jet fuel blendstock candidate was developed, and each step was efficiently demonstrated. The catalytic steps include 1) 2,3-BDO dehydration into methyl ethyl ketone (MEK) over AlPO4, 2) MEK conversion into olefins over Zn1Zr10Ox, 3) oligomerization of olefins over a zeolite beta, and 4) hydrogenation over platinum/carbon. Both the model feed and real 2,3-BDO fermentation broth were tested for upgrading 2,3-BDO to MEK. With the real feed, a continuous loss of conversion (i.e., >50% loss over ~140 h time-on-stream [TOS]) was partly attributed to reversible deactivation from coking species. However, the conversion remained stable with the model feed, which demonstrates the efficiency of the first step for converting aqueous 2,3-BDO (10 wt% in water). For upgrading MEK to olefins, high selectivity to olefins (i.e., 82.5%) was obtained at high conversion levels (i.e., 93-98%) with stable conditions being achieved for > 70-hours TOS. Oligomerization of light olefins, which was demonstrated for > 270 h TOS, mainly led to the formation of dimers (C8-10) and trimers (C13-14). The oligomerized product was hydrogenated and distilled to recover the jet fraction (35 mass% or 40.9% carbon based yield), which consists mostly of desired isoalkanes (31.7 wt%), n-alkanes (24.5 wt%), and cycloalkanes (29.6 wt%). While some improvement is still needed to meet ASTM D7566 specifications for viscosity and final boiling point temperature, freezing point, density, aromatics content, and sulfur content of the jet blendstock candidate were within acceptable ranges, thus highlighting the potential of this process for production of jet fuel blendstock.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

Renewable Diesel Production through Stand-Alone and Co-Hydrotreating of Catalytic Fast Pyrolysis Oil

Catalytic Fast Pyrolysis (CFP) of biomass followed by hydrotreating can be used for the production of renewable transportation fuels, such as sustainable aviation fuel and renewable diesel, which can reduce the dependence on fossil fuels and help achieve greenhouse gas reduction goals. Stand-alone hydrotreating of CFP oil and co-hydrotreating of the CFP oil with straight-run diesel (SRD) showed potential to produce high-quality diesel products in this study. Stand-alone hydrotreating of CFP oil produced a diesel fraction with oxygen content < 0.1 wt.% and an indicated cetane number (ICN) of 45. Co-hydrotreating of CFP oil and SRD using a 1:4 volumetric ratio produced diesel products with 0.1 wt.% of oxygen and ICNs of 42-45. Compared to CoMo/Al2O3, NiMo/Al2O3 was a more attractive catalyst for co-hydrotreating of two streams, leading to a higher carbon efficiency, a higher selectivity of cycloalkanes, a higher ICN, and enhanced desulfurization. Compared to stand-alone hydrotreating of CFP oil, co-hydrotreating with SRD could be achieved at a less severe operating condition and it produced hydrotreated products with a higher carbon efficiency. Synergy between CFP oil and SRD during co-hydrotreating process was suggested by the better experimental results in comparison with theoretical interpolation results. Co-hydrotreating gave high biogenic carbon incorporations of 91%-97% as determined by C-14 analysis.

biomass↗

Chapter 4: "Waste"-to-Energy for Decarbonization - Transforming Nut Shells Into Carbon-Negative Electricity

This chapter presents a study demonstrating waste pistachio nut shells as a renewable feedstock for climate-friendly electricity generation via industrial gasification technology. The study includes biomass feedstock characterization (i.e., pistachio waste critical material attributes), process variability (i.e., bulk material handling), and overall operational reliability and conversion performance through extended testing. Additionally, techno-economic analysis (TEA) and life cycle assessment (LCA) were performed to assess the economic feasibility and environmental impact of the technology to transform agricultural waste to biopower. For processing pistachio waste material, among critical material attributes, fines content in the biomass (<1/4") had the largest potential to reduce the operating time of the gasifiers due to plugging. Pelletizing fines and co-feeding them with the mixed pistachio waste increased the average feed density, feed rate, and biochar production. Compared to pine wood chips, mixed pistachio waste yielded higher biochar quantity but slightly reduced quality. In general, a systematic Quality by Design methodology is the preferred approach for designing preprocessing and material conveyance systems, where a downstream technology (end user) for the produced intermediate is specified at the outset. TEA results show that the biochar production rate and selling price had an overwhelming impact on the modeled Minimum Electricity Selling Price (MESP), which ranged from 35.5 to 39.9 cents/kWh for the cases studied (16 h/day operational basis). Moreover, LCA results show that the valorization of pistachio shells for biopower generation is a "carbon negative" process that can help decarbonize the U.S. electricity grid. The specific carbon intensity was -0.29 to -0.71 kg CO2e/kWh, compared to 0.45 kg CO2e/kWh for the average U.S. electricity mix. Biochar production from pistachio waste as a potential means for carbon sequestration was a significant driver for the LCA. The highly stable biochar permanently sequesters a considerable fraction of biochar carbon in the ground, more than enough to offset the life cycle emissions, and can be a complementary climate change mitigation strategy.

