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DOE OSTI2023

Shift in Peaks of PAH-Associated Health Risks From East Asia to South Asia and Africa in the Future

Lung cancer risk from exposure to ambient polycyclic aromatic hydrocarbons (PAHs) is expected to change significantly by 2050 compared to 2008 due to changes in climate and emissions. Integrating a global atmospheric chemistry model, a lung cancer risk model, and plausible future emissions trajectories of PAHs, we assess how global PAHs and their associated lung cancer risk will likely change in the future. Benzo(a)pyrene (BaP) is used as an indicator of cancer risk from PAH mixtures. From 2008 to 2050, the population-weighted global average BaP concentrations under all RCPs consistently exceeded the WHO-recommended limits, primarily attributed to residential biofuel use. Peaks in PAH-associated incremental lifetime cancer risk shift from East Asia (4 × 10 –5 ) in 2008 to South Asia (mostly India, 2–4 × 10 –5 ) and Africa (1–2 × 10 –5 ) by 2050. In the developing regions of Africa and South Asia, PAH-associated lung cancer risk increased by 30–64% from 2008 to 2050, due to increasing residential energy demand in households for cooking, heating, and lighting, the continued use of traditional biomass use, increases in agricultural waste burning, and forest fires, accompanied by rapid population growth in these regions. Due to more stringent air quality policies in developed countries, their PAH lung cancer risk substantially decreased by ~80% from 2008 to 2050. Climate change is likely to have minor effects on PAH lung cancer risk compared to the impact of emissions. Future policies, therefore, need to consider efficient combustion technologies that reduce air pollutant emissions, including incomplete combustion products such as PAH.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Theoretical studies of chemical reactions related to the formation and growth of polycyclic aromatic hydrocarbons (PAH) and molecular properties of their key intermediates (Final Progress Report)

The formation mechanisms of polycyclic aromatic hydrocarbons, (PAHs) – organic molecules carrying fused benzene rings – are of great interest to scientists and engineers due to their importance in combustion chemistry and astrochemistry. On Earth, PAHs are largely produced in incomplete combustion of fossil fuel and are considered as critical precursors to unwanted soot particles leading to combustion inefficiency and causing air pollution along with detrimental health effects. Simple PAH molecules initially formed in the gas phase, are further involved in a build-up process in combustion flames leading to larger PAH, bowl-shaped nanostructures, fullerenes, and solid-phase species including carbonaceous dust, graphene particles, and soot. In deep space, PAH and their derivatives are potential key intermediates and nucleation sites leading eventually to carbonaceous nanoparticles (“interstellar grains”). Therefore, the understanding of the key processes in the synthesis of PAHs along with their precursors and their degradation mechanisms in combustion systems and in interstellar, circumstellar, and planetary atmospheric environments will provide critical insights into how complex aromatic structures, carbonaceous nanoparticles, and fullerenes are formed and destroyed. Achieving this understanding is an important step in the development of the efficient combustion processes and of the ecofriendly devices with reduced environmental pollution as well as technological strategies for the production of hydrogen and solid carbon through thermal or plasma-assisted pyrolysis of natural gas and biomass. Also, the understanding of the key processes of PAH and soot growth will help in our comprehension of chemical evolution in the universe. Detailed information on the mechanisms and reliable rate constants of the key elementary chemical reactions involved in PAH formation and destruction processes and in inception of soot particles is often missing, with the main deficiencies being the absence of temperature- and pressure-dependent rate constants for the broad range of conditions occurring in various terrestrial and interstellar processes and the lack of data on the reaction products and their branching ratios. Complementary to experimental studies, these gaps in knowledge can be filled by using quantum chemical calculations of reaction potential energy surfaces providing us with accurate energies of reaction products, intermediates, and transition states, revealing the reaction mechanism, and giving the molecular properties required to compute rate constants for relevant reaction steps and product branching ratios using the RRKM-Master Equation (ME) method. Molecular dynamics (MD) simulations can be used in cases when a reaction rate cannot be properly described by statistical theories. During the terminal renewal project period we employed these ab initio/RRKM-ME and MD approaches to complete our studies on several key reactions relevant to the formation/growth of PAH and inception of soot particles including (1) the reaction mechanism and kinetics of the resonance stabilized fulvenallenyl radical with propargyl and C 3 H 4 isomers; (2) the reaction mechanism and kinetics for the C + indene and C 2 + styrene reactions producing naphthyl or azulenyl radicals in low-temperature environments; (3) the MD study of non-equilibrium dimerization of acepyrene and coronene and its radical. The information derived from our theoretical calculations contributed to a better fundamental understanding of the reaction mechanisms and provide missing critical kinetic data to improve combustion models of hydrocarbon fuels and astrochemical models of the growth of carbonaceous molecules and particles in cold molecular clouds, circumstellar envelopes, and planetary atmospheres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Competitive Metabolism of Polycyclic Aromatic Hydrocarbons (PAHs): An Assessment Using In Vitro Metabolism and Physiologically Based Pharmacokinetic (PBPK) Modeling

