Interstellar PAH in the Laboratory and in Space. What have we Learned from the New Generation of Laboratory and Observational Studies?

NASA Technical Reports Server (NTRS)

Salama, Farid

2005-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are an important and ubiquitous component of carbon-bearing materials in space. PAHs are the best-known candidates to account for the IR emission bands (UIR bands) and PAH spectral features are now being used as new probes of the ISM. PAHs are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). In the model dealing with the interstellar spectral features, PAHs are present as a mixture of radicals, ions and neutral species. PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge for laboratory astrophysics is to reproduce (in a realistic way) the physical conditions that exist in the emission and/or absorption interstellar zones. An extensive laboratory program has been developed at NASA Ames to assess the physical and chemical properties of PAHs in such environments and to describe how they influence the radiation and energy balance in space and the interstellar chemistry. In particular, laboratory experiments provide measurements of the spectral characteristics of interstellar PAH analogs from the ultraviolet and visible range to the infrared range for comparison with astronomical data. This paper will focus on the recent progress made in the laboratory to measure the direct absorption spectra of neutral and ionized PAHs in the gas phase in the near-UV and visible range in astrophysically relevant environments. These measurements provide data on PAHs and nanometer-sized particles that can now be directly compared to astronomical observations. The harsh physical conditions of the IS medium - characterized by a low temperature, an absence of collisions and strong VUV radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature (of the order of 100 K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS). These experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase. Intrinsic band profiles and band positions of cold gas-phase PAHs can now be measured with high-sensitivity spectroscopy and directly compared to the astronomical data. The electronic bands measured for ionized PAH are found to be intrinsically broad (about 20 cm(sup -1)) while the bands associated with the neutral precursors are narrower (of the order of 2 - 10 cm(sup -1)). The laboratory data are discussed and compared with recent astronomical spectra of large and narrow DIBs and with the spectra of circumstellar environments of selected carbon stars and the implications for the interstellar PAH population are derived. Preliminary results also show that carbon nanoparticles are formed during the short residence time of the precursors in the plasma.

Molecular Spectroscopy in Astrophysics: Interstellar PAHs

NASA Technical Reports Server (NTRS)

Salama, Farid; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

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.

Laboratory Astrochemistry: Interstellar PAH Analogs

NASA Technical Reports Server (NTRS)

Salama, Farid; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

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.

Laboratory Studies of Interstellar PAH Analogs

NASA Technical Reports Server (NTRS)

Salama, Farid; DeVincenzi, Donald (Technical Monitor)

2000-01-01

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.

PAHs and the Diffuse Interstellar Bands. What have we Learned from the New Generation of Laboratory and Observational Studies?

NASA Technical Reports Server (NTRS)

Salama, Farid

2005-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are an important and ubiquitous component of carbon-bearing materials in space. PAHs are the best-known candidates to account for the IR emission bands (UIR bands) and PAH spectral features are now being used as new probes of the ISM. PAHs are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). In the model dealing with the interstellar spectral features, PAHs are present as a mixture of radicals, ions and neutral species. PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge for laboratory astrophysics is to reproduce (in a realistic way) the physical conditions that exist in the emission and/or absorption interstellar zones, An extensive laboratory program has been developed at NASA Ames to characterize the physical and chemical properties of PAHs in astrophysical environments and to describe how they influence the radiation and energy balance in space and the interstellar chemistry. In particular, laboratory experiments provide measurements of the spectral characteristics of interstellar PAH analogs from the ultraviolet and visible range to the infrared range for comparison with astronomical data. This paper will focus on the recent progress made in the laboratory to measure the direct absorption spectra of neutral and ionized PAHs in the gas phase in the near-W and visible range in astrophysically relevant environments. These measurements provide data on PAHs and nanometer-sized particles that can now be directly compared to astronomical observations. The harsh physical conditions of the IS medium - characterized by a low temperature, an absence of collisions and strong V W radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature (of the order of 100 K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS). These experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase. Intrinsic band profiles and band positions of cold gas-phase PAHs can now be measured with high- sensitivity spectroscopy and directly compared to the astronomical data. The electronic bands measured for ionized PAH are found to be intrinsically broad (about 20/cm) while the bands associated with the neutral precursors are narrower (of the order of 2 - 10/cm).

Gas Phase Spectroscopy of Cold PAH Ions: Contribution to the Interstellar Extinction and the Diffuse Interstellar Bands

NASA Technical Reports Server (NTRS)

Biennier, L.; Salama, F.; Allamandola, L. J.; Scherer, J. J.; OKeefe, A.

2002-01-01

Polycyclic Aromatic Hydrocarbon molecules (PAHs) are ubiquitous in the interstellar medium (ISM) and constitute the building blocks of interstellar dust grains. Despite their inferred important role in mediating the energetic and chemical processes in thc ISM, their exact contribution to the interstellar extinction, and in particular to the diffuse interstellar bands (DIBs) remains unclear. The DIBs are spectral absorption features observed in the line of sight of stars that are obscured by diffuse interstellar clouds. More than 200 bands have been reported to date spanning from the near UV to the near IR with bandwidths ranging from 0.4 to 40 Angstroms (Tielens & Snow 1995). The present consensus is that the DIBs arise from free flying, gas-phase, organic molecules and/or ions that are abundant under the typical conditions reigning in the diffuse ISM. PAHs have been proposed as possible carriers (Allamandola et al. 1985; Leger & DHendecourt 1985). The PAH hypothesis is consistent with the cosmic abundance of Carbon and Hydrogen and with the required photostability of the DIB carriers against the strong VUV radiation field in the diffuse interstellar clouds. A significant fraction of PAHs is expected to be ionized in the diffuse ISM.

PAH in the laboratory and interstellar space

NASA Technical Reports Server (NTRS)

Wdowiak, Thomas J.; Flickinger, Gregory C.; Boyd, David A.

1989-01-01

The theory that polycyclic aromatic hydrocarbons (PAHs) are a constituent of the interstellar medium, and a source of the IR emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3 microns is being studied using PAH containing acid insoluble residue of the Orgueil CI meteorite and coal tar. FTIR spectra of Orgueil PAH material that has undergone thermal treatment, and a solvent insoluble fraction of coal tar that has been exposed to hydrogen plasma are presented. The UV excided luminescence spectrum of a solvent soluble coal tar film is also shown. Comparison of the lab measurements with observations appears to support the interstellar PAH theory, and shows the process of dehydrogenation expected to take place in the interstellar medium.

Photochemistry of Polycyclic Aromatic Hydrocarbons in Cosmic Water Ice: The Role of PAH Ionization and Concentration

NASA Astrophysics Data System (ADS)

Cook, Amanda M.; Ricca, Alessandra; Mattioda, Andrew L.; Bouwman, Jordy; Roser, Joseph; Linnartz, Harold; Bregman, Jonathan; Allamandola, Louis J.

2015-01-01

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H2O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H2O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts and PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) n ] and quinones [PAH(O) n ] for all PAH:H2O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati & Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO2 and H2CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) n and PAH(O) n to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ~2%-4% level relative to H2O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.

The Origins of Polycyclic Aromatic Hydrocarbons: Are They Everywhere?

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Morrison, David (Technical Monitor)

1994-01-01

During the past 15 years considerable progress in observational techniques has been achieved in the middle-infrared region (5000-500 per centimeter, 2-20 micron), the region where most diagnostic molecular vibrations occur. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds and others at their edges, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas and solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. The two lectures will focus on the evidence that polycyclic aromatic hydrocarbons (PAHs) are an important, ubiquitous and abundant interstellar species. PAHs are. extremely stable species which can range in size from a few angstroms across to several hundred angstroms (PAHs are also the building blocks of amorphous carbon particles). This identification rests on the suggestive agreement between the laboratory spectra of PAHs with a set of IR emission bands which emanate from many different sources where ultraviolet starlight impinges on a "dusty" region. The picture is that individual PAHs are first pumped into highly vibrationally excited states and relax by fluorescence at their fundamental vibrational frequencies. That PAHs are a ubiquitous interstellar component has serious ramifications in other spectral regions as well, including the strong extinction in the ultraviolet, and the classic visible diffuse interstellar bands discovered more than 50 years ago (but unexplained to this day) The first part of the course will focus on the interpretation of astronomical spectra. The second lecture will start by showing how recent laboratory data on PAHs taken under realistic interstellar conditions has con borated the PAH hypothesis and led to great insight into the conditions in the PAH containing regions. This lecture will end by reviewing the ever-increasing evidence for interstellar PAHs in meteorites and interplanetary dust particles. This in conjunction with the recent suggestion that PAHs are abundant in Jupiter's atmosphere will make the point that "PAHs are Everywhere".

Interstellar dehydrogenated PAH anions: vibrational spectra

NASA Astrophysics Data System (ADS)

Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

2018-03-01

Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

Infrared emission spectra of candidate interstellar aromatic molecules

NASA Technical Reports Server (NTRS)

Schlemmer, S.; Balucani, N.; Wagner, D. R.; Steiner, B.; Saykally, R. J.

1996-01-01

Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

Imaging of the PAH Emission Bands in the Orion Bar

NASA Technical Reports Server (NTRS)

Bregman, Jesse; Harker, David; Rank, David; Temi, Pasqiale; Morrison, David (Technical Monitor)

1994-01-01

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.

Interstellar Dust: Contributed Papers

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M. (Editor); Allamandola, Louis J. (Editor)

1989-01-01

A coherent picture of the dust composition and its physical characteristics in the various phases of the interstellar medium was the central theme. Topics addressed included: dust in diffuse interstellar medium; overidentified infrared emission features; dust in dense clouds; dust in galaxies; optical properties of dust grains; interstellar dust models; interstellar dust and the solar system; dust formation and destruction; UV, visible, and IR observations of interstellar extinction; and quantum-statistical calculations of IR emission from highly vibrationally excited polycyclic aromatic hydrocarbon (PAH) molecules.

The UV to Near-IR Optical Properties of PAHs: A Semi-Empirical Model

NASA Technical Reports Server (NTRS)

Mattioda, A. L.; Allamandola, L. J.; Hudgins, D. M.

2005-01-01

Interstellar Polycyclic Aromatic Hydrocarbon (PAH) infrared emission features represent an important and unique diagnostic tool of the chemical and physical conditions throughout the universe. However, one challenge facing the widely accepted PAH emission model has been the detection of infrared features in regions of low UV flux. Utilizing recently published laboratory Near Infrared VIR) PAH ion absorption data measured in our laboratory, we build upon previous models for PAH ion absorption in the UV-Vis to extrapolate a new model which incorporates PAH ion absorption in the NIR. This model provides a basis for comparing the relative energy absorption of PAH ions in the UV-Vis and NIR regions for a wide variety of stellar types. This model demonstrates that the radiation from late-type stars can pump the mid-IR PAH features.

PHOTOCHEMISTRY OF POLYCYCLIC AROMATIC HYDROCARBONS IN COSMIC WATER ICE: THE ROLE OF PAH IONIZATION AND CONCENTRATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Amanda M.; Mattioda, Andrew L.; Roser, Joseph

2015-01-20

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H{sub 2}O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H{sub 2}O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts andmore » PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) {sub n} ] and quinones [PAH(O) {sub n} ] for all PAH:H{sub 2}O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati and Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO{sub 2} and H{sub 2}CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) {sub n} and PAH(O) {sub n} to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ∼2%-4% level relative to H{sub 2}O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.« less

Variations in the Peak Position of the 6.2 micron Interstellar Emission Feature: A Tracer of N in the Interstellar Polycyclic Aromatic Hydrocarbon Population

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Bauschlicher, Charles W.; Allamandola, L. J.

2005-01-01

This paper presents the results of an investigation of the molecular characteristics that underlie the observed peak position and profile of the nominal 6.2 micron interstellar emission band generally attributed to the CC stretching vibrations of polycyclic aromatic hydrocarbons (PAHs). It begins with a summary of recent experimental and theoretical studies ofthe spectroscopic properties of large (>30 carbon atoms) PAH cations as they relate to this aspect of the astrophysical problem. It then continues with an examination of the spectroscopic properties of a number of PAH variants within the context of the interstellar 6.2 micron emission, beginning with a class of compounds known as polycyclic aromatic nitrogen heterocycles (PANHs; PAHs with one or more nitrogen atoms substituted into their carbon skeleton). In this regard, we summarize the results of recent relevant experimental studies involving a limited set of small PANHs and their cations and then report the results of a comprehensive computational study that extends that work to larger PANH cations including many nitrogen-substituted variants of coronene(+) (C24H12(+)), ovalene(+) (C32H14(+)), circumcoronene(+) (C54H18(+)), and circum-circumcoronene(+) (C96H24(+)). Finally, we report the results of more focused computational studies of selected representatives from a number of other classes of PAH variants that share one or more of the key attributes of the PANH species studied. These alternative classes of PAH variants include (1) oxygen- and silicon-substituted PAH cations; (2) PAH-metal ion complexes (metallocenes) involving the cosmically abundant elements magnesium and iron; and (3) large, asymmetric PAH cations. Overall, the studies reported here demonstrate that increasing PAH size alone is insuEcient to account for the position of the shortest wavelength interstellar 6.2 micron emission bands, as had been suggested by earlier studies. On the other hand, this work reveals that substitution of one or more nitrogen atoms within the interior of the carbon skeleton of a PAH cation induces a significant blueshift in the position of the dominant CC stretching feature of these compounds that is suf6cient to account for the position of the interstellar bands. Subsequent studies of the effects of substitution by other heteroatoms (O and Si), metal ion complexation (Fe(+), Mg(+), and Mg(2+)), and molecular symmetry variation-all of which fail to reproduce the blueshift observed in the PANH cations-indicate that N appears to be unique in its ability to accommodate the position of the interstellar 6.2 micron bands while simultaneously satisfying the other constraints of the astrophysical problem. This result implies that the peak position of the interstellar feature near 6.2 micron traces the degree of nitrogen substitution in the population, that most of the PAHs responsible for the interstellar IR emission features incorporate nitrogen within their aromatic networks, and that a lower limit of 1%-2% of the cosmic nitrogen is sequestered within the interstellar PAH population. Finally, in view of the ubiquity and abundance of interstellar PAHs and the permanent dipoles and distinctive electronic structures of these nitrogen-substituted variants, this work impacts a wide range of observational phenomena outside of the infrared region of the spectrum including the forest of unidentified molecular rotational features and the anomalous Galactic foreground emission in the microwave, and the diffuse interstellar bands (DIBs) and other structure in the interstellar extinction curve in the ulhviolet/visible. These astrophysical ramifications are discussed, and the dipole moments and rotational constants are tabulated to facilitate further investigations of the astrophysical role of nitrogen-substituted aromatic compounds.

Polycyclic aromatic hydrocarbon molecules in astrophysics

NASA Astrophysics Data System (ADS)

Rastogi, Shantanu; Pathak, Amit; Maurya, Anju

2013-06-01

Polycyclic aromatic hydrocarbon (PAH) molecules are responsible for the mid-infrared emission features. Their ubiquitous presence in almost all types of astrophysical environments and related variations in their spectral profilesmake them an important tool to understand the physics and chemistry of the interstellar medium. The observed spectrum is generally a composite superposition of all different types of PAHs possible in the region. In the era of space telescopes the spectral richness of the emission features has enhanced their importance as probe and also the need to understand the variations with respect to PAH size, type and ionic state. Quantum computational studies of PAHs have proved useful in elucidating the profile variations and put constraints on the possible types of PAHs in different environments. The study of PAHs has also significantly contributed to the problems of diffuse interstellar bands (DIBs), UV extinction and understanding the chemistry of the formation of complex organics in space. The review highlights the results of various computational models for the understanding of infrared emission features, the PAH-DIB relation, formation of prebiotics and possible impact in the understanding of far-infrared features.

Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in the Cosmic Simulation Chamber

NASA Technical Reports Server (NTRS)

Bejaoui, Salma; Salama, Farid; Contreras, Cesar; Sciamma O'Brien, Ella; Foing, Bernard; Pascale, Ehrenfreund

2015-01-01

Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser induced fluorescence (LIF) technique and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates a plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examined.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3; The Polyacenes Anthracene, Tetracence, and Pentacene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHS) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAHS. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400/cm (between about 1340 and 1500/cm) and near 1180/cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3. The Polyacenes Anthracene, Tetracene, and Pentacene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized Polycyclic Aromatic Hydrocarbons (PAH's) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAH's. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400 / cm (between about 1340 and 1500 / cm) and near 1180 /cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

ON THE VIABILITY OF THE PAH MODEL AS AN EXPLANATION OF THE UNIDENTIFIED INFRARED EMISSION FEATURES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yong; Kwok, Sun, E-mail: zhangy96@hku.hk, E-mail: sunkwok@hku.hk

2015-01-01

Polycyclic aromatic hydrocarbon (PAH) molecules are widely considered the preferred candidate for the carrier of the unidentified infrared emission bands observed in the interstellar medium and circumstellar envelopes. In this paper, we report the results of fitting a variety of non-PAH spectra (silicates, hydrogenated amorphous carbon, coal, and even artificial spectra) using the theoretical infrared spectra of PAHs from the NASA Ames PAH IR Spectroscopic Database. We show that these non-PAH spectra can be well fitted by PAH mixtures. This suggests that a general match between astronomical spectra and those of PAH mixtures does not necessarily provide definitive support formore » the PAH hypothesis.« less

Fifteen Years of Laboratory Astrophysics at Ames

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Sandford, S. A.; Salama, F.; Hudgins, D. M.; Bernstein, M.; Goorvitch, David (Technical Monitor)

1998-01-01

Tremendous strides have been made in our understanding of interstellar material over the past fifteen years thanks to significant, parallel developments in two closely related areas: observational astronomy and laboratory astrophysics. Fifteen years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon-rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, these cold dust particles are coated with mixed-molecular ices whose compositions are very well known. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the ISM. This great progress has only been made possible by the close collaboration of laboratory experimentalists with observers and theoreticians, all with the goal of applying their skills to astrophysical problems of direct interest to NASA programs. Such highly interdisciplinary collaborations ensure fundamental, in depth coverage of the wide-ranging challenges posed by astrophysics. These challenges include designing astrophysically focused experiments and data analysis, tightly coupled with astrophysical searches spanning 2 orders of magnitude in wavelength, and detailed theoretical modeling. The impact of our laboratory has been particularly effective as there is constant cross-talk and feedback between quantum theorists; theoretical astrophysicists and chemists; experimental physicists; organic, physical and petroleum chemists; and infrared and UV/Vis astronomers. In this paper, two examples of the Ames Program will be given. We have been involved in identifying 9 out of the 14 interstellar pre-cometary ice species known, determined their abundances and the physical nature of the ice structure. Details on our ice work are given in the paper by Sandford et al. Our group is among the pioneers of the PAH model. We built the theoretical framework, participated in the observations and developed the experimental techniques needed to test the model. We demonstrated that the ubiquitous infrared emission spectrum associated with many interstellar objects can be matched by laboratory spectra of neutral and positively charged PAHs and that PAHs were excellent candidates for the diffuse interstellar band (DIB) carriers. See Salama et al. and Hudgins et al.

Laboratory Formation of Fullerenes from PAHs: Top-down Interstellar Chemistry

NASA Astrophysics Data System (ADS)

Zhen, Junfeng; Castellanos, Pablo; Paardekooper, Daniel M.; Linnartz, Harold; Tielens, Alexander G. G. M.

2014-12-01

Interstellar molecules are thought to build up in the shielded environment of molecular clouds or in the envelope of evolved stars. This follows many sequential reaction steps of atoms and simple molecules in the gas phase and/or on (icy) grain surfaces. However, these chemical routes are highly inefficient for larger species in the tenuous environment of space as many steps are involved and, indeed, models fail to explain the observed high abundances. This is definitely the case for the C60 fullerene, recently identified as one of the most complex molecules in the interstellar medium. Observations have shown that, in some photodissociation regions, its abundance increases close to strong UV-sources. In this Letter we report laboratory findings in which C60 formation can be explained by characterizing the photochemical evolution of large polycyclic aromatic hydrocarbons (PAHs). Sequential H losses lead to fully dehydrogenated PAHs and subsequent losses of C2 units convert graphene into cages. Our results present for the first time experimental evidence that PAHs in excess of 60 C-atoms efficiently photo-isomerize to buckminsterfullerene, C60. These laboratory studies also attest to the importance of top-down synthesis routes for chemical complexity in space.

Spectroscopy of PAHs with carbon side chains

NASA Astrophysics Data System (ADS)

Rouille, G.; Steglich, M.; Carpentier, Y.; Huisken, F.; Henning, T.

2011-05-01

The presence of polycyclic aromatic hydrocarbons (PAHs) in space has been inferred ever since sp ecific infrared emission bands were interpreted as their collective fingerprint. In parallel, it has been admitted that the famous diffuse interstellar bands (DIBs), which are absorption features observed in the visible wavelength range, are bands belonging to the electronic spectra of free-flying interstellar molecules yet to be identified. As neutral PAHs of medium and large sizes exhibit absorption bands in the range where the DIBs are found, these molecules, which also fulfill other criteria, have been proposed as potential carriers. Studies of small PAHs in solutions have shown that adding an ethynyl side chain (--CCH) to their structure causes their electronic transitions to shift toward longer wavelengths. This fact, added to the observations of interstellar polyynyl radicals, motivated our current research project on PAHs carrying polyynyl side chains. In a first stage, we are measuring the electronic spectra of small PAHs and of their ethynyl and butadiynyl (--CCCCH) derivatives at cryogenic temperatures in rare gas matrices. Then, measurements will be carried out in supersonic jets, providing us with spectra obtained under conditions relevant to the study of free-flying interstellar molecules. The results of IR absorption measurements will be included in our set of new data. As a complement to our laboratory study on the substituted PAHs, quantum chemical calculations are carried out to interprete and simulate their IR and vibronic spectra. We use the density functional theory approach and its time-dependent extension for calculating the electronic ground states and the electronically excited states, respectively. Through the analysis of the new data, it will be determined whether PAHs carrying polyynyl side chains can play a role in interstellar phenomena. The latest results of this on-going project will be presented.

UV-visible spectroscopy of PAHs and PAHNs in supersonic jet. Astrophysical Implications

NASA Astrophysics Data System (ADS)

Salma, Bejaoui; Salama, Farid

2017-06-01

Polycyclic Aromatic Hydrocarbon (PAHs) molecules are attracting much attention of the astrophysical and astrochemical communities since they are ubiquitous presence in space and could survive in the harsh interstellar medium (ISM). They are proposed as plausible carriers of the still unassigned diffuse interstellar bands (DIBs) for more than two decades now. The so-called PAH - DIB proposal has been based on the abundance of PAHs in the ISM and their stability against the photo and thermo dissociation. Nitrogen is one of the most abundant elements after hydrogen, helium, and carbon [1]. PANHs exhibit spectral features similar to PAHs and may also contribute to unidentified spectral bands.To prove PAHs-DIBs hypothesis, laboratory absorption spectra of aromatic under astrophysical relevant conditions are of crucial importance to compare with the observed DIBs spectra. The most challenging task is to reproduce as closely as technically possible, the physical and chemical conditions that are present in space. Interstellar PAHs are expected to be present as free, cold, neutral molecules and/or charged species [2]. In our laboratory, comparable conditions are achieved using an excellent platform developed in NASA Ames. Our cosmic simulation chamber (COSmIC) allow the measurements of gas phase spectra of neutral and ionized interstellar PAHs analogs by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion (˜ 100 K) [3]. Our approach to assign PAH as carriers of some DIBs is record the electronic spectra of cold PAHs in gas phase and systematic search for a possible correspondence in astronomical DIBs spectra. We report in this work UV-visible absorption spectra of neutral PAHs and PAHNs using the cavity ring down spectroscopy (CRDS) technique. We discuss the effect of the substitution of C-H bond(s) by a nitrogen atom(s) in spectroscopic features of PAHs and their astrophysical application.[1] L. Spitzer, 1978, Physical processes in the interstellar medium. New York Wiley-Interscience[2] F. Salama, E. Bakes, L.J. Allamandola, A.G.G.M. Tielens, Astrophys. J. 458 (1996) 621[3] L. Biennier, F. Salama, L. J. Allamandola, & J. J. Scherer, (2003) J. of Chemical Physics, 118(17), 7863-7872

Abundances of Neutral and Ionized PAH Along The Lines-of-Sight of Diffuse and Translucent Interstellar Clouds

NASA Technical Reports Server (NTRS)

Salama, Farid; Galazutdinov, Gazinur; Krewloski, Jacek; Biennier, Ludovic; Beletsky, Yuri; Song, In-Ok

2013-01-01

The spectra of neutral and ionized PAHs isolated in the gas phase at low temperature have been measured in the laboratory under conditions that mimic interstellar conditions and are compared with a set of astronomical spectra of reddened, early type stars. The comparisons of astronomical and laboratory data provide upper limits for the abundances of neutral PAH molecules and ions along specific lines-of-sight. Something that is not attainable from infrared observations. We present the characteristics of the laboratory facility (COSmIC) that was developed for this study and discuss the findings resulting from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. COSmIC combines a supersonic jet expansion with discharge plasma and cavity ringdown spectroscopy and provides experimental conditions that closely mimic the interstellar conditions. The column densities of the individual PAH molecules and ions probed in these surveys are derived from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. The comparisons of astronomical and laboratory data lead to clear conclusions regarding the expected abundances for PAHs in the interstellar environments probed in the surveys. Band profile comparisons between laboratory and astronomical spectra lead to information regarding the molecular structures and characteristics associated with the DIB carriers in the corresponding lines-of-sight. These quantitative surveys of neutral and ionized PAHs in the optical range open the way for quantitative searches of PAHs and complex organics in a variety of interstellar and circumstellar environments.

Laboratory evidence for ionized polycyclic aromatic hydrocarbons in the interstellar medium

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin

1993-01-01

The infrared absorption from neutrals and cations of four PAHs - naphthalene, anthracene, pyrene, and perylene - integrated over the spectral regions corresponding to the interstellar bands are compared with astronomical observations. It is found that the interstellar bands cannot be explained solely on the basis of neutral PAH species, but that cations must be a significant, and in some cases dominant, component.

VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

PubMed Central

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

2016-01-01

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 – 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models. PMID:27212712

VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes.

PubMed

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M

2016-05-10

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 - 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.

Polycyclic Aromatic Hydrocarbons and Infrared Astrophysics with Spitzer

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Allamandola, L. J.

2004-01-01

Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role that carbon-rich plays in the interstellar medium (ISM). Twenty years ago, the possible existence of an abundant population of large, carbon-rich molecules in the ISM was unthinkable. Today, the unmistakable spectroscopic signatures of polycyclic aromatic hydrocarbons (PAHs) - shockingly large molecules by the standards of traditional interstellar chemistry -are recognized throughout the Universe. In this presentation, we will examine the current state of the interstellar PAH model and explore how this data, in conjunction with the unparalleled observational data provided by the Spitzer Space Telescope, can be used to draw ever-deeper insights into the physical and chemical natures of a wide range of astrophysical environments.

Molecular hydrogen formation on interstellar PAHs through Eley-Rideal abstraction reactions

NASA Astrophysics Data System (ADS)

Foley, Nolan; Cazaux, S.; Egorov, D.; Boschman, L. M. P. V.; Hoekstra, R.; Schlathölter, T.

2018-06-01

We present experimental data on H2 formation processes on gas-phase polycyclic aromatic hydrocarbon (PAH) cations. This process was studied by exposing coronene radical cations, confined in a radio-frequency ion trap, to gas phase H atoms. Sequential attachment of up to 23 hydrogen atoms has been observed. Exposure to atomic D instead of H allows one to distinguish attachment from competing abstraction reactions, as the latter now leave a unique fingerprint in the measured mass spectra. Modeling of the experimental results using realistic cross sections and barriers for attachment and abstraction yield a 1:2 ratio of abstraction to attachment cross sections. The strong contribution of abstraction indicates that H2 formation on interstellar PAH cations is an order of magnitude more relevant than previously thought.

Interstellar PAH emission in the 11-14 micron region: new insights from laboratory data and a tracer of ionized PAHs

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1999-01-01

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHS) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For solo- and duet-CH groups, the shift is pronounced and consistently toward higher frequencies. The solo-CH modes are blueshifted by an average of 27 cm-1 and the duet-CH modes by an average of 17 cm-1. For trio- and quartet-CH groups, the ionization shifts of the out-of-plane modes are more erratic and typically more modest. As a result of these ionization shifts, the solo-CH out-of-plane modes move out of the region classically associated with these vibrations in neutral PAHS, falling instead at frequencies well above those normally attributed to out-of-plane bending, vibrations of any type. In addition, for the compact PAHs studied, the duet-CH out-of-plane modes are shifted into the frequency range traditionally associated with the solo-CH modes. These results refine our understanding of the origin of the dominant interstellar infrared emission feature near 11.2 microns, whose envelope has traditionally been attributed only to the out-of-plane bending of solo-CH groups on PAHS, and provide a natural explanation for the puzzling emission feature near 11.0 microns within the framework of the PAH model. Specifically, the prevalent but variable long-wavelength wing or shoulder that is often observed near 11.4 microns likely reflects the contributions of duet-CH units in PAH cations. Also, these results indicate that the emission between 926 and 904 cm-1 (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the out-of-plane wagging, of solo-CH units in moderately sized (fewer than 50 carbon atom) PAH cations, making this emission an unequivocal tracer of ionized interstellar PAHS.

Laboratory Spectroscopy of Large Carbon Molecules and Ions in Support of Space Missions. A New Generation of Laboratory & Space Studies

NASA Technical Reports Server (NTRS)

Salama, Farid; Tan, Xiaofeng; Cami, Jan; Biennier, Ludovic; Remy, Jerome

2006-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are an important and ubiquitous component of carbon-bearing materials in space. A long-standing and major challenge for laboratory astrophysics has been to measure the spectra of large carbon molecules in laboratory environments that mimic (in a realistic way) the physical conditions that are associated with the interstellar emission and absorption regions [1]. This objective has been identified as one of the critical Laboratory Astrophysics objectives to optimize the data return from space missions [2]. An extensive laboratory program has been developed to assess the properties of PAHs in such environments and to describe how they influence the radiation and energy balance in space. We present and discuss the gas-phase electronic absorption spectra of neutral and ionized PAHs measured in the UV-Visible-NIR range in astrophysically relevant environments and discuss the implications for astrophysics [1]. The harsh physical conditions of the interstellar medium characterized by a low temperature, an absence of collisions and strong VUV radiation fields - have been simulated in the laboratory by associating a pulsed cavity ringdown spectrometer (CRDS) with a supersonic slit jet seeded with PAHs and an ionizing, penning-type, electronic discharge. We have measured for the {\\it first time} the spectra of a series of neutral [3,4] and ionized [5,6] interstellar PAHs analogs in the laboratory. An effort has also been attempted to quantify the mechanisms of ion and carbon nanoparticles production in the free jet expansion and to model our simulation of the diffuse interstellar medium in the laboratory [7]. These experiments provide {\\it unique} information on the spectra of free, large carbon-containing molecules and ions in the gas phase. We are now, for the first time, in the position to directly compare laboratory spectral data on free, cold, PAH ions and carbon nano-sized carbon particles with astronomical observations in the UV-NIR range (interstellar UV extinction, DIBs in the NUV-NIR range). This new phase offers tremendous opportunities for the data analysis of current and upcoming space missions geared toward the detection of large aromatic systems Le., the "new frontier space missions" (Spitzer, HST, COS, JWST, SOFIA,...).

A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

Investigations of the Formation of Carbon Grains in Circumstellar Outflows

NASA Technical Reports Server (NTRS)

Contreras, Cesar; Salama, Farid

2013-01-01

The study of formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of carbonaceous dust. PAHs are important chemical building blocks of interstellar dust. They are detected in interplanetary dust particles and in meteoritic samples. Additionally, observational, laboratory, and theoretical studies have shown that PAHs, in their neutral and ionized forms, are an important, ubiquitous component of the interstellar medium. Also, the formation of PAHs from smaller molecules has not been extensively studied. Therefore, it is imperative that laboratory experiments be conducted to study the dynamic processes of carbon grain formation from PAH precursors. Studies of interstellar dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include the atoms O, N, and S, have recently been performed in our laboratory under conditions that simulate interstellar and circumstellar environments. The species formed in the pulsed discharge nozzle (PDN) plasma source are detected and characterized with a high-sensitivity cavity ringdown spectrometer (CRDS) coupled to a Reflectron time-of-flight mass spectrometer (ReTOF-MS), thus providing both spectroscopic and ion mass information in-situ. We report the first set of measurements obtained in these experiments and identify the species present in the experiments and the ions that are formed in the plasma process. From these unique measurements, we derive information on the size and the structure of interstellar dust grain particles, the growth and the destruction processes of interstellar dust and the resulting budget of extraterrestrial organic molecules.

VUV PHOTO-PROCESSING OF PAH CATIONS: QUANTITATIVE STUDY ON THE IONIZATION VERSUS FRAGMENTATION PROCESSES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine

2016-05-10

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7–20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation andmore » photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ∼13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies all species behave similarly; the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ∼18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them; all are in good agreement with theoretical ones, confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.« less

Experimental Electronic Spectroscopy of Two PAHs: Naphthalene and 2-METHYL Naphthalene

NASA Astrophysics Data System (ADS)

Friha, H.; Feraud, G.; Pino, T.; Brechignac, Ph.; Parneix, P.; Dhaoudi, Z.; Jaidane, N.; Galila, H.; Troy, T.; Schmidt, T.

2011-06-01

The presence of polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM) was suggested in the mid-80's. Since then, their important role in the physico-chemical evolution of the ISM has been confirmed. Interstellar PAHs have been in particular proposed as possible carriers of some Diffuse Interstellar Bands (DIBs). These absorption bands are seen in the spectra of reddened stars from the visible to the near infrared and constitute a major astrophysical issue. Our purpose is to obtain electronic spectra of gas phase PAHs which will be used to probe their participation to the interstellar extinction curve from the visible (DIBs) to the UV (bump). For this goal PAHs cations represent an excellent set of target species. A new way of forming PAH+-Ar_n clusters cations has been implemented in the experimental set-up 'ICARE' at ISMO (Orsay) giving us the capability to measure the electronic spectra of cold PAH cations in the gas phase through the "Ar tagging" trick. Two molecules have been investigated in this way: naphthalene (C_1_0H_8) and 2- methyl naphthalene (C_1_1H_1_0). Clusters of naphthalene and (or 2-methyl-naphthalene) with Ar atoms are first formed in a supersonic jet, before being hit by a 281 nm laser beam which photo-ionizes the clusters which are then injected in a molecular beam through a skimmer. A tunable laser beam crossing downstream photo-dissociates the cations. The bare PAH fragments are detected using a Time-Of-Flight spectrometer while scanning the visible laser wavelength from 470 to 690 nm.

Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons under Interstellar Conditions

NASA Technical Reports Server (NTRS)

Stone, Bradley M.

1996-01-01

The presence and importance of polycyclic aromatic hydrocarbons (PAHs, a large family of organic compounds containing carbon and hydrogen) in the interstellar medium has already been well established. The Astrochemistry Laboratory at NASA Ames Research Center (under the direction of Louis Allamandola and Scott Sandford) has been the center of pioneering work in performing spectroscopy on these molecules under simulated interstellar conditions, and consequently in the identification of these species in the interstellar medium by comparison to astronomically obtained spectra. My project this summer was twofold: (1) We planned on obtaining absorption spectra of a number of PAHs and their cations in cold (4K) Ne matrices. The purpose of these experiments was to increase the number of different PAHs for which laboratory spectra have been obtained under these simulated interstellar conditions; and (2) I was to continue the planning and design of a new laser facility that is being established in the Astrochemistry laboratory. The laser-based experimental set-up will greatly enhance our capability in examining this astrophysically important class of compounds.

Interstellar PAH Emission in the 11-14 micron Region: New Insights and a Tracer of Ionized PAHs

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

1999-01-01

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHs) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For non-adjacent and doubly-adjacent CH groups, the shift is pronounced and consistently toward higher frequencies. The non-adjacent modes are blueshifted by an average of 27 per cm and the doubly-adjacent modes by an average of 17 per cm. For triply- and quadruply-adjacent CH out-of-plane modes the ionization shifts are more erratic and typically more modest. As a result of these ionization shifts, both the non-adjacent and doubly-adjacent CH out-of-plane modes move out of the regions classically associated with their respective vibrations in neutral PAHs. The doubly-adjacent modes of ionized PAHs tend to fall into the frequency range traditionally associated with the non-adjacent modes, while the non-adjacent modes are shifted to frequencies above those normally attributed to out-of-plane bending vibrations. Consequently, the origin of the interstellar infrared emission feature near 11.2 microns, traditionally attributed to the out-of-plane bending of non-adjacent CH groups on PAHs is rendered ambiguous. Instead, this feature likely reflects contributions from both non-adjacent CH units in neutral PAHs and doubly-adjacent CH units in PAH cations, the dominant charge state in the most energetic emission regions. This greatly relieves the structural constraints placed on the interstellar PAH population by the dominance of the 11.2 micron band in this region and eliminates the necessity to invoke extensive dehydrogenation of the emitting species. Furthermore, these results indicate that the emission between 926 and 904 per cm (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the non-adjacent CH out-of-plane bending modes of moderately-sized (fewer than 50 carbon atom) PAH cations making this emission an unequivocal tracer of ionized interstellar PAHs.

DISSOCIATIVE PHOTOIONIZATION OF POLYCYCLIC AROMATIC HYDROCARBON MOLECULES CARRYING AN ETHYNYL GROUP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouillé, G.; Krasnokutski, S. A.; Fulvio, D.

The life cycle of the population of interstellar polycyclic aromatic hydrocarbon (PAH) molecules depends partly on the photostability of the individual species. We have studied the dissociative photoionization of two ethynyl-substituted PAH species, namely, 9-ethynylphenanthrene and 1-ethynylpyrene. Their adiabatic ionization energy and the appearance energy of fragment ions have been measured with the photoelectron photoion coincidence spectroscopy technique. The adiabatic ionization energy has been found at 7.84 ± 0.02 eV for 9-ethynylphenanthrene and at 7.41 ± 0.02 eV for 1-ethynylpyrene. These values are similar to those determined for the corresponding non-substituted PAH molecules phenanthrene and pyrene. The appearance energy ofmore » the fragment ion indicative of the loss of a H atom following photoionization is also similar for either ethynyl-substituted PAH molecule and its non-substituted counterpart. The measurements are used to estimate the critical energy for the loss of a H atom by the PAH cations and the stability of ethynyl-substituted PAH molecules upon photoionization. We conclude that these PAH derivatives are as photostable as the non-substituted species in H i regions. If present in the interstellar medium, they may play an important role in the growth of interstellar PAH molecules.« less

Spectroscopy of Cosmic Carbon Analogs in Inert-Gas Matrices and in the Gas-Phase: Comparative Results and Perspectives for Astrophysics

NASA Technical Reports Server (NTRS)

Salama, Farid; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

Recent studies of the spectroscopy of large (up to approx. 50 carbon atoms) neutral and Ionized polycyclic aromatic hydrocarbons (PAHs) and Fullerenes isolated in inert gas matrices will be presented. The advantages and the limitations of matrix isolation spectroscopy for the study of the molecular spectroscopy of interstellar dust analogs will be discussed. The laboratory data will be compared to the astronomical spectra (the interstellar extinction, the diffuse interstellar bands). Finally, the spectra of PAH ions isolated in neon/argon matrices will be compared to the spectra obtained for PAH ion seeded in a supersonic expansion. The astrophysical implications and future perspectives will be discussed.

Deuterium Enrichment of PAHs by VUV Irradiation of Interstellar Ices

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Gillette, J. Seb; Zare, Richard N.; DeVincenzi, Donald (Technical Monitor)

1998-01-01

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

Polycyclic Aromatic Hydrocarbons and the Diffuse Interstellar Bands: a Survey

NASA Technical Reports Server (NTRS)

Salama, F.; Galazutdinov, G. A.; Krelowski, J.; Allamandola, L. J.; Musaev, F. A.; DeVincenzi, Donald L. (Technical Monitor)

1999-01-01

We discuss the proposal relating the origin of some of the diffuse interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons (PAHs) present in interstellar clouds. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices, are compared with an extensive set of astronomical spectra of reddened, early type stars. From this comparison, it is concluded that PAN ions are good candidates to explain some of the DIBs. Unambiguous assignments are difficult, however, due to the shift in wavelengths and the band broadening induced in the laboratory spectra by the solid matrix. Definitive band assignments and, ultimately, the test of the of the proposal that PAH ions carry some of the DIB must await the availability of gas-phase measurements in the laboratory. The present assessment offers a guideline for future laboratory experiments by allowing the preselection of promising PAH molecules to be studied in jet expansions.

A TALE OF TWO MYSTERIES IN INTERSTELLAR ASTROPHYSICS: THE 2175 A EXTINCTION BUMP AND DIFFUSE INTERSTELLAR BANDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiang, F. Y.; Zhong, J. X.; Li Aigen, E-mail: jxzhong@xtu.edu.cn, E-mail: lia@missouri.edu

2011-06-01

The diffuse interstellar bands (DIBs) are ubiquitous absorption spectral features arising from the tenuous material in the space between stars-the interstellar medium (ISM). Since their first detection nearly nine decades ago, over 400 DIBs have been observed in the visible and near-infrared wavelength range in both the Milky Way and external galaxies, both nearby and distant. However, the identity of the species responsible for these bands remains as one of the most enigmatic mysteries in astrophysics. An equally mysterious interstellar spectral signature is the 2175 A extinction bump, the strongest absorption feature observed in the ISM. Its carrier also remainsmore » unclear since its first detection 46 years ago. Polycyclic aromatic hydrocarbon (PAH) molecules have long been proposed as a candidate for DIBs as their electronic transitions occur in the wavelength range where DIBs are often found. In recent years, the 2175 A extinction bump is also often attributed to the {pi}-{pi}* transition in PAHs. If PAHs are indeed responsible for both the 2175 A extinction feature and DIBs, their strengths may correlate. We perform an extensive literature search for lines of sight for which both the 2175 A extinction feature and DIBs have been measured. Unfortunately, we found no correlation between the strength of the 2175 A feature and the equivalent widths of the strongest DIBs. A possible explanation might be that DIBs are produced by small free gas-phase PAH molecules and ions, while the 2175 A bump is mainly from large PAHs or PAH clusters in condensed phase so that there is no tight correlation between DIBs and the 2175 A bump.« less

Abundances of Neutral and Ionized PAH Along The Lines-of-Sight of Diffuse and Translucent Interstellar Clouds

NASA Astrophysics Data System (ADS)

Salama, Farid; Galazutdinov, G.; Krelowski, J.; Biennier, L.; Beletsky, Y.; Song, I.

2013-06-01

The spectra of neutral and ionized PAHs isolated in the gas phase at low temperature have been measured in the laboratory under conditions that mimic interstellar conditions and are compared with a set of astronomical spectra of reddened, early type stars. The comparisons of astronomical and laboratory data provide upper limits for the abundances of neutral PAH molecules and ions along specific lines-of-sight. Something that is not attainable from infrared observations. We present the characteristics of the laboratory facility (COSmIC) that was developed for this study and discuss the findings resulting from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. COSmIC combines a supersonic jet expansion with discharge plasma and cavity ringdown spectroscopy and provides experimental conditions that closely mimic the interstellar conditions. The column densities of the individual PAH molecules and ions probed in these surveys are derived from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. The comparisons of astronomical and laboratory data lead to clear conclusions regarding the expected abundances for PAHs in the interstellar environments probed in the surveys. Band profile comparisons between laboratory and astronomical spectra lead to information regarding the molecular structures and characteristics associated with the DIB carriers in the corresponding lines-of-sight. These quantitative surveys of neutral and ionized PAHs in the optical range open the way for quantitative searches of PAHs and complex organics in a variety of interstellar and circumstellar environments. Acknowledgements: F.S. acknowledges the support of the Astrophysics Research and Analysis Program of the NASA Space Mission Directorate and the technical support provided by R. Walker at NASA ARC. J.K. acknowledges the financial support of the Polish State. The authors are deeply grateful to the ESO archive as well as to the ESO staff members for their active support.

Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Salama, Farid

2010-01-01

Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of the carbonaceous materials. PAHs are the best-known candidates to account for the IR emission bands. They are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge is to reproduce in the laboratory the physical conditions that exist in the emission and absorption interstellar zones. The harsh physical conditions of the ISM -low temperature, collisionless, strong UV radiation fields- are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions and radicals are formed from the neutral precursors in an isolated environment at low temperature and probed with high-sensitivity cavity ringdown spectroscopy in the NUV-NIR range. Carbon nanoparticles are also formed during the short residence time of the precursors in the plasma and are characterized with time-offlight mass spectrometry. These experiments provide unique information on the spectra of large carbonaceous molecules and ions in the gas phase that can now be directly compared to interstellar and circumstellar observations (IR emission bands, DIBs, extinction curve). These findings also hold great potential for understanding the formation process of interstellar carbonaceous grains. We will review recent progress in the experimental and theoretical studies of PAHs, compare the laboratory data with astronomical observations and discuss the global implications.

On the Relative "Transparency" of Gas-phase Coronene Molecules to Low-energy Electrons: Effects on the Interstellar Medium

NASA Astrophysics Data System (ADS)

Carelli, F.; Gianturco, F. A.

2011-12-01

Free, gas-phase polycyclic aromatic hydrocarbons (PAHs) are understood to play an important role in the interstellar medium (ISM), as they are thought to significantly contribute to both diffused and unidentified infrared interstellar bands. They are also considered fundamental blocks of the interstellar dust, whose nature has important implications for a plethora of physical and chemical nanoscopic processes within the ISM. Since free electrons represent a versatile alternative way to transport energy in the interstellar space, in this paper we compute from quantum scattering methods the angular redistributions of free electrons by gas-phase coronene molecules, the latter of which are believed to be one of the most representative PAHs, in order to assess their role in describing the efficiency of electron deflection by this molecule. The associated rates can provide useful information about the coupling mechanism between external radio-frequency fields and complex molecular plasmas containing neutral and ionized PAHs. They can also yield information on the possible presence of such species in the dust phase of the medium.

Recent Progress in DIB Research: Survey of PAHS and DIBS

NASA Technical Reports Server (NTRS)

Salama, Farid; Galazutdinov, G.; Krelowski, J.; Biennier, L.; Beletsky, Y.; Song, I.

2013-01-01

The spectra of several neutral and ionized PAHs isolated in the gas phase at low temperature have been measured in the laboratory under experimental conditions that mimic interstellar conditions and are compared with an extensive set of astronomical spectra of reddened, early type stars [1, 2]. The comparisons of astronomical and laboratory data provide upper limits for the abundances of specific neutral PAH molecules and ions along specific lines-of-sight. Something that is not attainable from infrared observations alone. We present the characteristics of the laboratory facility (COSmIC) that was developed for this study and discuss the findings resulting from the comparison of these unique laboratory data with high resolution, high S/N ratio astronomical observations. COSmIC combines a supersonic free jet expansion with discharge plasma and high-sensitivity cavity ringdown spectroscopy and provides experimental conditions that closely mimic the interstellar conditions. The column densities of the individual neutral PAH molecules and ions probed in these surveys are derived from the comparison of these unique laboratory data with high resolution, high S/N ratio astronomical observations. The comparisons of astronomical and laboratory data lead to clear and unambiguous conclusions regarding the expected abundances for PAHs of various sizes and charge states in the interstellar environments probed in the surveys. Band profile comparisons between laboratory and astronomical spectra lead to information regarding the molecular structures and characteristics associated with the DIB carriers in the corresponding lines-of-sight. These quantitative surveys of neutral and ionized PAHs in the optical range open the way for unambiguous quantitative searches of PAHs and complex organics in a variety of interstellar and circumstellar environments.

Assessment of the Polycyclic Aromatic Hydrocarbon-Diffuse Interstellar Band Proposal

NASA Technical Reports Server (NTRS)

Salama, Farid; Bakes, F.; Allamandola, L.; Tielens, A. G. G. M.; Witteborn, Fred C. (Technical Monitor)

1995-01-01

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high energy range of the spectrum, and possess a large oscillator strength), and seems to correlate with strong and broad DIBs. In the case of non-compact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low energy range of the spectrum, and possess a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that: (i) Only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narrow bands on the other hand can easily be interpreted in the context of the PAH proposal by a distribution between compact and non-compact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would provide tracers of conditions within a cloud which globally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations of the ultraviolet range, is called for.

Assessment of the polycyclic aromatic hydrocarbon-diffuse interstellar band proposal

NASA Technical Reports Server (NTRS)

Salama, F.; Bakes, E. L.; Allamandola, L. J.; Tielens, A. G.

1996-01-01

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high-energy range of the spectrum, and possesses a large oscillator strength), and seems to correlate with strong and broad DIBs. For noncompact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low-energy range of the spectrum, and possesses a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that (i) only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narow bands on the other can easily be interpreted in the context of the PAH proposal by a distribution of compact and noncompact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would reflect conditions within a cloud which locally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations in the ultraviolet range, is called for.

Infrared spectra of interstellar deuteronated PAHs

NASA Astrophysics Data System (ADS)

Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter

2015-08-01

Polycyclic Aromatic Hydrocarbon (PAH) molecules have emerged as a potential constituent of the ISM that emit strong features at 3.3, 6.2, 7.7, 8.6, 11.2 and 12.7 μm with weaker and blended features in the 3-20μm region. These features are proposed to arise from the vibrational relaxation of PAH molecules on absorption of background UV photons (Tielens 2008). These IR features have been observed towards almost all types of astronomical objects; say H II regions, photodissociation regions, reflection nebulae, planetary nebulae, young star forming regions, external galaxies, etc. A recent observation has proposed that interstellar PAHs are major reservoir for interstellar deuterium (D) (Peeters et al. 2004). According to the `deuterium depletion model' as suggested by Draine (2006), some of the Ds formed in the big bang are depleted in PAHs, which can account for the present value of D/H in the ISM. Hence, study of deuterated PAHs (PADs) is essential in order to measure D/H in the ISM.In this work, we consider another probable category of the large PAH family, i.e. Deuteronated PAHs (DPAH+). Onaka et al. have proposed a D/H ratio which is an order of magnitude smaller than the proposed value of D/H by Draine suggesting that if Ds are depleted in PAHs, they might be accommodated in large PAHs (Onaka et al. 2014). This work reports a `Density Functional Theory' calculation of large deuteronated PAHs (coronene, ovalene, circumcoronene and circumcircumcoronene) to determine the expected region of emission features and to find a D/H ratio that is comparable to the observational results. We present a detailed analysis of the IR spectra of these molecules and discuss the possible astrophysical implications.ReferencesDraine B. T. 2006, in ASP Conf. Ser. 348, Proc. Astrophysics in the Far Ultraviolet: Five Years of Discovery with FUSE, ed. G. Sonneborn, H. Moos, B-G Andersson (San Francisco, CA:ASP) 58Onaka T., Mori T. I., Sakon I., Ohsawa R., Kaneda H., Okada Y., Tanaka M., 2014, ApJ,780,114Peeters E., Allamandola L. J., Bauschlicher C. W., Jr., Hudgins D. M., Sandford S. A., Tielens A. G. G. M., 2004, ApJ, 604, 252Tielens A. G. G. M. 2008, ARA&A, 46, 289

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.; Gillette, J. S.; Zare, R. N.

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

Direct spectroscopic evidence for ionized polycyclic aromatic hydrocarbons in the interstellar medium.

PubMed

Sloan, G C; Hayward, T L; Allamandola, L J; Bregman, J D; DeVito, B; Hudgins, D M

1999-03-01

Long-slit 8-13 micrometers spectroscopy of the nebula around NGC 1333 SVS 3 reveals spatial variations in the strength and shape of emission features that are probably produced by polycyclic aromatic hydrocarbons (PAHs). Close to SVS 3, the 11.2 micrometers feature develops an excess at approximately 10.8-11.0 micrometers and a feature appears at approximately 10 micrometers. These features disappear with increasing distance from the central source, and they show striking similarities to recent laboratory data of PAH cations, providing the first identification of emission features arising specifically from ionized PAHs in the interstellar medium.

Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in a Cosmic Simulation Chamber

NASA Astrophysics Data System (ADS)

Bejaoui, Salma; Salama, Farid

2015-08-01

Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs [1, 2]. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions [see 3 for a review]. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser-induced fluorescence (LIF) technique [4] and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examinedReferences[1] F. Salama, E. Bakes, L.J. Allamandola, A.G.G.M. Tielens, Astrophys. J., 458 (1996) p.621[2] F. Salama, The ISO Revolution, EDP Sciences, Les Ulis, France (1999) p.65[3] Salama F., In Organic Matter in Space, IAU Symposium 251, Kwok & Sandford Eds.Cambridge University Press,4, S251,(2008), p. 357 (2008) and references therein.[4] Salma Bejaoui, Xavier Mercier, Pascale Desgroux, Eric Therssen, Comb.& Fl, 161 (2014) p. 2479

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

2002-01-01

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Polycyclic aromatic hydrocarbons in stellar medium

NASA Astrophysics Data System (ADS)

Rastogi, Shantanu

2005-06-01

Polycyclic Aromatic Hydrocarbons (PAHs) are an important com- ponent of the Interstellar Medium (ISM). They are being used as probes for understanding of process and conditions of different astrophysical environments. The understanding of their IR spectra and its variations with PAH size and ionization state is useful in characterizing the ISM. Spectral features of model graphene sheets and also that of smaller PAH molecules are reported. The variation of intensity with charge state of the molecule shows that cations give a better correlation with observations. The relationship between changes in charge distribution with intensity changes upon ionization has been probed.

New Interstellar Dust Models Consistent with Interstellar Extinction, Emission and Abundances Constraints

NASA Technical Reports Server (NTRS)

Zubko, V.; Dwek, E.; Arendt, R. G.; Oegerle, William (Technical Monitor)

2001-01-01

We present new interstellar dust models that are consistent with both, the FUV to near-IR extinction and infrared (IR) emission measurements from the diffuse interstellar medium. The models are characterized by different dust compositions and abundances. The problem we solve consists of determining the size distribution of the various dust components of the model. This problem is a typical ill-posed inversion problem which we solve using the regularization approach. We reproduce the Li Draine (2001, ApJ, 554, 778) results, however their model requires an excessive amount of interstellar silicon (48 ppM of hydrogen compared to the 36 ppM available for an ISM of solar composition) to be locked up in dust. We found that dust models consisting of PAHs, amorphous silicate, graphite, and composite grains made up from silicates, organic refractory, and water ice, provide an improved fit to the extinction and IR emission measurements, while still requiring a subsolar amount of silicon to be in the dust. This research was supported by NASA Astrophysical Theory Program NRA 99-OSS-01.

Laboratory spectroscopy and astronomical significance of the fully-benzenoid PAH triphenylene and its cation

NASA Astrophysics Data System (ADS)

Kofman, V.; Sarre, P. J.; Hibbins, R. E.; ten Kate, I. L.; Linnartz, H.

2017-06-01

Triphenylene (C18H12) is a highly symmetric polycyclic aromatic hydrocarbon (PAH) molecule with a 'fully-benzenoid' electronic structure. This confers a high chemical stability compared with PAHs of similar size. Although numerous infrared and UV-vis experimental spectroscopic and theoretical studies of a wide range PAHs in an astrophysical context have been conducted, triphenylene and its radical cation have received almost no attention. There exists a huge body of spectroscopic evidence for neutral and ionised PAHs in astrophysical sources, obtained principally through detection of infrared emission features that are characteristic of PAHs as a chemical class. However, it has so far not proved possible to identify spectroscopically a single isolated PAH in space, although PAHs including triphenylene have been detected mass spectrometrically in meteorites. In this work we focus on recording laboratory electronic spectra of neutral and ionised triphenylene between 220 and 780 nm, trapped in H2O ice and solid argon at 12 K. The studies are motivated by the potential for spectroscopic astronomical detection of electronic absorption spectra of PAHs in ice mantles on interstellar grains as discussed by Linnartz (2014), and were performed also in a cold Ar matrix to provide guidance as to whether triphenylene (particularly in its singly positively ionised form) could be a viable candidate for any of the unidentified diffuse interstellar absorption bands. Based on the argon-matrix experimental results, comparison is made with previously unpublished astronomical spectra near 400 nm which contain broad interstellar absorption features consistent with the predictions from the laboratory matrix spectra, thus providing motivation for the recording of gas-phase electronic spectra of the internally cold triphenylene cation.

The ultraviolet and visible spectrum of the polycyclic aromatic hydrocarbon C10H8(+) - Possible contributions to the diffuse interstellar bands and to the ultraviolet-visible extinction

NASA Technical Reports Server (NTRS)

Salama, F.; Allamandola, L. J.

1992-01-01

The properties of the cation of the PAH naphthalene (C10H8(+)) isolated in inert gas matrices under conditions relevant to astrophysical environments are described. The band at 6741 A is the strongest and falls close to the weak 6742 A diffuse interstellar bands (DIBs). Five other weaker bands also fall remarkably close to the positions of known DIBs. A very intense and broad continuum extended from the UV to the visible, which seems to be associated with the ion, is reported. The molar absorption coefficient at the peak of the continuum is 2.0 x 10 exp 6 cu dm/mol cm. If a continuum is a general property of PAH cations, this characteristic will have a strong impact on the understanding of how PAHs convert interstellar UV and visible radiation into IR radiation.

Laboratory Spectroscopy of Large Carbon Molecules and Ions in Support of Space Missions

NASA Technical Reports Server (NTRS)

Salana, Farid; Tan, X.; Cami, J.; Remy, J.

2006-01-01

One of the major objectives of Laboratory Astrophysics is the optimization of data return from space missions by measuring spectra of atomic and molecular species in laboratory environments that mimic interstellar conditions (WhitePaper (2002, 2006)). Among interstellar species, PAHs are an important and ubiquitous component of carbon-bearing materials that represents a particularly difficult challenge for gas-phase laboratory studies. We present the absorption spectra of jet-cooled neutral and ionized PAHs and discuss the implications for astrophysics. The harsh physical conditions of the interstellar medium have been simulated in the laboratory. We are now, for the first time, in the position to directly compare laboratory spectra of PAHs and carbon nanoparticles with astronomical observations. This new phase offers tremendous opportunities for the data analysis of current and upcoming space missions geared toward the detection of large aromatic systems (HST/COS, FUSE, JWST, Spitzer).

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

NASA Technical Reports Server (NTRS)

Sagan, Carl; Khare, B. N.; Thompson, W. R.; Mcdonald, G. D.; Wing, Michael R.; Bada, Jeffrey L.; Vo-Dinh, Tuan; Arakawa, E. T.

1993-01-01

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

Interstellar Dust Models Consistent with Extinction, Emission, and Abundance Constraints

NASA Technical Reports Server (NTRS)

Zubko, Viktor; Dwek, Eli; Arendt, Richard G.

2004-01-01

We present new interstellar dust models which have been derived by simultaneously fitting the far ultraviolet to near infrared extinction, the diffuse infrared emission, and, unlike previous models, the elemental abundances in dust for the diffuse interstellar medium. We found that dust models consisting of a mixture of spherical graphite and silicate grains, polycyclic aromatic hydrocarbon (PAH) molecules, in addition to porous composite particles containing silicate, organic refractory, and water ice, provide an improved .t to the UV-to-infrared extinction and infrared emission measurements, while consuming the amounts of elements well within the uncertainties of adopted interstellar abundances, including B star abundances. These models are a signi.cant improvement over the recent Li & Draine (2001, ApJ, 554, 778) model which requires an excessive amount of silicon to be locked up in dust: 48 ppm (atoms per million of H atoms), considerably more than the solar abundance of 34 ppm or the B star abundance of 19 ppm.

LABORATORY PHOTO-CHEMISTRY OF PAHS: IONIZATION VERSUS FRAGMENTATION

PubMed Central

Zhen, Junfeng; Castellanos, Pablo; Paardekooper, Daniel M.; Ligterink, Niels; Linnartz, Harold; Nahon, Laurent; Joblin, Christine; Tielens, Alexander G. G. M.

2015-01-01

Interstellar Polycyclic Aromatic Hydrocarbons (PAH) are expected to be strongly processed by Vacuum Ultra-Violet (VUV) photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C24H12), ovalene (C32H14) and hexa-peri-hexabenzocoronene (HBC; C42H18) cations by exposure to synchrotron radiation in the range of 8–40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs, fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium (ISM) are briefly discussed. PMID:26688710

LABORATORY PHOTO-CHEMISTRY OF PAHs: IONIZATION VERSUS FRAGMENTATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhen, Junfeng; Castellanos, Pablo; Ligterink, Niels

2015-05-01

Interstellar polycyclic aromatic hydrocarbons (PAHs) are expected to be strongly processed by vacuum ultraviolet photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C{sub 24}H{sub 12}), ovalene (C{sub 32}H{sub 14}) and hexa-peri-hexabenzocoronene (HBC; C{sub 42}H{sub 18}) cations by exposure to synchrotron radiation in the range of 8–40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs,more » fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium are briefly discussed.« less

Polycyclic aromatic hydrocarbons and the unidentified infrared emission bands - Auto exhaust along the Milky Way

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

1985-01-01

The unidentified infrared emission features (UIR bands) are attributed to a collection of partially hydrogenated, positively charged polycyclic aromatic hydrocarbons (PAHs). This assignment is based on a spectroscopic analysis of the UIR bands. Comparison of the observed interstellar 6.2 and 7.7-micron bands with the laboratory measured Raman spectrum of a collection of carbon-based particulates (auto exhaust) shows a very good agreement, supporting this identification. The infrared emission is due to relaxation from highly vibrationally and electronically excited states. The excitation is probably caused by UV photon absorption. The infrared fluorescence of one particular, highly vibrationally excited PAH (chrysene) is modeled. In this analysis the species is treated as a molecule rather than bulk material and the non-thermodynamic equilibrium nature of the emission is fully taken into account. From a comparison of the observed ratio of the 3.3 to 11.3-micron UIR bands with the model calculations, the average number of carbon atoms per molecule is estimated to be about 20. The abundance of interstellar PAHs is calculated to be about 2 x 10 to the -7th with respect to hydrogen.

From Interstellar PAHs and Ices to the Origin of Life

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In dense molecular clouds, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier interstellar chemistry standards, is widespread throughout the Universe. The first part of this lecture will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, concentrations, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the solar nebula during the star and planet formation stage, the materials frozen into interstellar/precometary ices are photoprocessed by ultraviolet light, producing more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the early Earth. As these materials are thought to be the building blocks of comets and related to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex organic materials on the early Earth and their composition may be related to the origin of life.

The diffuse interstellar bands: a tracer for organics in the diffuse interstellar medium?

NASA Technical Reports Server (NTRS)

Salama, F.

1998-01-01

The diffuse interstellar bands (DIBs) are absorption bands seen in the spectra of stars obscured by interstellar dust. DIBs are recognized as a tracer for free, organic molecules in the diffuse interstellar medium (ISM). The potential molecular carriers for the DIBs are discussed with an emphasis on neutral and ionized polycyclic aromatic hydrocarbons (PAHs) for which the most focused effort has been made to date. From the combined astronomical, laboratory and theoretical study, it is concluded that a distribution of free neutral and ionized complex organics (PAHs, fullerenes, unsaturated hydrocarbons) represents the most promising class of candidates to account for the DIBs. The case for aromatic hydrocarbons appears particularly strong. The implied widespread distribution of complex organics in the diffuse ISM bears profound implications for our understanding of the chemical complexity of the ISM, the evolution of prebiotic molecules and its impact on the origin and the evolution of life on early Earth through the exogenous delivery (cometary encounters and metoritic bombardments) of prebiotic organics.

In-situ Probing of Radiation-induced Processing of Organics in Astrophysical Ice Analogs—Novel Laser Desorption Laser Ionization Time-of-flight Mass Spectroscopic Studies

NASA Astrophysics Data System (ADS)

Gudipati, Murthy S.; Yang, Rui

2012-09-01

Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Lyα radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K—close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies—the first glimpses into interstellar ice chemistry through analog studies—show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

Polycyclic Aromatic Hydrocarbon Ionization Energy Lowering in Water Ices

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.; Allamandola, Louis J.

2004-01-01

In studying various interstellar and solar system ice analogs, we have recently found that upon vacuum ultraviolet photolysis, polycyclic aromatic hydrocarbons (PAHs) frozen in water ice at low temperatures are easily ionized and indefinitely stabilized as trapped ions (Gudipati; Gudipati & Allamandola). Here we report the first experimental study that shows that PAH ionization energy is significantly lowered in PAH/H2O ices, in agreement with recent theoretical work (Woon & Park). The ionization energy (IE) of the PAH studied here, quaterrylene (C40H20, IE = 6.11 eV), is lowered by up to 2.11 eV in water ice. PAH ionization energy reduction in low-temperature water ice substantially expands the astronomical regions in which trapped ions and electrons may be important. This reduction in ionization energy should also hold for other types of trapped species in waterrich interstellar, circumstellar, and solar system ices. Subject headings: ISM: clouds - methods: laboratory - molecular processes - radiation mechanisms: nonthermal -ultraviolet: ISM - ultraviolet: solar system

Steps Toward Identifying PAHs: A Child's Garden of Recent Results

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.

2005-01-01

Based on over two decades of experimental, observational and theoretical studies by scientists around the world. It is now widely accepted that the composite emission of mixtures of vibrationally-excited PAHs and PAH ions can accommodate the general pattern of band positions, intensities, and profiles observed in the discreet IR emission features of carbon-rich interstellar dust, as well as the variations in those characteristics. These variations provide insight into the detailed nature of the emitting PAH population and reflect conditions within the emitting regions giving the population enormous potential as probes of astrophysical environments. Moreover, the ubiquity and abundance of this material has impacts that extend well beyond the IR. In this presentation we will examine recent, combined experimental, theoretical, and observational studies that indicate that nitrogen-substituted PAHs represent an important component of the interstellar dust population, and we will go on to explore some of the ramifications of this result. We will also explore the results of recent experimental studies of the strong, low-lying electronic transitions of ionized PAH ions in the Near-IR (0.7 - 2.5 microns) and explore the role that these transitions might play in pumping the PAH IR emission in regions of low-excitation.

Interstellar fullerene compounds and diffuse interstellar bands

NASA Astrophysics Data System (ADS)

Omont, Alain

2016-05-01

Recently, the presence of fullerenes in the interstellar medium (ISM) has been confirmed and new findings suggest that these fullerenes may possibly form from polycyclic aromatic hydrocarbons (PAHs) in the ISM. Moreover, the first confirmed identification of two strong diffuse interstellar bands (DIBs) with the fullerene, C60+, connects the long standing suggestion that various fullerenes could be DIB carriers. These new discoveries justify reassessing the overall importance of interstellar fullerene compounds, including fullerenes of various sizes with endohedral or exohedral inclusions and heterofullerenes (EEHFs). The phenomenology of fullerene compounds is complex. In addition to fullerene formation in grain shattering, fullerene formation from fully dehydrogenated PAHs in diffuse interstellar clouds could perhaps transform a significant percentage of the tail of low-mass PAH distribution into fullerenes including EEHFs. But many uncertain processes make it extremely difficult to assess their expected abundance, composition and size distribution, except for the substantial abundance measured for C60+. EEHFs share many properties with pure fullerenes, such as C60, as regards stability, formation/destruction and chemical processes, as well as many basic spectral features. Because DIBs are ubiquitous in all lines of sight in the ISM, we address several questions about the interstellar importance of various EEHFs, especially as possible carriers of diffuse interstellar bands. Specifically, we discuss basic interstellar properties and the likely contributions of fullerenes of various sizes and their charged counterparts such as C60+, and then in turn: 1) metallofullerenes; 2) heterofullerenes; 3) fulleranes; 4) fullerene-PAH compounds; 5) H2@C60. From this reassessment of the literature and from combining it with known DIB line identifications, we conclude that the general landscape of interstellar fullerene compounds is probably much richer than heretofore realized. EEHFs, together with pure fullerenes of various sizes, have many properties necessary to be suitably carriers of DIBs: carbonaceous nature; stability and resilience in the harsh conditions of the ISM; existing with various heteroatoms and ionization states; relatively easy formation; few stable isomers; spectral lines in the right spectral range; various and complex energy internal conversion; rich Jahn-Teller fine structure. This is supported by the first identification of a DIB carrier as C60+. Unfortunately, the lack of any precise information about the complex optical spectra of EEHFs and most pure fullerenes other than C60 and about their interstellar abundances still precludes definitive assessment of the importance of fullerene compounds as DIB carriers. Their compounds could significantly contribute to DIBs, but it still seems difficult that they are the only important DIB carriers. Regardless, DIBs appear as the most promising way of tracing the interstellar abundances of various fullerene compounds if the breakthrough in identifying C60+ as a DIB carrier can be extended to more spectral features through systematic studies of their laboratory gas-phase spectroscopy.

The IR emission features - Emission from PAH molecules and amorphous carbon particles

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

1987-01-01

Techniques for the assessment of the importance of the various forms of PAHs, and recent infrared observations concerning the PAH problem, are considered. Spectroscopic data suggest that the observed interstellar spectrum is due to both free molecule-sized PAHs producing the narrow features, and amorphous carbon particles contributing to the broad underlying components. Explanations for the multicomponent emission spectrum are discussed. A model of the emission mechanism for the example of chrysene is presented, and an exact treatment of the IR fluorescence from highly vibrationally excited large molecules shows that species containing 20-30 carbon atoms are responsible for the narrow features, although the spectra more closely resemble those of amorphous carbon particles. It is suggested that future emphasis should be placed on the spatial characteristics of the component spectra.

Peripherally hydrogenated neutral polycyclic aromatic hydrocarbons as carriers of the 3 micron interstellar infrared emission complex: results from single-photon infrared emission spectroscopy

NASA Technical Reports Server (NTRS)

Wagner, D. R.; Kim, H. S.; Saykally, R. J.

2000-01-01

Infrared emission spectra of five gas-phase UV laser-excited polycyclic aromatic hydrocarbons (PAHs) containing aliphatic hydrogens are compared with the main 3.3 microns and associated interstellar unidentified infrared emission bands (UIRs). We show that neutral PAHs can account for the majority of the 3 microns emission complex while making little contribution to the other UIR bands; peripherally hydrogenated PAHs produce a better match to astrophysical data than do those containing methyl side groups; 3.4 microns plateau emission is shown to be a general spectral feature of vibrationally excited PAHs containing aliphatic hydrogens, especially those containing methyl groups; and finally, hot-band and overtone emissions arising from aromatic C-H vibrations are not observed in laboratory emission spectra, and therefore, in contrast to current assignments, are not expected to be observed in the UIRs.

Evidence for the Presence of Hn-PAHs in Post AGB Stars

NASA Technical Reports Server (NTRS)

Materese, Christopher K.; Bregman, Jesse D.; Sandford, Scott A.

2017-01-01

Polycyclic aromatic hydrocarbons (PAHs) are believed to be ubiquitous in space therefore represent an important class of molecules for the field of astrochemistry. PAHs are relatively stable under interstellar conditions, account for a significant fraction of the known Universe's molecular carbon inventory, and are believed responsible for numerous telltale interstellar infrared emission bands. PAHs can be subdivided into numerous classes, one of which is Hydrogenated PAHs (Hn-PAHs). Hn-PAHs are multi-ringed partially aromatic compounds with excess hydrogenation, leading to a partial disruption of the aromatic system. The infrared spectra of these compounds produce telltale signatures that make them distinct from ordinary aromatic or aliphatic molecules (or a mixture of both). Hn-PAHs may be an important subclass of PAHs that could explain the spectra of some astronomical objects with anomalously large 3.4 micron features. The 3.4 micron feature observed in these objects may be associated with the aliphatic C-H stretching vibrations of the excess hydrogen. If this presumption is correct, we also expect to observe methylene scissoring modes at 6.9 microns. We have recently conducted a series of follow-up observations to compliment our laboratory experiments into the properties of Hn-PAHs. Here we present our laboratory and observational results in support of the hypothesis that Hn-PAHs are a viable candidate molecule as the emission source for numerous post-asymptotic giant branch objects with abnormally large 3.4 micron features.