bio-char↗

Coupling gas purging with inorganic carbon supply to enhance biohydrogen production with Clostridium thermocellum

Clostridium thermocellum is a desirable biocatalyst for biohydrogen production, with a native ability to simultaneously saccharify cellulose and to metabolize released cellodextrins for hydrogen production. During fermentation with C. thermocellum , partial pressures of two gases - CO 2 and H 2 - are critical drivers of overall reaction kinetics. Biohydrogen production is enhanced by maintaining a low hydrogen partial pressure, while high concentrations of dissolved CO 2 promote microbial biomass synthesis. Our study evaluates the inherent trade-offs between hydrogen stripping and inorganic carbon supply for optimized biohydrogen synthesis. Here, we find that nitrogen sparging at low flow rates increases hydrogen production when compared with an equivalent nitrogen overlay, but that high rates of nitrogen sparging inhibit cell growth and hydrogen production. Decreasing dissolved hydrogen partial pressure via nitrogen sparging also lowers the production of reduced metabolites, including lactate and ethanol. To address potential stripping of inorganic carbon from the production medium, we supplemented CO 2 to the sparging gas and co-optimized for gas flow rate and for the CO 2 fraction of the sparging gas. Total hydrogen production increased from 50 mmol∙L -1 in the base condition, when the bioreactor was sparged with 0.1 LPM of pure nitrogen, to 181.3 mmol∙L -1 when sparged with 1.3 LPM of 33 % CO 2 , demonstrating that biohydrogen production is highly sensitive to both parameters. Fine sensitivity of biohydrogen production to sparging conditions highlights the critical importance of bioreactor design and operation to achieve maximum H 2 removal without compromising inorganic carbon supply to bacterial central metabolism.

09 BIOMASS FUELS↗

Aromatic Monomer Production from Lignin Through Catalytic Carbon-Carbon Bond Cleavage

The conversion of lignin, the heterogeneous aromatic polymer found in terrestrial plant cell walls, into renewable bio-derived chemicals is critical to enable a viable lignocellulose-based bioeconomy. While lignin finds some limited industrial uses today, cost-effective and robust processes for the depolymerization of lignin to aromatic monomers would substantially expand lignin applications to larger markets, such as sustainable polymers and commodity chemicals. Historically, catalytic lignin depolymerization has focused on aryl-ether bond cleavage. A large fraction of aromatics in lignin, however, is linked by various recalcitrant carbon-carbon (C-C) bonds, which present a challenging substrate for depolymerization to aromatic monomers at high yields. To increase monomer yields above those accessible through aryl-ether bond cleavage alone, here we report that autoxidation catalysis cleaves C-C bonds in various lignin substrates with high atom economy. The catalyzed autoxidations of phenol-protected reductive catalytic fractionation (RCF) oil oligomers and hydrodeoxygenation (HDO) oil are described. The stream oxygenated monomers produced from the various lignin substrates are bioavailable as demonstrated by their bioconversion to cis,cis-muconate by engineered strains of Pseudonomas putida.

autoxidation↗

Data for Application of Time-Domain 1H NMR for Investigating Dynamics of Vegetative Lipids in Bioenergy Crops at Different Developmental Stages

Sweet sorghum is typically cultivated for the food and fodder market. Recently, sweet sorghum varieties are being metabolically transitioned to enhance energy density by accumulating oil droplets in their vegetative tissues for bioenergy applications. Owing to the high biomass yield of sorghum, the transgenic lines can compete with oil-seed crops for biodiesel yield per unit area. In the initial phase of transgenic development, a high-throughput phenotyping method can bridge the gap between the production pipeline and analysis to improve the efficiency of the process. To meet the requirement, the present study extends the application of time-domain 1H-NMR spectroscopy for rapid quantification and characterization of the total in-situ lipids of sweet sorghum ‘ramada’ to lay the groundwork for analyzing the upcoming large quantity of transgenic samples. NMR technology has been successfully established for analyzing lipid contents of vegetative tissues of non-transgenic variety. The multiexponential analysis of spin-lattice (T1) relaxation spectra obtained from TD-NMR aided the investigation of the dynamics of the free and bound lipid fraction with plant development. The total lipid concentration of bagasse and leaves of non-transgenic sweet sorghum remained unchanged throughout the plant development. Leaves displayed a higher percentage of bound lipids as compared to bagasse. A significant variation in the lipid concentration of juice was observed at the different growth stages with a maximum lipid accumulation of 1.21 ± 0.04% w/w at the boot stage that decreased with further maturity of the plant.