Humans are routinely exposed to complex mixtures such as polycyclic aromatic hydrocarbons (PAHs) rather than to single compounds, as are often assessed for hazards. Cytochrome P450 enzymes (CYPs) metabolize PAHs, and multiple PAHs found in mixtures can compete as substrates for individual CYPs (e.g., CYP1A1, CYP1B1, etc.). The objective of this study was to assess competitive inhibition of metabolism of PAH mixtures in humans and evaluate a key assumption of the Relative Potency Factor approach that common human exposures will not cause interactions among mixture components. To test this objective, we co-incubated binary mixtures of benzo[a]pyrene (BaP) and dibenzo[def,p]chrysene (DBC) in human hepatic microsomes and measured rates of enzymatic BaP and DBC disappearance. We observed competitive inhibition of BaP and DBC metabolism and measured inhibition coefficients (K i ), observing that BaP inhibited DBC metabolism more potently than DBC inhibited BaP metabolism (0.061 vs. 0.44 µM K i , respectively). We developed a physiologically based pharmacokinetic (PBPK) interaction model by integrating PBPK models of DBC and BaP and incorporating measured metabolism inhibition coefficients. The PBPK model predicts significant increases in BaP and DBC concentrations in blood AUCs following high oral doses of PAHs (≥100 mg), five orders of magnitude higher than typical human exposures. We also measured inhibition coefficients of Supermix-10, a mixture of the most abundant PAHs measured at the Portland Harbor Superfund Site, on BaP and DBC metabolism. We observed similar potencies of inhibition coefficients of Supermix-10 compared to BaP and DBC. Overall, results of this study demonstrate that these PAHs compete for the same enzymes and, at high doses, inhibit metabolism and alter internal dosimetry of exposed PAHs. This approach predicts that BaP and DBC exposures required to observe metabolic interaction are much higher than typical human exposures, consistent with assumptions used when applying the Relative Potency Factor approach for PAH mixture risk assessment.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2010

Recent Advances in Laboratory Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbons: PAHs in the Far Infrared

Over 25 years of observations and laboratory work have shown that the mid-IR spectra of a majority of astronomical sources are dominated by emission features near 3.3, 6.2, 7.7, and 11.2 microns, which originate in free polycyclic aromatic hydrocarbon (PAH) molecules. PAHs dominate the mid-IR emission from many galactic and extragalactic objects. As such, this material tracks a wide variety of astronomical processes, making this spectrum a powerful probe of the cosmos Apart from bands in the mid-IR, PAHs have bands spanning the Far-IR (FIR) and emission from these FIR features should be present in astronomical sources showing the Mid-IR PAH bands. However, with one exception, the FIR spectral characteristics are known only for a few neutral small PAHs trapped in salt pellets or oils at room temperature, data which is not relevant to astrophysics. Furthermore, since most emitting PAHs responsible for the mid-IR astronomical features are ionized, the absence of any experimental or theoretical PAH ion FIR spectra will make it impossible to correctly interpret the FIR data from these objects. In view of the upcoming Herschel space telescope mission and SOFIA's FIR airborne instrumentation, which will pioneer the FIR region, it is now urgent to obtain PAH FIR spectra. This talk will present an overview recent advances in the laboratory spectroscopy of PAHs, Highlighting the FIR spectroscopy along with some quantum calculations.