Laboratory rotational spectroscopy of cyano substituted polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

McNaughton, Don; Jahn, Michaela K.; Travers, Michael J.; Wachsmuth, Dennis; Godfrey, Peter D.; Grabow, Jens-Uwe

2018-06-01

The rotational spectra of the four cyano substituted polycyclic aromatic hydrocarbon (PAH) molecules 1-cyanonaphthalene, 2-cyanonaphthalene, 9-cyanoanthracene, and 9-cyanophenanthrene have been recorded in molecular expansions using a Stark-modulated millimetre-wave spectrometer and a Fourier transform microwave spectrometer in the centimetre-wave region. The spectra have been assigned and fitted to provide molecular constants and quadrupole hyperfine constants of sufficient accuracy to enable complete hyperfine structure line predictions for interstellar searches. The data may provide a route into detection of small PAHs in the interstellar medium.

Formation of Meteoritic Organic Molecules by Aqueous Alteration of Interstellar Carbonaceous Materials: a Laboratory Model

NASA Astrophysics Data System (ADS)

Saperstein, E.; Arnoult, K. M.; Wdowiak, T. J.; Gerakines, P. A.

2002-09-01

Polycyclic aromatic hydrocarbons (PAHs) have been proposed as a component of interstellar dust. PAHs have also been positively identified in interplanetary dust particles (IDPs) and in carbonaceous meteorites. Many such meteorites show strong evidence for aqueous alteration of their mineral phases, which can be spatially correlated to the presence of organics. This suggests the possibility that PAHs, incorporated into a meteorite parent body, may have been altered along with neighboring minerals and other constituents in the presence of liquid water. We present preliminary results of the alteration of a laboratory analog of interstellar carbonaceous dust, produced by processing naphthalene in a hydrogen plasma, by exposing it to water at elevated temperature (100, 150, and 200 C) and pressure in a sealed container for 24 hours. This is a simulation of pressure capping during the accretion of the parent body. The high temperatures chosen here bring water near its critical point, at which it becomes extremely reactive. One sign of this reactivity is seen in the observed color of the aqueously altered product, changing from golden yellow (original color) to black at 200 C. Comparison of the infrared spectra of the original dust analog with those of the aqueously altered product show an oxidation feature at 1700 cm-1, present in all three products but absent in the dust analog. High performance liquid chromatography (HPLC) of the aqueously altered product, refluxed in tetrahydrafuran, shows a variety of low retention peaks (<600 s), absent in the original dust analog.

Infrared emission from hydrogenated amorphous carbon and amorphous carbon grains in the interstellar medium

NASA Technical Reports Server (NTRS)

Duley, W. W.; Jones, A. P.; Taylor, S. D.; Williams, D. A.

1993-01-01

The correlations deduced by Boulanger et al. (1990) from IRAS maps of the Chamaeleon, Taurus and Ursa Major molecular cloud complexes are interpreted in terms of the evolutionary hydrogenated amorphous carbon model of interstellar dust. In particular, regions of relatively strong 12-micron emission may be regions where recently accreted carbon is being converted by ambient UV to small PAHs in situ. Regions of weak 12-micron emission are probably quiescent regions where carbon has been annealed to amorphous carbon. Observational consequences of these inferences are briefly described.

The Identification of Complex Organic Molecules in the Interstellar Medium: Using Lasers and Matrix Isolation Spectroscopy to Simulate the Interstellar Environment

NASA Technical Reports Server (NTRS)

Stone, Bradley M.

1998-01-01

The Astrochemistry Group at NASA Ames Research Center is interested in the identification of large organic molecules in the interstellar medium Many smaller organic species (e.g. hydrocarbons, alcohols, etc.) have been previously identified by their radiofrequency signature due to molecular rotations. However, this becomes increasingly difficult to observe as the size of the molecule increases. Our group in interested in the identification of the carriers of the Diffuse Interstellar Bands (absorption features observed throughout the visible and near-infrared in the spectra of stars, due to species in the interstellar medium). Polycyclic Aromatic Hydrocarbons (PAHs) and related molecules are thought to be good candidates for these carriers. Laboratory experiments am performed at Ames to simulate the interstellar environment, and to compare spectra obtained from molecules in the laboratory to those derived astronomically. We are also interested in PAHs with respect to their possible connection to the UIR (Unidentified infrared) and ERE (Extended Red Emission) bands - emission features found to emanate from particular regions of our galaxy (e.g. Orion nebula, Red Rectangle, etc.). An old, "tried and proven spectroscopic technique, matrix isolation spectroscopy creates molecular conditions ideal for performing laboratory astrophysics.

Website for the Astrochemistry Laboratory, Astrophysics Branch, Space Sciences Division

NASA Technical Reports Server (NTRS)

Sandford, Scott; DeVincenzi, D. (Technical Monitor)

2002-01-01

The Astrochemistry Laboratory in the Astrophysics Branch (SSA) of the Space Sciences Division at NASA's Ames Research Center specializes in the study of extraterrestrial materials and their analogs. The staff has pioneered laboratory studies of space environments including interstellar, cometary, and planetary ices, simulations of the so-called 'Unidentified' Infrared Emission Bands and Diffuse Interstellar Bands using PAHs (Polycyclic Aromatic Hydrocarbons) and PAH-related materials, and has extensive experience with low-temperature spectroscopy and astronomical observation. Important discoveries made by the Astrochemistry Group include: (1) The recognition that polycyclic aromatic hydrocarbons and their ions are common in space; (2) The identification of a major fraction of the known molecular species frozen in interstellar/pre-cometary ices; (3) The recognition that a significant fraction of the carbon in the interstellar medium is carried by both microdiamonds and organic materials; (4) The expansion of the types of molecules expected to be synthesized in interstellar/pre-cometary ices. These could be delivered to the early Earth (or other body) and influence the origin or early evolution of life.

A survey for PAH emission in H II regions, planetary and proto-planetary nebulae

NASA Technical Reports Server (NTRS)

Demuizon, M.; Cox, P.; Lequeux, J.

1989-01-01

The results of a systematic investigation of polycyclic aromatic hydrocarbon (PAH) emission in H II regions, planetary nebulae (PN), and proto-planetary nebulae (PNN), are reported. Data is obtained from the low resolution spectra (LRS) of IRAS. The results show that: PAHs are formed in carbon rich objects; and PAH emission is ubiquitous in general interstellar medium and requires the presence of ultraviolet photons, in planetary and proto-planetary nebulae, PAH emission is seen only where an ionizing flux is present and in carbon rich objects.

Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Hardegree-Ullman, E.E.; Gudipati, M.S.; Boogert, A.C.A.; Lignell, H.; Allamandola, L.J.; Stapelfeldt, K. R.; Werner, M.

2014-01-01

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometers) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10 to 20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conducted to determine the positions and strengths of the bands of pyrene mixed with H2O and deuterium oxide ices. The deuterium oxide mixtures are used to measure pyrene bands that are masked by the strong bands of H2O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 micrometers. Our infrared band strengths were normalized to experimentally determined ultraviolet (UV) band strengths, and we find that they are generally approximately 50% larger than those reported by Bouwman et al. (2011) based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. (2008) to estimate the contribution of frozen PAHs to absorption in the 5 to 8 micrometer spectral region, taking into account the strength of the 3.25 micrometer CH stretching mode. It is found that frozen neutral PAHs contain 5 to 9% of the cosmic carbon budget, and account for 2 to 9% of the unidentified absorption in the 5 to 8 micrometer region.

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

NASA Technical Reports Server (NTRS)

Zare, Richard N.; Boyce, Joseph M. (Technical Monitor)

2001-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

High Abundance of Ions in Cosmic Ices

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.; Allamandola, Louis J.; Fonda, Mark (Technical Monitor)

2002-01-01

Water-rich, mixed molecular ices and polycyclic aromatic hydrocarbons (PAHs) are common throughout interstellar molecular clouds and the Solar System. Vacuum ultraviolet (VUV) irradiation and particle bombardment of these abiotic ices produces complex organic species, including important biogenic molecules such as amino acids and functionalized PAHs which may have played a role in the origin of life. This ability of such water-rich, oxygen dominated ices to promote production of complex organic species is surprising and points to an important, unusual, but previously overlooked mechanism at play within the ice. Here we report the nature of this mechanism using electronic spectroscopy. VUV-irradiation of PAH/H2O ices leads to an unprecedented and efficient (greater than 70 %) conversion of the neutral PAHs to their cation form (PAH+). Further, these H2O/PAH+ ices are stabile at temperatures below 50 K, a temperature domain common throughout interstellar clouds and the Solar System. Between 50 and 125 K they react to form the complex organics. In view of this, we conclude that charged PAHs and other molecular ions should be common and abundant in many cosmic ices. The chemical, spectroscopic and physical properties of these ion-rich ices can be of fundamental importance for objects as diverse as comets, planets, and molecular clouds and may account for several poorly understood phenomena associated with each of these object classes.

Evidence that Polycyclic Aromatic Hydrocarbons in Two Carbonaceous Chondrites Predate Parent-Body Formation

NASA Technical Reports Server (NTRS)

Plows, F. L.; Elsila, J. E.; Zare, R. N.; Buseck, P. R.

2003-01-01

Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated using spatially resolved microprobe laser-desorption laser-ionization mass spectrometry. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating prior to or contemporary with the formation of the parent body, consistent with proposed interstellar formation mechanisms.

Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes

NASA Technical Reports Server (NTRS)

Frenklach, Michael; Feigelson, Eric D.

1989-01-01

Production of polycyclic aromatic hydrocarbons in carbon-rich circumstellar envelopes was investigated using a kinetic approach. A detailed chemical reaction mechanism of gas-phase PAH formation and growth, containing approximately 100 reactions of 40 species, was numerically solved under the physical conditions expected in cool stellar winds. The chemistry is based on studies of soot production in hydrocarbon pyrolysis and combustion. Several first-ring and second-ring cyclization processes were considered. A linear lumping algorithm was used to describe PAH growth beyond the second aromatic ring. PAH production using this mechanism was examined with respect to a grid of idealized constant velocity stellar winds as well as several published astrophysical models. The basic result is that the onset of PAH production in the interstellar envelopes is predicted to occur within the temperature interval of 1100 to 900 K. The absolute amounts of the PAHs formed, however, are very sensitive to a number of parameters, both chemical and astrophysical, whose values are not accurately known. Astrophysically meaningful quantities of PAHs require particularly dense and slow stellar winds and high initial acetylene abundance. It is suggested that most of the PAHs may be produced in a relatively small fraction of carbon-rich red giants.

From Interstellar Polycyclic Aromatic Hydrocarbons and Ice to the Origin of Life

NASA Technical Reports Server (NTRS)

Allamandola, Louis

2004-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. The first part of this talk will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, abundances, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the presolar nebula, the materials frozen into the interstellar/precometary ices are photoprocessed by ultraviolet light and produce more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex materials on the early Earth and their composition may be related to the origin of life.

Probing the chemical environments of early star formation: A multidisciplinary approach

NASA Astrophysics Data System (ADS)

Hardegree-Ullman, Emily Elizabeth

Chemical compositions of prestellar and protostellar environments in the dense interstellar medium are best quantified using a multidisciplinary approach. For my dissertation, I completed two projects to measure molecular abundances during the earliest phases of star formation. The first project investigates gas phase CO depletion in molecular cloud cores, the progenitors of star systems, using infrared photometry and molecular line spectroscopy at radio wavelengths. Hydrogenation of CO depleted onto dust is an important first step toward building complex organic molecules. The second project constrains polycyclic aromatic hydrocarbon (PAH) abundances toward young stellar objects (YSO). Band strengths measured from laboratory spectroscopy of pyrene/water ice mixtures were applied to estimate abundances from features attributed to PAHs in observational YSO spectra. PAHs represent a distinct but important component of interstellar organic material that is widely observed but not well quantified in star-forming regions.

PRESSURE EFFECTS IN POLYCYCLIC AROMATIC NITROGENATED HETEROCYCLES (PANHs): DIAGNOSTIC QUALITIES AND COSMOBAROMETRY POTENTIAL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montgomery, Wren; Sephton, Mark A., E-mail: w.montgomery@imperial.ac.uk

2016-03-01

The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responsesmore » of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.« less

Blue Luminescence and Extended Red Emission: Possible Connections to the Diffuse Interstellar Bands

NASA Astrophysics Data System (ADS)

Witt, A. N.

2014-02-01

Blue luminescence (BL) and extended red emission (ERE) are observed as diffuse, optical-wavelength emissions in interstellar space, resulting from photoluminescence by ultraviolet(UV)-illuminated interstellar grains. Faintness and the challenge of separating the BL and ERE from the frequently much brighter dust-scattered continuum present major observational hurdles, which have permitted only slow progress in testing the numerous models that have been advanced to explain these two phenomena. Both the ERE, peaking near 680 nm (FWHM ~ 60 - 120 nm) and the BL, asymmetrically peaking at ~ 378 nm (FWHM ~ 45 nm), were first discovered in the Red Rectangle nebula. Subsequently, ERE and BL have been observed in other reflection nebulae, and in the case of the ERE, in carbon-rich planetary nebulae, H II regions, high-latitude cirrus clouds, the galactic diffuse ISM, and in external galaxies. BL exhibits a close spatial and intensity correlation with emission in the aromatic emission feature at 3.3 micron, most likely arising from small, neutral polycyclic aromatic hydrocarbon (PAH) molecules. The spectral characteristics of the BL also agree with those of fluorescence by PAH molecules with 13 to 19 carbon atoms. The BL phenomenon is thus most readily understood as the optical fluorescence of small, UV-excited aromatic molecules. The ERE, by contrast, though co-existent with mid-IR PAH emissions, does not correlate with emissions from either neutral or ionized PAHs. Instead, the spatial ERE morphology appears to be strictly governed by the density of far-UV (E >= 10.5 eV) photons, which are required for the ERE excitation. The most restrictive observational constraint for the ERE process is its exceptionally high quantum efficiency. If the ERE results from photo-excitation of a nano-particle carrier by photons with E >= 10.5 eV in a single-step process, the quantum efficiency exceeds 100%. Such a process, in which one to three low-energy optical photons may be emitted following a single far-UV excitation, is possible in highly isolated small clusters, e.g. small, dehydrogenated carbon clusters with about 20 to 28 carbon atoms. A possible connection between the ERE carriers and the carriers of DIBs may exist in that both are ubiquitous throughout the diffuse interstellar medium and both have an abundance of low-lying electronic levels with E <= 2.3 eV above the ground state.

Polycyclic Aromatic Hydrocarbons and Infrared Astrophysics with Spitzer

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Hudgins, D. M.

2004-01-01

PAH spectral features are now being used as new probes of the ISM. PAH ionization states reflect the ionization balance of the medium while PAH size and structure reflect the energetic and chemical history of the medium. This paper will focus on recent applications of the NASA Ames PAH IR spectral Database to interpret astronomical observations made by the Spitzer Space telescope and other space based infrared instruments. Examples will be given showing how changes in the spectral characteristics of different objects reveal interstellar PAH characteristics such as structure, size and composition, as well as provide insight into the chemical history and physical nature of the emission zones.

Analogs of solid nanoparticles as precursors of aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Gadallah, K. A. K.; Mutschke, H.; Jäger, C.

2013-06-01

Context. Aromatic =CH and C=C vibrational bands have been observed within shocked interstellar regions, indicating the presence of aromatic emission carriers such as PAHs, which may have been created from adjacent molecular cloud material by interaction with a shock front. Aims: We investigate the evolution of the aromatic =CH and C=C vibrational modes at 3.3 and 6.2 μm wavelength in heated HAC materials, PAHs and mixed PAHs and HACs, respectively, aiming at an explanation of the evolution of carbonaceous dust grains in the shocked regions. Methods: Materials used in these analogs (HAC and PAH materials) were prepared by the laser ablation and the laser pyrolysis methods, respectively. The transmission electron microscopy (TEM) in high-resolution mode was used as an analytical technique to characterize the aromatic layers in HACs. Spectroscopic analysis was prformed in the mid-IR range. Results: A remarkable destruction of aliphatic structures in HACs has been observed with the thermal processing, while aromatic structures become dominating by increasing the diameters of the graphene layers. The aromatic bands at 3.3 and 6.2 μm, observed in the laboratory spectra of PAHs and of the combination of the PAHs and HAC materials, are also clearly observed in the spectrum of the heated HACs. These bands agree with those of aromatic bands observed in astronomical observations. Conclusions: Aromatization of HACs could be a pre-stage in the decomposition process of hydrocarbons that form PAH-clusters in such hot interstellar medium.

Laboratory determination of the infrared band strengths of pyrene frozen in water ice: Implications for the composition of interstellar ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hardegree-Ullman, E. E.; Gudipati, M. S.; Werner, M.

2014-04-01

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 μm) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conductedmore » to determine the positions and strengths of the bands of pyrene mixed with H{sub 2}O and D{sub 2}O ices. The D{sub 2}O mixtures are used to measure pyrene bands that are masked by the strong bands of H{sub 2}O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 μm. Our infrared band strengths were normalized to experimentally determined ultraviolet band strengths, and we find that they are generally ∼50% larger than those reported by Bouwman et al. based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. to estimate the contribution of frozen PAHs to absorption in the 5-8 μm spectral region, taking into account the strength of the 3.25 μm CH stretching mode. It is found that frozen neutral PAHs contain 5%-9% of the cosmic carbon budget and account for 2%-9% of the unidentified absorption in the 5-8 μm region.« less

Mid and Near-IR Absorption Spectra of PAH Neutrals and Ions in H20 Ice to Facilitate their Astronomical Detection

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.

2004-01-01

Polycyclic aromatic hydrocarbons (PAHs) are believed to be the most abundant and widespread class of organic compounds in the universe, having been observed in emission towards energetic regions and absorption towards colder ones.We will present IR spectra of PAHs and their cations in H20 ice measured in the laboratory in the hopes that this will facilitate the detection of these features in the interstellar medium.

The Curators of the University of Missouri Modeling the Infrared Emission of C_60 in Space

NASA Astrophysics Data System (ADS)

Li, Aigen

Fullerenes are cage-like molecules of pure carbon, such as C_60, C_70, C_76, and C_84. C_60, also known as buckminsterfullerene, is the most stable fullerene and has a soccer- ball like structure. The presence of fullerenes in space has been suggested and observationally explored since their first synthesis in the laboratory in 1985 by Harry Kroto and his colleagues which earned them the 1996 Nobel prize in chemistry. C_60 (as well as C_70) has recently been detected in reflection nebulae, post-AGB stars, protoplanetary nebulae, planetary nebulae, Herbig Ae/Be stars, and young stellar objects through their characteristic infrared emission bands. The formation of C_60 in interstellar and circumstellar environments is not firmly established. Experimental studies have shown that C_60 can be made by gas-phase condensation (e.g. through vaporization of graphite) in a hydrogen-poor environment. In view of the simultaneous detection of C_60 and PAHs in hydrogen-rich interstellar and circumstellar regions, it has also been suggested that C_60 could be generated by the decomposition of hydrogenated amorphous carbon, or the destruction of PAHs, both induced by shocks and/or UV photoprocessing. The phase (gas or solid) and excitation mechanism of C_60 in interstellar and circumstellar conditions are also hotly debated in the literature. One model suggests that C_60 is attached to dust and emits in solid-phase at the equilibrium temperature of the dust. Another model suggests that C_60 is stochastically excited by UV photons and emits in the gas-phase. We prefer the latter model as in interstellar and circumstellar conditions the energy content of a C_60 molecule is often smaller than the energy of a single starlight photon and C_60 is expected to undergo stochastical heating. We propose a two-year project to model the vibrational excitation of C_60 and calculate its infrared emission spectra in a wide variety of regions (e.g. reflection nebulae excited by stars of a range of effective temperatures, protoplanetary nebulae, planetary nebulae, the diffuse interstellar medium, and protoplanetary disks around Herbig Ae/Be stars), using the ``exact-statistical'' method developed by Draine & Li (2001) for modeling the photoexcitation of PAHs. We will calculate the intensity of each vibrational band of C_60 excited by a given-type radiation field of a given radiation strength. These results will be tabulated and made available to the community through the PI's website. We will use the calculated C_60 band intensities to analyze the observed C_60 spectra. This will allow us to derive the C_60 abundance and the emitting condition (e.g. starlight intensities) of the regions where C_60 is observed. Similarly, the same research will be applied to C_70 as well. This research supports the NASA Strategic Subgoal 3C: Discover the origin, structure, evolution, and destiny of the universe.

PAHs molecules and heating of the interstellar gas

NASA Technical Reports Server (NTRS)

Verstraete, Laurent; Leger, Alain; Dhendecourt, Louis B.; Dutuit, O.; Defourneau, D.

1989-01-01

Until now it has remained difficult to account for the rather high temperatures seen in many diffuse interstellar clouds. Various heating mechanisms have been considered: photoionization of minor species, ionization of H by cosmic rays, and photoelectric effect on small grains. Yet all these processes are either too weak or efficient under too restricting conditions to balance the observed cooling rates. A major heat source is thus still missing in the thermal balance of the diffuse gas. Using photoionization cross sections measured in the lab, it was shown that in order to balance the observed cooling rates in cold diffuse clouds (T approx. 80 K) the PAHs would have to contain 15 percent of the cosmic abundance of carbon. This value does not contradict the former estimation of 6 percent deduced from the IR emission bands since this latter is to be taken as a lower limit. Further, it was estimated that the contribution to the heating rate due to PAH's in a warm HI cloud, assuming the same PAH abundance as for a cold HI cloud, would represent a significant fraction of the value required to keep the medium in thermal balance. Thus, photoionization of PAHs might well be a major heat source for the cold and warm HI media.

Extended infrared emission around IRAS 21282 + 5050

NASA Technical Reports Server (NTRS)

Bregman, Jesse D.; Booth, John; Gilmore, D. K.; Kay, Laura; Rank, David

1992-01-01

Multiaperture 3-4-micron spectra along with K- and L-band images of the compact planetary nebula IRAS 21282 + 5050 show a 5 arcsec - 20 arcsec diameter nebula with structure similar to many other planetary nebulae. The spectral observations and the L-band image show evidence for extended PAH emission out to a radius of 20 arcsec, while the K-band image shows a 5 arcsec diameter nebula. An observed linear increase of integrated brightness with aperture size at L band implies a 1/r exp 2 volume emissivity for a spherically symmetric model. The spectral similarity of the emission in the small and large apertures suggests fluorescent emission by the PAHs. If the observed emission is from PAHs which formed during the planetary nebulae stage of IRAs 21282 + 5050, then PAHs have been forming for not less than 3000 yr. If the PAH emission is from material produced during the earlier red giant phase, then the formation time frame was much longer. The morphological and spectral similarity of IRAS 21282 + 5050 to many other planetary nebulae suggests that this phenomenon may be widespread, and that planetary nebulae may be a significant source of interstellar PAHs.

Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto

2017-02-01

Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

UV IRRADIATION OF AROMATIC NITROGEN HETEROCYCLES IN INTERSTELLAR ICE ANALOGS

NASA Technical Reports Server (NTRS)

Elsila, J. E.; Bernstein, M. P.; Sanford, S. A.

2005-01-01

Here, we present information on the properties of the ANH quinoline frozen in interstellar water-ice analogs. Quinoline is a two-ring compound structurally analogous to the PAH naphthalene. In this work, binary mixtures of water and quinoline were frozen to create interstellar ice analogs, which were then subjected to ultraviolet photolysis. We will present the infrared spectra of the resulting ices at various temperatures, as well as chromatographic analysis of the residues remaining upon warm-up of these ices to room temperature.

On Graphene in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Chen, X. H.; Li, Aigen; Zhang, Ke

2017-11-01

The possible detection of C24, a planar graphene that was recently reported to be in several planetary nebulae by García-Hernández et al., inspires us to explore whether and how much graphene could exist in the interstellar medium (ISM) and how it would reveal its presence through its ultraviolet (UV) extinction and infrared (IR) emission. In principle, interstellar graphene could arise from the photochemical processing of polycyclic aromatic hydrocarbon (PAH) molecules, which are abundant in the ISM, due to the complete loss of their hydrogen atoms, and/or from graphite, which is thought to be a major dust species in the ISM, via fragmentation caused by grain–grain collisional shattering. Both quantum-chemical computations and laboratory experiments have shown that the exciton-dominated electronic transitions in graphene cause a strong absorption band near 2755 \\mathringA . We calculate the UV absorption of graphene and place an upper limit of ∼5 ppm of C/H (i.e., ∼1.9% of the total interstellar C) on the interstellar graphene abundance. We also model the stochastic heating of graphene C24 in the ISM, excited by single starlight photons of the interstellar radiation field and calculate its IR emission spectra. We also derive the abundance of graphene in the ISM to be <5 ppm of C/H by comparing the model emission spectra with that observed in the ISM.

Hydrogenation of polycyclic aromatic hydrocarbons as a factor affecting the cosmic 6.2 micron emission band

NASA Technical Reports Server (NTRS)

Beegle, L. W.; Wdowiak, T. J.; Harrison, J. G.

2001-01-01

While many of the characteristics of the cosmic unidentified infrared (UIR) emission bands observed for interstellar and circumstellar sources within the Milky Way and other galaxies, can be best attributed to vibrational modes of the variants of the molecular family known as polycyclic aromatic hydrocarbons (PAH), there are open questions that need to be resolved. Among them is the observed strength of the 6.2 micron (1600 cm(-1)) band relative to other strong bands, and the generally low strength for measurements in the laboratory of the 1600 cm(-1) skeletal vibration band of many specific neutral PAH molecules. Also, experiments involving laser excitation of some gas phase neutral PAH species while producing long lifetime state emission in the 3.3 micron (3000 cm(-1)) spectral region, do not result in significant 6.2 micron (1600 cm(-1)) emission. A potentially important variant of the neutral PAH species, namely hydrogenated-PAH (H(N)-PAH) which exhibit intriguing spectral correlation with interstellar and circumstellar infrared emission and the 2175 A extinction feature, may be a factor affecting the strength of 6.2 micron emission. These species are hybrids of aromatic and cycloalkane structures. Laboratory infrared absorption spectroscopy augmented by density function theory (DFT) computations of selected partially hydrogenated-PAH molecules, demonstrates enhanced 6.2 micron (1600 cm(-1)) region skeletal vibration mode strength for these molecules relative to the normal PAH form. This along with other factors such as ionization or the incorporation of nitrogen or oxygen atoms could be a reason for the strength of the cosmic 6.2 micron (1600 cm(-1)) feature.

Evolution of Interstellar Ices

NASA Astrophysics Data System (ADS)

Allamandola, Louis J.; Bernstein, Max P.; Sandford, Scott A.; Walker, Robert L.

1999-10-01

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

The Production of Complex Organics from Interstellar Ices

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Allamandola, Louis; Bernstein, Max; Deamer, David; Dworkin, Jason; Zare, Richard

2001-01-01

Infrared spectroscopy of ices in interstellar dense molecular clouds has shown that they contain a variety of simple molecules, as well as aromatic hydrocarbons. While in these clouds, these ices are processed by ultraviolet light and cosmic rays. High vacuum, UV irradiation laboratory simulations conducted using various realistic approx. 10 K interstellar mixed-molecular ice analogs, both with and without polycyclic aromatic hydrocarbons (PAHs), have been carried out in NASA-Ames' Astrochemistry Laboratory. Upon warming, these irradiated ices are found to produce refractory organic residues. These residues have been analyzed using a variety of techniques, including HPLC and laser desorption mass spectrometry, and they have been shown to contain a variety of complex organic compounds. Several of these compounds may be of prebiotic significance. In particular, we will discuss the detection of quinones (substituted PAHs that are used by living systems for electron transport) and amphiphiles (molecules that self-assemble to form membranes). Laboratory simulations have also demonstrated that the organic products can show isotopic enrichments in D that provide clues for the mechanisms of their formation. Similar compounds and D enrichments are seen in the organics found in primitive meteorites, suggesting a direct link between interstellar chemistry and the delivery of organics to newly formed planets.

The discovery of a new infrared emission feature at 1905 wavenumbers (5.25 microns) in the spectrum of BD + 30 deg 3639 and its relation to the polycyclic aromatic hydrocarbon model

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Bregman, J. D.; Sandford, S. A.; Tielens, A. G. G. M.; Witteborn, F. C.

1989-01-01

A new IR emission feature at 1905/cm (5.25 microns) has been discovered in the spectrum of BD + 30 deg 3639. This feature joins the family of well-known IR emission features at 3040, 2940, 1750, 1610, '1310', 1160, and 890/cm. The origin of this new feature is discussed and it is assigned to an overtone or combination band involving C-H bending modes of polycyclic aromatic hydrocarbons (PAHs). Laboratory work suggests that spectral studies of the 2000-1650/cm region may be very useful in elucidating the molecular structure of interstellar PAHs. The new feature, in conjunction with other recently discovered spectral structures, suggests that the narrow IR emission features originate in PAH molecules rather than large carbon grains.

An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

PubMed Central

Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

2016-01-01

A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs. PMID:26942230

Laboratory Studies of Extraterrestrial Ices and PAHs: Making an Astrobiological Silk Purse Out of An Interstellar Sow's Ear

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

2002-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Today, the composition of dust in the ISM is reasonably well constrained to cold, micron-sized particles of various refractory materials. Shrouded within the protective confines of cold, opaque molecular clouds--the birthplace of stars and planets--these particles secrete mantles of mixed molecular lees whose major components are also well constrained. Finally, amidst the molecular inventory of these ice mantles are likely to be found polycyclic aromatic hydrocarbons (PAHs), whose telltale infrared signature I is now recognized throughout the Universe. However, of what significance is this scenario to the origin of life in our solar system--or any other? The major components of the icy materials observed in interstellar clouds and in our own solar system are uniformly quite simple. In addition, despite the fact that PAHs likely represent the single largest molecular reservoir of organic carbon in evolving planetary systems, they are not what would be considered "biogenic" molecules. Although interesting from a chemical and astrophysical standpoint, in the absence of a mechanism by which these materials can be transformed into more biochemically significant structures, they are of little Astrobiological significance. In this talk, we will begin with a brief review of the nature and abundance of the "raw" population of PAHs and PAH-related materials in the ISM. From there, we will move on to explore our laboratory simulations of the photochemical evolution of realistic mixed molecular ices under conditions which simulate those encountered in the ISM and in evolving planetary systems. Particular attention will be paid to the surprisingly complex array of organic species that are produced in these ices from such a deceptively simple inventory of starting materials. In addition, we will explore the chemistry of PAHs under these conditions and consider its potential for transforming that rich repository of pre-biotic organic "ore" into materials of greater importance to Astrobiology.

The IR emission features - Emission from PAH molecules and amorphous carbon particles

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

1987-01-01

Given the current understanding of polycyclic aromatic hydrocarbons (PAHs), the spectroscopic data suggest that are at least two components which contribute to the interstellar emission spectrum: (1) free molecule-sized PAHs producing the narrow features and (2) amorphous carbon particles (which are primarily composed of an irregular 'lattice' of PAHs) contributing to the broad underlying components. An exact treatment of the IR fluorescence from highly vibrationally excited large molecules demonstrates that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphous carbon particles. It is concluded that, since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is required along with an observational program focusing on the spatial characteristics of the spectra.

Stellar Evolutionary Effects on the Abundance of PAHS and SN-Condensed Dust in Galaxies

NASA Technical Reports Server (NTRS)

Dwek, Eli

2007-01-01

Spectral aid photometric observations of nearby galaxies show a correlation between the strength of their mid-IR aromatic features and their metal abundance, and a deficiency of these features in low-metallicity galaxies. The aromatic features are most commonly attributed to emission from PAH molecules. In this paper, we suggest that the observed correlation represents a trend of PAH abundance with galactic age, reflecting the delayed injection of PAHs and carbon dust into the ISM, by AGB stars in their final, post-AGB phase of their evolution. These AGB stars are the primary sources of PAHs and carbon dust in galaxies, and recycle their ejecta back to the interstellar medium only after a few hundred million years of evolution on the main sequence. In contrast, more massive stars that explode as Type II supernovae inject their metals and dust almost instantaneously after their formation. After determining the PAH abundances in 35 nearby galaxies, we use a chemical evolution model to show that the delayed injection of carbon dust by AGB stars provides a natural explanation to the dependence of the PAH content, in galaxies with metallicity. We also show that larger dust particles giving rise to the far-IR emission follow a distinct evolutionary trend closely related to the injection of dust by massive stars into the ISM.

Constraints on interstellar dust models from extinction and spectro-polarimetry

NASA Astrophysics Data System (ADS)

Siebenmorgen, R.; Voshchinnikov, N. V.; Bagnulo, S.; Cox, N. L. J.

2017-12-01

We present polarisation spectra of seven stars in the lines-of-sight towards the Sco OB1 association. Our spectra were obtained within the framework of the Large Interstellar Polarization Survey carried out with the FORS instrument of the ESO VLT. We have modelled the wavelength-dependence of extinction and linear polarisation with a dust model for the diffuse interstellar medium which consists of a mixture of particles with size ranging from the molecular domain of 0.5 nm up to 350 nm. We have included stochastically heated small dust grains with radii between 0.5 and 6 nm made of graphite and silicate, as well as polycyclic aromatic hydrocarbon molecules (PAHs), and we have assumed that larger particles are prolate spheroids made of amorphous carbon and silicate. Overall, a dust model with eight free parameters best reproduces the observations, and is in agreement with cosmic abundance constraints. Reducing the number of free parameters leads to results that are inconsistent with the cosmic abundances of silicate and carbon. We found that aligned silicates are the dominant contributor to the observed polarisation, and that the polarisation spectra are best-fit by a lower limit of the equivolume sphere radius of aligned grains of 70-200 nm.

AKARI Near-infrared Spectroscopic Observations of Interstellar Ices in the Edge-on Starburst Galaxy NGC 253

NASA Astrophysics Data System (ADS)

Yamagishi, Mitsuyoshi; Kaneda, Hidehiro; Ishihara, Daisuke; Oyabu, Shinki; Onaka, Takashi; Shimonishi, Takashi; Suzuki, Toyoaki

2011-04-01

We present the spatially resolved near-infrared (2.5-5.0 μm) spectra of the edge-on starburst galaxy NGC 253 obtained with the Infrared Camera on board AKARI. Near the center of the galaxy, we clearly detect the absorption features of interstellar ices (H2O: 3.05 μm, CO2: 4.27 μm, and XCN: 4.62 μm) and the emission of polycyclic aromatic hydrocarbons (PAHs) at 3.29 μm and the hydrogen recombination line Brα at 4.05 μm. We find that the distributions of the ices differ from those of the PAH and gas. We calculate the column densities of the ices and derive the abundance ratios of N(CO2)/N(H2O) = 0.17 ± 0.05. They are similar to those obtained around the massive young stellar objects in our Galaxy (0.17 ± 0.03), although a much stronger interstellar radiation field and higher dust temperature are expected near the center of NGC 253.

Inference of a 7.75 eV lower limit in the ultraviolet pumping of interstellar polycyclic aromatic hydrocarbon cations with resulting unidentified infrared emissions

NASA Technical Reports Server (NTRS)

Robinson, M. S.; Beegle, L. W.; Wdowiak, T. J.

1997-01-01

The discrete infrared features known as the unidentified infrared (UIR) bands originating in starburst regions of other galaxies, and in H II regions and planetary nebulae within the Milky Way, are widely thought to be the result of ultraviolet pumped infrared fluorescence of polycyclic aromatic hydrocarbon (PAH) molecules and ions. These UIR emissions are estimated to account for 10%-30% of the total energy emitted by galaxies. Laboratory absorption spectra including the vacuum ultraviolet region, as described in this paper, show a weakening of the intensity of absorption features as the population of cations increases, suggesting that strong pi* <-- pi transitions are absent in the spectra of PAH cations. This implies a lower energy bound for ultraviolet photons that pump infrared emissions from such ions at 7.75 eV, an amount greater than previously thought. The implications include size and structure limitations on the PAH molecules and ions which are apparent constituents of the interstellar medium. Also, this might affect estimations of the population of early-type stars in regions of rapid star formation.

UV action spectroscopy of protonated PAH derivatives. Methyl substituted quinolines

NASA Astrophysics Data System (ADS)

Klærke, B.; Holm, A. I. S.; Andersen, L. H.

2011-08-01

Aims: We investigate the production of molecular photofragments upon UV excitation of PAH derivatives, relevant for the interstellar medium. Methods: The action absorption spectra of protonated gas-phase methyl-substituted quinolines (CH3 - C9H7NH+) have been recorded in the 215-338 nm spectral range using the electrostatic storage ring ELISA, an electrospray ion source and 3 ns UV laser pulses. Results: It is shown that the absorption profile is both redshifted and broadened when moving the methyl group from the heterocycle containing nitrogen to the homoatomic ring. The absorption profiles are explained by TD-DFT calculations. The dissociation time of the studied molecules is found to be of several milliseconds at 230 nm and it is shown that after redistribution of the absorbed energy the molecules dissociate in several channels. The dissociation time found is an order of magnitude faster than the estimated IR relaxation time. Photophysical properties of both nitrogen containing and methyl-substituted PAHs are interesting in an astrophysical context in connection with identifying the aromatic component of the interstellar medium.

Laboratory Experiments on the Reactions of PAH Cations with Molecules and Atoms of Interstellar Interest

NASA Technical Reports Server (NTRS)

LePage, V.; Lee, H. S.; Bierbaum, V. M.; Snow, T. P.

1996-01-01

The C10H8(+) cation and its dehydrogenated derivatives, C10H7(+) and C10H6(+), have been studied using a selected ion flow tube (SIFT). Reactions with molecules and atoms of interstellar interest show that C10H8(+) reacts with N md O to give neutral products HCN and CO, respectively. C10H6(+) and C10H6(+) are moderately reactive and reactions proceed through association with molecules. The implications of these results for the depletion of C10H(n)(+) in the interstellar medium are briefly discussed.

Computational Spectroscopy of Polycyclic Aromatic Hydrocarbons In Support of Laboratory Astrophysics

NASA Technical Reports Server (NTRS)

Tan, Xiaofeng; Salama, Farid

2006-01-01

Polycyclic aromatic hydrocarbons (PAHs) are strong candidates for the molecular carriers of the unidentified infrared bands (UIR) and the diffuse interstellar bands (DIBs). In order to test the PAH hypothesis, we have systematically measured the vibronic spectra of a number of jet-cooled neutral and ionized PAHs in the near ultraviolet (UV) to visible spectral ranges using the cavity ring-down spectroscopy. To support this experimental effort, we have carried out theoretical studies of the spectra obtained in our measurements. Ab initio and (time-dependent) density.functiona1 theory calculations are performed to obtain the geometries, energetics, vibrational frequencies, transition dipole moments, and normal coordinates of these PAH molecules. Franck-Condon (FC) calculations and/or vibronic calculations are then performed using the calculated normal coordinates and vibrational frequencies to simulate the vibronic spectra. It is found that vibronic interactions in these conjugated pi electron systems are often strong enough to cause significant deviations from the Born-Oppenheimer (BO) approximation. For vibronic transitions that are well described by the BO approximation, the vibronic band profiles are simulated by calculating the rotational structure of the vibronic transitions. Vibronic oscillator strength factors are calculated in the frame of the FC approximation from the electronic transition dipole moments and the FC factors. This computational effort together with our experimental measurements provides, for the first time, powerful tools for comparison with space-based data and, hence, a powerful approach to understand the spectroscopy of interstellar PAH analogs and the nature of the UIR and DIBs.

Angular motion of a PAH molecule in interstellar environment

NASA Technical Reports Server (NTRS)

Rouan, D.; Leger, Alain; Omont, A.; Giard, Martin

1989-01-01

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Induced nucleation of carbon dust in red giant stars

NASA Technical Reports Server (NTRS)

Cadwell, Brian J.; Wang, Hai; Feigelson, Eric D.; Frenklach, Michael

1994-01-01

This study quantitatively tests the proposed model of induced nucleation of carbonaceous grains in carbon-rich red giant stars. Induced nucleation is the process of grain growth initiated by the presence of reactive surfaces provided by seed particles. The numerical study was performed using a deailed chemical kinetic model of carbon deposition, grain coagulation, and homogeneous nucleation of polycyclic aromatic hydrocarbons (PAHs). The model uses a method of moments to keep track of developing grain population in the forming dust shell. We test the efficiency of grain formation for large ranges of dust shell parameters typical for carbon stars. Our model is capable of producing a range of optically thick and thin dust shells in carbon stars. Results are in accord with (IRAS) spectral classes of carbon stars. The resulting composite grains produced are consistent with those recently found in ancient meteorites. This model also provides a realistic explanation for high abundances of (PAHs) in the interstellar medium and some planetary nebulae.

PAH Spectroscopy: Past, Present and Future

NASA Technical Reports Server (NTRS)

Mattioda, Andrew

2016-01-01

Since their discovery in the 1970's, astronomers, astrophysicists and astrochemists have been intrigued by the nearly ubiquitous unidentified infrared emission (UIR) bands. In the 1980's, investigators determined the most probably source of these emissions was a family of molecules known as Polycyclic Aromatic Hydrocarbons or simply PAHs. In order to better understand these interstellar IR features and utilize them as chemical probes of the cosmos, laboratory spectroscopists have spent the last three decades investigating the spectroscopy of PAHs under astrophysically relevant conditions. This presentation will discuss the similarities and differences in the spectroscopic properties of PAHs as one goes from the Far to Mid to Near infrared wavelength regions and probe the changes observed in PAH spectra as they go from neutral to ionized molecules suspended in an inert gas matrix, to PAHs in a water ice matrix and as a thin film. In selected instances, the experimental results will be compared to theoretical values. The presentation will conclude with a discussion on the future directions of PAH spectroscopy.

PAH formation in carbon-rich circumstellar envelopes

NASA Technical Reports Server (NTRS)

Feigelson, Eric D.; Frenklach, Michael

1989-01-01

While there is growing observational evidence that some fraction of interstellar carbon is in polycyclic aromatic hydrocarbons (PAH's), the mechanisms by which these molecules might be formed have not been extensively studied. A detailed investigation of PAH production in the outflowing molecular envelopes of carbon-rich red giant star is presented. The gasphase kinetics of a chemical reaction mechanism developed to study soot production in hydrocarbon flames is modified to apply in circumstellar environments. It was found that astrophysically significant quantities of PAH's can be formed in carbon star envelopes provided the gas is sufficiently dense and resides for a long time in the temperature range of 900 to 1100 k. The precise yield of PAH's is very sensitive to astronomical parameters of the envelope (e.g., mass loss rate, outflow velocity, and acetylene abundance) and certain poorly determined chemical reaction rates.

On the state of the emitter of the 3.3 micron unidentified infrared band - Absorption spectroscopy of polycyclic aromatic hydrocarbon species

NASA Technical Reports Server (NTRS)

Flickinger, Gregory C.; Wdowiak, Thomas J.; Gomez, Percy L.

1991-01-01

Results of absorption measurements indicate that the PAH species responsible for the UIR (unidentified infrared) emission probably exist in a condensed form rather than as isolated molecules. It is shown that the peak absorption of the C-H stretch feature of vapor-phase PAHs occurs at a higher frequency than that of the condensed-phase PAHs and does not match the 3.289-micron interstellar feature. The vapor-phase experiments duplicate the phenomenon of the 3.3-micron profile simplification of PAH in KBr at elevated temperature. This confirms that the change of the profile with temperature is an intrinsic molecular effect, and is not a consequence of matrix (KBr) or condensed state interactions.

Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbon Cations. 3; The Members

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.; Wittebon, Fred C. (Technical Monitor)

1994-01-01

In spite of the fact that the infrared spectroscopic properties of only a few isolated ionized polycyclic aromatic hydrocarbons (PAHs) are known, gaseous, ionized PAHs are thought to be responsible for a very common family of infrared interstellar emission bands. In order to provide a data base to test this hypothesis and, if borne out, to use this emission band family as a probe of many different interstellar environments, we are carrying out a thorough study of the infrared spectroscopic properties of neutral and ionized PAHs in argon matrices. Here we present the near and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo[ghilperylene, and coronene. The properties of naphthalene, the first member of the series, are given elsewhere. The spectra of perdeuterated phenanthrene and pyrene are also reported. For those molecules which have been previously studied (pyrene, d(10)-pyrene, and coronene), band positions and relative intensities are in agreement. In all cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeutero-phenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene,the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 5-20 times weaker than in the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Time Dependent Density Functional Theory Calculations of Large Compact PAH Cations: Implications for the Diffuse Interstellar Bands

NASA Technical Reports Server (NTRS)

Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Gordon-Head, Martin; Kwak, Dochan (Technical Monitor)

2002-01-01

We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcoronene, the largest species containing more than 50 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.

Understanding Organics in Meteorites and the Pre-Biotic Environment

NASA Technical Reports Server (NTRS)

Zare, Richard N.

2003-01-01

(1) Refinement of the analytic capabilities of our experiment via characterization of molecule-specific response and the effects upon analysis of the type of sample under investigation; (2) Measurement of polycyclic aromatic hydrocarbons (PAHs) with high sensitivity and spatial resolution within extraterrestrial samples; (3) Investigation of the interstellar reactions of PAHs via the analysis of species formed in systems modeling dust grains and ices; (4) Investigations into the potential role of PAHs in prebiotic and early biotic chemistry via photoreactions of PAHs under simulated prebiotic Earth conditions. To meet these objectives, we use microprobe laser-desorption, laser-ionization mass spectrometry (MuL(exp 2)MS), which is a sensitive, selective, and spatially resolved technique for detection of aromatic compounds. Appendix A presents a description of the MuL(exp 2)MS technique. The initial grant proposal was for a three-year funding period, while the award was given for a one-year interim period. Because of this change in time period, emphasis was shifted from the first research goal, which was more development-oriented, in order to focus more on the other analysis-oriented goals. The progress made on each of the four research areas is given below.

Decoding IR Spectra of Cosmic Ices and Organics in the Laboratory

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.

2006-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty-five years thanks to significant developments in observational IR astronomy and dedicated laboratory experiments. Twenty-five years ago the composition of interstellar dust was largely guessed at. Today the composition of interstellar dust is reasonably well understood. In the diffuse interstellar medium (ISM) the dust population is mainly comprised of small grains of silicates and amorphous carbon. In dark molecular clouds, the birthplace of stars and planets, these cold refractory dust particles are coated with mixed molecular ices whose composition is reasonably well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. This extraordinary progress has been made possible by the close collaboration of laboratory experimentalists and theoreticians with IR astronomers using groundbased, air-borne, and orbiting telescopes.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

2017-10-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Facile Generation and Storage of Polycyclic Aromatic Hydrocarbon Ions in Astrophysical Ices

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.; Allamandola, Louis J.

2003-01-01

In situ ultraviolet-visible absorption and emission studies of vacuum ultraviolet (VUV) irradiated water-rich, cosmic ice analogs containing polycyclic aromatic hydrocarbons (PAHs) are described. W V irradiation of 12 K water ices containing the PAHs naphthalene (H2O/C10H8 = 200) and 4-methylpyrene (H2O/C17H12 > 500) readily converts the PAHs into their cation form (PAH(+)). Under these conditions, PAH photoionization is the predominant reaction. These ions are trapped and stored in the ices at temperatures between 10 and 50 K, a temperature domain common to ices throughout interstellar clouds and the solar system. Unlike the approx.15% ionization typical after W V irradiation of PAHs isolated in rare-gas matrices, in water ice, PAH photoionization and storage proceed efficiently and almost quantitatively with a greater than 70% ionization yield. As the temperature is increased from 50 to 150 K, the PAH ion bands slowly diminish as the PAH ions ultimately react to form more complex organic species involving the water host. The chemical, spectroscopic, and physical properties of these ion-rich ices can be important in icy objects such as molecular clouds, comets, and planets. Several astrophysical applications are presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia

A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that allmore » small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.« less

The discovery of a new infrared emission feature at 1905 wavenumbers (5.25 microns) in the spectrum of BD +30 degrees 3639 and its relation to the polycyclic aromatic hydrocarbon model

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Bregman, J. D.; Sandford, S. A.; Tielens, A. G.; Witteborn, F. C.; Wooden, D. H.; Rank, D.

1989-01-01

We have discovered a new IR emission feature at 1905 cm-1 (5.25 microns) in the spectrum of BD +30 degrees 3639. This feature joins the family of well-known IR emission features at 3040, 2940, 1750, 1610, "1310," 1160, and 890 cm-1 (3.3, 3.4, 5.7, 6.2, "7.7," 8.6, and 11.2 microns). The origin of this new feature is discussed and it is assigned to an overtone or combination band involving C-H bending modes of polycyclic aromatic hydrocarbons (PAHs). Laboratory work suggests that spectral studies of the 2000-1650 cm-1 (5.0-6.1 microns) region may be very useful in elucidating the molecular structure of interstellar PAHs. The new feature, in conjunction with other recently discovered spectral structure, suggests that the narrow IR emission features originate in PAH molecules rather than large carbon grains. Larger species are likely to be the source of the broad underlying "plateaus" seen in many of the spectra.

Hydrogenation and dehydrogenation of interstellar PAHs: Spectral characteristics and H2 formation

NASA Astrophysics Data System (ADS)

Andrews, H.; Candian, A.; Tielens, A. G. G. M.

2016-10-01

Context. We have modelled the abundance distribution and IR emission of the first 3 members of the coronene family in the north-west photodissociation region of the well-studied reflection nebulae NGC 7023. Aims: Our aim was 3-fold: I) analyze the distribution of abundances; (II) examine the spectral footprints from the hydrogenation state of polycyclic aromatic hydrocarbons (PAHs); and (III) assess the role of PAHs in the formation of H2 in photodissociation regions. Methods: To model the physical conditions inside the cloud, we used the Meudon PDR Code, and we gave this as input to our kinetic model. We used specific molecular properties for each PAH, based on the latest data available at the present time. We considered the loss of an H atom or an H2 molecule as multiphoton processes, and we worked under the premise that PAHs with extra H atoms can form H2 through an Eley-Rideal abstraction mechanism. Results: In terms of abundances, we can distinguish clear differences with PAH size. The smallest PAH, coronene (C24H12), is found to be easily destroyed down to the complete loss of all of its H atoms. The largest species circumcircumcoronene (C96H24), is found in its normal hydrogenated state. The intermediate size molecule, circumcoronene (C54H18), shows an intermediate behaviour with respect to the other two, where partial dehydrogenation is observed inside the cloud. Regarding spectral variations, we find that the emission spectra in NGC 7023 are dominated by the variation in the ionization of the dominant hydrogenation state of each species at each point inside the cloud. It is difficult to "catch" the effect of dehydrogenation in the emitted PAH spectra since, for any conditions, only PAHs within a narrow size range will be susceptible to dehydrogenation, being quickly stripped off of all H atoms (and may isomerize to cages or fullerenes). The 3 μm region is the most sensitive one towards the hydrogenation level of PAHs. Conclusions: Based on our results, we conclude that PAHs with extra H atoms are not the carriers of the 3.4 μm band observed in NGC 7023, since these species are only found in very benign environments. Finally, concerning the role of PAHs in the formation of H2 in photodissociation regions, we find that H2 abstraction from PAHs with extra H atoms is an inefficient process compared to grains. Instead, we propose that photodissociation of PAHs of small-to-intermediate sizes could contribute to H2 formation in PDR surfaces, but they cannot account by themselves for the inferred high H2 formation rates in these regions.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Barros, A. L. F.; Mattioda, A. L.; Ricca, A.

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) are formed. The rate constants for the decay of neutralmore » coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.« less

The mid-infrared spectrum of the carbon star HD 38218 and its possible relation to polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Buss, Richard H., Jr.; Tielens, A. G. G. M.; Snow, Theodore P.

1991-01-01

The mid-infrared spectra of carbon giant stars with hot companions are investigated in order to search for infrared emission bands from polycyclic aromatic hydrocarbons (PAH) in the envelopes of the C giants. A strong 8-micron emission band found in TU Tau = HD 38218 is attributed to the binary A star companion. It is argued that if the 8-micron feature in HD 38218 arises from PAHs, they seem to be important constituents of the C-giant shell, and they might be large compared with some interstellar PAHs. It is suggested that because no other IR spectra of C giants show clear PAH features, the greater flux of hard radiation in the binary HD 38218 seems likely to be responsible for the 8-micron feature and for its absence in many other C giants. Thus, PAHs could be present in the same amounts relative to SiC grains in the shells of similar single C giants, and the formation of carbonaceous grains could proceed through the formation of PAHs in C giant shells.

Radiation Processing of Polycyclic Aromatic Hydrocarbons (PAHs) in Space: ICEE PoC

NASA Technical Reports Server (NTRS)

Mattioda, Andrew; Cruz-Diaz, Gustavo; Barnhardt, Michael; Ging, Andrew; Schneider, Todd; Vaughn, Jason; Quigley, Emmett; Phillips, Brandon

2017-01-01

Small Polycyclic Aromatic Hydrocarbon molecules or PAHs (<30 carbon atoms) have been identified in comets, meteorites, asteroids, and interplanetary dust particles in our Solar System, while PAHs in the Interstellar Medium (ISM) tend to be much larger, usually between 50 to 100 carbon atoms in size. The cause of the size disparity between PAHs found in the ISM and Solar System as well as their influence on Solar System organics is not yet understood. Two chemical evolutionary paths have been proposed to explain the inventory of solar system organics. In one the prebiotic material was formed from the radiation induced modification of large pre-solar carbon-bearing species (e.g. ISM PAHs). The second path suggests that Solar System prebiotic matter is the result of bottom-up synthesis from small reactive molecules after the Solar System was formed. In this second scenario very few ISM PAHs survived the harsh pre-solar radiation as aromatic structures. ICEE PoC (ICEE Proof of Concept) investigated factors impacting the chemical evolution of large PAHs irradiated under conditions similar to the proto-solar nebula. Likewise ICEE PoC will refine the technical parameters of the proposed ICEE (Institute for Carbon Evolution Experiment) laboratory.

Gas-phase Absorptions of {{\\rm{C}}}_{42}{{\\rm{H}}}_{18}^{+} near 8300 Å below 10 K: Astronomical Implications

NASA Astrophysics Data System (ADS)

Campbell, E. K.; Maier, J. P.

2017-11-01

The gas-phase electronic spectrum of {{{C}}}42{{{H}}}18+ ({{HBC}}+) with an origin band at 8281 \\mathringA has been measured below 10 {{K}} by photofragmentation of helium complexes ({{{C}}}42{{{H}}}18+{--}{{He}}n) in a radiofrequency trap. {{HBC}}+ is a medium-sized polycyclic aromatic hydrocarbon (PAH) cation, and using an ion trapping technique it has been possible to record a high-quality gas-phase spectrum to directly compare with astronomical observations. No diffuse interstellar bands (DIBs) have been reported at the wavelengths of the strongest absorption bands in the {{{C}}}42{{{H}}}18+ spectrum. Measurement of absolute absorption cross sections in the ion trap allows upper limits to the column density of this ion to be {10}12 {{cm}}-2, indicating that even PAH cations of this size, which are believed to be stable in the interstellar medium, should be excluded as candidates for at least the strong DIBs.

UV-Visible Spectra of PAHs and Derivatives Seeded in Supersonic Jet. Astrophysical Implications

NASA Astrophysics Data System (ADS)

Salma, Bejaoui; Salama, Farid

2018-06-01

Laboratory absorption spectra of Polycyclic Aromatic Hydrocarbons (PAHs) and PAH derivatives measured under astrophysical relevant conditions are crucial to test the PAHs-DIBs hypothesis as well as the PAH model for the IR emission bands. Our dedicated experimental setup on the COsmic SImulation Chamber (COSmIC) provides an excellent platform to study neutral and ionized PAHs under the low temperature and pressure conditions that are representative of interstellar environments [1]. In this work, we study the effect of the substitution of CH bond(s) by a nitrogen atom(s) on the electronic spectra of phenanthrene. The electronic transitions associated with the lower excited states of neutral phenanthrene (C14H10) and phenanthridine (C13H9N) are measured in gas phase in the 315-345 nm region. Molecules are seeded in a supersonic expansion of argon gas and the absorption spectra are measured using the Cavity Ring Down Spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of phenanthrene, phenantridine and 1,10-phenanthroline (C12H8N2) isolated in 10 K argon matrices are also performed. The comparison between the CRDS spectra with the absorption of the matrix-isolated molecules highlight the matrix-induced perturbations in band position, profiles and broadening and illustrates the need of gas phase measurements for more accurate comparisons with astronomical spectra.[1] Salama, F., Galazutdinov, G., Krelowski, et al. ApJ 728, 154[FS1] (2011).[2] A. Tielens, ApJ 526 Pt 1265–273 (2008),Acknowledgements: This research is supported by the APRA Program of NASA SMD

A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons.

PubMed

Thomas, Aaron M; Lucas, Michael; Yang, Tao; Kaiser, Ralf I; Fuentes, Luis; Belisario-Lara, Daniel; Mebel, Alexander M

2017-08-05

The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. These aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared Spectroscopy of Naphthalene Aggregation and Cluster Formation in Argon Matrices

NASA Technical Reports Server (NTRS)

Roser, J. E.; Allamondola, L. J.

2011-01-01

Fourier-transform mid-infrared absorption spectra of mixed argon/naphthalene matrices at 5 K are shown with ratios of argon-to-naphthalene that vary from 1000 to 0. These spectra show the changes as naphthalene clustering and aggregation occurs, with moderate spectral shifts affecting the C-H vibrational modes and relatively small or no shifts to the C-C and C-C-C vibrational modes. The possible contribution of homogeneous naphthalene clusters to the interstellar unidentified infrared bands is discussed. The contribution of polycyclic aromatic hydrocarbon (PAH) clusters to the 7.7 micron emission plateau and the blue shading of the 12.7 micron emission band are identified as promising candidates for future research. In addition, since PAH clusters are model components of Jupiter and Titan's atmospheres, the information presented here may also be applicable to the spectroscopy of these objects.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gencaga, Deniz; Knuth, Kevin H.; Carbon, Duane F.

Understanding the origins of life has been one of the greatest dreams throughout history. It is now known that star-forming regions contain complex organic molecules, known as Polycyclic Aromatic Hydrocarbons (PAHs), each of which has particular infrared spectral characteristics. By understanding which PAH species are found in specific star-forming regions, we can better understand the biochemistry that takes place in interstellar clouds. Identifying and classifying PAHs is not an easy task: we can only observe a single superposition of PAH spectra at any given astrophysical site, with the PAH species perhaps numbering in the hundreds or even thousands. This ismore » a challenging source separation problem since we have only one observation composed of numerous mixed sources. However, it is made easier with the help of a library of hundreds of PAH spectra. In order to separate PAH molecules from their mixture, we need to identify the specific species and their unique concentrations that would provide the given mixture. We develop a Bayesian approach for this problem where sources are separated from their mixture by Metropolis Hastings algorithm. Separated PAH concentrations are provided with their error bars, illustrating the uncertainties involved in the estimation process. The approach is demonstrated on synthetic spectral mixtures using spectral resolutions from the Infrared Space Observatory (ISO). Performance of the method is tested for different noise levels.« less

POLYCYCLIC AROMATIC HYDROCARBON PROCESSING IN THE BLAST WAVE OF THE SUPERNOVA REMNANT N132D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tappe, A.; Rho, J.; Boersma, C.

2012-08-01

We present Spitzer Infrared Spectrograph 14-36 {mu}m mapping observations of the supernova remnant N132D in the Large Magellanic Cloud. This study focuses on the processing of polycyclic aromatic hydrocarbons (PAHs) that we previously identified in the southern blast wave. The mid-infrared spectra show strong continuum emission from shock-heated dust and a unique, nearly featureless plateau in the 15-20 {mu}m region, which we attribute to PAH molecules. The typical PAH emission bands observed in the surrounding interstellar medium ahead of the blast wave disappear, which indicates shock processing of PAH molecules. The PAH plateau appears most strongly at the outer edgemore » of the blast wave and coincides with diffuse X-ray emission that precedes the brightest X-ray and optical filaments. This suggests that PAH molecules in the surrounding medium are swept up and processed in the hot gas of the blast wave shock, where they survive the harsh conditions long enough to be detected. We also observe a broad emission feature at 20 {mu}m appearing with the PAH plateau. We speculate that this feature is either due to FeO dust grains or connected to the processing of PAHs in the supernova blast wave shock.« less

The PAH Emission Characteristics of the Reflection Nebula NGC 2023

NASA Astrophysics Data System (ADS)

Peeters, Els; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; Tielens, Alexander G. G. M.; Ricca, Alessandra; Wolfire, Mark G.

2017-02-01

We present 5-20 μm spectral maps of the reflection nebula NGC 2023 obtained with the Infrared Spectrograph SL and SH modes on board the Spitzer Space Telescope, which reveal emission from polycyclic aromatic hydrocarbons (PAHs), C60, and H2 superposed on a dust continuum. We show that several PAH emission bands correlate with each other and exhibit distinct spatial distributions that reveal a spatial sequence with distance from the illuminating star. We explore the distinct morphology of the 6.2, 7.7, and 8.6 μm PAH bands and find that at least two spatially distinct components contribute to the 7-9 μm PAH emission in NGC 2023. We report that the PAH features behave independently of the underlying plateaus. We present spectra of compact, oval PAHs ranging in size from C66 to C210, determined computationally using density functional theory, and we investigate trends in the band positions and relative intensities as a function of PAH size, charge, and geometry. Based on the NASA Ames PAH database, we discuss the 7-9 μm components in terms of band assignments and relative intensities. We assign the plateau emission to very small grains with possible contributions from PAH clusters and identify components in the 7-9 μm emission that likely originate in these structures. Based on the assignments and the observed spatial sequence, we discuss the photochemical evolution of the interstellar PAH family as the PAHs are more and more exposed to the radiation field of the central star in the evaporative flows associated with the Photo-Dissociation Regions in NGC 2023.

The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

Vibrational Spectroscopy after OSU - From C2- to Interstellar Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.

2006-01-01

The composition of interstellar ice and dust provides insight into the chemical history of the interstellar medium and early solar system. It is now possible to probe this unique and unusual chemistry and determine the composition of these microscopic interstellar particles which are hundreds to many thousands of light years away thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of chemical composition, and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with giant, dark molecular clouds -the birthplace of stars and planets- and others in more tenuous, UV radiation rich regions are now available. The fundamentals of IR spectroscopy and what comparisons of astronomical IR spectra with laboratory spectra of materials prepared under realistic simulated interstellar conditions tell us about the components of these materials is the subject of this talk. These observations have shown that mixed molecular ices comprised of H2O, CH3OH, CO, NH3 and H2CO contain most of the molecular material in molecular clouds and that gas phase, ionized polycyclic aromatic hydrocarbons (PAHs) are widespread and surprisingly abundant throughout most of the interstellar medium.

The Interstellar Medium

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.

1995-01-01

The Interstellar Medium (ISM) forms an integral part of the lifecycle of stars and the galaxy. Stars are formed by gravitational contraction of interstellar clouds. Over their life, stars return much of their mass to the ISM through winds and supernova explosions, resulting in a slow enrichment in heavy elements. Understanding the origin and evolution of the ISM is a key problem within astrophysics. The KAO has made many important contributions to studies of the interstellar medium both on the macro and on the micro scale. In this overview, I will concentrate on two breakthroughs in the last decade in which KAO observations have played a major role: (1) the importance of large Polycyclic Aromatic Hydrocarbon (PAH) molecules for the ISM (section 3) and (2) the study of Photodissociation Regions (PDRs) as an analog for the diffuse ISM at large (section 4). Appropriately, the micro and macro problem are intricately interwoven in these problems. Finally, section 5 reviews the origin of the (CII) emission observed by COBE.

Infrared spectroscopy of hydrated polycyclic aromatic hydrocarbon cations: naphthalene+-water.

PubMed

Chatterjee, Kuntal; Dopfer, Otto

2017-12-13

Polycyclic aromatic hydrocarbons (PAHs) are suggested to occur in interstellar media and ice grains. It is important to characterize hydrated PAHs and their cations to explore their stability in interstellar and biological media. Herein, the infrared photodissociation (IRPD) spectrum of the naphthalene + -H 2 O radical cation (Np + -H 2 O) recorded in the O-H and C-H stretch range is analysed by dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level to determine its structure and intermolecular bonding. Monohydration of Np + in its 2 A u ground electronic state leads to the formation of a bifurcated CHO ionic hydrogen bond (H-bond), in which the lone pairs of H 2 O bind to two adjacent CH proton donors of the two aromatic rings. The frequency-dependent branching ratios observed for IRPD of cold Np + -H 2 O-Ar clusters allows the estimation of the dissociation energy of Np + -H 2 O as D 0 ∼ 2800 ± 300 cm -1 . The monohydration motif of Np + differs qualitatively from that of the benzene cation in both structure and binding energy, indicating the strong influence of the multiple aromatic rings on the hydration of PAH + cations. This difference is rationalized by natural bond orbital analysis of the ionic H-bond motif. Comparison with neutral Np-H 2 O reveals the large change in structure and bond strength of the hydrated PAHs upon ionization. While neutral Np-H 2 O is stabilized by weak π H-bonds (OHπ, π-stacking), strong cation-dipole forces favour a planar bifurcated CHO ionic H-bond in Np + -H 2 O.

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Thomas, J. D.; Witt, A. N.

2006-01-01

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

Life and the Universe: From Astrochemistry to Astrobiology

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.

2013-01-01

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the cosmos. In cold molecular clouds, the birthplace of planets and stars, interstellar atoms and molecules freeze onto extremely cold dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. As these materials are the building blocks of comets and related to carbonaceous micrometeorites, they are likely to be important sources of complex organic materials delivered to habitable planets (including the primordial Earth) and their composition may be related to the origin of life. This talk will focus on the chemical evolution of these cosmic materials and their relevance to astrobiology.

The PAH Emission Characteristics of the Reflection Nebula NGC 2023

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peeters, Els; Bauschlicher, Charles W. Jr.; Allamandola, Louis J.

We present 5–20 μ m spectral maps of the reflection nebula NGC 2023 obtained with the Infrared Spectrograph SL and SH modes on board the Spitzer Space Telescope, which reveal emission from polycyclic aromatic hydrocarbons (PAHs), C{sub 60}, and H{sub 2} superposed on a dust continuum. We show that several PAH emission bands correlate with each other and exhibit distinct spatial distributions that reveal a spatial sequence with distance from the illuminating star. We explore the distinct morphology of the 6.2, 7.7, and 8.6 μ m PAH bands and find that at least two spatially distinct components contribute to themore » 7–9 μ m PAH emission in NGC 2023. We report that the PAH features behave independently of the underlying plateaus. We present spectra of compact, oval PAHs ranging in size from C{sub 66} to C{sub 210}, determined computationally using density functional theory, and we investigate trends in the band positions and relative intensities as a function of PAH size, charge, and geometry. Based on the NASA Ames PAH database, we discuss the 7–9 μ m components in terms of band assignments and relative intensities. We assign the plateau emission to very small grains with possible contributions from PAH clusters and identify components in the 7–9 μ m emission that likely originate in these structures. Based on the assignments and the observed spatial sequence, we discuss the photochemical evolution of the interstellar PAH family as the PAHs are more and more exposed to the radiation field of the central star in the evaporative flows associated with the Photo-Dissociation Regions in NGC 2023.« less

PAHs in the Ices of Saturn's Satellites: Connections to the Solar Nebula and the Interstellar Medium

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; Pendleton, Yvonne J.

2015-01-01

Aliphatic hydrocarbons and PAHs have been observed in the interstellar medium (e.g., Allamandola et al. 1985, Pendleton et al. 1994, Pendleton & Allamandola 2002, Tielens 2013, Kwok 2008, Chiar & Pendleton 2008) The inventory of organic material in the ISM was likely incorporated into the molecular cloud in which the solar nebula condensed, contributing to the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Additional organic synthesis occurred in the solar nebula (Ciesla & Sandford 2012). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn (Johnson & Lunine 2005). VIMS spectral maps of Phoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and aliphatic hydrocarbon (=CH2, -CH3) absorption bands (3.2-3.6 micrometers). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles ((is) approximately 5-20 micrometers size) spiral inward toward Saturn (Verbiscer et al. 2009). They encounter Iapetus and Hyperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is approximately 10 times as abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, and in carbonaceous meteorites (Cruikshank et al. 2014). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 (is) approximately 4, which is larger than the value found in the diffuse ISM ((is) approximately 2-2.5). Insofar as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key in understanding the content and degree of processing of that nebular material. A dynamical subset of TNOs define the Kuiper Belt, from which the short-period comets originate. Particles collected from comet 81P/Wild contain PAHs with an interstellar signature of deuterium. By inference, the PAHs contained in Phoebe and now dusted on the surfaces of two other Saturn satellites share that interstellar origin. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST will open that possibility for a number of objects.

Modeling the Anomalous Microwave Emission with Spinning Nanoparticles: No PAHs Required

NASA Astrophysics Data System (ADS)

Hensley, Brandon S.; Draine, B. T.

2017-02-01

In light of recent observational results indicating an apparent lack of correlation between the anomalous microwave emission (AME) and mid-infrared emission from polycyclic aromatic hydrocarbons, we assess whether rotational emission from spinning silicate and/or iron nanoparticles could account for the observed AME without violating observational constraints on interstellar abundances, ultraviolet extinction, and infrared emission. By modifying the SpDust code to compute the rotational emission from these grains, we find that nanosilicate grains could account for the entirety of the observed AME, whereas iron grains could be responsible for only a fraction, even for extreme assumptions on the amount of interstellar iron concentrated in ultrasmall iron nanoparticles. Given the added complexity of contributions from multiple grain populations to the total spinning dust emission, as well as existing uncertainties due to the poorly constrained grain size, charge, and dipole moment distributions, we discuss generic, carrier-independent predictions of spinning dust theory and observational tests that could help identify the AME carrier(s).

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Gillette, J. S.; Clemett, S. J.; Zare, R. N.

1999-01-01

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

Carriers of the mid-IR emission bands in PNe reanalysed. Evidence of a link between circumstellar and interstellar aromatic dust

NASA Astrophysics Data System (ADS)

Joblin, C.; Szczerba, R.; Berné, O.; Szyszka, C.

2008-10-01

Context: It has been shown that the diversity of the aromatic emission features can be rationalized into different classes of objects, in which differences between circumstellar and interstellar matter are emphasised. Aims: We probe the links between the mid-IR emitters observed in planetary nebulae (PNe) and their counterparts in the interstellar medium in order to probe a scenario in which the latter have been formed in the circumstellar environment of evolved stars. Methods: The mid-IR (6-14 μm) emission spectra of PNe and compact H II regions were analysed on the basis of previous work on photodissociation regions (PDRs). Galactic, Large Magellanic Cloud (LMC), and Small Magellanic Cloud (SMC) objects were considered in our sample. Results: We show that the mid-IR emission of PNe can be decomposed as the sum of six components. Some components made of polycyclic aromatic hydrocarbon (PAH) and very small grain (VSG) populations are similar to those observed in PDRs. Others are fitted in an evolutionary scenario involving the destruction of the aliphatic component observed in the post-AGB stage, as well as strong processing of PAHs in the extreme conditions of PNe that leads to a population of very large ionized PAHs. This species called PAHx are proposed as the carriers of a characteristic band at 7.90 μm. This band can be used as part of diagnostics that identify PNe in nearby galaxies and is also observed in galactic compact H II regions. Conclusions: These results support the formation of the aromatic very small dust particles in the envelopes of evolved stars, in the Milky Way, as well as in the LMC and SMC, and their subsequent survival in the interstellar medium. This work is based on observations made with the Spitzer Space Telescope, which is operated by the Jet Propulsion Laboratory, California Institute of Technology under a contract with NASA. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) and with the participation of ISAS and NASA. Tables A.1 and A.2 are only available in electronic form at http://www.aanda.org

Polycyclic aromatic hydrocarbons and molecular hydrogen in oxygen-rich planetary nebulae: the case of NGC 6720

PubMed Central

Cox, N. L. J.; Pilleri, P.; Berné, O.; Cernicharo, J.; Joblin, C.

2015-01-01

Evolved stars are primary sources for the formation of polycyclic aromatic hydrocarbons (PAHs) and dust grains. Their circumstellar chemistry is usually designated as either oxygen-rich or carbon-rich, although dual-dust chemistry objects, whose infrared spectra reveal both silicate- and carbon-dust features, are also known. The exact origin and nature of this dual-dust chemistry is not yet understood. Spitzer-IRS mid-infrared spectroscopic imaging of the nearby, oxygen-rich planetary nebula NGC 6720 reveals the presence of the 11.3 μm aromatic (PAH) emission band. It is attributed to emission from neutral PAHs, since no band is observed in the 7–8 μm range. The spatial distribution of PAHs is found to closely follow that of the warm clumpy molecular hydrogen emission. Emission from both neutral PAHs and warm H2 is likely to arise from photo-dissociation regions associated with dense knots that are located within the main ring. The presence of PAHs together with the previously derived high abundance of free carbon (relative to CO) suggest that the local conditions in an oxygen-rich environment can also become conducive to in-situ formation of large carbonaceous molecules, such as PAHs, via a bottom-up chemical pathway. In this scenario, the same stellar source can enrich the interstellar medium with both oxygen-rich dust and large carbonaceous molecules. PMID:26924856

Properties and evolution of dust in the interstellar medium.