Biomass Analytics↗

Manufacturing of Continuous Microporous Polymeric Fibers for Separation Applications

Polyolefin plastic waste, particularly polypropylene, is one of the most prevalent components in the plastic waste stream generated globally. However, only a small fraction of this waste is recycled and reintegrated into second applications. These materials have significant embedded energy that could be used for additional productivity if recycled properly. Therefore, there is a critical need to develop scalable processing techniques with high throughput to effectively recycle it. We report the continuous manufacturing of microporous fibers using waste polypropylene plastic and melt-processable lignin, a plant biomass constituent produced as a byproduct in paper mills or biorefineries, as a template to create pores. Further, these filaments with hierarchical porosity─created by controlled microphase separation during high-speed extensional flow followed by removal of lignin─exhibit exceptional capillary action for hydrophobic liquids. The resulting porous fibers can be used for various separation applications. For example, the oil uptake of the fibers is 9.59 ± 0.82 g/g for applications in oil recovery in bodies of water. In addition, polyethylenimine infiltration within these nanoporous fibers introduces cyclic room temperature sorption and thermal desorption potential of acidic gases such as CO 2 in a bench-scale experiment. The fibers exhibit multiple cycles of CO 2 absorption, with a range of 0.15 to 0.17 mmol/g. Thus, these polyethylenimine-infiltered nanoporous polypropylene fibers can also be used in removing acidic gases from a gas mixture.

36 MATERIALS SCIENCE↗

Which Plant Traits Increase Soil Carbon Sequestration? Empirical Evidence From a Long‐Term Poplar Genetic Diversity Trial

Plants play a key role in mediating soil response to global change, and breeding or engineering crops to increase soil organic carbon (SOC) storage is a potential route to land-based carbon dioxide removal in agricultural systems. However, due to limited observational datasets plus shifting paradigms of SOC stabilization, it is unclear which plant traits are most important for enhancing different types of soil organic matter. Existing long-term common gardens of genetically diverse plant populations may provide an opportunity to evaluate biological controls on SOC, separate from environmental or management variability. Here we report on soil and root chemical data collected for 24 genotypes within a 13-year-old common garden in northwestern Oregon planted with a large natural variant population of Populus trichocarpa. Fractionating surface soil (0–15 cm) revealed substantial variation in stocks of mineral-associated organic matter (MAOM; 18–67 t C/ha) and particulate organic matter (POM; 2–22 t C/ha). Tree genotype explained 24% and 26% of the MAOM and POM stock variability, respectively, after controlling for background variability. We found minimal association between SOC concentration and either aboveground tree productivity or root biomass recalcitrance (C/N ratios and lignin content). In contrast, root elemental content appeared influential for MAOM-C concentration, which showed a strong positive association with root aluminum (Al) and a strong negative association with root boron (B) and magnesium (Mg). Furthermore, root concentrations of these elements were highly heritable (57%–78%) and not simply a reflection of background variation in soil elemental concentrations. We estimate that surface SOC stocks under these 24 genotypes have diverged at rates of up to 1.2–4.3 t C/ha/year. These results suggest that long-term genetic diversity trials have value for elucidating biological controls on soil organic matter dynamics, and that traits associated with root elemental content may be a useful target for enhancing biosequestration.

biomass recalcitrance↗

Method and system embodiments for converting ethanol to para-xylene and ortho-xylene

Disclosed herein are embodiments of a method and system for converting ethanol to para-xylene. The method also provides a pathway to produce terephthalic acid from biomass-based feedstocks. In some embodiments, the disclosed method produces p-xylene with high selectivity over other aromatics typically produced in the conversion of ethanol to xylenes, such as m-xylene, ethyl benzene, benzene, toluene, and the like. And, in some embodiments, the method facilitates the ability to use ortho/para mixtures of methylbenzyaldehyde for preparing ortho/para xylene product mixtures that are amendable to fractionation to separate the para- and ortho-xylene products thereby providing a pure feedstock of para-xylene that can be used to form terephthalic anhydride and a pure feedstock of ortho-xylene that can be used for other purposes, such as phthalic anhydride.

Ramasamy, Karthikeyan K.↗

Method and system embodiments for converting ethanol to para-xylene and ortho-xylene

Disclosed herein are embodiments of a method and system for converting ethanol to para-xylene. The method also provides a pathway to produce terephthalic acid from biomass-based feedstocks. In some embodiments, the disclosed method produces p-xylene with high selectivity over other aromatics typically produced in the conversion of ethanol to xylenes, such as m-xylene, ethyl benzene, benzene, toluene, and the like. And, in some embodiments, the method facilitates the ability to use ortho/para mixtures of methylbenzyaldehyde for preparing ortho/para xylene product mixtures that are amendable to fractionation to separate the para- and ortho-xylene products thereby providing a pure feedstock of para-xylene that can be used to form terephthalic anhydride and a pure feedstock of ortho-xylene that can be used for other purposes, such as phthalic anhydride.

Ramasamy, Karthikeyan Kallupalayam↗