Mattioda, Andrew L.↗

DOE OSTI2022

Formation of PAHs, phenol, benzofuran, and dibenzofuran in a flow reactor from the oxidation of ethylene, toluene, and n-decane

The necessity to reveal the formation mechanism of not only polycyclic aromatic hydrocarbons (PAHs) but also oxygenated PAHs (OPAHs) during combustion is increasing. Although many studies on PAHs have been conducted, fundamental studies investigating OPAH formation are still limited. Phenol, benzofuran, and dibenzofuran were selected as OPAHs in this study. We experimentally investigated fuel-rich oxidation in a flow reactor at atmospheric pressure, mean gas temperatures from 1050 to 1350 K, residence times from 0.2 to 1.5 s, and equivalence ratios from 3.0 to 12.0. Ethylene, toluene, and n-decane were used as fuels. Three kinds of OPAHs as well as 23 kinds of PAHs including monocyclic structures were quantitatively measured through a direct sampling using gas chromatography mass spectrometry. The results showed that concentrations of PAHs and OPAHs were strongly affected by the fuel type, with increasing concentrations in the following order: ethylene < n-decane < toluene. A chemical kinetic model for OPAH formation was developed based on a recent PAH growth model. The model showed that the predicted concentrations of OPAHs and PAHs were in reasonable agreement with the measured data in this study. Some modifications were made to the previous model based on recent literature studies and on the comparison of the simulated and measured results. The effect of the fuel type on the formation of PAHs and OPAHs was investigated through kinetic analysis using the model to discuss their reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1989

The effect of ionization on the infrared absorption spectra of PAHs: A preliminary report

The emission lines observed in many interstellar IR sources at 3.28, 6.2, 7.7, 8.7, and 11.3 microns are theorized to originate from polycyclic aromatic hydrocarbons (PAHs). These assignments are based on analyses of lab IR spectra of neutral PAHs. However, it is likely that in the interstellar medium that PAHs are ionized, i.e., are positively charged. Besides, as pointed out by Allamandola et al., although the IR emission band spectrum resembles what one might expect from a mixture of PAHs, it does not match in details such as frequency, band profile, or relative intensities predicted from the absorption spectra of any known PAH molecule. One source of more information to test the PAH theory is ab initio molecular orbital theory. It can be used to compute, from first principles, the geometries, vibrational frequencies, and vibrational intensities for model PAH compounds which are difficult to study in the lab. The Gaussian 86 computer program was used to determine the effect of ionization on the infrared absorption spectra of several small PAHs: naphthalene and anthracene. A preliminary report is presented of the results of these calculations.

Defrees, Doug J.↗

NASA NTRS1995

Airborne and laboratory studies of interstellar PAHs

A brief history of the observations which have led to the hypothesis that polycyclic aromatic hydrocarbons (PAH's) are the carriers of the widespread interstellar emission features near 3050, 1615, '1300' and 890 cm(exp -1) (3.29, 6.2, '7.7', and 11.2 mu m) is presented. The central role of airborne spectroscopy is stressed. The principal reason for the assignment to PAH's was the resemblance of the interstellar emission spectrum to the laboratory absorption spectra of PAH's and PAH-like materials. Since precious little information was available on the properties of PAH's in the forms that are thought to exist under interstellar conditions -isolated and ionized in the emission zones, with the smallest PAH's being dehydrogenated- there was a need for a spectral data base on PAH's taken in these states. Here, the relevant infrared spectroscopic properties of PAH's will be reviewed. These laboratory spectra show that relative band intensities are severely altered and that band frequencies shift. It is shown that these new data alleviate several of the spectroscopic criticisms previously leveled at the hypothesis.