NASA Astrophysics Data System (ADS)

Flagey, N.

2007-10-01

My thesis is dedicated to the properties and evolution of the dust in the Galactic interstellar medium (ISM), particularly the small sizes end of the dust size distribution. Throughout these three years, new infrared (IR) observations provided by the Spitzer Space Telescope helped me to bring my own contribution to the knowledge of the dust lifecycle. In order to get a view as global as possible, I have studied three different interstellar environments : the diffuse Galactic medium, a molecular cloud and a star forming region. I analyzed one line of sight that points towards the diffuse Galactic ISM, away from bright star forming regions. Combining spectroscopic and photometric data, I have built a mean Galactic near to mid IR spectrum of the dust, that I have afterwards used as a reference. The Polycyclic Aromatic Hydrocarbons (PAHs) bands are present on top of a continuum. In order to interpret the band intensity ratios in terms of PAHs size and ionization state, I have updated our dust model so that it takes into account the size dependent ionization state of the PAHs. The diffuse ISM spectrum is fit for a PAH mean size of about 60 carbon atoms and a cation fraction of about 40%. Molecular size and charged PAHs are thus present within the diffuse medium. A 3-5 μm continuum, first detected in reflection nebulae, is observed to be present in the diffuse ISM emission. This continuum accounts for 70% of the emission in the Spitzer/IRAC 3.6μm filter. Its origin is still unknown. I show that it is neither scattered light nor PAH fluorescence, as this process would require a photon conversion efficiency above 100%. I used Spitzer observations to quantify spatial variations of PAHs properties across the galaxy and on small scales within the Taurus molecular cloud. Analysis of a set of Galactic diffuse ISM sight lines show that the PAHs mean size exhibits significant dispersion, from 40 to 80 carbon atoms, while their ionization fraction stays constant within error bars. I have also analyzed mid and far-IR Spitzer images of the Taurus Molecular Cloud. Each dust component (PAHs, VSGs for Very Small Grains and BGs for Big Grains) can be related to one Spitzer channel (IRAC 8, MIPS 24 and MIPS 160 microns). A first difficulty was to obtain images of the low brightness diffuse emission across the entire cloud. I worked with Spitzer Science Center (SSC) experts to produce the IRAC 8 and MIPS 24 images. For the MIPS 160 I used an inversion algorithm developed to destripe the data. I validated the photometry of each image. The observations show that PAHs are present within a surface layer thinn! er than that penetrated by ultraviolet photons and that of VSGs emission. Such variations cannot be only explained by the extinction and must thus trace real PAH depletion within dense gas where the smallest dust particles may stick on large grains and/or coagulate. During my PhD thesis, I applied for a SSC Visiting Graduate Student grant in order to study the Eagle Nebula (M16), the object that made me decide to do astrophysics, more than ten years ago, when the Hubble Space Telescope imaged the iconic Pillars of Creation. My application was accepted and I spent 6 months within the MIPSGAL Science Team. My aim was to combine IRAC and MIPS data of M16 in order to analyze the properties of the dust within the dusty and gaseous structures, while being involved in the data processing enhancement. The MIPS 24 microns image defines a shell-like structure within the nebula while the pillars are observed at other wavelengths. M16 is a massive star forming region where the dust emission is expected to be powered by the massive stars radiation. However, we show that the UV field is one order of magnitude too small to account for the shell dust temperature. For comparison we analyzed several other Galactic shells. The M16 nebula stands out for having unusually high far-IR color temperature.We considered an alternative interpretation where the dust is heated by gas grain collisions. This interpretation would imply that the shell is a supernova remnant (SNR) about 3000 years old. If confirmed, the Eagle SNR would be the first one detected through dust emission and within a stellar cradle. Moreover, it would illustrate the importance of dust infrared emission within energetics of SNRs. At last, but not at least, the question of the formation and/or destruction of the iconic Pillars of Creation would be (re)opened.

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands

NASA Technical Reports Server (NTRS)

Salama, F.; Allamandola, L. J.

1995-01-01

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these Polycyclic Aromatic Hydrocarbons (PAHs) absorb in the visible. C10H8(+) has 12 discrete absorption bands which fall between 6800 and 5000 A. The strongest band at 6741 A falls close to the weak 6742 A diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8(+) is responsible for some of the DIBs can be tested by searching for new DIBS at 6520, 6151, and 5965 A, other moderately strong naphthalene cation band positions. If C10H8(+) is indeed responsible for the 6742 A feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10(+) is dominated by a strong band at 4435 A in an Ar matrix and 4395 A in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 A. If C16H10(+), or a closely related pyrene-like ion is indeed responsible for the 4430 A feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.

Neutral and ionized polycyclic aromatic hydrocarbons, diffuse interstellar bands and the ultraviolet extinction curve

NASA Technical Reports Server (NTRS)

Salama, Farid; Allamandola, Louis John

1993-01-01

Neutral naphthalene C10H8, phenanthrene C14H10 and pyrene C16H10 absorb strongly in the ultraviolet region and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these polycyclic aromatic hydrocarbons (PAHs) absorb in the visible C10H8(+) has 13 discrete absorption bands which fall between 6800 and 4500 A. The strongest band at 6741 A falls close to the weak 6742 A diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8(+) is responsible for some of the DIBs can be tested by searching for new DIBs at 6520 and 6151 A, other strong naphthalene cation band positions. If C10H8(+) is indeed responsible for the 6742 A feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10(+) is dominated by a strong band at 4435 A in an Ar matrix and 4395 A in Ne, wavelengths which fall very close to the strongest DIB at 4430 A. If C16H10(+) or a closely related pyrene-like ion, is indeed responsible for the 4430 A feature, it accounts for 0.2% of the cosmic carbon. An intense, very broad UV-to-visible continuum is reported which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR radiation.

Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

Organic Synthesis in Simulated Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Dworkin, Jason P.; Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Deamer, David W.; Elsila, Jamie; Zare, Richard N.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. ID We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with LTV light from a hydrogen plasma lamp: The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

Organic Synthesis in Simulated Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Dworkin, Jason P.; Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Deamer, David W.; Elsila, Jamie; Zare, Richard N.

2001-01-01

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

[PAH Cations as Viable Carriers of DIBs

NASA Technical Reports Server (NTRS)

Snow, Ted

1998-01-01

This report is intended to fill in the blanks in NASA's file system for our lab astro study of molecular ions of astrophysical interest. In order to give NASA what it needs for its files, I attach below the text of the section from our recent proposal to continue this work, in which we describe progress to date, including a large number of publications. Our initial studies were focused on PAH cations, which appear to be viable candidates as the carriers of the DIBs, an idea that has been supported by laboratory spectroscopy of PAH cations in inert matrices. Beginning with the simplest aromatic (benzene; C6H6) and moving progressively to larger species (naphthalene, C10OH8; pyrene, C16H10; and most recently chrysene, C18H12), we have been able to derive rate coefficients for reactions with neutral spices that are abundant in the diffuse interstellar medium.

Infrared frequencies and intensities for astrophysically important polycyclic aromatic hydrocarbon cations

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin

1993-01-01

Polycyclic aromatic hydrocarbons (PAHs) have been implicated as the carriers of the 'unidentified infrared' (UIR) emission bands observed from the interstellar medium. It has long been thought that these molecules, if present, probably exist as cations. In this paper we present infrared spectra of the cations of five moderate-sized PAHs. The PAH cations have been produced by low-energy electron impact and then trapped and stabilized in argon matrices at 12 K. To date, results have been obtained on naphthalene, anthracene, pyrene, perylene, and coronene. A common feature of the infrared spectra of all these cations is the very different intensity pattern of the ions compared to the neutral parents. Visible and (partial) infrared spectra of the coronene cation are also presented. It is shown that the out-of-plane CH bending mode shifts to a position very close to the UIR band at 11.3 microns. The astrophysical impact of these observations is discussed.

Nature of very small grains - PAH molecules or silicates?. [Polycyclic Aromatic Hydrocarbon in interstellar dust

NASA Technical Reports Server (NTRS)

Desert, F. X.; Leger, A.; Puget, J. L.; Boulanger, F.; Sellgren, K.

1986-01-01

The predictions of the model of Puget et al. (1985) for the emission from Very Small Grains (VSGs) including both graphitic and silicate components are compared with published 8-13-micron observations of astronomical sources. The VSGs are found to be mainly graphitic and an upper limit is placed on the relative mass of silicates based on lack of the 9.7-micron silicate emission feature on M 82 and NGC 2023. This dissymetry in the composition of VSGs supports the suggestion that they are formed in grain-grain collisions where the behaviors of graphite and silicate grains are expected to be quite different.

Identification and discrimination of polycyclic aromatic hydrocarbons using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Cloutis, Edward; Szymanski, Paul; Applin, Daniel; Goltz, Douglas

2016-08-01

Polycyclic aromatic hydrocarbons (PAHs) are widely present throughout the Solar System and beyond. They have been implicated as a contributor to unidentified infrared emission bands in the interstellar medium, comprise a substantial portion of the insoluble organic matter in carbonaceous chondrites, are expected stable components of organic matter on Mars, and are present in a wide range of terrestrial hydrocarbons and as components of biomolecules. However, PAH structures can be very complicated, making their identification challenging. Raman spectroscopy is known to be especially sensitive to the highly polarizable C-C and C=C bonds found in PAHs, and therefore, can be a powerful tool for PAH structural and compositional elucidation. This study examined Raman spectra of 48 different PAHs to determine the degree to which Raman spectroscopy could be used to uniquely identify different species, factors that control the positions of major Raman peaks, the degree to which induced fluorescence affects the intensity of Raman peaks, its usefulness for PAH discrimination, and the effects of varying excitation wavelength on some PAH Raman spectra. It was found that the arrangement and composition of phenyl (benzene) rings, and the type and position of functional groups can greatly affect fluorescence, positions and intensities of Raman peaks associated with the PAH backbone, and the introduction of new Raman peaks. Among the functional groups found on many of the PAHs that were analyzed, only a few Raman peaks corresponding to the molecular vibrations of these groups could be clearly distinguished. Comparison of the PAH Raman spectra that were acquired with both 532 and 785 nm excitation found that the longer wavelength resulted in reduced fluorescence, consistent with previous studies.

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Dworkin, Jason P.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Do the Infrared Emission Features Need UV Excitation? The PAH Model in UV-poor Reflection Nebulae

NASA Astrophysics Data System (ADS)

Li, A.; Draine, B. T.

2001-12-01

One of the major challenges of identifying the 3.3, 6.2, 7.7, 8.6, and 11.3μ m interstellar infrared emission bands with polycyclic aromatic hydrocarbon (PAH) molecules has been the recent detection of these bands in regions with little ultraviolet (UV) illumination since small, neutral PAH molecules have little or no absorption at visible wavelengths and thus are excited primarily by UV photons. The ``astronomical'' PAH model (Li & Draine 2001), incorporating the experimental result that the visual absorption edge shifts to longer wavelength upon ionization and/or as the PAH size increases (Allamandola, Hudgins, & Sandford 1999), is shown to be able to closely reproduce the observed infrared emission bands of vdB 133, a UV-poor reflection nebula (Uchida, Sellgren, & Werner 1998) as well as the 6.2, 7.7, and 11.3μ m band ratios of the UV-deficient ring in the Andromeda galaxy M31 (Pagani et al. 1999). It is also shown that ``astronomical'' PAHs can be heated sufficiently by a T eff=3000 K black-body to emit at 6.2, 7.7, 8.6, and 11.3μ m. Illustrative mid-IR emission spectra are calculated for reflection nebulae illuminated by cool stars with T eff=3600, 4500, 5000 K. These will allow comparison with future Space Infrared Telescope Facility (SIRTF) observations of vdB 135 (T eff=3600 K), vdB 47 (T eff=4500 K), and vdB 101 (T eff=5000 K) (Houck 2001). This research was supported in part by NASA grant NAG5-7030 and NSF grant AST-9619429. { References:} Allamandola, L.J., Hudgins, D.M., & Sandford, S.A. 1999, ApJ, 511, L115 Houck, J.R. 2001, SIRTF Observations of the Mid IR Features in Reflection Nebulae, {\\sf http://sirtf.caltech.edu/ROC/pid19} Li, A., & Draine, B.T. 2001, ApJ, 554, 778 Pagani, L., et al. 1999, A&A, 351, 447 Uchida, K.I., Sellgren, K., & Werner, M.W. 1998, ApJ, 493, L109

Laboratory investigation of the contribution of complex aromatic/aliphatic polycyclic hybrid molecular structures to interstellar ultraviolet extinction and infrared emission

NASA Technical Reports Server (NTRS)

Arnoult, K. M.; Wdowiak, T. J.; Beegle, L. W.

2000-01-01

We have demonstrated by experiment that, in an energetic environment, a simple polycyclic aromatic hydrocarbon (PAH) such as naphthalene will undergo chemical reactions that produce a wide array of more complex species (an aggregate). For a stellar wind of a highly evolved star (post-asymptotic giant branch [post-AGB]), this process would be in addition to what is expected from reactions occurring under thermodynamic equilibrium. A surprising result of that work was that produced in substantial abundance are hydrogenated forms that are hybrids of polycyclic aromatic and polycyclic alkanes. Infrared spectroscopy described here reveals a spectral character for these materials that has much in common with that observed for the constituents of circumstellar clouds of post-AGB stars. It can be demonstrated that a methylene (-CH2-) substructure, as in cycloalkanes, is the likely carrier of the 6.9 microns band emission of dust that has recently been formed around IRAS 22272+5433, NGC 7027, and CPD -56 8032. Ultraviolet spectroscopy previously done with a lower limit of 190 nm had revealed that this molecular aggregate can contribute to the interstellar extinction feature at 2175 angstroms. We have now extended our UV spectroscopy of these materials to 110 nm by a vacuum ultraviolet technique. That work, described here, reveals new spectral characteristics and describes how material newly formed during the late stages of stellar evolution could have produced an extinction feature claimed to exist at 1700 angstroms in the spectrum of HD 145502 and also how the newly formed hydrocarbon material would be transformed/aged in the general interstellar environment. The contribution of this molecular aggregate to the rise in interstellar extinction at wavelengths below 1500 angstroms is also examined. The panspectral measurements of the materials produced in the laboratory, using plasmas of H, He, N, and O to convert the simple PAH naphthalene to an aggregate of complex species, provide insight into possible molecular structure details of newly formed hydrocarbon-rich interstellar dust and its transformation into aged material that becomes resident in the interstellar medium. Specifically the presence of naphthalene-like and butadiene-like conjugated structures as chromophores for the 2175 angstroms ultraviolet extinction feature is indicated.

Formation of Prebiotic Molecules in Interstellar and Cometary Ices

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Dworkin, Jason; Gilette, J. Seb; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

2000-01-01

We report here on our lab studies of ice photochemistry of large organic molecules under cometary conditions. We focus on polycyclic aromatic hydrocarbons (PAHs), their photoproducts, and their similarities to molecules seen in living systems today. We note that these kinds of compounds are seen in meteorites and we propose an explanation for both their formation and their observed deuterium enrichments.

The Formation of N- and O-Heterocycles from the Irradiation of Benzene and Naphthalene in H2O/NH3- Containing Ices

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Materese, C. K.; Nuevo, M.

2015-01-01

Aromatic hydrocarbons are an important class of molecules for both astrochemistry and astrobiology (Fig. 1). Within this class of molecules, polycyclic aromatic hydrocarbons (PAHs) are known to be ubiquitous in many astrophysical environments, and are likely present in interstellar clouds and protostellar disks. In dense clouds, PAHs are expected to condense onto grains as part of mixed molecular ice mantles dominated by small molecules like H2O,CH3OH, NH3, CO, and CO2. These ices are exposed to ionizing radiation in the form of cosmic rays and ambient high-energy X-ray and UV photons.

Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

NASA Technical Reports Server (NTRS)

Salama, F.; Biennier, L.

2004-01-01

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the plasma. From these unique measurements, we derive information on the nature, the size and the structure of interstellar dust particles, the growth and the destruction processes of IS dust and the resulting budget of extraterrestrial organic molecules.

The Infrared Spectra of Polycyclic Aromatic Hydrocarbons with Excess Peripheral H Atoms (H(sub n)-PAHs) and their Relation to the 3.4 and 6.9 Micrometer PAH Emission Features

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Materese, Christopher K.

2013-01-01

A population of polycyclic aromatic hydrocarbons (PAHs) and related materials are thought to be responsible for the family of infrared emission features that are seen towards a wide variety of astrophysical environments. A potentially important subclass of these materials are polycyclic aromatic hydrocarbons whose edges contain excess H atoms (H(sub n)-PAHs). While it has been suggested that this type of compound may be present in the interstellar population, it has been difficult to properly assess this possibility because of a lack of suitable infrared laboratory spectra to assist with analysis of the astronomical data. We present the 4000-500 cm(exp -1) (2.5-20 micrometers) infrared spectra of 23 H(sub n)-PAHs and related molecules isolated in argon matrices, under conditions suitable for use in the interpretation of astronomical data. The spectra of molecules with mixed aromatic and aliphatic domains show unique characteristics that distinguish them from their fully aromatic PAH equivalents. We discuss the changes to the spectra of these types of molecules as they transition from fully aromatic to fully aliphatic forms. The implications for the interpretation of astronomical spectra are discussed with specific emphasis on the 3.4 and 6.9 micrometer features. Laboratory data is compared with emission spectra from IRAS 21282+5050, an object with normal PAH emission features, in addition to IRAS 22272+5435 and IRAS 0496+3429, two protoplanetary nebulae with abnormally large 3.4 micrometer features. We show that 'normal' PAH emission objects contain relatively few H(sub n)-PAHs in their emitter populations, but less evolved protoplanetary nebulae may contain significant abundances of these molecules.

The anharmonic quartic force field infrared spectra of hydrogenated and methylated PAHs.

PubMed

Mackie, Cameron J; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Buma, Wybren Jan; Lee, Timothy J; Tielens, Alexander G G M

2018-01-03

Polycyclic aromatic hydrocarbons (PAHs) have been shown to be ubiquitous in a large variety of distinct astrophysical environments and are therefore of great interest to astronomers. The majority of these findings are based on theoretically predicted spectra, which make use of scaled DFT harmonic frequencies for band positions and the double harmonic approximation for intensities. However, these approximations have been shown to fail at predicting high-resolution gas-phase infrared spectra accurately, especially in the CH-stretching region (2950-3150 cm -1 , 3 μm). This is particularly worrying for the subset of hydrogenated or methylated PAHs to which astronomers attribute the observed non-aromatic features that appear in the CH-stretching region of spectral observations of the interstellar medium (ISM). In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs and five non-linear PAHs, demonstrating the importance of including anharmonicities into theoretical calculations. In this work we extend these techniques to two methylated PAHs (9-methylanthracene, and 9,10-dimethylanthracene) and four hydrogenated PAHs (9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydronaphthalene, and 1,2,3,6,7,8-hexahydropyrene) in order to better understand the aliphatic IR features of substituted PAHs. The theoretical spectra are compared with the spectra obtained under matrix isolation low-temperature conditions for the full vibrational fundamental range and under high-resolution, low-temperature gas-phase conditions for the CH-stretching region. Excellent agreement is observed between the theoretical and high-resolution experimental spectra with a deviation of 0.00% ± 0.17%, and changes to the spectra of PAHs upon methylation and hydrogenated are tracked accurately and explained.

The Detection of 6.9 μm Emission Features in the Infrared Spectra of IRAS 04296+3429, IRAS 05341+0852, and IRAS 22272+5435: Evidence for the Presence of Hn-PAHs in Post-AGB Stars

NASA Astrophysics Data System (ADS)

Materese, Christopher K.; Bregman, Jesse D.; Sandford, Scott A.

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) are generally believed to be ubiquitous in space and responsible for numerous telltale interstellar infrared emission bands. In Sandford et al., we suggested that PAHs with excess hydrogenation at their periphery ({{{H}}}{{n}}-PAHs) may be an important subclass of these molecules in some astrophysical environments. These molecules are candidates to explain objects with anomalously large 3.4 μm features, which are presumed to be associated with the aliphatic C-H stretching vibrations of the excess hydrogen. In that work, we suggest that for Hn-PAHs to be a viable candidate as the source for this 3.4 μm feature, we must also expect to observe methylene scissoring modes at 6.9 μm. In this work, we continue to develop the {{{H}}}{{n}} - {PAH} hypothesis with a focus on the 6.9 μm feature. We also present some new observations of three post-asymptotic giant branch (post-AGB) objects with abnormally large 3.4 μm features, IRAS 04296+3429, IRAS 05341+0852, and IRAS 22272+5435, in addition to one post-AGB object with normal PAH emissions, IRAS 20000+3239. These observations were made using the FORCAST instrument in grism mode on the Stratospheric Observatory for Infrared Astronomy aircraft and demonstrate the presence of a 6.9 μm feature for the three objects with abnormally large 3.4 μm features and no detectable 6.9 μm feature for the normal PAH emitter. These results are consistent with the hypothesis that Hn-PAHs are a possible source of these infrared emission bands.

AKARI observations of dust processing in merger galaxies: NGC2782 and NGC7727

NASA Astrophysics Data System (ADS)

Onaka, Takashi; Nakamura, Tomohiko; Sakon, Itsuki; Ohsawa, Ryou; Mori, Tamami; Wu, Ronin; Kaneda, Hidehiro

2015-08-01

Dust grains are the major reservoir of heavy elements and play significant roles in the thermal balance and chemistry in the interstellar medium. Where dust grains are formed and how they evolve in the ISM are one of the key issues for the understanding of the material evolution in the Universe. Although theoretical studies have been made, very little is so far known observationally about the lifecycle of dust grains in the ISM and that associated with Galactic scale events. The lifecycle of very small carbonaceous grains that contain polycyclic aromatic hydrocarbons (PAHs) or PAH-like atomic groups are of particular interest because they emit distinct band emission in the near- to mid-infrared region and they are thought to be most vulnerable to environmental conditions. PAHs may be formed in carbon-rich stars, while recent AKARI observations suggest that they may be formed by fragmentation of large carbonaceous grains in shocks in a supernova remnant or a galactic wind (Onaka et al. 2010, A&A, 514, 15; Seok et al. 2012, ApJ, 744, 160).Here we report results of AKARI observations of two mergers. NGC2782 (Arp 215) and NGC7727 (Arp 222). NGC2782 is a merger of 200Myr old. It shows a very long western tail of HI gas by a tidal interaction and the eastern tail that consists mainly of stellar components without an appreciable amount of gas and is thought to be a relic of the colliding low-mass galaxy whose gas component has been stripped off Smith 1994, AJ, 107, 1695. We found significant emission at the 7 μm band of the IRC onboard AKARI, which must come from PAH 6.2 and 7.7 μm bands, in the eastern tail. Based on dust model fitting, we found a low abundance of ~10nm size dust despite of the presence of PAHs, suggesting that PAHs may be formed from fragmentation of ~10nm carbonaceous dust grains. NGC7727 is a 1.2Gyr old merger and shows a SED similar to the NGC2782 tail in the northern tail of the merger event product, suggesting also the formation of PAHs from fragmentation. The observations of both galaxies indicate that PAHs can survive in violent events. We discuss these results in relation to the PAH formation and destruction.

IR Laboratory Astrophysics at Forty: Some Highlights and a Look to the Future

NASA Astrophysics Data System (ADS)

Allamandola, Louis John

2016-06-01

Space was thought to be chemically barren until about forty years ago. Astrochemistry was in its infancy, the composition of interstellar dust was largely guessed at, the presence of mixed molecular ices in dense molecular clouds was not taken seriously, and the notion of large, gas phase, carbon-rich molecules (PAHs) abundant and widespread throughout the interstellar medium (ISM) was inconceivable. The rapid development of infrared astronomy between 1970 and 1985, especially observations made by the Kuiper Airborne Observatory (KAO) and the Infrared Astronomical Satellite IRAS), which made it possible to measure mid-infrared spectra between 2.5 to 14 µm, changed all that. Since then observations made from ground-based, airborne and orbiting IR telescopes, together with radio and submm observations, have revealed that we live in a Universe that is not a hydrogen-dominated, physicist's paradise, but in a molecular Universe with complex molecules directly interwoven into its fabric. Today we recognize that molecules are an abundant and important component of astronomical objects at all stages of their evolution and that they play important roles in many processes that contribute to the structure and evolution of galaxies. Furthermore, many of these organic molecules are thought to be delivered to habitable planets such as Earth, and their composition may be related to the origin of life. Laboratory astrophysics has been key to making this great progress; progress which has only been made possible thanks to the close collaboration of laboratory experimentalists with astronomers and theoreticians. These collaborations are essential to meet the growing interdisciplinary challenges posed by astrophysics. This talk will touch on some of the milestones that have been reached in IR astrospectroscopy over the past four decades, focusing on the experimental work that revealed the widespread presence of interstellar PAHs and the composition of interstellar/precometary ices, and concluding with a personal view of important, key objectives in each area

Theoretical study of deuteronated PAHs as carriers for IR emission features in the ISM

NASA Astrophysics Data System (ADS)

Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Onaka, Takashi; Sakon, Itsuki

2015-11-01

This work proposes deuteronated PAH (DPAH+) molecules as a potential carrier of the 4.4 and 4.65 μm mid-infrared emission bands that have been observationally detected towards the Orion and M17 regions. Density Functional Theory calculations have been carried out on DPAH+ molecules to see the variations in the spectral behaviour from that of a pure polycyclic aromatic hydrocarbon (PAH). DPAH+ molecules show features that arise due to the stretching of the aliphatic C-D bond. Deuterated PAHs have been previously reported as carriers for such features. However, preferred conditions of ionization of PAHs in the interstellar medium (ISM) indicates the possibility of the formation of DPAH+ molecules. Comparison of band positions of DPAH+s shows reasonable agreement with the observations. We report the effect of size of the DPAH+ molecules on band positions and intensities. This study also reports a D/H ratio ([D/H]_{sc}; the ratio of C-D stretch and C-H stretch bands per [D/H]_{num}) that is decreasing with the increasing size of DPAH+s. It is noted that large DPAH+ molecules (no. of C atoms ˜50) match the D/H ratio that has been estimated from observations. This ratio offers prospects to study the deuterium abundance and depletion in the ISM.

Polycyclic Aromatic Hydrocarbon Far-infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Boersma, C.; Bauschlicher, C. W., Jr.; Ricca, A.; Mattioda, A. L.; Peeters, E.; Tielens, A. G. G. M.; Allamandola, L. J.

2011-03-01

The far-IR characteristics of astrophysically relevant polycyclic aromatic hydrocarbons (PAHs) averaging in size around 100 carbon atoms have been studied using the theoretical spectra in the NASA Ames PAH IR Spectroscopic Database. These spectra were calculated using density functional theory. Selections of PAH species are made, grouped together by common characteristics or trends, such as size, shape, charge, and composition, and their far-IR spectra compared. The out-of-plane modes involving the entire molecule are explored in detail, astronomical relevance is assessed, and an observing strategy is discussed. It is shown that PAHs produce richer far-IR spectra with increasing size. PAHs also produce richer far-IR spectra with increasing number of irregularities. However, series of irregular-shaped PAHs with the same compact core have common "Jumping-Jack" modes that "pile up" at specific frequencies in their average spectrum. For the PAHs studied here, around 100 carbon atoms in size, this band falls near 50 μm. PAH charge and nitrogen inclusion affect band intensities but have little effect on far-IR band positions. Detailed analysis of the two-dimensional, out-of-plane bending "drumhead" modes in the coronene and pyrene "families" and the one-dimensional, out-of-plane bending "bar" modes in the acene "family" show that these molecular vibrations can be treated as classical vibrating sheets and bars of graphene, respectively. The analysis also shows that the peak position of these modes is very sensitive to the area of the emitting PAH and does not depend on the particular geometry. Thus, these longest wavelength PAH bands could provide a unique handle on the size of the largest species in the interstellar PAH family. However, these bands are weak. Observing highly excited regions showing the mid-IR bands in which the emission from classical dust peaks at short wavelengths offers the best chance of detecting PAH emission in the far-IR. For these regions sensitivity is not an issue, spectral contrast is maximized and the PAH population is only comprised of highly stable, compact symmetric PAHs, such as the members of the pyrene and coronene "families" discussed in detail here.

Spitzer Observations of Dust Destruction in the Puppis A Supernova Remnant

NASA Technical Reports Server (NTRS)

Arendt, Richard G.; Dwek, Eli,; Blair, William P.; Ghavamian, Parviz; Long, Knox S.

2010-01-01

Imaging and spectral observations of the Puppis A supernova remnant (SNR) with the Spitzer Space Telescope confirm that its IR emission is dominated by the thermal continuum emission of swept-up interstellar dust which is collisionally heated by the X-ray emitting gas of the SNR. Line emission is too weak to affect the fluxes measured in broadband observations, and is poorly correlated with the IR or X-ray emission. Modeling of spectra from regions both in the SNR and in the associated ISM show that the ubiquitous polycyclic aromatic hydrocarbons (PAHs) of the ISM are destroyed within the SNR, along with nearly 25% of the mass of graphite and silicate dust grains.

Properties of grains derived from IRAS observations of dust

NASA Technical Reports Server (NTRS)

Wesselius, P. R.; Chlewicki, Grzegorz; Laureijs, Rene J.

1989-01-01

The authors used the results of Infrared Astronomy Satellite (IRAS) observations of diffuse medium dust to develop a theoretical model of the infrared properties of grains. Recent models based entirely on traditional observations of extinction and polarization include only particles whose equilibrium temperatures do not exceed 20 K in the diffuse interstellar medium. These classical grains, for which the authors have adopted the multipopulation model developed by Hong and Greenberg (1980), can explain only the emission in the IRAS 100 micron band. The measurements at shorter wavelengths (12, 25 and 60 microns) require two new particle populations. Vibrational fluorescence from aromatic molecules provides the most likely explanation for the emission observed at 12 microns, with polycyclic aeromatic hydrocarbons (PAHs) containing about 10 percent of cosmic carbon. A simplified model of the emission process shows that PAH molecules can also explain most of the emission measured by IRAS at 25 microns. The authors identified the warm particles responsible for the excess 60 microns emission with small (a approx. equals 0.01 microns) iron grains. A compilation of the available data on the optical properties of iron indicates that the diffuse medium temperature of small iron particles should be close to 50 K and implies that a large, possibly dominant, fraction of cosmic iron must be locked up in metallic particles in order to match the observed 60 microns intensities. The model matches the infrared fluxes typically observed by IRAS in the diffuse medium and can also reproduce the infrared surface brightness distribution in individual clouds. In particular, the combination of iron and classical cool grains can explain the surprising observations of the 60/100 microns flux ratio in clouds, which is either constant or increases slightly towards higher opacities. The presence of metallic grains has significant implications for the physics of the interstellar medium, including catalytic H2 formation, for which iron grains could be the main site; differences in depletion patterns between iron and other refractory elements (Mg, Si); and superparamagnetic behavior of large grains with embedded iron clusters giving rise to the observed high degree of alignment by the galactic magnetic field.

Observational Evidence Linking Interstellar UV Absorption to PAH Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blasberger, Avi; Behar, Ehud; Perets, Hagai B.

The 2175 Å UV extinction feature was discovered in the mid-1960s, yet its physical origin remains poorly understood. One suggestion is absorption by polycyclic aromatic hydrocarbon (PAH) molecules, which is supported by theoretical molecular structure computations and by laboratory experiments. PAHs are positively detected by their 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μ m IR emission bands, which are specified by their modes of vibration. A definitive empirical link between the 2175 Å UV extinction and the IR PAH emission bands, however, is still missing. We present a new sample of hot stars that have both 2175 Å absorptionmore » and IR PAH emission. We find significant shifts of the central wavelength of the UV absorption feature, up to 2350 Å, but predominantly in stars that also have IR PAH emission. These UV shifts depend on stellar temperature in a fashion that is similar to the shifts of the 6.2 and 7.7 μ m IR PAH bands, that is, the features are increasingly more redshifted as the stellar temperature decreases, but only below ∼15 kK. Above 15 kK both UV and IR features retain their nominal values. Moreover, we find a suggestive correlation between the UV and IR shifts. We hypothesize that these similar dependences of both the UV and IR features on stellar temperature hint at a common origin of the two in PAH molecules and may establish the missing link between the UV and IR observations. We further suggest that the shifts depend on molecular size, and that the critical temperature of ∼15 kK above which no shifts are observed is related to the onset of UV-driven hot-star winds and their associated shocks.« less

Observational Evidence Linking Interstellar UV Absorption to PAH Molecules

NASA Astrophysics Data System (ADS)

Blasberger, Avi; Behar, Ehud; Perets, Hagai B.; Brosch, Noah; Tielens, Alexander G. G. M.

2017-02-01

The 2175 Å UV extinction feature was discovered in the mid-1960s, yet its physical origin remains poorly understood. One suggestion is absorption by polycyclic aromatic hydrocarbon (PAH) molecules, which is supported by theoretical molecular structure computations and by laboratory experiments. PAHs are positively detected by their 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μm IR emission bands, which are specified by their modes of vibration. A definitive empirical link between the 2175 Å UV extinction and the IR PAH emission bands, however, is still missing. We present a new sample of hot stars that have both 2175 Å absorption and IR PAH emission. We find significant shifts of the central wavelength of the UV absorption feature, up to 2350 Å, but predominantly in stars that also have IR PAH emission. These UV shifts depend on stellar temperature in a fashion that is similar to the shifts of the 6.2 and 7.7 μm IR PAH bands, that is, the features are increasingly more redshifted as the stellar temperature decreases, but only below ˜15 kK. Above 15 kK both UV and IR features retain their nominal values. Moreover, we find a suggestive correlation between the UV and IR shifts. We hypothesize that these similar dependences of both the UV and IR features on stellar temperature hint at a common origin of the two in PAH molecules and may establish the missing link between the UV and IR observations. We further suggest that the shifts depend on molecular size, and that the critical temperature of ˜15 kK above which no shifts are observed is related to the onset of UV-driven hot-star winds and their associated shocks.

Spatial variations of the 3 micron emission features within UV-excited nebulae - Photochemical evolution of interstellar polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Geballe, T. R.; Tielens, A. G. G. M.; Allamandola, L. J.; Moorhouse, A.; Brand, P. W. J. L.

1989-01-01

Spectra at 3 microns have been obtained at several positions in the Orion Bar region and in the nebula surrounding HD 44179. Weak emission features at 3.40, 3.46, 3.51, and 3.57 microns are prominent in the Orion Bar region. The 3.40- and 3.51-micron features increase in intensity relative to the dominant 3.29-micron feature. The spectrum obtained in the Red Rectangle region 5 arcsecs north of HD 44179 are similar to those in the Orion Bar, with a weak, broad 3.40-micron feature at the position of HD 44179. The spatial behavior of the weak emission features is explained in terms of hot bands of the CH stretch and overtones, and combination bands of other fundamental vibrations in simple PAHs. Based on the susceptibility of PAHs to destruction by the far UV fields in both regions, PAH sizes are estimated at 20-50 carbon atoms.

Investigation of the Reactions and Distribution of Polycyclic Aromatic Hydrocarbons and Fullerenes in Extraterrestrial Material

NASA Technical Reports Server (NTRS)

Zare, Richard N.

2005-01-01

The work funded by this research grant includes four specific projects: (1) Mapping the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. (2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe laser-desorption laser-ionization mass spectrometry ( pL2MS) and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. (3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. (4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames.

Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

NASA Technical Reports Server (NTRS)

Du, Ping

1993-01-01

As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

Herschel-PACS observation of gas lines from the disc around HD141569A

NASA Astrophysics Data System (ADS)

Thi, Wing-Fai; Pinte, Christophe; Pantin, Eric; Augereau, Jean-Charles; Meeus, Gwendolyn; Ménard, Francois; Martin-Zaidi, Claire; Woitke, Peter; Riviere-Marichalar, Pablo; Kamp, Inga; Carmona, Andres; Sandell, Goran; Eiroa, Carlos; Dent, William; Montesinos, Benjamin; Aresu, Giambattista; Meijerink, Rowin; Spaans, Marco; White, Glenn; Ardila, David; Lebreton, Jeremy; Mendigutia, Ignacio; Brittain, Sean

2013-07-01

At the distance of ˜ 99-116 pc, HD141569A is one of the nearest HerbigAe stars that is surrounded by a tenuous disc, probably in transition between a massive primordial disc and a debris disc. We observed the fine-structure lines of O I at 63 and 145 μm , and the C II line at 157 μm with the PACS instrument on board the Herschel Space Telescope as part of the open-time large programme GASPS. We complemented the atomic line observations with Spitzer spectroscopic and photometric continuum data, ground-based VLT-VISIR image at 8.6 microns, and 12CO J=3-2 observations. We simultaneously modelled the continuum emission and the line fluxes with the Monte-Carlo radiative transfer code MCFOST and the thermo-chemical code ProDiMo to derive the disc gas and dust properties. We modelled the [O I] lines at 63 μm and at 145 μm, and the [C II] line at 157 μm. The models show that the oxygen lines are emitted from the inner disc around HD141569A, whereas the [C II] line emission is more extended. The CO submillimeter flux is emitted from the outer disc. Simultaneous modelling of the photometric and line data using a realistic disc structure suggests a dust mass derived from grains having a radius less than 1 mm of ˜ 2.1 × 10-7M⊙ and a total solid mass of 4.9 × 10-6 M⊙ . We constrained the PAH mass to be between 2 × 10-11 and 1.4 × 10-10 M⊙ depending on the size of the PAH. The associated PAH abundance is lower than those found in the interstellar medium by two to three orders of magnitude. The gas mass is a few 10-4M⊙. We constrained simultaneously the silicate dust grain, PAH, and gas mass in an evolved Herbig Ae disc. The uncertainty on the gas mass is large (around a factor 5) because the different gas tracers give estimates that do not agree with each other.

Spectroscopy of prospective interstellar ions and radicals isolated in para-hydrogen matrices.

PubMed

Tsuge, Masashi; Tseng, Chih-Yu; Lee, Yuan-Pern

2018-02-21

para-Hydrogen (p-H 2 ) serves as a new host in matrix-isolation experiments for an investigation of species of astrochemical interest. Protonated and mono-hydrogenated species are produced upon electron bombardment during deposition of p-H 2 containing a precursor in a small proportion. The applications of this novel technique to generate protonated polycyclic aromatic hydrocarbons (H + PAH), protonated polycyclic nitrogen heterocycles (H + PANH), and their neutral counterparts, which are important in the identification of interstellar unidentified infrared emission bands, demonstrate its superiority over other methods. The clean production with little fragmentation, ease of distinction between protonated and neutral species, narrow lines and reliable relative infrared intensities of the lines, and broad coverage of the spectral range associated with this method enable us to assign the isomers unambiguously. The application of this method to the protonation of small molecules is more complicated partly because of the feasible fragmentation and reactions, and partly because of the possible proton sharing between the species of interest and H 2 , but, with isotopic experiments and secondary photolysis, definitive assignments are practicable. Furthermore, the true relative infrared intensities are critical to a comparison of experimental results with data from theoretical calculations. The spectra of a proton-shared species in solid p-H 2 might provide insight into a search for spectra of proton-bound species in interstellar media. Investigations of hydrogenated species involving the photolysis of Cl 2 or precursors of OH complement those using electron bombardment and provide an improved ratio of signal to noise. With careful grouping of observed lines after secondary photolysis and a comparison with theoretical predictions, various isomers of these species have been determined. This photolytic technique has been applied in an investigation of hydrogenated PAH and PANH, and the hydrogenation reactions of small molecules, which are important in interstellar ice and the evolution of life. The electronic transitions of molecules in solid p-H 2 have been little investigated. The matrix shift of the origins of transitions and the spectral width seem to be much smaller than those of noble-gas matrices; these features might facilitate a direct comparison of matrix spectra with diffuse interstellar bands, but further data are required to assess this possibility. The advantages and disadvantages of applying these techniques of p-H 2 matrix isolation to astrochemical research and their future perspectives are discussed.

Analysis of Mars analogue soil samples using solid-phase microextraction, organic solvent extraction and gas chromatography/mass spectrometry

NASA Astrophysics Data System (ADS)

Orzechowska, G. E.; Kidd, R. D.; Foing, B. H.; Kanik, I.; Stoker, C.; Ehrenfreund, P.

2011-07-01

Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g-1. The texture of soils is mostly sandy loam with few samples being 100 % silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

Analysis of Mars Analogue Soil Samples Using Solid-Phase Microextraction, Organic Solvent Extraction and Gas Chromatography/Mass Spectrometry

NASA Technical Reports Server (NTRS)

Orzechowska, G. E.; Kidd, R. D.; Foing, B. H.; Kanik, I.; Stoker, C.; Ehrenfreund, P.

2011-01-01

Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g(sup -1). The texture of soils is mostly sandy loam with few samples being 100% silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

The peculiar behaviour of the 5780 and 5797 DIBs in HD25137

NASA Technical Reports Server (NTRS)

Porceddu, Ignazio; Benvenuti, P.

1994-01-01

The interstellar environment close to the high latitude molecular cloud Lynds 1569 (L1569, Lynds 1962), also known as MBM 18 (Magnani, Blitz and Mundy, 1985), has been analyzed by Penrase et al. (1990) and Penrase (1993). Their observations of the CH, CH(sup+), and CN molecular features, are consistent with a region having a high molecular and reduced dust content. They also observed the background star HD 24263- located 8 degrees far from the center of L1569 - reporting a CH rich line of sight and the presence of two intervening clouds from a sodium lines spectra. The infrared excess which has been revealed by the IRAS survey at 12 microns might suggest the presence of PAH's molecules, the well know candidate for the Unidentified Infrared Bands and Diffuse Interstellar Bands. This interesting scenario led to the investigation of the behavior of the diffuse interstellar bands toward HD 25137, which is supposed to be a background object for L1569 (Penrase et al., 1990); as well as the field star HD 24263. As part of a wider observational program devoted to study the HLC's special environments, the observations of the diffuse interstellar bands (DIB's) at 5780 and 5797 lambda lambda in the direction of the two above mentioned stars, HD 24263 and HD 25137 are presented here.

Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 2. The members of the thermodynamically most favorable series through coronene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene:phenanthrene, pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d10, and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo(e)pyrene, benzo-(ghi)perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo(ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Laboratory Studies of Stabilities of Heterocyclic Aromatic Molecules: Suggested Gas Phase Ion-Molecule Routes to Production in Interstellar Gas Clouds

NASA Technical Reports Server (NTRS)

Adams, Nigel G.; Fondren, L. Dalila; McLain, Jason L.; Jackson, Doug M.

2006-01-01

Several ring compounds have been detected in interstellar gas clouds, ISC, including the aromatic, benzene. Polycyclic aromatic hydrocarbons, PAHs, have been implicated as carriers of diffuse interstellar bands (DIBs) and unidentified infrared (UIR) bands. Heterocyclic aromatic rings of intermediate size containing nitrogen, possibly PreLife molecules, were included in early searches but were not detected and a recent search for Pyrimidine was unsuccessful. Our laboratory investigations of routes to such molecules could establish their existence in ISC and suggest conditions under which their concentrations would be maximized thus aiding the searches. The stability of such ring compounds (C5H5N, C4H4N2, C5H11N and C4H8O2) has been tested in the laboratory using charge transfer excitation in ion-molecule reactions. The fragmentation paths, including production of C4H4(+), C3H3N(+) and HCN, suggest reverse routes to the parent molecules, which are presently under laboratory investigation as production sources.

Infrared Photometric Properties of 709 Candidate Stellar Bowshock Nebulae

NASA Astrophysics Data System (ADS)

Kobulnicky, Henry A.; Schurhammer, Danielle P.; Baldwin, Daniel J.; Chick, William T.; Dixon, Don M.; Lee, Daniel; Povich, Matthew S.

2017-11-01

Arcuate infrared nebulae are ubiquitous throughout the Galactic Plane and are candidates for partial shells, bubbles, or bowshocks produced by massive runaway stars. We tabulate infrared photometry for 709 such objects using images from the Spitzer Space Telescope, the Wide-field Infrared Explorer, and the Herschel Space Observatory (HSO). Of the 709 objects identified at 24 or 22 μm, 422 are detected at the HSO 70 μm bandpass. Of these, only 39 are detected at HSO 160 μm. The 70 μm peak surface brightnesses are 0.5-2.5 Jy arcmin-2. Color temperatures calculated from the 24 to 70 μm ratios range from 80 to 400 K. Color temperatures from 70 to 160 μm ratios are systematically lower, 40-200 K. Both of these temperature are, on average, 75% higher than the nominal temperatures derived by assuming that dust is in steady-state radiative equilibrium. This may be evidence of stellar wind bowshocks sweeping up and heating—possibly fragmenting but not destroying—interstellar dust. Infrared luminosity correlates with standoff distance, R 0, as predicted by published hydrodynamical models. Infrared spectral energy distributions are consistent with interstellar dust exposed to either single radiant energy density, U={10}3{--}{10}5 (in more than half of the objects) or a range of radiant energy densities U min = 25 to U max = 103-105 times the mean interstellar value for the remainder. Hence, the central OB stars dominate the energetics, making these enticing laboratories for testing dust models in constrained radiation environments. The spectral energy densities are consistent with polycyclic aromatic hydrocarbon fractions {q}{PAH}≲ 1 % in most objects.

The anharmonic quartic force field infrared spectra of five non-linear polycyclic aromatic hydrocarbons: Benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene

NASA Astrophysics Data System (ADS)

Mackie, Cameron J.; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Mattioda, Andrew L.; Buma, Wybren Jan; Lee, Timothy J.; Tielens, Alexander G. G. M.

2016-08-01

The study of interstellar polycyclic aromatic hydrocarbons (PAHs) relies heavily on theoretically predicted infrared spectra. Most earlier studies use scaled harmonic frequencies for band positions and the double harmonic approximation for intensities. However, recent high-resolution gas-phase experimental spectroscopic studies have shown that the harmonic approximation is not sufficient to reproduce experimental results. In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs, showing the importance of including anharmonicities into the theoretical calculations. In this paper, we continue this work by extending the study to include five non-linear PAHs (benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene), thereby allowing us to make a full assessment of how edge structure, symmetry, and size influence the effects of anharmonicities. The theoretical anharmonic spectra are compared to spectra obtained under matrix isolation low-temperature conditions, low-resolution, high-temperature gas-phase conditions, and high-resolution, low-temperature gas-phase conditions. Overall, excellent agreement is observed between the theoretical and experimental spectra although the experimental spectra show subtle but significant differences.

The anharmonic quartic force field infrared spectra of five non-linear polycyclic aromatic hydrocarbons: Benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene.

PubMed

Mackie, Cameron J; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Mattioda, Andrew L; Buma, Wybren Jan; Lee, Timothy J; Tielens, Alexander G G M

2016-08-28

The study of interstellar polycyclic aromatic hydrocarbons (PAHs) relies heavily on theoretically predicted infrared spectra. Most earlier studies use scaled harmonic frequencies for band positions and the double harmonic approximation for intensities. However, recent high-resolution gas-phase experimental spectroscopic studies have shown that the harmonic approximation is not sufficient to reproduce experimental results. In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs, showing the importance of including anharmonicities into the theoretical calculations. In this paper, we continue this work by extending the study to include five non-linear PAHs (benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene), thereby allowing us to make a full assessment of how edge structure, symmetry, and size influence the effects of anharmonicities. The theoretical anharmonic spectra are compared to spectra obtained under matrix isolation low-temperature conditions, low-resolution, high-temperature gas-phase conditions, and high-resolution, low-temperature gas-phase conditions. Overall, excellent agreement is observed between the theoretical and experimental spectra although the experimental spectra show subtle but significant differences.

Theoretical infrared and electronic absorption spectra of C16H10 isomers, their ions and doubly ions

NASA Astrophysics Data System (ADS)

Naganathappa, Mahadevappa; Chaudhari, Ajay

2012-09-01

Polycyclic aromatic hydrocarbons (PAHs) or PAH-related molecules are considered to be responsible for the unidentified infrared (UIR) emission features at 3.3, 6.2, 7.7, 8.6 and 11.2 μm. However, the exact identification of PAH or PAH-related molecules is difficult. There have been several investigations on the spectroscopic characterization of PAH molecules. But none of them compared the spectra of isomers of PAHs, which might have help in the identification of the UIR emission features. This work presents the infrared and electronic absorption spectra of isomers of C16H10. The aim of the present work is to compare infrared and electronic absorption spectra of four isomers of C16H10 PAH viz. pyrene, aceanthrylene, acephenanthrylene and fluoranthene, their ions and doubly ions. We also compare the spectra of pyrene in the gas-phase and in H2O ice. We have used the density functional theory with B3LYP exchange and correlation functional and 6-311++g** basis set to study the infrared spectra. The time-dependent density functional theory (TDDFT) has been used to obtain the electronic absorption spectra. Significant difference in the CC stretching, CH in-plane bending and CH out-of-plane bending vibration modes is observed for the isomers of C16H10 whereas there is no large difference in the CH stretching vibration band. A significant change in the vibrational band is observed for pyrene in H2O ice compared to gas-phase pyrene. Though isomers of C16H10 PAH have the same number of carbon and hydrogen atoms, their spectroscopic characteristics are different. This study should help in identifying the isomers of C16H10, their ions and doubly cation in the interstellar medium.

Ultraviolet Irradiation of Naphthalene in H2O Ice: Implications for Meteorites and Biogenesis

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason; Sandford, Scott A.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

Dust spectral energy distributions of nearby galaxies: an insight from the Herschel Reference Survey

NASA Astrophysics Data System (ADS)

Ciesla, L.; Boquien, M.; Boselli, A.; Buat, V.; Cortese, L.; Bendo, G. J.; Heinis, S.; Galametz, M.; Eales, S.; Smith, M. W. L.; Baes, M.; Bianchi, S.; De Looze, I.; di Serego Alighieri, S.; Galliano, F.; Hughes, T. M.; Madden, S. C.; Pierini, D.; Rémy-Ruyer, A.; Spinoglio, L.; Vaccari, M.; Viaene, S.; Vlahakis, C.

2014-05-01

Although it accounts only for a small fraction of the baryonic mass, dust has a profound impact on the physical processes at play in galaxies. Thus, to understand the evolution of galaxies, it is essential not only to characterize dust properties per se, but also in relation to global galaxy properties. To do so, we derive the dust properties of galaxies in a volume limited, K-band selected sample, the Herschel Reference Survey (HRS). We gather infrared photometric data from 8 μm to 500 μm from Spitzer, WISE, IRAS, and Herschel for all of the HRS galaxies. Draine & Li (2007, ApJ, 663, 866) models are fit to the data from which the stellar contribution has been carefully removed. We find that our photometric coverage is sufficient to constrain all of the parameters of the Draine & Li models and that a strong constraint on the 20-60 μm range is mandatory to estimate the relative contribution of the photo-dissociation regions to the infrared spectral energy distribution (SED). The SED models tend to systematically underestimate the observed 500 μm flux densities, especially for low-mass systems. We provide the output parameters for all of the galaxies, i.e., the minimum intensity of the interstellar radiation field, the fraction of polycyclic aromatic hydrocarbon (PAH), the relative contribution of PDR and evolved stellar population to the dust heating, the dust mass, and the infrared luminosity. For a subsample of gas-rich galaxies, we analyze the relations between these parameters and the main integrated properties of galaxies, such as stellar mass, star formation rate, infraredluminosity, metallicity, Hα and H-band surface brightness, and the far-ultraviolet attenuation. A good correlation between the fraction of PAH and the metallicity is found, implying a weakening of the PAH emission in galaxies with low metallicities and, thus, low stellar masses. The intensity of the diffuse interstellar radiation field and the H-band and Hα surface brightnesses are correlated, suggesting that the diffuse dust component is heated by both the young stars in star-forming regions and the diffuse evolved population. We use these results to provide a new set of infrared templates calibrated with Herschel observations on nearby galaxies and a mean SED template to provide the z = 0 reference for cosmological studies. For the same purpose, we place our sample on the SFR - M∗ diagram. The templates are compared to the most popular infrared SED libraries, enlightening a large discrepancy between all of them in the 20-100 μm range. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Table 4 and appendices are available in electronic form at http://www.aanda.org

Enigmatic Extinction: An Investigation of the 2175Å Extinction Bump in M101

NASA Astrophysics Data System (ADS)

Danowski, Meredith E.; Cook, Timothy; Gordon, Karl D.; Chakrabarti, Supriya; Lawton, Brandon L.; Misselt, Karl A.

2014-06-01

Evidence from studies of starburst galaxies indicates that active formation of high mass stars modifies the UV dust extinction curve as seen by a lack of the characteristic 2175Å bump. For over 45 years, the source of the 2175Å extinction feature has yet to be positively identified. Small aromatic/PAH grains are suggested as a leading contender in dust grain models. The face-on spiral galaxy M101 is an ideal laboratory for the study of dust, with many well-studied HII regions and a steep metallicity and ionization gradient.The Interstellar Medium Absorption Gradient Experiment Rocket (IMAGER) probes the correlation between dust extinction, and the metallicity and radiation environment in M101 at ultraviolet wavelengths. IMAGER simultaneously images M101 in three 400Å-wide bandpasses, measuring the apparent strength of the 2175Å bump and the UV continuum.Combining data from IMAGER with high S/N far- and near- UV observations from the MAMA detectors on the Hubble STIS instrument, we examine the apparent strength of the 2175Å bump in HII regions of M101. With additional infrared data from Spitzer, the DIRTY radiative transfer model, and stellar evolution models, we probe the correlation between the 2175Å feature and the aromatic/PAH features across HII regions of varying metallicity and radiation field hardness. The results of this experiment will directly impact our understanding of the nature of dust and our ability to accurately account for the effects of dust on observations at all redshifts.

Investigating the 3.3 micron infrared fluorescence from naphthalene following ultraviolet excitation

NASA Technical Reports Server (NTRS)

Williams, Richard M.; Leone, Stephen R.

1994-01-01

Polycyclic aromatic hydrocarbon (PAH) type molecules are proposed as the carriers of the unidentified infrared (UIR) bands. Detailed studies of the 3.3 micrometer infrared emission features from naphthalene, the simplest PAH, following ultraviolet laser excitation are used in the interpretation of the 3.29 micrometer (3040 cm(sup -1)) UIR band. A time-resolved Fourier transform spectrometer is used to record the infrared emission spectrum of gas-phase naphthalene subsequent to ultraviolet excitation facilitated by an excimer laser operated at either 193 nm or 248 nm. The emission spectra differ significantly from the absorption spectrum in the same spectral region. Following 193 nm excitation the maximum in the emission profile is red-shifted 45 cm(sup -1) relative to the absorption maximum; a 25 cm(sup -1) red-shift is observed after 248 nm excitation. The red-shifting of the emission spectrum is reduced as collisional and radiative relaxation removes energy from the highly vibrationally excited molecules. Coupling between the various vibrational modes is thought to account for the differences between absorption and emission spectra. Strong visible emission is also observed following ultraviolet excitation. Visible emission may play an important role in the rate of radiative relaxation, which according to the interstellar PAH hypothesis occurs only by the slow emission of infrared photons. Studying the visible emission properties of PAH type molecules may be useful in the interpretation of the DIB's observed in absorption.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. Part 2; The Members of the Thermodynamically Most Favorable Series through Coronene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHS) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo-[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Is the dissociation of coronene in stellar winds a source of molecular hydrogen? application to the HD 44179 nebula

NASA Astrophysics Data System (ADS)

Champeaux, J.-P.; Moretto-Capelle, P.; Cafarelli, P.; Deville, C.; Sence, M.; Casta, R.

2014-06-01

The physical interactions of polycyclic aromatic hydrocarbons (PAHs) with stellar particular radiation are key to understanding the life cycle of PAHs, their abundance and their role in the complex astrochemistry of the interstellar medium. In this context, we present experimental results on the ionization/fragmentation of isolated coronene by a 100-keV proton, reproducing interactions between stellar winds and PAH molecules in the star's environment. In particular, we show, without ambiguity, that such ionization/fragmentation induces intense dehydrogenation processes for which the loss of even numbers of hydrogen atoms and the detection of CH_2+ cations as a possible H2 precursor strongly suggest the formation of H2 neutral molecules along a scenario revealed by a quantum chemical calculation. We have evaluated the H2 emission cross-section from the coronene/proton interaction at 100 and 1.6 keV to be 2.97 × 10-16 and 3.3 × 10-16 cm2, respectively. A qualitative discussion on the formation rate of H2 in the HD 44179 Red Rectangle (RR) nebula leads to the conclusion that such processes could be very efficient, especially inside planetary nebulae rich in PAH molecules interacting with high proton mass-loss rate stars (such as post-asymptotic giant branch stars) or high velocity jets produced by an accretion disc.

The adsorption of helium atoms on coronene cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurzthaler, Thomas; Rasul, Bilal; Kuhn, Martin

2016-08-14

We report the first experimental study of the attachment of multiple foreign atoms to a cationic polycyclic aromatic hydrocarbon (PAH). The chosen PAH was coronene, C{sub 24}H{sub 12}, which was added to liquid helium nanodroplets and then subjected to electron bombardment. Using mass spectrometry, coronene cations decorated with helium atoms were clearly seen and the spectrum shows peaks with anomalously high intensities (“magic number” peaks), which represent ion-helium complexes with added stability. The data suggest the formation of a rigid helium layer consisting of 38 helium atoms that completely cover both faces of the coronene ion. Additional magic numbers canmore » be seen for the further addition of 3 and 6 helium atoms, which are thought to attach to the edge of the coronene. The observation of magic numbers for the addition of 38 and 44 helium atoms is in good agreement with a recent path integral Monte Carlo prediction for helium atoms on neutral coronene. An understanding of how atoms and molecules attach to PAH ions is important for a number of reasons including the potential role such complexes might play in the chemistry of the interstellar medium.« less

Photochemistry of coronene in cosmic water ice analogs at different concentrations.

PubMed

de Barros, A L F; Mattioda, A L; Ricca, A; Cruz, G; Allamandola, L J

2017-10-20

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K, studied using mid-infrared Fourier transform (FTIR) spectroscopy for C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300) and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO are formed at very low temperatures. Like-wise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene-H + ) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that PAHs and their UV-induced PAH:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μ m region that can contribute to the interstellar ice components described by Boogert et al. (2008) as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the ISM where water-rich ices are important.

Hydrogenated Benzene in Circumstellar Environments: Insights into the Photostability of Super-hydrogenated PAHs

NASA Astrophysics Data System (ADS)

Quitián-Lara, Heidy M.; Fantuzzi, Felipe; Nascimento, Marco A. C.; Wolff, Wania; Boechat-Roberty, Heloisa M.

2018-02-01

Polycyclic aromatic hydrocarbons (PAHs), comprised of fused benzene (C6H6) rings, emit infrared radiation (3–12 μm) due to the vibrational transitions of the C–H bonds of the aromatic rings. The 3.3 μm aromatic band is generally accompanied by the band at 3.4 μm assigned to the vibration of aliphatic C–H bonds of compounds such as PAHs with an excess of peripheral H atoms (H n –PAHs). Herein we study the stability of fully hydrogenated benzene (or cyclohexane, C6H12) under the impact of stellar radiation in the photodissociation region (PDR) of NGC 7027. Using synchrotron radiation and time-of-flight mass spectrometry, we investigated the ionization and dissociation processes at energy ranges of UV (10–200 eV) and soft X-rays (280–310 eV). Density Functional Theory (DFT) calculations were used to determine the most stable structures and the relevant low-lying isomers of singly charged C6H12 ions. Partial Ion Yield (PIY) analysis gives evidence of the higher tendency toward dissociation of cyclohexane in comparison to benzene. However, because of the high photoabsorption cross-section of benzene at the C1s resonance edge, its photodissociation and photoionization cross-sections are enhanced, leading to a higher efficiency of dissociation of benzene in the PDR of NGC 7027. We suggest that a similar effect is experienced by PAHs in X-ray photon-rich environments, which ultimately acts as an auxiliary protection mechanism of super-hydrogenated polycyclic hydrocarbons. Finally, we propose that the single photoionization of cyclohexane could enhance the abundance of branched molecules in interstellar and circumstellar media.

Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

NASA Technical Reports Server (NTRS)

Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

2006-01-01

A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides; synthesis of hydrogen terminated carbon chains as precursors to complex PAHs and to carbonaceous dust grains in general; nitriles as precursor to amino acids).

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices.

PubMed

Kofman, V; Witlox, M J A; Bouwman, J; Ten Kate, I L; Linnartz, H

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools-UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry-can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, n λ , of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices

NASA Astrophysics Data System (ADS)

Kofman, V.; Witlox, M. J. A.; Bouwman, J.; ten Kate, I. L.; Linnartz, H.

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools—UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry—can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, nλ, of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

A solid state physics approach to the interaction between organic molecules and interstellar dust grains: (C60) on SiC

NASA Astrophysics Data System (ADS)

Merino, P.; Martin-Gago, J. A.; Cernicharo, J.

2011-05-01

We have modeled the interaction of large organic molecules and dust grains in the interstellar medium by means of conventional surface science techniques such as scanning probe microscopes (SPM) and X-ray photoelectron spectroscopy (XPS) among others. With these surface analysis techniques, no frequently used in astrochemistry, we can recreate model systems where the interstellar environment, in a wide range of conditions of pressure and temperature, can be studied. The accurate control of the species that can be studied enables us to simulate in our laboratory the reactions of important molecules on the surface of dust grains. These new kind of experiments provide new information about the chemical mechanisms of the interaction between dust grains and organic molecules which can be compared with the models and the observations. We use a state of the art ultra high vacuum chamber (UHV) with base pressure of 1× 10-10 mbar (2× 106 ppcm^3) where we can prepare macroscopic single-crystal samples simulating a particular dust grain surface. The clean surfaces are exposed to different molecules. The complete system molecule-substrate can be characterized down to the Armstrong scale with the scanning tunneling microscope (STM) and even single molecule orbitals can be resolved. The combination of this technique with diffraction and spectroscopic tools allows us to fully understand the adsorption configuration and chemistry of a particular molecular species on a modeled dust grain surface. Here we present, as a proof-of-concept, the study of a broadly studied molecule, fullerene, (C60) on a silicon carbide (SiC) surface. The stellar winds of carbon-rich red-giants are rich in SiC grains in the inner hot (1500K) shell. These grains can then be covered with C_2 H_2, C H_4 and other hydrocarbons that could lead to complex organic molecules, even PAHs, when they move apart from the star. In the present study we simulate the reaction of C60 molecules with the Si rich (3x3) 6H α-SiC(0001). Although 6H α-SiC is not one of the most common polytypes of SiC in the interstellar atmospheres (mostly abundant in 2H α-SiC and 3C β-SiC) we will use these first results to compare with our on-going measurements on 3C β-SiC.

[Activities of Colorado University

NASA Technical Reports Server (NTRS)

Snow, Theodore P.; Bierbaum, Veronica

2003-01-01

During the report period we completed several studies and embarked on a new set of laboratory experiments. We also hired a new post-doctoral Research Associate, Momir Stepanovic, who has gradually assumed leadership in the laboratory work. The other person involved has been graduate student Brian Eichelberger, who will complete his Ph.D. based on this work by late spring of this year. We have also continued to collaborate with our previous postdoctoral Research Associate, Valery Le Page, through a consulting arrangement. In the following sections we summarize work that has been completed and either in print, in press, or in final stages of preparation for publication; current work being carried out in the laboratory; and plans for the coming year. Work completed in 2002: 1. Modeling the physical and chemical states of PAHs in the diffuse interstellar medium. 2. Hydrogenation and charge states of polycyclic aromatic hydrocarbons in diffuse clouds. 3. Laboratory studies of chemical reactions involving carbon chain anions.

FT-IR spectroscopic studies of polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Salisbury, D. W.; Allen, J. E., Jr.; Donn, B.; Moore, W. J.; Khanna, R. K.

1990-01-01

Proper assessment of the hypothesis which correlates polycyclic aromatic hydrocarbons (PAHs) with the unidentified infrared emission bands requires additional experimental laboratory data. In order to address this need, thermal infrared emission studies were performed on a subset of PAHs suggested to be of astrophysical importance. It was proposed that infrared emission from interstellar PAHs occurs following absorption of an ultraviolet photon. Since energy transfer to the ground electronic state can be rapid for a species in which intersystem crossing is negligible, the emission spectrum may be viewed as resulting from an equilibrium vibrational temperature (Leger and d'Hendecourt, 1987). This has been the basis for using infrared absorption spectra to calculate the corresponding emission spectra at various temperatures. These calculations were made using room temperature infrared absorption coefficients instead of those at the temperature of interest because of the latter's unavailability. The present studies are designed to address the differences between the calculated and experimental thermal emission spectra and to provide information which will be useful in future ultraviolet induced infrared fluorescence studies. The emission spectra have been obtained for temperatures up to 825K using an emission cell designed to mount against an external port of an FT-IR spectrometer. These spectra provide information concerning relative band intensities and peak positions which is unavailable from previous calculations.

Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

NASA Astrophysics Data System (ADS)

Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

1994-12-01

We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The AV/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous materials in the DISM may be physically correlated and (2) there is either dust compositional variation in the galaxy or galactic variation in the grain population density distribution. We also note a possible absorption feature near 3050/cm (3.28 micrometers), a wavelength position that is characteristic of polycyclic aromatic hydrocarbons (PAHs).

Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

NASA Technical Reports Server (NTRS)

Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

1994-01-01

We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous materials in the DISM may be physically correlated and (2) there is either dust compositional variation in the galaxy or galactic variation in the grain population density distribution. We also note a possible absorption feature near 3050/cm (3.28 micrometers), a wavelength position that is characteristic of polycyclic aromatic hydrocarbons (PAHs).

QUANTIFYING THE HEATING SOURCES FOR MID-INFRARED DUST EMISSIONS IN GALAXIES: THE CASE OF M 81

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, N.; Zhao, Y.; Bendo, G. J.

2014-12-20

With the newly available photometric images at 250 and 500 μm from the Herschel Space Observatory, we study quantitative correlations over a sub-kiloparsec scale among three distinct emission components in the interstellar medium of the nearby spiral galaxy M 81 (NGC 3031): (1) I {sub 8} or I {sub 24}, the surface brightness of the mid-infrared emission observed in the Spitzer Space Telescope 8 or 24 μm band, with I {sub 8} and I {sub 24} being dominated by the emissions from polycyclic aromatic hydrocarbons (PAHs) and very small grains (VSGs) of dust, respectively; (2) I {sub 500}, that of the coldmore » dust continuum emission in the Herschel Space Observatory 500 μm band, dominated by the emission from large dust grains heated by evolved stars; and (3) I {sub Hα}, a nominal surface brightness of the Hα line emission, from gas ionized by newly formed massive stars. The results from our correlation study, free from any assumption on or modeling of dust emissivity law or dust temperatures, present solid evidence for significant heating of PAHs and VSGs by evolved stars. In the case of M 81, about 67% (48%) of the 8 μm (24 μm ) emission derives its heating from evolved stars, with the remainder attributed to radiation heating associated with ionizing stars.« less

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1990-01-01

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Source characterization and exposure modeling of gas-phase polycyclic aromatic hydrocarbon (PAH) concentrations in Southern California

NASA Astrophysics Data System (ADS)

Masri, Shahir; Li, Lianfa; Dang, Andy; Chung, Judith H.; Chen, Jiu-Chiuan; Fan, Zhi-Hua (Tina); Wu, Jun

2018-03-01

Airborne exposures to polycyclic aromatic hydrocarbons (PAHs) are associated with adverse health outcomes. Because personal air measurements of PAHs are labor intensive and costly, spatial PAH exposure models are useful for epidemiological studies. However, few studies provide adequate spatial coverage to reflect intra-urban variability of ambient PAHs. In this study, we collected 39-40 weekly gas-phase PAH samples in southern California twice in summer and twice in winter, 2009, in order to characterize PAH source contributions and develop spatial models that can estimate gas-phase PAH concentrations at a high resolution. A spatial mixed regression model was constructed, including such variables as roadway, traffic, land-use, vegetation index, commercial cooking facilities, meteorology, and population density. Cross validation of the model resulted in an R2 of 0.66 for summer and 0.77 for winter. Results showed higher total PAH concentrations in winter. Pyrogenic sources, such as fossil fuels and diesel exhaust, were the most dominant contributors to total PAHs. PAH sources varied by season, with a higher fossil fuel and wood burning contribution in winter. Spatial autocorrelation accounted for a substantial amount of the variance in total PAH concentrations for both winter (56%) and summer (19%). In summer, other key variables explaining the variance included meteorological factors (9%), population density (15%), and roadway length (21%). In winter, the variance was also explained by traffic density (16%). In this study, source characterization confirmed the dominance of traffic and other fossil fuel sources to total measured gas-phase PAH concentrations while a spatial exposure model identified key predictors of PAH concentrations. Gas-phase PAH source characterization and exposure estimation is of high utility to epidemiologist and policy makers interested in understanding the health impacts of gas-phase PAHs and strategies to reduce emissions.

Source Characterization and Exposure Modeling of Gas-Phase Polycyclic Aromatic Hydrocarbon (PAH) Concentrations in Southern California.

PubMed

Masri, Shahir; Li, Lianfa; Dang, Andy; Chung, Judith H; Chen, Jiu-Chiuan; Fan, Zhi-Hua Tina; Wu, Jun

2018-03-01

Airborne exposures to polycyclic aromatic hydrocarbons (PAHs) are associated with adverse health outcomes. Because personal air measurements of PAHs are labor intensive and costly, spatial PAH exposure models are useful for epidemiological studies. However, few studies provide adequate spatial coverage to reflect intra-urban variability of ambient PAHs. In this study, we collected 39-40 weekly gas-phase PAH samples in southern California twice in summer and twice in winter, 2009, in order to characterize PAH source contributions and develop spatial models that can estimate gas-phase PAH concentrations at a high resolution. A spatial mixed regression model was constructed, including such variables as roadway, traffic, land-use, vegetation index, commercial cooking facilities, meteorology, and population density. Cross validation of the model resulted in an R 2 of 0.66 for summer and 0.77 for winter. Results showed higher total PAH concentrations in winter. Pyrogenic sources, such as fossil fuels and diesel exhaust, were the most dominant contributors to total PAHs. PAH sources varied by season, with a higher fossil fuel and wood burning contribution in winter. Spatial autocorrelation accounted for a substantial amount of the variance in total PAH concentrations for both winter (56%) and summer (19%). In summer, other key variables explaining the variance included meteorological factors (9%), population density (15%), and roadway length (21%). In winter, the variance was also explained by traffic density (16%). In this study, source characterization confirmed the dominance of traffic and other fossil fuel sources to total measured gas-phase PAH concentrations while a spatial exposure model identified key predictors of PAH concentrations. Gas-phase PAH source characterization and exposure estimation is of high utility to epidemiologist and policy makers interested in understanding the health impacts of gas-phase PAHs and strategies to reduce emissions.

Mechanistic quantitative structure-activity relationship model for the photoinduced toxicity of polycyclic aromatic hydrocarbons. 1: Physical model based on chemical kinetics in a two-compartment system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krylov, S.N.; Huang, X.D.; Zeiler, L.F.

1997-11-01

A quantitative structure-activity relationship model for the photoinduced toxicity of 16 polycyclic aromatic hydrocarbons (PAHs) to duckweed (Lemna gibba) in simulated solar radiation (SSR) was developed. Lemna gibba was chosen for this study because toxicity could be considered in two compartments: water column and leaf tissue. Modeling of photoinduced toxicity was described by photochemical reactions between PAHs and a hypothetical group of endogenous biomolecules (G) required for normal growth, with damage to G by PAHs and/or photomodified PAHs in SSR resulting in impaired growth. The reaction scheme includes photomodification of PAHs, uptake of PAHs into leaves, triplet-state formation of intactmore » PAHs, photosensitization reactions that damage G, and reactions between photomodified PAHs and G. The assumptions used were: the PAH photomodification rate is slower than uptake of chemicals into leaves, the PAH concentration in aqueous solution is nearly constant during a toxicity test, the fluence rate of actinic radiation is lower within leaves than in the aqueous phase, and the toxicity of intact PAHs in the dark is negligible. A series of differential equations describing the reaction kinetics of intact and photomodifed PAHs with G was derived. The resulting equation for PAH toxicity was a function of treatment period, initial PAH concentration, relative absorbance of SSR by each PAH, quantum yield for formation of triplet-state PAH, and rate of PAH photomodification. Data for growth in the presence of intact and photomodified PAHs were used to empirically solve for a photosensitization constant (PSC) and a photomodification constant (PMC) for each of the 16 PAHs tested. For 9 PAHs the PMC dominates and for 7 PAHs the PSC dominates.« less

Spatial Variation of the 3.29 and 3.40 Micron Emission Bands Within Reflection Nebulae and The Photochemical Evolution of Methylated Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Joblin, C.; Tielens, A. G. G. M.; Allamandola, L. J.; Geballe, T. R.