Allamandola, L. J.↗

NASA NTRS2000

Laboratory Astrochemistry: Interstellar PAHs

Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are thought to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A major, dedicated, laboratory effort has been undertaken to measure the physical and chemical characteristics of these complex molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The Astrochemistry Laboratory program will be discussed through its multiple aspects: (1) objectives, (2) approach and techniques adopted, (3) adaptability to the nature of the problem(s), and (4) results and implications for astronomy as well as for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. The discussion will also introduce the newest generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.

Salama, Farid↗

NASA NTRS2000

Laboratory Astrochemistry: Interstellar PAH Analogs

Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are though to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A major, dedicated, laboratory effort has been undertaken over the past years to measure the physical and chemical characteristics of these complex molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The Astrochemistry Laboratory program will be discussed through its multiple aspects: objectives, approach and techniques adopted, adaptability to the nature of the problem(s), results and implications for astronomy as well as for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. The discussion will also introduce the newest generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.

Salama, Farid↗

NASA NTRS2000

Molecular Spectroscopy in Astrophysics: Interstellar PAHs

Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are thought to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A long-term laboratory effort has been undertaken to measure the physical and chemical characteristics of these carbon molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The laboratory results will be discussed as well as the implications for astronomy and for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. We will also present the new generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.

Salama, Farid↗

NASA NTRS2000

Laboratory Studies of Interstellar PAH Analogs

Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are though to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A major, dedicated, laboratory effort has been undertaken over the past years to measure the physical and chemical characteristics of these complex molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The Astrochemistry Laboratory program will be discussed through its multiple aspects: objectives, approach and techniques adopted, adaptability to the nature of the problem(s), results and implications for astronomy as well as for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. The discussion will also introduce the newest generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.

Salama, Farid↗

NASA NTRS1994

Imaging of the PAH Emission Bands in the Orion Bar

The infrared spectrum of many planetary nebulae, HII regions, galactic nuclei, reflection nebulae, and WC stars are dominated by a set of narrow and broad features which for many years were called the "unidentified infrared bands". These bands have been attributed to several carbon-rich molecular species which all contain only carbon and hydrogen atoms, and fall into the class of PAH molecules or are conglomerates of PAH skeletons. If these bands are from PAHs, then PAHs contain 1-10% of the interstellar carbon, making them the most abundant molecular species in the interstellar medium after CO. From ground based telescopes, we have studied the emission bands assigned to C-H bond vibrations in PAHs (3.3, 11.3 microns) in the Orion Bar region, and showed that their distribution and intensities are consistent with a quantitative PAH model. We have recently obtained spectral images of the Orion Bar from the KAO at 6.2 and 7.7 microns using a 128 x 128 Si:Ga array camera in order to study the C-C modes of the PAH molecules. We will show these new data along with our existing C-H mode data set, and make a quantitative comparison of the data with the existing PAH model.

Bregman, Jesse↗

NASA NTRS1996

Variations in the 3 Micron Spectrum Across the Orion Bar: PAHS and Related Molecules

Long-slit spectra across the Orion Bar reveal significant differences in the spatial behavior of the components of the 3 micrometer PAH spectrum. The strong PAH band at 3.29 micrometers generally decreases exponentially with distance from the ionization front into the molecular cloud (scale height approximately 12"), although excesses appear approximately 10" and approximately 20" behind the ionization front, close to layers of H2 and CO emission respectively. The 3.40 micrometer PAH feature separates into two components with very different spatial distributions. The main component (at 3.395 micrometers), along with the 3.51 micrometer band and the PAH plateau (3.3-3.6 micrometers), shows excess emission approximately 10" and approximately 20" behind the ionization front, stronger than the excesses in the 3.29 micrometer band. The extra component of the 3.40 micrometer band, which peaks at approximately 3.405 micrometers, has a spatial distribution very similar to the H2 emission. Aromatic C-H stretches in PAHs most likely produce the 3.29 micrometer feature. Aliphatic C-H stretches in either attached methyl sidegroups or super-hydrogenated PAHs (H-PAHs), or perhaps both, could produce the complicated spectral and spatial structure at 3.40 micrometers. The distribution of these fragile PAH-based species traces the physical and chemical conditions in the interface between the ionized region and molecular cloud.

Sloan, G. C.↗

NASA NTRS2021

SOFIA/FLITECAM 3-5.4 Micron Spectroscopy of PAHs in Planetary Nebulae

We present stratospheric observations of the ~3-5.4 micron spectra of young planetary nebulae by the SOFIA instrument FLITECAM. The goal of this study was to characterize the NIR emission of Polycyclic Aromatic Hydrocarbons (PAHs) in planetary nebulae and study the evolution of PAH features within these objects. Using airborne 3-5.4 micron grism spectroscopy of three young, Carbon-rich planetary nebulae: IC 5117, PNG 093.9-00.1, and BD +30 3639, we investigated the spectral variation of the 3.3 micron PAH feature, its associated aliphatic features (3.4-3.6 microns), characterized the weak 5.25 PAH emission feature, and set limits on the theoretical contribution of the 4.4-4.8 micron deuterated-PAH features. All features, including atomic emission lines, were fit with a series of Gaussians to determine their flux. We further characterized the 3.3 micron PAH feature using equivalent width and central wavelength, and classified the shape of the emission. We also determined the PAH/Aliphatic ratio for each target. The 3.3 micron PAH emission feature is observed in all three objects, as is PAH emission at 5.25 microns. PNG 093.9-00.1 exhibits NGC 7027-like aliphatic emission in the 3.4–3.6 micron region while aliphatic emission in IC 5117 and BD +30 3639 is weaker, and exhibits less structure.

Erin C Smith↗

NASA NTRSDate not supplied

Formation of Complex Organic Molecules (COMs) from Polycyclic Aromatic Hydrocarbons (PAHs): Top-Down Synthesis of organics in planetary systems

Complex, organic molecules have been found in many solar system objects (i.e., dust, comets, meteorites, moons, etc.); however, their origins and formation remain a mystery. Two chemical evolutionary pathways have been proposed to explain the organic inventory of our solar system. The first pathway, the top-down approach, suggests an interstellar (ISM) heritage whereby the organic material found in the solar system formed from the erosion and functionalization of large pre-solar carbon-bearing species (mainly large Polycyclic Aromatic Hydrocarbons or PAHs). The second pathway suggests that the origin of the Solar System prebiotic matter is the result of bottom-up synthesis from small reactive molecules (e.g., formaldehyde – H2CO, acetylene – H2C2, and similar species). In this second scenario, it is supposed that very few, if any, pre-solar large molecules could have survived due to the proto - solar nebula radiation environment. Polycyclic Aromatic Hydrocarbons or PAHs comprise ~20-30% of all available carbon in the Universe. The PAHs found within our Solar System tend to be smaller than those suspected to be in the ISM, comprised of only 14 to 18 carbon atoms in size whereas ISM PAHs are typically 50 to 100 carbon atoms. The disparity in PAH sizes between the ISM and Solar System environments is not understood, but may point to conversion of large ISM PAHs to Solar System Organics. This presentation details recent experiments regarding the stability of large PAHs to the various types of radiation found within a proto - solar disk and the production of smaller, complex, molecules from the degradation of the larger PAHs. The presentation will highlight differences and similarities in degradation products based on experimental conditions (e.g., radiation type) and discuss future work with a new experimental setup known as ICEE (Institute for Carbon Evolution Experiments).

molecukes↗

NASA NTRS2019

PAH Clusters as Interstellar Very Small Grains

PAH clusters are one candidate species for the interstellar "very small grains" or "VSGs", i.e., dust grains small enough to be stochastically heated and contribute to the aromatic infrared emission bands (AIBs). This possibility motivated laboratory experiments on the infrared spectroscopy of PAH clusters using matrix isolation spectroscopy. The spectral shifts due to PAH clustering in argon matrices provide clues for the AIB contribution from PAH clusters in the interstellar medium. Here we review results from a number of small PAH species, extrapolation to the much larger PAHs believed to be present in the interstellar medium, and the implications for a PAH cluster contribution to the VSG population.