1996-01-01

Spectra of 3 microns emission features have been obtained at several positions within the reflection nebulae NGC 1333 SVS3 and NGC 2023. Strong variations of the relative intensities of the 3.29 microns feature and its most prominent satellite band at 3.40 microns are found. It is shown that: (1) the 3.40 microns band is too intense with respect to the 3.29 microns band at certain positions to arise from hot band emission alone, (2) the 3.40 microns band can be reasonably well matched by new laboratory spectra of gas-phase polycyclic aromatic hydrocarbons (PAHs) with alkyl (-CH3) side groups, and (3) the variations in the 3.40 microns to 3.29 microns band intensity ratios are consistent with the photochemical erosion of alkylated PAHs. We conclude that the 3.40 microns emission feature is attributable to -CH3 side groups on PAH molecules. We predict a value of 0.5 for the peak intensity ratio of the 3.40 and 3.29 microns emission bands from free PAHs in the diffuse interstellar medium, which would correspond to a proportion of one methyl group for four peripheral hydrogens. We also compare the 3 microns spectrum of the proto-planetary nebula IRAS 05341 + 0852 with the spectrum of the planetary nebula IRAS 21282 + 5050. We suggest that a photochemical evolution of the initial aliphatic and aromatic hydrocarbon mixture formed in the outflow is responsible for the changes observed in the 3 microns emission spectra of these objects.

Spatial variation of the 3.29 and 3.40 micron emission bands within reflection nebulae and the photochemical evolution of methylated polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Joblin, C.; Tielens, A. G.; Allamandola, L. J.; Geballe, T. R.

1996-01-01

Spectra of 3 micrometers emission features have been obtained at several positions within the reflection nebulae NGC 1333 SVS3 and NGC 2023. Strong variations of the relative intensities of the 3.29 micrometers feature and its most prominent satellite band at 3.40 micrometers are found. It is shown that (i) the 3.40 micrometers band is too intense with respect to the 3.29 micrometers band at certain positions to arise from hot band emission alone, (ii) the 3.40 micrometers band can be reasonably well matched by new laboratory spectra of gas-phase polycyclic aromatic hydrocarbons (PAHs) with alkyl (-CH3) side groups, and (iii) the variations in the 3.40 micrometers to 3.29 micrometers band intensity ratios are consistent with the photochemical erosion of alkylated PAHs. We conclude that the 3.40 micrometers emission feature is attributable to -CH3 side groups on PAH molecules. We predict a value of 0.5 for the peak intensity ratio of the 3.40 and 3.29 micrometers emission bands from free PAHs in the diffuse interstellar medium, which would correspond to a proportion of one methyl group for four peripheral hydrogens. We also compare the 3 micrometers spectrum of the proto-planetary nebula IRAS 05341+0852 with the spectrum of the planetary nebula IRAS 21282+5050. We suggest that a photochemical evolution of the initial aliphatic and aromatic hydrocarbon mixture formed in the outflow is responsible for the changes observed in the 3 micrometers emission spectra of these objects.

Infrared spectroscopy of polycyclic aromatic hydrocarbon cations. 1: Matrix-isolated naphthalene and perdeuterated naphthalene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Sandford, S. A.; Allamandola, Louis J.

1994-01-01

Ionized polycyclic aromatic hydrocarbons (PAHs) are thought to constitute an important component of the interstellar medium. Despite this fact, the infrared spectroscopic properties of ionized PAHs are almost unknown. The results we present here derive from our ongoing spectroscopic study of matrix isolated PAH ions and include the spectra of the naphthalene cation, C10H8(+), and its fully deuterated analog, C10D8(+), between 4000 and 200/cm. Ions are generated by in situ Lyman-alpha photoionization of the neutral precursor. Bands of the C10H8(+) ion are observed at 1525.7, 1518.8, 1400.9, 1218.0, 1216.9, 1214.9, 1023.2, and 758.7/cm. Positions and relative intensities of these bands agree well with those in the available literature. The 758.7/cm band has not previously been reported. C10D8(+) ion bands appear at 1466.2, 1463.8, 1379.4, 1373.8, 1077.3, 1075.4, and 1063.1/cm. Compared to the analogous modes in the neutral molecule, the intensities of the cation's CC modes are enhanced by an order of magnitude, while CH modes are depressed by this same factor. Integrated absorption intensities are calculated for the strongest bands of C10H8 and for the observed bands of C10H8(+). Absolute intensities derived for the naphthalene cation differ from earlier experimental results by a factor of approximately 50, and from theoretical predictions by a factor of approximately 300. Reasons for these discrepancies and from the astronomical implications of PAH cation spectra are discussed.

Physical model for the photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenburg, B.M.; Krylov, S.N.; Huang, H.D.

1994-12-31

A model for photo-induced toxicity of PAHs to duckweed was developed. Growth inhibition was described by photochemical reactions between PAHs and a hypothetical group of biomolecules (given the notation G) which are required for growth of the plants. Light activation of PAHs was considered in a two compartment system (water and leaves). The reaction scheme includes: photooxidation of PAHs, partitioning of PAHs into leaves, triplet formation of intact PAHs, photosensitization reactions that consume G, and reaction between photooxidized PAHs and G. The assumptions used in the model are: the rate of PAH photooxidation is slower than the rate of assimilation,more » PAH content in solution is approximately constant over the length of the toxicity test, the fluence rate of actinic radiation is lower in the leaves than in solution, the toxicity of intact PAHs with G in the absence of light is negligible, and the reaction of photooxidized PAHs with G does not require light. The authors then analyzed a series of differential equations that described toxicity. The result was an expression for growth inhibition as a function of the initial concentration of the PAH, the spectral distribution of the light source, the absorption spectrum of the PAH, the quantum yield for formation of triplet state PAH, and the rate of photo-oxidation of the PAH. The expression also includes two complex constants that can be solved by a least squares analysis of the empirical data for growth inhibition. Thus, the model allows a prediction of PAH photo-induced toxicity using only physical parameters of PAHs.« less

A study on the coagulation of polycyclic aromatic hydrocarbon clusters to determine their collision efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, Abhijeet; Sander, Markus; Janardhanan, Vinod

2010-03-15

This paper presents a theoretical study on the physical interaction between polycyclic aromatic hydrocarbons (PAHs) and their clusters of different sizes in laminar premixed flames. Two models are employed for this study: a detailed PAH growth model, referred to as the kinetic Monte Carlo - aromatic site (KMC-ARS) model [Raj et al., Combust. Flame 156 (2009) 896-913]; and a multivariate PAH population balance model, referred to as the PAH - primary particle (PAH-PP) model. Both the models are solved by kinetic Monte Carlo methods. PAH mass spectra are generated using the PAH-PP model, and compared to the experimentally observed spectramore » for a laminar premixed ethylene flame. The position of the maxima of PAH dimers in the spectra and their concentrations are found to depend strongly on the collision efficiency of PAH coagulation. The variation in the collision efficiency with various flame and PAH parameters is studied to determine the factors on which it may depend. A correlation for the collision efficiency is proposed by comparing the computed and the observed spectra for an ethylene flame. With this correlation, a good agreement between the computed and the observed spectra for a number of laminar premixed ethylene flames is found. (author)« less

Secondary Interstellar Oxygen in the Heliosphere: Numerical Modeling and Comparison with IBEX-Lo Data

NASA Astrophysics Data System (ADS)

Baliukin, I. I.; Izmodenov, V. V.; Möbius, E.; Alexashov, D. B.; Katushkina, O. A.; Kucharek, H.

2017-12-01

Quantitative analysis of the interstellar heavy (oxygen and neon) atom fluxes obtained by the Interstellar Boundary Explorer (IBEX) suggests the existence of the secondary interstellar oxygen component. This component is formed near the heliopause due to charge exchange of interstellar oxygen ions with hydrogen atoms, as was predicted theoretically. A detailed quantitative analysis of the fluxes of interstellar heavy atoms is only possible with a model that takes into account both the filtration of primary and the production of secondary interstellar oxygen in the boundary region of the heliosphere as well as a detailed simulation of the motion of interstellar atoms inside the heliosphere. This simulation must take into account photoionization, charge exchange with the protons of the solar wind and solar gravitational attraction. This paper presents the results of modeling interstellar oxygen and neon atoms through the heliospheric interface and inside the heliosphere based on a three-dimensional kinetic-MHD model of the solar wind interaction with the local interstellar medium and a comparison of these results with the data obtained on the IBEX spacecraft.

New Dust Features Observed with ISO

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.; Young, Richard E. (Technical Monitor)

1997-01-01

This paper will review our current knowledge of circumstellar and interstellar dust with the emphasis on infrared spectroscopy with ISO. Objects embedded in or located behind molecular clouds show a wealth of absorption features due to simple molecules in an icy mantle. The SWS on ISO has provided us, for the first time, with complete 3-45 um spectra which allow an inventory of interstellar ice. Among the species identified are H2O, CH3OH, CH4, CO2, CO, and OCS. These species are formed through simple reactions among gas phase species accreted on grain surfaces, possibly modified by FUV photolysis and warm-up (ie., outgassing). The implications of the observations for our understanding of these processes will be reviewed. The IR spectra of many UV bright objects are dominated by strong emission features at 3.3, 6.2, 7.7, and 11.3 micrometers. These are generally attributed to Polycyclic Aromatic Hydrocarbons (PAHs) molecules. The observational evidence will be reviewed. The emphasis will be on recent data which show widespread spectral variations, particularly among protoplanetary and planetary nebulae, and their implications. One of the most exciting, recent discoveries on interstellar and circumstellar dust has been the detection of spectral structure due to crystalline olivine and enstatite in a variety of objects surrounded by circumstellar silicates. These spectra will be reviewed and circumstellar silicate mineralogy will be discussed.

Receptor modeling for source apportionment of polycyclic aromatic hydrocarbons in urban atmosphere.

PubMed

Singh, Kunwar P; Malik, Amrita; Kumar, Ranjan; Saxena, Puneet; Sinha, Sarita

2008-01-01

This study reports source apportionment of polycyclic aromatic hydrocarbons (PAHs) in particulate depositions on vegetation foliages near highway in the urban environment of Lucknow city (India) using the principal components analysis/absolute principal components scores (PCA/APCS) receptor modeling approach. The multivariate method enables identification of major PAHs sources along with their quantitative contributions with respect to individual PAH. The PCA identified three major sources of PAHs viz. combustion, vehicular emissions, and diesel based activities. The PCA/APCS receptor modeling approach revealed that the combustion sources (natural gas, wood, coal/coke, biomass) contributed 19-97% of various PAHs, vehicular emissions 0-70%, diesel based sources 0-81% and other miscellaneous sources 0-20% of different PAHs. The contributions of major pyrolytic and petrogenic sources to the total PAHs were 56 and 42%, respectively. Further, the combustion related sources contribute major fraction of the carcinogenic PAHs in the study area. High correlation coefficient (R2 > 0.75 for most PAHs) between the measured and predicted concentrations of PAHs suggests for the applicability of the PCA/APCS receptor modeling approach for estimation of source contribution to the PAHs in particulates.

A statistical approach to develop a detailed soot growth model using PAH characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, Abhijeet; Celnik, Matthew; Shirley, Raphael

A detailed PAH growth model is developed, which is solved using a kinetic Monte Carlo algorithm. The model describes the structure and growth of planar PAH molecules, and is referred to as the kinetic Monte Carlo-aromatic site (KMC-ARS) model. A detailed PAH growth mechanism based on reactions at radical sites available in the literature, and additional reactions obtained from quantum chemistry calculations are used to model the PAH growth processes. New rates for the reactions involved in the cyclodehydrogenation process for the formation of 6-member rings on PAHs are calculated in this work based on density functional theory simulations. Themore » KMC-ARS model is validated by comparing experimentally observed ensembles on PAHs with the computed ensembles for a C{sub 2}H{sub 2} and a C{sub 6}H{sub 6} flame at different heights above the burner. The motivation for this model is the development of a detailed soot particle population balance model which describes the evolution of an ensemble of soot particles based on their PAH structure. However, at present incorporating such a detailed model into a population balance is computationally unfeasible. Therefore, a simpler model referred to as the site-counting model has been developed, which replaces the structural information of the PAH molecules by their functional groups augmented with statistical closure expressions. This closure is obtained from the KMC-ARS model, which is used to develop correlations and statistics in different flame environments which describe such PAH structural information. These correlations and statistics are implemented in the site-counting model, and results from the site-counting model and the KMC-ARS model are in good agreement. Additionally the effect of steric hindrance in large PAH structures is investigated and correlations for sites unavailable for reaction are presented. (author)« less

The Exobiological Role of Interstellar Polycyclic Aromatic Hydrocarbons and Ices

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

2002-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Before this time, the composition of interstellar dust was largely guessed-at, the presence of ices in interstellar clouds ignored, and the notion that large, gas phase, carbon rich molecules might be abundant and widespread throughout the interstellar medium (ISM) considered impossible. Today, the composition of dust in the ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. Shrouded within the protective confines of cold, opaque molecular clouds--the birthplace of stars and planets--these cold dust particles secrete mantles of mixed molecular ices whose compositions are also well constrained. Finally, amidst the molecular inventory of these ice mantles are likely to be found polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by the standards of interstellar chemistry, the telltale infrared spectral signature of which is now recognized throughout the Universe. In the first part of this talk, we will review the spectroscopic evidence that forms the basis for the currently accepted abundance and ubiquity of PANs in the ISM. We will then look at a few specific examples which illustrate how experimental and theoretical data can be applied to interpret the interstellar spectra and track how the PAN population evolves as it passes from its formation site in the circumstellar outflows of dying stars, through the various phases of the ISM, and into forniing planetary systems. Nevertheless, despite the fact that PANs likely represent the single largest molecular reservoir of organic carbon in evolving planetary systems, they are not what would be considered "biogenic" molecules. Although interesting from a chemical and astrophysical standpoint, in the absence of a mechanism by which this population can be dislodged from the precipitous thermodynamic well afforded by their extensive aromatic networks, they are of little Astrobiological significance. Consequently, for the remainder of the talk, we will consider the photochemical evolution of PANS under conditions similar to those found in the ISM and in proto-planetary systems with an eye toward means by which this rich repository of pre-biotic organic "ore" might be converted into materials of greater importance to Astrobiology.

Recent Advances in Organic Cosmochemistry

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Witteborn, Fred C. (Technical Monitor)

1994-01-01

The Astrochemistry Laboratory at NASA's Ames Research Center pursues a variety of activities, most of which center around the use of spectroscopy (ultraviolet to far-infrared) for the interpretation of astronomical and meteoritic data. One of our key activities is the study of the chemical and physical properties of cometary, interstellar, and planetary ice analogs and matrix-isolated molecules of astrophysical interest. As a result of these studies it is now known that a significant fraction of the carbon in the interstellar medium (ISM) is in reasonably complex forms, some of which are clearly of interest for exobiology. Examples of compounds known or suspected to be present in space include polycyclic aromatic hydrocarbons (PAHs), microdiamonds, an aliphatic-rich component found in the diffuse interstellar medium, and a variety of molecular species produced by the irradiation of mixed molecular ices in dense clouds. A number of the species produced by irradiation contain nitrogen and appear to offer an additional means of producing some of the amino acids found in meteorites. I will review these complex carbonaceous materials and discuss how they are connected with each other and the organic materials that ultimately ended up as part of our own Solar System. Specific points that will probably be covered include: (1) the composition of the ices in interstellar dense molecular clouds; (2) the more complex organic compounds produced when these ices are irradiated and/or warmed; (3) the detection of microdiamonds in space; (4) the discovery that aliphatic materials may constitute as much as 15% of all the carbon in the diffuse ISM, appears to be present everywhere in the galaxy, and yet seems to be present everywhere in the galaxy, and yet seems to be significantly concentrated towards the center of the galaxy.

Probing the infrared counterparts of diffuse far-ultraviolet sources in the Galaxy

NASA Astrophysics Data System (ADS)

Saikia, Gautam; Shalima, P.; Gogoi, Rupjyoti; Pathak, Amit

2017-12-01

Recent availability of high quality infrared (IR) data for diffuse regions in the Galaxy and external galaxies have added to our understanding of interstellar dust. A comparison of ultraviolet (UV) and IR observations may be used to estimate absorption, scattering and thermal emission from interstellar dust. In this paper, we report IR and UV observations for selective diffuse sources in the Galaxy. Using archival mid-infrared (MIR) and far-infrared (FIR) observations from Spitzer Space Telescope, we look for counterparts of diffuse far-ultraviolet (FUV) sources observed by the Voyager, Far Ultraviolet Spectroscopic Explorer (FUSE) and Galaxy Evolution Explorer (GALEX) telescopes in the Galaxy. IR emission features at 8 μm are generally attributed to Polycyclic Aromatic Hydrocarbon (PAH) molecules, while emission at 24 μm are attributed to Very Small Grains (VSGs). The data presented here is unique and our study tries to establish a relation between various dust populations. By studying the FUV-IR correlations separately at low and high latitude locations, we have identified the grain component responsible for the diffuse FUV emission.

Structure and Electronic Properties of Ionized PAH Clusters

NASA Astrophysics Data System (ADS)

Joblin, Christine; Kokkin, Damian L.; Sabbah, Hassan; Bonnamy, Anthony; Dontot, Leo; Rapacioli, Mathias; Simon, Aude; Spiegelman, Fernand; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Falvo, Cyril; Gamboa, Antonio; Brechignac, Philippe; Garcia, Gustavo A.; Nahon, Laurent

2014-06-01

Polycyclic aromatic hydrocarbon (PAH) clusters have been proposed as candidates for evaporating very small grains that are revealed by their mid-IR emission at the surface of UV-irradiated clouds in interstellar space. This suggestion is a motivation for further characterization of the properties of these clusters in particular when they are ionized. We have used a molecular beam coupled to the photoelectron-photoion coincidence spectrometer DELICIOUS II/ III at the VUV beamline DESIRS of the synchrotron SOLEIL to characterize the electronic properties of cationic coronene (C24H12) and pyrene (C16H10) clusters up to the pentamer and heptamer, respectively. These experimental results are analysed in the light of electronic structure calculations. Simulations of the properties of ionized PAH clusters are faced with the difficulty of describing charge delocalization in these large systems. We will show that recent developments combining a Density Functional Tight Binding method with Configuration Interaction scheme is successful in simulating the ionization potential, which gives strong confidence into the predicted structures for these PAH clusters. We will also present current effort to study charge transfer states by performing complementary measurements with the PIRENEA ion trap set-up. Joint ANR project GASPARIM, ANR-10-BLAN-501 M. Rapacioli, C. Joblin and P. Boissel Astron. & Astrophys., 429 (2005), 193-204. G. Garcia, H. Soldi-Lose and L. Nahon Rev. Sci. Instrum., 80 (2009), 023102; G. Garcia, B. Cunha de Miranda, M. Tia, S. Daly, L. Nahon, Rev. Sci. Instrum., 84 (2013), 053112 M. Rapacioli, A. Simon, L. Dontot and F. Spiegelman Phys. Status Solidi B, 249 (2) (2012), 245-258; L. Dontot, M. Rapacioli and F. Spiegelman (2014) submitted

After the Fall: The Dust and Gas in E+A Post-starburst Galaxies

NASA Astrophysics Data System (ADS)

Smercina, A.; Smith, J. D. T.; Dale, D. A.; French, K. D.; Croxall, K. V.; Zhukovska, S.; Togi, A.; Bell, E. F.; Crocker, A. F.; Draine, B. T.; Jarrett, T. H.; Tremonti, C.; Yang, Yujin; Zabludoff, A. I.

2018-03-01

The traditional picture of post-starburst galaxies as dust- and gas-poor merger remnants, rapidly transitioning to quiescence, has been recently challenged. Unexpected detections of a significant interstellar medium (ISM) in many post-starburst galaxies raise important questions. Are they truly quiescent, and if so, what mechanisms inhibit further star formation? What processes dominate their ISM energetics? We present an infrared spectroscopic and photometric survey of 33 E+A post-starbursts selected by the Sloan Digital Sky Survey, aimed at resolving these questions. We find compact, warm dust reservoirs with high PAH abundances and total gas and dust masses significantly higher than expected from stellar recycling alone. Both polycyclic aromatic hydrocarbon (PAH)/total infrared (TIR) and dust-to-burst stellar mass ratios are seen to decrease with post-burst age, indicative of the accumulating effects of dust destruction and an incipient transition to hot, early-type ISM properties. Their infrared spectral properties are unique, with dominant PAH emission, very weak nebular lines, unusually strong H2 rotational emission, and deep [C II] deficits. There is substantial scatter among star formation rate (SFR) indicators, and both PAH and TIR luminosities provide overestimates. Even as potential upper limits, all tracers show that the SFR has typically experienced a decline of more than two orders of magnitude since the starburst and that the SFR is considerably lower than expected given both their stellar masses and molecular gas densities. These results paint a coherent picture of systems in which star formation was, indeed, rapidly truncated, but in which the ISM was not completely expelled, and is instead supported against collapse by latent or continued injection of turbulent or mechanical heating. The resulting aging burst populations provide a “high-soft” radiation field that seemingly dominates the E+A galaxies’ unusual ISM energetics.

The anharmonic quartic force field infrared spectra of three polycyclic aromatic hydrocarbons: Naphthalene, anthracene, and tetracene.

PubMed

Mackie, Cameron J; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Buma, Wybren Jan; Lee, Timothy J; Tielens, Alexander G G M

2015-12-14

Current efforts to characterize and study interstellar polycyclic aromatic hydrocarbons (PAHs) rely heavily on theoretically predicted infrared (IR) spectra. Generally, such studies use the scaled harmonic frequencies for band positions and double harmonic approximation for intensities of species, and then compare these calculated spectra with experimental spectra obtained under matrix isolation conditions. High-resolution gas-phase experimental spectroscopic studies have recently revealed that the double harmonic approximation is not sufficient for reliable spectra prediction. In this paper, we present the anharmonic theoretical spectra of three PAHs: naphthalene, anthracene, and tetracene, computed with a locally modified version of the SPECTRO program using Cartesian derivatives transformed from Gaussian 09 normal coordinate force constants. Proper treatments of Fermi resonances lead to an impressive improvement on the agreement between the observed and theoretical spectra, especially in the C-H stretching region. All major IR absorption features in the full-scale matrix-isolated spectra, the high-temperature gas-phase spectra, and the most recent high-resolution gas-phase spectra obtained under supersonically cooled molecular beam conditions in the CH-stretching region are assigned.

The anharmonic quartic force field infrared spectra of three polycyclic aromatic hydrocarbons: Naphthalene, anthracene, and tetracene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mackie, Cameron J., E-mail: mackie@strw.leidenuniv.nl; Candian, Alessandra; Tielens, Alexander G. G. M.

2015-12-14

Current efforts to characterize and study interstellar polycyclic aromatic hydrocarbons (PAHs) rely heavily on theoretically predicted infrared (IR) spectra. Generally, such studies use the scaled harmonic frequencies for band positions and double harmonic approximation for intensities of species, and then compare these calculated spectra with experimental spectra obtained under matrix isolation conditions. High-resolution gas-phase experimental spectroscopic studies have recently revealed that the double harmonic approximation is not sufficient for reliable spectra prediction. In this paper, we present the anharmonic theoretical spectra of three PAHs: naphthalene, anthracene, and tetracene, computed with a locally modified version of the SPECTRO program using Cartesianmore » derivatives transformed from Gaussian 09 normal coordinate force constants. Proper treatments of Fermi resonances lead to an impressive improvement on the agreement between the observed and theoretical spectra, especially in the C–H stretching region. All major IR absorption features in the full-scale matrix-isolated spectra, the high-temperature gas-phase spectra, and the most recent high-resolution gas-phase spectra obtained under supersonically cooled molecular beam conditions in the CH-stretching region are assigned.« less

Photoacoustic spectroscopic studies of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Zaidi, Zahid H.; Kumar, Pardeep; Garg, R. K.

1999-02-01

Because of their involvement in environmental pollutants, in carcinogenic activity, plastics, pharmaceuticals, synthesis of some laser dyes and presence in interstellar space etc., Polycyclic aromatic hydrocarbons (PAHs) are important. As their structure and properties can be varied systematically, they form a beautiful class of molecules for experimental and quantum chemical investigations. These molecules are being studied for last several years by using conventional spectroscopy. In recent years, Photoacoustic (PA) spectroscopy has emerged as a new non-destructive technique with unique capability and sensitivity. The PA effect is the process of generation of acoustic waves in a sample resulting from the absorption of photons. This technique not only reveals non- radiative transitions but also provides information about forbidden singlet-triplet transitions which are not observed normally by the conventional spectroscopy. The present paper deals with the spectroscopic studies of some PAH molecules by PA spectroscopy in the region 250 - 400 nm. The CNDO/S-CI method is used to calculate the electronic transitions with the optimized geometries. A good agreement is found between the experimental and calculated results.

The Mysterious 6565 Å Absorption Feature of the Galactic Halo

NASA Astrophysics Data System (ADS)

Sethi, Shiv K.; Shchekinov, Yuri; Nath, Biman B.

2017-12-01

We consider various possible scenarios to explain the recent observation of what has been called a broad Hα absorption in our Galactic halo, with peak optical depth τ ≃ 0.01 and equivalent width W≃ 0.17 \\mathringA . We show that the absorbed feature cannot arise from the circumgalactic and ISM Hα absorption. As the observed absorption feature is quite broad ({{Δ }}λ ≃ 30 \\mathringA ), we also consider CNO lines that lie close to Hα as possible alternatives to explain the feature. We show that such lines could also not account for the observed feature. Instead, we suggest that it could arise from diffuse interstellar bands (DIBs) carriers or polyaromatic hydrocarbons (PAHs) absorption. While we identify several such lines close to the Hα transition, we are unable to determine the molecule responsible for the observed feature, partly because of selection effects that prevent us from identifying DIBs/PAHs features close to Hα using local observations. Deep integration of a few extragalactic sources with high spectral resolution might allow us to distinguish between different possible explanations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bréchignac, Philippe, E-mail: philippe.brechignac@u-psud.fr; Falvo, Cyril; Parneix, Pascal

Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail.more » Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.« less

Multimedia Model for Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs in Lake Michigan

PubMed Central

2015-01-01

Polycyclic aromatic hydrocarbon (PAH) contamination in the U.S. Great Lakes has long been of concern, but information regarding the current sources, distribution, and fate of PAH contamination is lacking, and very little information exists for the potentially more toxic nitro-derivatives of PAHs (NPAHs). This study uses fugacity, food web, and Monte Carlo models to examine 16 PAHs and five NPAHs in Lake Michigan, and to derive PAH and NPAH emission estimates. Good agreement was found between predicted and measured PAH concentrations in air, but concentrations in water and sediment were generally under-predicted, possibly due to incorrect parameter estimates for degradation rates, discharges to water, or inputs from tributaries. The food web model matched measurements of heavier PAHs (≥5 rings) in lake trout, but lighter PAHs (≤4 rings) were overpredicted, possibly due to overestimates of metabolic half-lives or gut/gill absorption efficiencies. Derived PAH emission rates peaked in the 1950s, and rates now approach those in the mid-19th century. The derived emission rates far exceed those in the source inventories, suggesting the need to reconcile differences and reduce uncertainties. Although additional measurements and physiochemical data are needed to reduce uncertainties and for validation purposes, the models illustrate the behavior of PAHs and NPAHs in Lake Michigan, and they provide useful and potentially diagnostic estimates of emission rates. PMID:25373871

Modelling the fate of PAH added with composts in amended soil according to the origin of the exogenous organic matter.

PubMed

Brimo, Khaled; Ouvrard, Stéphanie; Houot, Sabine; Lafolie, François; Garnier, Patricia

2018-03-01

A new model that was able to simulate the behaviours of polycyclic aromatic hydrocarbons (PAH) during composting and after the addition of the composts to agricultural soil is presented here. This model associates modules that describe the physical, biological and biochemical processes involved in PAH dynamics in soils, along with a module describing the compost degradation resulting in PAH release. The model was calibrated from laboratory incubations using three 14 C-PAHs, phenanthrene, fluoranthene and benzo(a)pyrene, and three different composts consisting of two mature and one non-mature composts. First, the labelled PAHs were added to the compost over 28days, and spiked composts were then added to the soil over 55days. The model calculates the proportion of biogenic and physically bound residues in the non-extractable compartment of PAHs at the end of the compost incubation to feed the initial conditions of the model for soil amended with composts. For most of the treatments, a single parameter set enabled to simulate the observed dynamics of PAHs adequately for all the amended soil treatments using a Bayesian approach. However, for fluoranthene, different parameters that were able to simulate the growth of a specific microbial biomass had to be considered for mature compost. Processes that occurred before the compost application to the soil strongly influenced the fate of PAHs in the soil. Our results showed that the PAH dissipation during compost incubation was higher in mature composts because of the higher specific microbial activity, while the PAH dissipation in amended soil was higher in the non-mature compost because of the higher availability of PAHs and the higher co-metabolic microbial activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Regional modelling of polycyclic aromatic hydrocarbons: WRF-Chem-PAH model development and East Asia case studies

NASA Astrophysics Data System (ADS)

Mu, Qing; Lammel, Gerhard; Gencarelli, Christian N.; Hedgecock, Ian M.; Chen, Ying; Přibylová, Petra; Teich, Monique; Zhang, Yuxuan; Zheng, Guangjie; van Pinxteren, Dominik; Zhang, Qiang; Herrmann, Hartmut; Shiraiwa, Manabu; Spichtinger, Peter; Su, Hang; Pöschl, Ulrich; Cheng, Yafang

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRF-Chem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

Metabolic reprogramming of the urea cycle pathway in experimental pulmonary arterial hypertension rats induced by monocrotaline.

PubMed

Zheng, Hai-Kuo; Zhao, Jun-Han; Yan, Yi; Lian, Tian-Yu; Ye, Jue; Wang, Xiao-Jian; Wang, Zhe; Jing, Zhi-Cheng; He, Yang-Yang; Yang, Ping

2018-05-11

Pulmonary arterial hypertension (PAH) is a rare systemic disorder associated with considerable metabolic dysfunction. Although enormous metabolomic studies on PAH have been emerging, research remains lacking on metabolic reprogramming in experimental PAH models. We aim to evaluate the metabolic changes in PAH and provide new insight into endogenous metabolic disorders of PAH. A single subcutaneous injection of monocrotaline (MCT) (60 mg kg - 1 ) was used for rats to establish PAH model. Hemodynamics and right ventricular hypertrophy were adopted to evaluate the successful establishment of PAH model. Plasma samples were assessed through targeted metabolomic profiling platform to quantify 126 endogenous metabolites. Orthogonal partial least squares discriminant analysis (OPLS-DA) was used to discriminate between MCT-treated model and control groups. Metabolite Set Enrichment Analysis was adapted to exploit the most disturbed metabolic pathways. Endogenous metabolites of MCT treated PAH model and control group were well profiled using this platform. A total of 13 plasma metabolites were significantly altered between the two groups. Metabolite Set Enrichment Analysis highlighted that a disruption in the urea cycle pathway may contribute to PAH onset. Moreover, five novel potential biomarkers in the urea cycle, adenosine monophosphate, urea, 4-hydroxy-proline, ornithine, N-acetylornithine, and two candidate biomarkers, namely, O-acetylcarnitine and betaine, were found to be highly correlated with PAH. The present study suggests a new role of urea cycle disruption in the pathogenesis of PAH. We also found five urea cycle related biomarkers and another two candidate biomarkers to facilitate early diagnosis of PAH in metabolomic profile.

In situ modeling of PAH dynamics in agricultural soils amended with composts using the "VSOIL" platform

NASA Astrophysics Data System (ADS)

Brimo, Khaled; Ouvrard, Stéphanie; Houot, Sabine; Lafolie, François; Deschamps, Marjolaine; Benoit, Pierre; Garnier, Patricia

2017-04-01

Numerous studies have shown the presence of organic pollutants (OPs) in composts. Compost application in agricultural soil generates flux of OPs and among them polycyclic aromatic hydrocarbons (PAHs). A potential accumulation of PAHs in soils from successive compost applications could imply risks to environment. To explore and design scenarios that help land managers in their impact evaluations when composts are added in soils, there is a need to a new generation of models built from multi-modules that mimic the whole interactions between the different processes describing OP dynamic in soil. Our work is based on the implementation of an interdisciplinary global model for PAHs in soil by coupling modules describing the major physical, biochemical and biological processes influencing the fate of PAHs in soil, with modules that simulate water transfer, heat transfer, solute transport, and organic matter transformation under climatic conditions. The coupling is being facilitated by the «VSOIL» modeling platform. The steps of our modelling study are the following: 1) calibrate the field model using parameters previously estimated in laboratory completed with field data on a short period, 2) test the simulations using field experimental data, 3) build scenarios to explore the impact of PAHs accumulation in a long term (40 years). Our results show that the model can adequately predict the fate of PAHs in soil and can contribute to clarify some of unexplored aspects regarding the behavior of PAHs in soil like their mineralization and stabilization. Scenarios that predict the dynamic of PAHs in soil at long terms show a low PAH accumulation in soil after 40 years due to a high sequestration of the PAH in soils that is slightly higher for municipal solid waste composts than for green waste sludge composts.

The violent interstellar medium

NASA Technical Reports Server (NTRS)

Mccray, R.; Snow, T. P., Jr.

1979-01-01

Observational evidence for high-velocity and high-temperature interstellar gas is reviewed. The physical processes that characterize this gas are described, including the ionization and emissivity of coronal gas, the behavior and appearance of high-velocity shocks, and interfaces between coronal gas and cooler interstellar gas. Hydrodynamical models for the action of supernova explosions and stellar winds on the interstellar medium are examined, and recent attempts to synthesize all the processes considered into a global model for the interstellar medium are discussed.

The interstellar N2 abundance towards HD 124314 from far-ultraviolet observations.

PubMed

Knauth, David C; Andersson, B-G; McCandliss, Stephan R; Moos, H Warren

2004-06-10

The abundance of interstellar molecular nitrogen (N2) is of considerable importance: models of steady-state gas-phase interstellar chemistry, together with millimetre-wavelength observations of interstellar N2H+ in dense molecular clouds predict that N2 should be the most abundant nitrogen-bearing molecule in the interstellar medium. Previous attempts to detect N2 absorption in the far-ultraviolet or infrared (ice features) have hitherto been unsuccessful. Here we report the detection of interstellar N2 at far-ultraviolet wavelengths towards the moderately reddened star HD 124314 in the constellation of Centaurus. The N2 column density is larger than expected from models of diffuse clouds and significantly smaller than expected for dense molecular clouds. Moreover, the N2 abundance does not explain the observed variations in the abundance of atomic nitrogen (N I) towards high-column-density sightlines, implying that the models of nitrogen chemistry in the interstellar medium are incomplete.

Contribution of PAHs from coal-tar pavement sealcoat and other sources to 40 U.S. lakes

USGS Publications Warehouse

Van Metre, Peter C.; Mahler, Barbara J.

2010-01-01

Contamination of urban lakes and streams by polycyclic aromatic hydrocarbons (PAHs) has increased in the United States during the past 40 years. We evaluated sources of PAHs in post-1990 sediments in cores from 40 lakes in urban areas across the United States using a contaminant mass-balance receptor model and including as a potential source coal-tar-based (CT) sealcoat, a recently recognized source of urban PAH. Other PAH sources considered included several coal- and vehicle-related sources, wood combustion, and fuel-oil combustion. The four best modeling scenarios all indicate CT sealcoat is the largest PAH source when averaged across all 40 lakes, contributing about one-half of PAH in sediment, followed by vehicle-related sources and coal combustion. PAH concentrations in the lakes were highly correlated with PAH loading from CT sealcoat (Spearman's rho=0.98), and the mean proportional PAH profile for the 40 lakes was highly correlated with the PAH profile for dust from CT-sealed pavement (r=0.95). PAH concentrations and mass and fractional loading from CT sealcoat were significantly greater in the central and eastern United States than in the western United States, reflecting regional differences in use of different sealcoat product types. The model was used to calculate temporal trends in PAH source contributions during the last 40 to 100 years to eight of the 40 lakes. In seven of the lakes, CT sealcoat has been the largest source of PAHs since the 1960s, and in six of those lakes PAH trends are upward. Traffic is the largest source to the eighth lake, located in southern California where use of CT sealcoat is rare.

Evaluation of the phototoxicity of unsubstituted and alkylated polycyclic aromatic hydrocarbons to mysid shrimp (Americamysis bahia): Validation of predictive models.

PubMed

Finch, Bryson E; Marzooghi, Solmaz; Di Toro, Dominic M; Stubblefield, William A

2017-08-01

Crude oils are composed of an assortment of hydrocarbons, some of which are polycyclic aromatic hydrocarbons (PAHs). Polycyclic aromatic hydrocarbons are of particular interest due to their narcotic and potential phototoxic effects. Several studies have examined the phototoxicity of individual PAHs and fresh and weathered crude oils, and several models have been developed to predict PAH toxicity. Fingerprint analyses of oils have shown that PAHs in crude oils are predominantly alkylated. However, current models for estimating PAH phototoxicity assume toxic equivalence between unsubstituted (i.e., parent) and alkyl-substituted compounds. This approach may be incorrect if substantial differences in toxic potency exist between unsubstituted and substituted PAHs. The objective of the present study was to examine the narcotic and photo-enhanced toxicity of commercially available unsubstituted and alkylated PAHs to mysid shrimp (Americamysis bahia). Data were used to validate predictive models of phototoxicity based on the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap approach and to develop relative effect potencies. Results demonstrated that photo-enhanced toxicity increased with increasing methylation and that phototoxic PAH potencies vary significantly among unsubstituted compounds. Overall, predictive models based on the HOMO-LUMO gap were relatively accurate in predicting phototoxicity for unsubstituted PAHs but are limited to qualitative assessments. Environ Toxicol Chem 2017;36:2043-2049. © 2017 SETAC. © 2017 SETAC.

Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

NASA Astrophysics Data System (ADS)

Gatchell, M.; Stockett, M. H.; de Ruette, N.; Chen, T.; Giacomozzi, L.; Nascimento, R. F.; Wolf, M.; Anderson, E. K.; Delaunay, R.; Vizcaino, V.; Rousseau, P.; Adoui, L.; Huber, B. A.; Schmidt, H. T.; Zettergren, H.; Cederquist, H.

2015-11-01

A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C24H12+m +m =0 -7 , led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014), 10.1103/PhysRevLett.113.053002]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C16H10+m + , m =0 , 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

Laboratory Studies of DIB Carriers

NASA Technical Reports Server (NTRS)

Allamandola, L. J.

1995-01-01

Spectroscopic studies of the following potential diffuse interstellar band (DIB) carriers are reviewed: unspecified organics, carbon chains, polycyclic aromatic hydrocarbons (PAHs), fullerenes and derivatives, as well as porphyrins and related material. An assessment of each is given, along with suggestions for further experimental studies needed to fully test each candidate. Of the experimental techniques in common use matrix isolation spectroscopy with neon matrices is the most appropriate for the DIBs. The low vapor pressure and high reactivity of these materials preclude gas phase studies on many of these species. At this point, given the type and quality of published data available, carbon chains and PARs are the most promising candidates for a number of the DIBs.

Global time trends in PAH emissions from motor vehicles

NASA Astrophysics Data System (ADS)

Shen, Huizhong; Tao, Shu; Wang, Rong; Wang, Bin; Shen, Guofeng; Li, Wei; Su, Shenshen; Huang, Ye; Wang, Xilong; Liu, Wenxin; Li, Bengang; Sun, Kang

2011-04-01

Emission from motor vehicles is the most important source of polycyclic aromatic hydrocarbons (PAHs) in urban areas. Emission factors of individual PAHs for motor vehicles reported in the literature varied 4 to 5 orders of magnitude, leading to high uncertainty in emission inventory. In this study, key factors affecting emission factors of PAHs (EF PAH) for motor vehicles were evaluated quantitatively based on thousands of EF PAH measured in 16 countries for over 50 years. The result was used to develop a global emission inventory of PAHs from motor vehicles. It was found that country and vehicle model year are the most important factors affecting EF PAH, which can be quantified using a monovariate regression model with per capita gross domestic production (purchasing power parity) as a sole independent variable. On average, 29% of variation in log-transformed EF PAH could be explained by the model, which was equivalent to 90% reduction in overall uncertainty on arithmetic scale. The model was used to predict EF PAH and subsequently PAH emissions from motor vehicles for various countries in the world during a period from 1971 to 2030. It was estimated that the global emission reached its peak value of approximate 101 Gg in 1978 and decreased afterwards due to emission control in developed countries. The annual emission picked up again since 1990 owing to accelerated energy consumption in China and other developing countries. With more and more rigid control measures taken in the developing world, global emission of PAHs is currently passing its second peak. It was predicted that the emission would decrease from 77 Gg in 2010 to 42 Gg in 2030.

The role of disturbed blood flow in the development of pulmonary arterial hypertension: lessons from preclinical animal models.

PubMed

Dickinson, Michael G; Bartelds, Beatrijs; Borgdorff, Marinus A J; Berger, Rolf M F

2013-07-01

Pulmonary arterial hypertension (PAH) is a progressive pulmonary vasoproliferative disorder characterized by the development of unique neointimal lesions, including concentric laminar intima fibrosis and plexiform lesions. Although the histomorphology of neointimal lesions is well described, the pathogenesis of PAH and neointimal development is largely unknown. After three decades of PAH pathobiology research the focus has shifted from vasoconstriction towards a mechanism of cancer-like angioproliferation. In this concept the role of disturbed blood flow is seen as an important trigger in the development of vascular remodeling. For instance, in PAH associated with congenital heart disease, increased pulmonary blood flow (i.e., systemic-to-pulmonary shunt) is an essential trigger for the occurrence of neointimal lesions and PAH development. Still, questions remain about the exact role of these blood flow characteristics in disease progression. PAH animal models are important for obtaining insight in new pathobiological processes and therapeutical targets. However, as for any preclinical model the pathophysiological mechanism and clinical course has to be comparable to the human disease that it mimics. This means that animal models mimicking human PAH ideally are characterized by: a hit recognized in human disease (e.g., altered pulmonary blood flow), specific vascular remodeling resembling human neointimal lesions, and disease progression that leads to right ventriclular dysfunction and death. A review that underlines the current knowledge of PAH due to disturbed flow is still lacking. In this review we will summarize the current knowledge obtained from PAH animal models associated with disturbed pulmonary blood flow and address questions for future treatment strategies for PAH.

Microbial Factors Rather Than Bioavailability Limit the Rate and Extent of PAH Biodegradation in Aged Crude Oil Contaminated Model Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huesemann, Michael H.; Hausmann, Tom S.; Fortman, Timothy J.

The rate and extent of PAH biodegradation in a set of aged, crude oil contaminated model soils were measured in 90-week slurry bioremediation experiments. Soil properties such as organic matter content, mineral type, particle diameter, surface area, and porosity did not significantly influence the PAH biodegradation kinetics among the ten different model soils. A comparison of aged and freshly spiked soils indicates that aging affects the biodegradation rates and extents only for higher molecular weight PAHs while the effects of aging are insignificant for 3-ring PAHs and total PAHs. In all model soils with the exception of kaolinite clay, themore » rate of abiotic desorption was faster than the rate of biodegradation during the initial phase of bioremediation treatment indicating that PAH biodegradation was limited by microbial factors. Similarly, any of the higher molecular weight PAHs that were still present after 90 weeks of treatment were released rapidly during abiotic desorption tests which demonstrates that bioavailability limitations were not responsible for the recalcitrance of these hydrocarbons. Indeed, an analysis of microbial counts indicates that a severe reduction in hydrocarbon degrader populations may be responsible for the observed incomplete PAH biodegradation. It can therefore be concluded that the recalcitrance of PAHs during bioremediation is not necessarily due to bioavailability limitations and that these residual contaminants might, therefore, pose a greater risk to environmental receptors than previously thought.« less

Modeling personal particle-bound polycyclic aromatic hydrocarbon (pb-pah) exposure in human subjects in Southern California.

PubMed

Wu, Jun; Tjoa, Thomas; Li, Lianfa; Jaimes, Guillermo; Delfino, Ralph J

2012-07-11

Exposure to polycyclic aromatic hydrocarbon (PAH) has been linked to various adverse health outcomes. Personal PAH exposures are usually measured by personal monitoring or biomarkers, which are costly and impractical for a large population. Modeling is a cost-effective alternative to characterize personal PAH exposure although challenges exist because the PAH exposure can be highly variable between locations and individuals in non-occupational settings. In this study we developed models to estimate personal inhalation exposures to particle-bound PAH (PB-PAH) using data from global positioning system (GPS) time-activity tracking data, traffic activity, and questionnaire information. We conducted real-time (1-min interval) personal PB-PAH exposure sampling coupled with GPS tracking in 28 non-smoking women for one to three sessions and one to nine days each session from August 2009 to November 2010 in Los Angeles and Orange Counties, California. Each subject filled out a baseline questionnaire and environmental and behavior questionnaires on their typical activities in the previous three months. A validated model was used to classify major time-activity patterns (indoor, in-vehicle, and other) based on the raw GPS data. Multiple-linear regression and mixed effect models were developed to estimate averaged daily and subject-level PB-PAH exposures. The covariates we examined included day of week and time of day, GPS-based time-activity and GPS speed, traffic- and roadway-related parameters, meteorological variables (i.e. temperature, wind speed, relative humidity), and socio-demographic variables and occupational exposures from the questionnaire. We measured personal PB-PAH exposures for 180 days with more than 6 h of valid data on each day. The adjusted R2 of the model was 0.58 for personal daily exposures, 0.61 for subject-level personal exposures, and 0.75 for subject-level micro-environmental exposures. The amount of time in vehicle (averaging 4.5% of total sampling time) explained 48% of the variance in daily personal PB-PAH exposure and 39% of the variance in subject-level exposure. The other major predictors of PB-PAH exposures included length-weighted traffic count, work-related exposures, and percent of weekday time. We successfully developed regression models to estimate PB-PAH exposures based on GPS-tracking data, traffic data, and simple questionnaire information. Time in vehicle was the most important determinant of personal PB-PAH exposure in this population. We demonstrated the importance of coupling real-time exposure measures with GPS time-activity tracking in personal air pollution exposure assessment.

Modelling Poly-Aromatic Hydrocarbons "online" with the GEOS-Chem Europe and Asia regional models.

NASA Astrophysics Data System (ADS)

Ivatt, P.; Evans, M. J.

2017-12-01

Poly-Aromatic Hydrocarbons (PAHs) are carcinogens and so are restricted by international treaties. PAHs are mainly emitted into the atmosphere by domestic (heating and cooking), natural (forest fires burning), as well as some industrial processes (coke ovens). PAHs partition between the gas and particle phase (notably carbonaceous particles) based on their volatility. In recent years, interest has turned to the possible health effects of their oxidation products (both nitrogenated and oxygenated) as it has been suggested that these oxidation products may be even more carcinogenic than the parent PAHs. To increase our understanding of the processes controlling the regional concentrations of PAHs and their oxidation products an "online" PAH model has been developed within the GEOS-Chem framework. This provides for the representation of the coupled aerosol/gas phase chemistry of the parent PAH and its secondary oxidation products. Benzo[a]pyrene is used as an exemplar but the methodology is flexible and the approach can be used for any PAH species. Comparisons are made with observations and the sources of variability discussed.

The search for shock-excited H{sub 2} in Virgo spirals experiencing ram pressure stripping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wong, O. Ivy; Kenney, Jeffrey D. P.; Murphy, Eric J.

We investigate the presence of shock-excited H{sub 2} in four Virgo cluster galaxies that show clear evidence of ongoing ram pressure stripping. Mid-infrared spectral mapping of the rotational H{sub 2} emission lines were performed using the Infrared Spectrograph on board the Spitzer Space Telescope. We target four regions along the leading side of galaxies where the intracluster medium appears to be pushing back the individual galaxy's interstellar medium. For comparison purposes, we also study two regions on the trailing side of these galaxies: a region within an edge-on disk and an extraplanar star-forming region. We find a factor of 2.6more » excess of warm H{sub 2}/PAH in our sample relative to the observed fractions in other nearby galaxies. We attribute the H{sub 2}/PAH excess to contributions of shock-excited H{sub 2} which is likely to have been triggered by ongoing ram pressure interaction in our sample galaxies. Ram pressure driven shocks may also be responsible for the elevated ratios of [Fe II]/[Ne II] found in our sample.« less

THE INFRARED SPECTRUM OF PROTONATED OVALENE IN SOLID PARA-HYDROGEN AND ITS POSSIBLE CONTRIBUTION TO INTERSTELLAR UNIDENTIFIED INFRARED EMISSION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsuge, Masashi; Bahou, Mohammed; Lee, Yuan-Pern

The mid-infrared emission from galactic objects, including reflection nebulae, planetary nebulae, proto-planetary nebulae, molecular clouds, etc, as well as external galaxies, is dominated by the unidentified infrared (UIR) emission bands. Large protonated polycyclic aromatic hydrocarbons (H{sup +}PAHs) were proposed as possible carriers, but no spectrum of an H{sup +}PAH has been shown to exactly match the UIR bands. Here, we report the IR spectrum of protonated ovalene (7-C{sub 32}H{sub 15} {sup +}) measured in a para -hydrogen ( p -H{sub 2}) matrix at 3.2 K, generated by bombarding a mixture of ovalene and p -H{sub 2} with electrons during matrixmore » deposition. Spectral assignments were made based on the expected chemistry and on the spectra simulated with the wavenumbers and infrared intensities predicted with the B3PW91/6-311++G(2d,2p) method. The close resemblance of the observed spectral pattern to that of the UIR bands suggests that protonated ovalene may contribute to the UIR emission, particularly from objects that emit Class A spectra, such as the IRIS reflection nebula, NGC 7023.« less

Variations in the 6.2 μm emission profile in starburst-dominated galaxies: a signature of polycyclic aromatic nitrogen heterocycles (PANHs)?

NASA Astrophysics Data System (ADS)

Canelo, Carla M.; Friaça, Amâncio C. S.; Sales, Dinalva A.; Pastoriza, Miriani G.; Ruschel-Dutra, Daniel

2018-04-01

Analyses of the polycyclic aromatic hydrocarbon (PAH) feature profiles, especially the 6.2 μm feature, could indicate the presence of nitrogen incorporated in their aromatic rings. In this work, 155 predominantly starburst-dominated galaxies (including H II regions and Seyferts, for example), extracted from the Spitzer/Infrared Spectrograph ATLAS project, have their 6.2 μm profiles fitted allowing their separation into the Peeters' A, B, and C classes. 67 per cent of these galaxies were classified as class A, 31 per cent were as class B, and 2 per cent as class C. Currently, class A sources, corresponding to a central wavelength near 6.22 μm, seem only to be explained by polycyclic aromatic nitrogen heterocycles (PANHs), whereas class B may represent a mix between PAHs and PANHs emissions or different PANH structures or ionization states. Therefore, these spectra suggest a significant presence of PANHs in the interstellar medium (ISM) of these galaxies that could be related to their starburst-dominated emission. These results also suggest that PANHs constitute another reservoir of nitrogen in the Universe, in addition to the nitrogen in the gas phase and ices of the ISM.

Source apportionment of polycyclic aromatic hydrocarbons in Louisiana

NASA Astrophysics Data System (ADS)

Han, F.; Zhang, H.

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) in the environment are of significant concern due to their high toxicity that may result in adverse health effects. PAHs measurements at the limited air quality monitoring stations alone are insufficient to gain a complete concept of ambient PAH levels. This study simulates the concentrations of PAHs in Louisiana and identifies the major emission sources. Speciation profiles for PAHs were prepared using data assembled from existing emission profile databases. The Sparse Matrix Operator Kernel Emission (SMOKE) model was used to generate the estimated gridded emissions of 16 priority PAH species directly associated with health risks. The estimated emissions were then applied to simulate ambient concentrations of PAHs in Louisiana for January, April, July and October 2011 using the Community Multiscale Air Quality (CMAQ) model (v5.0.1). Through the formation, transport and deposition of PAHs species, the concentrations of PAHs species in gas phase and particulate phase were obtained. The spatial and temporal variations were analyzed and contributions of both local and regional major sources were quantified. This study provides important information for the prevention and treatment of PAHs in Louisiana.

Estimating population exposure to ambient polycyclic aromatic hydrocarbon in the United States - Part I: Model development and evaluation.

PubMed

Zhang, Jie; Li, Jingyi; Wang, Peng; Chen, Gang; Mendola, Pauline; Sherman, Seth; Ying, Qi

2017-02-01

PAHs (polycyclic aromatic hydrocarbons) in the environment are of significant concern due to their negative impact on human health. PAH measurements at the air toxics monitoring network stations alone are not sufficient to provide a complete picture of ambient PAH levels or to allow accurate assessment of public exposure in the United States. In this study, speciation profiles for PAHs were prepared using data assembled from existing emission profile data bases, and the Sparse Matrix Operator Kernel Emissions (SMOKE) model was used to generate the gridded national emissions of 16 priority PAHs in the US. The estimated emissions were applied to simulate ambient concentration of PAHs for January, April, July and October 2011, using a modified Community Multiscale Air Quality (CMAQ) model (v5.0.1) that treats the gas and particle phase partitioning of PAHs and their reactions in the gas phase and on particle surface. Predicted daily PAH concentrations at 61 air toxics monitoring sites generally agreed with observations, and averaging the predictions over a month reduced the overall error. The best model performance was obtained at rural sites, with an average mean fractional bias (MFB) of -0.03 and mean fractional error (MFE) of 0.70. Concentrations at suburban and urban sites were underestimated with overall MFB=-0.57 and MFE=0.89. Predicted PAH concentrations were highest in January with better model performance (MFB=0.12, MFE=0.69; including all sites), and lowest in July with worse model performance (MFB=-0.90, MFE=1.08). Including heterogeneous reactions of several PAHs with O 3 on particle surface reduced the over-prediction bias in winter, although significant uncertainties were expected due to relative simple treatment of the heterogeneous reactions in the current model. Copyright © 2016 Elsevier Ltd. All rights reserved.

PAH distribution and mass fluxes in the Three Gorges Reservoir after impoundment of the Three Gorges Dam.

PubMed

Deyerling, Dominik; Wang, Jingxian; Hu, Wei; Westrich, Bernhard; Peng, Chengrong; Bi, Yonghong; Henkelmann, Bernhard; Schramm, Karl-Werner

2014-09-01

Mass fluxes of polycyclic aromatic hydrocarbons (PAHs) were calculated for the Three Gorges Reservoir (TGR) in China, based on concentration and discharge data from the Yangtze River. Virtual Organisms (VOs) have been applied during four campaigns in 2008, 2009 (twice) and 2011 at sampling sites distributed from Chongqing to Maoping. The total PAH mass fluxes ranged from 110 to 2,160 mg s(-1). Highest loads were determined at Chongqing with a decreasing trend towards Maoping in all four sampling campaigns. PAH remediation capacity of the TGR was found to be high as the mass flux reduced by more than half from upstream to downstream. Responsible processes are thought to be adsorption of PAH to suspended particles, dilution and degradation. Furthermore, the dependence of PAH concentration upon water depth was investigated at Maoping in front of the Three Gorges Dam. Although considerable differences could be revealed, there was no trend observable. Sampling of water with self-packed filter cartridges confirmed more homogenous PAH depth distribution. Moreover, PAH content of suspended particles was estimated from water concentrations gathered by VOs based on a water-particle separation model and subsequently compared to PAH concentration measured in water and in filter cartridges. It could be shown that the modeled data predicts the concentration caused by particle-bound PAHs to be about 6 times lower than PAHs dissolved in water. Besides, the model estimates the proportions of 5- and 6-ring PAHs being higher than in water phase. Copyright © 2014 Elsevier B.V. All rights reserved.

A spatial-temporal regression model to predict daily outdoor residential PAH concentrations in an epidemiologic study in Fresno, CA

NASA Astrophysics Data System (ADS)

Noth, Elizabeth M.; Hammond, S. Katharine; Biging, Gregory S.; Tager, Ira B.

2011-05-01

BackgroundPolycyclic aromatic hydrocarbons (PAHs) are generated as a byproduct of combustion, and are associated with respiratory symptoms and increased risk of asthma attacks. ObjectivesTo assign daily, outdoor exposures to participants in the Fresno Asthmatic Children's Environment Study (FACES) using land use regression models for the sum of 4-, 5- and 6-ring PAHs (PAH456). MethodsPAH data were collected daily at the EPA Supersite in Fresno, CA from 10/2000 through 2/2007. From 2/2002 to 2/2003, intensive air pollution sampling was conducted at 83 homes of participants in the FACES study. These measurement data were combined with meteorological data, source data, and other spatial variables to form a land use regression model to assign daily exposure at all FACES homes for all years of the study (2001-2008). ResultsThe model for daily, outdoor residential PAH456 concentrations accounted for 80% of the between-home variability and 18% of the within-home variability. Both temporal and spatial variables were significant in the model. Traffic characteristics and home heating fuel were the main spatial explanatory variables. ConclusionsBecause spatial and temporal distributions of PAHs vary on an intra-urban scale, the location of the child's home within the urban setting plays an important role in the level of exposure that each child has to PAHs.

Time-dependent interstellar chemistry

NASA Technical Reports Server (NTRS)

Glassgold, A. E.

1985-01-01

Some current problems in interstellar chemistry are considered in the context of time-dependent calculations. The limitations of steady-state models of interstellar gas-phase chemistry are discussed, and attempts to chemically date interstellar clouds are reviewed. The importance of studying the physical and chemical properties of interstellar dust is emphasized. Finally, the results of a series of studies of collapsing clouds are described.

Dynamics and kinetics of reversible homo-molecular dimerization of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Mao, Qian; Ren, Yihua; Luo, K. H.; van Duin, Adri C. T.

2017-12-01

Physical dimerization of polycyclic aromatic hydrocarbons (PAHs) has been investigated via molecular dynamics (MD) simulation with the ReaxFF reactive force field that is developed to bridge the gap between the quantum mechanism and classical MD. Dynamics and kinetics of homo-molecular PAH collision under different temperatures, impact parameters, and orientations are studied at an atomic level, which is of great value to understand and model the PAH dimerization. In the collision process, the enhancement factors of homo-molecular dimerizations are quantified and found to be larger at lower temperatures or with smaller PAH instead of size independent. Within the capture radius, the lifetime of the formed PAH dimer decreases as the impact parameter increases. Temperature and PAH characteristic dependent forward and reverse rate constants of homo-molecular PAH dimerization are derived from MD simulations, on the basis of which a reversible model is developed. This model can predict the tendency of PAH dimerization as validated by pyrene dimerization experiments [H. Sabbah et al., J. Phys. Chem. Lett. 1(19), 2962 (2010)]. Results from this study indicate that the physical dimerization cannot be an important source under the typical flame temperatures and PAH concentrations, which implies a more significant role played by the chemical route.

SINGLE AND DOUBLE PHOTOIONIZATION AND PHOTODISSOCIATION OF TOLUENE BY SOFT X-RAYS IN A CIRCUMSTELLAR ENVIRONMENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monfredini, T.; Boechat-Roberty, H. M.; Fantuzzi, F.

The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C–H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large numbermore » of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.« less

Single and Double Photoionization and Photodissociation of Toluene by Soft X-Rays in a Circumstellar Environment

NASA Astrophysics Data System (ADS)

Monfredini, T.; Fantuzzi, F.; Nascimento, M. A. C.; Wolff, W.; Boechat-Roberty, H. M.

2016-04-01

The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C-H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large number of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.

Large-scale modeling on the fate and transport of polycyclic aromatic hydrocarbons (PAHs) in multimedia over China

NASA Astrophysics Data System (ADS)

Huang, Y.; Liu, M.; Wada, Y.; He, X.; Sun, X.

2017-12-01

In recent decades, with rapid economic growth, industrial development and urbanization, expanding pollution of polycyclic aromatic hydrocarbons (PAHs) has become a diversified and complicated phenomenon in China. However, the availability of sufficient monitoring activities for PAHs in multi-compartment and the corresponding multi-interface migration processes are still limited, especially at a large geographic area. In this study, we couple the Multimedia Fate Model (MFM) to the Community Multi-Scale Air Quality (CMAQ) model in order to consider the fugacity and the transient contamination processes. This coupled dynamic contaminant model can evaluate the detailed local variations and mass fluxes of PAHs in different environmental media (e.g., air, surface film, soil, sediment, water and vegetation) across different spatial (a county to country) and temporal (days to years) scales. This model has been applied to a large geographical domain of China at a 36 km by 36 km grid resolution. The model considers response characteristics of typical environmental medium to complex underlying surface. Results suggest that direct emission is the main input pathway of PAHs entering the atmosphere, while advection is the main outward flow of pollutants from the environment. In addition, both soil and sediment act as the main sink of PAHs and have the longest retention time. Importantly, the highest PAHs loadings are found in urbanized and densely populated regions of China, such as Yangtze River Delta and Pearl River Delta. This model can provide a good scientific basis towards a better understanding of the large-scale dynamics of environmental pollutants for land conservation and sustainable development. In a next step, the dynamic contaminant model will be integrated with the continental-scale hydrological and water resources model (i.e., Community Water Model, CWatM) to quantify a more accurate representation and feedbacks between the hydrological cycle and water quality at even larger geographical domains. Keywords: PAHs; Community multi-scale air quality model; Multimedia fate model; Land use

Interstellar Polycyclic Aromatic Compounds and Astrophysics

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role polycyclic aromatic compounds (PAC) in the interstellar medium (ISM). Twenty years ago, the notion of an abundant population of large, carbon rich molecules in the ISM was considered preposterous. Today, the unmistakable spectroscopic signatures of PAC - shockingly large molecules by previous interstellar chemistry standards - are recognized throughout the Universe. In this paper, we will examine the interstellar PAC model and its importance to astrophysics, including: (1) the evidence which led to inception of the model; (2) the ensuing laboratory and theoretical studies of the fundamental spectroscopic properties of PAC by which the model has been refined and extended; and (3) a few examples of how the model is being exploited to derive insight into the nature of the interstellar PAC population.

Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons over the northwestern Pacific Ocean: Role of East Asian continental outflow

NASA Astrophysics Data System (ADS)

Wu, Z.; Guo, Z.

2017-12-01

We measured 15 parent polycyclic aromatic hydrocarbons (PAHs) in atmosphere and water during a research cruise from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) in the spring of 2015 to investigate the occurrence, air-sea gas exchange, and gas-particle partitioning of PAHs with a particular focus on the influence of East Asian continental outflow. The gaseous PAH composition and identification of sources were consistent with PAHs from the upwind area, indicating that the gaseous PAHs (three- to five-ring PAHs) were influenced by upwind land pollution. In addition, air-sea exchange fluxes of gaseous PAHs were estimated to be -54.2 to 107.4 ng m-2 d-1, and was indicative of variations of land-based PAH inputs. The logarithmic gas-particle partition coefficient (logKp) of PAHs regressed linearly against the logarithmic subcooled liquid vapor pressure, with a slope of -0.25. This was significantly larger than the theoretical value (-1), implying disequilibrium between the gaseous and particulate PAHs over the NWP. The non-equilibrium of PAH gas-particle partitioning was shielded from the volatilization of three-ring gaseous PAHs from seawater and lower soot concentrations in particular when the oceanic air masses prevailed. Modeling PAH absorption into organic matter and adsorption onto soot carbon revealed that the status of PAH gas-particle partitioning deviated more from the modeling Kp for oceanic air masses than those for continental air masses, which coincided with higher volatilization of three-ring PAHs and confirmed the influence of air-sea exchange. Meanwhile, significant linear regressions between logKp and logKoa (logKsa) for PAHs were observed for continental air masses, suggesting the dominant effect of East Asian continental outflow on atmospheric PAHs over the NWP during the sampling campaign.

Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons over the northwestern Pacific Ocean: Role of East Asian continental outflow.

PubMed

Wu, Zilan; Lin, Tian; Li, Zhongxia; Jiang, Yuqing; Li, Yuanyuan; Yao, Xiaohong; Gao, Huiwang; Guo, Zhigang

2017-11-01

We measured 15 parent polycyclic aromatic hydrocarbons (PAHs) in atmosphere and water during a research cruise from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) in the spring of 2015 to investigate the occurrence, air-sea gas exchange, and gas-particle partitioning of PAHs with a particular focus on the influence of East Asian continental outflow. The gaseous PAH composition and identification of sources were consistent with PAHs from the upwind area, indicating that the gaseous PAHs (three-to five-ring PAHs) were influenced by upwind land pollution. In addition, air-sea exchange fluxes of gaseous PAHs were estimated to be -54.2-107.4 ng m -2 d -1 , and was indicative of variations of land-based PAH inputs. The logarithmic gas-particle partition coefficient (logK p ) of PAHs regressed linearly against the logarithmic subcooled liquid vapor pressure (logP L 0 ), with a slope of -0.25. This was significantly larger than the theoretical value (-1), implying disequilibrium between the gaseous and particulate PAHs over the NWP. The non-equilibrium of PAH gas-particle partitioning was shielded from the volatilization of three-ring gaseous PAHs from seawater and lower soot concentrations in particular when the oceanic air masses prevailed. Modeling PAH absorption into organic matter and adsorption onto soot carbon revealed that the status of PAH gas-particle partitioning deviated more from the modeling K p for oceanic air masses than those for continental air masses, which coincided with higher volatilization of three-ring PAHs and confirmed the influence of air-sea exchange. Meanwhile, significant linear regressions between logK p and logK oa (logK sa ) for PAHs were observed for continental air masses, suggesting the dominant effect of East Asian continental outflow on atmospheric PAHs over the NWP during the sampling campaign. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

NASA Technical Reports Server (NTRS)

Allamandola, Lou J.; Bernstein, Max; Sandford, Scott; Witteborn, Fred (Technical Monitor)

1996-01-01

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Removing polycyclic aromatic hydrocarbons from water using granular activated carbon: kinetic and equilibrium adsorption studies.

PubMed

Eeshwarasinghe, Dinushika; Loganathan, Paripurnanda; Kalaruban, Mahatheva; Sounthararajah, Danious Pratheep; Kandasamy, Jaya; Vigneswaran, Saravanamuthu

2018-05-01

Polycyclic aromatic hydrocarbons (PAHs) constitute a group of highly persistent, toxic and widespread environmental micropollutants that are increasingly found in water. A study was conducted in removing five PAHs, specifically naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene, from water by adsorption onto granular activated carbon (GAC). The pseudo-first-order (PFO) model satisfactorily described the kinetics of adsorption of the PAHs. The Weber and Morris diffusion model's fit to the data showed that there were faster and slower rates of intra-particle diffusion probably into the mesopores and micropores of the GAC, respectively. These rates were negatively related to the molar volumes of the PAHs. Batch equilibrium adsorption data fitted well to the Langmuir, Freundlich and Dubinin-Radushkevich models, of which the Freundlich model exhibited the best fit. The adsorption affinities were related to the hydrophobicity of the PAHs as determined by the log K ow values. Free energies of adsorption calculated from the Dubinin-Radushkevich model and the satisfactory kinetic data fitting to the PFO model suggested physical adsorption of the PAHs. Adsorption of naphthalene, acenaphthylene and acenaphthene in fixed-bed columns containing a mixture of GAC (0.5 g) + sand (24.5 g) was satisfactorily simulated by the Thomas model.

Spatial and Temporal Distribution of Polycyclic Aromatic Hydrocarbons and Elemental Carbon in Bakersfield, California

PubMed Central

Noth, Elizabeth M.; Lurmann, Fred; Northcross, Amanda; Perrino, Charles; Vaughn, David; Hammond, S. Katharine

2016-01-01

Despite increasing evidence that airborne polycyclic aromatic hydrocarbon (PAH) exposures contribute to adverse health outcomes for sensitive populations, limited data are available on short-term intraurban spatial distributions for use in epidemiologic research. Exposure assessments for airborne PAHs are uncommon because air sampling for PAHs is a labor-, equipment-, and time-intensive task. To address this gap we measured wintertime PAH concentrations during 2010-2011 in Bakersfield, California, USA, a major city in the Southern San Joaquin Valley. Specifically, 58 96-hour integrated PAH samples were collected during 4 time periods at 14 locations from November 2010 to January 2011; duplicates were collected at two sites. We also collected elemental carbon (EC) at the same 14 sites and analyzed the two time periods with the highest ambient PAH pollution. We used linear regression models to quantify the relationship between potential spatial and temporal predictors of PAH concentrations. We found that wintertime PAH concentrations in Bakersfield, CA, are best predicted by meteorological variables and traffic proximity. Our model explains a moderate amount of the variability in the data (R2=0.58), likely reflecting the major sources of PAHs in Bakersfield. We also observed that PAH concentrations were more spatially variable than EC concentrations. Comparing our data to historical monitoring data at one location in Bakersfield showed that the relatively low PAH concentrations during the 2010-2011 winter in Bakersfield is part of a long-term trend in decreasing PAH concentrations. PMID:28083077

Quantitative assessment of human health risk posed by polycyclic aromatic hydrocarbons in urban road dust.

PubMed

Ma, Yukun; Liu, An; Egodawatta, Prasanna; McGree, James; Goonetilleke, Ashantha

2017-01-01

Among the numerous pollutants present in urban road dust, polycyclic aromatic hydrocarbons (PAHs) are among the most toxic chemical pollutants and can pose cancer risk to humans. The primary aim of the study was to develop a quantitative model to assess the cancer risk from PAHs in urban road dust based on traffic and land use factors and thereby to characterise the risk posed by PAHs in fine (<150μm) and coarse (>150μm) particles. The risk posed by PAHs was quantified as incremental lifetime cancer risk (ILCR), which was modelled as a function of traffic volume and percentages of different urban land uses. The study outcomes highlighted the fact that cancer risk from PAHs in urban road dust is primarily influenced by PAHs associated with fine solids. Heavy PAHs with 5 to 6 benzene rings, especially dibenzo[a,h]anthracene (D[a]A) and benzo[a]pyrene (B[a]P) in the mixture contribute most to the risk. The quantitative model developed based on traffic and land use factors will contribute to informed decision making in relation to the management of risk posed by PAHs in urban road dust. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural equation modeling of PAHs in ambient air, dust fall, soil, and cabbage in vegetable bases of Northern China.

PubMed

Zhang, YunHui; Hou, DeYi; Xiong, GuanNan; Duan, YongHong; Cai, ChuanYang; Wang, Xin; Li, JingYa; Tao, Shu; Liu, WenXin

2018-08-01

A series of field samples including ambient air (gaseous and particulate phases), dust fall, surface soil, rhizosphere soil and cabbage tissues (leaf, root and core), were collected in vegetable bases near a large coking manufacturer in Shanxi Province, Northern China, during a harvest season. A factor analysis was employed to apportion the emission sources of polycyclic aromatic hydrocarbons (PAHs), and the statistical results indicated coal combustion was the dominant emission source that accounted for different environmental media and cabbage tissues, while road traffic, biomass burning and the coking industry contributed to a lesser extent. A structural equation model was first developed to quantitatively explore the transport pathways of PAHs from surrounding media to cabbage tissues. The modeling results showed that PAHs in ambient air were positively associated with those in dust fall, and a close relationship was also true for PAHs in dust fall and in surface soil due to air-soil exchange process. Furthermore, PAHs in surface soil were correlated with those in rhizosphere soil and in the cabbage leaf with the path coefficients of 0.83 and 0.39, respectively. PAHs in the cabbage leaf may dominantly contribute to the accumulation of PAHs in the edible part of cabbages. Copyright © 2018 Elsevier Ltd. All rights reserved.

Remediation of soil-bound polynuclear aromatic hydrocarbons using nonionic surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeom, IckTae; Ghosh, Mriganka; Cox, C.