AIBs↗

DOE OSTI2024

Compact and accurate chemical mechanism for methane pyrolysis with PAH growth

In this study, a reliable and compact chemical mechanism of gas-phase methane pyrolysis leading to formation of large polycyclic aromatic hydrocarbon (PAH) molecules has been developed. This model is designed for studies of carbon nanostructure synthesis such as carbon black and graphene flakes, including soot growth kinetics. Methane pyrolysis with carbon nanostructure synthesis is a two-stage process where conversion of CH 4 to C 2 H 2 precedes the growth of PAH molecules from acetylene. We present a single chemical mechanism that accurately describes both stages. We have constructed a compact and accurate chemical mechanism capable of modeling both stages of methane pyrolysis based on the ABF mechanism which was expanded with the most prominent reaction pathways from the mechanism by Tao for small PAH molecules and HACA pathways for larger PAH molecules, up to 37 aromatic rings. The resulting mechanism was validated through comparison to multiple available sets of experimental data. Good agreement with the experimental data for both processes was obtained. Performance of the mechanism was tested for pyrolysis of methane-rich mixtures under long residence times leading to abundant formation of PAH molecules. It is shown that the inclusion of larger PAH species (up to A37) in the chemical mechanism is important for accurate prediction of the fraction of carbon converted to PAH molecules and, correspondingly, the residual fraction of acetylene in the mixture. The mechanism file is available upon request.

08 HYDROGEN↗

DOE OSTI2024

Activity-Based Protein Profiling to Probe Relationships between Cytochrome P450 Enzymes and Early-Age Metabolism of Two Polycyclic Aromatic Hydrocarbons (PAHs): Phenanthrene and Retene

A growing body of literature has linked early life exposures to polycyclic aromatic hydrocarbons (PAH) with adverse neurodevelopmental effects. Once in the body, metabolism serves as a powerful mediator of PAH toxicity by bioactivating and detoxifying PAH metabolites. Since enzyme expression and activity varies considerably throughout human development, we evaluated infant metabolism of PAHs as a potential contributing factor to PAH susceptibility. Here, we measured and compared rates of phenanthrene and retene (two primary PAH constituents of woodsmoke) metabolism in human hepatic microsomes from individuals ≤21 months of age to a pooled sample (n = 200) consisting primarily of adults. We used activity-based protein profiling (ABPP) to characterize cytochrome P450 enzymes (CYPs) in the same hepatic microsome samples. Once incubated in microsomes, phenanthrene demonstrated rapid depletion. Best fit models for phenanthrene metabolism demonstrated either 1 or 2 phases, depending on the sample, indicating that multiple enzymes could metabolize phenanthrene. We observed no statistically significant differences in phenanthrene metabolism as a function of age, although samples from the youngest individuals had the slowest phenanthrene metabolism rates. We observed slower rates of retene metabolism compared to phenanthrene also in multiple phases. Rates of retene metabolism increased in an age-dependent manner until adult (pooled) levels were achieved at ~12 mo. ABPP identified 28 unique CYPs among all samples, and we observed lower amounts of active CYPs in individuals ≤21 months of age compared to the pooled sample. Phenanthrene metabolism correlated to CYPs 1A1, 1A2, 2C8, 4A22, 3A4, and 3A43 and activities and retene metabolism correlated to CYPs 1A1, 1A2, and 2C8 activities measured by ABPP and vendor-supplied substrate marker activities. These results will aid efforts to determine human health risk and susceptibility to PAHs exposures during early life.

59 BASIC BIOLOGICAL SCIENCES↗