1996-12-31

The solubilization and biodegradation of soil-bound PAHs from a manufactured gas plant (MGP) site soil was investigated using surfactants. Three nonionic polyoxyethylene (POE) surfactants, Triton X-100, Tween 80, and Brij 35, were used. The fate of four PAHs, phenanthrene, anthracene, pyrene, and benzo(a)pyrene were monitored during the remediation process. The measured concentrations of solubilized PAHs agreed well with those estimated using micelle-water partitioning coefficient, K{sub m}, and Raoult`s law. The solubilization of soil-bound PAHs by surfactants is a slow, nonequilibrium process. Diffusion of PAH molecules within the weathered soil-tar matrix is proposed as the rate-limiting step in solubilizing PAHs frommore » such soils. A radial diffusion model is used to describe solubilization of PAHs by surfactant washing. The model predicts experimental results fairly well at low surfactant dosages while at high dosages it somewhat overestimates the extent of solubilization. Biodegradation studies were performed using a natural consortium of microorganisms enriched from PAH-contaminated soils. Surfactants enhanced biodegradation of PAHs except for Tween 80. However, biodegradation of surfactants themselves appear to attenuate the beneficial effects of surfactant-mediated bioremediation.« less

Time trend of polycyclic aromatic hydrocarbon emission factors from motor vehicles

NASA Astrophysics Data System (ADS)

Tao, Shu; Shen, Huizhong; Wang, Rong; Sun, Kang

2010-05-01

Motor vehicle is an important emission source of polycyclic aromatic hydrocarbons (PAHs) and this is particularly true in urban areas. Motor vehicle emission factors (EFs) for individual PAH compound reported in the literature varied for 4 to 5 orders of magnitude, leading to high uncertainty in emission estimation. In this study, the major factors affecting EFs were investigated and characterized by regression models. Based on the model developed, a motor vehicle PAH emission inventory at country level was developed. It was found that country and model year are the most important factors affecting EFs for PAHs. The influence of the two factors can be quantified by a single parameter of per capita gross domestic production (purchasing power parity), which was used as the independent variables of the regression models. The models developed using randomly selected 80% of measurements and tested with the remained data accounted for 28 to 48% of the variations in EFs for PAHs measured in 16 countries over 50 years. The regression coefficients of the EF prediction models were molecular weight dependent. Motor vehicle emission of PAHs from individual countries in the world in 1985, 1995, 2005, 2015, and 2025 were calculated and the global emission of total PAHs were 470, 390, and 430 Gg in 1985, 1995, and 2005 and will be 290 and 130 Gg in 2015 and 2025, respectively. The emission is currently passing its peak and will decrease due to significant decrease in China and other developing countries.

The spatial extent of polycyclic aromatic hydrocarbons emission in the Herbig star HD 179218

NASA Astrophysics Data System (ADS)

Taha, A. S.; Labadie, L.; Pantin, E.; Matter, A.; Alvarez, C.; Esquej, P.; Grellmann, R.; Rebolo, R.; Telesco, C.; Wolf, S.

2018-04-01

Aim. We investigate, in the mid-infrared, the spatial properties of the polycyclic aromatic hydrocarbons (PAHs) emission in the disk of HD 179218, an intermediate-mass Herbig star at 300 pc. Methods: We obtained mid-infrared images in the PAH-1, PAH-2 and Si-6 filters centered at 8.6, 11.3, and 12.5 μm, and N-band low-resolution spectra using CanariCam on the 10-m Gran Telescopio Canarias (GTC). We compared the point spread function (PSF) profiles measured in the PAH filters to the profile derived in the Si-6 filter, where the thermal continuum emission dominates. We performed radiative transfer modeling of the spectral energy distribution (SED) and produced synthetic images in the three filters to investigate different spatial scenarios. Results: Our data show that the disk emission is spatially resolved in the PAH-1 and PAH-2 filters, while unresolved in the Si-6 filter. Thanks to very good observing conditions, an average full width at half maximum (FWHM) of 0.232'', 0.280'' and 0.293'' is measured in the three filters, respectively. Gaussian disk fitting and quadratic subtraction of the science and calibrator PSFs suggests a lower-limit characteristic angular diameter of the emission of 100 mas, or 30 au. The photometric and spectroscopic results are compatible with previous findings. Our radiative transfer (RT) modeling of the continuum suggests that the resolved emission should result from PAH molecules on the disk atmosphere being UV-excited by the central star. Simple geometrical models of the PAH component compared to the underlying continuum point to a PAH emission uniformly extended out to the physical limits of the disk model. Furthermore, our RT best model of the continuum requires a negative exponent of the surface density power-law, in contrast with earlier modeling pointing to a positive exponent. Conclusions: We have spatially resolved - for the first time to our knowledge - the PAHs emission in the disk of HD 179218 and set constraints on its spatial extent. Based on spatial and spectroscopic considerations as well as on qualitative comparison with IRS 48 and HD 97048, we favor a scenario in which PAHs extend out to large radii across the flared disk surface and are at the same time predominantly in an ionized charge state due to the strong UV radiation field of the 180 L⊙ central star.

The interstellar depletion mystery, or where have all those atoms gone. [cosmic abundance as grain model evidence

NASA Technical Reports Server (NTRS)

Greenberg, J. M.

1974-01-01

The observed depletion of intermediate-weight elements O, C, and N from the interstellar medium is shown to be significantly greater than can be accounted for by accretion on interstellar dust. A number of possible explanations are presented, ranging from the existence in interstellar space of many 'snowballs' intermediate in size between dust grains and comets to the existence of many far more complicated interstellar molecules than have been detected.

Ultraviolet interstellar linear polarization. I - Applicability of current dust grain models

NASA Technical Reports Server (NTRS)

Wolff, Michael J.; Clayton, Geoffrey C.; Meade, Marilyn R.

1993-01-01

UV spectropolarimetric observations yielding data on the wavelength-dependence of interstellar polarization along eight lines of sight facilitate the evaluation of dust grain models previously used to fit the extinction and polarization in the visible and IR. These models pertain to bare silicate/graphite grains, silicate cores with organic refractory mantles, silicate cores with amorphous carbon mantles, and composite grains. The eight lines-of-sight show three different interstellar polarization dependences.

Neutral interstellar helium parameters based on Ulysses/GAS and IBEX-LO observations: What are the reasons for the differences?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katushkina, O. A.; Izmodenov, V. V.; Wood, B. E.

Recent analysis of the interstellar helium fluxes measured in 2009-2010 at Earth's orbit by the Interstellar Boundary Explorer (IBEX) has suggested that the interstellar velocity (both direction and magnitude) is inconsistent with that derived previously from Ulysses/GAS observations made in the period from 1990 to 2002 at 1.5-5.5 AU from the Sun. Both results are model dependent, and models that were used in the analyses are different. In this paper, we perform an analysis of the Ulysses/GAS and IBEX-Lo data using our state-of-the-art three-dimensional time-dependent kinetic model of interstellar atoms in the heliosphere. For the first time, we analyze Ulysses/GASmore » data from year 2007, the closest available Ulysses/GAS observations in time to the IBEX observations. We show that the interstellar velocity derived from the Ulysses 2007 data is consistent with previous Ulysses results and does not agree with the velocity derived from IBEX. This conclusion is very robust since, as is shown in the paper, it does not depend on the ionization rates adopted in theoretical models. We conclude that Ulysses data are not consistent with the new local interstellar medium (LISM) velocity vector from IBEX. In contrast, IBEX data, in principle, could be explained with the LISM velocity vector derived from the Ulysses data. This is possible for the models where the interstellar temperature increased from 6300 K to 9000 K. There is a need to perform further studies of possible reasons for the broadening of the helium signal core measured by IBEX, which could be an instrumental effect or could be due to unconsidered physical processes.« less

PAH concentrations simulated with the AURAMS-PAH chemical transport model over Canada and the USA

NASA Astrophysics Data System (ADS)

Galarneau, E.; Makar, P. A.; Zheng, Q.; Narayan, J.; Zhang, J.; Moran, M. D.; Bari, M. A.; Pathela, S.; Chen, A.; Chlumsky, R.

2014-04-01

The offline Eulerian AURAMS (A Unified Regional Air quality Modelling System) chemical transport model was adapted to simulate airborne concentrations of seven PAHs (polycyclic aromatic hydrocarbons): phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene + triphenylene, and benzo[a]pyrene. The model was then run for the year 2002 with hourly output on a grid covering southern Canada and the continental USA with 42 km horizontal grid spacing. Model predictions were compared to ~5000 24 h-average PAH measurements from 45 sites, most of which were located in urban or industrial areas. Eight of the measurement sites also provided data on particle/gas partitioning which had been modelled using two alternative schemes. This is the first known regional modelling study for PAHs over a North American domain and the first modelling study at any scale to compare alternative particle/gas partitioning schemes against paired field measurements. The goal of the study was to provide output concentration maps of use to assessing human inhalation exposure to PAHs in ambient air. Annual average modelled total (gas + particle) concentrations were statistically indistinguishable from measured values for fluoranthene, pyrene and benz[a]anthracene whereas the model underestimated concentrations of phenanthrene, anthracene and chrysene + triphenylene. Significance for benzo[a]pyrene performance was close to the statistical threshold and depended on the particle/gas partitioning scheme employed. On a day-to-day basis, the model simulated total PAH concentrations to the correct order of magnitude the majority of the time. The model showed seasonal differences in prediction quality for volatile species which suggests that a missing emission source such as air-surface exchange should be included in future versions. Model performance differed substantially between measurement locations and the limited available evidence suggests that the model's spatial resolution was too coarse to capture the distribution of concentrations in densely populated areas. A more detailed analysis of the factors influencing modelled particle/gas partitioning is warranted based on the findings in this study.

The effect of catastrophic collisional fragmentation and diffuse medium accretion on a computational interstellar dust system

NASA Technical Reports Server (NTRS)

Liffman, Kurt

1990-01-01

The effects of catastrophic collisional fragmentation and diffuse medium accretion on a the interstellar dust system are computed using a Monte Carlo computer model. The Monte Carlo code has as its basis an analytic solution of the bulk chemical evolution of a two-phase interstellar medium, described by Liffman and Clayton (1989). The model is subjected to numerous different interstellar processes as it transfers from one interstellar phase to another. Collisional fragmentation was found to be the dominant physical process that shapes the size spectrum of interstellar dust. It was found that, in the diffuse cloud phase, 90 percent of the refractory material is locked up in the dust grains, primarily due to accretion in the molecular medium. This result is consistent with the observed depletions of silicon. Depletions were found to be affected only slightly by diffuse cloud accretion.

Residue pattern of polycyclic aromatic hydrocarbons during green tea manufacturing and their transfer rates during tea brewing.

PubMed

Gao, Guanwei; Chen, Hongping; Liu, Pingxiang; Hao, Zhenxia; Ma, Guicen; Chai, Yunfeng; Wang, Chen; Lu, Chengyin

2017-06-01

Residues of polycyclic aromatic hydrocarbons (PAHs) in green tea and tea infusion were determined using gas chromatography-tandem mass spectrometry to study their dissipation pattern during green tea processing and infusion. Concentration and evaporation of PAHs during tea processing were the key factors affecting PAH residue content in product intermediates and in green tea. PAH residues in tea leaves increased by 2.4-3.1 times during the manufacture of green tea using the electric heating model. After correction to dry weight, PAH residue concentrations decreased by 33.5-48.4% during green tea processing because of PAH evaporation. Moreover, spreading and drying reduced PAH concentrations. The transfer rates of PAH residues from green tea to infusion varied from 4.6% to 7.2%, and PAH leaching was higher in the first infusion than in the second infusion. These results are useful for assessing exposure to PAHs from green tea and in formulating controls for the maximum residue level of PAHs in green tea.

Concentrations and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs (NPAHs) in the atmosphere of North China, and the transformation from PAHs to NPAHs.

PubMed

Lin, Yan; Qiu, Xinghua; Ma, Yiqiu; Ma, Jin; Zheng, Mei; Shao, Min

2015-01-01

The occurrence of polycyclic aromatic hydrocarbons (PAHs) and nitrated derivatives (NPAHs), as well as their transformation may have significant health impacts on humans. To investigate the level, spatial distribution and the transformation process of PAHs and NPAHs in North China, we performed a griddedfield passive air sampling campaign in summer of 2011. The median concentration of 25 PAH congeners and 13 NPAHs was 294 ng m(-3) (or 26.7 mg sample(-1)) and 203 ng sample(-1), respectively. Relative higher level of PAHs in Shanxi Province and NPAHs in megacities was observed. In North China, coal/biomass combustion and photochemical formation was the predominant source of PAHs and NPAHs, respectively.To investigate the relationship between these pollutants, a model incorporating NPAHs, PAHs and NO(2) was established, and the result indicated that NO(2) will promote the transformation processes from PAHs to NPAHs, which may increase the total toxicity of PAH-NPAH mixtures.

Laboratory Needs for Interstellar Ice Studies

NASA Astrophysics Data System (ADS)

Boogert, Abraham C. A.

2012-05-01

A large fraction of the molecules in dense interstellar and circumstellar environments is stored in icy grain mantles. The mantles are formed by a complex interplay between chemical and physical processes. Key questions on the accretion and desorption processes and the chemistry on the grain surfaces and within the icy mantles can only be answered by laboratory experiments. Recent infrared (2-30 micron) spectroscopic surveys of large samples of Young Stellar Objects (YSOs) and background stars tracing quiescent cloud material have shown that the ice band profiles and depths vary considerably as a function of environment. Using laboratory spectra in the identification process, it is clear that a rather complex mixture of simple species (CH3OH, CO2, H2O, CO) exists even in the quiescent cloud phase. Variations of the local physical conditions (CO freeze out) and time scales (CH3OH formation) appear to be key factors in the observed variations. Sublimation and thermal processing dominate as YSOs heat their environments. The identification of several ice absorption features is still disputed. I will outline laboratory work (e.g., on salts, PAHs, and aliphatic hydrocarbons) needed to further constrain the ice band identification as well as the thermal and chemical history of the carriers. Such experiments will also be essential to interpret future high spectral resolution SOFIA and JWST observations.

Properties of nearby interstellar hydrogen deduced from Lyman-alpha sky background measurements

NASA Technical Reports Server (NTRS)

Thomas, G. E.

1972-01-01

For a sufficiently rapid relative motion of the solar system and the nearby interstellar gas, neutral atoms may be expected to penetrate the heliosphere before becoming ionized. Recent satellite measurements of the Lyman alpha emission above the geocorona indicate such an interstellar wind of neutral hydrogen emerging from the direction of Sagittarius and reaching to within a few astronomical units of the sun. A detailed model of the scattering of solar Lyman alpha from the spatial distribution of neutral hydrogen in interplanetary space is presented. This asymmetric distribution is established by solar wind and solar ultraviolet ionization processes along the trajectories of the incoming hydrogen atoms. The values of the interstellar density, the relative velocity, and the gas temperature are adjusted to agree with the Lyman alpha measurements. The results may be interpreted in terms of two models, the cold model and the hot model of the interstellar gas, depending on whether galactic Lyman alpha emission is present at its maximum allowable value or negligibly small.

SILICATE COMPOSITION OF THE INTERSTELLAR MEDIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fogerty, S.; Forrest, W.; Watson, D. M.

2016-10-20

The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. An analysis of the well-known 9.7 μ m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modeled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modeling the optical depth alongmore » lines of sight toward the extinguished objects Cyg OB2 No. 12 and ζ Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as “polivene.” Finally, we compare these results to models of silicate emission from the Trapezium and protoplanetary disks in Taurus.« less

PAH concentrations simulated with the AURAMS-PAH chemical transport model over Canada and the USA

NASA Astrophysics Data System (ADS)

Galarneau, E.; Makar, P. A.; Zheng, Q.; Narayan, J.; Zhang, J.; Moran, M. D.; Bari, M. A.; Pathela, S.; Chen, A.; Chlumsky, R.

2013-07-01

The off-line Eulerian AURAMS chemical transport model was adapted to simulate the atmospheric fate of seven PAHs: phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene + triphenylene, and benzo[a]pyrene. The model was then run for the year 2002 with hourly output on a~grid covering southern Canada and the continental USA with 42 km horizontal grid spacing. Model predictions were compared to ~ 5000 24 h average PAH measurements from 45 sites, eight of which also provided data on particle/gas partitioning which had been modelled using two alternative schemes. This is the first known regional modelling study for PAHs over a North American domain and the first modelling study at any scale to compare alternative particle/gas partitioning schemes against paired field measurements. Annual average modelled total (gas + particle) concentrations were statistically indistinguishable from measured values for fluoranthene, pyrene and benz[a]anthracene whereas the model underestimated concentrations of phenanthrene, anthracene and chrysene + triphenylene. Significance for benzo[a]pyrene performance was close to the statistical threshold and depended on the particle/gas partitioning scheme employed. On a day-to-day basis, the model simulated total PAH concentrations to the correct order of magnitude the majority of the time. Model performance differed substantially between measurement locations and the limited available evidence suggests that the model spatial resolution was too coarse to capture the distribution of concentrations in densely populated areas. A more detailed analysis of the factors influencing modelled particle/gas partitioning is warranted based on the findings in this study.

Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM.

PubMed

Gomes, Rui B; Nogueira, Regina; Oliveira, José M; Peixoto, João; Brito, António G

2009-09-01

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin. Headspace SPME was used for analyzing PAH since the presence of a complex or dirty matrix in direct contact with the fiber may damage it. Four model PAHs-anthracene, fluorene, phenanthrene, and pyrene-were analyzed by GC-MS. Negligible depletion SPME technique was used to determine the free fraction. Total PAH was determined by enhancing the mass transfer from the bonded phase to the freely dissolved phase by temperature optimization and the use of the method of standard additions. The PAH absorption kinetics were determined in order to define the optimal sampling conditions for this method. The fitting of the experimental data to a mathematical model was accomplished using Berkeley Madonna software. Humic acid and silicon oil were used as model NOM and NAPL, respectively, to study the effect of these compounds on the decrease of SPME response. Then, the method was evaluated with wastewater from a fuel station spill retention basin. The SPME kinetic parameters-k (1) (uptake rate), k (2) (desorption rate), and K (SPME) (partition coefficient)-were determined from experimental data modeling. The determination of the free fraction required 15-min sampling to ensure that PAH depletion from sample was below 1%. For total PAH, a 30-min extraction at 100 degrees C ensured the maximum signal response in the GC-MS. For the determination of free and total PAHs, extractions were performed before reaching the SPME equilibrium. The wastewater used in this study had no free fraction of the analyzed PAHs. However, the four studied PAHs were found when the method for total PAH was used. The addition of NOM and NAPL dramatically decreased the efficiency of the SPME. This decrease was the result of a greater partition of the PAHs to the NAPL and NOM phases. This fact was also observed in the analysis of the fuel station spill retention basin, where no free PAH was measured. However, using the method of standard addition for the determination of total PAH, it was possible to quantify all four PAHs. The method developed in the present study was found to be adequate to differentiate between free and total PAH present in oily wastewater. It was determined that the presence of NOM and NAPL had a negative effect on SPME efficiency. The presence of binding substances had a great influence on SPME kinetics. Therefore, it is of extreme importance to determine their degree of interference when analyzing oily wastewaters or results can otherwise be erroneous. Other factors influencing the total PAH determinations should be considered in further studies.

Removal of polycyclic aromatic hydrocarbons in soil spiked with model mixtures of petroleum hydrocarbons and heterocycles using biosurfactants from Rhodococcus ruber IEGM 231.

PubMed

Ivshina, Irina; Kostina, Ludmila; Krivoruchko, Anastasiya; Kuyukina, Maria; Peshkur, Tatyana; Anderson, Peter; Cunningham, Colin

2016-07-15

Removal of polycyclic aromatic hydrocarbons (PAHs) in soil using biosurfactants (BS) produced by Rhodococcus ruber IEGM 231 was studied in soil columns spiked with model mixtures of major petroleum constituents. A crystalline mixture of single PAHs (0.63g/kg), a crystalline mixture of PAHs (0.63g/kg) and polycyclic aromatic sulfur heterocycles (PASHs), and an artificially synthesized non-aqueous phase liquid (NAPL) containing PAHs (3.00g/kg) dissolved in alkanes C10-C19 were used for spiking. Percentage of PAH removal with BS varied from 16 to 69%. Washing activities of BS were 2.5 times greater than those of synthetic surfactant Tween 60 in NAPL-spiked soil and similar to Tween 60 in crystalline-spiked soil. At the same time, amounts of removed PAHs were equal and consisted of 0.3-0.5g/kg dry soil regardless the chemical pattern of a model mixture of petroleum hydrocarbons and heterocycles used for spiking. UV spectra for soil before and after BS treatment were obtained and their applicability for differentiated analysis of PAH and PASH concentration changes in remediated soil was shown. The ratios A254nm/A288nm revealed that BS increased biotreatability of PAH-contaminated soils. Copyright © 2016 Elsevier B.V. All rights reserved.

Measurements of gas and particle polycyclic aromatic hydrocarbons (PAHs) in air at urban, rural and near-roadway sites

NASA Astrophysics Data System (ADS)

Pratt, G. C.; Herbrandson, C.; Krause, M. J.; Schmitt, C.; Lippert, C. J.; McMahon, C. R.; Ellickson, K. M.

2018-04-01

We measured polycyclic aromatic hydrocarbons (PAHs) in gas and particle phases over two years using high volume samplers equipped with quartz fiber filters and XAD-4 at a rural site, an urban site, and a site adjacent to a heavily trafficked roadway. Overall results were generally as expected, in that concentrations increased from rural to urban to near-roadway sites, and PAHs with high vapor pressures (liquid subcooled, PoL) and low octanol-air partition coefficients (Koa) were mainly in the gas phase, while those with low PoL and high Koa were predominantly in the particle phase. Intermediate PAHs existed in both phases with the phase distribution following a seasonal pattern of higher gas phase concentrations in summer due to temperature effects. The overall pattern of phase distribution was consistent with PAH properties and ambient conditions and was similar at all three sites. The particle-bound fraction (ϕ) was well-described empirically by nonlinear regressions with log Koa and log PoL as predictors. Adsorption and absorption models underestimated the particle-bound fraction for most PAHs. The dual aerosol-air/soot-air model generally represented the gas-particle partitioning better than the other models across all PAHs, but there was a tendency to underestimate the range in the particle-bound fraction seen in measurements. There was a statistically insignificant tendency for higher PAHs in the particle phase at the near roadway site, and one piece of evidence that PAHs may be enriched on ultrafine particles at the near roadway site. Understanding the phase and particle size distributions of PAHs in highly polluted, high exposure microenvironments near traffic sources will help shed light on potential health effects.

Hydrocarbons on Saturn's satellites Iapetus and Phoebe

USGS Publications Warehouse

Cruikshank, D.P.; Wegryn, E.; Dalle, Ore C.M.; Brown, R.H.; Bibring, J.-P.; Buratti, B.J.; Clark, R.N.; McCord, T.B.; Nicholson, P.D.; Pendleton, Y.J.; Owen, T.C.; Filacchione, G.; Coradini, A.; Cerroni, P.; Capaccioni, F.; Jaumann, R.; Nelson, R.M.; Baines, K.H.; Sotin, Christophe; Bellucci, G.; Combes, M.; Langevin, Y.; Sicardy, B.; Matson, D.L.; Formisano, V.; Drossart, P.; Mennella, V.

2008-01-01

Material of low geometric albedo (pV ??? 0.1) is found on many objects in the outer Solar System, but its distribution in the saturnian satellite system is of special interest because of its juxtaposition with high-albedo ice. In the absence of clear, diagnostic spectral features, the composition of this low-albedo (or "dark") material is generally inferred to be carbon-rich, but the form(s) of the carbon is unknown. Near-infrared spectra of the low-albedo hemisphere of Saturn's satellite Iapetus were obtained with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft at the fly-by of that satellite of 31 December 2004, yielding a maximum spatial resolution on the satellite's surface of ???65 km. The spectral region 3-3.6 ??m reveals a broad absorption band, centered at 3.29 ??m, and concentrated in a region comprising about 15% of the low-albedo surface area. This is identified as the C{single bond}H stretching mode vibration in polycyclic aromatic hydrocarbon (PAH) molecules. Two weaker bands attributed to {single bond}CH2{single bond} stretching modes in aliphatic hydrocarbons are found in association with the aromatic band. The bands most likely arise from aromatic and aliphatic units in complex macromolecular carbonaceous material with a kerogen- or coal-like structure, similar to that in carbonaceous meteorites. VIMS spectra of Phoebe, encountered by Cassini on 11 June 2004, also show the aromatic hydrocarbon band, although somewhat weaker than on Iapetus. The origin of the PAH molecular material on these two satellites is unknown, but PAHs are found in carbonaceous meteorites, cometary dust particles, circumstellar dust, and interstellar dust. ?? 2007 Elsevier Inc. All rights reserved.

Fullerenes in Allende Meteorite

NASA Technical Reports Server (NTRS)

Becker, L.; Bada, J. L.; Winans, R. E.; Bunch, T. E.

1994-01-01

The detection of fullerenes in deposits from meteor impacts has led to renewed interest in the possibility that fullerenes are present in meteorites. Although fullerenes have not previously been detected in the Murchison and Allende meteorites, the Allende meteorite is known to contain several well-ordered graphite particles which are remarkably similar in size and appearance to the fullerene-related structures carbon onions and nanotubes. We report that fullerenes are in fact present in trace amounts in the Allende meteorite. In addition to fullerenes, we detected many polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite, consistent with previous reports. In particular, we detected benzofluoranthene and corannulene (C20H10), five-membered ring structures which have been proposed as precursors to the formation of fullerene synthesis, perhaps within circumstellar envelopes or other sites in the interstellar medium.

The Formation of Complex Organic Compounds in Astrophysical Ices and their Implications for Astrobiology

NASA Technical Reports Server (NTRS)

Sandford, Scott A.

2015-01-01

Ices in astrophysical environments are generally dominated by very simple molecules like H2O, CH3OH, CH4, NH3, CO, CO2, etc, although they likely contain PAHs as well. These molecules, particularly H2O, are of direct interest to astrobiology in-and-of themselves since they represent some of the main carriers of the biogenic elements C, H, O, and N. In addition, these compounds are present in the dense interstellar clouds in which new stars and planetary systems are formed and may play a large role in the delivery of volatiles and organics to the surfaces of new planets. However, these molecules are all far simpler than the more complex organic compounds found in living systems.

Pore Water PAH Transport in Amended Sediment Caps

NASA Astrophysics Data System (ADS)

Gidley, P. T.; Kwon, S.; Ghosh, U.

2009-05-01

Capping is a common remediation strategy for contaminated sediments that creates a physical barrier between contaminated sediments and the water column. Diffusive flux of contaminants through a sediment cap is small. However, under certain hydrodynamic conditions such as groundwater potential and tidal pumping, groundwater advection can accelerate contaminant transport. Hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) could be transported through the cap under advective conditions. To better understand PAH migration under these conditions, physical models of sediment caps were evaluated in the laboratory through direct measurement of pore water using solid phase micro-extraction with gas chromatography and mass spectrometry. Contaminated sediment and capping material was obtained from an existing Superfund site that was capped at Eagle Harbor, Washington. A PAH dissolution model linked to an advection-dispersion equation with retardation using published organic carbon-water partitioning coefficients (Koc) was compared to measured PAHs in the sediment and cap porewater of the physical model.

Polycyclic aromatic hydrocarbons in model bacterial membranes - Langmuir monolayer studies.

PubMed

Broniatowski, Marcin; Binczycka, Martyna; Wójcik, Aneta; Flasiński, Michał; Wydro, Paweł

2017-12-01

High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. Copyright © 2017. Published by Elsevier B.V.

A screening level probabilistic ecological risk assessment of PAHs in sediments of San Francisco Bay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Febbo, E.J.; Arnold, W.R.; Biddinger, G.R.

1995-12-31

As part of the Regional Monitoring Program administered by the San Francisco Estuary Institute (SFEI), sediment samples were collected at 20 stations in San Francisco Bay and analyzed to determine concentrations of 43 PAHs. These data were obtained from SFEI and used to calculate the potential risk to aquatic organisms using probabilistic modeling and Monte Carlo statistical procedures. Sediment chemistry data were used in conjunction with a sediment equilibrium model, a bioconcentration model, biota-sediment accumulation factors, and critical body burden effects concentrations to assess potential risk to bivalves. Bivalves were the chosen receptors because they lack a well-developed enzymatic systemmore » for metabolizing PAHs. Thus, they more readily accumulate PAHs and represent a species at greater risk than other taxa, such as fish and crustaceans. PAHs considered in this study span a broad range of octanol-water partition coefficients. Results indicate that risk of non-polar narcotic effects from PAHs was low in the Northern Bay Area, but higher in the South Bay near the more urbanized sections of the drainage basin.« less

PAH sorption mechanism and partitioning behavior in lampblack-impacted soils from former oil-gas plant sites.

PubMed

Hong, Lei; Ghosh, Upal; Mahajan, Tania; Zare, Richard N; Luthy, Richard G

2003-08-15

This study assessed polycyclic aromatic hydrocarbon (PAH) association and aqueous partitioning in lampblack-impacted field soils from five sites in California that formerly housed oil-gas process operations. Lampblack is the solid residue resulting from the decomposition of crude oil at high temperatures in the gas-making operation and is coated or impregnated with oil gasification byproducts, among which PAHs are the compounds of the greatest regulatory concern. A suite of complementary measurements investigated the character of lampblack particles and PAH location and the associated effects on PAH partitioning between lampblack and water. PAH analyses on both whole samples and density-separated components demonstrated that 81-100% of PAHs in the lampblack-impacted soils was associated with lampblack particles. FTIR, 13C NMR, and SEM analyses showed that oil-gas lampblack solids comprise primarily aromatic carbon with soot-like structures. A free-phase aromatic oil may be present in some of the lampblack soils containing high PAH concentrations. Comparable long-term aqueous partitioning measurements were obtained with an air-bridge technique and with a centrifugation/alum flocculation procedure. Large solid/water partition coefficient (Kd) values were observed in samples exhibiting lower PAH and oil levels, whereas smaller Kd values were measured in lampblack samples containing high PAH levels. The former result is in agreement with an oil-soot partitioning model, and the latter is in agreement with a coal tar-water partitioning model. Lampblack containing high PAH levels appears to exhaust the sorption capacity of the soot-carbon, creating a free aromatic oil phase that exhibits partitioning behavior similar to PAHs in coal tar. This study improves mechanistic understanding of PAH sorption on aged lampblack residuals at former oil-gas sites and provides a framework for mechanistic assessment of PAH leaching potential and risk from such site materials.

High-energy Gamma Rays from the Milky Way: Three-dimensional Spatial Models for the Cosmic-Ray and Radiation Field Densities in the Interstellar Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Porter, T. A.; Moskalenko, I. V.; Jóhannesson, G., E-mail: tporter@stanford.edu

High-energy γ -rays of interstellar origin are produced by the interaction of cosmic-ray (CR) particles with the diffuse gas and radiation fields in the Galaxy. The main features of this emission are well understood and are reproduced by existing CR propagation models employing 2D galactocentric cylindrically symmetrical geometry. However, the high-quality data from instruments like the Fermi Large Area Telescope reveal significant deviations from the model predictions on few to tens of degrees scales, indicating the need to include the details of the Galactic spiral structure and thus requiring 3D spatial modeling. In this paper, the high-energy interstellar emissions frommore » the Galaxy are calculated using the new release of the GALPROP code employing 3D spatial models for the CR source and interstellar radiation field (ISRF) densities. Three models for the spatial distribution of CR sources are used that are differentiated by their relative proportion of input luminosity attributed to the smooth disk or spiral arms. Two ISRF models are developed based on stellar and dust spatial density distributions taken from the literature that reproduce local near- to far-infrared observations. The interstellar emission models that include arms and bulges for the CR source and ISRF densities provide plausible physical interpretations for features found in the residual maps from high-energy γ -ray data analysis. The 3D models for CR and ISRF densities provide a more realistic basis that can be used for the interpretation of the nonthermal interstellar emissions from the Galaxy.« less

PAH clearance after renal ischemia and reperfusion is a function of impaired expression of basolateral Oat1 and Oat3.

PubMed

Bischoff, Ariane; Bucher, Michael; Gekle, Michael; Sauvant, Christoph

2014-02-01

Determination of renal plasma flow (RPF) by para-aminohippurate (PAH) clearance leads to gross underestimation of this respective parameter due to impaired renal extraction of PAH after renal ischemia and reperfusion injury. However, no mechanistic explanation for this phenomenon is available. Based on our own previous studies we hypothesized that this may be due to impairment of expression of the basolateral rate limiting organic anion transporters Oat1 and Oat3. Thus, we investigated this phenomenon in a rat model of renal ischemia and reperfusion by determining PAH clearance, PAH extraction, PAH net secretion, and the expression of rOat1 and rOat3. PAH extraction was seriously impaired after ischemia and reperfusion which led to a threefold underestimation of RPF when PAH extraction ratio was not considered. PAH extraction directly correlated with the expression of basolateral Oat1 and Oat3. Tubular PAH secretion directly correlated with PAH extraction. Consequently, our data offer an explanation for impaired renal PAH extraction by reduced expression of the rate limiting basolateral organic anion transporters Oat1 and Oat3. Moreover, we show that determination of PAH net secretion is suitable to correct PAH clearance for impaired extraction after ischemia and reperfusion in order to get valid results for RPF.

Pollution status of polycyclic aromatic hydrocarbons in surface sediments from the Yangtze River Estuary and its adjacent coastal zone.

PubMed

Wang, Chenglong; Zou, Xinqing; Gao, Jianhua; Zhao, Yifei; Yu, Wenwen; Li, Yali; Song, Qiaochu

2016-11-01

Polycyclic aromatic hydrocarbons (PAHs) are mainly produced by incomplete combustion and are used as indicators of anthropogenic activities on the environment. This study analyses the PAHs level in the Yangtze River Estuary (YRE), an important component of Yangtze River and a developed and populated region in China. Surface sediments were collected from 77 sites at the YRE and its adjacent coastal zone (IACZ) for a comprehensive study of PAHs. Kriging interpolation technology and Positive matrix factorization (PMF) model were applied to explore the spatial distribution and sources of PAHs. Concentrations of 16 PAHs (ΣPAHs) varied from 27.2 ng g(-1) to 621.6 ng g(-1) dry weight, with an average value of 158.2 ng g(-1). Spatially, ΣPAHs exhibited wide fluctuation and exhibited an increasing tendency from north to south. In addition, ΣPAHs exhibited a decreasing trend with increasing distance between the estuary and IACZ. The deposition flux of PAHs indicated that more than 107.8 t a(-1) PAHs was deposited in the study area annually. The results of the PMF model revealed that anthropogenic activities were the main sources of PAHs in the study area. Vehicle emissions and marine engines were the most important sources and accounted for 40.9% of the pollution. Coal combustion, petrogenic sources, and wood combustion were other sources that contributed 23.9%, 23.6%, and 11.5%, respectively. The distribution patterns of PAHs in the YRE and IACZ were influenced by many complicated factors such as sediment grain size, hydrodynamics and so on. Copyright © 2016 Elsevier Ltd. All rights reserved.

Regional-scale simulation of transport and transformations of semi-volatile polycyclic aromatic hydrocarbons (PAHs) in East Asia: diurnal variations investigation

NASA Astrophysics Data System (ADS)

Mu, Qing; Lammel, Gerhard; Cheng, Yafang

2015-04-01

Semi-volatile PAHs are major pollutants of urban air, mostly regionally transported and reaching remote environments[1]. Some semi-volatile PAHs are carcinogenic. About 22% of global PAHs emissions are in China. The transport and sinks (atmospheric reactions, deposition) of semi-volatile PAHs in East Asia are studied using a modified version of the Weather Research and Forecasting model coupled with chemistry (WRF/Chem [2]). For this purpose, PAHs' gas and particulate phase chemical reactions and dry and wet deposition processes are included. We use emissions of 2008 [3] which include technical combustion processes (coal, oil, gas, waste and biomass) and open fires and apply diurnal time functions as those of black carbon. The model was run for phenanthrene (3-ring PAH, p = 1.5×10-2 Pa at 298 K) and benzo(a)pyrene (5-ring PAH, p = 7×10-7 Pa) for July 2013 with hourly output and 27 km horizontal grid spacing. The comparison of model predicted phenanthrene concentrations with measurements at a rural site near Beijing (own data, unpublished) validates the model's ability to simulate diurnal variations of gaseous PAHs. The model's performance is better in simulating day time than night time gaseous PAHs. The concentrations of PAHs had experienced significant diurnal variations in rural and remote areas of China. Elevated concentration levels of 40-60 ng m-3 for phenanthrene and 1-10 ng m-3 for benzo(a)pyrene are predicted in Shanxi, Guizhou, the North China Plain, the Sichuan Basin and Chongqing metropolitan areas due to the high emission densities at those locations. References [1] Keyte, I.J., Harrison, R.M., and Lammel, G., 2013: Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons - a review, Chem. Soc. Rev., 42, 9333-9391. [2] Grell, G.A, Peckham, S.E, Schmitz, R, McKeen, S.A, Frost, G, Skamarock, W.C, and Eder, B., 2005: Fully coupled online chemistry within the WRF model, Atmos. Environ., 39, 6957-6975. [3] Shen, H. Z., Huang, Y., Wang, R., Zhu, D., Li, W., Shen, G. F., Wang, B., Zhang, Y. Y., Chen, Y. C., Lu, Y., Chen, H., Li, T. C., Sun, K., Li, B. G., Liu, W. X., Liu, J. F., and Tao, S., 2013: Global atmospheric emissions of polycyclic aromatic hydrocarbons from 1960 to 2008 and future predictions, Environ. Sci. Technol., 47, 6415-6424.

Heating of the Interstellar Diffuse Ionized Gas via the Dissipation of Turbulence

NASA Astrophysics Data System (ADS)

Minter, Anthony H.; Spangler, Steven R.

1997-08-01

We have recently published observations that specify most of the turbulent and mean plasma characteristics for a region of the sky containing the interstellar diffuse ionized gas (DIG). These observations have provided virtually all of the information necessary to calculate the heating rate from dissipation of turbulence. We have calculated the turbulent dissipation heating rate employing two models for the interstellar turbulence. The first is a customary modeling as a superposition of magnetohydrodynamic waves. The second is a fluid-turbulence-like model based on the ideas of Higdon. This represents the first time that such calculations have been carried out with full and specific interstellar turbulence parameters. The wave model of interstellar turbulence encounters the severe difficulty that plausible estimates of heating by Landau damping exceed the radiative cooling capacity of the interstellar DIG by 3-4 orders of magnitude. Clearly interstellar turbulence does not behave like an ensemble of obliquely propagating fast magnetosonic waves. The heating rate due to two other wave dissipation mechanisms, ion-neutral collisional damping and the parametric decay instability, are comparable to the cooling capacity of the diffuse ionized medium. We find that the fluid-like turbulence model is an acceptable and realistic model of the turbulence in the interstellar medium once the effects of ion-neutral collisions are included in the model. This statement is contingent on an assumption that the dissipation of such turbulence because of Landau damping is several orders of magnitude less than that from an ensemble of obliquely propagating magnetosonic waves with the same energy density. Arguments as to why this may be the case are made in the paper. Rough parity between the turbulent heating rate and the radiative cooling rate in the DIG also depends on the hydrogen ionization fraction being in excess of 90% or on a model-dependent lower limit to the heating rate being approximately valid. We conclude that the dissipation of turbulence is capable of providing a substantial and perhaps major contribution to the energy budget of the diffuse ionized medium.

Biodegradation of PAHs and PCBs in soils and sludges

USGS Publications Warehouse

Liu, L.; Tindall, J.A.; Friedel, M.J.

2007-01-01

Results from a multi-year, pilot-scale land treatment project for PAHs and PCBs biodegradation were evaluated. A mathematical model, capable of describing sorption, sequestration, and biodegradation in soil/water systems, is applied to interpret the efficacy of a sequential active-passive biotreatment process of organic chemicals on remediation sites. To account for the recalcitrance of PAHs and PCBs in soils and sludges during long-term biotreatment, this model comprises a kinetic equation for organic chemical intraparticle sequestration process. Model responses were verified by comparison to measurements of biodegradation of PAHs and PCBs in land treatment units; a favorable match was found between them. Model simulations were performed to predict on-going biodegradation behavior of PAHs and PCBs in land treatment units. Simulation results indicate that complete biostabilization will be achieved when the concentration of reversibly sorbed chemical (S RA) reduces to undetectable levels, with a certain amount of irreversibly sequestrated residual chemical (S IA) remaining within the soil particle solid phase. The residual fraction (S IA) tends to lose its original chemical and biological activity, and hence, is much less available, toxic, and mobile than the "free" compounds. Therefore, little or no PAHs and PCBs will leach from the treatment site and constitutes no threat to human health or the environment. Biotreatment of PAHs and PCBs can be terminated accordingly. Results from the pilot-scale testing data and model calculations also suggest that a significant fraction (10-30%) of high-molecular-weight PAHs and PCBs could be sequestrated and become unavailable for biodegradation. Bioavailability (large K d , i.e., slow desorption rate) is the key factor limiting the PAHs degradation. However, both bioavailability and bioactivity (K in Monod kinetics, i.e., number of microbes, nutrients, and electron acceptor, etc.) regulate PCBs biodegradation. The sequential active-passive biotreatment can be a cost-effective approach for remediation of highly hydrophobic organic contaminants. The mathematical model proposed here would be useful in the design and operation of such organic chemical biodegradation processes on remediation sites. ?? 2007 Springer Science+Business Media B.V.

The physics of interstellar shock waves

NASA Technical Reports Server (NTRS)

Shull, J. Michael; Draine, Bruce T.

1987-01-01

This review discusses the observations and theoretical models of interstellar shock waves, in both diffuse cloud and molecular cloud environments. It summarizes the relevant gas dynamics, atomic, molecular and grain processes, radiative transfer, and physics of radiative and magnetic precursors in shock models. It then describes the importance of shocks for observations, diagnostics, and global interstellar dynamics. It concludes with current research problems and data needs for atomic, molecular and grain physics.

Source apportionment of chlorinated polycyclic aromatic hydrocarbons associated with ambient particles in a Japanese megacity

PubMed Central

Kamiya, Yuta; Iijima, Akihiro; Ikemori, Fumikazu; Okuda, Tomoaki; Ohura, Takeshi

2016-01-01

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are novel species of environmental contaminants whose possible sources remain unclear. The occurrence of ClPAHs within total suspended particles (TSP) is compared with weekly air samples at two sites of differing characteristics (industrial and residential) in the megacity of Nagoya, Japan. Samples were collected over 12 months during 2011–2012. All 24 species of targeted ClPAHs were detected at both industrial and residential sites, where mean concentrations of total ClPAHs in TSP were 20.7 and 14.1 pg/m3, respectively. High concentrations at the industrial site were frequently observed during winter, suggesting potent seasonal ClPAH sources there. Positive matrix factorization modeling of particulate ClPAH source identification and apportioning were conducted for datasets including ClPAHs, PAHs, elements and ions, plus elemental carbons in TSP. Eight factors were identified as possible ClPAH sources, with estimates that the dominant one was a specific source of ClPAH emission (31%), followed by traffic (23%), photodegradable and semi-volatile species (18%), long-range transport (11%), and industry and oil combustion (10%). Source contributions of ClPAHs differed substantially from those of PAHs. This suggests specific and/or potent ClPAH sources in the local area, and that the production mechanisms between ClPAHs and PAHs are substantially different. PMID:27922081

Assessing the polycyclic aromatic hydrocarbon (PAH) pollution of urban stormwater runoff: a dynamic modeling approach.

PubMed

Zheng, Yi; Lin, Zhongrong; Li, Hao; Ge, Yan; Zhang, Wei; Ye, Youbin; Wang, Xuejun

2014-05-15

Urban stormwater runoff delivers a significant amount of polycyclic aromatic hydrocarbons (PAHs), mostly of atmospheric origin, to receiving water bodies. The PAH pollution of urban stormwater runoff poses serious risk to aquatic life and human health, but has been overlooked by environmental modeling and management. This study proposed a dynamic modeling approach for assessing the PAH pollution and its associated environmental risk. A variable time-step model was developed to simulate the continuous cycles of pollutant buildup and washoff. To reflect the complex interaction among different environmental media (i.e. atmosphere, dust and stormwater), the dependence of the pollution level on antecedent weather conditions was investigated and embodied in the model. Long-term simulations of the model can be efficiently performed, and probabilistic features of the pollution level and its risk can be easily determined. The applicability of this approach and its value to environmental management was demonstrated by a case study in Beijing, China. The results showed that Beijing's PAH pollution of road runoff is relatively severe, and its associated risk exhibits notable seasonal variation. The current sweeping practice is effective in mitigating the pollution, but the effectiveness is both weather-dependent and compound-dependent. The proposed modeling approach can help identify critical timing and major pollutants for monitoring, assessing and controlling efforts to be focused on. The approach is extendable to other urban areas, as well as to other contaminants with similar fate and transport as PAHs. Copyright © 2014 Elsevier B.V. All rights reserved.

Are urinary PAHs biomarkers of controlled exposure to diesel exhaust?

PubMed Central

Lu, Sixin S.; Sobus, Jon R.; Sallsten, Gerd; Albin, Maria; Pleil, Joachim D.; Gudmundsson, Anders; Madden, Michael C.; Strandberg, Bo; Wierzbicka, Aneta; Rappaport, Stephen M.

2016-01-01

Urinary polycyclic aromatic hydrocarbons (PAHs) were evaluated as possible biomarkers of exposure to diesel exhaust (DE) in two controlled-chamber studies. We report levels of 14 PAHs from 28 subjects in urine that were collected before, immediately after and the morning after exposure. Using linear mixed-effects models, we tested for effects of DE exposure and several covariates (time, age, gender and urinary creatinine) on urinary PAH levels. DE exposures did not significantly alter urinary PAH levels. We conclude that urinary PAHs are not promising biomarkers of short-term exposures to DE in the range of 106–276 μg/m3. PMID:24754404

Photodissociation Regions in the Interstellar Medium of Galaxies

NASA Technical Reports Server (NTRS)

Hollenbach, David J.; Tielens, A. G. G. M.; DeVincenzi, Donald L. (Technical Monitor)

1999-01-01

The interstellar medium of galaxies is the reservoir out of which stars are born and into which stars inject newly created elements as they age. The physical properties of the interstellar medium are governed in part by the radiation emitted by these stars. Far-ultraviolet (6 eV less than h(nu) less than 13.6 eV) photons from massive stars dominate the heating and influence the chemistry of the neutral atomic gas and much of the molecular gas in galaxies. Predominantly neutral regions of the interstellar medium in which the heating and chemistry are regulated by far ultraviolet photons are termed Photo-Dissociation Regions (PDRs). These regions are the origin of most of the non-stellar infrared (IR) and the millimeter and submillimeter CO emission from galaxies. The importance of PDRs has become increasingly apparent with advances in IR and submillimeter astronomy. The IR emission from PDRs includes fine structure lines of C, C+, and O; rovibrational lines of H2, rotational lines of CO; broad middle features of polycyclic aromatic hydrocarbons; and a luminous underlying IR continuum from interstellar dust. The transition of H to H2 and C+ to CO occurs within PDRs. Comparison of observations with theoretical models of PDRs enables one to determine the density and temperature structure, the elemental abundances, the level of ionization, and the radiation field. PDR models have been applied to interstellar clouds near massive stars, planetary nebulae, red giant outflows, photoevaporating planetary disks around newly formed stars, diffuse clouds, the neutral intercloud medium, and molecular clouds in the interstellar radiation field-in summary, much of the interstellar medium in galaxies. Theoretical PDR models explain the observed correlations of the [CII] 158 microns with the COJ = 1-0 emission, the COJ = 1-0 luminosity with the interstellar molecular mass, and the [CII] 158 microns plus [OI] 63 microns luminosity with the IR continuum luminosity. On a more global scale, MR models predict the existence of two stable neutral phases of the interstellar medium, elucidate the formation and destruction of star-forming molecular clouds, and suggest radiation-induced feedback mechanisms that may regulate star formation rates and the column density of gas through giant molecular clouds.

Is received dose from ingested soil independent of soil PAH concentrations?-Animal model results.

PubMed

Peters, Rachel E; James, Kyle; Cave, Mark; Wickstrom, Mark; Siciliano, Steven D

2016-09-01

Polycyclic aromatic hydrocarbon (PAH) bioavailability from ingested soils will vary between soils; however, the nature of this variation is not well characterized. A juvenile swine model was used to link external exposure to internal benzo[a]pyrene (BaP) and anthracene exposure following oral PAH ingestion of 27 different impacted site soils, soots, or spiked artificial soils. Internal exposure of BaP and anthracene, represented by area under the plasma-time curve, did not relate to soil concentration in impacted site soils, but did relate in spiked artificial soil. Point of departure modeling identified soil PAH concentrations greater than 1900 mg kg(-1) as the point where area under the curve becomes proportional to external dose. A BaP internal exposure below 1900 mg kg(-1) had an upper 95% confidence interval estimate of 33% of external exposure. Weak relationships between soil:simulated gastrointestinal fluid PAH partitioning and area under the curve values suggest that differences in internal PAH exposure between soils may not be dominated by differences in PAH partitioning. The data seem to best support exposure assessment assuming constant internal PAH exposure below soil concentrations of 1900 mg kg(-1) . However, because constant internal exposure would challenge several existing paradigms, a bioavailability estimate of 33% of the external exposure is suggested as a likely workable solution. Environ Toxicol Chem 2016;35:2261-2269. © 2016 SETAC. © 2016 SETAC.

Time-dependent MHD modeling of the global structure of the heliosphere

NASA Technical Reports Server (NTRS)

Liewer, P. C.; Brackbill, J. U.; Karmesin, S. Roy

1995-01-01

We present results from time-dependent modeling of the global structure of the heliosphere with neutral and magnetic field effects included. The magnetic field is assumed parallel to the interstellar flow in this two-dimensional axisymmetric model; the neutrals are treated as a fluid. The effects of interstellar neutrals and the interplanetary magnetic field on the location of the termination shock are studied using the most recent estimate of the interstellar medium parameters, results will be compared to those of Baranov and Zaitsev. The effect of the solar wind - VLISM interaction on the density and velocity of interstellar neutrals within the heliosphere will also be presented and related to observations. The response of the termination shock to the solar cycle variation in the solar wind will be compared to the response found previously using an axisymmetric hydrodynamic model without neutrals.

Development of a high resolution interstellar dust engineering model - overview of the project

NASA Astrophysics Data System (ADS)

Sterken, V. J.; Strub, P.; Soja, R. H.; Srama, R.; Krüger, H.; Grün, E.

2013-09-01

Beyond 3 AU heliocentric distance, the flow of interstellar dust through the solar system is a dominant component of the total dust population. The modulation of this flux with the solar cycle and the position in the solar system has been predicted by theoretical studies since the seventies. The modulation was proven to exist by matching dust trajectory simulations with real spacecraft data from Ulysses in 1998. The modulations were further analyzed and studies in detail in 2012. The current ESA interplanetary meteoroid model IMEM includes an interstellar dust component, but this component was modelled only with straight line trajectories through the solar system. For the new ESA IMEX model, a high-resolution interstellar dust component is implemented separately from a dust streams module. The dust streams module focuses on dust in streams that was released from comets (cf. Abstract R. Soja). Parallel processing techniques are used to improve computation time (cf. Abstract P. Strub). The goal is to make predictions for the interstellar dust flux as close to the Sun as 1 AU or closer, for future space mission design.

Stochastic and Deterministic Approaches to Gas-grain Modeling of Interstellar Sources

NASA Astrophysics Data System (ADS)

Vasyunin, Anton; Herbst, Eric; Caselli, Paola

During the last decade, our understanding of the chemistry on surfaces of interstellar grains has been significantly enchanced. Extensive laboratory studies have revealed complex structure and dynamics in interstellar ice analogues, thus making our knowledge much more detailed. In addition, the first qualitative investigations of new processes were made, such as non-thermal chemical desorption of species from dust grains into the gas. Not surprisingly, the rapid growth of knowledge about the physics and chemistry of interstellar ices led to the development of a new generation of astrochemical models. The models are typically characterized by more detailed treatments of the ice physics and chemistry than previously. The utilized numerical approaches vary greatly from microscopic models, in which every single molecule is traced, to ``mean field'' macroscopic models, which simulate the evolution of averaged characteristics of interstellar ices, such as overall bulk composition. While microscopic models based on a stochastic Monte Carlo approach are potentially able to simulate the evolution of interstellar ices with an account of most subtle effects found in a laboratory, their use is often impractical due to limited knowledge about star-forming regions and huge computational demands. On the other hand, deterministic macroscopic models that often utilize kinetic rate equations are computationally efficient but experience difficulties in incorporation of such potentially important effects as ice segregation or discreteness of surface chemical reactions. In my talk, I will review the state of the art in the development of gas-grain astrochemical models. I will discuss how to incorporate key features of ice chemistry and dynamics in the gas-grain astrochemical models, and how the incorporation of recent laboratory findings into gas-grain models helps to better match observations.

The Charge State of Polycyclic Aromatic Hydrocarbons Across Reflection Nebulae: PAH Charge Balance and Calibration

NASA Astrophysics Data System (ADS)

Boersma, C.; Bregman, J.; Allamandola, L. J.

2016-11-01

Low-resolution Spitzer spectral map data (>1700 spectra) of ten reflection nebulae (RNe) fields are analyzed using the data and tools available through the NASA Ames PAH IR Spectroscopic Database. The PAH emission is broken down into PAH charge state using a database fitting approach. Here, the physics of the PAH emission process is taken into account and uses target appropriate parameters, e.g., a stellar radiation model for the exciting star. The breakdown results are combined with results derived using the traditional PAH band strength approach, which interprets particular PAH band strength ratios as proxies for the PAH charge state, e.g., the 6.2/11.2 μm PAH band strength ratio. These are successfully calibrated against their database equivalent; the PAH ionized fraction (f I ). The PAH ionized fraction is converted into the PAH ionization parameter, which relates the PAH ionized fraction to the strength of the radiation field, gas temperature and electron density. The behavior of the 12.7 μm PAH band is evaluated as a tracer for PAH ionization and erosion. The plot of the 8.6 versus 11.2 μm PAH band strength for the northwest photo-dominated region (PDR) in NGC 7023 is shown to be a robust diagnostic template for the PAH ionized fraction. Remarkably, most of the other RNe fall within the limits set by NGC 7023. Finally, PAH spectroscopic templates are constructed and verified as principal components. Template spectra derived from NGC 7023 and NGC 2023 compare extremely well with each other, with those derived for NGC 7023 successfully reproducing the PAH emission observed from NGC 2023.

THE CHARGE STATE OF POLYCYCLIC AROMATIC HYDROCARBONS ACROSS REFLECTION NEBULAE: PAH CHARGE BALANCE AND CALIBRATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boersma, C.; Bregman, J.; Allamandola, L. J., E-mail: Christiaan.Boersma@nasa.gov

Low-resolution Spitzer spectral map data (>1700 spectra) of ten reflection nebulae (RNe) fields are analyzed using the data and tools available through the NASA Ames PAH IR Spectroscopic Database. The PAH emission is broken down into PAH charge state using a database fitting approach. Here, the physics of the PAH emission process is taken into account and uses target appropriate parameters, e.g., a stellar radiation model for the exciting star. The breakdown results are combined with results derived using the traditional PAH band strength approach, which interprets particular PAH band strength ratios as proxies for the PAH charge state, e.g.,more » the 6.2/11.2 μ m PAH band strength ratio. These are successfully calibrated against their database equivalent; the PAH ionized fraction ( f {sub i} ). The PAH ionized fraction is converted into the PAH ionization parameter, which relates the PAH ionized fraction to the strength of the radiation field, gas temperature and electron density. The behavior of the 12.7 μ m PAH band is evaluated as a tracer for PAH ionization and erosion. The plot of the 8.6 versus 11.2 μ m PAH band strength for the northwest photo-dominated region (PDR) in NGC 7023 is shown to be a robust diagnostic template for the PAH ionized fraction. Remarkably, most of the other RNe fall within the limits set by NGC 7023. Finally, PAH spectroscopic templates are constructed and verified as principal components. Template spectra derived from NGC 7023 and NGC 2023 compare extremely well with each other, with those derived for NGC 7023 successfully reproducing the PAH emission observed from NGC 2023.« less

Collisional excitation of molecules in dense interstellar clouds

NASA Technical Reports Server (NTRS)

Green, S.

1985-01-01

State transitions which permit the identification of the molecular species in dense interstellar clouds are reviewed, along with the techniques used to calculate the transition energies, the database on known molecular transitions and the accuracy of the values. The transition energies cannot be measured directly and therefore must be modeled analytically. Scattering theory is used to determine the intermolecular forces on the basis of quantum mechanics. The nuclear motions can also be modeled with classical mechanics. Sample rate constants are provided for molecular systems known to inhabit dense interstellar clouds. The values serve as a database for interpreting microwave and RF astrophysical data on the transitions undergone by interstellar molecules.

Emissions databases for polycyclic aromatic compounds in the Canadian Athabasca oil sands region - development using current knowledge and evaluation with passive sampling and air dispersion modelling data

NASA Astrophysics Data System (ADS)

Qiu, Xin; Cheng, Irene; Yang, Fuquan; Horb, Erin; Zhang, Leiming; Harner, Tom

2018-03-01

Two speciated and spatially resolved emissions databases for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region (AOSR) were developed. The first database was derived from volatile organic compound (VOC) emissions data provided by the Cumulative Environmental Management Association (CEMA) and the second database was derived from additional data collected within the Joint Canada-Alberta Oil Sands Monitoring (JOSM) program. CALPUFF modelling results for atmospheric polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes (DBTs), obtained using each of the emissions databases, are presented and compared with measurements from a passive air monitoring network. The JOSM-derived emissions resulted in better model-measurement agreement in the total PAH concentrations and for most PAH species concentrations compared to results using CEMA-derived emissions. At local sites near oil sands mines, the percent error of the model compared to observations decreased from 30 % using the CEMA-derived emissions to 17 % using the JOSM-derived emissions. The improvement at local sites was likely attributed to the inclusion of updated tailings pond emissions estimated from JOSM activities. In either the CEMA-derived or JOSM-derived emissions scenario, the model underestimated PAH concentrations by a factor of 3 at remote locations. Potential reasons for the disagreement include forest fire emissions, re-emissions of previously deposited PAHs, and long-range transport not considered in the model. Alkylated PAH and DBT concentrations were also significantly underestimated. The CALPUFF model is expected to predict higher concentrations because of the limited chemistry and deposition modelling. Thus the model underestimation of PACs is likely due to gaps in the emissions database for these compounds and uncertainties in the methodology for estimating the emissions. Future work is required that focuses on improving the PAC emissions estimation and speciation methodologies and reducing the uncertainties in VOC emissions which are subsequently used in PAC emissions estimation.

A New Model for Allosteric Regulation of Phenylalanine Hydroxylase: Implications for Disease and Therapeutics

PubMed Central

Stith, Linda; Lawrence, Sarah H.; Andrake, Mark; Dunbrack, Roland L.

2013-01-01

The structural basis for allosteric regulation of phenylalanine hydroxylase (PAH), whose dysfunction causes phenylketonuria (PKU), is poorly understood. A new morpheein model for PAH allostery is proposed to consist of a dissociative equilibrium between two architecturally different tetramers whose interconversion requires a ~90° rotation between the PAH catalytic and regulatory domains, the latter of which contains an ACT domain. This unprecedented model is supported by in vitro data on purified full length rat and human PAH. The conformational change is both predicted to and shown to render the tetramers chromatographically separable using ion exchange methods. One novel aspect of the activated tetramer model is an allosteric phenylalanine binding site at the inter-subunit interface of ACT domains. Amino acid ligand-stabilized ACT domain dimerization follows the multimerization and ligand binding behavior of ACT domains present in other proteins in the PDB. Spectroscopic, chromatographic, and electrophoretic methods demonstrate a PAH equilibrium consisting of two architecturally distinct tetramers as well as dimers. We postulate that PKU-associated mutations may shift the PAH quaternary structure equilibrium in favor of the low activity assemblies. Pharmacological chaperones that stabilize the ACT:ACT interface can potentially provide PKU patients with a novel small molecule therapeutic. PMID:23296088

Elucidating the urban levels, sources and health risks of polycyclic aromatic hydrocarbons (PAHs) in Pakistan: Implications for changing energy demand.

PubMed

Hamid, Naima; Syed, Jabir Hussain; Junaid, Muhammad; Mahmood, Adeel; Li, Jun; Zhang, Gan; Malik, Riffat Naseem

2018-04-01

Due to the severe fuel crisis in terms of natural gas, a paradigm shift in fuel combustion (diesel, gasoline, and biomass) may increase the atmospheric emissions and associated health risks in Pakistan. Present study was aimed to investigate the concentration of fugitive PAHs in the environment (outdoor and indoor settings), associated probabilistic health risk assessment in the exposed population, and possible linkage between fuel consumption patterns and PAHs emissions in twin cities (Rawalpindi and Islamabad) of Pakistan. Results showed that the mean PAHs concentrations (air: 2390pgm -3 ; dust: 167ngg -1 ) in the indoor environment were higher than that of the outdoor environment (air: 2132pgm -3 ; dust: 90.0ngg -1 ). Further, the source apportionment PCA-MLR receptor model identified diesel and gasoline combustion as the primary PAHs sources in the urban and sub-urban settings. Estimated life cancer risk (LCR) potential via inhalation to indoor PAHs was higher with a probability of 2.0 cases per 10,000 inhabitants as compared to outdoor exposure. Incremental lifetime cancer risk (ILCR) model from exposure to dust bound PAHs showed risk in the order of ingestion>dermal>inhalation for various exposure pathways. Likewise, estimated daily intake (EDI) model reflects that PAHs in surface dust enter into the human body mainly through the respiratory system because EDI for breathing was reported higher than that of oral intake. Therefore, adoption of sustainable fuels is recommended to meet the energy requirements and to reduce PAHs emissions and related health risks in the twin cities of Pakistan. Copyright © 2017 Elsevier B.V. All rights reserved.

Theoretical Modeling of Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Charnley, Steven

2009-01-01

The chemistry of complex interstellar organic molecules will be described. Gas phase processes that may build large carbon-chain species in cold molecular clouds will be summarized. Catalytic reactions on grain surfaces can lead to a large variety of organic species, and models of molecule formation by atom additions to multiply-bonded molecules will be presented. The subsequent desorption of these mixed molecular ices can initiate a distinctive organic chemistry in hot molecular cores. The general ion-molecule pathways leading to even larger organics will be outlined. The predictions of this theory will be compared with observations to show how possible organic formation pathways in the interstellar medium may be constrained. In particular, the success of the theory in explaining trends in the known interstellar organics, in predicting recently-detected interstellar molecules, and, just as importantly, non-detections, will be discussed.

Dust evolution, a global view I. Nanoparticles, nascence, nitrogen and natural selection … joining the dots

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

The role and importance of nanoparticles for interstellar chemistry and beyond is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), focusing on their active surface chemistry, the effects of nitrogen doping and the natural selection of interesting nanoparticle sub-structures. Nanoparticle-driven chemistry, and in particular the role of intrinsic epoxide-type structures, could provide a viable route to the observed gas phase OH in tenuous interstellar clouds en route to becoming molecular clouds. The aromatic-rich moieties present in asphaltenes probably provide a viable model for the structures present within aromatic-rich interstellar carbonaceous grains. The observed doping of such nanoparticle structures with nitrogen, if also prevalent in interstellar dust, could perhaps have important and observable consequences for surface chemistry and the formation of precursor pre-biotic species.

The gas/particle partitioning of nitro- and oxy-polycyclic aromatic hydrocarbons in the atmosphere of northern China

NASA Astrophysics Data System (ADS)

Li, Wei; Shen, Guofeng; Yuan, Chenyi; Wang, Chen; Shen, Huizhong; Jiang, Huai; Zhang, Yanyan; Chen, Yuanchen; Su, Shu; Lin, Nan; Tao, Shu

2016-05-01

The gas/particle partitioning of nitro-polycyclic aromatic hydrocarbons (nPAHs) and oxy-PAHs (oPAHs) is pivotal to estimate their environmental fate. Simultaneously measured atmospheric concentrations of nPAHs and oPAHs in both gaseous and particulate phases at 18 sites in northern China make it possible to investigate their partitioning process in a large region. The gas/particle partitioning coefficients (Kp) in this study were higher than those measured in the emission exhausts. The Kp for most individual nPAHs was higher than those for their corresponding parent PAHs. Generally higher Kp values were found at rural field sites compared to values in the rural villages and cities. Temperature, subcooled liquid-vapor pressure (Pl0) and octanol-air partition coefficient (Koa) were all significantly correlated with Kp. The slope values between log Kp and log Pl0, ranging from - 0.54 to - 0.34, indicate that the equilibrium of gas/particle partitioning might not be reached, which could be also revealed from a positive correlation between log Kp and particulate matter (PM) concentrations. Underestimation commonly exists in all three partitioning models, but the predicted values of Kp from the dual model are closer to the measured Kp for derivative PAHs in northern China.

Polycyclic aromatic hydrocarbon contamination in stormwater detention pond sediments in coastal South Carolina.

PubMed

Weinstein, John E; Crawford, Kevin D; Garner, Thomas R

2010-03-01

The purpose of this study was to characterize the polycyclic aromatic hydrocarbon (PAH) contamination in the sediments of stormwater detention ponds in coastal South Carolina. Levels of the sum of PAH analytes were significantly higher in the sediments of commercial ponds compared to that of reference, golf course, low-density residential, and high-density residential ponds. Isomer ratio analysis suggested that the predominant source of PAHs were pyrogenic; however, many ponds had a PAH signature consistent with mixed uncombusted and combusted PAH sources. PAH levels in these sediments could be modeled using both pond drainage area and pond surface area. These results demonstrate that the sediment from most commercial ponds, and a few residential and golf course ponds, were moderately contaminated with PAHs. PAH levels in these contaminated ponds exceeded between 42% and 75% of the ecological screening values for individual PAH analytes established by US EPA Region IV, suggesting that they may pose a toxicological risk to wildlife.

From simple to complex prebiotic chemistry in a carbon-rich universe

NASA Astrophysics Data System (ADS)

Lage, C.; Janot-Pacheco, E.; Domiciano de Souza, A.; Suárez, O.; Bendjoya, P.; Gadotti, D. A.

2012-09-01

It is well known that the main components of important biomolecules are quite common not only in the Solar System, but also in other planetary systems and in the Galactic ISM. The ubiquitous presence of C in the Universe and the unique carbon chemical properties and carbon bonding thermodynamics supports the spontaneous self-replication of monomers into larger polymers, yielding the formation of large molecules. The detection of an ever increasing number of organic molecules in the interstellar medium (ISM) by radio-telescopes and chemical analysis of meteorites boosted astrochemical theories on radiation-induced chemistry, supported by laboratory experiments. In this scenario of exogenous origin of carbon compounds, polyaromatic hydrocarbons (PAHs) may represent a resilient way of accumulating carbon as a robust cosmic reservoir. Consisting of a family of compounds with fused aromatic rings, the abundances of its larger members (50-100 carbon atoms) were estimated to be on top scores just after H2 and CO. PAHs have been detected in the ISM, in star-forming regions, ~14% of low-mass premainsequence stars, and, remarkably, in some 54% of intermediate mass stars. They have also been detected by SPITZER in distant galaxies up to z = 3. PAHs were promptly photolysed into a family of radicals if exposed to UV and oxygen-bearing molecules in laboratory. The presence of oxygenbearing molecules was shown in the laboratory to bring aromatic rings into an unstable chemistry leading to the production of e.g. alcohols, ketones and ether radicals. It has already been observed that carbon-and oxygen-rich stellar envelopes give rise to richer carbon chemistry. It appears very tempting to think that key prebiotic fragments should appear along planetary formation as C-O reaction byproducts such as methanol (CH3OH), formaldehyde (H2CO) and also simpler hydrocarbons as methyl acetylene (CH3CCH). Under an Astrobiology perspective it is plausible to map PAHs and oxygen compounds together in the same target - envelopes of young stars - with the ALMA facility. We intend to do it in the frame of a CNRS funded international collaboration between Brazilian groups, OCA and ESO.

Simulation of polycyclic aromatic hydrocarbons transport in multimedia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, L.; Chu, C.J.

1999-07-01

Many studies have indicated that the threat from toxic air pollutants such as VOCs comes not through inhalation by humans while the pollutants are in a gaseous state but through absorption when the pollutants are in a solid state such as in an aerosol or particulate form. Pollutants such as Polycyclic Aromatic Hydrocarbons (PAHs) usually exist in a semi-volatile state. To assess the risk of the PAHs, one needs to estimate the dose of the pollutants to which a human would be exposed through various pathways. In this study, the authors modified a Spatial Multimedia Compartmental Model (SMCM) originally developedmore » by UCLA Professor Cohen to predict the PAHs distribution among multimedia such as air, water, soil and sediment in the Taipei metropolitan area. Three PAHs were considered in this study. They are Benzo(a)pyrene, Pyrene and Chrysene. When PAHs are emitted into atmosphere, physical and chemical mechanisms may redistribute the PAHs among multimedia. Five cases of PAHs distribution in multimedia were simulated: (1) PAHs distribution in a dry condition, (2) PAHs distribution when there are different dry deposition velocities, (3) PAHs distribution under a single rainfall event, (4) PAHs distribution when there are different soil properties, (5) PAHs distribution under a random rainfall case. The simulation results are concluded: (1) In the dry case, the PAHs accumulate mostly in soil and air compartments, (2) Different dry depositing velocities will affect the PAHs distribution among compartments. (3) Different soil properties affect the PAHs concentration in the soil and sediment compartments, (4) The soil PAHs concentrations usually increase for those PAHs with a high solid/gas ratio. (5) The random rainfall only affects the PAHs concentration in the soil.« less

Dust composition and mass-loss return from the luminous blue variable R71 in the LMC

NASA Astrophysics Data System (ADS)

Guha Niyogi, S.; Min, M.; Meixner, M.; Waters, L. B. F. M.; Seale, J.; Tielens, A. G. G. M.

2014-09-01

Context. We present an analysis of mid- and far-infrared (IR) spectrum and spectral energy distribution (SED) of the luminous blue variable (LBV) R71 in the Large Magellanic Cloud (LMC). Aims: This work aims to understand the overall contribution of high-mass LBVs to the total dust-mass budget of the interstellar medium (ISM) of the LMC and compare this with the contribution from low-mass asymptotic giant branch (AGB) stars. As a case study, we analyze the SED of R71. Methods: We compiled all the available photometric and spectroscopic observational fluxes from various telescopes for a wide wavelength range (0.36-250 μm). We determined the dust composition from the spectroscopic data, and derived the ejected dust mass, dust mass-loss rate, and other dust shell properties by modeling the SED of R71. We noted nine spectral features in the dust shell of R71 by analyzing Spitzer Space Telescope spectroscopic data. Among these, we identified three new crystalline silicate features. We computed our model spectrum by using 3D radiative transfer code MCMax. Results: Our model calculation shows that dust is dominated by amorphous silicates, with some crystalline silicates, metallic iron, and a very tiny amount of polycyclic aromatic hydrocarbon (PAH) molecules. The presence of both silicates and PAHs indicates that the dust has a mixed chemistry. We derived a dust mass of 0.01 M⊙, from which we arrive at a total ejected mass of ≈5 M⊙. This implies a time-averaged dust mass-loss rate of 2.5 × 10-6 M⊙ yr-1 with an explosion about 4000 years ago. We assume that the other five confirmed dusty LBVs in the LMC loose mass at a similar rate, and estimate the total contribution to the mass budget of the LMC to be ≈10-5 M⊙ yr-1, which is comparable to the contribution by all the AGB stars in the LMC. Conclusions: Based on our analysis on R71, we speculate that LBVs as a class may be an important dust source in the ISM of the LMC.

Dietary risk evaluation for 28 polycyclic aromatic hydrocarbons (PAHs) in tea preparations made of teas available on the Polish retail market.

PubMed

Roszko, Marek; Kamińska, Marta; Szymczyk, Krystyna; Jędrzejczak, Renata

2018-01-02

The aim of this work was to assess dietary risk resulting from consumption of polycyclic aromatic hydrocarbons (PAHs) with tea infusions. To this end, levels of 28 PAHs in black, green, red and white teas available on the Polish retail market have been assessed. Profiles and correlation between concentrations of individual PAHs have been identified. A model study on transfer of PAHs from tea leaves into tea preparations has been conducted. Relatively high concentrations of 28 evaluated PAHs have been found in 58 tested samples of black, green, red and white teas sampled on the Polish retail market. Total concentration ∑28PAH ranged from 57 to 696 µg kg -1 with mean 258 µg kg -1 (dry tea leaves). The most mature tea leaves fermented to a small degree contained relatively the highest PAH levels among all four tested tea types. Relatively low PAH transfer rates into tea infusions and limited volumes of the consumed tea keep the risks associated with PAH dietary intake at a safely low level. The worst-case scenario dietary intake values were 7.62/0.82/0.097 ng kg -1 b.w. day -1 (estimated on the basis of the maximum found concentrations 696/113/23 µg kg -1 and maximum observed transfer rates 24/16/9%) for ∑28PAH/∑PAH4/B[a]P, respectively. MOE values calculated using the above worst case estimates exceeded 700,000 and 400,000 (BMDL 10 0.07 and 0.34 mg kg -1 b.w. day -1 ) for B[a]P and PAH4, respectively. Both B[a]P and PAH4 concentrations may be used as indicators of total PAH concentration in tea leaves; PAH4 slightly better fits low molecular weight PAHs. Several correlations between various PAHs/groups of PAHs have been identified, the strongest one (R 2 = 0.92) between PAH4 and EU PAH 15+1.

Elabela/Toddler Is an Endogenous Agonist of the Apelin APJ Receptor in the Adult Cardiovascular System, and Exogenous Administration of the Peptide Compensates for the Downregulation of Its Expression in Pulmonary Arterial Hypertension

PubMed Central

Yang, Peiran; Read, Cai; Kuc, Rhoda E.; Buonincontri, Guido; Southwood, Mark; Torella, Rubben; Upton, Paul D.; Crosby, Alexi; Sawiak, Stephen J.; Carpenter, T. Adrian; Glen, Robert C.; Morrell, Nicholas W.; Maguire, Janet J.

2017-01-01

Background: Elabela/toddler (ELA) is a critical cardiac developmental peptide that acts through the G-protein–coupled apelin receptor, despite lack of sequence similarity to the established ligand apelin. Our aim was to investigate the receptor pharmacology, expression pattern, and in vivo function of ELA peptides in the adult cardiovascular system, to seek evidence for alteration in pulmonary arterial hypertension (PAH) in which apelin signaling is downregulated, and to demonstrate attenuation of PAH severity with exogenous administration of ELA in a rat model. Methods: In silico docking analysis, competition binding experiments, and downstream assays were used to characterize ELA receptor binding in human heart and signaling in cells expressing the apelin receptor. ELA expression in human cardiovascular tissues and plasma was determined using real-time quantitative polymerase chain reaction, dual-labeling immunofluorescent staining, and immunoassays. Acute cardiac effects of ELA-32 and [Pyr1]apelin-13 were assessed by MRI and cardiac catheterization in anesthetized rats. Cardiopulmonary human and rat tissues from PAH patients and monocrotaline- and Sugen/hypoxia-exposed rats were used to show changes in ELA expression in PAH. The effect of ELA treatment on cardiopulmonary remodeling in PAH was investigated in the monocrotaline rat model. Results: ELA competed for binding of apelin in human heart with overlap for the 2 peptides indicated by in silico modeling. ELA activated G-protein– and β-arrestin–dependent pathways. We detected ELA expression in human vascular endothelium and plasma. Comparable to apelin, ELA increased cardiac contractility, ejection fraction, and cardiac output and elicited vasodilatation in rat in vivo. ELA expression was reduced in cardiopulmonary tissues from PAH patients and PAH rat models, respectively. ELA treatment significantly attenuated elevation of right ventricular systolic pressure and right ventricular hypertrophy and pulmonary vascular remodeling in monocrotaline-exposed rats. Conclusions: These results show that ELA is an endogenous agonist of the human apelin receptor, exhibits a cardiovascular profile comparable to apelin, and is downregulated in human disease and rodent PAH models, and exogenous peptide can reduce the severity of cardiopulmonary remodeling and function in PAH in rats. This study provides additional proof of principle that an apelin receptor agonist may be of therapeutic use in PAH in humans. PMID:28137936

Elabela/Toddler Is an Endogenous Agonist of the Apelin APJ Receptor in the Adult Cardiovascular System, and Exogenous Administration of the Peptide Compensates for the Downregulation of Its Expression in Pulmonary Arterial Hypertension.

PubMed

Yang, Peiran; Read, Cai; Kuc, Rhoda E; Buonincontri, Guido; Southwood, Mark; Torella, Rubben; Upton, Paul D; Crosby, Alexi; Sawiak, Stephen J; Carpenter, T Adrian; Glen, Robert C; Morrell, Nicholas W; Maguire, Janet J; Davenport, Anthony P

2017-03-21

Elabela/toddler (ELA) is a critical cardiac developmental peptide that acts through the G-protein-coupled apelin receptor, despite lack of sequence similarity to the established ligand apelin. Our aim was to investigate the receptor pharmacology, expression pattern, and in vivo function of ELA peptides in the adult cardiovascular system, to seek evidence for alteration in pulmonary arterial hypertension (PAH) in which apelin signaling is downregulated, and to demonstrate attenuation of PAH severity with exogenous administration of ELA in a rat model. In silico docking analysis, competition binding experiments, and downstream assays were used to characterize ELA receptor binding in human heart and signaling in cells expressing the apelin receptor. ELA expression in human cardiovascular tissues and plasma was determined using real-time quantitative polymerase chain reaction, dual-labeling immunofluorescent staining, and immunoassays. Acute cardiac effects of ELA-32 and [Pyr 1 ]apelin-13 were assessed by MRI and cardiac catheterization in anesthetized rats. Cardiopulmonary human and rat tissues from PAH patients and monocrotaline- and Sugen/hypoxia-exposed rats were used to show changes in ELA expression in PAH. The effect of ELA treatment on cardiopulmonary remodeling in PAH was investigated in the monocrotaline rat model. ELA competed for binding of apelin in human heart with overlap for the 2 peptides indicated by in silico modeling. ELA activated G-protein- and β-arrestin-dependent pathways. We detected ELA expression in human vascular endothelium and plasma. Comparable to apelin, ELA increased cardiac contractility, ejection fraction, and cardiac output and elicited vasodilatation in rat in vivo. ELA expression was reduced in cardiopulmonary tissues from PAH patients and PAH rat models, respectively. ELA treatment significantly attenuated elevation of right ventricular systolic pressure and right ventricular hypertrophy and pulmonary vascular remodeling in monocrotaline-exposed rats. These results show that ELA is an endogenous agonist of the human apelin receptor, exhibits a cardiovascular profile comparable to apelin, and is downregulated in human disease and rodent PAH models, and exogenous peptide can reduce the severity of cardiopulmonary remodeling and function in PAH in rats. This study provides additional proof of principle that an apelin receptor agonist may be of therapeutic use in PAH in humans. © 2017 The Authors.

Polycyclic Aromatic Hydrocarbon Exposure and Wheeze in a Cohort of Children with Asthma in Fresno, CA

PubMed Central

Gale, Sara L.; Noth, Elizabeth M.; Mann, Jennifer; Balmes, John; Hammond, S. Katharine; Tager, Ira B.

2014-01-01

Polycyclic aromatic hydrocarbons (PAHs) are found widely in the ambient air and result from combustion of various fuels and industrial processes. PAHs have been associated with adverse human health effects such as cognitive development, childhood IQ, and respiratory health. The Fresno Asthmatic Children’s Environment Study (FACES) enrolled 315 children ages 6-11 years with asthma in Fresno, CA and followed the cohort from 2000 to 2008. Subjects were evaluated for asthma symptoms in up to three 14-day panels per year. Detailed ambient pollutant concentrations were collected from a central site and outdoor pollutants were measured at 83 homes for at least one 5-day period. Measurements of particle-bound PAHs were used with land use regression models to estimate individual exposures to PAHs with 4-, 5- or 6-member rings (PAH456) and phenanthrene for the cohort (approximately 22 000 individual daily estimates). We used a cross-validation based algorithm for model fitting and a generalized estimated equation approach to account for repeated measures. Multiple lags and moving averages of PAH exposure were associated with increased wheeze for each of the three types of PAH exposure estimates. The odds ratios for asthmatics exposed to PAHs (ng/m3) ranged from 1.01 (95% CI, 1.00-1.02) to 1.10 (95% CI, 1.04-1.17)]. This trend for increased wheeze persisted among all PAHs measured. Phenanthrene was found to have a higher relative impact on wheeze. These data provide further evidence that PAHs contribute to asthma morbidity. PMID:22549720

Polycyclic aromatic hydrocarbon exposure and wheeze in a cohort of children with asthma in Fresno, CA.

PubMed

Gale, Sara L; Noth, Elizabeth M; Mann, Jennifer; Balmes, John; Hammond, S Katharine; Tager, Ira B

2012-07-01

Polycyclic aromatic hydrocarbons (PAHs) are found widely in the ambient air and result from combustion of various fuels and industrial processes. PAHs have been associated with adverse human health effects such as cognitive development, childhood IQ, and respiratory health. The Fresno Asthmatic Children's Environment Study enrolled 315 children aged 6-11 years with asthma in Fresno, CA and followed the cohort from 2000 to 2008. Subjects were evaluated for asthma symptoms in up to three 14-day panels per year. Detailed ambient pollutant concentrations were collected from a central site and outdoor pollutants were measured at 83 homes for at least one 5-day period. Measurements of particle-bound PAHs were used with land-use regression models to estimate individual exposures to PAHs with 4-, 5-, or 6-member rings (PAH456) and phenanthrene for the cohort (approximately 22,000 individual daily estimates). We used a cross-validation-based algorithm for model fitting and a generalized estimated equation approach to account for repeated measures. Multiple lags and moving averages of PAH exposure were associated with increased wheeze for each of the three types of PAH exposure estimates. The odds ratios for asthmatics exposed to PAHs (ng/m(3)) ranged from 1.01 (95% CI, 1.00-1.02) to 1.10 (95% CI, 1.04-1.17). This trend for increased wheeze persisted among all PAHs measured. Phenanthrene was found to have a higher relative impact on wheeze. These data provide further evidence that PAHs contribute to asthma morbidity.

Impact of bacterial activity on turnover of insoluble hydrophobic substrates (phenanthrene and pyrene)-Model simulations for prediction of bioremediation success.

PubMed

Rein, Arno; Adam, Iris K U; Miltner, Anja; Brumme, Katja; Kästner, Matthias; Trapp, Stefan

2016-04-05

Many attempts for bioremediation of polycyclic aromatic hydrocarbon (PAH) contaminated sites failed in the past, but the reasons for this failure are not well understood. Here we apply and improve a model for integrated assessment of mass transfer, biodegradation and residual concentrations for predicting the success of remediation actions. First, we provide growth parameters for Mycobacterium rutilum and Mycobacterium pallens growing on phenanthrene (PHE) or pyrene (PYR) degraded the PAH completely at all investigated concentrations. Maximum metabolic rates vmax and growth rates μ were similar for the substrates PHE and PYR and for both strains. The investigated Mycobacterium species were not superior in PHE degradation to strains investigated earlier with this method. Real-world degradation scenario simulations including diffusive flux to the microbial cells indicate: that (i) bioaugmentation only has a small, short-lived effect; (ii) Increasing sorption shifts the remaining PAH to the adsorbed/sequestered PAH pool; (iii) mobilizing by solvents or surfactants resulted in a significant decrease of the sequestered PAH, and (iv) co-metabolization e.g. by compost addition can contribute significantly to the reduction of PAH, because active biomass is maintained at a high level by the compost. The model therefore is a valuable contribution to the assessment of potential remediation action at PAH-polluted sites. Copyright © 2015 Elsevier B.V. All rights reserved.

Measurement of polynuclear aromatic hydrocarbons (PAHs) in epiphytic lichens and from PM 2.5 filters for receptor modeling in the Alberta Oil Sands Region (Invited)

NASA Astrophysics Data System (ADS)

Studabaker, W. B.; Jayanty, J.; Raymer, J. H.; Krupa, S.

2013-12-01

As mining and refinery operations in the Alberta Oil Sands Region (AOSR) have expanded, there has been increasing concern for the impacts of air pollution generated by those operations on both human and ecosystem health. The inaccessibility of much of the AOSR makes it difficult to establish conventional air quality monitoring stations to the extent needed to model long-range impacts of emissions from the AOSR operations. Epiphytic lichens are important markers of ecosystem health, are well-established bioaccumulators of trace metals, and are potentially useful biomonitors of air pollution. However, their ability to take up organic pollutants has not been extensively explored, and only recently have they been used for biomonitoring of pollution by PAHs. Here we describe the determination of polynuclear aromatic hydrocarbons (PAHs) in lichens, collected from sites throughout the AOSR, for modeling emissions associated with mining and oil extraction operations. We also describe preliminary results of the determination of PAHs in PM 2.5 filters from dichotomous samplers stationed in the AOSR, in the context of the biological sample data. Lichens (Hypogymnia physodes) were collected on two separate occasions. During the summer of 2009, single samples were taken from 200 sites in the AOSR; a subset of 20 of these was selected for determination of PAHs. During the summer of 2011, triplicate samples (from separate trees within a site) were collected from 20 sites representing similar locations to the 2008 sites. Lichens were milled in a cryogenic impactor, then were extracted with cyclohexane. Extracts were purified on silica gel using automated solid phase extraction and analyzed by gas chromatography with mass selective detection. Method detection limits for individual PAHs were 2-4 ng/g. Total PAHs in the samples from both collection events ranged from 50 ng/g to 350 ng/g, and declined with increasing distance from the mining and refinery operations. The relative contribution of low ring number PAHs to total PAHs increased with increasing distance. Total PAHs correlated strongly (R2 > 0.80, p < 0.05) with crustal elements, suggesting similar transport mechanisms. Analytical data for PAHs on PM 2.5 filters, including relationships between concentrations, PAH profiles, and distance from the mines, will be presented. The lichen data are consistent with PAH transport close to the mines being more influenced by particulate matter transport mechanisms, whereas PAHs in samples collected from remote areas reflect more of the vapor phase transport mechanisms.

Mapping PAH sizes in NGC 7023 with SOFIA

NASA Astrophysics Data System (ADS)

Croiset, B. A.; Candian, A.; Berné, O.; Tielens, A. G. G. M.

2016-05-01

Context. NGC 7023 is a well-studied reflection nebula, which shows strong emission from polycyclic aromatic hydrocarbon (PAH) molecules in the form of aromatic infrared bands (AIBs). The spectral variations of the AIBs in this region are connected to the chemical evolution of the PAH molecules which, in turn, depends on the local physical conditions. Aims: Our goal is to map PAH sizes in NGC 7023 with respect to the location of the star. We focus on the north west (NW) photo-dissociation region (PDR) and the south PDR of NGC 7023 to understand the photochemical evolution of PAHs, using size as a proxy. Methods: We use the unique capabilities of the Stratospheric Observatory for Infrared Astronomy (SOFIA) to observe a 3.2' × 3.4' region of NGC 7023 at wavelengths that we observe with high spatial resolution (2.7'') at 3.3 and 11.2 μm. We compare the SOFIA images with existing images of the PAH emission at 8.0 μm (Spitzer), emission from evaporating very small grains (eVSG) extracted from Spitzer-IRS spectral cubes, the extended red emission (Hubble Space Telescope and Canadian French Hawaiian Telescope), and H2 (2.12 μm). We create maps of the 11.2/3.3 μm ratio to probe the morphology of the PAH size distribution and the 8.0/11.2 μm ratio to probe the PAH ionization. We make use of an emission model and of vibrational spectra from the NASA Ames PAH database to translate the 11.2/3.3 μm ratio to PAH sizes. Results: The 11.2/3.3 μm ratio map shows the smallest PAH concentrate on the PDR surface (H2 and extended red emission) in the NW and south PDR. We estimated that PAHs in the NW PDR bear, on average, a number of carbon atoms (Nc) of ~70 in the PDR cavity and ~50 at the PDR surface. In the entire nebula, the results reveal a factor of 2 variation in the size of the PAH. We relate these size variations to several models for the evolution of the PAH families when they traverse from the molecular cloud to the PDR. Conclusions: The high-resolution PAH size map enables us to follow the photochemical evolution of PAHs in NGC 7023. Small PAHs result from the photo-evaporation of VSGs as they reach the PDR surface. Inside the PDR cavity, the PAH abundance drops as the smallest PAH are broken down. The average PAH size increases in the cavity where only the largest species survive or are converted into C60 by photochemical processing.

Obesity-related pulmonary arterial hypertension in rats correlates with increased circulating inflammatory cytokines and lipids and with oxidant damage in the arterial wall but not with hypoxia

PubMed Central

Irwin, David C.; Garat, Chrystelle V.; Crossno, Joseph T.; MacLean, Paul S.; Sullivan, Timothy M.; Erickson, Paul F.; Jackman, Matthew R.; Harral, Julie W.; Reusch, Jane E. B.

2014-01-01

Abstract Obesity is causally linked to a number of comorbidities, including cardiovascular disease, diabetes, renal dysfunction, and cancer. Obesity has also been linked to pulmonary disorders, including pulmonary arterial hypertension (PAH). It was long believed that obesity-related PAH was the result of hypoventilation and hypoxia due to the increased mechanical load of excess body fat. However, in recent years it has been proposed that the metabolic and inflammatory disturbances of obesity may also play a role in the development of PAH. To determine whether PAH develops in obese rats in the absence of hypoxia, we assessed pulmonary hemodynamics and pulmonary artery (PA) structure in the diet-resistant/diet-induced obesity (DR/DIO) and Zucker lean/fatty rat models. We found that high-fat feeding (DR/DIO) or overfeeding (Zucker) elicited PA remodeling, neomuscularization of distal arterioles, and elevated PA pressure, accompanied by right ventricular (RV) hypertrophy. PA thickening and distal neomuscularization were also observed in DIO rats on a low-fat diet. No evidence of hypoventilation or chronic hypoxia was detected in either model, nor was there a correlation between blood glucose or insulin levels and PAH. However, circulating inflammatory cytokine levels were increased with high-fat feeding or calorie overload, and hyperlipidemia and oxidant damage in the PA wall correlated with PAH in the DR/DIO model. We conclude that hyperlipidemia and peripheral inflammation correlate with the development of PAH in obese subjects. Obesity-related inflammation may predispose to PAH even in the absence of hypoxia. PMID:25610600

Modelling injection rates of PUIs from photoionization using kinetic simulations of interstellar neutrals traversing the heliosphere

NASA Astrophysics Data System (ADS)

Keilbach, D.; Drews, C.; Taut, A.; Wimmer-Schweingruber, R. F.

2016-12-01

Recent studies of the inflow direction of the local insterstellar medium from PUI density distributions have shown that the extrema of the longitudinal distribution of PUI velocities (with respect to the solar wind speed) can be attributed to the radial velocity of the interstellar neutral seed population and is symmetric around the inflow direction of the local interstellar medium. This work is aimed to model pickup ion injection rates from photoionization (which is the main process of interstellar PUI production) throughout the heliosphere. To that end a seed population of interstellar neutrals is injected into a model heliosphere at 60 AU distance from the sun, whereas each particle's initial speed is given by a maxwellian distribution at a temperature of 1 eV and an inflow speed of 22 km/s. Then the density of the interstellar neutrals is integrated over the model heliosphere, while the movement of the neutrals is simulated using timestep methods. To model the focusing of the interstellar neutral trajectories from the sun's gravitational potential the model heliosphere contains a central gravitational potential.Each neutral test particle can be ionized via photoionization with a per-timestep probability antiproportional to the neutral's distance to the sun squared. By tracking the ionization rate location-dependently, PUI injection rates have been determined. Therefore using these simulations the density distributions of different species of interstellar neutrals have been calculated. In addition location-dependent injection rates of different species of PUIs have been calculated, which show an increased rate of PUI production in the focusing cone region (e.g. for He+ PUIs), but also in the crescent region (e.g. for O+ PUIs).Furthermore the longitudinal distribution of the neutrals' velocity at 1 AU is calculated from the simulation's results in order to estimate the PUI cut-off as a function of ecliptic longitude. Figure: Simulated He neutral density (left) and simulated He PUI production rates from photoionization (right). The sun is located at 0 AU at both x-and y-axes.

Connection of the solar wind with the interstellar medium through numerical modeling

DOE PAGES

Heerikhuisen, J.; Zirnstein, E.; Kawamura, A. D.; ...

2013-06-13

In this article we investigate the interaction between the solar wind (SW) and the local interstellar medium (LISM) using spacecraft data and numerical simulations. In particular, we focus on neutral atom results from NASA's Interstellar Boundary EXplorer (IBEX) mission, and compare these with implementations of our neutral atom models that look at both the energetic neutral atoms (ENAs) which are created as hydrogen of LISM origin interacts with the heliosphere, as well as the transmission of interstellar Oxygen through the heliospheric interface. Lastly, the goal of this work is to better understand the global structure of the heliosphere and itsmore » interaction with the galaxy.« less

Small interstellar molecules and what they tell us

NASA Astrophysics Data System (ADS)

Neufeld, David A.

2018-06-01

Observations at ultraviolet, visible, infrared and radio wavelengths provide a wealth of information about the molecular inventory of the interstellar medium (ISM). Because of the different chemical pathways responsible for their formation and destruction, different molecules probe specific aspects of the interstellar environment. Carefully interpreted with the use of astrochemical models, they provide unique information of general astrophysical importance, yielding estimates of the cosmic ray density, the molecular fraction, the ultraviolet radiation field, and the dissipation of energy within the turbulent ISM. Laboratory experiments and quantum-mechanical calculations are essential both in providing the spectroscopic data needed to identify interstellar molecules and for elucidating the fundamental physical and chemical processes that must be included in astrochemical models.

Energy and mass balance in the three-phase interstellar medium

NASA Technical Reports Server (NTRS)

Wang, Zhong; Cowie, Lennox L.

1988-01-01

Details of the energy and mass balances are considered in the context of a three-phase interstellar medium. The rates of mass exchange between the different phases are derived based on the pressure variations created by supernova remnant expansions. It is shown that the pressure-confined warm and cold gases have stable temperatures under a variety of interstellar conditions. The three-phase quasi-static configuration is found to be a natural outcome, and both warm and cold phases generally contribute about half of the total mass density to the diffuse interstellar gas. The model is also likely to be self-regulatory in the sense that variations of the input parameters do not strongly alter the general result, which is consistent with most current observations. The consequences of extreme conditions on this model are considered, and the possible implications for interstellar medium in other galaxies are briefly discussed.

Diagnosing the Neutral Interstellar Gas Flow at 1 AU with IBEX-Lo

NASA Astrophysics Data System (ADS)

Möbius, E.; Kucharek, H.; Clark, G.; O'Neill, M.; Petersen, L.; Bzowski, M.; Saul, L.; Wurz, P.; Fuselier, S. A.; Izmodenov, V. V.; McComas, D. J.; Müller, H. R.; Alexashov, D. B.

2009-08-01

Every year in fall and spring the Interstellar Boundary Explorer (IBEX) will observe directly the interstellar gas flow at 1 AU over periods of several months. The IBEX-Lo sensor employs a powerful triple time-of-flight mass spectrometer. It can distinguish and image the O and He flow distributions in the northern fall and spring, making use of sensor viewing perpendicular to the Sun-pointing spin axis. To effectively image the narrow flow distributions IBEX-Lo has a high angular resolution quadrant in its collimator. This quadrant is employed selectively for the interstellar gas flow viewing in the spring by electrostatically shutting off the remainder of the aperture. The operational scenarios, the expected data, and the necessary modeling to extract the interstellar parameters and the conditions in the heliospheric boundary are described. The combination of two key interstellar species will facilitate a direct comparison of the pristine interstellar flow, represented by He, which has not been altered in the heliospheric boundary region, with a flow that is processed in the outer heliosheath, represented by O. The O flow distribution consists of a depleted pristine component and decelerated and heated neutrals. Extracting the latter so-called secondary component of interstellar neutrals will provide quantitative constraints for several important parameters of the heliosheath interaction in current global heliospheric models. Finding the fraction and width of the secondary component yields an independent value for the global filtration factor of species, such as O and H. Thus far filtration can only be inferred, barring observations in the local interstellar cloud proper. The direction of the secondary component will provide independent information on the interstellar magnetic field strength and orientation, which has been inferred from SOHO SWAN Ly- α backscattering observations and the two Voyager crossings of the termination shock.

Interaction of the Local Interstellar Medium with the Heliosphere: Role of the Interior and Exterior Magnetic Fields

NASA Technical Reports Server (NTRS)

Barnes, Aaron; DeVincenzi, Donald (Technical Monitor)

2000-01-01

A complete model of the global interaction between the solar wind and the local interstellar medium must take account of interstellar neutral atoms, interstellar ionized gas, solar and galactic magnetic fields, galactic and anomalous cosmic rays. For now, however, in view of the many uncertainties about conditions in the interstellar medium, etc., all models must be regarded as highly idealized and incomplete. In the present review I concentrate on the role of magnetic fields of solar and interstellar origin. The former, the interior field, has negligible influence on the unshocked solar wind; the immediate post-shock solar wind is probably low-beta, so that the interior magnetic field is still unimportant, but this situation changes as the plasma flows through the heliosheath, and a ridge of strong magnetic field may form to separate materials of polar and equatorial origin. The exterior (interstellar) field is likely to play an important role in determining the global morphology of the system outside the termination shock. If the exterior field is strong enough, it can compress the heliosphere (although exterior neutral and/or ionized hydrogen may play the dominant role). Even if the interstellar magnetic field does not provide the dominant pressure, its orientation can substantially affect the configuration of the heliosphere, especially the location and orientation of the heliospheric discontinuities. The configurations can be quite different for the situations in which the field and flow are (a) aligned or (b) transverse. Obliquity of the field produces asymmetry in the geometry of the system; in particular the noses of heliopause and interstellar bow shock are shifted away from the interstellar flow direction, and in opposite directions, due to the asymmetric draping of the magnetic field.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE PAGES

Geier, Mitra C.; James Minick, D.; Truong, Lisa; ...

2018-04-01

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geier, Mitra C.; James Minick, D.; Truong, Lisa

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Global time trends in PAH emissions from motor vehicles

PubMed Central

Shen, Huizhong; Tao, Shu; Wang, Rong; Wang, Bin; Shen, Guofeng; Li, Wei; Su, Shenshen; Huang, Ye; Wang, Xilong; Liu, Wenxin; Li, Bengang; Sun, Kang

2013-01-01

Emission from motor vehicles is the most important source of polycyclic aromatic hydrocarbons (PAHs) in urban areas. Emission factors of individual PAHs for motor vehicles reported in the literature varied 4 to 5 orders of magnitude, leading to high uncertainty in emission inventory. In this study, key factors affecting emission factors of PAHs (EFPAH) for motor vehicles were evaluated quantitatively based on thousands of EFPAH measured in 16 countries for over 50 years. The result was used to develop a global emission inventory of PAHs from motor vehicles. It was found that country and vehicle model year are the most important factors affecting EFPAH, which can be quantified using a monovariate regression model with per capita gross domestic production (purchasing power parity) as a sole independent variable. On average, 29% of variation in log-transformed EFPAH could be explained by the model, which was equivalent to 90% reduction in overall uncertainty on arithmetic scale. The model was used to predict EFPAH and subsequently PAH emissions from motor vehicles for various countries in the world during a period from 1971 to 2030. It was estimated that the global emission reached its peak value of approximate 101 Gg in 1978 and decreased afterwards due to emission control in developed countries. The annual emission picked up again since 1990 owing to accelerated energy consumption in China and other developing countries. With more and more rigid control measures taken in the developing world, global emission of PAHs is currently passing its second peak. It was predicted that the emission would decrease from 77 Gg in 2010 to 42 Gg in 2030. PMID:24198716

Stardust Interstellar Preliminary Examination X: Impact Speeds and Directions of Interstellar Grains on the Stardust Dust Collector

NASA Technical Reports Server (NTRS)

Sterken, Veerle J.; Westphal, Andrew J.; Altobelli, Nicolas; Grun, Eberhard; Hillier, Jon K.; Postberg, Frank; Allen, Carlton; Stroud, Rhonda M.; Sandford, S. A.; Zolensky, Michael E.

2014-01-01

On the basis of an interstellar dust model compatible with Ulysses and Galileo observations, we calculate and predict the trajectories of interstellar dust (ISD) in the solar system and the distribution of the impact speeds, directions, and flux of ISD particles on the Stardust Interstellar Dust Collector during the two collection periods of the mission. We find that the expected impact velocities are generally low (less than 10 km per second) for particles with the ratio of the solar radiation pressure force to the solar gravitational force beta greater than 1, and that some of the particles will impact on the cometary side of the collector. If we assume astronomical silicates for particle material and a density of 2 grams per cubic centimeter, and use the Ulysses measurements and the ISD trajectory simulations, we conclude that the total number of (detectable) captured ISD particles may be on the order of 50. In companion papers in this volume, we report the discovery of three interstellar dust candidates in the Stardust aerogel tiles. The impact directions and speeds of these candidates are consistent with those calculated from our ISD propagation model, within the uncertainties of the model and of the observations.

Silicon chemistry in interstellar clouds

NASA Technical Reports Server (NTRS)

Langer, William D.; Glassgold, A. E.

1990-01-01

A new model of interstellar silicon chemistry is presented that explains the lack of SiO detections in cold clouds and contains an exponential temperature dependence for the SiO abundance. A key aspect of the model is the sensitivity of SiO production by neutral silicon reactions to density and temperature, which arises from the dependence of the rate coefficients on the population of the excited fine-structure levels of the silicon atom. As part of the explanation of the lack of SiO detections at low temperatures and densities, the model also emphasizes the small efficiencies of the production routes and the correspondingly long times needed to reach equilibrium. Measurements of the abundance of SiO, in conjunction with theory, can provide information on the physical properties of interstellar clouds such as the abundance of oxygen bearing molecules and the depletion of interstellar silicon.

EVALUATING THE MORPHOLOGY OF THE LOCAL INTERSTELLAR MEDIUM: USING NEW DATA TO DISTINGUISH BETWEEN MULTIPLE DISCRETE CLOUDS AND A CONTINUOUS MEDIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Redfield, Seth; Linsky, Jeffrey L., E-mail: sredfield@wesleyan.edu, E-mail: jlinsky@jila.colorado.edu

Ultraviolet and optical spectra of interstellar gas along the lines of sight to nearby stars have been interpreted by Redfield and Linsky and previous studies as a set of discrete warm, partially ionized clouds each with a different flow vector, temperature, and metal depletion. Recently, Gry and Jenkins proposed a fundamentally different model consisting of a single cloud with nonrigid flows filling space out to 9 pc from the Sun that they propose better describes the local ISM. Here we test these fundamentally different morphological models against the spatially unbiased Malamut et al. spectroscopic data set, and find that themore » multiple cloud morphology model provides a better fit to both the new and old data sets. The detection of three or more velocity components along the lines of sight to many nearby stars, the presence of nearby scattering screens, the observed thin elongated structures of warm interstellar gas, and the likely presence of strong interstellar magnetic fields also support the multiple cloud model. The detection and identification of intercloud gas and the measurement of neutral hydrogen density in clouds beyond the Local Interstellar Cloud could provide future morphological tests.« less

A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene--toward the formation of methylnaphthalenes.

PubMed

Yang, Tao; Muzangwa, Lloyd; Kaiser, Ralf I; Jamal, Adeel; Morokuma, Keiji

2015-09-07

Crossed molecular beam experiments and electronic structure calculations on the reaction of the meta-tolyl radical with vinylacetylene were conducted to probe the formation of methyl-substituted naphthalene isomers. We present the compelling evidence that under single collision conditions 1- and 2-methylnaphthalene can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the meta-tolyl radical and vinylacetylene. The electronic structure calculations, conducted at the UCCSD(T)-F12b/cc-pVDZ//UM06-2x/cc-pVTZ + ZPE(UM06-2x/cc-pVTZ) level of theory, reveal that this reaction is initiated by the barrierless addition of the meta-tolyl radical to the terminal vinyl carbon (C1) of vinylacetylene, via a van-der-Waals complex implying that this mechanism can play a key role in forming methyl-substituted PAHs in low temperature extreme environments such as the low temperature interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer solar system. The reaction mechanism, proposed from the C11H11 potential energy surface, involves a sequence of isomerizations involving hydrogen transfer and ring closure, followed by hydrogen dissociation, which eventually leads to 1- and 2-methylnaphthalene in an overall exoergic process.

Integrating geophysical data for mapping the contamination of industrial sites by polycyclic aromatic hydrocarbons: A geostatistical approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colin, P.; Nicoletis, S.; Froidevaux, R.

1996-12-31

A case study is presented of building a map showing the probability that the concentration in polycyclic aromatic hydrocarbon (PAH) exceeds a critical threshold. This assessment is based on existing PAH sample data (direct information) and on an electrical resistivity survey (indirect information). Simulated annealing is used to build a model of the range of possible values for PAH concentrations and of the bivariate relationship between PAH concentrations and electrical resistivity. The geostatistical technique of simple indicator kriging is then used, together with the probabilistic model, to infer, at each node of a grid, the range of possible values whichmore » the PAH concentration can take. The risk map is then extracted for this characterization of the local uncertainty. The difference between this risk map and a traditional iso-concentration map is then discussed in terms of decision-making.« less

The 11.2 μm emission of PAHs in astrophysical objects

NASA Astrophysics Data System (ADS)

Candian, A.; Sarre, P. J.

2015-04-01

The 11.2-μm emission band belongs to the family of the `unidentified' infrared emission bands seen in many astronomical environments. In this work, we present a theoretical interpretation of the band characteristics and profile variation for a number of astrophysical sources in which the carriers are subject to a range of physical conditions. The results of Density Functional Theory calculations for the solo out-of-plane vibrational bending modes of large polycyclic aromatic hydrocarbon (PAH) molecules are used as input for a detailed emission model which includes the temperature and mass dependence of PAH band wavelength, and a PAH mass distribution that varies with object. Comparison of the model with astronomical spectra indicates that the 11.2-μm band asymmetry and profile variation can be explained principally in terms of the mass distribution of neutral PAHs with a small contribution from anharmonic effects.

Polycyclic Aromatic Hydrocarbons in Residential Dust: Sources of Variability

PubMed Central

Metayer, Catherine; Petreas, Myrto; Does, Monique; Buffler, Patricia A.; Rappaport, Stephen M.

2013-01-01

Background: There is interest in using residential dust to estimate human exposure to environmental contaminants. Objectives: We aimed to characterize the sources of variability for polycyclic aromatic hydrocarbons (PAHs) in residential dust and provide guidance for investigators who plan to use residential dust to assess exposure to PAHs. Methods: We collected repeat dust samples from 293 households in the Northern California Childhood Leukemia Study during two sampling rounds (from 2001 through 2007 and during 2010) using household vacuum cleaners, and measured 12 PAHs using gas chromatography–mass spectrometry. We used a random- and a mixed-effects model for each PAH to apportion observed variance into four components and to identify sources of variability. Results: Median concentrations for individual PAHs ranged from 10 to 190 ng/g of dust. For each PAH, total variance was apportioned into regional variability (1–9%), intraregional between-household variability (24–48%), within-household variability over time (41–57%), and within-sample analytical variability (2–33%). Regional differences in PAH dust levels were associated with estimated ambient air concentrations of PAH. Intraregional differences between households were associated with the residential construction date and the smoking habits of residents. For some PAHs, a decreasing time trend explained a modest fraction of the within-household variability; however, most of the within-household variability was unaccounted for by our mixed-effects models. Within-household differences between sampling rounds were largest when the interval between dust sample collections was at least 6 years in duration. Conclusions: Our findings indicate that it may be feasible to use residential dust for retrospective assessment of PAH exposures in studies of health effects. PMID:23461863

First structure of full-length mammalian phenylalanine hydroxylase reveals the architecture of an autoinhibited tetramer

PubMed Central

Arturo, Emilia C.; Gupta, Kushol; Héroux, Annie; Stith, Linda; Cross, Penelope J.; Parker, Emily J.; Loll, Patrick J.; Jaffe, Eileen K.

2016-01-01

Improved understanding of the relationship among structure, dynamics, and function for the enzyme phenylalanine hydroxylase (PAH) can lead to needed new therapies for phenylketonuria, the most common inborn error of amino acid metabolism. PAH is a multidomain homo-multimeric protein whose conformation and multimerization properties respond to allosteric activation by the substrate phenylalanine (Phe); the allosteric regulation is necessary to maintain Phe below neurotoxic levels. A recently introduced model for allosteric regulation of PAH involves major domain motions and architecturally distinct PAH tetramers [Jaffe EK, Stith L, Lawrence SH, Andrake M, Dunbrack RL, Jr (2013) Arch Biochem Biophys 530(2):73–82]. Herein, we present, to our knowledge, the first X-ray crystal structure for a full-length mammalian (rat) PAH in an autoinhibited conformation. Chromatographic isolation of a monodisperse tetrameric PAH, in the absence of Phe, facilitated determination of the 2.9 Å crystal structure. The structure of full-length PAH supersedes a composite homology model that had been used extensively to rationalize phenylketonuria genotype–phenotype relationships. Small-angle X-ray scattering (SAXS) confirms that this tetramer, which dominates in the absence of Phe, is different from a Phe-stabilized allosterically activated PAH tetramer. The lack of structural detail for activated PAH remains a barrier to complete understanding of phenylketonuria genotype–phenotype relationships. Nevertheless, the use of SAXS and X-ray crystallography together to inspect PAH structure provides, to our knowledge, the first complete view of the enzyme in a tetrameric form that was not possible with prior partial crystal structures, and facilitates interpretation of a wealth of biochemical and structural data that was hitherto impossible to evaluate. PMID:26884182

Survival of adults with systemic autoimmune rheumatic diseases and pulmonary arterial hypertension after lung transplantation.

PubMed

Bernstein, Elana J; Bathon, Joan M; Lederer, David J

2018-05-01

Pulmonary arterial hypertension (PAH) is a major cause of morbidity and mortality in adults with systemic autoimmune rheumatic diseases (ARDs). The aim of this study was to determine whether adults with ARDs and PAH on right-sided heart catheterization (ARD-PAH) have increased mortality following lung transplantation compared with those with PAH not due to an ARD. We conducted a retrospective cohort study of 93 adults with ARD-PAH and 222 adults with PAH who underwent lung transplantation in the USA between 4 May 2005 and 9 March 2015 using data from the United Network for Organ Sharing. We examined associations between diagnosis and survival after lung transplantation using stratified Cox models adjusted for potential confounding recipient factors. Among adults undergoing lung transplantation in the USA, we did not detect a difference in the multivariable-adjusted mortality rate between those with ARD-PAH and those with PAH [hazard ratio 0.75 (95% CI 0.47, 1.19)]. The presence of an ARD was not associated with increased mortality after lung transplantation in adults with PAH.

Structural basis for ligand-dependent dimerization of phenylalanine hydroxylase regulatory domain

PubMed Central

Patel, Dipali; Kopec, Jolanta; Fitzpatrick, Fiona; McCorvie, Thomas J.; Yue, Wyatt W.

2016-01-01

The multi-domain enzyme phenylalanine hydroxylase (PAH) catalyzes the hydroxylation of dietary I-phenylalanine (Phe) to I-tyrosine. Inherited mutations that result in PAH enzyme deficiency are the genetic cause of the autosomal recessive disorder phenylketonuria. Phe is the substrate for the PAH active site, but also an allosteric ligand that increases enzyme activity. Phe has been proposed to bind, in addition to the catalytic domain, a site at the PAH N-terminal regulatory domain (PAH-RD), to activate the enzyme via an unclear mechanism. Here we report the crystal structure of human PAH-RD bound with Phe at 1.8 Å resolution, revealing a homodimer of ACT folds with Phe bound at the dimer interface. This work delivers the structural evidence to support previous solution studies that a binding site exists in the RD for Phe, and that Phe binding results in dimerization of PAH-RD. Consistent with our structural observation, a disease-associated PAH mutant impaired in Phe binding disrupts the monomer:dimer equilibrium of PAH-RD. Our data therefore support an emerging model of PAH allosteric regulation, whereby Phe binds to PAH-RD and mediates the dimerization of regulatory modules that would bring about conformational changes to activate the enzyme. PMID:27049649

Thermodynamics and Charging of Interstellar Iron Nanoparticles

NASA Astrophysics Data System (ADS)

Hensley, Brandon S.; Draine, B. T.

2017-01-01

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

Gas lines from the 5-Myr old optically thin disk around HD 141569A . Herschel observations and modeling

NASA Astrophysics Data System (ADS)

Thi, W.-F.; Pinte, C.; Pantin, E.; Augereau, J. C.; Meeus, G.; Ménard, F.; Martin-Zaïdi, C.; Woitke, P.; Riviere-Marichalar, P.; Kamp, I.; Carmona, A.; Sandell, G.; Eiroa, C.; Dent, W.; Montesinos, B.; Aresu, G.; Meijerink, R.; Spaans, M.; White, G.; Ardila, D.; Lebreton, J.; Mendigutía, I.; Brittain, S.

2014-01-01

Context. The gas- and dust dissipation processes in disks around young stars remain uncertain despite numerous studies. At the distance of ~99-116 pc, HD 141569A is one of the nearest HerbigAe stars that is surrounded by a tenuous disk, probably in transition between a massive primordial disk and a debris disk. Atomic and molecular gases have been found in the structured 5-Myr old HD 141569A disk, making HD 141569A the perfect object within which to directly study the gaseous atomic and molecular component. Aims: We wish to constrain the gas and dust mass in the disk around HD 141569A. Methods: We observed the fine-structure lines of O i at 63 and 145 μm and the C ii line at 157 μm with the PACS instrument onboard the Herschel Space Telescope as part of the open-time large program GASPS. We complemented the atomic line observations with archival Spitzer spectroscopic and photometric continuum data, a ground-based VLT-VISIR image at 8.6 μm, and 12CO fundamental ro-vibrational and pure rotational J = 3-2 observations. We simultaneously modeled the continuum emission and the line fluxes with the Monte Carlo radiative transfer code MCFOST and the thermo-chemical code ProDiMo to derive the disk gas- and dust properties assuming no dust settling. Results: The models suggest that the oxygen lines are emitted from the inner disk around HD 141569A, whereas the [C ii] line emission is more extended. The CO submillimeter flux is emitted mostly by the outer disk. Simultaneous modeling of the photometric and line data using a realistic disk structure suggests a dust mass derived from grains with a radius smaller than 1 mm of ~2.1 × 10-7M⊙ and from grains with a radius of up to 1 cm of 4.9 × 10-6M⊙. We constrained the polycyclic aromatic hydrocarbons (PAH) mass to be between 2 × 10-11 and 1.4 × 10-10M⊙ assuming circumcircumcoronene (C150H30) as the representative PAH. The associated PAH abundance relative to hydrogen is lower than those found in the interstellar medium (3 × 10-7) by two to three orders of magnitude. The disk around HD 141569A is less massive in gas (2.5 to 4.9 × 10-4M⊙ or 67 to 164 M⊕) and has a flat opening angle (<10%). Conclusions: We constrained simultaneously the silicate dust grain, PAH, and gas mass in a ~5-Myr old Herbig Ae disk. The disk-averaged gas-to-dust-mass is most likely around 100, which is the assumed value at the disk formation despite the uncertainties due to disagreements between the different gas tracers. If the disk was originally massive, the gas and the dust would have dissipated at the same rate. Based on observations made with ESO Telescopes at the La Silla Paranal Observatory under programme ID 079.C-0602(A).Appendix A is available in electronic form at http://www.aanda.orgHerschel is an ESA space observatory with science instruments provided by Principal Investigator consortia. It is open for proposals for observing time from the worldwide astronomical community.

Fate of polycyclic aromatic hydrocarbons from the North Pacific to the Arctic: Field measurements and fugacity model simulation.

PubMed

Ke, Hongwei; Chen, Mian; Liu, Mengyang; Chen, Meng; Duan, Mengshan; Huang, Peng; Hong, Jiajun; Lin, Yan; Cheng, Shayen; Wang, Xuran; Huang, Mengxue; Cai, Minggang

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) have accumulated ubiquitously inArctic environments, where re-volatilization of certain organic pollutants as a result of climate change has been observed. To investigate the fate of semivolatile organic compounds in the Arctic, dissolved PAHs in the surface seawaters from the temperate Pacific Ocean to the Arctic Ocean, as well as a water column in the Arctic Ocean, were collected during the 4th Chinese National Arctic Research Expedition in summer 2010. The total concentrations of seven dissolved PAHs in surface water ranged from 1.0 to 5.1 ng L -1 , decreasing with increasing latitude. The vertical profile of PAHs in the Arctic Ocean was generally characteristic of surface enrichment and depth depletion, which emphasized the role of vertical water stratification and particle settling processes. A level III fugacity model was developed in the Bering Sea under steady state assumption. Model results quantitatively simulated the transfer processes and fate of PAHs in the air and water compartments, and highlighted a summer air-to-sea flux of PAHs in the Bering Sea, which meant that the ocean served as a sink for PAHs, at least in summer. Acenaphthylene and acenaphthene reached equilibrium in air-water diffusive exchange, and any perturbation, such as a rise in temperature, might lead to disequilibrium and remobilize these compounds from their Arctic reservoirs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evolutionary models of interstellar chemistry

NASA Technical Reports Server (NTRS)

Prasad, Sheo S.

1987-01-01

The goal of evolutionary models of interstellar chemistry is to understand how interstellar clouds came to be the way they are, how they will change with time, and to place them in an evolutionary sequence with other celestial objects such as stars. An improved Mark II version of an earlier model of chemistry in dynamically evolving clouds is presented. The Mark II model suggests that the conventional elemental C/O ratio less than one can explain the observed abundances of CI and the nondetection of O2 in dense clouds. Coupled chemical-dynamical models seem to have the potential to generate many observable discriminators of the evolutionary tracks. This is exciting, because, in general, purely dynamical models do not yield enough verifiable discriminators of the predicted tracks.

Concentrations of polycyclic aromatic hydrocarbons in New York City community garden soils: Potential sources and influential factors.

PubMed

Marquez-Bravo, Lydia G; Briggs, Dean; Shayler, Hannah; McBride, Murray; Lopp, Donna; Stone, Edie; Ferenz, Gretchen; Bogdan, Kenneth G; Mitchell, Rebecca G; Spliethoff, Henry M

2016-02-01

A total of 69 soil samples from 20 community gardens in New York City (New York, USA) were collected and analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) and black carbon. For each garden, samples were collected from nongrowing areas (non-bed) and from vegetable-growing beds, including beds with and without visible sources of PAHs. The sum of the US Environmental Protection Agency's 16 priority PAHs ranged up to 150 mg/kg, and the median (5.4 mg/kg) and mean (14.2 mg/kg) were similar to those previously reported for urban areas in the northeast United States. Isomer ratios indicated that the main sources of PAHs were petroleum, coal, and wood combustion. The PAH concentrations were significantly and positively associated with black carbon and with modeled air PAH concentrations, suggesting a consistent relationship between historical deposition of atmospheric carbon-adsorbed PAHs and current PAH soil concentrations. Median PAH soil concentration from non-bed areas was higher (7.4 mg/kg) than median concentration from beds in the same garden (4.0 mg/kg), and significantly higher than the median from beds without visible sources of PAHs (3.5 mg/kg). Median PAH concentration in beds from gardens with records of soil amendments was 58% lower compared with beds from gardens without those records. These results suggest that gardening practices in garden beds without visible sources of PAHs contribute to reduce PAH soil concentrations. © 2015 SETAC.

Health risk represented by inhaling polycyclic aromatic hydrocarbons (PAH) during daily commuting involving using a high traffic flow route in Bogotá.

PubMed

Pachón, Jorge E; Sarmiento, Hugo; Hoshiko, Tomomi

2013-01-01

Assessing the risk to health by inhaling particles and particle-bound PAH during daily commuting along a high traffic flow route/corridor in Bogotá. A van was equipped with a PAS2000 photo-electric sensor for real-time measurement of particle-bound PAH and a Dust Trakfor monitoring PM10 concentration; it drove along typical commuting routes in the city. Exposure to particles and particle-bound PAH was assessed by using an inhalation intake model. A similar trend was observed for both PM10 and PAH concentration, indicating that traffic was the same source for both contaminants. Extreme PM10 and PAH inhalation concentrations were recorded every time direct bus and microbus emissions were measured by the van. Inhalation model results indicated that exposure was significantly greater when using a venues having mixed traffic use (i.e. buses, microbuses, passenger vehicles, motorcycles) compared to using roads where the TransMilenio system (articulated buses) had been implemented. The results may support evaluating bus drivers, commuters and bike users' exposure to toxic compounds in the city.

Effect of central ventilation and air conditioner system on the concentration and health risk from airborne polycyclic aromatic hydrocarbons.

PubMed

Lv, Jinze; Zhu, Lizhong

2013-03-01

Central ventilation and air conditioner systems are widely utilized nowadays in public places for air exchange and temperature control, which significantly influences the transfer of pollutants between indoors and outdoors. To study the effect of central ventilation and air conditioner systems on the concentration and health risk from airborne pollutants, a spatial and temporal survey was carried out using polycyclic aromatic hydrocarbons (PAHs) as agent pollutants. During the period when the central ventilation system operated without air conditioning (AC-off period), concentrations of 2-4 ring PAHs in the model supermarket were dominated by outdoor levels, due to the good linearity between indoor air and outdoor air (r(p) > 0.769, p < 0.05), and the slopes (1.2-4.54) indicated that ventilating like the model supermarket increased the potential health risks from low molecular weight PAHs. During the period when the central ventilation and air conditioner systems were working simultaneously (AC-on period), although the total levels of PAHs were increased, the concentrations and percentage of the particulate PAHs indoors declined significantly. The BaP equivalency (BaPeq) concentration indicated that utilization of air conditioning reduced the health risks from PAHs in the model supermarket.

An Integrated Approach to Assess Exposure and Health-Risk from Polycyclic Aromatic Hydrocarbons (PAHs) in a Fastener Manufacturing Industry

PubMed Central

Hsu, Hsin-I; Lin, Ming-Yeng; Chen, Yu-Cheng; Chen, Wang-Yi; Yoon, Chungsik; Chen, Mei-Ru; Tsai, Perng-Jy

2014-01-01

An integrated approach was developed to assess exposure and health-risk from polycyclic aromatic hydrocarbons (PAHs) contained in oil mists in a fastener manufacturing industry. One previously developed model and one new model were adopted for predicting oil mist exposure concentrations emitted from metal work fluid (MWF) and PAHs contained in MWF by using the fastener production rate (Pr) and cumulative fastener production rate (CPr) as predictors, respectively. By applying the annual Pr and CPr records to the above two models, long-term workplace PAH exposure concentrations were predicted. In addition, true exposure data was also collected from the field. The predicted and measured concentrations respectively served as the prior and likelihood distributions in the Bayesian decision analysis (BDA), and the resultant posterior distributions were used to determine the long-term exposure and health-risks posed on workers. Results show that long term exposures to PAHs would result in a 3.1%, 96.7%, and 73.4% chance of exceeding the PEL-TWA (0.2 mg/m3), action level (0.1 mg/m3), and acceptable health risk (10−3), respectively. In conclusion, preventive measures should be taken immediately to reduce workers’ PAH exposures. PMID:25226413

A framework for the use of single-chemical transcriptomics data in predicting the hazards associated with complex mixtures of polycyclic aromatic hydrocarbons.

PubMed

Labib, Sarah; Williams, Andrew; Kuo, Byron; Yauk, Carole L; White, Paul A; Halappanavar, Sabina

2017-07-01

The assumption of additivity applied in the risk assessment of environmental mixtures containing carcinogenic polycyclic aromatic hydrocarbons (PAHs) was investigated using transcriptomics. MutaTMMouse were gavaged for 28 days with three doses of eight individual PAHs, two defined mixtures of PAHs, or coal tar, an environmentally ubiquitous complex mixture of PAHs. Microarrays were used to identify differentially expressed genes (DEGs) in lung tissue collected 3 days post-exposure. Cancer-related pathways perturbed by the individual or mixtures of PAHs were identified, and dose-response modeling of the DEGs was conducted to calculate gene/pathway benchmark doses (BMDs). Individual PAH-induced pathway perturbations (the median gene expression changes for all genes in a pathway relative to controls) and pathway BMDs were applied to models of additivity [i.e., concentration addition (CA), generalized concentration addition (GCA), and independent action (IA)] to generate predicted pathway-specific dose-response curves for each PAH mixture. The predicted and observed pathway dose-response curves were compared to assess the sensitivity of different additivity models. Transcriptomics-based additivity calculation showed that IA accurately predicted the pathway perturbations induced by all mixtures of PAHs. CA did not support the additivity assumption for the defined mixtures; however, GCA improved the CA predictions. Moreover, pathway BMDs derived for coal tar were comparable to BMDs derived from previously published coal tar-induced mouse lung tumor incidence data. These results suggest that in the absence of tumor incidence data, individual chemical-induced transcriptomics changes associated with cancer can be used to investigate the assumption of additivity and to predict the carcinogenic potential of a mixture.

Simulated infrared emission spectra of highly excited polyatomic molecules: a detailed model of the PAH-UIR hypothesis

NASA Technical Reports Server (NTRS)

Cook, D. J.; Saykally, R. J.

1998-01-01

A detailed description of the polycyclic aromatic hydrocarbon (PAH)/unidentified infrared band (UIR) mechanism is presented in which experimental spectral bandshape functions are used to simulate IR emission spectra for individual molecules. These spectra are additively superimposed to produce a conglomerate spectrum representative of a family of PAH molecules. Ab initio vibrational frequencies and intensities for nine PAHs (neutral and cationic) as large as ovalene are used in conjunction with measured bandshape and temperature-dependent redshift data to simulate the UIR bands. The calculated spectra of cations provide a closer match to the UIRs than do those of the neutrals. However, the PAH cations used in the simulations fail to reproduce the details of the UIR emission spectra. The discrepancies are potentially alleviated if both larger PAHs and a greater number of PAHs were included in the simulation.

Mechanistic quantitative structure-activity relationship model for the photoinduced toxicity of polycyclic aromatic hydrocarbons. 2: An empirical model for the toxicity of 16 polycyclic aromatic hydrocarbons to the duckweed Lemna gibba L. G-3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, X.D.; Krylov, S.N.; Ren, L.

1997-11-01

Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) occurs via photosensitization reactions (e.g., generation of singlet-state oxygen) and by photomodification (photooxidation and/or photolysis) of the chemicals to more toxic species. The quantitative structure-activity relationship (QSAR) described in the companion paper predicted, in theory, that photosensitization and photomodification additively contribute to toxicity. To substantiate this QSAR modeling exercise it was necessary to show that toxicity can be described by empirically derived parameters. The toxicity of 16 PAHs to the duckweed Lemna gibba was measured as inhibition of leaf production in simulated solar radiation (a light source with a spectrum similar to thatmore » of sunlight). A predictive model for toxicity was generated based on the theoretical model developed in the companion paper. The photophysical descriptors required of each PAH for modeling were efficiency of photon absorbance, relative uptake, quantum yield for triplet-state formation, and the rate of photomodification. The photomodification rates of the PAHs showed a moderate correlation to toxicity, whereas a derived photosensitization factor (PSF; based on absorbance, triplet-state quantum yield, and uptake) for each PAH showed only a weak, complex correlation to toxicity. However, summing the rate of photomodification and the PSF resulted in a strong correlation to toxicity that had predictive value. When the PSF and a derived photomodification factor (PMF; based on the photomodification rate and toxicity of the photomodified PAHs) were summed, an excellent explanatory model of toxicity was produced, substantiating the additive contributions of the two factors.« less

THE DUST PROPERTIES OF TWO HOT R CORONAE BOREALIS STARS AND A WOLF-RAYET CENTRAL STAR OF A PLANETARY NEBULA: IN SEARCH OF A POSSIBLE LINK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clayton, Geoffrey C.; Gallagher, J. S.; Freeman, W. R.

2011-08-15

We present new Spitzer/IRS spectra of two hot R Coronae Borealis (RCB) stars, one in the Galaxy, V348 Sgr, and one lying in the Large Magellanic Cloud, HV 2671. These two objects may constitute a link between the RCB stars and the late Wolf-Rayet ([WCL]) class of central stars of planetary nebulae (CSPNe), such as CPD -56{sup 0} 8032, that has little or no hydrogen in their atmospheres. HV 2671 and V348 Sgr are members of a rare subclass that has significantly higher effective temperatures than most RCB stars, but shares the traits of hydrogen deficiency and dust formation thatmore » define the cooler RCB stars. The [WC] CSPN star, CPD -56{sup 0} 8032, displays evidence of dual-dust chemistry showing both polycyclic aromatic hydrocarbons (PAHs) and crystalline silicates in its mid-IR spectrum. HV 2671 shows strong PAH emission but no sign of having crystalline silicates. The spectrum of V348 Sgr is very different from that of CPD -56{sup 0} 8032 and HV 2671. The PAH emission seen strongly in the other two stars is not present. Instead, the spectrum is dominated by a broad emission centered at about 8.2 {mu}m. This feature is not identified with either PAHs or silicates. Several other cool RCB stars, novae, and post-asymptotic giant branch stars show similar features in their IR spectra. The mid-IR spectrum of CPD -56{sup 0} 8032 shows emission features that may be associated with C{sub 60}. The other two stars do not show evidence of C{sub 60}. The different nature of the dust around these stars does not help us in establishing further links that may indicate a common origin. HV 2671 has also been detected by Herschel/PACS and SPIRE. V348 Sgr and CPD -56{sup 0} 8032 have been detected by AKARI/Far-Infrared Surveyor. These data were combined with Spitzer, IRAS, Two Micron All Sky Survey, and other photometry to produce their spectral energy distributions (SEDs) from the visible to the far-IR. Monte Carlo radiative transfer modeling was used to study the circumstellar dust around these stars. HV 2671 and CPD -56{sup 0} 8032 require both a flared inner disk with warm dust and an extended diffuse envelope with cold dust to fit their SEDs. The SED of V348 Sgr can be fit with a much smaller disk and envelope. The cold dust in the extended diffuse envelopes inferred around HV 2671 and CPD -56{sup 0} 8032 may consist of interstellar medium swept up during mass-loss episodes.« less

Urinary polycyclic aromatic hydrocarbons as a biomarker of exposure to PAHs in air: a pilot study among pregnant women.

PubMed

Nethery, Elizabeth; Wheeler, Amanda J; Fisher, Mandy; Sjödin, Andreas; Li, Zheng; Romanoff, Lovisa C; Foster, Warren; Arbuckle, Tye E

2012-01-01

Recent studies have linked increased polycyclic aromatic hydrocarbons (PAHs) in air and adverse fetal health outcomes. Urinary PAH metabolites are of interest for exposure assessment if they can predict PAHs in air. We investigated exposure to PAHs by collecting air and urine samples among pregnant women pre-selected as living in "high" (downtown and close to steel mills, n=9) and "low" (suburban, n=10) exposure areas. We analyzed first-morning urine voids from all 3 trimesters of pregnancy for urinary PAH metabolites and compared these to personal air PAH/PM(2.5)/NO(2)/NO(X) samples collected in the 3rd trimester. We also evaluated activities and home characteristics, geographic indicators and outdoor central site PM(2.5)/NO(2)/NO(X) (all trimesters). Personal air exposures to the lighter molecular weight (MW) PAHs were linked to indoor sources (candles and incense), whereas the heavier PAHs were related to outdoor sources. Geometric means of all personal air measurements were higher in the "high" exposure group. We suggest that centrally monitored heavier MW PAHs could be used to predict personal exposures for heavier PAHs only. Urine metabolites were only directly correlated with their parent air PAHs for phenanthrene (Pearson's r=0.31-0.45) and fluorene (r=0.37-0.58). Predictive models suggest that specific metabolites (3-hydroyxyfluorene and 3-hydroxyphenanthrene) may be related to their parent air PAH exposures. The metabolite 2-hydroxynaphthalene was linked to smoking and the metabolite 1-hydroxypyrene was linked to dietary exposures. For researchers interested in predicting exposure to airborne lighter MW PAHs using urinary PAH metabolites, we propose that hydroxyfluorene and hydroxyphenanthrene metabolites be considered.

The Diffuse Interstellar Bands: Solving a Century Old Problem

NASA Technical Reports Server (NTRS)

Salama, Farid

2017-01-01

The Diffuse Interstellar Bands (DIBs) are a set of apporoximately 500 absorption bands that are seen in the spectra of reddened stars (i.e., stars obscured by the presence of interstellar clouds in their line of sight). The first DIBs were detected in the visible over a century ago. Diffuse Interstellar Bands are now detected from the near ultraviolet to the near infrared in the spectra of reddened stars spanning a variety of interstellar environments in our local, and in other galaxies. Although DIB carriers are a significant part of the interstellar chemical inventory as they account for a noticeable fraction of the interstellar extinction, the nature of their carriers is still unknown over a century after the detection of the first bands. DIB carriers are stable and ubiquitous in a broad variety of interstellar environments and play a unique role in interstellar physics and chemistry. It has long been realized that the solving of the DIB problem requires a strong synergy between astronomical observations, laboratory astrophysics and astrochemistry, quantum chemistry calculations and astrophysical modeling of line-of-sights. In this review, we'll present and discuss the current state of this perplexing problem. We'll review the progress and the failures that have been encountered in the long quest for the identification of the carriers of these ubiquitous interstellar bands.

Use of a numerical simulation approach to improve the estimation of air-water exchange fluxes of polycyclic aromatic hydrocarbons in a coastal zone.

PubMed

Lai, I-Chien; Lee, Chon-Lin; Ko, Fung-Chi; Lin, Ju-Chieh; Huang, Hu-Ching; Shiu, Ruei-Feng

2017-07-15

The air-water exchange is important for determining the transport, fate, and chemical loading of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere and in aquatic systems. Investigations of PAH air-water exchange are mostly based on observational data obtained using complicated field sampling processes. This study proposes a new approach to improve the estimation of long-term PAH air-water exchange fluxes by using a multivariate regression model to simulate hourly gaseous PAH concentrations. Model performance analysis and the benefits from this approach indicate its effectiveness at improving the flux estimations and at decreasing the field sampling difficulty. The proposed GIS mapping approach is useful for box model establishment and is tested for visualization of the spatiotemporal variations of air-water exchange fluxes in a coastal zone. The air-water exchange fluxes illustrated by contour maps suggest that the atmospheric PAHs might have greater impacts on offshore sites than on the coastal area in this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

Emission characteristics for gaseous- and size-segregated particulate PAHs in coal combustion flue gas from circulating fluidized bed (CFB) boiler.

PubMed

Wang, Ruwei; Liu, Guijian; Sun, Ruoyu; Yousaf, Balal; Wang, Jizhong; Liu, Rongqiong; Zhang, Hong

2018-07-01

The partitioning behavior of polycyclic aromatic hydrocarbons (PAHs) between gaseous and particulate phases from coal-fired power plants (CFPPs) is critically important to predict PAH removal by dust control devices. In this study, 16 US-EPA priority PAHs in gaseous and size-segregated particulate phases at the inlet and outlet of the fabric filter unit (FFs) of a circulating fluidized bed (CFB) boiler were analyzed. The partitioning mechanisms of PAHs between gaseous and particulate phases and in particles of different size classes were investigated. We found that the removal efficiencies of PAHs are 45.59% and 70.67-89.06% for gaseous and particulate phases, respectively. The gaseous phase mainly contains low molecular weight (LMW) PAHs (2- and 3-ring PAHs), which is quite different from the particulate phase that mainly contains medium and high molecular weight (MMW and HMW) PAHs (4- to 6-ring PAHs). The fractions of LMW PAHs show a declining trend with the decrease of particle size. The gas-particle partitioning of PAHs is primarily controlled by organic carbon absorption, in addition, it has a clear dependence on the particle sizes. Plot of log (TPAH/PM) against logD p shows that all slope values were below -1, suggesting that PAHs were mainly adsorbed to particulates. The adsorption effect of PAHs in size-segregated PMs for HMW PAHs is more evident than LMW PAHs. The particle size distributions (PSDs) of individual PAHs show that most of PAHs exhibit bi-model structures, with one mode peaking in the accumulation size range (2.1-1.1 μm) and another mode peaking in coarse size range (5.8-4.7 μm). The intensities of these two peaks vary in function of ring number of PAHs, which is likely attributed to Kelvin effect that the less volatile HMW PAH species preferentially condense onto the finer particulates. The emission factor of PAHs was calculated as 3.53 mg/kg of coal burned, with overall mean EF PAH of 0.55 and 2.98 mg/kg for gaseous and particulate phase, respectively. Moreover, the average emission amount of PAHs for the investigated CFPP was 1016.6 g/day and 371073.6 g/y, respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Technical Civilizations in the Galaxy

NASA Technical Reports Server (NTRS)

Jones, Harry

2005-01-01

Are there other technical civilizations in the galaxy? Past analyses come to different conclusions. Cocconi and Morrison demonstrated in 1959 that interstellar radio communication was possible and Drake conducted the first search for beacons in 1960. The Drake equation estimates the number of galactic civilizations that are transmitting beacons as the product of the rate of star formation in the galaxy, the fraction of stars with planets, their average number of earthlike planets, the fraction with intelligent life and interstellar communication, and the average lifetime of a technical civilization. The Drake model of the galaxy contains many technical civilizations with communication but no interstellar travel. Michael Hart in 1975 strongly challenged this model. Starting with the fact that no extraterrestrials have been observed on Earth, and assuming that interstellar colonization is possible, he concluded that it was very likely that we are the first civilization in our galaxy and that searching or beacons is probably a waste of time and money. The Fermi paradox similarly reasons that if extraterrestrials exist: they should be here, and asks, Where are they? The Hart/Fermi model of the galaxy contains only our civilization and suggests we may colonize the galaxy. A third galactic model is that we are alone but will never develop interstellar travel. The fourth alternate model has many technical civilizations, with interstellar travel and colonization. The possibilities are clear and momentous. Either we are the only technical civilization in the galaxy or there are others. Technical civilizations will colonize the galaxy or not. We have four cosmic conjectures - one or many, colonization or not - but however unlikely they seem based on our limited evidence, one of these four models must be collect.

Application of Stochastic and Deterministic Approaches to Modeling Interstellar Chemistry

NASA Astrophysics Data System (ADS)

Pei, Yezhe

This work is about simulations of interstellar chemistry using the deterministic rate equation (RE) method and the stochastic moment equation (ME) method. Primordial metal-poor interstellar medium (ISM) is of our interest and the socalled “Population-II” stars could have been formed in this environment during the “Epoch of Reionization” in the baby universe. We build a gas phase model using the RE scheme to describe the ionization-powered interstellar chemistry. We demonstrate that OH replaces CO as the most abundant metal-bearing molecule in such interstellar clouds of the early universe. Grain surface reactions play an important role in the studies of astrochemistry. But the lack of an accurate yet effective simulation method still presents a challenge, especially for large, practical gas-grain system. We develop a hybrid scheme of moment equations and rate equations (HMR) for large gas-grain network to model astrochemical reactions in the interstellar clouds. Specifically, we have used a large chemical gas-grain model, with stochastic moment equations to treat the surface chemistry and deterministic rate equations to treat the gas phase chemistry, to simulate astrochemical systems as of the ISM in the Milky Way, the Large Magellanic Cloud (LMC) and Small Magellanic Cloud (SMC). We compare the results to those of pure rate equations and modified rate equations and present a discussion about how moment equations improve our theoretical modeling and how the abundances of the assorted species are changed by varied metallicity. We also model the observed composition of H2O, CO and CO2 ices toward Young Stellar Objects in the LMC and show that the HMR method gives a better match to the observation than the pure RE method.

Modeling Shocks Detected by Voyager 1 in the Local Interstellar Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, T. K.; Pogorelov, N. V.; Burlaga, L. F.

The magnetometer (MAG) on Voyager 1 ( V1 ) has been sampling the interstellar magnetic field (ISMF) since 2012 August. The V1 MAG observations have shown draped ISMF in the very local interstellar medium disturbed occasionally by significant enhancements in magnetic field strength. Using a three-dimensional, data-driven, multi-fluid model, we investigated these magnetic field enhancements beyond the heliopause that are supposedly associated with solar transients. To introduce time-dependent effects at the inner boundary at 1 au, we used daily averages of the solar wind parameters from the OMNI data set. The model ISMF strength, direction, and proton number density aremore » compared with V1 data beyond the heliopause. The model reproduced the large-scale fluctuations between 2012.652 and 2016.652, including major events around 2012.9 and 2014.6. The model also predicts shocks arriving at V1 around 2017.395 and 2019.502. Another model driven by OMNI data with interplanetary coronal mass ejections (ICMEs) removed at the inner boundary suggests that ICMEs may play a significant role in the propagation of shocks into the interstellar medium.« less

Assessing the long-range transport of PAH to a sub-Arctic site using positive matrix factorization and potential source contribution function

NASA Astrophysics Data System (ADS)

Sofowote, Uwayemi M.; Hung, Hayley; Rastogi, Ankit K.; Westgate, John N.; Deluca, Patrick F.; Su, Yushan; McCarry, Brian E.

2011-02-01

Gas-phase and particle-phase atmospheric samples collected in a sparsely populated sub-Arctic environment in the Yukon Territory, Canada were analyzed for a wide range of organic pollutants including polycyclic aromatic hydrocarbons (PAH). Receptor modeling using positive matrix factorization (PMF) was applied to a PAH data set from samples collected between August 2007 and December 2008 to afford four factors. These factors were designated as fossil fuel combustion emissions, particle-phase wood combustion emissions, gas-phase wood combustion emissions, and unburned petroleum/petrogenic emissions. The multiple linear regression-derived average contributions of these factors to the total PAH concentrations were 14% for fossil fuel combustion, 6% for particle-phase wood combustion emissions, 46% for gas-phase wood combustion emissions and 34% for petrogenic emissions. When the total PAH concentrations (defined as the sum of twenty-two PAH) and the PMF-modeled PAH concentrations set were compared, the correlation was excellent ( R2 = 0.97). Ten-day back trajectories starting at four different heights were used in a potential source contribution function analysis (PSCF) to assess the potential source regions of these PAH factors. Mapping the computed PSCF values for the four PMF factors revealed different source regions in the northern hemisphere for each PMF factor. Atmospheric transport of PAH occurred from both relatively short and long distances with both continental (North American) and trans-oceanic (Asian) sources contributing significantly to the total PAH. This study provides evidence of the transport of fossil fuel and wood combustion emissions from Asia, continental North America and northern Europe to sub-Arctic Canada (and by extension to the Canadian Arctic) primarily during cooler (fall-winter) months. This study demonstrates for the first time that the combined PMF-PSCF methodology can be used to identify geographically-disperse PAH source contributors on a hemispherical scale.

Hospitalizations Among Nursing Home Residents in the Last Year of Life: Nursing Home Characteristics and Variation in Potentially Avoidable Hospitalizations

PubMed Central

Xing, Jingping; Mukamel, Dana B.; Temkin-Greener, Helena

2013-01-01

Objectives 1) To examine the incidence, variations, and costs in potentially avoidable hospitalizations (PAHs) among nursing home (NH) residents at the end-of-life. 2) To identify the association between NH characteristics and a facility-level quality measure (QM) for PAH. Design Retrospective study. Setting Hospitalizations originating from NHs. Participants Long-term care NH residents who died in 2007. Measurements We constructed a risk-adjusted QM for PAH. Poisson regression model was used to predict the count of PAH given residents’ risk factors. For each facility, the QM was defined as the difference between the observed facility-specific rate (per 1,000 person-years) of PAH (O) and the expected risk-adjusted rate (E). We then fit a logistic regression model with state fixed-effects to examine the association between facility characteristics and the likelihood of having higher than expected rates of PAH (O-E>0). QM values higher than 0 indicate worse than average quality. Results Almost 50% of hospital admissions for NH residents in their last year of life were for potentially avoidable diagnoses, costing Medicare $1billion. Five conditions were responsible for over 80% of PAHs. PAH QM across facilities showed significant variation (mean=11.96; std dev=142.26; range: −399.48-398.09). Chain and hospital-based facilities were more likely to exhibit better performance (O-E<0). Facilities with higher nursing staffing were more likely to have better performance, as did facilities with higher skilled staff ratio, facilities with nurse practitioners/physician assistants, and those with on-site x-ray services. Conclusion Variations in facility-level PAHs suggest that a potential for reducing hospital admissions for these conditions may exist. Presence of modifiable facility characteristics associated with PAH performance provides insights into possible interventions for reducing PAHs at the end-of-life. PMID:24219191

Emission and atmospheric transport of particulate PAHs in Northeast Asia.

PubMed

Inomata, Yayoi; Kajino, Mizuo; Sato, Keiichi; Ohara, Toshimasa; Kurokawa, Jun-Ichi; Ueda, Hiromasa; Tang, Ning; Hayakawa, Kazuichi; Ohizumi, Tsuyoshi; Akimoto, Hajime

2012-05-01

The emission, concentration levels, and transboundary transport of particulate polycyclic aromatic hydrocarbons (PAHs) in Northeast Asia were investigated using particulate PAH measurements, the newly developed emission inventory (Regional Emission inventory in ASia for Persistent Organic Pollutants version, REAS-POP), and the chemical transport model (Regional Air Quality Model ver2 for POPs version, RAQM2-POP). The simulated concentrations of the nine particulate PAHs agreed well with the measured concentrations, and the results firmly established the efficacy of REAS/RAQM2-POP. It was found that the PAH concentrations in Beijing (China, source region), which were emitted predominantly from domestic coal, domestic biofuel, and other transformations of coal (including coke production), were approximately 2 orders of magnitude greater than those monitored at Noto (Japan, leeward region). In Noto, the PAH concentrations showed seasonal variations; the PAH concentrations were high from winter to spring due to contributions from domestic coal, domestic biofuel, and other transformations of coal, and low in summer. In summer, these contribution were decrease, instead, other sources, such as the on-road mobile source, were relatively increased compared with those in winter. These seasonal variations were due to seasonal variations in emissions from China, as well as transboundary transport across the Asian continent associated with meteorological conditions. © 2012 American Chemical Society

Inhalation Exposure to PM-Bound Polycyclic Aromatic Hydrocarbons Released from Barbecue Grills Powered by Gas, Lump Charcoal, and Charcoal Briquettes.

PubMed

Badyda, Artur J; Widziewicz, Kamila; Rogula-Kozłowska, Wioletta; Majewski, Grzegorz; Jureczko, Izabela

2018-01-01

The present study seeks to define the possible cancer risk arising from the inhalation exposure to particle (PM)-bound polycyclic aromatic hydrocarbons (PAHs) present in barbecue emission gases and to compare the risk depending on the type of fuel used for grill powering. Three types of fuel were compared: liquid propane gas, lump charcoal, and charcoal briquettes. PM 2.5 and PM 2.5-100 were collected during grilling. Subsequently, 16 PAHs congeners were extracted from the PM samples and measured quantitatively using gas chromatography. The content of PM-bound PAHs was used to calculate PAHs deposition in the respiratory tract using the multiple path particle dosimetry model. Finally, a probabilistic risk model was developed to assess the incremental lifetime cancer risk (ILCR) faced by people exposed to PAHs. We found a distinctly greater PAHs formation in case of grills powered by charcoal briquettes. The summary concentration of PAHs (Σ16PAH) ranged from <0.002 μg/m 3 (gas grill) to 21.52 μg/m 3 (grill powered by briquettes). Daily exposure of a grill operator, while grilling meat, to PM 2.5 -bound PAHs, adjusted to benzo[a]pyrene toxicity equivalent (BaP eq ), was 326.9, 401.6, and 0.04 ng/d for lump charcoal, charcoal briquettes, and gas powered grill, respectively. Exposure to PAHs emitted from charcoal briquettes was four orders of magnitude greater than that for gas grill. The ILCR followed a log-normal distribution, with a geometric mean of 8.38 × 10 -5 for exposure to PM 2.5 -bound PAHs emitted from gas grills unloaded with food and as high as 8.68 × 10 -1 for the grills loaded with food over charcoal briquettes. The estimated cancer risk for people who would inhale barbecue particles for 5 h a day, 40 days a year exceeds the acceptable level set by the U.S. Environmental Protection Agency. We conclude that the type of heat source used for grilling influences the PM-bound PAHs formation. The greatest concentration of PAHs is generated when grilling over charcoal briquettes. Loading grills with food generates conspicuously more PAHs emissions. Traditional grilling poses cancer risk much above the acceptable limit, as opposed to much less risk involving gas powered grills.

Diamonds in dense molecular clouds - A challenge to the standard interstellar medium paradigm

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Sandford, S. A.; Tielens, A. G. G. M.; Herbst, T. M.

1993-01-01

Observations of a newly discovered infrared C-H stretching band indicate that interstellar diamond-like material appears to be characteristic of dense clouds. In sharp contrast, the spectral signature of dust in the diffuse interstellar medium is dominated by -CH2- and -CH3 groups. This dichotomy in the aliphatic organic component between the dense and diffuse media challenges standard assumptions about the processes occurring in, and interactions between, these two media. The ubiquity of this interstellar diamond-like material rules out models for meteoritic diamond formation in unusual circumstellar environments and implies that the formation of the diamond-like material is associated with common interstellar processes or stellar types.

INTERACTION ANALYSES OF BINARY MIXTURES OF CARCINOGENIC PAHS USING MORPHOLOGICAL CELL TRANSFORMATION OF C3H1OT1/2CL8 MOUSE EMBRYO FIBROBLASTS IN CULTURE.

EPA Science Inventory

Studies of defined mixtures of carcinogenic polycyclic aromatic hydrocarbons (PAH) have shown three major categories of interactions: antagonism, synergism, and additivity depending on the biological model, tissue, route of exposure, and specific PAH. To understand the bases of t...

THERMODYNAMICS AND CHARGING OF INTERSTELLAR IRON NANOPARTICLES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Brandon S.; Draine, B. T., E-mail: brandon.s.hensley@jpl.nasa.gov

Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar ironmore » is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.« less

25 years monitoring of PAHs and petroleum hydrocarbons biodegradation in soil.

PubMed

Harmsen, Joop; Rietra, René P J J

2018-05-10

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPH) in sediment and soil has been monitored on seven experimental fields during periods up to 25 years. With this unique dataset, we investigated long-term very slow biodegradation under field conditions. . The data show that three biodegradation rates can be distinguished for PAHs: 1) rapid degradation during the first year, 2) slow degradation during the following 6 years and 3), subject of this paper, a very slow degradation after 7 years until at least 25 years. Beside 2-, 3- and 4-ring PAHs, also 5- and 6-ring PAHs (aromatic rings) were degraded, all at the same rate during very slow degradation. In the period of very slow degradation, 6% yr -1 of the PAHs present were removed in five fields and 2% yr -1 in two other fields, while in the same period no very slow degradation of TPH could be observed. The remaining petroleum hydrocarbons were high boiling and non-toxic. Using the calculated degradation rates and the independently measured bioavailability of the PAHs (Tenax-method), the PAHs degradation curves of all seven monitored fields could be modelled. Applying the model and data obtained with the Tenax-method for fresh contaminated material, results of long-term biodegradation can be predicted, which can support the use of bioremediation in order to obtain a legally acceptable residual concentration. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Bioacessibility of PAHs in fuel soot assessed by an in vitro digestive model: effect of including an absorptive sink.

PubMed

Zhang, Yanyan; Pignatello, Joseph J; Tao, Shu; Xing, Baoshan

2015-03-17

Polycyclic aromatic hydrocarbons (PAHs) associated with soot or black carbon can enter the human digestive tract by unintentional ingestion of soil or other particles. This study investigated the bioaccessibility of 11 PAHs in a composite fuel soot sample using an in vitro digestive model that included silicone sheet as an absorptive sink during the small intestinal digestion stage. The sheet was meant to simulate the passive transfer of PAHs in lumen fluid across the small intestinal epithelium, which was postulated to promote desorption of labile PAHs from the soot by steepening the soot-fluid concentration gradient. We show that the presence of silicone sheet during a 4 h default digestion time significantly increased the apparent bioaccessible fraction (Bapp, %), defined as the sum in the sheet and digestive fluid relative to the total PAH determined. The ability to increase Bapp for most PAHs leveled off above a sheet-to-soot ratio of 2.0 g per 50 mg, indicating that the sheet is an effective absorptive sink and promotes desorption in the mentioned way. Enhancement of Bapp by the sheet correlated positively with the octanol-water partition coefficient (Kow), even though the partition coefficient of PAH between sheet and digestive fluid (which contains bile acid micelles) correlated negatively with Kow. It was hypothesized that PAHs initially in the soot exist in labile and nonlabile states. The fraction of labile PAH still sorbed to the soot residue after digestion, and the maximum possible (limiting) bioaccessibility (Blim) could be estimated by varying the sheet-to-soot ratio. We show conclusively that the increase in bioccessibility due to the presence of the sheet is accounted for by a corresponding decrease in fraction of labile PAH still sorbed to the soot. The Blim ranged from 30.8 to 62.4%, independent of molecular size. The nonlabile fraction of individual PAHs (69.2-37.6% in this case) is therefore large and needs to be taken into account in risk assessment.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish.

PubMed

Geier, Mitra C; James Minick, D; Truong, Lisa; Tilton, Susan; Pande, Paritosh; Anderson, Kim A; Teeguardan, Justin; Tanguay, Robert L

2018-04-06

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. We constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilization (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures. Copyright © 2018 Elsevier Inc. All rights reserved.

DEVELOPMENT OF THE MODEL OF GALACTIC INTERSTELLAR EMISSION FOR STANDARD POINT-SOURCE ANALYSIS OF FERMI LARGE AREA TELESCOPE DATA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acero, F.; Ballet, J.; Ackermann, M.

2016-04-01

Most of the celestial γ rays detected by the Large Area Telescope (LAT) on board the Fermi Gamma-ray Space Telescope originate from the interstellar medium when energetic cosmic rays interact with interstellar nucleons and photons. Conventional point-source and extended-source studies rely on the modeling of this diffuse emission for accurate characterization. Here, we describe the development of the Galactic Interstellar Emission Model (GIEM), which is the standard adopted by the LAT Collaboration and is publicly available. This model is based on a linear combination of maps for interstellar gas column density in Galactocentric annuli and for the inverse-Compton emission producedmore » in the Galaxy. In the GIEM, we also include large-scale structures like Loop I and the Fermi bubbles. The measured gas emissivity spectra confirm that the cosmic-ray proton density decreases with Galactocentric distance beyond 5 kpc from the Galactic Center. The measurements also suggest a softening of the proton spectrum with Galactocentric distance. We observe that the Fermi bubbles have boundaries with a shape similar to a catenary at latitudes below 20° and we observe an enhanced emission toward their base extending in the north and south Galactic directions and located within ∼4° of the Galactic Center.« less

Development of the Model of Galactic Interstellar Emission for Standard Point-Source Analysis of Fermi Large Area Telescope Data

DOE PAGES

Acero, F.

2016-04-22

Most of the celestial γ rays detected by the Large Area Telescope (LAT) aboard the Fermi Gamma-ray Space Telescope originate from the interstellar medium when energetic cosmic rays interact with interstellar nucleons and photons. Conventional point and extended source studies rely on the modeling of this diffuse emission for accurate characterization. We describe here the development of the Galactic Interstellar Emission Model (GIEM) that is the standard adopted by the LAT Collaboration and is publicly available. The model is based on a linear combination of maps for interstellar gas column density in Galactocentric annuli and for the inverse Compton emissionmore » produced in the Galaxy. We also include in the GIEM large-scale structures like Loop I and the Fermi bubbles. The measured gas emissivity spectra con rm that the cosmic-ray proton density decreases with Galactocentric distance beyond 5 kpc from the Galactic Center. The measurements also suggest a softening of the proton spectrum with Galactocentric distance. We observe that the Fermi bubbles have boundaries with a shape similar to a catenary at latitudes below 20° and we observe an enhanced emission toward their base extending in the North and South Galactic direction and located within ~4° of the Galactic Center.« less

Development of the Model of Galactic Interstellar Emission for Standard Point-Source Analysis of Fermi Large Area Telescope Data

NASA Technical Reports Server (NTRS)

Acero, F.; Ackermann, M.; Ajello, M.; Albert, A.; Baldini, L.; Ballet, J.; Barbiellini, G.; Bastieri, D.; Bellazzini, R.; Brandt, T. J.;

Solubilization, Solution Equilibria, and Biodegradation of PAH's under Thermophilic Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Viamajala, S.; Peyton, B. M.; Richards, L. A.

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 C, 40 C and 60 C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energymore » of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.« less

Tyrosine kinase inhibitors in pulmonary arterial hypertension: a double-edge sword?

PubMed

Godinas, Laurent; Guignabert, Christophe; Seferian, Andrei; Perros, Frederic; Bergot, Emmanuel; Sibille, Yves; Humbert, Marc; Montani, David

2013-10-01

New treatments for pulmonary arterial hypertension (PAH) are a crucial need. The increased proliferation, migration, and survival of pulmonary vascular cells within the pulmonary artery wall in PAH have allowed successful transposition of pathophysiological elements from oncologic researches. Next steps will require translation of these biological advances in PAH therapeutic arsenal and guidelines. This review synthesizes recent data concerning the role of receptor tyrosine kinases and their inhibitors in PAH, with implications in animal models and humans. Results of clinical trials are now accumulating to establish beneficial role of tyrosine kinase inhibitors (TKIs) in PAH and further findings are expected in the near future. Beside this curative approach, evidences of a possible TKI-induced cardiotoxicity are emerging. These safety issues raise concern about a potential amplified harmful effect in PAH, a pathology characterized by an underlying cardiac dysfunction. In addition, analyses of PAH registries shed light on a selective pulmonary vascular toxicity triggered by TKIs, especially dasatinib. These possible dual effects of the TKIs in PAH need to be taken in account for future pharmacological development of this therapeutic class in PAH. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

Interstellar Isotopes: Prospects with ALMA

NASA Technical Reports Server (NTRS)

Charnley Steven B.

2010-01-01

Cold molecular clouds are natural environments for the enrichment of interstellar molecules in the heavy isotopes of H, C, N and O. Anomalously fractionated isotopic material is found in many primitive Solar System objects, such as meteorites and comets, that may trace interstellar matter that was incorporated into the Solar Nebula without undergoing significant processing. Models of the fractionation chemistry of H, C, N and O in dense molecular clouds, particularly in cores where substantial freeze-out of molecules on to dust has occurred, make several predictions that can be tested in the near future by molecular line observations. The range of fractionation ratios expected in different interstellar molecules will be discussed and the capabilities of ALMA for testing these models (e.g. in observing doubly-substituted isotopologues) will be outlined.

Phototransformation Rate Constants of PAHs Associated with Soot Particles

PubMed Central

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

Mechanism-based classification of PAH mixtures to predict carcinogenic potential

DOE PAGES

Tilton, Susan C.; Siddens, Lisbeth K.; Krueger, Sharon K.; ...

2015-04-22

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[ a]pyrene (BaP). Therefore, we developed a pathway based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[ def,p]chrysene (DBC), BaP or environmental PAH mixtures (Mix 1-3) following a two-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC>>BaP=Mix2=Mix3>Mix1=Control, based on statistical significance. Gene expression profilesmore » measured in skin of mice collected 12 h post-initiation were compared to tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (p<0.05) for DNA damage, apoptosis, response to chemical stimulus and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. As a result, these data further provide a ‘source-to outcome’ model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action based risk assessment could be employed for environmental PAH mixtures.« less

Mechanism-Based Classification of PAH Mixtures to Predict Carcinogenic Potential.

PubMed

Tilton, Susan C; Siddens, Lisbeth K; Krueger, Sharon K; Larkin, Andrew J; Löhr, Christiane V; Williams, David E; Baird, William M; Waters, Katrina M

2015-07-01

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[a]pyrene (BaP). Therefore, we developed a pathway-based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[def,p]chrysene (DBC), BaP, or environmental PAH mixtures (Mix 1-3) following a 2-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC > BaP = Mix2 = Mix3 > Mix1 = Control, based on statistical significance. Gene expression profiles measured in skin of mice collected 12 h post-initiation were compared with tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (P < .05) for DNA damage, apoptosis, response to chemical stimulus, and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. These data further provide a 'source-to-outcome' model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action-based risk assessment could be employed for environmental PAH mixtures. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

The efficiency of photodissociation for molecules in interstellar ices

NASA Astrophysics Data System (ADS)

Kalvāns, J.

2018-05-01

Processing by interstellar photons affects the composition of the icy mantles on interstellar grains. The rate of photodissociation in solids differs from that of molecules in the gas phase. The aim of this work was to determine an average, general ratio between photodissociation coefficients for molecules in ice and gas. A 1D astrochemical model was utilized to simulate the chemical composition for a line of sight through a collapsing interstellar cloud core, whose interstellar extinction changes with time. At different extinctions, the calculated column densities of icy carbon oxides and ammonia (relative to water ice) were compared to observations. The latter were taken from literature data of background stars sampling ices in molecular clouds. The best-fit value for the solid/gas photodissociation coefficient ratio was found to be ≈0.3. In other words, gas-phase photodissociation rate coefficients have to be reduced by a factor of 0.3 before applying them to icy species. A crucial part of the model is a proper inclusion of cosmic-ray induced desorption. Observations sampling gas with total extinctions in excess of ≈22 mag were found to be uncorrelated to modelling results, possibly because of grains being covered with non-polar molecules.

Detecting the building blocks of aromatics

NASA Astrophysics Data System (ADS)

Joblin, Christine; Cernicharo, José

2018-01-01

Interstellar clouds are sites of active organic chemistry (1). Many small, gasphase molecules are found in the dark parts of the clouds that are protected from ultraviolet (UV) photons, but these molecules photodissociate in the external layers of the cloud that are exposed to stellar radiation (see the photo). These irradiated regions are populated by large polycyclic aromatic hydrocarbons (PAHs) with characteristic infrared (IR) emission features. These large aromatics are expected to form from benzene (C6H6), which is, however, difficult to detect because it does not have a permanent dipole moment and can only be detected via its IR absorption transitions against a strong background source (2). On page 202 of this issue, McGuire et al. (3) report the detection of benzonitrile (c-C6H5CN) with radio telescopes. Benzonitrile likely forms in the reaction of CN with benzene; from its observation, it is therefore possible to estimate the abundance of benzene itself.

Atmospheric concentrations, sources and gas-particle partitioning of PAHs in Beijing after the 29th Olympic Games.

PubMed

Ma, Wan-Li; Sun, De-Zhi; Shen, Wei-Guo; Yang, Meng; Qi, Hong; Liu, Li-Yan; Shen, Ji-Min; Li, Yi-Fan

2011-07-01

A comprehensive sampling campaign was carried out to study atmospheric concentration of polycyclic aromatic hydrocarbons (PAHs) in Beijing and to evaluate the effectiveness of source control strategies in reducing PAHs pollution after the 29th Olympic Games. The sub-cooled liquid vapor pressure (logP(L)(o))-based model and octanol-air partition coefficient (K(oa))-based model were applied based on each seasonal dateset. Regression analysis among log K(P), logP(L)(o) and log K(oa) exhibited high significant correlations for four seasons. Source factors were identified by principle component analysis and contributions were further estimated by multiple linear regression. Pyrogenic sources and coke oven emission were identified as major sources for both the non-heating and heating seasons. As compared with literatures, the mean PAH concentrations before and after the 29th Olympic Games were reduced by more than 60%, indicating that the source control measures were effective for reducing PAHs pollution in Beijing. Copyright © 2011 Elsevier Ltd. All rights reserved.

Combining measurements and modelling to quantify the contribution of atmospheric fallout, local industry and road traffic to PAH stocks in contrasting catchments.

PubMed

Gateuille, David; Evrard, Olivier; Lefevre, Irène; Moreau-Guigon, Elodie; Alliot, Fabrice; Chevreuil, Marc; Mouchel, Jean-Marie

2014-06-01

Various sources supply PAHs that accumulate in soils. The methodology we developed provided an evaluation of the contribution of local sources (road traffic, local industries) versus remote sources (long range atmospheric transport, fallout and gaseous exchanges) to PAH stocks in two contrasting subcatchments (46-614 km²) of the Seine River basin (France). Soil samples (n = 336) were analysed to investigate the spatial pattern of soil contamination across the catchments and an original combination with radionuclide measurements provided new insights into the evolution of the contamination with depth. Relationships between PAH concentrations and the distance to the potential sources were modelled. Despite both subcatchments are mainly rural, roadside areas appeared to concentrate 20% of the contamination inside the catchment while a local industry was found to be responsible for up to 30% of the stocks. Those results have important implications for understanding and controlling PAH contamination in rural areas of early-industrialized regions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Impact of carbonaceous materials in soil on the transport of soil-bound PAHs during rainfall-runoff events.

PubMed

Luo, Xiaolin; Zheng, Yi; Wu, Bin; Lin, Zhongrong; Han, Feng; Zhang, Wei; Wang, Xuejun

2013-11-01

Polycyclic Aromatic Hydrocarbons (PAHs) transported from contaminated soils by surface runoff pose significant risk for aquatic ecosystems. Based on a rainfall-runoff simulation experiment, this study investigated the impact of carbonaceous materials (CMs) in soil, identified by organic petrology analysis, on the transport of soil-bound PAHs under rainfall conditions. The hypothesis that composition of soil organic matter significantly impacts the enrichment and transport of PAHs was proved. CMs in soil, varying significantly in content, mobility and adsorption capacity, act differently on the transport of PAHs. Anthropogenic CMs like black carbon (BC) largely control the transport, as PAHs may be preferentially attached to them. Eventually, this study led to a rethink of the traditional enrichment theory. An important implication is that CMs in soil have to be explicitly considered to appropriately model the nonpoint source pollution of PAHs (possibly other hydrophobic chemicals as well) and assess its environmental risk. Copyright © 2013 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons in ambient air, surface soil and wheat grain near a large steel-smelting manufacturer in northern China.

PubMed

Liu, Weijian; Wang, Yilong; Chen, Yuanchen; Tao, Shu; Liu, Wenxin

2017-07-01

The total concentrations and component profiles of polycyclic aromatic hydrocarbons (PAHs) in ambient air, surface soil and wheat grain collected from wheat fields near a large steel-smelting manufacturer in Northern China were determined. Based on the specific isomeric ratios of paired species in ambient air, principle component analysis and multivariate linear regression, the main emission source of local PAHs was identified as a mixture of industrial and domestic coal combustion, biomass burning and traffic exhaust. The total organic carbon (TOC) fraction was considerably correlated with the total and individual PAH concentrations in surface soil. The total concentrations of PAHs in wheat grain were relatively low, with dominant low molecular weight constituents, and the compositional profile was more similar to that in ambient air than in topsoil. Combined with more significant results from partial correlation and linear regression models, the contribution from air PAHs to grain PAHs may be greater than that from soil PAHs. Copyright © 2016. Published by Elsevier B.V.

Boundary conditions for the paleoenvironment: Chemical and Physical Processes in dense interstellar clouds

NASA Technical Reports Server (NTRS)

Irvine, W. M.; Schloerb, F. P.; Ziurys, L. M.

1986-01-01

The present research includes searches for important new interstellar constituents; observations relevant to differentiating between different models for the chemical processes that are important in the interstellar environment; and coordinated studies of the chemistry, physics, and dynamics of molecular clouds which are the sites or possible future sites of star formation. Recent research has included the detection and study of four new interstellar molecules; searches which have placed upper limits on the abundance of several other potential constituents of interstellar clouds; quantitative studies of comparative molecular abundances in different types of interstellar clouds; investigation of reaction pathways for astrochemistry from a comparison of theory and the observed abundance of related species such as isomers and isotopic variants; studies of possible tracers of energenic events related to star formation, including silicon and sulfur containing molecules; and mapping of physical, chemical, and dynamical properties over extended regions of nearby cold molecular clouds.

Estimation of the emission factors of PAHs by traffic with the model of atmospheric dispersion and deposition from heavy traffic road.

PubMed

Ozaki, N; Tokumitsu, H; Kojima, K; Kindaichi, T

2007-01-01

In order to consider the total atmospheric loadings of the PAHs (polycyclic aromatic hydrocarbons) from traffic activities, the emission factors of PAHs were estimated and from the obtained emission factors and vehicle transportation statistics, total atmospheric loadings were integrated and the loadings into the water body were estimated on a regional scale. The atmospheric concentration of PAHs was measured at the roadside of a road with heavy traffic in the Hiroshima area in Japan. The samplings were conducted in summer and winter. Atmospheric particulate matters (fine particle, 0.6-7 microm; coarse particle, over 7 microm) and their PAH concentration were measured. Also, four major emission sources (gasoline and diesel vehicle emissions, tire and asphalt debris) were assumed for vehicle transportation activities, the chemical mass balance method was applied and the source partitioning at the roadside was estimated. Furthermore, the dispersion of atmospheric particles from the vehicles was modelled and the emission factors of the sources were determined by the comparison to the chemical mass balance results. Based on emission factors derived from the modelling, an atmospheric dispersion model of nationwide scale (National Institute of Advanced Industrial Science and Technology - Atmospheric Dispersion Model for Exposure and Risk assessment) was applied, and the atmospheric concentration and loading to the ground were calculated for the Hiroshima Bay watershed area.

Seasonal changes, identification and source apportionment of PAH in PM1.0

NASA Astrophysics Data System (ADS)

Agudelo-Castañeda, Dayana Milena; Teixeira, Elba Calesso

2014-10-01

The objective of this research was to evaluate the seasonal variation of PAHs in PM1.0, as well as to identify and quantify the contributions of each source profile using the PMF receptor model. PM1.0 samples were collected on PTFE filters from August 2011 to July 2013 in the Metropolitan Area of Porto Alegre, Rio Grande do Sul, Brazil. The samples were extracted using the EPA method TO-13A and 16 Polycyclic Aromatic Hydrocarbons (PAHs) were analyzed using a gaseous chromatograph coupled with a mass spectrometer (GC-MS). Also, the data discussed in this study were analyzed to identify the relations of the PAHs concentrations with NOx, NO, O3 and meteorological parameters (temperature, solar radiation, wind speed, relative humidity). The results showed that in winter, concentrations of total PAHs were significantly higher than in summer, thus showing their seasonal variation. The identification of emission sources by applying diagnostic ratios confirmed that PAHs in the study area originate from mobile sources, especially, from diesel and gasoline emissions. The analysis by PMF receptor model showed the contribution of these two main sources of emissions, too, followed by coal combustion, incomplete combustion/unburned petroleum and wood combustion. The toxic equivalent factors were calculated to characterize the risk of cancer from PAH exposure to PM1.0 samples, and BaP and DahA dominated BaPeq levels.

Modeling Dust in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Zonca, Alberto; Casu, Silvia; Mulas, Giacomo; Aresu, Giambattista; Cecchi-Pestellini, Cesare

2015-09-01

We model the extinction profiles observed in the Small and Large Magellanic clouds with a synthetic population of dust grains consisting of core-mantle particles and a collection of free-flying polycyclic aromatic hydrocarbons (PAHs). All different flavors of the extinction curves observed in the Magellanic Clouds (MCs) can be described by the present model, which has been previously (successfully) applied to a large sample of diffuse and translucent lines of sight in the Milky Way. We find that in the MCs the extinction produced by classical grains is generally larger than absorption by PAHs. Within this model, the nonlinear far-UV rise is accounted for by PAHs, whose presence in turn is always associated with a gap in the size distribution of classical particles. This hints either at a physical connection between (e.g., a common cause for) PAHs and the absence of middle-sized dust particles or the need for an additional component in the model that can account for the nonlinear far-UV rise without contributing to the UV bump at ∼217 nm such as, e.g., nanodiamonds.

Characterization and source apportionment of PM2.5-bound polycyclic aromatic hydrocarbons from Shanghai city, China.

PubMed

Wang, Qing; Liu, Min; Yu, Yingpeng; Li, Ye

2016-11-01

Polycyclic aromatic hydrocarbons (PAHs) were studied in 230 daily fine particulate matter (PM2.5) samples collected in four seasons at urban and suburban sites of Shanghai, China. This study focused on the emission sources of PAHs and its dynamic results under different weather conditions and pollution levels and also emphasized on the spatial sources of PM2.5 and PAHs at a regional level. Annual concentrations of PM2.5 and 16 EPA priority PAHs were 53 μg/m 3 and 6.9 ng/m 3 , respectively, with highest levels in winter. Positive matrix factorization (PMF) modeling identified four sources of PAHs: coal combustion, traffic, volatilization and biomass combustion, and coking, with contributions of 34.9%, 27.5%, 21.1% and 16.5%, respectively. The contribution of traffic, a local-indicative source, increased from 17.4% to 28.7% when wind speed changed from >2m/s to <2m/s, and increased from 18.3% to 31.3% when daily PAH concentrations changed from below to above the annual mean values. This indicated that local sources may have larger contributions under stagnant weather when poorer dispersion conditions and lower wind speed led to the accumulation of local-emitted pollutants. The trajectory clustering and potential source contribution function (PSCF) and concentration weighted trajectory (CWT) models showed clearly that air parcels moved from west had highest concentrations of PM2.5, total PAHs and high molecular weight (HMW) PAHs. While small differences were found among all five clusters in low molecular weight (LMW) PAHs. Sector analyses determined that regional transport source contributed 39.8% to annual PM2.5 and 52.5% to PAHs, mainly from western regions and varying with seasons. This work may make contribution to a better understanding and control of the increasingly severe air pollution in China as well as other developing Asian countries. Copyright © 2016 Elsevier Ltd. All rights reserved.

Seasonal variations and source apportionment of complex polycyclic aromatic hydrocarbon mixtures in particulate matter in an electronic waste and urban area in South China.

PubMed

Chen, She-Jun; Wang, Jing; Wang, Tao; Wang, Ting; Mai, Bi-Xian; Simonich, Staci L Massey

2016-12-15

Complex polycyclic aromatic hydrocarbon (PAH) mixtures including parent PAHs, high molecular weight PAHs (MW 302 PAHs), and halogenated PAHs (HPAHs) were measured in particulate matter (PM) in an urban area and a rural electronic waste area in South China. The concentrations of MW < 302 PAHs at two sites were not significantly different with annual means of 23.2 ± 17.2 and 33.7 ± 29.0 ng/m 3 , respectively. However the concentrations of both MW 302 PAHs (5.35 ± 3.72 ng/m 3 ) and HPAH (49.9 pg/m 3 ) were significantly higher at the e-waste site than the urban site (2.81 ± 2.36 ng/m 3 and 28.2 ± 28.5 pg/m 3 ), suggesting e-waste recycling being a significant source of these PAHs. The majority of PAHs exhibited higher concentrations in winter and spring and lower concentrations in fall and summer. Meteorological conditions and increased emissions of PAHs in northern China due to domestic heating in colder seasons are important factors influencing the PAH seasonal variations. Source apportionment by the chemical mass balance (CMB) model indicated that residential stoves (coal combustion), industrial boilers (coal combustion), biomass burning, and vehicular emission accounted for 38 ± 14%, 30 ± 11%, 22 ± 22%, and 10 ± 7% of the PAHs in the urban PM, respectively. Comparable contributions from these sources were also observed for PM at the e-waste site. PAH emission factors are needed for primitive e-waste recycling to further understand the importance of this source to ambient air. Copyright © 2016 Elsevier B.V. All rights reserved.

Polycyclic Aromatic Hydrocarbons in Protoplanetary Disks around Herbig Ae/Be and T Tauri Stars

NASA Astrophysics Data System (ADS)

Seok, Ji Yeon; Li, Aigen

2017-02-01

A distinct set of broad emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μm, is often detected in protoplanetary disks (PPDs). These features are commonly attributed to polycyclic aromatic hydrocarbons (PAHs). We model these emission features in the infrared spectra of 69 PPDs around 14 T Tauri and 55 Herbig Ae/Be stars in terms of astronomical PAHs. For each PPD, we derive the size distribution and the charge state of the PAHs. We then examine the correlations of the PAH properties (I.e., sizes and ionization fractions) with the stellar properties (e.g., stellar effective temperature, luminosity, and mass). We find that the characteristic size of the PAHs tends to correlate with the stellar effective temperature ({T}{eff}) and interpret this as the preferential photodissociation of small PAHs in systems with higher {T}{eff} of which the stellar photons are more energetic. In addition, the PAH size shows a moderate correlation with the red-ward wavelength shift of the 7.7 μm PAH feature that is commonly observed in disks around cool stars. The ionization fraction of PAHs does not seem to correlate with any stellar parameters. This is because the charging of PAHs depends on not only the stellar properties (e.g., {T}{eff}, luminosity) but also their spatial distribution in the disks. The marginally negative correlation between PAH size and stellar age suggests that continuous replenishment of PAHs via the outgassing of cometary bodies and/or the collisional grinding of planetesimals and asteroids is required to maintain the abundance of small PAHs against complete destruction by photodissociation.

Comparing PAH availability from manufactured gas plant soils and sediments with chemical and biological tests. 1. PAH release during water desorption and supercritical carbon dioxide extraction.

PubMed

Hawthorne, Steven B; Poppendieck, Dustin G; Grabanski, Carol B; Loehr, Raymond C

2002-11-15

Soil and sediment samples from oil gas (OG) and coal gas (CG) manufactured gas plant (MGP) sites were selected to represent a range of PAH concentrations (150-40,000 mg/kg) and sample matrix compositions. Samples varied from vegetated soils to lampblack soot and had carbon contents from 3 to 87 wt %. SFE desorption (120 min) and water/XAD2 desorption (120 days) curves were determined and fit with a simple two-site model to determine the rapid-released fraction (F) for PAHs ranging from naphthalene to benzo[ghi]perylene. F values varied greatly among the samples, from ca. 10% to >90% for the two- and three-ring PAHs and from <1% to ca. 50% for the five- and six-ring PAHs. Release rates did not correlate with sample matrix characteristics including PAH concentrations, elemental composition (C, H, N, S), or "hard" and "softs" organic carbon, indicating that PAH release cannot easily be estimated on the basis of sample matrix composition. Fvalues for CG site samples obtained with SFE and water desorption agreed well (linear correlation coefficient, r2 = 0.87, slope = 0.93), but SFE yielded higher F values for the OG samples. These behaviors were attributed to the stronger ability of carbon dioxide than water to desorb PAHs from the highly aromatic (hard) carbon of the OG matrixes, while carbon dioxide and water showed similar abilities to desorb PAHs from the more polar (soft) carbon of the CG samples. The combined SFE and water desorption approaches should improve the understanding of PAH sequestration and release from contaminated soils and sediments and provide the basis for subsequent studies using the same samples to compare PAH release with PAH availability to earthworms.

Radiative Feedback from Massive Stars as Traced by Multiband Imaging and Spectroscopic Mosaics

NASA Astrophysics Data System (ADS)

Tielens, Alexander; "PDRs4ever" team

2018-06-01

Massive stars disrupt their natal molecular cloud material by dissociating molecules, ionizing atoms and molecules, and heating the gas and dust. These processes drive the evolution of interstellar matter in our Galaxy and throughout the Universe from the era of vigorous star formation at redshifts of 1-3, to the present day. Much of this interaction occurs in Photo-Dissociation Regions (PDRs) where far-ultraviolet photons of these stars create a largely neutral, but warm region of gas and dust. PDR emission dominates the IR spectra of star-forming galaxies and also provides a unique tool to study in detail the physical and chemical processes that are relevant for inter- and circumstellar media including diffuse clouds, molecular cloud and protoplanetary disk surfaces, globules, planetary nebulae, and starburst galaxies.We propose to provide template datasets designed to identify key PDR characteristics in the full 1-28 μm JWST spectra in order to guide the preparation of Cycle 2 proposals on star-forming regions in our Galaxy and beyond. We plan to obtain the first spatially resolved, high spectral resolution IR observations of a PDR using NIRCam, NIRSpec and MIRI. We will observe a nearby PDR with well-defined UV illumination in a typical massive star-forming region. JWST observations will, for the first time, spatially resolve and perform a tomography of the PDR, revealing the individual IR spectral signatures from the key zones and sub-regions within the ionized gas, the PDR and the molecular cloud. These data will test widely used theoretical models and extend them into the JWST era. We will assist the community interested in JWST observations of PDRs through several science-enabling products (maps of spectral features, template spectra, calibration of narrow/broad band filters in gas lines and PAH bands, data-interpretation tools e.g. to infer gas physical conditions or PAH and dust characteristics). This project is supported by a large international team of one hundred scientists collaborators.

[Beneficial effects of renal denervation on pulmonary vascular remodeling in experimental pulmonary artery hypertension].

PubMed

Zhang, Shujuan; Zhao, Qingyan; Jiang, Xuejun; Yang, Bo; Dai, Zixuan; Wang, Xiaozhan; Wang, Xule; Guo, Zongwen; Yu, Shengbo; Tang, Yanhong; Hu, Wei; Huang, Congxin

2015-04-14

To explore the effects of renal sympathetic denervation (RSD) on pulmonary vascular remodeling in a model of pulmonary arterial hypertension (PAH). According to the random number table, 24 beagles were randomized into control, PAH and PAH+RSD groups (n=8 each). The levels of neurohormone, echocardiogram and dynamics parameters were measured. Then 0.1 ml/kg dimethylformamide (control group) or 2 mg/kg dehydromonocrotaline (PAH and PAH+RSD groups) were injected. The PAH+RSD group underwent RSD after injection. At week 8 post-injection, the neurohormone levels, echocardiogram, dynamics parameters and pulmonary tissue morphology were observed. The values of right ventricular systolic pressure (RVSP) and pulmonary arterial systolic pressure (PASP) in PAH and PAH+RSD groups were both significantly higher than those in control group ((42.8±8.7), (30.8±6.8) vs (23.2±5.7) mmHg (1 mmHg=0.133 kPa) and (45.1±11.2), (32.6±7.9) vs (24.7±7.1) mmHg). Meanwhile, the values of RVSP and PASP in PAH group were higher than those in PAH+RSD group (all P<0.01). The levels of serum angiotensin II (Ang II) and endothelin-1 significantly increased after 8 weeks in PAH dogs ((228±41) vs (113±34) pg/ml and (135±15) vs (77±7) pg/ml, all P<0.01). And Ang II and endothelin-1 were higher in lung tissues of PAH group ((65±10) and (96±10) pg/ml) than in those of control group ((38±7) and (54±6) pg/ml) and PAH+RSD group ((46±8) and (67±9) pg/ml) (all P<0.01). Pulmonary tissues had marked collagen hyperplasia and lamellar corpuscles of type 2 alveolar cells were damaged more severely in PAH dogs than in PAH+RSD dogs. RSD suppresses pulmonary vascular remodeling and decreases pulmonary arterial pressure in experimental PAH. And the effect of RSD on PAH may contribute to decreased neurohormone levels.

Perillaldehyde attenuates cerebral ischemia-reperfusion injury-triggered overexpression of inflammatory cytokines via modulating Akt/JNK pathway in the rat brain cortex.

PubMed

Xu, Lixing; Li, Yuebi; Fu, Qiang; Ma, Shiping

2014-11-07

Perillaldehyde (PAH), one of the major oil components in Perilla frutescens, has anti-inflammatory effects. Few studies have examined the neuroprotective effect of PAH on stroke. So the aim of our study is to investigate the effect of PAH on ischemia-reperfusion-induced injury in the rat brain cortex. Middle cerebral artery occlusion (MCAO) model was selected to make cerebral ischemia-reperfusion injury. Rats were assigned randomly to groups of sham, MCAO, and two treatment groups by PAH at 36.0, 72.0mg/kg. Disease model was set up after intragastrically (i.g.) administering for 7 consecutive days. The neurological deficit, the cerebral infarct size, biochemical parameters and the relative mRNA and protein levels were examined. The results showed that the NO level, the iNOS activity, the neurological deficit scores, the cerebral infarct size and the expression of inflammatory cytokines including interleukin (IL)-1β, interleukin (IL)-6 and tumor necrosis factor (TNF)-α were significantly decreased by PAH treatment. PAH also increased the Phospho-Akt level and decrease the Phospho-JNK level by Western blot analysis. Meanwhile, the PAH groups exhibited a dramatically decrease of apoptosis-related mRNA expression such as Bax and caspase-3. Our findings shown that PAH attenuates cerebral ischemia/reperfusion injury in the rat brain cortex, and suggest its neuroprotective effect is relate to regulating the inflammatory response through Akt /JNK pathway. The activation of this signalling pathway eventually inhibits apoptotic cell death induced by cerebral ischemia-reperfusion. Copyright © 2014 Elsevier Inc. All rights reserved.

Evaluating officially reported polycyclic aromatic hydrocarbon emissions in the Athabasca oil sands region with a multimedia fate model.

PubMed

Parajulee, Abha; Wania, Frank

2014-03-04

Emissions of organic substances with potential toxicity to humans and the environment are a major concern surrounding the rapid industrial development in the Athabasca oil sands region (AOSR). Although concentrations of polycyclic aromatic hydrocarbons (PAHs) in some environmental samples have been reported, a comprehensive picture of organic contaminant sources, pathways, and sinks within the AOSR has yet to be elucidated. We sought to use a dynamic multimedia environmental fate model to reconcile the emissions and residue levels reported for three representative PAHs in the AOSR. Data describing emissions to air compiled from two official sources result in simulated concentrations in air, soil, water, and foliage that tend to fall close to or below the minimum measured concentrations of phenanthrene, pyrene, and benzo(a)pyrene in the environment. Accounting for evaporative emissions (e.g., from tailings pond disposal) provides a more realistic representation of PAH distribution in the AOSR. Such indirect emissions to air were found to be a greater contributor of PAHs to the AOSR atmosphere relative to reported direct emissions to air. The indirect pathway transporting uncontrolled releases of PAHs to aquatic systems via the atmosphere may be as significant a contributor of PAHs to aquatic systems as other supply pathways. Emission density estimates for the three PAHs that account for tailings pond disposal are much closer to estimated global averages than estimates based on the available emissions datasets, which fall close to the global minima. Our results highlight the need for improved accounting of PAH emissions from oil sands operations, especially in light of continued expansion of these operations.

Ionically Cross-Linked Polymer Networks for the Multiple-Month Release of Small Molecules

PubMed Central

2016-01-01

Long-term (multiple-week or -month) release of small, water-soluble molecules from hydrogels remains a significant pharmaceutical challenge, which is typically overcome at the expense of more-complicated drug carrier designs. Such approaches are payload-specific and include covalent conjugation of drugs to base materials or incorporation of micro- and nanoparticles. As a simpler alternative, here we report a mild and simple method for achieving multiple-month release of small molecules from gel-like polymer networks. Densely cross-linked matrices were prepared through ionotropic gelation of poly(allylamine hydrochloride) (PAH) with either pyrophosphate (PPi) or tripolyphosphate (TPP), all of which are commonly available commercial molecules. The loading of model small molecules (Fast Green FCF and Rhodamine B dyes) within these polymer networks increases with the payload/network binding strength and with the PAH and payload concentrations used during encapsulation. Once loaded into the PAH/PPi and PAH/TPP ionic networks, only a few percent of the payload is released over multiple months. This extended release is achieved regardless of the payload/network binding strength and likely reflects the small hydrodynamic mesh size within the gel-like matrices. Furthermore, the PAH/TPP networks show promising in vitro cytocompatibility with model cells (human dermal fibroblasts), though slight cytotoxic effects were exhibited by the PAH/PPi networks. Taken together, the above findings suggest that PAH/PPi and (especially) PAH/TPP networks might be attractive materials for the multiple-month delivery of drugs and other active molecules (e.g., fragrances or disinfectants). PMID:26811936

Impacts of urbanization on surface sediment quality: evidence from polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) contaminations in the Grand Canal of China.

PubMed

Hong, Youwei; Yu, Shen; Yu, Guangbin; Liu, Yi; Li, Guilin; Wang, Min

2012-06-01

Organic pollutants, especially synthetic organic compounds, can indicate paces of anthropogenic activities. Effects of urbanization on polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in surface sediment were conducted in urban sections of the Grand Canal, China, consisting of a four-level urbanization gradient. The four-level urbanization gradients include three countryside towns, two small-size cities, three medium-size cities, and a large-size city. Diagnostic ratio analysis and factor analysis-multiple linear regression model were used for source apportionment of PAHs. Sediment quality guidelines (SQGs) of USA and Canada were employed to assess ecological risks of PAHs and PCBs in surface sediments of the Canal. Ranges of PAH and PCB concentrations in surface sediments were 0.66-22 mg/kg and 0.5-93 μg/kg, respectively. Coal-related sources were primary PAH sources and followed by vehicular emission. Total concentration, composition, and source apportionment of PAHs exhibited urbanization gradient effects. Total PCB concentrations increased with the urbanization gradient, while total PAHs concentration in surface sediments presented an inverted U Kuznets curve with the urbanization gradient. Elevated concentrations of both PAHs and PCBs ranged at effect range low levels or interim SQG, assessed by USA and Canadian SQGs. PAHs and PCBs in surface sediments of the Grand Canal showed urbanization gradient effects and low ecological risks.

Galactic civilizations: Population dynamics and interstellar diffusion

NASA Technical Reports Server (NTRS)

Newman, W. I.; Sagan, C.

1978-01-01

The interstellar diffusion of galactic civilizations is reexamined by potential theory; both numerical and analytical solutions are derived for the nonlinear partial differential equations which specify a range of relevant models, drawn from blast wave physics, soil science, and, especially, population biology. An essential feature of these models is that, for all civilizations, population growth must be limited by the carrying capacity of the environment. Dispersal is fundamentally a diffusion process; a density-dependent diffusivity describes interstellar emigration. Two models are considered: the first describing zero population growth (ZPG), and the second which also includes local growth and saturation of a planetary population, and for which an asymptotic traveling wave solution is found.

Developing the Infrared PAH Emission Bands Into Calibrated Probes of Astrophysical Conditions with The NASA Ames PAH IR Spectroscopic Database

NASA Astrophysics Data System (ADS)

Boersma, Christiaan

We propose to quantitatively calibrate the PAH band strength ratios that have been traditionally used as qualitative proxies of PAH properties and linking PAH observables with local astrophysical conditions, thus developing PAHs into quantitative probes of astronomical environments. This will culminate in a toolbox (calibration charts) that can be used by PAH experts and non-PAH experts alike to unlock the information hidden in PAH emission sources that are part of the Spitzer and ISO archives. Furthermore, the proposed work is critical to mine the treasure trove of information JWST will return as it will capture, for the first time, the complete mid-infrared (IR) PAH spectrum with fully resolved features, through a single aperture, and along single lines-of-sight; making it possible to fully extract the information contained in the PAH spectra. In short, the work proposed here represents a major step in enabling the astronomical PAH model to reach its full potential as a diagnostic of the physical and chemical conditions in objects spanning the Universe. Polycyclic aromatic hydrocarbons (PAHs), a common and important reservoir of accessible carbon across the Universe, play an intrinsic part in the formation of stars, planets and possibly even life itself. While most PAH spectra appear quite similar, they differ in detail and contain a wealth of untapped information. Thanks to recent advances in laboratory studies and computer-based calculations of PAH spectra, the majority of which have been made at NASA Ames, coupled with the astronomical modeling tools we have developed, we can interpret the spectral details at levels never before possible. This enables us to extract local physical conditions and track subtle changes in these conditions at levels previously impossible. Building upon the tools and paradigms developed as part of the publicly available NASA Ames PAH IR Spectroscopic Database (PAHdb; www.astrochem.org/pahdb/), the purpose of our proposed research is to extend and test the applicability of the PAH proxy (band strength ratio) calibrations we have developed that are based on a single object, the reflection nebula (RN) NGC7023, to, and within, a variety of objects, each representing different types of astronomical environments. Starting with the results for NGC7023, our initial focus will be placed on other RNe for which high-quality Spitzer spectral maps are available. After this, the focus will shift to Spitzer and ISO catalogs holding PAH spectra from different object types and extragalactic sources at different quality levels. We will first fit the astronomical spectra using the PAH spectra and tools in PAHdb, a database and toolset developed by the proposers and perfectly suited for dealing with large spectral data sets. This approach quantitatively breaks down the emission into the different subclasses, of, PAH size, charge, structure and composition. Following this, the data will be analyzed using the traditional, qualitative, proxy approach in which the PAH bands are isolated and their strengths measured. Combining the results of these two approaches enables us to test the validity of, and to quantitatively calibrate, the PAH proxies that have been traditionally used to probe astronomical environments, and make a quantitative link between PAH observables and local astrophysical conditions. Previous work on NGC7023 demonstrated the potential of this approach, and applying it to different object types at varying quality levels will establish whether his approach holds in general or if adjustments must be made to tackle the full range of PAH-emitting astronomical environments. In parallel, we will perform stability analysis on the fits; establish quality requirements for spectral resolution, spectral range, and signal-to-noise; and make uncertainty estimates for the derived parameters. This is of particular importance for extragalactic sources, as it will establish a data quality threshold.

Determination of octanol-air partition coefficients and supercooled liquid vapor pressures of PAHs as a function of temperature: Application to gas-particle partitioning in an urban atmosphere

NASA Astrophysics Data System (ADS)

Odabasi, Mustafa; Cetin, Eylem; Sofuoglu, Aysun

Octanol-air partition coefficients ( KOA) for 14 polycyclic aromatic hydrocarbons (PAHs) were determined as a function of temperature using the gas chromatographic retention time method. log KOA values at 25° ranged over six orders of magnitude, between 6.34 (acenaphthylene) and 12.59 (dibenz[ a,h]anthracene). The determined KOA values were within factor of 0.7 (dibenz[ a,h]anthracene) to 15.1 (benz[ a]anthracene) of values calculated as the ratio of octanol-water partition coefficient to dimensionless Henry's law constant. Supercooled liquid vapor pressures ( PL) of 13 PAHs were also determined using the gas chromatographic retention time technique. Activity coefficients in octanol calculated using KOA and PL ranged between 3.2 and 6.2 indicating near-ideal solution behavior. Atmospheric concentrations measured in this study in Izmir, Turkey were used to investigate the partitioning of PAHs between particle and gas-phases. Experimental gas-particle partition coefficients ( Kp) were compared to the predictions of KOA absorption and KSA (soot-air partition coefficient) models. Octanol-based absorptive partitioning model predicted lower partition coefficients especially for relatively volatile PAHs. Ratios of measured/modeled partition coefficients ranged between 1.1 and 15.5 (4.5±6.0, average±SD) for KOA model. KSA model predictions were relatively better and measured to modeled ratios ranged between 0.6 and 5.6 (2.3±2.7, average±SD).

Interstellar Grains: 50 Years On

NASA Astrophysics Data System (ADS)

Wickramasinghe, N. Chandra

2011-12-01

Our understanding of the nature of interstellar grains has evolved considerably over the past half century with the present author and Fred Hoyle being intimately involved at several key stages of progress. The currently fashionable graphite-silicate-organic grain model has all its essential aspects unequivocally traceable to original peer-reviewedpublicationsbytheauthorand/orFredHoyle. Theprevailingreluctancetoaccepttheseclear-cut priorities may be linked to our further work that argued for interstellar grains and organics to have a biological provenance - a position perceived as heretical. The biological model, however, continues to provide a powerful unifying hypothesis for a vast amount of otherwise disconnected and disparate astronomical data.

H2 formation on interstellar dust grains: The viewpoints of theory, experiments, models and observations

NASA Astrophysics Data System (ADS)

Wakelam, Valentine; Bron, Emeric; Cazaux, Stephanie; Dulieu, Francois; Gry, Cécile; Guillard, Pierre; Habart, Emilie; Hornekær, Liv; Morisset, Sabine; Nyman, Gunnar; Pirronello, Valerio; Price, Stephen D.; Valdivia, Valeska; Vidali, Gianfranco; Watanabe, Naoki

2017-12-01

Molecular hydrogen is the most abundant molecule in the universe. It is the first one to form and survive photo-dissociation in tenuous environments. Its formation involves catalytic reactions on the surface of interstellar grains. The micro-physics of the formation process has been investigated intensively in the last 20 years, in parallel of new astrophysical observational and modeling progresses. In the perspectives of the probable revolution brought by the future satellite JWST, this article has been written to present what we think we know about the H2 formation in a variety of interstellar environments.

Ionization of Interstellar Hydrogen

NASA Astrophysics Data System (ADS)

Whang, Y. C.

1996-09-01

Interstellar hydrogen can penetrate through the heliopause, enter the heliosphere, and may become ionized by photoionization and by charge exchange with solar wind protons. A fluid model is introduced to study the flow of interstellar hydrogen in the heliosphere. The flow is governed by moment equations obtained from integration of the Boltzmann equation over the velocity space. Under the assumption that the flow is steady axisymmetric and the pressure is isotropic, we develop a method of solution for this fluid model. This model and the method of solution can be used to study the flow of neutral hydrogen with various forms of ionization rate β and boundary conditions for the flow on the upwind side. We study the solution of a special case in which the ionization rate β is inversely proportional to R2 and the interstellar hydrogen flow is uniform at infinity on the upwind side. We solve the moment equations directly for the normalized density NH/NN∞, bulk velocity VH/VN∞, and temperature TH/TN∞ of interstellar hydrogen as functions of r/λ and z/λ, where λ is the ionization scale length. The solution is compared with the kinetic theory solution of Lallement et al. The fluid solution is much less time-consuming than the kinetic theory solutions. Since the ionization rate for production of pickup protons is directly proportional to the local density of neutral hydrogen, the high-resolution solution of interstellar neutral hydrogen obtained here will be used to study the global distribution of pickup protons.

Export Mechanisms of Persistent Toxic Substances (PTSs) in Urban Land Uses during Rainfall-Runoff Events: Experimental and Modeling Studies

NASA Astrophysics Data System (ADS)

Zheng, Y.; Luo, X.; Lin, Z.

2016-12-01

The urban environment has a variety of Persistent Toxic Substances (PTS), such as Polycyclic Aromatic Hydrocarbons (PAHs) and mercury. Soil in pervious lands and dust deposited on impervious surfaces are two major sinks of PTSs in urbanized areas, which could contribute significant nonpoint source loadings of PTSs to adjacent waterbodies during rainfall-runoff events and therefore jeopardize aquatic ecosystems. However, PTSs have been much less understood regarding their export mechanisms in urban land uses, and efforts to model nonpoint source pollution processes of PTSs have been rare. We designed and performed in-lab rainfall-runoff simulation experiments to investigate transport of PAHs and mercury by runoff from urban soils. Organic petrology analysis (OPA) techniques were introduced to analyze the soil and sediment compositions. Our study revealed the limitation of the classic enrichment theory which attributes enrichment of pollutants in eroded sediment solely to the sediment's particle size distribution and adopts simple relationships between enrichment ratio and sediment flux. We found that carbonaceous materials (CMs) in soil are the direct and major sorbents for PAHs and mercury, and highly different in content, mobility and adsorption capacity for the PTSs. Anthropogenic CMs like black carbon components largely control the transport of soil PAHs, while humic substances have a dominant influence on the transport of soil mercury. A model was further developed to estimate the enrichment ratio of PAHs, which innovatively applies the fugacity concept.We also conducted field studies on export of PAHs by runoff from urban roads. A variable time-step model was developed to simulate the continuous cycles of PAH buildup and washoff on urban roads. The dependence of the pollution level on antecedent weather conditions was investigated and embodied in the model. The applicability of this approach and its value to environmental management was demonstrated by a case study in Beijing, China. Overall, our studies advanced the understanding of nonpoint source pollution of PTSs in the urban environment. The quantitative approaches developed can help improve existing nonpoint source pollution models. The study results also have important implications to watershed water quality management.

Real-time monitoring of polycyclic aromatic hydrocarbons and respirable suspended particles from environmental tobacco smoke in a home

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ott, W.; Wilson, N.K.; Klepeis, N.

Real-time measurement of polycyclic aromatic hydrocarbons (PAH) on fine particles was evaluated in a home with environmental tobacco smoke (ETS) as a source. Respirable suspended particles (RSP) were also monitored. Comparison of PAH and RSP concentrations from these experiments suggests: (1) the PAH concentrations for the two types of cigarettes--a regular Marlboro filter cigarette and a University of Kentucky reference cigarette No. 2R1--were similar, but the RSP concentrations were different; (2) concentrations from the real-time PAH monitor were linearly related to RSP concentrations; (3) the slopes of the regression lines between PAH and RSP differed for the two types ofmore » cigarettes. The real-time PAH monitor appears to be a useful tool for evaluating mathematical models to predict the concentration time series in indoor microenvironments.« less

Atypical kinetic behavior of chloroperoxidase-mediated oxidative halogenation of polycyclic aromatic hydrocarbons.

PubMed

Aburto, Jorge; Correa-Basurto, Jose; Torres, Eduardo

2008-12-01

We have identified an atypical kinetic behavior for the oxidative halogenation of several polycyclic aromatic hydrocarbons (PAHs) by chloroperoxidase (CPO) from Caldariomyces fumago. This behavior resembles the capacity of some members of the P450 family to simultaneously recognize several substrate molecules at their active sites. Indeed, fluorometric studies showed that PAHs exist in solution as monomers and pi-pi dimers that interact to different extents with CPO. The dissociation constants of dimerization were evaluated for every single PAH by spectrofluorometry. Furthermore, docking studies also suggest that CPO might recognize either one or two substrate molecules in its active site. The atypical sigmoidal kinetic behavior of CPO in the oxidative halogenation of PAHs is explained in terms of different kinetic models for non-heteroatomic PAHs (naphthalene, anthracene and pyrene). The results suggest that the actual substrate for CPO in this study was the pi-pi dimer for all evaluated PAHs.

Primary sources and toxicity of PAHs in Milwaukee-area streambed sediment

USGS Publications Warehouse

Baldwin, Austin K.; Corsi, Steven R.; Lutz, Michelle A.; Ingersoll, Christopher G.; Dorman, Rebecca A.; Magruder, Christopher; Magruder, Matthew

2017-01-01

High concentrations of polycyclic aromatic hydrocarbons (PAHs) in streams can be a significant stressor to aquatic organisms. To understand the likely sources and toxicity of PAHs in Milwaukee-area streams, streambed sediment samples from 40 sites and parking lot dust samples from 6 sites were analyzed for 38 parent PAHs and 25 alkylated PAHs. Diagnostic ratios, profile correlations, principal components analysis, source-receptor modeling, and mass fractions analysis were used to identify potential PAH sources to streambed sediment samples, and land-use analysis was used to relate streambed sediment PAH concentrations to different urban-related land uses. On the basis of this multiple lines-of-evidence approach, coal-tar pavement sealant was indicated as the primary source of PAHs in a majority of streambed sediment samples, contributing an estimated 77% of total PAHs to samples, on average. Comparison to the Probable Effect Concentrations and (or) the Equilibrium Partitioning Sediment Benchmark indicates that 78% of stream sediment samples are likely to cause adverse effects to benthic organisms. Laboratory toxicity tests on a 16-sample subset of the streambed sites using the amphipod Hyalella azteca (28-day) and the midge Chironomus dilutus (10-day) measured significant reductions in one or more biological endpoints, including survival, in 75% of samples, with H. azteca more responsive than C. dilutus.

Measurements and source apportionment of particle-associated polycyclic aromatic hydrocarbons in ambient air in Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

Bian, Qijing; Alharbi, Badr; Collett, Jeffrey; Kreidenweis, Sonia; Pasha, Mohammad J.

2016-07-01

Ambient air samples were obtained in Riyadh, the capital and largest city of Saudi Arabia, during two measurement campaigns spanning September 2011 to September 2012. Sixteen particle-phase polycyclic aromatic hydrocarbons (PAH) were quantified in 167 samples. Pyrene and fluoranthene were the most abundant PAH, with average of 3.37 ± 14.01 ng m-3 and 8.00 ± 44.09 ng m-3, respectively. A dominant contribution from low molecular weight (LMW) PAH (MW < 228) suggested a large influence of industrial emissions on PAH concentrations. Monte Carlo source apportionment using diagnostic ratios showed that 80 ± 10% of the average LMW PAH concentrations were contributed by petroleum vapor emissions, while 53 ± 19% of high molecular weight (HMW) PAH were from solid fuel combustion emissions. The positive matrix factorization model estimated that oil combustion emissions dominated total PAH concentrations, accounting for on average 96%, likely due to widespread use of oil fuels in energy production (power plants and industries). Our results demonstrate the significant influence of petroleum product production and consumption on particulate-phase PAH concentrations in Riyadh, but also point to the importance of traffic and solid fuel burning, including coke burning and seasonal biomass burning, especially as they contribute to the ambient levels of HMW PAH.

Pavement Sealcoat, PAHs, and the Environment

NASA Astrophysics Data System (ADS)

Van Metre, P. C.; Mahler, B. J.

2011-12-01

Recent research by the USGS has identified coal-tar-based pavement sealants as a major source of polycyclic aromatic hydrocarbons (PAHs) to the environment. Coal-tar-based sealcoat is commonly used to coat parking lots and driveways and is typically is 20-35 percent coal tar pitch, a known human carcinogen. Several PAHs are suspected mutagens, carcinogens, and (or) teratogens. In the central and eastern U.S. where the coal-tar-based sealants dominate use, sum-PAH concentration in dust particles from sealcoated pavement is about 1,000 times higher than in the western U.S. where the asphalt-based formulation is prevalent. Source apportionment modeling indicates that particles from sealcoated pavement are contributing the majority of the PAHs to recent lake sediment in 35 U.S. urban lakes and are the primary cause of upward trends in PAHs in many of these lakes. Mobile particles from parking lots with coal-tar-based sealcoat are tracked indoors, resulting in elevated PAH concentrations in house dust. In a recently completed study, volatilization fluxes of PAHs from sealcoated pavement were estimated to be about 60 times fluxes from unsealed pavement. Using a wide variety of methods, the author and colleagues have shown that coal-tar-based sealcoat is a major source of PAHs to the urban environment and might pose risks to aquatic life and human health.

Interstellar matter in early-type galaxies. II - The relationship between gaseous components and galaxy types

NASA Technical Reports Server (NTRS)

Bregman, Joel N.; Hogg, David E.; Roberts, Morton S.

1992-01-01

Interstellar components of early-type galaxies are established by galactic type and luminosity in order to search for relationships between the different interstellar components and to test the predictions of theoretical models. Some of the data include observations of neutral hydrogen, carbon monoxide, and radio continuum emission. An alternative distance model which yields LX varies as LB sup 2.45, a relation which is in conflict with simple cooling flow models, is discussed. The dispersion of the X-ray luminosity about this regression line is unlikely to result from stripping. The striking lack of clear correlations between hot and cold interstellar components, taken together with their morphologies, suggests that the cold gas is a disk phenomenon while the hot gas is a bulge phenomenon, with little interaction between the two. The progression of galaxy type from E to Sa is not only a sequence of decreasing stellar bulge-to-disk ratio, but also of hot-to-cold-gas ratio.

New Insights Concerning the Local Interstellar medium

NASA Astrophysics Data System (ADS)

Linsky, Jeffrey L.; Redfield, Seth

2015-08-01

We have been analyzing HST high-resolution ultraviolet spectra of nearby stars to measure the radial velocities, turbulence, temperature, and depletions on warm diffuse interstellar gas within a few parsecs of the Sun. These data reveal a picture of many partially-ionized warm gas clouds, each with their own vector velocity and physical characteristics. This picture has been recently challenged by Gry and Jenkins (2014), who argue for a single nonrigid cloud surrounding the Sun. We present a test of these two very different morphological structure by checking how well each predicts the radial velocities in a new data set (Malamut et al. 2014) that was not available when both models were constructed. We find that the multicloud model (Redfield & Linsky 2008) provides a much better fit to the new data. We compare the new IBEX results for the temperature and velocity of inflowing He gas (McComas et al. 2015) with the properties of the Local Interstellar Cloud and the G cloud. We also show a preliminary three-dimensional model for the local interstellar medium.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of `polar ice' mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm `carbonyl' absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes.

Phototransformation rate constants of PAHs associated with soot particles.

PubMed

Kim, Daekyun; Young, Thomas M; Anastasio, Cort

2013-01-15

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

Interstellar Polycyclic Aromatic Compounds and Astrophysics

NASA Technical Reports Server (NTRS)

Hodgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

1999-01-01

Polycyclic aromatic compounds (PACs), a class of organic molecules whose structures are characterized by the presence of two or more fused aromatic rings, have been the subject of astrophysical interest for nearly two decades. Large by interstellar standards (from as few as 20 to perhaps as many as several hundred atoms), it has been suggested that these species are among the most abundant interstellar molecules impacting a wide range of astrophysical phenomena including: the ubiquitous family of infrared emission bands observed in an ever-increasing assortment of astronomical objects; the subtle but rich array of discrete visible/near-infrared interstellar molecular absorption features known as the diffuse interstellar bands (DIBs); the broad near-infrared quasi-continuum observed in a number of nebulae known as excess red emission (ERE); the interstellar ultraviolet extinction curve and broad '2200 Angstrom bump'; the heating/cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of good-quality laboratory spectroscopic data on PACs under astrophysically relevant conditions (i.e. isolated, ionized molecules; ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model

Autonomic nervous system involvement in pulmonary arterial hypertension.

PubMed

Vaillancourt, Mylène; Chia, Pamela; Sarji, Shervin; Nguyen, Jason; Hoftman, Nir; Ruffenach, Gregoire; Eghbali, Mansoureh; Mahajan, Aman; Umar, Soban

2017-12-04

Pulmonary arterial hypertension (PAH) is a chronic pulmonary vascular disease characterized by increased pulmonary vascular resistance (PVR) leading to right ventricular (RV) failure. Autonomic nervous system involvement in the pathogenesis of PAH has been demonstrated several years ago, however the extent of this involvement is not fully understood. PAH is associated with increased sympathetic nervous system (SNS) activation, decreased heart rate variability, and presence of cardiac arrhythmias. There is also evidence for increased renin-angiotensin-aldosterone system (RAAS) activation in PAH patients associated with clinical worsening. Reduction of neurohormonal activation could be an effective therapeutic strategy for PAH. Although therapies targeting adrenergic receptors or RAAS signaling pathways have been shown to reverse cardiac remodeling and improve outcomes in experimental pulmonary hypertension (PH)-models, the effectiveness and safety of such treatments in clinical settings have been uncertain. Recently, novel direct methods such as cervical ganglion block, pulmonary artery denervation (PADN), and renal denervation have been employed to attenuate SNS activation in PAH. In this review, we intend to summarize the multiple aspects of autonomic nervous system involvement in PAH and overview the different pharmacological and invasive strategies used to target autonomic nervous system for the treatment of PAH.

The Evolution of Dust in the Multiphase Interstellar Medium

NASA Technical Reports Server (NTRS)

Oliversen, Ronald J. (Technical Monitor); Slavin, Jonathan

2003-01-01

Interstellar dust has a profound effect on the structure and evolution of the interstellar medium (ISM) and on the processes by which stars form from it. Dust obscures regions of star formation from view, and the uncertain quantities of elements in dust makes it difficult to measure accurately the abundances of the elements in low density regions. Despite the central importance of dust in astrophysics, we cannot answer some of the most basic questions about it: Why is it that most of the refractory elements are in dust grains? What determines the sizes of interstellar grains? It has been the goal of our proposed theoretical investigations to address these questions by studying the destruction of interstellar grains, and to develop observational diagnostics that can test the models we develop.

Towards an improved understanding of processes controlling absorption efficiency and biomagnification of organic chemicals by fish.

PubMed

Xiao, Ruiyang; Arnot, Jon A; MacLeod, Matthew

2015-11-01

Dietary exposure is considered the dominant pathway for fish exposed to persistent, hydrophobic chemicals in the environment. Here we present a dynamic, fugacity-based three-compartment bioaccumulation model that describes the fish body as one compartment and the gastrointestinal tract (GIT) as two compartments. The model simulates uptake from the GIT by passive diffusion and micelle-mediated diffusion, and chemical degradation in the fish and the GIT compartments. We applied the model to a consistent measured dietary uptake and depuration dataset for rainbow trout (n=215) that is comprised of chlorinated benzenes, biphenyls, dioxins, diphenyl ethers, and polycyclic aromatic hydrocarbons (PAHs). Model performance relative to the measured data is statistically similar regardless of whether micelle-mediated diffusion is included; however, there are considerable uncertainties in modeling this process. When degradation in the GIT is assumed to be negligible, modeled chemical elimination rates are similar to measured rates; however, predicted concentrations of the PAHs are consistently higher than measurements by up to a factor of 20. Introducing a kinetic limit on chemical transport from the fish compartment to the GIT and increasing the rate constant for degradation of PAHs in tissues of the liver and/or GIT are required to achieve good agreement between the modelled and measured concentrations for PAHs. Our results indicate that the apparent low absorption efficiency of PAHs relative to the chemicals with similar hydrophobicity is attributable to biotransformation in the liver and/or the GIT. Our results provide process-level insights about controls on the extent of bioaccumulation of chemicals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Investigation of polycyclic aromatic hydrocarbon content in fly ash and bottom ash of biomass incineration plants in relation to the operating temperature and unburned carbon content.

PubMed

Košnář, Zdeněk; Mercl, Filip; Perná, Ivana; Tlustoš, Pavel

2016-09-01

The use of biomass fuels in incineration power plants is increasing worldwide. The produced ashes may pose a serious threat to the environment due to the presence of polycyclic aromatic hydrocarbons (PAHs), because some PAHs are potent carcinogens, mutagens and teratogens. The objective of this study was to investigate the content of total and individual PAHs in fly and bottom ash derived from incineration of phytomass and dendromass, because the data on PAH content in biomass ashes is limited. Various operating temperatures of incineration were examined and the relationship between total PAH content and unburned carbon in ashes was also considered. The analysis of PAHs was carried out in fly and bottom ash samples collected from various biomass incineration plants. PAH determination was performed using gas chromatography coupled with mass spectrometry. The correlations between the low, medium and high molecular weight PAHs and each other in ashes were conducted. The relationship between PAH content and unburned carbon, determined as a loss on ignition (L.O.I.) in biomass ashes, was performed using regression analysis. The PAH content in biomass ashes varied from 41.1±1.8 to 53,800.9±13,818.4ng/g dw. This variation may be explained by the differences in boiler operating conditions and biomass fuel composition. The correlation coefficients for PAHs in ash ranged from 0.8025 to 0.9790. The regression models were designed and the coefficients of determination varied from 0.908 to 0.980. The PAH content in ash varied widely with fuel type and the effect of operating temperature on PAH content in ash was evident. Fly ashes contained higher amounts of PAHs than bottom ashes. The low molecular weight PAHs prevailed in tested ashes. The exponential relationship between the PAH content and L.O.I. for fly ashes and the linear for bottom ashes was observed. Copyright © 2016 Elsevier B.V. All rights reserved.

Global atmospheric emissions of polycyclic aromatic hydrocarbons from 1960 to 2008 and future predictions.

PubMed

Shen, Huizhong; Huang, Ye; Wang, Rong; Zhu, Dan; Li, Wei; Shen, Guofeng; Wang, Bin; Zhang, Yanyan; Chen, Yuanchen; Lu, Yan; Chen, Han; Li, Tongchao; Sun, Kang; Li, Bengang; Liu, Wenxin; Liu, Junfeng; Tao, Shu

2013-06-18

Global atmospheric emissions of 16 polycyclic aromatic hydrocarbons (PAHs) from 69 major sources were estimated for a period from 1960 to 2030. Regression models and a technology split method were used to estimate country and time specific emission factors, resulting in a new estimate of PAH emission factor variation among different countries and over time. PAH emissions in 2007 were spatially resolved to 0.1° × 0.1° grids based on a newly developed global high-resolution fuel combustion inventory (PKU-FUEL-2007). The global total annual atmospheric emission of 16 PAHs in 2007 was 504 Gg (331-818 Gg, as interquartile range), with residential/commercial biomass burning (60.5%), open-field biomass burning (agricultural waste burning, deforestation, and wildfire, 13.6%), and petroleum consumption by on-road motor vehicles (12.8%) as the major sources. South (87 Gg), East (111 Gg), and Southeast Asia (52 Gg) were the regions with the highest PAH emission densities, contributing half of the global total PAH emissions. Among the global total PAH emissions, 6.19% of the emissions were in the form of high molecular weight carcinogenic compounds and the percentage of the carcinogenic PAHs was higher in developing countries (6.22%) than in developed countries (5.73%), due to the differences in energy structures and the disparities of technology. The potential health impact of the PAH emissions was greatest in the parts of the world with high anthropogenic PAH emissions, because of the overlap of the high emissions and high population densities. Global total PAH emissions peaked at 592 Gg in 1995 and declined gradually to 499 Gg in 2008. Total PAH emissions from developed countries peaked at 122 Gg in the early 1970s and decreased to 38 Gg in 2008. Simulation of PAH emissions from 2009 to 2030 revealed that PAH emissions in developed and developing countries would decrease by 46-71% and 48-64%, respectively, based on the six IPCC SRES scenarios.

Global atmospheric emissions of polycyclic aromatic hydrocarbons from 1960 to 2008 and future predictions

PubMed Central

Shen, Huizhong; Huang, Ye; Wang, Rong; Zhu, Dan; Li, Wei; Shen, Guofeng; Wang, Bin; Zhang, Yanyan; Chen, Yuanchen; Lu, Yan; Chen, Han; Li, Tongchao; Sun, Kang; Li, Bengang; Liu, Wenxin; Liu, Junfeng; Tao, Shu

2013-01-01

Global atmospheric emissions of 16 polycyclic aromatic hydrocarbons (PAHs) from 69 major sources were estimated for a period from 1960 to 2030. Regression models and a technology split method were used to estimate country and time specific emission factors, resulting in a new estimate of PAH emission factor variation among different countries and over time. PAH emissions in 2007 were spatially resolved to 0.1°× 0.1° grids based on a newly developed global high-resolution fuel combustion inventory (PKU-FUEL-2007). The global total annual atmospheric emission of 16 PAHs in 2007 was 504 Gg (331-818 Gg, as interquartile range), with residential/commercial biomass burning (60.5%), open-field biomass burning (agricultural waste burning, deforestation, and wildfire, 13.6%), and petroleum consumption by on-road motor vehicles (12.8%) as the major sources. South (87 Gg), East (111 Gg), and Southeast Asia (52 Gg) were the regions with the highest PAH emission densities, contributing half of the global total PAH emissions. Among the global total PAH emissions, 6.19% of the emissions were in the form of high molecular weight carcinogenic compounds and the percentage of the carcinogenic PAHs was higher in developing countries (6.22%) than in developed countries (5.73%), due to the differences in energy structures and the disparities of technology. The potential health impact of the PAH emissions was greatest in the parts of the world with high anthropogenic PAH emissions, because of the overlap of the high emissions and high population densities. Global total PAH emissions peaked at 592 Gg in 1995 and declined gradually to 499 Gg in 2008. Total PAH emissions from developed countries peaked at 122 Gg in the early 1970s and decreased to 38 Gg in 2008. Simulation of PAH emissions from 2009 to 2030 revealed that PAH emissions in developed and developing countries would decrease by 46-71% and 48-64%, respectively, based on the six IPCC SRES scenarios. PMID:23659377

Occurrence, sources, and potential human health risks of polycyclic aromatic hydrocarbons in agricultural soils of the coal production area surrounding Xinzhou, China.

PubMed

Zhao, Long; Hou, Hong; Shangguan, Yuxian; Cheng, Bin; Xu, Yafei; Zhao, Ruifen; Zhang, Yigong; Hua, Xiaozan; Huo, Xiaolan; Zhao, Xiufeng

2014-10-01

A comprehensive investigation of the levels, distribution patterns, and sources of polycyclic aromatic hydrocarbons (PAHs) in agricultural soils of the coal production area surrounding Xinzhou, China, was conducted, and the potential human health risks associated with the levels observed were addressed. A total of 247 samples collected from agricultural soils from the area were analyzed for sixteen PAHs, including highly carcinogenic isomers. The PAH concentrations had a range of n.d. to 782ngg(-1), with a mean value of 202ngg(-1). The two-three ring PAHs were the dominant species, making up 60 percent of total PAHs. Compared with the pollution levels and carcinogenic potential risks reported in other studies, the soil PAH concentrations in the study area were in the low to intermediate range. A positive matrix factorization model indicates that coal/biomass combustion, coal and oil combustion, and coke ovens are the primary PAH sources, accounting for 33 percent, 26 percent, and 24 percent of total PAHs, respectively. The benzo[a]pyrene equivalent (BaPeq) concentrations had a range of n.d. to 476ngg(-1) for PAH7c, with a mean value of 34ngg(-1). The BaPeq concentrations of PAH7c accounted for more than 99 percent of the ∑PAH16, which suggests that seven PAHs were major carcinogenic contributors of ∑PAH16. According to the Canadian Soil Quality Guidelines, only six of the soil samples had concentrations above the safe BaPeq value of 600ngg(-1); the elevated concentrations observed at these sites can be attributed to coal combustion and industrial activities. Exposure to these soils through direct contact probably poses a significant risk to human health as a result of the carcinogenic effects of PAHs. Copyright © 2014 Elsevier Inc. All rights reserved.

Observational evidence of dust evolution in galactic extinction curves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cecchi-Pestellini, Cesare; Casu, Silvia; Mulas, Giacomo

Although structural and optical properties of hydrogenated amorphous carbons are known to respond to varying physical conditions, most conventional extinction models are basically curve fits with modest predictive power. We compare an evolutionary model of the physical properties of carbonaceous grain mantles with their determination by homogeneously fitting observationally derived Galactic extinction curves with the same physically well-defined dust model. We find that a large sample of observed Galactic extinction curves are compatible with the evolutionary scenario underlying such a model, requiring physical conditions fully consistent with standard density, temperature, radiation field intensity, and average age of diffuse interstellar clouds.more » Hence, through the study of interstellar extinction we may, in principle, understand the evolutionary history of the diffuse interstellar clouds.« less

Evaluating environmental modeling and sampling data with biomarker data to identify sources and routes of exposure

NASA Astrophysics Data System (ADS)

Shin, Hyeong-Moo; McKone, Thomas E.; Bennett, Deborah H.

2013-04-01

Exposure to environmental chemicals results from multiple sources, environmental media, and exposure routes. Ideally, modeled exposures should be compared to biomonitoring data. This study compares the magnitude and variation of modeled polycyclic aromatic hydrocarbons (PAHs) exposures resulting from emissions to outdoor and indoor air and estimated exposure inferred from biomarker levels. Outdoor emissions result in both inhalation and food-based exposures. We modeled PAH intake doses using U.S. EPA's 2002 National Air Toxics Assessment (NATA) county-level emissions data for outdoor inhalation, the CalTOX model for food ingestion (based on NATA emissions), and indoor air concentrations from field studies for indoor inhalation. We then compared the modeled intake with the measured urine levels of hydroxy-PAH metabolites from the 2001-2002 National Health and Nutrition Examination Survey (NHANES) survey as quantifiable human intake of PAH parent-compounds. Lognormal probability plots of modeled intakes and estimated intakes inferred from biomarkers suggest that a primary route of exposure to naphthalene, fluorene, and phenanthrene for the U.S. population is likely inhalation from indoor sources. For benzo(a)pyrene, the predominant exposure route is likely from food ingestion resulting from multi-pathway transport and bioaccumulation due to outdoor emissions. Multiple routes of exposure are important for pyrene. We also considered the sensitivity of the predicted exposure to the proportion of the total naphthalene production volume emitted to the indoor environment. The comparison of PAH biomarkers with exposure variability estimated from models and sample data for various exposure pathways supports that both indoor and outdoor models are needed to capture the sources and routes of exposure to environmental contaminants.

Development and validation of a new soot formation model for gas turbine combustor simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di Domenico, Massimiliano; Gerlinger, Peter; Aigner, Manfred

2010-02-15

In this paper a new soot formation model for gas turbine combustor simulations is presented. A sectional approach for the description of Polycyclic Aromatic Hydrocarbons (PAHs) and a two-equation model for soot particle dynamics are introduced. By including the PAH chemistry the formulation becomes more general in that the soot formation is neither directly linked to the fuel nor to C{sub 2}-like species, as it is the case in simpler soot models currently available for CFD applications. At the same time, the sectional approach for the PAHs keeps the required computational resources low if compared to models based on amore » detailed description of the PAH kinetics. These features of the new model allow an accurate yet affordable calculation of soot in complex gas turbine combustion chambers. A careful model validation will be presented for diffusion and partially premixed flames. Fuels ranging from methane to kerosene are investigated. Thus, flames with different sooting characteristics are covered. An excellent agreement with experimental data is achieved for all configurations investigated. A fundamental feature of the new model is that with a single set of constants it is able to accurately describe the soot dynamics of different fuels at different operating conditions. (author)« less

Sources and mass inventory of sedimentary polycyclic aromatic hydrocarbons in the Gulf of Thailand: Implications for pathways and energy structure in SE Asia.

PubMed

Hu, Limin; Shi, Xuefa; Qiao, Shuqing; Lin, Tian; Li, Yuanyuan; Bai, Yazhi; Wu, Bin; Liu, Shengfa; Kornkanitnan, Narumol; Khokiattiwong, Somkiat

2017-01-01

Surface sediments obtained from a matrix of 92 sample sites in the Gulf of Thailand (GOT) were analyzed for a comprehensive study of the distribution, sources, and mass inventory of polycyclic aromatic hydrocarbons (PAHs) to assess their input pathways and impacts of the regional land-based energy structure on the deposition of PAHs on the adjacent continental margins. The concentration of 16 PAHs in the GOT ranged from 2.6 to 78.1ng/g (dry weight), and the mean concentration was 19.4±15.1ng/g. The spatial distribution pattern of 16 PAH was generally consistent with that of sediment grain size, suggesting the influence of regional hydrodynamic conditions. Correlation and principal component analysis of the PAHs indicated that direct land-based inputs were dominantly responsible for the occurrence of PAHs in the upper GOT and the low molecular weight (LMW) PAHs in the coastal region could be from petrogenic sources. A positive matrix factorization (PMF) model apportioned five contributors: petroleum residues (~44%), biomass burning (~13%), vehicular emissions (~11%), coal combustion (~6%), and air-water exchange (~25%). Gas absorption may be a significant external input pathway for the volatile PAHs in the open GOT, which further implies that atmospheric loading could be important for the sink of PAHs in the open sea of the Southeast Asia (SE Asia). The different PAH source patterns obtained and a significant disparity of PAH mass inventory in the sediments along the East and Southeast Asia continental margins can be ascribed mainly to different land-based PAH emission features under the varied regional energy structure in addition to the depositional environment and climatic conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Excretion Profiles and Half-Lives of Ten Urinary Polycyclic Aromatic Hydrocarbon Metabolites after Dietary Exposure

PubMed Central

Li, Zheng; Romanoff, Lovisa; Bartell, Scott; Pittman, Erin N.; Trinidad, Debra A.; McClean, Michael; Webster, Thomas F.; Sjödin, Andreas

2015-01-01

Human exposure to polycyclic aromatic hydrocarbons (PAHs) can be assessed by biomonitoring of their urinary mono-hydroxylated metabolites (OH-PAHs). Limited information exists on the human pharmacokinetics of OH-PAHs. This study aimed to investigate the excretion half-life of 1-hydroxypyrene (1-PYR), the most used biomarker for PAH exposure, and 9 other OH-PAHs following a dietary exposure in 9 non-smoking volunteers with no occupational exposure to PAHs. Each person avoided food with known high PAH-content during the study period, except for a high PAH-containing lunch (barbecued chicken) on the first day. Individual urine samples (n = 217) were collected from 15 hours before to 60 hours following the dietary exposure. Levels of all OH-PAHs in all subjects increased rapidly by 9–141 fold after the exposure, followed by a decrease consistent with first order kinetics, and returned to background levels 24–48 hours after the exposure. The average time to reach maximal concentration ranged from 3.1 h (1-naphthol) to 5.5 h (1-PYR). Creatinine-adjusted urine concentrations for each metabolite were analyzed using a non-linear mixed effects model including a term to estimate background exposure. The background-adjusted half-life estimate was 3.9 h for 1-PYR and ranged 2.5–6.1 h for the other 9 OH-PAHs, which in general, were shorter than those previously reported. The maximum concentrations after the barbecued chicken consumption were comparable to the levels found in reported occupational settings with known high PAH exposures. It is essential to consider the relatively short half-life, the timing of samples relative to exposures, and the effect of diet when conducting PAH exposure biomonitoring studies. PMID:22663094

Dysregulated renin-angiotensin-aldosterone system contributes to pulmonary arterial hypertension

PubMed Central

De Man, Frances; Tu, Ly; Handoko, Louis; Rain, Silvia; Ruiter, Gerrina; François, Charlène; Schalij, Ingrid; Dorfmüller, Peter; Simonneau, Gérald; Fadel, Elie; Perros, Frederic; Boonstra, Anco; Postmus, Piet; Van Der Velden, Jolanda; Vonk-Noordegraaf, Anton; Humbert, Marc; Eddahibi, Saadia; Guignabert, Christophe

2012-01-01

Rationale Patients with idiopathic pulmonary arterial hypertension (iPAH) often have a low cardiac output. To compensate, neurohormonal systems like renin-angiotensin-aldosterone system (RAAS) and sympathetic nervous system are upregulated but this may have long-term negative effects on the progression of iPAH. Objectives Assess systemic and pulmonary RAAS-activity in iPAH-patients and determine the efficacy of chronic RAAS-inhibition in experimental PAH. Measurements and Main Results We collected 79 blood samples from 58 iPAH-patients in the VU University Medical Center Amsterdam (between 2004–2010), to determine systemic RAAS-activity. We observed increased levels of renin, angiotensin (Ang) I and AngII, which was associated with disease progression (p<0.05) and mortality (p<0.05). To determine pulmonary RAAS-activity, lung specimens were obtained from iPAH-patients (during lung transplantation, n=13) and controls (during lobectomy or pneumonectomy for cancer, n=14). Local RAAS-activity in pulmonary arteries of iPAH-patients was increased, demonstrated by elevated ACE-activity in pulmonary endothelial cells and increased AngII type 1 (AT1) receptor expression and signaling. In addition, local RAAS- upregulation was associated with increased pulmonary artery smooth muscle cell proliferation via enhanced AT1-receptor signaling in iPAH-patients compared to controls. Finally, to determine the therapeutic potential of RAAS-activity, we assessed the chronic effects of an AT1-receptor antagonist (losartan) in the monocrotaline PAH-rat model (60 mg/kg). Losartan delayed disease progression, decreased RV afterload and pulmonary vascular remodeling and restored right ventricular-arterial coupling in PAH-rats. Conclusions Systemic and pulmonary RAAS-activities are increased in iPAH-patients and associated with increased pulmonary vascular remodeling. Chronic inhibition of RAAS by losartan is beneficial in experimental PAH. PMID:22859525

Theoretical studies in interstellar cloud chemistry

NASA Technical Reports Server (NTRS)

Chiu, Y. T.; Prasad, S. S.

1993-01-01

This final report represents the completion of the three tasks under the purchase order no. SCPDE5620,1,2F. Chemical composition of gravitationally contracting, but otherwise quiescent, interstellar clouds and of interstellar clouds traversed by high velocity shocks, were modeled in a comprehensive manner that represents a significant progress in modeling these objects. The evolutionary chemical modeling, done under this NASA contract, represents a notable advance over the 'classical' fixed condition equilibrium models because the evolutionary models consider not only the chemical processes but also the dynamical processes by which the dark interstellar clouds may have assumed their present state. The shock calculations, being reported here, are important because they extend the limited chemical composition derivable from dynamical calculations for the total density and temperature structures behind the shock front. In order to be tractable, the dynamical calculations must severely simplify the chemistry. The present shock calculations take the shock profiles from the dynamical calculations and derive chemical composition in a comprehensive manner. The results of the present modeling study are still to be analyzed with reference to astronomical observational data and other contemporary model predictions. As far as humanly possible, this analysis will be continued with CRE's (Creative Research Enterprises's) IR&D resources, until a sponsor is found.

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Frenklach, M.

1997-07-01

A computational study was performed for the formation and growth of polycyclic aromatic hydrocarbons (PAHs) in laminar premixed acetylene and ethylene flames. A new detailed reaction mechanism describing fuel pyrolysis and oxidation, benzene formation, and PAH mass growth and oxidation is presented and critically tested. It is shown that the reaction model predicts reasonably well the concentration profiles of major and intermediate species and aromatic molecules in a number of acetylene and ethylene flames reported in the literature. It is demonstrated that reactions of n-C{sub 4}H{sub x} + C{sub 2}H{sub 2} leading to the formation of one-ring aromatics are asmore » important as the propargyl recombination, and hence must be included in kinetic modeling of PAH formation in hydrocarbon flames. It is further demonstrated that the mass growth of PAHs can be accounted for by the previously proposed H-abstraction-C{sub 2}H{sub 2}-addiction mechanism.« less

Approach to Assessing the Effects of Aerial Deposition on Water Quality in the Alberta Oil Sands Region.

PubMed

Dayyani, Shadi; Daly, Gillian; Vandenberg, Jerry

2016-02-01

Snow cover forms a porous medium that acts as a receptor for aerially deposited polycyclic aromatic hydrocarbons (PAHs) and metals. The snowpack, acting as a temporary storage reservoir, releases contaminants accumulating over the winter during a relatively short melt period. This process could result in elevated concentrations of contaminants in melt water. Recent studies in the Alberta oil sands region have documented increases in snowpack and lake sediment concentrations; however, no studies have addressed the fate and transport of contaminants during the snowmelt period. This study describes modelling approaches that were developed to assess potential effects of aerially deposited PAHs and metals to snowpack and snowmelt water concentrations. The contribution of snowmelt to freshwater PAH concentrations is assessed using a dynamic, multi-compartmental fate model, and the contribution to metal concentrations is estimated using a mass-balance approach. The modelling approaches described herein were applied to two watersheds in the Alberta oil sands region for two planned oil sands developments. Accumulation of PAHs in a lake within the deposition zone was also modelled for comparison to observed concentrations.

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation.

PubMed

Hu, Jing; Aitken, Michael D

2012-10-01

Dermal exposure can represent a significant health risk in settings involving potential contact with soil contaminated with polycyclic aromatic hydrocarbons (PAHs). However, there is limited work on the ability of PAHs in contaminated soil to reach the skin surface via desorption from the soil. We evaluated PAH desorption from a field-contaminated soil to a two-dimensional hydrophobic surface (C18 extraction disk) as a measure of potential dermal exposure as a function of soil loading (5-100 mg dry soil cm(-2)), temperature (20-40°C), and soil moisture content (2-40%) over periods up to 16d. The efficacy of bioremediation in removing the most readily desorbable PAH fractions was also evaluated. Desorption kinetics were described well by an empirical two-compartment kinetic model. PAH mass desorbed to the C18 disk kept increasing at soil loadings well above the estimated monolayer coverage, suggesting mechanisms for PAH transport to the surface other than by direct contact. Such mechanisms were reinforced by observations that desorption occurred even with dry or moist glass microfiber filters placed between the C18 disk and the soil. Desorption of all PAHs was substantially reduced at a soil moisture content corresponding to field capacity, suggesting that transport through pore air contributed to PAH transport to the C18 disk. The lower molecular weight PAHs had greater potential to desorb from soil than higher molecular weight PAHs. Biological treatment of the soil in a slurry-phase bioreactor completely eliminated PAH desorption to the C18 disks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation

PubMed Central

Hu, Jing; Aitken, Michael D.

2012-01-01

Dermal exposure can represent a significant health risk in settings involving potential contact with soil contaminated with polycyclic aromatic hydrocarbons (PAHs). However, there is limited work on the ability of PAHs in contaminated soil to reach the skin surface via desorption from the soil. We evaluated PAH desorption from a field-contaminated soil to a two-dimensional hydrophobic surface (C18 extraction disk) as a measure of potential dermal exposure as a function of soil loading (5 to 100 mg dry soil/cm2), temperature (20 °C to 40 °C), and soil moisture content (2% to 40%) over periods up to 16 d. The efficacy of bioremediation in removing the most readily desorbable PAH fractions was also evaluated. Desorption kinetics were described well by an empirical two-compartment kinetic model. PAH mass desorbed to the C18 disk kept increasing at soil loadings well above the estimated monolayer coverage, suggesting mechanisms for PAH transport to the surface other than by direct contact. Such mechanisms were reinforced by observations that desorption occurred even with dry or moist glass microfiber filters placed between the C18 disk and the soil. Desorption of all PAHs was substantially reduced at a soil moisture content corresponding to field capacity, suggesting that transport through pore air contributed to PAH transport to the C18 disk. The lower molecular weight PAHs had greater potential to desorb from soil than higher molecular weight PAHs. Biological treatment of the soil in a slurry-phase bioreactor completely eliminated PAH desorption to the C18 disks. PMID:22704210

Kinetics of degradation of surfactant-solubilized fluoranthene by a Sphingomonas paucimobilis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willumsen, P.A.; Arvin, E.

To achieve a better quantitative understanding of the stimulating or inhibiting effect of surfactants on the metabolism of polycyclic aromatic hydrocarbons (PAHs), a biodegradation model describing solubilization, bioavailability, and biodegradation of crystalline fluoranthene is proposed and used to model experimental data. The degradation was investigated in batch systems containing the PAH-degrading bacterium Sphingomonas paucimobilis strain EPA505, the nonionic surfactant Triton X-100, and a fluoranthene-amended liquid mineral salts medium. Surfactant-enhanced biodegradation is complex; however, the biodegradation model predicted fluoranthene disappearance and the initial mineralization well. Surfactant-amendment did increase fluoranthene mineralization rates by strain EPA505; however, the increases were not proportional tomore » the rates of fluoranthene solubilization. The surfactant clearly influenced the microbial PAH metabolism as indicated by a rapid accumulation of colored products and by a surfactant -related decreased in the overall extent of fluoranthene mineralization. Model estimations of the bioavailability of micelle-solubilized fluoranthene, the relatively fast fluoranthene disappearance, and the accumulation of extracellular compounds in the degradation system suggest that low availability of micellar fluoranthene is not the only factor controlling surfactant-enhanced biodegradation. Also factors such as the extent of accumulation and bioavailability of the PAH metabolites and the crystalline solubilization rate in the presence of surfactants may determine the overall effect of surfactant-enhanced biodegradation of high molecular weight PAHs.« less

Numerical evaluation of bioaccumulation and depuration kinetics of PAHs in Mytilus galloprovincialis.

PubMed

Yakan, S D; Focks, A; Klasmeier, J; Okay, O S

2017-01-01

Polycyclic aromatic hydrocarbons (PAHs) are important organic pollutants in the aquatic environment due to their persistence and bioaccumulation potential both in organisms and in sediments. Benzo(a)anthracene (BaA) and phenanthrene (PHE), which are in the priority pollutant list of the U.S. EPA (Environmental Protection Agency), are selected as model compounds of the present study. Bioaccumulation and depuration experiments with local Mediterranean mussel species, Mytilus galloprovincialis were used as the basis of the study. Mussels were selected as bioindicator organisms due to their broad geographic distribution, immobility and low enzyme activity. Bioaccumulation and depuration kinetics of selected PAHs in Mytilus galloprovincialis were described using first order kinetic equations in a three compartment model. The compartments were defined as: (1) biota (mussel), (2) surrounding environment (seawater), and (3) algae (Phaeodactylum tricornutum) as food source of the mussels. Experimental study had been performed for three different concentrations. Middle concentration of the experimental data was used as the model input in order to represent other high and low concentrations of selected PAHs. Correlations of the experiment and model data revealed that they are in good agreement. Accumulation and depuration trend of PAHs in mussels regarding also the durations can be estimated effectively with the present study. Thus, this study can be evaluated as a supportive tool for risk assessment in addition to monitoring studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Magnetofluid Simulations of the Global Solar Wind Including Pickup Ions and Turbulence Modeling

NASA Technical Reports Server (NTRS)

Goldstein, Melvyn L.; Usmanov, Arcadi V.; Matthaeus, William H.

2011-01-01

I will describe a three-dimensional magnetohydrodynamic model of the solar wind that takes into account turbulent heating of the wind by velocity and magnetic fluctuations as well as a variety of effects produced by interstellar pickup protons. In this report, the interstellar pickup protons are treated as one fluid and the protons and electrons are treated together as a second fluid. The model equations include a Reynolds decomposition of the plasma velocity and magnetic field into mean and fluctuating quantities, as well as energy transfer from interstellar pickup protons to solar wind protons that results in the deceleration of the solar wind. The model is used to simulate the global steady-state structure of the solar wind in the region from 0.3 to 100 AU. Where possible, the model is compared with Voyager data. Initial results from generalization to a three-fluid model is described elsewhere in this session.

In situ investigation of the mechanisms of the transport to tissues of polycyclic aromatic hydrocarbons adsorbed onto the root surface of Kandelia obovata seedlings.

PubMed

Li, Ruilong; Zhu, Yaxian; Zhang, Yong

2015-06-01

A novel method for in situ determination of the polycyclic aromatic hydrocarbons (PAHs) adsorbed onto the root surface of Kandelia obovata seedlings was established using laser-induced time-resolved nanosecond fluorescence spectroscopy (LITRF). The linear dynamic ranges for the established method were 1.5-1240ng/spot for phenanthrene, 1.0-1360ng/spot for pyrene and 5.0-1220ng/spot for benzo[a]pyrene. Then, the mechanisms of PAHs transport from the Ko root surface to tissues were investigated. The three-phase model including fast, slow and very slow fractions was superior to the single or dual-phase model to describe the PAHs transport processes. Moreover, the fast fraction of PAHs transport process was mainly due to passive movement, while the slow and very slow fractions were not. Passive movement was the main process of B[a]P adsorbed onto Ko root surface transport to tissues. In addition, the extent of the PAHs transport to Ko root tissues at different salinity were evaluated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Metal-PAH mixtures in the aquatic environment: a review of co-toxic mechanisms leading to more-than-additive outcomes.

PubMed

Gauthier, Patrick T; Norwood, Warren P; Prepas, Ellie E; Pyle, Greg G

2014-09-01

Mixtures of metals and polycyclic aromatic hydrocarbons (PAHs) occur ubiquitously in aquatic environments, yet relatively little is known regarding their combined toxicities. Emerging reports investigating the additive mortality in metal-PAH mixtures have indicated that more-than-additive effects are equally as common as strictly-additive effects, raising concern for ecological risk assessment typically based on the summation of individual toxicities. Moreover, the current separation of focus between in vivo and in vitro studies, and fine- and coarse-scale endpoints, creates uncertainty regarding the mechanisms of co-toxicity involved in more-than-additive effects on whole organisms. Drawing from literature on metal and PAH toxicity in bacteria, protozoa, invertebrates, fish, and mammalian models, this review outlines several key mechanistic interactions likely to promote more-than-additive toxicity in metal-PAH mixtures. Namely, the deleterious effects of PAHs on membrane integrity and permeability to metals, the potential for metal-PAH complexation, the inhibitory nature of metals to the detoxification of PAHs via the cytochrome P450 pathway, the inhibitory nature of PAHs towards the detoxification of metals via metallothionein, and the potentiated production of reactive oxygenated species (ROS) in certain metal (e.g. Cu) and PAH (e.g., phenanthrenequinone) mixtures. Moreover, the mutual inhibition of detoxification suggests the possibility of positive feedback among these mechanisms. The individual toxicities and interactive aspects of contaminant transport, detoxification, and the production of ROS are herein discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

On the cosmic ray diffusion in a violent interstellar medium

NASA Technical Reports Server (NTRS)

Bykov, A. M.; Toptygin, I. N.

1985-01-01

A variety of the available observational data on the cosmic ray (CR) spectrum, anisotropy and composition are in good agreement with a suggestion on the diffusion propagation of CR with energy below 10(15) eV in the interstellar medium. The magnitude of the CR diffusion coefficient and its energy dependence are determined by interstellar medium (ISM) magnetic field spectra. Direct observational data on magnetic field spectra are still absent. A theoretical model to the turbulence generation in the multiphase ISM is resented. The model is based on the multiple generation of secondary shocks and concomitant large-scale rarefactions due to supernova shock interactions with interstellar clouds. The distribution function for ISM shocks are derived to include supernova statistics, diffuse cloud distribution, and various shock wave propagation regimes. This permits calculation of the ISM magnetic field fluctuation spectrum and CR diffusion coefficient for the hot phase of ISM.

Evaluating officially reported polycyclic aromatic hydrocarbon emissions in the Athabasca oil sands region with a multimedia fate model

PubMed Central

Parajulee, Abha; Wania, Frank

2014-01-01

Emissions of organic substances with potential toxicity to humans and the environment are a major concern surrounding the rapid industrial development in the Athabasca oil sands region (AOSR). Although concentrations of polycyclic aromatic hydrocarbons (PAHs) in some environmental samples have been reported, a comprehensive picture of organic contaminant sources, pathways, and sinks within the AOSR has yet to be elucidated. We sought to use a dynamic multimedia environmental fate model to reconcile the emissions and residue levels reported for three representative PAHs in the AOSR. Data describing emissions to air compiled from two official sources result in simulated concentrations in air, soil, water, and foliage that tend to fall close to or below the minimum measured concentrations of phenanthrene, pyrene, and benzo(a)pyrene in the environment. Accounting for evaporative emissions (e.g., from tailings pond disposal) provides a more realistic representation of PAH distribution in the AOSR. Such indirect emissions to air were found to be a greater contributor of PAHs to the AOSR atmosphere relative to reported direct emissions to air. The indirect pathway transporting uncontrolled releases of PAHs to aquatic systems via the atmosphere may be as significant a contributor of PAHs to aquatic systems as other supply pathways. Emission density estimates for the three PAHs that account for tailings pond disposal are much closer to estimated global averages than estimates based on the available emissions datasets, which fall close to the global minima. Our results highlight the need for improved accounting of PAH emissions from oil sands operations, especially in light of continued expansion of these operations. PMID:24596429

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

PubMed

Valderrama, C; Cortina, J L; Farran, A; Gamisans, X; Lao, C

2007-06-01

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.

ASK1 Inhibition Halts Disease Progression in Preclinical Models of Pulmonary Arterial Hypertension.

PubMed

Budas, Grant R; Boehm, Mario; Kojonazarov, Baktybek; Viswanathan, Gayathri; Tian, Xia; Veeroju, Swathi; Novoyatleva, Tatyana; Grimminger, Friedrich; Hinojosa-Kirschenbaum, Ford; Ghofrani, Hossein A; Weissmann, Norbert; Seeger, Werner; Liles, John T; Schermuly, Ralph T

2018-02-01

Progression of pulmonary arterial hypertension (PAH) is associated with pathological remodeling of the pulmonary vasculature and the right ventricle (RV). Oxidative stress drives the remodeling process through activation of MAPKs (mitogen-activated protein kinases), which stimulate apoptosis, inflammation, and fibrosis. We investigated whether pharmacological inhibition of the redox-sensitive apical MAPK, ASK1 (apoptosis signal-regulating kinase 1), can halt the progression of pulmonary vascular and RV remodeling. A selective, orally available ASK1 inhibitor, GS-444217, was administered to two preclinical rat models of PAH (monocrotaline and Sugen/hypoxia), a murine model of RV pressure overload induced by pulmonary artery banding, and cellular models. Oral administration of GS-444217 dose dependently reduced pulmonary arterial pressure and reduced RV hypertrophy in PAH models. The therapeutic efficacy of GS-444217 was associated with reduced ASK1 phosphorylation, reduced muscularization of the pulmonary arteries, and reduced fibrotic gene expression in the RV. Importantly, efficacy was observed when GS-444217 was administered to animals with established disease and also directly reduced cardiac fibrosis and improved cardiac function in a model of isolated RV pressure overload. In cellular models, GS-444217 reduced phosphorylation of p38 and JNK (c-Jun N-terminal kinase) induced by adenoviral overexpression of ASK1 in rat cardiomyocytes and reduced activation/migration of primary mouse cardiac fibroblasts and human pulmonary adventitial fibroblasts derived from patients with PAH. ASK1 inhibition reduced pathological remodeling of the pulmonary vasculature and the right ventricle and halted progression of pulmonary hypertension in rodent models. These preclinical data inform the first description of a causal role of ASK1 in PAH disease pathogenesis.

Interstellar Grains: 50 Years on

NASA Astrophysics Data System (ADS)

Wickramasinghe, N. C.

Our understanding of the nature of interstellar grains has evolved considerably over the past half century with the present author and Fred Hoyle being intimately involved at several key stages of progress. The currently fashionable graphite-silicate-organic grain model has all its essential aspects unequivocally traceable to original peer-reviewed publications by the author and/or Fred Hoyle. The prevailing reluctance to accept these clear-cut priorities may be linked to our further work that argued for interstellar grains and organics to have a biological provenance -- a position perceived as heretical. The biological model, however, continues to provide a powerful unifying hypothesis for a vast amount of otherwise disconnected and disparate astronomical data.

Global atmospheric emissions and transport of polycyclic aromatic hydrocarbons: Evaluation of modeling and transboundary pollution

NASA Astrophysics Data System (ADS)

Shen, Huizhong; Tao, Shu

2014-05-01

Global atmospheric emissions of 16 polycyclic aromatic hydrocarbons (PAHs) from 69 major sources were estimated for a period from 1960 to 2030. Regression models and a technology split method were used to estimated country and time specific emission factors, resulting in a new estimate of PAH emission factor variation among different countries and over time. PAH emissions in 2007 were spatially resolved to 0.1° × 0.1° grids based on a newly developed global high-resolution fuel combustion inventory (PKU-FUEL-2007). MOZART-4 (The Model for Ozone and Related Chemical Tracers, version 4) was applied to simulate the global tropospheric transport of Benzo(a)pyrene, one of the high molecular weight carcinogenic PAHs, at a horizontal resolution of 1.875° (longitude) × 1.8947° (latitude). The reaction with OH radical, gas/particle partitioning, wet deposition, dry deposition, and dynamic soil/ocean-air exchange of PAHs were considered. The simulation was validated by observations at both background and non-background sites, including Alert site in Canadian High Arctic, EMEP sites in Europe, and other 254 urban/rural sites reported from literatures. Key factors effecting long-range transport of BaP were addressed, and transboundary pollution was discussed.

PAHs content of sewage sludge in Europe and its use as soil fertilizer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suciu, Nicoleta A., E-mail: nicoleta.suciu@unicatt.it; Lamastra, Lucrezia; Trevisan, Marco

2015-07-15

Highlights: • Sewage sludge contamination by PAHs may restrict its use as soil fertilizer. • Long term data concerning sewage sludge contamination by PAHs is lacking. • Literature review for EU countries and monitoring data for Italy is presented. • Focus PEARL model was used to simulate B(a)Pyr, the most toxic PAH, fate in soil. • The simulated B(a)Pyr soil concentration was much lower than its LOEC for soil organisms. - Abstract: The European Commission has been planning limits for organic pollutants in sewage sludge for 14 years; however no legislation has been implemented. This is mainly due to lackmore » of data on sewage sludge contamination by organic pollutants, and possible negative effects to the environment. However, waste management has become an acute problem in many countries. Management options require extensive waste characterization, since many of them may contain compounds which could be harmful to the ecosystem, such as heavy metals, organic pollutants. The present study aims to show the true European position, regarding the polycyclic aromatic hydrocarbons (PAHs) content of sewage sludge, by comparing the Italian PAHs content with European Union countries, and at assessing the suitability of sewage sludge as soil fertilizer. The FOCUS Pearl model was used to estimate the concentration of benzo [a] pyrene (B(a)Pyr), the most toxic PAH in soil, and its exposure to organisms was then evaluated. The simulated B(a)Pyr and PAHs, expressed as B(a)Pyr, concentrations in soil were much lower than the B(a)Pyr’s most conservative lowest observable effect concentration (LOEC) for soil organisms. Furthermore, the results obtained indicate that it is more appropriate to apply 5 t ha{sup −1} sewage sludge annually than 15 t ha{sup −1} triennially. Results suggest, the EU maximum recommended limit of 6 mg kg{sup −1} PAHs in sewage sludge, should be conservative enough to avoid groundwater contamination and negative effects on soil organisms.« less

Temperature dependence of Henry's law constants and KOA for simple and heteroatom-substituted PAHs by COSMO-RS

NASA Astrophysics Data System (ADS)

Parnis, J. Mark; Mackay, Donald; Harner, Tom

2015-06-01

Henry's Law constants (H) and octanol-air partition coefficients (KOA) for polycyclic aromatic hydrocarbons (PAHs) and selected nitrogen-, oxygen- and sulfur-containing derivatives have been computed using the COSMO-RS method between -5 and 40 °C in 5 °C intervals. The accuracy of the estimation was assessed by comparison of COSMOtherm values with published experimental temperature-dependence data for these and similar PAHs. COSMOtherm log H estimates with temperature-variation for parent PAHs are shown to have a root-mean-square (RMS) error of 0.38 (PAH), based on available validation data. Estimates of O-, N- and S-substituted derivative log H values are found to have RMS errors of 0.30 at 25 °C. Log KOA estimates with temperature variation from COSMOtherm are shown to be strongly correlated with experimental values for a small set of unsubstituted PAHs, but with a systematic underestimation and associated RMS error of 1.11. Similar RMS error of 1.64 was found for COSMO-RS estimates of a group of critically-evaluated log KOA values at room temperature. Validation demonstrates that COSMOtherm estimates of H and KOA are of sufficient accuracy to be used for property screening and preliminary environmental risk assessment, and perform very well for modeling the influence of temperature on partitioning behavior in the temperature range -5 to 40 °C. Temperature-dependent shifts of up to 2 log units in log H and one log unit for log KOA are predicted for PAH species over the range -5 and 40 °C. Within the family of PAH molecules, COSMO-RS is sufficiently accurate to make it useful as a source of estimates for modeling purposes, following corrections for systematic underestimation of KOA. Average changes in the values for log H and log KOA upon substitution are given for various PAH substituent categories, with the most significant shifts being associated with the ionizing nitro functionality and keto groups.

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples.

PubMed

Hong, Lei; Luthy, Richard G

2008-05-01

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.

Persistent activation of DNA damage signaling in response to complex mixtures of PAHs in air particulate matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Ian W.H., E-mail: Ian.Jarvis@ki.se; Bergvall, Christoffer, E-mail: Christoffer.Bergvall@anchem.su.se; Bottai, Matteo, E-mail: Matteo.Bottai@ki.se

2013-02-01

Complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are present in air particulate matter (PM) and have been associated with many adverse human health effects including cancer and respiratory disease. However, due to their complexity, the risk of exposure to mixtures is difficult to estimate. In the present study the effects of binary mixtures of benzo[a]pyrene (BP) and dibenzo[a,l]pyrene (DBP) and complex mixtures of PAHs in urban air PM extracts on DNA damage signaling was investigated. Applying a statistical model to the data we observed a more than additive response for binary mixtures of BP and DBP on activation of DNAmore » damage signaling. Persistent activation of checkpoint kinase 1 (Chk1) was observed at significantly lower BP equivalent concentrations in air PM extracts than BP alone. Activation of DNA damage signaling was also more persistent in air PM fractions containing PAHs with more than four aromatic rings suggesting larger PAHs contribute a greater risk to human health. Altogether our data suggests that human health risk assessment based on additivity such as toxicity equivalency factor scales may significantly underestimate the risk of exposure to complex mixtures of PAHs. The data confirms our previous findings with PAH-contaminated soil (Niziolek-Kierecka et al., 2012) and suggests a possible role for Chk1 Ser317 phosphorylation as a biological marker for future analyses of complex mixtures of PAHs. -- Highlights: ► Benzo[a]pyrene (BP), dibenzo[a,l]pyrene (DBP) and air PM PAH extracts were compared. ► Binary mixture of BP and DBP induced a more than additive DNA damage response. ► Air PM PAH extracts were more potent than toxicity equivalency factor estimates. ► Larger PAHs (> 4 rings) contribute more to the genotoxicity of PAHs in air PM. ► Chk1 is a sensitive marker for persistent activation of DNA damage signaling from PAH mixtures.« less

Modeling the exposure functions of atmospheric polycyclic aromatic hydrocarbon mixtures in occupational environments.

PubMed

Petit, Pascal; Maître, Anne; Persoons, Renaud; Bicout, Dominique J

2017-04-15

The health risk assessment associated with polycyclic aromatic hydrocarbon (PAH) mixtures faces three main issues: the lack of knowledge regarding occupational exposure mixtures, the accurate chemical characterization and the estimation of cancer risks. To describe industries in which PAH exposures are encountered and construct working context-exposure function matrices, to enable the estimation of both the PAH expected exposure level and chemical characteristic profile of workers based on their occupational sector and activity. Overall, 1729 PAH samplings from the Exporisq-HAP database (E-HAP) were used. An approach was developed to (i) organize E-HAP in terms of the most detailed unit of description of a job and (ii) structure and subdivide the organized E-HAP into groups of detailed industry units, with each group described by the distribution of concentrations of gaseous and particulate PAHs, which would result in working context-exposure function matrices. PAH exposures were described using two scales: phase (total particulate and gaseous PAH distribution concentrations) and congener (16 congener PAH distribution concentrations). Nine industrial sectors were organized according to the exposure durations, short-term, mid-term and long-term into 5, 36 and 47 detailed industry units, which were structured, respectively, into 2, 4, and 7 groups for the phase scale and 2, 3, and 6 groups for the congener scale, corresponding to as much distinct distribution of concentrations of several PAHs. For the congener scale, which included groups that used products derived from coal, the correlations between the PAHs were strong; for groups that used products derived from petroleum, all PAHs in the mixtures were poorly correlated with each other. The current findings provide insights into both the PAH emissions generated by various industrial processes and their associated occupational exposures and may be further used to develop risk assessment analyses of cancers associated with PAH mixtures. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct Observations of Interstellar H, He, and O by the Interstellar Boundary Explorer (Invited)

NASA Astrophysics Data System (ADS)

Moebius, E.; Bochsler, P. A.; Bzowski, M.; Crew, G. B.; Funsten, H. O.; Fuselier, S. A.; Ghielmetti, A.; Heirtzler, D.; Izmodenov, V.; Kubiak, M.; Kucharek, H.; Lee, M. A.; Leonard, T.; McComas, D. J.; Petersen, L.; Saul, L. A.; Scheer, J.; Schwadron, N. A.; Witte, M.; Wurz, P.

2009-12-01

Due to the motion of the Sun relative to its neighborhood, the neutral gas of the local in-terstellar medium (LISM) flows through the inner heliosphere where it is subject to ioni-zation, the Sun’s gravity, and radiation pressure. Observing the resulting spatial distribu-tion and flow pattern of several interstellar gas species with UV backscatter, pickup ion, and neutral atom imaging techniques allows us to unravel the physical conditions of the LISM and its interaction with the heliosphere. Imaging of the neutral gas flow directly with energetic neutral atom (ENA) cameras yields the most accurate account of the ki-netic parameters of the interstellar gas, but so far this has been carried out only for He using Ulysses GAS. IBEX, which was launched in October 2008, provides the capability for simultaneous flow observations of several interstellar species with its triple-time-of-flight IBEX-Lo sensor. Because H and O are strongly affected by the heliospheric inter-face while He is not, a direct comparison between these species enables an independent assessment of the slowdown and heating processes in the outer heliosheath. Likewise, IBEX observations will constrain models of the heliospheric interaction and provide a test of the heliospheric asymmetry - recently inferred from Voyager and SOHO SWAN observations - that is seen as an indicator for the interstellar magnetic field direction. During the first half year of its mission IBEX has observed the interstellar He, O, and H flow. We will present an overview and preliminary analysis of these first interstellar mul-tispecies scans of the interstellar gas flow in spring and fall 2009.

Improved source apportionment of PAHs and Pb by integrating Pb stable isotopes and positive matrix factorization application (PAHs): A historical record case study from the northern South China Sea.

PubMed

Cai, Minggang; Lin, Yan; Chen, Meng; Yang, Weifeng; Du, Huihong; Xu, Ye; Cheng, Shayen; Xu, Fangjian; Hong, Jiajun; Chen, Mian; Ke, Hongwei

2017-12-31

To obtain the historical changes of pyrogenic sources, integrated source apportionment methods, which include PAH compositions, diagnostic ratios (DRs), Pb isotopic ratios, and positive matrix factorization (PMF) model, were developed and applied in sediments of the northern South China Sea. These methods provided a gradually clear picture of energy structural change. Spatially, Σ 15 PAH (11.3 to 95.5ng/g) and Pb (10.2 to 74.6μg/g) generally exhibited decreasing concentration gradient offshore; while the highest levels of PAHs and Pb were observed near the southern Taiwan Strait, which may be induced by accumulation of different fluvial input. Historical records of pollutants followed closely with the economic development of China, with fast growth of Σ 15 PAH and Pb occurring since the 1980s and 1990s, respectively. The phasing-out of leaded gasoline in China was captured with a sharp decrease of Pb after the mid-1990s. PAHs and Pb correlated well with TOC and clay content for core sediments, which was not observed for surface sediments. There was an up-core increase of high molecular PAH proportions. Coal and biomass burning were then qualitatively identified as the major sources of PAHs with DRs. Furthermore, shift toward less radiogenic signatures of Pb isotopic ratios after 1900 revealed the start and growing importance of industrial sources. Finally, a greater separation and quantification of various input was achieved by a three-factor PMF model, which made it clear that biomass burning, coal combustion, and vehicle emissions accounted for 40±20%, 41±13%, and 19±12% of PAHs through the core. Biomass and coal combustion acted as major sources before 2000, while contributions from vehicle emission soared thereafter. The integrated multi-methodologies here improved the source apportionment by reducing biases with a step-down and cross-validation perspective, which could be similarly applied to other aquatic systems. Copyright © 2017 Elsevier B.V. All rights reserved.

[Health risk assessment of coke oven PAHs emissions].

PubMed

Bo, Xin; Wang, Gang; Wen, Rou; Zhao, Chun-Li; Wu, Tie; Li, Shi-Bei

2014-07-01

Polycyclic aromatic hydrocarbons (PAHs) produced by coke oven are with strong toxicity and carcinogenicity. Taken typical coke oven of iron and steel enterprises as the case study, the dispersion and migration of 13 kinds of PAHs emitted from coke oven were analyzed using AERMOD dispersion model, the carcinogenic and non-carcinogenic risks at the receptors within the modeling domain were evaluated using BREEZE Risk Analyst and the Human Health Risk Assessment Protocol for Hazardous Waste Combustion (HHRAP) was followed, the health risks caused by PAHs emission from coke oven were quantitatively evaluated. The results indicated that attention should be paid to the non-carcinogenic risk of naphthalene emission (the maximum value was 0.97). The carcinogenic risks of each single pollutant were all below 1.0E-06, while the maximum value of total carcinogenic risk was 2.65E-06, which may have some influence on the health of local residents.

Article title misstates the role of pavement sealers.

PubMed

O'Reilly, Kirk

2014-08-01

The claim made in the title of Witter et al. (2014) "Coal-tar-based sealcoated pavement: A major PAH source to urban stream sediments" is not supported by the data presented. The author's use of Pearson correlation coefficients is insufficient to indicate causation. The application of spatial analysis and principle component analysis did not include sealer specific inputs, so provides no basis for the claim. To test the hypothesis that sealers are a source of PAHs in the stream studied, EPA's Chemical Mass Balance (CMB) source evaluation model was applied to Witter's sediment data. CMB found an excellent fit (R(2) > 0.999) between measured and modeled PAH concentrations when sealers were not included as a potential source. This finding does not support Witter et al. (2014) claim that sealers are a major source of PAHs. Copyright © 2013 Elsevier Ltd. All rights reserved.

The interaction of the solar wind with the interstellar medium

NASA Technical Reports Server (NTRS)

Axford, W. I.

1972-01-01

The expected characteristics of the solar wind, extrapolated from the vicinity of the earth are described. Several models are examined for the interaction of the solar wind with the interstellar plasma and magnetic field. Various aspects of the penetration of neutral interstellar gas into the solar wind are considered. The dynamic effects of the neutral gas on the solar wind are described. Problems associated with the interaction of cosmic rays with the solar wind are discussed.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

PubMed Central

2016-01-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of ‘polar ice’ mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm ‘carbonyl’ absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes. PMID:28083090

An astrosphere around the blue supergiant κ Cas: possible explanation of its filamentary structure

NASA Astrophysics Data System (ADS)

Katushkina, O. A.; Alexashov, D. B.; Gvaramadze, V. V.; Izmodenov, V. V.

2018-01-01

High-resolution mid-infrared observations carried out by the Spitzer Space Telescope allowed one to resolve the fine structure of many astrospheres. In particular, they showed that the astrosphere around the B0.7 Ia star κ Cas (HD 2905) has a clear-cut arc structure with numerous cirrus-like filaments beyond it. Previously, we suggested a physical mechanism for the formation of such filamentary structures. Namely, we showed theoretically that they might represent the non-monotonic spatial distribution of the interstellar dust in astrospheres (viewed as filaments) caused by interaction of the dust grains with the interstellar magnetic field disturbed in the astrosphere due to colliding of the stellar and interstellar winds. In this paper, we invoke this mechanism to explain the structure of the astrosphere around κ Cas. We performed 3D magnetohydrodynamic modelling of the astrosphere for realistic parameters of the stellar wind and space velocity. The dust dynamics and the density distribution in the astrosphere were calculated in the framework of a kinetic model. It is found that the model results with the classical MRN (Mathis, Rumpl & Nordsieck 1977) size distribution of dust in the interstellar medium do not match the observations, and that the observed filamentary structure of the astrosphere can be reproduced only if the dust is composed mainly of big (μm-sized) grains. Comparison of the model results with observations allowed us to estimate parameters (number density and magnetic field strength) of the surrounding interstellar medium.

Evaluating the Morphology of the Local Interstellar Medium: Using New Data to Distinguish between Multiple Discrete Clouds and a Continuous Medium

NASA Astrophysics Data System (ADS)

Redfield, Seth; Linsky, Jeffrey L.

2015-10-01

Ultraviolet and optical spectra of interstellar gas along the lines of sight to nearby stars have been interpreted by Redfield & Linsky and previous studies as a set of discrete warm, partially ionized clouds each with a different flow vector, temperature, and metal depletion. Recently, Gry & Jenkins proposed a fundamentally different model consisting of a single cloud with nonrigid flows filling space out to 9 pc from the Sun that they propose better describes the local ISM. Here we test these fundamentally different morphological models against the spatially unbiased Malamut et al. spectroscopic data set, and find that the multiple cloud morphology model provides a better fit to both the new and old data sets. The detection of three or more velocity components along the lines of sight to many nearby stars, the presence of nearby scattering screens, the observed thin elongated structures of warm interstellar gas, and the likely presence of strong interstellar magnetic fields also support the multiple cloud model. The detection and identification of intercloud gas and the measurement of neutral hydrogen density in clouds beyond the Local Interstellar Cloud could provide future morphological tests. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the Data Archive at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS AR-09525.01A. These observations are associated with programs #11568.

Detection of Polarized Infrared Emission by Polycyclic Aromatic Hydrocarbons in the MWC 1080 Nebula

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Han; Telesco, Charles M.; Pantin, Eric

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in astrophysical environments, as revealed by their pronounced emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μ m commonly ascribed to the C–H and C–C vibrational modes. Although these features have long been predicted to be polarized, previous searches for PAH polarization led to null or, at best, tentative detections. Here we report the definite detection of polarized PAH emission at 11.3 μ m in the nebula associated with the Herbig Be star MWC 1080. We measure a polarization degree of 1.9% ± 0.2%, which is unexpectedly high compared to models. Thismore » poses a challenge in the current understanding of the alignment of PAHs, which is required to polarize the PAH emission but thought to be substantially suppressed. PAH alignment with a magnetic field via a resonance paramagnetic relaxation process may account for such a high level of polarization.« less

Influence of rice straw burning on the levels of polycyclic aromatic hydrocarbons in agricultural county of Taiwan.

PubMed

Lai, Chia-Hsiang; Chen, Kang-Shin; Wang, Hsin-Kai

2009-01-01

Atmospheric particulate and polycyclic aromatic hydrocarbons (PAHs) size distribution were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan during the rice straw burning and non-burning periods. The concentrations of total PAHs accounting for a roughly 58% (34%) increment in the concentrations of total PAHs due to rice-straw burning. Combustion-related PAHs during burning periods were 1.54-2.57 times higher than those during non-burning periods. The mass median diameter (MMD) of 0.88-1.21 microm in the particulate phase suggested that rice-straw burning generated the increase in coarse particle number. Chemical mass balance (CMB) receptor model analyses showed that the primary pollution sources at the two sites were similar. However, rice-straw burning emission was specifically identified as a significant source of PAH during burning periods at the two sites. Open burning of rice straws was estimated to contribute approximately 6.3%-24.6% to total atmospheric PAHs at the two sites.

Detection of Polarized Infrared Emission by Polycyclic Aromatic Hydrocarbons in the MWC 1080 Nebula

NASA Astrophysics Data System (ADS)

Zhang, Han; Telesco, Charles M.; Hoang, Thiem; Li, Aigen; Pantin, Eric; Wright, Christopher M.; Li, Dan; Barnes, Peter

2017-07-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in astrophysical environments, as revealed by their pronounced emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μm commonly ascribed to the C-H and C-C vibrational modes. Although these features have long been predicted to be polarized, previous searches for PAH polarization led to null or, at best, tentative detections. Here we report the definite detection of polarized PAH emission at 11.3 μm in the nebula associated with the Herbig Be star MWC 1080. We measure a polarization degree of 1.9% ± 0.2%, which is unexpectedly high compared to models. This poses a challenge in the current understanding of the alignment of PAHs, which is required to polarize the PAH emission but thought to be substantially suppressed. PAH alignment with a magnetic field via a resonance paramagnetic relaxation process may account for such a high level of polarization.

Inferring sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from the western Taiwan Strait through end-member mixing analysis.

PubMed

Li, Tao; Sun, Guihua; Ma, Shengzhong; Liang, Kai; Yang, Chupeng; Li, Bo; Luo, Weidong

2016-11-15

Concentration, spatial distribution, composition and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated based on measurements of 16 PAH compounds in surface sediments of the western Taiwan Strait. Total PAH concentrations ranged from 2.41 to 218.54ngg -1 . Cluster analysis identified three site clusters representing the northern, central and southern regions. Sedimentary PAHs mainly originated from a mixture of pyrolytic and petrogenic in the north, from pyrolytic in the central, and from petrogenic in the south. An end-member mixing model was performed using PAH compound data to estimate mixing proportions for unknown end-members (i.e., extreme-value sample points) proposed by principal component analysis (PCA). The results showed that the analyzed samples can be expressed as mixtures of three end-members, and the mixing of different end-members was strongly related to the transport pathway controlled by two currents, which alternately prevail in the Taiwan Strait during different seasons. Copyright © 2016. Published by Elsevier Ltd.

Polycyclic Aromatic Hydrocarbon Exposure in Household Air Pollution from Solid Fuel Combustion among the Female Population of Xuanwei and Fuyuan Counties, China

PubMed Central

2015-01-01

Exposure to polycyclic aromatic hydrocarbons (PAHs) from burning “smoky” (bituminous) coal has been implicated as a cause of the high lung cancer incidence in the counties of Xuanwei and Fuyuan, China. Little is known about variations in PAH exposure from throughout the region nor how fuel source and stove design affects exposure. Indoor and personal PAH exposure resulting from solid fuel combustion in Xuanwei and Fuyuan was investigated using repeated 24 h particle bound and gas-phase PAH measurements, which were collected from 163 female residents of Xuanwei and Fuyuan. 549 particle bound (283 indoor and 266 personal) and 193 gas phase (all personal) PAH measurements were collected. Mixed effect models indicated that PAH exposure was up to 6 times higher when burning smoky coal than smokeless coal and varied by up to a factor of 3 between different smoky coal geographic sources. PAH measurements from unventilated firepits were up to 5 times that of ventilated stoves. Exposure also varied between different room sizes and season of measurement. These findings indicate that PAH exposure is modulated by a variety of factors, including fuel type, coal source, and stove design. These findings may provide valuable insight into potential causes of lung cancer in the area. PMID:25393345

Characteristics of PAH tar oil contaminated soils-Black particles, resins and implications for treatment strategies.

PubMed

Trellu, Clément; Miltner, Anja; Gallo, Rosita; Huguenot, David; van Hullebusch, Eric D; Esposito, Giovanni; Oturan, Mehmet A; Kästner, Matthias

2017-04-05

Tar oil contamination is a major environmental concern due to health impacts of polycyclic aromatic hydrocarbons (PAH) and the difficulty of reaching acceptable remediation end-points. Six tar oil-contaminated soils with different industrial histories were compared to investigate contamination characteristics by black particles. Here we provide a simple method tested on 6 soils to visualize and identify large amounts of black particles (BP) as either solid aggregates of resinified and weathered tar oil or various wood/coke/coal-like materials derived from the contamination history. These materials contain 2-10 times higher PAH concentrations than the average soil and were dominantly found in the sand fraction containing 42-86% of the total PAH. The PAH contamination in the different granulometric fractions was directly proportional to the respective total organic carbon content, since the PAH were associated to the carbonaceous particulate materials. Significantly lower (bio)availability of PAH associated to these carbonaceous phases is widely recognized, thus limiting the efficiency of remediation techniques. We provide a conceptual model of the limited mass transfer of PAH from resinated tar oil phases to the water phase and emphasize the options to physically separate BP based on their lower bulk density and slower settling velocity. Copyright © 2017 Elsevier B.V. All rights reserved.

Ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in Changhua County, central Taiwan: Seasonal variation, source apportionment and cancer risk assessment.

PubMed

Chen, Yu-Cheng; Chiang, Hung-Che; Hsu, Chin-Yu; Yang, Tzu-Ting; Lin, Tzu-Yu; Chen, Mu-Jean; Chen, Nai-Tzu; Wu, Yuh-Shen

2016-11-01

This study investigates PM 2.5 -bound PAHs for rural sites (Dacheng and Fangyuan) positioned close to heavy air-polluting industries in Changhua County, central Taiwan. A total of 113 PM 2.5 samples with 22 PAHs collected from 2014 to 2015 were analyzed, and Positive Matrix Factorization (PMF) and diagnostic ratios of PAHs were applied to quantify potential PAH sources. The influences of local and regional sources were also explored using the conditional probability function (CPF) and potential source contribution function (PSCF) with PMF-modeled results, respectively. Annual mean concentrations of total PAHs were 2.91 ± 1.34 and 3.04 ± 1.40 ng/m 3 for Dacheng and Fangyuan, respectively, and their corresponding BaP eq were measured at 0.534 ± 0.255 and 0.563 ± 0.273 ng/m 3 in concentration. Seasonal variations with higher PAHs found for the winter than for the spring and summer were observed for both sites. The lifetime excess cancer risk (ECR) from inhalation exposure to PAHs was recorded as 4.7 × 10 -5 overall. Potential sources of PM 2.5 -bound PAHs include unburned petroleum and traffic emissions (42%), steel industry and coal combustion (31%), and petroleum and oil burning (27%), and unburned petroleum and traffic emission could contribute the highest ECR (2.4 × 10 -5 ). The CPF results show that directional apportionment patterns were consistent with the actual locations of local PAH sources. The PSCF results indicate that mainly northeastern regions of China have contributed elevated PM 2.5 -bound PAHs from long-range transports. Copyright © 2016 Elsevier Ltd. All rights reserved.

LONG TERM EFFECTS OF PRENATAL AND POSTNATAL AIRBORNE PAH EXPOSURE ON VENTILATORY LUNG FUNCTION OF NON-ASTHMATIC PREADOLESCENT CHILDREN. PROSPECTIVE BIRTH COHORT STUDY IN KRAKOW

PubMed Central

Jedrychowski, Wieslaw A.; Perera, Frederica P.; Maugeri, Umberto; Majewska, Renata; Mroz, Elzbieta; Flak, Elzbieta; Camman, David; Sowa, Agata; Jacek, Ryszard

2014-01-01

The main goal of the study was to test the hypothesis that prenatal and postnatal exposure to polycyclic aromatic hydrocarbons (PAH) is associated with depressed lung function in non-asthmatic children. The study sample comprises 195 non-asthmatic children of non-smoking mothers, among whom the prenatal PAH exposure was assessed by personal air monitoring in pregnancy. At the age of 3, residential air monitoring was carried out to evaluate the residential PAH exposure indoors and outdoors. At the age of 5 to 8, children were given allergic skin tests for indoor allergens; and between 5–9 years lung function testing (FVC, FEV05, FEV1 and FEF25–75) was performed. The effects of prenatal PAH exposure on lung function tests repeated over the follow-up were adjusted in the General Estimated Equation (GEE) model for the relevant covariates. No association between FVC with prenatal PAH exposure was found; however for the FEV1 deficit associated with higher prenatal PAH exposure (above 37ng/m3) amounted to 53 mL (p = 0.050) and the deficit of FEF25–75 reached 164 mL (p=0.013). The corresponding deficits related to postnatal residential indoor PAH level (above 42 ng/m3) were 59 mL of FEV1 (p=0.028) and 140 mL of FEF25–75 (p=0.031). At the higher residential outdoor PAH level (above 90 ng/m3) slightly greater deficit of FEV1 (71mL, p = 0.009) was observed. The results of the study suggest that transplacental exposure to PAH compromises the normal developmental process of respiratory airways and that this effect is compounded by postnatal PAH exposure. PMID:25300014

Biological Monitoring of Occupational Exposure to Polycyclic Aromatic Hydrocarbons at an Electric Steel Foundry in Tunisia.

PubMed

Campo, Laura; Hanchi, Mariem; Olgiati, Luca; Polledri, Elisa; Consonni, Dario; Zrafi, Ines; Saidane-Mosbahi, Dalila; Fustinoni, Silvia

2016-07-01

Occupational exposures during iron and steel founding have been classified as carcinogenic to humans, and the exposure to polycyclic aromatic hydrocarbons (PAHs) in this industrial setting may contribute to cancer risk. The occupational exposure to PAHs was assessed in 93 male workers at an electric steel foundry in Tunisia by biomonitoring, with the aims of characterizing the excretion profile and investigating the influence of job title and personal characteristics on the biomarkers. Sixteen 2-6 ring unmetabolized PAHs (U-PAHs) and eight hydroxylated PAH metabolites (OHPAHs) were analyzed by gas chromatography-triple quadrupole tandem mass spectrometry and liquid chromatography triple quadrupole tandem mass spectrometry, respectively. Among U-PAHs, urinary naphthalene (U-NAP) was the most abundant compound (median level: 643ng l(-1)), followed by phenanthrene (U-PHE, 18.5ng l(-1)). Urinary benzo[a]pyrene (U-BaP) level was <0.30ng l(-1) Among OHPAHs, 2-hydroxynaphthalene (2-OHNAP) was the most abundant metabolite (2.27 µg l(-1)). Median 1-hydroxypyrene (1-OHPYR) was 0.52 µg l(-1) Significant correlations among urinary biomarkers were observed, with Pearson's r ranging from 0.177 to 0.626. 1-OHPYR was correlated to benzo[a]pyrene, but not to five- and six-rings PAHs. A multiple linear regression model showed that job title was a significant determinant for almost all U-PAHs. In particular, employees in the steel smelter workshop had higher levels of high-boiling U-PAHs and lower levels of low-boiling U-PAHs than those of workers with other job titles. Among OHPAHs, this model was significant only for naphthols and 1-hydroxyphenanthrene (1-OHPHE). Smoking status was a significant predictor for almost all biomarkers. Among all analytes, U-PHE and 1-OHPHE were the less affected by tobacco smoke, and they were significantly correlated with both low- and high-molecular-weight compounds, and their levels were related to job titles, so they could be proposed as suitable biomarkers of PAH exposure at steel foundries. Based on 1-OHPYR levels, our findings show that occupational exposure of these workers was similar to that reported in recent studies of electric steel foundry workers. The multianalytic approach is useful in revealing different exposure levels among job titles. © The Author 2016. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Where is the Most Likely Location Where the Secondary Interstellar Oxygen Atoms Are Created Around the Heliosheath?

NASA Astrophysics Data System (ADS)

Park, J.; Kucharek, H.; Szabo, A.; Paschalidis, N.; Grocer, A.; Jones, S.

2017-12-01

The secondary component of the interstellar neutral gas flow is originated from charge exchange between the undisturbed primary interstellar neutrals and the ions that have been deflected as they approach the heliopause. The secondary neutrals that are emitted from the interstellar ion flow through charge exchange carry information on the diverted flow and a fraction of them can travel to the Sun. Therefore, the secondary component of the interstellar neutrals is an excellent diagnostic tool to provide important information to constrain the shape of the heliopause. The presence of the secondary neutrals was predicted in the global heliospheric models and they are observed by Interstellar Boundary Explorer (IBEX) at Earth's orbit. Using the IBEX observations of neutral helium atoms, Kubiak et al. (2016, ApJS, 223, 25) approximated the parent distribution of the secondary interstellar He atoms (so-called Warm Breeze) with a homogeneous Maxwellian distribution function. Park et al. (2016, ApJ, 833, 130) analyzed IBEX observations of secondary interstellar helium and oxygen distributions at Earth's orbit. Lee et al. (2012, ApJS, 198, 10) constructed the heliospheric phase-space distribution function of an interstellar gas species in the Earth frame as a function of solar longitude. In this distribution, the authors assume that the distribution is a drifting Maxwellian at large distances from the Sun. In this study, we assume that a fraction of the secondary neutral atoms has a velocity vector toward the Sun and they can be described as a flow with a drifting Maxwellian distribution near the heliopause. Unlike the primary interstellar gas flow, the distribution of the secondary neutrals is expected to have a wide width and their bulk speeds are slower than the bulk speed of the primary interstellar gas flow. We compare Lee's distribution and IBEX observations of neutral oxygen atoms and then estimate the most likely direction where the secondary interstellar oxygen atoms are created near the heliopause.

Modulation of Intersectin-1s Lung Expression Induces Obliterative Remodeling and Severe Plexiform Arteriopathy in the Murine Pulmonary Vascular Bed.

PubMed

Patel, Monal; Predescu, Dan; Bardita, Cristina; Chen, Jiwang; Jeganathan, Niranjan; Pritchard, Melanie; DiBartolo, Salvatore; Machado, Roberto; Predescu, Sanda

2017-03-01

Murine models of pulmonary arterial hypertension (PAH) that recapitulate the plexiform and obliterative arteriopathy seen in PAH patients and help in defining the molecular mechanisms involved are missing. Herein, we investigated whether intersectin-1s (ITSN) deficiency and prolonged lung expression of an ITSN fragment with endothelial cell (EC) proliferative potential (EH ITSN ), present in the lungs of PAH animal models and human patients, induce formation of plexiform/obliterative lesions and defined the molecular mechanisms involved. ITSN-deficient mice (knockout/heterozygous and knockdown) were subjected to targeted lung delivery of EH ITSN via liposomes for 20 days. Immunohistochemistry and histological and morphometric analyses revealed a twofold increase in proliferative ECs and a 1.35-fold increase in proliferative α-smooth muscle actin-positive cells in the lungs of ITSN-deficient mice, transduced with the EH ITSN relative to wild-type littermates. Treated mice developed severe medial wall hypertrophy, intima proliferation, and various forms of obliterative and plexiform-like lesions in pulmonary arteries, similar to PAH patients. Hemodynamic measurements indicated modest increases in the right ventricular systolic pressure and right ventricle hypertrophy. Transcriptional and protein assays of lung tissue indicated p38 MAPK -dependent activation of Elk-1 transcription factor and increased expression of c-Fos gene. This unique murine model of PAH-like plexiform/obliterative arteriopathy induced via a two-hit pathophysiological mechanism without hypoxia provides novel druggable targets to ameliorate and, perhaps, reverse the EC plexiform phenotype in severe human PAH. Copyright © 2017 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

Serum osteoprotegerin is increased and predicts survival in idiopathic pulmonary arterial hypertension

PubMed Central

Condliffe, Robin; Pickworth, Josephine A.; Hopkinson, Kay; Walker, Sara J.; Hameed, Abdul G.; Suntharaligam, Jay; Soon, Elaine; Treacy, Carmen; Pepke-Zaba, Joanna; Francis, Sheila E.; Crossman, David C.; Newman, Christopher M. H.; Elliot, Charles A.; Morton, Allison C.; Morrell, Nicholas W.; Kiely, David G.; Lawrie, Allan

2012-01-01

We previously reported that osteoprotegerin (OPG) is regulated by pathways associated with pulmonary arterial hypertension (PAH), and is present at elevated levels within pulmonary vascular lesions and sera from patients with idiopathic PAH (IPAH). Since OPG is a naturally secreted protein, we investigated the relationship between serum OPG and disease severity and outcome in patients with IPAH and animal models. OPG mRNA expression was measured in pulmonary artery smooth muscle cells (PASMC) from pulmonary arteries of patients with and without IPAH. Serum concentrations of OPG were measured in a retrospective and prospective group of patients. OPG levels were compared with phenotypic data and other putative PAH biomarkers. Prognostic significance was assessed and levels compared with healthy controls. Correlation of OPG and pulmonary vascular remodeling was also performed in rodent models of PAH. OPG mRNA was significantly increased 2-fold in PASMC isolated from explanted PAH lungs compared with control. Serum OPG concentrations were markedly elevated in IPAH compared with controls. In Cohort 1 OPG levels significantly correlated with mean right atrial pressure and cardiac index, while in Cohort 2 significant correlations existed between age-adjusted OPG levels and gas transfer. In both cohorts an OPG concentration above a ROC-derived threshold of 4728 pg/ml predicted poorer survival. In two rodent models, OPG correlated with the degree of pulmonary vascular remodeling. OPG levels are significantly elevated in patients with idiopathic PAH and are of prognostic significance. The role of OPG as a potential biomarker and therapeutic target merits further investigation. PMID:22558516

A New Model for the Heliosphere’s “IBEX Ribbon”

NASA Astrophysics Data System (ADS)

Giacalone, J.; Jokipii, J. R.

2015-10-01

We present a model for the narrow, ribbon-like enhancement in the emission of ∼keV energetic neutral atoms (ENA) coming from the outer heliosphere, coinciding roughly with the plane of the very local interstellar magnetic field (LISMF). We show that the pre-existing turbulent LISMF has sufficient amplitude in magnitude fluctuations to efficiently trap ions with initial pitch-angles near 90°, primarily by magnetic mirroring, leading to a narrow region of enhanced pickup-proton intensity. The pickup protons interact with cold interstellar hydrogen to produce ENAs seen at 1 AU. The computed width of the resulting ribbon of emission is consistent with observations. We also present results from a numerical model that are also generally consistent with the observations. Our interpretation relies only on the pre-existing turbulent interstellar magnetic field to trap the pickup protons. This leads to a broader local pitch-angle distribution compared to that of a ring. Our numerical model also predicts that the ribbon is double-peaked with a central depression. This is a further consequence of the (primarily) magnetic mirroring of pickup ions with pitch-angles close to 90° in the pre-existing, turbulent interstellar magnetic field.

A NEW MODEL FOR THE HELIOSPHERE’S “IBEX RIBBON”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giacalone, J.; Jokipii, J. R.

We present a model for the narrow, ribbon-like enhancement in the emission of ∼keV energetic neutral atoms (ENA) coming from the outer heliosphere, coinciding roughly with the plane of the very local interstellar magnetic field (LISMF). We show that the pre-existing turbulent LISMF has sufficient amplitude in magnitude fluctuations to efficiently trap ions with initial pitch-angles near 90°, primarily by magnetic mirroring, leading to a narrow region of enhanced pickup-proton intensity. The pickup protons interact with cold interstellar hydrogen to produce ENAs seen at 1 AU. The computed width of the resulting ribbon of emission is consistent with observations. Wemore » also present results from a numerical model that are also generally consistent with the observations. Our interpretation relies only on the pre-existing turbulent interstellar magnetic field to trap the pickup protons. This leads to a broader local pitch-angle distribution compared to that of a ring. Our numerical model also predicts that the ribbon is double-peaked with a central depression. This is a further consequence of the (primarily) magnetic mirroring of pickup ions with pitch-angles close to 90° in the pre-existing, turbulent interstellar magnetic field.« less

Desorption and Bioavailability of PAHs in Contaminated Soil Subjected to Long-Term In Situ Biostimulation

PubMed Central

Richardson, Stephen D.; Aitken, Michael D.

2011-01-01

The distribution and potential bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil from a former manufactured-gas plant (MGP) site were examined before and after long-term biostimulation under simulated in situ conditions. Treated soil was collected from the oxygenated zones of two continuous-flow columns, one subjected to biostimulation and the other serving as a control, and separated into low- and high-density fractions. In the original soil, over 50% of the total PAH mass was associated with lower-density particles, which comprised < 2% of the total soil mass. However, desorbable fractions of PAHs were much lower in the low-density material than in the high-density material. After over 500 d of biostimulation, significant removal of total PAHs occurred in both the high- and low-density materials (77% and 53%, respectively), with three- and four-ring PAHs accounting for the majority of the observed mass loss. Total PAHs that desorbed over a 28-d period were substantially lower in treated soil from the biostimulated column than in the original soil for both the high-density material (23 versus 63%) and low-density material (5 versus 20%). The fast-desorbing fractions quantified by a two-site desorption model ranged from 0.1 to 0.5 for most PAHs in the original soil but were essentially zero in the biostimulated soil. The fast-desorbing fractions in the original soil underestimated the extent of PAH biodegradation observed in the biostimulated column, and thus was not a good predictor of PAH bioavailability after long-term, simulated in situ biostimulation. PMID:21932296